HIGH-VOLTAGE SOLID-STATE LITHIUM-ION BATTERY WITH RATIONAL ELECTRODE-ELECTROLYTE COMBINATIONS

Abstract

A lithium-ion battery cell is formed of a layer of anode material comprising a mixture of anode active material particles and particles of a first solid electrolyte composition, an electrolyte layer of solid electrolyte particles of a second solid electrolyte composition, and a layer of cathode material comprising a mixture of cathode active material particles and particles of a third solid electrolyte compositions. In the cell, the three solid electrolyte compositions are varied to enhance the performance of the cell. Layers of interlayer material are placed between one or both of the layers of electrode material and the solid electrolyte material and/or between electrolyte layers. And, optionally, the otherwise solid-state cell is infiltrated with a suitable liquid electrolyte. These variables are managed to enhance macro/micro interfaces between the solid materials and layers and to improve the electrochemical performance of the cell, especially for high-voltage cathode material.

Claims

1. A solid-state lithium-ion battery cell comprising an anode member which is in the form of a layer having a two-dimensional size and shape with opposing facial sides and a uniform thickness up to about 500 micrometers, the anode layer comprising a bonded mixture of particles of anode active material and solid electrolyte particles of a first solid electrolyte composition, the respective particles having maximum dimensions in the nanometer and micrometer range up to about 1000 micrometers; a solid electrolyte member which is in the form of a layer comprising bonded solid electrolyte particles of a second electrolyte composition, the solid electrolyte layer having a two-dimensional size and shape with opposing facial sides and a uniform thickness up to about 500 micrometers, the solid electrolyte layer having a first facial side facing toward a facial side of the anode layer and an opposing facial side, the solid electrolyte particles having maximum dimensions in the nanometer and micrometer range up to about 1000 micrometers; a cathode member which is in the form of a layer having a two-dimensional size and shape with opposing facial sides and a uniform thickness up to about 500 micrometers, the cathode layer comprising a bonded mixture of particles of cathode active material and solid electrolyte particles of a third solid electrolyte composition, the respective particles having maximum dimensions in the nanometer and micrometer range up to about 1000 micrometers, the cathode layer having a first facial side facing toward the opposing facial side of the layer of solid electrolyte particles; and a co-extensive interlayer film placed in face-to-face contact between opposing facial sides of the anode layer and the solid electrolyte layer or between opposing facial sides of the cathode layer and the solid electrolyte layer, or in both locations; the first solid electrolyte composition, the second solid electrolyte composition, and the third solid electrolyte composition being such that at least one of the solid electrolyte compositions is different from the other two solid electrolyte compositions.

2. A solid-state lithium-ion battery cell as stated in claim 1 in which each of the three solid electrolyte compositions is different from the other two solid electrolyte compositions.

3. A solid-state lithium-ion battery cell as stated in claim 1 in which the first solid electrolyte composition and the third solid electrolyte compositions are the same, but they differ from the second solid electrolyte composition.

4. A solid-state lithium-ion battery cell as stated in claim 1 in which the second and third solid electrolyte compositions are the same, but they differ from the first solid electrolyte composition.

5. A solid-state lithium-ion battery as stated in claim 1 in which the first solid electrolyte and the second solid electrolyte compositions are the same, but they differ from the third solid electrolyte composition.

6. A solid-state lithium-ion battery as stated in claim 1 in which an interlayer film comprising a mixture of polyethylene oxide and lithium bis(trifluoromethanesulfonyl)imide is placed between the anode member layer and the solid electrolyte member layer, or between the solid electrolyte member layer and the cathode member layer, or in both locations.

7. A solid-state lithium-ion battery as stated in claim 1 in which the solid electrolyte layer comprises a first layer of solid electrolyte particles facing the anode layer and having the same composition as the particles of the solid electrolyte composition of the anode layer, and a second layer of solid electrolyte particles facing the cathode layer and having the same composition as the solid electrolyte composition of the cathode layer.

8. A solid-state lithium-ion battery as stated in claim 7 in which an interlayer is placed between the two solid electrolyte layers.

9. A solid-state lithium-ion battery as stated in claim 1 in which the anode layer, the layer of solid electrolyte, and the cathode layer are porous and are uniformly infiltrated with a liquid electrolyte conductive of lithium cations and compatible with the solid electrolyte.

10. A solid-state lithium-ion battery as stated in claim 1 in which (i) the anode layer comprises a bonded mixture of graphite particles as anode active material and particles of Li.sub.9.6P.sub.3S.sub.12 as solid electrolyte particles, (ii) the solid electrolyte layer comprises bonded particles of Li.sub.10GeP.sub.2S.sub.12, and (iii) the cathode layer comprises a bonded mixture of LiNbO.sub.3-coated LiNi.sub.0.5Mn.sub.1.5O.sub.4 particles of cathode active material and particles of Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride/lithium bis(trifluoromethanesulfonyl)imide hybrid electrolyte as solid electrolyte particles.

11. A solid-state lithium-ion battery as stated in claim 1 in which an interlayer film comprising a mixture of polyethylene oxide and lithium bis(trifluoromethanesulfonyl)imide is placed between the anode member layer and the solid electrolyte member layer, or between the solid electrolyte member layer and the cathode member layer, or in both locations.

12. A solid-state lithium-ion battery as stated in claim 1 in which (i) the anode member layer comprises a mixture of graphite particles as anode active material and particles of Li.sub.10GeP.sub.2S.sub.12 as solid electrolyte particles, (ii) the solid electrolyte member layer comprises particles of Li.sub.10GeP.sub.2S.sub.12, and (iii) the cathode member layer comprises a mixture of LiNbO.sub.3-coated LiNi.sub.0.5Mn.sub.1.5O.sub.4 particles of cathode active material and particles of Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride/lithium bis(trifluoromethanesulfonyl)imide hybrid electrolyte as solid electrolyte particles.

13. A solid-state lithium-ion battery as stated in claim 1 in which (i) the anode member layer comprises a mixture of graphite particles as anode active material and particles of Li.sub.9.6P.sub.3S.sub.12 as solid electrolyte particles, (ii) the solid electrolyte member layer comprises particles of Li.sub.10GeP.sub.2S.sub.12, and (iii) the cathode member layer comprises a mixture of LiNbO.sub.3-coated LiNi.sub.0.5Mn.sub.1.5O.sub.4 particles of cathode active material and particles of Li.sub.10GeP.sub.2S.sub.12 as solid electrolyte particles.

14. A solid-state lithium-ion battery as stated in claim 1 in which (i) the anode member layer comprises a mixture of graphite particles as anode active material and particles of Li.sub.9.6P.sub.3S.sub.12 as solid electrolyte particles, (ii) the solid electrolyte member layer comprises particles of Li.sub.10GeP.sub.2S.sub.12, and (iii) the cathode member layer comprises a mixture of LiNbO.sub.3-coated LiNi.sub.0.5Mn.sub.1.5O.sub.4 particles of cathode active material and particles of Li.sub.9.6P.sub.3S.sub.12 as solid electrolyte particles.

15. A solid-state lithium-ion battery as stated in claim 1 in which (i) the anode member layer comprises a mixture of graphite particles as anode active material and particles of Li.sub.9.6P.sub.3S.sub.12 as solid electrolyte particles, (ii) the solid electrolyte member layer comprises a first layer of particles of Li.sub.9.6P.sub.3S.sub.12 lying adjacent to the anode member layer and a second coextensive layer of particles of Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride/lithium bis(trifluoromethanesulfonyl)imide hybrid solid electrolyte lying adjacent to the cathode member layer, and (iii) the cathode member layer comprises a mixture of LiNbO.sub.3-coated LiNi.sub.0.5Mn.sub.1.5O.sub.4 particles of cathode active material and particles of Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride lithium bis(trifluoromethanesulfonyl)imide hybrid electrolyte as solid electrolyte particles.

16. A solid-state lithium-ion battery as stated in claim 15 in which a solid interlayer film is placed between the first solid electrolyte layer and the second solid electrolyte layer.

17. A solid-state lithium-ion battery as stated in claim 15 in which the interlayer comprises a mixture of polyethylene oxide and lithium bis(trifluoromethanesulfonyl)imide.

18. A solid-state lithium-ion battery as stated in claim 9 in which the liquid electrolyte is lithium bis (trifluoromethane sulfonyl) imide-triethylene glycol dimethyl ether ionic liquid.

19. A solid-state lithium-ion battery cell comprising an anode layer having a two-dimensional size and shape with opposing faces and a uniform thickness, the anode layer comprising a mixture of particles of anode active material with particles of a first solid electrolyte composition; a layer of solid electrolyte particles of a second electrolyte composition, the electrolyte layer having a two-dimensional size and shape and a uniform thickness, the solid electrolyte layer having a first face lying against a face of the anode layer and an opposing face; and a cathode layer having a two-dimensional size and shape with opposing faces and a uniform thickness, the cathode layer comprising a mixture of particles of cathode active material with particles of a third solid electrolyte composition, the cathode layer having a first face lying against the opposing face of the layer of solid electrolyte particles; a co-extensive interlayer film placed in face-to-face contact between opposing facial sides of the anode layer and the solid electrolyte layer or between opposing facial sides of the cathode layer and the solid electrolyte layer, or in both locations; the first solid electrolyte composition, the second solid electrolyte composition, and the third solid electrolyte composition being such that at least one of the solid electrolyte compositions is different from the other two solid electrolyte compositions.

20. A solid-state lithium-ion battery as stated in claim 19 in which the interlayer film comprises a mixture of polyethylene oxide and lithium bis(trifluoromethanesulfonyl)imide.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] FIG. 1 is a schematic, cross-sectional view of a cell of a solid-state lithium-ion battery. This illustrated battery cell is a six-layer structure of substantially like-shaped, overlying layers of different (but uniform) thicknesses and different material compositions. Starting from the top layer and proceeding downwardlythe top member is a non-porous nickel or copper current collector foil with its lower side in coextensive contact with a surface of a particulate anode material layer. The anode material layer contains particles of anode active material and a first solid electrolyte material (SE1). In this embodiment, the opposite side of the anode layer lies in coextensive contact against one side of an interposed interlayer material film. The opposite side of the interlayer is in co-extensive face-to face contact with a layer of particles of solid electrolyte material of a second electrolyte composition (SE2). The fifth layer is a cathode layer which contains particles of cathode active material uniformly mixed with particles of a third solid electrolyte material (SE3). The bottom layer of the battery cell is a non-porous aluminum current collector foil with one side in substantially coextensive contact with one side of the cathode layer. Each thin current collector foil may (optionally) have an un-coated tab on one edge for an electric contact with another interconnected cell unit and/or with a device requiring the electrical current produced by the cell. Obviously, groups of such cells may be electrically connected in series (such as bipolar stacking) or parallel arrangement to produce a required voltage and capacity/energy in a battery of such cells.

[0020] In FIG. 1, each member of the cell is identified with a numeral 1xx which is identified and described in the following specification. In many of the following figures, the battery cell contains some identical or closely-identical members. In these figures, each member is identified with a numeral Xxx in which X is the number of the figure, and the numerals xx correspond to the numeral used in FIG. 1 to identify the described cell member.

[0021] FIG. 2A is a schematic cross-sectional view of a cell of a solid-state battery. The six-layer structure is a schematic, cross-sectional view, quite similar to that of FIG. 1. The six-layer structure of FIG. 2A is like that of FIG. 1, except that the composition of the particles of solid electrolyte material (SE1) in the anode layer and the composition of the solid electrolyte particles (SE2) of the solid electrolyte layer are the same solid electrolyte composition. In the embodiment illustrated in FIG. 2A, SE1=SE2. In the embodiment of solid electrolyte compositions in FIG. 2A, the compositions of SE1 and SE2 are not the same as the SE3 composition.

[0022] FIG. 2B is a schematic cross-sectional view of a cell of a solid-state battery like that of FIG. 2A, except that the composition of the particles of solid electrolyte material (SE2) of the solid electrolyte layer and the composition of the solid electrolyte particles (SE3) mixed with the particles of cathode active material are the same. In the embodiment illustrated in FIG. 2B, SE2=SE3. In the embodiment of solid electrolyte compositions in FIG. 2B, the compositions of SE1 and SE2 are not the same.

[0023] FIG. 2C is a schematic cross-sectional view of a cell of a solid-state battery like that of FIGS. 2A and 2B, except that the composition of the particles of the solid electrolyte (SE1) mixed with the anode active material particles and the particles of the solid electrolyte (SE3) mixed with the particles of cathode active material particles are the same. The anode material layer and the cathode material layer use the same composition of solid electrolyte particles, SE1=SE3, which is different from the composition of the solid electrolyte layer (SE2).

[0024] FIG. 3 is a three-part, fragmented, schematic, cross-sectional view of a cell of a solid-state lithium-ion battery illustrating different embodiments of the placement of an interlayer between the anode material layer and the solid electrolyte layer and/or between the cathode material layer and the solid electrolyte layer. In the left fragmental view of FIG. 3, the interlayer is placed between upper layer of mixed anode material particles and solid electrolyte particles (SE1) and the layer of solid electrolyte particles. In the center fragmental view of FIG. 3, the interlayer is placed between the layer of solid electrolyte particles (SE2) and the lower layer of mixed cathode material particles and solid electrolyte particles (SE3). In the right-side fragmental view of FIG. 3, a particulate interlayer is placed between both the anode material layer and the solid electrolyte layer and the cathode material layer. In FIG. 3 SE1SE2SE3.

[0025] FIG. 4A is a schematic cross-sectional view of a solid-state lithium-ion battery illustrating two co-extensive layers of solid electrolyte material placed between the layer of anode material and the layer of cathode material. In FIG. 4A the upper particulate layer of solid electrolyte material is of the same composition as the particles of solid electrolyte material (SE1) mixed with the particles of anode active material, and the lower particulate layer of solid electrolyte material is of the same composition as the particles of solid electrolyte material (SE3) mixed with the particles of cathode active material particles. SE1SE3.

[0026] FIG. 4B is a schematic cross-sectional view (similar to FIG. 4A) of a cell of a solid-state lithium-ion battery illustrating two co-extensive layers of solid electrolyte material placed between the layer of anode material and the layer of cathode material. In FIG. 4B, an interlayer is placed between the two layers of solid electrolyte materials.

[0027] FIG. 5 is a schematic cross-sectional view of a cell of a solid-state lithium-ion battery similar to FIG. 1. In FIG. 5, the solid-state cell of FIG. 1 has been infiltrated with a liquid electrolyte of a composition compatible with the solid battery electrode and solid electrolyte members of FIG. 1.

DETAILED DESCRIPTION

[0028] As stated, it is desired to form lithium battery cells in which cathode active material compositions and anode active electrode material compositions are paired with compatible and supportive particulate solid electrolyte material compositions in the respective electrode layers. Further, it is intended to utilize compatible solid electrolyte compositions, and, when necessary, suitable interlayer film compositions between layers of electrode materials and a solid electrolyte layer. Following are lists of exemplary, but non-limiting, compositions of such cathode, anode, electrolyte and interlayer materials:

[0029] Examples of suitable cathode active materials include high-voltage oxides. e.g., LiNi.sub.0.5Mn.sub.1.5O.sub.4, rock salt layered oxides (LiCoO.sub.2, LiNi.sub.xMn.sub.yCo.sub.1xyO.sub.2, LiNi.sub.xMn.sub.1xO.sub.2, Li.sub.1+xMO.sub.2), spinel (LiMn.sub.2O.sub.4), polyanion cathode (LiV.sub.2(PO.sub.4).sub.3), and other lithium transition-metal oxides and coated and/or doped cathode materials mentioned above. e.g., LiNbO.sub.3-coated LiNi.sub.0.5Mn.sub.1.5O.sub.4,

[0030] Examples of suitable solid electrolyte materials for use with particles of cathode active materials include:

[0031] Oxide solid electrolyte (SE) such as Perovskite type (Li.sub.3xLa.sub.2/3xTiO.sub.3), NASICON type (Li.sub.1.4Al.sub.0.4Ti.sub.1.6(PO.sub.4).sub.3 and Li.sub.1+xAl.sub.xGe.sub.2x(PO.sub.4).sub.3, LISICON type (Li.sub.2+2xZn.sub.1xGeO.sub.4), garnet type (Li.sub.7La.sub.3Zr.sub.2O.sub.12).

[0032] Inorganic oxide SE/polymer hybrid electrolytes, e.g., Li.sub.6.4La.sub.3Zr.sub.1.4Ta.sub.0.6O.sub.12/Li-salt-free polyethylene oxides (PEOs), Li.sub.6.75La.sub.3Zr.sub.1.75Ta.sub.0.25O.sub.12/poly (propylene carbonate), Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyethylene oxide, Li.sub.7La.sub.3Zr.sub.2O.sub.12/poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP).

[0033] Inorganic oxide SE/polymer/lithium salt hybrid electrolyte. e.g., garnet/polyethylene-oxide/lithium salt (Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride (PVDF)/LiTFSI hybrid electrolyte)

[0034] Metal-doped or aliovalent-substituted oxide SE. e.g., Al (or Nb)-doped Li.sub.7La.sub.3Zr.sub.2O.sub.12, Sb-doped Li.sub.7La.sub.3Zr.sub.2O.sub.12 Ga-substituted Li.sub.7La.sub.3Zr.sub.2O.sub.12, Cr and V-substituted LiSn.sub.2P.sub.3O.sub.12, Al-substituted perovskite.

[0035] high-voltage-stable sulfide solid electrolyte, such as core-shell Li.sub.9.54Si.sub.1.74P.sub.1.44S.sub.11.7Cl.sub.0.3.

[0036] Lithium Phosphorus Oxynitride

[0037] Examples of suitable anode active material particles include:

[0038] Carbonaceous material (e.g. graphite, hard carbon, soft carbon etc.), silicon, silicon mixed with graphite, Li.sub.4Ti.sub.5O.sub.12, transition-metal (e.g., Sn), metal oxide/sulfide (e.g., SnO.sub.2, FeS and the likes), and other lithium-accepting anode materials.

[0039] Li Metal Foil and Li-Metal Alloy (LiIn).

[0040] Examples of solid electrolyte particles for use with particles of anode active electrolyte particles include:

[0041] Sulfide-based SE. e.g., Li.sub.2SP.sub.2S.sub.5, Li.sub.2S-P.sub.2S.sub.5-MS.sub.x, Li.sub.2SP.sub.2S.sub.5 with LiI, LGPS (Li.sub.10GeP.sub.2S.sub.12), thio-LISICON (Li.sub.3.25Ge.sub.0.25P.sub.0.75S.sub.4), Li.sub.3.4Si.sub.0.4P.sub.0.6S.sub.4, Li.sub.10GeP.sub.2S.sub.11.7O.sub.0.3, Li.sub.9.54Si.sub.1.74P.sub.1.44S.sub.11.7Cl.sub.0.3, Li.sub.9.6P.sub.3S.sub.12, Li.sub.7P.sub.3S.sub.11, Li.sub.9P.sub.3S.sub.9O.sub.3, Li.sub.10.35Ge.sub.1.35P.sub.1.65S.sub.12, Li.sub.10.35Si.sub.1.35P.sub.1.65S.sub.12, Li.sub.9.81Sn.sub.0.81P.sub.2.19S.sub.12, Li.sub.10(Si.sub.0.5Ge.sub.0.5)P.sub.2S.sub.12, Li.sub.10(Ge.sub.0.5Sn.sub.0.5)P.sub.2S.sub.12, and Li.sub.10(Si.sub.0.5Sn.sub.0.5)P.sub.2S.sub.12.

[0042] Surface-modified sulfide SEs. e.g., ZnO-deposited Li.sub.2SP.sub.2S.sub.5.

[0043] Lithium argyrodite-type SE. e.g., Li.sub.6PS.sub.5X (XCl, Br, or I).

[0044] Inorganic sulfide SE/polymer hybrid electrolyte. e.g., 77.5 Li.sub.2S-22.5 P.sub.2S.sub.5/polyimine, LGPS/polyethylene oxide.

[0045] Inorganic sulfide SE/polymer/lithium salt hybrid electrolyte. e.g., LGPS/polyethylene oxide/LiTFSI.

[0046] Other SEs. e.g., LiPON.

[0047] Examples of suitable solid electrolyte compositions for the layer of solid electrolyte particles include: Sulfide-based SE. e.g., Li.sub.2SP.sub.2S.sub.5, Li.sub.2S-P.sub.2S.sub.5-MS.sub.x, LGPS (Li.sub.10GeP.sub.2S.sub.12), thio-LISICON (Li.sub.3.25Ge.sub.0.25P.sub.0.75S.sub.4), Li.sub.3.4Si.sub.0.4P.sub.0.6S.sub.4, Li.sub.10GeP.sub.2S.sub.11.7O.sub.0.3, lithium argyrodite Li.sub.6PS.sub.5X (XCl, Br, or I), Li.sub.9.54Si.sub.1.74P.sub.1.44S.sub.11.7Cl.sub.0.3 (25 mS/cm), Li.sub.9.6P.sub.3S.sub.12, Li.sub.7P.sub.3S.sub.11, Li.sub.9P.sub.3S.sub.9O.sub.3, Li.sub.10.35Ge.sub.1.35P.sub.1.65S.sub.12, Li.sub.10.35Si.sub.1.35P.sub.1.65S.sub.12, Li.sub.9.81Sn.sub.0.81P.sub.2.19S.sub.12, Li.sub.10(Si.sub.0.5Ge.sub.0.5)P.sub.2S.sub.12, Li.sub.10(Ge.sub.0.5Sn.sub.0.5)P.sub.2S.sub.12, and Li.sub.10(Si.sub.0.5Sn.sub.0.5)P.sub.2S.sub.12.

[0048] Oxide-based SE. e.g., perovskite type (Li.sub.3xLa.sub.2/3.sub.xTiO.sub.3), NASICON type (LiTi.sub.2(PO.sub.4).sub.3), Li.sub.1+xAl.sub.xTi.sub.2x(PO.sub.4).sub.3 (LATP), Li.sub.1+xAl.sub.xGe.sub.2x(PO.sub.4).sub.3 (LAGP), Li.sub.1+xY.sub.xZr.sub.2x(PO.sub.4).sub.3 (LYZP), LISICON type (Li.sub.14Zn(GeO.sub.4).sub.4), Garnet type (Li.sub.6.5La.sub.3Zr.sub.1.75Te.sub.0.25O.sub.12).

[0049] Polymer-based SE: a polymer host is combined with a lithium salt solid electrolyte to act as a solid solvent. Polymer host: PEO, PPO, PEG, PMMA, PAN, PVDF, PVDF-HFP, PVC. Salts: lithium bis(trifluoromethanesulfonyl) imide (LiTFSI).

[0050] Nitride-based SE. e.g. Li.sub.3N, Li.sub.7PN.sub.4, LiSi.sub.2N.sub.3.

[0051] Hydride-based SE. e.g. LiBH.sub.4, LiBH.sub.4Li.sub.X (XCl, Br or I), LiNH.sub.2, Li.sub.2NH, LiBH.sub.4LiNH.sub.2, Li.sub.3AlH.sub.6

[0052] Halide-based SE. e.g. LiI, Li.sub.2CdCl.sub.4, Li.sub.2MgCl.sub.4, Li.sub.2CdI.sub.4, Li.sub.2ZnI.sub.4, Li.sub.3OCl

[0053] Borate-based SE. e.g. Li.sub.2B.sub.4O.sub.7, Li.sub.2OB.sub.2O.sub.3P.sub.2O.sub.5

[0054] Inorganic SE/polymer-based hybrid electrolyte.

[0055] Surface-modified solid electrolyte materials. In-deposited Li.sub.7La.sub.3Zr.sub.2O.sub.12

[0056] Examples of suitable compositions for interlayer particle compositions include:

[0057] Inorganic interlayer (e.g., 70% Li.sub.2S-29% P.sub.2S.sub.5-1% P.sub.2O.sub.5).

[0058] Polymer-based interlayer (e.g., poly (ethylene glycol) methyl ether acrylate with Al.sub.2O.sub.3 and LiTFSI; polyethylene oxide with LiTFSI; poly (vinylidene fluoride) copolymer with hexafluoropropylene (PVDF-HFP)-based gel electrolyte.).

[0059] Metal/metal oxide (e.g., Nb, Al, Si or Al.sub.2O.sub.3).

[0060] In the following illustrative figures, various embodiments of this disclosure are illustrated, particularly concerning the combinations of particulate electrode active materials and particulate solid electrolyte materials, adjoining solid electrolyte layers and interlayers used with solid electrolyte layers. In the respective illustrative figures, the thicknesses of the respective layers and the sizes of the particles of electrode materials are enlarged for purposes of the illustration. Illustrative, representative sizes of the electrode materials and the electrode elements themselves are presented above in this text and in following portions of this text. Further, only single battery unit cells are drawn and with the cell member layers presented in a horizontal posture to better fit the illustrations on a drawing sheet. In use, many battery cells may be assembled in upstanding stacks or rolls and many cells may be combined in an assembly in which they are connected in electrical series combination, electrical parallel combination, or in both electrical series and parallel combinations.

[0061] In FIG. 1, a lithium-ion battery cell 100 is illustrated in which three different solid electrolyte compositions are employed. Starting at the top of the figure, a thin, solid (non-perforated) current collector foil 102 has a uniformly thick, layer of anode material 104 co-extensively bonded to its lower side. In an assembled battery, comprising more than one cell, a like layer of anode material would likely be placed, coextensively, against its opposite side, its top side as illustrated in FIG. 1. The contact, which may be a resin-bonded contact (not illustrated), is such that, during cell operation, electrons enter the current collector 102, from the anode material layer 104 during cell discharge, flowing from an optional smaller tab 102 at one side or edge of the current collector foil to an electrical energy consuming device. Thus, during cell discharge, anode current collector 102 is negatively charged. Anode current collector 102 is often a nickel or copper foil having a thickness of about five to fifty micrometers and a two-dimensional shape corresponding to the required shape and area of the attached anode material.

[0062] Anode material layer 104 is an intimate mixture of nanometer-size to micrometer-size particles of anode active material, for example graphite particles 106, intimately mixed with like-size particles of a selected solid electrolyte 108 and other components such as polymer binder and conductive particles. (Not shown in figure) In this example, the composition of the solid electrolyte particles 108, intimately mixed with the graphite anode material particles 106, is Li.sub.9.6P.sub.3Si.sub.12. For purposes of comparison with other examples of the selection of suitable solid electrolyte particles for an electrode member, the composition of the solid electrolyte material for an anode of a lithium-ion cell is also designated in this text as SE1.

[0063] In the embodiment of FIG. 1, the opposite side of the layer of anode material 104 is in face-to-face, coextensive contact with an interlayer 110 which is the thinner (like a flat film) than the layer of anode material 104 and the solid electrolyte layer 112 of solid electrolyte particles 114 (typically resin-bonded) which intimately engages the opposite side of interlayer 110. The composition of interlayer 110 is suitably a mixture of polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The composition of the small particles 114 of solid electrolyte layer 112, is suitably Li.sub.10GeP.sub.2S.sub.12 (LGPS). Again, for comparison with other embodiments of the selection of the composition of suitable solid electrolyte materials, the composition of the particles of the solid electrolyte layer is herein designated or referred to as SE2.

[0064] Placed in intimate, coextensive contact with the opposite side of solid electrolyte layer 112, is a layer 116 of cathode material. Cathode material layer 116 is suitably formed of a mixture of nanometer-size to micrometer-size particles of cathode active material 118, particles of suitable solid electrolyte material 120 and other components such as polymer binder and conductive particles. (Not shown in figure). An example of the composition of a suitable cathode active material is LiNbO.sub.3-coated LiNi.sub.0.5Mn.sub.1.5O.sub.4, and a suitable compatible solid electrolyte material is Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride (PVDF)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) hybrid electrolyte (SE3). Attached in face-to-face-coextensive contact with the opposite side of cathode layer 116 is cathode current collector 122 with its optional tab 122 for connection with an energy requiring device. During cell discharge, cathode current collector displays a positive electrical charge.

[0065] Thus, in the embodiment of FIG. 1, each of the solid electrolyte materials is of a different composition. SE1SE2SE3. SE1 and SE3 are selected to electrochemically match well with anode material and cathode material, respectively. It is desirable that SEs are not continuously decomposed during cycling and that a stabilized micro interface is built up to ensure a lower interfacial resistance and extend the cycling life. Suitably the interlayer, is selected to avoid the side-reaction between high-ionic-conductivity SE2 with electrode active materials, while enabling an intimate macro interfacial connection and minimizing the interfacial resistance.

[0066] In the embodiments of FIGS. 2A-2C, various combinations of compositions of solid electrolyte materials are demonstrated.

[0067] In FIGS. 2A-2C, lithium ion cells 200A-200C are constructed, similarly composed and illustrated like that in FIG. 1. In the illustrations of FIG. 2A-2C, the related elements of the lithium ion cell assemblies, which are unchanged with respect to FIG. 1, are numbered 2xx in which the values of xx are the same as in FIG. 1. And, in these embodiments, the compositions of the particles of anode active material 206 and the particles of cathode active material 218 are of the same compositions as the corresponding anode particles 106 and cathode particles 118 used in the anode layer 104 and cathode layer 116 used in the lithium-ion battery cell 100 of FIG. 1. And the composition of the interlayer 210 is the same in each of FIGS. 2A, 2B, and 2C. But the compositions of the solid electrolyte particles which are changed are given new numbers.

[0068] In the embodiment illustrated in FIG. 2A, the composition of the particles of solid electrolyte material 214 used in the anode layer 205 and the particles of solid electrolyte 214 used in the solid electrolyte layer 212 are the same. SE1=SE2. But the composition of the solid electrolyte particles 218 used in cathode layer 216 are unchanged from the solid electrolyte particles 118 used in the cathode layer 116 of FIG. 1. In the lithium-ion battery cell 200A of FIG. 2A, SE1=SE2SE3.

[0069] In the lithium-ion battery cell 200B illustrated FIG. 2B, the compositions of the particles of solid electrolyte material 214 used in the cathode layer 217 and the particles of the solid electrolyte 214 used in the solid electrolyte layer 212 are the same. SE2=SE3. But the composition of the solid electrolyte particles 208 used in the anode layer 204 is unchanged from the FIG. 1 embodiment. SE1SE2=SE3.

[0070] And in the lithium-ion battery cell 200C illustrated in FIG. 2C, the compositions of the solid electrolyte material 208 used in the anode layer 204 and in, an again modified, cathode layer 219 are the same, but they differ from the composition of solid electrolyte particles 214 in the solid electrolyte layer 212. SE1=SE3SE2. Again, it is desirable that SEs are not continuously decomposed during cycling, and that a stabilized micro-interface is built up to ensure a lower interfacial resistance and extend the cycling life. Suitably the interlayer, is selected to avoid the side-reaction between high-ionic-conductivity SE2 with electrode active materials, while enabling an intimate macro-interfacial connection and minimizing the interfacial resistance.

[0071] In the embodiments of the solid-state lithium-ion battery cell illustrated in the fragmented schematic cross-sectional view of FIG. 3, the use of one or more interlayers between a layer of electrode material and the solid electrolyte layer is illustrated.

[0072] In the broken-off view at the left side of FIG. 3, the cross-sectional view of the lithium-ion battery cell 300A is the same is the illustration of FIG. 1. The members of the cell structure are numbered 3xx in which the values of xx correspond to the 1xx values presented in FIG. 1. In the illustration of lithium-ion battery cell 300A, interlayer 310 is positioned between anode layer 304 and solid electrolyte layer 312. Illustrative compositions of the respective members and constituents of the broken-off cells 300A, 300B and 300C are the same as provided for the members and constituents of the cell 100 in FIG. 1. As stated with respect to interlayer 110 of FIG. 1 positioned between anode layer 104 and solid electrolyte layer 112, the composition of interlayer 110 and 310 may, for example be PEO-LiTFSI.

[0073] In the broken-off view of solid-state lithium-ion battery cell 300B at the center of FIG. 3, a single interlayer 310 is placed between solid electrolyte layer 312 and cathode layer 316. An example of a suitable composition of interlayer 310, positioned between the specified solid electrolyte layer 312 and the cathode layer 316, is 70% Li.sub.2S-29% P.sub.2S.sub.5-1% P.sub.2O.sub.5. And in the broken-off view of solid-state lithium-ion battery cell 300C at the right side of FIG. 3, an interlayer 310 is positioned between anode layer 304 and solid electrolyte layer 312, and interlayer 310 is placed between the specified solid electrolyte layer 312 and the cathode layer 316. Preferably, the interlayer material is selected and placed between anode layer and SE layer to provide good reduction stability and a softened nature to enable a good contact with other particles.

[0074] In the embodiments of the disclosure presented and illustrated in FIGS. 4A and 4B, changes are made in the organization of the solid electrolyte. In FIG. 4A, the solid electrolyte layer is assembled with a first particulate solid electrolyte composition layer 412 adjacent to and co-extensive with the anode electrode layer 404 and with a second layer of solid electrolyte particles 412 adjacent to and coextensive with the cathode layer 416. In FIG. 4A the anode electrode layer 404 may, for example, be composed of a mixture of graphite particles 406 as anode active material and solid electrolyte particles 408 of Li.sub.9.6P.sub.3S.sub.12 (SE1). The first layer of solid electrolyte material 412 is also composed of particles of Li.sub.9.6P.sub.3S.sub.12. Cathode layer 416 may, for example, be composed of a mixture of LiNbO.sub.3-coated LiNi0.5Mn1.5O4 cathode particles 418, mixed with Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride (PVDF)/lithium bis(trifluoromethanesulfonyl)imide hybrid solid electrolyte particles 420. And the second layer of solid electrolyte material 412 also is formed of Li.sub.7La.sub.3Zr.sub.2O.sub.12/polyvinylidene fluoride/lithium bis(trifluoromethanesulfonyl)imide hybrid solid electrolyte particles 420. Thus, the two-layer solid electrolyte 412, 412 matches the solid electrolyte materials 408, 420 used on the anode layer 404 and the cathode layer 416.

[0075] In the embodiment of FIG. 4B, an interlayer 410 of PEO-LiTFSI is interposed between the described layers 412, 412 of solid electrolyte materials 408, 420. Sometimes, the SE layer of 412 or 412 is very thin, which will cause short-circuit of battery. Then, a thin film interlayer is introduced to reduce the short-circuit risks and build a good contact between 412 and 412.

[0076] In the embodiment of FIG. 5 an otherwise solid-state lithium-ion battery cell is infiltrated with a suitable quantity of a liquid electrolyte. For purposes of illustration, the solid-state lithium ion battery cell of FIG. 1 is used. The numerals 5xx identifying the materials and constituents of the cell correspond to the values of 1xx applied and described in that figure. However, in the embodiment of FIG. 1, the entire cell 500 has been infiltrated with a non-aqueous liquid electrolyte, indicated by black line dashes (-). The compositions of the electrode and solid electrolyte materials presented in FIG. 5 may be considered the same as in FIG. 1. In that embodiment the composition of a suitable liquid electrolyte is Li(triethylene glycol dimethyl ether)bis(trifluoromethanesulfonyl)imide (Li(G3)TFSI) solvate ionic liquid.

[0077] While the use of a liquid electrolyte in combination is illustrated with the illustrated lithium-ion solid state cell of FIG. 1 and the electrode and electrolyte compositions described therein, the use of a suitable liquid electrolyte may be used in any of the lithium-ion solid state battery structures and selected solid electrolyte combinations described above in this specification. The ionic contact between the electrode/electrolyte particles is solid-solid, which is still not so sufficient as conventional liquid-based lithium-ion battery. Adding a liquid electrolyte into the battery can build favorable ionic contacts.

[0078] The above description of preferred exemplary embodiments and specific examples are descriptive in nature; they are not intended to limit the scope of the claims that follow. Each of the terms used in the appended claims should be given its ordinary and customary meaning unless specifically and unambiguously stated otherwise in the specification.