Materials for solid electrolyte

Patent metadata

Field	Value
Publication number	US-10879558-B2
Application number	US-201516060176-A
Country	US
Kind code	B2
Filing date	Dec 22, 2015
Priority date	Dec 22, 2015
Publication date	Dec 29, 2020
Grant date	Dec 29, 2020

Abstract

The present disclosure relates to a material containing the elements Li, M, P, S and X wherein M=Si, Ge or Sn, and X=F, Cl, Br or I. The material can be used as a sulfide solid electrolyte material, notably for an all-solid-state lithium battery.

First claim

The invention claimed is:

1. A material comprising the elements Li, M, P, S and X,
wherein M is at least one element selected from the group consisting of: Si, Ge, and Sn; and
X is at least one halogen element selected from the group consisting of F, Cl, Br and I,
wherein the material has a composition represented by the following general formula (1):
(1−Y)[Li 4+(2−δ)x MS 4 (S 1−δ X δ ) x ]·Y(PS 2.5 )  (1)

wherein:
0.5≤x≤2;
0≤δ≤1; and
0.05≤Y≤0.35.

2. The material according to claim 1 , wherein M is Si.

3. The material according to claim 1 , wherein X is Br.

4. The material according to claim 1 , wherein 0.7≤x≤1.5.

5. The material according to claim 1 , wherein 0.3≤δ≤0.7.

6. The material according to claim 1 ,
wherein, in an X-ray diffraction measurement of the material using a CuKα line, the material shows a peak in the positions of 2θ=15.26° (±0.50°), 17.4° (±0.50°), 25.06° (±0.50°), 29.48° (±0.50°), and 30.08° (±0.50°).

7. A process for preparing the material according to claim 1 , comprising the steps of:
(a) providing solid sulfides Li 2 S, MS 2 (M=Si, Ge or Sn) and P 2 S 5 , as well as LiX (X=F, Cl, Br, I) as dry powders, in the stoichiometric proportions corresponding to the target product, and mixing the powders;
(b) milling the mixture obtained in step (a) under an inert atmosphere; and
(c) heating the milled mixture obtained in step (b) at a temperature T of 300° C.≤T≤700° C., under a pressure P of 0.1 Pa≤P≤200 Pa, for a duration t of 1 h≤t≤50 h.

8. An all-solid-state lithium battery comprising the following elements:
a positive electrode active material layer;
a solid electrolyte; and
a negative electrode active material layer,
wherein the solid electrolyte contains the material according to claim 1 .

9. The material according to claim 1 , wherein 0.8≤x≤1.3.

10. The material according to claim 1 , wherein 0.9≤x≤1.1.

11. The material according to claim 1 , wherein x is substantially equal to 1.0.

12. The material according to claim 1 , wherein 0.4≤δ≤0.6.

13. The material according to claim 1 , wherein δ is substantially equal to 0.5.

14. The material according to claim 1 , wherein 0.10≤Y≤0.25.

15. A material comprising the elements Li, M, P, S and X, wherein
M is at least one element selected from the group consisting of: Si, Ge, and Sn;
X is Br; and
the material has a composition represented by the following general formula (1):
(1−Y)[Li 4+(2−δ)x MS 4 (S 1−δ X δ ) x ]·Y(PS 2.5 )  (1)

wherein:
0.5≤x≤2;
0.3≤δ≤0.7; and
0<Y≤0.5.

16. The material according to claim 15 , wherein M is Si.

17. The material according to claim 15 , wherein 0.7≤x≤1.5.

18. The material according to claim 15 , wherein, in an X-ray diffraction measurement of the material using a CuKα line, the material shows a peak in the positions of 2θ=15.26° (±0.50°), 17.4° (±0.50°), 25.06° (±0.50°), 29.48° (±0.50°), and 30.08° (±0.50°).

19. A process for preparing the material according to claim 15 , comprising the steps of:
(a) providing solid sulfides Li 2 S, MS 2 (M=Si, Ge or Sn) and P 2 S 5 , as well as LiBr as dry powders, in the stoichiometric proportions corresponding to the target product, and mixing the powders;
(b) milling the mixture obtained in step (a) under an inert atmosphere; and
(c) heating the milled mixture obtained in step (b) at a temperature T of 300° C.≤T≤700° C., under a pressure P of 0.1 Pa≤P≤200 Pa, for a duration t of 1 h≤t≤50 h.

20. An all-solid-state lithium battery comprising the following elements:
a positive electrode active material layer;
a solid electrolyte; and
a negative electrode active material layer,
wherein the solid electrolyte contains the material according to claim 15 .

Assignees

• Toyota Motor Europe

Inventors

• Katoh Yuki

Classifications

• C01G19/006

  Compounds containing tin, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• C01G17/006

  Compounds containing germanium, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• C01B25/14

  Sulfur, selenium, or tellurium compounds of phosphorus · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01B1/10

  sulfides · CPC title