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

Patent metadata

Field	Value
Publication number	US-2015099188-A1
Application number	US-201414509025-A
Country	US
Kind code	A1
Filing date	Oct 7, 2014
Priority date	Oct 7, 2013
Publication date	Apr 9, 2015
Grant date	—

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

1 . A method for making a lithium (Li) ion conducting garnet material thin film, the method comprising:
providing a reaction mixture comprising garnet chemical precursors and optionally a source of lithium; optionally mixing the mixture; optionally milling the mixture; optionally providing a slurry comprising the mixture and a solvent; depositing the mixture or the slurry onto a substrate to form a film; and sintering the film to react the precursors and to form a lithium stuffed garnet thin film.

2 . The method of claim 1 , wherein the precursors comprise one or more members selected from the group consisting of LiOH, Li 2 O, ZrO 2 , La 2 O 3 , Al 2 O 3 , AlNO 3 , Nb 2 O 5 , Ta 2 O 5 , Li 2 CO 3 , AlNO 3 -hydrate, AlNO 3 .9H 2 O, and combinations thereof.

3 . The method of claim 1 , wherein the source of lithium is present in the mixture and is a member selected from LiF, LiCl, LiBr, LiOH, Li 2 CO 3 , L 2 O, Li 2 O 2 , lithium stuffed garnet, or Li (s) , and combinations thereof.

4 . The method of claim 2 , further comprising depositing an additional layer of the mixture or the slurry onto the lithium stuffed garnet film to form a multilayer.

5 . The method of claim 4 , further comprising sintering the multilayer.

6 . The method of claim 1 , wherein the mixture comprises a flux.

7 . The method of claim 1 , comprising the milling step, wherein the milling is selected from the group consisting of ball milling, solvent milling, horizontal milling, attritor milling, jet milling, immersion milling, and high energy milling.

8 . The method of claim 7 , wherein the milling step results in precursor particle sizes that have a d 50 of 1 μm or less.

9 . (canceled)

10 . The method of claim 8 , wherein the particle sizes have a d 50 of about 50-200 nm.

11 . The method of claim 7 , wherein the milling comprises solvent milling and wherein the solvent is a polar solvent.

12 . The method of claim 11 , wherein the solvent is selected from the group consisting of toluene, isopropanol, ethanol, acetic acid, diacetone alcohol, acetonitrile, ethyl acetate, methyl ethyl ketone, and combinations thereof.

13 . The method of claim 1 , comprising milling and mixing simultaneously.

14 . The method of claim 1 , wherein the substrate comprises a metal selected from the group consisting of Al, Ni, Cu, Au, Ag, Fe, steel, stainless steel, Li, alloys thereof, and combinations thereof.

15 . The method of claim 1 , comprising calcining the film prior to sintering the film and at a temperature from about 300° C. to about 1000° C.

16 . The method of claim 1 , further comprising applying pressure to the film prior to, or concurrent with, sintering the film.

17 . (canceled)

18 . The method of claim 1 , wherein the reaction mixture further comprises a member selected from the group consisting of NASICON, LISICON, and a tungsten bronze.

19 . The method of claim 1 , wherein the reaction mixture further comprises a binder selected from the group consisting of from the group consisting of polypropylene (PP), polyvinyl butyral (PVB), polyvinyl pyrrolidone (PVP), atactic polypropylene (aPP), isotactive polypropylene ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), ZEON™, styrene butadiene rubber (SBR), polyolefins, polyethylene-co-poly-1-octene (PE-co-PO), PE-co-poly(methylene cyclopentane) (PE-co-PMCP), stereoblock polypropylenes, polypropylene polymethylpentene copolymer and silicone.

20 . The method of claim 1 , further comprising a thermal treatment step to remove the binder.

21 . (canceled)

22 . The method of claim 1 , further comprising sintering the film at about 1100° C. for about 15 minutes to about 2 hours.

23 . A method for making a lithium (Li) ion conducting garnet material powder, the method comprising:
providing a reaction mixture comprising garnet chemical precursors and optionally a source of lithium; optionally mixing the mixture; optionally milling the mixture; optionally providing a slurry comprising the mixture and a solvent; depositing the mixture or the slurry onto a surface or into a reaction container; and calcining the slurry to react the precursors and to form a lithium stuffed garnet powder.

24 . The method of claim 23 , wherein the precursors comprise one or more members selected from the group consisting of LiOH, Li 2 O, ZrO 2 , La 2 O 3 , Al 2 O 3 ), AlNO 3 , Nb 2 O 5 , Ta 2 O 5 , Li 2 CO 3 , AlNO 3 -hydrate, AlNO 3 .9H 2 O, and combinations thereof.

25 . The method of claim 23 , wherein the source of lithium is present in the mixture and is a member selected from LiF, LiCl, LiBr, LiOH, Li 2 CO 3 , Li 2 O, Li 2 O 2 , lithium stuffed garnet, Li (s) , and combinations thereof.

26 . (canceled)

27 . The method of claim 23 , wherein the mixture comprises a flux.

28 . The method of claim 23 , wherein the milling step is present and the milling is selected from the group consisting of ball milling, solvent milling, horizontal milling, attritor milling, immersion milling, or high energy milling.

29 . The method of claim 28 , wherein the milling step results in precursor particle sizes that have a d 50 of 1 μm or less.

30 . (canceled)

31 . The method of claim 28 , wherein the milling step results in precursor particle sizes that have a d 50 of about 50-200 nm.

32 - 37 . (canceled)

38 . The method of claim 23 , further comprising calcining the film prior to sintering the film at a temperature from about 300° C. to about 1000° C.

39 . The method of claim 23 , wherein the reaction mixture further comprises a member selected from the group consisting of NASICON, LISICON, and a tungsten bronze.

40 . A nanostructured lithium stuffed garnet prepared by the method of claim 23 .

41 . The method of claim 23 , further comprising sintering the film at 1000 to 1200° C. for about 15 minutes to about 2 hours.

42 . (canceled)

Assignees

• Quantumscape Corp

Inventors

• Holme Tim
• Donnelly Niall

Classifications

• C04B2235/3215

  Barium oxides or oxide-forming salts thereof · CPC title

• C04B35/6262

  of calcined, sintered clinker or ceramics · CPC title

• C04B2235/3217

  Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina · CPC title

• H01M10/052

  Li-accumulators · CPC title

• C04B2235/3227

  Lanthanum oxide or oxide-forming salts thereof · CPC title