Surface protection of lithium metal anodes

Abstract

A method and apparatus for forming high-performance electrochemical devices, such as metal electrode structures, more specifically lithium-containing anodes, and primary and secondary electrochemical devices including the aforementioned lithium-containing electrodes. In one embodiment, the method includes forming a lithium metal film on a current collector. The current collector includes copper and / or stainless steel. The method further includes forming a protective film stack on the lithium metal film, including forming a first protective film on the lithium metal film. The first protective film is selected from a bismuth chalcogenide film, a copper chalcogenide film, a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, a lithium fluoride film, or a combination thereof.

Description

Technical Field

[0001] The implementations described herein generally relate to high-performance electrochemical devices such as metal electrodes, more specifically lithium-containing anodes, primary and secondary electrochemical devices including the aforementioned lithium-containing electrodes, and methods for manufacturing them.

Background Art

[0002] Rechargeable electrochemical storage systems are becoming increasingly valuable in many areas of daily life. High-capacity electrochemical energy storage devices such as lithium-ion (Li-ion) batteries are being increasingly used in many applications including portable electronic devices, medical, transportation, grid-connected large-scale energy storage, renewable energy storage, and uninterruptible power supplies (UPS). Conventional lead / sulfuric acid batteries often have insufficient capacitance and are often unable to fully cycle for these growing applications. Both lithium-ion batteries and subsequent all-solid-state batteries are considered to be the best options for meeting increasing performance requirements.

[0003] Lithium provides excellent anode materials for both lithium-ion batteries and all-solid-state batteries. Lithium is a lightweight alkali metal with a high voltage and theoretical capacity. However, like the heavier elemental homologues in Group 1, lithium is characterized by strong reactivity with various substances. Lithium reacts violently with water, alcohols, and other substances containing aprotic hydrogen and often catches fire. Lithium is unstable in air and reacts with oxygen, nitrogen, and carbon dioxide. Lithium is usually handled in an inert gas atmosphere (such as a noble gas like argon), and due to its strong reactivity, other processing operations are also carried out under the requirement of an inert gas atmosphere. As a result, lithium poses several challenges regarding processing, storage, and transportation.

[0004] A protective surface treatment for lithium metal has been developed. One method of protective surface treatment of lithium metal involves coating the lithium metal with a wax layer, such as polyethylene wax. However, typically, a large amount of coating agent is applied that hinders subsequent processing of the lithium metal film.

[0005] Another method of protective surface treatment has been proposed that involves producing stabilized lithium metal powder ("SLMP") with a continuous carbonate coating, a polymer coating such as polyurethane, PTFE, PVC, polystyrene, etc. However, these polymer coatings can cause problems when prelithiating the electrode material.

[0006] Accordingly, there is a need for methods and systems for depositing and processing lithium metal in energy storage systems. SUMMARY OF THE INVENTION

[0007] The implementations described herein generally relate to metal electrodes, more specifically lithium-containing anodes, high-performance electrochemical devices such as primary and secondary electrochemical devices including the aforementioned lithium-containing electrodes, and methods for manufacturing them. In one implementation, a method is provided. The method includes forming a lithium metal film on a current collector. The current collector is composed of copper and / or stainless steel. The method further includes forming a protective film stack on the lithium metal film, including forming a first protective film on the lithium metal film. The first protective film is selected from a bismuth chalcogenide film, a copper chalcogenide film, a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, a lithium fluoride film, or a combination thereof.

[0008] In another implementation, an anode electrode structure is provided. The anode electrode structure includes a current collector containing copper and / or stainless steel, a lithium metal film formed on the current collector, and a protective film stack formed on the lithium metal film. The protective film stack includes a first protective film formed on the lithium metal film. The first protective film is selected from a bismuth chalcogenide film, a copper chalcogenide film, a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, a lithium fluoride film, or a combination thereof. The protective film stack further includes a second protective film formed on the first protective film. The second protective film is selected from a lithium fluoride (LiF) film, a metal film, a carbon-containing film, or a combination thereof.

[0009] To better understand the above features of the present disclosure, a more detailed description of the embodiments briefly summarized above can be obtained by referring to the embodiments, some of which are shown in the accompanying drawings. However, it should be noted that since the present disclosure may admit other equally effective embodiments, the accompanying drawings show only typical embodiments of the present disclosure and should not be considered as limiting the scope of the present disclosure.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

[0011] For ease of understanding, the same reference numerals are used to denote the same elements common to multiple figures, where possible. It is assumed that the elements and features of one embodiment can be beneficially incorporated into other embodiments without further description. DETAILED DESCRIPTION

[0012] The following disclosure describes anode electrodes, high-performance electrochemical cells and batteries including the aforementioned anode electrodes, and methods for manufacturing them. To fully understand the various embodiments of the present disclosure, specific details are presented in the following description of the specification and Figures 1-6. In many cases, other details describing well-known structures and systems related to electrochemical cells and batteries are described in the following disclosure so that the description of the various implementations is not needlessly obscured.

[0013] Many of the details, dimensions, angles, and other features shown in the drawings are merely illustrative of specific embodiments. Accordingly, other embodiments can have other details, components, dimensions, angles, and features without departing from the spirit and scope of the present disclosure. In addition, it is possible to implement further embodiments of the present disclosure without some of the details described below.

[0014] The implementations described herein are explained below with reference to reel-to-reel coating systems such as TopMet (trademark), SMARTWEB (trademark), TOPBEAM (trademark). All of these are available from Applied Materials, Inc. of Santa Clara, California. Other tools capable of performing deposition processes (e.g., physical vapor deposition (PVD) processes, chemical vapor deposition (CVD) processes, atomic layer deposition (ALD) processes) can also be adapted to benefit from the implementations described herein. Additionally, any system enabling the deposition processes described herein can be advantageously used. The description of the apparatuses described herein is illustrative and should not be understood or construed as limiting the scope of the implementations described herein. Although described herein as a reel-to-reel process, it should also be understood that the implementations described herein can be performed on individual substrates. In some implementations, reel-to-reel coating systems can be combined to form device stacks.

[0015] As described herein, flexible substrates can be considered to include, among other things, films, foils, webs, strips of plastic material, metals, papers, or other materials. Usually, terms such as “web,” “foil,” “strip,” “substrate,” etc. are used synonymously.

[0016] Energy storage devices, such as lithium-ion batteries, typically include a positive electrode (e.g., cathode) and a negative electrode separated by a polymer separator with a liquid electrolyte. All-solid-state batteries also typically include a positive electrode (e.g., cathode) and a negative electrode (e.g., anode), but replace both the polymer separator and the liquid electrolyte with an ion-conductive material.

[0017] Graphite anodes are the current state-of-the-art technology, but the industry is shifting from graphite-based anodes to silicon-blended graphite anodes to increase the energy density of cells. However, silicon-blended graphite anodes often suffer from irreversible capacity loss that occurs during the first cycle. Therefore, a method to replenish this first-cycle capacity loss is needed. Current batteries use graphite anodes, porous polymer separators, and liquid electrolytes. Liquid electrolytes usually contain additives that form a solid electrolyte interface (SEI) in-situ during formation on the electrodes. The SEI helps determine the cycle life of the battery. The energy density of state-of-the-art graphite anode-based batteries is limited to about 650 Wh / l. The energy density of silicon powder blended graphite anodes helps increase the energy density to 700 Wh / l or more. Manufacturing techniques are needed to compensate for the irreversible capacity loss of the first cycle of lithium associated with silicon anodes. Therefore, the ability to use lithium in next-generation batteries, including both lithium-ion and all-solid-state batteries, is becoming increasingly important. However, lithium technology has significant challenges related to device integration, such as handling lithium around a dry room, appropriate surface protection technology, and the need to suppress or eliminate lithium metal dendrites during battery cycling. From the perspective of electrochemical devices, an interface material that not only helps prevent surface oxidation but also improves the performance of the device is desirable.

[0018] The lithium metal deposited on either one or both sides using the implementations described herein can be protected during winding and rewinding of the downstream reel. Deposition of one or more thin protective films as described herein has several advantages. In some implementations, the one or more protective films described herein provide adequate surface protection for transportation, handling, and storage and avoid surface reactions of lithium during device integration. In some implementations, the one or more protective films described herein are compatible with lithium ions and reduce the impedance for ions to move across. In some implementations, the one or more protective films described herein are ion-conductive and can thus be incorporated into the formed energy storage device. In some implementations, the one or more protective films described herein can also help suppress or eliminate lithium dendrites, particularly in high current density operations. In some implementations, the use of the protective films described herein reduces the complexity of the manufacturing system and is compatible with current manufacturing systems.

[0019] Figure 1 shows a schematic cross-sectional view of one embodiment of an energy storage device 100 incorporating an anode electrode structure formed in accordance with the embodiments described herein. The energy storage device 100 can be a solid energy storage device or a lithium-ion-based energy storage device. Although the energy storage device 100 is shown as a planar structure, it can also be formed into a cylinder by rolling a stack of layers; furthermore, other cell configurations (e.g., prismatic cells, button cells, or stacked electrode cells) can be formed. The energy storage device 100 includes an anode electrode structure 110 and a cathode electrode structure 120 with a solid electrolyte membrane 130 disposed therebetween. In embodiments where the energy storage device 100 is a lithium-ion energy storage device, the solid electrolyte membrane is replaced with a polymer separator and a liquid electrolyte. The cathode electrode structure 120 includes a cathode current collector 140 and a cathode film 150. The anode electrode structure 110 includes an anode current collector 160, an anode film 170, and one or more protective films 180. The one or more protective films 180 include at least one or more lithium fluoride (LiF) films; dielectric or ceramic films (e.g., oxides of titanium (Ti), aluminum (Al), niobium (Nb), tantalum (Ta), zirconium (Zr), or combinations thereof); one or more metal films (e.g., tin (Sn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), copper film, silver film, gold film, or combinations thereof); copper chalcogenide films (e.g., CuS, Cu 2 Se, Cu 2 S); bismuth chalcogenide films (e.g., Bi 2 Te 3 , Bi 2 Se 3 ); tin chalcogenide films (e.g., SnTe, SnSe, SnSe 2 , SnS), gallium chalcogenide films (e.g., GaS, Ga 2 S 3 , GaSe, Ga 2 Se 3, gallium telluride (GaTe), germanium chalcogenide films (GeTe, GeSe, GeS), indium chalcogenide films (e.g., InS, In 6 S 7 、In 2 S 3 、InSe, InS 4 Se 3 、In 6 Se 7 、In 2 Se 3 、InTe, In 4 Te 3 、In 3 Te4, In 7 Te 10 、In 2 Te 3 、In 2 Te 5 )、 silver chalcogenide films (Ag 2 Se, Ag 2 S, Ag 2 Te), boron nitride, lithium nitrate, lithium hydride, and combinations thereof; and carbon-containing films.

[0020] The cathode electrode structure 120 includes a cathode current collector 140 having a cathode film 150 formed thereon. It should be understood that the cathode electrode structure 120 may include other elements or films.

[0021] The current collectors 140 and 160 on the cathode film 150 and the anode film 170, respectively, may be the same electron conductor or different electron conductors. In some embodiments, at least one of the current collectors 140 and 160 is a flexible substrate. In some embodiments, the flexible substrate is a CPP film (i.e., a cast polypropylene film), an OPP film (i.e., an oriented polypropylene film), or a PET film (i.e., an oriented polyethylene terephthalate film). Alternatively, the flexible substrate can be pre-coated paper, a polypropylene (PP) film, a PEN film, a polylactate acetate (PLA) film, or a PVC film. Examples of metals that can constitute the current collectors 140 and 160 include aluminum (Al), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), stainless steel, clad materials, alloys thereof, and combinations thereof. In one embodiment, at least one of the current collectors 140 and 160 is perforated. In one embodiment, at least one of the current collectors 140 and 160 is a polymer substrate coated with a metal material (e.g., including polyethylene terephthalate (“PET”). In one embodiment, the anode current collector 160 is a polymer substrate coated with copper (e.g., a PET film). In another embodiment, the anode current collector 160 is a multi-layer metal layer on a polymer substrate. The multi-layer metal layer can be a combination of copper, chromium, nickel, etc. In one embodiment, the anode current collector 160 is a multi-layer structure including a copper-nickel clad material. In one embodiment, the multi-layer structure includes a first layer of nickel or chromium, a second layer of copper formed on the first layer, and a third layer including nickel, chromium, or both formed on the second layer. In one embodiment, the anode current collector 160 is nickel-coated copper. Further, the current collector may be of any form factor (e.g., a metal foil, sheet, or plate), shape, and micro / macro structure.

[0022] Generally, in a prismatic cell, the tab is formed of the same material as the current collector and can be formed during the manufacture of the stack or added later. In some embodiments, the current collector extends beyond the stack, and the portion of the current collector that extends beyond the stack can be used as the tab. In one embodiment, the cathode current collector 140 is aluminum. In another embodiment, the cathode current collector 140 comprises aluminum deposited on a polymer substrate (e.g., a PET film). In one embodiment, the cathode current collector 140 has a thickness of less than 50 μm, more specifically 5 μm, or even more specifically 2 μm. In one embodiment, the cathode current collector 140 has a thickness of about 0.5 μm to about 20 μm (e.g., about 1 μm to about 10 μm; about 2 μm to about 8 μm; or about 5 μm to about 10 μm). In one implementation, the anode current collector 160 is copper. In one embodiment, the anode current collector 160 is stainless steel. In one embodiment, the anode current collector 160 has a thickness of less than 50 μm, more specifically 5 μm, or even more specifically 2 μm. In one embodiment, the anode current collector 160 has a thickness of about 0.5 μm to about 20 μm (e.g., about 1 μm to about 10 μm; about 2 μm to about 8 μm; about 6 μm to about 12 μm; or about 5 μm to about 10 μm).

[0023] The cathode film 150 or cathode can be any material compatible with the anode and can include intercalation compounds, insertion compounds, or electrochemically active polymers. Suitable intercalation materials include, for example, lithium-containing metal oxides, MoS 2 , FeS 2 , BiF 3 , Fe 2 OF 4 , MnO 2 , TiS 2 , NbSe 3 , LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , V 6 O 13 and V 2 O 5is included. Suitable polymers include, for example, polyacetylene, polypyrrole, polyaniline, and polythiophene. The cathode membrane 150 or the cathode can be made from a layered oxide such as lithium cobalt oxide, a olivine such as lithium iron phosphate, or a spinel such as lithium manganese oxide. Exemplary lithium-containing oxides are layered such as lithium cobalt oxide (LiCoO 2 ) or LiNi x Co 1-2x MnO 2 , (where x is a number that is 0 or not 0), LiNiMnCoO 2 (“NMC”), LiNi 0.5 Mn 1.5 O 4 , Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 , LiMn 2 O 4 and the like, mixed oxides, and doped lithium-rich layered materials. Exemplary phosphates are lithium iron phosphate (LiFePO 4 ) and its variants (LiFe (1-x) Mg x PO 4 (where x is a number that is 0 or not 0), etc.), LiMoPO 4 , LiCoPO 4 , LiNiPO 4 , Li 3 V 2 (PO 4 ) 3 , LiVOPO 4 , LiMP 2 O 7 , or LiFe 1.5 P 2 O 7 . Exemplary fluorophosphates are LiVPO 4 F, LiAlPO 4 F, Li 5 V(PO 4 ) 2 F 2 , Li 5 Cr(PO 4 ) 2 F 2 , Li2 CoPO 4 F, or Li 2 NiPO 4 may be F. Exemplary silicates are Li 2 FeSiO 4 , Li 2 MnSiO 4 , or Li 2 VOSiO 4 may be. Exemplary non-lithium compounds are Na 5 V 2 (PO 4 ) 2 F 3 may be.

[0024] The anode electrode structure 110 includes an anode current collector 160, and the anode film 170 is formed on the anode current collector 160. The anode electrode structure 110 includes one or more protective films 180, which are at least one or more of lithium fluoride (LiF) films; dielectric or ceramic films (e.g., oxides of titanium (Ti), aluminum (Al), niobium (Nb), tantalum (Ta), zirconium (Zr), or combinations thereof); one or more metal films (e.g., tin (Sn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), copper film, silver film, gold film, or combinations thereof); copper chalcogenide films (e.g., CuS, Cu 2 Se, Cu 2 S); bismuth chalcogenide films (e.g., Bi 2 Te 3 , Bi 2 Se 3 ); tin chalcogenide films (e.g., SnTe, SnSe, SnSe2, SnS), gallium chalcogenide films (e.g., GaS, Ga 2 S 3 , GaSe, Ga 2 Se 3 , GaTe), germanium chalcogenide films (GeTe, GeSe, GeS), indium chalcogenide films (e.g., InS, In 6 S 7 , In 2 S 3 , InSe, InS 4 Se 3, In 6 Se 7 , In 2 Se 3 , InTe, In 4 Te 3 , In 3 Te 4 , In 7 Te 10 , In 2 Te 3 , In 2 Te 5 ), silver chalcogenide films (Ag 2 Se, Ag 2 S, Ag 2 Te), boron nitride, lithium nitrate, lithium hydride, and combinations thereof; and carbon-containing films. In some embodiments, one or more of the protective films are ion-conductive films.

[0025] The anode film 170 can be any material compatible with the cathode film 150. The anode film 170 can have an energy capacity of 372 mAh / g or more, preferably 700 mAh / g or more, and most preferably 1000 mAh / g or more. The anode film 170 can be composed of graphite, silicon-containing graphite, lithium metal, lithium metal foil or lithium alloy foil (e.g., lithium aluminum alloy), or a mixture of lithium metal and / or lithium alloy with materials such as carbon (e.g., coke, graphite), nickel, copper, tin, indium, silicon, oxides thereof, or combinations thereof. The anode film 170 typically includes an intercalation compound containing lithium or an insertion compound containing lithium. In some embodiments, the anode film is a lithium metal film. In some implementations where the anode film 170 contains lithium metal, the lithium metal can be deposited using the methods described herein.

[0026] In one embodiment, the anode film 170 has a thickness of about 10 μm to about 200 μm (e.g., about 1 μm to about 100 μm; about 10 μm to about 30 μm; about 20 μm to about 30 μm; about 30 μm; about 1 μm to about 20 μm; or about 50 μm to about 100 μm).

[0027] In some embodiments, one or more protective films 180 are formed on the anode film 170. The one or more protective films 180 include at least one or more lithium fluoride (LiF) films; dielectric or ceramic films (e.g., oxides of titanium (Ti), aluminum (Al), niobium (Nb), tantalum (Ta), zirconium (Zr), or combinations thereof); one or more metal films (e.g., tin (Sn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), copper film, silver film, gold film, or combinations thereof); copper chalcogenide films (e.g., CuS, Cu 2 Se, Cu 2 S); bismuth chalcogenide films (e.g., Bi 2 Te 3 、Bi 2 Se 3 ); tin chalcogenide films (e.g., SnTe, SnSe, SnSe 2 、SnS), gallium chalcogenide films (e.g., GaS, Ga 2 S 3 、GaSe, Ga 2 Se 3 、GaTe), germanium chalcogenide films (GeTe, GeSe, GeS), indium chalcogenide films (e.g., InS, In 6 S 7 、In 2 S 3 、InSe, InS 4 Se 3 、In 6 Se 7 、In 2 Se 3 、InTe, In 4 Te 3 、In 3 Te 4 、In 7 Te 10 、In 2 Te 3 、In 2 Te 5 )、silver chalcogenide films (Ag 2 Se, Ag 2 S, Ag 2Te), boron nitride, lithium nitrate, lithium hydride, and combinations thereof; and include a carbon-containing film. In some embodiments, one or more of the protective films is an ion-conductive film. In some embodiments, one or more of the protective films 180 is permeable to at least one of lithium ions and lithium atoms. One or more of the protective films 180 provides surface protection for the anode film 170, which enables handling of the anode film in a dry chamber. In some embodiments where the energy storage device 100 is a solid energy storage device, one or more of the protective films 180 contributes to the formation of an improved SEI layer and thus improves the performance of the device. One or more of the protective films 180 can be deposited directly on the anode film 170 by evaporation (e.g., thermal or electron beam) or sputtering, physical vapor deposition (PVD) such as atomic layer deposition (ALD), atomic layer deposition (ALD), slot die process, dip coating, planar flow melt spin process, thin film transfer process, gravure coating, or three-dimensional lithium printing process.

[0028] In some embodiments, one or more of the protective films 180 includes a lithium fluoride (LiF) film.

[0029] In some embodiments, one or more of the protective films 180 includes one or more dielectric films. In some embodiments, the dielectric film is a ceramic film. In some embodiments, the dielectric film is an ion-conductive ceramic film. Suitable dielectric films include titanium oxide (e.g., TiO 2 ), aluminum oxide (e.g., Al 2 O 3 , AlO x , AlO x N y ), boron nitride, aluminum oxyhydroxide AlO(OH), niobium oxide (e.g., NbO, NbO 2 , Nb 2 O 5 ), tantalum oxide (e.g., Ta 2 O 5 ), zirconium oxide (ZrO 2) or combinations thereof. In some embodiments, the dielectric film is a binder-free ceramic coating. In some embodiments, the dielectric film is a porous aluminum oxide film.

[0030] In some embodiments, one or more protective films 180 include one or more metal films. Suitable metal films include, but are not limited to, tin films, antimony films, bismuth films, gallium films, germanium films, copper, silver, gold, or combinations thereof. The one or more metal films can be ultrathin metal seed films.

[0031] In some embodiments, one or more protective films 180 include one or more metal chalcogenide films. Suitable chalcogenide films include copper chalcogenides (e.g., CuS, Cu 2 Se, Cu 2 S) and bismuth chalcogenides (e.g., Bi 2 Te 3 , Bi 2 Se 3 ), tin chalcogenides (e.g., SnTe, SnSe, SnSe 2 , SnS), gallium chalcogenides (e.g., GaS, Ga 2 S 3 , GaSe, Ga 2 Se 3 , GaTe), germanium chalcogenides (GeTe, GeSe, GeS), indium chalcogenides (e.g., InS, In 6 S 7 , In 2 S 3 , InSe, InS 4 Se 3 , In 6 Se 7 , In 2 Se 3 , InTe, In 4 Te 3 , In 3 Te 4 , In 7 Te 10 , In 2 Te 3 , In 2 Te 5) silver chalcogenides (Ag 2 Se, Ag 2 S, Ag 2 Te), boron nitride, lithium nitrate, lithium borohydride, and combinations thereof, but are not limited thereto.

[0032] In some embodiments, one or more protective films 180 include a carbon-containing film. Suitable carbon-containing films include, but are not limited to, amorphous carbon films (e.g., diamond-like carbon (DLC)), CVD diamond films, graphite films, and graphene oxide.

[0033] In some embodiments, each layer of one or more protective films 180 is a coating or an individual film having a thickness in the range of 1 nanometer to 3000 nanometers (e.g., in the range of 10 nanometers to 600 nanometers, in the range of 50 nanometers to 100 nanometers, in the range of 50 nanometers to 200 nanometers, in the range of 100 nanometers to 150 nanometers). In some embodiments, each layer of one or more protective films 180 is a coating or an individual film having a thickness of 500 nanometers or less (e.g., about 1 nm to about 400 nm; about 25 nm to about 300 nm; about 50 nm to about 200 nm; about 100 nm to about 150 nm; about 10 nm to about 80 nm; or about 30 to about 60 nanometers). In some embodiments, each layer of one or more protective films 180 is a coating or an individual film having a thickness of 100 nanometers or less (e.g., about 5 nanometers to about 100 nanometers; about 5 nanometers to about 40 nanometers; about 10 nanometers to about 20 nanometers; or about 50 nanometers to about 100 nanometers).

[0034] In some embodiments, at least one of the one or more protective films 180 is porous. In some embodiments, at least one of the one or more protective films 180 has nanopores. In some embodiments, at least one of the one or more protective films 180 has a plurality of nanopores sized such that the average pore size or diameter is less than about 10 nanometers (e.g., from about 1 nanometer to about 10 nanometers; from about 3 nanometers to about 5 nanometers). In another embodiment, at least one of the one or more protective films 180 has a plurality of nanopores sized to have an average pore size or diameter of less than about 5 nanometers. In one embodiment, at least one of the one or more protective films 180 has a plurality of nanopores having a diameter in the range of about 1 nanometer to about 20 nanometers (e.g., from about 2 nanometers to about 15 nanometers; or from about 5 nanometers to about 10 nanometers).

[0035] In some embodiments, the solid electrolyte membrane 130 is a lithium ion conductive material. In some embodiments, the lithium ion conductive material is a lithium ion conductive ceramic or a lithium ion conductive glass. The lithium ion conductive material is one or more doped variants of the crystalline or amorphous phases of LiPON, Li7La 3 Zr 2 O 12 and doped variants of the crystalline or amorphous phases of, doped antiperovskite compositions, argyrodite compositions (e.g., Li 6 PS 5 Br, Li 6 PS 5 Cl, Li 7 PS 6 and, Li 3 SBF 4 and A 3-2×0.005 Ba 0.005 OCl (A = alkali metal), Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 and, Li 6 PS 5 I, Li 6 PO 5 Cl), lithium-sulfur-phosphorus materials, (Li 0.7 Na0.3 ) 3 BH 4 B 12 H 12 、Li 2 S-P 2 S 5 、Li 10 GeP 2 S 12 , and Li 3 PS 4 、lithium phosphate glass, (1-x)LiI-(x)Li 4 SnS 4 、xLiI-(1-x)Li 4 SnS 4 、a mixed electrolyte of sulfide and oxide (crystalline LLZO, amorphous (1-x)LiI-(x)Li 4 SnS 4 mixture, amorphous xLiI-(1-x)Li 4 SnS 4 )、Li 3 S(BF 4 ) 0.5 Cl 0.5 、Li 4 Ti 5 O 12 ,, lithium-doped lanthanum titanate (LATP), Li 2+2x Zn 1-x GeO 4 、LiM 2 (PO 4 ) 3 (wherein, for example, M = Ti, Ge, Hf. ) can be composed of. In one embodiment, x is between 0 and 1 (for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9).

[0036] FIG. 2 shows a cross-sectional view of one embodiment of the anode electrode structure 200 formed according to the embodiments described herein. In FIG. 2, the anode current collector 160 need not extend beyond the stack, but it is shown that the anode current collector 160 extends beyond the stack, and it should be noted that the portion extending beyond the stack can be used as a tab. The anode electrode structure 200 is depicted as a double-sided electrode structure, but it should be understood that the embodiments described herein are also applicable to a single-sided electrode structure.

[0037] The anode electrode structure 200 has an anode current collector 160 and anode films 170a and 170b (collectively referred to as 170) formed on the opposite side of the anode current collector 160. In one embodiment, the anode film 170 is a lithium metal film. In one embodiment, the anode film 170 has a thickness of 20 micrometers or less (for example, about 1 micrometer to about 20 micrometers). The first protective films 210a and 210b (collectively referred to as 210) are formed on each of the anode films 170a and 170b. In some embodiments, the first protective film 210 has a thickness in the range of 1 nanometer to 3000 nanometers (for example, in the range of 10 nanometers to 600 nanometers; in the range of 50 nanometers to 100 nanometers; in the range of 50 nanometers to 200 nanometers; in the range of 100 nanometers to 150 nanometers). In some embodiments, the first protective film 210 has a thickness of 100 nanometers or less (for example, about 5 nanometers to 100 nanometers; about 5 nanometers to about 40 nanometers; about 10 nanometers to about 20 nanometers; or about 50 nanometers to about 100 nanometers). In some embodiments, as shown in FIG. 2, the first protective film 210 coats the exposed surfaces (for example, the upper surface and side walls) of the anode film 170 that extends to contact the anode current collector 160.

[0038] The second protective films 220a and 220b (collectively referred to as 220) are formed on each of the first protective films 210. In some embodiments, the second protective film 220 is permeable to at least one of lithium ions and lithium atoms. In one embodiment, the second protective film 220 is selected from the group including a lithium fluoride film, a metal film, a carbon-containing film, or a combination thereof. In some embodiments, the second protective film 220 has a thickness in the range of 1 nanometer to 3000 nanometers (for example, in the range of 10 nanometers to 600 nanometers; in the range of 50 nanometers to 100 nanometers; in the range of 50 nanometers to 200 nanometers; in the range of 100 nanometers to 150 nanometers). In some embodiments, the second protective film 220 has a thickness of 100 nanometers or less (for example, about 5 nanometers to 100 nanometers; about 5 nanometers to about 40 nanometers; about 10 nanometers to about 20 nanometers; or about 50 nanometers to about 100 nanometers).

[0039] In some embodiments, the first protective film 210 is a metal chalcogenide film and the second protective film 220 is a lithium fluoride film. In some embodiments, the first protective film 210 is a dielectric film and the second protective film 220 is a lithium fluoride film. In some embodiments, the first protective film 210 is a metal chalcogenide film and the second protective film 220 is a metal film. In some embodiments, the first protective film 210 is a metal film and the second protective film 220 is a lithium fluoride film. In some embodiments, the first protective film 210 is a LiF film and the second protective film 220 is carbon or graphene oxide.

[0040] FIG. 3 shows a cross-sectional view of one embodiment of an anode electrode structure 300 formed according to the embodiments described herein. In FIG. 3, although the anode current collector 160 does not need to extend beyond the stack, it is shown that the anode current collector 160 extends beyond the stack, and it should be noted that the portion extending beyond the stack can be used as a tab. Although the anode electrode structure 300 is depicted as a double-sided electrode structure, it should be understood that the mounting forms described herein are also applicable to a single-sided electrode structure.

[0041] The anode electrode structure 300 has an anode current collector 160 and anode films 170a and 170b (collectively 170) formed on the side opposite to the anode current collector 160. In one embodiment, the anode film 170 is a lithium metal film. In one embodiment, the anode film 170 has a thickness of 20 micrometers or less (e.g., about 1 micrometer to about 20 micrometers). Carbon-containing protective films 310a and 310b (collectively 310) are formed on each of the anode films 170a and 170b. In one embodiment, the carbon-containing protective film 310 is selected from the group including an amorphous carbon film (e.g., diamond-like carbon (DLC)), a CVD diamond film, a graphite film, and graphene oxide. In some implementations, the carbon protective film 310 has a thickness of 500 nanometers or less (e.g., about 1 nm to about 400 nm; about 25 nm to about 300 nm; about 50 nm to about 200 nm; about 100 nm to about 150 nm; about 10 nm to about 80 nm; or about 30 to about 60 nanometers). In some implementations, the carbon protective film 310 has a thickness of 100 nanometers or less (e.g., about 5 nanometers to 100 nanometers; about 5 nanometers to about 40 nanometers; about 10 nanometers to about 20 nanometers; or about 50 nanometers to about 100 nanometers). In some implementations, as shown in FIG. 3, the carbon-containing protective film 310 coats the exposed surfaces (e.g., the upper surface and the sidewalls) of the anode film 170 that extends to contact the anode current collector 160.

[0042] FIG. 4 shows a process flow chart summarizing one implementation of a method 400 for forming an anode electrode structure according to the implementation described herein. The anode electrode structure can be the anode electrode structure 200 shown in FIG. 2. In step 410, a substrate is provided. In one implementation, the substrate is a continuous sheet of material 650 as shown in FIG. 6. In one form, the substrate is the anode current collector 160. Examples of metals that can constitute the substrate include aluminum (Al), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), stainless steel, clad materials, their alloys, and combinations thereof. In one form, the substrate is a copper material. In one implementation, the substrate is a stainless steel material. In one form, the substrate is perforated. Further, the substrate can be of any form factor (e.g., a metal foil, sheet, or plate), shape, and micro / macro structure.

[0043] In some implementations, the substrate is exposed to a pretreatment process that includes at least one of a plasma treatment or a corona discharge process to remove organic matter from the exposed surface of the current collector. The pretreatment process is performed prior to depositing a film on the substrate.

[0044] In operation 420, a lithium metal film is formed on a substrate. In one implementation, the lithium metal film is the anode film 170 and the substrate is the anode current collector 160. In one implementation, the lithium metal film is formed on a copper current collector. In some implementations, if the anode film is already present on the substrate, an alkali metal film is formed on the anode film. If the anode film 170 is not present, the alkali metal film can be formed directly on the substrate. Any suitable lithium metal film deposition process for depositing a thin film of lithium metal can be used to deposit the thin film of lithium metal. The deposition of the thin film of lithium metal can be performed by a PVD process such as evaporation (e.g., thermal evaporation or electron beam), a slot die process, a transfer process, or a three-dimensional lithium printing process. Chambers for depositing thin films of alkali metals can include PVD systems such as electron beam evaporators, thermal evaporators, or sputtering systems, thin film transfer systems (including large area pattern printing systems such as gravure printing systems), or slot die deposition systems.

[0045] In operation 430, a first protective film is formed on the lithium metal film. Referring to FIG. 2, the first protective film may be the first protective film 210, and the lithium metal film may be the anode film 170. The first protective films 210a, 210b (collectively 210) are formed on the respective anode films 170a, 170b. In some implementations, the first protective film 210 has a thickness in the range of 1 nanometer to 3000 nanometers (e.g., in the range of 10 nanometers to 600 nanometers; in the range of 50 nanometers to 100 nanometers; in the range of 50 nanometers to 200 nanometers; in the range of 100 nanometers to 150 nanometers). In some implementations, the first protective film 210 has a thickness of 500 nanometers or less (e.g., about 1 nm to about 400 nm; about 25 nm to about 300 nm; about 50 nm to about 200 nm; about 100 nm to about 150 nm; about 10 nm to about 80 nm; or about 30 to about 60 nanometers). In some implementations, the first protective film 210 has a thickness of 100 nanometers or less (e.g., about 5 nanometers to 100 nanometers; about 10 nanometers to about 20 nanometers; or about 50 nanometers to about 100 nanometers).

[0046] In some embodiments, the first protective film 210 is a metal chalcogenide film. In some embodiments, the metal chalcogenide film is deposited using a PVD process having an RF power source coupled to a target. The target is typically composed of the material of the metal chalcogenide film. For example, in one embodiment, the target is a bismuth telluride alloy target. In one embodiment, the bismuth-telluride alloy target contains from about 5 atomic % to about 95 atomic % bismuth and from about 5 atomic % to about 95 atomic % tellurium. The plasma can be generated from a non-reactive gas such as argon (Ar), krypton (Kr), nitrogen, etc. For example, the plasma can be generated from argon gas having a flow rate in the range of about 30 standard cubic centimeters per minute (sccm) to about 200 sccm, for example, about 100 sccm to about 150 sccm. The RF power can be applied to the target at a power level in the range of about 50 W to about 4000 W, for example, about 1000 W to about 3000 W, for example, about 2000 W. The deposition chamber can be pressurized to about 0.1 mTorr to about 500 mTorr. The deposition chamber can be pressurized to about 0.1 mTorr to about 100 mTorr, for example, about 10 mTorr to about 30 mTorr, for example 25 mTorr. The substrate can be electrically "floating" and may have no bias. In one embodiment, the deposition process of operation 430 can be performed at a deposition temperature of about 50 °C to about 400 °C, for example, about 100 °C to about 200 °C, for example, about 120 °C.

[0047] In another implementation, the plasma can be generated using a DC power source coupled to a bismuth telluride alloy target. The substrate can be electrically “floating” and may have no bias. In this implementation, the plasma can be generated from argon gas having a flow rate in the range of about 30 standard cubic centimeters per minute (sccm) to about 200 sccm, for example, about 100 sccm to about 150 sccm. The DC power can be applied to the target at a power level in the range of about 50 W to about 5000 W, about 1000 W to about 3000 W, for example, about 1000 W to about 2000 W, for example, about 2000 W. The deposition chamber can be pressurized to about 0.1 mTorr to about 500 mTorr. The deposition chamber can be pressurized to about 0.1 mTorr to about 500 mTorr. The deposition chamber can be pressurized to about 0.1 mTorr to about 100 mTorr, for example, about 10 mTorr to about 30 mTorr, for example 25 mTorr. The substrate can be electrically “floating” and may have no bias. The deposition process of operation 430 can be carried out at a deposition temperature of about 50 °C to about 400 °C, for example, about 100 °C to about 200 °C, for example, about 120 °C.

[0048] In some implementations, the first protective film 210 is a dielectric. Suitable methods for depositing a dielectric film include, but are not limited to, physical vapor deposition (PVD) such as evaporation or sputtering, slot die processes, thin film transfer processes, chemical vapor deposition (CVD) processes, or three-dimensional lithium printing processes.

[0049] In some embodiments, the first protective film 210 is a metal film. In some embodiments, the metal film is a copper film, a bismuth film, a tin film, a gallium film, or a germanium film. In some embodiments, the metal film is an ultrathin metal film. Any suitable metal film deposition process for depositing a thin film of metal can be used to deposit the thin film of metal. The deposition of the thin film of metal can be performed by a PVD process such as evaporation (e.g., thermal or electron beam), a CVD process, a slot-die process, a transfer process, or a three-dimensional lithium printing process. Chambers for depositing thin films of metal can include PVD systems such as electron beam evaporators, thermal evaporators, or sputtering systems, thin film transfer systems (including large area pattern printing systems such as gravure printing systems), or slot-die deposition systems.

[0050] In operation 440, a second protective film is formed on the first protective film. Referring to FIG. 2, the second protective film can be the second protective film 220 and the first protective film can be the first protective film 210. In one embodiment, the second protective film 220 is selected from the group including a lithium fluoride film, a metal film, a carbon-containing film, or combinations thereof. In some embodiments, the second protective film 220 has a thickness in the range of 1 nanometer to 3000 nanometers (e.g., in the range of 10 nanometers to 600 nanometers; in the range of 50 nanometers to 100 nanometers; in the range of 50 nanometers to 200 nanometers; in the range of 100 nanometers to 150 nanometers). In some embodiments, the second protective film 220 has a thickness of 500 nanometers or less (e.g., about 1 nm to about 400 nm; about 25 nm to about 300 nm; about 50 nm to about 200 nm; about 100 nm to about 150 nm; about 10 nm to about 80 nm; or about 30 to about 60 nanometers). In some embodiments, the second protective film 220 has a thickness of 100 nanometers or less (e.g., about 5 nanometers to 100 nanometers; about 10 nanometers to about 20 nanometers; or about 50 nanometers to about 100 nanometers).

[0051] In some implementations, the second protective film 220 is a lithium fluoride film. Suitable methods for depositing the lithium fluoride film include, but are not limited to, physical vapor deposition (PVD) such as evaporation or sputtering, slot die processes, thin film transfer processes, chemical vapor deposition (CVD) processes, or three-dimensional lithium printing processes. In some implementations, PVD is a method for depositing the lithium fluoride film. In some implementations, the lithium fluoride film is deposited using a thermal evaporation process. In some implementations, the lithium fluoride film is deposited using an electron beam evaporation process.

[0052] In some implementations, the second protective film 220 is a metal film. In some implementations, the metal film is a copper film, a bismuth film, a tin film, a gallium film, or a germanium film. In some implementations, the metal film is an ultrathin metal film. Any suitable metal film deposition process for depositing a thin film of metal can be used to deposit the thin film of metal. Deposition of the thin film of metal can be performed by a PVD process such as evaporation (e.g., thermal or electron beam), a CVD process, a slot die process, a transfer process, or a three-dimensional lithium printing process. Chambers for depositing the thin film of metal can include PVD systems such as electron beam evaporators, thermal evaporators, or sputtering systems, thin film transfer systems (including large area pattern printing systems such as gravure printing systems), or slot die deposition systems.

[0053] FIG. 5 shows a process flow chart summarizing one implementation of a method 500 for forming an anode electrode structure according to one or more implementations described herein. The anode electrode structure can be the anode electrode structure 300 shown in FIG. 3. In step 510, a substrate is provided. In one implementation, the substrate is a continuous sheet of material 650 as shown in FIG. 6. In one form, the substrate is the anode current collector 160. Examples of metals that can constitute the substrate include aluminum (Al), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), stainless steel, clad materials, alloys thereof, and combinations thereof. In one form, the substrate is a copper material. In one implementation, the substrate is stainless steel. In one implementation, the substrate is perforated. Further, the substrate can be of any form factor (e.g., a metal foil, sheet, or plate), shape, and micro / macro structure.

[0054] In some implementations, the substrate is exposed to a pretreatment process that includes at least one of a plasma treatment or a corona discharge process to remove organic matter from the exposed surface of the current collector. The pretreatment process is performed prior to depositing a film on the substrate.

[0055] In operation 520, a lithium metal film is formed on a substrate. In one implementation, the lithium metal film is the anode film 170 and the substrate is the anode current collector 160. In one implementation, the lithium metal film is formed on a copper current collector. In some implementations, when the anode film already exists on the substrate, an alkali metal film is formed on the anode film. When the anode film 170 does not exist, the alkali metal film can be formed directly on the substrate. Any suitable lithium metal film deposition process for depositing a thin film of lithium metal can be used to deposit the thin film of lithium metal. The deposition of the thin film of lithium metal can be done by a PVD process such as evaporation, a slot die process, a transfer process, or a three-dimensional lithium printing process. Chambers for depositing a thin film of lithium metal can include PVD systems such as electron beam evaporators, thermal evaporators, or sputtering systems, thin film transfer systems (including large area pattern printing systems such as gravure printing systems), or slot die deposition systems.

[0056] In operation 530, a carbon-containing protective film is formed on the lithium metal film. Referring to FIG. 3, the first protective film can be the first protective film 310 and the lithium metal film can be the anode film 170. In one implementation, the carbon-containing protective film 310 is selected from the group including amorphous carbon films (e.g., diamond-like carbon (DLC)), CVD diamond films, graphite films, and graphene oxide. In some implementations, the carbon-containing protective film 310 has a thickness of 500 nanometers or less (e.g., about 1 nm to about 400 nm; about 25 nm to about 300 nm; about 50 nm to about 200 nm; about 100 nm to about 150 nm; about 10 nm to about 80 nm; or about 30 to about 60 nanometers). In one implementation, the carbon-containing protective film 310 has a thickness of 100 nanometers or less (e.g., about 5 nanometers to 100 nanometers; about 10 nanometers to about 20 nanometers; or about 50 nanometers to about 100 nanometers).

[0057] A carbon-containing protective film can be deposited using any suitable carbon-containing film deposition process. The deposition of the carbon-containing film can be by a PVD process such as evaporation (e.g., thermal or electron beam), a CVD process, a slot die process, a transfer process, or a three-dimensional lithium printing process. Chambers for depositing the carbon-containing film can include PVD systems such as electron beam evaporators, thermal evaporators or sputtering systems, thin film transfer systems (including large area pattern printing systems such as gravure printing systems) or slot die deposition systems.

[0058] FIG. 6 shows a schematic view of a flexible substrate coating apparatus 600 for forming an anode electrode structure according to the implementation described herein. The flexible substrate coating apparatus 600 may be a SMARTEVEB (registered trademark) manufactured by Applied Materials, adapted to manufacture a lithium anode device according to the implementation described herein. According to a typical implementation, the flexible substrate coating apparatus 600 can be used to manufacture a lithium anode, particularly for an SEI film stack for a lithium anode. The flexible substrate coating apparatus 600 is configured as a roll-to-roll system including a feed module 602, a processing module 604, and a take-up module 606. In some implementations, the processing module 604 includes a plurality of processing modules or chambers 610, 620, 630, and 640 arranged in sequence, each configured to perform one processing operation on a continuous sheet or web of material 650. In one implementation, as shown in FIG. 6, the processing chambers 610-640 are arranged radially around a coating drum 655. Other than radial arrangements are conceivable. For example, in another implementation, the processing chambers can be arranged in a linear configuration.

[0059] In one implementation, the processing chambers 610-640 are stand-alone modular processing chambers, and each modular processing chamber is structurally separated from the other modular processing chambers. Thus, the independent modular processing chambers can be arranged, rearranged, exchanged, or maintained without affecting each other. Although four processing chambers 610-640 are shown, it should be understood that any number of processing chambers can be included in the flexible substrate coating apparatus 600.

[0060] The processing chambers 610-640 can include any suitable structure, configuration, arrangement, and / or components that enable the flexible substrate coating apparatus 600 to deposit lithium anode devices according to the implementation of the present disclosure. For example, but not limited to, the processing chamber can include a suitable deposition system including a coating source, a power source, individual pressure control, a deposition control system, and temperature control. According to a typical implementation, the chambers are provided with individual gas supplies. The chambers are usually separated from each other to provide good gas separation. The flexible substrate coating apparatus 600 according to the implementation described herein is not limited to the number of deposition chambers. For example, but not limited to, the flexible substrate coating apparatus 600 can include three, six, or twelve processing chambers.

[0061] The processing chambers 610 - 640 typically include one or more deposition units 612, 622, 632, and 642. Generally, the one or more deposition units described herein can be selected from CVD sources, PECVD sources, and PVD sources. The one or more deposition units can include evaporation sources (thermal evaporation or electron beam), magnetron sputtering sources, DC sputtering sources, AC sputtering sources, pulsed sputtering sources, sputtering sources such as radio frequency (RF) sputtering, or can provide medium frequency (MF) sputtering. For example, MF sputtering with frequencies in the range of 5 kHz to 100 kHz, for example, 30 kHz to 50 kHz, can be provided. The one or more deposition units can include an evaporation source. In one implementation, the evaporation source is a thermal evaporation source or an electron beam evaporation. In one implementation, the evaporation source is a lithium (Li) source. Further, the evaporation source can also be an alloy of two or more metals. The material to be deposited (e.g., lithium fluoride) can be provided within a crucible. For example, aluminum can be evaporated by thermal evaporation technology or by electron beam evaporation technology.

[0062] In some implementations, any of the processing chambers 610 - 640 of the flexible substrate coating apparatus 600 can be configured to perform deposition by sputtering such as magnetron sputtering. As used herein, "magnetron sputtering" refers to sputtering performed using a magnet assembly, i.e., a unit capable of generating a magnetic field. Typically, such a magnet assembly includes permanent magnets. The permanent magnets are typically disposed inside a rotatable target or coupled to a planar target such that free electrons are trapped inside the generated magnetic field generated below the surface of the rotatable target. Such a magnet assembly can also be disposed in combination with a planar cathode.

[0063] Magnetron sputtering can also be achieved by a dual magnetron cathode such as, but not limited to, a TwinMag (trademark) cathode assembly. In some implementations, the cathode within the processing chamber can be replaceable. Thus, a modular design of the apparatus is provided that facilitates optimizing the apparatus for a particular manufacturing process. In some implementations, the number of cathodes within the chamber for sputtering deposition is selected to optimize the optimal productivity of the flexible substrate coating apparatus 600.

[0064] In some implementations, one or some of the processing chambers 610 - 640 can be configured to perform sputtering without a magnetron assembly. In some implementations, one or some of the chambers can be configured to perform deposition by other methods such as, but not limited to, chemical vapor deposition, atomic laser deposition, or pulsed laser deposition. In some implementations, one or some of the chambers can be configured to perform a plasma processing process such as a plasma oxidation or plasma nitridation process.

[0065] In some implementations, the processing chambers 610 - 640 are configured to process both sides of a continuous sheet of material 650. The flexible substrate coating apparatus 600 is configured to process a horizontally oriented continuous sheet of material 650, but the flexible substrate coating apparatus 600 can be configured to process substrates arranged in different orientations. For example, the continuous sheet of material 650 can be vertically oriented. In some implementations, the continuous sheet of material 650 is a flexible conductive substrate. In some implementations, the continuous sheet of material 650 includes a conductive substrate with one or more layers formed thereon. In some implementations, the conductive substrate is a copper substrate.

[0066] In some implementations, the flexible substrate coating apparatus 600 includes a transfer mechanism 652. The transfer mechanism 652 can include any transfer mechanism capable of moving a continuous sheet of material 650 through the processing regions of the processing chambers 610-640. The transfer mechanism 652 can include a common transport architecture. The common transport architecture can include a reel-to-reel system having a common take-up reel 654 disposed in the unwind module 606, a coating drum 655 disposed in the processing module 604, and a supply reel 656 disposed in the payout module 602. The take-up reel 654, the coating drum 655, and the supply reel 656 can be heated individually. The take-up reel 654, the coating drum 655, and the supply reel 656 can be heated individually using internal or external heat sources disposed within each reel. The general transport architecture can further include one or more auxiliary transfer reels 653a, 653b (collectively 653) disposed between the take-up reel 654, the coating drum 655, and the supply reel 656. The flexible substrate coating apparatus 600 is shown as having a single processing region, but in some implementations, it may be advantageous to have separate or individual processing regions for each of the individual processing chambers 610-640. In implementations having separate processing regions, modules, or chambers, the common transport architecture can be a reel-to-reel system in which each chamber or processing region has an individual take-up reel and payout reel, and one or more optional intermediate transfer reels positioned between the take-up reel and the payout reel.

[0067] The flexible substrate coating apparatus 600 may include a supply reel 656 and a take-up reel 654 for moving a continuous sheet of material 650 through different processing chambers 610-640. In one implementation, the first processing chamber 610 and the second processing chamber 620 are each configured to deposit a portion of a lithium metal film. The third processing chamber 630 is configured to deposit a chalcogenide film. The fourth processing chamber 640 is configured to deposit a lithium fluoride film on the chalcogenide film. In another implementation, the first processing chamber 610 and the second processing chamber 620 are each configured to deposit a portion of a lithium metal film. The third processing chamber 630 is configured to deposit a dielectric film. The fourth processing chamber 640 is configured to deposit a lithium fluoride film on the dielectric film. In yet another implementation, the first processing chamber 610 and the second processing chamber 620 are each configured to deposit a portion of a lithium metal film. The third processing chamber 630 is configured to deposit a chalcogenide film. The fourth processing chamber 640 is configured to deposit a metal film on the chalcogenide film. In yet another implementation, the first processing chamber 610 and the second processing chamber 620 are each configured to deposit a portion of a lithium metal film. The third processing chamber 630 is configured to deposit a metal film on the lithium metal film. The fourth processing chamber 640 is configured to deposit a lithium fluoride film on the metal film.

[0068] In one implementation, the processing chambers 610 - 620 are configured to deposit a thin film of lithium metal on a continuous sheet of material 650. Any suitable lithium deposition process for depositing a thin film of lithium metal may be used to deposit the thin film of lithium metal. The deposition of the thin film of lithium metal can be performed by a PVD process such as evaporation (e.g., thermal evaporation or electron beam), a slot die process, a transfer process, a lamination process, or a three-dimensional lithium printing process. Chambers for depositing a thin film of lithium metal can include PVD systems such as thermal evaporators, electron beam evaporators, thin film transfer systems (including large area pattern printing systems such as gravure printing systems), lamination systems, or slot die deposition systems.

[0069] In one implementation, the third processing chamber 630 is configured to deposit a chalcogenide film on the lithium metal film. The chalcogenide film can be deposited using the PVD sputtering techniques described herein. In one implementation, the fourth processing chamber 640 is configured to form a lithium fluoride film on the chalcogenide film. Any suitable lithium deposition process for depositing a thin film of lithium metal may be used to deposit the thin film of lithium metal. The deposition of the thin film of lithium metal can be performed by a PVD process such as evaporation, a slot die process, a transfer process, a lamination process, or a three-dimensional lithium printing process. In one implementation, the fourth processing chamber 640 is an evaporation chamber or a PVD chamber configured to deposit a lithium fluoride film on a continuous sheet of material 650. In one implementation, the evaporation chamber has a processing region shown to include an evaporation source that can be disposed in a crucible, which can be, for example, a thermal evaporator or an electron beam evaporator (low temperature) in a vacuum environment.

[0070] During operation, the continuous sheet of material 650 is fed from supply reel 656 as indicated by the substrate movement direction shown by arrow 608. The continuous sheet of material 650 can be guided through one or more auxiliary transfer reels 653a, 653b. It is also possible for the continuous sheet of material 650 to be guided by one or more substrate guide control units (not shown) that must control the proper running of the flexible substrate, for example, by finely adjusting the orientation of the flexible substrate.

[0071] Fed from supply reel 656, traveling over auxiliary transfer reel 653a, next, the continuous sheet of material 650 is moved through deposition regions provided on coating drum 655 corresponding to the positions of deposition units 612, 622, 632, and 642. During operation, coating drum 655 rotates about axis 651 such that the flexible substrate moves in the direction of arrow 608.

[0072] Implementation: Item 1 Forming a lithium metal film on a current collector, the current collector being copper and / or stainless steel; and forming a first protective film on the lithium metal film, including forming a lithium metal film on the current collector; forming a protective film stack on the lithium metal film, including forming a first protective film on the lithium metal film, the first protective film being selected from a bismuth chalcogenide film, a copper chalcogenide film, a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, a lithium fluoride film, or a combination thereof.

[0073] Item 2 The method according to item 1, wherein forming the protective film stack further includes forming a second protective film on the second protective film selected from a first protective film, a lithium fluoride (LiF) film, a metal film, a carbon-containing film, or a combination thereof.

[0074] Item 3. The method according to item 1 or 2, wherein the dielectric film is selected from oxides of titanium (Ti), aluminum (Al), niobium (Nb), tantalum (Ta), zirconium (Zr), or combinations thereof.

[0075] Item 4. The method according to any one of items 1 to 3, wherein the bismuth chalcogenide film and the copper chalcogenide film are selected from CuS, Cu 2 Se, Cu 2 S, Cu 2 Te, CuTe, Bi 2 Te 3 、Bi 2 Se 3 、or combinations thereof.

[0076] Item 5. The method according to any one of items 2 to 4, wherein the metal film is selected from tin (Sn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), copper (Cu), silver (Ag), gold (Au), or combinations thereof.

[0077] Item 6. The method according to any one of items 1 to 5, wherein the first protective film is a bismuth chalcogenide film or a copper chalcogenide film, and the second protective film is lithium fluoride.

[0078] Item 7. The method according to any one of items 1 to 6, wherein the first protective film is a bismuth chalcogenide film or a copper chalcogenide film, and the second protective film is a metal film.

[0079] Item 8. The method according to any one of items 2 to 7, wherein the first protective film is a lithium fluoride film, and the second protective film is a carbon-containing film.

[0080] Item 9. The method according to any one of items 1 to 8, wherein the first protective film has a thickness of 100 nanometers or less.

[0081] The method according to any one of items 1 to 9, further comprising removing an organic material from the exposed surface of the current collector by exposing the current collector to a plasma treatment or a corona discharge process before forming a lithium metal film on the current collector.

[0082] The method according to any one of items 1 to 10, wherein forming the first protective film includes performing at least one of a sputtering process, a thermal evaporation process, an electron beam evaporation process, and a chemical vapor deposition (CVD) process.

[0083] The method according to any one of items 2 to 11, wherein forming the second protective film includes performing at least one of a sputtering process, a thermal evaporation process, an electron beam evaporation process, and a chemical vapor deposition (CVD) process.

[0084] The method according to any one of items 2 to 12, wherein the second protective film has a thickness of 100 nanometers or less.

[0085] An anode electrode structure including: a current collector including copper and / or stainless steel; a lithium metal film formed on the current collector; and a protective film stack formed on the lithium metal film, the protective film stack including a first protective film selected from a bismuth chalcogenide film, a copper chalcogenide film, a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, a lithium fluoride film, or a combination thereof; and a second protective film formed on the first protective film, the second protective film selected from a lithium fluoride (LiF) film, a metal film, a carbon-containing film, or a combination thereof.

[0086] The anode electrode structure according to item 14, wherein the dielectric film is selected from oxides of titanium (Ti), aluminum (Al), niobium (Nb), tantalum (Ta), zirconium (Zr), or a combination thereof.

[0087] Item 16. The anode electrode structure according to item 14 or 15, wherein the bismuth chalcogenide film and the copper chalcogenide film are selected from CuS, Cu 2 Se, Cu 2 S, Cu 2 Te, CuTe, Bi 2 Te 3 , Bi 2 Se 3 , or a combination thereof.

[0088] Item 17. The anode electrode structure according to any one of items 14 to 16, wherein the metal film is selected from tin (Sn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), copper (Cu), silver (Ag), gold (Au), or a combination thereof.

[0089] Item 18. The anode electrode structure according to any one of items 14 to 17, wherein the first protective film is a bismuth chalcogenide film or a copper chalcogenide film, and the second protective film is lithium fluoride.

[0090] Item 19. The anode electrode structure according to any one of items 14 to 18, wherein the first protective film is a bismuth chalcogenide film or a copper chalcogenide film, and the second protective film is a metal film.

[0091] Item 20. The anode electrode structure according to any one of items 14 to 19, wherein the first protective film is a lithium fluoride film, and the second protective film is a carbon-containing film.

[0092] Item 21. The anode electrode structure according to any one of items 14 to 20, wherein the first protective film has a thickness of 100 nanometers or less.

[0093] Item 22. The anode electrode structure according to any one of items 14 to 21, wherein the second protective film has a thickness of 100 nanometers or less.

[0094] Item 23. An energy storage device including the anode electrode structure according to any one of items 14 to 22; a cathode electrode structure; and a solid electrolyte film formed between the anode electrode structure and the cathode electrode structure.

[0095] Item 24 The solid electrolyte membrane is: LiPON, Li 7 La 3 Zr 2 O 12 doped variants of the crystalline phase or amorphous phase of, doped antiperovskite compositions, argyrodite compositions, lithium-sulfur-phosphorus materials, Li2S-P2S5, Li10GeP2S12, and Li3PS4, lithium phosphate glass, (1-x)LiI-(x)Li 4 SnS 4 , xLiI-(1-x)Li 4 SnS 4 , mixed electrolytes of sulfides and oxides (crystalline LLZO, amorphous (1-x)LiI-(x)Li 4 SnS 4 mixture, amorphous xLiI-(1-x)Li 4 SnS 4 ), Li 3 S(BF 4 ) 0.5 Cl 0.5 , Li 4 Ti 5 O 12 , lithium-doped lanthanum titanate (LATP), Li 2+2x Zn 1-x GeO 4 , LiTi 2 (PO 4 ) 3 , LiHf 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , and one or more combinations thereof, the energy storage device according to item 23.

[0096] In summary, some of the advantages of the present disclosure include the efficient integration of lithium metal deposition into currently available processing systems. Currently, the deposition of lithium metal is performed in a dry chamber or an argon gas atmosphere. Since lithium metal is volatile, subsequent processing operations are carried out in an argon gas atmosphere. The execution of subsequent processing operations in an argon gas atmosphere involves the modification of current manufacturing tools. The inventors have found that by coating the lithium metal with a protective film prior to subsequent processing, the subsequent processing can be carried out under vacuum or in the atmosphere. The protective film eliminates the need to perform additional processing operations in an inert gas atmosphere, reducing the complexity of the tool. The protective film also enables the transportation, storage, or both of the negative electrode on which the lithium metal film is formed. Further, in embodiments where the protective film is an ion-conducting film, the ion-conducting film can be incorporated into the final battery structure, reducing the complexity of the battery formation process. This reduces the complexity of the tool and subsequently the ownership cost.

[0097] When introducing elements of the present disclosure or exemplary aspects or implementations thereof, the articles "a", "an", "the", and "said" are intended to mean that one or more elements are present.

[0098] The terms "comprising", "including", and "having" are intended to be inclusive and mean that there may be additional elements other than the recited elements.

[0099] The foregoing is related to embodiments of the present disclosure, but other and further embodiments of the present disclosure can be devised without departing from the basic scope thereof, which is determined by the following claims.

Claims

1. Forming a lithium metal film on a current collector comprising copper and / or stainless steel; forming a protective film stack on the lithium metal film, the protective film stack including forming a first protective film on the lithium metal film and forming a second protective film on the first protective film; forming the protective film stack, wherein the first protective film is selected from a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, or a combination thereof, and the second protective film is a carbon-containing film. Including, The method, wherein the carbon-containing film is selected from a diamond-like carbon film or a graphene oxide film.

2. The method of claim 1 , wherein the first protective film is a silver chalcogenide film.

3. 2. The method of claim 1, wherein the dielectric film is selected from oxides of titanium (Ti), aluminum (Al), niobium (Nb), tantalum (Ta), zirconium (Zr), or combinations thereof.

4. 10. The method of claim 1, wherein forming the first protective film comprises performing at least one of a sputtering process, a thermal evaporation process, an electron beam evaporation process, and a chemical vapor deposition (CVD) process.

5. 5. The method of claim 4, wherein forming the second protective film comprises performing at least one of a sputtering process, a thermal evaporation process, an electron beam evaporation process, and a chemical vapor deposition (CVD) process.

6. The method of claim 1 , wherein the first protective film has a thickness of 100 nanometers or less.

7. 10. The method of claim 1, further comprising exposing the current collector to a plasma treatment or corona discharge process to remove organic material from an exposed surface of the current collector prior to forming the lithium metal film on the current collector.

8. a current collector comprising copper and / or stainless steel; a lithium metal film formed on the current collector; a protective film stack formed on the lithium metal film, a first protective film formed on the lithium metal film, the first protective film being selected from a tin chalcogenide film, a gallium chalcogenide film, a germanium chalcogenide film, an indium chalcogenide film, a silver chalcogenide film, a dielectric film, or a combination thereof; and a second protective film formed on the first protective film, the second protective film being a carbon-containing film selected from a diamond-like carbon film and a graphene oxide film; the protective film stack comprising:

2. An anode electrode structure comprising:

9. 9. The anode electrode structure of claim 8, wherein the dielectric film is selected from oxides of titanium (Ti), aluminum (Al), niobium (Nb), tantalum (Ta), zirconium (Zr), or combinations thereof.

10. The anode electrode structure according to claim 8 ; A cathode electrode structure; a solid electrolyte membrane formed between the anode electrode structure and the cathode electrode structure; 16. An energy storage device comprising:

11. The solid electrolyte membrane is: LiPON, Li ７ La ３ Zr ２ O １２ doped variants of the crystalline or amorphous phase of Li, doped antiperovskite compositions, argyrodite compositions, lithium-sulfur-phosphorus materials, Li ２ S-P ２ S ５ , Li １０ GeP ２ S １２ , and Li ３ P.S. ４ , lithium phosphate glass, (1-x)LiI-(x)Li ４ SnS ４ , xLiI-(1-x)Li ４ SnS ４ , sulfide and oxide mixed electrolytes (crystalline LLZO, amorphous (1-x)LiI-(x)Li ４ SnS ４ Mixture, amorphous xLiI-(1-x)Li ４ SnS ４ ), Li ３ S (BF ４ ) ０．５ C ０．５ , Li ４ Ti ５ O １２ , lithium-doped lanthanum titanate (LATP), Li ２＋２ｘ Zinc １－ｘ GeO ４ , LiTi ２ (P.O. ４ ) ３ , LiHf ２ (P.O. ４ ) ３ , LiGe ２ (P.O. ４ ) ３ 11. The energy storage device of claim 10, comprising one or more of:

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