Sulfide solid electrolyte and all-solid-state battery

Patent metadata

Field	Value
Publication number	US-12288842-B2
Application number	US-201917270728-A
Country	US
Kind code	B2
Filing date	Aug 30, 2019
Priority date	Aug 30, 2018
Publication date	Apr 29, 2025
Grant date	Apr 29, 2025

Abstract

An aspect of the present invention is a sulfide solid electrolyte that contains at least one element M selected from the group consisting of Al, Si, B, Mg, Zr, Ti, Hf, Ca, Sr, Sc, Ce, Ta, Nb, W, Mo, and V, and N and has a crystalline structure. Another aspect of the present invention is a sulfide solid electrolyte that contains Al and N and that has a crystalline structure.

First claim

The invention claimed is:

1. A sulfide solid electrolyte comprising N and at least one element M selected from the group consisting of Al, Si, B, Mg, Zr, Ti, Hf, Ca, Sr, Sc, Ce, Ta, Nb, W, Mo, and V, and having a crystalline structure,
wherein an ion conductivity at 25° C. is 0.4×10 −3 S/cm or more, and
wherein the sulfide solid electrolyte has a composition represented by a general formula (100-z) (yLi 2 S·(1-y)P 2 S 5 )·zLi α M ß N where 0<z≤40, 0.50≤y≤0.75, α and ß represent numerical values that provide stoichiometric ratios depending on a type of the element M.

2. A sulfide solid electrolyte according to claim 1 , wherein the at least one element M includes Al.

3. A sulfide solid electrolyte comprising Li, P, S, N and at least one element M selected from the group consisting of Al, Si, and B, and having a crystalline structure,
wherein the crystalline structure includes a crystalline structure that has a crystal phase of Li 7 P 3 S 11 , Li 4 P 2 S 6 , or ß-Li 3 PS 4 , or a first crystalline structure that has diffraction peaks at 2θ=17.9°±0.5°, 19.1°±0.5°, 29.1°±0.5°, and 29.8°±0.5° in X-ray diffraction measurement with a CuKα line,
wherein a content ratio of the N to the P is 0.02 or more in terms of mole ratio, and
wherein a content ratio of the M to the P is 0.01 or more in terms of mole ratio.

4. The sulfide solid electrolyte according to claim 3 , wherein the first crystalline structure includes a specific crystalline structure A that has diffraction peaks at 2θ=17.9°+0.5°, 19.1°±0.5°, 29.1°±0.5°, 29.8°±0.5°, and 30.9°±0.5° in the X-ray diffraction measurement, or a specific crystalline structure B that has diffraction peaks at 2θ=17.9°±0.5°, 19.1°±0.5°, 29.1°±0.5°, and 29.8°±0.5° and has no diffraction peak at 30.9°±0.5° in the X-ray diffraction measurement.

5. The sulfide solid electrolyte according to claim 3 ,
wherein a content ratio of the Li to the P is 1.64 or more and 4.00 or less in terms of mole ratio, and the content ratio of the N to the P is 0.02 or more and 1.11 or less in terms of mole ratio.

6. The sulfide solid electrolyte according to claim 5 , wherein the content ratio of the Li to the P is 2.77 or more and 3.38 or less in terms of mole ratio, and the content ratio of the N to the P is 0.28 or more and 0.65 or less in terms of mole ratio.

7. A sulfide solid electrolyte comprising N, Ge and at least one element M selected from the group consisting of Al, Si, B, Mg, Zr, Ti, Hf, Ca, Sr, Sc, Ce, Ta, Nb, W, Mo, and V, and having a crystalline structure,
wherein an ion conductivity at 25° C. is 0.4×10 −3 S/cm or more, and
wherein the sulfide solid electrolyte has a composition represented by a general formula (100-z)Li 10 GeP 2 S 12 ·zLi α M ß N where 0<z≤50, α and ß represent numerical values that provide stoichiometric ratios depending on a type of the element M.

8. The sulfide solid electrolyte according to claim 1 , wherein the ion conductivity at 25° C. is 1.0×10 −3 S/cm or more.

9. An all-solid-state battery comprising:
a negative electrode layer;
a solid electrolyte layer; and
a positive electrode layer,
wherein the negative electrode layer, the solid electrolyte layer, the positive electrode layer, or a combination thereof contains the sulfide solid electrolyte according to claim 1 .

10. A sulfide solid electrolyte comprising Li, P, S, N, Ge and at least one element M selected from the group consisting of Al, Si, and B, and having a crystalline structure,
wherein the crystalline structure includes a crystalline structure that has a crystal phase of Li 10 GeP 2 S 12 ,
wherein a content ratio of the N to the P is 0.02 or more in terms of mole ratio, and
wherein a content ratio of the M to the P is 0.01 or more in terms of mole ratio.

11. A sulfide solid electrolyte according to claim 3 , wherein the crystalline structure includes the crystalline structure that has the crystal phase of Li 7 P 3 S 11 .

12. A sulfide solid electrolyte according to claim 3 , wherein the at least one element M includes Al.

13. An all-solid-state battery comprising:
a negative electrode layer;
a solid electrolyte layer; and
a positive electrode layer,
wherein the negative electrode layer, the solid electrolyte layer, the positive electrode layer, or a combination thereof contains the sulfide solid electrolyte according to claim 3 .

14. A sulfide solid electrolyte according to claim 7 , wherein the at least one element M includes Al.

15. An all-solid-state battery comprising:
a negative electrode layer;
a solid electrolyte layer; and
a positive electrode layer,
wherein the negative electrode layer, the solid electrolyte layer, the positive electrode layer, or a combination thereof contains the sulfide solid electrolyte according to claim 7 .

16. A sulfide solid electrolyte according to claim 10 , wherein the at least one element M includes Al.

17. The sulfide solid electrolyte according to claim 10 ,
wherein a content ratio of the Li to the P is 1.64 or more and 4.00 or less in terms of mole ratio, and the content ratio of the N to the P is 0.02 or more and 1.11 or less in terms of mole ratio.

18. The sulfide solid electrolyte according to claim 17 , wherein the content ratio of the Li to the P is 2.77 or more and 3.38 or less in terms of mole ratio, and the content ratio of the N to the P is 0.28 or more and 0.65 or less in terms of mole ratio.

19. An all-solid-state battery comprising:
a negative electrode layer;
a solid electrolyte layer; and
a positive electrode layer,
wherein the negative electrode layer, the solid electrolyte layer, the positive electrode layer, or a combination thereof contains the sulfide solid electrolyte according to claim 10 .

20. The sulfide solid electrolyte according to claim 3 , consisting of Li, P, S, N and at least one element M selected from the group consisting of AI, Si, and B.

21. The sulfide solid electrolyte according to claim 10 , consisting of Li, P, S, N, Ge and at least one element M selected from the group consisting of AI, Si, and B.

Assignees

• Gs Yuasa Int Ltd

Inventors

• Fukushima Akihiro
• Sakuma Ryo
• Kakeya Tadashi

Classifications

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title

• C01B25/14

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

• H01M2300/0068

  inorganic · CPC title

• H01M10/0525

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

• H01M2004/027

  Negative electrodes · CPC title