High power cathode electrode for solid state battery

Abstract

A solid state battery cell includes A anode electrodes including an anode active material layer disposed on an anode current collector and C cathode electrodes including a cathode active material layer disposed on a cathode current collector. The cathode active material layer comprises a cathode active material comprising particles comprising an outer layer of a material selected from the group consisting of LiNbO3, Li2ZrO3, Li3PO4, and combinations thereof. The D50 size of the solid electrolyte is 4 [mu] m to 12 [mu] m. The S separators are disposed between the A anode electrodes and the C cathode electrodes, where A, C and S are integers greater than 1.

Description

Technical Field

[0001] The present disclosure relates to battery cells and, more particularly, to high power cathode electrodes for solid-state batteries. Background Art

[0002] The information provided in this section is intended to generally introduce the background of the present disclosure. To the extent that work currently named as inventors is described in this section, and aspects of the specification that may not have been otherwise identified as prior art at the time of filing, are not admitted, either explicitly or implicitly, as prior art to the present disclosure.

[0003] The present disclosure relates to battery cells and, more particularly, to high power cathode electrodes for solid-state batteries.

[0004] Electric vehicles (EVs), such as battery electric vehicles (BEVs), hybrid vehicles, and / or fuel cell vehicles, include one or more motors and a battery system including one or more battery cells, modules, and / or battery packs. A power control system is used to control the charging and / or discharging of the battery system during charging and / or driving. Summary of the invention

[0005] The solid-state battery cell includes A anode electrodes and C cathode electrodes, the anode electrode including an anode active material layer disposed on an anode current collector, the cathode electrode including a cathode active material layer disposed on a cathode current collector. The cathode active material layer includes a cathode active material comprising particles, the particles including an outer layer of a material selected from the group consisting of LiNbO3, Li2ZrO3, Li3PO4, and combinations thereof. The solid electrolyte has a D 50 S separators are arranged between A anode electrodes and C cathode electrodes, where A, C and S are integers greater than 1.

[0006] In other features, the particles include lithium-nickel-cobalt-manganese (NMC) particles and the outer layer includes LiNbO3. The NMC particles have a 2 μm <D 50 <5 μm in diameter. Nickel accounts for 50 to 72 mol %, manganese accounts for 8 to 40 mol % of the NMC particles, and cobalt accounts for 10 to 20 mol % of the NMC particles. The outer layer has a thickness of 7 nm to 13 nm. The solid electrolyte in the cathode active material layer has a diameter D of <15 μm. 90 The solid electrolyte comprises a sulfide solid electrolyte selected from pseudo binary sulfide, pseudo ternary sulfide and pseudo quaternary sulfide.

[0007] In other features, the solid electrolyte is selected from a halide-based solid electrolyte and a hydride-based solid electrolyte. The cathode active material is selected from rock salt layered oxides, spinels, polyanion cathodes, olivine cathodes, other lithium transition metal oxides, surface coatings and / or doped cathode materials and combinations thereof. The cathode active material layer also includes a conductive additive selected from carbon black, graphite, graphene, graphene oxide, SuperP, acetylene black, carbon nanofibers, carbon nanotubes and combinations thereof. The cathode active material layer also includes a binder selected from polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS) and combinations thereof.

[0008] A dry method for making a cathode electrode for a solid-state battery cell comprises mixing a cathode active material comprising particles having an outer layer selected from the group consisting of LiNbO3, Li2ZrO3, Li3PO4 and combinations thereof with a 50 A solid electrolyte having particles with a size of 4 μm to 12 μm is mixed. A binder and a conductive additive are added to the cathode active material and the solid electrolyte. A substrate is coated with the cathode active material, the solid electrolyte, the binder and the conductive additive.

[0009] In other features, the cathode active material is selected from rock salt layered oxides, spinels, polyanion cathodes, olivine cathodes, other lithium transition metal oxides, and surface coated and / or doped cathode materials. The solid electrolyte is selected from pseudo binary sulfides, pseudo ternary sulfides, pseudo quaternary sulfides, halide-based solid electrolytes, and hydride-based solid electrolytes.

[0010] In other features, the conductive additive is selected from carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers and carbon nanotubes. The binder is selected from polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP) fibrils, perfluoroalkoxy alkane (PFA) fibrils and / or ethylene tetrafluoroethylene (ETFE) fibrils.

[0011] In other features, the cathode active material comprises a 2 μm diameter <D 50 Lithium-nickel-cobalt-manganese (NMC) particles <5 μm, and an outer layer comprising LiNbO3 with a thickness of 7 nm to 13 nm. Nickel accounts for 50 to 72 mol %, Mn accounts for 8 to 40 mol % of the NMC particles, and Co accounts for 10 to 20 mol % of the NMC particles.

[0012] A wet process for making a cathode electrode for a solid-state battery cell, comprising producing a mixture comprising a cathode active material, a solid electrolyte, a binder, a conductive additive, and a solvent, wherein the cathode active material comprises particles having an outer layer selected from the group consisting of LiNbO3, Li2ZrO3, Li3PO4, and combinations thereof, and the solid electrolyte comprises D 50 Particles with a size of 4 μm to 12 μm. The method comprises coating the mixture onto a substrate.

[0013] In other features, the cathode active material is selected from rock salt layered oxides, spinels, polyanion cathodes, olivine cathodes, other lithium transition metal oxides, and surface coated and / or doped cathode materials. The solid electrolyte is selected from pseudo binary sulfides, pseudo ternary sulfides, pseudo quaternary sulfides, halide-based solid electrolytes, and hydride-based solid electrolytes.

[0014] In other features, the conductive additive is selected from carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers and carbon nanotubes. The binder is selected from sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), and styrene-butadiene-styrene copolymer (SBS).

[0015] In other features, the cathode active material comprises a 2 μm diameter <D 50 Lithium-nickel-cobalt-manganese (NMC) particles <5 μm, and an outer layer comprising LiNbO3 with a thickness of 7 nm to 13 nm. Nickel accounts for 50 to 72 mol %, manganese accounts for 8 to 40 mol % of the NMC particles, and cobalt accounts for 10 to 20 mol % of the NMC particles.

[0016] The present invention discloses the following scheme:

[0017] Solution 1. A solid-state battery cell comprising:

[0018] A anode electrode comprising an anode active material layer disposed on an anode current collector;

[0019] C cathode electrodes, comprising a cathode active material layer disposed on a cathode current collector, wherein the cathode active material layer comprises:

[0020] A cathode active material comprising particles comprising an outer layer of a material selected from the group consisting of LiNbO3, Li2ZrO3, Li3PO4, and combinations thereof; and

[0021] A solid electrolyte having a D of 4 μm to 12 μm 50 size; and

[0022] S separators are arranged between the A anode electrodes and the C cathode electrodes, wherein A, C and S are integers greater than 1.

[0023] Option 2. A solid-state battery cell according to Option 1, wherein the particles include lithium-nickel-cobalt-manganese (NMC) particles and the outer layer includes LiNbO3.

[0024] Option 3. A solid-state battery cell according to Option 2, wherein the NMC particles have a diameter of 2 μm. <D 50 <5μm in diameter.

[0025] Option 4. A solid-state battery cell according to Option 2, wherein nickel accounts for 50 to 72 mol% of the NMC particles, manganese accounts for 8 to 40 mol% of the NMC particles, and cobalt accounts for 10 to 20 mol% of the NMC particles.

[0026] Option 5. A solid-state battery cell according to Option 1, wherein the outer layer has a thickness of 7nm to 13nm.

[0027] Option 6. A solid-state battery cell according to Option 1, wherein the solid electrolyte in the cathode active material layer has a diameter D of <15 μm 90 .

[0028] Option 7. A solid-state battery cell according to Option 1, wherein the solid electrolyte comprises a sulfide solid electrolyte selected from pseudo-binary sulfides, pseudo-ternary sulfides and pseudo-quaternary sulfides.

[0029] Option 8. A solid-state battery cell according to Option 1, wherein the solid electrolyte is selected from a halide-based solid electrolyte and a hydride-based solid electrolyte.

[0030] Option 9. A solid-state battery cell according to Option 1, wherein the cathode active material is selected from rock salt layered oxides, spinels, polyanion cathodes, olivine cathodes, other lithium transition metal oxides, surface-coated and / or doped cathode materials and combinations thereof.

[0031] Option 10. A solid-state battery cell according to Option 1, wherein the cathode active material layer further comprises a conductive additive selected from carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes and combinations thereof.

[0032] Option 11. A solid-state battery cell according to Option 1, wherein the cathode active material layer also contains a binder selected from polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS) and combinations thereof.

[0033] Solution 12. A dry manufacturing method for a cathode electrode for a solid-state battery cell, comprising:

[0034] A cathode active material comprising particles having an outer layer selected from the group consisting of LiNbO3, Li2ZrO3, Li3PO4 and combinations thereof is mixed with a 50 A solid electrolyte mixture of particles having a size of 4 μm to 12 μm; and

[0035] Adding a binder and a conductive additive to the cathode active material and the solid electrolyte; and

[0036] A substrate is coated with the cathode active material, the solid electrolyte, the binder, and the conductive additive.

[0037] Scheme 13. The dry manufacturing method according to Scheme 12, wherein:

[0038] The cathode active material is selected from rock salt layered oxides, spinels, polyanion cathodes, olivine cathodes, other lithium transition metal oxides, and surface coated and / or doped cathode materials, and

[0039] The solid electrolyte is selected from the group consisting of pseudo binary sulfides, pseudo ternary sulfides, pseudo quaternary sulfides, halide-based solid electrolytes, and hydride-based solid electrolytes.

[0040] Scheme 14. The dry manufacturing method according to Scheme 12, wherein:

[0041] The conductive additive is selected from carbon black, graphite, graphene, graphene oxide, SuperP, acetylene black, carbon nanofibers and carbon nanotubes, and

[0042] The binder is selected from polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP) fibrils, perfluoroalkoxyalkane (PFA) fibrils and / or ethylene tetrafluoroethylene (ETFE) fibrils.

[0043] Scheme 15. The dry manufacturing method according to Scheme 12, wherein:

[0044] The cathode active material comprises a 2 μm diameter <D 50Lithium-nickel-cobalt-manganese (NMC) particles <5 μm with an outer layer comprising LiNbO3 with a thickness of 7 nm to 13 nm, and

[0045] Nickel accounts for 50 to 72 mol % of the NMC particles, Mn accounts for 8 to 40 mol % of the NMC particles, and Co accounts for 10 to 20 mol % of the NMC particles.

[0046] Scheme 16. A wet manufacturing method for a cathode electrode for a solid-state battery cell, comprising:

[0047] A mixture is formed comprising:

[0048] A cathode active material comprising particles having an outer layer selected from the group consisting of LiNbO3, Li2ZrO3, Li3PO4 and combinations thereof,

[0049] A solid electrolyte comprising a D having a diameter of 4 μm to 12 μm 50 Size of particles, binder,

[0050] Conductive additives, and

[0051] Solvents; and

[0052] The mixture is applied to a substrate.

[0053] Scheme 17. The wet manufacturing method according to Scheme 16, wherein:

[0054] The cathode active material is selected from rock salt layered oxides, spinels, polyanion cathodes, olivine cathodes, other lithium transition metal oxides, and surface coated and / or doped cathode materials, and

[0055] The solid electrolyte is selected from the group consisting of pseudo binary sulfides, pseudo ternary sulfides, pseudo quaternary sulfides, halide-based solid electrolytes, and hydride-based solid electrolytes.

[0056] Scheme 18. The wet manufacturing method according to Scheme 16, wherein:

[0057] The conductive additive is selected from carbon black, graphite, graphene, graphene oxide, SuperP, acetylene black, carbon nanofibers and carbon nanotubes, and

[0058] The binder is selected from sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), and styrene-butadiene-styrene copolymer (SBS).

[0059] Scheme 19. The wet manufacturing method according to Scheme 16, wherein:

[0060] The cathode active material comprises a 2 μm diameter <D 50 <5 μm lithium-nickel-cobalt-manganese (NMC) particles, and the outer layer comprises LiNbO3 with a thickness of 7 nm to 13 nm, and

[0061] Nickel comprises 50 to 72 mol % of the NMC particles, manganese comprises 8 to 40 mol % of the NMC particles, and cobalt comprises 10 to 20 mol % of the NMC particles.

[0062] 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 to be illustrative only and are not intended to limit the scope of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] The present disclosure will be more fully understood through the detailed description and accompanying drawings, in which:

[0064] Figure 1 is a side cross-sectional view of an example of a solid-state battery cell according to the present disclosure, the solid-state battery cell including a cathode electrode, an anode electrode, and a separator disposed in a battery cell housing;

[0065] Figure 2 is a more detailed side cross-sectional view of an example of a solid-state battery cell including a cathode electrode, an anode electrode, and a separator according to the present disclosure;

[0066] Figure 3 The present invention discloses a battery having lithium niobate (LiNbO3), lithium zirconate (Li2ZrO3) and / or lithium phosphate (Li3PO 4) A side cross-sectional view of a cathode active material particle of the outer layer produced;

[0067] Figure 4A is a graph illustrating the variation of voltage with capacity for solid electrolytes of different sizes;

[0068] Figure 4B is a graph illustrating impedance for solid electrolytes of different sizes;

[0069] Figure 4C is a graph illustrating the capacity as a function of the number of cycles for solid electrolytes of different sizes;

[0070] Figure 5 is a flow chart illustrating an example of dry processing of a cathode electrode according to the present disclosure;

[0071] Figure 6 is a flow chart illustrating an example of wet processing of a cathode electrode according to the present disclosure;

[0072] Figure 7 is an enlarged view of a solid electrolyte and electrodes of solid electrolytes of different sizes according to the present disclosure; and

[0073] Figure 8 is an enlarged view illustrating dispersion of a solid electrolyte in a cathode electrode for solid electrolytes of different sizes according to the present disclosure.

[0074] Among the drawings, reference numerals may be repeated to identify similar and / or identical elements. DETAILED DESCRIPTION

[0075] Although the high power cathode for a solid state battery (SSB) cell according to the present disclosure is illustrated in the context of an electric vehicle, the high power cathode for a solid state battery cell may be used in stationary applications and / or other applications.

[0076] Sulfide electrolytes can provide comparable ionic conductivity to carbonate-based electrolytes. However, the power of composite cathode electrodes using sulfide electrolytes is hampered by unfavorable ionic conduction due to sluggish ion transport in the active material / solid electrolyte interface and poor solid electrolyte percolation within the electrode.

[0077] A high power cathode electrode for an all-solid-state battery (ASSB) according to the present disclosure includes single crystal cathode particles including an outer layer comprising lithium niobate (LiNbO3), lithium zirconate (Li2ZrO3) and / or lithium phosphate (Li3PO4) to suppress interfacial side reactions. The cathode particles are used together with a solid electrolyte having a predetermined size to achieve an efficient ion transport path within the cathode electrode. When the solid electrolyte particles in the cathode are too small, high solid electrolyte percolation occurs and lower ion transport occurs. The larger the solid electrolyte particles, the higher the porosity and the worse the solid electrolyte percolation. Similarly, the thickness of the coating on the cathode particles is tailored to prevent chemical reactions (which occur in the absence of the coating) while optimizing lithium ion transport.

[0078] For example, the cathode electrode may include lithium nickel manganese cobalt (NMC) particles coated with a lithium niobate (LiNbO3) coating (e.g., having a thickness of 10 μm) to suppress interfacial side reactions. 50 =8 μm) is selected to achieve an efficient ion transport path within the cathode electrode. For example, the high-power composite cathode electrode can provide a 3C discharge capacity of 88 mAh / g and a 5C discharge capacity of 74 mAh / g at 25°C.

[0079] Reference now Figure 1, the solid-state battery cell 10 includes C cathode electrodes 20, A anode electrodes 40, and S separators 32, which are arranged in a predetermined order in a battery stack 12 located in a housing 50, where C, S, and A are integers greater than 0. The C cathode electrodes 20-1, 20-2, ..., and 20-C include a cathode active layer 24 arranged on one or both sides of a cathode current collector 26. The A anode electrodes 40-1, 40-2, ..., and 40-A include an anode active layer 42 arranged on one or both sides of an anode current collector 46.

[0080] In some instances, anode active layer 42 and / or cathode active layer 24 are free-standing electrodes adjacent to (or attached to) current collector arrangement. In some instances, anode active layer 42 and / or cathode active layer 24 include a coating applied to the current collector, and the coating includes one or more active materials, one or more conductive fillers / additives, and / or one or more adhesive materials. In some instances, cathode current collector 26 and / or anode current collector 46 include a wire mesh, foil and / or porous metal mesh. In some instances, the current collector is made of one or more materials selected from copper, stainless steel, brass, bronze, zinc, aluminum and / or its alloy. External pole ears 28 and 48 can be connected to the current collectors of cathode electrode and anode electrode on the same side or opposite side of the battery stack.

[0081] Reference now Figure 2 and Figure 3 , shows a more detailed example of a solid-state battery cell. Figure 2 , cathode active material layer 24 includes cathode active material 210 and solid electrolyte 212 (e.g., sulfide solid electrolyte). Separator 32 includes solid electrolyte 220 (e.g., sulfide solid electrolyte). Anode active material layer 40 includes anode active material 230 and solid electrolyte 232 (e.g., sulfide solid electrolyte).

[0082] exist Figure 3 , the cathode active material 210 includes a single crystal particle 250 of the cathode active material and an outer layer 252 coated or otherwise applied on the radially outer surface of the particle 250. In some examples, the particle 250 comprises NMC or another cathode active material described below. In some examples, the outer layer 252 comprises lithium niobate (LiNbO3), lithium zirconate (Li2ZrO3) and / or lithium phosphate (Li3PO4), but other materials may also be used. In some examples, the NMC particles 250 account for 68 wt% to 92 wt% and the outer layer accounts for 8 wt% to 32 wt%. In some examples, the weight ratio of the particles 250 to the outer layer 252 is 70:30. In some examples, the coated NMC particles suppress interfacial side reactions, and the solid electrolyte enables an effective ion transport path in the cathode electrode.

[0083] In some examples, particles 250 have a size of 2 μm <D 50 In some examples, the Brunauer, Emmett, and Teller (BET) surface area is 0.2 to 0.8 m 2 / g. In some examples, nickel (Ni) accounts for 50 to 72 mol %, manganese (Mn) accounts for 8 to 40 mol %, and cobalt (Co) accounts for 10 to 20 mol %. In some examples, outer layer 252 has a thickness of 7 nm to 13 nm (e.g., 10 nm). In some examples, sulfide electrolyte 212 has a thickness of 4 μm. <D 50 <12 μm (e.g., 8 μm) and D 90 <15 μm (eg, 14.7 μm). In some examples, the sulfide electrolyte 212 has a diameter of 5 μm. <D 50 <10μm in diameter. Ionic conductivity greater than 1mS / cm.

[0084] Reference now FIG. 4A to FIG. 4C , showing the performance of NMC particles with different thickness of outer layer. Figure 4A In the graph, voltage is shown as a function of capacity (mAh / g) for NMC with no outer layer (at 300), NMC with a 5nm outer layer (at 305), NMC with a 10nm outer layer (at 310), and NMC with a 15nm outer layer (at 315). Some coated NMC examples (e.g., 5nm and 10nm coatings) perform better than uncoated NMC. Figure 4B , the impedance of coated and uncoated NMC is shown. Some coated NMC examples (eg, 5nm and 10nm coatings) have lower resistance.

[0085] exist Figure 4C In Figure 1, the capacity is shown as a function of cycle number. Some coated NMC examples (e.g., 5nm and 10nm coatings) have higher capacity compared to uncoated NMC. It can be understood that an electrochemically / chemically stable NMC / SE interface is achieved by the LiNbO3 coating. NMC with a 10nm coating shows the lowest interface resistance in the case of sulfide electrolytes.

[0086] Reference now Figure 5, a method 400 for manufacturing a cathode electrode using a dry method is shown. At 410, the coated cathode active material and solid sulfide electrolyte particles are mixed. At 414, a binder and a conductive additive are added to the coated cathode active material and the solid sulfide electrolyte and mixed. At 416, the mixture is sheared (e.g., to fibrillate the binder) and pressed and / or rolled to form a self-supporting cathode film. At 418, the film is attached to the cathode current collector. In some instances, one or more sets of rollers may be used to apply pressure and / or heat (or another device may be used). At 426, the anode electrode, cathode electrode, and separator are arranged in a battery cell.

[0087] Reference now Figure 6 , a method 500 for making a cathode electrode is shown. At 510, the coated cathode active material, solid sulfide electrolyte, solvent, binder, and conductive additive are mixed. At 514, the mixture is applied to a cathode current collector. At 518, the mixture is pressed and / or heated with a roller or other device to form a cathode electrode. At 522, the anode electrode, cathode electrode, and separator are arranged in a battery cell.

[0088] Reference now Figure 7 and Figure 8 , showing the effect of the size of the sulfide solid electrolyte. Figure 7 In the figure, a magnified view of the solid electrolyte and cathode electrode is shown. When 5μm and 8μm are used, the densest packing of the cathode electrode occurs after pressing. Random sizes and larger sizes (such as 15μm) have voids after pressing. Figure 8 In the results, the distribution of sulfide solid electrolyte is more uniform for 5 μm and 8 μm compared with random or larger sizes (e.g., 15 μm).

[0089] In some examples, the solid electrolyte includes a sulfide solid electrolyte selected from pseudo binary sulfides, pseudo ternary sulfides, and pseudo quaternary sulfides. Examples of pseudo binary sulfides include Li2S-P2S5 systems (Li3PS4, Li7P3S 11 and Li 9.6 P3S 12 ), Li2S-SnS2 system (Li4SnS4), Li2S-SiS2 system, Li2S-GeS2 system, Li2S-B2S3 system, Li2S-Ga2S3 system, Li2S-P2S3 system, Li2S-Al2S3 system and combinations thereof.

[0090] Examples of pseudo-ternary sulfides include the Li2O-Li2S-P2S5 system, the Li2S-P2S5-P2O5 system, the Li2S-P2S5-GeS2 system (e.g., Li 3.25 Ge0.25 P 0.75 S4 and Li 10 GeP2S 12 )、Li2S-P2S5-LiX (X=F, Cl, Br, I) system (Li6PS5Br, Li6PS5Cl, L7P2S8I and Li4PS4I), Li2S-As2S5-SnS2 system (Li 3.833 Sn 0.833 As 0.166 S4), Li2S-P2S5-Al2S3 system, Li2S-LiX-SiS2 (X=F, Cl, Br, I) system, 0.4LiI·0.6Li4SnS4, Li 11 Si2PS 12 and combinations thereof.

[0091] Examples of pseudo-quaternary sulfides include the Li2O-Li2S-P2S5-P2O5 system, Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li7P 2.9 Mn 0.1 S 10.7 I 0.3 , Li 10.35 [Sn 0.27 Si 1.08 ]P 1.65 S 12 and combinations thereof.

[0092] In other examples, the solid electrolyte includes a halide-based solid electrolyte, a hydride-based solid electrolyte, or other solid electrolytes with low grain boundary resistance. Examples of halide-based solid electrolytes include, for example, Li3YCl6, Li3InCl6, Li3YBr6, LiI, Li2CdCl4, Li2MgCl4, Li2CdI4, Li2ZnI4, and Li3OCl. Examples of hydride-based solid electrolytes include LiBH4, LiBH4-LiX (X = chlorine (Cl), bromine (Br) or iodine (I)), LiNH2, Li2NH, LiBH4-LiNH2, Li3AlH6, and combinations thereof.

[0093] In some examples, the cathode active material is selected from rock salt layered oxides, spinels, polyanion cathodes, olivine cathodes, other lithium transition metal oxides, surface coated and / or doped cathode materials, and low voltage cathode materials.

[0094] In some examples, the anode active material is selected from carbonaceous materials (e.g., graphite, hard carbon, soft carbon, etc.), silicon, silicon mixed with graphite, Li4Ti5O 12 , transition metals (e.g., tin (Sn)), metal oxides / sulfides (e.g., titanium oxide (TiO2), iron sulfide (FeS) etc.), and other lithium-accepting anode materials.

[0095] Examples of rock salt layered oxides (LiCoO2, LiNi x Mn y Co 1-x-y O2、LiNi x Mn y Al 1-x-y O2、LiNi x Mn 1- x O2、Li 1+x MO2). Examples of spinels include LiMn2O4, LiNi 0.5 Mn 1.5 O4. Examples of polyanion cathodes include LiV2(PO4)3). Examples of olivine include LiFePO4 and LiMn x Fe 1-x PO4.

[0096] Examples of surface coated and / or doped cathode materials are as described above and further include LiNbO3 coated LiMn2O4, Li2ZrO3 or Li3PO4 coated LiNi x Mn y Co 1-x-y O2 and Al doped LiMn2O4. Examples of low voltage cathode materials include lithiated metal oxides / sulfides (eg LiTiS2), lithium sulfide, and sulfur.

[0097] In some examples, the conductive additive is selected from carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes, and other electronically conductive additives.

[0098] In some examples, the binder is selected from polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS) and styrene-butadiene-styrene copolymer (SBS).

[0099] The foregoing description is essentially only exemplary and is absolutely not intended to limit the present disclosure, its application or use. The broad teachings of the present disclosure can be implemented in various forms. Therefore, although the present disclosure includes specific examples, the true scope of the present disclosure should not be limited thereto, because after studying the drawings, the specification and the following claims, other modifications will become apparent. It should be understood that one or more steps in the method may be implemented in different orders (or simultaneously) without changing the principles of the present disclosure. In addition, although each embodiment is described above as having certain features, any one or more features described with respect to any embodiment of the present disclosure may be implemented in any other embodiment and / or combined with the features of any other embodiment, even if the combination is not explicitly described. In other words, the embodiments are not mutually exclusive, and the mutual replacement of one or more embodiments is still within the scope of the present disclosure.

[0100] Various terms are used to describe the spatial and functional relationships between elements (e.g., between modules, circuit elements, semiconductor layers, etc.), including "connected," "engaged," "coupled," "adjacent," "next to," "on top of," "on," "under," and "disposed." Unless explicitly described as "directly," when describing the relationship between a first element and a second element in the above disclosure, the relationship can be a direct relationship in which no other intervening elements exist between the first element and the second element, or an indirect relationship in which one or more intervening elements exist between the first element and the second element (spatially or functionally). The phrase "at least one of A, B, and C" as used herein should be interpreted to mean a logical (A or B or C) using a non-exclusive logical OR, and should not be interpreted to mean "at least one A, at least one B, and at least one C."

[0101] In the drawings, the direction of the arrows, as shown by arrows, generally demonstrates the flow of information (such as data or instructions) related to the diagram. For example, when component A and component B exchange various information but the information transmitted from component A to component B is related to the diagram, the arrow may point from component A to component B. Such a unidirectional arrow does not mean that no other information is transmitted from component B to component A. In addition, for the information transmitted from component A to component B, component B may send a request for the information to component A or a receipt of the information.

Claims

1. A solid-state battery cell, comprising: A anode electrode comprising an anode active material layer disposed on an anode current collector; C cathode electrodes, comprising a cathode active material layer disposed on a cathode current collector, wherein the cathode active material layer comprises: A cathode active material comprising particles comprising an outer layer of a material selected from the group consisting of LiNbO3, Li2ZrO3, Li3PO4, and combinations thereof; and A solid electrolyte having a D of 4 μm to 12 μm 50 size; and S separators are arranged between the A anode electrodes and the C cathode electrodes, wherein A, C and S are integers greater than 1.

2. The solid-state battery cell of claim 1, wherein the particles comprise lithium-nickel-cobalt-manganese (NMC) particles and the outer layer comprises LiNbO3.

3. The solid-state battery cell according to claim 2, wherein the NMC particles have a diameter of 2 μm. <D 50 <5μm in diameter.

4. The solid-state battery cell of claim 2, wherein nickel comprises 50 to 72 mol % of the NMC particles, manganese comprises 8 to 40 mol % of the NMC particles, and cobalt comprises 10 to 20 mol % of the NMC particles.

5. The solid-state battery cell of claim 1, wherein the outer layer has a thickness of 7 nm to 13 nm.

6. The solid-state battery cell according to claim 1, wherein the solid electrolyte in the cathode active material layer has a diameter D of <15 μm 90 .

7. The solid-state battery cell according to claim 1, wherein the solid electrolyte comprises a sulfide solid electrolyte selected from the group consisting of pseudo binary sulfides, pseudo ternary sulfides, and pseudo quaternary sulfides.

8. The solid-state battery cell according to claim 1, wherein the solid electrolyte is selected from the group consisting of a halide-based solid electrolyte and a hydride-based solid electrolyte.

9. The solid-state battery cell of claim 1, wherein the cathode active material is selected from rock salt layered oxides, spinels, polyanion cathodes, olivine cathodes, other lithium transition metal oxides, surface coated and / or doped cathode materials, and combinations thereof.

10. The solid-state battery cell of claim 1, wherein the cathode active material layer further comprises a conductive additive selected from the group consisting of carbon black, graphite, graphene, graphene oxide, SuperP, acetylene black, carbon nanofibers, carbon nanotubes, and combinations thereof.

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