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

Patent metadata

Field	Value
Publication number	US-10033065-B2
Application number	US-201314375571-A
Country	US
Kind code	B2
Filing date	Feb 5, 2013
Priority date	Feb 6, 2012
Publication date	Jul 24, 2018
Grant date	Jul 24, 2018

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 M1 element (such as a Li element), an M2 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 IA and a diffraction intensity at a peak of 2θ=27.33°±0.50° is regarded as IB, a value of IB/IA is less than 0.50, and M2 contains at least P and Si.

First claim

The invention claimed is:

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 mate

Assignees

• Tokyo Inst Tech
• Toyota Motor Co Ltd

Inventors

• Kanno Ryoji
• Hirayama Masaaki
• Kato Yuki
• Otomo Takamasa
• Sakano Mitsuru

Classifications

• H01M2300/0068

  inorganic · CPC title

• C01G19/006

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

• C01P2002/77

  by unit-cell parameters, atom positions or structure diagrams · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title

• C01B17/20

  Methods for preparing sulfides or polysulfides, in general (ammonium sulfides or polysulfides C01C; sulfides or polysulfides of metals, other than alkali metals, magnesium, calcium, strontium and barium, see the relevant groups of subclasses C01F or C01G, according to the metal) · CPC title