CN116636034A

CN116636034A - Lithium metal anode assembly and manufacturing equipment and method

Info

Publication number: CN116636034A
Application number: CN202180083124.9A
Authority: CN
Inventors: 蒂莫西·乔治·约翰斯顿; 梅西耶·贾斯特热布斯基
Original assignee: Limet Group
Current assignee: Limet Group
Priority date: 2020-10-16
Filing date: 2021-10-16
Publication date: 2023-08-22

Abstract

A multi-layered lithium anode assembly for a lithium-based battery may include a substrate region having a current collector comprising a continuous copper foil having a thickness between 4 and 10 microns and having a support surface compatible with lithium. The lithium bearing region may overlie the support surface and may comprise a film of lithium material deposited directly on the support surface by thermal evaporation and having a thickness of between 1 and 10 microns. The cover region may be located outside the lithium bearing region and may have a cover film formed of a passivation material and covering the lithium material film. The cover region may allow lithium ion flow between the electrolyte and the lithium bearing region and inhibit irreversible reactions between the lithium bearing region and the electrolyte or the surrounding environment.

Description

Lithium metal anode assembly and manufacturing equipment and method

Cross Reference to Related Applications

The present application claims the benefit and priority of U.S. provisional application number 63/092,849, U.S. provisional application number 63/190,738, filed on 10, 16, 2021, 5, 19, and U.S. provisional application number 63/222,857, filed on 7, 2021. The entire contents of these applications are incorporated herein by reference.

Technical Field

In one aspect thereof, the present disclosure relates to the production and use of a multi-layer anode assembly suitable for use in batteries including, for example, lithium ion and lithium metal solid state batteries, but without the use of lithium foil, and methods and apparatus for producing the multi-layer anode assembly.

Background

Japanese patent publication No. JP2797390B2 discloses a negative electrode and carbonaceous material and a current collector as an anode active material, having a positive electrode of a lithium compound as a positive electrode active material, a secondary battery and a nonaqueous electrolyte, the positive electrode active material, and the second having a main active material composed of a first lithium compound having a higher potential than the oxidation potential of the current collector and a lower potential than the oxidation potential of the current collector. By including an auxiliary active material composed of a lithium compound, an auxiliary active material having excellent over-discharge prevention performance can be obtained.

Us patent No. 10,177,366 discloses a high purity lithium and related products. In a general embodiment, the present disclosure provides a lithium metal product in which lithium metal is obtained using a selective lithium ion conducting layer. The selective lithium ion conducting layer comprises a reactive metal ion conducting glass or glass ceramic that conducts only lithium ions. The present lithium metal products produced using selective lithium ion conductive layers advantageously provide improved lithium purity compared to commercial lithium metals. According to the present disclosure, metal-based lithium metal having a purity of at least 99.96 weight percent may be obtained.

U.S. Pat. No. 7,390,591 discloses ion-conductive membranes for protecting active metal anodes and methods of making the same. The membrane may be incorporated into active metal anode (anode) structures and battery cells. According to the invention, the film has the desired properties: overall high ionic conductivity and chemical stability to environmental conditions encountered in anode, cathode and battery fabrication. The membrane is capable of protecting the active metal anode from detrimental reactions with other battery components or environmental conditions while providing a high level of ionic conductivity to facilitate manufacturing and/or enhance the performance of the battery cell in which the membrane is incorporated.

U.S. patent publication 2020/0194786 discloses a system for generating electrical energy from chemical reagents in separate battery cells, comprising: at least two electrodes (including at least one anode and at least one cathode); at least one separator separating the anode and the cathode; and an ionic liquid electrolyte system. The system may be a battery or one or more battery cells of a battery system. The ionic liquid electrolyte system includes an ionic liquid solvent; ether co-solvents (a minority part of the electrolyte by weight); and lithium salts. In a preferred variant, the anode is a lithium metal anode, the cathode is a metal oxide cathode, and the separator is a polyolefin separator.

Disclosure of Invention

Attempts have been made previously to provide lithium anodes suitable for use in liquid electrolyte metal lithium ions (LMB), mixed lithium metals (HLB) and Solid State Batteries (SSB). These anodes are typically made by foil rolling and extrusion processes. Lithium is active, physically weak and self-adhesive, the difficulty of rolling lithium is well known, and limits the actual thickness of foil that can be rolled and handled to greater than 20 microns.

One way to eliminate some of the difficulties of handling lithium anodes is to form the anode in place on a stronger substrate. This allows the load to pass through a stronger material, which in some cases may also serve as the anode current collector.

For example, U.S. patent No. 10,177,366 teaches a lithium anode deposited on a substrate that is made by electrolysis of an aqueous solution of a lithium chemistry through a lithium ion selective membrane. This method applies a lithium coating to one of a variety of substrates. This process requires a strip coater, using a relatively small area of film to effect the coating. This process has several drawbacks in terms of battery fabrication, which makes it unattractive for producing SSB lithium anodes:

Electrodeposition rate is low, so mass production requires a large capital investment, resulting in high overall production cost.

The process uses flammable organic electrolyte, and when an electrolysis system is added, sparks are easily generated, so that fire hazards can be caused.

The inability to manufacture large, durable solid electrolytes or ion selective membranes means that the productivity of such machines is not high and therefore economically attractive costs cannot be realized.

U.S. Pat. No. 7,390,591 discloses a protected lithium anode formed on a lithium ion conductive glass substrate by various processes, including physical vapor deposition. The ion-conductive glass is intended to be used as a separator and a part of a layered solid electrolyte. The process is suitable for manufacturing lithium SSB with glass separator and overcomes the problems associated with lithium activity by protecting the lithium from atmospheric attack. However, the disclosed anode has several disadvantages:

it requires a current collector made of copper, which is expensive in nature and results in a considerably higher minimum cost (see table 7 for a comparison of substrate material costs).

It is applicable to batteries using glass separators, but not to other battery designs.

Us patent No. 5,522,955 discloses a lithium anode and production equipment based on a physical vapor deposition process. The proposed device deposits a lithium layer 8-25 microns thick on copper, nickel, stainless steel or conductive polymers. Vapor deposition is an inexpensive process for mass production of packaging materials, and thus enables the manufacture of anodes at extremely attractive costs. However, the present disclosure further contemplates applying an ion-conducting polymer to the anode surface to protect its surface from oxidation and nitridation when exposed to air and to create a portion of the cell assembly. This second step is accomplished in a different chamber than the chamber in which the vapor deposition is performed. This creates several disadvantages, including:

Other materials proposed in the prior art have relatively high cost and low conductivity, which reduces cell performance and exacerbates plating and stripping problems.

The equipment required to apply the protective coating is complex and requires a separate process chamber.

In addition to being costly, metallic lithium anodes have been plagued by operational problems (issues in operation) that undermine the benefits provided by their high energy density. Among these, the most common is the tendency to form dendrites, especially at high plating current densities (i.e., rapid charging). Dendrites are structures that form where preferential lithium plating occurs, resulting in protrusions that can penetrate the separator of the cell, resulting in shorts, performance loss, and potential fire. Other drawbacks of electroplating include high porosity or mossy lithium deposits that are prone to undesirable chemical reactions with the electrolyte, leading to simultaneous consumption of lithium and electrolyte and premature failure of the cell. In battery cells using a liquid electrolyte, even well-formed lithium reacts with the electrolyte over time, resulting in limited cycle life, shelf life, energy density, and charge rate of the battery performance.

Several approaches have been developed to address the above problems. For example, US20160233549A1 and US20200194786A1 disclose lithium metal anode cells that use a specialized electrolyte, with the aim of minimizing reactions between the electrolyte and the lithium metal anode and inhibiting dendrite formation. These methods are at least partially effective, however, the extraneous electrolyte can place additional cost burden on the cell and may compromise other performance and manufacturability.

US20200194786A1 also proposes the use of a lithium metal alloy foil comprising 3-60% magnesium (Mg) in the anode to inhibit dendrite and moss lithium formation. This approach increases the bulk density of the anode material and, due to the large excess of material, reduces the energy density of the cell in which the anode is used.

Other prior art suggests using sputtered intermetallic compounds of lithium with gold (Au), zinc (Zn) or zinc oxide (ZnO) on the surface of lithium foil to improve its cycle performance. However, such methods are limited by the minimum thickness and high cost of the lithium foil and complicate the problem by introducing expensive vacuum treatment steps.

While the prior art addresses some of the disadvantages of lithium foil anodes, to date, an efficient process has not been developed to produce low cost SSB lithium anodes that have superior electroplating and stripping characteristics over rolled lithium foil. There remains a need for an improved anode assembly that can be used in lithium-based batteries and that is stable enough to be cost-effective for disposable and/or consumer batteries, and that has desirable and adequate performance. The present disclosure aims to address this obstacle by providing improved, low cost lithium metal anode assemblies, manufacturing processes, and apparatus for their production.

According to one broad aspect of the teachings herein, a multi-layered lithium anode assembly for a lithium-based battery may include a substrate region having a current collector comprising a continuous copper foil having a thickness between 4 and 10 microns and having a support surface compatible with lithium. The lithium bearing region may overlie the support surface and may comprise a film of lithium material deposited directly on the support surface by thermal evaporation and having a thickness of between 1 and 10 microns. The cover region may be located outside the lithium bearing region and may include at least one cover film formed of a passivation material and covering the lithium material film. The cover region may allow lithium ion flow between the electrolyte and the lithium bearing region and inhibit irreversible reactions between the lithium bearing region and the electrolyte or the surrounding environment.

The passivation material may include at least one of nitride, hydride, carbonate, lithium nitride, lithium oxide, lithium sulfide, oxide, lithium aluminate, sulfide, gold, platinum, polyethylene oxide, lithium catecholate, and lithium ion conductive polymer.

The passivation material may include lithium nitride.

The at least one capping film may be formed in situ by exposing the surface of the lithium material film to pure nitrogen and promoting a chemical reaction between the nitrogen and the lithium material film to generate lithium nitride on the surface of the lithium material film.

The total assembly thickness of the anode assembly is less than 50 microns.

According to another broad aspect of the present teachings, a multi-layered lithium anode assembly for a lithium-based battery may include a substrate region having a current collector that may include a continuous copper foil having a thickness between 4 and 10 microns and having a support surface compatible with lithium. The lithium bearing region may overlie the support surface and may comprise a film of lithium material deposited directly on the support surface by thermal evaporation and having a thickness of between 1 and 10 microns. The cover region may be located outside of the lithium bearing region, and may have at least one cover film comprising a lithium-philic material deposited directly onto the exposed surface of the lithium material film by physical vapor deposition. The capping region may thus enhance the mobility of lithium ions through the capping region and moving between the electrolyte and the lithium bearing region such that dendrite formation is inhibited when lithium is deposited in the lithium bearing region when the anode assembly is used, as compared to providing direct contact between the electrolyte and the lithium material film.

The lithium-philic material may include at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb).

The lithium-philic material may include a lithium-zinc alloy formed in situ within the anode assembly by physical vapor deposition of zinc directly onto the exposed surface of the lithium material film.

The total assembly thickness of the anode assembly is less than 50 microns.

According to another broad aspect of the teachings herein, a multi-layered lithium anode assembly for a lithium-based battery may include a substrate region having a current collector that may include a continuous stainless steel foil between 3 and 8 microns thick and having a support surface compatible with lithium. The interface region may be located between the lithium bearing region and the support surface and may include at least one interfacial film located between the support surface and the lithium bearing region to physically separate the substrate region and the lithium bearing region. At least one layer of interfacial film may be formed of copper deposited directly on the support surface and have a thickness between 0.5 and 2 microns and allow electron flow between the lithium bearing region and the support surface. The lithium bearing region may cover the interface region and may include a film of lithium material deposited directly on the at least one interface film by thermal evaporation and having a thickness between 1 micron and 10 microns. The cover region may be located outside the lithium bearing region, and may have at least one cover film formed of a passivation material and covering the lithium material film. The cover region allows lithium ion flow between the electrolyte and the lithium bearing region and inhibits irreversible reactions between the lithium bearing region and the electrolyte or the surrounding environment.

The passivation material may include lithium carbonate (Li ₂ CO ₃ )。

The at least one cover film is formed in situ by exposing the surface of the lithium material film to pure carbon dioxide gas and promoting a chemical reaction between the carbon dioxide and the lithium material film to produce lithium carbonate on the surface of the lithium material film.

The total assembly thickness of the anode assembly is less than 50 microns.

According to another broad aspect of the teachings herein, a multi-layered lithium anode assembly for a lithium-based battery may include a substrate region having a current collector that may include a continuous aluminum foil 5 to 15 microns thick and having a support surface compatible with lithium. The interface region may be located between the lithium bearing region and the support surface and may include at least one interfacial film located between the support surface and the lithium bearing region to physically separate the substrate region and the lithium bearing region. At least one of the interfacial films is formed of nickel deposited directly on the support surface, has a thickness between 200nm and 400nm and allows electron flow and inhibits lithium ion flow between the lithium bearing region and the support surface. The lithium bearing region may cover the interface region and may include a film of lithium material deposited directly on the at least one interface film by thermal evaporation and having a thickness between 1 micron and 10 microns. The cover region may be located outside the lithium bearing region, and may have at least one cover film formed of a passivation material and covering the lithium material film. The cover region may allow lithium ion flow between the electrolyte and the lithium bearing region and inhibit irreversible reactions between the lithium bearing region and the electrolyte or the surrounding environment.

The passivation material may include lithium carbonate (Li ₂ CO ₃ )。

The at least one cover film may be formed in situ by exposing the surface of the lithium material film to pure carbon dioxide gas and promoting a chemical reaction between the carbon dioxide and the lithium material film to produce lithium carbonate on the surface of the lithium material film.

The total assembly thickness of the anode assembly is less than 50 microns.

According to another broad aspect of the teachings herein, a multi-layered lithium anode assembly for a lithium-based battery may include a substrate region having a current collector with a continuous aluminum foil 5 to 15 microns thick and having a support surface. The interface region may be located between the lithium bearing region and the support surface and may include at least one interface film to physically separate the substrate region and the lithium bearing region. At least one of the interfacial films may be formed of nickel deposited directly on the support surface, having a thickness between 200nm and 400nm and allowing electron flow and inhibiting lithium ion flow between the lithium bearing region and the support surface. The lithium bearing region may cover the interface region and may include a film of lithium material deposited directly onto the at least one interface film by thermal evaporation. The cover region outside the lithium bearing region may have a first cover film formed of a lithium-philic material deposited directly onto the exposed surface of the lithium material film by physical vapor deposition. The capping region may enhance mobility of lithium ions moving through the capping region and between the electrolyte and the lithium bearing region such that dendrite formation is inhibited when lithium is deposited in the lithium bearing region when the anode assembly is used as compared to providing direct contact between the electrolyte and the lithium material film.

The total assembly thickness of the anode assembly is less than 50 microns.

According to another broad aspect of the teachings herein, a multi-layered lithium anode assembly for a lithium-based battery may include a substrate region having a support surface compatible with lithium and a non-lithium current collector. The lithium bearing region may overlie the support surface and may be configured to retain at least the first film of lithium material. The interface region may be located between the lithium bearing region and the support surface and may include at least one interfacial film located between the support surface and the lithium bearing region to physically separate the substrate region and the lithium bearing region. At least one interfacial film may be formed by physically depositing a lithium-compatible material onto the support surface and is electrically conductive to allow electron flow between the lithium bearing region and the support surface. The cover region may be located outside of the lithium support region and may have at least one cover film covering the outside of the lithium support region. The cover region allows lithium ion flow between the electrolyte and the lithium bearing region.

The interface region is operable to inhibit dendrite formation when lithium is deposited in the lithium bearing region in use and to improve lithium ion flow or ion distribution between the lithium bearing region and the substrate region in use;

the coverage area is operable to at least one of: inhibit irreversible reactions between the lithium bearing region and the electrolyte or surrounding environment, inhibit dendrite formation when lithium is deposited in the lithium bearing region in use, and enhance lithium ion flow or ion distribution between the lithium bearing region and the electrolyte in use.

The anode assembly may include an interface region and a coverage region.

The first lithium material film may be formed by physically depositing a lithium-compatible material into the lithium bearing region.

The current collector may include at least one of copper, aluminum, nickel, stainless steel, conductive polymers, and polymers.

The current collector may be configured as a continuous web.

The current collector may have a current collector thickness of between about 1 and about 100 microns, preferably between about 4 and about 70 microns or between about 5 and 15 microns.

The current collector may be formed of a lithium-compatible material and may have a front surface that may include a support surface.

The lithium-compatible material may include a metal foil, which may have at least one of copper, steel, and stainless steel.

The current collector may be formed of a material that is not compatible with lithium, and may include a first protective film that is bonded to and covers the front surface of the current collector and provides a support surface. The first protective film may be formed of a protective metal that is electrically conductive and prevents the flow of lithium ions, whereby electrons may pass from the lithium bearing region through the first protective film to the current collector, and the lithium bearing region is spaced apart from the current collector and at least substantially isolated from the current collector ions, thereby substantially preventing the diffusion of lithium ions from the lithium bearing region to the current collector through the first protective film.

The protective metal may include at least one of copper (Cu), nickel (Ni), silver (Ag), stainless steel and steel, titanium (Ti), zirconium (Zr), molybdenum (Mo), or an alloy thereof.

The lithium-incompatible material may comprise a metal foil, which may have aluminum, zinc or magnesium or an alloy thereof.

The thickness of the first protective film may be between about 1 to about 75000 angstroms, and preferably between about 200 to about 7500 angstroms.

The first protective film may have an isolation thickness and be shaped such that the current collector is fully ion isolated from the lithium bearing region.

The first lithium material film may be deposited on and bonded to the first protective film by physical vapor deposition.

The at least one interface film may include at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), copper (Cu), indium (In), silver (Ag), bismuth (Bi), lead (Pb), cadmium (Cd), antimony (Sb), and selenium (Se).

The thickness of the at least one interfacial film may be between about 1 and about 75000 angstroms, and preferably between about 200 and about 7500 angstroms.

The at least one interfacial film may include at least a first deposition enhancement film that may have at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb) and be positioned to contact the lithium bearing region, thereby inhibiting dendrite formation when the first lithium material film is deposited In the lithium bearing region.

The first deposition enhancement film may be a deposition film formed by physically depositing at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), and lead (Pb) to an underlying surface.

The interface region may further include at least a first bonding film adjacent to the first deposition enhancement film and may have at least one of zinc (Zn), cadmium (Cd), magnesium (Mg), antimony (Sb), indium (In), bismuth (Bi), nickel (Ni), lead (Pb), and selenium (Se), and may be located between the support surface and the lithium bearing region, thereby providing a better bond between the support surface and the lithium bearing region (than would be achieved without the first bonding film).

The at least one interfacial film may include at least a first bonding film that may have at least one of zinc (Zn), cadmium (Cd), magnesium (Mg), antimony (Sb), indium (In), bismuth (Bi), nickel (Ni), lead (Pb), and selenium (Se), and may be located between the support surface and the lithium bearing region, thereby providing better bonding between the support surface and the lithium bearing region (than bonding achieved between the support surface and the lithium bearing region without the first bonding film).

The bonding film may be formed by physical vapor deposition of at least one of zinc (Zn), cadmium (Cd), magnesium (Mg), antimony (Sb), indium (In), bismuth (Bi), nickel (Ni), lead (Pb), and selenium (Se) to the underlying surface.

The interface region may further include at least one layer of a first deposition enhancement film adjacent to the bonding film and may have at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb), and may be positioned to contact the lithium bearing region, thereby inhibiting dendrite formation when the first lithium material film is deposited In the lithium bearing region.

The interface region may be free of metal foil.

The lithium bearing region may comprise a film of a first lithium material.

The first lithium material film may be formed by physically depositing lithium metal onto the support surface.

The assembly may include at least one cover film in the cover region, and the first film of lithium material may include lithium metal deposited into the lithium bearing region after the at least one cover film is in place.

The lithium bearing region may be free of lithium foil.

The lithium bearing region may be free of metal foil.

The at least one cover film may include at least a first passivation film that covers an outer side of the lithium bearing region and inhibits a reaction between the lithium bearing region and an ambient environment. The first passivation film is formed of a passivation material that suppresses gas diffusion and allows lithium ions passing through the first passivation film to flow.

The passivation material may include lithium carbonate (Li ₂ CO ₃ )。

The lithium carbonate may include a film formed in situ on a surface of the first lithium material film: the lithium carbonate is formed by exposing the surface to a gas of pure carbon dioxide and reacting the lithium material of the surface with carbon dioxide.

The capping region may include at least a first deposition enhancement film formed of a wetting material and covering an outer side of the lithium bearing region, and enhancing wetting between the first wetting film and the lithium bearing region, such that dendrite formation is inhibited by the first deposition enhancement film in the capping region when the first lithium material film is deposited on the lithium bearing region.

The at least one capping film may include at least a first deposition enhancement film formed of a wetting material and capping an outside of the lithium bearing region and enhancing wetting between the first deposition enhancement film and the electrolyte, thereby inhibiting dendrite formation in the lithium bearing region by reaching the first deposition enhancement film of the lithium bearing region when the first lithium material film is deposited in the lithium bearing region.

The wetting material may comprise polyethylene oxide (PEO).

Polyethylene oxide may be deposited by physical vapor deposition and bonded to adjacent films.

Polyethylene oxide may be deposited onto the first lithium material film.

The polyethylene oxide may be deposited and bonded to an intermediate transfer film that is disposed between the first deposition enhancement film and the first lithium material film and enhances charge transfer to and from the first lithium material film.

The transfer film may include at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), and lead (Pb).

The covering region may include at least a first passivation film covering the outside of the lithium bearing region and inhibiting a reaction between the lithium bearing region and the surrounding environment. The first passivation film may be formed of a passivation material that suppresses gas diffusion and allows lithium ions passing through the first passivation film to flow.

The cover region may include at least a lithium-philic cover film covering an outside of the lithium bearing region and may include at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb), whereby the lithium-philic cover film enhances mobility of lithium ions through the lithium-philic cover film and between the electrolyte and the lithium bearing region, thereby inhibiting dendrite formation when lithium is deposited In the lithium bearing region when the anode assembly is used.

The cover region may be free of metal foil.

The anode assembly may be free of lithium metal foil.

The current collector may comprise a non-lithium metal foil and may be the only foil in the anode assembly.

The anode assembly may have an assembly thickness of less than about 60 μm.

The thickness of the component may be less than about 50 μm.

The thickness of the component may be between about 10 μm and about 50 μm.

The thickness of the component may be between about 15 μm and about 30 μm.

The thickness of the component may be between about 16 to about 25 μm.

The anode assembly may have a weight of less than about 80g/m ² Is a surface density of the glass.

The areal density may be less than about 70g/m ² 。

The areal density can be less than about 60g/m ² 。

The areal density can be about 30g/m ² And 70g/m ² Between them.

The areal density can be about 40g/m ² And 65g/m ² Between them.

According to another broad aspect of the teachings herein, a single pass method of manufacturing a multi-layer anode assembly for a lithium-based battery may comprise the steps of:

a) Unwinding a continuous substrate web from a substrate feed roll and transporting the substrate web in a process direction along a deposition path within a process chamber of a single pass physical vapor deposition apparatus, the substrate web may include a continuous current collector and a lithium-compatible support surface disposed on a first side of a current collector;

b) Transporting the substrate web in a process direction through a lithium deposition zone along a deposition path and depositing at least a first lithium film onto an outside of the component support surface using a lithium physical vapor deposition applicator;

at least one of the following steps:

c) Transporting the substrate web in a process direction through an interface deposition zone along a deposition path and upstream of the lithium deposition zone and depositing a first interface film formed of an interface material onto the support surface using an interface physical vapor deposition applicator, whereby the first interface film is located between the support surface and the first lithium film, the interface material being electrically conductive to allow electron flow between the first lithium film and the support surface; and

d) Transporting the substrate web in a process direction through a blanket deposition zone along a deposition path and downstream of the lithium deposition zone, wherein a first blanket film is formed from a blanket material that allows lithium ion flow between the electrolyte and the first lithium film and is located outside of the first lithium film, whereby the first lithium film is located between the first blanket film and the support surface, thereby forming a multi-layered anode assembly; and

e) After performing at least one of steps b) and c) and d), winding the multi-layer anode assembly on an output roll at an outlet of the deposition path, and wherein at least one of steps b), and at least one of steps c) and d) is completed during a single pass of the substrate web through the deposition path.

At least one of steps b), and steps c) and d) may be accomplished during a single PVD vacuum cycle, wherein the process chamber is maintained at less than 10 during at least one of steps b), and steps c) and d) ^-2 At the operating pressure of the tray.

The current collector may comprise a continuous metal foil.

The current collector may have a thickness of between about 1 and about 100 microns.

The current collector may include at least one of copper, aluminum, magnesium, nickel, stainless steel, conductive polymers, and polymers.

The current collector may comprise a lithium-compatible metal foil and the front surface of the current collector may provide a support surface. The first lithium film may be deposited directly onto the front surface of the current collector by a lithium physical vapor deposition applicator.

The current collector may comprise a lithium-incompatible metal foil, and the method may further comprise transporting the substrate web in a process direction through a protective layer deposition zone upstream of the lithium deposition zone, and forming a first protective film by depositing a protective material compatible with lithium directly onto a front side of the current collector by a protective film vapor deposition applicator, wherein the protective material is electrically conductive and inhibits lithium ion flow, whereby electrons may pass from the first lithium film through the first protective film to the current collector, and the first lithium film is spaced apart from the current collector and at least substantially isolated from the current collector ions, thereby substantially preventing diffusion of lithium ions from the lithium bearing zone to the current collector through the first protective film, and wherein the first protective film may comprise a support surface, the first lithium film being deposited directly onto the first protective film.

The protective material may include at least one of copper, nickel, silver, stainless steel and steel, titanium, zirconium, molybdenum, or alloys thereof.

The first cover film may be formed by depositing the first cover material onto the first lithium film using a cover gas phase deposition applicator.

The first capping film may be a lithium-philic capping film, and may include at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), and lead (Pb), whereby the lithium-philic capping film enhances diffusion of lithium ions through the lithium-philic capping film and between the electrolyte and the lithium bearing region, such that formation of dendrites is suppressed when lithium is deposited In the lithium film when the anode assembly is used.

The first capping film may be formed in situ by subjecting the surface of the first lithium film to a gas treatment, thereby forming the first capping material.

The first cover material may include at least one of nitride, hydride, carbonate, lithium nitride, lithium oxide, lithium sulfide, oxide, lithium aluminate, sulfide, gold, platinum, polyethylene oxide, lithium catechol, and lithium ion conductive polymer, whereby the first cover film allows lithium ion flow between the electrolyte and the first lithium film and inhibits irreversible reaction between the first lithium film and the electrolyte or the surrounding environment.

At least one of steps b) and steps c) and d) may be performed while the substrate web is moving between the input roll and the output roll at a process speed of between about 1m/min and about 100m/min, preferably between 2m/min and 50 m/min.

During at least one of step b) and steps c) and d), the process chamber may be substantially free of oxygen.

The operating pressure may be about 10 ^-2 And 10 ^-6 And the brackets are arranged between the two brackets.

The method may comprise, prior to step b), reducing the pressure inside the metallization chamber from substantially atmospheric pressure to an operating pressure.

The method may comprise steps c) and d), and step c) may be performed before step b).

After completing step b) and at least one of steps c) and d), but before completing step e), the method may further comprise:

f) Transporting the substrate web in a process direction through a second lithium deposition zone along a deposition path and depositing at least a second lithium film onto a second support surface disposed on an opposite second side of the current collector using a lithium physical vapor deposition applicator; and

at least one of the following steps:

g) Transporting the substrate web in a process direction through a second interfacial deposition area along a deposition path and upstream of the second lithium deposition area and depositing a second interfacial film formed of an interfacial material onto the second support surface using an interfacial physical vapor deposition applicator, whereby the second interfacial film is located between the second support surface and the second lithium film, the interfacial material being electrically conductive to allow electron flow between the second lithium film and the second support surface; and

h) Transporting the substrate web in the process direction through a second blanket deposition zone along the deposition path and downstream of the second lithium deposition zone, wherein the second blanket film is formed of a blanket material that allows lithium ion flow between the electrolyte and the second lithium film and is located outside of the second lithium film, whereby the second lithium film is located between the second blanket film and the second support surface; and is also provided with

Wherein step f) and at least one of steps g) and h) are performed during a single pass of the substrate web through the deposition path, and step e) is performed after step h).

According to another broad aspect of the teachings herein, a multi-layer anode assembly may be formed using any of the methods or portions of methods described herein, and all of the films may be deposited using physical vapor deposition.

b) Transporting the substrate web in a process direction through an interfacial deposition area along a deposition path and depositing a first interfacial film formed of an interfacial material onto the support surface using an interfacial physical vapor deposition applicator, the interfacial material being electrically conductive to allow electron flow between the first lithium film and the support surface;

c) Transporting the substrate web in a process direction through a lithium deposition zone along a deposition path and downstream of the interface deposition zone, and depositing at least a first lithium film onto the first interface film using a lithium physical vapor deposition applicator, whereby the first interface film is located between the support surface and the first lithium film;

d) Transporting the substrate web in a process direction through a cover deposition zone along a deposition path and downstream of the lithium deposition zone, wherein the first cover film is formed of a cover material that allows lithium ions between the electrolyte and the first lithium film to flow and is located outside of the first lithium film, whereby the first lithium film is located between the first cover film and the support surface;

i) Transporting the web of substrate in the process direction through a second interfacial deposition area along a deposition path and downstream of the blanket deposition area, and depositing a second interfacial film formed of an interfacial material onto a second support surface disposed on an opposite second side of the current collector using a second interfacial physical vapor deposition applicator;

j) Transporting the web of substrates in a process direction through a second lithium deposition zone along a deposition path and downstream of the second interface deposition zone, and depositing at least a second lithium film onto the second interface film using a lithium physical vapor deposition applicator; and

k) Transporting the substrate web in a process direction through a second blanket deposition zone along the deposition path and downstream of the second lithium deposition zone, wherein the second blanket film is formed from a blanket material that permits lithium ion flow between the electrolyte and the second lithium film and is located outside of the second lithium film, whereby the second lithium film is between the second blanket film and the second support surface, thereby providing a double-sided multilayer anode assembly;

l) after performing steps a) to k), winding the double-sided multilayer anode assembly on an output roll at the outlet of the deposition path;

and at least a) through k) are completed during a single pass of the substrate web through the deposition path.

According to another broad aspect of the teachings described herein, a single pass method of manufacturing a double sided multi-layer anode assembly for a lithium-based battery may comprise the steps of:

a) Unwinding a continuous substrate web from a substrate feed roll and transporting the substrate web in a process direction along a deposition path within a process chamber of a single pass physical vapor deposition apparatus, the substrate web may include a continuous current collector having a first side and an opposing second side;

b) Transporting the current collector in a process direction while applying at least first and second films on a first side of the current collector using respective first and second physical phase deposition applicators positioned to face the first side of the current collector;

c) Transporting the current collector in a process direction while applying at least third and fourth films on a second side of the current collector using respective third and fourth physical vapor deposition applicators positioned to face the second side of the current collector, wherein steps b) and c) are completed during a single pass of the substrate web through the deposition path, thereby providing a double-sided multilayer anode assembly; and

d) After performing steps b) and c), the double-sided multilayer anode assembly is wound on an output roll at the exit of the deposition path.

The first film may include a first lithium film formed of a lithium material, and wherein the second film may include at least one of:

a) An interface film located inside the lithium film, configured to suppress dendrite formation and/or improve lithium ion flow or ion distribution between the first lithium film and the current collector when lithium is deposited In the lithium film, and formed of an interface material of at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), copper (Cu), indium (In), silver (Ag), bismuth (Bi), lead (Pb), cadmium (Cd), antimony (Sb), and selenium (Se); and

b) A cover film located outside the first lithium film, formed of: i) A passivation material configured to inhibit reaction between the first lithium film and the surrounding environment by inhibiting gas diffusion while allowing lithium ions to flow through the cover film, or ii) a lithium-philic cover material configured to enhance mobility of lithium ions through the cover film and between the electrolyte and the first lithium bearing region such that dendrite formation is inhibited when lithium is deposited in the first lithium film when the anode assembly is in use.

The lithium-philic capping material may include at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), and lead (Pb).

The third film may include a second lithium film formed of a lithium material, and wherein the fourth film may include at least one of:

According to another broad aspect of the teachings herein, a method of manufacturing a multi-layer anode assembly for a battery may comprise:

a) Unwinding a continuous substrate web from a substrate feed roll and transporting the substrate web in a process direction along a deposition path within a process chamber of a single pass physical vapor deposition apparatus, the substrate web may include a continuous current collector and a lithium-compatible support surface;

And at least one of the following steps:

b) Transporting the substrate web in a process direction through an interface deposition zone along a deposition path and depositing a first interface film formed of an interface material onto the support surface using an interface physical vapor deposition applicator, the interface material being electrically conductive to allow electron flow through the first interface film; and

c) Transporting the substrate web in a process direction through a blanket deposition zone along a deposition path and downstream of the interfacial deposition zone and forming a first blanket film outside the support surface, the first blanket film formed of a blanket material that is conductive to lithium ions to allow lithium ions to flow through the first blanket film;

wherein at least one of steps b) and c) is completed during a single pass of the substrate web along the deposition path, thereby providing an intermediate web assembly, and may further comprise:

d) Positioning at least a first portion of the intermediate mesh assembly in an electrochemical cell, which may include a positive electrode and a lithium source; and

e) An electrical potential is applied between the positive electrode and the first portion of the intermediate web, thereby driving lithium ions from the lithium source and depositing the lithium ions as a first lithium film on the intermediate web assembly in a lithium bearing region outside the support surface.

The component may be free of lithium prior to performing step e).

At least one of steps b) and c) may be accomplished during a single PVD vacuum cycle, wherein the interior of the processing chamber is maintained at less than 10 ^-2 Operating pressure of the tray.

The current collector may comprise a continuous metal foil.

The current collector may comprise a lithium-compatible metal foil, the front surface of the current collector providing a support surface, and the first lithium film being deposited directly onto the front surface of the current collector by a lithium physical vapor deposition applicator.

The current collector may include a lithium-incompatible metal foil, and the method may include transporting the substrate web in a process direction through a protective layer deposition zone upstream of the lithium deposition zone, and depositing a protective material compatible with lithium directly onto a front side of the current collector by a protective film vapor deposition applicator to form a first protective film. The protective material may be electrically conductive and prevent lithium ions from flowing, whereby electrons may pass from the first lithium film through the first protective film to the current collector, and the first lithium film is spaced apart from the current collector and at least substantially ion-isolated from the current collector such that lithium ions are substantially prevented from diffusing from the lithium bearing region to the current collector through the first protective film, and wherein the first protective film may include a support surface. The first lithium film may be directly deposited on the first protective film.

The first cover film may be formed by depositing the first cover material using a cover gas phase deposition applicator prior to adding the first lithium film.

The first capping film may be a lithium-philic capping film, and may include at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), and lead (Pb), whereby the lithium-philic capping film enhances mobility of lithium ions through the lithium-philic capping film and between the electrolyte and the lithium bearing region, thereby inhibiting dendrite formation when lithium is deposited In the lithium film when the anode assembly is used.

The first cover material may include at least one of lithium zinc alloy, lithium carbonate, and lithium nitride, whereby the first cover film allows lithium ions between the electrolyte and the first lithium film to flow and inhibits irreversible reactions between the first lithium film and the electrolyte or the surrounding environment.

At least one of steps c) and d) may be performed while the substrate web is moving between the input roll and the output roll at a process speed of between about 1m/min and about 100m/min, preferably between 2m/min and 50 m/min.

During at least one of steps b) and c), the process chamber may be substantially free of oxygen.

The operating pressure may be about 10 ^-2 To 10 ^-6 And the brackets are arranged between the two brackets.

The method may comprise, prior to step c), reducing the pressure inside the metallization chamber from substantially atmospheric pressure to an operating pressure.

The method may further comprise at least one of:

f) Transporting the substrate web in a process direction through a second interface deposition zone along a deposition path and depositing a second interface film formed of an interface material onto an opposite second side of the substrate web support surface using a second interface physical vapor deposition applicator; and

g) Transporting the substrate web in the process direction through a second blanket deposition zone along the deposition path and downstream of the second interface deposition zone, and forming a second blanket film on an outside of the second side of the substrate web, the second blanket film being formed of a blanket material;

wherein at least one of steps b) and c) and at least one of steps f) and g) are completed during a single pass of the substrate web along the deposition path, thereby providing a double-sided intermediate web assembly prior to step d).

The method may comprise steps b) and c) and f) and g).

Drawings

Embodiments of the present invention will be described with reference to the accompanying drawings, wherein like reference numerals refer to like parts, and wherein:

FIG. 1 is a partially exploded schematic illustration of a multi-layered anode assembly;

FIG. 2 is an exemplary schematic view of an anode assembly for use with a lithium-based battery;

FIG. 3 is an enlarged view of a portion of the anode assembly of FIG. 2;

FIG. 4 is a perspective view of the anode assembly of FIG. 2;

FIG. 5 is a schematic diagram of another example of an anode assembly for use with a lithium-based battery;

FIG. 6 is a flow chart illustrating an example of a method of manufacturing an anode assembly;

fig. 7 is a flowchart showing another example of the manufacturing method of the anode assembly;

fig. 8 is a flowchart showing another example of the manufacturing method of the anode assembly;

FIG. 9 is a schematic diagram of one example of a battery incorporating the anode assembly of FIG. 2;

FIG. 10 is a schematic diagram of one example of an apparatus for manufacturing an anode assembly;

fig. 11 is a sectional view of fig. 10 taken along line D;

fig. 12 is a cross-sectional view of fig. 10 taken along line C;

FIG. 13 is a schematic view of one example of a double sided anode assembly;

FIG. 14 is a schematic view of another example of an anode assembly;

FIG. 15 is a schematic view of another example of an anode assembly;

FIG. 16 is a schematic diagram of another example of an apparatus for manufacturing an anode assembly;

FIG. 17 is a schematic diagram of another example of an apparatus for manufacturing an anode assembly;

FIG. 18 is a schematic diagram of another example of an apparatus for manufacturing an anode assembly;

FIG. 19 is a schematic diagram of one example of a battery cell;

FIG. 20 is a schematic view of another example of an anode assembly;

FIG. 21 is a schematic view of yet another example of an anode assembly;

FIG. 22 is a schematic diagram of one example of a battery cell including an anode assembly without a lithium reaction layer;

FIG. 23 is a schematic illustration of the battery of FIG. 22 in a charged state;

FIG. 24 is a schematic view of another example of an apparatus for manufacturing an anode assembly;

FIG. 25 is a schematic view of another example of an apparatus for manufacturing an anode assembly;

FIG. 26 is a schematic diagram of another example of an apparatus for manufacturing an anode assembly;

FIG. 27 is a graph showing cycle data for a conventional foil and a material according to example 4, showing that the two perform similarly;

fig. 28 is a photograph of a conventional foil after symmetric cycling 50 times using sulfide electrolyte (white particles are electrolyte residues); and

fig. 29 is a photograph of an example of PVD deposited lithium after 50 symmetric cycles using sulfide electrolyte (white particles are electrolyte residues).

Detailed Description

Various devices or processes will be described below to provide examples of embodiments of each of the claimed inventions. The embodiments described below are not limiting of any claimed invention, and any claimed invention may encompass processes or apparatuses other than those described below. The claimed invention is not limited to devices or processes having all of the features of any one device or process described below or common features of multiple or all devices described below. The apparatus or process described below may not be any of the embodiments of the present invention as claimed. Any inventions disclosed in the following devices or processes not claimed in this document may be the subject of another protection document (e.g., a continuation-in patent application), and applicant, inventor or owner does not intend to forego, leave protection, or present themselves to the public by disclosing any such inventions in this document.

The teachings described herein are directed to providing a suitable multi-layered lithium anode assembly that can reduce and/or eliminate the need for the use of lithium foil and can be manufactured at relatively low cost and relatively large scale by providing an anode assembly that includes one or more functional film layers to help provide relatively improved/excellent plating and stripping characteristics. That is, the present teachings relate to multi-layer anode assemblies that are applicable to liquid electrolyte metal lithium ion batteries (LMBs), hybrid lithium metal batteries (HLBs), and lithium metal Solid State Batteries (SSBs), and processes and apparatus/devices that may be used in their manufacture. The multi-layer assembly may include at least two or more regions that may have different functions, and in which various layers may be grouped to help provide an anode assembly having a desired range of mechanical and electrical operating capabilities. Preferably, the multi-layer anode is configured to include only one metal foil layer/substrate (e.g., current collector foil) and the remaining layers (in their respective functional areas) are deposited onto the foil layer using material deposition and/or surface reaction techniques (e.g., electroplating, physical vapor deposition, etc.), rather than being provided as a separate foil or web that is required to be bonded to the base foil layer. Unlike the application of metal foils or other types of preformed layers or planar structures, the functional layers described herein are described as films because they are formed by depositing a plurality of smaller particles of material onto an underlying surface or substrate (e.g., by physical vapor deposition), by plating metal onto an underlying surface or substrate, or by promoting gaseous surface reactions on a surface/substrate, etc. Those skilled in the art will recognize that these films are formed as part of the manufacturing process rather than having prefabricated layers of solid materials joined together. A given film may be formed from two or more different layers or may be formed in two or more steps/material applications (particularly if formed by successive physical deposition steps). The term film is used in this specification for convenience and includes structures/layers formed using the techniques and processes described herein as well as other suitable alternative techniques and processes.

Such anodes having different functional areas and films deposited in the manner described herein are understood to be different from existing anodes, which may technically include areas that produce the desired component thickness, for example, by providing two or more layers of a given foil material, or areas that laminate different layers of metal foil together to provide a substantially uniform foil structure. The anode assembly of the present invention also differs from anode assemblies that include only a current collector (protected by a protective layer or unprotected) in combination with a film of lithium material, in that such assemblies may include the form of a substrate region (only current collector, or current collector plus one or more protective film coatings) and a lithium bearing region (lithium hosting region), but do not include a functionally identifiable interface region or coverage region as described herein.

Aspects of the present disclosure may also relate to relatively low cost production of lithium anode assemblies for one or more types of lithium-based batteries. The present teachings may also relate to relatively low cost production of roll-to-roll (roll-to-roll) metallized substrates that may be used for anode assemblies. According to certain non-limiting embodiments, the present disclosure may disclose a low cost lithium anode and current collector assembly, a process for producing such an assembly, and a physical vapor deposition apparatus that may perform such a process. The present teachings may also relate to a battery including examples of the anode assemblies described herein.

According to one embodiment described herein, an anode assembly for a lithium-based battery may include a current collector substrate comprising aluminum and having a support surface for receiving/supporting other components of the assembly. The reactive film comprising lithium metal is configured to contact the electrolyte within the cell when the anode assembly is in use and is typically supported by a current collector substrate. To help reduce the chance of unwanted reactions between the lithium reaction film (reactive lithium film) and the aluminum in the current collector, the assembly may also include a suitable protective film that bonds to and covers the support surface and includes a suitably conductive protective metal. In this configuration, a protective film is disposed between the support surface and the reaction film such that electrons can move from the first reaction film to the current collector (e.g., to allow electron flow between the support surface and the reaction film), and the first reaction film is spaced apart from the support surface and at least substantially ion-isolated. Thus, the protective film may help to at least substantially prevent or inhibit, and possibly completely prevent, diffusion of the reactive film to the current collector, which may help to at least substantially inhibit, and optionally completely prevent, unwanted reactions between the lithium metal and the current collector. This type of separation between the current collector substrate and the reaction membrane may help facilitate the use of lithium in the reaction membrane, while at the same time helping to facilitate the use of materials in the current collector that may normally be desirable for use as current collectors that would otherwise react with lithium in the reaction membrane (e.g., without a suitable protective membrane) in a manner that would reduce the effectiveness of the anode assembly and/or that could damage or reduce the effectiveness of the anode assembly or sub-layers thereof.

According to another broad aspect of the teachings described herein, a protected current collector subassembly useful for a variety of different anode assemblies using different reactive materials may include a current collector substrate at least partially covered with one or more suitable protective films (which may optionally be deposited in the substrate region and/or interface region) that bond to and cover the front surface of the current collector and that include a suitably conductive protective metal or combination of metals and may have other desirable properties. In this configuration, the protective film is disposed between the current collector and the reactive film such that electrons can move from the first reactive film to the current collector, and the first reactive film is spaced apart from and at least substantially ion-isolated from the front surface of the current collector. Thus, the one or more protective films may help at least substantially prevent or inhibit, and possibly completely prevent, diffusion of the reactive film to the current collector, which may help at least substantially inhibit, and optionally completely prevent, unwanted reactions between lithium metal or other such reactive materials that may be present in the reactive film (materials that may accumulate within the reactive film upon initial construction/assembly of the anode assembly or material or upon charging and/or use of the battery) and the protected current collector material.

As used herein, the term film or layer describes a given amount of material, e.g., protective material, gas protective layer material, conductive film material, performance enhancing film material, etc., that is generally continuous and is not interrupted by intermediate materials or structures. Any given film or layer may be formed by applying the material in a single pass (e.g., performing a single-pass physical vapor deposition process step as described herein), which applies all of the material of a given thickness of film in a single step or process. Alternatively, a single film as described herein may also be applied as a result/combination of two or more applications of film material (e.g., performing a multiple pass physical vapor deposition process as described herein), a portion of the film material at a time, and the total film thickness measured on a film formed by accumulating material from two or more applications.

According to another broad aspect of the teachings described herein, at least some anode assemblies are configured as multi-layer anode assemblies or components thereof (e.g., protected current collectors, substrates, etc.), including specific combinations of layers and films, and their order of application in the manufacturing process may vary depending on various factors including cost, mechanical and/or electrical characteristics, the intended use of the assembly, etc. For example, some anode assemblies may benefit from a protective outer film to help reduce oxidation of functional portions of the assembly during or after fabrication, some anode assemblies may benefit from an intermediate film between a lithium-reactive film and an underlying current collector to help reduce unwanted reactions or to help enhance conductivity and/or performance matching or bonding between two different materials, while other anodes may benefit from including a lithium-philic film (lithiophilic film) that is generally compatible with lithium metal and to help provide the ion mobility/deposition enhancement effects described herein.

Referring to fig. 1, a schematic diagram of the arrangement of the various functional areas of a given anode assembly, the elements being partially exploded from one another for clarity, includes a substrate area 190, a lithium bearing area 192, an interface area 194, and a cover area 196, which areas are schematically shown using dashed lines. Each region 190, 192, 194, and 196 may comprise a suitable film of material as described herein. Referring also to fig. 2 and 3, in this example, the substrate region includes the current collector 102 and its protective coating film 104, the lithium bearing region includes the lithium reactive material 106, and the interface and cover regions 194 and 196 are empty (represented using an internal dashed box). In other examples, such as the embodiment of fig. 14, the substrate region 190 includes the current collector 102, the lithium-bearing region 192 includes the lithium-reactive film 106, the interface region includes two different interface films (performance film 150 and conductive film 152), and the cover region includes the passivation or gas-protective film 156. Although this schematic is shown in fig. 1 as a single-sided anode, it will be appreciated that the same arrangement of regions may be provided on the other side of the substrate region to provide a double-sided anode as described herein.

In general, the substrate region of the anode assembly may be understood as a base or web of material that helps provide the mechanical strength of the anode assembly, and is the base upon which other regions and films may be deposited/built. The substrate region will include at least a current collector, which may be a suitable metal foil as described herein. The metal foil mesh may be provided on a source or supply roll (source or supply roll) and may be fed through suitable processing equipment by which one or more functional films/layers may be deposited onto a suitable support surface of the foil mesh, and the resulting layered material may then be wound onto an intermediate or product roll (intermediary or product roll) for storage or further processing. In some examples described herein, the substrate region may include only the current collector, for example, where the current collector is generally compatible with other membranes in the anode assembly. Alternatively, the substrate region may also include one or more protective films that may be applied to the support surface of the current collector to help form at least a portion of the structure of the protected current collector that may be used in an assembly in which the material of the current collector may react with other components of the assembly in an undesirable manner.

As used herein, a protected current collector is understood to mean a multi-layer structure that does not include lithium metal or lithium-bearing material at the time of its manufacture and that includes a metal foil current collector formed of a material that is not compatible with lithium, meaning that the metal foil will tend to react with lithium in a manner that is unsuitable for the intended use described herein, such as aluminum, zinc, magnesium or other lithium-philic materials and alloys thereof. In addition to the foil mesh that is incompatible with lithium, the protected current collector will include at least one protective film (e.g., film 104 described herein) that helps mitigate potential reactions between the foil mesh that is incompatible with lithium and any lithium material that is ultimately added to the anode assembly. The two films may also define a substrate area for a given assembly. In addition to the protective film in the substrate region, the protected current collector may also include one or more other suitable films as described herein, and may have at least one film present in the interface region 194 and/or the cover region 196. Materials that do not tend to react with lithium in these adverse ways, such as copper, steel, and stainless steel, may be referred to as lithium compatible materials/foils.

Whether the assembly includes a protected current collector or an unprotected/uncoated current collector, the lithium bearing region 192 may be understood as the region of the anode assembly that is outside of and overlying the support surface (e.g., surface 112) of the substrate region 190. The material in the lithium bearing region 192 may be deposited onto one or more layers of material film in the interface region 194 (if present), or the material in the lithium bearing region 192 may be deposited directly onto the substrate region 190 without any layers of material in the interface region 194. This may include contacting the lithium material directly with a compatible current collector, or contacting the lithium material with a protective film (e.g., film 104).

Interface region 194, defined as the region between the lithium bearing region and the substrate region, may include one or more layers of suitable interface materials that may provide a variety of functions within the anode assembly. For example, the interfacial films may have performance enhancing properties that may be lithium ion blocking and conductive (e.g., allow electron flow through the interfacial film and interfacial region), that may be conductive but not lithium ion blocking, that may have lithiaphilic or plating enhancing properties, and that may help promote bonding or other performance matching between adjacent layers, films, or regions, such as thermal expansion matching, improving interlayer bonding, etc.

For example, if one material is deposited onto another material as described herein, some materials may not be directly bonded to each material in an acceptable manner. To help overcome this challenge, an intermediate interface film may be provided, and may be formed of a material that can satisfactorily bond with both of the original materials. Similarly, if two materials having significantly different thermal expansion characteristics are directly bonded to each other, the force/strain at the material interface may be higher than expected during a significant change in temperature, and may result in connection failure, damage to at least one layer, and the like. However, if an intermediate layer having intermediate thermal expansion properties is bonded between two original layers, the amount of force or strain experienced at each interface may be reduced to an acceptable level.

Examples of materials that may be suitable for use as interface materials and that may have enhanced deposition and lithium-philic properties (and for forming a film within the interface region) may include, for example, tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb). Examples of materials suitable for use as lithium ion flow-inhibiting interface materials that are electrically conductive (to facilitate electron transfer) and help block lithium ion flow (and to form a flow-inhibiting or protective film in the interface region or alternatively in the substrate region) may include, for example, copper (Cu), nickel (Ni), chromium (Cr), tungsten (W), tantalum (Ta), iron (Fe), titanium (Ti), zirconium (Zr), molybdenum (Mo), and alloys thereof. Examples of materials that may be suitable for use as interface materials and that may help provide performance matching and/or improved material bonding properties (and for forming layers within the interface region) may include, for example, zinc (Zn), cadmium (Cd), copper (Cu), magnesium (Mg), antimony (Sb), indium (In), bismuth (Bi), nickel (Ni), lead (Pb), and selenium (Se).

The cover region 196 may comprise any film, coating, or other material that is located outside of the lithium bearing region, and at least one of which will ultimately serve as the outermost layer or surface of the anode assembly. The membrane in the capping region may include, for example, a passivation film (configured to inhibit irreversible reactions between the lithium bearing region and the electrolyte or ambient, e.g., by inhibiting gas diffusion and allowing lithium ion flow through the first passivation film), a deposition enhancement film (configured to improve lithium ion flow or ion distribution between the lithium bearing region and the electrolyte in use), a lithium-philic capping film (configured to help enhance transfer of lithium ions so as to inhibit dendrite formation when lithium is deposited in the lithium bearing region in use of the anode assembly). Some examples of materials that may be used to form deposition enhancing and/or lithium-philic films In the capping region may include, for example, tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), and lead (Pb). Some example materials that may be used to form a passivation film in the cap region may include nitrides (e.g., lithium nitride), hydrides (e.g., lithium hydride), carbonates (e.g., lithium carbonate), oxides (e.g., lithium oxide), sulfides (e.g., lithium sulfide), lithium ion conductive polymers (e.g., PEO, lithium catecholate (lithium catehcols)), gold (Au), platinum (Pt), and the like.

As indicated above, some membranes/materials may be included in two or more different layers, optionally in different regions 190, 192, 194, or 196 within a single anode assembly. The materials used in the film may provide substantially the same function in each region (e.g., to enhance electroplating by reducing dendrite formation, or a combination of functions, such as suppressing unwanted reactions and improving lithium ion transport, etc.), or may provide different functions in the assembly depending on its location. For example, zinc (Zn) or magnesium (Mg) may be used in at least one layer of interfacial film within the interfacial region to help provide a mechanical/chemical property match between the current collector and the material in the lithium bearing region.

While different anode assemblies may have different combinations of different types of membranes described herein, as well as different numbers and types of layers from other embodiments of the described anode assemblies, for the purposes of the present teachings, an anode assembly may be understood to define four primary functional areas, including a base or substrate area, a reaction or lithium bearing area, an internal interface area defined as being inboard of and between the substrate area and the lithium bearing area, and a footprint area defined as being outboard of the lithium bearing area and being the outermost area of a given anode assembly. As described herein, each of these conceptual regions may include one or more layers and/or films that may provide different functions and may be formed of suitable/appropriate and compatible materials. For example, the lithium bearing region may comprise a lithium metal film, while the cover region may comprise a film of a lithium-philic material and a protective coating that helps reduce oxidation. It is also contemplated that in some examples of anode assemblies, one or more of these regions may be empty and may not contain any functional film. For example, in some anodes, it may be desirable for the interface region to include a bonding film to help promote the desired bonding/engagement between the materials in the lithium bearing region and the substrate region (e.g., the interface region includes a layer of film), but in other examples, the materials in the lithium bearing region and the substrate region may readily bond to one another, such that an intermediate bonding film is not required and the interface region does not need to include any film of material. Such examples may be described as omitting any interfacial film, or the interfacial region containing zero layer material. Thus, as described herein, it is understood that each functional region may comprise 0, 1, 2, 3 or more individual films.

In some examples, the content of each region may be determined during the manufacturing process and may be fixed or generally difficult or impossible to modify once the anode assembly is constructed. Particularly in examples where sequential layering processes such as multi-stage PVD processes are used to apply the various films, it is practically impossible to add the intermediate layers retrospectively after assembly is complete. However, for certain layers, such as those in the lithium bearing region, portions of the layered anode assembly may be created, and then the intermediate film may be subsequently introduced into the assembly in a secondary process (e.g., a secondary manufacturing step) or preferably as a result of generating a lithium film in situ (in situ) within the anode assembly within a battery (battery) or other electrochemical cell (electrochemical cell), such as by applying an appropriate potential and charging the battery. Some examples of these different assembly processes are described herein. Thus, in a given anode assembly, the lithium bearing region may be empty (or at least free of lithium material) when the assembly is first manufactured, and lithium is plated only on the assembly-thereby providing a film of lithium material within the lithium bearing region-when the anode is first put into use.

The anode assembly described herein may be manufactured by a variety of processes including electroplating, electroless plating, lamination, hot dip metallization, wave soldering, etc., however, roll-to-roll vacuum metallization (roll-to-roll vacuum metallizing) (including electron beam or magnetron evaporation), or the Physical Vapor Deposition (PVD) processes and apparatus disclosed herein may provide advantageous methods of manufacturing the anode assembly of the invention for reasons to be elucidated. That is, preferably, the multi-layer anode assembly described herein may fully or substantially fully utilize a physical vapor deposition process to form the layers, and more preferably, all physical vapor deposition processes may be performed on a given substrate during a single pass of the substrate through the PVD apparatus. This may allow the typically raw or bare current collector foil to be fed into the PVD apparatus and the complete or at least substantially complete anode assembly (e.g. allowing lithium material to be added in situ in the battery or cell and thus not added in a single pass PVD process) -and preferably the double sided anode assembly may be removed from the PVD apparatus after a single pass.

The specific number of PVD applicators, the type of applicators, and the order in which the applicators are deposited along a given PVD apparatus deposition path can be determined by the number and order of films desired. While any suitable type of physical deposition apparatus may be used, the inventors have determined that a thermal evaporation source may be used to apply the lithium material, a thermal evaporation source may be used to apply the polymer, chromium (Cr), tungsten (W), titanium (Ti), zirconium (Zr), molybdenum (Mo), etc. may be applied by a magnetron or an electron beam applicator (preferably a magnetron), other metals described herein may be applied by thermal evaporation, a magnetron or an electron beam applicator (but preferably a magnetron), oxides, hydrides and carbonates, and other such materials may be generated using suitable gas sources to produce an in situ reaction on the surface of the assembly or by a magnetron.

Existing commercial roll-to-roll metallization equipment typically uses a vacuum chamber in which a roll of the desired substrate is held. The chamber is then evacuated to 10 ^-2 To 10 ^-6 The pressure of the support. Then, when the roll is transferred from the reel (drum) on which it is loaded, the resistive, inductive, electron beam or magnetron source evaporates the metal. When the entire roll has been metallized, the chamber is re-pressurized and the roll is removed. Sputtering sources may also be used to provide physical vapor. In a typical cycle, loading for 15-30 minutes, evacuation for 30-60 minutes, metallization for 60-120 minutes, repressurization for 5-10 minutes, unloading for 15-30 minutes results in overall production utilization (production availability) at 30% and 65%. These numbers are only approximations and not all machines are identical.

Surface contaminants on the substrate to be treated, such as contaminants from handling materials (handling material), can result in relatively poor surface quality and adhesion of the coating, resulting in rework and relatively low overall productivity and high production costs. Oxidation and nitridation of lithium-based anodes (e.g., by atmospheric gases) can damage the anode assembly, thereby increasing the rejection rate and reducing productivity, or more generally, reducing the performance of batteries containing contaminated anode materials. Furthermore, the process of using lithium foil as input may be disadvantageous due to the relatively high cost of such materials.

Thus, the anodes and anode production processes taught herein may achieve one or more of the following: avoiding the use of lithium foil, increasing the equipment utilization and reducing rework, and can help to improve the surface quality or surface purity of the anode material.

Another aspect of the teachings herein relates to a method of producing a multi-layer anode or anode assembly by depositing inert and reactive metals and/or other materials (including solid electrolyte films, including polymer, glass, or ceramic films) onto a substrate by a PVD process such that the deposition of the films can be performed in the same apparatus without breaking vacuum, thereby greatly reducing cycle times. This may help provide one or more of the following advantages over some known systems: lithium foil can be avoided; the chance of substrate pollution is reduced; the probability of carrying and exposing to the atmosphere is reduced; the utilization rate of the equipment can be improved; the energy costs associated with establishing a vacuum can be reduced. This helps to provide a low cost anode assembly suitable for use in lithium-based batteries.

Apparatuses that achieve some of these advantages may include roll-to-roll vacuum metallization apparatuses having a vacuum metallization chamber, a vacuum set-up system, two or more sources of vaporized metal (at least one lithium metal source and one inert metal source), a roll magazine (for holding additional raw materials to be coated), an air lock (air lock), a roll exchange mechanism, a control system, and an optional inert gas containment system (containerizing system). Providing multiple sources of vaporized metal in a common vacuum metallization chamber may help allow two or more different materials to be applied in the chamber without having to repressurize and evacuate the vacuum chamber between metal applicators. This can save energy as well as improve utilization. For example, the apparatus may include two, three, four, or more deposition sources in a common environment, which may be configured as a vacuum environment or a low oxygen and low nitrogen environment (e.g., by applying a vacuum and/or providing an inert gas environment). Advantageously, the incremental cost (incremental cost) of the additional metallization or vacuum processing step is relatively low compared to the cost of the first metallization step, thereby allowing for the production of a multi-layer anode assembly without imposing a significant additional cost burden on the product. This is in contrast to rolled (rolled) foil anode assemblies, which in all cases incur rolling costs and the cost of additional process steps is additional.

Alternatively, the vacuum metallization chamber may be accessed through an air lock or other such structure that may allow materials, personnel and/or equipment to enter and exit the vacuum metallization chamber without having to place the interior of the vacuum metallization chamber in direct fluid communication with the ambient environment. The use of suitable air locks and roll cassettes may facilitate loading and unloading of one or more additional sets of rolls during the roll metallization process. Once the metallization is completed, the treated rolls can be replaced with new, untreated rolls without breaking the vacuum (e.g., within a single vacuum cycle), thereby increasing equipment utilization. The inert gas containment system may allow the finished rolls to be placed under an inert atmosphere and sealed in a container without leaving the apparatus, thereby reducing the likelihood of the treated rolls being contaminated or unnecessary reactions between the reactive metal and the atmosphere's gases (e.g., oxygen). Alternatively, the system need not include an airlock mechanism, and the vacuum metallization chamber may be opened to the ambient environment to load and unload materials, etc., and then closed and a new vacuum may be applied.

Referring to fig. 2-4, one example of an anode assembly 100 includes a current collector 102, a reaction membrane 106, and a protective membrane 104 positioned between the current collector 102 and the reaction membrane 106, the protective membrane 104 at least substantially ionically isolating the reaction membrane 106 from the current collector 102. In this arrangement, the substrate region 190 includes the current collector 102 and the protective film 104, the interface region 194 is empty and does not include any interface film, the lithium bearing region 192 contains the reaction film 106, and the cover region 196 is empty and does not include any cover material film.

The current collector may be formed of any suitable material, including known metal foils suitable for use in batteries as described herein. In the example shown in fig. 2-4, the current collector 102 is formed from a substantially continuous web of aluminum foil. Although aluminum is generally considered to be a current collector material that is not compatible with lithium, the inventors have found that, unlike the previously contemplated lithium metal anodes, the inclusion of the protective film 104 may allow for the use of an aluminum foil material for the current collector 102, which is a lower cost conductive substrate than copper or other conventional materials. This may help reduce the input material cost of the anode assembly 100 relative to assemblies in which other metals or polymers are used as current collector substrates in the prior art. Other materials may be used for the current collector metal foil if desired in some embodiments, including copper, aluminum, nickel, stainless steel, magnesium, conductive polymers, and combinations thereof. In some examples, the current collector may not require the protective film 104, and the substrate region 190 may include only the current collector 102.

In some cases, aluminum may be a preferred material for the current collector 102 because it has a relatively low density and relatively high conductivity, and is relatively low cost, as compared to some alternatives. This helps provide current collector 102 with the desired size and weight for a given application. However, aluminum may have some drawbacks under certain operating conditions, which may lead to the desire to use different current collector materials. For example, aluminum may have relatively low strength at high temperatures (e.g., as may be experienced in PVD processes), which may lead to material failure. In addition, aluminum readily reacts with lithium metal, which the present inventors have overcome by using the protective film 104. The current collector including the protective film 104 may be described as a protected current collector or a protected substrate and may optionally be used with a variety of different conductive, reactive or performance films and other features of the different anode assembly configurations described herein.

In this example, when the anode assembly 100 is used within a cell, the current collector 102 has an inner side or front side 108 facing the electrolyte and cathode assembly and an opposite outer side or rear side 110. The front side 108 may include a coated portion or surface 111, the coated portion or surface 111 being the portion of the current collector 102 that is adhered and covered by the protective film 104. The coating surface 111 may cover all or at least substantially all of the front side 108 (as shown in this embodiment), or may cover less than 100% of the front side 108. In this arrangement, the coating surface 111 is covered by the protective film 104, and the support surface 112 of the substrate region 190 is defined by the front side or surface of the protective film 104. In other arrangements, the support surface 112 of the substrate region may be provided by the coated surface 111 of the current collector 102, for example without the protective film 104.

The current collector 102 may be formed of any suitable metal and preferably may be formed of aluminum. In this example, the current collector 102 is formed from a continuous web of aluminum foil, but may have a different configuration in other examples. It is the presence of the protective film 104 that may facilitate the use of aluminum foil as the current collector 102 and ultimately the physical substrate supporting the lithium metal in the reaction film 106. Preferably, the anode assembly 100 only requires that aluminum foil be included in the current collector 102 as a continuous physical substrate to help support other portions of the assembly 100, and may be formed without the use of lithium foil or copper foil (e.g., may not contain lithium foil).

The use of aluminum to form the current collector 102 may have several beneficial characteristics that make it an excellent current collector. For example, aluminum may be one of the least costly metals in volume from the standpoint of the available and suitable metals for forming the current collector. Aluminum as a thin foil may also be strong enough to prevent tearing during the manufacturing process of the anode assembly 100 and may be relatively easier to wind, unwind, and handle during the manufacturing process than other foils, such as lithium foil. Aluminum is also a sufficient, relatively efficient electrical conductor that can help ensure that the anode assembly 100 functions as desired.

In fact, these characteristics may be some factors that lead to the frequent use of aluminum foil for the cathode current collector in lithium ion batteries. However, aluminum is generally considered unsuitable as the anode current collector contemplated herein (typically because it is not compatible with lithium metal when exposed directly). For example, aluminum is considered unsuitable for use as an anode current collector because it readily alloys with lithium at relatively small potentials. By substituting aluminum in the crystal structure, lithium causes the current collector to expand significantly, causing it to degrade and eventually decompose, thereby limiting the life of the battery. Thus, to the inventors' knowledge, aluminum has not been used for this purpose in lithium ion batteries or in anode current collectors for solid state batteries.

The current collector 102 in this example may be formed to have any suitable size, shape, and thickness suitable for a given cell design or similar application. For example, depending on the given application, current collector 102 has a current collector thickness 114 that may be between about 1 and about 100 microns or greater, between about 4 and about 70 microns or between about 10 and 20 microns or between about 5 and 15 microns. However, under some manufacturing conditions, including those that utilize relatively high temperatures (e.g., temperatures greater than 150 ℃), the relatively low strength of aluminum may limit the minimum practical thickness 114 of the aluminum current collector 102 to between about 10 and about 20 microns while still providing a desired degree of mechanical strength. In embodiments where other characteristics of the current collector 102 are desired (e.g., relatively high strength, a small current collector thickness 114 (e.g., less than 10-20 microns), etc.), other current collector materials as described herein may be used (e.g., with reference to the embodiments shown in fig. 14 and 15).

Preferably, the aluminum foil used to form the current collector 102 in this embodiment may be provided as a continuous foil web that is unwound from a first or source roll of aluminum foil and may be passed through a treatment or manufacturing zone in a manufacturing process, wherein the material used to form at least one (and preferably both) of the protective film 104 and the reactive film 106 may be applied to the continuous foil web. In this arrangement, the aluminum current collector 102 and the support surface 112 thereon may physically support the protective film 104 and/or the reactive film 106. This may help reduce and/or eliminate the need for the protective film 104 and the reactive film 106 to be formed from a continuous foil or web, which, in turn, may allow the material used to form the protective film 104 and the reactive film 106 to be directly deposited or otherwise applied to the support surface 112 of the current collector 102. Some examples of suitable manufacturing processes with this property are described herein.

The protective film 104 is formed of any suitable protective material that can provide a desired degree of electronic conductivity between the reactive film 106 and the current collector 102 and that can also (when applied at a suitable thickness) ion isolate the reactive film 106 from the current collector 102. The metal used to form the reactive film 104 is also preferably completely inert, or at least substantially inert, with respect to the material of the current collector 102 and the material of the reactive film 106 to help prevent galvanic corrosion or other unwanted reactions between the films 102 and 104 or 104 and 106. The particular materials used in a given assembly 100 are affected by the particular materials used to form the current collector and the reactive film in this embodiment.

Some examples of suitable materials for forming the protective film 104 are typically metals, and may include copper, nickel, silver, steel, stainless steel, chromium, and other metals or alloys into which lithium in the reaction film 106 is not readily intercalated (e.g., does not react at all with lithium metal).

The protective film 104 has a protective or isolation thickness 116 that can be selected to be any thickness that is capable of sufficiently isolating the reactive film 106 from the collector 102, and is preferably selected to be the minimum thickness that provides the desired degree of isolation. For example, the thickness 116 may be between 1-75000 angstroms, and more preferably may be between about 1-15000 angstroms, and in some embodiments the thickness is most preferably between about 200-7500 angstroms.

The thicknesses 114 and 116 of the current collector 102 and the protective film 104 may be modified to achieve different cell characteristics and different performance characteristics of the substrate region 190. This may help provide some flexibility for the battery manufacturer to weigh the relatively high anode costs associated with the relatively thick lithium coating of capital and inventory costs VS associated with trickle charging. This flexibility allows manufacturers to tailor their production processes to accommodate product requirements and their business constraints.

Optionally, another metal layer, such as silver, gold, nickel or stainless steel, or any other suitable metal, may be introduced between the protective film 104 and the current collector 102, for example to help improve the bonding of the protective film 104 to the aluminum foil in the current collector 102, and may be contained within the substrate region 190.

The material forming the protective film 104 may be applied to the current collector 102 using any suitable technique. One preferred application technique is physical vapor deposition, in which the protective material may be provided as a suitable metal vapor that is deposited as a thin, highly adherent, and substantially pure metal (or alloy) coating on the support surface 112. The protective film 104 may preferably be formed in one deposition process (pass)/step (step), or alternatively may be built using two or more processes to build the protective layer 104 having the desired thickness 116. Such a deposition technique may allow the protective metal material to be bonded to the current collector 102 without the use of a separate bonding material, adhesive, or the like.

The reactive film 106 and any other film or films located within the lithium bearing region 192 may be formed of any desired active material (including lithium, potassium, rubidium, cesium, calcium, magnesium, and aluminum), and in the examples described herein, lithium metal. The reactive film 106 is sized and shaped to provide the intended contact surface 120 for contacting electrolyte material in a cell, and may have an outer surface 119, the outer surface 119 being configured to face and contact a layer in the covered region 196 (if present), or to face and contact a separator within a cell or electrochemical cell.

The reactive film 106 may have any suitable thickness 118 (fig. 3), and preferably may have a thickness between about 0.001 and about 100 microns, or between about 0.1 microns and about 20 microns.

The reactive film 106 of this nature may be provided using any suitable technique, and preferably may be applied using a deposition technique and without the use of a lithium foil (e.g., without a lithium foil, but with lithium metal). In the present example, in the second deposition process performed after the protective film 104 has been deposited, the reactive film 106 is further applied by physical vapor deposition. Preferably, both deposition processes can be performed using a common machine, and more preferably in the same process chamber (processing chamber) by a single production process and under the same vacuum cycle, as described herein. This may help to simplify the production of the anode assembly and/or reduce the likelihood of portions of the assembly being damaged or contaminated between production steps. It may also help reduce assembly production time because the process chamber does not need to be cycled between vacuum and non-vacuum conditions during processing.

Anode assembly 100 may be further processed or combined with any suitable electrolyte material, including optional solid electrolyte, cathode, and other elements, to produce a battery cell, such as electrochemical cell 300 schematically illustrated in fig. 19, for use in an electric vehicle or other electronic device. A given battery cell, while perhaps different from that schematically illustrated, still utilizes one or more aspects of the teachings herein. A given battery may include two or more such battery cells and may have a variety of suitable physical and electrical configurations.

In the embodiment of fig. 2 and 3, the protective film 104 is disposed on the front surface 108 of the current collector 102. This may be sufficient for some intended uses of the anode assembly 100, such as when used in a solid state battery and/or when combined with a solid electrolyte material that is in physical contact with only the reaction membrane 106 or at least substantially only the reaction membrane 106. That is, by inserting a protective metal film between the lithium reaction film and the aluminum current collector 102, the aluminum current collector 102 can be made substantially inert to lithium in the reaction film 106 forming the external contact surface of the anode assembly 100. Because the solid electrolyte cell limits the conductive surfaces exposed to the electrolyte, the aluminum current collector 102 will not typically share an ionic connection with the copper protective layer 104, and thus the assembly 100 is less susceptible to galvanic corrosion.

Alternatively, the current collector 102 may be coated on both sides with a protective metal material such that another example of the anode assembly 1100 includes a first front protective film 104a on the front side 108 of the current collector 102 (e.g., between the current collector 102 and the reactive film 106) and a second rear protective film 104b bonded to the opposite rear surface 110 of the current collector 102. This may help prevent unwanted chemical reactions (e.g., galvanic corrosion) from affecting at least substantially all, optionally all, of the front and back sides of the current collector 102.

Alternatively, the perimeters of the front and rear protective films 104a, 104b may be joined to one another, thereby effectively sealing the current collector 102 within the protective material and substantially ion isolating the current collector 102 from the surrounding environment. The protective films 104a and 104b may be bonded to each other using any suitable technique, including, for example, PVD, application of a polymer film or resin, crimping, and the like. Protecting at least the rear surface 108 of the current collector 102, and optionally also protecting the side edges of the current collector 102 by sealing the front and rear membranes 104a and 104b, may help facilitate use of the anode assembly 1100 in a battery (e.g., a conventional lithium battery) that uses a non-solid electrolyte (e.g., a liquid and/or gel, which may increase the likelihood of the rear surface 108 of the current collector 102 coming into contact with the electrolyte material).

The rear protective film 104b may be formed using the same process (e.g., physical vapor deposition) as the front protective film 104a or by a different process, and more preferably may be formed in a single manufacturing process through the process chamber.

Alternatively, some embodiments of the anode assembly may be configured as a double sided anode, wherein both the front and back sides (or more generally, the opposite first and second sides) of the current collector are coated with respective protective and reactive films. One example of a double sided anode assembly 2100 is schematically shown in fig. 13. In this example, the current collector 102 has a first protective film 104a on one side, and a first reactive film 106a is applied to the first protective film 104a. The second protective film 104b is disposed on the opposite rear side of the current collector 102 and is covered with a second reaction film 106b. Alternatively, as described above, the protective films 104a and 104b may be bonded together, and in some examples, the reactive films 106a and 106b may be bonded to each other in a similar manner. In this arrangement, the substrate region 190 may include the current collector 102 and the protective films 104a and 104b, and a separate lithium bearing region 192 may be provided on each side of the substrate region 190. Although not shown in this example, separate interface regions 194 and coverage regions 196 may also be provided on each side of the assembly 2100.

Referring to fig. 14, another example of an anode assembly 3100 is shown. In this example, the current collector 102 is formed of stainless steel (rather than aluminum). Thus, a protective film (e.g., film 104) is not required to protect the current collector 102 from lithium in the lithium bearing region 192, and the substrate region 190 in this example includes only the current collector 102. Stainless steel may have a relatively high density (about 3 times that of aluminum) and a relatively high mechanical/tensile strength at high temperatures, but a relatively low electrical conductivity (about 1/25 times that of aluminum) compared to aluminum, which is generally considered to make it a relatively less desirable material for use as current collector 102. However, the inventors have found that the relatively high strength of stainless steel can help facilitate the creation of a stainless steel current collector having a thickness that is less than the thickness of a similar aluminum current collector, and can have a thickness of less than about 15 microns, less than about 10 microns, and optionally less than or equal to about 5 microns. Such a relatively thin stainless steel current collector may help provide the current collector with a similar gravimetric energy density (gravimetric energy density) and a relatively higher volumetric energy density as compared to a similar aluminum current collector.

As noted above, one potential disadvantage of using stainless steel is its relatively low electrical conductivity, which can reduce the performance of the anode assembly, e.g., increase electrical resistance and cause uneven deposition of lithium on the anode during successive charge cycles. This may be undesirable if the anode assembly is to be used in a Solid State Battery (SSB) because it may lead to contact problems between the anode assembly and the solid electrolyte material. However, the inventors have found that applying a suitable conductive enhancement film (e.g., copper, aluminum, silver, gold, or other conductive material) on stainless steel can increase the electrical conductivity of the assembly and make it nearly equivalent to aluminum, which can help overcome the significant disadvantages.

The inventors have also found that other significant limitations of stainless steel materials can be overcome when using a relatively thin stainless steel current collector 102 by using alternative anode assembly configurations that can utilize one or more additional functional films (e.g., conductive films, performance films that can be provided in the interface region 194, and gas-barrier films that can be provided in the cover region 196) to help provide an overall anode assembly having desired physical and electrical parameters.

For example, referring to fig. 14, in this embodiment, the substrate region 190 of the anode assembly 3100 includes a current collector 102 formed of a relatively thin (e.g., less than about 15 microns) stainless steel foil, and the lithium bearing region 192 includes a reaction film 106 formed of lithium (preferably deposited as described herein). Since stainless steel does not react with lithium like aluminum, this embodiment does not need to include a protective film (e.g., film 104 above) to help isolate the reactive film 106 from the current collector 102. However, alternative membranes may be provided to help provide the stainless steel current collector 102 and lithium-reactive membrane 106 with the desired levels of conductivity, performance, and oxygen/gas protection.

Optionally, the interface region 104 of the anode assembly 3100 may include one or more performance films, such as performance film 150, positioned between the reaction film 106 and the current collector 102. The performance film 150 is preferably configured to help enhance or positively influence the deposition of lithium metal (forming the reaction film 106) on the current collector 102 or any intermediate film (as described herein) (and during successive charge and discharge cycles of the anode assembly in use), such as by material formation that helps reduce the tendency of the lithium material to form dendrites upon deposition. In this example, performance film 150 is formed of silver, but other similar materials or combinations of materials may also be used and may help provide the desired deposition enhancement while still providing the desired electrical conductivity and other mechanical properties. For example, one or more performance films 150 may include a lithium-philic material that is generally compatible with lithium metal and may help provide enhanced ion mobility within the lithium-philic film layer, which may facilitate the deposition enhancement effects described herein. In some configurations, two lithium-philic material films, such as lithium-philic interface film 150 and lithium-philic cover film 150b, may be included in the anode assembly, but may be located in different areas, such as interface area 194 and cover area 196 as shown. Preferably, the lithium-philic cover film 150b located in the cover region 196 may allow a reactive film material (e.g., lithium) to pass through the cover region 196 and deposit in the lithium bearing region 102 (rather than accumulating in the cover region 196, on the outer surface of the lithium-philic cover film 150b or any other intermediate film in the cover region 196), and in fact migrating the reactive material through the lithium-philic cover film 150b may help the reactive material diffuse into the lithium bearing region 192 and/or diffuse the reactive material relative to the support surface 112 of the substrate region 190 (whether provided by the current collector 102 or the protective film 104), which may help shape/form the reactive film 106 and may help reduce dendrite formation during the reactive material deposition process. Although two optional films of a lithium-philic material (150 and 150 b) are shown in fig. 14, if only a single film of a lithium-philic material is included, it may be preferable to locate within the covered region 196 (as indicated by reference numeral 150b in fig. 14) rather than in the interface region 194.

Alternatively, performance film 150 or 150b may be formed from a suitable alloy of aluminum, indium, magnesium, zinc, tin, carbon (preferably vapor deposited as black carbon), silver, and combinations thereof. Further, a given performance film 150 in a given anode may comprise a single layer film formed of a single material, two layers of films formed of different materials, or multiple layers of films formed of an alloy or mixture of two or more materials, all of which may be understood to be performance films as described herein.

Although the performance film 150 is shown in one location in this example, the performance film may also and/or alternatively be incorporated between the reaction film 106 and the coated current collector 102, between successive films of lithium material within the reaction film 106 (or between successive reaction films 106), co-deposited with lithium in the reaction film 106 (i.e., substantially as an alloy reaction film), and/or on the outer surface of the lithium reaction film 106 (as shown by optional film 150 b), all by physical vapor deposition. More than one performance membrane (i.e., in some examples, membranes 150 and 150b may be included) may be provided on a given side of current collector 102.

The film 150 of this nature may act as a protective film, which may help reduce unwanted reactions between the lithium film (if any) and the electrolyte (which may be a solid or liquid electrolyte) within a given cell. These films may also help protect the lithium-reactive film from exposure to air or the surrounding atmosphere during the manufacturing and/or assembly process.

Optionally, assembly 3100 can also include one or more conductive films (in addition to the lithiated performance film 150) in interface region 194, such as conductive film 152, which can be located between reaction film 106 and current collector 102, and preferably between performance film 150 (if any) and current collector 102. The conductive film 152 is preferably formed of a material having a higher electrical conductivity than the material forming the current collector 102 (e.g., stainless steel in this example) to help improve the performance of the anode assembly 3100. Suitable materials for the conductive film may include copper, aluminum, silver, gold, or other such materials, as well as combinations or alloys thereof. The addition of conductive film 152 may help to increase the electrical conductivity of stainless steel current collector 102 to a level approximately within the same order of magnitude as the aluminum current collector described in other embodiments herein. Conductive film 152 may have any suitable thickness and may be between 0.1 and 5 microns.

In some environments, lithium in the reactive film 106 may react with the surrounding environment, which may affect the performance and/or lifetime of the component 3100. For example, if exposed to air or ambient environment, the reactive film 106 may be prone to react with oxygen, nitrogen, and/or water vapor present in the air. Such exposure may degrade the reactive film 106. To help limit such reaction and/or degradation, the footprint 196 of the component 3100 may include one or more suitable gas-protecting films, such as the passivation film 156, that may be deposited over the reaction film and any other films within the lithium bearing region, such as by PVD. Preferably, the one or more materials used for passivation film 156 are low compared to the reactivity of the environment, but still have the desired electrical conductivity and mechanical properties, and importantly, when an anode assembly is used, can allow sufficient lithium ion flow to allow lithium ions to move between the electrolyte and the lithium bearing region. Some examples of suitable materials that may be used for passivation or gas-barrier film 156 may include metallic materials, such as gold, platinum, or other noble/inert metals, and/or may include oxide materials, such as aluminum oxide, lithium aluminate, mixed metal oxides (preferably containing at least some lithium), or any gas-barrier material (gas-blocking material) that may be deposited by PVD. Depositing a layer of a suitable metal or oxide material may help reduce the amount of gas diffusion to the coated surface of anode assembly 3100 while still allowing/facilitating the desired lithium transport. Preferably, the thickness of the gas barrier film may be selected such that it is thick enough to inhibit the diffusion of gas into the lithium bearing region 192 but thin enough not to substantially impede the rate of lithium metal oxidation for a given embodiment. In some examples, the thickness of the gas barrier film may be between 0.01 and 5 microns thick. If the anode assembly includes the optional gas-barrier film 156, it is preferably the outermost film in the cover region 192.

While assembly 3100 is shown as a single-sided assembly (e.g., the functional layer is disposed on only one side of current collector 102), it may alternatively be configured as a double-sided assembly by providing the same or similar but non-identical functional layer sets on opposite sides of current collector 102 (i.e., on opposite sides of centerline 158 shown in fig. 14).

Referring to fig. 15, another example of an anode assembly 4100 is configured to utilize an aluminum current collector 102 and includes a protective film 104 (as described herein) positioned between the current collector 102 and the reaction film 106. This example omits the conductive film 152 of fig. 14 (not required when using an aluminum current collector 102) but includes the performance film 150 and the gas-protective film 156 in their respective regions 194 and 196 (as described with reference to fig. 14).

In addition to helping to protect the completed anode assembly, the gas-protective film 156 may be used to help protect the reactive film 106 and/or other components during the assembly process, particularly if the assembly is to be performed in an environment containing oxygen, nitrogen, moisture, and the like. For example, the gas-protecting film 156 may be applied shortly after the reactive film 106 is applied in order to prevent the reactive film 106 from being exposed to the surrounding environment during handling or production. This may allow the anode assembly to be produced in a wider ambient environment. Anode assemblies including protected current collectors may still benefit from the use of relatively lighter and/or less costly substrate materials while limiting their reactivity with other cell components even though the anode itself does not contain lithium metal.

According to one embodiment described herein, another example of an anode assembly for a battery (including a lithium-based battery or alternatively an alkaline battery or other battery type) may include a protected current collector having a substrate formed of a suitable current collector material and having a support surface for receiving/supporting other components of the assembly. The current collector material may be any suitable material described herein, such as aluminum, copper, aluminum, nickel, stainless steel, magnesium, zinc, silver, conductive polymers, and combinations or alloys thereof, and alloys of lithium with these materials including, for example, lithium-silver alloys, lithium-magnesium alloys, lithium-zinc alloys, and the like. For discussion purposes, the current collector material in this example will be referred to as aluminum, but in other examples may be other suitable materials.

To help reduce the chance of unwanted reactions between potentially reactive materials within the anode assembly or other portions of the cell, the aluminum in the protected current collector is covered with a suitable protective film that at least bonds to and covers the support surface and includes a suitably conductive protective metal as described herein. In such an arrangement, the protective film is preferably disposed between the current collector substrate and the potentially reactive material within the cell such that electrons can move within the cell as desired, and the current collector substrate is at least substantially ionically isolated from the reactive material. Thus, the protective film may help at least substantially prevent or inhibit, and may completely prevent, active materials within the battery cell from diffusing to the current collector, which may help at least substantially inhibit, and optionally completely prevent, unwanted reactions between lithium metal and the current collector. This type of separation between the current collector substrate and the reaction membrane may help facilitate the use of lithium in the reaction membrane, while at the same time helping to facilitate the use of materials in the current collector that are typically intended to be used as current collectors but (e.g., without a suitable protective membrane) would react with lithium or other such materials within the cell to reduce the effectiveness of the current collector, the anode assembly, and/or possibly damage or reduce the effectiveness of the anode assembly or sub-layers thereof.

For example, referring again to the schematic diagram of anode assembly 4100 in fig. 15, another example of an anode assembly may include an example of a protected current collector that includes an aluminum current collector 102 and a protective film 104 covering at least a portion of the surface of the collector substrate 102. In other examples, other materials may be used for the reactive film 106.

This variation/example of anode assembly 4100 may be assembled using the techniques described herein, and protective film 104 may be deposited on current collector substrate 102 via PVD to provide a protected current collector sub-assembly.

In some examples, the reaction film 106 may not contain lithium when first deposited, however when the anode assembly 4100 is used within a battery cell, lithium ions may accumulate within the material of the reaction film 106 or plate directly onto the protective film 10 (e.g., during charging), and tend to react with the aluminum material in the current collector 102 if the intermediate protective film 104 is not present.

In a further example of anode assembly 4100, the protected current collector may include a performance film 156 deposited directly on the surface of protective film 104. When properly selected, the materials in the performance film 156 may allow lithium to be deposited directly onto the protective films herein through the performance film 156, thereby allowing the active film to form in situ between the performance film 156 and the protective film 104 after battery assembly. The material or combination of materials in the performance film 156 may be selected to improve the plating/stripping behavior of the final anode assembly and increase cycle life by, for example, reducing the tendency to dendrite formation, preventing unwanted reactions with the electrolyte material, improving the mechanical properties of the active film, increasing chemical and mechanical compatibility between different layers in the anode structure or between the anode interface and the electrolyte. Suitable materials for performance film 156 include metallic aluminum, arsenic, bismuth, indium, lead, magnesium, tin, zinc, and combinations thereof, as well as lithium ion conductive oxides such as lithium ion conductive oxides, nitrides, sulfides, and fluorides, such as lithium nitride, liPON, lithium sulfur silver germanium ore (lithium argyrodites), and lithium ion conductive polymers such as polyethylene oxide, or combinations of any of the foregoing.

Referring to fig. 19, an exemplary electrochemical/cell 300 that may utilize the anode described herein may further include a housing 302 (which contains any suitable electrolyte material 304), a suitable cathode 306, and a suitable separator 308 disposed between the anode and the cathode.

In this embodiment, another example of anode 6100 may optionally be configured to utilize an aluminum current collector 102 and include a protective film 104 (as described herein) between the current collector 102 and the reaction film 106, the protective film 104 may help isolate the current collector 102 from lithium in the reaction film 106. Anode 6100 also includes performance film 150 that covers and separates reactive film 106 from electrolyte material 304 within cell 300. Some or all of the films 104, 106, and 150 may be applied by PVD as described herein. In this arrangement, the anode 6100 may optionally provide a lithium reaction membrane thereof.

Alternatively, the anode used within a cell (such as cell 300) may not include a lithium-reactive film when initially formed, or may include a portion of a lithium-reactive film (which contains less lithium than is present when cell 300 is charged). That is, when first produced, the anode may include a substantially complete lithium reaction film, a portion of a lithium reaction film, or need not include a lithium metal reaction film at the time of manufacture.

For example, a method of forming an anode for a lithium-based battery cell may include the steps of: providing a suitable current collector 102, depositing a protective film 104 onto at least a portion of the current collector 102 (preferably by PVD), and depositing a performance film 150 onto at least a portion of the protective film 104 (preferably by PVD). This may provide a lithium-free multi-membrane anode, such as anode 7100 schematically shown in fig. 20. Alternatively, such a lithium-free multi-membrane anode 7100 may be disposed in a suitable battery cell, such as battery cell 300, and lithium may be added to the anode 7100 to provide the desired reactive membrane 106, with the anode 7100 being located in situ within the battery cell 300 by charging the battery cell (e.g., applying a potential between the anode and cathode).

For example, referring to fig. 22, an anode 7100 may be disposed within the battery cell 300 and the battery cell 300 may be charged. Referring also to fig. 23, during this charging operation, lithium ions may migrate toward anode 7100 (and may generally migrate from cathode 306 to anode 7100) and may collect/accumulate on anode 7100 to form a suitable reaction membrane 106. In examples where performance film 150 is formed of a suitable lithium-philic material, lithium ions driven in this manner may migrate through performance film 150 and/or alloy with performance film 150, and lithium-reactive film 106 may be formed on the surface of protective film 104 (e.g., plated under performance film 150). Migrating lithium ions through at least a portion of performance film 150 may help distribute lithium metal on the sides of protective film 104 and may help reduce dendrite formation during lithium metal deposition.

Alternatively, the anode may be fabricated in an assembly process to include a partially reacted film (e.g., a layer having some lithium but less than the intended operating amount of lithium), and then some additional lithium metal may be added in situ within the cell to the partially reacted layer. For example, an anode 8100 for use with a lithium-based battery cell 300 as shown in fig. 21 may be formed using a process comprising the steps of: providing a suitable current collector 102, depositing a protective film 104 onto at least a portion of the current collector 102 (preferably by PVD), depositing a performance film 150 onto at least a portion of the protective film 104 (preferably by PVD), and depositing lithium metal to form a partially reacted film 106c, the partially reacted film 106c comprising some lithium metal but having less lithium metal than is present in the anode when the anode is charged when used within a battery cell. Anode 8100 can then be positioned within cell 300 (in a manner similar to anode 7100 shown in fig. 22) and cell 300 can be charged. During the charging operation, additional lithium metal may migrate from the cathode, may pass through performance film 150, and may be added to a portion of reaction film 106c, providing a complete reaction layer 106 having a desired size/thickness. In this arrangement, the reactive film 106 is partially formed (e.g., to provide a partial film 106 c) during the anode assembly process and then completed during the in situ charging process.

In this example, deposition of lithium metal in the reactive film 106c may occur prior to formation of the performance film 150, or alternatively may occur after deposition of the performance film 150 (as lithium metal may alloy with the performance film 150 or migrate through the performance film 150 to form a desired portion of the reactive film 106 c). That is, the reactive film 106 or a portion of the reactive film 106c may be deposited before the performance film 150 or may be deposited after the performance film 150. The partial reaction film 106c formed in this manner may include less than 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20% or less than 10% of the amount of metallic lithium present in the reaction film 106 when the battery cell 300 is charged. That is, a given anode may include about 0% to 100% lithium metal that is contained in the charged reaction film 106 when first formed.

Forming anodes (e.g., 7100 and 8100) that include less lithium metal and optionally are substantially free of lithium metal (e.g., no reaction film 106 or only a portion of reaction film 106 c) may help simplify the manufacturing and/or assembly process because the anode may contain less reacted lithium metal. This may help reduce the reactivity of the anode, may help reduce the need to use a modified atmosphere (modified atmosphere) and/or a low oxygen manufacturing environment, and/or may help make the anode relatively more stable to storage and transport than a similar anode manufactured to include the fully charged reactive film 106.

For exemplary purposes only, some comparative cost estimates are included in tables 1-7 below, including some estimates of the input material costs for manufacturing some conventional anode assemblies and those for the anode assemblies described herein.

TABLE 1 evaluation cost of traditional lithium foil anode (2019)

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TABLE 2 evaluation cost of conventional copper foil and lithium foil anode assembly (2019)

TABLE 3 lithium metal anode assembly evaluation cost (2019)

Table 4-low cost lithium metal anode assembly evaluation cost according to the present disclosure (2019)

TABLE 5 thin lithium Metal anode Assembly (for trickle Charge) evaluation cost (2019)

Table 6-thin low cost lithium metal anode assembly evaluation cost (2019) for trickle charge according to the present disclosure

TABLE 7 approximate cost of current collector substrate materials (evaluation in 2019)

Anode assemblies 100 and 1100 can be used in combination with other components to provide a lithium-based battery that includes any suitable cathode assembly including a cathode current collector and a cathode reaction surface, as well as a lithium anode assembly as described herein. The electrolyte may be disposed between and may contact the cathode reaction surface and the anode reaction membrane, and the first protective film may be disposed between the support surface and the reaction membrane such that electrons may pass through the first reaction membrane and the first protective film from the electrolyte to the anode current collector. The first reaction film may be spaced apart from the support surface and at least substantially ion-isolated, whereby the first protective film substantially prevents diffusion of the reaction film to the current collector, thereby inhibiting reaction between the lithium metal and the current collector. That is, the first protective film may at least substantially isolate the support surface from electrolyte ions. One schematic example of a battery 130 is shown in fig. 9 and includes a schematic representation of an anode assembly 100, as well as an electrolyte 132 and a suitable cathode assembly 134.

Depending on the cell design, the electrolyte may comprise a solid electrolyte material that directly contacts the first reactive film but not the anode current collector, or may comprise a different type of electrolyte material. Preferably, the anode current collector (e.g., current collector 102) is surrounded by a protective metal in one or more layers of protective film 104 and is physically and ionically isolated from the electrolyte.

The anode assemblies described herein can be manufactured using any suitable manufacturing process, including those described herein. Preferably, the manufacturing process may utilize at least two physical vapor deposition processes to apply the protective and reactive films 104 and 106 to the current collector 102, and more preferably may be performed in at least a semi-continuous process (semi-continuous process) in which the layers 104 and 106 are deposited on a moving aluminum foil web in a roll-to-roll process. Since physical vapor deposition will be performed under low pressure/vacuum conditions, the fabrication process may preferably be configured such that both the protective and reactive films 104 and 106 are deposited onto the current collector 102 in a common process/metallization chamber while under the same vacuum cycle and conditions. This may help reduce or eliminate the need to break the vacuum condition between depositing the protective film 104 and the reactive film 106, which may help reduce manufacturing time and/or reduce the energy required to recreate the second vacuum condition when depositing the reactive film 106. Alternatively, the finished material (e.g., current collector 102 with protective and reactive films 104 and 106) may be wound onto an output roll at the end of the roll-to-roll process, and preferably the output roll may then be packaged and/or otherwise processed (while still within the same vacuum chamber) so that packaging and/or processing may be completed before the output roll is exposed to oxygen in the surrounding environment.

Referring to fig. 6, one example of a method of manufacturing an anode assembly 600 includes, at step 602, metallizingOr the interior of the process chamber, which may be configured at atmospheric pressure, and may be selectively configured (e.g., by using a suitable vacuum pump apparatus, etc.) to have an internal operating pressure less than atmospheric pressure. The operating pressure in the metallization chamber may be any suitable pressure that facilitates the intended physical vapor deposition process, and in some examples may be at about 10 ^-2 And 10 ^-6 And the brackets are arranged between the two brackets. Preferably, this may help provide a process chamber interior that is substantially oxygen free when forming the films 104 and 106.

At step 604, the support surface 112 on the current collector 102 is at least partially coated with a protective metal material by a first physical metal deposition process, using one or two or more steps, to build and provide the protective film 104.

At step 606, the protective film 104 is at least partially coated with a reactive metal material by a second physical metal deposition process, using one or two or more steps, to build and provide a reactive film 104, whereby the first protective film 104 is disposed between the support surface 112 and the reactive film 106 such that electrons can move from the first reactive film 106 to the current collector 102, and the first reactive film 106 is spaced apart from the support surface 112 and at least substantially ion-isolated, whereby the first protective film prevents diffusion of the reactive film 106 to the support surface 112, thereby inhibiting reaction between the reactive metal and the current collector 102.

Preferably, the current collector 102 material is a continuous metal foil that is unwound from a first input or feed roll by optional step 608 before step 602 and then wound onto a first output roll by optional step 610 after step 606. In this arrangement, steps 604 and 606 may preferably be performed as the continuous web of metal foil moves along the deposition path between the first feed roll and the first output roll.

The first and subsequent feed rolls may be supported by any suitable unwind apparatus (unwinding apparatus) that is preferably also located within the low pressure processing chamber so that the rolls may be unwound and the web (web) acquired while maintaining a vacuum in the chamber. Similarly, the output roll may be held on a suitable winding device (winding apparatus), which is preferably also located within the low pressure processing chamber, so that the output roll may be wound while maintaining a vacuum in the chamber. The web may be moved between the input and output rolls at any suitable processing speed that allows for successful completion of the intended deposition process and may be between about 1 or 2m/min and about 1500m/min, and alternatively may be between about 1m/min and about 20m/min, or in some preferred examples, between about 2m/min and about 10 m/min.

Alternatively, step 604 may include providing the guard metal from at least one guard metal vapor source device (e.g., a guard metal vapor source configured to deposit between about 0.001 microns and about 10 microns of guard metal on the support surface 112 in a single pass while the web is moving at the process speed. The deposition process may then be repeated if desired, for example, by reversing the direction of movement of the web and then passing the previously coated portion of the support surface 112 through a source of protective metal vapor to perform a second and/or subsequent pass and deposit a protective metal onto the support surface 112 until the first protective film has a thickness of between about 1 angstrom and about 75000 angstroms. Alternatively, as described herein, these steps may be accomplished in a single pass using a suitable deposition apparatus having a suitable number and arrangement of deposition zones.

Alternatively, step 606 may include providing the reactive metal from at least one reactive metal vapor source device (e.g., a reactive metal vapor source configured to deposit between about 0.001 and about 20 microns of reactive metal on the protective film 104 in a single pass while the web is moving at the process speed). The deposition process may then be repeated if desired, for example, by reversing the direction of movement of the web and then passing the previously coated portion of the protective film 104 through a source of reactive metal vapor to perform a second and/or subsequent pass and deposit reactive metal onto the protective film 104 until the first reactive film has a thickness of between about 1 and about 40 microns. Preferably, the reactive metal vapor source may be spaced apart from the protective metal vapor source in the direction of web movement, and optionally may be located downstream of the protective metal vapor source. This may allow both the protective film 104 and the reactive film 106 to be formed in a single pass of the current collector mesh, provided that the reactive metal vapor source and the protective metal vapor source are operated to deposit a sufficient amount of the respective metals in a single pass.

Optionally, prior to beginning the unwinding of the current collector mesh and beginning the deposition process, method 600 may include step 612: the pressure inside the process chamber is reduced from about atmospheric pressure to operating pressure and then the first feed roll is introduced into the interior of the process chamber via the air lock, whereby the first feed roll can be transferred from the exterior of the process chamber to the interior of the process chamber without increasing the pressure inside the process chamber above 1 KPa.

Preferably, the pressure in the air lock may be reduced to less than about 10 ^-2 The proper delivery pressure of the tray and preferably substantially matches the operating pressure prior to opening the chamber door to connect the chamber, but in some examples the delivery pressure of the air lock may be below atmospheric pressure but still be above the operating pressure. This may help to maintain the metallization chamber at or at least substantially close to the operating pressure while a new current collector foil roll is brought into the chamber without breaking the vacuum, e.g. during the same vacuum cycle. Vacuum cycling may be understood to include significant depressurization of the metallization chamber (e.g., from about atmospheric pressure to near operating pressure or to operating pressure), a period of operation during which the chamber remains substantially at operating pressure and metal deposition may occur, and then subsequently repressurizing the metallization chamber to a pressure that is significantly greater than operating pressure and at which the deposition process may not proceed as desired (e.g., from operating pressure back to about atmospheric pressure, or other pressurization of about 50KPa or more). Small differences in air lock pressure or transfer and metallization chamber pressure during transfer of the foil roll require small corrections to be made to the metallization chamber pressure at the completion of the transfer, but such pressure differences will preferably be less than about 10 ^-2 A tray, preferably less than about 10 ^-6 A tray or less and may be considered to be within the same vacuum cycle for the purposes of the teachings herein. Because pressurizing and depressurizing the metallization chamber may require time and additional energy input to drive the appropriate vacuum apparatus, incorporating the airlock described herein may reduce the time taken to introduce a new foil roll into the processing chamber because the vacuum does not have to be broken and then restoredVacuum conditions within the process chamber (e.g., it may allow two or more rolls of foil to be processed by the physical vapor deposition apparatus within a single vacuum cycle of the metallization chamber).

Similarly, the method 600 may include an optional step 614 in which the first output roll (handling finished component material) may pass through a damper (optionally the same or different damper as used to introduce the feed roll) whereby the first output roll may be transferred from within the process chamber to outside the metallization chamber without increasing the pressure inside the process chamber to about 10 a ^-2 Above the support.

The method may also include an optional packaging step 616 during which the first output roll may be packaged, handled and/or sealed while still contained within the airtight low pressure interior of the process chamber or airlock, or within the airtight interior of a separate receiving chamber (having a substantially oxygen-free interior) prior to removal of the first output roll from the airlock. This helps reduce the chance of exposing the finished anode assembly to oxygen.

It will be appreciated by those skilled in the art that the process described herein does not describe every optional operation or equipment that may be performed or used in processing/coating the rolls, for example certain surface preparation steps such as plasma cleaning, flame treatment, corona discharge or adhesive roll contact (tacky roller contact), or instrumentation such as pressure sensors, tension sensors and gas analyzers, or various equipment commonly used in vacuum metallization systems, such as cooled deposition reels (cooled deposition drums), idler rolls (idlers) and rewinder rolls (rewinder rolls). Such processes and equipment are omitted for clarity and are deemed to be incorporated herein as needed.

Alternatively, the methods described herein may also be supplemented to include additional vapor deposition sources, or other deposition sources suitable for applying films to a roll. Such a process may, for example, apply additional tie layers or solid electrolyte layers, cathode layers and cathode current collector layers to the coated aluminum foil web while still operating in the same metallization chamber without having to repress the chamber between successive operations/coatings.

The methods described herein may be modified and applied to other suitable reactive metal metallization processes of the substrate, such as copper, nickel, stainless steel, magnesium, conductive polymers, or non-conductive polymers.

The methods described herein may be applied to other suitable reactive metal metallization processes in which layered structures are produced for various applications, and are not necessarily limited to the production of anode assemblies only.

The anode assemblies and methods described herein may be produced using any suitable apparatus, which may suitably include a variety of different components and subsystems.

One example of an apparatus that may be used to produce the anode assemblies described herein is described below and schematically illustrated in fig. 10-12. These schematic diagrams show how various aspects of the device may work together, but for clarity, not every piece of hardware, etc., contained in the production form of the device is shown.

In this example, the roll-to-roll metallization apparatus 400 includes a metallization or processing chamber 41 having an interior configurable at an operating pressure of less than about 0.001KPa during a first vacuum cycle. The roll-to-roll winding assembly is located within the metallization chamber and in this example includes first and second reversible driven spools 42. The vacuum pumping system 44 is preferably capable of achieving a desired operating pressure of 10 f ^-2 -10 ^-6 The vacuum of the tray is connected to the metallization chamber and may be controlled by any suitable controller 445, in this example the controller 445 includes a computer control system 445 (but may include other controllers such as a PLC, etc., and may also include any desired sensors, transducers, and user input/output devices). The controller 445 may be configured to control typical parameters such as scroll speed, source intensity, vacuum level, scroll direction, etc. Unlike conventional control systems, the controller may also control the damper cycle and reel change cycle processes through position encoders, vacuum gauges, and the like.

The chamber 41 is delimited by chamber walls and comprises at least one openable chamber door, as indicated by door 46, through which a feed roll 410 of foil/substrate can be introduced into the metallization chamber 41. A vacuum metallization chamber 41 for holding feed and/or output rolls during the manufacturing process, a vacuum pumping system 44, and a reversible reel 42 are schematically shown for reference and may be of any suitable design for a given example of the apparatus 400.

The apparatus 400 may also optionally be equipped with tensioners, idler rollers, typical sensors and/or suitable pre-treatment apparatus (roll cleaning, plasma cleaning, corona treatment, etc.) as desired, which may be suitably combined, but are not shown in the present figures for clarity.

In this example, the treated foil roll is also removed by the same door 46, e.g. held in the storage area 49 by the handling device 411, but in other examples the chamber 41 may have two or more separately positioned and openable chamber doors.

The physical vapor deposition apparatus is also positioned at least partially within the metallization chamber 41 and is configured to process the foil roll within the metallization chamber 41 during the first vacuum cycle in the following manner: by independently depositing I) a protective metal layer onto the first foil moving between the first and second shafts 42; and II) a layer of reactive material on the protective material layer. In the example shown, the physical vapor deposition apparatus includes a metal vapor source 43, the metal vapor source 43 including a protective applicator 43A (fig. 12) that may apply a protective material and a reactive applicator 43B that may apply a reactive material. These applicators 43A and 43B are spaced apart from each other along the deposition path 58 in one or more process directions, and as the foil web 60 moves between rolls of material held on the shaft 42 (as described herein), the foil web 60 will move within the process chamber 41, thereby also defining respective deposition zones 45A and 45B on the deposition path.

In this example, deposition path 58 is understood to be defined by the path traveled by substrate web 60 within process chamber 41 where the deposition step will occur. The path need not be linear, but may be serpentine and may include various orientation variations of the substrate web 60, although the substrate web 60 may still be understood to move in a first direction or an opposite second direction (e.g., forward and backward) between rolls of material at a first end and a second end of the deposition path. In this example, the shaft 42 is reversible and the web 60 can move in both directions along the deposition path and can move through the process chamber and pass through a given deposition zone 45A and 45B more than once. In other arrangements, the deposition apparatus and deposition path may be configured in a one-way or single pass arrangement, wherein the substrate web 60 moves in only one direction (e.g., forward) along the substrate path and only once through each deposition zone.

In this example, deposition zones 45A and 45B are also spaced apart from each other and aligned over their respective applicators 43A and 43B. In other examples, the deposition zones may at least partially overlap one another. The source of the applicator 43 may be of any suitable type including, for example, a resistive or inductive heating source, a jet source, a magnetron source, an electron beam sputtering source, and the like. Depending on the desired deposition rate, desired coating adhesion, etc., the applicator source is selected and sized according to known principles.

16-18, the physical vapor deposition apparatus may be configured to include three or more applicators 43A, 43B, and 43C associated with three respective deposition zones 45A, 45B, and 45C within the chamber 41. Each applicator 43A-C may apply a different material to the substrate material, which may help facilitate fabrication of the three-layer anode assembly, including, for example, a reactive film, a conductive film, and a performance film, or a reactive film, a protective film, and gas protection, or any other suitable combination of films described herein. This may also facilitate the production of a four layer assembly, for example, if the assembly includes two different performance films (or other films) deposited in a continuous process (although a common applicator may be used). While these embodiments show three applicators 43A-C, other examples may include 4, 5, 6, or more applicators.

Optionally, the apparatus may include a cooling apparatus that may be used to help reduce and/or control the temperature of the current collector foil substrate as deposition proceeds. This may help to maintain the foil substrate at a desired operating temperature-e.g., aluminum foil below about 100 ℃. This may help reduce the likelihood of the foil substrate or coating being damaged during the deposition process. Since each deposition operation is performed at a high temperature and uses material, in some arrangements increasing the number of deposition operations performed may result in a greater temperature rise in the foil substrate. To help control the temperature of the substrate, the cooling apparatus may be configured to include a cooling member, such as cooling roll 50 in fig. 17, that may be in contact with the moving substrate. The plurality of deposition applicators 43A-43C may be arranged such that the associated deposition zones on the substrate are in communication with a common cooling roll 50.

Alternatively, as an alternative to using a common roll 50 to cool two or more deposition zones, the cooling apparatus may comprise a plurality of coolers, such as the plurality of rolls 50A, 50B and 50C shown in fig. 18, each aligned with a respective applicator 43A-C and configured to cool a respective deposition zone.

It is possible, and in some examples may be preferable, to sequentially apply the desired coatings and materials (including reactive and inert metal coatings) during the same rolling operation (i.e., in a single pass of the web along the deposition path), so long as the total mass flow of each metal is sufficient to deposit the desired thickness of each respective metal in a single pass of the substrate web. This may help simplify the operation of the deposition apparatus and may help reduce manufacturing time and complexity in some cases. This may reduce the need to use a reversible shaft, for example.

For example, the method for manufacturing a multilayer anode assembly is a single pass method in which a substrate web comprising at least a current collector web and optionally a protective film as described herein is transported in a process direction along a deposition path comprising a plurality of deposition zones (with corresponding deposition applicators or other devices) arranged in sequence. As the substrate web passes through successive deposition zones, different materials may be applied and various films may be formed and layered on top of each other. Preferably, the apparatus may be configured such that the substrate web only needs to pass once along the deposition path-starting from the inlet (where the incoming substrate web is received), preferably from the feed roll.

The method may comprise the steps of: the continuous substrate web is unwound from a suitable substrate feed roll and transported in a first/forward process direction (process direction) along a deposition path disposed within a suitable process chamber of a single pass physical vapor deposition apparatus. The incoming substrate web will preferably include the desired current collector foil, which may be unwound from a foil supply or feed roll or other suitable source.

The process may then include transporting the substrate web along a process direction through one or more deposition zones positioned along a deposition path. The number and configuration of each deposition zone may vary between different equipment or process operations and may be based on, for example, the number and type of different films that are intended to be deposited on a given assembly. This may include one or more optional substrate deposition zones (which may apply material (e.g., a protective film) to the current collector foil), and optionally one or more lithium deposition zones, one or more interface deposition zones, and one or more cover deposition zones. In some arrangements, the apparatus may include a unique deposition zone for application to each layer/film of the assembly, while in other arrangements a given deposition zone may include two or more suitable applicators or may be otherwise configured to allow deposition of two or more layers/films within a common deposition zone. In some examples, it is also possible that the apparatus may not include all possible types of deposition zones if no corresponding film is required in a given assembly production, or that one or more applicators and deposition zones be activated during a given production cycle. For example, in some examples, if lithium is to be added in situ to the component, the apparatus need not include a lithium deposition zone within the process chamber (or it may be present and inactive). In other examples, if a given component does not include any interfacial film layers, the interfacial deposition area may not be present (or be inactive).

Continuing with the example mentioned above, the incoming substrate web may be conveyed along a deposition path through a lithium deposition zone, and the apparatus may deposit at least a first lithium film onto the outside of the component support surface using a suitable lithium physical vapor deposition applicator. In examples where the current collector is compatible with lithium and no interfacial film, lithium may be deposited directly onto the current collector foil. In other examples, lithium may be deposited onto the protective film (if present) or onto the exposed surface of the outermost interfacial film (if present). Each of these arrangements is understood to be outside the support surface of the substrate web.

In addition to deposition of lithium material, the manufacturing process may include at least one additional deposition step, or may include two, three, four, or more additional deposition steps that will be performed in a prescribed order or sequence of operations along the deposition path using the appropriate deposition zones. For example, the process may include transporting the substrate web along a process direction through an interfacial deposition area along a deposition path and upstream of a lithium deposition area. The process may then include depositing a first interfacial film formed of an interfacial material onto the support surface using an interfacial physical vapor deposition applicator. If the interfacial film and the lithium film are to be provided simultaneously, one or more interfacial films are first deposited so that the one or more interfacial films can be positioned at their intended locations, for example, between the support surface and the first lithium film, so that they can perform their intended functions.

Optionally, the process may further include transporting the substrate web along the process direction through an overburden deposition zone that is along the deposition path and downstream of both the interface deposition zone (if present) and the lithium deposition zone (if present). In the blanket deposition area, one or more blanket films may be formed of a blanket material that allows lithium ions to flow between the electrolyte and the first lithium film and preferably outside of any previously deposited interface or lithium film. Positioning one or more overlay deposition zones downstream of other deposition zones (if present) can help position one or more films in the overlay zone in their intended, generally outboard, positions so that they can overlay the underlying lithium film and interfacial film.

After a single pass through the intended deposition zone, the substrate to include the desired film may be a completed or at least substantially completed multi-layer anode assembly, which may then reach the end/outlet of the deposition path and may be stored for further processing or use, for example, by winding the multi-layer anode assembly onto an output roll provided at the deposition path outlet.

Referring to fig. 7, a method 700 of manufacturing an anode assembly One example includes step 702: the metal current collector substrate (e.g., current collector 102) is provided inside a metallization or processing chamber (which may be configured at atmospheric pressure and may be selectively configured (e.g., by using a suitable vacuum pump apparatus, etc.) to have an internal operating pressure less than atmospheric pressure). The operating pressure in the metallization chamber may be any suitable pressure that facilitates the intended physical vapor deposition process, and in some examples may be at about 10 ^-2 And 10 ^-6 And the brackets are arranged between the two brackets. Preferably, this may help provide a process chamber interior that is substantially oxygen free when forming the films 104 and 106.

Optional step 704: the substrate is transferred to an interface deposition zone (if desired for a given design) and an appropriate applicator may be used to deposit an interface film.

Step 706: the web is transported to a lithium deposition zone and a lithium film is deposited. Then, in optional step 708, the web may continue and optionally may pass through one or more blanket deposition areas, and then may exit the deposition path and be wound onto an output roll in step 710. Alternatively, if a protective layer is desired based on the characteristics of the particular film used, then in step 714, the protective layer may be applied to the current collector foil. This may be done prior to the interfacial deposition step 704, and if a protective layer is to be included, in this example, the protective layer will be deposited prior to the deposition of the lithium film at step 706. In this arrangement, steps 714-708 as shown may be performed in a single pass along the deposition path, and preferably within a common deposition process chamber (shown schematically at 716) and during a single vacuum cycle of process chamber 716.

The roll may then be stored and/or sent for further processing at step 712, such as in a battery or the like using the resulting anode assembly. Preferably, the current collector 102 material is a continuous metal foil that is unwound from a first input or feed roll prior to step 602 via optional step 608 and then wound onto a first output roll after step 606 via optional step 610. In this arrangement, steps 604 and 606 may preferably be performed as the continuous web of metal foil moves along the deposition path between the first feed roll and the first output roll.

Alternatively, in some examples described herein, lithium material may not be included in the component as it exits the deposition path, and may be added in a later step. In that case, the deposition apparatus may omit the lithium deposition zone or it may become inactive. As the substrate moves along the deposition path, it may be covered by one or more suitable films, such as protective films, interfacial films, and cover films, applied by suitable, sequential applicators. In these cases, the multilayer substrate emerging from the end of the deposition path may be referred to as an anode assembly (without lithium) or as an intermediate web, which includes substantially all of the components of the anode assembly but just as much lithium is added. The intermediate web may be wound onto an output roll for temporary storage or may be transported and handled using any suitable technique. To add lithium material, a portion of the intermediate mesh (or alternatively the entire mesh) may be placed in a suitable electrochemical cell that includes a positive electrode and a lithium source (as shown and described with reference to fig. 19-23). The electrochemical cell may be in a battery or other such end product, or may be a stand-alone device for electroplating lithium onto an intermediate mesh to provide a lithiated anode assembly that may then be removed from the electroplating cell and inserted into other batteries or devices.

For example, referring to fig. 8, another example of a method 800 of manufacturing an anode assembly includes providing a metallic current collector substrate inside a metallization or processing chamber 818 in step 802, the metallization or processing chamber 818 may be configured at atmospheric pressure and may be selectively configured (e.g., by using a suitable vacuum pump apparatus, etc.) to have an internal operating pressure less than atmospheric pressure. In optional step 704, the substrate is transferred to an interface deposition zone (if desired for a given design) and an appropriate applicator may be used to deposit an interface film.

In this example, the lithium film is applied outside of the process chamber 818 and the lithium application step bypasses the process chamber 818 so that the substrate may be transferred from the one or more interface deposition steps 804 to the one or more optional blanket deposition steps 808. That is, at optional step 808, the web may then continue and optionally may pass through one or more blanket deposition areas, and may then exit the deposition path as an intermediate web assembly to be wound onto an output or transport roll at step 810. Alternatively, if a protective layer is desired based on the characteristics of the particular film used, then at step 814, a protective layer may be applied to the current collector foil. This may be done prior to the interfacial deposition step 804, and if a protective layer is to be included, then in this example the protective layer will be deposited prior to the substrate exiting the deposition chamber 818.

When a lithium film is created by electroplating lithium into the lithium bearing region of the intermediate mesh assembly in a lithium application step 806, the intermediate mesh assembly or portion thereof may then be positioned in a suitable electrochemical cell 820. The lithiated component may then remain in the electrochemical cell 820 (e.g., if the cell 820 is a finished battery), or may be removed and further processed or used in optional step 812.

At step 706, the web is transported to a lithium deposition zone and a lithium film is deposited. In this arrangement, steps 714-708 as shown may be performed in a single pass along the deposition path, and preferably within a common deposition process chamber (shown schematically at 716) and during a single vacuum cycle of process chamber 716.

Referring to fig. 24, an example of a single pass deposition apparatus 1000 is schematically illustrated. Preferably, as described herein, the apparatus 1000 and other apparatus described herein are configured to include a first set of physical vapor deposition applicators (e.g., applicators 1020 and 1024) positioned to deposit material (or provide gas for reaction, etc.) on a first side of a substrate web and a second set of physical vapor deposition applicators (e.g., applicators 1020A and 1024A) positioned to deposit material (or provide gas for reaction, etc.) on a second side of the substrate web. Alternatively, as shown, the second set of applicators may be downstream of the first set of applicators such that the first side of the substrate web is coated before the second side. Alternatively, some of the second set of applicators may be mixed with some of the first set of applicators such that portions of the first and second sides are alternately treated along the deposition path. For example, two lithium films or the like may be deposited before either of the capping films is provided. Having two sets of applicators (regardless of their arrangement) may allow a generally bare web of substrates to enter the process chamber and a substantially complete, two-sided, multi-layer anode assembly to be extracted at the end of the deposition path. This is an advantage over conventional techniques in which the web requires at least two or more passes through suitable equipment to adequately coat the first side of the substrate web or to adequately coat the first and second sides of the substrate web.

Although only a portion of apparatus 100 is schematically illustrated for clarity, apparatus 1000 may include any suitable features, mechanisms, feed systems, controllers, and other features of deposition apparatus 400 described herein, and the following description of apparatus 1000 will focus on single pass process chamber 1002 (which may be used in place of chamber 41 where appropriate).

The apparatus 1000 is configured to receive an incoming substrate web 1004 (which may be similar to the web 60 described herein) that is fed from a substrate supply or feed roll 1006 and moves along a deposition path 1108 within the chamber 1102 along a process direction 1010 from a path inlet 1012 to a path outlet 1014. A product or output roll 1016 is positioned at the outlet 1014 to receive and wind the multi-layer anode assembly web exiting the deposition path 1008.

In this example, the apparatus 1000 is configured to produce an assembly having a current collector substrate, a film in a lithium bearing region, and a film in a coverage region in a single pass, and includes suitable deposition zones and applicators sequentially arranged along a deposition path 1008. Specifically, in this example, the apparatus 1000 is configured to utilize a lithium-compatible metal foil current collector as the substrate mesh, and thus, does not require a protective layer deposition zone. Conversely, web 1004 may be advanced to a lithium deposition zone 1018 (e.g., zones 45A-C) having an applicator 1020 (e.g., applicators 43A-C) that includes a source of lithium heat. Lithium material may be deposited directly on the mesh 1004 to provide a lithium film.

Downstream of the lithium deposition zone 1018, the apparatus 1000 includes a blanket deposition zone 1022 that includes a blanket applicator 1024 configured to form a blanket film. In this example, the cover applicator 1024 includes a gas supply nozzle/device that can be used to provide a gas treatment on the exposed surface of the lithium film (deposited in region 1018). For example, the applicator 1024 may be connected to a suitable gas source and provide a substantially pure, e.g., at least 99%, preferably 99.9%, or 99.99%, or 99.999% pure cover gas that can react with the exposed face of the lithium film and can form a reactive cover layer in situ. Suitable gases may include nitrogen and carbon dioxide, which may react with the exposed lithium to form a film/skin of lithium nitride or lithium carbonate, respectively, which may help protect the underlying lithium film and may help inhibit oxidation, etc. If these layers are the only layers required by the assembly, any equipment or deposition zone downstream of the blanket deposition zone 1022 may be deactivated and the web 1004 may be moved to the output roll 1016 without any further processing on the front side of the web. If the resulting anode assembly is double-sided, a pair of matching backside/second side deposition zones, identified with like reference numerals having the suffix "A", may be provided downstream of the front side/first side deposition zones described above. In this arrangement, both sides of the substrate web may be coated as desired along the deposition path 1004 in a single pass. If double sided coating is not required, it is not necessary to provide a second deposition zone and applicators 1018A, 1020A, 1022A, and 1024A and the deposition path 1104 may be closer to the blanket deposition zone 1022.

Referring to fig. 25, another illustrative example of a single pass deposition apparatus 2000 is shown. The device 2000 is similar to the device 1000 and like reference numerals to 1000 are used to describe like features. In this example, the apparatus 2000 is configured to produce an assembly having a current collector substrate, a film in an interface region, a film in a lithium bearing region, and a film in a coverage region in a single pass, and includes suitable deposition zones and applicators arranged sequentially along a deposition path 2008.

Specifically, in this example, the apparatus 2000 is configured to utilize a lithium-compatible metal foil current collector as a substrate mesh, and thus, a protective layer deposition zone is not required. Instead, web 2004 may be advanced to lithium deposition zone 2018 (e.g., zones 45A-C) having an applicator 2020 (e.g., applicators 43A-C) that includes a source of lithium heat.

However, unlike apparatus 1000, apparatus 2000 also includes an interface deposition zone 2026 that includes a deposition applicator 2028 that is located upstream of lithium deposition zone 2018 and is operable to deposit an interface material, such as depositing a copper film by a thermal evaporation source or depositing a layer of nickel from a magnetron sputtering source (or the like) onto a substrate web prior to reaching lithium deposition zone 2018. In this arrangement, the lithium layer deposited in the lithium deposition region 2108 is deposited onto the interfacial copper film, rather than directly onto the mesh 2004.

Downstream of the lithium deposition zone 2018, the apparatus 2000 includes a blanket deposition zone 2022 that includes a blanket applicator 2024 configured to form a blanket film. In this example, the cover applicator 2024 includes a gas supply nozzle/apparatus that may be used to provide a gas treatment on the exposed surface of the lithium film (deposited in region 2018). In other examples, the applicator 2024 may deposit a metal cover film, including any of the cover materials described herein.

Referring to fig. 26, another illustrative example of a single pass deposition apparatus 3000 is shown. Device 3000 is similar to device 1000 and like features are shown using like reference numerals to 1000. In this example, the apparatus 3000 is configured to produce an assembly having a current collector substrate, a membrane in an interface region, a membrane in a lithium bearing region, and two membranes in a footprint in a single pass, and includes suitable deposition zones and applicators arranged sequentially along a deposition path 2008.

Specifically, in this example, the apparatus 3000 is configured to utilize an aluminum metal foil current collector, and thus the first deposition zone provided along the deposition path 3008 may be used to apply a protective film on the aluminum foil. This first deposition region may be referred to as a protective deposition region or a protective film material such as a nickel layer may include a protective deposition region 3030, which is not required. As shown in fig. 26, the apparatus 3000 includes a deposition zone 3026 that includes a deposition applicator 3028 that is positioned upstream of the lithium deposition zone 3018 and that is operable to deposit a material that can be used as an interface film or a protective film, or both, such as a layer of nickel from a magnetron sputtering source.

Downstream of the deposition zone 3026, including the deposition applicator 3028, is a lithium deposition zone 3018 and an applicator 3020 operable to deposit a lithium film onto the nickel film.

Downstream of the lithium deposition zone 3018, the apparatus 3000 includes a first blanket deposition zone 3022 containing a blanket applicator 3024 configured to form a first blanket film, such as a tin layer deposited from a second magnetron sputtering source. In addition to the first blanket deposition area 3022, a second blanket deposition area 3030 is included in the deposition path and includes a second applicator 3032 for applying a second blanket film over the tin layer (or any other intermediate layer as an example) that may help impart different characteristics to the assembly. In this example, a 750nm thick polyethylene oxide (PEO) layer may be from a second thermal evaporation source (e.g., applicator 3032) to provide an outermost skin/film on the assembly. This sequence of steps may be repeated on the second side of the substrate using a second set of deposition zones and applicators denoted by the "a" suffix.

As described herein, previous attempts to provide lithium anodes suitable for liquid electrolyte metal lithium ions (LMBs), mixed lithium metals (HLBs), and Solid State Batteries (SSBs) do not provide all of the advantages described herein, and are typically made by foil rolling and extrusion processes, as described above. Lithium is active, physically weak and self-adhesive, the difficulty of rolling lithium is well known, and limits the actual thickness of foil that can be rolled and handled to greater than 20 microns. These difficulties lead to excessive use of materials, high unit costs and negatively impact the economic viability of the anode. Furthermore, as shown in SEM micrographs of fig. 28 and 29, the lubricants introduced during rolling, inclusions in the ingot, and the rolling atmosphere all caused physical and chemical defects to the surface of the rolled foil. Fig. 28 shows an anode sample formed using conventional foil materials and assembly techniques after a symmetric 50-cycle with sulfide electrolyte, various ridges and other surface defects were visible in the micrograph (note that white particles in the image are electrolyte residues). In contrast, fig. 29 shows an example of an assembly using PVD according to the present teachings to deposit a lithium film (rather than foil) after 50 cycles of symmetric cycling using sulfide electrolyte, the surface appearing relatively smoother (again, white particles are electrolyte residues). Surface defects in conventional assemblies (fig. 28) can negatively impact the performance of the foil as a battery anode because it can create non-uniformities in the electroplating and stripping characteristics of the anode, increase impedance, interfere with contact between the anode and electrolyte, and introduce chemical impurities that can react with other components of the battery.

Based on the teachings herein, the inventors created and examined several examples of anode assemblies having different features and combinations of the various layers and regions described herein. Some of these illustrative examples are described below.

Example 1: one example of an anode assembly includes a current collector substrate, a lithium bearing region, and a coverage region. The current collector substrate is 150mm wide, 6 microns thick (or about 4 to about 10 microns) electrodeposited copper foil. A layer of 5 microns (or about 1 to 10 microns) thick lithium metal is applied on both sides of the substrate at a rate of about 15 microns-meters per minute by a thermal evaporation type of physical vapor deposition. A substantially pure, preferably up to 99.9999% pure, nitrogen treatment is applied outside the deposition zone to form a lithium nitride layer in the footprint of the anode without breaking the vacuum. The lithium nitride has high ionic conductivity of about 10 < -3 > S/cm, forms a stable solid electrolyte interface with part of electrolyte, and improves the durability of the anode.

Example 2: another example of an anode assembly includes a current collector substrate, a lithium bearing region, and a coverage region. The current collector substrate is 150mm wide and 6 microns thick (alternatively between about 4 microns and about 10 microns) electrodeposited copper foil. A 5 micron (or about 1 to 10 micron) thick layer of lithium metal was applied by thermal evaporation at a rate of about 15 microns-meters per minute on both sides of the substrate. The continuous process was simulated, the material was moved into an argon glove box and 100nm and 200nm zinc (Zn) was applied to the covered areas of the two samples to form an alloy in situ on the sample surface. LiZn alloys have the beneficial property of improving the transfer of charge to the anode surface, thereby making the electroplating and stripping of lithium metal more uniform.

Example 3: another example of an anode assembly includes a current collector substrate, an interface region, a lithium bearing region, and a cover region. The current collector substrate may be a rolled stainless steel foil 5 microns thick (or about 1 to 10 microns). A copper layer 1 micron thick (optionally between about 0.5 micron and about 2 microns) is applied by a thermal evaporation source in the interface region, and then lithium metal is applied on both sides of the substrate by thermal evaporation in the lithium bearing region. Outside the deposition zone, a substantially pure, preferably up to 99.9999% pure, carbon dioxide gas treatment can be applied without breaking vacuum to form lithium carbonate (Li) in the anode's covered region ₂ CO ₃ ) And a gas protection layer.

Stainless steel is a relatively inexpensive substrate because it contains mainly low cost materials such as iron and chromium. It is not an ideal current collector material because it has low conductivity, about 40 times lower than copper. This disadvantage is overcome by introducing a thin layer of copper in the interface region, providing an effective anode material using a rich low cost substrate material. In addition, the inclusion of a lithium carbonate layer in the covered region can passivate the surface of the lithium to make it more durable in contact with the atmosphere, allowing for longer periods of handling and storage in a dry chamber environment without degrading the anode surface.

Example 4: reference is made to another anode assembly embodiment that includes a current collector substrate, an interface region, a lithium bearing region, and a cover region. The current collector substrate may be a rolled aluminum foil 150mm wide and 12 microns (or between 5 and 15 microns) thick. A 300 nm (or 100 to 500 nm, preferably 200 nm to 400 nm) thick nickel layer may be applied from a magnetron sputtering source at the interface region, then lithium metal is applied by thermal evaporation at the lithium bearing region without breaking the vacuum, and a substantially pure, preferably up to 99.9999% pure, carbon dioxide gas treatment may be applied outside the deposition zone to form a lithium carbonate layer in the footprint of the anode, the sequence being repeated on both sides of the substrate. Fig. 27 is a graph showing cycle data for a conventional foil and a material according to this example 4, showing material similarity properties between a conventional lithium foil-based component and a component formed according to the present teachings. This helps demonstrate that components having at least some of the processing and cost advantages described herein can provide acceptable performance comparable to conventional designs.

The anode assembly of example 4 provides several advantages. First, the aluminum substrate material is much less dense than copper, so that a specific thickness of aluminum substrate has approximately the same area mass as a 4 micron thick copper current collector, and therefore has a specific energy advantage over a similar anode assembly made with the latter material. Second, since aluminum generally accounts for one third to one fourth of the mass cost, the material cost of the current collector is significantly reduced. This is accomplished by using a nickel layer as the protective material layer in the interface region (or substrate region) to reduce or eliminate the transfer of lithium ions from the lithium bearing region to the aluminum current collector where they may alloy with the substrate and mechanically degrade it. The lithium carbonate passivation layer or gas protection layer functions similarly to that described in example 3.

Fig. 27 shows a comparative critical current test of a material made according to example 4 and a conventional rolled foil. Under similar conditions, the anode has nearly identical cycling behavior, while a cell assembly with significantly reduced cost can be manufactured in a larger form and with less overall material usage than conventional rolled foils.

Example 5: referring to still another example of an anode assembly, a current collector substrate with a protective film applied thereto, a lithium bearing region, and a cover region. The current collector substrate may be a rolled aluminum foil 600mm wide and 12 microns thick. A 300 nm thick nickel layer may be applied from a first magnetron sputter source in the interface region, then lithium metal is applied by thermal evaporation from a first thermal evaporation source in the lithium bearing region, then a 200 nm thick tin layer is applied from a second magnetron sputter source in the coverage region, and a 750nm thick polyethylene oxide (PEO) layer is applied from a second thermal evaporation source outside the coverage region, the sequence being repeated on both sides of the substrate.

The anode assembly of example 5 provides the same advantages as example 4, but with two additional advantages. PEO deposited in the covered area is a solid electrolyte that can easily interface with the cathode material, solid electrolyte separator, or some potential liquid electrolyte in the hybrid cell. PEO is a known solid electrolyte and has the disadvantage of low ionic conductivity at room temperature. Ultra-thin PEO films can be formed using the methods of the present invention that are practically impossible to achieve using conventional assembly methods. This greatly eases the low room temperature ionic conductivity of the material and facilitates its use in various battery cells. Advantageously, deposition of PEO allows excellent wetting between the layer and the underlying layer, improving uniformity of ion transfer and further reducing the tendency to dendrite formation. Second, a transfer layer or transfer film, such as a tin layer (or, for example, zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb)) is partially alloyed with lithium In the covered region, resulting In a Li-Sn alloy with good charge transfer properties. This promotes rapid recombination of the interface during electroplating and stripping, thereby inhibiting dendrite and other defect formation.

Table 8 summarizes some of the characteristics of the examples described herein and provides relative areal density, thickness, and dominant (additive) raw material costs to illustrate some of the benefits of the invention. In each of these examples, the anode assembly according to the present teachings provides significantly lower areal density (higher cell specific energy), smaller thickness (increased cell energy density) and reduced input material cost (reduced cost per kilowatt-hour energy storage) even though some of the performance advantages conferred by the functional layer are not considered, thereby imparting a significant performance advantage to the cells using such anode assemblies.

TABLE 8

The total thickness of the anode assembly or assembly thickness (measured from the rear side of the substrate region to the outer surface of the cover region in a single-sided anode) is preferably less than about 60 μm or about 50 μm, and may be between about 10 μm and about 50 μm, between about 15 μm and about 30 μm, between about 16 and about 25 μm, or other suitable ranges, when constructed in accordance with the teachings herein.

The anode assembly, when constructed in accordance with the teachings herein, can have a weight of less than about 80g/m ² Or less than about 70g/m ² Or less than about 60g/m ² And optionally may be at about 30g/m ² And 70g/m ² Between, or at about 40g/m ² And 65g/m ² The areal density between.

While the teachings herein have been described with reference to exemplary embodiments and examples, this description is not intended to be limiting. Accordingly, various modifications of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to the description. It is therefore contemplated that the appended claims will cover any such modifications or embodiments.

As used herein, the term "about" is understood to mean that the characteristic of a given component differs from the stated value or range by a relatively small amount, such as 10% or 15% of the stated value, so long as such variation does not materially affect the function or capability of the component. For example, an areal density of less than about 70g/m ² The components of the sheet will be understood by those skilled in the art to include a sheet density of 70.1g/m ² Or possibly 71-74 or 75g/m ² If such an assembly is used to function in a substantially similar manner to the described examples, but would not be understood by one of ordinary skill to include an areal density of greater than 80g/m ² Is a component of (a). Such minor variations in the ranges may be due to manufacturing tolerances, measurement errors or challenges, and refer to embodiments of the described assembly that are not materially different from those described and that may be used as alternatives to the examples described herein.

All publications, patents, and patent applications mentioned herein are incorporated by reference in their entirety to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference in its entirety.

Claims

1. A multi-layered lithium anode assembly for a lithium-based battery, the anode assembly comprising:

a) A substrate region having a current collector comprising a continuous copper foil having a thickness between 4 and 10 microns and having a support surface compatible with lithium;

b) A lithium bearing region overlying the support surface, and comprising a film of lithium material deposited directly on the support surface by thermal evaporation and having a thickness between 1 micron and 10 microns; and

c) A cover region located outside the lithium bearing region, comprising at least one cover film formed of a passivation material, and covering the lithium material film, the cover region allowing lithium ion flow between an electrolyte and the lithium bearing region and inhibiting irreversible reaction between the lithium bearing region and the electrolyte or surrounding environment.

2. The anode assembly of claim 1, wherein the passivation material comprises at least one of a nitride, a hydride, a carbonate, lithium nitride, lithium oxide, lithium sulfide, an oxide, lithium aluminate, sulfide, gold, platinum, polyethylene oxide, lithium catecholate, and a lithium ion conductive polymer.

3. The anode assembly of claim 2, wherein the passivation material comprises lithium nitride.

4. The anode assembly of claim 3, wherein the at least one capping film is formed in situ by exposing a surface of the lithium material film to pure nitrogen gas and promoting a chemical reaction between the nitrogen gas and the lithium material film to produce lithium nitride at the surface of the lithium material film.

5. The anode assembly of any one of claims 1 to 4, wherein the total assembly thickness of the anode assembly is less than 50 microns.

6. A multi-layered lithium anode assembly for a lithium-based battery, the anode assembly comprising:

c) A cover region outside the lithium bearing region comprising at least one cover film comprising a lithium-philic material deposited directly on the exposed surface of the lithium material film by physical vapor deposition, whereby the cover region enhances the mobility of lithium ions through the cover region and between electrolyte and the lithium bearing region such that lithium is deposited in the lithium bearing region when using the anode assembly to inhibit dendrite formation as compared to providing direct contact between the electrolyte and the lithium material film.

7. The anode assembly of claim 5, wherein the lithium-philic material comprises at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb).

8. The anode assembly of claim 7, wherein the lithium-philic material comprises a lithium-zinc alloy formed in situ within the anode assembly by physical vapor deposition of zinc directly onto an exposed surface of the lithium material film.

9. The anode assembly of any one of claims 6 to 8, wherein the total assembly thickness of the anode assembly is less than 50 microns.

10. A multi-layered lithium anode assembly for a lithium-based battery, the anode assembly comprising:

a) A substrate region having a current collector comprising a continuous stainless steel foil having a thickness between 3 and 8 microns and having a support surface compatible with lithium;

b) An interface region between the lithium bearing region and the support surface and comprising at least one layer of interface film between the support surface and the lithium bearing region to physically separate the substrate region and the lithium bearing region, the at least one layer of interface film being formed of copper deposited directly on the support surface, having a thickness between 0.5 and 2 microns, and allowing electron flow between the lithium bearing region and the support surface;

c) A lithium bearing region overlying the interface region and comprising a film of lithium material deposited directly on the at least one layer of interface film by thermal evaporation and having a thickness between 1 micron and 10 microns; and

d) A cover region located outside the lithium bearing region, comprising at least one cover film formed of a passivation material and covering the lithium material film, the cover region allowing lithium ion flow between an electrolyte and the lithium bearing region and inhibiting irreversible reaction between the lithium bearing region and the electrolyte or surrounding environment.

11. The anode assembly of claim 10, wherein the passivation material comprises at least one of a nitride, a hydride, a carbonate, lithium nitride, lithium oxide, lithium sulfide, an oxide, lithium aluminate, sulfide, gold, platinum, polyethylene oxide, lithium catecholate, and a lithium ion conductive polymer.

12. The anode assembly of claim 11, wherein the passivation material comprises lithium carbonate (Li ₂ CO ₃ )。

13. The anode assembly of claim 12, wherein the at least one cover film is formed in situ by exposing a surface of the lithium material film to pure carbon dioxide gas and promoting a chemical reaction between the carbon dioxide and the lithium material film to produce lithium carbonate at the surface of the lithium material film.

14. The anode assembly of any one of claims 10 to 13, wherein the total assembly thickness of the anode assembly is less than 50 microns.

15. A multi-layered lithium anode assembly for a lithium-based battery, the anode assembly comprising:

a) A substrate region having a current collector comprising a continuous aluminum foil having a thickness of between 5 and 15 microns and having a support surface compatible with lithium;

b) An interface region between the lithium bearing region and the support surface and comprising at least one layer of interface film between the support surface and the lithium bearing region to physically separate the substrate region and the lithium bearing region, the at least one layer of interface film formed of nickel deposited directly on the support surface, having a thickness between 200nm and 400nm and allowing electron flow and inhibiting lithium ion flow between the lithium bearing region and the support surface;

16. The anode assembly of claim 15, wherein the passivation material comprises at least one of a nitride, a hydride, a carbonate, lithium nitride, lithium oxide, lithium sulfide, an oxide, lithium aluminate, sulfide, gold, platinum, polyethylene oxide, lithium catecholate, and a lithium ion conductive polymer.

17. The anode assembly of claim 16, wherein the passivation material comprises lithium carbonate (Li ₂ CO ₃ )。

18. The anode assembly of claim 17, wherein the at least one cover film is formed in situ by exposing a surface of the lithium material film to pure carbon dioxide gas and promoting a chemical reaction between the carbon dioxide and the lithium material film to produce lithium carbonate at the surface of the lithium material film.

19. The anode assembly of any one of claims 15 to 18, wherein the total assembly thickness of the anode assembly is less than 50 microns.

20. A multi-layered lithium anode assembly for a lithium-based battery, the anode assembly comprising:

a) A substrate region having a current collector comprising a continuous aluminum foil having a thickness of between 5 and 15 microns and having a support surface;

b) An interface region between the lithium bearing region and the support surface and comprising at least one layer of interface film to physically separate the substrate region and the lithium bearing region, the at least one layer of interface film formed of nickel deposited directly on the support surface, having a thickness between 200nm and 400nm and allowing electron flow and inhibiting lithium ion flow between the lithium bearing region and the support surface;

c) A lithium bearing region overlying the interface region and comprising a film of lithium material deposited directly on the at least one interface film by thermal evaporation; and

d) A cover region outside the lithium bearing region comprising a first cover film formed of a lithium-philic material deposited directly on the exposed surface of the lithium material film by physical vapor deposition, whereby the cover region enhances the mobility of lithium ions through the cover region and between electrolyte and the lithium bearing region such that lithium is deposited in the lithium bearing region when using the anode assembly to inhibit dendrite formation as compared to providing direct contact between the electrolyte and the lithium material film.

21. The anode assembly of claim 20, wherein the lithium-philic material comprises at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb).

22. The anode assembly of claim 21, wherein the lithium-philic material comprises a lithium-zinc alloy formed in situ within the anode assembly by physical vapor deposition of zinc directly onto an exposed surface of the lithium material film.

23. The anode assembly of any one of claims 20 to 22, wherein the total assembly thickness of the anode assembly is less than 50 microns.

24. A multi-layered lithium anode assembly for a lithium-based battery, the anode assembly comprising:

a) A substrate region having a support surface compatible with lithium and comprising a non-lithium current collector;

b) A lithium bearing region overlying the support surface and configured to hold at least a first film of lithium material;

c) At least one of the following:

i. an interface region between the lithium bearing region and the support surface, comprising at least one layer of interface film between the support surface and the lithium bearing region to physically separate the substrate region and the lithium bearing region, the at least one layer of interface film being formed by physically depositing a lithium compatible material onto the support surface and being electrically conductive to allow electron flow between the lithium bearing region and the support surface; and

a cover region outside the lithium bearing region, comprising at least one cover film covering the outside of the lithium bearing region, the cover region allowing lithium ion flow between electrolyte and the lithium bearing region.

25. The anode assembly of claim 24, wherein the interface region is operable to at least one of: suppressing dendrite formation when lithium is deposited in the lithium bearing region in use and improving lithium ion flow or ion distribution between the lithium bearing region and the substrate region in use.

26. The anode assembly of claim 24 or 25, wherein the interface region is operable to at least one of: inhibit irreversible reactions between the lithium bearing region and the electrolyte or surrounding environment, inhibit dendrite formation when lithium is deposited in the lithium bearing region in use, and enhance lithium ion flow or ion distribution between the lithium bearing region and the electrolyte in use.

27. The anode assembly of any one of claims 24 to 26, comprising the interface region and the cover region.

28. The anode assembly of any one of claims 24 to 27, wherein the first film of lithium material is formed by physically depositing a lithium-compatible material into the lithium bearing region.

29. The anode assembly of any one of claims 24 to 28, wherein the current collector comprises at least one of copper, aluminum, nickel, stainless steel, conductive polymer, polymer.

30. The anode assembly of any one of claims 24 to 29, wherein the current collector is configured as a continuous web.

31. The anode assembly of any one of claims 24 to 30, wherein the current collector has a current collector thickness of between about 1 and about 100 microns, preferably between about 4 and about 70 microns or between about 5 and 15 microns.

32. The anode assembly of any one of claims 24 to 31, wherein the current collector is formed of a lithium-compatible material and has a front surface comprising the support surface.

33. The anode assembly of claim 32, wherein the lithium-compatible material comprises a metal foil comprising at least one of copper, steel, and stainless steel.

34. An anode assembly according to any one of claims 24 to 33 wherein the current collector is formed of a material that is not compatible with lithium and further comprising a first protective film that bonds to and covers the front surface of the current collector and provides the support surface, the first protective film being formed of a protective metal that is electrically conductive and inhibits the flow of lithium ions, whereby electrons can pass through the first protective film from the lithium bearing region to the current collector and the lithium bearing region is spaced apart from and at least substantially isolated from the current collector ions, thereby substantially preventing diffusion of lithium ions from the lithium bearing region to the current collector through the first protective film.

35. The anode assembly of claim 34, wherein the protective metal comprises at least one of copper (Cu), nickel (Ni), silver (Ag), stainless steel and steel, titanium (Ti), zirconium (Zr), molybdenum (Mo), or alloys thereof.

36. The anode assembly of claim 35, wherein the lithium-incompatible material comprises a metal foil comprising aluminum, zinc, or magnesium, or alloys thereof.

37. The anode assembly of any one of claims 24 to 36, wherein the first protective film has a thickness of between about 1 to about 75000 angstroms, preferably between about 200 to about 7500 angstroms.

38. The anode assembly of claim 37, wherein the first protective film has an isolation thickness and is shaped such that the current collector is fully ion isolated from the lithium bearing region.

39. The anode assembly of any one of claims 24 to 38, wherein the first film of lithium material is deposited on and bonded to the first protective film by physical vapor deposition.

40. The anode assembly of any one of claims 24-39, wherein the at least one layer of interfacial film comprises at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), copper (Cu), indium (In), silver (Ag), bismuth (Bi), lead (Pb), cadmium (Cd), antimony (Sb), and selenium (Se).

41. The anode assembly of any one of claims 24 to 40, wherein the at least one interfacial film has a thickness between about 1 and about 75000 angstroms, and preferably between about 200 and about 7500 angstroms.

42. The anode assembly of any one of claims 24 to 41, wherein the at least one layer of interfacial film comprises at least a first deposition enhancement film comprising at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb) and positioned to contact the lithium bearing region, thereby inhibiting dendrite formation when the first lithium material film is deposited In the lithium bearing region.

43. The anode assembly of claim 42, wherein the first deposition enhancement film is a deposition film formed from physical deposition of at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb) to an underlying surface.

44. The anode assembly of claims 42 to 43, wherein the interface region further comprises at least a first bonding film adjacent to the first deposition enhancement film and comprising at least one of zinc (Zn), cadmium (Cd), magnesium (Mg), antimony (Sb), indium (In), bismuth (Bi), nickel (Ni), lead (Pb), and selenium (Se), and located between the support surface and the lithium bearing region, thereby providing a better bond between the support surface and the lithium bearing region than would be achieved between the support surface and the lithium bearing region without the first bonding film.

45. The anode assembly of any one of claims 24 to 44, wherein the at least one layer of interfacial film comprises at least a first bonding film comprising at least one of zinc (Zn), cadmium (Cd), magnesium (Mg), antimony (Sb), indium (In), bismuth (Bi), nickel (Ni), lead (Pb), and selenium (Se) and is located between the support surface and the lithium bearing region, thereby providing a better bond between the support surface and the lithium bearing region than would be achieved between the support surface and the lithium bearing region without the first bonding film.

46. The anode assembly of claim 45, wherein the bond film is formed by physical vapor deposition of at least one of zinc (Zn), cadmium (Cd), magnesium (Mg), antimony (Sb), indium (In), bismuth (Bi), nickel (Ni), lead (Pb), and selenium (Se) to an underlying surface.

47. The anode assembly of claim 45 or 46, wherein the interface region further comprises at least a first deposition enhancement film adjacent to the bonding film and comprising at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb), and positioned to contact the lithium bearing region, thereby inhibiting dendrite formation when the first lithium material film is deposited In the lithium bearing region.

48. The anode assembly of any one of claims 24 to 47, wherein the interface region is free of metal foil.

49. The anode assembly of any one of claims 24 to 48, wherein the lithium bearing region comprises the first film of lithium material.

50. The anode assembly of claim 49, wherein the first film of lithium material is formed by physically depositing lithium metal onto the support surface.

51. The anode assembly of claim 48, further comprising at least one cover film in said cover region, and said first film of lithium material comprises lithium metal deposited into said lithium bearing region after said at least one cover film is in place.

52. The anode assembly of any one of claims 24 to 51, wherein the lithium bearing region is free of lithium foil.

53. The anode assembly of any one of claims 24 to 52, wherein the lithium bearing region is free of metal foil.

54. An anode assembly according to any one of claims 24 to 53 wherein the at least one cover film comprises at least a first passivation film covering the outside of the lithium bearing region and inhibiting reaction between the lithium bearing region and ambient, the first passivation film being formed of a passivation material that inhibits gas diffusion and allows lithium ion flow through the first passivation film.

55. The anode assembly of claim 54, wherein the passivation material comprises at least one of a nitride, a hydride, a carbonate, lithium nitride, lithium oxide, lithium sulfide, an oxide, lithium aluminate, sulfide, gold, platinum, polyethylene oxide, lithium catecholate, and a lithium ion conductive polymer.

56. The anode assembly of claim 54 or 55, wherein the passivation material comprises lithium carbonate (Li ₂ CO ₃ )。

57. The anode assembly of claim 56, wherein the lithium carbonate comprises a film of the lithium carbonate formed in situ on a surface of the first film of lithium material by exposing the surface to a gas treatment of pure carbon dioxide and reacting lithium material at the surface with the carbon dioxide.

58. The anode assembly of any one of claims 24 to 57, wherein the overlay region further comprises at least a first deposition enhancement film formed of a wetting material and covering an outside of the lithium bearing region and enhancing wetting between the first wetting material and the lithium bearing region, whereby dendrite formation is inhibited by the first deposition enhancement film in the overlay region when the first lithium material film is deposited in the lithium bearing region.

59. The anode assembly of any one of claims 24 to 58, wherein the at least one cover film comprises at least a first deposition enhancement film formed of a wetting material and covering an outside of the lithium bearing region and enhancing wetting between the first deposition enhancement film and the electrolyte, whereby formation of dendrites in the lithium bearing region is inhibited by the first deposition enhancement film reaching the lithium bearing region when the first lithium material film is deposited on the lithium bearing region.

60. The anode assembly of claim 59, wherein the wetting material comprises polyethylene oxide (PEO).

61. The anode assembly of claim 60, wherein the polyethylene oxide is deposited by physical vapor deposition and bonded to an adjacent film.

62. The anode assembly of claim 60 or 61, wherein the polyethylene oxide is deposited on the first lithium material film.

63. The anode assembly of claim 60 or 61, wherein the polyethylene oxide is deposited and bonded to an intermediate transfer film disposed between and enhancing charge transfer to and from the first deposition enhancement film and the first lithium material film.

64. The anode assembly of claim 63, wherein the transfer film comprises at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb).

65. The anode assembly of any one of claims 59 to 64, wherein the cover region further comprises at least a first passivation film covering the outside of the lithium bearing region and inhibiting reaction between the lithium bearing region and the surrounding environment, the first passivation film being formed of a passivation material that inhibits gas diffusion and allows lithium ion flow through the first passivation film.

66. The anode assembly of any one of claims 24 to 65, wherein the cover region comprises at least a lithium-philic cover film covering an outside of the lithium bearing region and comprising at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb), whereby the lithium-philic cover film enhances mobility of lithium ions through the lithium-philic cover film and between electrolyte and the lithium bearing region such that dendrite formation is inhibited when lithium is deposited In the lithium bearing region when the anode assembly is In use.

67. The anode assembly of any one of claims 24 to 66, wherein the covered region is free of metal foil.

68. The anode assembly of any one of claims 24 to 67, wherein the anode assembly is free of lithium metal foil.

69. The anode assembly of any one of claims 24 to 68, wherein the current collector comprises a non-lithium metal foil and is the only foil in the anode assembly.

70. The anode assembly of any one of claims 24-69, wherein the anode assembly has an assembly thickness of less than about 60 μιη.

71. The anode assembly of claim 70, wherein the assembly thickness is less than about 50 μm.

72. The anode assembly of claim 71, wherein the assembly thickness is between about 10 μιη and about 50 μιη.

73. The anode assembly of claim 72, wherein the assembly thickness is between about 15 μιη and about 30 μιη.

74. The anode assembly of claim 73, wherein the assembly thickness is between about 16 and about 25 μm.

75. The anode assembly of any one of claims 24 to 74, wherein the anode assembly has a weight of less than about 80g/m ² Is a surface density of the glass.

76. The anode assembly of claim 75, wherein said areal density is less than about 70g/m ² And preferably wherein said areal density is less than about 60g/m ² 。

77. The anode assembly of claim 76, wherein the areal density is about 30g/m ² And 70g/m ² Between them.

78. The method according to claim 77The anode assembly wherein the areal density is about 40g/m ² And 65g/m ² Between them.

79. A single pass method of manufacturing a multi-layer anode assembly for a lithium-based battery, the method comprising:

a) Unwinding a continuous substrate web from a substrate feed roll and transporting the substrate web in a process direction along a deposition path within a process chamber of a single pass physical vapor deposition apparatus, the substrate web comprising a continuous current collector and a lithium-compatible support surface disposed on a first side of the current collector;

b) Transporting the substrate web in the process direction through a lithium deposition zone along the deposition path and depositing at least a first lithium film onto an outside of the support surface of the assembly using a lithium physical vapor deposition applicator;

at least one of the following steps:

c) Transporting the substrate web in the process direction through an interface deposition zone along the deposition path and upstream of the lithium deposition zone and depositing a first interface film formed of an interface material onto the support surface using an interface physical vapor deposition applicator, whereby the first interface film is located between the support surface and the first lithium film, the interface material being electrically conductive to allow electron flow between the first lithium film and the support surface; and

d) Transporting the substrate web in the process direction through a blanket deposition zone along the deposition path and downstream of the lithium deposition zone, wherein a first blanket film is formed from a blanket material that allows lithium ion flow between electrolyte and the first lithium film and is located outside of the first lithium film, whereby the first lithium film is located between the first blanket film and the support surface;

thereby forming a multi-layered anode assembly; and is also provided with

e) After performing at least one of steps b) and c) and d), winding the multi-layered anode assembly on an output roll at an outlet of the deposition path;

wherein at least step b) and at least one of steps c) and d) are completed during a single pass of the substrate web through the deposition path.

80. The method of claim 79, wherein at least one of steps b) and c) and d) is completed during a single PVD vacuum cycle, wherein the process chamber is maintained at less than 10 during at least one of steps b) and c) and d) ^-2 At the operating pressure of the tray.

81. The method of claim 79 or 80, wherein the current collector comprises a continuous metal foil.

82. The method of any one of claims 79 to 81, wherein the current collector has a thickness of between about 1 to about 100 microns.

83. The method of any of claims 79 to 82, wherein the current collector comprises at least one of copper, aluminum, magnesium, nickel, stainless steel, conductive polymers, and polymers.

84. The method of any one of claims 79 to 83, wherein the current collector comprises a lithium-compatible metal foil and a front surface of the current collector provides a support surface and the first lithium film is deposited directly onto the front surface of the current collector by the lithium physical vapor deposition applicator.

85. The method of any one of claims 79 to 83, wherein the current collector comprises a lithium-incompatible metal foil, and the method further comprises transporting the substrate web in the process direction through a protective layer deposition zone upstream of the lithium deposition zone, and depositing a lithium-compatible protective material directly to a front side of the current collector by a protective film vapor deposition applicator to form a first protective film, wherein the protective material is electrically conductive and inhibits lithium ion flow, whereby electrons can pass from the first lithium film to the current collector through the first protective film, and the first lithium film is spaced apart from the current collector and at least substantially isolated from the current collector ions, such that lithium ions are substantially prevented from diffusing from the lithium bearing zone through the first protective film to the current collector, and wherein the first protective film comprises the support surface, and the first lithium film is deposited directly on the first protective film.

86. The method of claim 85, wherein the protective material comprises at least one of copper, nickel, silver, stainless steel and steel, titanium, zirconium, molybdenum, or alloys thereof.

87. The method of any one of claims 79 to 86, wherein the first cover film is formed by depositing a first cover material onto the first lithium film using a cover gas phase deposition applicator.

88. The method of claim 87, wherein the first cover film is a lithium-philic cover film comprising at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb), whereby the lithium-philic cover film enhances diffusion of lithium ions through the lithium-philic cover film and between electrolyte and the lithium bearing region such that dendrite formation is inhibited when lithium is deposited In the lithium film when the anode assembly is In use.

89. The method of any one of claims 79 to 86, wherein the first cover film is formed in situ by subjecting the surface of the first lithium film to a gas treatment, thereby forming a first cover material.

90. The method of claim 89, wherein the first cover material comprises at least one of a nitride, a hydride, a carbonate, a lithium nitride, a lithium oxide, a lithium sulfide, an oxide, a lithium aluminate, a sulfide, gold, platinum, polyethylene oxide, lithium catecholate, and a lithium ion conducting polymer, whereby the first cover film allows lithium ion flow between an electrolyte and the first lithium film and inhibits irreversible reaction between the first lithium film and the electrolyte or ambient.

91. The method of any one of claims 79 to 86, wherein at least one of steps b) and c) and d) is performed while the substrate web is moving between the input roll and the output roll at a process speed of between about 1m/min and about 100m/min, and preferably between 2m/min and 50 m/min.

92. The method of any one of claims 79 to 91, wherein during at least one of step b) and steps c) and d), the process chamber is substantially free of oxygen.

93. The method of any one of claims 79 to 92, wherein the operating pressure is at about 10 ^-2 And 10 ^-6 And the brackets are arranged between the two brackets.

94. The method of any one of claims 79 to 93, further comprising, prior to step b), reducing the pressure inside the metallization chamber from substantially atmospheric pressure to the operating pressure.

95. The method according to any one of claims 79 to 94, wherein the method comprises steps c) and d), and wherein step c) is performed before step b).

96. The method of any one of claims 79 to 94, wherein after completing step b) and at least one of steps c) and d) but before completing step e), the method further comprises:

f) Transporting the substrate web in the process direction through a second lithium deposition zone along the deposition path and depositing at least a second lithium film onto a second support surface disposed on an opposite second side of the current collector using a lithium physical vapor deposition applicator; and

at least one of the following steps:

g) Transporting the substrate web in the process direction through a second interface deposition zone along a deposition path and upstream of the second lithium deposition zone and depositing a second interface film formed of the interface material onto the second support surface using an interface physical vapor deposition applicator, whereby the second interface film is located between the second support surface and the second lithium film, the interface material being electrically conductive to allow electron flow between the second lithium film and the second support surface; and

h) Transporting the substrate web in the process direction through a second blanket deposition zone along the deposition path and downstream of the second lithium deposition zone, wherein a second blanket film is formed from the blanket material that allows lithium ion flow between electrolyte and the second lithium film and is located outside of the second lithium film, whereby the second lithium film is located between the second blanket film and the second support surface; and is also provided with

97. A multilayer anode assembly formed using the method of any one of claims 79 to 96, wherein all of the films are deposited using physical vapor deposition.

98. A single pass method of manufacturing a multi-layer anode assembly for a lithium-based battery, the method comprising:

b) Transporting the substrate web in the process direction through an interfacial deposition zone along the deposition path and depositing a first interfacial film formed of an interfacial material onto the support surface using an interfacial physical vapor deposition applicator, the interfacial material being electrically conductive to allow electron flow between the first lithium film and the support surface;

c) Transporting the web of substrates in the process direction through a lithium deposition zone along the deposition path and downstream of the interface deposition zone, and depositing at least a first lithium film onto the first interface film using a lithium physical vapor deposition applicator, whereby the first interface film is located between the support surface and the first lithium film;

i) Transporting the web of substrate in the process direction through a second interfacial deposition zone along the deposition path and downstream of the blanket deposition zone, and depositing a second interfacial film formed of the interfacial material onto a second support surface disposed on an opposite second side of the current collector using a second interfacial physical vapor deposition applicator;

j) Transporting the web of substrates in the process direction through a second lithium deposition zone along the deposition path and downstream of the second interface deposition zone, and depositing at least a second lithium film onto the second interface film using a lithium physical vapor deposition applicator; and

k) Transporting the substrate web in the process direction through a second blanket deposition zone along the deposition path and downstream of the second lithium deposition zone, wherein a second blanket film is formed from the blanket material that allows lithium ion flow between electrolyte and the second lithium film and is located outside of the second lithium film, whereby the second lithium film is between the second blanket film and the second support surface, thereby providing a double-sided multilayer anode assembly;

wherein at least a) to k) are completed during a single pass of the substrate web through the deposition path.

99. A single pass method of manufacturing a double sided multi-layer anode assembly for a lithium-based battery, the method comprising:

a) Unwinding a continuous substrate web from a substrate feed roll and transporting the substrate web in a process direction along a deposition path within a process chamber of a single pass physical vapor deposition apparatus, the substrate web comprising a continuous current collector having a first side and an opposing second side;

b) Transporting the current collector in the process direction while applying at least first and second films on the first side of the current collector using respective first and second physical phase deposition applicators positioned to face the first side of the current collector;

c) Transporting the current collector in the process direction while applying at least third and fourth films on the second side of the current collector using respective third and fourth physical vapor deposition applicators positioned to face the second side of the current collector, wherein steps b) and c) are completed during a single pass of the substrate web through the deposition path, thereby providing a double-sided multilayer anode assembly; and

d) After performing steps b) and c), winding the double-sided multilayer anode assembly on an output roll at the exit of the deposition path.

100. The method of claim 99, wherein the first film comprises a first lithium film formed of a lithium material, and wherein the second film comprises at least one of:

a) An interfacial film located inside the lithium film, configured to inhibit dendrite formation and/or improve lithium ion flow or ion distribution between the first lithium film and the current collector when lithium is deposited In the lithium film, and formed of an interfacial material of at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), copper (Cu), indium (In), silver (Ag), bismuth (Bi), lead (Pb), cadmium (Cd), antimony (Sb), and selenium (Se); and

b) A cover film located outside the first lithium film, formed of: i) A passivation material configured to inhibit reaction between the first lithium film and the surrounding environment by inhibiting gas diffusion while allowing lithium ions to flow through the cover film, or ii) a lithium-philic cover material configured to enhance mobility of lithium ions through the cover film and between electrolyte and the first lithium bearing region such that dendrite formation is inhibited when lithium is deposited in the first lithium film when the anode assembly is in use.

101. The method of claim 100, wherein the passivation material comprises at least one of a nitride, a hydride, a carbonate, lithium nitride, lithium oxide, lithium sulfide, an oxide, lithium aluminate, sulfide, gold, platinum, polyethylene oxide, lithium catecholate, and a lithium ion conductive polymer.

102. The method of claim 100 or 101, wherein the lithium-philic capping material comprises at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb).

103. The method of any one of claims 99-103, wherein the third film comprises a second lithium film formed from the lithium material, and wherein the fourth film comprises at least one of:

a) An interfacial film inside the lithium film configured to inhibit dendrite formation and/or improve lithium ion flow or ion distribution between the first lithium film and a current collector when lithium is deposited In the lithium film, and formed of an interfacial material of at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), copper (Cu), indium (In), silver (Ag), bismuth (Bi), lead (Pb), cadmium (Cd), antimony (Sb), and selenium (Se); and

104. The method of claim 103, wherein the passivation material comprises at least one of a nitride, a hydride, a carbonate, lithium nitride, lithium oxide, lithium sulfide, an oxide, lithium aluminate, sulfide, gold, platinum, polyethylene oxide, lithium catecholate, and a lithium ion conductive polymer.

105. The method of claim 103 or 104, wherein the lithium-philic capping material comprises at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb).

106. A method of manufacturing a multi-layer anode assembly for a battery, the method comprising:

at least one of the following steps:

b) Transporting the web of substrates in the process direction through an interface deposition zone along the deposition path and depositing a first interface film formed of an interface material onto the support surface using an interface physical vapor deposition applicator, the interface material being electrically conductive to allow electron flow through the first interface film; and

c) Transporting the substrate web in the process direction through a blanket deposition zone along the deposition path and downstream of the interfacial deposition zone, and forming a first blanket film on the outside of the support surface, the first blanket film formed of a blanket material that is electrically conductive to lithium ions to allow lithium ions to flow through the first blanket film;

wherein at least one of steps b) and c) is completed during a single pass of the substrate web along the deposition path, thereby providing an intermediate web assembly, and further comprising:

d) Positioning at least a first portion of the intermediate mesh assembly in an electrochemical cell comprising a positive electrode and a lithium source; and

e) An electrical potential is applied between the positive electrode and the first portion of the intermediate web, thereby driving lithium ions from the lithium source and depositing lithium ions as a first lithium film on the intermediate web assembly in a lithium bearing region outside of the support surface.

107. The method of claim 106, wherein the component is free of lithium prior to performing step e).

108. The method of claim 106 or 107, wherein at least one of steps b) and c) is completed during a single PVD vacuum cycle, wherein the interior of the process chamber is maintained at less than 10 ^-2 Operating pressure of the tray.

109. The method of any one of claims 106 to 108, wherein the current collector comprises a continuous metal foil.

110. The method of any one of claims 106 to 109, wherein the current collector has a thickness of between about 1 and about 100 microns.

111. The method of any of claims 106-110, wherein the current collector comprises at least one of copper, aluminum, magnesium, nickel, stainless steel, conductive polymers, and polymers.

112. The method of any one of claims 106 to 111, wherein the current collector comprises a lithium-compatible metal foil and a front surface of the current collector provides a support surface and the first lithium film is deposited directly onto the front surface of the current collector by the lithium physical vapor deposition applicator.

113. The method of any one of claims 106 to 112, wherein the current collector comprises a lithium-incompatible metal foil, and the method further comprises transporting the substrate web in the process direction through a protective layer deposition zone upstream of the lithium deposition zone, and depositing a lithium-compatible protective material directly to a front side of the current collector by a protective film vapor deposition applicator to form a first protective film, wherein the protective material is electrically conductive and inhibits lithium ion flow, whereby electrons can pass from the first lithium film to the current collector through the first protective film, and the first lithium film is spaced apart from the current collector and at least substantially isolated from the current collector ions, such that lithium ions are substantially prevented from diffusing from the lithium bearing zone through the first protective film to the current collector, and wherein the first protective film comprises the support surface, and the first lithium film is deposited directly on the first protective film.

114. The method of claim 113, wherein the protective material comprises at least one of copper, nickel, silver, stainless steel and steel, titanium, zirconium, molybdenum, or alloys thereof.

115. The method of any one of claims 106 to 114, wherein the first cover film is formed by depositing a first cover material using a cover gas phase deposition applicator prior to adding the first lithium film.

116. The method of claim 115, wherein the first cover film is a lithium-philic cover film comprising at least one of tin (Sn), zinc (Zn), magnesium (Mg), carbon (C), indium (In), silver (Ag), bismuth (Bi), lead (Pb), whereby the lithium-philic cover film enhances mobility of lithium ions moving through the lithium-philic cover film and between electrolyte and the lithium bearing region such that dendrite formation is inhibited when lithium is deposited In the lithium film when the anode assembly is In use.

117. The method of any one of claims 106 to 116, wherein the first cover film is formed in situ by subjecting a surface of the first lithium film to a gas treatment, thereby forming a first cover material.

118. The method of claim 117, wherein the first cover material comprises at least one of lithium zinc alloy, lithium carbonate, and lithium nitride, whereby the first cover film allows lithium ion flow between electrolyte and the first lithium film and inhibits irreversible reaction between the first lithium film and the electrolyte or ambient.

119. The method according to any one of claims 106 to 118, wherein at least one of steps c) and d) is performed while the substrate web is moving between the input roll and the output roll at a process speed of between about 1m/min and about 100m/min, preferably between 2m/min and 50 m/min.

120. The method of any one of claims 106 to 119, wherein during at least one of steps b) and c), the process chamber is substantially free of oxygen.

121. The method of any one of claims 106 to 120, wherein the operating pressure is at about 10 ^-2 To 10 ^-6 And the brackets are arranged between the two brackets.

122. The method of any one of claims 106 to 121, further comprising, prior to step c), reducing the pressure inside the metallization chamber from substantially atmospheric pressure to the operating pressure.

123. The method of any one of claims 106 to 122, further comprising at least one of:

f) Transporting the substrate web in the process direction through a second interface deposition zone along the deposition path and depositing a second interface film formed of the interface material onto an opposite second side of the substrate web support surface using a second interface physical vapor deposition applicator; and

g) Transporting the substrate web in the process direction through a second blanket deposition zone along the deposition path and downstream of the second interface deposition zone, and forming a second blanket film on an outside of a second side of the substrate web, the second blanket film formed from the blanket material;

124. The method of any one of claims 106 to 122, comprising steps b) and c) and f) and g).