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

• US 10,033,065 B2
• Filed: 02/05/2013
• Issued: 07/24/2018
• Est. Priority Date: 02/06/2012
• 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, Kato, Yuki, Otomo, Takamasa, Sakano, Mitsuru
• Primary Examiner(s): Crepeau, Jonathan
• Assistant Examiner(s): Martin, Angela
• Application Number:
  US14/375,571
• Publication Number:
  US 20150037687A1
• Time in Patent Office: 1,995 Days
• 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: C01G 19/006 Compounds containing, besides tin, 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: C01P 2006/40 Electric properties
• 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 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 2300/0068 inorganic
• CPC Class Codes: H01M 4/623 fluorinated polymers
• 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

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 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, and M₂ contains at least P and Si.

Claims

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

the M₁ comprises at least Li;

the M₂ 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<sub>2x(1-δ

)</sub>Si_δ

)_(1-x)P_x(S_1-yO_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 M₂ 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 M₁ is within a range of 3.35 to 3.4 in the case where a total of a molar fraction of the M₂ 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.

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 M₁ element, the M₂ element and the S 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 and a S element wherein

the M₁ comprises at least Li;

the M₂ 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<sub>2x(1-δ

)</sub>Si_δ

)_(1-x)P_x(S_1-yO_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).

14. The sulfide solid electrolyte material according to claim 2, wherein a molar fraction of Si to the M₂ 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 M₁ is within a range of 3.35 to 3.4 in the case where a total of a molar fraction of the M₂ 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 material by mechanical milling while using a raw material composition containing the M₁ 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.

6. 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, and that 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 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<sub>2x(1-δ

)</sub>Si_δ

)_(1-x)P_x(S_1-yO_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 M₁ 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.

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.

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 M₁ 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.