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

• US 10,128,532 B2
• Filed: 12/18/2013
• Issued: 11/13/2018
• Est. Priority Date: 01/11/2013
• Status: Active Grant

• Current Assignee: MSN Laboratories Limited, Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Original Assignee: Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Inventors: Kato, Yuki, Osaki, Mayuko
• Primary Examiner(s): D'Aniello, Nicholas P
• Assistant Examiner(s): Ojo-Amoo, Abibatu O
• Application Number:
  US14/758,712
• Publication Number:
  US 20150372345A1
• Time in Patent Office: 1,791 Days
• Field of Search: 429322
• CPC Class Codes: H01B 1/10 sulfides
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• 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

Sulfide solid electrolyte material with favorable ion conductivity, wherein charge and discharge efficiency is inhibited from decreasing. Solves problem by providing a sulfide solid electrolyte material including a Li element, Si element, P element, S element and O element, having peak at position of 2θ=29.58°±0.50° in X-ray diffraction measurement using CuKα ray, wherein sulfide solid electrolyte material does not have peak at position of 2θ=27.33°±0.50° in X-ray diffraction measurement using CuKα ray, or in case of having peak at position of 2θ=27.33°±0.50°, value of I_B/I_A is 1 or less when diffraction intensity at peak of 2θ=29.58°±0.50° is regarded as I_A and diffraction intensity at peak of 2θ=27.33°±0.50° is regarded as I_B; and wherein molar fraction of O element to total of S element and O element is larger than 0.2.

Claims

1. A sulfide solid electrolyte material comprising a Li element, a Si element, a P element, a S element and an O element,

having a peak at a position of 2θ

=29.58°

±

0.50°

in X-ray diffraction measurement using a CuKα

ray,

wherein 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

ray, or

in a case of having a peak at the position of 2θ

=27.33°

±

0.50°

, a value of I_B/I_A is 1 or less when diffraction intensity at the peak of 2θ

=29.58°

±

0.50°

is regarded as I_A and diffraction intensity at the peak of 2θ

=27.33°

±

0.50°

is regarded as I_B; and

wherein a molar fraction (O/(S+O)) of the O element to a total of the S element and the O element is larger than 0.2.

3. The sulfide solid electrolyte material according to claim 1, wherein the molar fraction (O/(S+O)) satisfies 0.25≤

(O/(S+O))≤

0.35.

5. The sulfide solid electrolyte material according to claim 1, wherein a molar fraction (P/(P+Si)) of the P element to a total of the P element and the Si element satisfies 0.65≤

(P/(P+Si))≤

0.75.

7. A 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.

9. A method for producing 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 Li element, the Si element, the P element, the S element and the O element; and

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

11. The method for producing the sulfide solid electrolyte material according to claim 9, wherein the raw material composition contains a material having an Si—

O bond.

13. The sulfide solid electrolyte material according to claim 1, wherein the molar fraction (O/(S+O)) satisfies 0.2<

(O/(S+O))≤

0.4.

2. A sulfide solid electrolyte material comprising:

an octahedron O composed of a Li element and a S element;

a tetrahedron T₁ composed of an M_a element and a S element; and

a tetrahedron T₂ composed of an M_b element and a S element,

wherein the tetrahedron T₁ and the octahedron O share an edge, and the tetrahedron T₂ and the octahedron O contain a crystal structure sharing a corner as a main body; and

at least one of the M_a and the M_b contains Si,

at least one of the M_a and the M_b contains P,

at least one of the tetrahedron T₁ and the tetrahedron T₂ is such that a part or all of the S element bonding to the Si element is substituted with an O element, and

a molar fraction (O/(S+O)) of the O element to a total of the S element and the O element is larger than 0.2.

4. The sulfide solid electrolyte material according to claim 2, wherein the molar fraction (O/(S+O)) satisfies 0.25≤

(O/(S+O))≤

0.35.

6. The sulfide solid electrolyte material according to claim 2, wherein a molar fraction (P/(P+Si)) of the P element to a total of the P element and the Si element satisfies 0.65≤

(P/(P+Si))≤

0.75.

8. A 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.

10. A method for producing 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 Li element, the M_a element, the M_b element, the S element and the O element; and

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

12. The method for producing the sulfide solid electrolyte material according to claim 10, wherein the raw material composition contains a material having an Si—

O bond.

14. The sulfide solid electrolyte material according to claim 2, wherein the molar fraction (O/(S+O)) satisfies 0.2<

(O/(S+O))≤

0.4.