# US 12,218,357 B2 · All-solid-state secondary battery using polymer binder made from unsaturated carboxylic acid ester not having hydroxyl groups and compound having a teriary amine group and method of manufacturing same

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- Number: US 12,218,357 B2
- Document ID: US12218357B2
- Status: Granted
- Kind: B2
- Application number: 17/599,277
- Filed: 2020-03-06
- Published: 2022-06-16
- Granted: 2025-02-04
- Earliest claimed: 2019-03-29
- Assignees: ENEOS Materials Corporation
- Applicants: Eneos Materials Corporation
- Inventors: Keigo Aso; Taira Ohashi; Motohisa Azechi; Daisuke Sukeguchi; Shingo Itai
- Web page: https://patentgrep.com/patent/US12218357B2

## CPC

- H01M 4/622: {being polymers}
- C08F 220/18: with acrylic or methacrylic acids
- C08F 220/1804: {C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate}
- C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate}
- C08F 220/1812: {C12-(meth)acrylate, e.g. lauryl (meth)acrylate}
- H01M 4/139: Processes of manufacture
- H01M 10/04: Construction or manufacture in general (H01M10/058, H01M10/12, H01M10/28, H01M10/38 take precedence)
- H01M 10/0562: Solid materials
- H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
- H01M 2300/0068: inorganic
- H01M 2300/0071: Oxides
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A binder for an all-solid-state secondary battery that can control a decrease in ionic conductivity, is excellent in binding properties and oxidation resistance, and can realize favorable cycle life characteristics even under a high voltage; and a binder composition for an all-solid-state secondary battery containing the binder. A binder for an all-solid-state secondary battery includes a polymer (A) which includes a repeating unit (a1) derived from an unsaturated carboxylic acid ester (excluding an unsaturated carboxylic acid ester having a hydroxyl group) and a repeating unit (a2) derived from a compound having a tertiary amino group, a weight-average molecular weight (Mw) of the polymer (A) being from 250000 to 3000000, and an endothermic peak being observed at −10° C. or lower when differential scanning calorimetry (DSC) is performed on the polymer (A) in accordance with JIS K 7121.

## Claims

### Claim 1

A solid electrolyte sheet, comprising:
a layer comprising, in dried form, a solid electrolyte and a binder composition comprising a polymer (A) comprising, in polymerized form, (a1) an unsaturated carboxylic acid ester not having a hydroxyl group; and (a2) a tertiary amino compound comprising a tertiary amino group,
wherein the polymer (A) has a weight-average molecular weight (Mw) in a range of from 250,000 to 3,000,000, and
wherein an endothermic peak is observed at −10° C. or lower when differential scanning calorimetry (DSC) is performed on the polymer (A) in accordance with JIS K 7121,
wherein no electrolyte solution is present in the sheet or contacts the sheet.

### Claim 2 (depends on 1)

The sheet of claim 1, wherein the polymer (A) further comprises, in polymerized form:
(a3) an unsaturated carboxylic acid ester having a hydroxyl group.

### Claim 3 (depends on 1)

The sheet of claim 1, wherein the unsaturated carboxylic acid ester (a3) is comprised in the polymer (A) in a range of from 0.1 to 20 parts by mass, when a total amount of repeating units in the polymer (A) is 100 parts by mass.

### Claim 4 (depends on 1)

The sheet of claim 1, wherein the tertiary amino compound (a2) is comprised in the polymer (A) in a range of from 0.1 to 20 parts by mass, when a total amount of repeating units contained in the polymer (A) is 100 parts by mass.

### Claim 5 (depends on 1)

The sheet of claim 1, wherein the solid electrolyte comprises an oxide-based solid electrolyte.

### Claim 6 (depends on 1)

The sheet of claim 1, wherein the solid electrolyte comprises a sulfide-based solid electrolyte.

### Claim 7 (depends on 1)

A method of manufacturing the solid electrolyte sheet of claim 1, the method comprising:
applying a slurry on a substrate and drying the slurry,
wherein the slurry comprises (i) a liquid medium, (ii) a solid electrolyte, and (iii) a binder comprising a polymer (A) comprising, in polymerized form, (a1) an unsaturated carboxylic acid ester not having a hydroxyl group; and (a2) a tertiary amino compound comprising a tertiary amino group,
wherein the polymer (A) has a weight-average molecular weight (Mw) in a range of from 250,000 to 3,000,000, and
wherein an endothermic peak is observed at −10° C. or lower when differential scanning calorimetry (DSC) is performed on the polymer (A) in accordance with JIS K 7121.

### Claim 8 (depends on 7)

A method of manufacturing an all-solid-state secondary battery, the method comprising:
manufacturing an all-solid-state secondary battery by the method of claim 7 and forming the all-solid-state secondary battery.

### Claim 9

An all-solid-state secondary battery, comprising:
a positive electrode active material layer;
a solid electrolyte layer; and
a negative electrode active material layer,
wherein at least one layer of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer, comprises, in dried form, a solid electrolyte and a binder composition comprising a polymer (A) comprising, in polymerized form, (a1) an unsaturated carboxylic acid ester not having a hydroxyl group; and (a2) a tertiary amino compound comprising a tertiary amino group,
wherein the polymer (A) has a weight-average molecular weight (Mw) in a range of from 250,000 to 3,000,000,
wherein an endothermic peak is observed at −10° C. or lower when differential scanning calorimetry (DSC) is performed on the polymer (A) in accordance with JIS K 7121, and
wherein no electrolyte solution is used in the all-solid-state secondary battery.

### Claim 10 (depends on 9)

The battery of claim 9, wherein the polymer (A) further comprises, in polymerized form:
(a3) an unsaturated carboxylic acid ester having a hydroxyl group.

### Claim 11 (depends on 9)

The battery of claim 9, wherein the unsaturated carboxylic acid ester (a3) is comprised in the polymer (A) in a range of from 0.1 to 20 parts by mass, when a total amount of repeating units in the polymer (A) is 100 parts by mass.

### Claim 12 (depends on 9)

The battery of claim 9, wherein the tertiary amino compound (a2) is comprised in the polymer (A) in a range of from 0.1 to 20 parts by mass, when a total amount of repeating units contained in the polymer (A) is 100 parts by mass.

### Claim 13 (depends on 9)

The battery of claim 9, wherein the solid electrolyte comprises an oxide-based solid electrolyte.

### Claim 14 (depends on 9)

The battery of claim 9, wherein the solid electrolyte comprises a sulfide-based solid electrolyte.