All-solid-state lithium-ion battery and method for manufacturing the same

Abstract

The lithium-ion secondary battery cell has a negative electrode including a plurality of spaced-apart lithium storage layer segments in electrical contact with a negative electrode current collector. The lithium storage layer segments contain at least 40 atomic % silicon, tin, germanium, or a combination thereof. The cell has a positive electrode including a positive electrode active material layer in electrical contact with a positive electrode current collector. The cell also has a lithium-ion-containing solid electrolyte (SSE) i) interposed between the plurality of spaced-apart lithium storage layer segments and the positive electrode active material, and ii) at least partially disposed within the gaps separating the spaced-apart lithium storage layer segments. A method for manufacturing the lithium-ion battery cell is also described.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority to U.S. Provisional Application No. 63 / 484,847, filed February 14, 2023, and U.S. Provisional Application No. 63 / 607,211, filed December 7, 2023, each of which is incorporated herein by reference in its entirety.

[0002] STATEMENT OF RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT This invention was made with government support under Contract No. W911NF2220021 awarded by the United States Army. The government has certain rights in this invention.

[0003] (Technical field) The present disclosure relates to all-solid-state lithium-ion batteries and related energy storage devices. [Background technology]

[0004] BACKGROUND OF THE INVENTION Silicon has been proposed as an alternative to conventional carbon-based anodes in lithium-ion batteries, which are limited to a storage capacity of ~370 mAh / g. Silicon readily alloys with lithium and has a much higher theoretical storage capacity (~3600–4200 mAh / g at room temperature) than carbon anodes. In addition to improving energy storage density, silicon-based anodes may also offer additional safety benefits, such as more robust performance in the well-known "nail penetration test." To further improve the safety of lithium-ion batteries, research is also underway to replace electrolytes based on volatile small-molecule solvents with safer solid-state electrolytes. Summary of the Invention [Problem to be solved by the invention]

[0005] Unfortunately, the insertion and extraction of lithium into the silicon matrix can cause significant volume expansion (>300%) and contraction. As a result, the silicon can rapidly break down into small particles and become electrically disconnected from the current collector. The expansion and contraction of silicon-containing anodes poses additional challenges to the fabrication of solid-state battery cells. These volume changes can make it difficult to maintain functionally sufficient physical contact between the anode active material and the solid electrolyte.

[0006] Despite various approaches being investigated, silicon-based batteries, especially those using solid electrolytes, have yet to make a significant impact on the market due to unresolved issues. [Means for solving the problem]

[0007] (Summary of the Invention) There remains a need for all-solid-state lithium-ion batteries based on silicon anodes that are easy to fabricate, safe, robust to handle, have high charge capacity, are capable of fast charging, and have good cycle life.

[0008] According to one embodiment of the present disclosure, a lithium-ion battery cell includes a negative electrode including a plurality of spaced-apart lithium storage layer segments in electrical contact with a negative electrode current collector. The lithium storage layer segments include at least 40 atomic % silicon, tin, germanium, or a combination thereof. The cell includes a positive electrode including a positive electrode active material layer in electrical contact with a positive electrode current collector. The cell also includes a lithium-ion-containing solid-state electrolyte (SSE). The lithium-ion-containing solid electrolyte is i) interposed between the plurality of spaced-apart lithium storage layer segments and the positive electrode active material, and ii) at least partially disposed within the gaps separating the spaced-apart lithium storage layer segments.

[0009] According to another embodiment of the present disclosure, a method for manufacturing a lithium-ion battery cell includes providing an anode having a plurality of spaced-apart lithium storage layer segments in electrical contact with an anode current collector. At least upper surfaces of the lithium storage layer segments are in contact with a lithium-ion-containing solid-state electrolyte (SSE) material. A cathode is provided including: i) in electrical contact with the cathode current collector; and ii) an active cathode material layer in contact with the SSE material, such that the SSE material is interposed between the lithium storage layer segments and the active cathode material layer. [Brief explanation of the drawings]

[0010] [Figure 1A] FIG. 1A is a cross-sectional view of a non-limiting example of a negative electrode precursor according to some embodiments. [Figure 1B] FIG. 1B is a cross-sectional view of a non-limiting example of a negative electrode according to some embodiments. [Figure 1C] FIG. 1C is a cross-sectional view of a non-limiting example of a negative electrode according to some embodiments. [Figure 1D] FIG. 1D is a cross-sectional view of a precursor cell according to some embodiments. [Figure 1E] FIG. 1E is a cross-sectional view of a non-limiting example of a lithium-ion battery cell according to some embodiments. [Figure 1F] FIG. 1F is a top view of a non-limiting example of a segmented lithium storage layer according to some embodiments. [Figure 1G] FIG. 1G is a cross-sectional view of a non-limiting example of a negative electrode according to some embodiments. [Figure 2] FIG. 2 is a cross-sectional view of a prior art negative electrode. [Figure 3A] 3A and 3B are cross-sectional views illustrating a non-limiting example of the fabrication of a precursor cell. [Figure 3B] 3A and 3B are cross-sectional views illustrating a non-limiting example of the fabrication of a precursor cell. [Figure 3C] FIG. 3C is a cross-sectional view illustrating another non-limiting example of fabricating a precursor cell according to some embodiments. [Figure 3D]3D and 3E are cross-sectional views of another non-limiting example of fabricating a precursor cell according to some embodiments. [Figure 3E] 3D and 3E are cross-sectional views of another non-limiting example of fabricating a precursor cell according to some embodiments. [Figure 4] FIG. 4 is a cross-sectional view of a non-limiting example of a negative electrode according to some embodiments. [Figure 5A] 5A-5E are cross-sectional views of some non-limiting examples of all-solid-state cells using negative electrodes with segmented lithium storage layers. [Figure 5B] 5A-5E are cross-sectional views of some non-limiting examples of all-solid-state cells using negative electrodes with segmented lithium storage layers. [Figure 5C] 5A-5E are cross-sectional views of some non-limiting examples of all-solid-state cells using negative electrodes with segmented lithium storage layers. [Figure 5D] 5A-5E are cross-sectional views of some non-limiting examples of all-solid-state cells using negative electrodes with segmented lithium storage layers. [Figure 5E] 5A-5E are cross-sectional views of some non-limiting examples of all-solid-state cells using negative electrodes with segmented lithium storage layers. DETAILED DESCRIPTION OF THE INVENTION

[0011] (Detailed Description of the Invention) It should be understood that the drawings are for purposes of illustrating concepts of the present disclosure and may not be to scale. Terms such as "overlying," "over," and the like include, but do not necessarily require, direct contact (unless such direct contact is indicated or clearly required for functionality). Here, "average" may represent a mean, median, or mode, and "average thickness" may be based on at least three measurements. Additional details of specific embodiments of the present application can be found in U.S. Patent Application Publication Nos. 2019 / 0267631, 2020 / 0411851, 2021 / 0050584, 2021 / 0057733, 2021 / 0057757, 2021 / 0057755, 2021 / 0066702, and PCT International Publication Nos. WO2022 / 0100901 and WO2022 / 0100901. No. 005999, PCT International Publication No. WO2021 / 207357, PCT International Publication No. WO2023113813, U.S. Patent Application Publication No. 2022 / 0344627, PCT International Publication No. WO2023129408, PCT International Application No. PCT / US2023 / 024254, and PCT International Application No. PCT / US23 / 25773, the entire contents of which are incorporated herein by reference for all purposes.

[0012] Lithium ion batteries (LIBs) of the present disclosure may include a negative electrode, a solid-state electrolyte ("SSE"), and a positive electrode. In particular, the negative electrode includes multiple lithium storage layer segments. In some cases, such segments may be silicon-containing lithium storage segments. FIG. 1A is a cross-sectional view of a negative electrode precursor 100p according to some embodiments. XYZ coordinate axes are also provided for additional reference. The negative electrode precursor 100p may include a current collector 101 and a precursor lithium storage layer 107p overlying the current collector. In some cases, the precursor lithium storage layer may be a silicon-containing precursor lithium storage layer. The precursor lithium storage layer material has the ability to form an electrochemically reversible alloy with lithium. The current collector 101 may include a conductive layer 103 and may optionally further include a surface layer 105 disposed between the conductive layer 103 and the precursor lithium storage layer 107p. In some embodiments, the precursor lithium storage layer may include silicon, germanium, tin, or an alloy thereof. In some embodiments, the precursor lithium storage layer is a silicon-containing lithium storage layer that comprises at least 40 atomic % silicon, alternatively at least 80 atomic % silicon, or even at least 90 atomic % silicon.

[0013] In some embodiments, the top surface of precursor lithium storage layer 107p corresponds to top surface 108p of negative electrode precursor 100p. Precursor lithium storage layer 107p may optionally have an average precursor thickness T pThe precursor lithium storage layer 107p is in electrical and physical contact with the current collector 101. For convenience in the figures, the current collector is shown with a flat surface; however, as described elsewhere herein, the current collector may have a roughened surface. In some embodiments, the precursor lithium storage layer is provided by a physical vapor deposition (PVD) process (e.g., by sputtering or e-beam) or a chemical vapor deposition (CVD) process (e.g., including, but not limited to, hot-wire chemical vapor deposition (CVD) or plasma-enhanced chemical vapor deposition (PECVD)). In some embodiments, the precursor lithium storage layer 107p, or portions thereof, may comprise a continuous porous lithium storage layer. PVD and CVD, particularly PECVD, deposition methods are highly manufacturable because they may avoid many of the extra steps involved in traditional binder-based (particulate) lithium storage layers. Because the precursor lithium storage layer is relatively flat, it may be more robust to handling and compatible with other manufacturing processes than anodes made with binders, particulates, or high-aspect-ratio nanostructures (which may break or flake off more easily). For example, coating an SSE onto a precursor lithium storage layer deposited by PVD or CVD may be more robust than depositing it onto a nanostructured or particulate lithium storage layer.

[0014] In the present disclosure, a precursor lithium storage layer 107p, such as a continuous porous lithium storage layer, may be substantially free of high-aspect-ratio lithium storage nanostructures (e.g., in the form of spaced wires, pillars, tubes, etc.). FIG. 2 shows a cross-sectional view of a prior art anode 170 including some non-limiting examples of high-aspect-ratio lithium storage nanostructures, such as nanowires 190, nanopillars 192, and nanotubes 194, disposed on a current collector 180. Unless otherwise noted, the term “lithium storage nanostructure” herein generally refers to a lithium storage active material structure (e.g., a structure of silicon, germanium, or an alloy thereof) having at least one cross-sectional dimension, other than a dimension generally perpendicular to the underlying substrate (e.g., layer thickness), less than about 2,000 nm, excluding dimensions attributable to random pores and channels. Similarly, the terms “nanowire,” “nanopillar,” and “nanotube” refer to a wire, pillar, and tube, respectively, at least some of which have a diameter less than 2,000 nm. "High aspect ratio" nanostructures have an aspect ratio greater than 4:1. The aspect ratio is generally the feature height or length (which may be measured along a feature axis aligned at a 45-90 degree angle with respect to the underlying current collector surface) divided by the feature width (which may be measured generally perpendicular to the feature axis). In some embodiments, a lithium storage layer (e.g., a continuous porous lithium storage layer) is considered to be "substantially free" of high aspect ratio lithium storage nanostructures when the negative electrode has an average (e.g., mean, median, or mode) of less than 10 lithium storage nanostructures per 1600 square micrometers (where the number of lithium storage nanostructures is the sum of the number of nanowires, nanopillars, and nanotubes in the same unit area), and such lithium storage nanostructures have an aspect ratio of 4:1 or greater. Alternatively, such lithium storage nanostructures average less than 1 per 1600 square micrometers. In some embodiments, the negative electrode precursor may have patterned regions of precursor lithium storage layer 107p and other regions that may intentionally contain lithium storage nanostructures. In such cases, the term "substantially free" may refer only to certain regions of the lithium storage layer. As discussed below, the current collector may have high surface roughness or include nanostructures, but these features are separate from the lithium storage layer and are not considered to be or induce lithium storage nanostructures.

[0015] FIG. 1B is a cross-sectional view of a negative electrode 100 according to some embodiments. The negative electrode 100 includes a segmented lithium storage layer 107 including multiple silicon-containing lithium storage layer segments (107-1, 107-2, 107-3, and 107-4) defined by gaps or discontinuities 117. Note that the segments are not considered nanostructures herein (e.g., the height aspect ratio of the lithium storage layer segments is generally less than 4:1). In some embodiments, the discontinuities may extend through some or all of the lithium storage layer in an average direction approximately perpendicular (e.g., within 30° of perpendicular) to the surface of the current collector. The discontinuities may appear in an SEM cross section as cracks or fissures between the segments. The discontinuities 117 are illustrated as straight lines, but may appear as curved lines. A complete discontinuity is when there is no physical contact between adjacent segments. In some embodiments, segments may be in partial physical contact with adjacent segments, but the connectivity along the discontinuities may be weaker than the connectivity of the lithium storage material within a segment. That is, the discontinuities may be partial. The partial discontinuities may include some bridging regions corresponding to where the lithium storage layer material connects one segment to another. The partial physical contact may include spaced-apart segments having less than 50%, 40%, 30%, 20%, or 10% of the thickness of the segments in physical contact. The negative electrode 100 has the aforementioned current collector 101 including a conductive layer 103 and, optionally, a surface layer 105 interposed between the conductive layer 103 and a segmented lithium storage layer 107. In some embodiments, the negative electrode 100 may be formed from the negative electrode precursor 100p, for example, by inducing the formation of discontinuities in the precursor lithium storage layer. Such discontinuities may be caused by the application of pressure, temperature changes, bending forces, or the like. The separated lithium storage layer segments are characterized by an average lateral width LW and an average thickness T.

[0016] Alternatively, the anode 100 may be formed directly during PVD or CVD deposition of the lithium storage layer material. For example, as shown in FIG. 1C , the current collector may have grooves 104 or a patterned or structured surface layer such that discontinuous surfaces 117c are naturally formed during PVD or CVD deposition to produce an anode 100c having a segmented lithium storage layer 107c including segments (107-1c, 107-2c, 107-3c, and 107-4c).

[0017] In some embodiments, LIBs can be fabricated by heating the precursor cell. FIG. 1D is a cross-sectional view of a precursor cell according to some embodiments. The precursor cell 161 includes an anode 100, a cathode 140, and a solid-state electrolyte ("SSE") 130 disposed between the anode and cathode. The anode 100 may be as described with respect to FIG. 1A or 1C and includes an anode current collector 101 and a segmented lithium storage layer 107. The cathode 140 may include a cathode current collector 143 and a cathode active material layer 147 disposed in contact with the cathode current collector facing the lithium storage layer 107.

[0018] The solid electrolyte comprises lithium ions and is described in more detail elsewhere herein. It is worth noting that in some cases, the SSE may be reversibly convertible from a low-fluidity state (e.g., a glassy or solid state) below temperature T2 to a high-fluidity state (e.g., a fluid or liquid state) at temperature T1 or higher without degrading the desired properties of the SSE. For example, temperature T2 may be at least 40°C, and T1 is equal to or higher than T2. ​​Alternatively, the SSE may be a quasi-solid-state material that has some degree of fluidity at room temperature (e.g., under pressure without heating).

[0019] In some embodiments, referring now to FIG. 1E (also a cross-sectional view), the negative electrode and positive electrode current collectors may be connected to a voltage source (V), and the precursor cell may undergo one or more charge-discharge cycles, which may also be referred to herein as one or more voltage cycles. The voltage cycles include applying a relatively negative voltage (first voltage) to the negative electrode to cause at least partial lithiation of the negative electrode, followed by applying a relatively positive voltage (second voltage) to cause at least partial delithiation of the negative electrode. This may be referred to as electrochemical formation or treatment, and refers to a cycle performed prior to a normal use cycle of the completed cell functioning as a battery. Note that, when describing such initial cycles of the negative electrode or cell herein, terms such as “electrochemical formation,” “electrochemically forming,” and “electrochemically treating” may be interchangeable with terms such as “electrochemical treatment,” “electrochemically treating,” and “treatment.” It has been found that during electrochemical treatment, silicon-containing lithium storage layers (e.g., continuous porous lithium storage layers) tend to reconfigure as segmented lithium storage layers. In the present disclosure, some degree of segmentation of the lithium storage layer occurs prior to electrochemical processing, which may help guide further segmentation. Unlike milling, which renders much of the silicon unusable, the segmented lithium storage layer maintains high lithium storage activity. Without being bound by theory, the negative electrode of the present disclosure may expand primarily (but not necessarily exclusively) in the Z direction during lithiation, and upon delithiation, the negative electrode active material may also shrink in the Z direction and in the XY plane, such that the segmented lithium storage layer is reconstituted as a segmented lithium storage layer with more widely spaced segments than the original segmentation in FIGS. 1B and 1C. As a result, a segmented lithium storage layer 107′ is produced, including lithium storage segments (107-1′, 107-2′, 107-3′, and 107-4′).

[0020] During electrochemical processing, the precursor cell may optionally be heated to a temperature T1 to convert the SSE to a highly fluid state. Pressure 151 may optionally be applied during heating so that the lithium storage layer and the positive electrode active material layer press against the SSE. Pressure 151 may sometimes be characterized as a compressive force. Upon heating, the SSE material, in its highly fluid state, flows into the spaces between the lithium storage segments to form the modified SSE layer 130′. The SSE of the precursor cell should be provided in a volume sufficient to fill the subspaces and maintain physical separation of the positive electrode active material from the segmented lithium storage layer 107′. In some embodiments, a lithium ion conductive current separator (discussed elsewhere) may be added to ensure there is no contact between the negative and positive electrodes while the SSE is in its highly fluid state.

[0021] Upon cooling below temperature T2, the SSE may revert from the high-fluidity state to a low-fluidity state, e.g., become glassy or solid, and be partially fixed into the structure of the lithium-ion battery cell 165. In some cases, the pressure 151 (if used) may be reduced or eliminated after cooling, although in some embodiments the applied pressure 151 may be maintained or even increased.

[0022] As noted above, if the SSE is sufficiently fluid at room temperature, it is not necessary to heat the cell during electrochemical processing. Additionally, the SSE material may be a reactive material that crosslinks or polymerizes after or during electrochemical processing to partially fix the structure of cell 165.

[0023] The upper portion of the lithium storage layer 107′ and the lower portion of the positive electrode active material layer 147 of the LIB cell 165 may be closer in some cases than the precursor cell 161 of FIG. 1D. For example, the distance may be 5% to 10%, 10% to 15%, 15% to 20%, 20% to 25%, or more than 25% closer.

[0024] FIG. 1F is a top view of a non-limiting example of a segmented lithium storage layer 107′ including multiple lithium storage segments 107-x′. The dark lines 106 represent the dividing spaces. For clarity, other lithium-ion battery elements are not shown. In some embodiments, the dividing spaces may occupy 1-5% of the surface area of ​​the negative electrode (e.g., in a two-dimensional top-down view), or 5-10%, 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, or 35-40% of the surface area, or any combination of these ranges.

[0025] 1F shows a generally random pattern of lithium storage segments. In some other embodiments (not shown), the pattern may be more uniform, geometric, or partially or completely predetermined.

[0026] In some embodiments, rather than heating to T1 during electrochemical processing, heat may be applied thereafter to cause the SSEs in a highly fluid state to flow into the spaces between the segments. Whether heat is applied during or after electrochemical processing, in some embodiments, the completed battery cell may have normal operating conditions such that the SSEs generally remain in a less fluid state; that is, the SSEs do not change to a more fluid state during normal use (charging and discharging). Alternatively, there may be occasional or more frequent heating to T1 during normal cell operation.

[0027] FIG. 1G is another cross-sectional view showing an anode 100′ formed as described with respect to FIG. 1E. FIG. 1G may be similar to FIG. 1E, but for clarity, the SSE and the cathode are not shown in FIG. 1G. An SEI (“solid-electrolyte-interphase”) layer 127 may be formed on the lithium storage layer segment. The SEI layer may be formed by partial decomposition or reaction of the SSE during electrochemical cycling. The SEI is generally electrically insulating but ionically conductive, thereby allowing lithium ions to pass through. The SEI may reduce decomposition of the SSE during subsequent electrochemical cycling.

[0028] FIG. 1G also illustrates some dimensional characteristics that the segmented storage layer 107′ may have after electrochemical processing. For example, segments 107-x′ may be characterized by an average lateral width LW′ and an average thickness T′, which may be approximately the same as or different from the initial average lateral width LW and average thickness T of the segmented storage layer 107 (e.g., from FIG. 1B, FIG. 1C, or some other segmented storage layer prior to electrochemical processing). In some cases, LW′ and T′ may be measured to include the SEI thickness, but alternatively, they may be measured excluding the SEI thickness. As shown in FIGS. 1E and 1G, LW′ may in some cases be smaller than LW and / or the average spacing between segments may be larger in lithium storage layer 107′ than in 107.

[0029] In some embodiments, for most lithium storage segments within at least one 1 mm x 1 mm area of ​​the negative electrode, the ratio of the average lateral width LW' (or LW) of the lithium storage layer segments to the average thickness T' (or T) of the lithium storage layer segments, i.e., the ratio of LW' / T' or LW / T, may be at least 0.3. In some embodiments, such ratio of LW' / T' or LW / T may be less than 50. In some embodiments, the ratio of LW' / T' or LW / T can be in the range of 0.3 to 0.4, alternatively 0.4 to 0.5, alternatively 0.5 to 0.75, alternatively 0.75 to 1.0, alternatively 1.0 to 1.5, alternatively 1.5 to 2, alternatively 2 to 3, alternatively 3 to 4, alternatively 4 to 5, alternatively 5 to 7, alternatively 7 to 10, alternatively 10 to 15, alternatively 15 to 20, alternatively 20 to 25, alternatively 25 to 30, alternatively 30 to 40, alternatively 40 to 50, or any combination of these ranges, or can be greater than 50.

[0030] 1E, by having the SSE adjacent to the sidewall of the lithium storage segment in addition to the top surface, the SSE can contact a larger surface area of ​​the lithium storage material. This can result in faster charging or discharging of the negative electrode during operation than if the SSE contacted only the top surface of the lithium storage layer or segmented layer. The segmentation and increased surface area contacted by the SSE can reduce other cycling stresses and extend cycle life.

[0031] Numerous methods are available for manufacturing precursor cells. FIGS. 3A and 3B are cross-sectional views illustrating one non-limiting example of how to fabricate a precursor cell according to some embodiments. In FIG. 3A , an SSE 330 may be extruded onto an anode 300 from an extruder, which may include an extrusion nozzle as part 335. The anode 300 may have a current collector 301 including a conductive layer 303 and a surface layer 305. The anode 300 further has a segmented lithium storage layer 307 disposed on the current collector 301. The extruded SSE material may be in a relatively flowable state at the nozzle. When the extruded SSE material contacts the lithium storage layer, it may optionally cool and change to a less flowable state. In some embodiments, the anode may optionally undergo active temperature control as it is extruded. In some cases, the anode may be actively heated before, during, or after extrusion, for example, to maintain the SSE above its flow temperature. Alternatively, for example, the negative electrode may be actively cooled so that the extruded SSE material quickly falls below its flow temperature. In some cases, the extruded SSE material may contain one or more solvents that evaporate or are driven off to reduce the flowability of the SSE after application to the negative electrode.

[0032] In FIG. 3B , a cathode 340 having a cathode current collector 343 and an active cathode material layer 347 can be laminated to the SSE 330. In particular, the surface of the active cathode material layer 347 can be in contact with the top surface of the SSE 330. Such lamination can optionally include heating to improve adhesion between the SSE 330 and the active cathode material layer 347. Such heating can optionally include an elevated temperature to convert at least an interfacial portion of the SSE adjacent to the cathode to a more fluid state. Lamination can further include applying some pressure between the anode and cathode. In some embodiments, in addition to or instead of heating, a solvent material can be applied to soften at least the surface of the SSE 330 and promote adhesion to the active cathode material layer 347.

[0033] In another embodiment of FIG. 3A , rather than being extruded, the SSE material may instead be coated from a mixture that includes a solvent that is removed by drying. Portion 335 may represent a coating head. Some non-limiting examples of coating processes may include gravure, slot die, spray, dip coat, inkjet, flexographic, rod, or blade coating methods. In some other embodiments, the SSE material may be a free-standing film that is laid down on the negative electrode and laminated to it during lamination of the positive electrode. In some cases, the SSE material may be transferred from a donor sheet.

[0034] 3C is a cross-sectional view of another non-limiting example of fabricating a precursor cell according to some embodiments. An SSE layer 330 is first applied to a cathode 340 having a cathode current collector 343 and an active cathode material layer 347 disposed between the cathode current collector 343 and the SSE layer 330. This structure and an anode 300 may then be optionally laminated at elevated temperature and / or pressure to form a structure that may resemble precursor cell 161 of FIG. 1A. Although not shown, after applying a portion of the SSE layer to the cathode and a portion of the SSE layer to the anode, the two structures may be laminated to form the precursor cell.

[0035] 3D and 3E are cross-sectional views of another non-limiting example of fabricating a precursor cell according to some embodiments. Referring to FIG. 3D, in an embodiment that may be similar to FIG. 3A, an SSE layer may be applied to a lithium storage layer 307, followed by deposition of a cathode active material layer 347 (e.g., from a slurry or by extrusion). Alternatively, layers 330 and 347 may be a free-standing bilayer film laminated onto the lithium storage layer. Referring to FIG. 3E, a cathode current collector 343 may be deposited (e.g., by physical vapor deposition of a conductive material) or laminated to the structure from FIG. 3D (e.g., by laminating a free-standing conductive material).

[0036] The lamination method may optionally include nip rollers, which may be heated. Furthermore, it should be recognized that the negative and positive electrodes are often coated on both sides of their respective current collectors with their respective active battery materials (e.g., a lithium storage layer for the negative electrode and a cathode active material for the positive electrode). While the figures illustrate single-sided negative and positive electrode structures, similar teachings can be applied to negative and positive electrodes coated on both sides of their respective current collectors.

[0037] In some embodiments, the segmented lithium storage layer may have larger gaps and discontinuities than those shown in FIGS. 1B and 1C prior to assembly into a LIB cell. For example, FIG. 4 is a cross-sectional view of a non-limiting example of a negative electrode according to some embodiments. The negative electrode 400 has a segmented lithium storage layer 407 including multiple lithium storage layer segments 407-1, 407-2, 407-3, and 407-4 defined by gaps or discontinuities 417. The segmented lithium storage layer may be characterized by an average lateral length LW and a thickness W. The negative electrode 400 may have a current collector 401 including a conductive layer 403 and, optionally, a surface layer 405 interposed between the conductive layer 403 and the segmented lithium storage layer 407. The discontinuities 417 may be characterized by an average spacing S measured between the lithium storage layer segments. Such spacing S may, in some cases, be measured at or near (e.g., within 10%) the bottom of the lithium storage layer segment, or alternatively, midway (e.g., at about T / 2) or at or near (e.g., within 10%) the top of the lithium storage layer segment. In some embodiments, S may be in the range of 10-20 nm, 20-50 nm, 50-100 nm, 100-200 nm, 200-300 nm, 300-500 nm, 500-700 nm, 700 nm-1 μm, 1-2 μm, 2-3 μm, 3-5 μm, 5-7 μm, 7-10 μm, 10-12 μm, 12-15 μm, 15-20 μm, or any combination of these ranges. In some cases, for example, when measured across a 1 mm cross-sectional distance of the negative electrode, the sum of the individual spacings S may occupy 1-5% of the cross-sectional distance, alternatively 5-10%, 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, or 35-40% of the cross-sectional distance, or any combination of these ranges. The cross-sectional distance may be about 50% of the average thickness of the storage layer segments.

[0038] The spaces or segments may form a random pattern in some cases, or alternatively, may form a recognizable geometric pattern. In some embodiments, the pattern of spaces and segments may be partially or completely predetermined. Negative electrode 400 can be prepared in a variety of ways.

[0039] In some embodiments, the lithium storage layer segments may be pattern-deposited onto the current collector. For example, the lithium storage layer may be deposited by CVD or PVD through a shadow mask having a pattern corresponding to the desired pattern of segments and spaces. In some cases, the surface layer may be patterned so that the lithium storage layer material selectively forms an adhesive deposit on the surface layer, for example, as described in U.S. Patent 11,024,842, the entire contents of which are incorporated herein by reference for all purposes. In some embodiments, the lithium storage layer segments may be pre-patterned on a donor sheet and transferred to the current collector. In some cases, the lithium storage layer segments may be electrodeposited through a patterned photoresist (e.g., it is known that silicon, tin, and / or germanium can each be electrodeposited from solution). In some cases, the lithium storage layer segments may be pattern printed (e.g., by inkjet, offset, gravure, flexography, or some other printing technique) from a mixture or slurry containing a high weight percent (e.g., at least 40% by weight, or alternatively at least 50%, 60%, 70%, or 80% by weight) of silicon, tin, or germanium, and dried or sintered.

[0040] In some cases, lithium storage layer segments can be formed from a negative electrode precursor, such as those described with respect to FIG. 1A. For example, lithium storage layer material can be removed by patterned laser ablation or by etching through a patterned resist material to form spaced-apart lithium storage layer segments. In some cases, the negative electrode precursor can undergo an electrochemical pretreatment in a liquid electrolyte, including (full or partial) lithiation and (full or partial) delithiation. It has been found that such electrochemical cycling can form a segment structure such as that shown in FIG. 1G, particularly for lithium storage layers having high silicon and / or silicon-containing films, e.g., greater than 50 atomic %, deposited by a CVD process (e.g., PECVD) or PVD.

[0041] In addition to forming a cell structure such as that shown in FIG. 1E, a segmented lithium storage layer with several gaps enables many other useful cell structure options. FIGS. 5A-5E are cross-sectional views of several non-limiting examples of all-solid-state lithium-ion battery cells using a negative electrode with a segmented lithium storage layer. Each of these figures includes a negative electrode 500 having a segmented lithium storage layer 507 (individual segments are not labeled) disposed on a current collector 501 (optional surface layer not shown). The cell includes a positive electrode 541 including a current collector 543 and a positive electrode active material layer 547 disposed thereon, and a solid electrolyte layer 530 interposed between the positive electrode active material layer 547 and the segmented lithium storage layer 507.

[0042] In FIG. 5A, LIB cell 565a shows SSE layer 530 disposed on lithium storage layer 507, but unlike FIG. 1D, it is substantially absent from the discontinuities or interstices 517 between lithium storage layer segments (e.g., less than 10% of the segment's void volume is occupied by SSE material). In some cases, cell 565a represents a state before electrochemical cycling, and after cycling, the interstices are partially or entirely filled with SSE material, as in FIG. 1D. Alternatively, the SSE material may not substantially flow during cycling, and cell 565a may represent a state after several cycles. In such cases, interstices 517 can provide lateral space for the lithium storage segments to expand during lithiation.

[0043] Referring to Figure 5B, cell 565b is similar to cell 565a of Figure 5A, except that the volume of discontinuities or gaps 517b is partially filled with SSE material. For example, the void volume of the segment occupied by SSE material may be in the range of 10-25%, 25-50%, 50-75%, 75-90%, or any combination of these ranges. Cell 565b may represent a pre-cycling or post-cycling state.

[0044] In some embodiments, an SSE may include two or more layers of different SSE materials. In FIG. 5C, cell 565c includes multiple SSE materials. A first SSE layer 530-1 including a first SSE material is disposed adjacent to the negative electrode. In this illustration, the first SSE material also substantially fills the interstitial volume between the lithium storage layer segments; however, in some other embodiments, the first SSE material may only partially fill or not substantially fill such interstitial volume. Alternatively, the first SSE material may substantially fill only the interstitial volume. A second SSE layer 530-2 including a second SSE material is disposed on the first SSE layer. Optionally, a third SSE layer 530-3 including a third SSE material may be disposed between the second SSE layer 530-2 and the positive electrode active material layer 547. The third SSE material has a different chemical structure from the second SSE material. The third SSE material may also have a different chemical structure than the first SSE material, although in some cases the first and third SSE materials may be substantially identical in terms of chemical composition.

[0045] The materials and properties of each SSE layer can be independently selected, and adjacent SSE layers typically differ in some way. Such properties include thickness, elasticity, compressibility, viscosity, melting point, lithium ion conductivity, electrical conductivity, lithium ion concentration, lithium counterions, crosslinkers, additives, chemical composition, composition gradients, and the like. Each SSE layer can be applied by the same coating / application method or by a different method. In some embodiments, the first SSE layer 530-1 can have higher elasticity, higher compressibility, and / or lower viscosity than the second or third SSE layer. In other embodiments, opposite properties can exist. In some cases, the SSE layer adjacent to the positive electrode active material can have lower elasticity, lower compressibility, and / or higher viscosity than at least the SSE layer adjacent to the negative electrode. In other cases, opposite properties can exist. In some embodiments, instead of three SSE layers, there can be only two, or alternatively, four or more SSE layers. In some cases, the first SSE layer 530-1 includes a solid polymer electrolyte, and the second SSE layer 530-2 includes a solid inorganic electrolyte, such as a solid sulfide. In such embodiments, the optional third SSE layer 530-3 may include a solid polymer electrolyte, a solid inorganic electrolyte, or a hybrid electrolyte. In some cases, the space between the lithium storage segments is filled with one type of SSE material, and the surfaces (facing the positive electrode) of the lithium storage segments are adjacent to another type of SSE material. The SSE provided in the interstitial volume may be referred to herein as the interstitial solid electrolyte material. In FIG. 5C, the interstitial solid electrolyte material may have a different chemical structure from at least a portion of the SSE material interposed between the lithium storage layer segments and the positive electrode active material layer.

[0046] Referring to FIG. 5D , cell 565d may include other types of functional materials 570 (other than SSE material) disposed in the spaces between the lithium storage segments. While shown as substantially filling the spaces, in other cases, only a portion may be filled with the functional material, other portions with the SSE material, or perhaps no material other than gas (or all three). The functional material may, in some cases, be an active anode material other than that of the lithium storage layer segments. In some embodiments, the functional material may include a conductive material such as conductive carbon, graphene, carbon nanotubes, metal nanoparticles, or metal nanowires. In some embodiments, the functional material may include a polymeric binder combined with a conductive material and / or another active anode material. In some embodiments, the functional material may include an insulating, compressible polymer that may provide some structural support to the lithium storage layer segments during expansion and contraction caused by lithiation and delithiation (cycling).

[0047] In FIG. 5E, cell 565e includes a second lithium storage layer 580 disposed on segmented lithium storage layer 507, at least partially filling the gaps between the lithium storage segments. An SSE layer 530 is disposed on second lithium storage layer 580. The second lithium storage layer includes a different lithium storage material than lithium storage layer 507 and may include graphite, silicon, tin, germanium, or other practical lithium storage materials. In some cases, the second lithium storage layer may be coated from a slurry (which may include binders, conductive agents, etc.). In some embodiments, the second lithium storage layer is deposited by a PVD or CVD process (which may optionally include PECVD). The second lithium storage layer may be selected to have a composition that is more compatible (chemically or physically) with SSE layer 530 than lithium storage layer 507, which may improve cycle life and calendar life. Using multiple negative electrode active materials can also increase charge capacity and enable a wider range of charge / discharge rates.

[0048] (Negative electrode current collector) In some embodiments, the current collector or conductive layer may be characterized by a tensile strength Rm or a yield strength Re. In some cases, the tensile strength and yield strength properties of the current collector depend primarily on the conductive layer, which in some embodiments may be thicker than any surface layer. Too high or too low a tensile strength can lead to handling difficulties during manufacturing, such as in a roll-to-roll process. During electrochemical cycling of the negative electrode, too low a tensile strength can result in deformation of the negative electrode, or too high a tensile strength can impair the adhesion of the lithium storage layer.

[0049] Negative electrode deformation is not necessarily an issue in all products; such deformation may occur only at higher capacities, i.e., higher loadings of lithium storage layer material. For such products, the current collector or conductive layer, as the case may be, is characterized by a tensile strength Rm in the range of 100-150 MPa, alternatively 150-200 MPa, alternatively 200-250 MPa, alternatively 250-300 MPa, alternatively 300-350 MPa, alternatively 350-400 MPa, alternatively 400-500 MPa, 500-600 MPa, 600-700 MPa, 700-800 MPa, 800-900 MPa, 900-1000 MPa, 1000-1200 MPa, 1200-1500 MPa, or any combination of these ranges.

[0050] In some embodiments, significant negative electrode deformation should be avoided, but low battery capacity may not be acceptable, for example, when the negative electrode contains amorphous silicon of 7 μm or greater and / or the electrochemical cycling capacity is less than 1.5 mAh / cm. 2If the tensile strength (Rm) is greater than 450 MPa, alternatively, greater than 500 MPa, alternatively, greater than 550 MPa, or alternatively, greater than 600 MPa, the current collector or conductive layer can be selected to be characterized by a tensile strength (Rm) of greater than 450 MPa, alternatively, greater than 500 MPa, alternatively, greater than 550 MPa, or alternatively, greater than 600 MPa. In such embodiments, the tensile strength may be in the range of about 450-500 MPa, alternatively, 500-550 MPa, alternatively, 550-600 MPa, alternatively, 600-650 MPa, alternatively, 650-700 MPa, alternatively, 700-750 MPa, alternatively, 750-800 MPa, alternatively, 800-850 MPa, alternatively, 850-900 MPa, alternatively, 900-950 MPa, alternatively, 950-1000 MPa, alternatively, 1000-1200 MPa, alternatively, 1200-1500 MPa, or any combination of ranges therein. In some embodiments, the current collector or conductive layer may have a tensile strength greater than 1500 MPa. In some embodiments, the current collector or conductive layer is in the form of a foil having a tensile strength greater than 600 MPa and an average thickness ranging from 4 to 8 μm, alternatively from 8 to 10 μm, alternatively from 10 to 14 μm, alternatively from 14 to 18 μm, alternatively from 18 to 20 μm, alternatively from 20 to 25 μm, alternatively from 25 to 30 μm, alternatively from 30 to 40 μm, alternatively from 40 to 50 μm, or any combination of these ranges.

[0051] In some embodiments, the conductive layer is at least 10 3 S / m, or at least 10 6 S / m, or at least 10 7 The conductive layer may have a conductivity of 0.15 S / m and may comprise an inorganic conductive material or an organic conductive material, or a combination thereof. For negative electrodes with low capacity and / or where there is no concern about deformation of the negative electrode during use, a wide variety of conductive materials can be used as the conductive layer.

[0052] In some embodiments, the conductive layer comprises a metallic material, such as titanium (and its alloys), nickel (and its alloys), copper (and its alloys), or stainless steel. In some embodiments, metals that can typically react or alloy with lithium, such as tin or aluminum, may also be suitable, provided the surface layer is sufficiently protected. In some embodiments, the conductive layer may comprise a multilayer structure (e.g., multiple layers of metal). In some embodiments, the conductive layer may be a clad foil. In some embodiments, the conductive layer comprises a conductive carbon, such as carbon black, carbon nanotubes, graphene, graphene oxide, reduced graphene oxide, or graphite. In some embodiments, the conductive layer may be in the form of a foil, mesh, fiber, cloth, or sheet of conductive material. Here, "mesh" includes any conductive structure with openings, such as those found in woven wires, foam structures, foils with an array of holes, etc. In some embodiments, the conductive layer may comprise multiple layers of different conductive materials. The conductive layer may be in the form of a layer deposited on an insulating substrate (e.g., a polymer sheet or ceramic substrate coated with a conductive material, including, but not limited to, nickel or copper, optionally on both sides). In some embodiments, the conductive layer comprises a mesh or sheet of conductive carbon, including but not limited to those formed from bundled carbon nanotubes or nanofibers, carbon fiber or cloth.

[0053] If a higher tensile strength is desired (e.g., Rm greater than 450 MPa, or greater than 500 MPa, or greater than 550 MPa, or greater than 600 MPa), the conductive layer may comprise an alloy of nickel (and its alloys) or copper, such as, for example, brass (an alloy based on copper and zinc), bronze (an alloy based on copper and tin), CuMgAgP (an alloy based on copper, magnesium, silver, and phosphorus), CuFeP (an alloy based on copper, iron, and phosphorus), CuNiSi (an alloy based on copper, nickel, and silicon), CuCrZr (an alloy based on copper, chromium, and zirconium), or CuCrSiTi (an alloy based on copper, chromium, silicon, and titanium). The nomenclature for metal alloys is not the stoichiometric molecular formula used in chemistry, but rather is that used by one of ordinary skill in the alloy art. For example, CuNi3Si does not mean that for every atom of copper there are three atoms of nickel and one atom of silicon. In some embodiments, these nickel- or copper-based high tensile strength conductive layers may comprise roll-formed nickel or copper alloy foils.

[0054] Alternatively, a mesh or sheet of conductive carbon, including but not limited to those formed from bundled carbon nanotubes or nanofibers, can provide a conductive layer with higher tensile strength in some cases. In some embodiments, an intermediate layer of conductive metal may be interposed between the conductive carbon and the surface layer.

[0055] In some embodiments, any of the above-described conductive layers (low tensile strength or high tensile strength) may function as the primary conductive layer and may further include a conductive intermediate layer (e.g., a metal intermediate layer) disposed between the primary conductive layer and the surface layer. For example, the conductive layer may be similar to that described in PCT International Publication No. WO2022 / 005999, which is incorporated herein by reference in its entirety for all purposes.

[0056] The metal interlayer can be applied by, for example, sputtering, vapor deposition, electrolytic plating, electroless plating, or any convenient method. The metal interlayer generally has an average thickness that is less than 50% of the average thickness of the entire conductive layer, i.e., the combined thickness of the primary conductive layer and the metal interlayer. In some embodiments, the surface layer forms more uniformly on or adheres better to the metal interlayer than to the primary conductive layer.

[0057] (General surface roughness) In some embodiments, the current collector may be characterized as having a surface roughness. In some embodiments, for example, referring to FIG. 1B, the top surface 108 of the lithium storage layer 107 may have a surface roughness that is less than the surface roughness of the current collector 101. Here, the comparison and measurement of surface roughness is based on the roughness average (R a ), RMS roughness (R q ), maximum peak height (R p ), average maximum height (R z ) or peak density (P c In some embodiments, the current collector may have a surface roughness R z ≧2.5μm and surface roughness R a In some embodiments, R z is in the range of 2.5 to 3.0 μm, alternatively 3.0 to 3.5 μm, alternatively 3.5 to 4.0 μm, alternatively 4.0 to 4.5 μm, alternatively 4.5 to 5.0 μm, alternatively 5.0 to 5.5 μm, alternatively 5.5 to 6.0 μm, alternatively 6.0 to 6.5 μm, alternatively 6.5 to 7.0 μm, alternatively 7.0 to 8.0 μm, alternatively 8.0 to 9.0 μm, alternatively 9.0 to 10 μm, 10 to 12 μm, 12 to 14 μm, or any combination of these ranges. nis in the range of 0.25 to 0.30 μm, alternatively 0.30 to 0.35 μm, alternatively 0.35 to 0.40 μm, alternatively 0.40 to 0.45 μm, alternatively 0.45 to 0.50 μm, alternatively 0.50 to 0.55 μm, alternatively 0.55 to 0.60 μm, alternatively 0.60 to 0.65 μm, alternatively 0.65 to 0.70 μm, alternatively 0.70 to 0.80 μm, alternatively 0.80 to 0.90 μm, alternatively 0.90 to 1.0 μm, alternatively 1.0 to 1.2 μm, alternatively 1.2 to 1.4 μm, or any combination of these ranges.

[0058] In some embodiments, some or most of the surface roughness of the current collector may be imparted by the conductive layer and / or the metallic interlayer. Alternatively, some or most of the surface roughness of the current collector may be imparted by the surface layer. Alternatively, some combination of the conductive layer, metallic interlayer, and surface layer may substantially contribute to the surface roughness.

[0059] In some embodiments, the conductive layer may include roughened features (e.g., electrodeposited roughened features) to increase surface roughness. In some embodiments, the electrodeposited roughened features may include copper features. The current collector roughened features may optionally take the form of nodules, hemispheroids, nanopillars, dendrites, etc. In some cases, the roughened features may be characterized by a height H and a maximum width extending from the conductive layer. In some embodiments, the roughened features may be characterized by a height H in the range of about 0.1 μm to 0.2 μm, alternatively 0.2 μm to 0.4 μm, alternatively 0.4 μm to 0.6 μm, alternatively 0.6 μm to 0.8 μm, alternatively 0.8 μm to 1.0 μm, 1.0 μm to 1.5 μm, alternatively 1.5 μm to 2 μm, alternatively 2 μm to 3 μm, alternatively 3 μm to 4 μm, alternatively 4 μm to 5 μm, or any combination of these ranges. In some embodiments, the roughened features may be characterized by a maximum width W in the range of about 0.1 μm to 0.2 μm, alternatively 0.2 μm to 0.4 μm, alternatively 0.4 μm to 0.6 μm, alternatively 0.6 μm to 0.8 μm, alternatively 0.8 μm to 1.0 μm, alternatively 1.0 μm to 1.5 μm, alternatively 1.5 μm to 2 μm, alternatively 2 μm to 3 μm, or any combination of these ranges. In some cases, the roughened features may be characterized by an aspect ratio H / W in the range of about 0.8 to 1.0, alternatively 1.0 to 1.5, alternatively 1.5 to 2.0, alternatively 2.0 to 2.5, alternatively 2.5 to 3, alternatively 3 to 4, alternatively 4 to 5, alternatively 5 to 6, alternatively 6 to 8, alternatively 6 to 10, or any combination of ranges thereof. In some embodiments, the average 10 μm×10 μm surface of the conductive layer may include at least 3 roughened features, alternatively at least 4 roughened features, alternatively at least 5 roughened features, alternatively at least 6 roughened features, alternatively at least 7 roughened features, alternatively at least 8 roughened features, alternatively at least 9 roughened features, alternatively at least 10 roughened features.

[0060] Alternatively, or in combination with the roughening feature, the conductive layer may be subjected to another electrochemical, chemical, or physical treatment to impart the desired surface roughness prior to the formation of the surface layer.

[0061] In some embodiments, roughening of the conductive layer may include, for example, physical abrasion (sandpaper, sandblasting, polishing, etc.), ablation (laser ablation, etc.), embossing, stamping, casting, imprinting, chemical treatment, electrochemical treatment, or heat treatment. In some cases, such roughening can be used to form one or more of the roughened features described above, such as nodular features, nanopillar features, broad roughened features, pit features, etc. In some cases, the roughened features can be random or patterned.

[0062] (Surface layer) In some embodiments, the surface layer can provide a chemical composition that promotes the formation of an adherent lithium storage layer, such as a lithium storage layer deposited by a CVD or PVD process, particularly at commercially useful lithium storage layer loadings or thicknesses. In some cases, deposition onto a conductive layer alone may be insufficient to provide even initial adhesion such that the lithium storage layer material can be easily brushed or peeled off. Even satisfactory initial adhesion may be insufficient during electrochemical formation and cycling. Some non-limiting examples of surface layers are described below. In some cases, the surface layer may include two or more different surface underlayers having different chemical compositions. In some cases, the surface layer or even the surface underlayer may include a mixture of different surface layer materials.

[0063] In some embodiments, the thickness of the surface layer may be as small as a monolayer. In some embodiments, the thickness of the surface layer may be in the range of 0.0001 μm to 0.0002 μm, alternatively 0.0002 μm to 0.0005 μm, alternatively 0.0005 μm to 0.001 μm, alternatively 0.001 μm to 0.005 μm, alternatively 0.002 μm to 0.005 μm, alternatively 0.005 μm to 0.01 μm, alternatively 0.01 μm to 0.02 μm, alternatively 0.02 μm to 0.03 μm, alternatively 0.03 μm to 0.05 μm, alternatively 0.05 μm to 0.1 μm, alternatively 0.1 μm to 0.2 μm, alternatively 0.2 μm to 0.5 μm, alternatively 0.5 μm to 1 μm, alternatively 1 μm to 2 μm, alternatively 2 μm to 5 μm, or any combination of these ranges.

[0064] In some embodiments, the surface layer or the underlayer may comprise a metal-oxygen compound. In some cases, the metal-oxygen compound may comprise a metal oxide or metal hydroxide (e.g., a transition metal oxide or transition metal hydroxide). In some cases, the metal-oxygen compound may comprise an oxometalate (e.g., a transition metal oxometalate). In some embodiments, the surface layer may comprise a silicon compound including or derived from a siloxane, a silane (i.e., a silane-containing compound), a silazane, or a reaction product thereof. Here, "silicon compound" does not include simple elemental silicon, such as amorphous silicon. These materials are described in more detail below. In some embodiments, the surface layer may comprise a silicate compound. In some embodiments, the surface layer may comprise a metal silicide (e.g., a transition metal silicide). In some embodiments, the surface layer may comprise a metal chalcogenide, such as a metal sulfide (e.g., a transition metal sulfide).

[0065] (metal-oxygen compounds) In some embodiments, the surface layer or the under-surface layer comprises a metal-oxygen compound. The metal-oxygen compound may comprise an alkali metal, alkaline earth metal, transition metal, or post-transition metal. Unless otherwise specified, the term "transition metal" as used anywhere in this application includes any element from Groups 3 to 12 of the periodic table, including the lanthanides and actinides. The metal-oxygen compound may comprise a metal oxide, a metal hydroxide, an oxometalate, or a mixture thereof. In some cases, the metal-oxygen compound may comprise a transition metal oxide, a transition metal hydroxide, a transition metal oxometalate, or a mixture thereof. In some embodiments, a metal interlayer may be provided between the conductive layer and the surface layer comprising the metal-oxygen compound. In some embodiments, the metal interlayer may be a transition metal. In some cases, the metal interlayer may comprise zinc, nickel, or an alloy of zinc and nickel. The interlayer may be considered part of the conductive layer, such that the metal interlayer is interposed between the surface layer and the remainder of the underlying conductive layer.

[0066] (metal oxides) In some embodiments, the surface layer or the under-surface layer may comprise a metal oxide. In some embodiments, the metal oxide may comprise a transition metal oxide. In some embodiments, the metal oxide may comprise an oxide of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zinc, molybdenum, tungsten, silver, zirconium, tantalum, hafnium, tin, aluminum, indium, or niobium. In some embodiments, the metal oxide may be a conductive doped oxide, including, but not limited to, indium-doped tin oxide (ITO) or aluminum-doped zinc oxide (AZO). In some embodiments, the metal oxide may comprise an alkali metal oxide or an alkaline earth metal oxide. In some embodiments, the metal oxide may comprise an oxide of lithium. The metal oxide may comprise a mixture of metal oxides. For example, "oxide of nickel" may optionally include other metal oxides in addition to nickel oxide. In some embodiments, the metal oxide comprises an oxide of an alkali metal (e.g., lithium or sodium) or alkaline earth metal (e.g., magnesium or calcium) along with an oxide of a transition metal (e.g., titanium, nickel, or copper). In some embodiments, the metal oxide may contain an amount of hydroxide, such that the ratio of oxygen atoms in the form of hydroxide to oxide is 1:1 or less, or 1:2 or less, or 1:3 or less, or 1:4 or less, respectively. The metal oxide may include stoichiometric oxides, non-stoichiometric oxides, or both. In some embodiments, the metal within the metal oxide may exist in multiple oxidation states. Oxometalates are generally considered a subclass of metal oxides. For clarity, reference herein to "metal oxide" for use in a surface or underlayer excludes oxometalates unless otherwise specified.

[0067] In some embodiments, a surface or underlayer of a metal oxide may be at least 1 monolayer thick, or at least 2, 3, 5, or 10 monolayers thick. In some embodiments, a surface or underlayer comprising a metal oxide material may have an average thickness of at least 0.1 nm, or at least 0.2 nm. In some embodiments, a surface or underlayer comprising a metal oxide material may have an average thickness of less than 5000 nm, or less than 3000 nm. In some embodiments, a surface layer or an underlayer comprising a metal oxide material may have an average thickness in the range of 0.1 to 0.2 nm, alternatively 0.2 to 0.5 nm, alternatively 0.5 to 1 nm, alternatively 1 to 2 nm, alternatively 2 to 5 nm, alternatively 5 to 10 nm, alternatively 10 to 20 nm, alternatively 20 to 50 nm, alternatively 50 to 100 nm, alternatively 100 to 200 nm, alternatively 200 to 500 nm, alternatively 500 to 1000 nm, alternatively 1000 to 1500 nm, alternatively 1500 to 2000 nm, alternatively 2000 to 2500 nm, alternatively 2500 to 3000 nm, alternatively 3000 to 4000 nm, alternatively 4000 to 5000 nm, or any combination of these ranges.

[0068] In some embodiments, the metal oxide can be formed by atomic layer deposition (ALD), chemical vapor deposition (CVD), thermal evaporation, or sputtering. In some cases, the metal oxide may be formed by coating a suspension of metal oxide particles. In some embodiments, the metal oxide may be electrolytically deposited or electrolessly deposited (which may include "electroless plating").

[0069] In some embodiments, the metal oxide precursor composition may be coated or printed onto a current collector having one or more surface primer layers as described above, and then processed to form the metal oxide. Some non-limiting examples of metal oxide precursor compositions include sol-gels (metal alkoxides), metal carbonates, metal acetates (including organic acetates), metal hydroxides, and metal oxide dispersions. The metal oxide precursor composition may be heat-treated to form the metal oxide.

[0070] (metal hydroxide) In some embodiments, the surface layer or the under-surface layer may comprise a metal hydroxide. In some embodiments, the metal hydroxide may comprise a transition metal hydroxide. In some embodiments, the metal hydroxide may comprise a hydroxide of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zinc, molybdenum, tungsten, silver, zirconium, tantalum, hafnium, tin, aluminum, indium, or niobium. In some embodiments, the metal hydroxide may comprise an alkali metal hydroxide or an alkaline earth metal hydroxide. In some embodiments, the metal hydroxide may comprise a hydroxide of lithium. The metal hydroxide may comprise a mixture of metal hydroxides. For example, "hydroxide of nickel" may optionally include hydroxides of other metals in addition to nickel hydroxide. In some embodiments, the metal hydroxide comprises a hydroxide of an alkali metal (e.g., lithium or sodium) or an alkaline earth metal (e.g., magnesium or calcium) along with a hydroxide of a transition metal (e.g., titanium, nickel, or copper). In some embodiments, the metal hydroxide underlayer may include an amount of oxide such that the ratio of oxygen atoms in the form of oxide to hydroxide is less than 1 to 1, or less than 1 to 2, or less than 1 to 3, or less than 1 to 4, respectively. The metal hydroxide may include stoichiometric hydroxides, non-stoichiometric hydroxides, or both. In some embodiments, the metal within the metal hydroxide may exist in multiple oxidation states.

[0071] In some embodiments, a surface or underlayer of metal hydroxide may be at least 1 monolayer thick, or at least 2, 3, 5, or 10 monolayers thick. In some embodiments, a surface or underlayer having a metal hydroxide material may have an average thickness of at least 0.1 nm, or at least 0.2 nm. In some embodiments, a surface or underlayer having a metal hydroxide material may have an average thickness of less than 5000 nm, or less than 3000 nm. In some embodiments, a surface layer or an underlayer comprising a metal hydroxide material may have an average thickness in the range of 0.1 to 0.2 nm, alternatively 0.2 to 0.5 nm, alternatively 0.5 to 1 nm, alternatively 1 to 2 nm, alternatively 2 to 5 nm, alternatively 5 to 10 nm, alternatively 10 to 20 nm, alternatively 20 to 50 nm, alternatively 50 to 100 nm, alternatively 100 to 200 nm, alternatively 200 to 500 nm, alternatively 500 to 1000 nm, alternatively 1000 to 1500 nm, alternatively 1500 to 2000 nm, alternatively 2000 to 2500 nm, alternatively 2500 to 3000 nm, alternatively 3000 to 4000 nm, alternatively 4000 to 5000 nm, or any combination of these ranges.

[0072] In some embodiments, the metal hydroxide may be formed by atomic layer deposition (ALD), chemical vapor deposition (CVD), thermal evaporation, or sputtering. In some cases, the metal hydroxide may be formed by coating a suspension of metal hydroxide particles. In some embodiments, the metal hydroxide may be electrolytically deposited or electrolessly deposited (which may include "electroless plating").

[0073] In some embodiments, the metal hydroxide precursor composition may be coated or printed onto a current collector having one or more surface primer layers as described above, and then processed to form the metal hydroxide. Some non-limiting examples of metal hydroxide precursor compositions include sol-gels (metal alkoxides), metal carbonates, metal acetates (including organic acetates), and metal oxide dispersions. The metal hydroxide precursor composition may optionally be heat-treated in the presence of water or an alkaline aqueous medium to form the metal hydroxide.

[0074] In some embodiments, a metal hydroxide precursor composition may include a metal (e.g., a metal-containing particle or a metal layer). The metal may then be oxidized (e.g., thermally) in the presence of oxygen, electrolytically oxidized, chemically oxidized in an oxidizing liquid or gaseous medium, etc., to form the metal hydroxide. Such oxidation may optionally be carried out in the presence of water or under alkaline conditions.

[0075] (oxometalates) As noted above, oxometalates are considered herein separately from other non-anionic metal oxides. Oxometalates can be considered a class of metal oxides in which a portion of the metal oxide is anionic in nature, optionally associated with a cation, which may be an alkali metal, alkaline earth metal, transition metal, or post-transition metal. In some embodiments, the transition metal oxometalate may include scandium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, tantalum, or tungsten. In some embodiments, the transition metal oxometalate may include a chromate, tungstate, vanadate, or molybdate. In some embodiments, the surface layer or under-surface layer may include or be formed from a transition metal oxometalate other than a chromate.

[0076] In some embodiments, the oxometallates may be formed by sputtering. In some cases, the oxometallates may be formed by coating a suspension or solution of oxometallate material or particles. In some embodiments, the oxometallates may be electrolytically or electrolessly plated (which may include "electroless plating"). In some embodiments, such electrolytic or electroless plating may use a solution containing a transition metal oxometallate. In some cases, the nature of the deposited coating may include a mixture of transition metal oxides, hydroxides, and / or oxometalates.

[0077] In some embodiments, the amount of transition metal from the transition metal oxometalate in the surface layer or underlayer is at least 0.5 mg / m 2 , or at least 1 mg / m 2 , or at least 2 mg / m 2 In some embodiments, the amount of transition metal from the transition metal oxometalate is 250 mg / m 2 In some embodiments, the amount of transition metal from the transition metal oxometalate is 0.5 to 1 mg / m 2 , or 1-2 mg / m 2 , or 2 to 5 mg / m 2 , or 5-10 mg / m 2 , or 10-20 mg / m 2 , or 20-50 mg / m 2 , or 50-75 mg / m 2 , or 75-100 mg / m 2 , or 100-250 mg / m 2or any combination of these ranges. In some embodiments, a surface layer or underlayer comprising an oxometallate material may be at least 0.2 nm thick, alternatively at least 0.5 nm thick, alternatively at least 1 nm thick, or at least 2 nm thick. In some embodiments, a surface layer or underlayer comprising an oxometallate material may have a thickness in the range of 0.2-0.5 nm, alternatively 0.5-1.0 nm, alternatively 1.0-2.0 nm, alternatively 2.0-5.0 nm, alternatively 5.0-10 nm, alternatively 10-20 nm, alternatively 20-50 nm, alternatively 50-100 nm, or any combination of these ranges.

[0078] A transition metal metalate generally refers to a transition metal compound having a negative charge. An anionic transition metal compound may be associated with one or more cations ("transition metal metalate compound"), which may optionally be an alkali metal, alkaline earth metal, ammonium, alkylammonium, another transition metal (which may be the same or different from the transition metal of the anionic transition metal compound), or other cationic species. A transition metal oxometalate is a specific type of transition metal metalate. In addition to transition metal oxometalates, non-limiting examples of useful transition metal metalates include sulfometalates, cyanometalates, and halometalates, which may be used alone or in combination, or in combination with oxometalates. Unless otherwise specified, in embodiments using a transition metal oxometalate, a transition metal metalate may be used instead.

[0079] (Silicon compounds) In some embodiments, the surface layer or underlayer comprises a silicon compound formed by treatment with a silane, siloxane, or silazane compound, any of which may be referred to herein as a silicon compound agent. As noted above, the silicon compound or silicon compound agent does not include silicate compounds. In some embodiments, the silicon compound agent treatment can enhance adhesion to the overlying underlayer or lithium storage layer. In some embodiments, the silicon compound may be a polymer, including, but not limited to, a polysiloxane. In some embodiments, the siloxane compound may have the general structure shown in Formula (1): Si(R) n (OR') 4-n (1) wherein n=1, 2, or 3, and R and R′ are independently selected from substituted or unsubstituted alkyl, alkenyl, or aryl groups.

[0080] The silicon compound of a layer or underlayer may be derived from a silicon compound agent but have a different chemical structure than the material used to form it. In some embodiments, the silicon compound may react with the underlayer surface to form bonds, such as metal-oxygen-silicon bonds, in which the silicon compound may lose one or more functional groups (e.g., OR′ groups from siloxane). In some embodiments, the silicon compound agent may include groups that polymerize to form a polymer. In some embodiments, the silicon compound agent may form a matrix of Si—O—Si crosslinks. In some embodiments, PECVD deposition of the lithium storage material may change the chemical structure of the silicon compound agent or form secondary derivative species. The silicon compound includes silicon. The silicon compound may be the result of the silicon compound agent reacting with one, two, three, or four reactants in one, two, three, or four different reactions.

[0081] The silicon compounding agent can be provided in water or an organic solvent, for example, in a solution of about 0.3 g / L to 15 g / L. Methods for adsorbing the silicon compounding agent include, but are not limited to, immersion, showering, and spraying. In some embodiments, the silicon compounding agent can be supplied as a vapor and adsorbed onto the underlying layer. In some embodiments, the silicon compounding agent can be deposited by initiated chemical vapor deposition (iCVD). In some embodiments, the silicon compounding agent can include an olefin-functional silane moiety, an epoxy-functional silane moiety, an acryl-functional silane moiety, an amino-functional silane moiety, or a mercapto-functional silane moiety, optionally in combination with a siloxane group or a silazane group. In some embodiments, the silicon compounding agent can be a siloxysilane. In some embodiments, the silicon compounding agent can undergo polymerization during or after deposition. Some non-limiting examples of silicon compound agents include hexamethyldisilazane (HMDS), vinyltrimethoxysilane, vinylphenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidylbutyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N- Examples of suitable silanes include 3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, imidazole silane, triazine silane, 3-mercaptopropyltrimethoxysilane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, pentavinylpentamethylcyclopentasiloxane, and octavinyl-T8-silesquioxane. In some embodiments, the layer or underlayer containing a silicon compound may contain silicon, oxygen, and carbon, and may further contain nitrogen or sulfur.

[0082] In some embodiments, treatment with a silicon compounding agent may be followed by a step to drive off solvent or to initiate polymerization or another chemical transformation. This step may include heating, contact with a reactive agent, or both. In some embodiments, a surface layer or underlayer formed with a silicon compounding agent may have a concentration of 0.1 to 0.2 mg / m 2 or 0.1 to 0.25 mg / m 2 or 0.25-0.5 mg / m 2 or 0.5-1 mg / m 2 , or 1-2 mg / m 2 , or 2 to 5 mg / m 2 , or 5-10 mg / m 2 , or 10-20 mg / m 2 , or 20-50 mg / m 2 , or 50-100 mg / m 2 , or 100-200 mg / m 2 , or 200-300 mg / m 2 or any combination of these ranges. In some embodiments, a surface layer or underlayer formed from a silicon compound agent may comprise up to 1 monolayer, or up to 2 monolayers, or up to 4 monolayers, or up to 6 monolayers, or up to 8 monolayers, or up to 10 monolayers, or up to 15 monolayers, or up to 20 monolayers, or up to 50 monolayers, or up to 100 monolayers, or up to 200 monolayers of the silicon compound agent or its reaction product. A surface layer or underlayer comprising a silicon compound may be porous. In some embodiments, the silicon compound may decompose or partially decompose during deposition of the lithium storage layer.

[0083] (silicate) The surface layer may include a silicate compound. The silicate compound may include silicic acid or anionic silicate species, or may be formed from a solution containing the same. Here, the anionic silicate species includes silicon and oxygen, and is typically associated with a suitable cationic moiety. In some cases, the anionic silicate species may be represented by formula (2): ([SiO (4-x) ] (4-2x)- )n (2) where 0≦x<2 and n≧1. In some cases, the anionic silicate species is [SiO4] 4- (x=0, n=1, sometimes referred to as orthosilicate), [SiO3] 2- (x=1, n=1, sometimes referred to as metasilicate), or [Si2O7] 6- (x=0.5, n=2, which may sometimes be referred to as pyrosilicates). The anionic silicate species may sometimes include larger structures such as polysilicates, where n≦3.

[0084] In some embodiments, the associated cationic moiety may comprise a proton, a metal ("metal silicate"), an alkylammonium moiety, or a mixture thereof. The metal silicate may comprise an alkali metal, an alkaline earth metal, a transition metal, or a post-transition metal. In some embodiments, the silicon compound may comprise a mixture of silicic acid and a metal silicate.

[0085] In some embodiments, the surface layer can be formed by contacting the current collector precursor with a silicating treating agent. The current collector precursor generally includes a conductive layer and may optionally include one or more additional surface primer layers, as discussed elsewhere herein. The silicating treating agent may include, for example, an aqueous mixture (solution, dispersion, emulsion, etc.) including a silicate compound. In some cases, the silicate compound may have a water solubility of at least 10 ppm, alternatively at least 50 ppm, or alternatively at least 100 ppm. In some cases, the treating agent may include silicic acid, sodium silicate, potassium silicate, or a mixture thereof. In some embodiments, the aqueous mixture may have a pH of at least 2, alternatively at least 4. In some embodiments, the aqueous mixture may have a pH ranging from about 4 to 5, alternatively from 5 to 6, alternatively from 6 to 7, alternatively from 7 to 8, alternatively from 8 to 9, alternatively from 9 to 10, alternatively from 10 to 11, alternatively from 11 to 12, or any combination of these ranges.

[0086] In some cases, the silicate treating agent may be provided as a bath into which the current collector precursor is immersed, or alternatively, may be sprayed or otherwise coated onto the current collector precursor. Contact with the silicate treating agent may optionally include agitation, such as bath circulation, sparging, stirring, or moving the current collector precursor. The silicate treating agent may be at ambient temperature or may be controlled at a temperature range, for example, from about 0°C to about 5°C, alternatively from about 5°C to about 10°C, alternatively from about 10°C to about 15°C, alternatively from about 15°C to about 20°C, alternatively from about 20°C to about 25°C, alternatively from about 25°C to about 30°C, alternatively from about 30°C to about 40°C, alternatively from about 40°C to about 50°C, alternatively from about 50°C to about 60°C, alternatively from about 60°C to about 80°C, or any combination thereof. In some embodiments, contact with the silicate treating agent may be followed by rinsing with a rinse agent. In some embodiments, the rinse agent may include water, such as distilled water or tap water. The rinse agent may optionally include other materials such as surfactants, dispersants, neutralizing materials, and the like.

[0087] In some embodiments, the areal density of silicon from the silicate compound in the surface layer is at least 0.2 mg / m 2 , or at least 0.5 mg / m 2 In some embodiments, the areal density of silicon from the silicate compound in the surface layer may be 0.2 to 0.5 mg / m 2 , or 0.5 to 1.0 mg / m 2 , or 1.5 to 2 mg / m 2 , or 2-3 mg / m 2 , or 3-5 mg / m 2 , or 5-7 mg / m 2 , or 7 to 10 mg / m 2 , or 10-15 mg / m 2 , or 15-20 mg / m 2 , or 20-30 mg / m 2 , or 30-50 mg / m 2 or any combination of these ranges.

[0088] (metal silicide) The surface layer may comprise a metal silicide. In some embodiments, the metal silicide is M x Si y where M is a transition metal, x is the total atomic % of one or more transition metals, and y is the atomic % of silicon, with the ratio of x to y ranging from about 0.25 to about 7. The ratio of x to y may vary throughout the metal silicide layer. In some embodiments, the surface layer may include a metal silicide having a metal content gradient, e.g., the atomic % of the transition metal decreases in a direction toward the lithium storage layer. When the ratio of x to y is below 0.25, in some embodiments, silicon is considered to be part of the lithium storage layer. When the ratio of x to y is greater than 7, the transition metal may be considered to be part of the conductive layer, as used herein. In some embodiments, M=Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Mo, or W, or a binary or ternary combination thereof. The metal silicide may be stoichiometric or non-stoichiometric. The metal silicide layer may comprise a stoichiometrically homogeneous or heterogeneously distributed mixture of metal silicides, a mixture of metals, or both.

[0089] In some embodiments, the areal density of silicon from the metal silicide in the surface layer is at least 0.2 mg / m 2 , or at least 0.5 mg / m 2 In some embodiments, the areal density of silicon from the metal silicide in the surface layer may be between 0.2 and 0.5 mg / m 2 , or 0.5 to 1.0 mg / m 2 , or 1.5 to 2 mg / m 2 , or 2-3 mg / m 2 , or 3-5 mg / m 2 , or 5-7 mg / m 2 , or 7 to 10 mg / m 2 , or 10-15 mg / m 2 , or 15-20 mg / m 2 , or 20-30 mg / m 2, or 30-50 mg / m 2 , or 50-100 mg / m 2 , or 100-200 mg / m 2 , or 200-300 mg / m 2 , or 300-400 mg / m 2 , or 400-500 mg / m 2 or any combination of these ranges.

[0090] In some embodiments, the metal silicide has at least 10 2 S / m, or at least 10 3 S / m, or at least 10 4 S / m, or at least 10 5 S / m, or at least 10 6 It has an electrical conductivity of S / m.

[0091] In some embodiments, the metal silicide can be formed before the deposition of the lithium storage layer. For example, the metal silicide layer can be formed directly by a PVD process such as atomic layer deposition (ALD), PECVD, or sputtering. Sputtering can use a single metal silicide sputter source or two sources (one for the metal and the other for silicon). In some embodiments, a slurry of metal silicide particles can be coated onto the conductive layer and optionally dried or sintered. In some embodiments, the metal silicide layer can be formed by heating a metal layer (e.g., a metal portion of the conductive layer) in contact with the silicon layer.

[0092] (Lithium Storage / Lithium Storage Segment) The following discussion can apply to either the lithium storage layer segments or the undivided precursor lithium storage layer (or both). For convenience, both embodiments will be referred to simply as the lithium storage layer in this section. In some embodiments, the lithium storage layer can be a porous material (e.g., a continuous porous lithium storage layer) capable of reversibly incorporating lithium. In some embodiments, the lithium storage layer comprises silicon, germanium, antimony, tin, or a mixture of two or more of these elements. In some embodiments, the lithium storage layer is substantially amorphous. In some embodiments, the lithium storage layer comprises substantially amorphous silicon. Such a substantially amorphous storage layer may contain a small amount (e.g., less than 20 atomic %) of crystalline material dispersed therein. The lithium storage layer may include a dopant, such as hydrogen, boron, phosphorus, sulfur, fluorine, aluminum, gallium, indium, arsenic, antimony, bismuth, nitrogen, or a metallic element. In some embodiments, the lithium storage layer may comprise porous, substantially amorphous hydrogenated silicon (a-Si:H), for example, having a hydrogen content of 0.1 to 20 atomic % or more. In some embodiments, the lithium storage layer may comprise methylated amorphous silicon. Note that unless specifically mentioned, the atomic % designations used herein for lithium storage materials or layers refer to atoms other than hydrogen.

[0093] In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) may comprise at least 40 atomic %, alternatively at least 50 atomic %, alternatively at least 60 atomic %, alternatively at least 70 atomic %, alternatively at least 80 atomic %, or alternatively at least 90 atomic % silicon, germanium, or a combination thereof. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) may comprise at least 40 atomic %, alternatively at least 50 atomic %, alternatively at least 60 atomic %, alternatively at least 70 atomic %, alternatively at least 80 atomic %, alternatively at least 90 atomic %, alternatively at least 95 atomic %, alternatively at least 97 atomic %, alternatively at least 98 atomic %, or alternatively at least 99 atomic % silicon. Note that for prelithiated negative electrodes, as described below, the lithium content is excluded from this atomic % characterization.

[0094] In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) contains less than 10 atomic %, alternatively less than 5 atomic %, alternatively less than 2 atomic %, alternatively less than 1 atomic %, alternatively less than 0.5 atomic % carbon. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) is substantially free of carbon-based binders, graphitic carbon, graphene, graphene oxide, reduced graphene oxide, carbon black, and conductive carbon (i.e., the lithium storage layer contains less than 1 wt %, alternatively less than 0.5 wt %, alternatively less than 0.3 wt %, alternatively less than 0.1 wt %, alternatively less than 0.01 wt %). Some non-limiting examples of carbon-based binders include organic polymers such as those based on styrene butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, carboxymethyl cellulose, or polyacrylonitrile.

[0095] The lithium storage layer (e.g., a continuous porous lithium storage layer) may contain voids or interstices (pores). These voids may be random or non-uniform with respect to size, shape, and distribution. Such porosity does not result in or result in the formation of recognizable lithium storage nanostructures, such as nanowires, nanopillars, nanotubes, ordered nanochannels, etc. In some embodiments, the pores may be polydisperse. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) may be characterized as nanoporous. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) has a density of 1.0-1.1 g / cm. 3 , or 1.1 to 1.2 g / cm 3 , or 1.2 to 1.3 g / cm 3 , or 1.3 to 1.4 g / cm 3 , or 1.4 to 1.5 g / cm 3 , or 1.5 to 1.6 g / cm 3 , or 1.6 to 1.7 g / cm 3 , or 1.7 to 1.8 g / cm 3 , or 1.8 to 1.9 g / cm 3 , or 1.9 to 2.0 g / cm 3 , or 2.0 to 2.1 g / cm 3 , or 2.1 to 2.2 g / cm 3 , or 2.2 to 2.25 g / cm 3 , or 2.25 to 2.29 g / cm 3 or any combination of ranges, and containing at least 70 atomic % silicon, or 80 atomic % silicon, or at least 85 atomic % silicon, or at least 90 atomic % silicon, or at least 95 atomic % silicon, or at least 97 atomic % silicon, or at least 98 atomic % silicon, or at least 99 atomic % silicon. 3 Note that the density < 0.05 is evidence of the porosity of the a-Si, including the lithium storage layer.

[0096] In some embodiments, the majority of the active material (e.g., silicon, germanium, or alloys thereof) of a lithium storage layer (e.g., a continuous porous lithium storage layer) has substantial lateral connectivity throughout the portion that forms the current collector. Such connectivity extends around random pores and interstices. Referring again to FIG. 1 , in some embodiments, “substantial lateral connectivity” means that the active material at one point X in the lithium storage layer 107 can be connected to the active material at a second point X′ in the layer over a linear lateral distance LD that is at least as large as the average thickness T of the lithium storage layer, or a lateral distance at least twice the thickness, or a lateral distance at least three times the thickness. Although not shown, the total path distance of the material connections, including bypassing pores and following the current collector topography, can be longer than LD. In some embodiments, the continuous porous lithium storage layer can be described as an interconnected matrix of silicon, germanium, or alloys thereof, with random pores and interstices embedded therein. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) may have a sponge-like morphology in cross-section. It should be noted that the lithium storage layer (e.g., a continuous porous lithium storage layer) does not necessarily extend across the entire negative electrode without lateral breaks, but may include random discontinuities or cracks and still be considered continuous. In some embodiments, such discontinuities may occur more frequently on rough current collector surfaces. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) may have adjacent columns of active material, such as silicon, in cross-section. The adjacent columns may be characterized by an average height and an average width, and typically have a height-to-width aspect ratio of less than 4:1, alternatively less than 3:1, alternatively less than 2:1, or alternatively less than 1:1. Such adjacent columns are laterally continuous. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) may comprise a matrix of connected nanoparticle aggregates.In some embodiments, the lithium storage layer may include a mixture of amorphous silicon and crystalline silicon (nanocrystalline silicon) having an average grain size of, for example, less than about 100 nm, or less than 50 nm, 20 nm, 10 nm, or 5 nm. In some cases, the lithium storage layer may include up to 30 atomic % nanocrystalline silicon relative to the total silicon in the lithium storage layer.

[0097] In some embodiments, the lithium storage layer (e.g., the continuous porous lithium storage layer) is made of silicon (SiO x ), germanium (GeO x ), or tin (SnO x ) substoichiometric oxides, where the ratio of oxygen atoms to silicon, germanium, or tin atoms is less than 2:1 (i.e., x<2), or alternatively less than 1:1 (i.e., x<1). In some embodiments, x is in the range of 0.02 to 0.95, alternatively 0.02 to 0.10, alternatively 0.10 to 0.50, alternatively 0.50 to 0.95, alternatively 0.95 to 1.25, alternatively 1.25 to 1.50, or any combination of these ranges.

[0098] In some embodiments, the lithium storage layer (e.g., the continuous porous lithium storage layer) is a substoichiometric nitride of silicon (SiN y ), substoichiometric nitride of germanium (GeN y ), or substoichiometric nitride of tin (SnN y ), where the ratio of nitrogen atoms to silicon, germanium, or tin atoms is less than 1.25:1 (i.e., y<1.25). In some embodiments, y is in the range of 0.02 to 0.95, alternatively 0.02 to 0.10, alternatively 0.10 to 0.50, alternatively 0.50 to 0.95, alternatively 0.95 to 1.20, or any combination of these ranges. Lithium storage layers having substoichiometric nitrides of silicon are sometimes referred to as nitrogen-doped silicon or silicon-nitrogen alloys.

[0099] In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) is a substoichiometric oxynitride of silicon (SiO x N y ), substoichiometric oxynitride of germanium (GeO x N y ), or substoichiometric tin oxynitride (SnO x N y The ratio of the sum of oxygen and nitrogen atoms to silicon, germanium, or tin atoms is less than 1:1 (i.e., (x+y)<1). In some embodiments, (x+y) is in the range of 0.02 to 0.95, alternatively 0.02 to 0.10, alternatively 0.10 to 0.50, alternatively 0.50 to 0.95, or any combination of these ranges.

[0100] In some embodiments, the substoichiometric oxides, nitrides, or oxynitrides are provided by a CVD process, including but not limited to a PECVD process. The oxygen and nitrogen may be uniformly provided within the continuous porous lithium storage layer, or the oxygen or nitrogen content may vary as a function of the thickness of the storage layer.

[0101] (CVD) CVD generally involves flowing precursor gases, gasified liquids in the context of direct liquid injection CVD, or gases and liquids into a chamber containing one or more objects to be coated (usually heated). Chemical reactions occur at and near the hot surface, forming a thin film on the surface. This involves the production of chemical by-products that are exhausted from the chamber along with unreacted precursor gases. As expected given the wide variety and versatility of materials deposited, there are many types of CVD used to form lithium reservoir layers, surface or underlayer layers, auxiliary layers (see below), and other layers. In some embodiments, CVD can be performed in hot-wall or cold-wall reactors, at sub-Torr to above-atmospheric total pressures, with or without carrier gas, and at temperatures typically ranging from 100 to 1600 °C. There are also various enhanced CVD processes that use plasmas, ions, photons, lasers, hot filaments, combustion reactions, etc. to increase deposition rates or reduce deposition temperatures. A variety of process conditions can be used to control the deposition, including, but not limited to, temperature, precursor material, gas flow rate, pressure, substrate voltage bias (if applicable), and plasma energy (if applicable).

[0102] As described above, lithium storage layers, such as continuous porous lithium storage layers, for example, silicon or germanium or both, can be provided by plasma enhanced chemical vapor deposition (PECVD). Compared to conventional CVD, deposition by PECVD can often be performed at lower temperatures and higher rates, which can be advantageous for higher manufacturing throughput. In some embodiments, PECVD is used to deposit a substantially (optionally doped) amorphous silicon layer on the surface layer. In some embodiments, PECVD is used to deposit a substantially amorphous continuous porous silicon layer on the surface layer.

[0103] In a PECVD process, according to various embodiments, a plasma can be generated within or upstream of the chamber in which the substrate is located and delivered into the chamber. Various types of plasma can be used, including, but not limited to, capacitively coupled plasma, inductively coupled plasma, and conductively coupled plasma. Any suitable plasma source can be used, including DC, AC, RF, VHF, combinatorial PECVD, and microwave sources. In some embodiments, magnetron-assisted RF PECVD can be used.

[0104] PECVD process conditions (temperature, pressure, precursor gases, carrier gases, dopant gases, flow rates, energy, etc.) can vary depending on the particular process and tools used, as is well known in the art.

[0105] In some embodiments, the PECVD process is an Expanding Thermal Plasma Chemical Vapor Deposition (ETP (Expanding Thermal)-PECVD) process. In such a process, a plasma is formed by passing a plasma-generating gas through a direct current arc plasma generator, optionally with a web or other substrate, including a current collector, in an adjacent vacuum chamber. A silicon source gas is injected into the plasma, generating radicals. The plasma expands through a diverging nozzle and is sprayed into the vacuum chamber and toward the substrate. An example of a plasma-generating gas is argon (Ar). In some embodiments, ionized argon species in the plasma collide with silicon source molecules to form silicon source radical species, which then deposit on the current collector. Exemplary ranges for the voltage and current of the DC plasma source are 60-80 volts and 40-70 amperes, respectively.

[0106] Any suitable silicon source can be used to deposit silicon. In some embodiments, the silicon source can be a silane-based precursor gas(es), including, but not limited to, silane (SiH), dichlorosilane (HSiCl), monochlorosilane (HSiCl), trichlorosilane (HSiCl), silicon tetrachloride (SiCl), disilane, tetrafluorosilane, triethylsilane, and diethylsilane. Depending on the gas(es) used, the silicon layer can be formed by decomposition, such as hydrogen reduction, or by reaction with another compound. In some embodiments, the gas can include a silicon source such as silane, a noble gas such as helium, argon, neon, or xenon, optionally one or more dopant gases, and substantially no hydrogen. In some embodiments, the gas can include argon, silane, and hydrogen, and optionally some dopant gases. In some embodiments, the gas can include argon to the combined gas flow rate of silane and hydrogen is at least 3.0, or alternatively, at least 4.0. In some embodiments, the ratio of the gas flow rate of argon to the total gas flow rate of silane and hydrogen is in the range of 3 to 5, alternatively 5 to 10, alternatively 10 to 15, alternatively 15 to 20, or any combination of these ranges. In some embodiments, the ratio of the gas flow rate of hydrogen gas to silane is in the range of 0 to 0.1, alternatively 0.1 to 0.2, alternatively 0.2 to 0.5, alternatively 0.5 to 1, alternatively 1 to 2, alternatively 2 to 5, or any combination of these ranges. In some embodiments, increasing the ratio of the gas flow rate of silane to the total gas flow rate of silane and hydrogen may result in the formation of more porous silicon or an increased silicon deposition rate. In some embodiments, the dopant gas is borane or phosphine, optionally mixed with a carrier gas.In some embodiments, the gas flow ratio of the dopant gas (e.g., borane or phosphine) to the silicon source gas (e.g., silane) is in the range of 0.0001 to 0.0002, alternatively 0.0002 to 0.0005, alternatively 0.0005 to 0.001, alternatively 0.001 to 0.002, alternatively 0.002 to 0.005, alternatively 0.005 to 0.01, alternatively 0.01 to 0.02, alternatively 0.02 to 0.05, alternatively 0.05 to 0.10, or any combination of these ranges. Such gas flow ratios above may refer to relative gas flow rates in, for example, standard cubic centimeters per minute (SCCM). In some embodiments, the PECVD deposition conditions and gases may be varied during the course of deposition.

[0107] In some embodiments, the temperature at the current collector during at least a portion of the time of the PECVD deposition is in the range of 20°C to 50°C, 50°C to 100°C, alternatively 100°C to 200°C, alternatively 200°C to 300°C, alternatively 300°C to 400°C, alternatively 400°C to 500°C, alternatively 500°C to 600°C, or any combination of these ranges. In some embodiments, the temperature may vary during the time of the PECVD deposition. For example, the temperature may be higher in the early times of the PECVD than in the later times. Alternatively, the temperature may be higher in the later times of the PECVD than in the earlier times.

[0108] The thickness or mass per unit area of ​​the lithium storage layer (e.g., a continuous porous lithium storage layer) varies depending on the storage material, the desired charge capacity, and other operational and life considerations. In general, increasing the thickness results in greater capacity. If the lithium storage layer becomes too thick, electrical resistance may increase and stability may decrease. In some embodiments, the negative electrode has a thickness of at least 0.2 mg / cm 2 , or at least 0.5 mg / cm 2 , or at least 1.0 mg / cm 2 , or at least 1.5 mg / cm 2 , or at least 3 mg / cm 2 , or at least 5 mg / cm2 In some embodiments, the lithium storage structure may be characterized by having an areal density of active silicon of 0.2 to 0.5 mg / cm. 2 range, 0.5-1.0 mg / cm 2 range, 1.0-1.5 mg / cm 2 range, 1.5-2 mg / cm 2 range, 2-3 mg / cm 2 range, 3-5 mg / cm 2 range, 5-10 mg / cm 2 range, 10-15mg / cm 2 range, 15-20 mg / cm 2 or any combination of these ranges. "Active silicon" refers to silicon in electrical communication with the current collector that is available for reversible lithium storage early in the cell cycle (e.g., after electrochemical formation of the negative electrode). "Area density" refers to the surface area of ​​the conductive layer on which the active silicon is provided. In some embodiments, not all of the silicon content is active silicon; i.e., some may be associated in the form of inactive silicide or electrically isolated from the current collector.

[0109] In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) has an average thickness of at least 0.5 μm, alternatively at least 1 μm, alternatively at least 2.5 μm, alternatively at least 5 μm, alternatively at least 6.5 μm. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) has an average thickness in the range of about 0.5 μm to about 50 μm. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) comprises at least 80 atomic % amorphous silicon and / or has a thickness of 1 to 1.5 μm, alternatively 1.5 to 2.0 μm, alternatively 2.0 to 2.5 μm, alternatively 2.5 to 3.0 μm, alternatively 3.0 to 3.5 μm, alternatively 3.5 to 4.0 μm, alternatively 4.0 to 4.5 μm, alternatively 4.5 to 5.0 μm, alternatively 5.0 to 5.5 μm. m, alternatively 5.5 to 6.0 μm, alternatively 6.0 to 6.5 μm, alternatively 6.5 to 7.0 μm, alternatively 7.0 to 8.0 μm, alternatively 8.0 to 9.0 μm, alternatively 9.0 to 10 μm, alternatively 10 to 15 μm, alternatively 15 to 20 μm, alternatively 20 to 25 μm, alternatively 25 to 30 μm, alternatively 30 to 40 μm, alternatively 40 to 50 μm, or any combination of these ranges.

[0110] In some embodiments, rather than depositing the lithium storage material by CVD or PECVD, it can be formed by a physical vapor deposition (PVD) process such as sputtering. Although the deposition rate of sputtering is generally lower than that of PECVD, sputtering may be suitable, for example, for applications requiring a relatively low loading of active material such as silicon. For example, in some embodiments, a lithium storage layer (e.g., a continuous porous lithium storage layer) formed by a sputtering process may have a thickness of less than about 15 μm, alternatively less than about 10 μm, alternatively less than 7 μm, alternatively less than 5 μm, or alternatively less than 3 μm.

[0111] (Other negative electrode features) The negative electrode may optionally include various additional layers and features. The current collector may include one or more features to ensure a reliable electrical connection in an energy storage device. In some embodiments, an auxiliary layer is provided on the lithium storage structure. In some embodiments, the auxiliary layer is a protective layer to enhance lifetime or physical durability. In some embodiments, the auxiliary layer can improve the wettability of the liquid electrolyte or the coverage of the SSE to improve interfacial contact and / or cycling performance. The auxiliary layer may be an oxide formed from the lithium storage material itself (e.g., silicon dioxide in the case of silicon) or other suitable material. The auxiliary layer may be deposited by, for example, ALD, S-ALD, CVD, i-CVD, PECVD, MLD, evaporation, sputtering, solution coating, inkjet, or any method compatible with the negative electrode. In some embodiments, the top surface of the auxiliary layer may correspond to the top surface of the negative electrode. In some embodiments, two or more auxiliary layers may be used together.

[0112] The auxiliary layer should be reasonably conductive to lithium ions, i.e., allow lithium ions to enter and exit the lithium storage structure during charge and discharge. In some embodiments, the lithium ion conductivity of the auxiliary layer is at least 10 -9 S / cm, or at least 10 -8 S / cm, or at least 10 -7 S / cm, or at least 10 -6 S / cm.

[0113] Some non-limiting examples of materials for use in the auxiliary layer include metal oxides, nitrides, or oxynitrides, such as those containing aluminum, titanium, vanadium, zirconium, hafnium, or tin, or mixtures thereof. The metal oxides, nitrides, or oxynitrides may contain other elements, such as phosphorus or silicon. In some embodiments, the auxiliary layer may comprise an inorganic-organic hybrid structure having alternating underlayers of metal oxide and a crosslinked organic material, such as a so-called "metal-cone" material (e.g., zincone, titanicon, or zircon). Auxiliary layers may include lithium phosphate nitride (LIPON), lithium phosphate, lithium aluminum oxide, (Li,La) x Ti y O z or Li x Si y The sublayer may include a lithium-containing material such as Al2O3 (where x, y, and z are not zero). The thickness of the sublayer may be in the range of 0.1 to 0.5 nm, alternatively 0.5 to 1.0 nm, 1 to 2 nm, 2 to 5 nm, 5 to 10 nm, 10 to 20 nm, 20 to 50 nm, 50 to 100 nm, or any combination of these ranges, and in some cases may be greater than 100 nm. The appropriate thickness may depend in part on the lithium ion conductivity of the sublayer. Preferably, the thickness of the sublayer is 100 nm or less.

[0114] In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) may be at least partially prelithiated before the first electrochemical cycle after battery assembly or before battery assembly. That is, some lithium can be incorporated into the lithium storage layer to form a lithiated storage layer even before the first battery cycle. In some embodiments, the lithiated storage layer may break down into smaller structures, including, but not limited to, segments or platelets, that remain electrochemically active and continue to reversibly store lithium. Note that "lithiated storage layer" simply means that at least a portion, but not necessarily all, of the potential storage capacity of the lithium storage layer has been filled. In some embodiments, the lithiated storage layer may contain lithium in the range of 1% to 5%, alternatively 5% to 10%, alternatively 10% to 15%, alternatively 15% to 20%, alternatively 20% to 30%, alternatively 30% to 40%, alternatively 40% to 50%, alternatively 50% to 60%, alternatively 60% to 70%, alternatively 70% to 80%, alternatively 80% to 90%, alternatively 90% to 100%, or any combination of these ranges, of the theoretical lithium storage capacity of the lithium storage layer. In some embodiments, the surface layer may scavenge some of the lithium, and such scavenge may need to be taken into account to achieve the desired lithium range in the lithiated storage layer.

[0115] In some embodiments, prelithiation may include depositing lithium metal onto the lithium storage layer (e.g., a continuous porous lithium storage layer) and / or between one or more lithium storage underlayers, for example, by evaporation, electron beam, or sputtering. Alternatively, prelithiation may include contacting the negative electrode with a reducible lithium organic compound (e.g., lithium naphthalene, n-butyllithium, etc.). In some embodiments, prelithiation may include incorporating lithium by electrochemical reduction of lithium ions in a prelithiation solution. In some embodiments, prelithiation may include a heat treatment to aid in the diffusion of lithium into the lithium storage layer.

[0116] In some embodiments, the negative electrode may be heat-treated prior to battery assembly. In some embodiments, heat-treating the negative electrode can improve the adhesion or electrical conductivity of the various layers, for example, by inducing atomic migration from the metal from the current collector or any auxiliary layer to the lithium storage layer.

[0117] In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) comprises at least 0.05 atomic percent of one or more transition metals, alternatively at least 0.1 atomic percent, alternatively at least 0.2 atomic percent, alternatively at least 0.5 atomic percent, alternatively at least 1 atomic percent of copper. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) comprises less than about 10 atomic percent, alternatively less than 5 atomic percent, alternatively less than 2 atomic percent, alternatively less than 1 atomic percent, alternatively less than 0.5 atomic percent, alternatively less than 3 atomic percent of one or more transition metals. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) may comprise one or more transition metals in an atomic percent range of 0.05-0.1%, alternatively 0.1-0.2%, alternatively 0.2-0.5%, alternatively 0.5-1%, alternatively 1-2%, alternatively 2-3%, alternatively 3-5%, alternatively 5-7%, alternatively 7-10%, or any combination of these ranges. In some embodiments, the above ranges of atomic % of the transition metal(s) are at least 1 μm 2The cross-sectional area of ​​the lithium storage layer may correspond to the atomic percentage of the lithium storage layer, which may be measured, for example, by energy dispersive x-ray spectroscopy (EDS). In some embodiments, the atomic percentage values ​​of the transition metals above may represent the atomic percentage of a single transition metal, or, if there is a mixture of transition metals, may correspond to the combined atomic percentages. Non-limiting examples of transition metals that may be present in the lithium storage layer include copper, nickel, titanium, vanadium, and molybdenum. In some embodiments, a gradient exists in which the concentration of the transition metal is higher in the portion of the lithium storage layer closer to the current collector than in the portion farther from the current collector. In some embodiments, the lithium storage layer (e.g., a continuous porous lithium storage layer) may include the same transition metal as that found in the transition metal metalate of the conductive layer or surface layer. In some cases, one or more transition metals may be provided to the lithium storage layer by heat treatment to cause migration of the metals into the lithium storage layer, although other methods, such as co-evaporation of the lithium storage material with the metal, may be used.

[0118] In some embodiments, the heat treatment of the negative electrode can be carried out in a controlled environment with low oxygen and water (e.g., a partial pressure of less than 10 ppm or less than 0.1 Torr, or a content of less than 0.01 Torr to prevent degradation). In some embodiments, the heat treatment of the negative electrode can be carried out using an oven, an infrared heating element, contact with a hot plate, or exposure to a flash lamp. The temperature and time for heat treatment of the negative electrode depend on the material of the negative electrode. In some embodiments, the heat treatment of the negative electrode includes heating the negative electrode to a temperature of at least 50°C, optionally from 50°C to 950°C, alternatively from 100°C to 250°C, alternatively from 250°C to 350°C, alternatively from 350°C to 450°C, alternatively from 450°C to 550°C, alternatively from 550°C to 650°C, alternatively from 650°C to 750°C, alternatively from 750°C to 850°C, alternatively from 850°C to 950°C, or any combination of these ranges. In some embodiments, the heat treatment can be applied for a time period of 0.1 to 120 minutes.

[0119] In some embodiments, one or more of the processing steps described above can be carried out using a roll-to-roll process, where the conductive layer or current collector is in the form of a rolled film (e.g., a roll of metal foil, mesh, or fabric).

[0120] (SSE) Solid electrolytes contain a mobile lithium ion source that diffuses between the negative and positive electrodes (toward the negative electrode during charging and away from the negative electrode during discharge). The three main families of SSEs are solid polymer electrolytes (SPEs), solid inorganic electrolytes (SIEs), and hybrid SSEs that use both SPE and SIE materials. In some cases, the lithium ion source may include a lithium salt in the form of a small molecule (e.g., LiTSFI, LiPF6, or other lithium salts described below) suspended or dissolved in the SSE matrix. In some cases, the SPE material may contain anionic functional groups that act as counterions for the lithium salt. SSEs may optionally include plasticizers, rheology control agents, or small amounts of organic solvents.

[0121] Some non-limiting examples of polymeric materials that can be used in SSE compositions include poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinyl alcohol) (PVA), poly(trimethylene carbonate), diester-based polymers, PVdF-based polymers, polycaprolactone, and derivatives or copolymers thereof, which can be used alone or in combination. The polymers of the SSE may optionally be crosslinked or branched. The polymers may be block copolymers. The polymeric SSE may be completely amorphous or may contain some crystallinity. The polymers may contain anionic functional groups.

[0122] Non-limiting classes of SIE materials that can be used in the SSE composition include b-alumina, LISICON, thio-LISICON, NASICON, perovskites, antiperovskites, garnets, complex hydrides, and solid sulfides.

[0123] Solid sulfides include, but are not limited to, ceramic sulfides, glass sulfides, and glass-ceramic sulfides. Glass sulfides exhibit minimal long-range order, as identified by the absence of peaks in the X-ray diffraction (XRD) pattern. Glass-ceramic sulfides contain glassy structural regions and regions with long-range order, as identified by characteristic peaks in the X-ray diffraction pattern. Ceramic sulfides, also known as crystalline sulfides, are composed of regions with long-range order, as identified by characteristic peaks in the XRD pattern. Non-limiting examples of ceramic sulfides include argyrodite, silicon thiophosphate, and silicon halide thiophosphate. Exemplary, but non-limiting, solid sulfides include thiophosphates (PS4), which can be identified by features in the pattern obtained by either infrared or Raman spectroscopy. Additional examples of solid sulfides include Li6PS5Cl, Li 10 LGPS materials such as GeP2S12, and Li7P3S 11 Examples of LPS materials include:

[0124] In some embodiments, under battery operating conditions, the SSE may have a lithium ion conductivity in the range of 0.001 mS / cm to 0.01 mS / cm, alternatively in the range of 0.01 mS / cm to 0.1 mS / cm, alternatively in the range of 0.1 mS / cm to 1.0 mS / cm, or alternatively greater than 1 mS / cm.

[0125] The thickness of the SSE should be sufficient to prevent short circuits between the negative and positive electrodes, but not so thick as to increase resistance beyond desirable levels or reduce energy density. SSE thicknesses are typically between 100 nm and 800 μm. For microbatteries, the thickness ranges from 100 nm to 5 μm. For more conventional battery cells, SSEs typically have thicknesses in the range of 5 to 300 μm.

[0126] In some embodiments, the solid electrolyte comprises a material capable of reversibly changing from a low-flow state to a high-flow state and back to the low-flow state. In some cases, this cycle may be utilized only once, and such a system may be referred to as "single reversible." For example, an SSE in a first low-flow state may have a first chemical composition or a first morphology. After transitioning to a high-flow state, the SSE may return to a second low-flow state and have a second chemical composition or a second morphology different from the first. For example, the SSE may undergo a polymerization or crosslinking reaction during or after the high-flow state to form a second low-flow state. In other embodiments, this cycle may be repeated two or more times ("multiple reversibility"). In some cases, the low-flow state may correspond to a glassy or solid state. In some embodiments, the high-flow state may correspond to a liquid state. In some embodiments, the transformation from the low-flow state to the high-flow state may correspond approximately to the melting point or glass transition temperature (Tg) of the SSE material. In some embodiments, the transformation from the low-flow state to the high-flow state can be achieved by applying energy to the precursor cell such that the temperature of the SSE within the precursor cell is raised to T1, at which point the transformation can occur. Application of energy can be accomplished, for example, by placing the precursor cell on an oven or hotplate, exposing it to a flash lamp, encasing the cell in a heating coil, resistively heating the precursor cell components, irradiating it with microwaves, or by other methods. T 1cis generally room temperature or higher. In some embodiments, T1 is at least 40°C, or may be at least 50°C, 60°C, 80°C, 100°C, 125°C, 150°C, 175°C, or 200°C. In some embodiments, T1 may be in the range of 40-60°C, or in the range of 60-80°C, 80-100°C, 100-125°C, 125-150°C, 150-175°C, 175-200°C, 200-225°C, 225-250°C, or any combination of these ranges. In some embodiments, compression may be applied to the precursor cell (between the anode and cathode) while the SSE is in a highly fluid state. Such compression may include a force greater than 1 bar, or greater than 1.5 bar, 2 bar, 3 bar, 4 bar, 5 bar, 7 bar, or 10 bar. In some cases, the compression is in the range of 1.1 to 1.5 bar, 1.5 to 2 bar, 2 to 3 bar, 3 to 4 bar, 4 to 5 bar, 5 to 7 bar, 7 to 10 bar, 10 to 15 bar, 15 to 20 bar, 20 to 30 bar, 30 to 50 bar, 50 to 75 bar, 75 to 100 bar, or any combination of these ranges.

[0127] In some embodiments, the highly fluid state may be characterized by a viscosity of less than 1 MPa·sec, or alternatively, a viscosity of less than 500 kPa·sec, less than 200 kPa·sec, less than 100 kPa·sec, less than 50 kPa·sec, less than 20 kPa·sec, 10 kPa·sec, 5 kPa·sec, 2 kPa·sec, 1 kPa·sec, 500 Pa·sec, 200 Pa·sec, 100 Pa·sec, 50 Pa·sec, 20 Pa·sec, 10 Pa·sec, 5 Pa·sec, 2 Pa·sec, 1 Pa·sec, 0.5 Pa·sec, 0.2 Pa·sec, or 0.1 Pa·sec. In some cases, the highly fluid state may be characterized by a viscosity in the range of 0.001 to 0.01 Pa·sec, alternatively 0.01 to 0.1 Pa·sec, 0.1 to 1 Pa·sec, 1 to 10 Pa·sec, 10 to 100 Pa·sec, 100 to 1000 Pa·sec, 1 to 10 kPa·sec, 10 to 100 kPa·sec, 100 to 500 kPa·sec, or any combination of these ranges.

[0128] A low liquidity state is at least 1.1 times, or at least 1.5 times, 2 times, 5 times, 10 times, 20 times, 50 times, 100 times, 200 times, 500 times, 10 ... 4 double, or 10 5 In some embodiments, the low-flow state may have a viscosity of at least 100 Pa·sec, alternatively at least 1 kPa·sec, alternatively at least 10 kPa·sec, alternatively at least 100 kPa·sec, alternatively at least 1 MPa·sec.

[0129] Conversion from the high-flow state to the low-flow state involves active cooling to T2 (or below), e.g., removing heat from the cell using a chiller, heat pump, etc. Alternatively, passive cooling may be used where radiative cooling occurs (e.g., where room temperature is below T2). In some cases, T2 is lower than T1, e.g., T2 may be 1-5°C lower than T1, or 5-10°C lower, 10-20°C lower, 20-30°C lower, 30-40°C lower, 40-50°C lower, 50-75°C lower, 75-100°C lower, 100-150°C lower, or any combination of these ranges, or even 150°C or more lower.

[0130] (positive electrode) The positive electrode (cathode) active material may be a lithium metal oxide or a lithium compound (e.g., LiCoO2, LiFePO4, LiMnO2, LiNiO2, LiMn2O4, LiCoPO4, LiNi x Co y Mn z O2, LiNi X Co Y Al ZExamples of suitable cathode active materials include, but are not limited to, O2, LiFe2(SO4)3, or Li2FeSiO4), fluorocarbons, metal fluorides such as iron fluoride (FeF3), metal oxides, sulfur, selenium, and combinations thereof. The cathode active material can operate, for example, by intercalation, conversion, or a combination thereof. The cathode active material may optionally be mixed with and coated with one or more binders to form a cathode. In some cases, the cathode may include a polymeric, SIE, or hybrid SSE material, such as any of those described elsewhere, which may be the same as or different from the material used in the SSE layer between the negative and positive electrodes. In some cases, the solid electrolyte used in the cathode may be different from the SSE layer, e.g., less fluid than the SSE layer. The cathode active material is typically provided on or in electrical communication with a conductive cathode current collector.

[0131] (Battery type) In some embodiments, the battery may be formed into a multi-layer stack of anodes and cathodes, such as pouch cells, coin cells, or some prismatic cells. Alternatively, the anode / cathode stack may be formed into a so-called jelly roll, which can be used for cylindrical cells or some prismatic cells. Such structures are mounted in a suitable housing with the desired electrical contacts. The cell may include a compression system that applies a compressive force between the anode and cathode, which can improve cycle life.

[0132] (separator) When using an SSE, the battery may further include a current separator between the negative and positive electrodes, although this is not usually necessary. The current separator allows lithium ions to flow between the negative and positive electrodes but prevents direct electrical contact, such as when the SSE is in a highly fluid state. The current separator is typically made in the form of a porous sheet of electrically insulating material. In some cases, the separator is a single-layer or multi-layer polymer sheet (e.g., polyolefin-based, PET-based, PVDF-based). The separator may alternatively comprise a glass material, a ceramic material, a ceramic material embedded in a polymer, a ceramic-coated polymer, or other composite or multi-layer structure, for example, to provide greater mechanical and thermal stability. In some cases, the separator may have a porosity of greater than 30%, low ionic resistivity, a thickness of 10 to 50 μm, and high bulk puncture strength.

[0133] (lithium salts) As noted above, some SSEs may include one or more lithium salts. SSEs may include one or more of the following non-limiting examples: LiPF, LiBF, LiClO, LiAsF, LiN(CFSO), LiN(CFSO), LiCFSO, LiC(CFSO), LiPF(CF), LiPF(CF), LiPF(CF), LiPF(CF), LiPF(iso-CF), LiPF(iso-CF), lithium salts with cyclic alkyl groups (e.g., (CF)(SO), 2x Li and (CF2)3(SO2) 2x Li), LiFSI (lithium bis(fluorosulfonyl)imide), LiTDI (lithium 4,5-dicyano-2-(trifluoromethyl)imidazole), and combinations thereof. In some embodiments, the effective concentration of lithium ions in the SSE may be at least 0.3 M, alternatively at least 0.7 M, alternatively at least 1 M, alternatively at least 1.5 M.

[0134] In some embodiments, the SSE may include a relatively small amount of organic solvent, for example, to enhance lithium ion conductivity or simply as a vehicle for adding lithium salts. In some embodiments, the weight percent of the solvent relative to the other components of the SSE may be less than 10%, or alternatively less than 5%, less than 2%, less than 1%, less than 0.5%, less than 0.2%, or less than 0.1%. If used, non-limiting examples of suitable non-aqueous solvents for lithium-ion batteries include cyclic carbonates (such as ethylene carbonate (EC), fluoroethylene carbonate (FEC)), propylene carbonate (PC), butylene carbonate (BC), and vinylethylene carbonate (VEC)), vinylene carbonate (VC), lactones (e.g., γ-butyrolactone (GBL), γ-valerolactone (GVL), and α-angelicalactone (AGL)), linear carbonates (e.g., dimethyl carbonate (DMC), methyl ethyl carbonate (MEC, commonly abbreviated as EMC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC), methyl butyl carbonate (MPC), and methyl butyl carbonate (MPC). carbonates (NBC) and dibutyl carbonate (DBC)), ethers (e.g., tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane (DME), 1,2-diethoxyethane and 1,2-dibutoxyethane), nitriles (e.g., acetonitrile and adiponitrile), linear esters (e.g., methyl propionate, methyl pivalate, butyl pivalate and octyl pivalate), amides (e.g., dimethylformamide), organic phosphates (e.g., trimethyl phosphate and trioctyl phosphate), organic compounds containing an S═O group (e.g., dimethyl sulfone and divinyl sulfone), and combinations thereof.

[0135] In some embodiments, electrochemical cycling conditions can be set to use only a portion of the theoretical charge / discharge capacity of silicon (3600 mAh / g). In some embodiments, the electrochemical charge-discharge cycle can be configured to use 400-600 mAh / g, alternatively 600-800 mAh / g, alternatively 800-1000 mAh / g, alternatively 1000-1200 mAh / g, alternatively 1200-1400 mAh / g, alternatively 1400-1600 mAh / g, alternatively 1600-1800 mAh / g, alternatively 1800-2000 mAh / g, alternatively 2000-2200 mAh / g, alternatively 2200-2400 mAh / g, alternatively 2400-2600 mAh / g, alternatively 2600-2800 mAh / g, alternatively 2800-3000 mAh / g, alternatively 3000-3200 mAh / g, alternatively 3200-3400 mAh / g, or any combination of these ranges.

[0136] (Embodiment) Further embodiments herein include the following enumerated embodiments: 1. A negative electrode including a plurality of lithium storage layer segments in electrical contact with a single negative electrode current collector; a positive electrode including a positive electrode active material layer in electrical contact with a positive electrode current collector; a lithium-ion containing solid electrolyte (SSE), the lithium storage layer segment comprises at least 40 atomic % silicon, tin, germanium, or a combination thereof; each lithium storage layer segment of the plurality of lithium storage layer segments is at least partially spaced apart from the other lithium storage layer segments; The lithium ion-containing solid electrolyte is i) interposed between the plurality of lithium storage layer segments and the positive electrode active material, and ii) at least partially disposed in the gaps between adjacent lithium storage layer segments. Lithium-ion battery cell. 2. The lithium storage layer segment is substantially free of a carbon-based binder; 1 is a lithium-ion battery cell according to embodiment 1. 3. The lithium storage layer segment comprises at least 80 atomic % amorphous silicon; 3. The lithium-ion battery cell of embodiment 1 or 2. 4. The SSE comprises a solid polymer electrolyte; The lithium ion battery cell according to any one of embodiments 1 to 3. 5. The solid polymer electrolyte includes poly(ethylene oxide), poly(acrylonitrile), poly(methyl methacrylate), poly(vinyl alcohol), poly(trimethylene carbonate), diester-based polymers, PVdF-based polymers, polycaprolactone, or derivatives or copolymers thereof; 10 is a lithium-ion battery cell according to a fourth embodiment. 5. The SSE contains a solid inorganic electrolyte; The lithium ion battery cell according to any one of embodiments 1 to 4. 6. Solid inorganic electrolytes include solid sulfides, b-alumina, LISICON, thio-LISICON, NASICON, perovskite, antiperovskite, garnet or complex hydrides; 6. A lithium-ion battery cell according to embodiment 5. 7. The SSE is a hybrid SSE containing both solid polymer electrolyte and solid inorganic electrolyte; The lithium ion battery cell according to any one of embodiments 1 to 6. 8. At least a portion of the SSE in the interstices has a different chemical composition than the SSE interposed between the lithium storage layer segment and the positive electrode active material; The lithium ion battery cell according to any one of embodiments 1 to 7. 9. The SSE includes: i) a first SSE material disposed in a first SSE layer disposed adjacent to the negative electrode; and ii) a second SSE material disposed in a second SSE layer interposed between the positive electrode and the first SSE layer; the second SSE material has a different chemical composition than the first SSE material; The lithium ion secondary battery cell according to any one of embodiments 1 to 8. 10. The first SSE material comprises a solid polymer electrolyte; 10. A lithium-ion battery cell according to embodiment 9. 11. The second SSE material comprises a solid inorganic electrolyte, which is optionally a solid sulfide electrolyte; The lithium-ion battery cell of embodiment 9 or 10. 12. The positive electrode active material layer contains a solid electrolyte material; The lithium ion battery cell according to any one of embodiments 1 to 11. 13. The solid electrolyte material of the positive electrode active material layer has a different chemical composition from the SSE interposed between the lithium storage layer segment and the positive electrode active material; 13. The lithium-ion battery cell of embodiment 12. 14. The positive electrode active material layer contains a lithium metal compound, The lithium metal compound is optionally LiCoO2, LiFePO4, LiMnO2, LiNiO2, LiMn2O4, LiCoPO4, LiNi x Co y Mn z O2, LiNi X Co Y Al Z O2, LiFe2(SO4)3 or Li2FeSiO4, The lithium ion battery cell according to any one of embodiments 1 to 13. 15. At least a portion of the lithium storage layer segments are characterized by a continuous porous lithium storage layer comprising at least 60 atomic %, optionally 80 atomic %, silicon; The lithium ion battery cell according to any one of embodiments 1 to 14. 16. The negative electrode further includes an auxiliary layer disposed on an upper surface of each lithium storage layer segment; the auxiliary layer includes a material that is electrically conductive to lithium ions; The auxiliary layer is optionally further disposed on the sidewall of the lithium storage segment; The lithium ion battery cell according to any one of embodiments 1 to 15. 17. A method of manufacturing a lithium ion battery cell, comprising: providing a negative electrode including a plurality of lithium storage layer segments in electrical contact with a negative electrode current collector; contacting a top surface of each lithium storage layer segment of the plurality of lithium storage layer segments with a lithium ion-containing solid electrolyte (SSE) material; providing a positive electrode comprising: i) in electrical contact with a positive electrode current collector; and ii) a positive electrode active material layer in contact with the SSE material, such that the SSE material is interposed between the lithium storage layer segment and the positive electrode active material layer; each lithium storage layer segment of the plurality of lithium storage layer segments is at least partially spaced apart from the other lithium storage layer segments; method. 18. The lithium storage layer segment comprises at least 40 atomic % silicon, tin, germanium, or a combination thereof; 18. The method of embodiment 17. 19. The lithium storage layer segment comprises at least 60 atomic % amorphous silicon, or optionally at least 80 atomic % silicon; 19. The method of embodiment 17 or 18. 20. Further comprising: moving a portion of the SSE material into gaps between adjacent lithium storage layer segments; The method of any one of embodiments 17 to 19. 21. The SSE material is transferred into the gap before providing the positive electrode; The method of embodiment 20. 22. The SSE material is transferred into the gap after providing the positive electrode; The method of embodiment 20. 23. Moving a portion of the SSE material includes heating the SSE to a temperature T1 in the range of 80°C to 250°C; The method of any one of embodiments 20 to 22. 24. Displacing a portion of the SSE material includes compressing the SSE against the negative electrode with a force greater than 10 bar; The method of any one of embodiments 20 to 23. 25. At least a portion of the gaps between adjacent lithium storage layer segments are filled with an interstitial solid electrolyte material having a chemical structure different from at least a portion of the SSE material interposed between the plurality of lithium storage layer segments and the positive electrode active material layer prior to contact with the SSE material. The method of any one of embodiments 17 to 19. 26. The SSE includes: i) a first SSE material provided in a first SSE layer disposed adjacent to the negative electrode; and ii) a second SSE material provided in a second SSE layer interposed between the positive electrode and the first SSE layer; the second SSE material has a different chemical composition than the first SSE material; The method of any one of embodiments 17 to 25. 27. The first SSE material comprises a solid polymer electrolyte; The method of embodiment 26. 28. The second SSE material comprises a solid inorganic electrolyte, optionally a solid sulfide electrolyte; 28. The method of embodiment 26 or 27. 29. Further comprising providing a first SSE material in at least a portion of the gaps between adjacent lithium storage layer segments; The method of any one of embodiments 26 to 28. 30. The lithium storage layer segment is substantially free of carbon-based binders and conductive carbon; The method of any one of embodiments 17 to 29. 31. Further comprising pattern-depositing a silicon-containing negative electrode active material onto a negative electrode current collector by a CVD or PVD process to form a negative electrode; The method of any one of embodiments 17 to 30. 32. At least a portion of the lithium storage layer segment is characterized as a continuous porous lithium storage layer having at least 60 atomic % silicon, or optionally at least 80 atomic % silicon; The method of any one of embodiments 17 to 31. 33. The lithium storage layer segment comprises at least 80 atomic % amorphous silicon, or optionally at least 90 atomic % amorphous silicon, or optionally at least 95 atomic % amorphous silicon; The method of any one of embodiments 17 to 32. 34. The lithium storage layer segments have an average thickness of at least 4 μm, optionally at least 7 μm, or optionally at least 10 μm; The method of any one of embodiments 17 to 33. 35. The negative electrode current collector includes a conductive layer and a surface layer disposed between the conductive layer and the lithium storage layer segment; The method of any one of embodiments 17 to 34. 36. The surface layer comprises a metal oxide, an oxometalate, or a metal silicide; The method of embodiment 35. 37. The negative electrode further includes an auxiliary layer disposed on an upper surface of each lithium storage layer segment; The auxiliary layer comprises a material that is electrically conductive to lithium ions and optionally has a thickness of 100 nm or less. The method of any one of embodiments 17 to 36. 38. The auxiliary layer is further disposed on the side wall of the lithium storage layer segment; The method of embodiment 37. 39. The auxiliary layer can be metal oxide, metal nitride, metal cone, LiPON, lithium phosphate, lithium aluminum oxide, (Li, La) x Ti y Oz, or Li x Si y Contains Al2O3, 39. The method of embodiment 37 or 38. 40. Providing a negative electrode is providing a negative electrode precursor comprising a precursor lithium storage layer deposited on a negative electrode current collector by a CVD or PVD process; and processing a negative electrode precursor to form a negative electrode; the precursor lithium storage layer comprises at least 60 atomic % silicon and is substantially free of carbon-based binders or conductive carbon; The lithium storage layer segment is formed from a precursor lithium storage layer. The method of any one of embodiments 17 to 39. 41. The treating includes applying a physical force to form discontinuities corresponding to boundaries of one or more lithium storage layer segments; The method of embodiment 40. 42. The treating includes removing portions of the precursor lithium storage layer in a pattern to form gaps between lithium storage layer segments; 42. The method of embodiment 40 or 41. 43. The treating includes electrochemically treating the negative electrode precursor in a liquid electrolyte including a lithium ion salt; The method of any one of embodiments 40 to 42. 44. Treating includes lithiation; The method of any one of embodiments 40 to 43. 45. The precursor lithium storage layer comprises a continuous porous lithium storage layer; The method of any one of embodiments 40 to 44. 46. ​​The precursor lithium storage layer comprises at least 80 atomic % amorphous silicon, or optionally at least 90 atomic % amorphous silicon, or optionally at least 95 atomic % amorphous silicon; The method of any one of embodiments 40 to 45. 47. The density of the precursor lithium storage layer is 1.1 to 2.29 g / cm 3 is within the range of The method of embodiment 46. 48. The precursor lithium storage layer comprises pillars of aggregates of silicon nanoparticles; The method of any one of embodiments 40 to 47. 49. The precursor lithium storage layer has an average thickness of at least 4 μm, optionally at least 7 μm, or optionally at least 10 μm; The method of any one of embodiments 40 to 48. 50. Providing the negative electrode includes pattern printing of a mixture or slurry containing at least 50% by weight of silicon; The method of any one of embodiments 17 to 25. 51. Produced by any one of the methods of embodiments 17 to 50. Lithium-ion battery cell. 52. A negative electrode including a plurality of lithium storage layer segments in electrical contact with a negative electrode current collector; a positive electrode including a positive electrode active material layer in electrical contact with a positive electrode current collector; a lithium ion-containing solid electrolyte (SSE) interposed between the plurality of lithium storage layer segments and the positive electrode active material; i) the lithium storage layer segment comprises at least 40 atomic % silicon, tin, germanium, or a combination thereof; ii) each lithium storage layer segment of the plurality of lithium storage layer segments is at least partially spaced apart from other lithium storage layer segments; iii) a functional material is provided in the spaces between the lithium storage segments; The functional material has a function other than the conduction of lithium ions. Lithium-ion battery cell. 53. The functional material includes a conductive material; 53. The cell of embodiment 52. 54. The conductive material includes conductive carbon, graphene, carbon nanotubes, metal nanoparticles, or metal nanowires; 54. The cell of embodiment 53. 55. The functional material includes a negative electrode active material different from that of the lithium storage layer segment; A cell according to any one of embodiments 52 to 54. 56. The functional material further comprises a polymeric binder; 56. The cell of embodiment 54 or 55. 57. The functional material includes a compressible polymer that is electrically insulating and does not substantially conduct lithium ions; 53. The cell of embodiment 52. 58. A negative electrode including a plurality of lithium storage layer segments in electrical contact with a negative electrode current collector; a positive electrode including a positive electrode active material layer in electrical contact with a positive electrode current collector; a lithium ion-containing solid electrolyte (SSE) interposed between the second lithium storage layer and the positive electrode active material; i) the lithium storage layer segment comprises at least 40 atomic % silicon, tin, germanium, or a combination thereof; ii) each lithium storage layer segment of the plurality of lithium storage layer segments is at least partially spaced apart from other lithium storage layer segments; iii) a second lithium storage layer is disposed on the segmented lithium storage layer at least partially in the spaces between the lithium storage layer segments; the second lithium storage layer has a different chemical composition than the lithium storage layer segment; Lithium-ion battery cell. 59. The second lithium storage layer is provided by coating a slurry; 59. The cell of embodiment 58. 60. The second lithium storage layer is provided by a PVD or CVD process; 59. The cell of embodiment 58. 61. The SSE has a thickness in the range of 5 to 300 μm; The lithium-ion battery cell or method of any of the preceding embodiments.

[0137] The specific details of particular embodiments may be combined in any suitable manner without departing from the spirit and scope of the embodiments of the invention. However, other embodiments of the invention may be directed to particular embodiments with respect to each individual aspect, or to particular combinations of these individual aspects.

[0138] The foregoing description of the exemplary embodiments of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form described, and many modifications and variations are possible in light of the above teaching.

[0139] In the preceding description, for purposes of explanation, numerous details are set forth in order to provide an understanding of various embodiments of the present technology. However, it will be apparent to one skilled in the art that particular embodiments may be practiced without some of these details or with additional details.

[0140] While several embodiments have been described, those skilled in the art will recognize that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the invention. Moreover, a number of well-known steps and elements have not been described in order to avoid unnecessarily obscuring the invention. Furthermore, the details of a particular embodiment may not always be present in variations of that embodiment, and may be added to other embodiments.

[0141] Where a range of values ​​is provided, unless the context clearly dictates otherwise, it is understood that each intervening value, to the tenth of the unit of the lower limit, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated or intervening value in a range and any other stated or intervening value in that range is also encompassed. The upper and lower limits of these smaller ranges may each independently be included or excluded, and each range that includes either, either, or both upper limits in the smaller ranges is also encompassed within the invention, subject to any specifically excluded upper limits in the stated range. Where a stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

[0142] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, a reference to "a method" includes a plurality of such methods; a reference to "a negative electrode" includes a reference to one or more negative electrodes and equivalents thereof known to those skilled in the art, and so forth. The present invention has been described in detail for purposes of clarity and understanding. However, it will be understood that certain changes and modifications can be practiced within the scope of the appended claims.

[0143] All publications, patents, and patent applications cited herein are incorporated by reference in their entirety for all purposes, and none are admitted to be prior art.

Claims

1. a negative electrode including a plurality of lithium storage layer segments in electrical contact with a negative electrode current collector; a positive electrode including a positive electrode active material layer in electrical contact with a positive electrode current collector; a lithium ion-containing solid electrolyte (SSE: Solid State Electrolyte), the lithium storage layer segment comprises at least 40 atomic % silicon, tin, germanium, or a combination thereof; each lithium storage layer segment of the plurality of lithium storage layer segments is at least partially spaced apart from other lithium storage layer segments; the lithium ion-containing solid electrolyte is i) interposed between the plurality of lithium storage layer segments and the positive electrode active material, and ii) at least partially disposed in gaps between adjacent lithium storage layer segments; Lithium-ion battery cell.

2. the lithium storage layer segment is substantially free of a carbon-based binder; The lithium-ion battery cell of claim 1 .

3. the lithium storage layer segment comprises at least 80 atomic % amorphous silicon; The lithium-ion battery cell of claim 1 .

4. The SSE comprises a solid polymer electrolyte. The lithium-ion battery cell of claim 1 .

5. The solid polymer electrolyte comprises poly(ethylene oxide), poly(acrylonitrile), poly(methyl methacrylate), poly(vinyl alcohol), poly(trimethylene carbonate), diester-based polymers, PVdF-based polymers, polycaprolactone, or derivatives or copolymers thereof; The lithium-ion battery cell according to claim 4 .

6. The SSE comprises a solid inorganic electrolyte. The lithium-ion battery cell of claim 1 .

7. The solid inorganic electrolyte comprises a solid sulfide, b-alumina, LISICON, thio-LISICON, NASICON, perovskite, antiperovskite, garnet, or complex hydride; The lithium-ion battery cell according to claim 5 .

8. The SSE is a hybrid SSE containing both a solid polymer electrolyte and a solid inorganic electrolyte. The lithium-ion battery cell of claim 1 .

9. At least a portion of the SSE in the gap has a different chemical composition from the SSE interposed between the lithium storage layer segment and the positive electrode active material. The lithium-ion battery cell of claim 1 .

10. The SSE comprises: i) a first SSE material in a first SSE layer disposed adjacent to the negative electrode; and ii) a second SSE material in a second SSE layer interposed between the positive electrode and the first SSE layer; the second SSE material has a different chemical composition than the first SSE material; The lithium-ion battery cell of claim 1 .

11. the first SSE material comprises a solid polymer electrolyte; The lithium-ion battery cell of claim 9.

12. the second SSE material comprises a solid inorganic electrolyte; The lithium-ion battery cell of claim 9.

13. the second SSE material comprises a solid sulfide electrolyte; 12. The lithium-ion battery cell of claim 11.

14. The positive electrode active material layer contains a solid electrolyte material. The lithium-ion battery cell of claim 1 .

15. the solid electrolyte material of the positive electrode active material layer has a chemical composition different from that of the SSE interposed between the lithium storage layer segment and the positive electrode active material; 14. The lithium-ion battery cell of claim 13.

16. the positive electrode active material layer contains a lithium metal compound, The lithium metal compound is LiCoO ２ , LiFePO ４ , LiMnO ２ , LiNiO ２ , LiMn ２ O ４ , LiCoPO ４ , LiNi ｘ Co ｙ Mn ｚ O ２ , LiNi Ｘ Co Ｙ Al Ｚ O ２ , LiFe ２ (SO ４ ) ３ or Li ２ FeSiO ４ Including, The lithium-ion battery cell of claim 1 .

17. At least a portion of the lithium storage layer segments are characterized by a continuous porous lithium storage layer comprising at least 80 atomic % silicon. The lithium-ion battery cell of claim 1 .

18. the negative electrode further includes an auxiliary layer disposed on an upper surface of each lithium storage layer segment; the auxiliary layer has a thickness of 100 nm or less and is capable of conducting lithium ions from the SSE to the lithium storage layer segment; The lithium-ion battery cell of claim 1 .

19. The auxiliary layer is further disposed on a side wall of the lithium storage layer segment.

18. The lithium ion battery cell of claim 17.

20. The auxiliary layer may be made of a metal oxide, a metal cone, LIPON, lithium phosphate, lithium aluminum oxide, (Li, La) ｘ Ti ｙ O ｚ , or Li ｘ Si ｙ Al ２ O ３ Including, 18. The lithium ion battery cell of claim 17.

21. The SSE has a thickness in the range of 5 to 300 μm. The lithium-ion battery cell of claim 1 .

22. the negative electrode further includes a functional material disposed within the gap; the functional material comprises a conductive material, a negative electrode active material different from the lithium storage layer segment, or a compressible polymer that is not an SSE; The lithium-ion battery cell of claim 1 .

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