Garnet materials for Li secondary batteries and methods of making and using garnet materials

Patent metadata

Field	Value
Publication number	US-11171357-B2
Application number	US-201916257752-A
Country	US
Kind code	B2
Filing date	Jan 25, 2019
Priority date	Oct 7, 2013
Publication date	Nov 9, 2021
Grant date	Nov 9, 2021

Abstract

Set forth herein are garnet material compositions, e.g., lithium-stuffed garnets and lithium-stuffed garnets doped with alumina, which are suitable for use as electrolytes and catholytes in solid state battery applications. Also set forth herein are lithium-stuffed garnet thin films having fine grains therein. Disclosed herein are novel and inventive methods of making and using lithium-stuffed garnets as catholytes, electrolytes and/or anolytes for all solid state lithium rechargeable batteries. Also disclosed herein are novel electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Also set forth herein are methods for preparing novel structures, including dense thin (<50 um) free standing membranes of an ionically conducting material for use as a catholyte, electrolyte, and, or, anolyte, in an electrochemical device, a battery component (positive or negative electrode materials), or a complete solid state electrochemical energy storage device. Also, the methods set forth herein disclose novel sintering techniques, e.g., for heating and/or field assisted (FAST) sintering, for solid state energy storage devices and the components thereof.

First claim

What is claimed is:

1. A thin unsintered film, comprising:
lithium-stuffed garnet precursor powders or calcined lithium-stuffed garnet powder; and
at least one member selected from the group consisting of a binder, a solvent, a dispersant, and combinations thereof;
wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is at least 30% by volume (v/v);
wherein the unsintered film thickness is less than 100 μm; and
wherein the unsintered film is in contact with a second film comprising a metal powder.

2. The thin unsintered film of claim 1 , wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is at least 40% by volume (v/v).

3. The thin unsintered film of claim 1 , wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is at least 45% by volume (v/v).

4. The thin unsintered film of claim 1 , wherein the solid loading of the lithium-stuffed garnet precursor powders or the calcined lithium-stuffed garnet powder is from 40% to 80% by volume (v/v).

5. The thin unsintered film of claim 1 , wherein the lithium-stuffed garnet is characterized by the empirical formula:
Li A La B M′ C M″ D Zr E O F , wherein:
5<A<8, 1.5<B<4, 0.1≤C≤2, 0<D≤2; 1≤E≤2, 10<F≤13;
M′ is Al; and
M″ is selected from the group consisting of Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, and Rb.

6. The thin unsintered film of claim 1 , wherein the lithium-stuffed garnet is characterized by the empirical formula:
Li A La B M′ C M″ D Zr E O F , wherein:
6.5<A<8, 1.5<B<4, 0.1≤C≤2, 0<D≤2; 1≤E≤2, 10<F≤13;
M′ is Al; and
M″ is Ta.

7. The thin unsintered film of claim 1 , wherein the metal powder comprises a metal selected from the group consisting of Ni, Cu, Al, steel, and alloys and combinations thereof.

8. The thin unsintered film of claim 1 , wherein the thin unsintered film thickness is less than 50 μm and greater than 10 nm.

9. The thin unsintered film of claim 1 , wherein the thin unsintered film has a thickness from 10 μm to 100 μm.

Assignees

• Quantumscape Battery Inc

Inventors

• Winoto Adrian
• Donnelly Niall
• Holme Tim
• Hudson Will
• Iyer Sriram
• Karpenko Oleh
• Singh Mohit
• Choi Dong Hee Anna

Classifications

• C04B2235/3256

  Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate · CPC title

• C04B2235/3203

  Lithium oxide or oxide-forming salts thereof · CPC title

• C04B2235/3215

  Barium oxides or oxide-forming salts thereof · CPC title

• C04B2235/786

  Micrometer sized grains, i.e. from 1 to 100 micron · CPC title

• C04B35/6262

  of calcined, sintered clinker or ceramics · CPC title