Manufacturing method of pre-lithiated anode for solid-state battery

Patent metadata

Field	Value
Publication number	US-2025259986-A1
Application number	US-202418781462-A
Country	US
Kind code	A1
Filing date	Jul 23, 2024
Priority date	Feb 13, 2024
Publication date	Aug 14, 2025
Grant date	—

Abstract

An embodiment method of manufacturing a pre-lithiated anode includes preparing an anode assembly including an anode current collector and an intermediate layer disposed on a surface of the anode current collector, wherein the intermediate layer includes silver particles and a carbon material, applying an electrolyte solution to the intermediate layer, manufacturing a pressurization structure by stacking a lithium supply layer on the intermediate layer coated with the electrolyte solution, and performing pre-lithiation to convert the intermediate layer into a coating layer by applying pressure to the pressurization structure in a stacking direction thereof to form the pre-lithiated anode, wherein the coating layer includes a γ 3 phase Li—Ag alloy formed by reacting the silver particles with lithium in performing the pre-lithiation.

First claim

What is claimed is:

1 . A method of manufacturing a pre-lithiated anode, the method comprising:
preparing an anode assembly comprising an anode current collector and an intermediate layer disposed on a surface of the anode current collector, wherein the intermediate layer comprises silver particles and a carbon material; applying an electrolyte solution to the intermediate layer; manufacturing a pressurization structure by stacking a lithium supply layer on the intermediate layer coated with the electrolyte solution; and performing pre-lithiation to convert the intermediate layer into a coating layer by applying pressure to the pressurization structure in a stacking direction thereof to form the pre-lithiated anode, wherein the coating layer comprises a γ 3 phase Li—Ag alloy formed by reacting the silver particles with lithium in performing the pre-lithiation.

2 . The method of claim 1 , wherein the electrolyte solution comprises a lithium salt and an organic solvent.

3 . The method of claim 2 , wherein the lithium salt comprises a compound selected from the group consisting of LiCl, LiBr, LiI, LiBF 4 , LiClO 4 , LiB 10 Cl 10 , LiAlCl 4 , LiAlO 4 , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiCH 3 SO 3 , LiN(SO 2 F) 2 (lithium bis(fluorosulfonyl)imide, LiFSI), LiN(SO 2 CF 2 CF 3 ) 2 (lithium bis(pentafluoroethanesulfonyl)imide, LiBETI), LiN(SO 2 CF 3 ) 2 (lithium bis(trifluoromethane sulfonyl)imide, LiTFSI), and combinations thereof.

4 . The method of claim 2 , wherein the organic solvent comprises a solvent selected from the group consisting of an ester-based solvent, an ether-based solvent, a ketone-based solvent, an aromatic hydrocarbon-based solvent, a carbonate-based solvent, an alcohol-based solvent, a nitrile-based solvent, an amide-based solvent, a dioxolane-based solvent, a sulfolane-based solvent, and combinations thereof.

5 . The method of claim 1 , wherein an area of the lithium supply layer is greater than an area of the anode assembly.

6 . The method of claim 1 , wherein the pressure applied to the pressurization structure is 0.01 MPa to 0.1 MPa.

7 . The method of claim 1 , wherein the pre-lithiation is performed for 5 hours or more but less than 10 hours.

8 . The method of claim 1 , wherein the pre-lithiation is performed for 5 hours to 7 hours.

9 . The method of claim 1 , wherein the pre-lithiation is performed at room temperature.

10 . The method of claim 1 , wherein the γ 3 phase Li—Ag alloy is represented by Li x Ag, wherein x is 1.98 to 2.25.

11 . The method of claim 1 , wherein the γ 3 phase Li—Ag alloy is irreversibly formed.

12 . The method of claim 1 , wherein the coating layer does not comprise a γ 2 phase Li—Ag alloy or a γ 1 phase Li—Ag alloy.

13 . The method of claim 1 , wherein the carbon material comprises a material selected from the group consisting of a particulate carbon material, a fibrous carbon material, and a combination thereof.

14 . The method of claim 1 , further comprising, after performing the pre-lithiation:
collecting the pre-lithiated anode comprising the anode current collector and the coating layer; removing remaining impurities from the pre-lithiated anode with a washing solvent; and drying the pre-lithiated anode from which the impurities have been removed.

15 . An all-solid-state battery comprising:
the pre-lithiated anode prepared according to the method of claim 1 ; a solid electrolyte layer disposed on the pre-lithiated anode, the solid electrolyte layer comprising a solid electrolyte; and a cathode disposed on the solid electrolyte layer, the cathode comprising a cathode active material layer and a cathode current collector.

16 . A method of manufacturing an all-solid state battery, the method comprising:
manufacturing a pre-lithiated anode, wherein manufacturing the pre-lithiated anode comprises:
preparing an anode assembly comprising an anode current collector and an intermediate layer disposed on a surface of the anode current collector, wherein the intermediate layer comprises silver particles and a carbon material;
applying an electrolyte solution to the intermediate layer;
manufacturing a pressurization structure by stacking a lithium supply layer on the intermediate layer coated with the electrolyte solution; and
performing pre-lithiation to convert the intermediate layer into a coating layer by applying pressure to the pressurization structure in a stacking direction thereof to form the pre-lithiated anode, wherein the coating layer comprises a γ 3 phase Li—Ag alloy formed by reacting the silver particles with lithium in performing the pre-lithiation;
disposing a solid electrolyte layer on the pre-lithiated anode; and disposing a cathode on the solid electrolyte layer, the cathode comprising a cathode active material layer and a cathode current collector.

17 . The method of claim 16 , wherein:
the electrolyte solution comprises a lithium salt and an organic solvent; the lithium salt comprises a compound selected from the group consisting of LiCl, LiBr, LiI, LiBF 4 , LiClO 4 , LiB 10 Cl 10 , LiAlCl 4 , LiAlO 4 , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiCH 3 SO 3 , LiN(SO 2 F) 2 (lithium bis(fluorosulfonyl)imide, LiFSI), LiN(SO 2 CF 2 CF 3 ) 2 (lithium bis(pentafluoroethanesulfonyl)imide, LiBETI), LiN(SO 2 CF 3 ) 2 (lithium bis(trifluoromethane sulfonyl)imide, LiTFSI), and combinations thereof; and the organic solvent comprises a solvent selected from the group consisting of an ester-based solvent, an ether-based solvent, a ketone-based solvent, an aromatic hydrocarbon-based solvent, a carbonate-based solvent, an alcohol-based solvent, a nitrile-based solvent, an amide-based solvent, a dioxolane-based solvent, a sulfolane-based solvent, and combinations thereof.

18 . The method of claim 16 , wherein:
the pressure applied to the pressurization structure is 0.01 MPa to 0.1 MPa; and the pre-lithiation is performed at room temperature for 5 hours or more but less than 10 hours.

19 . The method of claim 16 , wherein the γ 3 phase Li—Ag alloy is represented by Li x Ag, wherein x is 1.98 to 2.25.

20 . The method of claim 16 , wherein the coating layer does not comprise a γ 2 phase Li—Ag alloy or a γ 1 phase Li—Ag alloy.

Assignees

• Hyundai Motor Co Ltd
• Kia Corp
• Kyungpook Nat Univ Ind Academic Coop Found

Inventors

• Bae Ki Yoon
• Son Sam Ick
• Kim Ji Young
• Lee Ju Hyeon
• Lee Ji Hoon

Classifications

• H01M2004/027

  Negative electrodes · CPC title

• H01M10/058

  Construction or manufacture · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/0435

  Rolling or calendering · CPC title

• H01M4/405

  Alloys based on lithium · CPC title