Solid electrolyte composition, solid electrolyte-containing sheet, all-solid state secondary battery, and methods for manufacturing solid electrolyte-containing sheet and all-solid state secondary battery

Patent metadata

Field	Value
Publication number	US-11489197-B2
Application number	US-202016820648-A
Country	US
Kind code	B2
Filing date	Mar 16, 2020
Priority date	Sep 28, 2017
Publication date	Nov 1, 2022
Grant date	Nov 1, 2022

Abstract

A solid electrolyte composition containing an inorganic solid electrolyte having conductivity of an ion of a metal belonging to Group I or II of the periodic table and an acid-modified cellulose nanofiber, a solid electrolyte-containing sheet and a manufacturing method therefor, and an all-solid state secondary battery having an inorganic solid electrolyte layer containing the inorganic solid electrolyte having conductivity of an ion of a metal belonging to Group I or II of the periodic table and an acid-modified cellulose nanofiber and a manufacturing method therefor.

First claim

What is claimed is:

1. A solid electrolyte composition comprising:
an inorganic solid electrolyte (A) having conductivity of an ion of a metal belonging to Group I or II of the periodic table;
an acid-modified cellulose nanofiber (B); and
a binder (D).

2. The solid electrolyte composition according to claim 1 ,
wherein the acid-modified cellulose nanofiber (B) is an acid-modified substance of at least any of a carboxy group or a phosphoric acid group and a salt thereof.

3. The solid electrolyte composition according to claim 1 ,
wherein an acid value of the acid-modified cellulose nanofiber (B) is 0.1 to 2.5 mmol/g.

4. The solid electrolyte composition according to claim 1 ,
wherein the acid-modified cellulose nanofiber (B) have an average fiber diameter of 1 to 1,000 nm and an average fiber length of 10 to 100,000 nm.

5. The solid electrolyte composition according to claim 1 ,
wherein a mass ratio (A)/(B) of a content of the inorganic solid electrolyte (A) to a content of the acid-modified cellulose nanofiber (B) is 99.9/0.1 to 50/50.

6. The solid electrolyte composition according to claim 1 ,
wherein a water content is 50 ppm or less.

7. The solid electrolyte composition according to claim 1 ,
wherein the inorganic solid electrolyte (A) is a sulfide-based inorganic solid electrolyte.

8. The solid electrolyte composition according to claim 1 , further comprising:
a non-aqueous dispersion medium (C).

9. The solid electrolyte composition according to claim 1 ,
wherein the non-aqueous dispersion medium (C) is a hydrocarbon compound solvent, an ether compound solvent, a ketone compound solvent, an ester compound solvent, or a combination of two or more thereof.

10. The solid electrolyte composition according to claim 1 ,
wherein the binder (D) includes a polymer having a basic functional group.

11. The solid electrolyte composition according to claim 1 , further comprising:
an active material (E).

12. A solid electrolyte-containing sheet comprising:
an inorganic solid electrolyte (A) having conductivity of an ion of a metal belonging to Group I or II of the periodic table;
an acid-modified cellulose nanofiber (B); and
a binder (D).

13. A method for manufacturing a solid electrolyte-containing sheet comprising:
a step of forming a film of the solid electrolyte composition according to claim 1 .

14. A method for manufacturing an all-solid state secondary battery,
wherein the all-solid state secondary battery is manufactured through the manufacturing method according to claim 13 .

15. An all-solid state secondary battery comprising:
a positive electrode active material layer;
a negative electrode active material layer; and
an inorganic solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer,
wherein the inorganic solid electrolyte layer contains an inorganic solid electrolyte (A) having conductivity of an ion of a metal belonging to Group I or II of the periodic table, an acid-modified cellulose nanofiber (B) and a binder (D).

16. The all-solid state secondary battery according to claim 15 ,
wherein the inorganic solid electrolyte layer has a thickness of 1 to 30 μm.

17. The all-solid state secondary battery according to claim 15 ,
wherein the negative electrode active material layer is a layer of lithium metal.

18. A solid electrolyte composition comprising:
an inorganic solid electrolyte (A) having conductivity of an ion of a metal belonging to Group I or II of the periodic table;
an acid-modified cellulose nanofiber (B); and
a conductive auxiliary agent (F).

19. The solid electrolyte composition according to claim 18 ,
wherein the acid-modified cellulose nanofiber (B) is an acid-modified substance of at least any of a carboxy group or a phosphoric acid group and a salt thereof.

20. The solid electrolyte composition according to claim 18 ,
wherein an acid value of the acid-modified cellulose nanofiber (B) is 0.1 to 2.5 mol/g.

21. The solid electrolyte composition according to claim 18 ,
wherein the acid-modified cellulose nanofiber (B) have an average fiber diameter of 1 to 1,000 nm and an average fiber length of 10 to 100,000 nm.

22. The solid electrolyte composition according to claim 18 ,
wherein a mass ratio (A)/(B) of a content of the inorganic solid electrolyte (A) to a content of the acid-modified cellulose nanofiber (B) is 99.9/0.1 to 50/50.

23. The solid electrolyte composition according to claim 18 ,
wherein a water content is 50 ppm or less.

24. The solid electrolyte composition according to claim 18 ,
wherein the inorganic solid electrolyte (A) is a sulfide-based inorganic solid electrolyte.

25. The solid electrolyte composition according to claim 18 , further comprising:
a non-aqueous dispersion medium (C).

26. The solid electrolyte composition according to claim 18 ,
wherein the non-aqueous dispersion medium (C) is a hydrocarbon compound solvent, an ether compound solvent, a ketone compound solvent, an ester compound solvent, or a combination of two or more thereof.

27. The solid electrolyte composition according to claim 18 ,
wherein the binder (D) includes a polymer having a basic functional group.

28. The solid electrolyte composition according to claim 18 , further comprising:
an active material (E).

29. A method for manufacturing a solid electrolyte-containing sheet comprising:
a step of forming a film of the solid electrolyte composition according to claim 18 .

30. A method for manufacturing an all-solid state secondary battery,
wherein the all-solid state secondary battery is manufactured through the manufacturing method according to claim 29 .

31. A solid electrolyte-containing sheet comprising:
an inorganic solid electrolyte (A) having conductivity of an ion of a metal belonging to Group I or II of the periodic table;
an acid-modified cellulose nanofiber (B); and
a conductive auxiliary agent (F).

32. An all-solid state secondary battery comprising:
a positive electrode active material layer;
a negative electrode active material layer; and
an inorganic solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer,
wherein the inorganic solid electrolyte layer contains an inorganic solid electrolyte (A) having conductivity of an ion of a metal belonging to Group I or II of the periodic table, an acid-modified cellulose nanofiber (B) and a conductive auxiliary agent (F).

33. The all-solid state secondary battery according to claim 32 ,
wherein the inorganic solid electrolyte layer has a thickness of 1 to 30 μm.

34. The all-solid state secondary battery according to claim 32 ,
wherein the negative electrode active material layer is a layer of lithium metal.

Assignees

• Fujifilm Corp

Inventors

• Makino Masaomi

Classifications

• H01M4/134 Primary

  Electrodes based on metals, Si or alloys · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0525

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

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title