Multi-layer anode for a solid-state battery, production and use thereof, and the solid-state battery containing the multi-layer anode

Abstract

The invention relates to a multi-layer anode (40) for a solid-state battery, said anode being applied to an anode current collector (50) and comprising or consisting of a first layer (42) and a second layer (44), wherein the first layer (42) has one or more metal elements selected from the group consisting of silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As) and / or titanium (Ti), and the second layer (44) consists of a protective oxide layer which has or consists of one or more oxides of silicon (Si) and / or the above elements. The invention is distinguished by the fact that the ultrathin multi-layer anode according to the invention makes it possible to provide solid-state batteries which exhibit high energy density, making it possible to improve the reversibility of the lithium plating / stripping process during charging / discharging and to improve the cycle life of the solid-state battery.

Description

[0001] Mercedes-Benz Group AG

[0002] Multilayer anode for a solid-state battery, its manufacture and use, and the solid-state battery containing the multilayer anode

[0003] The invention relates to a multilayer anode for a solid-state battery, its manufacture and use, and the solid-state battery containing the multilayer anode.

[0004] In recent years, lithium-ion battery systems have become increasingly prevalent in battery technology. These are characterized in particular by their high energy density and expected long lifespan, enabling more efficient battery configurations. The high chemical reactivity and low mass of lithium ions, as well as their high mobility, play a key role in this.

[0005] A battery typically consists of three layers: anode, separator and cathode, with the anode and cathode storing the active energy via lithium ions and the separator, in the form of a solid electrolyte, providing insulation between the electrodes and the transport of charge carriers in the form of lithium ions between the cathode and anode during charging and discharging.

[0006] However, solid-state batteries based on anode-free or anode-less concepts are increasingly being manufactured, as this offers several advantages over conventional anodes, such as smaller volume and weight, as well as lower costs in mass production. The invention is also based on an anode-free or anode-less concept.

[0007] Numerous proposals in this regard are known from the prior art. For example, US 2020 / 0144599 Al discloses an anodeless coating for a solid-state battery, wherein the anodeless coating comprises: an active anode material capable of forming an alloy with lithium or a compound with lithium; and a binder, wherein the binder comprises a block copolymer containing a conductive domain, a non-conductive domain, or a combination thereof, and wherein the conductive domain comprises an ion-conducting domain, an electron-conducting domain, or a combination thereof. Figure 3 of US 2020 / 0144599 Al shows a cathode 10 comprising a cathode current collector 11 and a layer of active cathode material 12. The anode 20 comprises an anode current collector 21, a thin film 24 formed on the anode current collector 21 and an anode-less coating 22.The thin film 24 can contain an element alloyable with lithium, such as gold (Au), silver (Ag), zinc (Zn), tin (Sn), indium (In), silicon (Si), aluminum (Al), or bismuth (Bi). The thickness of the thin film 24 can be in the range of approximately 1 nm to approximately 500 nm or in the range of approximately 20 nm to approximately 200 nm. The anode-less coating layer 22 can contain an active anode material capable of forming an alloy or compound with lithium. Examples of the active anode material for realizing this function include amorphous carbon, gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), zinc (Zn), or a combination thereof. Examples of amorphous carbon include carbon black (CB), acetylene black (AB), furnace black (FB), Ketjen black (KB), graphene, or a combination thereof.The thickness of the anodeless coating layer 22 can range from about 1 pm to about 20 pm.

[0008] Furthermore, US patent 2021 / 0036327 Al discloses an anode-free solid-state battery comprising: a cathode layer; an anode current collector layer; a separator layer between the cathode layer and the anode current collector layer; and an anti-dendrite layer arranged between the separator layer and the anode current collector layer. An adhesive layer is also arranged between the anti-dendrite layer and the anode current collector layer, the adhesive strength between the adhesive layer and the anode current collector layer being greater than that between the anti-dendrite layer and the adhesive layer.

[0009] German patent DE 10 2022 108 126 Al relates to a solid-state battery with an anode comprising at least one anode current collector, a cathode, and a solid electrolyte layer arranged between the anode and the cathode, wherein a protective layer, containing, for example, magnesium oxide and a polymer, is arranged between the anode current collector and the solid electrolyte layer. An anode active material layer, containing a lithium substance or a lithium alloy, may be present between the anode current collector and the protective layer. The protective layer has a thickness of 5 to 100 pm. US patent 2019 / 0044 186 Al describes a solid electrolyte, a method for its production, and a lithium battery containing the solid electrolyte. The solid-state battery has a completely different structure than according to the invention: The lithium battery has an intermediate layer 22b between the lithium metal cathode 20 and the solid electrolyte 22a.The anode has a positive active material layer 21 on a positive current collector 24.

[0010] PU, Jun [et al.]: Conductivity and lithiophilicity gradients guide lithium deposition to mitigate short circuits. In: Nature communications, Vol. 10, 2019. Art. No. 1896, 10 pp. - ISSN 2041-1723 describes the electrodeposition and selective etching of a highly porous, untreated nickel framework, the upper region of which is electrically passivated by coating with aluminum oxide and the lower region of which is provided with an Au layer (see Fig. lc)).

[0011] LU, Qiongqiong [et al.]: Carbon materials for stable Li metal anodes: challenges, solutions and outlook. In: Carbon energy, Vol. 3, 2021, No. 6, pp. 957-975. - ISSN 2637-9368) discloses carbon materials for stable lithium metal anodes.

[0012] However, there is still a need to further improve the properties of solid-state batteries.

[0013] The present invention is therefore based on the objective of further improving the properties of an anode for a solid-state battery and thus also the solid-state battery itself.

[0014] According to the invention, the above problem is solved by a multilayer anode for a solid-state battery, which is applied to an anode current collector, comprising or consisting of a first layer and a second layer, wherein the first layer comprises one or more metallic elements selected from the group consisting of silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As) and / or titanium (Ti). The second layer consists of a protective oxide layer composed of or containing one or more oxides of silicon (Si), silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As) and / or titanium (Ti).Examples of these oxides are SiOj, AgjO or Al2O3, where the second layer has a thickness of 5 nanometers to < 1 micrometer.

[0015] Any material known to those skilled in the art for solid-state batteries can be used as the anode current collector. The anode current collector can comprise or consist of materials that are unreactive towards lithium and do not form an alloy or compound with lithium. These include, for example, copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), indium (In), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.

[0016] The anode current collector can be designed, for example, as a plate, a film, or a foil. Preferably, the anode current collector consists of copper foil, stainless steel foil, or nickel foil.

[0017] The first layer is applied to the anode current collector and preferably has a thickness of 5 nanometers to 1 micrometer. Preferably, the layer thickness can be from 5 nanometers to < 1 micrometer, e.g. 0.99 micrometers.

[0018] The second layer is located on top of the first layer and has a thickness of 5 nanometers to

[0019] < 1 micrometer, e.g. 0.99 micrometers.

[0020] The thickness of the first layer and the thickness of the second layer can both be the same, or the thicknesses of both layers can be different.

[0021] In particular, if the thickness of the first and second layers for the multilayer anode is within the specified ranges, it is possible to improve the battery's performance.

[0022] Preferably, there is no intermediate layer between the first and second layers.

[0023] According to a preferred embodiment, a third layer, consisting of or comprising conductive carbon material, is present on the second layer of the multilayer anode. Preferably, the conductive carbon material is selected from carbon black, including acetylene black, channel black, furnace black, lamp black, thermal black, carbon nanotubes, carbon nanofibers, and / or graphene, and the like. The thickness of the third layer can preferably vary between 5 nanometers and 10 micrometers. Preferably, there is also no intermediate layer between the second and third layers.

[0024] The invention also relates to methods for manufacturing a multilayer anode for a solid-state battery, comprising:

[0025] (1) Provision of an anode current collector,

[0026] (2) Applying a first layer to the anode current collector comprising one or more metallic elements selected from the group consisting of silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As) and / or titanium (Ti); and

[0027] (3) Applying a second layer in the form of a protective oxide layer to the first layer, comprising or consisting of one or more oxides of silicon (Si), silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As) and / or titanium (Ti).

[0028] Optionally, after step (3) step (4) is carried out: applying a third layer to the second layer, consisting of conductive carbon materials, preferably selected from carbon black, including acetylene carbon black, sewer carbon black, furnace carbon black, lamp black, thermal black, carbon nanotubes, carbon nanofibers and / or graphene and the like.

[0029] The first and second layers each preferably have a thickness of 5 nanometers to < 1 micrometer. The thickness of the third layer preferably has a thickness of 5 nanometers to 10 micrometers. The thickness of the first layer and the thickness of the second layer can be the same or different from each other.

[0030] The thickness of the first layer, the thickness of the second layer, and the thickness of the third layer can each be chosen to be the same or different. According to a preferred embodiment, the thickness of the first and second layers is chosen to be the same, and the thickness of the third layer is chosen to be different.

[0031] In particular, if the thickness of the first, second, and third layers of the multilayer anode falls within the specified ranges, the battery's performance can be significantly improved. Therefore, an ultra-thin multilayer anode for a solid-state battery is provided.

[0032] For the production of the various layers according to steps (2) and (3) and, if applicable, step (4), any coating process known to those skilled in the art can be used that can be used to apply a thin layer to an anode of a solid-state battery. Examples of such coating processes are wet coating, dry coating, spin coating, dip coating, physical vapor deposition, and chemical vapor deposition. Other coating processes are also possible. If a slurry is used for the production of the layers, a suitable binder can be used to prepare the slurry. Such binders are known in the prior art. These include, for example, styrene-butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, or mixtures thereof.Polymers or block copolymers, such as those disclosed in US 2020 / 0144599 Al, may also be used. Unless otherwise specified, one or more additives, such as fillers, dispersing agents, or other additives, may also be used in the individual layers, provided that the material is suitable for use in a solid-state battery.

[0033] The invention also relates to the use of the described multilayer anode in a solid-state battery.

[0034] The invention also relates to a solid-state battery comprising a multilayer anode according to the present invention, arranged between an anode current collector and a solid electrolyte. According to a preferred embodiment, the solid-state battery is in pouch cell format and is also referred to as a 'pouch cell'. Pouch cells are particularly advantageous for certain applications. They can be manufactured with small thicknesses, low weight, and application-specific dimensions, and their flat outer shape provides good heat dissipation.

[0035] Any solid-state electrolyte known to a person skilled in the art can be used as the solid-state electrolyte in a solid-state battery. For example, one of the following can be used, or a hybrid solid-state electrolyte consisting of two or more of the following can be used: solid polymer electrolytes (SPE) or hybrid solid polymer electrolytes based on the following types with inorganic fillers:

[0036] 1. Polyether-based SPEs: e.g., poly(ethylene oxide) (PEO), propylene oxide (PPO), and the like;

[0037] 2. Polycarbonate-based SPEs: e.g. polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC) and the like;

[0038] 3. Polysiloxane-based SPEs; and

[0039] 4. SPEs based on polymer crystals.

[0040] Solid oxide electrolytes:

[0041] 1. Perovskite conductor: e.g. Lni / aNbOa (Ln = La, Ce, Pr, Nd);

[0042] 2. NASICON conductor: e.g. Nai+xZrzPs-xSixOu with 0 < x < 3

[0043] 3. Garnet-like conductors: e.g., LisLasMjOu (M=Nb, Ta, Zr); and

[0044] 4. Amorphous / glass: e.g. LiPON.

[0045] Solid sulfide electrolytes:

[0046] 1. LISICON: e.g. Lij+jxZni-xGeO Jwith X from 0-1)

[0047] Thio-LISICON: e.g. B. Li4-xMi.yM y S4 (M=Si, Ge, and M=P, AI, Zn, Ga, with X from 0-4 and Y between 0-1);

[0048] 2. LGPS family: e.g., LiioGePjSu; and

[0049] 3. Argyrodites: e.g. B. LigPSsX (X =CI, Br, I).

[0050] Solid halide electrolytes: e.g. Li a MXb (X = F, CI, Br, I, M = metallic elements, such as the lanthanides (M = Sc, Y, La - Lu), elements of group 13 (M = AI, Ga, In) and various divalent metals (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Mg, Pb) with a = e.g. 1.5 to 3 and b = e.g. 4 to 6.

[0051] 4. Closo-borate solid electrolytes.

[0052] Of course, other solid electrolytes known to experts can also be used.

[0053] For solid-state batteries, any type of material known to those skilled in the art in this field can be used as the active cathode material. Examples include lithium nickel cobalt manganese oxide (NCM, LiNii-x-yMmCOyC), such as LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNi0.8n0.1Co0.1O2 (NMC811) (see Patrick J. West et al. in J. Phys. Chem. C 2023, 127, 15, 7054-7070 https: / / doi.org / 10.1021 / acs.jpcc.2c08971), and lithium nickel cobalt aluminum oxide (NCA, LiNii-x-yCo). x AlyO2; see PH Duvigneaud et al. in Journal of the European Ceramic Society Vol. 24, Issue 6, 2004, pp. 1375-1380), lithium manganese oxide (LMO, LiMn2Ü4), lithium cobalt oxide (LCO, UCOO2), lithium iron phosphate (LFP, LiFePO4) and lithium iron manganese phosphate (LMFP, LiMn x Fei- x PO4 with x = 0 to 0.3).

[0054] Solid-state batteries implemented with an anode-free or anode-less design typically exhibit a rapid capacity decline due to irreversible lithium plating and stripping. Lithium plating is an aging or degradation process that leads to the formation of a metallic lithium phase, primarily occurring during the charging process of a lithium-ion battery. This process is accelerated by factors such as low temperatures and high charging currents (fast charging) and can lead to lifespan and safety issues in solid-state batteries. In principle, the reverse reaction of lithium plating should be completely reversible. This reverse reaction is known as lithium stripping. However, plating triggers further side reactions that result in aging and thus incomplete reversibility.

[0055] By using the ultrathin multilayer anode according to the present invention, it is now surprisingly possible to improve the overall lithium plating / stripping performance, i.e., to provide improved reversibility of the reverse reaction from lithium plating in the form of lithium stripping, which also increases the cell's lifetime.

[0056] The ultrathin multilayer anode according to the invention enables the production of solid-state batteries with high energy density. It improves the reversibility of the lithium plating / stripping process during charging / discharging of the battery. In particular, it also results in an improved cycle life, i.e., the frequency with which the solid-state battery can be recharged is significantly increased.

[0057] The solid-state battery provided according to the invention is preferably in pouch format. A single-layer pouch cell, comprising a multilayer anode according to the invention, is produced, for example, by first providing the components. These are, for example, a cathode current collector, a cathode, a separator, the anode according to the invention, and an anode current collector, each in suitable dimensions to produce a pouch cell. The components are stacked and carefully aligned with one another in the specified sequence.

[0058] Complete assembly is carried out under conditions of exclusion of moisture and oxygen (e.g., H₂O < 0.1 ppm, O₂ < 0.1 ppm). After stacking, the pouch cell is welded on three sides for closure or sealing, for example, using an impulse welder. The partially sealed pouch cell is then mounted on a plate, such as an aluminum plate, for compression molding, particularly cold isostatic pressing (CIP). If necessary, the pouch cell is additionally wrapped in a bag to prevent any oil contamination during the CIP process. The pouch cell is then compressed for a suitable duration under appropriate pressure. After compression, the remaining open side of the pouch cell is sealed with a vacuum sealer under conditions of exclusion of moisture and oxygen.

[0059] For example, the anode-free solid-state battery according to the invention can be used in a smartphone, a drone, a laptop, or an electric vehicle. Preferably, the anode-free solid-state battery of the present invention is a high-power battery; that is, the anode-free solid-state battery of the present invention is used in particular in an electric vehicle (BEV, battery electric vehicle).

[0060] Also described is an electrically powered vehicle (BEV) with one or more secondary, anode-free solid-state batteries that include the multilayer anode.

[0061] The anode-free solid-state battery of the present invention can be a secondary battery that can be repeatedly charged and discharged. Primary batteries can only be discharged once and cannot be recharged afterward. Secondary batteries, also known as accumulators, are rechargeable.

[0062] The present invention is explained in more detail with reference to the following embodiment, wherein the accompanying figures are drawn schematically and not to scale, so that no assumptions can be made about exact geometric values ​​in relation to the original size. The figures of this disclosure form part of the description and constitute a portion thereof, with the embodiment shown illustrating the present invention without limiting the invention thereto.

[0063] This shows:

[0064] Fig. 1: a schematically simplified representation of an embodiment according to the invention for a multilayer anode;

[0065] Fig. 2: a schematically simplified representation of a further embodiment according to the invention for a multilayer anode; and

[0066] Fig. 3: a schematically simplified representation of an unfolded structure of an anode-free solid-state battery according to an embodiment of the present invention;

[0067] Fig. 1 shows a schematically simplified representation of an embodiment of a multilayer anode according to the invention. On the anode current collector 50, there is a first layer 42 comprising one or more metallic elements selected from the group consisting of silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As), and / or titanium (Ti). The first layer 42 preferably has a thickness of 5 nanometers to 1 micrometer. According to a preferred embodiment, the layer thickness can be from 5 nanometers to < 1 micrometer, e.g., 0.99 micrometers.

[0068] The second layer 44 is present as a protective oxide layer on the first layer and consists of or comprises one or more oxides of silicon (Si), silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As), and / or titanium (Ti). The second layer 44 has a thickness of 5 nanometers to < 1 micrometer, e.g., 0.99 micrometers.

[0069] The thickness of the first layer 42 and the thickness of the second layer 44 can be the same or different from each other. According to Fig. 2, an additional third layer 46 is present, which is conductive.

[0070] The third layer 46 comprises or consists of carbon materials. These are preferably selected from carbon black, including acetylene carbon black, sewer carbon black, furnace carbon black, lamp carbon black, thermal black, carbon nanotubes, carbon nanofibers and / or graphene and the like. The third layer 46 preferably has a thickness of 5 nanometers to 10 micrometers.

[0071] The thickness of the first layer 42, the thickness of the second layer 44, and the thickness of the third layer 46 can each be the same or different. According to a preferred embodiment, the thickness of the first layer 42 and the second layer 44 is selected to be the same, while the thickness of the third layer 46 is selected to be different. This allows for particularly advantageous properties to be achieved. Preferably, there is no intermediate layer between the first, second, and third layers.

[0072] Fig. 3 shows a schematically simplified representation of an expanded structure of an anode-free solid-state battery according to an embodiment of the present invention. Shown are a cathode current collector 10, a cathode 20 in the form of a layer, a solid-state electrolyte 30 in the form of a thin, free-standing layer, a multilayer ultrathin anode 40 according to the present invention, and an anode current collector 50.

[0073] The construction of a single-layer pouch cell requires at least the components shown in Fig. 3. These components are provided in suitable sizes and dimensions. According to this embodiment, these components include: a cathode current collector 10 attached with black thermoplastic polymer adhesive, a 2.1 cm x 2.1 cm cathode 20, a separator 30 (here a sulfide separator) measuring 2.5 cm x 2.5 cm, a 2.3 cm x 2.3 cm multilayer ultrathin anode 40, and an anode current collector 50 attached with black thermoplastic polymer adhesive.

[0074] Following the provision of the individual components for the assembly of a solid-state battery in the form of a single-layer pouch cell according to one embodiment of the present invention, the stacking is carried out analogously to the steps shown in Figure 3. The cell is assembled under conditions of exclusion of moisture and oxygen. For example, assembly is carried out in a glove box under the following conditions: H₂O < 0.1 ppm, O₂ < 0.1 ppm. The components are stacked and carefully aligned with each other in the sequence cathode current collector 10, cathode 20, separator 30, anode 40, and anode current collector 50.

[0075] After stacking, the pouch cell is sealed on three sides, for example, using an impulse sealer. In this example, the pouch cell is carefully lifted with tweezers and placed on an impulse sealer for sealing on three sides, where each of the three sides is sealed together. The now partially sealed pouch cell is then mounted on a plate, in this example an aluminum plate, for compression, specifically cold isostatic pressing (CIP). The pouch cell is also wrapped in a bag to prevent potential oil contamination during the CIP process. The pouch cell is compressed for a suitable duration and pressure. In the described example, the pouch cell is compressed for 30 minutes at a pressure of 500 MPa. Other parameters are possible and depend on the specific application.

[0076] After the CIP step, the still open fourth side of the pouch cell is vacuum-sealed. In this example, the pouch cell is returned to the glove box and the open side is sealed with a vacuum sealer, preferably under conditions of exclusion of moisture and oxygen.

[0077] Following the described manufacturing process, the pouch cell was tested for its properties. For this purpose, the compressed pouch cell was fitted with stainless steel end plates to ensure uniform pressure distribution during the cell cycle.

[0078] The pouch cell was tested at a C-rate of 0.1C and 0.2C for charging and discharging, respectively, at a temperature of 60°C. The solid-state battery with the multilayer anode according to the invention showed a significantly improved cycle performance compared to a solid-state battery with an anode current collector and a conventional anode that is not a multilayer anode according to the invention.

Claims

Mercedes-Benz Group AG Patent claims 1. Multilayer anode (40) for a solid-state battery, applied to an anode current collector (50), comprising or consisting of a first layer (42) and a second layer (44), wherein the first layer (42) comprises one or more metallic elements selected from the group consisting of silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As) and / or titanium (Ti), and the second layer (44) consists of a protective oxide layer comprising one or more oxides of silicon (Si), silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As) and / or titanium (Ti) contains or consists of, wherein the second layer (44) has a thickness of 5 nanometers to < 1 micrometer.

2. Multilayer anode (40) according to claim 1, characterized in that the multilayer anode (40) has a third layer (46) on the second layer (44) which has or consists of conductive carbon material.

3. Multilayer anode (40) according to claim 2, characterized in that the conductive carbon material is selected from carbon black, including acetylene carbon black, sewer carbon black, furnace carbon black, lamp carbon black, thermal black, carbon nanotubes, carbon nanofibers and / or graphene.

4. Multilayer anode (40) according to claim 1, characterized in that the first layer (42) has a thickness of 5 nanometers to 1 micrometer.

5. Multilayer anode (40) according to one of claims 1 to 4, characterized in that the third layer (46) has a thickness of 5 nanometers to 10 micrometers.

6. Multilayer anode (40) according to one of claims 1 to 5, characterized in that the anode current collector (50) comprises or consists of copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), indium (In), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li) or an alloy thereof, preferably consisting of copper foil, stainless steel foil or nickel foil.

7. Method for producing a multilayer anode (40) according to any one of claims 1 to 6, comprising (1) Providing an anode current collector (50), (2) Applying a first layer (42) to an anode current collector (50) comprising one or more metallic elements selected from the group consisting of silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As) and / or titanium (Ti); and (3) Applying a second layer (44) in the form of a protective oxide layer to the first layer (42) which contains or consists of one or more oxides of silicon (Si), silver (Ag), magnesium (Mg), gold (Au), palladium (Pd), aluminum (Al), bismuth (Bi), indium (In), tin (Sn), gallium (Ga), platinum (Pt), cadmium (Cd), germanium (Ge), selenium (Se), antimony (Sb), arsenic (As) and / or titanium (Ti).

8. Method according to claim 7, characterized in that step (3) is followed by a step (4) comprising: Applying a third layer (46) to the second layer (44), wherein the third layer (46) is selected from conductive carbon material, preferably selected from carbon black, including acetylene carbon black, sewer carbon black, furnace carbon black, lamp carbon black, thermal black, carbon nanotubes, carbon nanofibers and / or graphene.

9. Anode-free solid-state battery, characterized in that it has as an anode a multi-layer anode (40) according to one of claims 1 to 6.

10. Anode-free solid-state battery according to claim 9, characterized in that the anode-free solid-state battery is a secondary battery in pouch cell format.

11. Use of the anode-free solid-state battery according to one of claims 9 or 10 in an electrically powered vehicle (BEV).

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