Systems and methods for lithium deposition

Abstract

Improved systems and methods for depositing metal layers (e.g., lithium layers) with improved speed and microstructural control are generally provided. In some embodiments, the disclosure relates towards simultaneous gas-cooling and contact-cooling of a vapor deposition substrate. Improved cooling achieved by the systems and methods provided herein may be used to prepare articles useful for batteries and, in particular, to prepare electrode materials for batteries.

Description

[0001] SYSTEMS AND METHODS FOR LITHIUM DEPOSITION

[0002] RELATED APPLICATIONS

[0003] This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 63 / 615,835, filed December 29, 2023, and entitled “SYSTEMS AND METHODS FOR LITHIUM DEPOSITION,” and to U.S. Provisional Application No. 63 / 569,916, filed March 26, 2024, and entitled “SYSTEMS AND METHODS FOR LITHIUM DEPOSITION,” which are incorporated herein by reference in their entirety for all purposes.

[0004] TECHNICAL FIELD

[0005] The present disclosure relates generally to lithium metal electrodes, deposition systems, and associated systems and methods.

[0006] BACKGROUND

[0007] Metals may be vapor deposited on contact-cooled substrates. Improved cooling methods for continuous manufacturing processes would be advantageous.

[0008] SUMMARY

[0009] Improved systems and methods for depositing metal layers (e.g., lithium layers) with improved speed and microstructural control are generally provided. In some embodiments, the disclosure relates towards simultaneous gas-cooling and contactcooling of a vapor deposition substrate. Improved cooling achieved by the systems and methods provided herein may be used to prepare articles useful for batteries and, in particular, to prepare electrode materials for batteries. The subject matter of the present disclosure involves, in some cases, interrelated products, alternative solutions to a particular problem, and / or a plurality of different uses of one or more systems and / or articles.

[0010] In one aspect, a method of metal deposition is provided. According to some embodiments, the method comprises: simultaneously performing the steps of: removing heat from a substrate using a gas and a face of a roller, wherein both the gas and the face of the roller contact a first side of the substrate, depositing metal on a second side of the substrate opposite the first side of the substrate, rolling the substrate across the face of the roller, and determining the microstructure of metal deposited on the substrate.

[0011] In another aspect, a method of metal deposition is provided. According to some embodiments, the method comprises: simultaneously performing the steps of: removing heat from a substrate using a gas and a face of a roller, wherein both the gas and the face of the roller contact a first side of the substrate, depositing metal on a second side of the substrate opposite the first side of the substrate, rolling the substrate across the face of the roller, and maintaining the substrate at a temperature between 50% and 100% of a melting point of the deposited metal.

[0012] In yet another aspect, a method of lithium deposition is provided. According to some embodiments, the method comprises: simultaneously performing the steps of: removing heat from a substrate using a gas and a face of a roller, wherein both the gas and the face of the roller contact a first side of the substrate, depositing Zone T, Zone 2, or Zone 3 lithium on a second side of the substrate opposite the first side of the substrate, and rolling the substrate across the face of the roller.

[0013] In still another aspect, a system is provided. According to some embodiments, the system comprises: a cooling apparatus comprising: a roller, a coolant conduit adjacent to at least a portion of a face of the roller, fluidically connecting a coolant inlet to a coolant outlet, and a gas diffuser configured to emit a gas from at least a portion of the face of the roller; a metal deposition system configured to deposit metal on a substrate disposed adjacent to at least a portion of the face of the roller; and a detection system configured to determine a microstructure of the metal deposited on the substrate; and one or more processors configured to receive information from the detection system and operatively coupled with at least one of the metal deposition system and the cooling apparatus, wherein the one or more processors is configured to adjust operation of the metal deposition system and / or the cooling apparatus based, at least in part, on information received by the detection system.

[0014] In one aspect, a system is provided. According to some embodiments, the system comprises: a cooling apparatus comprising: a roller, a coolant conduit adjacent to at least a portion of a face of the roller, fluidically connecting a coolant inlet to a coolant outlet, and a gas diffuser configured to emit a gas from at least a portion of the face of the roller; and a metal deposition system configured to deposit metal on a substrate disposed adjacent to at least a portion of the face of the roller; wherein the cooling apparatus and the metal deposition system are configured to maintain the substrate at a temperature between 50% and 100% of a melting point of the metal deposited by the metal deposition system.

[0015] In one aspect, a system is provided. According to some embodiments, the system comprises: a cooling apparatus comprising: a roller, a coolant conduit adjacent to at least a portion of a face of the roller, fluidically connecting a coolant inlet to a coolant outlet, and a gas diffuser configured to emit a gas from at least a portion of the face of the roller; and a substrate disposed adjacent to at least a portion of the face of the roller, wherein at least a portion of the substrate comprises Zone T, Zone 2, or Zone 3 lithium.

[0016] In another aspect, an article is provided. According to some embodiments, the article comprises: a substrate, and a lithium metal layer disposed on the substrate; wherein the lithium metal layer comprises a volume of greater than or equal to 50 mL wherein greater than or equal to 70% of the volume is occupied by Zone 3 lithium.

[0017] In yet another aspect, an article is provided. According to some embodiments, the article comprises: a substrate, and a lithium metal layer disposed on the substrate; wherein the lithium metal layer has a thickness of less than or equal to 20 microns and comprises Zone 3 lithium.

[0018] In still another aspect, an article is provided. According to some embodiments, the article comprises: a substrate, a lithium metal layer disposed on the substrate, and a passivating layer disposed on the lithium metal layer; wherein greater than or equal to 70% of the volume of the lithium metal layer is occupied by Zone 3 lithium, and wherein greater than or equal to 70% of the volume of the passivating layer is occupied by Zone 3 material.

[0019] In another aspect, a method is provided. According to some embodiments, the method comprises: charging a battery to form a lithium metal anode, wherein greater than or equal to 70% of the volume of the formed lithium metal anode is occupied by Zone 3 lithium.

[0020] In one aspect, an article is provided. According to some embodiments, the article comprises: a substrate, and a plurality of lithium metal layers disposed on the substrate; wherein the plurality of lithium metal layers have a total volume of greater than or equal to 50 mL, wherein greater than or equal to 70% of the volume is occupied by Zone 3 lithium.

[0021] Other advantages and novel features of the present disclosure will become apparent from the following detailed description of various non-limiting embodiments of the disclosure when considered in conjunction with the accompanying figures. In cases where the present specification and a document incorporated by reference include conflicting and / or inconsistent disclosure, the present specification shall control.

[0022] BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Non-limiting embodiments of the present disclosure will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale unless otherwise indicated. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the disclosure shown where illustration is not necessary to allow those of ordinary skill in the art to understand the disclosure. In the figures:

[0024] FIG. 1 presents a non-limiting, schematic illustration of a metal deposition system comprising a cooling apparatus, according to some embodiments;

[0025] FIG. 2 presents a perspective, schematic illustration of a cooling apparatus, according to some embodiments;

[0026] FIG. 3A presents a perspective, schematic illustration of a gas diffuser, according to some embodiments;

[0027] FIG. 3B presents a perspective, schematic illustration of a gas diffuser, according to some embodiments;

[0028] FIG. 3C presents a perspective, schematic illustration of a gas diffuser, according to some embodiments;

[0029] FIG. 3D presents an exploded perspective, schematic illustration of a plurality of gas diffusers, according to some embodiments; FIG. 3E presents a perspective, schematic illustration of a gas diffuser, according to some embodiments;

[0030] FIG. 4A presents a perspective, schematic illustration of a cooling apparatus, according to some embodiments;

[0031] FIG. 4B presents a perspective, schematic illustration of a cooling apparatus, according to some embodiments;

[0032] FIG. 5 presents a schematic flow diagram of a method of metal deposition, according to some embodiments;

[0033] FIG. 6 presents a schematic flow diagram of a method of metal deposition, according to some embodiments;

[0034] FIG. 7 presents a schematic illustration of a Thornton diagram, according to some embodiments;

[0035] FIG. 8 presents a schematic flow diagram of a method of metal deposition, according to some embodiments;

[0036] FIG. 9 presents a non-limiting, schematic illustration of a metal deposition system comprising a cooling apparatus, according to some embodiments;

[0037] FIG. 10A presents a non-limiting, schematic, perspective illustration of a cooling apparatus, according to some embodiments;

[0038] FIG. 10B presents a non-limiting, schematic, cross-sectional illustration of a cooling apparatus, according to some embodiments;

[0039] FIG. 10C presents a non-limiting, schematic, side-view illustration of a cooling apparatus, according to some embodiments;

[0040] FIG. 10D presents a non-limiting, schematic, end- view illustration of a cooling apparatus, according to some embodiments;

[0041] FIG. 10E presents a non-limiting, schematic, end-view illustration of a cooling apparatus, according to some embodiments;

[0042] FIG. 10F presents a non-limiting, schematic, side-view illustration of a valve actuator of a cooling apparatus, according to some embodiments;

[0043] FIG. 10G presents a non-limiting, schematic, end- view illustration of a plurality of valves of a cooling apparatus, according to some embodiments; FIG. 11 presents a non-limiting, schematic illustration of a deposition system comprising a roll-to-roll handling system, according to some embodiments;

[0044] FIG. 12 presents a non-limiting, schematic illustration of a source positioned in a container, according to some embodiments;

[0045] FIG. 13 presents a non-limiting, schematic illustration of a cooling system comprising walls in which channels are arranged, according to some embodiments;

[0046] FIG. 14 presents a non-limiting, schematic illustration of a container for a source comprising a shutter, according to some embodiments;

[0047] FIG. 15 presents a non-limiting, schematic illustration of a module comprising three sources, according to some embodiments;

[0048] FIG. 16 presents a non-limiting, schematic illustration of a module comprising a vacuum chamber in which a first roller and a second roller are positioned, according to some embodiments;

[0049] FIG. 17 presents a non-limiting, schematic illustration of a module comprising two or more sources positioned in a common container and / or in fluidic communication with a common port, according to some embodiments;

[0050] FIG. 18 presents a non-limiting, schematic illustration of a plurality of sources in the form of wires that are initially wound around a roll, and then unrolled onto the heated crucible, according to some embodiments;

[0051] FIG. 19 presents a non-limiting, schematic cross-sectional illustration of an article for inclusion in an electrochemical cell that comprises a layer comprising metal (e.g., lithium metal), according to some embodiments;

[0052] FIG. 20 presents a non-limiting, schematic cross-sectional illustration of an article having an additional species in a layer comprising a metal (e.g., lithium metal), according to some embodiments;

[0053] FIG. 21 presents a non-limiting, schematic cross-sectional illustration of an article having an additional species in a location other than the layer comprising metal (e.g., lithium metal), according to some embodiments;

[0054] FIG. 22 presents a non-limiting, schematic cross-sectional illustration of an article comprising a layer comprising metal (e.g., lithium metal) and a layer disposed thereon that comprises a plurality of columnar structures, according to some embodiments;

[0055] FIG. 23 shows the simulated temperature of the roller of the cooling apparatus and of the top and bottom of the substrate as a function of time, according to some embodiments;

[0056] FIG. 24 shows the results of the same simulation, where gas-cooling is added, according to some embodiments;

[0057] FIGS. 25 and 26 present rescaled versions of the data of FIGS. 23 and 24, respectively, to facilitate visual comparison of the roller temperatures across an identical Y-axis range, according to some embodiments;

[0058] FIGS. 27A-27B present scanning electron microscope (SEM) images of an exemplary layer of Zone 1 lithium, according to some embodiments;

[0059] FIG. 28 presents a scanning electron microscope (SEM) image of an exemplary layer of Zone T lithium, according to some embodiments;

[0060] FIGS. 29A-29B present scanning electron microscope (SEM) images of an exemplary layer of Zone 2 lithium, according to some embodiments;

[0061] FIGS. 30A-30B present scanning electron microscope (SEM) images of an exemplary layer of Zone 3 lithium, according to some embodiments;

[0062] FIG. 31 presents XRD peak intensities for non-limiting lithium metal layers deposited at various temperatures, according to some embodiments; and

[0063] FIGS. 32A-32K present SEM images for non-limiting lithium metal layers deposited at various temperatures, according to some embodiments.

[0064] DETAILED DESCRIPTION

[0065] Systems and methods for improving vapor deposition rates and / or the quality of vapor-deposited layers are generally provided. Vapor deposition is a robust technique for the deposition of materials such as metals, especially metals for use as anode materials in batteries. In order to obtain desirable microstructures during vapor deposition, condensation and / or solidification of deposited materials must be controlled. The present disclosure is directed, in various embodiments, towards improved cooling methods and systems that can increase the rate of vapor deposition and / or that can improve the quality of vapor deposited films by favorably altering condensation and / or solidification conditions. For example, in some aspects, the disclosure relates to simultaneously gas-cooling and contact-cooling a vapor deposition substrate using a roller comprising a gas diffuser. As discussed below, the systems and methods provided herein may have particular advantages for the vapor deposition of anode materials (e.g., pure lithium or a lithium alloy) with high-quality microstructures suitable for use in batteries.

[0066] In some aspects, systems and methods for cooling a substrate during metal deposition are provided. For example, in some embodiments, a system for cooling a substrate comprises a cooling apparatus configured to remove heat from a substrate. FIG. 1 presents a non-limiting, schematic illustration of a system 101 suitable for metal deposition, according to some embodiments. As illustrated, system 101 comprises a cooling apparatus 151, which comprises a roller 103 that may be configured to cool a substrate 105 (e.g., while the substrate is rolled across a face of the roller). Cooling apparatus 151 may be configured to cool the substrate by contacting the substrate with the roller and / or by using a gas diffuser 121 (illustrated in this non-limiting example as a perforated shell of the roller) to emit gas flow 153 from at least a portion of the face of roller 103 towards the substrate. In some embodiments, gas flowing towards the substrate and contacting the substrate with roller 103 are simultaneously performed to cool the substrate. Without wishing to be bound by any particular theory, simultaneous heat transfer via roller- substrate contact and substrate-gas contact may be advantageous, since substrate-gas contact may be used to cool portions of the substrate that are not in direct contact with the roller. For example, without wishing to be bound by any particular theory, the substrate and the roller may have intrinsic roughness values that limit contact between the substrate and the roller to only a fraction of the substrate’s total surface area. The uncontacted surface of the substrate may not be able to transfer heat because the vacuum environment used for metal deposition (e.g., vapor deposition) insulates the uncontacted portion of the substate’s surface from heat transfer. Without wishing to be bound by any particular theory, the flow of gas from the cooling apparatus can create a heat flow pathway through the gas, so that heat can be transferred away from the uncontacted surface area of the substrate, improving heat transfer away from the substrate.

[0067] As shown illustratively in FIG. 1, system 101 and cooling apparatus 151 may be suitable for use in a continuous deposition process. For example, in FIG. 1, substrate 105 is rolled in a direction 175 while roller 103 of the cooling apparatus rotates in direction 177. System 101 may further comprise a metal source 111 configured to direct a vapor (e.g., metal vapor from the metal source) 113 towards substrate 105. During deposition, heat transfer from the vapor to the substrate may result in condensation of the vapor to form a condensed phase (e.g., a solid or a liquid). The cooling apparatus may cool a first side of the substrate (e.g., by one or more of the cooling methods described herein) during deposition of the metal on a second side of the substrate opposite / opposing the first side of the substrate. In this way, the cooling apparatus may remove at least some of the heat transferred to the substrate from the vapor. By controlling the deposition and cooling rates, the micro structure of the deposited material may be controlled, according to some embodiments. As illustrated in FIG. 1, system 101 may comprise one or more optional components, such as additional rollers 191, which may be used to provide additional cooling, to better align substrate 105, and / or to impart momentum to substrate 105 during a deposition process. It should, of course, be understood that additional rollers are not required, as the disclosure is not so limited.

[0068] FIG. 2 provides a perspective illustration showing various features of a cooling apparatus 251. As shown, cooling apparatus 251 comprises a roller 203. A gas diffuser 221 of cooling apparatus 251 is configured to emit gas flows 253 from the surface of roller 203 during operation of cooling apparatus 251. (In FIG. 2, gas diffuser 221 is depicted as a transparent cylinder, to provide visual clarity of features disposed beneath the gas diffuser.) Any of a variety of suitable gas diffusers may be used. For example, in some embodiments, gas diffuser 221 is a plate (e.g., having a cylindrical shape) comprising a plurality of holes 226 (e.g., through-holes like circular holes or slits as described with reference to FIGS. 3A-3C below). According to some embodiments, the gas diffuser is a porous body (e.g., a metallic mesh) encircling the roller. For example, the gas diffuser may be a porous shell that surrounds the exterior of the roller and is mechanically coupled to the roller. As another example, in some embodiments, a plurality of porous gas diffusers are mechanically coupled to the roller such that each encloses at least a portion of the roller’s surface. Other gas diffusers are also possible, as the disclosure is not so limited.

[0069] According to some embodiments, the cooling apparatus further comprises a coolant conduit 241 as shown illustratively in FIG. 2. Coolant conduit 241 may be configured to permit a flow of coolant through the cooling apparatus, which may cool roller 203. As shown illustratively in FIG. 2, coolant conduit 241 may comprise a coolant inlet 243 and a coolant outlet 245 to permit coolant flow 257 into coolant conduit 241 at coolant inlet 243, through coolant conduit 241, and out of coolant conduit 241 at coolant outlet 245. Coolant conduit 241 may be used to cool (e.g., to continuously cool) roller 203 during operation of cooling apparatus 251 by the passage of coolant through the coolant conduit. For example, in some embodiments, coolant flow 257 is heated during its passage through cooling conduit 241 such that coolant exiting coolant conduit 241 via outlet 245 is hotter than coolant entering coolant conduit 241 via inlet 243. It should, of course, be understood that the particular disposition of the coolant conduit within the roller is not limited to the configuration of FIG. 2, and that cooling apparatuses may generally comprise one or a plurality of coolant conduits having any of a variety of dispositions within the cooling apparatus, depending on the embodiment. The use of a plurality of cooling conduits may be advantageous, for example, because in some embodiments the use of a plurality of cooling conduits may result in a more homogeneous surface temperature of the roller, depending on the embodiment.

[0070] The cooling conduit may be in thermal communication with an external surface of the roller and / or with a gas diffuser of the roller. For example, in some embodiments the coolant conduits directly contact an interior surface the roller such that it is in thermal communication with an external surface of the roller and / or with the gas diffuser via a direct pathway through the roller. In some embodiments, the cooling conduit thermally communicates with the external surface of the roller and / or with the gas diffuser indirectly, via one or more intervening components. Intervening components may be configured to facilitate rapid heat transfer between the coolant conduit and the external surface of the roller and / or the coolant conduit. For example, in some embodiments, the coolant conduit may be in thermal communication with the external surface of the roller and / or the gas diffuser via a thermal paste. Other embodiments and other intervening components are also possible, as the disclosure is not so limited.

[0071] Any of a variety of suitable coolants may be used in a cooling conduit as described herein. For example, the coolant may be a liquid or a gas, depending on the embodiment. According to some embodiments, for example, the coolant may comprise liquid water, liquid glycol, liquid CO2, gaseous CO2 and / or mixtures thereof. According to some embodiments, the coolant conduit is configured such that coolant can only flow into or out of the cooling apparatus via the inlet or the outlet. In some embodiments, a coolant conduit is fluidically isolated from the gas diffuser of the cooling apparatus. For example, referring again to FIG. 2, coolant conduit 241 is closed between inlet 243 and outlet 245 and thus does not provide gas flows 253; rather, gas flows 253 originate from an alternative gas source (not shown in FIG. 2) that is fluidically connected to gas diffuser 221. Exemplary fluidic connections to the gas diffuser are described and illustrated in greater detail elsewhere herein.

[0072] As discussed above with reference to FIGS. 1-2, in some embodiments, a metal (e.g., lithium) deposition system comprises a gas diffuser configured to emit a gas from at least a portion of the face of a roller. The gas diffuser may comprise a plurality of openings (e.g., through-holes, pores) configured to be fluidically connected to one or more gas sources. The openings may be arranged to distribute the gas across at least a portion of the face of the roller. In some embodiments, the openings are arranged to provide a relatively uniform gas distribution across the at least a portion of the face of the roller. For example, the plurality of openings may be distributed relatively uniformly (e.g., regularly or randomly spaced) across the at least a portion of the face of the roller. The use of a gas diffuser may provide a number of advantages for cooling a substrate. For example, according to some embodiments the gas diffuser may be used to cool the substrate at surfaces otherwise insulated from the face of the roller by providing gas to the substrate via the openings of the gas diffuser.

[0073] Any of a variety of types of gas diffuser may be used in the systems and methods provided herein. According to some embodiments, the gas diffuser comprises a plate including a plurality of through-holes. FIG. 3A presents such an embodiment, providing a perspective, schematic illustration of a gas diffuser 321 that comprises a plate 324 comprising a plurality of through holes 326. Although FIG. 3A presents through holes 326 as circular holes, it should be understood that the through-holes in a plate may be of any of a variety of appropriate shapes, as the disclosure is not so limited). To provide a few, non-limiting examples, the through-holes may have polygonal or circular crosssections (e.g., like the holes of FIG. 3A), or may be slits (e.g., elongated through-holes having an aspect ratio of greater than or equal to 5: 1, greater than or equal to 10:1, greater than or equal to 20:1, greater than or equal to 50:1, or greater). FIG. 3B provides a perspective, schematic illustration of a non-limiting gas diffuser 321 that comprises slits 328 which are through-holes in a plate 324, for example. According to some embodiments, the gas diffuser comprises a porous network, and the plurality of openings of the gas diffuser are a plurality of openings of pores of the porous network disposed on a surface of the gas diffuser. For example, in some embodiments, the gas diffuser comprises a wire web comprising a porous network. FIG. 3C provides a schematic, perspective illustration of a non-limiting gas diffuser 321 comprising wire web 330, for example. In some embodiments, the gas diffuser comprises a porous plate comprising a porous network through which gas may flow. Other embodiments of gas diffusers are also possible.

[0074] Any of a variety of appropriate proportions of an external surface of the gas diffuser may be occupied by openings (e.g., through-holes or pore openings), depending on the embodiment. In some embodiments, a gas diffuser comprises openings covering (or making up) greater than or equal to 2%, greater than or equal to 5%, greater than or equal to 7%, greater than or equal to 10%, greater than or equal to 12%, greater than or equal to 15%, greater than or equal to 17%, greater than or equal to 20%, greater than or equal to 22%, greater than or equal to 25%, greater than or equal to 27%, greater than or equal to 30%, greater than or equal to 32%, greater than or equal to 35%, greater than or equal to 37%, greater than or equal to 40%, greater than or equal to 42%, greater than or equal to 45%, greater than or equal to 47%, greater than or equal to 50%, greater than or equal to 52%, greater than or equal to 55%, greater than or equal to 57%, greater than or equal to 60%, greater than or equal to 62%, greater than or equal to 65%, greater than or equal to 67%, greater than or equal to 70%, greater than or equal to 72%, greater than or equal to 75%, greater than or equal to 77%, greater than or equal to 80%, greater than or equal to 82%, greater than or equal to 85%, greater than or equal to 87%, greater than or equal to 90%, or greater than or equal to 92% of the surface area of an external surface area of the gas diffuser. In some embodiments, a gas diffuser comprises openings covering (or making up) less than or equal to 95%, less than or equal to 92%, less than or equal to 90%, less than or equal to 87%, less than or equal to 85%, less than or equal to 82%, less than or equal to 80%, less than or equal to 77%, less than or equal to 75%, less than or equal to 72%, less than or equal to 70%, less than or equal to 67%, less than or equal to 65%, less than or equal to 62%, less than or equal to 60%, less than or equal to 57%, less than or equal to 55%, less than or equal to 52%, less than or equal to 50%, less than or equal to 47%, less than or equal to 45%, less than or equal to 42%, less than or equal to 40%, less than or equal to 37%, less than or equal to 35%, less than or equal to 32%, less than or equal to 30%, less than or equal to 27%, less than or equal to 25%, less than or equal to 22%, less than or equal to 20%, less than or equal to 17%, less than or equal to 15%, less than or equal to 12%, less than or equal to 10%, less than or equal to 7%, or less than or equal to 5% of the surface area of an external surface area of the gas diffuser. Combinations of these ranges are also possible (e.g., greater than or equal to 2% and less than or equal to 95%, greater than or equal to 2% and less than or equal to 20% (e.g., in the case of diffusers comprising through-holes), or greater than or equal to 50% and less than or equal to 95% (e.g., in the case of diffusers comprising p). Other ranges are also possible.

[0075] The gas diffuser may comprise one or more portions separate from the roller of the cooling apparatus. For example, gas diffuser 321 of FIG. 3C is shown as a separate component that may be mechanically coupled against the roller such that it encircle the roller, like gas diffuser 221 of FIG. 2. A gas diffuser may be mechanically coupled against the roller by any of a variety of suitable means. For example, in some embodiments, the gas diffuser is formed on the roller, is stretched over the roller, is welded such that it encircles the roller, or is fastened such that it encircles the roller. In some embodiments, the gas diffuser is integrally formed with the roller. For example, gas diffuser 321 of FIG. 3 A is a cylindrical shell that is designed to be integrally formed with a roller. According to some embodiments, advantages have been recognized for the use of gas diffusers that are removable from a cooling apparatus. For example, in some embodiments, a cooling apparatus comprises a plurality of gas diffusers. The gas diffusers may each be configured to mechanically couple to the roller of a cooling apparatus (e.g., using one or more fasteners and / or frictional forces between the gas diffusers and the roller). In some embodiments, the gas diffusers are configured so that some or all of the gas diffusers encircle at least a portion of the roller of the apparatus. In some embodiments, the gas diffusers are configured to be mechanically coupled (e.g., to the roller and / or to one another) such that they encircle at least a portion of the roller. FIG. 3D provides an exploded perspective, schematic illustration of a non-limiting plurality of gas diffusers 321a, 321b, 321c, and 321d that are configured such that each of the gas diffusers can encircle at least a portion of a roller (not shown). FIG. 3E shows a perspective, schematic illustration of non-limiting cooling apparatus 351 comprising gas diffusers 321a, 321b, 321c, and 321d, each of which is mechanically coupled to one another via fasteners 333, and mechanically coupled to roller 303 of cooling apparatus 351 via frictional forces (not illustrated, but existing where the roller contacts the gas diffusers). It should, of course, be understood that other configurations of gas diffusers not shown in FIG. 3E are also possible, including but not limited to embodiments where gas diffusers are mechanically coupled to the roller using one or more fasteners directly coupling the gas diffusers to the roller, and embodiments where one or more of the gas diffusers are separated from the roller by one or more intervening layers, through which frictional forces mechanically coupling the one or more gas diffusers to the roller may be transferred.

[0076] According to some embodiments, a gas diffuser is configured to physically contact a substrate rolled across the face of the roller during operation. It should be understood that a substrate may be rolled across a face of the roller without directly contacting the face of the roller, depending on the embodiment. For example, the substrate may be rolled across the face of a roller but separated from the face of the roller by a gas diffuser at least partially encircling the roller. According to some embodiments, the substrate directly contacts the face of the roller across which it rolls. For example, in some embodiments, a gas diffuser is integrally formed with the roller such that the gas diffuser forms at least a portion of the face of the roller.

[0077] By rolling the substrate across the face of the roller, the gas diffuser at least partially encircling the roller may act as a heat sink, conveying heat from a portion of the substrate into the roller via physical contact between the gas diffuser. The gas diffuser may, in addition to acting as a heat sink, supply gas to the substrate. The gas from the gas diffuser may contact the same side of the substrate contacted by the gas diffuser itself. It may therefore be advantageous to use a gas diffuser comprising a thermally conductive material, so that heat from the substrate can be more rapidly transferred to the roller. A few, non-limiting examples of materials that may be used for making a gas diffuser include, but are not limited to, copper, aluminum, and / or stainless steel.

[0078] A gas diffuser may be fluidically connected to (e.g., in fluid communication with) a gas source in any of a variety of suitable ways. For example, according to some embodiments, the cooling apparatus comprises one or more gas conduits configured to fluidically connect a gas diffuser to one or more gas inlets of a cooling apparatus. FIG. 4A provides a non-limiting, perspective illustration of a portion of a cooling apparatus 451 comprising a transparent gas diffuser 441 and gas conduits 459 fluidically connecting the gas diffuser to gas inlets 461. It should, of course, be understood that although FIG. 4A shows two distinct gas conduits, any of a variety of suitable numbers of gas conduits may be used (e.g., at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or more) as the disclosure is not so limited.

[0079] In some embodiments, the gas conduit is configured to transport gas to a surface (e.g., an internal surface facing the roller) of the gas diffuser. In some embodiments, such as the embodiment shown in FIG. 4A, through-holes 426 of gas diffuser 421 act as a direct extensions of the gas conduit 459, such that one or more outlets 446 of the gas conduit are connected to through-holes 426 as shown. In other embodiments, openings of internal surfaces of the gas diffuser may be mismatched with one or more outlets of the gas conduit. For example, one or more outlets of the gas conduit may be disposed beneath a porous internal surface of a porous gas diffuser and may be unaligned with any particular opening of the porous surface. In some embodiments, the gas diffuser is configured to receive gas into the middle of the gas diffuser, e.g., because the conduits extend partway into the gas diffuser. For example, a gas conduit may extend through a surface of the roller into a gas diffuser, such that gas bypasses at least a portion of the thickness of the gas diffuser. Other configurations of the gas diffuser are also possible as the disclosure is not so limited.

[0080] Gas may be transported to the gas diffuser by any of a variety of appropriate routes, as the disclosure is not limited to any particular gas transport route. For example, gas may be transported through the interior of the roller of a cooling apparatus, as shown by the path of coolant conduits 459 in FIG. 4A. In some embodiments, gas may be conveyed externally to the roller (e.g., via a gas conduit disposed between the roller and the gas diffuser). Other embodiments are also possible, as the disclosure is not so limited.

[0081] Referring again to FIG. 4A, gas flows 453 show the ingress of the gas into the gas conduit and the emission of the gas from the gas diffuser. Although gas conduits 459 are shown extending through gas diffuser 421 as they might, e.g., in an embodiment where gas diffuser 421 comprises a plurality of through-holes, it should of course be understood that the conduits do not extend through the gas diffuser in every embodiment. For example, in some embodiments (e.g., where the gas diffuser comprises a porous network), the gas conduit emits gas into the gas diffuser, where it may be scattered by the gas diffuser prior to emission of the gas from the cooling apparatus. Depending on the embodiment, gas diffusers that scatter the gas prior to emission of the gas may be advantageous, e.g., because they may achieve a more uniform flux of gas from the cooling apparatus. However, in some embodiments, gas diffusers that do not scatter the gas prior to emission of the gas from the cooling apparatus may be advantageous, e.g., because they may provide advantages for contact-cooling of a substrate. For example, without wishing to be bound by any particular theory, in some embodiments, gas diffusers that do not scatter the gas supplied from the gas conduits may have more solid- to-solid contact with substrates rolled across the gas diffuser than might be achieved with porous network gas diffusers such as wire web gas diffusers. Moreover, without wishing to be bound by any particular theory, gas diffusers that do not scatter the gas may be associated with shorter average substrate-to-coolant conduit distances, increasing a temperature gradient through the roller in a way favorable for removing heat from the substrate.

[0082] A cooling apparatus may be configured to supply gas to the entire gas diffuser — but in some embodiments, the gas diffuser is configured to supply gas only to a portion of the gas diffuser adjacent to a substrate. Supplying gas to only a portion of the gas diffuser adjacent to the substrate may provide a variety of advantages. For example, supplying gas to only a portion of the gas diffuser adjacent to the substrate may reduce gas waste. As another example, as discussed below, in some embodiments, metal deposition is performed in vacuum pressures. Selectively supplying gas to only a portion of a gas diffuser may help the metal deposition system to maintain the vacuum pressures used for metal deposition, depending on the embodiment.

[0083] As used herein, when a component is referred to as being “on” or “adjacent” another component, it can be directly on or adjacent the component, or an intervening component also may be present. A component that is “directly on”, “directly adjacent” or “in contact with” another component means that no intervening component is present.

[0084] Selective supply of gas to a portion of the cooling apparatus adjacent to the substrate is schematically represented in FIG. 1, where gas flows 153 are only emitted towards the substrate 105. Any of a variety of methods may be used to selectively supply the gas to the relevant portion of the cooling apparatus during operation. For example, FIG. 4B shows a more detailed illustration of the selective supply of gas using a valve actuator 487. FIG. 4B shows a schematic, perspective illustration of the same cooling apparatus 451 illustrated in FIG. 4A. However, gas conduit inlets 461 are connected to valves 488 (which is open, permitting gas flows 453) and 489 (which is closed, permitting no gas flows). Valve actuator 487 may be operatively coupled to valves 488 and 489, e.g., so that as the cooling apparatus rolls, valve 489 opens and valve 488 closes. Any of a variety of valve actuators may be used. For example, the valve actuator may be electronic, and may be configured to actuate the flow of gas to the cooling apparatus in response to, e.g., a set of processor-executable instructions. In some embodiments, the valve actuator is a mechanical actuator, and is configured to actuate the flow of gas into the gas conduit based, e.g., on the position of valves 488 and 489 as the conduit rotates. For example, the valve actuator may be a fixed-position rotary valve actuator that admits gas into a gas channel, out of which gas may flow into valve(s) aligned with the gas channel, as described in greater detail below. Thus, according to some embodiments, as a gas conduit rotates towards a substrate, gas flow to the gas conduit may be increased. Likewise, in some embodiments, as a gas conduit rotates away from a substrate, gas flow to the gas conduit may be decreased.

[0085] It should, of course, be understood that while valves and / or valve-actuators provide one way to selectively control the supply of gas to various portions of the substrate, other embodiments are also possible, and the disclosure is not so limited. For example, in some embodiments each gas supply outlet is connected to a different gas source, and each gas source is actuated independently, rather than using a centralized actuator like valve actuator 487 that commonly actuates all gas inlets of gas conduits of the cooling apparatus.

[0086] As described elsewhere herein, in some embodiments, one or more components of a deposition system are configured to be heated, cooled, and / or maintained at a temperature within a temperature range. For example, one or more components of a deposition system may be configured to be cooled using a coolant. According to some embodiments, for example, a cooling apparatus comprises a coolant conduit adjacent to at least a portion of a face of the roller. The coolant conduit may fluidically connect a coolant inlet to a coolant outlet, e.g., so that coolant may be circulated through the cooling conduit to heat, cool, or maintain the temperature of the roller. In this way, the coolant conduit may facilitate contact-cooling of a substrate using the roller. The coolant conduit may have any of a variety of appropriate dispositions within the roller. For example, referring back to FIG. 2, cooling apparatus 251 comprises a coolant conduit 241 visible through gas diffuser 221 (which is illustrated as a transparent shell so that the coolant conduit may be viewed). Coolant conduit 241 is coiled in a cylinder such that it is adjacent to face 237 of roller 203. The person of ordinary skill would, of course, appreciate that the coolant conduit may have any of a variety of appropriate dispositions within the cooling apparatus. For example, in some embodiments a coolant conduit extends in a straight line segment adjacent to a portion of the face of the roller, coils around the cylindrical axis of the roller, or adopts an alternative pattern adjacent to at least a portion of the face of the roller. Likewise, the person of ordinary skill would recognize that more than one coolant conduit may be used, and that the use of a plurality of coolant conduits may have advantages for achieving a uniform temperature distribution of the cooling apparatus. For example, in some embodiments, coolant is used to remove heat from the cooling apparatus, resulting in a temperature gradient of the coolant between the coolant inlet and the coolant outlet. The temperature gradient of the coolant may be associated with a temperature gradient across a portion of the roller, and it may thus be advantageous to use shorter coolant conduits and / or faster coolant transportation through the coolant conduit to reduce the temperature gradient of the coolant within the coolant conduit. The use of a plurality of coolant conduits may, advantageously, allow faster and / or more uniform cooling of a cooling apparatus than could be achieved using a single coolant conduit. A specific example of a coolant apparatus comprising multiple coolant conduits is provided with reference to FIGS. 10A-10E, discussed below. Any of a variety of suitable number of coolant conduits may be used. In some embodiments, a cooling apparatus comprises greater than or equal to 1, greater than or equal to 2, greater than or equal to 3, greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, greater than or equal to 7, greater than or equal to 8, greater than or equal to 9, greater than or equal to 10, or greater than or equal to 11 cooling conduits. In some embodiments, a cooling apparatus comprises less than or equal to 12, less than or equal to 11, less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, or less than or equal to 2 cooling conduits. Combinations of these ranges are also possible (e.g., greater than or equal to 1 and less than or equal to 12, or greater than or equal to 1 and less than or equal to 10). Other ranges are also possible.

[0087] One component of a deposition system that may be configured to be cooled to and / or maintained at a temperature within a range is a roller (e.g., a roller of a cooling apparatus, having a face adjacent to a coolant conduit). In some embodiments, the roller is configured to be cooled to and / or maintained at (e.g., by a cooling apparatus) a temperature of less than or equal to 60 °C, less than or equal to 55 °C, less than or equal to 50 °C, less than or equal to 45 °C, less than or equal to 40 °C, less than or equal to 35 °C, less than or equal to 30 °C, less than or equal to 25 °C, less than or equal to 20 °C, less than or equal to 15 °C, less than or equal to 10 °C, less than or equal to 5 °C, less than or equal to 0 °C, less than or equal to -5 °C, less than or equal to -10 °C, less than or equal to -15 °C, less than or equal to -20 °C, less than or equal to -25 °C, or less than or equal to -30 °C. In some embodiments, the roller is configured to be cooled to and / or maintained at (e.g., by a cooling apparatus) a temperature of greater than or equal to -35 °C, greater than or equal to -30 °C, greater than or equal to -25 °C, greater than or equal to -20 °C, greater than or equal to -15 °C, greater than or equal to -10 °C, greater than or equal to -5 °C, greater than or equal to 0 °C, greater than or equal to 5 °C, greater than or equal to 10 °C, greater than or equal to 15 °C, greater than or equal to 20 °C, greater than or equal to 25 °C, greater than or equal to 30 °C, greater than or equal to 35 °C, greater than or equal to 40 °C, greater than or equal to 45 °C, greater than or equal to 50 °C, or greater than or equal to 55 °C. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 60 °C and greater than or equal to -35 °C). Other ranges are also possible. The temperature of a roller may be determined by a temperature sensor as discussed below. It should further be understood that that the cooling apparatus may be configured to cool or maintain the temperature of one or more elements in thermal communication with the roller (e.g., a substrate, a gas diffuser, and / or a deposited layer) within one of the temperature ranges.

[0088] In some embodiments, the roller is configured to be cooled to and / or maintained at (e.g., by a cooling apparatus) a temperature of less than or equal to 100%, less than or equal to 99%, less than or equal to 95%, less than or equal to 90%, less than or equal to 85%, less than or equal to 80%, less than or equal to 75%, less than or equal to 70%, less than or equal to 65%, less than or equal to 60%, or less than or equal to 55% of a melting temperature (Tm) of the deposited material. In some embodiments, the roller is configured to be cooled to and / or maintained at (e.g., by a cooling apparatus) a temperature of greater than or equal to 50%, greater than or equal to 55%, greater than or equal to 60%, greater than or equal to 65%, greater than or equal to 70%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, greater than or equal to 95%, or greater than or equal to 99% of a melting temperature of the deposited material. Combinations of these ranges are also possible (e.g., greater than or equal to 50% and less than or equal to 100%, greater than or equal to 80% and less than or equal to 100%, or greater than or equal to 90% and less than or equal to 100%). Other ranges are also possible. It should further be understood that that the cooling apparatus may be configured to cool or maintain the temperature of one or more elements in thermal communication with the roller (e.g., a substrate, a gas diffuser, and / or a deposited layer) within one of the temperature ranges.

[0089] When the roller is configured to maintain a temperature as discussed in the foregoing paragraphs, it should be understood that the cooling apparatus may maintain a steady- state temperature of a roller and / or one or more components in thermal communication with a roller (e.g., a gas diffuser, a substrate, and / or a deposited layer). Generally, a steady-state temperature refers to a temperature that is effectively constant (e.g., varying by no more than 10%, 5%, 2%, 1%, or less from the average absolute temperature) for an extended period of time (e.g., greater than or equal to 200 ms, 500 ms, 1 s, 5 s, 10 s, 30 s, 1 min, 10 min, or longer).

[0090] When a deposition system comprises two or more rollers, each roller may independently be configured to be cooled to and / or maintained at a temperature in one or more of the above-referenced ranges. In some embodiments, a cooled fluid circulated across one or more surfaces of one or more rollers and / or through one or more walls of one or more rollers has a temperature in one or more of the above-referenced ranges.

[0091] FIGS. 5-6 present schematic illustrations of exemplary deposition methods, according to some embodiments. FIG. 5 presents a non-limiting method 501, comprising step 505 of rolling a substrate across a face of a roller, step 507 of removing heat from the substrate using a gas and the face of a roller, step 509 of depositing metal on the substrate, and step 511 of maintaining a steady-state temperature between 50% and 100% of the melting point of the deposited metal. The metal deposited in step 509 may be deposited on a different side of the substrate from the side where heat is removed in step 507. For example, in some embodiments, method 501 comprises removing heat from a first side of the substrate in step 507 and depositing metal on a second side of the substrate opposite the first side of the substrate in step 509. According to some embodiments, steps 505, 507, 509, and 511 are performed simultaneously, e.g., as part of a continuous manufacturing process. In some embodiments, performing steps 505, 507, 509, and 511 simultaneously may result in controlled deposition of a desired lithium microstructure, as discussed in greater detail below. In some embodiments, the method further comprises providing the substrate, as indicated in optional step 503.

[0092] Likewise, FIG. 6 presents a non-limiting method 601, comprising step 605 of rolling a substrate across a face of a roller, step 607 of removing heat from the substrate using a gas and the face of a roller, and step 609 of depositing Zone T, Zone 2, or Zone 3 lithium on the substrate. The lithium deposited in step 609 may be deposited on a different side of the substrate from the side where heat is removed in step 607. For example, in some embodiments, method 601 comprises removing heat from a first side of the substrate in step 607 and depositing lithium on a second side of the substrate opposite the first side of the substrate in step 609. According to some embodiments, steps 605, 607, and 609 are performed simultaneously, e.g., as part of a continuous process of manufacturing a Zone T, Zone 2, or Zone 3 lithium layer. In some embodiments, the method further comprises providing the substrate, as indicated in optional step 603.

[0093] Method steps such as those of methods 501 and 601 may be performed simultaneously for any of a variety of suitable time spans, depending on the embodiment. In some embodiments, for example, one or more method steps may be performed simultaneously for a timespan of greater than or equal to 1 second, greater than or equal to 1 minute, greater than or equal to 10 minutes, greater than or equal to 1 hour, greater than or equal to 4 hours, greater than or equal to 8 hours, greater than or equal to 12 hours, greater than or equal to 16 hours, greater than or equal to 20 hours, greater than or equal to 24 hours, greater than or equal to 28 hours, greater than or equal to 32 hours, greater than or equal to 36 hours, greater than or equal to 40 hours, or greater than or equal to 44 hours. In some embodiments, one or more method steps may be performed simultaneously for a timespan of less than or equal to 48 hours, less than or equal to 44 hours, less than or equal to 40 hours, less than or equal to 36 hours, less than or equal to 32 hours, less than or equal to 28 hours, less than or equal to 24 hours, less than or equal to 20 hours, less than or equal to 16 hours, less than or equal to 12 hours, less than or equal to 8 hours, less than or equal to 4 hours, less than or equal to 1 hour, less than or equal to 10 minutes, or less than or equal to 1 minute. Combinations of these ranges are also possible (e.g., or greater than or equal to 1 second and less than or equal to 48 hours). Other ranges are also possible.

[0094] As discussed briefly above, according to some embodiments, use of the cooling may present certain advantages for controlling the microstructure of deposited metal (e.g., deposited lithium). According to some embodiments, the micro structure of deposited lithium depends on the temperature of the substrate and on the ambient pressure. For example, without wishing to be bound by any particular theory, according to some embodiments the microstructure of a vapor deposited layer can be described in terms of “structure zones” associated with particular combinations of layer temperatures and ambient pressure of the vapor deposition chamber. In particular, the Thornton diagram shown in FIG. 7 illustrates four structure zones, designated as “Zone 1”, “Zone T”, “Zone 2”, and “Zone 3”, characterized by the size, shape, and distribution of grains that ultimately form in the deposited layer. For instance, in some embodiments, a deposited structure has a morphology consistent with Zone I of the Thornton diagram (e.g., comprising tapered crystallites separated by voids), Zone T of the Thornton diagram (e.g., comprising densely packed fibrous grains), Zone II of the Thornton diagram (e.g., comprising columnar grains), and / or Zone III of the Thornton diagram (e.g., comprising recrystallized grains). The Thornton diagram is described in Anders, A Structure Zone Diagram Including Plasma Based Deposition and Ion Etching, Thin Solid Films 2010; 518(15); 4087-90, which is incorporated herein by reference in its entirety for all purposes.

[0095] As indicated in FIG. 7, vapor deposition of materials in different zones tends to result from different combinations of ambient pressure (e.g., argon pressure, in vapor deposition systems) and the reduced temperature of the layer (i.e., the temperature, T, of the layer divided by the melting point of the layer material, Tm). Metal layers with different structure zones may be desirable for different applications, depending on the embodiment. For example, in the context of lithium batteries, the use of Zone T, Zone 2, or Zone 3 lithium layers may be particularly advantageous. For example, Zone T and, to a greater extent, Zone 2, and / or Zone 3 microstructures may be associated with columnar grains extending through the entire thickness of the layer, which may be advantageous in the context of battery applications. Of course, as indicated in the Thornton diagram of FIG. 7, a significant factor in controlling the micro structure of a deposited metal layer is the temperature of the deposited metal. In particular, maintaining elevated substrate temperatures may be important for attaining Zone T, Zone 2, or Zone 3 microstructures. However, if the temperature T exceeds the melting temperature (Tm), the material will not solidify, or will solidify unpredictably as it is conveyed away from the deposition source. Thus, according to some embodiments, it is advantageous to carefully cool the deposited material while maintaining temperature and pressure conditions suitable for deposition of desirable layer microstructures. In particular, it may be difficult to produce Zone T, Zone 2, or Zone 3 microstructures with a particularly high rate of throughput, as a result, for example, of poor temperature control.

[0096] An advantage of the cooling methods provided herein is that they can improve temperature control for a layer while nonetheless permitting a relatively high rate of substrate throughput. Thus, according to some embodiments, a layer deposited using a metal deposition system provided herein may be deposited with a Zone T, Zone 2, or Zone 3 micro structure. A metal deposition system provided herein may be configured to control the micro structure of a deposited metal layer (e.g., to ensure that the layer has a Zone T, Zone 2, or Zone 3 microstructure). In some embodiments, for example, the metal deposition system is configured to adjust a cooling rate (e.g., by varying a gas flow rate or a coolant temperature), a deposition rate (e.g., which may control heating of the deposited metal), or a rate at which the substrate is rolled across the face of the roller (e.g., which may affect a timespan during which deposition and / or the cooling apparatus are able to heat or cool the deposited layer).

[0097] A metal deposition system provided herein may comprise a detection system comprising one or more detectors configured to directly or indirectly determine one or more characteristics of the deposited metal, such as the microstructure (e.g., the grain structure of the metal, the Thornton Zone of the metal), surface roughness, conductivity, thickness, temperature of the deposited metal. The determined characteristic (e.g., microstructure, surface roughness) of the deposited metal may be used to adjust (e.g., automatically, in real-time) the deposition process, e.g., by changing the cooling rate, the deposition rate, and / or the rate at which the substrate is rolled across the face of a roller. In some embodiments, the detected characteristic may be used to provide feedback to the metal deposition system. The feedback may be used to modulate subsequent deposition processes. For example, in some embodiments, metal deposition comprises an iterative process of refining cooling conditions until the cooling, deposition, and / or rolling rates are tuned to facilitate continuous manufacture of a metal layer having a desired microstructure, e.g., as part of a closed-loop process. Greater detail is provided below.

[0098] For example, FIG. 8 provides a schematic flow diagram of a non-limiting method 801 of metal deposition that may be used to deposit a metal layer with a desired microstructure. Method 801 comprises step 805 of rolling a substrate across a face of a roller, step 807 of removing heat from the substrate using a gas and the face of a roller, step 809 of depositing metal on the substrate, and step 813 of determining the microstructure of the deposited metal. It should, of course, be understood that while the step 813 of FIG. 8 refers specifically to microstructure, any of a variety of properties of the deposited metal may be detected in other embodiments, as described elsewhere herein, and step 813 need not be limited to microstructural detection in all embodiments.

[0099] Advantageously, in some embodiments, the deposition system may be configured to allow for one or more properties of a module in the deposition to be adjusted based upon a property detected at step 813. The determination at step 813 may be used to provide feedback to the deposition system, upon which the deposition may optionally act, e.g., by providing a detection signal to a feedback control system (e.g., comprising a processor) operatively coupled to one or more components of the deposition system. For example, in some embodiments, the determined microstructure is used to change a rate at which the substrate is rolled across the face of the roller at optional step 815. As another example, in some embodiments, the determined microstructure is used to change a rate of heat removal from the substrate using the gas and the face of the roller at optional step 817. As still another example, in some embodiments, the determined microstructure is used to change a rate of metal deposition on the substrate at optional step 819. The metal deposited in step 809 may be deposited on a different side of the substrate from the side where heat is removed in step 807, as discussed with reference to methods 501 and 601 above. Likewise, according to some embodiments, steps 805, 807, 809, and 813, and optionally some or all of method steps 815, 817, and 819 are performed simultaneously, as discussed with reference to the steps of methods 501 and 601 above. In some embodiments, the method further comprises providing the substrate, as indicated in optional step 803. It should, of course, be understood that these optional actions are representative, and that any of a variety of other aspects of metal deposition could be changed in response to the detection performed at step 813, depending on the embodiment.

[0100] The detection at step 813 may be used for any of a variety of applications, depending on the embodiment. For example, in some embodiments, detection may be performed to conduct quality control to determine, for example, if a correct microstructure has been deposited (or any other suitable feature or condition, as described herein). If the quality control determination is negative (e.g., if an undesired microstructure has formed) or not within a preprogrammed range of acceptance, the feedback control system may modify the deposition process. For example, in some embodiments the method comprises cancelling deposition in response to formation of an incorrect microstructure. In other embodiments, the method comprises adjusting one or more deposition-related processes, e.g., at steps 815, 817, or 819 of method 801. In some embodiments, steps 813 and one or more of steps 815, 817, and 819 may be performed iteratively, e.g., until the detection step detects continuous deposition of metal (e.g., lithium) that has a positive quality control determination (e.g., that has a desired microstructure or is within a preprogrammed range of acceptance). Such an iterative process is referred to herein as a feedback loop, and is exemplified in FIG. 8, where adjustment steps 815, 817, and / or 819 may be followed sequentially by further rolling, deposition, and / or heat removal as well as additional feedback detection steps.

[0101] Additional, non-limiting examples of parameters that may be adjusted (e.g., by a feedback control system or an operator) in response to a detected property include the flow rate of a gas into the module in which the relevant layer is being deposited (e.g., from a source), a temperature in one or more locations (e.g., of a container containing a source, of a location in which a source is positioned, in a vacuum chamber in which the relevant layer is being deposited, of a roller on which the substrate on which the relevant layer is being deposited is disposed), and the state of a shutter (e.g., the shutter of a vapor deposition source, which may be opened or closed). Any of a variety of suitable detection systems may be used to detect the microstructure of the deposited metal. A detection system comprises one or more sensors. The sensor(s) may be configured to sense or determine one or more properties of the deposition system, a module therein, and / or of a layer being deposited therein (e.g., a layer comprising lithium metal, a layer comprising a species other than lithium metal, a passivating layer). The sensor may output a signal (e.g., to an operator of the deposition system, to a feedback control system) indicating the relevant deficiencies and allow the operator or feedback control system to adjust one or more properties deposition system compensate (e.g., in response to negative or positive feedback). Non-limiting examples of properties of deposited layers that may be sensed include micro structure (e.g., Thornton zone, grain structure), temperature, surface roughness, crystallographic orientation, electrical conductivity, capacitance, color, reflectivity, and thickness. Nonlimiting examples of properties of modules in a lithium deposition system that may be sensed include temperature and the amount of various gases present, the temperature of the cooling apparatus, the temperature of the substrate, and / or the ambient pressure in a deposition system.

[0102] According to some embodiments, sensing temperature (e.g., of the layer, of the substrate, of the cooling apparatus) is particularly useful for determining the microstructure of the deposited layer. For example, according to some embodiments, a detection system comprising a pressure sensor and a temperature sensor may be used to indirectly determine the microstructure of a deposited layer (e.g., by identifying the position of the layer on the Thornton diagram). Any of a variety of temperature sensors may be used, including but not limited to, a thermocouple, an infrared temperature sensor, and / or a resistance temperature detector (RTD). A temperature determined by the temperature sensor may be used to compute a reduced temperature (e.g., based on a known melting temperature of the deposited metal).

[0103] In some embodiments (e.g., as an alternative or supplement to using pressure / temperature data) the detection system comprises a detector configured to directly detect the microstructure of the deposited metal. For example, the detection system may comprise an imaging system configured to optically image the microstructure. As another example, the detection system may comprise a laser-based or probe-based system configured to identify the grain structure of the as-deposited layer. Other embodiments are also possible. It should be appreciated, for example, that in some embodiments the micro structure of the deposited metal may be determined, based at least in part, on past observations of the micro structure of deposited metal under detected conditions. For example, the metal deposition system may be calibrated to determine the microstructure of the deposited material based at least in part on previous microstructural determinations of layers deposited under similar conditions to those detected by the detection systems.

[0104] Determining the micro structure of the deposited metal may be performed using one or more processors. For example, according to some embodiments, the one or more processors may be configured to perform a method provided herein, e.g., in response to a set of processor-executable instructions. In some embodiments, the one or more processors are configured to receive information from the detection system. The information from the detection system may be used to determine the microstructure of the deposited layer using the one or more processors. In some embodiments, the one or more processors are operatively coupled with the metal deposition system. In some embodiments, the one or more processors are configured to adjust the operation of the metal deposition system (e.g., the cooling apparatus or the vapor deposition source) based at least in part on information obtained from the detection system. The one or more processors may be operatively coupled with the cooling apparatus, e.g., such that the one or more processers may control the rate of rolling of the roller, the temperature or flow-rate of the coolant, and / or the flow rate of a gas emitted from a gas diffuser of the cooling apparatus. According to some embodiments, the one or more processors are operatively coupled to the vapor deposition source, and are configured to control the deposition rate (e.g., by adjusting source temperature).

[0105] FIG. 9 presents a non-limiting, schematic illustration of continuous deposition of a metal layer 991 on a substrate 905 using a metal deposition system 701. As shown, metal layer 991 is deposited using metal source 711 to deposit vapor 713 on substrate 705 as substrate 705 is rolled across cooling apparatus 751 (which is identical to cooling apparatus 151 as shown in FIG. 1. Substrate 705 is rolled in direction 755 by the rotation of the cooling apparatus in direction 777, resulting in continuous deposition of metal layer 991. As shown, system 701 further comprises detection system 999 configured to determine the microstructure of the substrate. While detection system 999 is illustrated as a non-limiting light-based sensor (e.g., an optical micro structure detection sensor or an infrared temperature sensor), it should of course be understood that the types and placements of various detection systems are not limited to those represented in the embodiment of FIG. 9, and that any of a variety of other detection systems are possible, including any of those described in detail above.

[0106] FIGS. 10A-10G provide a variety of schematic illustrations of a non-limiting cooling apparatus 1051, according to some embodiments. FIG. 10A provides a schematic, perspective illustration of cooling apparatus 1051, which comprises a roller 1003 integrally formed with a gas diffuser 1021 in the form of a plate 1024 integrally formed with roller 1003 and comprising a plurality of circular through-holes 1026. The cooling apparatus further comprises gas conduits 1059, which may be fluidically connected to one or more gas sources (not shown) and coolant conduits 1041, which may be fluidically connected to one or more coolant reservoirs (not shown) via fluidic connections through a fluid actuator 1087 that comprises gas inlet 1061, coolant inlet 1043 and coolant outlet 1045. Actuator 1087 may be configured to selectively control the flow of gas through the cooling apparatus, according to some embodiments. For example, gas may be selectively emitted from a portion of gas diffuser 1021 via actuation of valves using actuator 1087, according to some embodiments. Roller 1003 is configured to be rolled by mechanical actuator 1095 (see FIG. 10E) which is configured to be operatively coupled with a metal deposition system (not shown) so that the metal deposition system may roll the roller. The mechanical actuator may also serve as a fluid (e.g., coolant, gas) inlet and / or outlet. For example, mechanical actuator 1095 comprises coolant inlet 1043 (see FIG. 10E).

[0107] FIG. 10B shows a schematic cross-section of cooling apparatus 1051, showing the internal configuration of gas conduits 1059 and coolant conduits 1041. Gas conduits 1059 are fluidically connected to gas inlet 1061 via valve 1088, which is configured to selectively permit gas flow from gas inlet 1061 to some of gas conduits 1059 depending on the alignment of the gas conduits with the valve. Fluid actuator 1087 is configured to remain stationary while roller 1003 rolls, so that valve 1061 is configured to permit gas emission from a portion of gas diffuser 1021 at the top of cooling apparatus 1051 as shown in FIG. 10B but not from the bottom of gas diffuser 1021 as shown in FIG. 10B based on alignment between fluid conduits of cooling apparatus 1051 with valve 1061.

[0108] FIGS. 10C-10E, meanwhile, provide various side-views of cooling apparatus 1051, showing various perspectives of features shown and described with reference to FIGS. 10A-10B, above.

[0109] FIG. 10F presents a schematic side-view of the side of valve actuator 1087 as it faces roller 1003, in order to illustrate the mechanism for valve actuation. FIG. 10G presents a schematic side-view of valves 1088 as they face valve actuator 1087, as well as O-ring 1009, which is configured to form a seal when compressed against O-ring seat 1019 of valve actuator 1087. As shown, valve actuator 1087 is a fixed-position rotary valve actuator (a type of mechanical valve actuator) that admits gas into a gas distribution channel 1029 formed in valve actuator 1087. Gas then passes from the gas distribution channel into whichever of valves 1088 are aligned with the valve actuator. As roller 1021 rotates, it causes valves 1088 to rotate such that the gas is distributed to whatever gas distribution channels of the cooling apparatus are connected with valves aligned with the gas distribution channel of valve actuator 1087. Valve actuator 1087 may easily be made or positioned to facilitate the transmission of gas into valves only when those valves are configured to distribute the gas to a substrate. Valves that are not configured to distribute gas to the substrate (e.g., because they are configured to distribute gas to a side of the roller opposite the substrate) may be closed by the valve actuator as a result of their mechanical misalignment with the valve actuator’s gas distribution channel. It should, of course, be understood that the pictured valves and valve actuator are just one of a variety of different types of valves and valve actuators that may be used. For example, rather than a single gas distribution channel, a gas actuator may comprise a plurality of gas inlets configured to the region sealed by O-ring 1009 at different rates depending on the position of the inlets relative to the O-ring. It should further be understood that other O-ring shapes and distributions (e.g., covering more or fewer valves, or sealed by an alternative method) are also possible, as the disclosure is not so limited. A cooling apparatus provided herein may have a roller with any of a variety of suitable geometries. Generally, a roller has at least one face across which a substrate may be rolled. Generally, the face of a roller is a surface of the roller that may be disposed adjacent to the substrate. In some embodiments, the face of the roller directly contacts the substrate. For example, the face of the roller may be a portion of a gas diffuser integrally formed with the roller, in some embodiments. According to some embodiments, the face of the roller is configured to be separated from the substrate by one or more intervening components. For example, in embodiments where a gas diffuser is not integrally formed with the roller, but rather is configured to be mechanically coupled to the roller, the gas diffuser may be disposed on the face of the roller such that when the substrate is rolled across the face of the roller, it is adjacent to the face of the roller but does not directly contact the face of the roller because it is separated from the roller by the gas diffuser.

[0110] In some embodiments, a cooling apparatus has a roller with a radius of greater than or equal to 1 cm, greater than or equal to 10 cm, greater than or equal to 20 cm, greater than or equal to 30 cm, greater than or equal to 40 cm, greater than or equal to 50 cm, greater than or equal to 60 cm, greater than or equal to 70 cm, greater than or equal to 80 cm, greater than or equal to 90 cm, greater than or equal to 100 cm, greater than or equal to 110 cm, greater than or equal to 120 cm, greater than or equal to 130 cm, greater than or equal to 140 cm, greater than or equal to 150 cm, greater than or equal to 160 cm, greater than or equal to 170 cm, greater than or equal to 180 cm, or greater than or equal to 190 cm. In some embodiments, a cooling apparatus has a roller with a radius of less than or equal to 200 cm, less than or equal to 190 cm, less than or equal to 180 cm, less than or equal to 170 cm, less than or equal to 160 cm, less than or equal to 150 cm, less than or equal to 140 cm, less than or equal to 130 cm, less than or equal to 120 cm, less than or equal to 110 cm, less than or equal to 100 cm, less than or equal to 90 cm, less than or equal to 80 cm, less than or equal to 70 cm, less than or equal to 60 cm, less than or equal to 50 cm, less than or equal to 40 cm, less than or equal to 30 cm, less than or equal to 20 cm, or less than or equal to 10 cm. Combinations of these ranges are also possible (e.g., greater than or equal to 1 cm and less than or equal to 200 cm, or greater than or equal to 10 cm and less than or equal to 100 cm). Other ranges are also possible. A roller of a cooling apparatus provided herein may roll with any of a variety of suitable rotational speeds. In some embodiments, a roller of a cooling apparatus rolls at greater than or equal to 1 rotation per minute (RPM), greater than or equal to 5 RPM, greater than or equal to 10 RPM, greater than or equal to 15 RPM, greater than or equal to 20 RPM, greater than or equal to 25 RPM, greater than or equal to 30 RPM, greater than or equal to 35 RPM, greater than or equal to 40 RPM, greater than or equal to 45 RPM, greater than or equal to 50 RPM, or greater than or equal to 55 RPM. In some embodiments, a roller of a cooling apparatus rolls at less than or equal to 60 RPM, less than or equal to 55 RPM, less than or equal to 50 RPM, less than or equal to 45 RPM, less than or equal to 40 RPM, less than or equal to 35 RPM, less than or equal to 30 RPM, less than or equal to 25 RPM, less than or equal to 20 RPM, less than or equal to 15 RPM, less than or equal to 10 RPM, or less than or equal to 5 RPM. Combinations of these ranges are also possible (e.g., greater than or equal to 1 RPM and less than or equal to 60 RPM, or greater than or equal to 1 RPM and less than or equal to 30 RPM). Other ranges are also possible.

[0111] In some embodiments, a metal deposition system comprises a plurality of rollers. The metal deposition system may be configured to pass the substrate over the rollers as it is being transported through the deposition system. For instance, FIG. 1 illustrates the use of additional rollers 191 in addition to roller 103 of cooling apparatus 151. While some rollers (e.g., those of a cooling apparatus) may be capable of and / or configured to be cooled (e.g., as detailed above) and / or heated, others may be unable to regulate temperature.

[0112] According to some embodiments, a metal deposition system comprises one or more modules. For example, a metal deposition system may comprise a plurality of modules, in some embodiments. Any of a variety of suitable modules may be included in the deposition systems described herein. In some embodiments, a deposition system comprises one or more modules that comprise a vacuum chamber. The vacuum chamber may be a vessel that can be held at a vacuum of less than or equal to 1 mTorr for an indefinite period of time. It may be formed of a material and / or combination of materials that can withstand a relatively large pressure difference across the interior of the vacuum chamber and the exterior of the vacuum chamber (e.g., a pressure difference of the difference between atmospheric pressure and 1 mTorr). Similarly, it may be formed of a material and / or combination of materials that can seal off the interior of the vacuum chamber from an environment exterior thereto to an appreciable degree (e.g., such that a pressure difference between atmospheric pressure and the pressure inside the vacuum chamber can be maintained without pumping and / or with minimal pumping for a period of time of seconds, minutes, hours, or longer). The vacuum chamber may be made from a rigid material and / or combination of materials (e.g., a material and / or combination of materials that maintains substantially the same shape when subject to the above- mentioned pressure difference) and / or from a deformable material and / or combination of materials (e.g., a material and / or combination of materials that does not maintain substantially the same shape when subject to the above-mentioned pressure difference).

[0113] In some embodiments, a vacuum chamber further contains, and / or is capable of being placed in fluidic communication with, one or more further system components (e.g., within the module, in another module). Such vacuum chambers may be advantageous for systems in which it is desirable to perform one or more processes in a vacuum chamber that require more than exposure to a vacuum. For instance, in some embodiments, a vacuum chamber may further contain and / or be capable of being placed in fluidic communication with a source of a material to be deposited on a substrate and / or a source of material reactive with a substrate and / or a material deposited thereon. The vacuum chamber may be capable of being and / or configured to be placed in fluidic communication with the further system component(s) when held at reduced pressure. This may be advantageous for, for example, processes in which it is desirable to deposit a material onto a substrate positioned in a vacuum chamber under reduced pressure and / or to perform a reaction on a material positioned in a vacuum chamber under reduced pressure.

[0114] In some embodiments, a deposition system comprises one or more vacuum chambers. The vacuum chamber(s) may be configured to be maintained at a pressure of less than atmospheric. By way of example, in some embodiments, a vacuum chamber is configured to be held at a pressure of less than or equal to IO"4Torr, less than or equal to 5*10'5Torr, less than or equal to 2*10'5Torr, less than or equal to 10'5Torr, less than or equal to 5*10'6Torr, less than or equal to 2*10'6Torr, less than or equal to 10'6Torr, less than or equal to 5*10'7Torr, or less than or equal to 2*10'7Torr. In some embodiments, a vacuum chamber is configured to be held at a pressure of greater than or equal to 10'7Torr, greater than or equal to 2*10'7Torr, greater than or equal to 5*10'7Torr, greater than or equal to 10'6Torr, greater than or equal to 2*10'6Torr, greater than or equal to 5*10'6Torr, greater than or equal to 10'5Torr, greater than or equal to 2*10'5Torr, or greater than or equal to 5*10'5Torr. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 10'6Torr and greater than or equal to 10'7Torr, or less than or equal to IO"4Torr and greater than or equal to 10'5Torr). Other ranges are also possible. The pressure of a vacuum chamber may be determined by a pressure gauge positioned therein.

[0115] When a deposition system comprises two or more vacuum chambers, each vacuum chamber may independently be configured to maintained at a pressure in one or more of the ranges described above.

[0116] Some deposition systems described herein are capable of and / or configured to operate in a roll-to-roll manner. Advantageously, this manner of operation may allow for the deposition system to be used in a more efficient manner. By way of example, in some embodiments, roll-to-roll operation of a deposition system allows for two (or more) different modules of the deposition system to perform two (or more) different processes on two (or more) different portions of a substrate simultaneously. This may allow for different substrates to be fabricated efficiently, e.g., as part of a continuous fabrication process, as they may be sequentially passed through modules that are operated simultaneously.

[0117] As another example, in some embodiments, a roll-to-roll operation of a deposition system may allow for a single module of the deposition system to perform a process on different portions of a substrate sequentially while minimizing exposure of the module to an environment external thereto. The module may need to only be exposed to an environment external thereto when the substrate is being translated therethrough, and, in embodiments in which the entire roll-to-roll handling system is positioned in a vacuum chamber or other desirable environment, the environment to which the module is exposed during this process may be relatively similar to the environment therein during the process it is configured to perform (e.g., it may be a vacuum environment, it may lack and / or include in only small quantities one or more components of the earth’s atmosphere that are undesirable, such as species reactive with lithium metal).

[0118] FIG. 11 shows one example of a deposition system comprising a roll-to-roll handling system. In FIG. 11, a metal deposition system 1504 configured for roll-to-roll handling comprises a first roll 1604, a second roll 1654, and a chamber 1704 positioned between a first module 1204 and a second module 1254 of the deposition system. The roll-to-roll handling system may be capable of transporting and / or configured unwind a substrate from the first roll, transport it through the system (e.g., through the modules, through any chambers positioned between the modules), and wind it onto the second roll. The substrate may be sufficiently long such that it is capable of simultaneously comprising portions disposed on the first roll, portions positioned in one or more modules of the deposition system, and portions disposed on the second roll. Accordingly, different portions of the substrate may be positioned in different environments and / or may have different processes performed thereon simultaneously. In some embodiments, the rolls of a roll-to-roll handling system may be positioned external to the modules in the lithium deposition system (e.g., as shown illustratively in FIG. 11). In other embodiments, one or more rolls in a roll-to-roll handling system are positioned inside one or more modules of the metal deposition system. By way of example, a roll may be positioned inside a vacuum chamber. In some embodiments, the first roll is positioned inside a first module and the second roll is positioned inside a second, different module.

[0119] A metal deposition system provided herein may be configured to deposit metal (e.g., lithium) using any of a variety of suitable techniques. For example, the metal deposition system may be configured to deposit metal via physical vapor deposition (e.g., sputtering). In some embodiments, the metal deposition system is configured to deposit metal via chemical vapor deposition. Other embodiments are also possible, as the disclosure is not limited to any particular form of metal deposition. A variety of system configurations for vapor deposition are described in greater detail below.

[0120] In some embodiments, a metal deposition system comprises one or more sources of metal for deposition. Such sources may be positioned in one or more of modules of a deposition system (e.g., in a vacuum chamber), external to all modules of the deposition system (e.g., in a location that may be placed, possibly reversibly, in fluidic communication with a module and / or component thereof, such as a vacuum chamber), and / or may form their own module of a deposition system (e.g., a module that may be placed, possibly reversibly, in fluidic communication with another module and / or component thereof, such as a vacuum chamber). In some embodiments, a source is positioned in a container (e.g., a container positioned in one or more of the abovereferenced locations). FIG. 12 shows one non-limiting embodiment of a source 2414 positioned in a container 2514.

[0121] Some sources may comprise a species that is configured to be incorporated into a layer deposited therein and / or is configured to undergo a reaction in the module to form a reaction product to be incorporated into a layer deposited therein. Non-limiting examples of such sources include sources of metal (e.g., lithium metal) and sources of species reactive with the metal. The former source may be suitable for forming a layer comprising a metal (e.g., lithium metal) and / or a reaction product thereof (e.g., a passivating layer), and the latter source may be configured to form a layer disposed on metal and / or comprising a reaction product of metal (e.g., a passivating layer).

[0122] Some sources may comprise a material that is not configured to be incorporated into a layer deposited therein or configured not to undergo a reaction in the module to form a reaction product to be incorporated into a layer deposited therein. By way of example, some sources may be sources of gases inert to metal (e.g., lithium metal) and / or gases generally-considered to be inert gases (e.g., argon, helium, other noble gases). Such gases may be configured to modulate the interaction of one or more other types of gases (e.g., gases comprising lithium, gases reactive with lithium) with each other and / or with one or more components of the module. For instance, as described above, in some embodiments, an inert gas may assist with cooling one or more portions of a module. As another example, an inert gas may affect the morphology of one or more layers deposited on a substrate. Without wishing to be bound by any particular theory, it is believed that inert gases may interact with gases comprising metal (e.g., lithium) and / or gases comprising a species reactive with metal (e.g., lithium) to reduce the tendency of these gases to form porous layers and enhance the tendency of these gases to form denser, more crystalline layers. It is believed that this effect is enhanced when the inert gas has a temperature sufficient to cool the relevant gas(es) depositing to form the layer, such as a gas provided at a lower temperature than these gas(es). It is also believed that this effect is enhanced when the inert gas is present in a manner sufficient to cause the local pressure at the location at which the relevant layer is being deposited to be of a character that promotes the formation of such layers.

[0123] Some sources and / or their containers may be configured to be heated and / or cooled. Heating a source may be advantageous when the source is a material that is not gaseous as provided (e.g., that is a solid or a liquid at room temperature and pressure, that is a solid or liquid at a temperature and pressure of the module into which it is introduced) but which is desirable to introduce into a module in the form of a gas and / or to deposit onto a substrate from a gas. The source may be heated by a heating system with which it is in thermal communication. The heating system may resistively heat a container in which the source is positioned and / or a location on which the substrate is disposed. In some embodiments, a heating system may heat the container and / or location by providing a source of heat at a set temperature (or within 1 °C of a set temperature, or within a range differing from the set temperature by less than or equal to the resolution of a temperature sensor employed with the cooling and / or heating system) in a manner that maintains the source at a set temperature (or within 1 °C of a set temperature, or within a range differing from the set temperature by less than or equal to the resolution of a temperature sensor employed with the cooling and / or heating system). It should also be understood that, as described elsewhere herein, some modules may comprise one or more sources of a material that is provided as a gas (e.g., a material that is a gas at room temperature and pressure, a material that is a gas at the temperature and pressure of the module into which it is introduced). Such sources may be provided in addition to, or instead of, sources of a material that is not provided as a gas.

[0124] Cooling a source may be advantageous when it is desirable to operate the deposition system at high speeds and / or when it is desirable to have a fairly short time between successive uses thereof. When the source is at an elevated temperature, it may evaporate and / or sublimate to form a gas that would be undesirable to introduce to an environment external to that in which the source is positioned, such as an environment external to a module and / or a component thereof (e.g., a vacuum chamber) in which the source is positioned. For instance, it may be undesirable to place molten metal (e.g., molten lithium) in fluidic communication with an environment external to the module because the molten metal may be undesirably reactive and / or undesirably volatile. Accordingly, the ability to rapidly cool a source, such as a source comprising metal, to a temperature at which it undergoes minimal evaporation and sublimation may allow for modules to be placed in fluidic communication with each other rapidly after performing a process in which a source positioned in one of the chambers is heated and / or to place a module in fluidic communication with the atmosphere after such a process. A source may be cooled by its container (e.g., when its container comprises and / or is in thermal communication with a cooling system). Like the cooling system that may be employed to cool one or more rollers, the cooling system configured and / or capable of cooling a container for a source may be configured to maintain one or more portions of the container (e.g., one or more external surfaces thereof, one or more internal surfaces thereof) at a set temperature or within 1 °C of a set temperature and / or within a range differing from the set temperature by less than or equal to the resolution of a temperature sensor employed with the cooling and / or heating system.

[0125] It noted that some deposition systems may comprise separate cooling and heating systems associated with a source therein (e.g., both a heating system configured to heat the source and a separate cooling system configured to cool the source) and that some deposition systems may comprise heating and cooling systems capable of and / or configured to be operated together to maintain a source at a set temperature.

[0126] In some embodiments, a cooling system for a container for a source comprises a plurality of channels arranged in one or more walls and / or across one or more surfaces of the container. A cooled fluid may be flowed through these channels (e.g., with the assistance of a pump and / or possibly chilled by a chiller), which may cool the container, one or more external and / or internal surfaces thereof, and / or a source contained therein (e.g., by contact with a cooled internal surface thereof). Non-limiting examples of suitable cooled fluids include cooled gases (e.g., cooled inert gases, such as cooled argon, cooled helium, and / or another cooled noble gas) and cooled liquids (e.g., cooled water). In some embodiments, the cooled fluid may be a fluid that does not have a boiling point between the temperature at which it is provided to the channels and the temperature of the source (e.g., the cooled fluid may be provided as a gas and remain a gas after flowing through the channels, the cooled fluid may be provided as a liquid and remain a liquid after flowing through the channels).

[0127] FIG. 13 shows one non-limiting embodiment of a cooling system 2516 comprising walls 2616 in which channels 2716 are arranged. Like the container shown in FIG. 13, some containers may comprise channels in all of their walls. Other containers may comprise channels in some, but not all, of their walls. For instance, some containers may comprise channels only in the wall or walls to which a source is directly adjacent. Similarly, it should be understood that the number of channels in each wall, positioning of the channels within the walls, and size of the channels relative to the walls shown in FIG. 13 are exemplary and that some embodiments may vary in these (and / or other) manners from the embodiment shown illustratively in FIG. 13.

[0128] Some containers suitable for containing a source have one or more features that make them well-suited for use with metal sources (e.g., lithium metal sources) and / or other sources having the features described herein. For instance, in some embodiments, a container is formed from a material having a relatively low coefficient of thermal expansion between room temperature and typical temperatures to which the container is heated, having a relatively high hardness, and / or having a relatively high toughness. Steel is one example of a suitable material having these properties.

[0129] As another example, in some embodiments, a container comprises a shutter that is capable of and / or configured to reversibly place the source in fluidic communication with another module and / or another component of the module in which it is positioned (e.g., by opening and closing). A module may comprise a vacuum chamber and a source positioned in a container positioned within the vacuum chamber, and the shutter may be capable of reversibly placing the source in fluidic communication with the vacuum chamber. FIG. 14 shows one non-limiting embodiment of a container for a source comprising a shutter having this property. In FIG. 14, the container 2518 comprises a shutter 2818 that may be reversibly opened and closed to place the interior of the container 2518 in and out of fluidic communication with an environment external thereto. In some embodiments, like the embodiment shown illustratively in FIG. 14, opening and closing a shutter of a container may place and remove the entirety interior of the container (in which the source is positioned) in and from fluidic communication with the other module and / or module component. It is also possible for the opening and closing of the shutter to place and remove one or more sub-portions of the interior of the container (e.g., a portion in which the metal source is positioned and / or in fluidic communication with) in and from fluidic communication with the other module and / or module component while not affecting the presence or lack of fluidic communication between one or more other portions of the interior of the container with the other module and / or module component. The presence of a shutter may allow the exposure of the source to the other module and / or module component to be controlled such that the source is in fluidic communication with the other module and / or module component when desirable (e.g., when the source is at a temperature suitable for the formation of gas to be introduced to the module and / or module component, when the substrate is appropriately positioned for receiving and / or reacting with the gas generated by the source) and not in fluidic communication with the other module and / or module component at other points in time (e.g., when the source is at a temperature too low for the formation of the desired gas in appropriate quantities and / or having a desired composition). This may advantageously prevent or reduce the introduction of gas from the source at inopportune times, thereby preventing or reducing the amount of substrate rendered unsuitable for introduction into an electrochemical cell and / or unsuitable for further fabrication steps.

[0130] In some embodiments, a shutter is configured to be heated. For instance, it may be heated by a heating system with which it is in thermal communication. The heating system may resistively heat the shutter and / or may provide a source of heat at a set temperature (or within 1 °C of a set temperature and / or within a range differing from the set temperature by less than or equal to the resolution of a temperature sensor employed with the heating system) in a manner that maintains the shutter at a set temperature (or within 1 °C of a set temperature and / or within a range differing from the set temperature by less than or equal to the resolution of a temperature sensor employed with the heating system). Some deposition systems and / or modules therein may comprise more than one source. Each source may be of the same type, each source may be of a different type, or the deposition system and / or module may comprise two or more of at least one type of source and further comprise one or more other, different types of sources. In some embodiments, it may be advantageous for a single module to comprise multiple sources of the same type. The different sources of the same type may complement each other. By way of example, in some embodiments, a module comprises a plurality of sources located at different positions within the module and / or a plurality of ports located at different positions around the module that each place a source in fluidic communication with the module. The plurality of sources may together assist with the formation of a layer from the source and / or reaction of the layer with a gas produced by the source in a uniform manner (e.g., having a variation in the cross web direction of less than or equal to 0.5 microns between its thickest and thinnest points).

[0131] FIG. 15 shows one example of a module comprising three sources of the same type. In FIG. 15, the module 2220 comprises a vacuum chamber 2920, a cooling apparatus 1551, a first metal source 2420, a second metal source 2450, and a third metal source 2480. The three metal sources 2420, 2450, and 2480 are positioned inside the vacuum chamber 2920, which further contains the cooling apparatus 1551. Although not shown in FIG. 15, it should be understood that three ports configured to reversibly place three sources of metal in fluidic communication with the interior of the vacuum chamber positioned at the same locations as the three metal sources shown in FIG. 15 would be expected to behave similarly to the embodiment shown in FIG. 15.

[0132] In FIG. 15, a portion of a substrate passing over the roller (e.g., being translated through the deposition thereby and / or with the assistance of a plurality of rollers) may be exposed sequentially to a gas from the second metal source, to a gas from the first metal source, and then to a gas from the third metal source. If the sources are employed to deposit a layer on the substrate, the majority of the layer may be deposited by a gas from one of the three sources (e.g., the first source), and the other two sources may be employed to deposit further portions of the layer that enhance its uniformity (e.g., that reduce its variation in thickness, chemical composition, and / or porosity in the cross-web direction). For instance, gas from the last source to which the portion of the substrate is exposed may modulate the amount of material it deposits based on the amount of material that has already been deposited on the portion of the substrate to which it is exposed. It may deposit more material on portions of the substrate on which a smaller amount of material has been deposited and less (or no) material on portions of the substrate on which a larger amount of material has been deposited. Gas from the first source to which the substrate is exposed may, if not the main source, deposit more material on portions of the substrate onto which the main source typically deposits less material (e.g., portions of the substrate closer to the edge of the main source) and deposit less (or no) material on portions of the substrate onto which the main source typically deposits more material (e.g., portions of the substrate closer to the center of the main source).

[0133] In some embodiments, like the embodiment shown in FIG. 15, multiple sources (e.g., multiple sources of the same type) may be positioned around a common cooling apparatus and / or may be configured to produce gas to be deposited to form a layer on portions of a substrate disposed on a common roller. It is also possible for multiple sources in a single module to be positioned proximate different cooling apparatuses in the module and / or configured to produce gas to be deposited to form layers on portions of the substrate disposed on different rollers in the module. FIG. 16 shows one example of a module 1 comprising a vacuum chamber 2922 in which a first roller 1651a and a second roller 1651b are positioned. The module 1 further comprises a source 2422 positioned proximate the first roller 1651a and a second source of the same type 2452 positioned proximate the second roller. A portion of a substrate 2922 translated through the module 1 to pass first over the first roller 1651a and then over the second roller 1651b would first be exposed to a gas originating from the first source 2422 and then to a gas originating from the second source 2452.

[0134] In some embodiments, like the embodiments shown in FIGS. 15-16, each source positioned in a module is contained in its own container. The amount of gas introduced from a source into the module may be controlled by the container (e.g., by opening and closing a shutter thereon, by adjusting the temperature of the container) and / or by a port in fluidic communication with the container. It is also possible for a module to comprise two or more sources positioned in a common container and / or in fluidic communication with a common port. FIG. 17 shows one example of a plurality of sources having this property. In FIG. 17, a single container 2524 comprises a plurality of sources 2424. In some such embodiments, the amount of gas introduced into the module from different sources positioned within a common container may be independently controlled. This may be accomplished by, for example, providing different amounts of heat to different sources (thereby adjusting the temperature, evaporation rate, and / or sublimation rate of the sources differently) and / or by heating different amounts of the source (thereby limiting the amount of source material that can evaporate and / or sublimate). The amount of a source that is heated may be varied by varying the amount of the source that is exposed to a source of heat. Like the embodiment described above with respect to FIGS. 15-16, the amount of gas produced by any particular source may be selected such that all of the sources together result in the production of gas that deposits on the substrate in the form of a relatively uniform layer (e.g., having a variation in the cross web direction of less than or equal to 0.5 microns between its thickest and thinnest points).

[0135] In one exemplary embodiment, a source is provided in the form of a material comprising a plurality of portions that can be translated onto a heated crucible relatively easily. The rate at which various portions of the source are translated onto the heated crucible may affect the amount of source sublimed and / or evaporated by the source of heat. For instance, when portions of the source are introduced to the heated crucible more rapidly, larger quantities of gas may be produced from the source and when portions of the source are introduced to the heated crucible more slowly, smaller quantities of gas may be produced from the source. One type of source that may be particularly suited for this design is a source that takes the form of a wire. The wire may initially be wound around a roll, and then unrolled onto the heated crucible. FIG. 18 shows one example of a plurality of sources and heated crucibles having this design.

[0136] In some embodiments, a deposition system comprises a combination of different types of sources and / or ports in fluidic communication with different types of sources positioned with respect to each other to promote the formation of a desirable combination of layers. By way of example, in some embodiments, a deposition system comprises one or more sources of a material other than (e.g., reactive with) metal (e.g., lithium) positioned proximate a source of metal. Similarly, a deposition system may comprise a port in fluidic communication with one or more sources of a material other than (e.g., reactive with) metal positioned proximate a source of metal. Such sources and / or ports may be capable of and / or configured to introduce both types of gases to a common portion of a substrate at relatively close points in time (e.g., concurrently or close to concurrently). When both such sources are placed in fluidic communication with the interior of the module concurrently, a layer comprising a reaction product therebetween and / or both metal and the condensed gas other than metal may be deposited on that portion of the substrate.

[0137] As another example, in some embodiments, a deposition system comprises one or more sources of a material other than (e.g., reactive with) metal positioned an appreciable distance from a source of metal. Similarly, a deposition system may comprise a port in fluidic communication with one or more sources of a material other than (e.g., reactive with) metal positioned an appreciable distance from a source of metal. Such sources and / or ports may be capable of and / or configured to introduce both types of gases to a common location at different points in time. This may be suitable for embodiments in which two distinct layers are deposited from the two different sources. For instance, in some embodiments, a layer comprising metal may be deposited first, and then the layer comprising metal may be exposed to the gas of the material other than metal. This gas may react with and / or deposit on the layer comprising metal to form a layer disposed on the layer comprising metal, such as a passivating layer.

[0138] A container for a metal source may be configured to be cooled to and / or maintained an external surface at a temperature within a chosen. In some embodiments, the exterior surface of this container is configured to be cooled to and / or maintained at (e.g., by a plurality of cooling channels passing therethrough) at a temperature of less than or equal to 50 °C, less than or equal to 45 °C, less than or equal to 40 °C, less than or equal to 35 °C, less than or equal to 30 °C, less than or equal to 25 °C, or less than or equal to 20 °C. In some embodiments, the exterior surface of this container is configured to be cooled to and / or maintained at (e.g., by a plurality of cooling channels passing therethrough) at a temperature of greater than or equal to 15 °C, greater than or equal to 20 °C, greater than or equal to 25 °C, greater than or equal to 30 °C, greater than or equal to 35 °C, greater than or equal to 40 °C, or greater than or equal to 45 °C. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 50 °C and greater than or equal to 15 °C). Other ranges are also possible. The temperature of an exterior surface of a container for a metal source may be determined by a thermocouple positioned thereon.

[0139] When a deposition system comprises two or more containers for metal sources, each container for a metal source may independently be configured to be cooled to and / or maintained at a temperature in one or more of the above-referenced ranges.

[0140] Some containers for metal sources may be configured to be heated (e.g., in addition to being cooled). In some embodiments, an interior surface of this container is configured to be heated to and / or maintained at (e.g., by a heating system, such as a resistive heating system) a temperature of greater than or equal to 550 °C, greater than or equal to 560 °C, greater than or equal to 570 °C, greater than or equal to 580 °C, greater than or equal to 590 °C, greater than or equal to 600 °C, greater than or equal to 610 °C, greater than or equal to 620 °C, or greater than or equal to 630 °C. In some embodiments, an interior surface of this container is configured to be heated to and / or maintained at (e.g., by a heating system, such as a resistive heating system) a temperature of less than or equal to 635 °C, less than or equal to 630 °C, less than or equal to 620 °C, less than or equal to 610 °C, less than or equal to 600 °C, less than or equal to 590 °C, less than or equal to 580 °C, less than or equal to 570 °C, or less than or equal to 560 °C. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 550 °C and less than or equal to 635 °C). Other ranges are also possible. The temperature of an interior surface of a container for a source may be determined by a thermocouple positioned thereon. In some embodiments, the interior surface configured to be heated to and / or maintained at a temperature in one or more of the above-referenced ranges is one in direct contact with a metal source.

[0141] When a deposition system comprises two or more containers for metal sources, each container for a metal source may independently be configured to be heated to and / or maintained at a temperature in one or more of the above-referenced ranges.

[0142] Another component of a deposition system that may be configured to be heated to and / or maintained at a temperature within a range is a shutter of a container containing a metal source. In some embodiments, a shutter is configured to be heated to and / or maintained at (e.g., by a heating system, such as a resistive heating system) a temperature of greater than or equal to 550 °C, greater than or equal to 560 °C, greater than or equal to 570 °C, greater than or equal to 580 °C, greater than or equal to 590 °C, greater than or equal to 600 °C, greater than or equal to 610 °C, greater than or equal to 620 °C, greater than or equal to 630 °C or greater than or equal to 640 °C. In some embodiments, a shutter is configured to be heated to and / or maintained at (e.g., by a heating system, such as a resistive heating system) a temperature of less than or equal to 645 °C, less than or equal to 640 °C, less than or equal to 630 °C, less than or equal to

[0143] 620 °C, less than or equal to 610 °C, less than or equal to 600 °C, less than or equal to

[0144] 590 °C, less than or equal to 580 °C, less than or equal to 570 °C, or less than or equal to

[0145] 560 °C. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 550 °C and less than or equal to 645 °C). Other ranges are also possible. The temperature of a shutter of a container for a source may be determined by a thermocouple positioned thereon.

[0146] When a deposition system comprises two or more containers for metal sources, each container for a metal source may independently comprise a shutter that is configured to be heated to and / or maintained at a temperature in one or more of the above-referenced ranges.

[0147] As described elsewhere herein, some embodiments relate to deposition systems comprising sources, such as sources of gases reactive with lithium metal and / or configured to deposit to form a layer disposed on a layer comprising lithium metal. As also described elsewhere herein, some embodiments relate to methods of depositing a layer, such as a passivating layer, on a layer comprising lithium metal. In some embodiments, the layer is deposited by condensing the gases thereon. It is also possible for a reaction product of the gases with each other and / or with lithium metal (e.g., in the lithium metal layer) may condense to form the relevant layer. A variety of suitable gases are suitable for such purposes, including CO2, O2, H2O, COS, SO2, CS2, H2, N2, N2O, NH3, SF6, freons, fluorobenzene, SiF4, C2H2, air (e.g., clean dry air, artificial air), species comprising boron (e.g., esters of boronic acids), species comprising phosphorus (e.g., esters of phosphoric acids), species comprising selenium, species comprising tellurium, and / or species comprising halogen (e.g., species comprising fluorine, bromine, and / or iodine, including those mentioned above). In some embodiments, one or more gases suitable use in atomic layer deposition are employed to deposit a layer comprising lithium metal and / or a layer thereon. Some gases that may be employed for depositing a layer comprising lithium metal and / or a layer thereon may be activated (e.g., by a plasma) prior to and / or concurrently with the deposition of the layer therefrom.

[0148] In some embodiments, two or more gases are used in combination. For instance, in some embodiments, it may be desirable to deposit a layer from a combination of gases including both H2O and another, different gas. As another example, in some embodiments, a combination of CO2 with N2 and / or O2 may be particularly advantageous. In some embodiments, as described elsewhere herein, the layer disposed on the layer comprising lithium metal may be deposited in the further presence of an inert gas, such as argon and / or helium.

[0149] When a layer is deposited from a combination of gases including both H2O and another, different gas, the relative humidity of the combination of gases may be a variety of suitable values. In other words, the ratio of the amount of H2O in the combination of gases to the amount of H2O soluble in the combination of gases may be selected as desired. In some embodiments, the relative humidity of the combination of gases is similar to that of a typical dry room (e.g., less than or equal to 10%). It is also possible for the relative humidity of the combination of gases to have another value (e.g., a value in excess of that in typical dry rooms). In some embodiments, a layer is deposited from a combination of gases having a relative humidity of greater than or equal to 0%, greater than or equal to 1%, greater than or equal to 2%, greater than or equal to 5%, greater than or equal to 7.5%, greater than or equal to 10%, greater than or equal to 12.5%, greater than or equal to 15%, greater than or equal to 20%, greater than or equal to 25%, greater than or equal to 30%, greater than or equal to 35%, greater than or equal to 40%, or greater than or equal to 45%. In some embodiments, a layer is deposited from a combination of gases having a relative humidity of less than or equal to 50%, less than or equal to 45%, less than or equal to 40%, less than or equal to 35%, less than or equal to 30%, less than or equal to 25%, less than or equal to 20%, less than or equal to 15%, less than or equal to 12.5%, less than or equal to 10%, less than or equal to 7.5%, less than or equal to 5%, less than or equal to 2%, or less than or equal to 1%. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0% and less than or equal to 50%, greater than or equal to 0% and less than or equal to 30%, or greater than or equal to 0% and less than or equal to 10%). Other ranges are also possible.

[0150] Another example of a further component that a deposition system may include is a module configured to generate an oxygen plasma (e.g., an oxygen plasma source). The module may comprise a vacuum chamber, and the vacuum chamber may be configured to generate the oxygen plasma (e.g., by allowing a controlled flow of oxygen thereinto and applying a high frequency voltage to the oxygen). In some embodiments, oxygen plasma may be particularly well-suited for cleaning a substrate prior to deposition of a layer thereon and / or of increasing the adhesiveness of the substrate to a layer deposited thereon. For this reason, it may be advantageous to position the module configured to generate an oxygen plasma such that a substrate passing through the deposition system passes therethrough prior to entering the module(s) configured to deposit one or more layers thereon.

[0151] The metals deposited herein may have any of a variety of suitable compositions. In some embodiments, for example, it is advantageous to use a system or method provided herein for depositing a metal comprising lithium. In some embodiments, the metal is lithium. For example, the metal may be lithium having a purity of greater than or equal to 50 wt%, greater than or equal to 55 wt%, greater than or equal to 60 wt%, greater than or equal to 65 wt%, greater than or equal to 70 wt%, greater than or equal to 75 wt%, greater than or equal to 80 wt%, greater than or equal to 85 wt%, greater than or equal to 90 wt%, or greater than or equal to 95 wt%. In some embodiments, a the metal may be lithium having a purity of less than or equal to 100 wt%, less than or equal to 95 wt%, less than or equal to 90 wt%, less than or equal to 85 wt%, less than or equal to 80 wt%, less than or equal to 75 wt%, less than or equal to 70 wt%, less than or equal to 65 wt%, less than or equal to 60 wt%, or less than or equal to 55 wt%. Combinations of these ranges are also possible (e.g., or greater than or equal to 50 wt% and less than or equal to 100 wt%). Other ranges are also possible.

[0152] In some embodiments, the metal is pure lithium. In other embodiments, the metal is a lithium alloy. In still other embodiments, the metal is substantially lithium- free (i.e., does not include non-trace amounts of lithium), as the disclosure is not so limited.

[0153] As described elsewhere herein, some embodiments relate to layers comprising metal (e.g., layers comprising lithium metal). For instance, some embodiments relate to the deposition of such layers, some embodiments relate to articles for inclusion in electrochemical cells comprising such layers, and some embodiments relate to deposition systems configured to deposit such layers. Further properties of layers comprising lithium metal are described in further detail below.

[0154] The term “layer” generally refers to an arrangement of material that, when the material is laid flat, has a thickness dimension, a depth dimension that is perpendicular to the thickness dimension, and a width dimension that is perpendicular to both the thickness dimension and the depth dimension, where the lengths of each of the depth dimension and the width dimension are at least 3 times the length of the thickness dimension. In some embodiments, the length of the depth dimension of the layer is at least 5 times, at least 10 times, at least 25 times, at least 50 times, at least 100 times, at least 500 times, or at least 1000 times the length of the thickness dimension of the layer. In some embodiments, the length of the width dimension of the layer is at least 5 times, at least 10 times, at least 25 times, at least 50 times, at least 100 times, at least 500 times, or at least 1000 times the length of the thickness dimension of the layer. The width and depth dimensions of a layer define its major surfaces.

[0155] Deposited metal layers may have a variety of suitable thicknesses. In some embodiments, a layer has a thickness of greater than or equal to 1 micron, greater than or equal to 2 microns, greater than or equal to 5 microns, greater than or equal to 7.5 microns, greater than or equal to 10 microns, greater than or equal to 15 microns, greater than or equal to 20 microns, greater than or equal to 25 microns, greater than or equal to 30 microns, greater than or equal to 35 microns, greater than or equal to 40 microns, or greater than or equal to 45 microns. In some embodiments, a layer has a thickness of less than or equal to 50 microns, less than or equal to 45 microns, less than or equal to 40 microns, less than or equal to 35 microns, less than or equal to 30 microns, less than or equal to 25 microns, less than or equal to 20 microns, less than or equal to 15 microns, less than or equal to 10 microns, less than or equal to 7.5 microns, less than or equal to 5 microns, or less than or equal to 2 microns. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1 micron and less than or equal to 50 microns, or greater than or equal to 2 microns and less than or equal to 30 microns). Other ranges are also possible. The thickness of a metal layer (e.g., a lithium metla layer) may be determined by eddy current sensing.

[0156] When an article for inclusion in an electrochemical cell comprises two or more metal layers, each metal layer may independently have a thickness in one or more of the above-referenced ranges.

[0157] The systems and methods provided herein may be particularly well-suited for the deposition of layers comprising lithium metal. Layers comprising lithium metal may, as a whole, be electroactive. In other words, the lithium metal in the layer may be capable of and / or configured to undergoing a redox process if the layer as a whole is subject to an appropriate stimulus. For instance, in some embodiments, a layer comprising both lithium metal and a species other than lithium metal may be configured to be placed in an electrochemical cell, and the lithium metal in the layer may be configured to serve as an anode and / or as a component of an anode that undergoes an oxidation process during discharging and / or a reduction process during charging. Such layers may comprise portions that are electroactive (e.g., portions comprising lithium metal) and portions that are non-electroactive. In some embodiments, only an electroactive layer (e.g., only a lithium layer) is deposited. Portions that are non-electroactive, if present, may comprise a ceramic (e.g., as described above).

[0158] A particular advantage of the systems and methods provided herein is that, according to some embodiments, they may be used to produce articles comprising Zone 3 lithium metal in large quantities. As discussed above, Zone 3 lithium metal may have particular advantages for battery applications. However, fabrication of Zone 3 lithium has presented serious technical challenges, and these advantages have consequently been difficult to realize or commercialize. But, as discussed above, the systems and methods provided herein can be used to produce Zone 3 lithium in large quantities and at scale, e.g., using roll-to-roll manufacturing processes. For example, in some embodiments, the disclosure relates to forming an article that is a roll. The systems and methods herein can be used to produce articles comprising lithium layers of any of a variety of suitable sizes. For example, in some embodiments, an article comprises a lithium metal layer or a plurality of lithium metal layers having a total volume of greater than or equal to 50 mL, greater than or equal to 100 mL, greater than or equal to 200 mL, greater than or equal to 300 mL, greater than or equal to 400 mL, greater than or equal to 500 mL, greater than or equal to 600 mL, greater than or equal to 700 mL, greater than or equal to 800 mL, greater than or equal to 900 mL, greater than or equal to 1 L, greater than or equal to 2 L, greater than or equal to 3 L, or greater than or equal to 4 L. In some embodiments, an article comprises a lithium metal layer or a plurality of lithium metal layers having a total volume of less than or equal to 5 L, less than or equal to 4 L, less than or equal to 3 L, less than or equal to 2 L, less than or equal to 1 L, less than or equal to 900 mL, less than or equal to 800 mL, less than or equal to 700 mL, less than or equal to 600 mL, less than or equal to 500 mL, less than or equal to 400 mL, less than or equal to 300 mL, less than or equal to 200 mL, or less than or equal to 100 mL. Combinations of these ranges are also possible (e.g., greater than or equal to 50 mL and less than or equal to 5 L, or greater than or equal to 50 mL and less than or equal to 1 L). Other ranges, both higher and lower than those described above, are also possible, as the disclosure is not so limited. The volume of lithium metal may be determined, according to some embodiments, by determining the thickness of a lithium metal layer or layers and multiplying the thickness by the area of the lithium metal layer or layers.

[0159] An appropriate proportion of the lithium (e.g., the lithium metal layer) may comprise (e.g., may essentially be formed from, or may be completely formed from) Zone 3 lithium. For example, in some embodiments, greater than or equal to 70%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, or greater than or equal to 95% of the lithium by volume is Zone 3 lithium. In some embodiments, less than or equal to 100%, less than or equal to 95%, less than or equal to 90%, less than or equal to 85%, less than or equal to 80%, or less than or equal to 75% of the lithium by volume is Zone 3 lithium. Combinations of these ranges are also possible (e.g., greater than or equal to 70% and less than or equal to 100%, greater than or equal to 90% and less than or equal to 100%, or greater than or equal to 95% and less than or equal to 100%). Other ranges, both higher and lower than those described above, are also possible, as the disclosure is not so limited.

[0160] Combinations of the foregoing ranges are also possible. For example, in some embodiments, an article comprises a lithium metal or layer a plurality of lithium metal layers having a total volume of greater than or equal to 50 mL, wherein greater than or equal to 70% of the lithium is Zone 3 lithium by volume. As another example, in some embodiments, an article comprises a lithium metal or layer a plurality of lithium metal layers having a total volume of greater than or equal to 50 mL and less than or equal to 5 L, wherein greater than or equal to 70% of the lithium and less than or equal to 100% of the lithium is Zone 3 lithium by volume.

[0161] Notably, the advantages of Zone 3 lithium for battery applications is not limited to a single use. It has been recognized in the present disclosure that a layer of Zone 3 lithium, incorporated into an electrochemical cell or battery, may be reformed as Zone 3 lithium when the battery or electrochemical is recharged, thus providing the advantages of Zone-3 lithium across multiple charge-discharge cycles. Thus, in some embodiments, the disclosure relates to forming a layer comprising an appropriate proportion of Zone 3 lithium (e.g., a proportion identified in the foregoing paragraph) by recharging a battery.

[0162] Reformation of the Zone 3 lithium layer may be ensured by any of a variety of approaches, one of which involves operating an electrochemical cell or battery at a cathodic deficit. For example, without wishing to be bound by any theory, the anode and the cathode may contain suitable quantities of electroactive material to ensure that, during discharge, the anode can generate (by the oxidation of an anode active material such as lithium) more electrons than the cathode can receive (by the reduction of cathode active material). For example, the anode may be configured to generate l.lx, 1.2x, 1.5x, 2x, or more electrons than the cathode can receive. Operating at a cathodic deficit may ensure that at least a portion of the original Zone 3 lithium remains as a seed layer that promotes reformation of the Zone 3 lithium. However, it should be understood that operating at a cathodic deficit is not required to reform Zone 3 lithium. For example, in some embodiments, Zone 3 lithium may reform during charging because the original Zone-3 lithium layer interacted with the substrate and / or a passivation layer of the article to make reformation of Zone 3 lithium more likely than reformation of other types of lithium layer.

[0163] The article, including the lithium metal layer, a substrate layer, and any of a variety of suitable additional layers (e.g., passivating layers) may have any of a variety of suitable thicknesses. In some embodiments, the article has a thickness of greater than or equal to 0.1 mm, greater than or equal to 0.2 mm, greater than or equal to 0.3 mm, greater than or equal to 0.4 mm, greater than or equal to 0.5 mm, greater than or equal to 0.6 mm, greater than or equal to 0.7 mm, greater than or equal to 0.8 mm, greater than or equal to 0.9 mm, greater than or equal to 1 mm, greater than or equal to 1.1 mm, greater than or equal to 1.2 mm, greater than or equal to 1.3 mm, greater than or equal to 1.4 mm, greater than or equal to 1.5 mm, greater than or equal to 1.6 mm, greater than or equal to 1.7 mm, greater than or equal to 1.8 mm, or greater than or equal to 1.9 mm. In some embodiments, the article has a thickness of less than or equal to 2 mm, less than or equal to 1.9 mm, less than or equal to 1.8 mm, less than or equal to 1.7 mm, less than or equal to 1.6 mm, less than or equal to 1.5 mm, less than or equal to 1.4 mm, less than or equal to 1.3 mm, less than or equal to 1.2 mm, less than or equal to 1.1 mm, less than or equal to 1 mm, less than or equal to 0.9 mm, less than or equal to 0.8 mm, less than or equal to 0.7 mm, less than or equal to 0.6 mm, less than or equal to 0.5 mm, less than or equal to 0.4 mm, less than or equal to 0.3 mm, or less than or equal to 0.2 mm.

[0164] Combinations of these ranges are also possible (e.g., greater than or equal to 0.1 mm and less than or equal to 2 mm, or greater than or equal to 0.5 mm and less than or equal to 2 mm). Other ranges, both higher and lower than those described above, are also possible, as the disclosure is not so limited.

[0165] According to some embodiments, the article is formed into a roll. The roll may have any of a variety of suitable diameters. In some embodiments, an article is in the form of a roll with a diameter of greater than or equal to 5 cm, greater than or equal to 10 cm, greater than or equal to 15 cm, greater than or equal to 20 cm, or greater than or equal to 25 cm. In some embodiments, an article is in the form of a roll with a diameter of less than or equal to 30 cm, less than or equal to 25 cm, less than or equal to 20 cm, less than or equal to 15 cm, or less than or equal to 10 cm. Combinations of these ranges are also possible (e.g., greater than or equal to 5 cm and less than or equal to 30 cm, or greater than or equal to 5 cm and less than or equal to 25 cm). Other ranges, both higher and lower than those described above, are also possible, as the disclosure is not so limited.

[0166] According to some embodiments, a layer comprising Zone 3 lithium has a suitable average grain size. In some embodiments, the lithium of the layer has an average grain size of greater than or equal to 2 microns, greater than or equal to 3 microns, greater than or equal to 4 microns, greater than or equal to 5 microns, greater than or equal to 6 microns, greater than or equal to 7 microns, greater than or equal to 8 microns, greater than or equal to 9 microns, greater than or equal to 10 microns, greater than or equal to 11 microns, greater than or equal to 12 microns, greater than or equal to 13 microns, or greater than or equal to 14 microns. In some embodiments, the lithium of the layer has an average grain size of less than or equal to 15 microns, less than or equal to 14 microns, less than or equal to 13 microns, less than or equal to 12 microns, less than or equal to 11 microns, less than or equal to 10 microns, less than or equal to 9 microns, less than or equal to 8 microns, less than or equal to 7 microns, less than or equal to 6 microns, less than or equal to 5 microns, less than or equal to 4 microns, or less than or equal to 3 microns. Combinations of these ranges are also possible (e.g., greater than or equal to 2 microns and less than or equal to 15 microns, or greater than or equal to 3 microns and less than or equal to 10 microns). Other ranges, both higher and lower than those described above, are also possible, as the disclosure is not so limited.

[0167] In some embodiments, Zone 3 lithium formation is associated with changes in the X-ray diffraction (XRD) profile of the lithium relative to other lithium zones. Without wishing to be bound by any particular theory, although the Zone 3 lithium has the same crystal structure and hence diffracts at the same angles as other lithium layers (e.g., Zone 1 and Zone 2 lithium), Zone 3 lithium grains have a different texture than, e.g., Zone 2, Zone 1, and Zone T lithium layers (in the sense that grains may tend to align differently in the thickness dimension), and may thus present diffraction profiles with different relative intensities for the diffraction peaks. For example, it has been identified that where XRD is performed on a flat article comprising lithium, the ratio of the integrated intensity of the LI peak (ILI) to the integrated intensity of the L2 peak (IL2) may increase for Zone 3 lithium compared to the other lithium types. (The LI and L2 peaks corresponding to { 110} and {200} planes, respectively).

[0168] In some embodiments, a lithium metal layer has an (ILI / IL2) ratio of greater than or equal to 3, greater than or equal to 3.5, greater than or equal to 4, greater than or equal to 4.5, greater than or equal to 5, greater than or equal to 5.5, or greater than or equal to 6. In some embodiments, a lithium metal layer has an (ILI / IL2) ratio of less than or equal to 7, less than or equal to 6.5, less than or equal to 6, less than or equal to 5.5, less than or equal to 5, less than or equal to 4.5, less than or equal to 4, or less than or equal to 3.5. Combinations of these ranges are also possible (e.g., greater than or equal to 3 and less than or equal to 7, or greater than or equal to 3 and less than or equal to 6). Other ranges, both higher and lower than those described above, are also possible, as the disclosure is not so limited.

[0169] Layers comprising lithium metal may have a variety of suitable porosities. As described elsewhere herein, some layers comprising lithium metal may be relatively dense (e.g., they may have a porosity of greater than or equal to 0% and less than or equal to 5%), or may comprise a plurality of pores that occupy an appreciable volume fraction thereof (e.g., they may have a porosity of greater than or equal to 5% and less than or equal to 25%, or greater than or equal to 5% and less than or equal to 15%). In some embodiments, a layer comprising lithium metal has a porosity of greater than or equal to 0%, greater than or equal to 0.5%, greater than or equal to 1%, greater than or equal to 1.5%, greater than or equal to 2%, greater than or equal to 3%, greater than or equal to 4%, greater than or equal to 5%, greater than or equal to 7.5%, greater than or equal to 10%, greater than or equal to 12.5%, greater than or equal to 15%, greater than or equal to 17.5%, greater than or equal to 20%, or greater than or equal to 22.5%. In some embodiments, a layer comprising lithium metal has a porosity of less than or equal to 25%, less than or equal to 22.5%, less than or equal to 20%, less than or equal to 17.5%, less than or equal to 15%, less than or equal to 12.5%, less than or equal to 10%, less than or equal to 7.5%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1.5%, less than or equal to 1%, or less than or equal to 0.5%. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0% and less than or equal to 25%, greater than or equal to 0% and less than or equal to 5%, greater than or equal to 5% and less than or equal to 25%, or greater than or equal to 5% and less than or equal to 25%). Other ranges are also possible.

[0170] A layer comprising lithium metal may have a porosity in one or more of the above-referenced ranges as determined by dividing the measured density of the layer comprising lithium metal by the theoretical density of the layer comprising lithium metal. The measured density of the layer comprising lithium metal may be determined by the following formula: Measured density of layer comprising lithium metal = [weight of layer comprising lithium metal] / [(area of layer comprising lithium metal)*(thickness of layer comprising lithium metal as measured by drop gauge)].

[0171] It is also possible for a layer comprising lithium to have a porosity in one or more of the above-referenced ranges as measured by scanning electron microscopy. Briefly, the layer comprising lithium may be imaged using a scanning electron microscope operated in immersion mode at an accelerating voltage of 5 kV, a working distance of 5 mm, a spot size of 3.5, and a magnification of 25,000. The image may be analyzed with ImageJ configured to have 8-bit type, 255 gray levels, a width of 27.43 inches, a height of 19.69 inches, an image size of 1.6 MB, and a resolution of 56 pixels per inch. In ImageJ, the brightness / contrast minimum may be set to 0, the brightness / contrast maximum may be set to 255, the threshold lower value may be set to 0, and the threshold upper value may be set at a value which makes the pores appear to be black. Then, ImageJ may be employed to analyze the resultant image to determine the percentage of the area that is black. This percentage may be taken to be equivalent to the porosity of the layer comprising lithium.

[0172] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a porosity in one or more of the above-referenced ranges as measured by either or both of the two-above described measurement techniques.

[0173] In some embodiments, information regarding the morphology of a layer comprising lithium metal may be obtained from the color space thereof. The color space is a combination of lightness, saturation, chroma, and hue that characterizes the visual appearance of an object. FIGS. 21A and 21B show how these parameters together describe the visual appearance of objects. It should also be understood that the layer comprising lithium may appear visually to have a variety of colors, such as red, yellow, green, and / or blue.

[0174] In some embodiments, a layer comprising lithium has a lightness of greater than or equal to 10, greater than or equal to 12.5, greater than or equal to 15, greater than or equal to 17.5, greater than or equal to 20, greater than or equal to 22.5, greater than or equal to 25, greater than or equal to 27.5, greater than or equal to 30, greater than or equal to 35, greater than or equal to 40, greater than or equal to 45, greater than or equal to 50, greater than or equal to 55, greater than or equal to 60, greater than or equal to 65, greater than or equal to 70, greater than or equal to 75, or greater than or equal to 80. In some embodiments, a layer comprising lithium has a lightness of less than or equal to 85, less than or equal to 80, less than or equal to 75, less than or equal to 70, less than or equal to 65, less than or equal to 60, less than or equal to 55, less than or equal to 50, less than or equal to 45, less than or equal to 40, less than or equal to 35, less than or equal to 30, less than or equal to 27.5, less than or equal to 25, less than or equal to 22.5, less than or equal to 20, less than or equal to 17.5, less than or equal to 15, or less than or equal to 12.5. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 10 and less than or equal to 85, or greater than or equal to 20 and less than or equal to 60). Other ranges are also possible.

[0175] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a lightness in one or more of the above-referenced ranges.

[0176] In some embodiments, a layer comprising lithium has a red / green saturation (an “a” saturation) of greater than or equal to -3, greater than or equal to -2.5, greater than or equal to -2, greater than or equal to -1.5, greater than or equal to -1, greater than or equal to -0.5, greater than or equal to 0, greater than or equal to 0.5, greater than or equal to 1, greater than or equal to 1.5, greater than or equal to 2, greater than or equal to 2.5, greater than or equal to 3, greater than or equal to 3.5, greater than or equal to 4, greater than or equal to 4.5, greater than or equal to 5, greater than or equal to 6, greater than or equal to 8, greater than or equal to 10, greater than or equal to 12.5, or greater than or equal to 15. In some embodiments, a layer comprising lithium has a red / green saturation of less than or equal to 20, less than or equal to 15, less than or equal to 12.5, less than or equal to 10, less than or equal to 8, less than or equal to 6, less than or equal to 5, less than or equal to 4.5, less than or equal to 4, less than or equal to 3.5, less than or equal to 3, less than or equal to 2.5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1, less than or equal to 0.5, less than or equal to 0, less than or equal to -0.5, less than or equal to -1, less than or equal to -1.5, less than or equal to -2., or less than or equal to -2.5. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to -3 and less than or equal to 20, or greater than or equal to -1 and less than or equal to 4). Other ranges are also possible.

[0177] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a red / green saturation in one or more of the above-referenced ranges.

[0178] In some embodiments, a layer comprising lithium has a yellow / blue saturation (a “b” saturation) of greater than or equal to -3, greater than or equal to -2.5, greater than or equal to -2, greater than or equal to -1.5, greater than or equal to -1, greater than or equal to -0.5, greater than or equal to 0, greater than or equal to 0.5, greater than or equal to 1, greater than or equal to 1.5, greater than or equal to 2, greater than or equal to 2.5, greater than or equal to 3, greater than or equal to 3.5, greater than or equal to 4, greater than or equal to 4.5, greater than or equal to 5, greater than or equal to 6, greater than or equal to 8, greater than or equal to 10, greater than or equal to 12.5, or greater than or equal to 15. In some embodiments, a layer comprising lithium has a yellow / blue saturation of less than or equal to 20, less than or equal to 15, less than or equal to 12.5, less than or equal to 10, less than or equal to 8, less than or equal to 6, less than or equal to 5, less than or equal to 4.5, less than or equal to 4, less than or equal to 3.5, less than or equal to 3, less than or equal to 2.5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1, less than or equal to 0.5, less than or equal to 0, less than or equal to -0.5, less than or equal to -1, less than or equal to -1.5, less than or equal to -2., or less than or equal to -2.5. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to -3 and less than or equal to 20, or greater than or equal to -1 and less than or equal to 4). Other ranges are also possible. When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a yellow / blue saturation in one or more of the above-referenced ranges.

[0179] In some embodiments, a layer comprising lithium has a chroma of greater than or equal to -2, greater than or equal to -1.5, greater than or equal to -1, greater than or equal to -0.5, greater than or equal to 0, greater than or equal to 0.5, greater than or equal to 1, greater than or equal to 1.5, greater than or equal to 2, greater than or equal to 2.5, greater than or equal to 3, greater than or equal to 3.5, greater than or equal to 4, greater than or equal to 4.5, greater than or equal to 5, greater than or equal to 6, greater than or equal to 8, greater than or equal to 10, greater than or equal to 12.5, or greater than or equal to 15. In some embodiments, a layer comprising lithium has a chroma of less than or equal to 20, less than or equal to 15, less than or equal to 12.5, less than or equal to 10, less than or equal to 8, less than or equal to 6, less than or equal to 5, less than or equal to 4.5, less than or equal to 4, less than or equal to 3.5, less than or equal to 3, less than or equal to 2.5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1, less than or equal to 0.5, less than or equal to 0, less than or equal to -0.5, less than or equal to -1, or less than or equal to -1.5. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to -2 and less than or equal to 20, or greater than or equal to -1 and less than or equal to 5). Other ranges are also possible.

[0180] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a chroma in one or more of the above-referenced ranges.

[0181] In some embodiments, a layer comprising lithium has a hue of greater than or equal to -2°, greater than or equal to 0°, greater than or equal to 2°, greater than or equal to 5°, greater than or equal to 7.5°, greater than or equal to 10°, greater than or equal to 20°, greater than or equal to 50°, greater than or equal to 75°, greater than or equal to 100°, greater than or equal to 125°, greater than or equal to 150°, greater than or equal to

[0182] 175°, greater than or equal to 200°, greater than or equal to 225°, greater than or equal to

[0183] 250°, greater than or equal to 275°, greater than or equal to 300°, or greater than or equal to 325°. In some embodiments, a layer comprising lithium has a hue of less than or equal to 360°, less than or equal to 325°, less than or equal to 300°, less than or equal to 275°, less than or equal to 250°, less than or equal to 225°, less than or equal to 200°, less than or equal to 175°, less than or equal to 150°, less than or equal to 125°, less than or equal to 100°, less than or equal to 75°, less than or equal to 50°, less than or equal to 20°, less than or equal to 10°, less than or equal to 7.5°, less than or equal to 5°, less than or equal to 2°, or less than or equal to 0°. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to -2° and less than or equal to 360°, or greater than or equal to 10° and less than or equal to 350°). Other ranges are also possible.

[0184] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a hue in one or more of the above-referenced ranges.

[0185] In some embodiments, a layer comprising lithium metal is relatively smooth. The smoothness or roughness of a layer comprising lithium metal may be characterized in a variety of manners. Suitable parameters that may be employed to characterize the roughness of a layer comprising lithium metal and suitable values of such parameters are described in further detail below. Some of the techniques below may be employed with reference to cross-section of the layer comprising lithium metal, and it should be understood that some layers comprising lithium metal may comprise at least one crosssection having one or more of the properties described below, that some layers comprising lithium metal may be made up exclusively of cross-sections having one or more of the properties described below, and that some layers comprising lithium metal may have a morphology such that a majority of the cross-sections have one or more of the properties below (e.g., at least 50% of the cross-sections, at least 75% of the crosssections, at least 90% of the cross-sections, at least 95% of the cross-sections, or at least 99% of the cross-sections).

[0186] One example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Ra, which is the arithmetic average deviation across the cross-section of the height of the layer from the mean line of the cross section (i.e., the line which is parallel to the surface and divides the cross-section such that the area between the surface topography and the line therebeneath is equivalent to the area between the surface topography and the line thereabove). In some embodiments, a layer comprising lithium metal has a value of Raof less than or equal to 1.5 microns, less than or equal to 1.25 microns, less than or equal to 1 micron, less than or equal to 0.75 microns, less than or equal to 0.5 microns, less than or equal to 0.25 microns, less than or equal to 0.2 microns, less than or equal to 0.18 microns, less than or equal to 0.15 microns, less than or equal to 0.125 microns, less than or equal to 0.1 micron, or less than or equal to 0.075 microns. In some embodiments, a layer comprising lithium metal has a value of Raof greater than or equal to 0.05 microns, greater than or equal to 0.075 microns, greater than or equal to 0.1 micron, greater than or equal to 0.125 microns, greater than or equal to 0.15 microns, greater than or equal to 0.18 microns, greater than or equal to 0.2 microns, greater than or equal to 0.25 microns, greater than or equal to 0.5 microns, greater than or equal to 0.75 microns, greater than or equal to 1 micron, or greater than or equal to 1.25 microns. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 1.5 microns and greater than or equal to 0.05 microns, or less than or equal to 1.5 microns and greater than or equal to 0.18 microns). Other ranges are also possible.

[0187] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Rain one or more of the above-referenced ranges.

[0188] A second example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Rq, which is the root mean square deviation across the cross-section of the height of the layer from the mean line of the cross section. In some embodiments, a layer comprising lithium metal has a value of Rqof less than or equal to 2.5 microns, less than or equal to 2.25 microns, less than or equal to 2 microns, less than or equal to 1.75 microns, less than or equal to 1.5 microns, less than or equal to 1.25 microns, less than or equal to 1 micron, less than or equal to 0.75 microns, less than or equal to 0.5 microns, less than or equal to 0.4 microns, less than or equal to 0.3 microns, or less than or equal to 0.2 microns. In some embodiments, a layer comprising lithium metal has a value of Rqof greater than or equal to 0.1 micron, greater than or equal to 0.2 microns, greater than or equal to 0.3 microns, greater than or equal to 0.4 microns, greater than or equal to 0.5 microns, greater than or equal to 0.75 microns, greater than or equal to 1 micron, greater than or equal to 1.25 microns, greater than or equal to 1.5 microns, greater than or equal to 1.75 microns, greater than or equal to 2 microns, or greater than or equal to 2.25 microns. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 2.5 microns and greater than or equal to 0.1 micron, or less than or equal to 2 microns and greater than or equal to 0.2 microns). Other ranges are also possible.

[0189] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Rqin one or more of the above-referenced ranges.

[0190] A third example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Rp, which is the difference between the maximum height in the cross-section and the height of the mean line. In some embodiments, a layer comprising lithium metal has a value of Rpof less than or equal to 15 microns, less than or equal to 12.5 microns, less than or equal to 10 microns, less than or equal to 7.5 microns, less than or equal to 5 microns, less than or equal to 2.5 microns, less than or equal to 2 microns, less than or equal to 1.5 microns, or less than or equal to 1 micron. In some embodiments, a layer comprising lithium metal has a value of Rpof greater than or equal to 0.5 microns, greater than or equal to 1 micron, greater than or equal to 1.5 microns, greater than or equal to 2 microns, greater than or equal to 2.5 microns, greater than or equal to 5 microns, greater than or equal to 7.5 microns, greater than or equal to 10 microns, or greater than or equal to 12.5 microns. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 15 microns and greater than or equal to 0.5 microns, or less than or equal to 15 microns and greater than or equal to 1 micron). Other ranges are also possible.

[0191] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Rpin one or more of the above-referenced ranges.

[0192] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Rv, which is the difference between the minimum height in the cross-section and the height of the mean line. In some embodiments, a layer comprising lithium metal has a value of Rvof greater than or equal to less than or equal to -15 microns, greater than or equal to -12.5 microns, greater than or equal to -10 microns, greater than or equal to -7.5 microns, greater than or equal to -5 microns, greater than or equal to -2.5 microns, greater than or equal to -2 microns, greater than or equal to -1.5 microns, or greater than or equal to -1 micron. In some embodiments, a layer comprising lithium metal has a value of Rvof less than or equal to -0.5 microns, less than or equal to -1 micron, less than or equal to -1.5 microns, less than or equal to -2 microns, less than or equal to -2.5 microns, less than or equal to -5 microns, less than or equal to -7.5 microns, less than or equal to -10 microns, or less than or equal to -12.5 microns. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to -15 microns and less than or equal to -0.5 microns, or greater than or equal to -15 microns and less than or equal to -1 micron). Other ranges are also possible.

[0193] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Rvin one or more of the above-referenced ranges.

[0194] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Rt, which is the sum of the absolute values of Rpand Rv. In some embodiments, a layer comprising lithium metal has a value of Rt of less than or equal to 30 microns, less than or equal to 25 microns, less than or equal to 20 microns, less than or equal to 15 microns, less than or equal to 10 microns, less than or equal to 7.5 microns, less than or equal to 5 microns, less than or equal to 4 microns, less than or equal to 3 microns, less than or equal to 2.5 microns, less than or equal to 2 microns, or less than or equal to 1.5 microns. In some embodiments, a layer comprising lithium metal has a value of Rt of greater than or equal to 1 micron, greater than or equal to 1.5 microns, greater than or equal to 2 microns, greater than or equal to 2.5 microns, greater than or equal to 3 microns, greater than or equal to 4 microns, greater than or equal to 5 microns, greater than or equal to 7.5 microns, greater than or equal to 10 microns, greater than or equal to 15 microns, greater than or equal to 20 microns, or greater than or equal to 25 microns. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 25 microns and greater than or equal to 1 micron, or less than or equal to 30 microns and greater than or equal to 2 microns). Other ranges are also possible. When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Rt in one or more of the above-referenced ranges.

[0195] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Rpm, which is the mean height of the peaks in the cross-section with respect to the mean line. In some embodiments, a layer comprising lithium metal has a value of Rpmof less than or equal to 15 microns, less than or equal to 12.5 microns, less than or equal to 10 microns, less than or equal to 7.5 microns, less than or equal to 5 microns, less than or equal to 3 microns, less than or equal to 2 microns, less than or equal to 1.5 microns, less than or equal to 1 micron, or less than or equal to 0.75 microns. In some embodiments, a layer comprising lithium metal has a value of Rpmof greater than or equal to 0.5 microns, greater than or equal to 0.75 microns, greater than or equal to 1 micron, greater than or equal to 1.5 microns, greater than or equal to 2 microns, greater than or equal to 3 microns, greater than or equal to 5 microns, greater than or equal to 7.5 microns, greater than or equal to 10 microns, or greater than or equal to 12.5 microns. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 15 microns and greater than or equal to 0.5 microns, or less than or equal to 10 microns and greater than or equal to 1 micron). Other ranges are also possible.

[0196] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Rpmin one or more of the above-referenced ranges.

[0197] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is RVm, which is the mean height of the valleys in the cross-section with respect to the mean line. In some embodiments, a layer comprising lithium metal has a value of Rvmof greater than or equal to -15 microns, greater than or equal to -12.5 microns, greater than or equal to -10 microns, greater than or equal to -7.5 microns, greater than or equal to -5 microns, greater than or equal to -3 microns, greater than or equal to -2 microns, greater than or equal to -1.5 microns, greater than or equal to -1 micron, or greater than or equal to -0.75 microns. In some embodiments, a layer comprising lithium metal has a value of Rvmof less than or equal to -0.5 microns, less than or equal to -0.75 microns, less than or equal to -1 micron, less than or equal to -1.5 microns, less than or equal to -2 microns, less than or equal to -3 microns, less than or equal to -5 microns, less than or equal to -7.5 microns, less than or equal to -10 microns, or less than or equal to -12.5 microns. Combinations of the abovereferenced ranges are also possible (e.g., greater than or equal to -15 microns and less than or equal to -1 micron, or greater than or equal to -10 microns and less than or equal to -0.5 microns). Other ranges are also possible.

[0198] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Rvmin one or more of the above-referenced ranges.

[0199] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Rz, which is the difference in height between the average height of the five highest peaks in the cross-section and the five deepest valleys in the cross-section. In some embodiments, a layer comprising lithium metal has a value of Rzof less than or equal to 20 microns, less than or equal to 17.5 microns, less than or equal to 15 microns, less than or equal to 12.5 microns, less than or equal to 10 microns, less than or equal to 7.5 microns, less than or equal to 5 microns, or less than or equal to 2.5 microns. In some embodiments, a layer comprising lithium metal has a value of Rzof greater than or equal to 1 micron, greater than or equal to 2.5 microns, greater than or equal to 5 microns, greater than or equal to 7.5 microns, greater than or equal to 10 microns, greater than or equal to 12.5 microns, greater than or equal to 15 microns, or greater than or equal to 17.5 microns. Combinations of the abovereferenced ranges are also possible (e.g., less than or equal to 20 microns and greater than or equal to 1 micron). Other ranges are also possible.

[0200] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Rzin one or more of the above-referenced ranges.

[0201] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Sm, which is the area of material in the cross-section that is present between the top of the cross-section and the height of the cross-section in the 90thpercentile (i.e., the value of height that is greater than 90% of the heights in the cross-section). In some embodiments, a layer comprising lithium metal has a value of Smof less than or equal to 1 square micron, less than or equal to 0.75 square microns, less than or equal to 0.5 square microns, less than or equal to 0.3 square microns, less than or equal to 0.2 square microns, less than or equal to 0.15 square microns, less than or equal to 0.1 square micron, less than or equal to 0.075 square microns, less than or equal to 0.05 square microns, less than or equal to 0.03 square microns, less than or equal to 0.02 square microns, less than or equal to 0.015 square microns, less than or equal to 0.01 square micron, less than or equal to 0.0075 square microns, less than or equal to 0.005 square microns, less than or equal to 0.003 square microns, or less than or equal to 0.002 square microns. In some embodiments, a layer comprising lithium metal has a value of Smof greater than or equal to 0.001 square micron, greater than or equal to 0.002 square microns, greater than or equal to 0.003 square microns, greater than or equal to 0.005 square microns, greater than or equal to 0.0075 square microns, greater than or equal to 0.01 square micron, greater than or equal to 0.02 square microns, greater than or equal to 0.05 square microns, greater than or equal to 0.075 square microns, greater than or equal to 0.1 square micron, greater than or equal to 0.15 square microns, greater than or equal to 0.2 square microns, greater than or equal to 0.3 square microns, greater than or equal to 0.5 square microns, or greater than or equal to 0.75 square microns. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 1 square micron and greater than or equal to 0.001 square micron, or less than or equal to 0.2 square microns and greater than or equal to 0.01 square micron). Other ranges are also possible.

[0202] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Smin one or more of the above-referenced ranges.

[0203] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Sbi, which is the difference in height between the height of the cross-section in the 95thpercentile (i.e., the value of height that is greater than 95% of the heights in the cross-section) and the height of the mean line. In some embodiments, a layer comprising lithium metal has a value of Sbi of less than or equal to 2 microns, less than or equal to 1.75 microns, less than or equal to 1.5 microns, less than or equal to 1.25 microns, less than or equal to 1.1 microns, less than or equal to 1 micron, less than or equal to 0.95 microns, less than or equal to 0.9 microns, less than or equal to 0.85 microns, less than or equal to 0.8 microns, less than or equal to 0.6 microns, less than or equal to 0.4 microns, less than or equal to 0.35 microns, less than or equal to 0.3 microns, less than or equal to 0.25 microns, less than or equal to 0.2 microns, less than or equal to 0.15 microns, or less than or equal to 0.125 microns. In some embodiments, a layer comprising lithium metal has a value of Sbi of greater than or equal to 0.1 micron, greater than or equal to 0.125 microns, greater than or equal to 0.15 microns, greater than or equal to 0.2 microns, greater than or equal to 0.25 microns, greater than or equal to 0.3 microns, greater than or equal to 0.35 microns, greater than or equal to 0.4 microns, greater than or equal to 0.6 microns, greater than or equal to 0.8 microns, greater than or equal to 0.85 microns, greater than or equal to 0.9 microns, greater than or equal to 0.95 microns, greater than or equal to 1 micron, greater than or equal to 1.1 microns, greater than or equal to 1.25 microns, greater than or equal to 1.5 microns, or greater than or equal to 1.75 microns. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 2 microns and greater than or equal to 0.1 micron, or less than or equal to 0.9 microns and greater than or equal to 0.3 microns). Other ranges are also possible.

[0204] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Sbi in one or more of the above-referenced ranges.

[0205] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Sdq, which is the root mean square of the slope of the surface of the layer. In some embodiments, a layer comprising lithium metal has a value of Sdq of less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, or less than or equal to 20. In some embodiments, a layer comprising lithium metal has a value of Sdq of greater than or equal to 10, greater than or equal to 20, greater than or equal to 30, greater than or equal to 40, greater than or equal to 50, greater than or equal to 60, greater than or equal to 70, greater than or equal to 80, or greater than or equal to 90. Combinations of the above- referenced ranges are also possible (e.g., less than or equal to 100 and greater than or equal to 10, or less than or equal to 80 and greater than or equal to 20). Other ranges are also possible.

[0206] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Sdq in one or more of the above-referenced ranges.

[0207] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Sku, which is the kurtosis of the height distribution of the cross-section. In some embodiments, a layer comprising lithium metal has a value of Sku of less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, less than or equal to 25, less than or equal to 20, less than or equal to 15, less than or equal to 12.5, less than or equal to 10, less than or equal to 8, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3.5, less than or equal to 3, or less than or equal to 2.5. In some embodiments, a layer comprising lithium metal has a value of Sku of greater than or equal to 2, greater than or equal to 2.5, greater than or equal to 3, greater than or equal to 3.5, greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, greater than or equal to 8, greater than or equal to 10, greater than or equal to 12.5, greater than or equal to 15, greater than or equal to 20, greater than or equal to 25, greater than or equal to 30, greater than or equal to 40, greater than or equal to 50, or greater than or equal to 60. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 70 and greater than or equal to 2, or less than or equal to 15 and greater than or equal to 2). Other ranges are also possible.

[0208] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Sku in one or more of the above-referenced ranges.

[0209] Another example of a parameter that may be employed to characterize the roughness of a layer comprising lithium metal is Ssk, which is the skewness of the height distribution of the cross-section. In some embodiments, a layer comprising lithium metal has a value of Ssk of less than or equal to 5, less than or equal to 4.5, less than or equal to 4, less than or equal to 3.5, less than or equal to 3, less than or equal to 2.5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1, less than or equal to 0.75, less than or equal to 0.5, less than or equal to 0.3, less than or equal to 0.2, less than or equal to 0.1, less than or equal to 0, less than or equal to -0.1, less than or equal to -0.2, less than or equal to -0.3, less than or equal to -0.5, less than or equal to -0.75, less than or equal to -1, or less than or equal to -1.5. In some embodiments, a layer comprising lithium metal has a value of Ssk of greater than or equal to -2, greater than or equal to - 1.5, greater than or equal to -1, greater than or equal to -0.75, greater than or equal to - 0.5, greater than or equal to -0.3, greater than or equal to -0.2, greater than or equal to - 0.1, greater than or equal to 0, greater than or equal to 0.1, greater than or equal to 0.2, greater than or equal to 0.3, greater than or equal to 0.5, greater than or equal to 0.75, greater than or equal to 1, greater than or equal to 1.5, greater than or equal to 2, greater than or equal to 2.5, greater than or equal to 3, greater than or equal to 3.5, greater than or equal to 4, or greater than or equal to 4.5. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 5 and greater than or equal to -2, or less than or equal to 3 and greater than or equal to -0.2). Other ranges are also possible.

[0210] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a value of Sku in one or more of the above-referenced ranges.

[0211] As described above, in some embodiments, a layer comprising lithium metal further comprises one or more species other than lithium metal. For instance, a layer comprising lithium may also comprise a metal, a non-metal and / or a metalloid. Suitable metals include aluminum, magnesium, indium, and / or tin (e.g., one or more such metals may be alloyed with the lithium metal). Suitable non-metals include carbon, oxygen, hydrogen (e.g., in hydride form, bonded covalently to carbon), sulfur, nitrogen, selenium, and various halogens (e.g., fluorine, bromine, iodine). Suitable metalloids include boron, silicon, antimony, and tellurium. In some embodiments, a layer comprising lithium comprises lithium and further comprises two or more further species (e.g., two or more non-metals). As also described above, such species may form a single phase with the lithium metal (e.g., in the form of an alloy) or a phase that is present in the layer in addition to a phase comprising lithium metal (e.g., a phase that is non-electroactive, a phase that comprises a ceramic). Phases separated from a phase comprising lithium metal may have one or more features described with respect to passivating layers elsewhere herein (e.g., chemical composition).

[0212] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently comprise one or more of the above-referenced species.

[0213] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently comprise an amount of lithium in one or more of the above-referenced ranges.

[0214] In some embodiments, a layer comprising lithium metal further comprises both carbon and oxygen. In such layers, the ratio of carbon to oxygen may generally be selected as desired. For instance, the ratio of carbon to oxygen may be greater than or equal to 0, greater than or equal to 0.01, greater than or equal to 0.02, greater than or equal to 0.05, greater than or equal to 0.075, greater than or equal to 0.1, greater than or equal to 0.15, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.3, greater than or equal to 0.35, greater than or equal to 0.4, or greater than or equal to 0.45. In some embodiments, the ratio of carbon to oxygen in a layer comprising lithium metal is less than or equal to 0.5, less than or equal to 0.45, less than or equal to 0.4, less than or equal to 0.35, less than or equal to 0.3, less than or equal to 0.25, less than or equal to 0.2, less than or equal to 0.15, less than or equal to 0.1, less than or equal to 0.075, less than or equal to 0.05, less than or equal to 0.02, or less than or equal to 0.01. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 and less than or equal to 0.1, or greater than or equal to 0.01 and less than or equal to 0.5). Other ranges are also possible. The ratio of carbon to oxygen in a layer comprising lithium metal may be determined by energy dispersive spectroscopy.

[0215] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a ratio of carbon to oxygen in one or more of the above-referenced ranges.

[0216] In some embodiments, a layer comprising lithium metal further comprises both carbon and sulfur. In such layers, the ratio of carbon to sulfur may generally be selected as desired. For instance, the ratio of carbon to sulfur may be greater than or equal to 0, greater than or equal to 0.01, greater than or equal to 0.02, greater than or equal to 0.05, greater than or equal to 0.075, greater than or equal to 0.1, greater than or equal to 0.15, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.3, greater than or equal to 0.35, or greater than or equal to 0.4. In some embodiments, the ratio of carbon to sulfur in a layer comprising lithium metal is less than or equal to 0.45, less than or equal to 0.4, less than or equal to 0.35, less than or equal to 0.3, less than or equal to 0.25, less than or equal to 0.2, less than or equal to 0.15, less than or equal to 0.1, less than or equal to 0.075, less than or equal to 0.05, less than or equal to 0.02, or less than or equal to 0.01. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 and less than or equal to 0.1, or greater than or equal to 0.01 and less than or equal to 0.45). Other ranges are also possible. The ratio of carbon to sulfur in a layer comprising lithium metal may be determined by energy dispersive spectroscopy.

[0217] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a ratio of carbon to sulfur in one or more of the above-referenced ranges.

[0218] In some embodiments, a layer comprising lithium metal further comprises both carbon and fluorine. In such layers, the ratio of carbon to fluorine may generally be selected as desired. For instance, the ratio of carbon to fluorine may be greater than or equal to 0, greater than or equal to 0.01, greater than or equal to 0.02, greater than or equal to 0.05, greater than or equal to 0.075, greater than or equal to 0.1, greater than or equal to 0.15, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.3, or greater than or equal to 0.35. In some embodiments, the ratio of carbon to fluorine in a layer comprising lithium metal is less than or equal to 0.4, less than or equal to 0.35, less than or equal to 0.3, less than or equal to 0.25, less than or equal to 0.2, less than or equal to 0.15, less than or equal to 0.1, less than or equal to 0.075, less than or equal to 0.05, less than or equal to 0.02, or less than or equal to 0.01. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 and less than or equal to 0.1, or greater than or equal to 0.01 and less than or equal to 0.4). Other ranges are also possible. The ratio of carbon to fluorine in a layer comprising lithium metal may be determined by energy dispersive spectroscopy. When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a ratio of carbon to fluorine in one or more of the above-referenced ranges.

[0219] Depending on the embodiment, a lithium layer may be solidified such that lithium grains are textured such that lithium crystals in the layer are preferentially oriented to have a desired crystallographic orientation. For example, depending on the embodiment, a lithium layer may be solidified such that it solidifies with a { 110} plane aligned with (e.g., oriented to be within 5°, 3°, 2°, 1°, or less of parallel with) the substrate. This crystallographic texture may have certain advantages for lithium layers used in battery applications. In some embodiments, lithium metal is deposited such that it solidifies with a {200} plane aligned with the substrate. According to some embodiments, the lithium metal is deposited such that it solidifies with a { 100} plane aligned with the substrate. It should, of course, be understood that the language “It solidifies with a {XYZ} plane aligned with the substrate,” does not imply that every crystallographic grain will have an identical alignment. Rather, the language “It solidifies with a {XYZ} plane aligned with the substrate,” means that grains in the layer are oriented anisotropically in a way that tends to align {XYZ} planes with the substrate. Texturing of the lithium layer, and identification of families of planes substantially parallel to the substrate may be identified using grazing incidence X-ray diffraction, according to some embodiments.

[0220] Advantageously, some layers comprising lithium may have a relatively low modulus of elasticity. The low modulus of elasticity may be indicative of a layer comprising lithium that is relatively deformable (e.g., that deforms upon the application of a relatively low amount of force). This may advantageously allow the layer comprising lithium to be compacted in a relatively facile manner to yield a layer comprising lithium having a relatively low surface area. As lithium present at the surface of a layer comprising lithium may undesirably undergo a depletion reaction with the electrolyte, layers comprising lithium having relatively low surface areas are believed to advantageously reduce the rate at which such reactions occur and / or to reduce to the total amount of such reactions that occur over the lifetime of the electrochemical cell. In some embodiments, a layer comprising lithium metal has a modulus of elasticity of less than 4.9 GPa, less than or equal to 4.5 GPa, less than or equal to 4.25 GPa, less than or equal to 4 GPa, less than or equal to 3.75 GPa, less than or equal to 3.5 GPa, less than or equal to 3.25 GPa, less than or equal to 3 GPa, less than or equal to 2.75 GPa, less than or equal to 2.5 GPa, less than or equal to 2.25 GPa, less than or equal to 2 GPa, less than or equal to 1.75 GPa, less than or equal to 1.5 GPa, less than or equal to 1.25 GPa, or less than or equal to 1 GPa. In some embodiments, a layer comprising lithium metal has a modulus of elasticity of greater than or equal to 0.75 GPa, greater than or equal to 1 GPa, greater than or equal to 1.25 GPa, greater than or equal to 1.5 GPa, greater than or equal to 1.75 GPa, greater than or equal to 2 GPa, greater than or equal to 2.25 GPa, greater than or equal to 2.5 GPa, greater than or equal to 2.75 GPa, greater than or equal to 3 GPa, greater than or equal to 3.25 GPa, greater than or equal to 3.5 GPa, greater than or equal to 3.75 GPa, greater than or equal to 4 GPa, greater than or equal to 4.25 GPa, or greater than or equal to 4.5 GPa. Combinations of the abovereferenced ranges are also possible (e.g., less than 4.9 GPa and greater than or equal to 0.75 GPa, or less than or equal to 4 GPa and greater than or equal to 0.75 GPa). Other ranges are also possible.

[0221] The modulus of elasticity of a layer comprising lithium metal may be determined by performing the procedure described in ASTM E2546 with the following parameters: (1) an approach speed of 1 micron / minute; (2) a contact load of 0.03 mN; (3) a load of between 1-2.5 mN; (4) a loading rate of double the load; and (5) an indentation depth of 1 micron.

[0222] When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently have a modulus of elasticity in one or more of the above-referenced ranges.

[0223] In some embodiments, a layer comprising lithium metal exhibits desirable behavior during the tape test described in ASTM 3359. For instance, in some embodiments, a layer comprising lithium metal does not drack, delaminate, and / or flake off a substrate on which it is disposed during tape testing. When an article for inclusion in an electrochemical cell comprises two or more layers comprising lithium metal, each layer comprising lithium metal may independently exhibit one or more of the properties described above during a tape test.

[0224] Layers comprising lithium metal may have a variety of suitable morphologies. Some layers comprising lithium metal (e.g., layers consisting of and / or consisting essentially of lithium metal, layers further comprising one or more non-lithium metal species) may be relatively dense and / or non-porous. Some layers comprising lithium metal (e.g., layers consisting of and / or consisting essentially of lithium metal, layers further comprising one or more non-lithium metal species) may comprise pores. Some layers comprising lithium metal and comprising a plurality of pores comprise pores that are open pores (i.e., pores in fluidic communication with an environment external to the layer comprising lithium metal). Similarly, some layers comprising lithium metal and comprising a plurality of pores comprise pores that are closed pores (i.e., pores not in fluidic communication with an environment external to the layer comprising lithium metal, such as some pores in the bulk of the layer). Some open pores may extend through the thickness of the layer comprising lithium metal, and some open pores may not. It is possible for a porous layer comprising lithium metal to comprise all of the above-described types of pores, to comprise some of the above-described types of pores but lack others, and / or to comprise pores of a type other than those described above.

[0225] Some embodiments relate to articles for inclusion in electrochemical cells, such as articles for inclusion in electrochemical cells that may be fabricated in the deposition systems described herein. In some embodiments, an article for inclusion in an electrochemical cell comprises a layer comprising lithium metal. FIG. 19 shows one example of an article having this property. In FIG. 19, the article 3026 comprises a layer 3126 comprising lithium metal. Articles suitable for inclusion in an electrochemical cell and comprising lithium metal may further comprise one or more additional species. The additional species may be positioned in the layer comprising lithium metal and / or may be positioned at a location other than the layer comprising lithium metal. FIG. 20 shows one example of an article 3028 having the former property (i.e., comprising layer 3126 wherein the additional species is positioned) and FIG. 21 shows one example of an article 3030 having the latter property (i.e., comprising first layer 3130 comprising lithium metal and second layer 3330 wherein the additional species is positioned).

[0226] It should also be understood that some articles for inclusion in electrochemical cells may comprise more components than those shown in FIGS. 19-21. By way of example, in some embodiments, an article for inclusion in an electrochemical cell further comprises a substrate, a current collector, a release layer, or any other suitable component.

[0227] In some embodiments, an article produced using a system or method provided herein comprises both (i) a layer comprising lithium metal and (ii) a layer disposed on the layer comprising lithium metal and comprising a species other than lithium metal. In some embodiments, a layer disposed on a layer comprising lithium metal is a layer that passivates the layer comprising lithium metal. In other words, it may be a passivating layer. For this reason, the layer comprising lithium positioned therebeneath may be understood to be “surface passivated”, or to be passivated at its surface.

[0228] Passivating layers may passivate the layers comprising lithium metal on which they are disposed by reducing their reactivity with species to which the article for inclusion in the electrochemical cell is exposed. For instance, a passivating layer may serve as a physical barrier positioned between the ambient environment and the layer comprising lithium metal. Species reactive with lithium metal may be transported therethrough in relatively small (or zero) amounts and / or at relatively slow (or zero) speeds, reducing the rate at which lithium reacts with such species. It should be understood that, although passivating layers may be relatively impermeable to some species reactive with lithium, such layers may be relatively permeable to other species. For instance, passivating layers are typically permeable to lithium ions.

[0229] Passivating layers may have a variety of suitable thicknesses. In some embodiments, a passivating layer has a thickness of 0.01 micron, greater than or equal to 0.02 microns, greater than or equal to 0.05 microns, greater than or equal to 0.075 microns, greater than or equal to 0.1 micron, greater than or equal to 0.2 microns, greater than or equal to 0.5 microns, greater than or equal to 0.75 microns, greater than or equal to 1 micron, greater than or equal to 1.5 microns, greater than or equal to 2 microns, greater than or equal to 2.5 microns, greater than or equal to 3 microns, or greater than or equal to 4 microns. In some embodiments, a passivating layer has a thickness of less than or equal to 5 microns, less than or equal to 4 microns, less than or equal to 3 microns, less than or equal to 2.5 microns, less than or equal to 2 microns, less than or equal to 1.5 microns, less than or equal to 1 micron, less than or equal to 0.75 microns, less than or equal to 0.5 microns, less than or equal to 0.2 microns, less than or equal to 0.1 micron, less than or equal to 0.075 microns, less than or equal to 0.05 microns, or less than or equal to 0.02 microns. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.01 micron and less than or equal to 5 microns). Other ranges are also possible. The thickness of a passivation layer may be determined by cross-sectional scanning electron microscopy.

[0230] When an article for inclusion in an electrochemical cell comprises two or more passivating layers, each passivating layer may independently have a thickness in one or more of the above-referenced ranges.

[0231] Like deposited metal layers, layers disposed on a metal layer (e.g., layers comprising species other than lithium metal, passivating layers) may also have a variety of suitable morphologies. In some embodiments a layer disposed on a layer comprising lithium metal comprises a plurality of columnar structures. FIG. 22 shows one example of an article 3034 comprising a layer 3134 comprising lithium metal and a layer 3334 disposed thereon that comprises a plurality of columnar structures 3534. When present, the plurality of columnar structures may make up the entirety of the layer (e.g., as shown in FIG. 22), or the layer may further comprise one or more components that are non- columnar. When present, the plurality of columnar structures may comprise columnar structures that are in topological contact with each other through the layer disposed on the layer comprising lithium metal. By way of example, with reference to FIG. 22, the columnar structures 3534A and 3534B are in topological contact with each other at the top of the layer disposed on the layer comprising lithium metal. Such embodiments may further comprise columnar structures that are not in topological contact with any other columnar structures through the layer disposed on the layer comprising lithium metal (e.g., the columnar structure 3534C in FIG. 22), or may lack such columnar structures. In some embodiments, a layer disposed on the layer comprising lithium metal lacks columnar structures in topological contact with other columnar structures therethrough. Columnar structures present in a layer disposed on a layer containing lithium metal (e.g., a layer comprising species other than lithium metal, a passivating layer) may have a morphology that can be characterized by one or more of the zones described in the Thornton diagram. In some embodiments, a layer disposed on a layer containing lithium metal comprises porous structures that have a morphology consistent with Zone I, Zone T, Zone II, and / or Zone III of the Thornton diagram as discussed above. Columnar structures may be in the form of a dense film and / or may comprise fine grained nanocrystals (e.g., having a preferred orientation). As can be seen from FIG. 22, a layer disposed on a layer comprising lithium metal (e.g., a layer comprising a species other than lithium metal, a passivating layer) comprising a plurality of columnar structures may be porous. For instance, the spaces between the columnar structures may take the form of pores and / or the columnar structures themselves may comprise pores. These pores may include open pores (e.g., pores that pass through the entirety of the layer, pores that do not) and / or closed pores.

[0232] Without wishing to be bound by any particular theory, it is believed that in at least some embodiments the Thornton Zone of the passivation layer may be influenced by the Thornton Zone of the layer on which it is deposited — e.g., by the Thornton Zone of a lithium metal layer. Accordingly, in some embodiments, a passivation layer comprising Zone 3 lithium is provided. Any of a variety of suitable proportions of the passivating layer may have a Zone 3 morphology. In some embodiments, greater than or equal to 70%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, or greater than or equal to 95% by volume of the passivating layer has a Zone 3 morphology. In some embodiments, less than or equal to 100%, less than or equal to 95%, less than or equal to 90%, less than or equal to 85%, less than or equal to 80%, or less than or equal to 75% by volume of the passivating layer has a Zone 3 morphology. Combinations of these ranges are also possible (e.g., greater than or equal to 70% and less than or equal to 100%, greater than or equal to 90% and less than or equal to 100%, or greater than or equal to 95% and less than or equal to 100%). Other ranges, both higher and lower than those described above, are also possible, as the disclosure is not so limited. In some embodiments, a layer disposed on a layer comprising lithium metal (e.g., a layer comprising a species other than lithium metal, a passivating layer) comprises a plurality of columnar structures and / or a plurality of pores that extend partway, but not all the way, therethrough. FIG. 20 shows one example of a layer having this property. In FIG. 20, the article 2036 comprises a layer 2136 comprising lithium, and a layer 2336 disposed thereon. The layer 2336 comprises a plurality of columnar structures 2536 that extend partially through the layer from the upper surface thereof and a plurality of pores 2636 that also that extend partially through the layer from the upper surface thereof. The lower portion of the layer 2336 lacks columnar structures and pores.

[0233] It should also be noted that some layers disposed on layers comprising lithium metal (e.g., layers comprising species other than lithium metal, passivating layers) may lack columnar structures and / or pores.

[0234] In some embodiments, an article for inclusion in an electrochemical cell comprises two or more of the above-described layers. By way of example, in some embodiments, an article for inclusion in an electrochemical cell comprises a layer comprising a species other than lithium metal disposed on a layer comprising lithium metal (e.g., a passivating layer). As another example, an article for inclusion in an electrochemical cell may comprise a layer comprising lithium metal disposed on a layer comprising a species other than lithium metal (e.g., a passivating layer). As a third example, some embodiments may relate to articles comprising one layer (e.g., a layer comprising lithium metal, a layer comprising a species other than lithium metal, a passivating layer) positioned between two layers of a different type (e.g., between two layers comprising lithium metal, between two layers comprising a species other than lithium metal, between two passivating layers). Other arrangements (e.g., comprising four or more layers, comprising two adjacent layers having identical composition) are also contemplated.

[0235] When present, a passivating layer may have a variety of suitable compositions. In some embodiments, a passivating layer comprises a reaction product of lithium metal with a gas reactive therewith. Accordingly, in some embodiments, a passivating layer comprises lithium in one or more forms (e.g., lithium ions, ceramics comprising lithium). It is also possible for a passivating layer to be deposited from a gas that has not undergone a reaction with lithium metal and / or has undergone such a reaction to a relatively low extent. Such passivating layers may lack lithium and / or may comprise lithium in relatively low amounts. For instance, they may comprise ceramics lacking lithium and / or including lithium in relatively low amounts. Some passivating layers may comprise, for instance, a non-metal and / or a metalloid. Suitable non-metals include carbon, oxygen, hydrogen, sulfur, nitrogen, selenium, phosphorous, and various halogens (e.g., fluorine, bromine, iodine). Suitable metalloids include boron, silicon, antimony, and tellurium. In some embodiments, a passivating layer comprises two or more species (e.g., two or more non-metals). Non-limiting examples of combinations of such species include: oxygen and carbon; oxygen and hydrogen; sulfur and oxygen; sulfur and carbon; sulfur, oxygen, and carbon; nitrogen and oxygen; nitrogen and hydrogen; fluorine and sulfur; fluorine, carbon, and hydrogen; fluorine and silicon; and carbon and hydrogen.

[0236] When an article for inclusion in an electrochemical cell comprises two or more passivating layers, each passivating layer may independently comprise one or more of the above-referenced species.

[0237] When a passivating layer comprises both carbon and oxygen, the ratio of carbon to oxygen may generally be selected as desired. For instance, the ratio of carbon to oxygen may be greater than or equal to 0.01, greater than or equal to 0.02, greater than or equal to 0.05, greater than or equal to 0.075, greater than or equal to 0.1, greater than or equal to 0.15, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.3, greater than or equal to 0.35, greater than or equal to 0.4, or greater than or equal to 0.45. In some embodiments, the ratio of carbon to oxygen in a passivating layer is less than or equal to 0.5, less than or equal to 0.45, less than or equal to 0.4, less than or equal to 0.35, less than or equal to 0.3, less than or equal to 0.25, less than or equal to 0.2, less than or equal to 0.15, less than or equal to 0.1, less than or equal to 0.075, less than or equal to 0.05, or less than or equal to 0.02. Combinations of the abovereferenced ranges are also possible (e.g., greater than or equal to 0.01 and less than or equal to 0.5). Other ranges are also possible. The ratio of carbon to oxygen in a passivating layer may be determined by energy dispersive spectroscopy. When an article for inclusion in an electrochemical cell comprises two or more passivating layers, each passivating layer may independently have a ratio of carbon to oxygen in one or more of the above-referenced ranges.

[0238] In some embodiments, a passivating layer comprises both carbon and sulfur. In such layers, the ratio of carbon to sulfur may generally be selected as desired. For instance, the ratio of carbon to sulfur may be greater than or equal to 0.01, greater than or equal to 0.02, greater than or equal to 0.05, greater than or equal to 0.075, greater than or equal to 0.1, greater than or equal to 0.15, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.3, greater than or equal to 0.35, or greater than or equal to 0.4. In some embodiments, the ratio of carbon to sulfur in a passivating layer is less than or equal to 0.45, less than or equal to 0.4, less than or equal to 0.35, less than or equal to 0.3, less than or equal to 0.25, less than or equal to 0.2, less than or equal to 0.15, less than or equal to 0.1, less than or equal to 0.075, less than or equal to 0.05, or less than or equal to 0.02. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.01 and less than or equal to 0.45). Other ranges are also possible. The ratio of carbon to sulfur in a passivating layer may be determined by energy dispersive spectroscopy.

[0239] When an article for inclusion in an electrochemical cell comprises two or more passivating layers, each passivating layer may independently have a ratio of carbon to sulfur in one or more of the above-referenced ranges.

[0240] In some embodiments, a passivating layer comprises both carbon and fluorine. In such layers, the ratio of carbon to fluorine may generally be selected as desired. For instance, the ratio of carbon to fluorine may be greater than or equal to 0.01, greater than or equal to 0.02, greater than or equal to 0.05, greater than or equal to 0.075, greater than or equal to 0.1, greater than or equal to 0.15, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.3, or greater than or equal to 0.35. In some embodiments, the ratio of carbon to fluorine in a passivating layer is less than or equal to 0.4, less than or equal to 0.35, less than or equal to 0.3, less than or equal to 0.25, less than or equal to 0.2, less than or equal to 0.15, less than or equal to 0.1, less than or equal to 0.075, less than or equal to 0.05, or less than or equal to 0.02. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.01 and less than or equal to 0.4). Other ranges are also possible. The ratio of carbon to fluorine in a passivating layer may be determined by energy dispersive spectroscopy.

[0241] When an article for inclusion in an electrochemical cell comprises two or more passivating layers, each passivating layer may independently have a ratio of carbon to fluorine in one or more of the above-referenced ranges.

[0242] As described elsewhere herein, in some embodiments, a layer comprising lithium metal and / or a layer disposed thereon (e.g., a passivating layer) is deposited and / or disposed on a substrate. Further details of such substrates are provided below.

[0243] Substrates suitable for use in combination with the deposition systems, articles for inclusion in electrochemical cells, and methods described herein may have a variety of suitable thicknesses. In some embodiments, a substrate has a thickness of greater than or equal to 3 mils, greater than or equal to 3.5 mils, greater than or equal to 4 mils, or greater than or equal to 4.5 mils. In some embodiments, a substrate has a thickness of less than or equal to 5 mils, less than or equal to 4.5 mils, less than or equal to 4 mils, or less than or equal to 3.5 mils. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 3 mils and less than or equal to 5 mils). Other ranges are also possible. The thickness of a substrate may be determined by drop gauge.

[0244] Substrates may have a variety of suitable compositions. In some embodiments, a substrate comprises a polymer, such as a poly(ester) (e.g., poly(ethylene terephthalate), such as optical-grade poly(ethylene terephthalate)). Further examples of suitable polymers include polyolefins, polypropylene, nylon, polyvinyl chloride, and polyethylene (which may optionally be metalized). In some cases, a substrate comprises a metal (e.g., a foil such as nickel foil and / or aluminum foil), a glass, or a ceramic material. In some embodiments, a substrate includes a film that may be optionally disposed on a thicker substrate material. For instance, in certain embodiments, a substrate includes one or more films, such as a polymer film (e.g., a poly(ethylene terephthalate) film) and / or a metalized polymer film (using various metals such as aluminum and copper). A substrate may also include additional components such as fillers, binders, and / or surfactants.

[0245] In some embodiments, the substrates described herein are configured to be removed from articles for incorporation into electrochemical cells prior to the incorporation thereof. According to some embodiments, the substrate may be left intact with such an article after fabrication thereof, but may be delaminated before the article is incorporated into an electrochemical cell. For instance, the article for incorporation into an electrochemical cell may be packaged and shipped to a manufacturer who may then incorporate it into the electrochemical cell. In such embodiments, the article for incorporation into the electrochemical cell may be inserted into an air and / or moisture- tight package to prevent or inhibit deterioration and / or contamination of one or more components thereof. Allowing the substrate to remain attached can facilitate handling and transportation of the article for incorporation into an electrochemical cell. For instance, the substrate may be relatively thick and / or may have a relatively rigidity and / or stiffness sufficient to prevent or inhibit the article for incorporation into an electrochemical cell from distorting during handling. In such embodiments, the substrate can be removed by the manufacturer before, during, or after assembly of an electrochemical cell.

[0246] In some embodiments, an article for inclusion in an electrochemical cell may be disposed on or deposited onto a release layer. For instance, a release layer may be disposed on a substrate onto which a layer comprising lithium metal is deposited (e.g., in a deposition system). Suitable release layers, and their properties, are described in further detail below.

[0247] Release layers contemplated for use with the systems, articles, and methods described herein may have a variety of suitable thicknesses. In some embodiments, a release layer has a thickness of greater than or equal to 2 microns, greater than or equal to 2.25 microns, greater than or equal to 2.5 microns, greater than or equal to 2.75 microns, greater than or equal to 3 microns, greater than or equal to 3.25 microns, greater than or equal to 3.5 microns, or greater than or equal to 3.75 microns. In some embodiments, a release layer has a thickness of less than or equal to 4 microns, less than or equal to 3.75 microns, less than or equal to 3.5 microns, less than or equal to 3.25 microns, less than or equal to 3 microns, less than or equal to 2.75 microns, less than or equal to 2.5 microns, or less than or equal to 2.25 microns. Combinations of the abovereferenced ranges are also possible (e.g., greater than or equal to 2 microns and less than or equal to 4 microns). Other ranges are also possible. The thickness of a release layer may be determined by drop gauge.

[0248] As described above, in some embodiments, it may be beneficial to deposit a layer comprising lithium metal onto a substrate, but not desirable for the substrate to be incorporated into the electrochemical cell comprising the resultant layer. In such embodiments, it may be advantageous for a release layer to be positioned between the substrate (and any layers disposed thereon not configured to be included in the resultant electrochemical cell) and any layers configured to be included in the resultant electrochemical cell. When the release layer is adjacent a substrate, the release layer may be partially or entirely delaminated from the layer comprising lithium metal during subsequent steps in electrochemical cell formation (e.g., if not configured to be retained in the final electrochemical cell) and / or it may be partially or entirely delaminated from the carrier substrate during subsequent steps in electrochemical cell formation (e.g., if configured to be retained in the final electrochemical cell).

[0249] In some embodiments, the release layer may have one or more features of the release layers described in U.S. Pat. Pub. No. 2014 / 272,565, U.S. Pat. Pub. No. 2014 / 272,597, and U.S. Pat. Pub. No. 2011 / 068,001, each of which are herein incorporated by reference in their entirety. In some embodiments, it may be preferred for the release layer to be a release layer comprising hydroxyl functional groups (e.g., comprising poly (vinyl alcohol) (PVOH) and / or EVAL) and having one of the structures described above.

[0250] In one set of embodiments, a release layer is formed of a polymeric material. Specific examples of appropriate polymers include, but are not limited to, polyoxides, poly(alkyl oxides) / polyalkylene oxides (e.g., polyethylene oxide, polypropylene oxide, polybutylene oxide), polyvinyl alcohols, polyvinyl butyral, polyvinyl formal, vinyl acetate- vinyl alcohol copolymers, ethylene- vinyl alcohol copolymers, vinyl alcoholmethyl methacrylate copolymers, poly siloxanes, and fluorinated polymers. Additional examples of polymeric materials include polysulfones, polyethersulfone, polyphenylsulfones (e.g., Ultrason® S 6010, S 3010 and S 2010, available from BASF), poly ethersulfone-poly alkyleneoxide copolymers , polyphenylsulfone-poly alkyleneoxide copolymers, polysulfone-polyalkylene oxide copolymers, polyisobutylene (e.g., Oppanol® BIO, B15, B30, B80, B150 and B200, available from BASF), polyisobutylene succinic anhydride (PIBSA), polyisobutylene-polyalkyleneoxide copolymers, polyamide 6 (e.g., Ultramid® B33, available from BASF) (e.g., extrusion of 2 pm polyamide layer on polyolefin carrier or solution casting of PA layer on polyolefin carrier substrate), polyvinylpyrrolidone, polyvinylpyrrolidone-polyvinylimidazole copolymers (e.g., Sokalan® HP56, available from BASF), polyvinylpyrrolidone-polyvinylactetate copolymers (e.g., Luviskol®, available from BASF), maleinimide- vinylether copolymers, polyacrylamides, fluorinated polyacrylates (optionally including surface reactive comonomers), polyethylene-polyvinylalcohol copolymers (e.g., Kuraray®, available from BASF), polyethylene-polyvinylacetate copolymers, polyvinylalcohol and polyvinylacetate copolymers, polyoxymethylene (e.g., extruded), polyvinylbutyral (e.g., Kuraray®, available from BASF), polyureas (e.g., branched), polymers based on photopolymerization of acrolein derivatives (CH2=CR-C(O)R), polysulfonepolyalkyleneoxide copolymers, polyvinylidene difluoride (e.g., Kynar® D155, available from BASF), and combinations thereof.

[0251] In one embodiment, a release layer comprises a poly ether sulfone-poly alkylene oxide copolymer. In one particular embodiment, the polyethersulfone-polyalkylene oxide copolymer is a polyarylethersulfone-polyalkylene oxide copolymer (PPC) obtained by polycondensation of reaction mixture (RG) comprising the components: (Al) at least one aromatic dihalogen compound, (Bl) at least one aromatic dihydroxyl compound, and (B2) at least one polyalkylene oxide having at least two hydroxyl groups. The reaction mixture may also include (C) at least one aprotic polar solvent and (D) at least one metal carbonate, where the reaction mixture (RG) does not comprise any substance which forms an azeotrope with water. The resulting copolymer may be a random copolymer or a block copolymer. For instance, the resulting copolymer may include blocks of Ai-Bi, and blocks of A1-B2. The resulting copolymer may, in some instances, include blocks of A1-B1-A1-B2.

[0252] Further examples of polymeric materials include polyimide (e.g., Kapton®) with a hexafluoropropylene (HFP) coating (e.g., available from Dupont); siliconized polyester films (e.g., a Mitsubishi polyester), metallized polyester films (e.g., available from Mitsubishi or Sion Power), polybenzimidazoles (PBI; e.g., low molecular weight PBI - available from Celanese), polybenzoxazoles (e.g., available from Foster-Miller, Toyobo), ethylene-acrylic acid copolymers (e.g., Poligen®, available from BASF), acrylate based polymers (e.g., Acronal®, available from BASF), (charged) polyvinylpyrrolidone- polyvinylimidazole copolymers (e.g., Sokalane® HP56, Luviquat®, available from BASF), polyacrylonitriles (PAN), styrene-acrylonitriles (SAN), thermoplastic polyurethanes (e.g., Elastollan® 1195 A 10, available from BASF), polysulfone- poly(akylene oxide) copolymers, benzophenone-modified polysulfone (PSU) polymers, polyvinylpyrrolidone-polyvinylactetate copolymers (e.g., Luviskol®, available from BASF), and combinations thereof.

[0253] In some embodiments, a release layer includes a polymer that is substantially electrically conductive. Examples of such materials include electrically conductive polymers (also known as electronic polymers or conductive polymers) that are doped with lithium salts (e.g., LiSCN, LiBr, Lil, LiC104, LiAsF6, LiSO3CF3, LiSO3CH3, LiBF4, LiB(Ph)4, LiPFe, LiC(SO2CF3)3, and LiN(SO2CF3)2). Examples of conductive polymers include, but are not limited to, poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(aniline)s, poly(fluorene)s, polynaphthalenes, poly(p-phenylene sulfide), and poly(para-phenylene vinylene)s. Electrically-conductive additives may also be added to polymers to form electrically-conductive polymers.

[0254] In some embodiments, a release layer includes a crosslinkable polymer. Nonlimiting examples of crosslinkable polymers include: polyvinyl alcohol, polyvinylbutyral, polyvinylpyridyl, polyvinyl pyrrolidone, polyvinyl acetate, acrylonitrile butadiene styrene (ABS), ethylene-propylene rubbers (EPDM), EPR, chlorinated polyethylene (CPE), ethylenebisacrylamide (EBA), acrylates (e.g., alkyl acrylates, glycol acrylates, polyglycol acrylates, ethylene ethyl acrylate (EEA)), hydrogenated nitrile butadiene rubber (HNBR), natural rubber, nitrile butadiene rubber (NBR), certain fluoropolymers, silicone rubber, polyisoprene, ethylene vinyl acetate (EVA), chlorosulfonyl rubber, fluorinated poly(arylene ether) (FPAE), polyether ketones, polysulfones, polyether imides, diepoxides, diisocyanates, diisothiocyanates, formaldehyde resins, amino resins, polyurethanes, unsaturated polyethers, polyglycol vinyl ethers, poly glycol divinyl ethers, copolymers thereof, and those described in U.S. Patent No. 6,183.901 to Ying et al. of the common assignee for protective coating layers for separator layers.

[0255] Additional examples of crosslinkable or crosslinked polymers include UV / E- beam crosslinked Ultrason® or similar polymers (i.e., polymers comprising an amorphous blend of one or more of poly(sulfone), poly(ethersulfone), and poly(phenylsulfone)), UV crosslinked Ultrason®-polyalkyleneoxide copolymers, UV / E- beam crosslinked Ultrason®-acrylamide blends, crosslinked polyisobutylenepolyalkyleneoxide copolymers, crosslinked branched polyimides (BPI), crosslinked maleinimide-Jeffamine polymers (MSI gels), crosslinked acrylamides, and combinations thereof.

[0256] Those of ordinary skill in the art can choose appropriate polymers that can be crosslinked, as well as suitable methods of crosslinking, based upon general knowledge of the art in combination with the description herein. Crosslinked polymer materials may further comprise salts, for example, lithium salts, to enhance lithium ion conductivity.

[0257] If a crosslinkable polymer is used, the polymer (or polymer precursor) may include one or more crosslinking agents. A crosslinking agent is a molecule with a reactive portion(s) designed to interact with functional groups on the polymer chains in a manner that will form a crosslinking bond between one or more polymer chains. Examples of crosslinking agents that can crosslink polymeric materials used for support layers described herein include, but are not limited to: poly amide-epichlorohy drin (polycup 172); aldehydes (e.g., formaldehyde and urea-formaldehyde); dialdehydes (e.g., glyoxal glutaraldehyde, and hydroxyadipaldehyde); acrylates (e.g., ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, methacrylates, ethylene glycol dimethacrylate, di(ethylene glycol) dimethacrylate, tri(ethylene glycol) dimethacrylate); amides (e.g., N,N’ -methylenebisacrylamide, N,N’- ethylenebisacrylamide, N,N’ -( 1 ,2-dihydroxyethylene)bisacrylamide, N-( 1 -hydroxy-2, 2- dimethoxyethyl)acrylamide); silanes (e.g., methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetrapropoxysilane, methyltris(methylethyldetoxime)silane, methyltris(acetoxime)silane, methyltris(methylisobutylketoxime)silane, dimethyldi(methylethyldetoxime)silane, trimethyl(methylethylketoxime)silane, vinyltris(methylethylketoxime)silane, methylvinyldi(mtheylethylketoxime)silane, methylvinyldi(cyclohexaneoneoxxime)silane, vinyltris(mtehylisobutylketoxime)silane, methyltriacetoxysilane, tetraacetoxysilane, and phenyltris(methylethylketoxime)silane); divinylbenzene; melamine; zirconium ammonium carbonate; dicyclohexylcarbodiimide / dimethylaminopyridine (DCC / DM AP) ; 2-chloropyridinium ion; 1 -hydroxycyclohexylphenyl ketone; acetophenon dimethylketal; benzoylmethyl ether; aryl triflourovinyl ethers; benzocyclobutenes; phenolic resins (e.g., condensates of phenol with formaldehyde and lower alcohols, such as methanol, ethanol, butanol, and isobutanol), epoxides; melamine resins (e.g., condensates of melamine with formaldehyde and lower alcohols, such as methanol, ethanol, butanol, and isobutanol); polyisocyanates; and dialdehydes.

[0258] Other classes of polymers that may be suitable for use in a release layer may include, but are not limited to, polyamines (e.g., poly(ethylene imine) and polypropylene imine (PPI)); polyamides (e.g., poly(e-caprolactam) (Nylon 6) , poly(hexamethylene adipamide) (Nylon 66)), polyimides (e.g., polyimide, polynitrile, and poly(pyromellitimide-l,4-diphenyl ether) (Kapton)); vinyl polymers (e.g., polyacrylamide, poly(2-vinyl pyridine), poly(N-vinylpyrrolidone), poly(methylcyanoacrylate), poly(ethylcyanoacrylate), poly (butylcyanoacrylate), poly(isobutylcyanoacrylate), poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly (vinyl fluoride), poly (2- vinyl pyridine), polychlorotrifluoro ethylene, and poly(isohexylcynaoacrylate)); polyacetals; polyolefins (e.g., poly(butene-l), poly(n- pentene-2), polypropylene, polytetrafluoroethylene); polyesters (e.g., polycarbonate, polybutylene terephthalate, poly hydroxybutyrate); poly ethers (poly (ethylene oxide) (PEO), poly(propylene oxide) (PPO), poly(tetramethylene oxide) (PTMO)); vinylidene polymers (e.g., polyisobutylene, poly(methyl styrene), poly(methylmethacrylate) (PMMA), poly (vinylidene chloride), poly (vinylidene fluoride), poly (vinylidene difluoride, poly(vinylidene difluoride) block copolymers); polyaramides (e.g., poly(imino-l,3-phenylene iminoisophthaloyl) and poly(imino-l,4-phenylene iminoterephthaloyl)); polyheteroaromatic compounds (e.g., polybenzimidazole (PBI), polybenzobisoxazole (PBO) and polybenzobisthiazole (PBT)); polyheterocyclic compounds (e.g., polypyrrole); polyurethanes; phenolic polymers (e.g., phenolformaldehyde); polyalkynes (e.g., poly acetylene); polydienes (e.g., 1,2-polybutadiene, cis or trans- 1,4-polybutadiene); polysiloxanes (e.g., poly(dimethylsiloxane) (PDMS), poly(diethylsiloxane) (PDES), polydiphenylsiloxane (PDPS), and polymethylphenylsiloxane (PMPS)); and inorganic polymers (e.g., polyphosphazene, polyphosphonate, polysilanes, polysilazanes).

[0259] In some embodiments, the molecular weight of a polymer may be chosen to achieve a particular adhesive affinity and can vary in a release layer. In some embodiments, the molecular weight of a polymer used in a release layer may be greater than or equal to 1,000 g / mol, greater than or equal to 5,000 g / mol, greater than or equal to 10,000 g / mol, greater than or equal to 15,000 g / mol, greater than or equal to 20,000 g / mol, greater than or equal to 25,000 g / mol, greater than or equal to 30,000 g / mol, greater than or equal to 50,000 g / mol, greater than or equal to 100,000 g / mol or greater than or equal to 150,000 g / mol. In certain embodiments, the molecular weight of a polymer used in a release layer may be less than or equal to 150,000 g / mol, less than or equal to 100,000 g / mol, less than or equal to 50,000 g / mol, less than or equal to 30,000 g / mol, less than or equal to 25,000 g / mol, less than or equal to 20,000 g / mol, less than less than or equal to 10,000 g / mol, less than or equal to 5,000 g / mol, or less than or equal to 1,000 g / mol. Other ranges are also possible. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 5,000 g / mol and less than or equal to 50,000 g / mol).

[0260] When polymers are used, the polymer may be substantially crosslinked, substantially uncrosslinked, or partially crosslinked as the current disclosure is not limited in this fashion. Further, the polymer may be substantially crystalline, partially crystalline, or substantially amorphous. Without wishing to be bound by theory, embodiments in which the polymer is amorphous may exhibit smoother surfaces since crystallization of the polymer may lead to increased surface roughness. In certain embodiments, the release layer is formed of or includes a wax.

[0261] As described elsewhere herein, in some embodiments, a layer comprising lithium metal and / or a layer disposed thereon (e.g., a passivating layer) is deposited and / or disposed on a current collector. Further details of such current collectors are provided below.

[0262] When present, a current collector may take the form of a layer disposed on a substrate (e.g., on a release layer disposed thereon). The thicknesses of such layers may generally be selected as desired. In some embodiments, a current collector has a thickness of greater than or equal to 0.1 micron, greater than or equal to 0.15 microns, greater than or equal to 0.2 microns, greater than or equal to 0.25 microns, greater than or equal to 0.3 microns, greater than or equal to 0.35 microns, greater than or equal to 0.4 microns, or greater than or equal to 0.45 microns. In some embodiments, a current collector has a thickness of less than or equal to 0.5 microns, less than or equal to 0.45 microns, less than or equal to 0.4 microns, less than or equal to 0.35 microns, less than or equal to 0.3 microns, less than or equal to 0.25 microns, less than or equal to 0.2 microns, or less than or equal to 0.15 microns. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.1 micron and less than or equal to 0.5 microns). Other ranges are also possible. The thickness of a current collector may be determined by optical profilometry.

[0263] Current collectors typically comprise conductive materials. For instance, a current collector may comprise a metal (e.g., copper, nickel, aluminum, a passivated metal), a metallized polymer (e.g., metallized poly(ethylene terephthalate)), an electrically conductive polymer, and / or a polymer comprising electrically conductive particles dispersed therein.

[0264] Current collectors may be formed in a variety of manners. For instance, a current collector may be deposited onto an electrode by physical vapor deposition, chemical vapor deposition, electrochemical deposition, sputtering, doctor blading, flash evaporation, or any other appropriate deposition technique for the selected material. Some such processes (e.g., physical vapor deposition, chemical vapor deposition, sputtering) may be performed in a deposition system described herein and / or may be performed on a substrate prior to the introduction thereof into a deposition system. In some embodiments, a current collector is formed separately from an article into which it is to be incorporated (e.g., an article for incorporation into an electrochemical cell) and then bonded to it (and / or to a component, such as a layer, thereof). It should be appreciated, however, that in some embodiments an article for incorporation into an electrochemical cell may lack a current collector. This may be true when the article itself (and / or electroactive material therein) is electrically conductive.

[0265] As described elsewhere herein, some embodiments relate to articles for incorporation into electrochemical cells. In some embodiments, an article for incorporation into an electrochemical cell comprises an anode and / or a portion of an anode (e.g., for a lithium metal electrochemical cell). Further details of the electrochemical cells into which such articles may be incorporated are described below.

[0266] Some electrochemical cells may further comprise an electrolyte. In some embodiments, the electrolyte is a non-aqueous electrolyte. Suitable non-aqueous electrolytes may include organic electrolytes such as liquid electrolytes, gel polymer electrolytes, and solid polymer electrolytes. These electrolytes may optionally include one or more ionic electrolyte salts (e.g., to provide or enhance ionic conductivity). Examples of useful non-aqueous liquid electrolyte solvents include, but are not limited to, non-aqueous organic solvents, such as, for example, N-methyl acetamide, acetonitrile, acetals, ketals, esters (e.g., esters of carbonic acid), carbonates (e.g., dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate), sulfones, sulfites, sulfolanes, suflonimidies (e.g., bis(trifluoromethane)sulfonimide lithium salt), aliphatic ethers, acyclic ethers, cyclic ethers, glymes, polyethers, phosphate esters (e.g., hexafluorophosphate), siloxanes, dioxolanes, N-alkylpyrrolidones, nitrate containing compounds, substituted forms of the foregoing, and blends thereof. Examples of acyclic ethers that may be used include, but are not limited to, diethyl ether, dipropyl ether, dibutyl ether, dimethoxymethane, trimethoxymethane, 1,2-dimethoxyethane, diethoxyethane, 1,2-dimethoxypropane, and 1,3-dimethoxypropane. Examples of cyclic ethers that may be used include, but are not limited to, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and trioxane. Examples of polyethers that may be used include, but are not limited to, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), higher glymes, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol dimethyl ether, and butylene glycol ethers. Examples of sulfones that may be used include, but are not limited to, sulfolane, 3-methyl sulfolane, and 3-sulfolene. Fluorinated derivatives of the foregoing are also useful as liquid electrolyte solvents.

[0267] In some cases, mixtures of the solvents described herein may also be used. For example, in some embodiments, mixtures of solvents are selected from the group consisting of 1,3-dioxolane and dimethoxyethane, 1,3-dioxolane and diethyleneglycol dimethyl ether, 1,3-dioxolane and triethyleneglycol dimethyl ether, and 1,3-dioxolane and sulfolane. In some embodiments, the mixture of solvents comprises dimethyl carbonate and ethylene carbonate. In some embodiments, the mixture of solvents comprises ethylene carbonate and ethyl methyl carbonate. The weight ratio of the two solvents in the mixtures may range, in some cases, from about 5 wt%:95 wt% to 95 wt%:5 wt%. For example, in some embodiments the electrolyte comprises a 50 wt%:50 wt% mixture of dimethyl carbonate:ethylene carbonate. In some other embodiments, the electrolyte comprises a 30 wt%:70 wt% mixture of ethylene carbonate:ethyl methyl carbonate. An electrolyte may comprise a mixture of dimethyl carbonate:ethylene carbonate with a ratio of dimethyl carbonate:ethylene carbonate that is less than or equal to 50 wt%:50 wt% and greater than or equal to 30 wt%:70 wt%.

[0268] In some embodiments, an electrolyte may comprise a mixture of fluoroethylene carbonate and dimethyl carbonate. A weight ratio of fluoroethylene carbonate to dimethyl carbonate may be 20 wt%:80 wt% or 25 wt%:75wt%. A weight ratio of fluoroethylene carbonate to dimethyl carbonate may be greater than or equal to 20 wt%:80 wt% and less than or equal to 25 wt%:75 wt%.

[0269] Non-limiting examples of suitable gel polymer electrolytes include polyethylene oxides, polypropylene oxides, polyacrylonitriles, polysiloxanes, polyimides, polyphosphazenes, polyethers, sulfonated polyimides, perfluorinated membranes (NAFION resins), polydivinyl polyethylene glycols, polyethylene glycol diacrylates, polyethylene glycol dimethacrylates, derivatives of the foregoing, copolymers of the foregoing, cross-linked and network structures of the foregoing, and blends of the foregoing.

[0270] Non-limiting examples of suitable solid polymer electrolytes include poly ethers, polyethylene oxides, polypropylene oxides, polyimides, polyphosphazenes, polyacrylonitriles, polysiloxanes, derivatives of the foregoing, copolymers of the foregoing, cross-linked and network structures of the foregoing, and blends of the foregoing.

[0271] In some embodiments, an electrolyte is in the form of a layer having a particular thickness. An electrolyte layer may have a thickness of, for example, at least 1 micron, at least 5 microns, at least 10 microns, at least 15 microns, at least 20 microns, at least 25 microns, at least 30 microns, at least 40 microns, at least 50 microns, at least 70 microns, at least 100 microns, at least 200 microns, at least 500 microns, or at least 1 mm. In some embodiments, the thickness of the electrolyte layer is less than or equal to 1 mm, less than or equal to 500 microns, less than or equal to 200 microns, less than or equal to 100 microns, less than or equal to 70 microns, less than or equal to 50 microns, less than or equal to 40 microns, less than or equal to 30 microns, less than or equal to 20 microns, less than or equal to 10 microns, or less than or equal to 5 microns. Other values are also possible. Combinations of the above-noted ranges are also possible. The thickness of an electrolyte layer may be determined by drop gauge.

[0272] In some embodiments, the electrolyte comprises at least one lithium salt. For example, in some cases, the at least one lithium salt is selected from the group consisting of LiSCN, LiBr, Lil, LiSO3CH3, LiNO3, LiPF6, LiBF4, LiB(Ph)4, LiClO4, LiAsF6, Li2SiFe, LiSbFe, LiAlCl4, lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, a salt comprising a tris(oxalato)phosphate anion (e.g., lithium tris(oxalato)phosphate), LiCF3SO3, LiN(SO2F)2, LiN(SO2CF3)2, LiC(CnF2n+iSO2)3wherein n is an integer in the range of from 1 to 20, and (CnF2n+iSO2)mXLi with n being an integer in the range of from 1 to 20, m being 1 when X is selected from oxygen or sulfur, m being 2 when X is selected from nitrogen or phosphorus, and m being 3 when X is selected from carbon or silicon.

[0273] When present, a lithium salt may be present in the electrolyte at a variety of suitable concentrations. In some embodiments, the lithium salt is present in the electrolyte at a concentration of greater than or equal to 0.01 M, greater than or equal to 0.02 M, greater than or equal to 0.05 M, greater than or equal to 0.1 M, greater than or equal to 0.2 M, greater than or equal to 0.5 M, greater than or equal to 1 M, greater than or equal to 2 M, or greater than or equal to 5 M. The lithium salt may be present in the electrolyte at a concentration of less than or equal to 10 M, less than or equal to 5 M, less than or equal to 2 M, less than or equal to 1 M, less than or equal to 0.5 M, less than or equal to 0.2 M, less than or equal to 0.1 M, less than or equal to 0.05 M, or less than or equal to 0.02 M. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.01 M and less than or equal to 10 M, or greater than or equal to 0.01 M and less than or equal to 5 M). Other ranges are also possible.

[0274] In some embodiments, an electrolyte may comprise LiPFe in an advantageous amount. In some embodiments, the electrolyte comprises LiPFe at a concentration of greater than or equal to 0.01 M, greater than or equal to 0.02 M, greater than or equal to 0.05 M, greater than or equal to 0.1 M, greater than or equal to 0.2 M, greater than or equal to 0.5 M, greater than or equal to 1 M, or greater than or equal to 2 M. The electrolyte may comprise LiPFe at a concentration of less than or equal to 5 M, less than or equal to 2 M, less than or equal to 1 M, less than or equal to 0.5 M, less than or equal to 0.2 M, less than or equal to 0.1 M, less than or equal to 0.05 M, or less than or equal to 0.02 M. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.01 M and less than or equal to 5 M). Other ranges are also possible.

[0275] In some embodiments, an electrolyte comprises a species with an oxalato(borate) group (e.g., LiBOB, lithium difluoro(oxalato)borate), and the total weight of the species with an (oxalato)borate group in the electrochemical cell may be less than or equal to 30 wt%, less than or equal to 28 wt%, less than or equal to 25 wt%, less than or equal to 22 wt%, less than or equal to 20 wt%, less than or equal to 18 wt%, less than or equal to 15 wt%, less than or equal to 12 wt%, less than or equal to 10 wt%, less than or equal to 8 wt%, less than or equal to 6 wt%, less than or equal to 5 wt%, less than or equal to 4 wt%, less than or equal to 3 wt%, less than or equal to 2 wt%, or less than or equal to 1 wt% versus the total weight of the electrolyte. In some embodiments, the total weight of the species with an (oxalato)borate group in the electrochemical cell is greater than 0.2 wt%, greater than 0.5 wt%, greater than 1 wt%, greater than 2 wt%, greater than 3 wt%, greater than 4 wt%, greater than 6 wt%, greater than 8 wt%, greater than 10 wt%, greater than 15 wt%, greater 18 wt%, greater than 20 wt%, greater than 22 wt%, greater than 25 wt%, or greater than 28 wt% versus the total weight of the electrolyte. Combinations of the above-referenced ranges are also possible (e.g., greater than 0.2 wt% and less than or equal to 30 wt%, greater than 0.2 wt% and less than or equal to 20 wt%, greater than 0.5 wt% and less than or equal to 20 wt%, greater than 1 wt% and less than or equal to 8 wt%, greater than 1 wt% and less than or equal to 6 wt%, greater than 4 wt% and less than or equal to 10 wt%, greater than 6 wt% and less than or equal to 15 wt%, or greater than 8 wt% and less than or equal to 20 wt%). Other ranges are also possible.

[0276] In some embodiments, an electrolyte comprises fluoroethylene carbonate, and the total weight of the fluoroethylene carbonate in the electrochemical cell may be less than or equal to 30 wt%, less than or equal to 28 wt%, less than or equal to 25 wt%, less than or equal to 22 wt%, less than or equal to 20 wt%, less than or equal to 18 wt%, less than or equal to 15 wt%, less than or equal to 12 wt%, less than or equal to 10 wt%, less than or equal to 8 wt%, less than or equal to 6 wt%, less than or equal to 5 wt%, less than or equal to 4 wt%, less than or equal to 3 wt%, less than or equal to 2 wt%, or less than or equal to 1 wt% versus the total weight of the electrolyte. In some embodiments, the total weight of the fluoroethylene carbonate in the electrolyte is greater than 0.2 wt%, greater than 0.5 wt%, greater than 1 wt%, greater than 2 wt%, greater than 3 wt%, greater than 4 wt%, greater than 6 wt%, greater than 8 wt%, greater than 10 wt%, greater than 15 wt%, greater than 18 wt%, greater than 20 wt%, greater than 22 wt%, greater than 25 wt%, or greater than 28 wt% versus the total weight of the electrolyte. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 0.2 wt% and greater than 30 wt%, less than or equal to 15 wt% and greater than 20 wt%, or less than or equal to 20 wt% and greater than 25 wt%). Other ranges are also possible.

[0277] In some embodiments, the wt% of one or more electrolyte components is measured prior to first use or first discharge of the electrochemical cell using known amounts of the various components. In other embodiments, the wt% is measured at a point in time during the cycle life of the cell. In some such embodiments, the cycling of an electrochemical cell may be stopped and the wt% of the relevant component in the electrolyte may be determined using, for example, gas chromatography-mass spectrometry. Other methods such as NMR, inductively coupled plasma mass spectrometry (ICP-MS), and elemental analysis can also be used.

[0278] In some embodiments, an electrolyte may comprise several species together that are particularly beneficial in combination. For instance, in some embodiments, the electrolyte comprises fluoroethylene carbonate, dimethyl carbonate, and LiPFe. The weight ratio of fluoroethylene carbonate to dimethyl carbonate may be between 20 wt%:80 wt% and 25 wt%:75 wt% and the concentration of LiPFe in the electrolyte may be approximately 1 M (e.g., between 0.05 M and 2 M). The electrolyte may further comprise lithium bis(oxalato)borate (e.g., at a concentration between 0.1 wt% and 6 wt%, between 0.5 wt% and 6 wt%, or between 1 wt% and 6 wt% in the electrolyte), and / or lithium tris(oxalato)phosphate (e.g., at a concentration between 1 wt% and 6 wt% in the electrolyte).

[0279] In some embodiments, an electrochemical described herein comprises an electrode other than one comprising lithium. This electrode may be a cathode and / or a positive electrode (e.g., an electrode at which reduction occurs during discharging and oxidation occurs during charging).

[0280] A cathode and / or positive electrode may comprise an electroactive material comprising a lithium intercalation compound (e.g., a compound that is capable of reversibly inserting lithium ions at lattice sites and / or interstitial sites). In some cases, the electroactive material comprises a lithium transition metal oxo compound (i.e., a lithium transition metal oxide or a lithium transition metal salt of an oxoacid). The electroactive material may be a layered oxide (e.g., a layered oxide that is also a lithium transition metal oxo compound). A layered oxide generally refers to an oxide having a lamellar structure (e.g., a plurality of sheets, or layers, stacked upon each other). Nonlimiting examples of suitable layered oxides include lithium cobalt oxide (LiCoC ), lithium nickel oxide (LiNiC ), and lithium manganese oxide (LiMnCh).

[0281] In some embodiments, a cathode and / or positive electrode comprises a layered oxide that is lithium nickel manganese cobalt oxide (LiNixMnyCozO2, also referred to as “NMC” or “NCM”). In some such embodiments, the sum of x, y, and z is 1. For example, a non-limiting example of a suitable NMC compound is LiNii / sMni / sCoi / sCh. Other non-limiting examples of suitable NMC compounds include LiNi3 / 5Mni / 5Coi / sO2 and LiNi7 / ioMm / ioCoi / 502.

[0282] In some embodiments, a cathode and / or positive electrode comprises a layered oxide that is lithium nickel cobalt aluminum oxide (LiNixCoyAlzO2, also referred to as “NCA”). In some such embodiments, the sum of x, y, and z is 1. For example, a nonlimiting example of a suitable NCA compound is LiNi0.sCo0.15Al0.05O2. In some embodiments, the electroactive material comprises a transition metal polyanion oxide (e.g., a compound comprising a transition metal, an oxygen, and / or an anion having a charge with an absolute value greater than 1). A non-limiting example of a suitable transition metal polyanion oxide is lithium iron phosphate (LiFePC , also referred to as “LFP”). Another non-limiting example of a suitable transition metal polyanion oxide is lithium manganese iron phosphate (LiMnxFei-xPO4, also referred to as “LMFP”). A non-limiting example of a suitable LMFP compound is LiMno.8Feo.2PO4. In some embodiments, the electroactive material comprises a spinel (e.g., a compound having the structure AB2O4, where A can be Li, Mg, Fe, Mn, Zn, Cu, Ni, Ti, or Si, and B can be Al, Fe, Cr, Mn, or V). A non-limiting example of a suitable spinel is lithium manganese oxide (LiMn2O4, also referred to as “LMO”). Another non-limiting example is lithium manganese nickel oxide (LiNixM2-xO4, also referred to as “LMNO”). A nonlimiting example of a suitable LMNO compound is LiNio.5Mn1.5O4. In some cases, the electroactive material comprises Li1.14Mno.42Nio.25Coo.29O2 (“HC-MNC”), lithium carbonate (Li2COa), lithium carbides (e.g., Li2C2, Li4C, LieC2, LLCs, LioCa, Li4Ca, Li4Cs), vanadium oxides (e.g., V2O5, V2O3, VeO ), and / or vanadium phosphates (e.g., lithium vanadium phosphates, such as Li3V2(PO4)3), or any combination thereof. In some embodiments, the electroactive material in a cathode and / or positive electrode comprises a conversion compound. For instance, the electroactive material may be a lithium conversion material. It has been recognized that a cathode comprising a conversion compound may have a relatively large specific capacity. Without wishing to be bound by a particular theory, a relatively large specific capacity may be achieved by utilizing all possible oxidation states of a compound through a conversion reaction in which more than one electron transfer takes place per transition metal (e.g., compared to 0.1-1 electron transfer in intercalation compounds). Suitable conversion compounds include, but are not limited to, transition metal oxides (e.g., CO3O4), transition metal hydrides, transition metal sulfides, transition metal nitrides, and transition metal fluorides (e.g., CUF2, FeF2, FcFs). A transition metal generally refers to an element whose atom has a partially filled d sub-shell (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs). In some cases, the electroactive material may comprise a material that is doped with one or more dopants to alter the electrical properties (e.g., electrical conductivity) of the electroactive material. Non-limiting examples of suitable dopants include aluminum, niobium, silver, and zirconium.

[0283] In some embodiments, the electroactive material in a cathode and / or positive electrode can comprise sulfur. In some embodiments, an electrode that is a cathode can comprise electroactive sulfur-containing materials. “Electroactive sulfur-containing materials,” as used herein, refers to electroactive materials which comprise the element sulfur in any form, wherein the electrochemical activity involves the oxidation or reduction of sulfur atoms or moieties. As an example, the electroactive sulfur-containing material may comprise elemental sulfur (e.g., Ss). In some embodiments, the electroactive sulfur-containing material comprises a mixture of elemental sulfur and a sulfur-containing polymer. Thus, suitable electroactive sulfur-containing materials may include, but are not limited to, elemental sulfur, sulfides or poly sulfides (e.g., of alkali metals) which may be organic or inorganic, and organic materials comprising sulfur atoms and carbon atoms, which may or may not be polymeric. Suitable organic materials include, but are not limited to, those further comprising heteroatoms, conductive polymer segments, composites, and conductive polymers. In some embodiments, an electroactive sulfur-containing material within a second electrode (e.g., a cathode) comprises at least 40 wt% sulfur. In some cases, the electroactive sulfur- containing material comprises at least 50 wt%, at least 75 wt%, or at least 90 wt% sulfur.

[0284] Examples of sulfur-containing polymers include those described in: U.S. Patent Nos. 5,601,947 and 5,690,702 to Skotheim et al.; U.S. Patent Nos. 5,529,860 and 6,117,590 to Skotheim et al.; U.S. Patent No. 6,201,100 issued Mar. 13, 2001, to Gorkovenko et al., and PCT Publication No. WO 99 / 33130. Other suitable electroactive sulfur-containing materials comprising poly sulfide linkages are described in U.S. Patent No. 5,441,831 to Skotheim et al.; U.S. Patent No. 4,664,991 to Perichaud et al., and in U.S. Patent Nos. 5,723,230, 5,783,330, 5,792,575 and 5,882,819 to Naoi et al. Still further examples of electroactive sulfur-containing materials include those comprising disulfide groups as described, for example in, U.S. Patent No. 4,739,018 to Armand et al.; U.S. Patent Nos. 4,833,048 and 4,917,974, both to De Jonghe et al.; U.S. Patent Nos. 5,162,175 and 5,516,598, both to Visco et al.; and U.S. Patent No. 5,324,599 to Oyama et al.

[0285] As described herein, in some embodiments, an electrochemical cell includes a separator. The separator generally comprises a polymeric material (e.g., polymeric material that does or does not swell upon exposure to electrolyte). In some embodiments, the separator is located between an electrolyte and an electrode (e.g., between the electrolyte and an electrode comprising a layer comprising lithium and / or a passivation layer, between the electrolyte and an anode and / or negative electrode, between the electrolyte and a cathode and / or positive electrode) and / or between two electrodes (e.g., between an anode and a cathode, between a positive electrode and a negative electrode).

[0286] The separator can be configured to inhibit (e.g., prevent) physical contact between two electrodes (e.g., between an anode and a cathode, between a positive electrode and a negative electrode), which could result in short circuiting of the electrochemical cell. The separator can be configured to be substantially electronically non-conductive, which can reduce the tendency of electric current to flow therethrough and thus reduce the possibility that a short circuit passes therethrough. In some embodiments, all or one or more portions of the separator can be formed of a material with a bulk electronic resistivity of at least 104, at least 105, at least IO10, at least 1015, or at least IO20Ohm-meters. The bulk electronic resistivity may be measured at room temperature (e.g., 25 °C).

[0287] In some embodiments, the separator can be ionically conductive, while in other embodiments, the separator is substantially ionically non-conductive. In some embodiments, the average ionic conductivity of the separator is at least 10'7S / cm, at least 10'6S / cm, at least 10'5S / cm, at least 10'4S / cm, at least 10'2S / cm, or at least 10 S / cm. In some embodiments, the average ionic conductivity of the separator may be less than or equal to 1 S / cm, less than or equal to 10 S / cm, less than or equal to 10'2S / cm, less than or equal to 10'3S / cm, less than or equal to IO"4S / cm, less than or equal to 10'5S / cm, less than or equal to 10'6S / cm, less than or equal to 10'7S / cm, or less than or equal to 10'8S / cm. Combinations of the above-referenced ranges are also possible (e.g., an average ionic conductivity of at least 10'8S / cm and less than or equal to 10'1S / cm). Other values of ionic conductivity are also possible.

[0288] The average ionic conductivity of the separator can be determined by employing a conductivity bridge (i.e., an impedance measuring circuit) to measure the average resistivity of the separator at a series of increasing pressures until the average resistivity of the separator does not change as the pressure is increased. This value is considered to be the average resistivity of the separator, and its inverse is considered to be the average conductivity of the separator. The conductivity bridge may be operated at 1 kHz. The pressure may be applied to the separator in 500 kg / cm2increments by two copper cylinders positioned on opposite sides of the separator that are capable of applying a pressure to the separator of at least 3 tons / cm2. The average ionic conductivity may be measured at room temperature (e.g., 25 °C).

[0289] In some embodiments, the separator can be a solid. The separator may be sufficiently porous such that it allows an electrolyte solvent to pass through it. In some embodiments, the separator does not substantially include a solvent (e.g., it may be unlike a gel that comprises solvent throughout its bulk), except for solvent that may pass through or reside in the pores of the separator. In other embodiments, a separator may be in the form of a gel.

[0290] A separator can comprise a variety of materials. The separator may comprise one or more polymers (e.g., the separator may be polymeric, the separator may be formed of one or more polymers), and / or may comprise an inorganic material (e.g., the separator may be inorganic, the separator may be formed of one or more inorganic materials). Examples of suitable polymers that may be employed in separators include, but are not limited to, polyolefins (e.g., polyethylenes, poly(butene-l), poly(n-pentene-2), polypropylene, polytetrafluoroethylene); polyamines (e.g., poly(ethylene imine) and polypropylene imine (PPI)); polyamides (e.g., polyamide (Nylon), poly(e-caprolactam) (Nylon 6), poly(hexamethylene adipamide) (Nylon 66)); polyimides (e.g., polyimide, polynitrile, and poly(pyromellitimide-l,4-diphenyl ether) (Kapton®) (NOMEX®) (KEVLAR®)); polyether ether ketone (PEEK); vinyl polymers (e.g., polyacrylamide, poly(2- vinyl pyridine), poly(N-vinylpyrrolidone), poly(methylcyanoacrylate), poly (ethylcyanoacrylate), poly(butylcyanoacrylate), poly(isobutylcyanoacrylate), poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinyl fluoride), poly(2- vinyl pyridine), vinyl polymer, polychlorotrifluoro ethylene, and poly(isohexylcyanoacrylate)); polyacetals; polyesters (e.g., polycarbonate, polybutylene terephthalate, poly hydroxybutyrate); polyethers (poly(ethylene oxide) (PEO), polypropylene oxide) (PPO), poly(tetramethylene oxide) (PTMO)); vinylidene polymers (e.g., polyisobutylene, poly(methyl styrene), poly(methylmethacrylate) (PMMA), poly(vinylidene chloride), and poly(vinylidene fluoride)); polyaramides (e.g., poly(imino-l,3-phenylene iminoisophthaloyl) and poly(imino-l,4-phenylene iminoterephthaloyl)); polyheteroaromatic compounds (e.g., polybenzimidazole (PBI), polybenzobisoxazole (PBO) and polybenzobisthiazole (PBT)); polyheterocyclic compounds (e.g., polypyrrole); polyurethanes; phenolic polymers (e.g., phenolformaldehyde); polyalkynes (e.g., poly acetylene); polydienes (e.g., 1,2-polybutadiene, cis or trans- 1,4-polybutadiene); polysiloxanes (e.g., poly(dimethylsiloxane) (PDMS), poly(diethylsiloxane) (PDES), polydiphenylsiloxane (PDPS), and polymethylphenylsiloxane (PMPS)); and inorganic polymers (e.g., polyphosphazene, polyphosphonate, polysilanes, polysilazanes). In some embodiments, the polymer may be selected from poly(n-pentene-2), polypropylene, polytetrafluoroethylene, polyamides (e.g., polyamide (Nylon), poly(e-caprolactam) (Nylon 6), poly(hexamethylene adipamide) (Nylon 66)), polyimides (e.g., polynitrile, and poly(pyromellitimide-l,4- diphenyl ether) (Kapton®) (NOMEX®) (KEVLAR®)), polyether ether ketone (PEEK), and combinations thereof.

[0291] Non-limiting examples of suitable inorganic separator materials include glass fibers. For instance, in some embodiments, an electrochemical cell comprises a separator that is a glass fiber filter paper.

[0292] When present, the separator may be porous. In some embodiments, the pore size of the separator is less than or equal to 5 microns, less than or equal to 3 microns, less than or equal to 1 micron, less than or equal to 500 nm, less than or equal to 300 nm, less than or equal to 100 nm, or less than or equal to 50 nm. In some embodiments, the pore size of the separator is greater than or equal to 50 nm, greater than or equal to 100 nm, greater than or equal to 300 nm, greater than or equal to 500 nm, greater than or equal to 1 micron, or greater than or equal to 3 microns. Other values are also possible. Combinations of the above-noted ranges are also possible (e.g., less than or equal to 5 microns and greater than or equal to 50 nm, less than or equal to 300 nm and greater than or equal to 100 nm, less than or equal to 1 micron and greater than or equal to 300 nm, or less than or equal to 5 microns and greater than or equal to 500 nm). In some embodiments, the separator is substantially non-porous. In other words, the separator may lack pores, include a minimal number of pores, and / or not include pores in large portions thereof.

[0293] The electrochemical cells described herein and the articles for inclusion in electrochemical cells described herein may be subject to an applied anisotropic force (e.g., for the latter, after being included in the electrochemical cell). As understood in the art, an “anisotropic force” is a force that is not equal in all directions. In some embodiments, the electrochemical cells and / or the articles for inclusion electrochemical cells can be configured to withstand an applied anisotropic force while maintaining their structural integrity (e.g., for the latter, after being included in the electrochemical cell). The applied anisotropic force may also enhance the morphology of an article for inclusion in the electrochemical cell (e.g., for the latter, after being included in the electrochemical cell) and / or the morphology of an electrode in the electrochemical cell (e.g., an electrode comprising and / or formed from an article for inclusion in an electrochemical cell described elsewhere herein). The electrochemical cells described herein may be adapted and arranged such that, during at least one period of time during charge and / or discharge thereof, an anisotropic force with a component normal to the active surface of an electrode within the electrochemical cell (e.g., an electrode comprising and / or formed from an article for inclusion in an electrochemical cell described elsewhere herein) is applied to the cell.

[0294] In some such cases, the anisotropic force comprises a component normal to an active surface of an electrode (e.g., an electrode comprising and / or formed from an article for inclusion in an electrochemical cell described elsewhere herein) within an electrochemical cell. As used herein, the term “active surface” is used to describe a surface of an electrode at which electrochemical reactions may take place. A force with a “component normal” to a surface is given its ordinary meaning as would be understood by those of ordinary skill in the art and includes, for example, a force which at least in part exerts itself in a direction substantially perpendicular to the surface. For example, in the case of a horizontal table with an object resting on the table and affected only by gravity, the object exerts a force essentially completely normal to the surface of the table. If the object is also urged laterally across the horizontal table surface, then it exerts a force on the table which, while not completely perpendicular to the horizontal surface, includes a component normal to the table surface. Those of ordinary skill will understand other examples of these terms, especially as applied within the description of this disclosure. In the case of a curved surface (for example, a concave surface or a convex surface), the component of the anisotropic force that is normal to an active surface of an electrode may correspond to the component normal to a plane that is tangent to the curved surface at the point at which the anisotropic force is applied. The anisotropic force may be applied, in some cases, at one or more pre-determined locations, in some cases distributed over the active surface of an electrode. In some embodiments, the anisotropic force is applied uniformly over the active surface of an electrode comprising and / or formed from an article for inclusion in an electrochemical cell described elsewhere herein.

[0295] Any of the electrochemical cell properties and / or performance metrics described herein may be achieved, alone or in combination with each other, while an anisotropic force is applied to the electrochemical cell (e.g., during charge and / or discharge of the cell). In some embodiments, an anisotropic force applied to an electrode (e.g., an electrode comprising and / or formed from an article for inclusion in an electrochemical cell described elsewhere herein) and / or to an electrochemical cell (e.g., during at least one period of time during charge and / or discharge of the cell) can include a component normal to an active surface of an electrode.

[0296] In some embodiments, the component of the anisotropic force that is normal to an active surface of an electrode (e.g., an electrode comprising and / or formed from an article for inclusion in an electrochemical cell described elsewhere herein) defines a pressure of greater than or equal to 1 kgf / cm2, greater than or equal to 2 kgf / cm2, greater than or equal to 4 kgf / cm2, greater than or equal to 6 kgf / cm2, greater than or equal to 7.5 kgf / cm2, greater than or equal to 8 kgf / cm2, greater than or equal to 10 kgf / cm2, greater than or equal to 12 kgf / cm2, greater than or equal to 14 kgf / cm2, greater than or equal to 16 kgf / cm2, greater than or equal to 18 kgf / cm2, greater than or equal to 20 kgf / cm2, greater than or equal to 22 kgf / cm2, greater than or equal to 24 kgf / cm2, greater than or equal to 26 kgf / cm2, greater than or equal to 28 kgf / cm2, greater than or equal to 30 kgf / cm2, greater than or equal to 32 kgf / cm2, greater than or equal to 34 kgf / cm2, greater than or equal to 36 kgf / cm2, greater than or equal to 38 kgf / cm2, greater than or equal to 40 kgf / cm2, greater than or equal to 42 kgf / cm2, greater than or equal to 44 kgf / cm2, greater than or equal to 46 kgf / cm2, greater than or equal to 48 kgf / cm2, or more. In some embodiments, the component of the anisotropic force normal to an active surface may, for example, define a pressure of less than or equal to 50 kgf / cm2, less than or equal to 48 kgf / cm2, less than or equal to 46 kgf / cm2, less than or equal to 44 kgf / cm2, less than or equal to 42 kgf / cm2, less than or equal to 40 kgf / cm2, less than or equal to 38 kgf / cm2, less than or equal to 36 kgf / cm2, less than or equal to 34 kgf / cm2, less than or equal to 32 kgf / cm2, less than or equal to 30 kgf / cm2, less than or equal to 28 kgf / cm2, less than or equal to 26 kgf / cm2, less than or equal to 24 kgf / cm2, less than or equal to 22 kgf / cm2, less than or equal to 20 kgf / cm2, less than or equal to 18 kgf / cm2, less than or equal to 16 kgf / cm2, less than or equal to 14 kgf / cm2, less than or equal to 12 kgf / cm2, less than or equal to 10 kgf / cm2, less than or equal to 8 kgf / cm2, less than or equal to 6 kgf / cm2, less than or equal to 4 kgf / cm2, less than or equal to 2 kgf / cm2, or less. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal tol kgf / cm2and less than or equal to 50 kgf / cm2). Other ranges are possible.

[0297] Anisotropic forces applied during at least a portion of charge and / or discharge may be applied using any method known in the art. In some embodiments, the force may be applied using compression springs. Forces may be applied using other elements (either inside or outside a containment structure) including, but not limited to Belleville washers, machine screws, pneumatic devices, and / or weights, among others. In some cases, cells may be pre-compressed before they are inserted into containment structures, and, upon being inserted to the containment structure, they may expand to produce a net force on the cell. Suitable methods for applying such forces are described in detail, for example, in U.S. Patent No. 9,105,938, which is incorporated herein by reference in its entirety. It should, of course, be understood that according to some embodiments articles (e.g., comprising lithium metal layers), passivating layers, substrates, release layers, current collectors, electrolytes, anodes, cathodes, separators, etc., described herein may be incorporated into an electrochemical cell and / or a battery. A battery may comprise a plurality of electrochemical cells, according to some embodiments. And it should further be understood that the electrochemical cells and / or batteries provided herein may be rechargeable, and may be cycled. According to some embodiments, therefore, the disclosure relates to cycled electrochemical cells or batteries comprising one or more layers of Zone 3 lithium metal. The electrochemical cells and / or batteries may be used in any of a variety of suitable applications. For example, in some embodiments, the electrochemical cells or batteries are incorporated into an electric vehicle (e.g., a car or an aircraft).

[0298] Above methods may be implemented by one or more controllers including at least one processor operatively coupled to the various controllable portions of a deposition system as disclosed herein. A method may be embodied as computer readable instructions stored on non-transitory computer readable memory associated with the at least one processor such that when executed by the at least one processor the deposition system may perform any of the actions related to the methods disclosed herein. Additionally, it should be understood that the disclosed order of the steps is exemplary and that the disclosed steps may be performed in a different order, simultaneously, and / or may include one or more additional intermediate steps not shown as the disclosure is not so limited.

[0299] The above-described embodiments of the technology described herein can be implemented in any of numerous ways. For example, the embodiments may be implemented using hardware, software or a combination thereof. When implemented in software, the software code can be executed on any suitable processor or collection of processors, whether provided in a single computing device or distributed among multiple computing devices. Such processors may be implemented as integrated circuits, with one or more processors in an integrated circuit component, including commercially available integrated circuit components known in the art by names such as CPU chips, GPU chips, microprocessor, microcontroller, or co-processor. Alternatively, a processor may be implemented in custom circuitry, such as an ASIC, or semicustom circuitry resulting from configuring a programmable logic device. As yet a further alternative, a processor may be a portion of a larger circuit or semiconductor device, whether commercially available, semi-custom or custom. As a specific example, some commercially available microprocessors have multiple cores such that one or a subset of those cores may constitute a processor. Though, a processor may be implemented using circuitry in any suitable format.

[0300] Further, it should be appreciated that a computing device may be embodied in any of a number of forms, such as a rack-mounted computer, a desktop computer, a laptop computer, or a tablet computer. Additionally, a computing device may be embedded in a device not generally regarded as a computing device but with suitable processing capabilities, including a Personal Digital Assistant (PDA), a smart phone, tablet, or any other suitable portable or fixed electronic device.

[0301] Also, a computing device may have one or more input and output devices. These devices can be used, among other things, to present a user interface. Examples of output devices that can be used to provide a user interface include display screens for visual presentation of output and speakers or other sound generating devices for audible presentation of output. Examples of input devices that can be used for a user interface include keyboards, individual buttons, and pointing devices, such as mice, touch pads, and digitizing tablets. As another example, a computing device may receive input information through speech recognition or in other audible format.

[0302] Such computing devices may be interconnected by one or more networks in any suitable form, including as a local area network or a wide area network, such as an enterprise network or the Internet. Such networks may be based on any suitable technology and may operate according to any suitable protocol and may include wireless networks, wired networks or fiber optic networks.

[0303] Also, the various methods or processes outlined herein may be coded as software that is executable on one or more processors that employ any one of a variety of operating systems or platforms. Additionally, such software may be written using any of a number of suitable programming languages and / or programming or scripting tools, and also may be compiled as executable machine language code or intermediate code that is executed on a framework or virtual machine.

[0304] In this respect, the embodiments described herein may be embodied as a computer readable storage medium (or multiple computer readable media) (e.g., a computer memory, one or more floppy discs, compact discs (CD), optical discs, digital video disks (DVD), magnetic tapes, flash memories, RAM, ROM, EEPROM, circuit configurations in Field Programmable Gate Arrays or other semiconductor devices, or other tangible computer storage medium) encoded with one or more programs that, when executed on one or more computers or other processors, perform methods that implement the various embodiments discussed above. As is apparent from the foregoing examples, a computer readable storage medium may retain information for a sufficient time to provide computer-executable instructions in a non-transitory form. Such a computer readable storage medium or media can be transportable, such that the program or programs stored thereon can be loaded onto one or more different computing devices or other processors to implement various aspects of the present disclosure as discussed above. As used herein, the term "computer-readable storage medium" encompasses only a non-transitory computer-readable medium that can be considered to be a manufacture (i.e., article of manufacture) or a machine. Alternatively or additionally, the disclosure may be embodied as a computer readable medium other than a computer- readable storage medium, such as a propagating signal.

[0305] The terms “program” or “software” are used herein in a generic sense to refer to any type of computer code or set of computer-executable instructions that can be employed to program a computing device or other processor to implement various aspects of the present disclosure as discussed above. Additionally, it should be appreciated that according to one aspect of this embodiment, one or more computer programs that when executed perform methods of the present disclosure need not reside on a single computing device or processor, but may be distributed in a modular fashion amongst a number of different computers or processors to implement various aspects of the present disclosure .

[0306] Computer-executable instructions may be in many forms, such as program modules, executed by one or more computers or other devices. Generally, program modules include routines, programs, objects, components, data structures, etc. that perform particular tasks or implement particular abstract data types. Typically the functionality of the program modules may be combined or distributed as desired in various embodiments.

[0307] The embodiments described herein may be embodied as a method, of which an example has been provided. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.

[0308] Further, some actions are described as taken by a “user.” It should be appreciated that a “user” need not be a single individual, and that in some embodiments, actions attributable to a “user” may be performed by a team of individuals and / or an individual in combination with computer-assisted tools or other mechanisms.

[0309] The following applications are incorporated herein by reference, in their entirety, for all purposes: U.S. Publication No. US-2007-0221265-A1 published on September 27, 2007, filed as U.S. Application No. 11 / 400,781 on April 6, 2006, and entitled “RECHARGEABLE LITHIUM / WATER, LITHIUM / AIR BATTERIES”; U.S. Publication No. US-2009-0035646-A1, published on February 5, 2009, filed as U.S. Application No. 11 / 888,339 on July 31, 2007, and entitled “SWELLING INHIBITION IN BATTERIES”; U.S. Publication No. US-2010-0129699-A1 published on May 17, 2010, filed as U.S. Application No. 12 / 312,764 on February 2, 2010; patented as U.S. Patent No. 8,617,748 on December 31, 2013, and entitled “SEPARATION OF ELECTROLYTES”; U.S. Publication No. US-2010-0291442-A1 published on November 18, 2010, filed as U.S. Application No. 12 / 682,011 on July 30, 2010, patented as U.S. Patent No. 8,871,387 on October 28, 2014, and entitled “PRIMER FOR BATTERY ELECTRODE”; U.S. Publication No. US-2009-0200986-A1 published on August 13, 2009, filed as U.S. Application No. 12 / 069,335 on February 8, 2008, patented as U.S. Patent No. 8,264,205 on September 11, 2012, and entitled “CIRCUIT FOR CHARGE AND / OR DISCHARGE PROTECTION IN AN ENERGY-STORAGE DEVICE”; U.S. Publication No. US-2007-0224502-A1 published on September 27, 2007, filed as U.S. Application No. 11 / 400,025 on April 6, 2006, patented as U.S. Patent No. 7,771,870 on August 10, 2010, and entitled “ELECTRODE PROTECTION IN BOTH AQUEOUS AND NON-AQUEOUS ELECTROCHEMICAL CELLS, INCLUDING RECHARGEABLE LITHIUM BATTERIES”; U.S. Publication No. US- 2008-0318128-A1 published on December 25, 2008, filed as U.S. Application No. 11 / 821,576 on June 22, 2007, and entitled “LITHIUM ALLOY / SULFUR BATTERIES”; U.S. Publication No. US-2006-0238203-Al published on October 26, 2006, filed as U.S. Application No. 11 / 111,262 on April 20, 2005, patented as U.S. Patent No. 7,688,075 on March 30, 2010, and entitled “LITHIUM SULFUR RECHARGEABLE BATTERY FUEL GAUGE SYSTEMS AND METHODS”; U.S. Publication No. US-2008-0187663-A1 published on August 7, 2008, filed as U.S. Application No. 11 / 728,197 on March 23, 2007, patented as U.S. Patent No. 8,084,102 on December 27, 2011, and entitled “METHODS FOR CO-FLASH EVAPORATION OF POLYMERIZABLE MONOMERS AND NON-POLYMERIZABLE CARRIER SOLVENT / SALT MIXTURES / SOLUTIONS”; U.S. Publication No. US-2011- 0006738-A1 published on January 13, 2011, filed as U.S. Application No. 12 / 679,371 on September 23, 2010, and entitled “ELECTROLYTE ADDITIVES FOR LITHIUM BATTERIES AND RELATED METHODS”; U.S. Publication No. US-2011-0008531- Al published on January 13, 2011, filed as U.S. Application No. 12 / 811,576 on September 23, 2010, patented as U.S. Patent No. 9,034,421 on May 19, 2015, and entitled “METHODS OF FORMING ELECTRODES COMPRISING SULFUR AND POROUS MATERIAL COMPRISING CARBON”; U.S. Publication No. US-2010- 0035128-Al published on February 11, 2010, filed as U.S. Application No. 12 / 535,328 on August 4, 2009, patented as U.S. Patent No. 9,105,938 on August 11, 2015, and entitled “APPLICATION OF FORCE IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2011-0165471-A9 published on July 15, 2011, filed as U.S. Application No. 12 / 180,379 on July 25, 2008, and entitled “PROTECTION OF ANODES FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2006- 0222954-A1 published on October 5, 2006, filed as U.S. Application No. 11 / 452,445 on June 13, 2006, patented as U.S. Patent No. 8,415,054 on April 9, 2013, and entitled “LITHIUM ANODES FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US- 2010-0239914-A1 published on September 23, 2010, filed as U.S. Application No. 12 / 727,862 on March 19, 2010, and entitled “CATHODE FOR LITHIUM BATTERY”; U.S. Publication No. US-2010-0294049-A1 published on November 25, 2010, filed as U.S. Application No. 12 / 471,095 on May 22, 2009, patented as U.S. Patent No. 8,087,309 on January 3, 2012, and entitled “HERMETIC SAMPLE HOLDER AND METHOD FOR PERFORMING MICROANALYSIS UNDER CONTROLLED ATMOSPHERE ENVIRONMENT”; U.S. Publication No. US-2011-0076560-Al published on March 31, 2011, filed as U.S. Application No. 12 / 862,581 on August 24, 2010, and entitled “ELECTROCHEMICAL CELLS COMPRISING POROUS STRUCTURES COMPRISING SULFUR”; U.S. Publication No. US-2011-0068001 -Al published on March 24, 2011, filed as U.S. Application No. 12 / 862,513 on August 24, 2010, and entitled “RELEASE SYSTEM FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2012-0048729-A1 published on March 1, 2012, filed as U.S. Application No. 13 / 216,559 on August 24, 2011, and entitled “ELECTRICALLY NON- CONDUCTIVE MATERIALS FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2011-0177398-Al published on July 21, 2011, filed as U.S. Application No. 12 / 862,528 on August 24, 2010, patented as U.S. Patent No. 10,629,947 on April 21, 2020, and entitled “ELECTROCHEMICAL CELL”; U.S. Publication No. US-2011- 0070494-A1 published on March 24, 2011, filed as U.S. Application No. 12 / 862,563 on August 24, 2010, and entitled “ELECTROCHEMICAL CELLS COMPRISING POROUS STRUCTURES COMPRISING SULFUR”; U.S. Publication No. US-2011- 0070491-A1 published on March 24, 2011, filed as U.S. Application No. 12 / 862,551 on August 24, 2010, and entitled “ELECTROCHEMICAL CELLS COMPRISING POROUS STRUCTURES COMPRISING SULFUR”; U.S. Publication No. US-2011- 0059361-A1 published on March 10, 2011, filed as U.S. Application No. 12 / 862,576 on August 24, 2010, patented as U.S. Patent No. 9,005,809 on April 14, 2015, and entitled

[0310] “ELECTROCHEMICAL CELLS COMPRISING POROUS STRUCTURES COMPRISING SULFUR”; U.S. Publication No. US-2012-0052339-A1 published on March 1, 2012, filed as U.S. Application No. 13 / 216,579 on August 24, 2011, and entitled “ELECTROLYTE MATERIALS FOR USE IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2012-0070746-A1 published on March 22, 2012, filed as U.S. Application No. 13 / 240,113 on September 22, 2011, and entitled “LOW ELECTROLYTE ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2011- 0206992-A1 published on August 25, 2011, filed as U.S. Application No. 13 / 033,419 on February 23, 2011, and entitled “POROUS STRUCTURES FOR ENERGY STORAGE DEVICES”; U.S. Publication No. US-2012-0082872-A1 published on April 5, 2012, filed as U.S. Application No. 13 / 249,605 on September 30, 2011, and entitled “ADDITIVE FOR ELECTROLYTES”; U.S. Publication No. US-2012-0082901-A1 published on April 5, 2012, filed as U.S. Application No. 13 / 249,632 on September 30,

[0311] 2011, and entitled “LITHIUM-BASED ANODE WITH IONIC LIQUID POLYMER GEL”; U.S. Publication No. US-2013-0164635-A1 published on June 27, 2013, filed as U.S. Application No. 13 / 700,696 on March 6, 2013, patented as U.S. Patent No. 9,577,243 on February 21 2017, and entitled “USE OF EXPANDED GRAPHITE IN LITHIUM / SULPHUR BATTERIES”; U.S. Publication No. US-2013-0017441 -Al published on January 17, 2013, filed as U.S. Application No. 13 / 524,662 on June 15,

[0312] 2012, patented as U.S. Patent No. 9,548,492 on January 17, 2017, and entitled “PLATING TECHNIQUE FOR ELECTRODE”; U.S. Publication No. US-2013- 0224601-A1 published on August 29, 2013, filed as U.S. Application No. 13 / 766,862 on February 14, 2013, patented as U.S. Patent No. 9,077,041 on July 7, 2015, and entitled “ELECTRODE STRUCTURE FOR ELECTROCHEMICAL CELL”; U.S. Publication No. US-2013-0252103-A1 published on September 26, 2013, filed as U.S. Application No. 13 / 789,783 on March 8, 2013, patented as U.S. Patent No. 9,214,678 on December 15, 2015, and entitled “POROUS SUPPORT STRUCTURES, ELECTRODES CONTAINING SAME, AND ASSOCIATED METHODS”; U.S. Publication No. US- 2015-0287998-A1 published on October 8, 2015, filed as U.S. Application No. 14 / 743,304 on June 18, 2015, patented as U.S. Patent No. 9,577,267 on February 21, 2017, and entitled “ELECTRODE STRUCTURE AND METHOD FOR MAKING SAME”; U.S. Publication No. US-2013-0095380-A1 published on April 18, 2013, filed as U.S. Application No. 13 / 644,933 on October 4, 2012, patented as U.S. Patent No. 8,936,870 on January 20, 2015, and entitled “ELECTRODE STRUCTURE AND METHOD FOR MAKING THE SAME”; U.S. Publication No. US-2012-0052397-A1 published on March 1, 2012, filed as U.S. Application No. 13 / 216,538 on August 24, 2011, patented as U.S. Patent No. 9,853,287 on December 26, 2017, and entitled - I l l -

[0313] “ELECTROLYTE MATERIALS FOR USE IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2014-0123477-A1 published on May 8, 2014, filed as U.S. Application No. 14 / 069,698 on November 1, 2013, patented as U.S. Patent No. 9,005,3 l ion April 14, 2015, and entitled “ELECTRODE ACTIVE SURFACE PRETREATMENT”; U.S. Publication No. US-2014-0193723-A1 published on July 10, 2014, filed as U.S. Application No. 14 / 150,156 on January 8, 2014, patented as U.S. Patent No. 9,559,348 on January 31, 2017, and entitled “CONDUCTIVITY CONTROL IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2014-0255780-A1 published on September 11, 2014, filed as U.S. Application No. 14 / 197,782 on March 5, 2014, patented as U.S. Patent No. 9,490,478 on November 8, 2016, and entitled “ELECTROCHEMICAL CELLS COMPRISING FIBRIL MATERIALS”; U.S. Publication No. US-2014-0272594-A1 published on September 18 2014, filed as U.S. Application No. 13 / 833,377 on March 15, 2013, and entitled “PROTECTIVE STRUCTURES FOR ELECTRODES”; U.S. Publication No. US-2014-0272597-A1 published on September 18, 2014, filed as U.S. Application No. 14 / 209,274 on March 13, 2014, patented as U.S. Patent No. 9,728,768 on August 8, 2017, and entitled “PROTECTED ELECTRODE STRUCTURES AND METHODS”; U.S. Publication No. US-2015-0280277-A1 published on October 1, 2015, filed as U.S. Application No. 14 / 668,102 on March 25, 2015, patented as U.S. Patent No. 9,755,268 on September 5,

[0314] 2017, and entitled “GEL ELECTROLYTES AND ELECTRODES”; U.S. Publication No. US-2015-0180037-A1 published on June 25, 2015, filed as U.S. Application No. 14 / 576,570 on December 19, 2014, patented as U.S. Patent No. 10,020,512 on July 10,

[0315] 2018, and entitled “POLYMER FOR USE AS PROTECTIVE LAYERS AND OTHER COMPONENTS IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2015- 0349310-A1 published on December 3, 2015, filed as U.S. Application No. 14 / 723,132 on May 27, 2015, patented as U.S. Patent No. 9,735,411 on August 15, 2017, and entitled “POLYMER FOR USE AS PROTECTIVE LAYERS AND OTHER COMPONENTS IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2014- 0272595-A1 published on September 18, 2014, filed as U.S. Application No. 14 / 203,802 on March 11, 2014, and entitled “COMPOSITIONS FOR USE AS PROTECTIVE LAYERS AND OTHER COMPONENTS IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2019-0006699-A1 published on January 3, 2019, filed as U.S. Application No. 15 / 727,438 on October 6, 2017, and entitled “PRESSURE AND / OR TEMPERATURE MANAGEMENT IN ELECTROCHEMICAL SYSTEMS”; U.S. Publication No. US-2014-0193713-Al published on July 10, 2014, filed as U.S. Application No. 14 / 150,196 on January 8, 2014, patented as U.S. Patent No. 9,531,009 on December 27, 2016, and entitled “PASSIVATION OF ELECTRODES IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2014-0127577-A1 published on May 8, 2014, filed as U.S. Application No. 14 / 068,333 on October 31, 2013, patented as U.S. Patent No. 10,243,202 on March 26, 2019, and entitled “POLYMERS FOR USE AS PROTECTIVE LAYERS AND OTHER COMPONENTS IN

[0316] ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2015-0318539-A1 published on November 5, 2015, filed as U.S. Application No. 14 / 700,258 on April 30, 2015, patented as U.S. Patent No. 9,711,784 on July 18, 2017, and entitled “ELECTRODE FABRICATION METHODS AND ASSOCIATED SYSTEMS AND ARTICLES”; U.S. Publication No. US-2014-0272565-A1 published on September 18, 2014, filed as U.S. Application No. 14 / 209,396 on March 13, 2014, patented as U.S. Patent No. 10,862,105 on December 8, 2020 and entitled “PROTECTED ELECTRODE STRUCTURES”; U.S. Publication No. US-2015-0010804-A1 published on January 8, 2015, filed as U.S. Application No. 14 / 323,269 on July 3, 2014, patented as U.S. Patent No. 9,994,959 on June 12, 2018, and entitled “CERAMIC / POLYMER MATRIX FOR ELECTRODE PROTECTION IN ELECTROCHEMICAL CELLS, INCLUDING RECHARGEABLE LITHIUM BATTERIES”; U.S. Publication No. US-2015-0162586-A1 published on June 11, 2015, filed as U.S. Application No. 14 / 561,305 on December 5, 2014, and entitled “NEW SEPARATOR”; U.S. Publication No. US-2015-0044517-Al published on February 12, 2015, filed as U.S. Application No. 14 / 455,230 on August 8, 2014, patented as U.S. Patent No. 10,020,479 on July 10, 2018, and entitled “SELF-HEALING ELECTRODE PROTECTION IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2015-0236322-A1 published on August 20, 2015, filed as U.S. Application No. 14 / 184,037 on February 19, 2014, patented as U.S. Patent No. 10,490,796 on November 26, 2019, and entitled “ELECTRODE PROTECTION USING ELECTROLYTEINHIBITING ION CONDUCTOR”; U.S. Publication No. US-2015-0236320- Al published on August 20, 2015, filed as U.S. Application No. 14 / 624 / 641 on February 18,

[0317] 2015, patented as U.S. Patent No. 9,653,750 on May 16, 2017, and entitled “ELECTRODE PROTECTION USING A COMPOSITE COMPRISING AN ELECTROLYTE-INHIBITING ION CONDUCTOR”; U.S. Publication No. US-2016- 0118638-Al published on April 28, 2016, filed as U.S. Application No. 14 / 921,381 on October 23, 2015, and entitled “COMPOSITIONS FOR USE AS PROTECTIVE LAYERS AND OTHER COMPONENTS IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2016-0118651-Al published on April 28, 2016, filed as U.S. Application No. 14 / 918,672 on October 21, 2015, and entitled “ION-CONDUCTIVE COMPOSITE FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2016- 0072132-A1 published on March 10, 2016, filed as U.S. Application No. 14 / 848 / 659 on September 9, 2015, patented as U.S. Patent No. 11,038,178 on June 15, 2021 and entitled “PROTECTIVE LAYERS IN LITHIUM-ION ELECTROCHEMICAL CELLS AND ASSOCIATED ELECTRODES AND METHODS”; U.S. Publication No. US-2018- 0138542-A1 published on May 17, 2018, filed as U.S. Application No. 15 / 567,534 on October 18, 2017, patented as U.S. Patent No. 10,847,833 on November 24, 2020 and entitled “GLASS -CERAMIC ELECTROLYTES FOR LITHIUM-SULFUR BATTERIES”; U.S. Publication No. US-2016-0344067-Al published on November 24,

[0318] 2016, filed as U.S. Application No. 15 / 160,191 on May 20, 2016, patented as U.S. Patent No. 10,461,372 on October 29, 2019, and entitled “PROTECTIVE LAYERS FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2020-0099108-A1 published on March 26, 2020, filed as U.S. Application No. 16 / 587,939 on September 30, 2019, and entitled “PROTECTIVE LAYERS FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2017-0141385-A1 published on May 18, 2017, filed as U.S. Application No. 15 / 343,890 on November 4, 2016, and entitled “LAYER COMPOSITE AND ELECTRODE HAVING A SMOOTH SURFACE, AND ASSOCIATED METHODS”; U.S. Publication No. US-2017-0141442-A1 published on May 18, 2017, filed as U.S. Application No. 15 / 349,140 on November 11, 2016, and entitled “ADDITIVES FOR ELECTROCHEMICAL CELLS”; patented as U.S. Patent No. 10 / 320,031 on June 11, 2019, and entitled “ADDITIVES FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2017-0149086-A1 published on May 25, 2017, filed as U.S. Application No. 15 / 343,635 on November 4, 2016, patented as U.S. Patent No.

[0319] 9,825,328 on November 21, 2017, and entitled “IONICALLY CONDUCTIVE COMPOUNDS AND RELATED USES”; U.S. Publication No. US-2018-0337406-A1 published on November 22, 2018, filed as U.S. Application No. 15 / 983,352 on May 18, 2018, patented as U.S. Patent No. 10,868,306 on December 15, 2020 and entitled “PASSIVATING AGENTS FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2018-0261820-Al published on September 13, 2018, filed as U.S. Application No. 15 / 916,588 on March 9, 2018, patented as U.S. Patent No. 11,024,923 on June 1, 2021 and entitled “ELECTROCHEMICAL CELLS COMPRISING SHORT-CIRCUIT RESISTANT ELECTRONICALLY INSULATING REGIONS”; U.S. Publication No. US-2020-0243824-A1 published on July 30, 2020, filed as U.S. Application No. 16 / 098,654 on November 2, 2018, patented as U.S. Patent No. 10,991,925 on April 27, 2021 and entitled “COATINGS FOR COMPONENTS OF ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2018-0351158-Al published on December 6, 2018, filed as U.S. Application No. 15 / 983,363 on May 18, 2018, patented as U.S. Patent No. 10,944,094 on March 9, 2021 and entitled “PASSIVATING AGENTS FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2018-0277850-A1 published on September 27, 2018, filed as U.S. Application No. 15 / 923,342 on March 16, 2018, and patented as U.S. Patent No. 10,720,648 on July 21, 2020, and entitled “ELECTRODE EDGE PROTECTION IN ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2018-0358651-Al published on December 13, 2018, filed as U.S. Application No. 16 / 002,097 on June 7, 2018, and patented as U.S. Patent No. 10,608,278 on March 31, 2020, and entitled “IN SITU CURRENT COLLECTOR”; U.S. Publication No. US-2017-0338475-A1 published on November 23, 2017, filed as U.S. Application No. 15 / 599,595 on May 19, 2017, patented as U.S. Patent No. 10,879,527 on December 29, 2020, and entitled “PROTECTIVE LAYERS FOR ELECTRODES AND ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2019-0088958-A1 published on March 21, 2019, filed as U.S. Application No. 16 / 124,384 on September 7, 2018, and entitled “PROTECTIVE MEMBRANE FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2019-0348672-A1 published on November 14, 2019, filed as U.S. Application No. 16 / 470,708 on June 18, 2019. patented as U.S. Patent No. 11,183,690 on November 23, 2021, and entitled “PROTECTIVE LAYERS COMPRISING METALS FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2017-0200975-A1 published July 13, 2017, filed as U.S. Application No. 15 / 429,439 on February 10, 2017, and patented as U.S. Patent No. 10,050,308 on August 14, 2018, and entitled “LITHIUM-ION ELECTROCHEMICAL CELL, COMPONENTS THEREOF, AND METHODS OF MAKING AND USING SAME”; U.S. Publication No. US-2018- 0351148-A1 published December 6, 2018, filed as U.S. Application No. 15 / 988,182 on May 24, 2018, patented as U.S. Patent No.11, 251, 501 on February 15, 2022, and entitled “IONICALLY CONDUCTIVE COMPOUNDS AND RELATED USES”; U.S. Publication No. US-2018-0254516-Al published September 6, 2018, filed as U.S. Application No. 15 / 765,362 on April 2, 2018, and entitled “NON-AQUEOUS ELECTROLYTES FOR HIGH ENERGY LITHIUM-ION BATTERIES”; U.S. Publication No. US-2020-0044460- Al published February 6, 2020, patented as U.S. Patent No.11,489,348 on November 1, 2022, filed as U.S. Application No. 16 / 527,903 on July 31, 2019, and entitled “MULTIPLEXED CHARGE DISCHARGE BATTERY MANAGEMENT SYSTEM”; U.S. Publication No. US-2020-0220146-A1 published July 9, 2020, patented as U.S. Patent No. 11,322,804 on May 3, 2022, filed as U.S. Application No. 16 / 724,586 on December 23, 2019, and entitled “ISOLATABLE ELECTRODES AND ASSOCIATED ARTICLES AND METHODS”; U.S. Publication No. US-2020-0220149-A1 published July 9, 2020, filed as U.S. Application No. 16 / 724,596 on December 23, 2019, and entitled “ELECTRODES, HEATERS, SENSORS, AND ASSOCIATED ARTICLES AND METHODS”; U.S. Publication No. US-2020-0220197-Al published July 9, 2020, filed as U.S. Application No. 16 / 724,612 on December 23, 2019, and entitled “FOLDED ELECTROCHEMICAL DEVICES AND ASSOCIATED METHODS AND SYSTEMS”, U.S. Publication No. US-2020-0373578- A1 published November 26, 2020, filed as U.S. Application No. 16 / 879,861 on May 21, 2020, and entitled “ELECTROCHEMICAL DEVICES INCLUDING POROUS LAYERS”, U.S. Publication No. US-2020-0373551-Al published November 26, 2020, filed as U.S. Application No. 16 / 879,839 on May 21, 2020, and entitled “ELECTRICALLY COUPLED ELECTRODES, AND ASSOCIATED ARTICLES AND METHODS”, U.S. Publication No. US-2020-0395585-A1 published December 17, 2020, filed as U.S. Application No. 16 / 057,050 on August 7, 2018, and entitled “LITHIUM-COATED SEPARATORS AND ELECTROCHEMICAL CELLS COMPRISING THE SAME”, U.S. Publication No. US-2021-0057753-A1 published February 25, 2021, filed as U.S. Application No. 16 / 994,006 on August 14, 2020, and entitled “ELECTROCHEMICAL CELLS AND COMPONENTS COMPRISING THIOL GROUP-CONTAINING SPECIES”, U.S. Publication No. US-2021-0135297- A1 published on May 6, 2021, patented as U.S. Patent No. 11,424,492 on August 23, 2022, filed as U.S. Application No. 16 / 670,905 on October 31, 2019, and entitled SYSTEM AND METHOD FOR OPERATING A RECHARGEABLE ELECTROCHEMICAL CELL OR BATTERY”, U.S. Publication No. US-2021- 0138673-A1 published on May 13, 2021, filed as U.S. Application No. 17 / 089,092 on November 4, 2020, and entitled “ELECTRODE CUTTING INSTRUMENT”, U.S. Publication No. US-2021-0135294-A1 published on May 6, 2021, filed as U.S. Application No. 16 / 670,933 on October 31, 2019, patented as U.S. Patent No.

[0320] 11,056,728 on July 6, 2021 and entitled “SYSTEM AND METHOD FOR OPERATING A RECHARGEABLE ELECTROCHEMICAL CELL OR BATTERY”; U.S. Publication No. US-2021-0151839-Al published on May 20, 2021, filed as U.S. Application No. 16 / 952,177 on November 19, 2020, and entitled “BATTERIES, AND ASSOCIATED SYSTEMS AND METHODS”; U.S. Publication No. US-2021-0151830-Al published on May 20, 2021, filed as U.S. Application No. 16 / 952,235 on November 19, 2020, and entitled “BATTERIES WITH COMPONENTS INCLUDING CARBON FIBER, AND ASSOCIATED SYSTEMS AND METHODS”; U.S. Publication No. US-2021-0151817- A1 published on May 20, 2021, filed as U.S. Application No. 16 / 952,228 on November 19, 2020, and entitled “BATTERY ALIGNMENT, AND ASSOCIATED SYSTEMS AND METHODS”; U.S. Publication No. US-2021-0151841-Al published on May 20,

[0321] 2021, filed as U.S. Application No. 16 / 952,240 on November 19, 2020, and entitled “SYSTEMS AND METHODS FOR APPLYING AND MAINTAINING COMPRESSION PRESSURE ON ELECTROCHEMICAL CELLS”; U.S. Publication No. US-2021-0151816-A1 published on May 20, 2021, filed as U.S. Application No. 16 / 952,223 on November 19, 2020, and entitled “THERMALLY INSULATING COMPRESSIBLE COMPONENTS FOR BATTERY PACKS”; U.S. Publication No. US-2021-0151840-Al published on May 20, 2021, filed as U.S. Application No. 16 / 952,187 on November 19, 2020, and entitled “COMPRESSION SYSTEMS FOR BATTERIES”; U.S. Publication No. US-2021-0193984-A1 published on June 24, 2021, filed as U.S. Application No. 17 / 125,124 on December 17, 2020, and entitled “SYSTEMS AND METHODS FOR FABRICATING LITHIUM METAL ELECTRODES”; U.S. Publication No. US-2021-0193985-A1 published on June 24, 2021, filed as U.S. Application No. 17 / 125,110 on December 17, 2020, and entitled “LITHIUM METAL ELECTRODES AND METHODS”; U.S. Publication No. US-

[0322] 2021-0193996-A1 published on June 24, 2021, filed as U.S. Application No. 17 / 125,070 on December 17, 2020, and entitled “LITHIUM METAL ELECTRODES”; U.S. Publication No. US-2021-0194069- Al published on June 24, 2021, filed as U.S. Application No. 17 / 126,390 on December 18, 2020, and entitled “SYSTEMS AND METHODS FOR PROVIDING, ASSEMBLING, AND MANAGING INTEGRATED POWER BUS FOR RECHARGEABLE ELECTROCHEMICAL CELL OR BATTERY”; U.S. Publication No. US-2021-0218243 published on July 15, 2021, filed as U.S. Application No. 17 / 126,424 on December 18, 2020, and entitled “SYSTEMS AND METHODS FOR PROTECTING A CIRCUIT, RECHARGEABLE ELECTROCHEMICAL CELL, OR BATTERY”; U.S. Publication No. 2022-0069593 published on March 3, 2022, filed as U.S. Application No. 17 / 463,467 filed on August 31, 2021, and entitled “Multiplexed Battery Management System”; U.S. Publication No.

[0323] 2022-0048121 published on February 17, 2022, filed as U.S. Application No. 17 / 397,114 filed on August 9, 2021, and entitled “Ultrasonic Blade for Cutting a Metal”, U.S.

[0324] Publication No. 2022-0115715 published on April 14, 2022, filed as U.S. Application No. 17 / 479,299 filed on September 20, 2021 and entitled “Electrolytes for Reduced Gassing”; U.S. Publication No. 2022-0359902 published on November 10, 2022, filed as U.S. Application No. 17 / 621,409 filed on December 21, 2021, and entitled “METHODS, SYSTEMS, AND DEVICES FOR APPLYING FORCES TO ELECTROCHEMICAL DEVICES”; U.S. Publication No. 2022-0352521 published on November 3, 2022, filed as U.S. Application No. 17 / 730,792 on April 27, 2022, and entitled “INTEGRATED BATTERY ELECTRODE AND SEPARATOR”; U.S. Publication No. 2022-0336872 published on October 20, 2022, filed as U.S. Application No. 17 / 592,406 on February 3, 2022, and entitled “CHARGE / DISCHARGE MANAGEMENT IN ELECTROCHEMICAL CELLS, INCLUDING PARTIAL CYCLE CONTROL”; U.S. Publication No. 2022-0328880 published on October 13, 2022, filed as U.S. Application No. 17 / 712,754 on April 4, 2022, and entitled “ELECTROLYTES FOR LITHIUM BATTERIES”; U.S. Publication No. 2022-0320586 published on October 6, 2022, filed as U.S. Application No. 17 / 703,415 on March 24, 2022, and entitled “IN-SITU CONTROL OF SOLID ELECTROLYTE INTERFACE FOR ENHANCED CYCLE PERFORMANCE IN LITHIUM METAL BATTERIES”; U.S. Publication No. 2022- 0311081 published on September 29, 2022, filed as U.S. Application No. 17 / 702,971 on March 24, 2022, and entitled “BATTERY PACK AND RELATED COMPONENTS AND METHODS”; U.S. Publication No. 2022-0271537 published on August 25, 2022, filed as U.S. Application No. 17 / 592,398 on February 3, 2022, and entitled “CHARGE / DISCHARGE MANAGEMENT IN ELECTROCHEMICAL CELLS, INCLUDING PARTIAL CYCLE CONTROL”; U.S. Publication No. 2022-0209327 published on June 30, 2022, filed as U.S. Application No. 17 / 565,317 on December 29, 2021, and entitled “TEMPERATURE MANAGEMENT FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. 2022-0199968 published on June 23, 2022, filed as U.S. Application No. 17 / 552,829 on December 16, 2021, and entitled “LASER CUTTING OF COMPONENTS FOR ELECTROCHEMICAL CELLS”; U.S. Publication No. 2022- 0181624 published on June 9, 2022, filed as U.S. Application No. 17 / 540,611 on December 2, 2021, and entitled “LOW POROSITY ELECTRODES AND RELATED METHODS”; U.S. Publication No. 2022-0181624 published on June 9, 2022, filed as U.S. Application No. 17 / 492,084 on October 1, 2021, and entitled “ELECTROCHEMICAL CELLS COMPRISING NITROGEN-CONTAINING SPECIES, AND METHODS OF FORMING THEM”; U.S. Publication No. 2023- 0006185 published on January 5, 2023, filed as U.S. Application No. 17 / 849,890 on June 27, 2022, and entitled “Systems and Methods for Roll to Roll Deposition of Electrochemical Cell Components and Other Articles”; U.S. Publication No. 2022- 0407127 published on December 22, 2022, filed as U.S. Application No. 17 / 849,814 on June 27, 2022, and entitled “System and Method for Operating a Rechargeable Electrochemical Cell or Battery”; U.S. Publication No. 2023-0118071 published on April 20, 2023, filed as U.S. Application No. 17 / 911,080 on September 12, 2022, and entitled “Application of Pressure to Electrochemical Devices Including Deformable Solids, and Related Systems”; U.S. Publication No. 2023-0111336 published on April 13, 2023, filed as U.S. Application No. 17 / 942,469 on September 12, 2022, and entitled “High Voltage Lithium-Containing Electrochemical Cells and Related Methods”; U.S. Publication No. 2023-0112241 published on April 13, 2023, filed as U.S. Application No. 17 / 942,489 on September 12, 2022, and entitled “High Voltage Lithium-Containing Electrochemical Cells Including Magnesium-Comprising Protective Layers and Related Methods”.

[0325] The following applications are also incorporated herein by reference, in their entirety, for all purposes: U.S. Publication No. 2023-0317959-Al published on October 5, 2023, filed as U.S. Application No. 18 / 024,229 on March 1, 2023, and entitled “ELECTRICALLY CONDUCTIVE RELEASE LAYER”; U.S. Publication No. US- 2023-0275256-A1 published on August 31, 2023, filed as U.S. Application No. 18 / 017,493 on January 23, 2023, and entitled “ELECTROCHEMICAL CELL CLAMPS AND RELATED METHODS”; U.S. Publication No. 2022-0115649- Al published on April 14, 2022, filed as U.S. Application No. 17 / 492,063 on October 1, 2021, patented as U.S. Patent No. 11,705,554 on July 18, 2023, and entitled “ELECTROCHEMICAL CELLS AND / OR COMPONENTS THEREOF COMPRISING NITROGENCONTAINING SPECIES, AND METHODS OF FORMING THEM”; and U.S. Publication No. 2024-0097208-Al published on March 21, 2024, filed as U.S. Application No. 18 / 270,720 on June 30, 2023, and entitled “MIXTURES AND / OR LAYERS COMPRISING CERAMIC PARTICLES AND A POLYMERIC SURFACTANT, AND RELATED ARTICLES AND METHODS”.

[0326] The following examples are intended to illustrate certain embodiments of the present disclosure, but do not exemplify the full scope of the disclosure.

[0327] EXAMPLE 1

[0328] This example describes the results of modeling the cooling effect from use of a non-limiting cooling apparatus. A COMSOL was used to model the temperature of the roller, the temperature at the bottom of an exemplary substrate, and the temperature at the top of an exemplary substrate during an exemplary period of simulated metal deposition in order to identify the change associated with combined use of gas-cooling and contact-cooling, relative to just contact cooling. FIGS. 23-24 present the results of the simulations.

[0329] FIG. 23 shows the simulated temperature of the roller of the cooling apparatus and of the top and bottom of the substrate as a function of time. As expected, the onset of simulated metal deposition was associated with a rise in temperature of both the substrate and the roller, but the substrate reached a much higher temperature. The top and bottom of the substrate had almost identical temperature distributions, indicating that the temperature gradient through the substrate was relatively small.

[0330] FIG. 24 shows the results of the same simulation, where gas-cooling is added. As indicated in the figures, the addition of gas-cooling resulted in a nearly 8-fold reduction in the substrate temperature under otherwise identical deposition conditions. FIGS. 25 and 26 show the same results as FIGS. 23 and 24, respectively, but rescaled to share the same Y-axis, to further illustrate this reduction in temperature. The increase of roller surface temperature in FIG. 24 relative to FIG. 23 shows the contribution of cooling gas in removing the heat generated. These simulations demonstrate the advantages of gas cooling for regulation of substrate temperatures.

[0331] EXAMPLE 2

[0332] This example describes the deposition of lithium metal layers at various temperatures and demonstrates that the methods provided herein can produce Zone 1, Zone T, Zone 2, and Zone 3 lithium, on demand. This example further demonstrates the physical characteriza...

Claims

CLAIMSWhat is claimed is:

1. A method of metal deposition, the method comprising: simultaneously performing the steps of: removing heat from a substrate using a gas and a face of a roller, wherein both the gas and the face of the roller contact a first side of the substrate, depositing metal on a second side of the substrate opposite the first side of the substrate, rolling the substrate across the face of the roller, and determining the micro structure of metal deposited on the substrate.

2. A method of metal deposition, the method comprising: simultaneously performing the steps of: removing heat from a substrate using a gas and a face of a roller, wherein both the gas and the face of the roller contact a first side of the substrate, depositing metal on a second side of the substrate opposite the first side of the substrate, rolling the substrate across the face of the roller, and maintaining the substrate at a temperature between 50% and 100% of a melting point of the deposited metal.

3. The method of any one of the preceding claims, wherein the deposited metal comprises lithium.

4. The method of any one of the preceding claims, wherein the deposited metal is lithium.

5. The method of any one of the preceding claims, wherein the metal is lithium with a purity that exceeds 50 wt%6. The method of any one of claims 1-5, wherein the metal is deposited as Zone T metal.

7. The method of any one of claims 1-5, wherein the metal is deposited as Zone 2 metal.

8. The method of any one of claims 1-5, wherein the metal is deposited as Zone 3 metal.

9. The method of any one of the previous claims, wherein the metal is deposited by physical vapor deposition (PVD).

10. The method of any one of the preceding claims, wherein the metal is deposited by chemical vapor deposition (CVD).

11. The method of any one of the previous claims, wherein the metal is deposited by sputtering.

12. A method of lithium deposition, the method comprising: simultaneously performing the steps of: removing heat from a substrate using a gas and a face of a roller, wherein both the gas and the face of the roller contact a first side of the substrate, depositing Zone T, Zone 2, or Zone 3 lithium on a second side of the substrate opposite the first side of the substrate, and rolling the substrate across the face of the roller.

13. The method of claim 12, wherein the lithium is deposited as Zone T lithium.

14. The method of claim 12, wherein the lithium is deposited as Zone 2 lithium.

15. The method of claim 12, wherein the lithium is deposited as Zone 3 lithium.

16. The method of any one of claims 12-15, wherein the lithium is a lithium alloy.

17. The method of any one of claims 12-15, wherein the lithium is elemental lithium.

18. The method of any one of claims 12-17, wherein the lithium has a purity that exceeds 50 wt%.

19. The method of any one of claims 12-18, wherein the lithium is deposited by PVD.

20. The method of any one of claims 12-19, wherein the lithium is deposited by CVD.

21. The method of any one of claims 12-20, wherein the lithium is deposited by sputtering.

22. The method of any one of claims 12-21, wherein the lithium metal is deposited such that it solidifies with a { 110} plane aligned with the substrate.

23. The method of any one of claims 12-21, wherein the lithium metal is deposited such that it solidifies with a {200} plane aligned with the substrate.

24. The method of any one of claims 12-21, wherein the lithium metal is deposited such that it solidifies with a { 100} plane aligned with the substrate.

25. The method of any one of the preceding claims, wherein the roller moves at a speed of 1 RPM.

26. The method of any one of the preceding claims, further comprising performing the removing, depositing, and rolling steps simultaneously for a continuous period of 1 second.

27. A system, comprising: a cooling apparatus comprising: a roller, a coolant conduit adjacent to at least a portion of a face of the roller, fluidically connecting a coolant inlet to a coolant outlet, and a gas diffuser configured to emit a gas from at least a portion of the face of the roller; a metal deposition system configured to deposit metal on a substrate disposed adjacent to at least a portion of the face of the roller; and a detection system configured to determine a micro structure of the metal deposited on the substrate; and one or more processors configured to receive information from the detection system and operatively coupled with at least one of the metal deposition system and the cooling apparatus, wherein the one or more processors is configured to adjust operation of the metal deposition system and / or the cooling apparatus based, at least in part, on information received by the detection system.

28. A system, comprising: a cooling apparatus comprising: a roller, a coolant conduit adjacent to at least a portion of a face of the roller, fluidically connecting a coolant inlet to a coolant outlet, and a gas diffuser configured to emit a gas from at least a portion of the face of the roller; and a metal deposition system configured to deposit metal on a substrate disposed adjacent to at least a portion of the face of the roller; wherein the cooling apparatus and the metal deposition system are configured to maintain the substrate at a temperature between 50% and 100% of a melting point of the metal deposited by the metal deposition system.

29. The system of any one of the preceding claims, wherein the metal comprises lithium.

30. The system of any one of the preceding claims, wherein the metal is lithium.

31. The system of any one of the preceding claims, wherein the metal is lithium with a purity that exceeds 50 wt%32. The system of any one of claims 27-31, wherein at least a portion of the substrate comprises Zone T lithium.

33. The system of any one of claims 27-31, wherein at least a portion of the substrate comprises Zone 2 lithium.

34. The system of any one of claims 27-31, wherein at least a portion of the substrate comprises Zone 3 lithium.

35. The system of any one of the preceding claims, wherein the metal deposition system is a PVD system.

36. The system of any one of the preceding claims, wherein the metal deposition system is a CVD system.

37. The system of any one of claims 27-35, wherein the metal deposition system is a sputtering system.

38. The system of any one of the preceding claims, further comprising a processor operatively coupled with the cooling apparatus and configured to maintain the substrate at a temperature between 50% and 100% of a melting point of the metal deposited by the system.

39. A system, comprising: a cooling apparatus comprising: a roller,a coolant conduit adjacent to at least a portion of a face of the roller, fluidically connecting a coolant inlet to a coolant outlet, and a gas diffuser configured to emit a gas from at least a portion of the face of the roller; and a substrate disposed adjacent to at least a portion of the face of the roller, wherein at least a portion of the substrate comprises Zone T, Zone 2, or Zone 3 lithium.

40. The system of claim 39, wherein the at least a portion of the substrate comprises Zone T lithium.

41. The system of claim 39, wherein the at least a portion of the substrate comprises Zone 2 lithium.

42. The system of claim 39, wherein the at least a portion of the substrate comprises Zone 3 lithium.

43. The system of any one of claims 39-42, wherein the lithium is a lithium alloy.

44. The system of any one of claims 39-42, wherein the lithium is elemental lithium.

45. The system of any one of claims 39-44, wherein the lithium has a purity that exceeds 50 wt%.

46. The system of any one of claims 39-44, further comprising a metal deposition system.

47. The system of claim 46, wherein the metal deposition system is a PVD system.

48. The system of claim 46, wherein the metal deposition system is a CVD system.

49. The system of any one of claims 46-47, wherein the metal deposition system is a sputtering system.

50. The system of any one of claims 39-49, wherein the lithium metal has a { 110} plane aligned with the substrate.

51. The system of any one of claims 39-49, wherein the lithium metal has a {200} plane aligned with the substrate.

52. The system of any one of claims 39-49, wherein the lithium metal has a { 100} plane aligned with the substrate.

53. The system of any one of claims 39-52, further comprising a processor operatively coupled with the cooling apparatus and configured to maintain the substrate at a temperature between 50% and 100% of a melting point of the lithium deposited by the system.

54. The system of any one of the preceding claims, wherein the roller is configured to move at a speed of 1 RPM.

55. The system of any one of the preceding claims, wherein the gas diffuser comprises a plurality of holes in the face of the roller.

56. The system of any one of the preceding claims, wherein the gas diffuser comprises a porous body at least partially encircling the roller.

57. The system of any one of the preceding claims, wherein the cooling apparatus comprises a plurality of gas diffusers at least partially encircling the roller.

58. An article, comprising: a substrate, and a lithium metal layer disposed on the substrate; wherein the lithium metal layer comprises a volume of greater than or equal to 50 mL wherein greater than or equal to 70% of the volume is occupied by Zone 3 lithium.

59. An article, comprising: a substrate, and a lithium metal layer disposed on the substrate; wherein the lithium metal layer has a thickness of less than or equal to 20 microns and comprises Zone 3 lithium.

60. An article, comprising: a substrate, a lithium metal layer disposed on the substrate, and a passivating layer disposed on the lithium metal layer; wherein greater than or equal to 70% of the volume of the lithium metal layer is occupied by Zone 3 lithium, and wherein greater than or equal to 70% of the volume of the passivating layer is occupied by Zone 3 material.

61. The article of any one of claims 58-60, wherein the article is a roll62. The article of claim 61, wherein the roll has a diameter of greater than or equal to 10 cm and article has a thickness of less than or equal to 1 mm.

63. The article of any one of claims 58-62, wherein the lithium metal layer has an average grain size of greater than or equal to 2 microns and less than or equal to 15 microns.

64. The article of any one of claims 58-63, wherein the integrated intensity of the lithium LI X-ray diffraction peak to the lithium L2 X-ray diffraction peak of the lithium metal layer is greater than or equal to 3.

65. The article of any one of claims 58-59 and 61-64, further comprising a passivating layer disposed on the lithium metal layer.

66. The article of any one of claims 60 and 65, wherein the passivating layer has a wherein the passivating layer comprises boron, phosphorus, antimony, selenium, tellurium, hydrogen, and / or a halogen.

67. The article of any one of claims 60 and 65-66, wherein the passivating layer comprises a reaction product of lithium metal from the layer comprising lithium metal and a gas reactive therewith.

68. The article of any one of claims 60 and 65-66, wherein the passivating layer comprises a ceramic or a glass.

69. An electrochemical cell comprising a portion of the article of any one of claims 58-68.

70. A cycled electrochemical cell comprising a portion of the article of any one of claims 58-68.

71. A battery comprising a portion of the article of any one of claims 58-68.

72. A cycled battery comprising a portion of the article of any one of claims 58-68.

73. An electric vehicle comprising a portion of the article of any one of claims 58-68.

74. A method, comprising: charging a battery to form a lithium metal anode, wherein greater than or equal to 70% of the volume of the formed lithium metal anode is occupied by Zone 3 lithium.

75. The method of claim 74, wherein the lithium metal anode has an average grain size in lateral direction of greater than or equal to 2 micrometers and less than or equal to 15 micrometers.

76. The method of any one of claims 74-75, wherein the integrated intensity of the lithium LI diffraction peak to the lithium L2 diffraction peak of the lithium metal layer is greater than or equal to 3.

77. The method of any one of claims 74-76, wherein the lithium metal layer comprises a plurality of columnar structures having an aspect ratio of greater than or equal to 0.5 and less than or equal to 5.

78. An article, comprising: a substrate, and a plurality of lithium metal layers disposed on the substrate; wherein the plurality of lithium metal layers have a total volume of greater than or equal to 50 mL, wherein greater than or equal to 70% of the volume is occupied by Zone 3 lithium.

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