# US 12,119,479 B2 · Anode for all solid-state secondary battery, all solid-state secondary battery including the anode, and method of manufacturing the anode

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- Number: US 12,119,479 B2
- Document ID: US12119479B2
- Status: Granted
- Kind: B2
- Application number: 17/471,268
- Filed: 2021-09-10
- Published: 2021-12-30
- Granted: 2024-10-15
- Earliest claimed: 2017-02-07
- Assignees: Samsung Electronics Co., Ltd.
- Applicants: Samsung Electronics Co., Ltd.
- Inventors: Satoshi Fujiki; Seitaro Ito; Taku Watanabe; Yuichi Aihara; Takanobu Yamada
- Web page: https://patentgrep.com/patent/US12119479B2

## CPC

- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/1395: of electrodes based on metals, Si or alloys
- H01M 4/38: of elements or alloys
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/44: Methods for charging or discharging (circuits for charging H02J7/00)
- H01M 4/387: {Tin or alloys based on tin}
- H01M 4/42: Alloys based on zinc
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 2004/027: {Negative electrodes}
- H01M 2300/0068: inorganic
- 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
- 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

An anode for an all solid-state secondary battery, the anode including an anode collector, and coating lithium distribution layer disposed on the anode collector, wherein the lithium distribution layer includes a metal capable of forming an alloy with lithium.

## Claims

### Claim 1

A method of charging an all solid-state secondary battery, the method comprising:
providing an all solid-state battery comprising
a cathode layer,
a solid electrolyte layer on the cathode layer, and
an anode layer on the solid electrolyte layer and opposite the cathode layer, the anode layer comprising an anode collector, and a lithium distribution layer disposed on the anode collector,
wherein the lithium distribution layer comprises a metal capable of forming an alloy with lithium and is disposed between the solid electrolyte layer and the anode collector,
wherein the anode collector comprises a different material than that of the lithium distribution layer,
wherein a diffusion coefficient of lithium in the lithium distribution layer during charging the all solid-state secondary battery is greater than a diffusion coefficient of lithium in lithium metal;
applying a voltage between the cathode layer and the anode layer to form a lithium metal layer on the lithium distribution layer and charge the all solid-state secondary battery,
wherein the lithium distribution layer has a thickness which is greater than or equal to 1 nanometer and less than or equal to 50 nanometers, and
wherein the lithium distribution layer consists of zinc.

### Claim 2 (depends on 1)

The method of claim 1, wherein before the applying a voltage between the cathode layer and the anode layer, the lithium metal layer is not present in the anode layer.

### Claim 3 (depends on 1)

The method of claim 1, wherein the applying a voltage between the cathode layer and the anode layer comprises charging the all solid-state secondary battery, and
wherein the charging comprises precipitating the lithium metal layer on a surface of the lithium distribution layer facing the solid electrolyte layer.

### Claim 4 (depends on 1)

The method of claim 1, wherein the lithium metal layer is formed on a surface of the lithium distribution layer.

### Claim 5 (depends on 1)

The method of claim 1, wherein the solid electrolyte layer is a porous sulfide solid electrolyte layer and the porous sulfide solid electrolyte layer comprises Li2S—P2S5, Li2S—P2S5—LiX wherein X is I or Cl, Li2S—P2S5—Li2O, Li2S—P2S5—Li2O—LiI, Li2S—SiS2, Li2S—SiS2—LiI, Li2S—SiS2—LiBr, Li2S—SiS2—LiCl, Li2S—SiS2—B2S3—LiI, Li2S—SiS2—P2S5—LiI, Li2S—B2S3, Li2S—P2S5—ZmSn wherein m and n are integers, and Z is Ge, Zn, or Ga, Li2S—GeS2, Li2S—SiS2—Li3PO4, Li2S—SiS2-LipMOq wherein p and q are integers, and M is P, Si, or Ge, or a combination thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein the lithium metal layer is a continuous layer on an entire surface of the lithium distribution layer.

### Claim 7

A method of manufacturing an all solid-state secondary battery, the method comprising:
providing a cathode layer,
disposing a solid electrolyte layer on the cathode layer, and
disposing an anode layer on the solid electrolyte layer and opposite the cathode layer to manufacture the all solid-state battery,
wherein the anode layer comprises
an anode collector, and
a lithium distribution layer consists of zinc, wherein the lithium distribution layer is disposed directly on the anode collector and between the solid electrolyte layer and the anode collector, and wherein the anode collector comprises a different material than that of the lithium distribution layer,
wherein a diffusion coefficient of lithium in the lithium distribution layer is greater than a diffusion coefficient of lithium in lithium metal during charge of the all solid-state secondary battery,
wherein the lithium distribution layer has a thickness which is greater than or equal to 1 nanometer and less than or equal to 50 nanometers.

### Claim 8 (depends on 7)

The method of claim 7, further comprising charging the all solid-state secondary battery to form a lithium metal layer on the lithium distribution layer.

### Claim 9 (depends on 8)

The method of claim 8, wherein the lithium metal layer is a continuous layer on an entire surface of the lithium distribution layer.

### Claim 10 (depends on 9)

The method of claim 9, wherein the entire surface of the lithium distribution layer faces the solid electrolyte layer.