Solid-state conductor materials

Patent metadata

Field	Value
Publication number	US-2025192224-A1
Application number	US-202318845050-A
Country	US
Kind code	A1
Filing date	Mar 8, 2023
Priority date	Mar 9, 2022
Publication date	Jun 12, 2025
Grant date	—

Abstract

A solid crystalline material of formula (I): LiaMY4XZ: wherein: a is from 5 to 8: M is selected from Si, Al, Sb, Sn, B, Ga and Ge, a mixture thereof, or a mixture thereof comprising P1-xM′ wherein M′ is selected from Si, Al, Sb, Sn, B, Ga and Ge or a mixture thereof and wherein 0<x≤1; wherein when M is Si at least one of X and Z is O; Y is O1-bSb, wherein b is from 0 to 0.5; and X and Z are each independently selected from O, S, F, Cl, Br, I or a mixture thereof. The solid crystalline material suitably provides a solid ionic conductor for use in a solid-state battery. A solid crystalline material comprising a solid solution, a solid-state battery comprising the solid crystalline material and a method of preparing the solid crystalline are also disclosed.

First claim

1 . A solid crystalline material of formula (I):
Li a MY 4 XZ; wherein: a is from 5 to 8; M is selected from Si, Al, Sb, Sn, B, Ga and Ge, a mixture thereof, or a mixture thereof comprising P 1-x M′ x , wherein M′ is selected from Si, Al, Sb, Sn, B, Ga and Ge or a mixture thereof and wherein 0<x≤1; wherein when M is Si at least one of X and Z is O; Y is O 1-b S b , wherein b is from 0 to 0.5; and X and Z are each independently selected from O, S, F, Cl, Br, I or a mixture thereof.

2 . The solid crystalline material according to claim 1 , having an argyrodite crystal structure.

3 . The solid crystalline material according to claim 1 , having a crystal structure with a space group selected from F 4 3m, F 4 3c, P2 1 3, P6 3 cm, Pmn2 1 , Pna2 1 , or Cc.

4 . The solid crystalline material according to claim 1 , wherein M is P 1-x M′ x ; wherein M′ is selected from Si, Al, Sb, Sn, B, Ga and Ge, or a mixture thereof and wherein 0<x≤1.

5 . The solid crystalline material according to claim 1 , having the formula (II):
Li 6+x P 1-x Si x Y 4 XZ; wherein: x is greater than 0 and up to 1. Y is O 1-b S b and wherein b is from 0 to 0.5; and X and Z are each independently selected from O, S, F, Cl, Br, I or a mixture thereof.

6 . The solid crystalline material according to claim 1 , wherein Y is O.

7 . The solid crystalline material according to claim 1 , wherein X is O.

8 . The solid crystalline material according to claim 1 , wherein Z is Cl or Br.

9 . The solid crystalline material according to claim 1 , having the formula (III) Li 6+x P 1-x Si x O 5 Z; wherein 0<x≤1 and Z is Cl or Br, or mixture thereof.

10 . The solid crystalline material according to claim 1 , wherein x is from 0.2 to 1.

11 . The solid crystalline material according to claim 1 , having the formula Li 7 SiO 5 Cl.

12 . The solid crystalline material according to claim 1 , having the formula Li 7 GeO 5 Cl.

13 . The solid crystalline material according to claim 1 , comprising a solid solution of a solid crystalline material of formula (IV): Li 6 PY 5 X and a solid crystalline material of formula (V): Li 7 SiY 5 X, wherein:
each Y is O 1-b S b , wherein b is from 0 to 0.5; and each X is independently selected from F, Cl, Br and I, or mixture thereof.

14 . The solid crystalline material according to claim 13 , wherein the solid crystalline material of formula (IV) is Li 6 PO 5 Cl and the solid crystalline material of formula (V) is Li 7 SiO 5 Cl.

15 . The solid crystalline material according to claim 13 , wherein the solid crystalline material of formula (IV) and the solid crystalline material of formula (V) are present in a ratio of from 1:10 to 10:1.

16 . The solid crystalline material according to claim 1 , having the formula (VII):
Li 6+x P 1-x Ge x Y 4 XZ; wherein:

0
<
x
≤

1
.

Y is O 1-b S b and wherein b is from 0 to 0.5; and
X and Z are each independently selected from O, S, F, Cl, Br, I or a mixture thereof.

17 . The solid crystalline material according to claim 1 , having the formula (IX): Li 6+x P 1-x Si v Ge w Y 4 XZ;
wherein:

0
<
x
<
1

;

0
<
v
<
1

;

0
<
w
<
1

;

v
+
w

=
x

;

Y is O 1-b S b and wherein b is from 0 to 0.5; and
X and Z are each independently selected from O, S, F, Cl, Br, I or a mixture thereof.

18 . A solid-state battery comprising:
an anode; a cathode; and an electrolyte comprising a solid crystalline material according to claim 1 .

19 . A method of preparing a solid crystalline material according to claim 1 , the method comprising the steps of:
(a) admixing a source of Li, a source of MY n , a source of X, a source of Z and optionally a source of PY 4 ; wherein n=2 to 4. (b) heating the mixture obtained in step (a); wherein M is selected from Si, Al, Sb, Sn, B, Ga and Ge, or a mixture thereof or comprises P 1-x M′ x ; wherein M′ is selected from Si, Al, Sb, Sn, B, Ga and Ge, or a mixture thereof and wherein 0<x≤1; wherein when M is Si and at least one of X and Z is O; Y is O 1-b S b , wherein b is from 0 to 0.5; and X and Z are each independently selected from O, S, F, Cl, Br, I or a mixture thereof.

20 . The method according to claim 19 , wherein the solid crystalline material is Li 6+x P 1-x Si x O 5 Cl, step (a) of the method involves admixing Li 4 SiO 4 , Li 2 O, and LiCl, and step (b) involves heating the mixture obtained in step (a) to a temperature of from 300 to 1000° C.

21 . (canceled)

22 . (canceled)

Assignees

• Univ Liverpool

Inventors

• Morscher Alexandra
• Dyer Matthew
• Rosseinsky Matthew
• Claridge John
• Daniels Luke

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2300/008

  Halides · CPC title

• H01M2300/0071

  Oxides · CPC title

• H01M10/0525

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

• H01M2300/0017

  Non-aqueous electrolytes · CPC title