Solid-state conductor materials

Patent metadata

Field	Value
Publication number	US-2023291001-A1
Application number	US-202117999586-A
Country	US
Kind code	A1
Filing date	May 21, 2021
Priority date	May 22, 2020
Publication date	Sep 14, 2023
Grant date	—

Abstract

A solid crystalline material of formula (I): AzDY4Xx, wherein each A is independently selected from Li, Na, K and Mg; D is selected from Si, Al, P, B, Ga, Ge, S, Mo, W, V, Sn, Sb, Nb and Ta, or a mixture thereof; each Y is independently selected from O, S, F, Cl, Br or a mixture thereof; each X is independently selected from F, Cl, Br, I, O, S, BH4 or a mixture thereof; z is from 2 to 8; and x is from 1 to 3. The solid crystalline material suitably provides a solid ionic conductor for use in a solid-state battery. A mixed solid crystalline material comprising the solid crystalline material, 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): A z DY 4 X x wherein:
each A is independently selected from Li, Na, K and Mg;
D is selected from Si, Al, P, B, Ga, Ge, S, Mo, W, V, Sn, Sb, Nb and Ta, or a mixture thereof;
each Y is independently selected from O, S, F, Cl, Br or a mixture thereof;
each X is independently selected from F, Cl, Br, I, O, S, BH 4 or a mixture thereof;
z is from 2 to 8; and
x is from 1 to 3.

2 . The solid crystalline material according to claim 1 , having a crystal structure comprising a hexagonal unit cell and/or an orthorhombic unit cell.

3 . The solid crystalline material according to claim 2 , wherein the hexagonal unit cell and/or orthorhombic unit cell comprises alternating layers of tetrahedral species of formula (II): A d DY 4 and species of formula (III): A e X y in an a-b-a-c stacking sequence, to provide the material of formula (I); wherein d and e are each from 1 to 7 and d + e ≤ a; wherein y is from 1 to 3 and y ≤ x.

4 . The solid crystalline material according to claim 1 , having a crystal structure with a space group selected from P6 3 mc, Pna2 1 , P6 3 , Pca2 1 , P31c.

5 . The solid crystalline material according to claim 1 , wherein each A is selected from Li, Na or K.

6 . The solid crystalline material according to claim 1 , wherein D is Si.

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

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

9 . The solid crystalline material according to claim 1 , having the formula Li 6 SiO 4 Cl 2-v Br v ; wherein v is from 0 to 2.

10 . A solid crystalline material having a hexagonal unit cell and/or an orthorhombic unit cell comprising alternating layers of tetrahedral species of formula (II):
A d DY 4 and species of formula (III): A e X y in an a-b-a-c stacking sequence; wherein:
each A is independently selected from Li, Na, K and Mg;
D is selected from Si, Al, P, B, Ga, Ge, S, Mo, W, V, Sn, Sb, Nb and Ta, or a mixture thereof;
each Y is independently selected from O, S, F, Cl, Br or a mixture thereof;
each X is independently selected from F, Cl, Br, I, O, S, BH 4 or a mixture thereof;
d and e are each from 1 to 7; and
y is from 1 to 3.

11 . A mixed solid crystalline material comprising a solid crystalline material according to claim 1 .

12 . A mixed solid crystalline material comprising a first solid material according to claim 1 and a second solid material.

13 . The mixed solid crystalline material according to claim 12 , wherein the second solid material has a formula Li 3 OX, wherein X is selected from F, Cl, Br, I, BH 4 , S and Se or a mixture thereof.

14 . The mixed solid crystalline material according to claim 12 , wherein the second solid material is a solid material having a different composition to the first solid material, the second solid state material comprising a solid crystalline material of formula (I): A z DY 4 X x wherein:
each A is independently selected from Li, Na, K and Mg;
D is selected from Si, Al, P, B, Ga, Ge, S, Mo, W, V, Sn, Sb, Nb and Ta, or a mixture thereof;
each Y is independently selected from O, S, F, Cl, Br or a mixture thereof;
each X is independently selected from F, Cl, Br, I, O, S, BH 4 or a mixture thereof;
z is from 2 to 8; and
x is from 1 to 3.

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

16 . A method of preparing a solid crystalline material according to claim 1 , the method comprising the steps of:
(a) admixing a source of A and a source of DY w , wherein w is from 1 to 3, to form a precursor comprising A, D and Y; (b) admixing the precursor obtained in step (a) with a source of AX; (c) heating the mixture obtained in step (b).

17 . The method according to claim 16 , wherein step (a) involves heating the source of A and the source of DY to a temperature of from 300 to 1000° C.

18 . The method according to claim 17 , wherein step (c) involves heating the precursor obtained in step (a) with the source of AX to a temperature of from 300 to 1000° C.

19 . The method according to claim 18 , wherein the solid crystalline material is of formula Li 6 SiO 4 Cl 2-v Br v ; wherein y is from 0 to 2; wherein the source of A is Li 2 CO 3 , the source of DY w is SiO 2 ; the precursor is Li 4 SiO 4 and the source of AX is LiCl, LiBr or a mixture thereof.

20 . (canceled)

Assignees

• Univ Liverpool

Inventors

• Morscher Alexandra
• Dyer Matthew
• Rosseinsky Matthew

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M10/0525

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

• H01M2300/0068

  inorganic · CPC title

• H01M2300/008

  Halides · CPC title

• C01D15/00

  Lithium compounds · CPC title