Mass production of alloy anodes for Li-ion batteries

Abstract

The embodiments of the present disclosure generally relate to the manufacture of flexible substrates. In particular, the embodiments described herein relate to methods for manufacturing flexible substrates that can be used to improve the lifespan of lithium-ion batteries. In one or more embodiments, a method for manufacturing alloy anodes comprises the steps of forming an alloy anode using a planar flow melt spinning process comprising solidifying a molten material on a quenching surface of a rotary casting drum, and performing a pre-lithiation surface treatment on the alloy anode.

Description

Technology Field

[0001] The embodiments of the present disclosure generally relate to the manufacture of flexible substrates. In particular, the embodiments described herein relate to methods for manufacturing flexible substrates to improve the lifespan of lithium-ion batteries. Background Technology

[0002] Flexible substrates can be used in packaging, semiconductor, and photovoltaic applications. Processing of flexible substrates may include the step of coating the flexible substrate with a desired material, such as metals, semiconductors, and / or dielectric materials. Systems for performing processing of flexible substrates generally include a processing drum, e.g., a cylindrical roller, which is coupled to the processing system to transport the substrate and upon which at least a portion of the substrate is processed. Thus, roll-to-roll coating systems provide relatively high throughput systems.

[0003] When lithium is stored in the anode as part of the charge, it causes unwanted volume expansion of the anode, which can consequently reduce the battery life of the resulting lithium-ion battery. Therefore, the industry needs methods for manufacturing flexible substrates to improve the life of lithium-ion batteries.

[0004] The embodiments of the present disclosure generally relate to the manufacture of flexible substrates. In particular, the embodiments described herein relate to methods for manufacturing flexible substrates to improve lithium-ion battery life. In one or more embodiments, a method for manufacturing alloy anodes comprises the step of forming an alloy anode using a planar flow melt spinning process comprising solidifying a molten material on a quenching surface of a rotary casting drum. The method further comprises the step of performing a pre-lithiation surface treatment on the alloy anode.

[0005] In some embodiments, a method for manufacturing alloy anodes comprises the step of forming a lithium-containing alloy anode using a planar flow melt spinning process comprising solidifying a molten material on a quenching surface of a rotary casting drum. The method further comprises the step of depositing a protective layer on the alloy anode.

[0006] In other embodiments, a method for manufacturing alloy anodes comprises the steps of forming an alloy anode using a planar flow melt spinning process, creating engineered porosity in the alloy anode through laser drilling, performing a pre-lithiation surface treatment, depositing a protective layer on the alloy anode, and stacking the alloy anode on a current collector.

[0007] In some embodiments, a non-transient computer-readable medium stores instructions that, when executed by a processor, cause the process to perform operations of the devices and / or methods. Brief explanation of the drawing

[0008] In order to make the features cited above of the present disclosure understandable in detail, a more detailed description of the present disclosure, briefly summarized above, may be made with reference to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the accompanying drawings are merely illustrative of exemplary embodiments and should not be construed as limiting the scope thereof, and that other equally valid embodiments may be permitted.

[0009] FIG. 1 depicts a schematic cross-sectional view of a coating chamber according to one or more embodiments described and discussed in this specification.

[0010] FIG. 2 is a flowchart illustrating a method for coating a flexible substrate according to one or more embodiments described and discussed in this specification.

[0011] FIG. 3a depicts a schematic cross-sectional view of a flexible substrate according to one or more embodiments described and discussed herein.

[0012] FIG. 3b depicts a schematic plan view of the flexible substrate of FIG. 3a according to one or more embodiments described and discussed herein.

[0013] FIG. 3c depicts a schematic cross-sectional view of a portion of the flexible substrate of FIG. 3a according to one or more embodiments described and discussed herein.

[0014] FIG. 4 is a flowchart illustrating a method for manufacturing the flexible substrates of FIG. 3a to 3c according to one or more embodiments.

[0015] FIG. 5a depicts a schematic cross-sectional view of a flexible substrate according to one or more embodiments described and discussed herein.

[0016] FIG. 5b depicts a schematic plan view of the flexible substrate of FIG. 5a according to one or more embodiments described and discussed herein.

[0017] FIG. 6 is a flowchart illustrating a method for manufacturing the flexible substrates of FIG. 5a and FIG. 5b according to one or more embodiments described and discussed in this specification.

[0018] For ease of understanding, the same reference numbers have been used where possible to designate the same elements common to the drawings. The elements and features of one embodiment are considered to be advantageously incorporated into other embodiments without further mention.

[0019] Many of the details, dimensions, angles, and other features depicted in the drawings are merely examples of specific embodiments. Accordingly, other embodiments may have other details, components, dimensions, angles, and features without departing from the spirit or scope of the present disclosure. Additionally, further embodiments of the present disclosure may be practiced without some of the details described below. Specific details for implementing the invention

[0020] The embodiments of the present disclosure generally relate to the manufacture of flexible substrates. In particular, the embodiments described herein relate to methods for manufacturing flexible substrates to improve lithium-ion battery life. To provide a complete understanding of the various embodiments of the present disclosure, specific details are provided in the following description and in FIGS. 1a through 6. Other details describing well-known structures and systems often associated with web coating, web delivery, and web tension control of a flexible substrate or web in a roll-to-roll deposition system are not described in the following disclosure to avoid unnecessarily obscuring the description of the various embodiments.

[0021] The embodiments described and discussed herein are provided below in relation to roll-to-roll coating systems. Exemplary roll-to-roll coating systems may be or include TopMet™ systems, SmartWeb™ systems, or TopBeam™ systems commercially available from Applied Materials, Inc., Santa Clara, California. Other tools capable of performing roll-to-roll processing may also be adapted to take advantage of the embodiments described herein. The description of the apparatus described herein is illustrative and should not be understood or interpreted as limiting the scope of the embodiments described herein. Additionally, the embodiments described herein may be applied to a flexible substrate having a coating on one side, a coating on opposing sides, or a "double-sided" coating.

[0022] It should be noted that while the specific substrates on which some of the embodiments described in this specification may be implemented are not limited, it is particularly advantageous to implement the embodiments on flexible substrates, such as web-based substrates, panels, and discrete sheets.

[0023] Additionally, it is noted herein that a flexible substrate or web as used within the embodiments described herein may typically be characterized as being bendable. The term “web” may be used synonymously with the terms “strip,” “flexible substrate,” etc. For example, a web as described in the embodiments described herein may be a foil. Synonyms for the term “web” include strip, foil, flexible substrate, etc. Typically, a web comprises a continuous sheet of thin, flexible material. Typical web materials are metals, plastics, paper, etc. A web as understood herein is typically a three-dimensional solid. The thickness of a web as understood herein may be less than 1 mm, more typically less than 500 mm, or even less than 10 mm. A web as understood herein may have a width of at least 0.1 m, more typically at least 1 m, or even at least 4 m. The web as understood in this specification may have a length of at least 1 km, 25 km, or even 60 km.

[0024] Additionally, it should be noted that in this disclosure, "roll" or "roller" may be understood as a device providing a surface to which a substrate (or a part of a substrate) can be contacted while the substrate is present in a processing system. At least a portion of the "roll" or "roller" as described herein may include a circular shape for contacting a substrate to be processed or a substrate that has already been processed. In some embodiments, the "roll" or "roller" may have a cylindrical or substantially cylindrical shape. A substantially cylindrical shape may be formed around a straight longitudinal axis or around a curved longitudinal axis. According to some embodiments, the "roll" or "roller" as described herein may be adapted to contact a flexible substrate. For example, the "roll" or "roller" as described herein may include a guide roller adapted to guide the substrate while the substrate is being processed (e.g., during a deposition process) or while the substrate is present in a processing system; A spreader roller adapted to provide defined tension to a substrate to be coated; a deflection roller for deflecting the substrate along a defined path of travel; a processing roller for supporting the substrate during processing, such as a process drum, e.g., a coating roller or a coating drum; and a adjusting roller, a feed roller, a take-up roller, etc. As described herein, the “roll” or “roller” may be metal or may comprise metal.

[0025] Lithium-ion (Li-ion) batteries using graphite anodes and new cell designs typically have a low proportion of silicon powder. Attempts are being made to produce silicon powder alloys to overcome issues related to volume expansion. If the electrode structure is engineered as a standalone membrane to accommodate volume changes, the use of standalone membranes will have a significant impact on manufacturing and integration. While current silicon and / or silicon oxide blend anodes manufactured by slurry coating show potential in cycle life (exceeding 500 cycles), calendar life (less than 2 to 3 years) remains a major challenge for electric vehicle (EV) adoption. Increased cell impedance over time is also a major issue faced by current slurry-coated powder anodes. The growth of the active material surface area and the consequent continuous solid electrolyte interphase (SEI) during electrochemical cycling are major issues limiting calendar life and cell impedance growth. In this disclosure, an engineering approach to surface problems is proposed.

[0026] Other approaches utilize micrometer-scale anode powder particles, but surface area control during growth presents manufacturing challenges. This disclosure relates to surface area control during cycling of anodes fabricated from monolithic foils. While deposition approaches such as physical vapor deposition (PVD) or chemical vapor deposition (CVD) for producing silicon anodes are relatively expensive, powder approaches suffer from calendar life issues despite their promising cycle life and rate capabilities. The approach proposed in this disclosure helps to produce alloy anodes from films and to improve calendar life by engineering the structure to generate a low surface area, thereby reducing impedance increase with cycles.

[0027] In some embodiments of the present disclosure, the molten metal or metal alloy is deposited directly onto a cold casting drum to form an alloy anode film. In one or more embodiments that may be combined with other embodiments described herein, the molten metal alloy is a silicon tin aluminum titanium alloy (Si 78 Sn 16 It is one of Al4Ti2), titanium aluminum carbon alloy (Ti2AlC or Ti3AlC), or iron copper silicon alloy (Fe2Cu2Si5). The alloy may be crystalline or amorphous. In one or more embodiments that may be combined with other embodiments described herein, the molten metal alloy is one of lithium bismuth (Li-Bi) alloy, lithium silver (Li-Ag) alloy, lithium tin (Li-Sn) alloy, or lithium silicon (Li-Si) alloy. The molten metal undergoes rapid solidification (e.g., at a rate of one million degrees per second). The solidified metal or metal alloy is then transferred to a substrate using a cold transfer process at low temperatures.

[0028] In some examples, the cold casting drum is coated with a transfer fluid before depositing molten metal or a metal alloy onto the casting drum. The transfer fluid prevents the deposited metal or metal alloy from adhering to the cold surface of the casting drum, thereby facilitating the easy transfer of the solidified molten metal or metal alloy onto the substrate. In one or more examples, the transfer fluid is a low vapor pressure and / or alkali metal compatible ionic liquid. The transfer fluid may be applied to the casting drum via a roller coating process. After applying the heat transfer fluid to the casting drum, the molten metal or metal alloy may be deposited onto the heat transfer layer via a deposition process. After solidification, the solidified metal or metal alloy is then transferred to the substrate by the casting drum. In one or more examples, the metal or metal alloy is lithium, and the substrate is a flexible substrate, such as a lithium-ion anode, a metallized plastic substrate, a copper current collector, or a combination thereof.

[0029] In some examples, after a transfer liquid is applied to a casting drum, a surface protection layer forming liquid is applied to the casting drum. The surface protection layer forming liquid solidifies rapidly to form a surface protection layer on top of the transfer liquid layer. Then, molten metal or a metal alloy is deposited onto the surface protection layer through a deposition process, for example, a spray coating process. After solidification, the solidified metal or metal alloy and the protection layer are transferred to a substrate by the casting drum. The solidified metal or metal alloy and the protection layer are transferred by the casting drum in the reverse order of deposition. For example, the solidified metal or metal alloy comes into contact with the substrate with the protection layer formed on the solidified metal or metal alloy layer. In one or more examples, the metal or metal alloy is lithium, the substrate is a flexible substrate, such as a lithium-ion anode, a metallized plastic substrate, a copper current collector, or a combination thereof, and the protective layer is a surface protective layer such as lithium fluoride, bismuth telluride (Bi2Te3), copper, indium, gallium, aluminum, aluminum oxide, zinc, zinc oxide, tin, lithium phosphorus nitride, lithium nitrate (LiNO3), phosphate, sulfate, carbon, or any combination thereof.

[0030] Examples of deposition processes that may be used with the embodiments described herein may be sputtering, evaporation (e.g., thermal or e-beam), direct liquid application (e.g., slot-die coating, comma bar coating, Meyer rod coating, planar flow melt spin, casting nozzle coating, or roller coating), spray coating processes (e.g., subsonic spray, electrostatic spray, gas pressure spray, thermal spray, and plasma spray), or any combination thereof, or may include these.

[0031] Examples of surface protective films that may be formed using the embodiments described herein include a lithium fluoride (LiF) film; a dielectric or ceramic film (e.g., oxides of titanium, aluminum, niobium, tantalum, zirconium, or combinations thereof); one or more metal films (e.g., tin, antimony, bismuth, gallium, germanium, copper films, silver films, gold films, or combinations thereof); a copper chalcogenide film (e.g., CuS, Cu2Se, Cu2S); a bismuth chalcogenide film (e.g., Bi2Te3, Bi2Se3); Tin chalcogenide films (e.g., SnTe, SnSe, SnSe2, SnS), gallium chalcogenide films (e.g., GaS, Ga2S3, GaSe, Ga2Se3, GaTe), germanium chalcogenide films (GeTe, GeSe, GeS), indium chalcogenide films (e.g., InS, In6S7, In2S3, InSe, InS4Se3, In6Se7, In2Se3, InTe, In4Te3, In3Te4, In7Te 10 The film may be at least one of the following: (In2Te3, In2Te5), chalcogenide films (Ag2Se, Ag2S, Ag2Te), boron nitride, lithium nitrate, lithium borohydride, and combinations thereof; and carbon-containing films, or may comprise at least one of these. In some examples, one or more surface protective films are ion-conducting films. In some examples, one or more surface protective films are permeable to at least one of lithium ions and lithium atoms. One or more surface protective films provide surface protection of the metal or metal alloy film, thereby allowing the metal or metal alloy film to be handled in a dry indoor environment.

[0032] Examples of transfer fluids that may be used with the embodiments described herein may be ionic liquids and heat transfer fluids (e.g., synthetic oils, mineral oils, and molten salts) or may include these. Examples of oils that may be used with the embodiments described herein may be synthetic hydrocarbons, silicons, hydrocarbons, aromatic oils, paraffin oils, and alkylated aromatic oils or may include these. Examples of synthetic oils that may be used with the embodiments described herein may be or include Therminol® VP-1 (FRAGOL AG), Therminol® D12 (FRAGOL AG), Diphyle® (Bayer AG), Dowtherm® (Dow Chemical), Therm® S300 (Nippon Steel), Fragoltherm® F-12 (FRAGOL AG), Paratherm™ LR Low Range Heat Transfer Fluid (plastiXs®), and Paratherm™ NF Heat Transfer Fluid (plastiXs®), which are eutectoid mixtures of 73.5 wt% biphenyl ether and 23.5 wt% biphenyl having a melting point of 12°C. Examples of mineral oils that may be used with the embodiments described herein may be Caloria HT 43 or may include it. Examples of molten salts that may be used with the embodiments described herein may be or include nitrate-based molten salts (e.g., NaNO3, KNO3, NaNO2, and Ca(NO3)3), chloride-based molten salts (e.g., KCl-MgCl2), and fluorine-based molten salts (e.g., LiF-NaF-KF). Examples of ionic liquids that may be used with the embodiments described herein are N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium [DEME] + , bis(fluorosulfonyl)imide[FSI]- , N-methyl-N-alkyl pyrrolidinium [C n mpyr], N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)amide [C3mpyr TFSI], N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide [C3mpyr FSI], bis(trifluoromethanesulfonyl)amide [NTf2] - , N-methyl-N-alkyl piperidinium [C n mpip] + , N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)amide [C3mpip TFSI], N-butyl-N-methylpyrulilidinium dicyanamide [C4mpyr][DCA], N-methyl-butylpyrrolidinium tetracyanoborate [C4mpyr TCB], tetrafluoroborate [BF4] - , 1,2-dialkyl methylimidazolium [C n C n mim] + , dicyanamide [dca] - , imide-based ionic liquids (e.g., bis(trifluoromethanesulfonyl)imide (TFSI) - ), bis(fluorosulfonyl)imide (FSI - ), N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 14TFSI) or N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMI][TFSI]), and polymerized ionic liquid block copolymers (e.g., poly(styrene-b-ethylene oxide) (PS-PEO) / [EMI][TFSI] solutions) may be or may comprise these. Examples of ionic liquids (cationic) that may be used with the embodiments described herein include quaternary ammoniums containing N, P, or S, imidazolium, pyrrolidinium, piperidinium, hexatrimethylphosphonium, and triethylsulfonium. Examples of ionic liquids (anionic) that can be used with the embodiments described herein include N,N-bis(trifluoromethane)-sulfonamide (TFSI), bis(fluorosulfonyl)imide (FSI), tetrafluoroborate (BF4) and hexafluorophosphate (PF6), and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide (Py14-TFSI).

[0033] Examples of solid electrolyte-forming materials that may be used with the embodiments described herein include vinyl carbonate (VC), fluorinated vinyl carbonate (FEC), fluorinated vinyl cyclosiloxanes, fluorinated sulfones, tri(hexafluoroisophosphate) (HFiP), tris(pentafluorophenyl)phosphine (TPFPP), biphenyl, 3,4-ethylenedioxythiophene (EDT), biphenyl, cyclohexylbenzene, cyclohexylbenzene (CHB), 1,3-propanesulfone (PS), 1-methyl-1,3-propanesulfone, 2-methyl-l,3-propanesulfone, 3-methyl-1,3-propanesulfone, 1-ethyl-1,3-propanesulfone, succinitrile, sebaconitrile, glutaronitrile, adiponitrile, 1,5-dicyanopentan, 1,6-dicyanohexane, It includes 1,7-dicyanoheptane, 1,8-dicyanooctane, 1,9-dicyanononane, siloxane backbone to polyethylene oxide, o-terphenyl, triphenylene, cyclohexylbenzene, biphenyl, 1,3-propanesulfonate, N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide (Py14-TFSI), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and PVDF.

[0034] FIG. 1 illustrates a schematic side view of an exemplary molten metal coating system (100) for manufacturing a flexible substrate according to one or more embodiments. The molten metal coating system (100) may be used to form a flexible layer stack. The molten metal coating system (100) includes a molten metal coating module (130) according to one or more embodiments described herein. The molten metal coating system (100) further includes an unwinding module (120) operable to supply a flexible substrate, such as a continuous flexible substrate (122), to the molten metal coating module (130). The molten metal coating module (130) further includes a winding module (140) operable to collect the flexible substrate from the molten metal coating module (130). The molten metal coating system (100) may be operable for single-sided or double-sided processing of the flexible substrate. In some embodiments, the molten metal coating system (100) can be operated to deposit molten metal (e.g., molten lithium) on a flexible substrate through a planar flow melt spinning process.

[0035] The molten metal coating system (100) may include any suitable structure, configuration, arrangement, and / or components that enable the molten metal coating system (100) to deposit molten metal and / or passivate the deposited molten metal onto a continuous flexible substrate (122) according to embodiments of the present disclosure. For example, in some embodiments, the molten metal coating system (100) may be suitable deposition systems including casting rollers, atomizers, evaporators, air bearings, power sources, individual pressure controllers, deposition control systems, load cells, servomotors, and temperature control components, or may include suitable deposition systems.

[0036] A molten metal coating system (100) comprises a chamber body (102). The chamber body (102) may be made of standard materials such as aluminum, quartz, ceramic, or stainless steel. The chamber body (102) may be cooled by a fluid, for example, water, one or more glycol-based fluids, or any combination thereof. The chamber body (102) defines an internal volume (103). Partition plates (104a, 104b) (collectively referred to as 104) extend across the internal volume (103) defined by the chamber body (102). Partition plate (104a) separates the internal volume (103) into an unwinding volume (106) operable to supply a continuous flexible substrate (122) and a processing volume (107) on which molten metal is deposited onto the continuous flexible substrate (122). The partition plate (104b) separates the internal volume (103) into a processing volume (107) and a winding volume (108) operable to collect the processed continuous flexible substrate (122). The partition plates (104a, 104b) each include one or more through holes (109a, 109b) (collectively referred to as 109) for receiving the continuous flexible substrate (122). Each through hole (109) within the partition plate (104) is sized to receive the continuous flexible substrate (122) while enabling differential pumping between the unwinding volume (106), the processing volume (107), and / or the winding volume (108). In one embodiment, the chamber body (102) defines a vacuum chamber. In other implementations, for non-vacuum deposition techniques such as roller coating and slot die coating, a dry room or glove box chamber may be used.

[0037] In some embodiments, an inert gas environment is maintained in at least one of the unwinding volume (106), the processing volume (107), and / or the winding volume (108). The inert gas environment may include an inert gas selected from argon, nitrogen, or combinations of argon and nitrogen. The inert gas environment of the unwinding volume (106), the processing volume (107), and / or the winding volume (108) is substantially isolated from the ambient (e.g., atmosphere) environment outside the molten metal coating system (100) (e.g., providing gas separation), thereby reducing the possibility of contamination of the deposited lithium film. These inert gas environments of the unwinding volume (106), processing volume (107), and / or winding volume (108) also, if desired, isolate the unwinding volume (106) from the processing volume (107) (e.g., providing gas separation) and isolate the processing volume (107) from the winding volume (108). Such isolation enables the use of incompatible chemistry in the unwinding volume (106), processing volume (107), and / or winding volume (108). In one or more examples, the processing volume (107) comprises an argon gas environment, and the winding volume (108) comprises a combination of argon and a passivation gas (e.g., nitrogen).

[0038] In some embodiments, at least one of the unwinding volume (106), processing volume (107) and winding volume (108) is coupled to a pressure control system (not shown), which pumps down and vents the unwinding volume (106), processing volume (107) and / or winding volume (108) as needed to facilitate passing a continuous flexible substrate (122) between an inert gas environment and a substantially ambient (e.g., atmosphere) environment outside the molten metal coating system (100).

[0039] The chamber body (102) includes one or more openings (not shown) to provide access to the internal volume (103). In one or more examples, one or more openings are positioned at the top of the chamber body (102). One or more openings providing access to chamber components may be positioned at other locations of the chamber body (102). The chamber body (102) may optionally include a cover (not shown) that can be opened and closed to allow a user to access components within the internal volume (103) of the chamber body (102). In one or more examples, the chamber body (102) includes transparent sections or windows used to monitor processing conditions within the chamber.

[0040] Although the unwinding volume (106), processing volume (107), and winding volume (108) are illustrated as sharing a common chamber body (102), it should be understood that in some embodiments, the unwinding volume (106), processing volume (107), and winding volume (108) are defined by separate chamber bodies, and the chamber body defining the unwinding volume (106) is stacked on or adjacent to (e.g., side by side) the chamber body defining the processing volume (107) and / or the winding volume (108). For example, in some embodiments, the molten metal coating system (100) includes an unwinding chamber defining the unwinding volume (106), a deposition chamber defining the processing volume (107), and a separate winding chamber defining the winding volume (108). The unwinding chamber, the deposition chamber, and the winding chamber are separate modular and stackable elements. In one or more examples, the unwinding chamber is positioned adjacent to one side of the deposition chamber, and the winding chamber is positioned adjacent to the opposite side of the deposition chamber.

[0041] The molten metal coating system (100) is composed of a roll-to-roll system comprising an unwinding module (120) operable to supply a continuous flexible substrate (122), a molten metal coating module (130) operable to deposit molten metal on the continuous flexible substrate (122), and a winding module (140) operable to form a passivation film and / or a protective film on the molten metal in the winding module (140). The unwinding module (120) includes an unwinding roller (150) operable to supply the continuous flexible substrate (122). The winding module (140) includes a winding roller (160) operable to receive the processed continuous flexible substrate (122). In some embodiments, the molten metal coating system (100) may further include a stacked film supply roller (not shown) operable to supply a protective film to the processed continuous flexible substrate (122).

[0042] A continuous flexible substrate (122) is provided as a web, which is wound on a roll such as an unwinding roller (150). In one or more examples, the continuous flexible substrate (122) has a width of about 15 cm to about 300 cm, typically about 160 cm. Additionally, the continuous flexible substrate (122) has a thickness of about 8 µm to about 200 µm, for example, about 50 µm. The continuous flexible substrate (122) has a front surface (124) and a back surface (126). In one embodiment, after processing, the continuous flexible substrate (122) comprises a flexible material having a lithium electrode structure and a passivation film formed thereon. In another embodiment, after processing, the continuous flexible substrate (122) comprises a flexible material having a lithiated electrode structure and a passivation film formed thereon.

[0043] The molten metal coating system (100) further includes a common transport architecture (180). The common transport architecture (180) may include any transfer mechanism capable of moving a continuous flexible substrate (122) through an unwinding volume (106), a processing volume (107), and a winding volume (108). In some embodiments, the common transport architecture (180) is a reel-to-reel system comprising an unwinding roller (150) and a winding roller (160). The unwinding roller (150) and the winding roller (160) may be heated or cooled independently depending on target process conditions. The unwinding roller (150) may be driven and rotated by a motor (152). The winding roller (160) may also be driven and rotated by a motor (162). The unwinding roller (150) and the winding roller (160) can be individually heated using an internal heat source or an external heat source positioned within each reel. The unwinding roller (150) and the winding roller (160) can be individually cooled using either an internal cooling source or an external cooling source positioned within each reel.

[0044] In some embodiments, the common transport architecture (180) further includes one or more auxiliary tension reels (182a-182d) (collectively referred to as 182) positioned between the unwinding roller (150) and the winding roller (160). The auxiliary tension reels are positioned on the travel path (142) along which the continuous flexible substrate (122) is transported between the unwinding roller (150) and the winding roller (160) to allow tension on the continuous flexible substrate (122). This tension not only prevents the continuous flexible substrate (122) from sagging downward but also serves to change the direction of movement of the continuous flexible substrate (122). Thus, even if the continuous flexible substrate (122) is moved continuously along a long path, a specific travel speed is maintained constant. In some embodiments, any of the auxiliary tension reels (182) may be replaced with gas cushion rollers. The auxiliary tension reels (182) may be individually heated using an internal heat source or an external heat source positioned within each reel. The auxiliary tension reels (182) may be individually cooled using an internal cooling source or an external cooling source positioned within each reel. The auxiliary tension reels (182) may provide at least one function selected from guiding the continuous flexible substrate (122), tensioning the continuous flexible substrate (122), charging the continuous flexible substrate (122), decharging the continuous flexible substrate (122), and heating or cooling the continuous flexible substrate (122). The auxiliary tension reels (182) may include one or more servo motors for advancing the continuous flexible substrate (122). The one or more servo motors enable precise control of the linear position, speed, and / or acceleration of the continuous flexible substrate (122). One or more servo motors can be combined with a sensor for position feedback.The common transport architecture (180) may further include one or more servo motors for advancing a continuous flexible substrate (122) and / or one or more load cells for converting web tension into an electrical signal that can be measured and standardized.

[0045] Generally, a molten metal coating system (100) includes a system controller (190) operable to control automated modes of the molten metal coating system (100). The system controller (190) may be provided to and coupled to various components of the molten metal coating system (100) to control their operation. The system controller (190) includes a central processing unit (CPU) (192), memory (194) (or computer-readable medium), and support circuits (196). The system controller (190) may control the molten metal coating system (100) directly, or through computers (or controllers) associated with specific process chambers and / or support system components. The system controller (190) may be any type of general-purpose computer processor that can be used in an industrial environment to control various chambers and subprocessors. The memory (194) of the system controller (190) may be one or more of readily available memory such as random access memory (RAM), read-only memory (ROM), floppy disk, hard disk, optical storage media (e.g., compact disc or digital video disc), flash drive, or any other form of local or remote digital storage. Support circuits (196) are coupled to the CPU (192) to support the processor in a conventional manner. These circuits include caches, power supplies, clock circuits, input / output circuits and subsystems, etc. Methods as described herein may be stored in the memory (194) as software routines that can be executed or called to control the operation of the molten metal coating system (100) in the manner described herein.The software routine may also be stored and / or executed by a second CPU (not shown) located remotely from hardware controlled by the CPU (192). In one or more examples, the system controller (190) may be operated to control the movement speed of the continuous flexible substrate (122) by monitoring the load cells and controlling the servomotors of the auxiliary tension reels (182).

[0046] When operated, the continuous flexible substrate (122) is transported from the unwinding roller (150) advancing to the molten metal coating module (130). The continuous flexible substrate (122) moves from the unwinding volume (106) through the through hole (109a) and advances into the processing volume (107) of the molten metal coating module (130). In the processing volume (107), the continuous flexible substrate (122) is exposed to a coating process for depositing a molten metal film on the continuous flexible substrate (122) and optionally depositing a surface protection film on the molten metal film. The continuous flexible substrate (122) moves through the through hole (109b) and advances from the processing volume (107) into the winding volume (108). In the winding volume (108), the processed continuous flexible substrate (122) is wound onto the winding roller (160).

[0047] The molten metal coating module (130) includes one or more processing stations operable to process a continuous flexible substrate (122). For example, a first deposition source array (132a, 132b) (collectively referred to as 132) operable to deposit a first layer containing a first material on the continuous flexible substrate (122) may be provided. Additionally, a second deposition source array (134a, 134b) (collectively referred to as 134) operable to deposit a second layer containing a second material on the first layer may be provided. Additionally, a third deposition source array (136a, 136b) (collectively referred to as 136) operable to deposit a third layer containing a third material on the second layer may be provided.

[0048] According to the examples described herein, each of the first deposition source array (132), the second deposition source array (134), and the third deposition source array (136) may include one or more deposition sources. Examples of deposition sources may be sputtering, evaporation (e.g., thermal or e-beam), direct liquid application (e.g., slot die coating, comma bar coating, Meyer rod coating, planar flow melt spin, casting nozzle coating, or roller coating), spray coating processes (e.g., subsonic spray, electrostatic spray, gas pressure spray, thermal spray, and plasma spray), or any combination thereof, or include these. Specifically, the number of deposition sources per deposition source array, such as the first deposition source array (132), the second deposition source array (134), and the third deposition source array (136), may be adjusted according to the intended thickness of the layer formed by each deposition source array. For example, in the case of a negative electrode for a lithium battery, it is desirable to have lithium layers that are thicker than the surface protection film formed thereon. The second deposition source array (134) may be configured to deposit lithium and may include more deposition sources than the first deposition source array (132) configured to deposit a surface protective film. The first deposition source array (132), the second deposition source array (134), and the third deposition source array (136) each include one deposition source.

[0049] The molten metal coating module (130) further comprises a pair of rotatable casting drums (138a, 138b) (collectively referred to as 138) positioned on opposite sides of a continuous flexible substrate (122). The casting drum (138) is a cylinder having a quenching surface (144a, 144b) (collectively referred to as 144) on which molten metal is deposited. The quenching surface (144) is a curved surface. The quenching surface (144) may be a smooth surface. The quenching surface (144) comprises at least one of stainless steel, copper, chrome, or a combination thereof. In one or more examples, the quenching surface (144) of the casting drum (138) is stainless steel. The casting drum (138) has a rotation axis, which is provided to the molten metal coating system (100). Each casting drum (138) can be driven and rotated by a motor (139a, 139b) (collectively referred to as 139).

[0050] According to some examples described herein, the casting drum (138) may be heated or cooled to a desired processing temperature. The heating or cooling device within the casting drum (138) may be connected to a controller by a connection. According to typical examples described herein, the casting drum (138) may be heated or cooled for deposition purposes. In one or more examples, the casting drum includes coolant channels operable to contain a coolant for cooling the quenching surface (144) of the casting drum (138). The coolant channels may be coupled to a coolant source supplying a heat transfer fluid. The fluid may be water, mixed hydrocarbon gases such as ethylene glycol, nitrogen (N2), helium, poly-cold, hydrocarbons such as Fragoltherm ® F-12; Paratherm™ LR; Paratherm™ NF; mineral oil; Mobil ®It may be oil, compressed CO2, or any other fluid used as a heat exchange medium. In some examples, the casting drum (138) is cooled using an internal cooling source positioned within the casting drum (138). In other examples, the casting drum (138) is cooled using an external cooling source. Additionally, the casting drum (138) may be cooled during the deposition of a material having a low melting point, such as lithium, for example.

[0051] The molten metal coating module (130) further comprises a stripping layer deposition source array (146a, 146b) (collectively referred to as 146) operable to deliver a transfer liquid to the quenching surface (144) of the casting drum (138). The transfer liquid forms a stripping layer on the quenching surface (144) of the casting drum (138). The stripping layer formed on the quenching surface (144) prevents subsequently deposited layers from adhering to the quenching surface (144). In one or more examples, the stripping layer deposition source array (146) is positioned adjacent to the casting drum (138) and in sequence before the first deposition source array (132) so that the transfer liquid is deposited on the quenching surface (144) before any material layers.

[0052] In one embodiment, the stripping layer deposition source array (146) includes a pick-up roller or a kiss roller (148a, 148b) (collectively referred to as 148). The kiss roller (148) picks up a wet film containing a transfer liquid from a transfer liquid source pool (152a, 152b) (collectively referred to as 152) by contact and discharges the transfer liquid to the quenching surface (144) of the casting drum (138). The kiss roller (148) may further include a servo motor for driving and rotating the kiss roller (148).

[0053] In one or more examples, the kiss roller (148) comes into contact with the casting drum (138) while moving in the opposite direction, which means that the kiss roller (148) rotates in a direction opposite to the rotational direction of the casting drum (138) (e.g., contact in the opposite direction). In some examples, the kiss roller (148) does not come into contact with the casting drum (138) while rotating in the same direction as the rotational direction of the casting drum (138) (e.g., non-contact in the same direction). In other examples, the kiss roller (148) comes into contact with the casting drum (138) while rotating in the same direction as the rotational direction of the casting drum (138) (e.g., contact in the same direction).

[0054] The molten metal coating module (130) further comprises a removal array (170a, 170b) (collectively referred to as 170) for removing any material remaining on the casting drum (138) after discharging the material layers to a continuous flexible substrate (122) and before applying a peeling layer forming liquid to the casting drum (138). The removal array comprises any tool capable of cleaning the quenching surface (144) of the casting drum (138). Examples of tools that may be used include mechanical tools (e.g., a scraper), a fluid jet, an air jet, or any combination thereof.

[0055] When in operation, the casting drum (138) rotates sequentially through: a stripping layer deposition source array (146), a first deposition source array (132), a second deposition source array (134), a third deposition source array (136), and a removal array (170). Although the deposition source arrays are often referred to as processing stations in this specification, other processing stations, such as etching stations or heating stations, may also be provided along the curved quenching surface (144) of the casting drum (138). Thus, the molten metal coating system (100) described in this specification may have compartments for various deposition sources and may allow for a modular combination of multiple deposition sources or processes in a single deposition apparatus. Exemplary deposition sources or processes may be sputtering, evaporation, spraying, PVD, CVD, plasma-enhanced CVD (PE-CVD), atomic layer deposition (ALD), plasma-enhanced ALD (PE-ALD), or any combination thereof, or may include these.

[0056] FIG. 2 is a flowchart illustrating a method for manufacturing a flexible substrate according to one or more embodiments. In one or more embodiments that may be combined with other embodiments described herein, the method (200) is a planar flow melt spinning process. The method (200) includes the step of discharging a transfer liquid onto a cooled quenching surface of a rotary casting drum according to operation (210). The transfer liquid may be applied to the casting drum by a kiss roller. The transfer liquid may solidify on the quenching surface of the casting drum to form a peeling layer. The peeling layer formed on the cooled quenching surface prevents subsequently deposited layers from adhering to the quenching surface. For example, if the subsequently deposited layer is a sticky material such as lithium, the peeling layer prevents the lithium from adhering to the quenching surface. The transfer liquid is selected to be compatible with both the cooled quenching surface and the subsequently deposited layer.

[0057] In operation (220), the material layer stack is formed on the stripping layer if a stripping layer is present, or directly on the quenching surface of the casting drum if a stripping layer is not present. In one or more examples, the first material layer of the material layer stack is a surface protection film, e.g., lithium fluoride. In some examples, the first material layer is a low melting temperature metal or metal alloy, e.g., lithium. The first material layer may be an alloy anode film. In operation (230), the first material layer may be deposited on the stripping layer by the first deposition source array (132). Optionally, in operation (240), a second material layer is formed on the first material layer. In one or more examples, the second material layer is an additional surface protection film. In some examples, the second material layer is a low melting temperature metal or metal alloy, e.g., lithium. The second material layer may be deposited by the second deposition source array (134). Optionally, in operation (250), a third material layer is formed on the second material layer. In one or more examples, the third material layer is a low melting temperature metal or metal alloy, e.g., lithium. The third material layer may be deposited by a third deposition source array (136).

[0058] In one or more examples, the surface protection layer forming liquid rapidly solidifies to form a surface protection layer over a layer of the transfer liquid. Molten metal or metal alloy is then deposited onto the surface protection layer through a deposition process, for example, a spray coating process. After solidification, the solidified metal or metal alloy and the protection layer are transferred to a substrate by a casting drum in operation (260).

[0059] In operation (260), the material layer stack is transferred from the casting drum to the flexible substrate. The flexible substrate may be a continuous flexible substrate (122). In one or more examples, the flexible substrate is a plastic substrate such as polypropylene, polyethylene, or a combination thereof. In some examples, the flexible substrate has a copper substrate on which a film formed thereon, for example, an anode film formed thereon. In some examples, the flexible substrate is a copper substrate or an aluminum substrate. In other examples, the flexible substrate is a plastic substrate coated with a thin metal layer (for example, polypropylene or polyethylene coated with copper). The layers of the material layer stack are transferred to the continuous flexible substrate in the reverse order of their deposition onto the casting drum. For example, in a planar flow melt spinning process, the solidified metal or metal alloy comes into contact with the flexible substrate with a protective layer formed on the solidified metal or metal alloy layer. In one or more examples, the metal or metal alloy is lithium, the substrate is a flexible substrate, e.g., a lithium-ion anode, a metallized plastic substrate, a copper current collector, or a combination thereof, and the protective layer is a surface protective layer such as LiF, Bi2Te3, Cu, Sn, LiNO3, or a combination thereof.

[0060] Optionally, in operation (270), the casting drum is exposed to a cleaning process. The cleaning process is performed to remove a stripping layer (if present) and any other contaminants from the quenching surface of the casting drum before repeating operations (210-260). The cleaning process may be performed, for example, using a removal array (170) to remove any material remaining on the casting drum after discharging the material layer stack to a continuous flexible substrate (122) and before applying / reapplying the transfer liquid to the casting drum (138). The cleaning process may be performed using any tool capable of removing contaminants from the quenching surface of the casting drum. Examples of tools that may be used to clean the quenching surface of the casting drum include mechanical tools (e.g., scrapers), fluid jets, air jets, or any combination thereof.

[0061] FIG. 3a is a schematic cross-sectional view of a flexible substrate (300) according to one or more embodiments. FIG. 3b is a schematic plan view of a portion of the flexible substrate (300) of FIG. 3a according to one or more embodiments. FIG. 4 is a flowchart illustrating a method (400) for manufacturing the flexible substrate (300) of FIG. 3a and FIG. 3b according to one or more embodiments. The flexible substrate (300) comprises an alloy anode (301). In one or more embodiments that may be combined with other embodiments described herein, the alloy anode (301) comprises silicon, tin, aluminum, titanium, carbon, iron, zinc, gallium, indium, niobium, molybdenum, copper, oxygen, nitrogen, halogens (e.g., F, Cl, Br, I), sulfur, phosphorus, alloys thereof, or any combination thereof.

[0062] The alloy anode (301) is formed from a flexible substrate (300) in operation (401) via a planar flow melt spinning process, for example, the method (200) described above. The resulting alloy anode (301) is essentially amorphous and glassy. Ideally, the amorphous metal composition of the alloy anode (301) is at least 80% amorphous, preferably at least 90%, more preferably at least 95%, and most preferably at least 98% amorphous. The degree of crystallinity can be determined by known techniques. Amorphous metals include metals that are rapidly solidified and quenched from a supply of molten metal at a rate of at least 104 °C / sec.

[0063] Once the alloy anode (301) is formed, in operation (402), engineered voids (305), for example, a plurality of pores (306) or one or more trenches (307), are created in the alloy anode (301). The engineered voids (305) allow for volumetric expansion of the alloy anode (301) during battery charging without causing expansion of the thickness (308) of the alloy anode (301). The expanding material expands into the engineered voids (305) instead of moving the outer boundary of the alloy anode (301). The engineered voids (305) are created by one of wet etching, electrochemical etching, or laser drilling. In one or more embodiments that may be combined with other embodiments described herein, wet etching includes acid treatment. In a wet etching process, according to one embodiment, silver nanoparticles are used as a catalyst on the surface of the alloy anode (301), and acid etching creates engineered pores (305). Silver dots can be patterned on the alloy anode (301) prior to wet etching to create a uniform pore distribution. In embodiments where laser drilling is performed, a single pulse may be applied to form a single through hole or pore (306) in the alloy anode (301). Multiple pulses may be applied to form a trench (307) in the alloy anode (301). In one or more embodiments that may be combined with other embodiments described herein, the laser has a wavelength of about 1.06 μm, about 1 × 10⁻⁶ 6 It is a repeating pulse neodymium-doped yttrium aluminum garnet (Nd:YAG) laser operating with a peak output of watts and a pulse repetition rate of about 10 pulses per second. In other embodiments that may be combined with other embodiments described herein, the laser has a wavelength of about 10.6 μm, about 1 × 10⁻⁶ 5It is a pulsed carbon dioxide (CO2) laser operating with a peak output of watts and a pulse repetition rate of about 100 pulses per second. In other embodiments that may be combined with other embodiments described herein, the laser has a wavelength of about 1.06 μm and about 1 × 10⁻⁶ 6 It is a neodymium glass (Nd:glass) laser operating with a peak output of watts and a pulse repetition rate of less than 1 pulse per second. The resulting alloy anode (301) and flexible substrate (300) improved battery life and overall calendar life by reducing undesirable volume expansion of the alloy anode (301).

[0064] One or more subsequent processes may be performed to improve the quality of the generated flexible substrate (300). In an optional operation (403), a pre-lithiation surface treatment is performed on the alloy anode (301). The pre-lithiation surface treatment includes the step of depositing a lithium layer (302) on the alloy anode (301). The lithium layer (302) reduces charge loss. In an optional operation (404), a protective layer (303) is deposited on the alloy anode (301). The protective layer (303) comprises one or more of lithium fluoride, carbon, silver, bismuth, zinc, antimony, aluminum, silver oxide, bismuth oxide, zinc oxide, antimony oxide, aluminum oxide, silicon oxide, lithium silicon oxide, or any combination thereof. In an optional operation (405), the alloy anode (301) is laminated onto a metallic current collector (304). In one or more embodiments that may be combined with other embodiments disclosed herein, the metallic current collector (304) comprises copper. The lamination process bonds the alloy anode (301) to the metallic current collector (304) using either a conductive carbon-based adhesive or mechanical bonding.

[0065] FIG. 5a is a schematic cross-sectional view of a flexible substrate (300) according to one or more embodiments. FIG. 5b is a schematic top view of the flexible substrate (500) of FIG. 5a according to one or more embodiments. FIG. 6 is a flowchart illustrating a method (600) for manufacturing the flexible substrate (500) of FIG. 5a and FIG. 5b according to one or more embodiments. The flexible substrate (500) comprises an alloy anode (501). In one or more embodiments that may be combined with other embodiments described herein, the alloy anode (501) comprises lithium, and one or more of silicon, tin, silver, bismuth, alloys thereof, or any combination thereof. In one or more embodiments that may be combined with other embodiments described herein, the alloy anode (501) is a lithium bismuth (Li-Bi) alloy, a lithium silver (Li-Ag) alloy, a lithium tin (Li-Sn) alloy, or a lithium silicon (Li-Si) alloy, alloys thereof, or any combination thereof. In one or more embodiments that may be combined with other embodiments described herein, the alloy anode (501) comprises doped metals or alloys having a relatively low melting point (e.g., less than 1,000 °C).

[0066] As discussed above in relation to FIGS. 2 and FIGS. 4, the alloy anode (501) is formed in operation (601) through a planar flow melt spinning process, e.g., the method (200) described above. The resulting alloy anode (501) is essentially amorphous and glassy. In one or more embodiments that may be combined with other embodiments described herein, the alloy anode (501) is one of a lithium bismuth (Li-Bi) alloy, a lithium silver (Li-Ag) alloy, a lithium tin (Li-Sn) alloy, or a lithium silicon (Li-Si) alloy. Ideally, the amorphous metal composition of the alloy anode (501) is at least 80% amorphous, preferably at least 90%, more preferably at least 95%, and most preferably at least 98% amorphous. When the alloy anode (501) is formed, in operation (602), engineered voids (505), for example, a plurality of pores (506) and / or trenches (507), are created in the alloy anode (501). In one or more embodiments that may be combined with other embodiments described herein, laser drilling is performed on the alloy anode (501) to create the engineered voids (505).

[0067] One or more subsequent processes may be performed to improve the quality of the alloy anode (501) and the resulting battery. In an optional operation (603), a protective layer (503) is placed on the alloy anode (501). In an optional operation (604), the alloy anode (501) is laminated onto a metallic current collector (504). In one or more embodiments that may be combined with other embodiments disclosed herein, the metallic current collector (504) comprises copper. The lamination process bonds the alloy anode (501) to the metallic current collector (504) using either a conductive carbon-based adhesive or mechanical bonding.

[0068] In the optional operation (605), if the operation (603) is not performed, the protective layer (503) is placed on the alloy anode (501). Accordingly, in one or more embodiments, the step of laminating the alloy anode (501) occurs before depositing the protective layer (503). In other embodiments, the step of laminating the alloy anode (501) occurs after depositing the protective layer (503). The resulting alloy anode (501) improved battery life and overall calendar life due to the reduction of undesirable volume expansion of the alloy anode (501).

[0069] In summary, these methods improve the quality of lithium-ion batteries formed in cost-effective roll-to-roll (RTR) processes. By controlling the surface area growth of the anode through engineered voids, calendar life is improved and impedance increase over cycles is reduced.

[0070] The embodiments of the present disclosure are further related to any one or more of the following Examples 1 to 13:

[0071] 1. A method for manufacturing alloy anodes comprises the steps of: forming an alloy anode using a planar flow melt spinning process comprising solidifying a molten material on a quenched surface of a rotary casting drum; and performing a pre-lithiation surface treatment on the alloy anode.

[0072] 2. A method for manufacturing alloy anodes comprises the steps of: forming a lithium-containing alloy anode using a planar flow melt spinning process comprising solidifying a molten material on a quenching surface of a rotary casting drum; and depositing a protective layer on the alloy anode.

[0073] 3. A method for manufacturing alloy anodes comprises the steps of: forming an alloy anode using a planar flow melt spinning process; creating engineered voids in the alloy anode through laser drilling; performing a pre-lithiation surface treatment; depositing a protective layer on the alloy anode; and stacking the alloy anode on a current collector.

[0074] 4. In the method of any one of Examples 1 to 3, the alloy anode comprises silicon, tin, aluminum, titanium, carbon, iron, copper, alloys thereof, or any combination thereof.

[0075] 5. In the method of any one of Examples 1 to 4, the alloy anode is at least 95% amorphous.

[0076] 6. The method of any one of Examples 1 to 5 further comprises the step of creating an engineered void in the alloy anode.

[0077] 7. In the method of any one of Examples 1 to 6, the step of creating engineered voids includes forming a plurality of pores, one or more trenches, or a combination thereof in the alloy anode.

[0078] 8. In the method of any one of Examples 1 to 7, a plurality of pores and one or more trenches are laser drilled into the alloy anode.

[0079] 9. The method of any one of Examples 1 to 8 further includes the step of depositing a protective layer on an alloy anode.

[0080] 10. In the method of any one of Examples 1 to 9, the protective layer comprises one or more of lithium fluoride, carbon, silver, bismuth, zinc, antimony, aluminum, silver oxide, bismuth oxide, zinc oxide, antimony oxide, aluminum oxide, silicon oxide, lithium silicon oxide, or any combination thereof.

[0081] 11. The method of any one of Examples 1 to 10 further comprises the step of laminating an alloy anode onto a metallic current collector.

[0082] 12. In the method of any one of Examples 1 to 11, the step of laminating the alloy anode is performed before depositing the protective layer.

[0083] 13. In the method of any one of Examples 1 to 12, the step of laminating the alloy anode is performed after the protective layer is deposited.

[0084] Although the foregoing relates to embodiments of the present disclosure, other and additional embodiments may be devised without departing from the basic scope of the present disclosure, the scope of which is determined by the following claims. All documents described herein are incorporated by reference into the present specification, including any priority documents and / or test procedures, to the extent that they do not contradict the present specification. As can be seen from the general description and specific embodiments above, forms of the present disclosure have been illustrated and described, but various modifications may be made without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited by this. Likewise, whenever the transition phrase “comprising” follows a composition, element, or group of elements, it is understood that the same composition or group of elements is considered using transition phrases such as “essentially comprising,” “composed of,” “selected from the group comprising,” or “is” following the mention of the composition, element, or elements, and vice versa.

[0085] Certain embodiments and features have been described using a series of numeric minimum values ​​and a series of numeric maximum values. Unless otherwise specified, it should be understood that ranges including any combination of two values, e.g., a combination of any minimum value and any maximum value, a combination of any two minimum values, and / or a combination of any two maximum values ​​are considered. Specific minimum values, maximum values, and ranges appear in one or more of the claims below.

Claims

Claim 1 A method for manufacturing alloy anodes, comprising the steps of: forming an alloy anode using a planar flow melt spinning process—the step of forming the alloy anode comprises: providing a transfer liquid to the quenching surface of a rotary casting drum; forming a first protective layer by providing a protective layer fluid or vapor over the transfer liquid on the quenching surface of the rotary casting drum; and solidifying a molten material over the first protective layer on the quenching surface of the rotary casting drum—and performing a pre-lithiation surface treatment on the alloy anode. Claim 2 A method for manufacturing alloy anodes according to claim 1, wherein the alloy anode comprises silicon, tin, aluminum, titanium, carbon, iron, copper, alloys thereof, or any combination thereof. Claim 3 A method for manufacturing alloy anodes according to claim 1, wherein the alloy anode is at least 95% amorphous by volume. Claim 4 A method for manufacturing alloy anodes according to claim 1, further comprising the step of creating engineered porosity in the alloy anode. Claim 5 A method for manufacturing alloy anodes, wherein the step of creating the engineered void comprises forming a plurality of pores, one or more trenches, or a combination thereof in the alloy anode. Claim 6 A method for manufacturing alloy anodes according to claim 5, wherein the plurality of pores and the one or more trenches are laser drilled into the alloy anode. Claim 7 A method for manufacturing alloy anodes according to claim 1, further comprising the step of depositing a second protective layer on the alloy anode. Claim 8 A method for manufacturing alloy anodes according to claim 7, wherein the second protective layer comprises one or more of lithium fluoride, carbon, silver, bismuth, zinc, antimony, aluminum, silver oxide, bismuth oxide, zinc oxide, antimony oxide, aluminum oxide, silicon oxide, lithium silicon oxide, or any combination thereof. Claim 9 A method for manufacturing alloy anodes according to claim 1, further comprising the step of laminating the alloy anode onto a metallic current collector. Claim 10 A method for manufacturing alloy anodes, comprising the step of forming a lithium-containing alloy anode using a planar flow melt spinning process comprising solidifying a molten material on a quenching surface of a rotary casting drum — said step of forming the alloy anode comprises: providing a transfer liquid to the quenching surface of the rotary casting drum; forming a first protective layer by providing a protective layer fluid or vapor on the transfer liquid on the quenching surface of the rotary casting drum; and solidifying a molten material on the first protective layer on the quenching surface of the rotary casting drum —; and depositing a second protective layer on said alloy anode. Claim 11 A method for manufacturing alloy anodes according to claim 10, further comprising the step of creating engineered voids on the alloy anode. Claim 12 A method for manufacturing alloy anodes according to claim 11, wherein the step of creating the engineered void comprises performing laser drilling treatment to form a plurality of pores, one or more trenches, or a combination thereof in the alloy anode. Claim 13 A method for manufacturing alloy anodes according to claim 10, wherein the second protective layer comprises one or more of lithium fluoride, carbon, silver, bismuth, zinc, antimony, aluminum, silver oxide, bismuth oxide, zinc oxide, antimony oxide, aluminum oxide, silicon oxide, lithium silicon oxide, or any combination thereof. Claim 14 A method for manufacturing alloy anodes according to claim 10, further comprising the step of laminating the alloy anode onto a metallic current collector. Claim 15 A method for manufacturing alloy anodes according to claim 14, wherein the step of laminating the alloy anode is performed before depositing the second protective layer. Claim 16 A method for manufacturing alloy anodes according to claim 14, wherein the step of laminating the alloy anode is performed after depositing the second protective layer. Claim 17 A method for manufacturing alloy anodes, comprising the steps of: providing a transfer liquid to a quenching surface of a rotary casting drum; forming a first protective layer by providing a protective layer fluid or vapor over the transfer liquid on the quenching surface of the rotary casting drum; forming an alloy anode on the first protective layer using a planar flow melt spinning process; creating engineered voids in the alloy anode through laser drilling; performing a pre-lithiation surface treatment; depositing a second protective layer on the alloy anode; and stacking the alloy anode on a current collector. Claim 18 A method for manufacturing alloy anodes according to claim 17, wherein the alloy anode comprises silicon, tin, aluminum, titanium, carbon, iron, copper, alloys thereof, or any combination thereof. Claim 19 A method for manufacturing alloy anodes according to claim 17, wherein the step of creating the engineered void comprises forming a plurality of pores, one or more trenches, or a combination thereof in the alloy anode. Claim 20 A method for manufacturing alloy anodes according to claim 17, wherein the second protective layer comprises one or more of lithium fluoride, carbon, silver, bismuth, zinc, antimony, aluminum, silver oxide, bismuth oxide, zinc oxide, antimony oxide, aluminum oxide, silicon oxide, lithium silicon oxide, or any combination thereof.

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