All-solid secondary battery, and method of manufacturing all-solid secondary battery

Patent metadata

Field	Value
Publication number	US-11777076-B2
Application number	US-202117172174-A
Country	US
Kind code	B2
Filing date	Feb 10, 2021
Priority date	Feb 18, 2020
Publication date	Oct 3, 2023
Grant date	Oct 3, 2023

Abstract

An all-solid secondary battery including: a cathode layer including a cathode active material layer; an anode layer; and a solid electrolyte layer including a solid electrolyte, wherein the solid electrolyte layer is disposed between the cathode layer and the anode layer, wherein the anode layer includes an anode current collector, a first anode active material layer in contact with the solid electrolyte layer, and a second anode active material layer disposed between the anode current collector and the first anode active material layer, wherein the first anode active material layer includes a first carbonaceous anode active material, and the second anode active material layer.

First claim

What is claimed is:

1. An all-solid secondary battery comprising:
a cathode layer comprising a cathode active material layer;
an anode layer; and
a solid electrolyte layer comprising a solid electrolyte, wherein the solid electrolyte layer is disposed between the cathode layer and the anode layer,
wherein the anode layer comprises:
an anode current collector, a first anode active material layer in contact with the solid electrolyte layer, and
a second anode active material layer disposed between the anode current collector and the first anode active material layer,
a third anode active material layer disposed between the anode current collector and the second anode active material layer or between the first anode active material layer and the second anode active material layer,
wherein the third anode active material layer is a metal layer comprising lithium or a lithium alloy,

wherein the first anode active material layer comprises a first carbonaceous anode active material, and the second anode active material layer comprises a second carbonaceous anode active material, and
a first intensity ratio of an intensity of a D band peak to an intensity of a G band peak in a Raman spectrum of the first carbonaceous anode active material is less than a second intensity ratio of an intensity of a D band peak to an intensity of a G band peak in a Raman spectrum of the second carbonaceous anode active material.

2. The all-solid secondary battery of claim 1 , wherein the first ratio is about 0.1 to about 0.95, and
the second ratio is about 1.0 to about 10.

3. The all-solid secondary battery of claim 1 , wherein a position of a D band peak center in the Raman spectrum of the first carbonaceous anode active material exhibits a blue shift of about 2 cm −1 to about 4 cm −1 with respect to a position of a D band peak center in the Raman spectrum of the second carbonaceous anode active material,
wherein a position of a G band peak center in the Raman spectrum of the first carbonaceous anode active material exhibits a blue shift of about 1 cm −1 to about 3 cm −1 with respect to a position of a G band peak center in the Raman spectrum of the second carbonaceous anode active material, and
wherein a full width at half maximum of the D band peak of the first carbonaceous anode active material is about 50% to about 80% less than a full width at half maximum of the D band peak of the second carbonaceous anode active material.

4. The all-solid secondary battery of claim 1 , wherein at least one of the first carbonaceous anode active material or the second carbonaceous anode active material is in a form of particles, and
wherein the particles have an average particle diameter of about 10 nm to about 4 micrometers or less.

5. The all-solid secondary battery of claim 1 , wherein at least one of the first carbonaceous anode active material or the second carbonaceous anode active material comprises amorphous carbon.

6. The all-solid secondary battery of claim 1 , wherein at least one of the first anode active material layer or the second anode active material layer consists of the first carbonaceous anode active material or the second carbonaceous anode active material, respectively.

7. The all-solid secondary battery of claim 1 , wherein at least one of the first anode active material layer or the second anode active material layer further comprises a metal or metalloid anode active material comprising a metal, a metalloid, or a combination thereof.

8. The all-solid secondary battery of claim 7 , wherein the metal or metalloid anode active material comprises at least one of indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, silver, or zinc.

9. The all-solid secondary battery of claim 7 , wherein each of the first anode active material layer and the second anode active material layer further comprises the metal or metalloid anode active material, and
wherein an amount of the metal or metalloid anode active material in the second anode active material layer is greater than an amount of the metal or metalloid anode active material in the first anode active material layer.

10. The all-solid secondary battery of claim 7 , wherein the first anode active material layer comprises a composite of first particles and second particles, wherein the first particles consist of the first carbonaceous material and the second particles consist of the metal or metalloid anode active material,
wherein the first carbonaceous material is amorphous carbon, and
wherein an amount of the second particles is about 1 weight percent to about 60 weight percent, based on a total weight of the composite.

11. The all-solid secondary battery of claim 10 , wherein the second anode active material layer comprises a mixture of first particles and second particles,
wherein the first particles consist of the second carbonaceous material and the second particles consist of the metal or metalloid anode active material,
wherein the second carbonaceous material is amorphous carbon, and
wherein an amount of the second particles is about 1 weight percent to about 60 weight percent based on a total weight of the mixture.

12. The all-solid secondary battery of claim 11 , wherein an average particle diameter of the first particles in the second anode active material layer is about 50% or less of an average particle diameter of the first particles in the first anode active material layer, and
wherein an average particle diameter of the second particles included in the second anode active material layer is about 50% or less of an average particle diameter of the second particles included in the first anode active material layer.

13. The all-solid secondary battery of claim 1 , wherein the first carbonaceous anode active material is bound to the solid electrolyte layer by at least one of a covalent bond or an ionic bond.

14. The all-solid secondary battery of claim 1 , wherein the first anode active material layer does not comprise an organic material.

15. The all-solid secondary battery of claim 1 , wherein the first carbonaceous anode active material is a sintered product of a carbonaceous precursor, and the carbonaceous precursor is the second carbonaceous anode active material.

16. The all-solid secondary battery of claim 1 , wherein a thickness of the first anode active material layer is about 5% to about 50% of a total thickness of the cathode active material layer, and
wherein the first anode active material layer has a thickness of about 10 nanometers to about 10 micrometers.

17. The all-solid secondary battery of claim 1 , wherein a thickness of the second anode active material layer is about 5% to about 50% of a total thickness of the cathode active material layer, and
wherein the second anode active material layer has a thickness of about 1 micrometer to about 50 micrometers.

18. The all-solid secondary battery of claim 1 , wherein a thickness of the first anode active material layer is less than a thickness of the second anode active material layer.

19. The all-solid secondary battery of claim 1 , wherein at least one of the first anode active material layer or the second anode active material layer further comprises a binder.

20. The all-solid secondary battery of claim 1 , wherein the second anode active material layer comprises the second carbonaceous anode active material and a metal or metalloid anode active material, and the first anode active material layer

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kim Jusik
• Kim Sewon
• Roev Victor
• Lee Myungjin
• Ryu Saebom
• Im Dongmin

Classifications

• H01M4/133 Primary

  Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M4/587

  for inserting or intercalating light metals · CPC title