Sulfide solid electrolyte

Patent metadata

Field	Value
Publication number	US-11264642-B2
Application number	US-201716324267-A
Country	US
Kind code	B2
Filing date	Aug 8, 2017
Priority date	Aug 10, 2016
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

A sulfide solid electrolyte containing lithium, phosphorus, sulfur; and one or more of elements X selected from the group consisting of halogen elements and chalcogen elements excluding sulfur, wherein the sulfide solid electrolyte includes an argyrodite-type crystal structure, and wherein a molar ratio of the lithium to the phosphorus, a (Li/P), a molar ratio of the sulfur to the phosphorus, b (S/P), and a molar ratio of the element X to the phosphorus, c (X/P), satisfy formulas (1) to (3): 5.0≤a≤7.1 (1) 1.0<a−b≤1.5 (2) 6.5≤a+c<7.1 (3) wherein b>0 and c>0 are satisfied.

First claim

The invention claimed is:

1. A sulfide solid electrolyte, comprising lithium, phosphorus, sulfur and at least one element X selected from the group consisting of a halogen element and a chalcogen element excluding sulfur, wherein:
the sulfide solid electrolyte comprises an argyrodite-type crystal structure;
a molar ratio of the lithium to the phosphorus, A (Li/P), a molar ratio of the sulfur to the phosphorus, B (S/P), and a molar ratio of the element X to the phosphorus, C (X/P), satisfy

formulas (1) to (3):
5.0 ≤A≤ 7.1  (1)

1.0 <A−B≤ 1.5  (2)

6.5≤ A+C< 7.1  (3); and

B>0 and C>0.

2. The sulfide solid electrolyte according to claim 1 , comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4),

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi;
X is one or more of elements selected from the group consisting of F, Cl, Br, I, O, Se and Te;
a is A(1−z);
b is B(1−z);
c is C(1−z); and
z satisfies 0≤z≤0.3.

3. The sulfide solid electrolyte according to claim 2 , wherein the X is one or more of halogen elements selected from the group consisting of F, Cl, Br and I.

4. The sulfide solid electrolyte according to claim 1 , wherein diffraction peaks are measured at 2θ=25.2 ±0.5 deg and 29.7±0.5 deg in a powder X-ray diffraction of the sulfide solid electrolyte using CuKα rays.

5. An electrode mix, comprising the sulfide solid electrolyte of claim 1 and an active material.

6. A lithium ion battery, comprising the sulfide solid electrolyte of claim 1 .

7. An electrode mix produced from the sulfide solid electrolyte of claim 1 .

8. A lithium ion battery produced from the electrode mix according to claim 7 .

9. A lithium ion battery, comprising the electrode mix of claim 5 .

10. The sulfide solid electrolyte according to claim 1 , wherein the sulfide solid electrolyte comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4)

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi;
X is one or more of elements selected from the group consisting of F, Cl, Br, I, O, Se and Te;
a is A(1−z);
b is B(1−z);
c is C(1−z); and
z is 0.

11. The sulfide solid electrolyte according to claim 1 , wherein the sulfide solid electrolyte comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4)

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi;
X is one or more of elements selected from the group consisting of F, Cl, Br and I;
a is A(1−z);
b is B(1−z);
c is C(1−z); and
z satisfies 0≤z≤0.3.

12. The sulfide solid electrolyte according to claim 1 , wherein the sulfide solid electrolyte comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4)

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi;
X is one or more of halogen elements selected from the group consisting of Cl and Br;
a is A(1−z);
b is B(1−z);
c is C(1−z); and
z satisfies 0≤z≤0.3.

13. The sulfide solid electrolyte according to claim 1 , wherein:
the sulfide solid electrolyte comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4)

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi; X is one or more of elements selected from the group consisting of F, Cl, Br, I, O, Se and Te;
a is A(1−z);
b is B(1−z);
c is C(1−z); and
z satisfies 0≤z≤0.3; and
diffraction peaks are measured at 2θ=25.2±0.5 deg and 29.7±0.5 deg in a powder X-ray diffraction of the sulfide solid electrolyte using CuKα rays.

14. The sulfide solid electrolyte according to claim 1 , wherein:
the sulfide solid electrolyte comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4)

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi; X is one or more of elements selected from the group consisting of F, Cl, Br, I, O, Se and Te;
a is A(1−z);
b is B(1−z);
c is C(1−z); and
z satisfies 0≤z≤0.3; and
the sulfide solid electrolyte does not have a diffraction peak at 2θ=17.6±0.4 deg and 2θ=18.1±0.4 deg in powder X-ray diffraction using CuKα rays, or the sulfide solid electrolyte has a diffraction peak at 2θ=17.6±0.4 deg and 2θ=18.1±0.4 deg in powder X-ray diffraction using CuKα rays and satisfies formula (5):
0 <I A /I B <0.05  (5)

wherein:
I A represents the intensity of the diffraction peak which is not a diffraction peak derived from the argyrodite-type crystal structure between diffraction peaks at 2θ=17.6±0.4 deg and 2θ=18.1±0.4 deg; and I B represents the intensity of the diffraction peak at 2θ=29.7±0.5 deg.

15. The sulfide solid electrolyte according to claim 1 , wherein the sulfide solid electrolyte comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4)

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi;
X is one or more of elements selected from the group consisting of F, Cl, Br and I;
a is A(1−z);
b is B(1−z);
c is C(1−z); and
z is 0.

16. The sulfide solid electrolyte according to claim 1 , wherein the sulfide solid electrolyte comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4)

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi;
X is one or more of halogen elements selected from the group consisting of Cl and Br;
a is A(1−z);
b is B(1−z);
c is C(1−z); and
z is 0.

17. The sulfide solid electrolyte according to claim 1 , wherein:
the sulfide solid electrolyte comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4)

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi; X is one or more of elements selected from the group consisting of F, Cl, Br, I, O, Se and Te;
a is A(1−z);
b is B(1−z);
c is C(1−z) and
z is 0; and
diffraction peaks are measured at 2θ=25.2±0.5 deg and 29.7±0.5 deg in a powder X-ray diffraction of the sulfide solid electrolyte using CuKα rays.

18. The sulfide solid electrolyte according to claim 1 , wherein:
the sulfide solid electrolyte comprising a composition represented by formula (4):
Li a (P 1-z M z )S b X c   (4)

wherein:
M is one or more of elements selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi; X is one or more of elements selected from the group consisting of F, Cl, Br, I, O, Se and Te;
a is A(1−z);
b is B(1−z);
c is C(1−z); and
z is 0; and
the sulfide solid electrolyte does not have a diffraction peak at 2θ=17.6±0.4 deg and 2θ=18.1±0.4 deg in powder X-ray diffraction using CuKα rays, or the sulfide solid electrolyte has a diffraction peak at 2θ=17.6±0.4 deg and 2θ=18.1±0.4 deg in powder X-ray diffraction using CuKα rays and satisfies formula (5):
0 <I A /I B <0.05  (5)

wherein:
I A represents the intensity of the diffraction peak which is not a diffraction peak derived from the argyrodite-type crystal structure between diffraction peaks at 2θ=17.6±0.4 deg a

Assignees

• Idemitsu Kosan Co

Inventors

• Utsuno Futoshi
• Terai Kota

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M10/052

  Li-accumulators · CPC title

• C01P2006/80

  Compositional purity · CPC title

• C01P2002/76

  by a space-group or by other symmetry indications · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title