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

• US 8,697,292 B2
• Filed: 03/25/2011
• Issued: 04/15/2014
• Est. Priority Date: 03/26/2010
• 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: Kanno, Ryoji, Hirayama, Masaaki, Kawamoto, Koji, Hama, Shigenori, Kato, Yuki, Otomo, Takamasa, Nobuhara, Kunihiro
• Primary Examiner(s): Ryan, Patrick
• Assistant Examiner(s): COLUCCI RIOS, JOSE A
• Application Number:
  US13/636,954
• Publication Number:
  US 20130040208A1
• Time in Patent Office: 1,117 Days
• Field of Search: None
• US Class Current: 429/322
• 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: C01B 25/14 Sulfur, selenium, or tellurium compounds of phosphorus
• 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 2002/50 Solid solutions
• 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 10/0562 Solid materials
• CPC Class Codes: H01M 2300/0068 inorganic
• 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

Abstract

The problem of the present invention is to provide a sulfide solid electrolyte material having excellent ion conductivity. The present invention solves the problem by providing a sulfide solid electrolyte material comprising an M₁ element (such as a Li element), an M₂ element (such as a Ge element and a P element), and an S element; having a peak in a position of 2θ=29.58°±0.50° in an X-ray diffraction measurement using a CuKα line; and having an I_B/I_A value of less than 0.50 when a diffraction intensity at the peak of 2θ=29.58°±0.50° is represented by I_A and a diffraction intensity at a peak of 2θ=27.33°±0.50° is represented by I_B.

Claims

1. A sulfide solid electrolyte material comprising an M₁ element, an M₂ element, and an S element;

wherein M₁ is at least one kind selected from the group consisting of Li, Na, K, Mg, Ca and Zn; and

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;

having a peak in positions of 2θ

=20.18°

±

0.50°

, 20.44°

±

0.50°

, 26.96°

±

0.50° and

29.58°

±

0.50°

in an X-ray diffraction measurement using a CuKα

line; and

having an I_B/I_A value of 0.25 or less when a diffraction intensity at the peak of 2θ

=29.58°

±

0.50°

is represented by I_A and a diffraction intensity at a peak of 2θ

=27.33°

±

0.50°

is represented by I_B.

2. The sulfide solid electrolyte material according to claim 1, having a peak in positions of 2θ

=17.38°

, 23.56°

, 23.96°

, 24.93°

, 29.07°

, 29.58°

, 31.71°

, 32.66° and

33.39°

(these positions may be within a range of ±

0.50°

) in the X-ray diffraction measurement using the CuKα

line.

3. The sulfide solid electrolyte material according to claim 1, wherein M₁ is Li and M₂ is Ge and P.

4. The sulfide solid electrolyte material according to claim 3, having a composition of Li_(4-X)Ge_(1-X)P_XS₄ (x satisfies 0<

x<

1).

5. The sulfide solid electrolyte material according to claim 4, wherein x satisfies 0.5≦

x≦

0.8.

9. 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.

11. The battery according to claim 9, wherein the electrolyte layer is a solid electrolyte layer containing the sulfide solid electrolyte material.

6. A sulfide solid electrolyte material comprising as a main body a crystal structure having an octahedron O comprising an M₁ element and an S element, a tetrahedron T₁ comprising an M_2a element and an S element, and a tetrahedron T₂ comprising an M_2b element and an S element, in which the tetrahedron T₁ and the octahedron O share an edge, and the tetrahedron T₂ and the octahedron O share a corner;

and

wherein M₁ is at least one kind selected from the group consisting of Li, Na, K, Mg, Ca and Zn; and

M_2a and 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.

7. The sulfide solid electrolyte material according to claim 6, wherein the octahedron O is an LiS₆ octahedron, in which M₁ is Li;

the tetrahedron T₁ is a GeS₄ tetrahedron and a PS₄ tetrahedron, in which M_2a is Ge and P respectively; and

the tetrahedron T₂ is a PS₄ tetrahedron, in which M_2b is P.

8. The sulfide solid electrolyte material according to claim 6, having a peak in a position of 2θ

=29.58°

±

0.50°

in an X-ray diffraction measurement using a CuKα

line; and

having an I_B/I_A value of 0.25 or less when a diffraction intensity at the peak of 2θ

=29.58°

±

0.50°

is represented by I_A and a diffraction intensity at a peak of 2θ

=27.33°

±

0.50°

is represented by I_B.

10. 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 6.

12. The battery according to claim 10, wherein the electrolyte layer is a solid electrolyte layer containing the sulfide solid electrolyte material.

13. A method for producing a sulfide solid electrolyte material, comprising the steps of:

an ion conductive material synthesizing step of synthesizing a crystalline ion conductive material by using a raw material composition containing an M₁ element (M₁ is at least one kind selected from the group consisting of Li, Na, K, Mg, Ca and Zn), an M₂ element (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 an S element;

a crystallinity decreasing step of decreasing crystallinity of the ion conductive material by mechanical milling; and

a heating step of heating the ion conductive material with the crystallinity decreased to obtain a sulfide solid electrolyte material having a peak in positions of 2θ

=20.18°

±

0.50°

, 20.44°

±

0.50°

, 26.96°

±

0.50° and

29.58°

±

0.50°

in an X-ray diffraction measurement using a CuKα

line, and having an I_B/I_A value of 0.25 or less when a diffraction intensity at the peak of 2θ

=29.58°

±

0.50°

is represented by I_A and a diffraction intensity at a peak of 2θ

=27.33°

±

0.50°

is represented by I_B.

14. The method for producing a sulfide solid electrolyte material according to claim 13, wherein the ion conductive material is synthesized by a solid phase method in the ion conductive material synthesizing step.

15. The method for producing a sulfide solid electrolyte material according to claim 13, wherein the mechanical milling is vibrating mill.

18. The method for producing a sulfide solid electrolyte material according to claim 13, wherein the raw material composition contains Li₂S, P₂S₅ and GeS₂.

16. A method for producing a sulfide solid electrolyte material, comprising the steps of:

an ion conductive material synthesizing step of synthesizing an amorphous ion conductive material by mechanical milling by using a raw material composition containing an M₁ element (M₁ is at least one kind selected from the group consisting of Li, Na, K, Mg, Ca and Zn), an M₂ element (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 an S element; and

a heating step of heating the amorphous ion conductive material to obtain a sulfide solid electrolyte material having a peak in positions of 2θ

=20.18°

±

0.50°

, 20.44°

±

0.50°

, 26.96°

±

0.50° and

29.58°

±

0.50°

in an X-ray diffraction measurement using a CuKα

line, and having an I_B/I_A value of 0.25 or less when a diffraction intensity at the peak of 2θ

=29.58°

±

0.50°

is represented by I_A and a diffraction intensity at a peak of 2θ

=27.33°

±

0.50°

is represented by I_B.

17. The method for producing a sulfide solid electrolyte material according to claim 16, wherein the mechanical milling is ball mill or vibrating mill.

19. The method for producing a sulfide solid electrolyte material according to claim 16, wherein the raw material composition contains Li₂S, P₂S₅ and GeS₂.