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

• US 9,263,763 B2
• Filed: 12/21/2012
• Issued: 02/16/2016
• Est. Priority Date: 12/22/2011
• Status: Active Grant

• Current Assignee: Tokyo Institute of Technology (National University Corporation Tokyo Institute of Technology), Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Original Assignee: Tokyo Institute of Technology (National University Corporation Tokyo Institute of Technology), Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Inventors: Hirayama, Masaaki, Kato, Yuki, Kawamoto, Koji, Otomo, Takamasa, Kanno, Ryoji
• Primary Examiner(s): Ryan, Patrick
• Assistant Examiner(s): O Donnell, Lucas J
• Application Number:
  US14/365,950
• Publication Number:
  US 20140363745A1
• Time in Patent Office: 1,152 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C01B 17/20 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 Class Codes: C01G 17/006 Compounds containing, besides germanium, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/74 by peak-intensities or a ratio thereof only
• CPC Class Codes: C01P 2002/77 by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: H01B 1/10 sulfides
• 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: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

The object of the present invention is to provide a sulfide solid electrolyte material with favorable ion conductivity. The present invention attains the object by providing a sulfide solid electrolyte material including an M₁ element (such as a Li element), an M₂ element (such as a Ge element and a P element), a S element and an O element, and having a peak at a position of 2θ=29.58°±0.50° in an X-ray diffraction measurement using a CuKα ray, characterized in that 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.

Claims

1. A sulfide solid electrolyte material comprising an M₁ element, an M₂ element, a S element and an O element, wherein

the M₁ contains at least Li;

the M₂ is at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb; and

having a peak at a position of 2θ

=20.18°

±

0.50°

, 2θ

=20.44°

±

0.50°

, 2θ

=26.96°

±

0.50° and

2θ

=29.58°

±

0.50°

in an X-ray diffraction measurement using a CuKα

ray; and

wherein 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.

4. The sulfide solid electrolyte material according to claim 1, comprising at least a Li element, a Ge element, a P element, the S element and the O element, wherein a ratio of the O element to a total of the S element and the O element is 25% or less.

5. The sulfide solid electrolyte material according to claim 1, comprising at least a Li element, a Si element, a P element, the S element and the O element, wherein a ratio of the O element to a total of the S element and the O element is 10% or less.

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 1.

7. 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 M₁ element, the M₂ 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.

2. A sulfide solid electrolyte material comprising an M₁ element, an M₂ element, a S element and an O element, wherein

the M₁ contains at least Li;

the M₂ is at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb; and

having a peak at a position of 2θ

=20.18°

±

0.50°

, 2θ

=20.44°

±

0.50°

, 2θ

=26.96°

±

0.50° and

2θ

=29.58°

±

0.50°

in an X-ray diffraction measurement using a CuKα

ray; and

wherein the sulfide solid electrolyte material does not have a peak at a position of 2θ

=27.33°

±

0.50°

in the X-ray diffraction measurement using the CuKα

ray, or wherein 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 in a case the sulfide solid electrolyte material has a peak at the position of 2θ

=27.33°

±

0.50°

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

3. A sulfide solid electrolyte material having an octahedron O composed of an M₁ element and a S element, a tetrahedron T₁ composed of an M_2a element and a S element, and a tetrahedron T₂ composed of an M_2b element and a S element,

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

the M₁ contains at least Li;

the M_2a and the M_2b are each independently at least one kind selected from the group consisting of P, Sb, Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, V and Nb; and

at least one of the octahedron O, the tetrahedron T₁ and the tetrahedron T₂ is such that a part of the S element is substituted with an O element.

8. 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 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 M₁ element, the M_2a element, the M_2b 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.