IP Library Granted Patent US 10,033,065
Granted Patent B2
US 10,033,065 · App. 14/375,571 · Granted Jul 24, 2018

Sulfide solid electrolyte material, battery, and producing method for sulfide solid electrolyte material

Inventors: Ryoji Kanno (Kawasaki, JP); Masaaki Hirayama (Yokohama, JP); Yuki Kato (Susono, JP); Takamasa Otomo (Susono, JP); Mitsuru Sakano (Toyota, JP)
Assignees: TOKYO INSTITUTE OF TECHNOLOGY; TOYOTA JIDOSHA KABUSHIKI KAISHA
H01M10/0562C01B17/20C01B25/14C01G17/006C01G19/006H01B1/10H01M10/052C01P2002/72C01P2002/74C01P2002/77C01P2006/40H01M4/623H01M2220/20H01M2220/30H01M2300/0068
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Quick Facts
Patent No.
US 10,033,065
App. No.
14/375,571
Granted
Jul 24, 2018
Kind
B2
Abstract

A main object of the present invention is to provide a sulfide solid electrolyte material having favorable ion conductivity and low reduction potential. The present invention solves the above-mentioned problem by providing a sulfide solid electrolyte material including an M 1 element (such as a Li element), an M 2 element (such as a Ge element, a Si element and a P element) and a S element, wherein the material has a peak at a position of 2θ=29.58°±0.50° in X-ray diffraction measurement using a CuKα line; and when a diffraction intensity at the peak of 2θ=29.58°±0.50° is regarded as I A and a diffraction intensity at a peak of 2θ=27.33°±0.50° is regarded as I B , a value of I B /I A is less than 0.50, and M 2 contains at least P and Si.

Claims (46)

1. A sulfide solid electrolyte material comprising an M 1 element, an M 2 element and a S element wherein

the M 1 comprises at least Li;

the M 2 is P, Si and an element other than P and Si;

the other element is at least one selected from the group consisting of Sn, Ti, Zr, and Nb;

the sulfide solid electrolyte material has a peak at a position of 2θ=20.18°±0.50°, 20.44°±0.50°, 26.96°±0.50° and 29.58°±0.50° in X-ray diffraction measurement using a CuKα line; and

when a diffraction intensity at the peak of 2θ=29.58°±0.50° is regarded as I A and a diffraction intensity at a peak of 2θ=27.33°±0.50° is regarded as I B , a value of I B /I A is less than 0.50,

wherein the sulfide solid electrolyte material is represented by Li (4-x) (M 2x(1-δ) Si δ ) (1-x) P x (S 1-y O y ) 4 (M 2x is at least one selected from the group consisting of Sn, Zr, Ti and Nb, 0<x<1, 0≤y≤0.25, 0<δ<1).

2. A sulfide solid electrolyte material comprising an M 1 element, an M 2 element and a S element wherein

the M 1 comprises at least Li;

the M 2 is P, Si and an element other than P and Si;

the other element is at least one selected from the group consisting of Sn, Ti, Zr, and Nb;

the sulfide solid electrolyte material has a peak at a position of 2θ=20.18°±0.50°, 20.44°±0.50°, 26.96°±0.50° and 29.58°±0.50° in X-ray diffraction measurement using a CuKα line; and either

the sulfide solid electrolyte material has a peak at a position of 2θ=27.33°±0.50° in X-ray diffraction measurement using a CuKα line, and the sulfide solid electrolyte material does not have a peak at a position of 2θ=27.33°±0.50° in X-ray diffraction measurement using a CuKα line; or

when a diffraction intensity at the peak of 2θ=29.58°±0.50° is regarded as I A and a diffraction intensity at the peak of 2θ=27.33°±0.50° is regarded as I B , a value of I B /I A is less than 0.50, and

wherein the sulfide solid electrolyte material is represented by Li (4-x) (M 2x(1-δ) Si δ ) (1-x) P x (S 1-y O y ) 4 (M 2x is at least one selected from the group consisting of Sn, Zr, Ti and Nb, 0<x<1, 0≤y≤0.25, 0<δ<1).

3. The sulfide solid electrolyte material according to claim 1 , wherein a molar fraction of Si to the M 2 excluding P is 30% or more.

4. The sulfide solid electrolyte material according to claim 1 , wherein an a-axial length of a lattice constant is within a range of 8.66 A to 8.69 A in a crystal phase having a peak at the position of 2θ=29.58°±0.50°.

5. The sulfide solid electrolyte material according to claim 1 , wherein a molar fraction of the M 1 is within a range of 3.35 to 3.4 in the case where a total of a molar fraction of the M 2 is regarded as 1.

6. A sulfide solid electrolyte material having an octahedron O composed of an M 1 element and a S element, a tetrahedron T 1 composed of an M 2a element and a S element, and a tetrahedron T 2 composed of an M 2b element and a S element, and that the tetrahedron T 1 and the octahedron O share an edge, the tetrahedron T 2 and the octahedron O contain a crystal structure sharing a corner as a main body;

the M 1 comprises at least Li;

at least one of the M 2a and the M 2b comprises P;

at least one of the M 2a and the M 2b comprises Si;

at least one of the M 2a and the M 2b comprises an element other than P and Si; and

the other element is at least one selected from the group consisting of Sn, Ti, Zr, and Nb,

wherein the sulfide solid electrolyte material is represented by Li (4-x) (M 2x(1-δ) Si δ ) (1-x) P x (S 1-y O y ) 4 (M 2x is at least one kind selected from the group consisting of Sn, Zr, Ti and Nb, 0<x<1, 0≤y≤0.25, 0<δ<1).

7. The sulfide solid electrolyte material according to claim 6 , wherein a molar fraction of Si to the M 2a and the M 2b which are excluding P is 30% or more.

8. The sulfide solid electrolyte material according to claim 6 , wherein an a-axial length of a lattice constant is within a range of 8.66 A to 8.69 A in the crystal structure.

9. The sulfide solid electrolyte material according to claim 6 , wherein a molar fraction of the M 1 is within a range of 3.35 to 3.4 in the case where a total of a molar fraction of the M 2a and the M 2b is regarded as 1.

10. A lithium battery comprising a cathode active material layer containing a cathode active material, an anode active material layer containing an anode active material, and an electrolyte layer formed between the cathode active material layer and the anode active material layer;

wherein at least one of the cathode active material layer, the anode active material layer and the electrolyte layer contains the sulfide solid electrolyte material according to claim 1 .

11. A lithium battery comprising a cathode active material layer containing a cathode active material, an anode active material layer containing an anode active material, and an electrolyte layer formed between the cathode active material layer and the anode active material layer;

wherein at least one of the cathode active material layer, the anode active material layer and the electrolyte layer contains the sulfide solid electrolyte material according to claim 6 .

12. A producing method for a sulfide solid electrolyte material, the sulfide solid electrolyte material being the sulfide solid electrolyte material according to claim 1 , comprising steps of:

an ion conductive material synthesizing step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the M 1 element, the M 2 element and the S element, and

a heating step of obtaining the sulfide solid electrolyte material by heating the amorphized ion conductive material.

13. A producing method for a sulfide solid electrolyte material, the sulfide solid electrolyte material being the sulfide solid electrolyte material according to claim 6 , comprising steps of:

an ion conductive material synthesizing step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the M 1 element, the M 2a element, the M 2b element and the S element, and

a heating step of obtaining the sulfide solid electrolyte material by heating the amorphized ion conductive material.

14. The sulfide solid electrolyte material according to claim 2 , wherein a molar fraction of Si to the M 2 element excluding P is 30% or more.

15. The sulfide solid electrolyte material according to claim 2 , wherein an a-axial length of a lattice constant is within a range of 8.66 A to 8.69 A in a crystal phase having a peak at the position of 2θ=29.58°±0.50°.

16. The sulfide solid electrolyte material according to claim 2 , wherein a molar fraction of the M 1 is within a range of 3.35 to 3.4 in the case where a total of a molar fraction of the M 2 is regarded as 1.

17. A lithium battery comprising a cathode active material layer containing a cathode active material, an anode active material layer containing an anode active material, and an electrolyte layer formed between the cathode active material layer and the anode active material layer;

wherein at least one of the cathode active material layer, the anode active material layer and the electrolyte layer contains the sulfide solid electrolyte material according to claim 2 .

18. A producing method for a sulfide solid electrolyte material, the sulfide solid electrolyte material being the sulfide solid electrolyte material according to claim 2 , comprising steps of:

an ion conductive material synthesizing step of synthesizing an amorphized ion conductive material by mechanical milling while using a raw material composition containing the M 1 element, the M 2a element, the M 2b element and the S element, and

a heating step of obtaining the sulfide solid electrolyte material by heating the amorphized ion conductive material.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 30, 2014
From: KANNO, RYOJI; HIRAYAMA, MASAAKI; KATO, YUKI; OTOMO, TAKAMASA; SAKANO, MITSURU
To: TOKYO INSTITUTE OF TECHNOLOGY; TOYOTA JIDOSHA KABUSHIKI KAISHA
Reel/Frame 033423/0147 →
Priority Claims (2)
JP 2012-022964 · Feb 6, 2012 · national
JP 2012-234144 · Oct 23, 2012 · national
Continuity (1)
Related Publication 20150037687A1 · Feb 5, 2015
Cited By (1)
US 12,482,856