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

Patent metadata

Field	Value
Publication number	US-10305141-B2
Application number	US-201715430375-A
Country	US
Kind code	B2
Filing date	Feb 10, 2017
Priority date	Oct 7, 2013
Publication date	May 28, 2019
Grant date	May 28, 2019

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. 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. Disclosed herein are novel electrochemical devices which incorporate these garnet catholytes, electrolytes and/or anolytes. Set forth herein are methods for preparing novel structures, including dense thin 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. The methods set forth herein disclose novel sintering techniques for solid state energy storage devices and the components thereof.

First claim

What is claimed is:

1. A composition comprising a lithium stuffed garnet and Al 2 O 3 ,
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, 0.4<C≤2, O<D≤2; 1≤E≤2, 10<F≤15, and
M′ is Al; and
M″ is selected from Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, and Rb.

2. The composition of claim 1 , wherein the composition is characterized by the empirical formula Li 7.0 La 3 Zr t1 Nb t2 O 12 0.35Al 2 O 3 ; wherein t1+t2 =2.

3. A composition comprising a lithium-stuffed garnet and Al 2 O 3 , 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, 0.4<C≤2, 0<D≤2; 1≤E≤2, 10<F≤15, and
M′ is Al; and
M″ is Ta.

4. The composition of claim 1 , wherein E is 1, 1.5, or 2.

5. The composition of claim 1 , wherein the molar ratio of Garnet:Al 2 O 3 is between 1:0.1 and 1:0.65.

6. The composition of claim 1 , wherein the molar ratio of Garnet:Al 2 O 3 is between 1:0.15 and 1:0.55.

7. The composition of claim 1 , wherein the molar ratio of Garnet:Al 2 O 3 is between 1:0.25 and 1:0.45.

8. The composition of claim 1 , wherein the subscript values represent elemental molar ratios of the precursor chemicals used to make the claimed composition.

9. The composition of claim 1 , wherein the composition is a thin film having a film thickness of about 10 nm to about 100 μm.

10. The composition of claim 9 , wherein the thickness is less than 20 μm and greater than 10 nm.

11. The composition of claim 9 , wherein the film has grains having a d 50 diameter less than 10 μm.

12. The composition of claim 9 , wherein the film has grains having a d 50 diameter less than 5 μm.

13. The composition of claim 9 , wherein the film has grains having a d 50 diameter less than 2 μm.

14. The composition of claim 9 , wherein the film has grains having a d 50 diameter less than 1 μm.

15. An energy storage device comprising an electrolyte comprising the composition of claim 1 .

16. An electrochemical device comprising a catholyte comprising the composition of claim 1 .

Assignees

• Quantumscape Corp

Inventors

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

Classifications

• C04B2235/3227

  Lanthanum oxide or oxide-forming salts thereof · CPC title

• C04B35/6262

  of calcined, sintered clinker or ceramics · CPC title

• C04B2235/3248

  Zirconates or hafnates, e.g. zircon · CPC title

• C04B2235/3205

  Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide · CPC title

• C04B2235/6025

  Tape casting, e.g. with a doctor blade · CPC title