Sandwich-structured, pre-lithiated anode electrode for all-solid-state batteries

Abstract

Anode electrode comprising: a current collector; a first anode layer disposed on the current collector and containing a first anode active material; a first pre-lithiation layer disposed on the first anode layer; and a second anode layer disposed on the first pre-lithiation layer and comprising a second anode active material, wherein the first anode layer contains the first anode active material in a range of 30 to 98 wt.%, a sulfide electrolyte in a range of 1 to 50 wt.% and a first binder in a range of 1 to 20 wt.%, and / or wherein the second anode layer comprises the second anode active material in a range of 30 to 97 wt.%, a sulfide electrolyte in a range of 1 to 50 wt.%, a first conductive additive in a range of 1 to 30 wt.%, and a fibrillating polymer binder in a range of 1 to 20 wt.%.

Description

INITIATIONThe information in this section is intended to generally illustrate the context of the disclosure. Work of the present inventors, insofar as described in this section, as well as aspects of the description that may not be prior art at the time of filing, are neither expressly nor silently admitted as prior art against the present disclosure.The present disclosure relates to battery cells, and more particularly, to a pre-lithiated anode electrode having a sandwich structure for an all-solid state battery.Electric vehicles (EVs), such as battery-powered electric vehicles (BEVs), hybrid vehicles, and / or fuel cell vehicles, include one or more electric machines and a battery system having one or more battery cells, modules, and / or packs. A power control system controls charging and / or discharging of the battery system during charging and / or driving. The manufacturers of EVs seek higher power density to increase the range of the vehicles.Lithium ion battery (LIB) cells are currently used for high power density applications. All-solid-state battery (ASSB) cells have improved properties with respect to abuse tolerance, performance and / or operating temperature range compared to LIB cells.CN 1 10 071 264 B discloses a method for producing a prelithiated silicon-carbon negative electrode having a film structure which contains a silicon-carbon active material and lithium phosphide.A prelithiated silicon-based negative electrode plate is described in CN 1 13 363 413 A.A method of manufacturing a negative electrode plate using a negative electrode slurry is disclosed in CN 1 12 201 481 A.CN 2 08 539 024 U discloses a further prelithiated negative electrode.SUMMARYAn anode electrode includes a current collector and a first anode layer disposed on the current collector and including a first anode active material. A first pre-lithiating layer is arranged on the first anode layer. A second anode layer is disposed on the first pre-lithiating layer and includes a second anode active material. According to the invention, the first anode layer contains the first anode active material in a range from 30 to 98 wt %, a sulfide electrolyte in a range from 1 to 50 wt % and a first binder in a range from 1 to 20 wt %, and / or the second anode layer comprises the second anode active material in a range from 30 to 97 wt %, a sulfide electrolyte in a range from 1 to 50 wt %, a first conductive additive in a range from 1 to 30 wt % and a fibrillation polymer binder in a range from 1 to 20 wt %.In other features, a second pre-lithiating layer is disposed on the second anode layer. On the second prelithiating layer, a third anode layer is arranged, which contains a third anode active material. The first anode active material is selected from a group consisting of a carbonaceous material, a metal oxide / sulfide, a lithium alloy type material, and combinations thereof. The first pre-lithiating layer is selected from a group consisting of lithium foil, stabilized lithium metal powder (SLMP), and lithium-doped material.In other features, the first anode layer has a thickness in the range of 5 μm to 200 μm, and the first pre-lithiating layer has a thickness in the range of 20 μm to 100 μm.The first anode active material is selected from a group consisting of a carbonaceous material, a metal oxide / sulfide material, a lithium alloy type material, and combinations thereof. The sulfide electrolyte is selected from a group consisting of pseudobinary sulfide, pseudoternary sulfide, pseudoquaternary sulfide, a halide-based sulfide electrolyte, a hydride-based sulfide electrolyte, and combinations thereof. The first binder is selected from a group consisting of: poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVD-FHFP), poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), and combinations thereof.The fibrillation polymer binder is selected from a group consisting of: polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA), ethylene tetrafluoroethylene (ETFE), or a combination thereof. The first conductive additive is selected from a group consisting of carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes, and combinations thereof.A battery cell includes the anode electrode, an electrolyte layer disposed adjacent to the anode electrode, a cathode electrode disposed adjacent to the electrolyte layer, and a second current collector disposed adjacent to the cathode electrode.In other features, the cathode electrode includes a sulfide electrolyte in a range of 1 to 50 wt %, a cathode active material in a range of 30 to 97 wt %, a first conductive additive in a range of 1 to 30 wt %, and a first binder in a range of 1 to 20 wt %. The cathode electrode comprises cathode active material selected from a group consisting of rock salt layered oxides, low voltage cathode material, surface coated active materials, doped cathode active materials, and combinations thereof.In other features, the first conductive additive is selected from a group consisting of carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes, and combinations thereof. The first binder is selected from a group consisting of: polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), and combinations thereof.A battery cell includes a first current collector. An anode electrode includes a first anode layer disposed on the first current collector and including a first anode active material in a range of 30 to 98 wt %, a sulfide electrolyte in a range of 1 to 50 wt %, and a first binder in a range of 1 to 20 wt %. A first pre-lithiating layer is arranged on the first anode layer. The first pre-lithiating layer is selected from a group consisting of lithium foil, stabilized lithium metal powder (SLMP), a lithium-doped material, and combinations thereof. A second anode layer is disposed on the first pre-lithiating layer and includes a second anode active material in a range of 30 to 97 wt %, a sulfide electrolyte in a range of 1 to 50 wt %, a first conductive additive in a range of 1 to 30 wt %, and a fibrillation polymer binder in a range of 1 to 20 wt %. An electrolyte layer is disposed adjacent to the anode electrode. A cathode electrode is arranged next to the electrolyte layer. A second current collector is disposed adjacent to the cathode electrode.In other features, the first anode active material is selected from a group consisting of a carbonaceous material, a metal oxide / sulfide, a lithium alloy type material, and combinations thereof. The first binder is selected from a group consisting of: poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVD-FHFP), poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), and combinations thereof.In other features, the fibrillation polymer binder is selected from a group consisting of: polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA), ethylene tetrafluoroethylene (ETFE), or a combination thereof. The first conductive additive is selected from a group consisting of carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes, and combinations thereof.In other features, the cathode electrode includes a sulfide electrolyte in a range of 1 to 50 wt %, a cathode active material in a range of 30 to 97 wt %, a conductive additive in a range of 1 to 30 wt %, and a binder in a range of 1 to 20 wt %. The cathode electrode comprises cathode active material selected from a group consisting of rock salt layered oxides, low voltage cathode material, surface coated active materials, doped cathode active materials, and combinations thereof.In other features, the conductive additive is selected from a group consisting of carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes, and combinations thereof. The binder is selected from a group consisting of: polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), and combinations thereof.Further areas of applicability of the present disclosure will become apparent from the detailed description, claims and drawings. The detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.BRIEF DESCRIPTION OF THE DRAWINGSThe present disclosure will become more fully apparent from the detailed description and the accompanying drawings, in which: FIG. 1 is a side cross-sectional view of an example of an anode electrode and a lithium metal layer; FIGS. 2A to 2C are side cross-sectional views of an example of an ASSB having the anode electrode and the lithium metal layer before the forming pressure, after the forming pressure, and after the complete pre-lithiating; FIGS. 3A and 3B are side cross-sectional views of an example of a sandwich-structured pre-lithiated anode electrode before and after pressing according to the present disclosure; FIGS. 4A and 4B are side cross-sectional views of an example of a sandwich-structured pre-lithiated anode electrode before and after pressing according to the present disclosure; and FIGS. 5-8 are side cross-sectional views of examples of sandwich-structured pre-lithiated anode electrodes according to the present disclosure.In the drawings, reference numerals may be reused to designate similar and / or identical elements.DETAILED DESCRIPTIONWhile the battery cells according to the present disclosure will be described below in connection with a vehicle, the battery cells according to the present disclosure may also be used in other applications.An all solid state battery (ASSB) includes anode electrodes having a lithium metal layer interposed between two anode active material layers to form a pre-lithiated anode electrode having a sandwich structure. This arrangement is compatible with existing manufacturing equipment (e.g. roll pressing) and allows adjustable anode pre-lithography by adjusting the pre-lithography layer thickness. This arrangement also increases the efficiency of lithium utilization by increasing the reaction area between Li and anode material. Consequently, an ASSB with the sandwiched pre-lithiated anode electrode can effectively compensate for the loss of active lithium and improve the cycle performance of the ASSB.Sulfide electrolyte all solid state battery (ASSB) cells have improved properties in abuse tolerance, performance, and / or operating temperature range compared to current lithium ion battery (LIB) cells. However, thermodynamically unstable sulfides inevitably decompose. For example, Li 6 PS 5 Cl is stable only in a voltage range of 1.9 V to 2.3 V as compared with Li / Li +. Irreversible Li +- ion intercalation or extraction may also occur for the sulfide contacting the cathode surface, the anode surface, or the current collector.In FIG. 1, an example of an anode electrode 20 is shown having a current collector 28, an anode layer 24 disposed on the current collector 28, and a pre-lithiating layer 32, e.g., lithium foil or powder.Referring now to FIGS. 2A through 2C, an example of an ASSB 38 having the anode electrode 20 is illustrated. The ASSB 38 also includes a sulfide electrolyte layer 36 disposed on the pre-lithiating layer 32. The ASSB 38 includes a cathode active material 40 disposed on the sulfide electrolyte layer 36, and a current collector 42 disposed on the cathode active material 40.In FIG. 2A, the ASSB 38 is shown prior to forming pressure. In FIG. 2B, the ASSB 38 is shown after the forming pressure. The typical forming pressure is more than 300 MPa and the forming time of the battery is 4 to 6 minutes. In FIG. 2C, the ASSB 38 is shown after complete prelithiation.This manufacturing method presents technical challenges. During manufacture, the lithium layer may adhere to rolls, calender rolls, press machines and / or other equipment. Creep deformation of the lithium layer by compression (as shown in FIG. 2B ) may result in mechanically induced cell short. Voids may be formed and lithium may be embedded in the sulfide electrolyte layer (as shown in FIG. 2C ).FIGS. 3A and 3B illustrate an example of a sandwich-structured, pre-lithiated anode electrode 110. In FIG. 3A, the sandwich-structured pre-lithiated anode electrode 100 is illustrated prior to pressing and includes a first anode layer 124 disposed on a current collector 120, a first pre-lithiating layer 128 disposed on the first anode layer 124, and a second anode layer 132 disposed on the first pre-lithiating layer 128.In some examples, the first anode layer 124 comprises a conventional solid state anode electrode having a thickness in the range of 5 μm to 200 μm. In some examples, the first anode layer 124 includes an anode active material in a range of 30 to 98 wt %, a sulfide electrolyte in a range of 1 to 50 wt %, and a binder in a range of 1 to 20 wt %.In some examples, the second anode layer 132 comprises a free-standing solid-state membrane having sufficient strength to be rolled, handled, and unrolled during an electrode fabrication process without further support layers.In some examples, the second anode layer 132 has a thickness in the range of 10 μm to 200 μm. In some examples, the second anode layer 132 is solvent-free. In some examples, the second anode layer 132 includes an alloy-like anode film (e.g., an indium (In) foil). In some examples, the second anode layer 132 has a high polymer content. In FIG. 3B, the sandwich-structured, pre-lithiated anode electrode is shown after pressing. As can be seen, pressing may result in deformation of one or more layers of the anode electrode.FIGS. 4A and 4B illustrate an example of a sandwich-structured, pre-lithiated anode electrode 160. In FIG. 4A, the sandwich-structured pre-lithiated anode electrode 160 is shown prior to pressing and includes the first anode layer 124, the first pre-lithiating layer 128, the second anode layer 132, a second pre-lithiating layer 162, and a third anode layer 164.In FIG. 4B, the sandwich-structured, pre-lithiated anode electrode is shown after pressing. Some deformation of the first pre-lithiating layer 128 and the second pre-lithiating layer 162 may occur due to the pressure during battery manufacture. More generally, the sandwich-structured pre-lithiated anode electrode 160 may comprise L anode active material layers (where L is an integer greater than 1) and L-1 pre-lithiating layers. As can be seen, the L anode active material layers may use the same or different chemistry and / or have the same or different thickness.The first and / or second pre-lithiating layers 128, 162 are protected by the anode layers 124, 132, and 164 during battery manufacturing printing without damaging the sulfide electrolyte layer. The pre-lithiating layer may be pressurized under the forming pressure of the all-solid-state battery, because the forming of the lithium is limited to the lithium reaction in the anode active material. The pre-lithography is completed during battery manufacture without voids being formed in the anode electrode, which improves battery performance. Due to the effective pre-lithiating produced by this approach, the battery cell with the pre-lithiated anode electrode sandwiched therebetween has a higher capacity and better performance than similar battery cells without pre-lithiating.In FIGS. 5 to 8, examples of sandwich-structured, prelithiated anode electrodes are shown. In FIG. 5, the first anode layer 124 and the second anode layer 132 are shown with electrode material 210, sulfide electrolyte 214, and polytetrafluoroethylene (PTFE) fibrils 218.In FIG. 6, the first anode layer 124 includes the electrode material 210, the sulfide electrolyte 214, and the polytetrafluoroethylene (PTFE) fibrils 218. The second anode layer 132 includes the electrode material 210 and the sulfide electrolyte 214.In FIG. 7, the first anode layer 124 includes the electrode material 210, the sulfide electrolyte 214, and the polytetrafluoroethylene (PTFE) fibrils 218. The second anode layer 132 includes the electrode material 210.In FIG. 8, the first anode layer 124 and the second anode layer 132 include the electrode material 210.In some examples, the first anode active material layer 124 comprises a free-standing dry anode or a wet-coated anode. In some examples, the first anode layer 124 has a thickness in the range of 5 μm to 200 μm. In some examples, the first anode layer 124 includes an anode active material in a range of 30 to 98 wt %, a sulfide electrolyte in a range of 1 to 50 wt %, and a binder in a range of 1 to 20 wt %.In some examples, the first anode active material layer 124 comprises anode active material selected from a group consisting of: carbonaceous material (e.g., graphite, hard carbon, soft carbon, etc.), metal oxide / sulfide (e.g., TiO 2, FeS, or the like), Li 4 Ti 5 O 12 or other lithium-accepting anode materials), lithium alloy-like material (e.g., silicon, transition metals (e.g., tin (Sn), indium (In)), or combinations thereof.In some examples, the first anode active material layer 124 comprises a conductive additive selected from a group consisting of carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes, other electronically conductive additives, and combinations thereof.In some examples, the first anode active material layer 124 comprises binder materials selected from a group consisting of: poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVD-FHFP), poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), and combinations thereof.In some examples, the second anode active material layer 134 is a free-standing membrane having sufficient strength to be rolled, handled, and unrolled during an electrode fabrication process without additional support members. In some examples, the second anode active material layer 134 has a thickness in the range of 20 μm to 200 μm.In some examples, the second anode active material layer 134 comprises a solvent-free solid-state membrane and includes anode active material in a range of 30 to 97 wt %, a sulfide electrolyte in a range of 1 to 50 wt %, a conductive additive in a range of 1 to 30 wt %, and a fibrillation polymer binder in a range of 1 to 20 wt %.In some examples, the fibrillation polymer binder is selected from a group consisting of: polytetrafluoroethylene (PTFE) binder, fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA), ethylene tetrafluoroethylene (ETFE), or a combination thereof. When the fibrillating polymer binder is used, fibrils are formed during pressing, which contribute to holding the second anode active material layer together.In some examples, the second anode active material layer 134 comprises an anode active material selected from a group consisting of: carbonaceous material (e.g., graphite, hard carbon, soft carbon, etc.), metal oxide / sulfide ((e.g., TiO 2, FeS, or the like), Li 4 Ti 5 O 12 or other lithium-accepting anode materials), lithium alloy-like material (e.g., silicon, transition metals (e.g., tin (Sn), indium (In)), or combinations thereof.In some examples, the second anode active material layer 134 comprises a conductive additive selected from a group consisting of carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes, other electronically conductive additives, and combinations thereof.In other examples, the second anode active material layer 134 includes an alloy-type anode film selected from a group consisting of a pure alloy-type anode film (100 wt %), a Li alloy-type semiconductor material (e.g., a silicon film), and a Li alloy-type metal film (e.g., a Sn or In film).In other examples, the second anode active material layer 134 comprises a high polymer content film containing anode active material in a range of 1 to 50 wt %, sulfide electrolyte in a range of 1 to 50 wt %, a conductive additive in a range of 1 to 30 wt %, and a polymeric binder of more than 50 wt %. In some examples, polymeric binder materials are selected from a group consisting of: poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride-cohexafluoropropylene) (PVdF-HFP), poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), styrene ethylene butylene styrene copolymer (SEBS), and combinations thereof.In some examples, the one or more pre-lithiating layers are integrated between a first solid anode layer and a second solid anode layer that provide active Li sources for anode pre-lithiating. In some examples, the one or more pre-lithiating layers are selected from a group consisting of lithium foil, stabilized lithium metal powder (SLMP), and lithium-doped material (e.g., Li / Al alloy, Li-doped silicon or silicon oxide (SiO), or silicon compound).In some examples, the one or more pre-lithiating layers comprise a free-standing Li foil having a thickness in the range of 20 μm to 100 μm. In some examples, the one or more pre-lithiating layers completely or partially cover the region between the first anode layer and the second anode layer to achieve a predetermined pre-lithiating amount.In other examples, the one or more pre-lithiating layers are applied to the first anode layer and have a thickness in the range of 2 μm to 100 μm. In some examples, the one or more pre-lithiating layers comprise SLMP deposited on the first anode layer.In some examples, the sulfide electrolyte layer includes a sulfide-based sulfide electrolyte selected from a group consisting of pseudobinary sulfide, pseudoternar sulfide, and pseudoquaternary sulfide. Examples of pseudobinary sulfide systems are Li 2 S-P 2 S 5- systems (such as Li 3 PS 4, Li 7 P 3 S 11 and Li 9,6 P 3 S12), Li2S-SnS2system (e.g., Li4SnS4), Li2S-SiS2system, Li 2 S-GeS 2- system, Li 2 S-B 2 S 3- system, Li 2 S-Ga 2 S 3- system, Li 2 S-P 2 S3system, and Li2S-Al2S3system. Examples of pseudoternary sulfide are Li 2 O-Li 2 S-P 2 S 5- System, Li 2 S-P 2 S 5- P 2 O 5- System, Li 2 S-P 2 S 5- GeS 2- systems (such as Li 3,25 Ge 0,25 P 0,75 S 4 and Li 10 GeP 2 S12), Li2S-P2S5LiX systems (where X is F, Cl, Br or I) (such as Li6PS5Br, Li 6 PS 5 Cl, Li 7 P 2 S 8 I and Li 4 PS 4 I), Li 2 S-As 2 S 5- SnS2system (Li3,833Sn0,833As0,166S4), Li2S-P2S5-Al2S3system, Li 2 S-LiX-SiS 2( X=F, Cl, Br, I) system, 0.4Li-0.6Li 4 SnS 4 and Li 11 Si 2 PS 12. Examples of pseudoquaternary sulfide are Li 2 O-Li 2 S-P 2 S 5- P 2 O 5- System, Li 9,54 Si 1,74 P 1,44 S 11,7 Cl0,3, Li 7 P 2,9 Mn 0,1 S 10,7 I 0,3 and Li 10,3 Sn 0,21 S 1,08] P 1,65 S 12.In some examples, the sulfide electrolyte layer comprises a halide-based sulfide electrolyte, a hydride-based sulfide electrolyte, or another sulfide electrolyte having low grain boundary resistance. Examples of halide-based sulfide electrolyte include Li 3 YCI 6, Li 3 InCl 6, Li 3 YBR 6, LiI, Li 2 CdC 14, Li 2 MgC 14, Li2Cd14, Li2Zn14, and Li3OCl. Examples of hydride-based sulfide electrolyte include LiBH 4, LiBH 4- LiX (X=Cl, Br, or I), LiNH 2, Li 2 NH, LiBH 4- LiNH 2 and Li 3 AlH 6.In some examples, a cathode electrode comprises sulfide electrolyte in a range of 1 to 50 wt %, cathode active material in a range of 30 to 97 wt %, a conductive additive in a range of 1 to 30 wt %, and binder in a range of 1 to 20 wt %. In some examples, the cathode electrode has a thickness in the range of 10 μm to 500 μm (e.g., 40 μm).In some examples, a cathode active material is selected from a group consisting of rock salt layered oxides, low voltage cathode material, and surface coated and / or doped cathode active materials. Examples of layered oxides of rock salt are LiCoO 2, LiNi x Mn y Co 1-x-y O 21, LiNi x Mn y Al 1-x-y O 2, LiNi x Mn1-xO2, Li1+xMO2, spinel (LiMn2O4, LiNi 0,5 Mn 1,5 O 4, polyanion cathode (LiV 2( PO 4)3), olivine cathode (LiFePO 4 and LiMn x Fe 1-x PO 4) and other lithium transition metal oxides. Examples of the surface-coated and / or doped cathode materials described above are, for example, LiMnO 3 coated LiMn 2 O 4, Li 2 ZrO 3 or Li 3 PO 4 coated LiNi x Mn y Co 1-x-y O_NERmn_and Al-doped LiMn_NERmn_O_NERmn_. Examples of low voltage cathode materials are lithium-containing metal oxide / sulfide (e.g., LiTiS 2), lithium sulfide, sulfur, and combinations thereof.In some examples, the conductive additive is selected from a group consisting of carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes, and other electronically conductive additives. In some examples, the binder is selected from a group consisting of: polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), and combinations thereof.The foregoing description is merely illustrative in nature and is not intended to limit the disclosure, its application, or use. The broad teachings of the disclosure may be practiced in a variety of forms. Therefore, although this disclosure includes particular examples, the true scope of the disclosure should not be so limited as other modifications will be apparent upon a study of the drawings, the specification, and the following claims. It should be appreciated that one or more steps within a method may be performed in different order (or simultaneously) without altering the principles of the present disclosure. Although each of the embodiments is described above with certain features, any one or more of those features described with respect to any embodiment of the disclosure may be implemented in any of the other embodiments and / or combined with features of any other embodiment, although that combination is not explicitly described. In other words, the described embodiments are not mutually exclusive, and permutations of one or more embodiments with each other remain within the scope of this disclosure.Spatial and functional relationships between elements (e.g., between modules, circuit elements, semiconductor layers, etc.) are described with various terms, e.g., "connected," "engaged," "coupled," "adjacent," "next," "on," "over," "under," and "arranged.". When a relationship between first and second elements is not expressly described as "direct" in the above disclosure, this relationship may be a direct relationship in which no other intervening elements are present between the first and second elements, but may also be an indirect relationship in which one or more intervening elements (either spatially or functionally) are present between the first and second elements. As used herein, the phrase "at least one of A, B, and C" should be construed as logical (A OR B OR C) using a non-exclusive logical OR, and should not be understood as "at least one of A, at least one of B, and at least one of C.".In the figures, the direction of an arrow, as indicated by the arrow head, generally indicates the flow of information (e.g., data or instructions) of interest for the display. For example, if element A and element B exchange a variety of information, but the information transmitted from element A to element B is relevant for presentation, the arrow may point from element A to element B. This unidirectional arrow does not imply that no further information is transmitted from element B to element A. In addition, element B for information sent from element A to element B may send requests for or acknowledgments for the information to element A.

Claims

An anode electrode, comprising: a current collector; a first anode layer disposed on the current collector and containing a first anode active material; a first pre-lithiating layer disposed on the first anode layer; and a second anode layer disposed on the first pre-lithiating layer and comprising a second anode active material, wherein the first anode layer contains the first anode active material in a range of 30 to 98 wt %, a sulfide electrolyte in a range of 1 to 50 wt %, and a first binder in a range of 1 to 20 wt %, and / or wherein the second anode layer comprises the second anode active material in a range of 30 to 97 wt %, a sulfide electrolyte in a range of 1 to 50 wt %, a first conductive additive in a range of 1 to 30 wt %, and a fibrillation polymer binder in a range of 1 to 20 wt %.The anode electrode of claim 1, further comprising: a second pre-lithiating layer disposed on the second anode layer; and a third anode layer disposed on the second pre-lithiating layer and comprising a third anode active material.The anode electrode of claim 1, wherein: the first anode active material is selected from a group consisting of carbonaceous material, a metal oxide / sulfide, a lithium alloy type material, and combinations thereof, and the first pre-lithiating layer is selected from a group consisting of lithium foil, stabilized lithium metal powder (SLMP), and lithium doped material.The anode electrode of claim 1, wherein: the first anode layer has a thickness in a range of 5 μm to 200 μm, and the first pre-lithiating layer has a thickness in a range of 20 μm to 100 μm.The anode electrode of claim 1, wherein the first anode active material is selected from a group consisting of a carbonaceous material, a metal oxide / sulfide material, a lithium alloy type material, and combinations thereof.The anode electrode of claim 1, wherein the sulfide electrolyte is selected from a group consisting of pseudobinary sulfide, pseudoternar sulfide, pseudoquaternary sulfide, a halide-based sulfide electrolyte, a hydride-based sulfide electrolyte, and combinations thereof.The anode electrode of claim 1, wherein the first binder is selected from a group consisting of: poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVD-FHFP), poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), and combinations thereof.The anode electrode of claim 1, wherein the fibrillation polymer binder is selected from a group consisting of: polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA), ethylene tetrafluoroethylene (ETFE), or a combination thereof.

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