# US 10,374,254 B2 · Composite electrolytes

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- Number: US 10,374,254 B2
- Document ID: US10374254B2
- Status: Granted
- Kind: B2
- Application number: 15/192,960
- Filed: 2016-06-24
- Published: 2017-01-05
- Granted: 2019-08-06
- Earliest claimed: 2015-06-24
- Assignees: QuantumScape Corporation
- Applicants: QuantumScape Corporation
- Inventors: Kim Van Berkel; Tim Holme; Mohit Singh; Amal Mehrotra; Zhebo Chen; Kian Kerman; Wes Hermann; William Hudson
- Web page: https://patentgrep.com/patent/US10374254B2

## CPC

- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01G 11/06: with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
- H01G 11/56: Solid electrolytes, e.g. gels; Additives therein
- H01M 6/181: {with polymeric electrolytes}
- H01M 6/185: {with oxides, hydroxides or oxysalts as solid electrolytes}
- H01M 10/052: Li-accumulators
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M 10/0562: Solid materials
- H01M 50/446: Composite material consisting of a mixture of organic and inorganic materials
- H01M 2300/0068: inorganic
- H01M 2300/0082: Organic polymers
- H01M 2300/0091: in the form of mixtures
- Y02E 60/10: Energy storage using batteries
- Y02T 10/70: Energy storage systems for electromobility, e.g. batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

Set forth herein are electrolyte compositions that include both organic and inorganic constituent components and which are suitable for use in rechargeable batteries. Also set forth herein are methods and systems for making and using these composite electrolytes.

## Claims

### Claim 1

An electrolyte comprising an inorganic material embedded in an organic material; wherein the inorganic material comprises necked particles of inorganic material which form a percolation network for lithium ion conduction through the electrolyte; wherein the organic material has a lithium ion conductivity of less than 10−8 S/cm at 80° C.;
wherein the inorganic material comprises a surface species which reacts with a functional group selected from an epoxide, a carboxylic acid, an ester, an amide, an amine, a sulfonic acid, a phosphate, a phosphine oxide, a phosphoric acid, an alkoxide, a nitrile, a thioether, thiol, and combinations thereof.

### Claim 2 (depends on 1)

The electrolyte of claim 1, wherein the electrolyte has a fracture strength of greater than 5 MPa and less than 250 MPa, as measured in a ring-on-ring test as specified in the ASTM C1499-09 standard.

### Claim 3 (depends on 1)

The electrolyte of claim 1, wherein the organic material is bonded to, adsorbed on, molded around, or entangled with the surface of the inorganic material, a surface attached species on the surface of the inorganic material, or an inorganic material particle.

### Claim 4 (depends on 1)

The electrolyte of claim 1, wherein the organic material is bonded to the surface of the inorganic material by covalent, ionic, electrostatic, or van Der Waals bonds.

### Claim 5 (depends on 1)

The electrolyte of claim 1, wherein the organic material comprises a functional group selected from a carboxylic acid, an ester, an amide, an amine, a silane, sulfonic acid, a phosphate, a phosphine oxide, a phosphoric acid, an alkoxide, a nitrile, a thioether, thiol, and combinations thereof.

### Claim 6 (depends on 1)

The electrolyte of claim 1, wherein the surface species is selected from a thiol, a hydroxide, a sulfide, an oxide, and a combination thereof.

### Claim 7 (depends on 1)

The electrolyte of claim 1, wherein the organic material has polar functional groups.

### Claim 8 (depends on 1)

The electrolyte of claim 1, wherein the organic material is entangled with the inorganic material.

### Claim 9 (depends on 1)

The electrolyte of claim 1, wherein the organic material is entangled with a surface species which is present on the inorganic material.

### Claim 10 (depends on 9)

The electrolyte of claim 9, wherein the surface species is a monomer, oligomer, or polymer attached to the surface of the inorganic material.

### Claim 11 (depends on 1)

The electrolyte of claim 1, wherein the electrolyte is a thin film having a thickness between 1 nm and 100 μm.

### Claim 12 (depends on 1)

The electrolyte of claim 1, wherein the inorganic material is a solid state electrolyte selected from a lithium-stuffed garnet oxide, an antiperovskite oxide, a lithium borohydride, a lithium iodide-containing material and a lithium sulfide-containing material.

### Claim 13 (depends on 12)

The electrolyte of claim 12, wherein the inorganic material is a solid state electrolyte of a lithium-stuffed garnet oxide characterized by the formula LiuLavZrxOy.zAl2O3, wherein
u is a rational number from 4 to 10;
v is a rational number from 2 to 4;
x is a rational number from 1 to 3;
y is a rational number from 10 to 14; and
z is a rational number from 0 to 1;
wherein u, v, x, y, and z are selected so that the lithium-stuffed garnet oxide is charge neutral.

### Claim 14 (depends on 12)

The electrolyte of claim 12, wherein the lithium-stuffed garnet oxide is characterized by the formula LiuLa3Zr2O12.zAl2O3, wherein 4≤u≤10 and 0<z≤1.

### Claim 15 (depends on 12)

The electrolyte of claim 12, wherein the lithium-stuffed garnet oxide is characterized by the formula Li6.75-7.1La3Zr2O12.0.5Al2O3 or Li6.4-7.7La3Zr2O12. 0.11Al2O3.

### Claim 16 (depends on 12)

The electrolyte of claim 12, wherein the inorganic material is a solid state electrolyte selected from a lithium sulfide characterized by one of the following Formula
LiaSibSncPdSeOf, wherein 2≤a≤8, b+c=1, 0.5≤d≤2.5, 4≤e≤12, and 0<f≤10 ;
LigAshSnjSkOl, wherein 2≤g≤6, 0≤h≤1, 0≤j≤1, 2≤k≤6, and 0≤1≤10;
LimPnSpIq, wherein 2≤m≤6, 0≤n≤1, 0≤p≤1, 2≤q≤6; or
a mixture of (Li2S):(P2S5) having a molar ratio from about 10:1 to about 6:4 and
LiI, wherein the ratio of [(Li2S):(P2S5)]:LiI is from 95:5 to 50:50;
a mixture of LiI and Al2O3;
Li3N;
LPS+X, wherein X is selected from Cl, I, or Br;
vLi2S+wP2S5+yLiX;
vLi2S+wSiS2+yLiX;
vLi2S+wB2S3+yLiX;
a mixture of LiBH4 and LiX wherein X is selected from Cl, I, or Br; or
vLiBH4+wLiX+yLiNH2, wherein X is selected from Cl, I, or Br; and
wherein coefficients v, w, and y are rational numbers from 0 to 1.

### Claim 17 (depends on 12)

The electrolyte of claim 12, wherein the inorganic material is a solid state electrolyte selected from a lithium sulfide characterized by Li10Si0.5Sn0.5P2S12and Li7.4P1.6S7.2I.

### Claim 18 (depends on 1)

The electrolyte of claim 1, wherein the organic material is a polymer.

### Claim 19 (depends on 1)

The electrolyte of claim 1, wherein the organic material is a polymer selected from the group consisting of polyolefins, natural rubbers, synthetic rubbers, polybutadiene, polyisoprene, epoxidized natural rubber, polyisobutylene, polypropylene oxide, polyacrylates, polymethacrylates, polyesters, polyvinyl esters, polyurethanes, styrenic polymers, epoxy resins, epoxy polymers, poly(bisphenol A-co-epichlorohydrin), vinyl polymers, polyvinyl halides, polyvinyl alcohol, polyethyleneimine, poly(maleic anhydride), silicone polymers, siloxane polymers, polyacrylonitrile, polyacrylamide, polychloroprene, polyvinylidene fluoride, polyvinyl pyrrolidone, polyepichlorohydrin, and blends or copolymers thereof.

### Claim 20 (depends on 19)

The electrolyte of claim 19, wherein the molecular weight of the polymer is greater than 50,000 g/mol.

### Claim 21 (depends on 1)

The electrolyte of claim 1, wherein the organic material comprises one or more polymerizable or crosslinkable members selected from the group consisting of vinyl esters, acrylates, methacrylates, styrenic monomers, vinyl-functionalized oligomers of polybutadiene, vinyl-functionalized oligomers of polysiloxanes, and mixtures thereof.

### Claim 22 (depends on 1)

The electrolyte of claim 1, wherein the organic material comprises one or more crosslinkable members selected from the group consisting of diglycidyl ethers, epoxy resins, polyamines, and mixtures thereof.

### Claim 23 (depends on 1)

The electrolyte of claim 1, wherein the organic material comprises one or more polymerizable monomers selected from the group consisting of vinyl esters, acrylates, methacrylates, and styrenic monomers.

### Claim 24 (depends on 1)

The electrolyte of claim 1, wherein the organic material comprises one or more crosslinkable members selected from the group consisting of diglycidyl ethers, triglycidyl ethers, epoxy resins, and polyamines.

### Claim 25 (depends on 1)

The electrolyte of claim 1, wherein the organic material comprises one or more crosslinkable oligomers selected from the group consisting of vinyl-functionalized oligomers of polybutadiene, polysiloxanes, and mixtures thereof.

### Claim 26 (depends on 1)

The electrolyte of claim 1, where the organic material comprises an epoxy resin.

### Claim 27 (depends on 1)

The electrolyte of claim 1, where the organic material comprises an epoxy polymer precursor selected from the group consisting of bisphenol A diglycidyl ether (DGEBA), poly(bisphenol A-co-epichlorohydrin) glycidyl end-capped polymers, diethylenetriamine (DETA) and derivatives thereof, tetraethylenepentamine and derivatives thereof, polyethyleneimine, carboxyl-terminated poly(butadiene-co-acrylonitrile), amine-terminated poly(butadiene-co-acrylonitrile), poly(propylene glycol) diglycidyl ether, poly(propylene glycol) bis(2-aminopropyl ether), and combinations thereof.

### Claim 28 (depends on 1)

The electrolyte of claim 1, further comprising carboxyl-terminated poly(butadiene-co-acrylonitrile), amine-terminated poly(butadiene-co-acrylonitrile), poly(propylene glycol) diglycidyl ether, poly(propylene glycol) bis(2-aminopropyl ether), or combinations thereof.

### Claim 29 (depends on 1)

The electrolyte of claim 1, where the organic material comprises
(a) an epoxy polymer of bisphenol A diglycidyl ether (DGEBA), diethylenetriamine (DETA), and amine-terminated poly(butadiene-co-acrylonitrile);
(b) an epoxy polymer of bisphenol A diglycidyl ether (DGEBA), diethylenetriamine; (c) (DETA), and poly(propylene glycol) bis(2-aminopropyl ether);
(d) an epoxy polymer of bisphenol A diglycidyl ether and diethylenetriamine (DETA);
(e) an epoxy polymer of bisphenol A diglycidyl ether (DGEBA) and poly(propylene glycol) bis(2-aminopropyl ether);
(f) an epoxy polymer of bisphenol A diglycidyl ether and diethylenetriamine (DETA); or
(g) an epoxy polymer of bisphenol A diglycidyl ether (DGEBA) and poly(propylene glycol) bis(2-aminopropyl ether).

### Claim 30 (depends on 29)

The electrolyte of claim 29, wherein the poly(propylene glycol) bis(2-aminopropyl ether) has a molecular weight (g/mol) of about 100 to 50,000.

### Claim 31 (depends on 29)

The electrolyte of claim 29, wherein the poly(propylene glycol) bis(2-aminopropyl ether) has a molecular weight (g/mol) of about 230 to 4000.

### Claim 32 (depends on 1)

The electrolyte of claim 1, wherein the electrolyte has a fracture strength of 25 MPa to 75 MPa.

### Claim 33 (depends on 1)

The electrolyte of claim 1, wherein the electrolyte has a total area specific resistance (ASR) of between 0 Ω·cm2 and 200 Ω·cm2 at 45° C.

### Claim 34 (depends on 1)

The electrolyte of claim 1, wherein the electrolyte comprises an inorganic material and an organic material in a weight ratio of (inorganic material):(organic material) of at least 1:1 to 99:1.

### Claim 35 (depends on 1)

The electrolyte of claim 1, wherein the electrolyte comprises an inorganic material and an organic material in a weight ratio of (inorganic material):(organic material) of at least 80:20 to 99:1.

### Claim 36 (depends on 1)

The electrolyte of claim 1, wherein the volumetric ratio of inorganic material to organic material is greater than 1.

### Claim 37 (depends on 1)

The electrolyte of claim 1, wherein the volumetric ratio of inorganic material to organic material is greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

### Claim 38 (depends on 1)

The electrolyte of claim 1, wherein the necked particles are sintered necked particles.

### Claim 39 (depends on 1)

The electrolyte of claim 1, wherein the necked particles are fuse necked particles.

### Claim 40 (depends on 1)

A composition comprising the electrolyte of claim 1 and a gel electrolyte; wherein the composition of claim 1 directly contacts the gel electrolyte.

### Claim 41 (depends on 1)

An electrochemical device comprising an electrolyte of claim 1.

### Claim 42 (depends on 1)

An electrochemical cell comprising a positive electrode, a negative electrode, and an electrolyte layer, wherein the electrolyte layer comprises an electrolyte selected from any one of the electrolytes in claim 1.

### Claim 43 (depends on 1)

An electrochemical cell comprising a positive electrode, a negative electrode, and a composite electrolyte layer;
wherein the composite electrolyte layer is positioned between the positive electrode and negative electrode;
wherein the composite electrolyte layer comprises a polymer and an inorganic solid state electrolyte;
wherein a volumetric ratio of the inorganic solid state electrolyte to the polymer is greater than 1;
wherein the positive electrode and the negative electrode directly contact the inorganic solid state electrolyte; and wherein the composite electrolyte is an electrolyte of claim 1.

### Claim 44 (depends on 43)

The electrochemical cell of claim 43, wherein the composite electrolyte has a fracture strength of about 50 to 200 MPa.

### Claim 45 (depends on 43)

The electrochemical cell of claim 43, wherein the inorganic solid state electrolyte is sintered or necked.

### Claim 46 (depends on 43)

The electrochemical cell of claim 43, wherein the solid state electrolyte is a lithium-stuffed garnet electrolyte characterized by the formula LiyLa3Zr2O12.X Al2O3, wherein 4≤y≤10 and 0<X≤1.

### Claim 47 (depends on 43)

The electrochemical cell of claim 43, wherein the solid state electrolyte is a sulfide electrolyte characterized by the formula
LiaSibSncPdSeOf, wherein 2≤a≤8, b+c=1, 0.5≤d≤2.5, 4≤e≤12, and 0<f≤10 ;
LigAshSnjSkOl, wherein 2≤g≤6, 0≤h≤1, 0≤j≤1, 2≤k≤6, and 0≤1≤10;
LimPnSpIq, wherein 2≤m≤6, 0≤n≤1, 0≤p≤1, 2≤q≤6; or
a mixture of (Li2S):(P2S5) having a molar ratio from about 10:1 to about 6:4 and
LiI, wherein the ratio of [(Li2S):(P2S5)]:LiI is from 95:5 to 50:50;
a mixture of LiI and Al2O3;
Li3N;
LPS+X, wherein X is selected from Cl, I, or Br;
vLi2S+wP2S5+yLiX;
vLi2S+wSiS2+yLiX;
vLi2S+wB2S3+yLiX;
a mixture of LiBH4 and LiX wherein X is selected from Cl, I, or Br; or
vLiBH4+wLiX+yLiNH2, wherein X is selected from Cl, I, or Br; and
wherein coefficients v, w, and y are rational numbers from 0 to 1.

### Claim 48

An electrolyte comprising an inorganic material and an organic material, wherein the inorganic material is embedded in the organic material, and the organic material is molded around, adsorbed to, bonded to, or entangled with the surface of the inorganic material or a particle thereof; and wherein the inorganic material comprises necked particles of inorganic material which form a percolation network for lithium ion conduction through the electrolyte; wherein the organic material has a lithium ion conductivity of less than 10−8 S/cm at 80° C.; wherein the inorganic material comprises a surface species which reacts with a functional group selected from an epoxide, a carboxylic acid, an ester, an amide, an amine, a sulfonic acid, a phosphate, a phosphine oxide, a phosphoric acid, an alkoxide, a nitrile, a thioether, thiol, and combinations thereof.