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

• US 9,748,602 B2
• Filed: 04/16/2014
• Issued: 08/29/2017
• Est. Priority Date: 04/16/2013
• Status: Active Grant

• Current Assignee: Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Original Assignee: Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Inventors: Osaki, Mayuko, Kato, Yuki
• Primary Examiner(s): Godo, Olatunji
• Application Number:
  US14/783,604
• Publication Number:
  US 20160064771A1
• Time in Patent Office: 1,231 Days
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: C01B 35/14 Compounds containing boron and nitrogen, phosphorus, sulfur, selenium or tellurium
• CPC Class Codes: H01B 1/10 sulfides
• CPC Class Codes: H01B 1/122 Ionic conductors
• 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 2220/20 Batteries in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 2220/30 Batteries in portable systems, e.g. mobile phone, laptop
• CPC Class Codes: H01M 2300/002 Inorganic electrolyte
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A sulfide solid electrolyte material with favorable ion conductivity and high reduction resistance. The object is attained by providing sulfide solid electrolyte material comprising: Li element; Ge element; P element; and S element, wherein the sulfide solid electrolyte material peaks at a position of 2θ=29.58°±0.50° in X-ray diffraction measurement using CuKα ray, the sulfide solid electrolyte material does not peak at a position of 2θ=27.33°±0.50° in X-ray diffraction measurement using CuKα ray or 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, a value of I_B/I_A is less than 1.0, and part of the P element in a crystal phase peaking at the position of 2θ=29.58°±0.50° is substituted with a B element.

Claims

1. A sulfide solid electrolyte material comprising:

a Li element;

a Ge element;

a P element; and

a S element, wherein

the sulfide solid electrolyte material has a peak at a position of 2θ

=29.58°

±

0.50°

in X-ray diffraction measurement using a CuKα

ray,

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 the sulfide solid electrolyte material having a peak at the position of 2θ

=27.33°

±

0.50°

, 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, a value of I_B/I_A is less than 0.50, and

a part of the P element in a crystal phase having the peak at the position of 2θ

=29.58°

±

0.50°

is substituted with a B element.

5. 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 producing method for a sulfide solid electrolyte material, the sulfide solid electrolyte material being the sulfide solid electrolyte material according to claim 1, comprising:

an ion conductive material synthesizing process of synthesizing an amorphized ion conductive material by mechanical milling with a raw material composition containing a constituent of the sulfide solid electrolyte material; and

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

2. A sulfide solid electrolyte material comprising:

a Li element;

a Ge element;

a B element; and

a S element, wherein

the sulfide solid electrolyte material has a peak at a position of 2θ

=29.58°

±

0.50°

in X-ray diffraction measurement using a CuKα

ray,

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 the sulfide solid electrolyte material having a peak at the position of 2θ

=27.33°

±

0.50°

, 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, a value of I_B/I_A is less than 0.50, and

a crystal phase having the peak at the position of 2θ

=29.58°

±

0.50°

does not contain a P element, and the B element is located at a site for the P element in a crystal structure of Li₁₀GeP₂S₁₂.

6. 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 producing method for a sulfide solid electrolyte material, the sulfide solid electrolyte material being the sulfide solid electrolyte material according to claim 2, comprising:

an ion conductive material synthesizing process of synthesizing an amorphized ion conductive material by mechanical milling with a raw material composition containing a constituent of the sulfide solid electrolyte material; and

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

3. A sulfide solid electrolyte material having 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, the tetrahedron T₁ and the octahedron O sharing an edge, and the tetrahedron T₂ and the octahedron O containing a crystal structure sharing a corner as a main body, wherein

the M_a element contains a Ge element and a P element,

the M_b element contains a P element, and

a part of the P element is substituted with a B element.

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 3.

11. A producing method for a sulfide solid electrolyte material, the sulfide solid electrolyte material being the sulfide solid electrolyte material according to claim 3, comprising:

an ion conductive material synthesizing process of synthesizing an amorphized ion conductive material by mechanical milling with a raw material composition containing a constituent of the sulfide solid electrolyte material; and

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

4. A sulfide solid electrolyte material having 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, the tetrahedron T₁ and the octahedron O sharing an edge, and the tetrahedron T₂ and the octahedron O containing a crystal structure sharing a corner as a main body, wherein

the M_a element contains a Ge element and a B element,

the M_b element contains a B element, and

the crystal structure does not contain a P element and the B element is located at a site for the P element in a crystal structure of Li₁₀GeP₂S₁₂.

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 4.

12. A producing method for a sulfide solid electrolyte material, the sulfide solid electrolyte material being the sulfide solid electrolyte material according to claim 4, comprising:

an ion conductive material synthesizing process of synthesizing an amorphized ion conductive material by mechanical milling with a raw material composition containing a constituent of the sulfide solid electrolyte material; and

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