Lithium ion conductive material, all-solid-state secondary battery, and method of manufacturing solid electrolyte

Patent metadata

Field	Value
Publication number	US-11575150-B2
Application number	US-202016816828-A
Country	US
Kind code	B2
Filing date	Mar 12, 2020
Priority date	Mar 22, 2019
Publication date	Feb 7, 2023
Grant date	Feb 7, 2023

Abstract

A lithium ion conductive material has a composition formula of Lia(OH)bFcCldBr1-d, where 1.8≤a≤2.3, b=a −c−1, 0<c≤0.30, 0<d<1, and includes an antiperovskite-type crystal phase. The lithium ion conductive material is manufactured, for example, by heating LiOH, LiF, LiCl, and LiBr at a temperature not lower than 250° C. and not higher than 600° C. for 0.1 hours or more while stirring them at a molar ratio of 1:X:Y:Z (where 0.03≤X≤0.3, 0.2≤Y<1.1, 0<Z<1) under an Ar gas atmosphere.

First claim

The invention claimed is:

1. A lithium ion conductive material,
having a composition formula of Li a (OH) b F c Cl d Br 1-d , where 1.8≤a≤2.3, b=a−c−1, 0<c≤0.30, 0<d<1, and
including an antiperovskite crystal phase and further including a crystal phase of LiF.

2. The lithium ion conductive material according to claim 1 , wherein the composition formula further satisfies 0.02≤c≤0.20 and 0.25≤d≤0.95.

3. The lithium ion conductive material according to claim 1 , being a melt-solidified solid.

4. An all-solid-state secondary battery, comprising:
a positive electrode;
a negative electrode; and
a lithium ion conductive material layer which is positioned between said positive electrode and said negative electrode and includes a lithium ion conductive material according to claim 1 .

5. The all-solid-state secondary battery according to claim 4 , wherein
said positive electrode includes a lithium composite oxide, and
said negative electrode includes Ti, and includes a material in which a lithium ion is insertable and removable at 0.4 V or more with the Li/Li + equilibrium potential as the reference.

6. The all-solid-state secondary battery according to claim 5 , wherein
said lithium composite oxide has a layered rock salt structure or a spinel structure.

7. The lithium ion conductive material according to claim 1 , wherein the composition formula further satisfies 0.75≤d≤0.95.

8. A method of manufacturing a solid electrolyte, wherein
LiOH, LiF, LiCl, and LiBr are heated at a temperature not lower than 250° C. and not higher than 600° C. for 0.1 hours or more while being stirred at a molar ratio of 1:X:Y:Z where 0.03≤X≤0.3, 0.2≤Y<1.1, 0<Z<1 under an Ar gas atmosphere,
wherein the solid electrolyte is a lithium ion conductive material having a composition formula of Li a (OH) b F c Cl d Br 1-d , where 1.8≤a≤2.3, b=a−c−1, 0<c≤0.30, 0<d<1, and including an antiperovskite crystal phase and further including a crystal phase of LiF.

Assignees

• Ngk Insulators Ltd

Inventors

• Yagi En
• Sato Yosuke

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2300/008

  Halides · CPC title

• C01D15/00

  Lithium compounds · CPC title

• H01B1/06

  mainly consisting of other non-metallic substances · CPC title