# US 11,967,678 B2 · All solid-state lithium-ion battery incorporating electrolyte-infiltrated composite electrodes

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- Number: US 11,967,678 B2
- Document ID: US11967678B2
- Status: Granted
- Kind: B2
- Application number: 18/097,384
- Filed: 2023-01-16
- Published: 2023-05-18
- Granted: 2024-04-23
- Earliest claimed: 2021-01-04
- Assignees: Solid Energies Inc.
- Applicants: Solid Energies Inc.
- Inventors: Zhigang Lin; Chunhu Tan; Tianyu Meng
- Web page: https://patentgrep.com/patent/US11967678B2

## CPC

- H01M 10/0562: Solid materials
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 4/622: {being polymers}
- H01M 4/625: {Carbon or graphite}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 50/434: Ceramics
- H01M 50/443: Particulate material
- H01M 50/446: Composite material consisting of a mixture of organic and inorganic materials
- H01M 50/497: Ionic conductivity
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2300/0071: Oxides
- H01M 2300/0082: Organic polymers
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Electrolyte-infiltrated composite electrode includes an electrolyte component consisting of a polymer matrix with ceramic nanoparticles embedded in the matrix to form a networking structure of electrolyte. Suitable ceramic nanoparticles have the basic formula Li7La3Zr2O12 (LLZO) and its derivatives such as AlxLi7-xLa3Zr2-y-zTayNbzO12 where x ranges from 0 to 0.85, y ranges from 0 to 0.50 and z ranges from 0 to 0.75, wherein at least one of x, y and z is not equal to 0. The networking structure of the electrolyte establishes an effective lithium-ion transport pathway in the electrode and strengthens the contact between electrode layer and solid-state electrolyte resulting in higher lithium-ion electrochemical cell's cycling stability and longer battery life. Sold-state electrolytes incorporating the ceramic particles demonstrate improved performance. Large dimensional electrolyte-infiltrated composite electrode sheets can be used in all solid-state lithium electrochemical pouch cells which can be assembled into battery packs.

## Claims

### Claim 1

A ceramic-polymer composite electrode that comprises:
(i) a polymer matrix, (ii) ceramic nanoparticles that are distributed in the polymer matrix wherein the nanoparticles comprise AlxLi7-xLa3Zr2-y-zTayNbzO12 wherein x ranges from 0.1 to 0.85, y ranges from 0 to 0.50, and z ranges from 0 to 0.75, and mixtures thereof, (iii) an anode active material which comprises graphite that is distributed in the polymer matrix, (iv) a conducting agent that is distributed in the polymer matrix, (v) a plasticizer and (vi) a lithium salt wherein the electrode comprises 60 to 96 wt % anode active material, 1 to 15 wt % conducting agent, 0.1 to 10 wt % lithium salt, 0.1 to 5 wt % ceramic nanoparticles, 0.1 to 10 wt % plasticizer, 0.1 to 5 wt % polymer matrix and 0 to 15 wt %, additional binder and wherein the ceramic nanoparticles have diameters that range from 10 to 2000 nm and wherein the electrode is in the form of a film that has an ionic conductivity that is higher than 0.1×10−3 S/cm when measured at a temperature between −30° C. to 10° C. and that is higher than 1×10−3 S/cm when measured at a temperature of 20° C. or higher.

### Claim 2 (depends on 1)

The electrode of claim 1 wherein the ceramic nanoparticles comprise Al0.15Li6.85La3Zr1.75Ta0.25O12.

### Claim 3 (depends on 1)

The electrode of claim 1 wherein the plasticizer is selected from the group consisting of succinonitrile (SCN), sulfolane (SL), ethylene carbonate (EC), dimethyl sulfoxide (DMSO), glutaronitrile (GN), propylene carbonate (PC) and mixtures thereof.

### Claim 4 (depends on 1)

The electrode of claim 1 wherein the lithium salt is selected from the group consisting of bis(trifluoromethanesulfonyl)imide (LiTFSI), LiClO4, LiPF6, LiAsF6, lithium bis(oxalato)borate (LiBOB), and mixtures thereof.

### Claim 5 (depends on 1)

The electrode of claim 1 wherein at least one of y and z is not equal to 0.

### Claim 6 (depends on 5)

The electrode of claim 5 wherein z ranges from 0.01 to 0.60.

### Claim 7

A ceramic-polymer composite electrode that comprises: (i) a polymer matrix, (ii) ceramic nanoparticles that are distributed in the polymer matrix wherein the nanoparticles comprise AlxLi7-xLa3Zr2-y-zTayNbzO12 wherein x ranges from 0.1 to 0.85, y ranges from 0 to 0.50, and z ranges from 0 to 0.75, (iii) an anode active material which comprises silicon that is distributed in the polymer matrix, (iv) a conducting agent that is distributed in the polymer matrix, (v) a plasticizer and (vi) a lithium salt wherein the electrode comprises 60 to 96 wt % anode active material, 1 to 15 wt % conducting agent, 0.1 to 10 wt % lithium salt, 0.1 to 5 wt % ceramic nanoparticles, 0.1 to 10 wt % plasticizer, 0.1 to 5 wt % polymer matrix and 0 to 15 wt %, additional binder and wherein the ceramic nanoparticles have diameters that range from 10 to 2000 nm and wherein the electrode is in the form of a film that has an ionic conductivity that is higher than 0.1×10−3 S/cm when measured at a temperature between −30° C. to 10° C. and that is higher than 1×10−3 S/cm when measured at a temperature of 20° C. or higher.

### Claim 8 (depends on 7)

The electrode of claim 7 wherein the ceramic nanoparticles comprise Al0.15Li6.85La3Zr1.75Ta0.25O12.

### Claim 9 (depends on 7)

The electrode of claim 7 wherein at least one of y and z is not equal to 0.

### Claim 10 (depends on 9)

The electrode of claim 9 wherein z ranges from 0.01 to 0.60.

### Claim 11 (depends on 7)

The electrode of claim 7 wherein the polymer matrix comprises polyethylene glycol diacrylate (PEGDA).

### Claim 12 (depends on 7)

The electrode of claim 7 wherein the plasticizer is selected from the group consisting of succinonitrile (SCN), sulfolane (SL), ethylene carbonate (EC), dimethyl sulfoxide (DMSO), glutaronitrile (GN), propylene carbonate (PC) and mixtures thereof.

### Claim 13 (depends on 7)

The electrode of claim 7 wherein the lithium salt is selected from the group consisting of bis(trifluoromethanesulfonyl)imide (LiTF SI), LiClO4, LiPF6, LiAsF6, lithium bis(oxalato)borate (LiBOB), and mixtures thereof.

### Claim 14

A ceramic-polymer composite electrode that comprises:
(i) a polymer matrix, (ii) ceramic nanoparticles that are distributed in the polymer matrix wherein the nanoparticles comprise AlxLi7-xLa3Zr2-y-zTayO12 wherein x ranges from 0.1 to 0.85, y ranges from 0 to 0.50, and z ranges from 0 to 0.75, (iii) a cathode active material that consists essentially of lithium based cathode material particles that are distributed in the polymer matrix, (iv) a conducting agent that is distributed in the polymer matrix, (v) a plasticizer and (vi) a lithium salt wherein the electrode comprises 60 to 96 wt % cathode active material, 1 to 15 wt % conducting agent, 0.1 to 10 wt % lithium salt, 0.1 to 5 wt % ceramic nanoparticles, 0.1 to 10 wt % plasticizer, 0.1 to 5 wt % polymer matrix and 0 to 15 wt %, additional binder and wherein the ceramic nanoparticles have diameters that range from 10 to 2000 nm and wherein the electrode is in the form of a film that has an ionic conductivity that is higher than 0.1×10−3 S/cm when measured at a temperature between −30° C. to 10° C. and that is higher than 1×10−3 S/cm when measured at a temperature of 20° C. or higher.

### Claim 15 (depends on 14)

The electrode of claim 14 wherein the ceramic nanoparticles comprise Al0.15Li6.85La3Zr1.75Ta0.25O12.

### Claim 16 (depends on 14)

The electrode of claim 14 wherein at least one of y and z is not equal to 0.

### Claim 17 (depends on 16)

The electrode of claim 16 wherein z ranges from 0.01 to 0.60.

### Claim 18 (depends on 14)

The electrode of claim 14 wherein the polymer matrix comprises polyethylene glycol diacrylate (PEGDA).

### Claim 19 (depends on 14)

The electrode of claim 14 comprising a cathode active material that is selected from the group consisting of LiFePO4 (LFP), LiNi0.8Co0.1Mn0.1O2 (NCM811), LiNi0.5Co0.2Mn0.3O2 (NCM 523), LiNi0.6Co0.2Mn0.2O2 (NCM 622) and mixtures thereof.

### Claim 20 (depends on 14)

The electrode of claim 14 wherein the plasticizer is selected from the group consisting of succinonitrile (SCN), sulfolane (SL), ethylene carbonate (EC), dimethyl sulfoxide (DMSO), glutaronitrile (GN), propylene carbonate (PC) and mixtures thereof.

### Claim 21 (depends on 14)

The electrode of claim 14 wherein the lithium salt is selected from the group consisting of bis(trifluoromethanesulfonyl)imide (LiTF SI), LiClO4, LiPF6, LiAsF6, lithium bis(oxalato)borate (LiBOB), and mixtures thereof.