Solid electrolyte material and all solid-state lithium secondary battery

• US 9,397,365 B2
• Filed: 03/25/2011
• Issued: 07/19/2016
• Est. Priority Date: 03/26/2010
• Status: Active Grant

• Current Assignee: Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Original Assignee: Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Inventors: Hama, Shigenori, Ohtomo, Takamasu, Tatsumisago, Masahiro, Hayashi, Akitoshi, Kawamoto, Koji
• Primary Examiner(s): Ruddock, Ula C
• Assistant Examiner(s): Park, Lisa S
• Application Number:
  US13/636,899
• Publication Number:
  US 20130011746A1
• Time in Patent Office: 1,943 Days
• US Class Current: 1/1
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A solid electrolyte material for an all solid-state lithium secondary battery represented by Li₂S-M^I_aS_b-M^II_xO_y, wherein M^I is selected from P, Si, Ge, B and Al; “a” and “b” respectively represent numbers that give a stoichiometric ratio in accordance with the kind of M^I; M^II is selected from Fe, Zn and Bi; and “x” and “y” respectively represent numbers that give a stoichiometric ratio in accordance with the kind of M^II.

Claims

1. A solid electrolyte material for an all solid-state lithium secondary battery represented by Li₂S-M^I_aS_b-M^II_xO_y,

wherein:

M^I is selected from P, Si, Ge, B and Al;

“

a” and

“

b”

respectively represent numbers that give a stoichiometric ratio in accordance with the kind of M^I;

M^II, “

x,” and

“

y”

are selected such that M^II_xO_y is Bi₂O₃;

M^II_xO_y is less stable than M^II_xS_y;

the Li₂S-M^I_aS_b-M^II_xO_y has a composition in which the ratio of M^II_xO_y to the total of Li₂S and M^I_aS_b is 60;

40 to 95;

5 (mole ratio); and

said solid electrolyte material is;

(i) used for the all solid-state lithium secondary battery comprising a positive electrode, a solid electrolyte layer, and a negative electrode;

(ii) contained in any of the positive electrode, the solid electrolyte layer, and the negative electrode; and

(iii) capable of suppressing generation of hydrogen sulfide.

2. The solid electrolyte material for an all solid-state lithium secondary battery of claim 1, wherein the M^I_aS_b is P₂S₅.

3. The solid electrolyte material for an all solid-state lithium secondary battery of claim 1, wherein the Li₂S-M^I_aS_b-M^II_xO_y has a composition in which the ratio of Li₂S and M^I_aS_b is 50:

50 to 90;

10 (mole ratio).

4. An all solid-state lithium secondary battery comprising:

a positive electrode;

a negative electrode; and

a solid electrolyte layer interposed between the positive electrode and the negative electrode, the solid electrolyte layer containing the solid electrolyte material of claim 1.

5. The all solid-state lithium secondary battery of claim 4, wherein at least one of the positive electrode and the negative electrode further contains the solid electrolyte material for the all solid-state lithium secondary battery.

6. The solid electrolyte material for an all solid-state lithium secondary battery of claim 1, wherein M^I, “

a,” and

“

b”

are selected such that M^I_aS_b is Al₂S₃.

7. A solid electrolyte material for an all solid-state lithium secondary battery represented by Li₂S-M^I_aS_b-M^II_xO_y,

wherein M^I is selected from P, Si, Ge, B and Al;

“

a” and

“

b”

respectively represent numbers that give a stoichiometric ratio in accordance with the kind of M^I;

M^II is selected from Fe, Zn, and Bi;

“

x” and

“

y”

respectively represent numbers that give a stoichiometric ratio in accordance with the kind of M^II; and

the Li₂S-M^I_aS_b-M^II_xO_y has a composition in which the ratio of M^II_xO_y to the total of Li₂S and M^I_aS_b is 60;

40 to 95;

5 (mole ratio).

9. The solid electrolyte material for an all solid-state lithium secondary battery of claim 7, wherein the M^II_xO_y is selected from Fe₂O₃, ZnO and Bi₂O₃.

10. The solid electrolyte material for an all solid-state lithium secondary battery of claim 7, wherein the M^I_aS_b is P₂S₅.

11. The solid electrolyte material for an all solid-state lithium secondary battery of claim 7, wherein the Li₂S-M^I_aS_b-M^II_xO_y has a composition in which the ratio of Li₂S and M^I_aS_b is 50:

50 to 90;

10 (mole ratio).

12. An all solid-state lithium secondary battery comprising:

a positive electrode;

a negative electrode; and

a solid electrolyte layer interposed between the positive electrode and the negative electrode, the solid electrolyte layer containing the solid electrolyte material of claim 7.

13. The all solid-state lithium secondary battery of claim 12, wherein at least one of the positive electrode and the negative electrode further contains the solid electrolyte material for the all solid-state lithium secondary battery.

8. An all solid-state lithium secondary battery, comprising:

a positive electrode;

a negative electrode;

a solid electrolyte layer interposed between the positive electrode and the negative electrode; and

a solid electrolyte material contained in the solid electrolyte layer and throughout at least one of the positive electrode and the negative electrode, wherein;

the solid electrolyte material is represented by Li₂S-M^I_aS_b-M^II_xO_y, in which;

M^I is selected from P, Si, Ge, B and Al;

“

a” and

“

b”

respectively represent numbers that give a stoichiometric ratio in accordance with the kind of M^I;

M^II is selected from Fe, Zn, and Bi; and

“

x” and

“

y”

respectively represent numbers that give a stoichiometric ratio in accordance with the kind of M^II; and

the Li₂S-M^I_aS_b-M^II_xO_y has a composition in which the ratio of M^II_xO_y to the total of Li₂S and M^I_aS_b is 60;

40 to 95;

5 (mole ratio).