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

Patent metadata

Field	Value
Publication number	US-2019280331-A1
Application number	US-201916359881-A
Country	US
Kind code	A1
Filing date	Mar 20, 2019
Priority date	Oct 7, 2013
Publication date	Sep 12, 2019
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

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 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2, 0≤E<2, 10<F<13, and M′ and M″ are, independently in each instance, either absent or are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; and wherein the molar ratio of Garnet:Al 2 O 3 is between 0.05 and 0.7.

2 . The composition of claim 1 , wherein the composition is characterized by the empirical formula Li x La 3 Zr 2 O 12 .y½Al 2 O 3 ; wherein 5.0<x<9 and 0.1<y<1.5.

3 . The composition of claim 1 , wherein the composition is characterized by the empirical formula Li 7.0 La 3 (Zr t1 +Nb t2 +Ta t3 )O 12 +0.35Al 2 O 3 ;
wherein t1+t2+t3=2 such that the molar ratio of La to the combined amount of (Zr+Nb+Ta) is 3:2.

4 . The composition of claim 1 , wherein the composition is characterized by the empirical formula Li 7 La 3 Zr 2 O 12 .0.35Al 2 O 3 .

5 . The composition of claim 1 , wherein A is 5, 6, 7, or 8.

6 . The composition of claim 5 , wherein A is 7.

7 . The composition of claim 1 , wherein M′ is Nb and M″ is Ta.

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

9 . The composition of claim 8 , wherein E is 2.

10 . The composition of claim 1 , wherein C and D are 0.

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

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

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

14 . The composition of claim 1 , wherein the molar ratio of Garnet:Al 2 O 3 is 0.35.

15 . The composition of claim 1 , wherein the molar ratio of Al to garnet is 0.35.

16 . The composition of claim 1 , wherein the lithium-stuffed garnet is characterized by the empirical formula Li 7 La 3 Zr 2 O 12 and is doped with 0.1 to 1 molar amounts of alumina.

17 . An electrochemical device having an electrolyte according to the composition in any one of claims 1 - 16 .

18 . An electrochemical device having a catholyte according to the composition in any one of claims 1 - 16 .

19 . The compositions of any one of claims 1 - 16 , wherein the subscript values represent elemental molar ratios of the precursor chemicals used to make the claimed composition.

20 . The compositions of any one of claims 1 - 16 , wherein the composition is a thin film having a film thickness of about 10 nm to about 100 μm.

21 . The film of claim 20 , wherein the thickness is less than 50 μm and greater than 10 nm.

22 . The film of claim 20 , wherein the thickness is less than 40 μm and greater than 10 nm.

23 . The film of claim 20 , wherein the thickness is less than 30 μm and greater than 10 nm.

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

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

26 . The film of claim 20 , wherein the thickness is less than 5 μm and greater than 10 nm.

27 . The film of claim 20 , wherein the thickness is less than 1 μm and greater than 10 nm.

28 . The film of claim 20 , wherein the thickness is less than 0.5 μm and greater than 10 nm.

29 . The film of claim 20 , wherein the film has grains having a d 50 diameter less than 10 μm.

30 . The film of claim 20 , wherein the film has grains having a d 50 diameter less than 9 μm.

31 . The film of claim 20 , wherein the film has grains having a d 50 diameter less than 8 μm.

32 . The film of claim 20 , wherein the film has grains having a d 50 diameter less than 7 μm.

33 . The film of claim 20 , wherein the film has grains having a d 50 diameter less than 6 μm.

34 . The film of claim 20 , wherein the film has grains having a d 50 diameter less than 5 μm.

35 . The composition of claim 20 , wherein the film has grains having a d 50 diameter less than 4 μm.

36 . The composition of claim 20 , wherein the film has grains having a d 50 diameter less than 3 μm.

37 . The composition of claim 20 , wherein the film has grains having a d 50 diameter less than 2 μm.

38 . The composition of claim 20 , wherein the film has grains having a d 50 diameter less than 1 μm.

39 . A method of making a lithium stuffed garnet doped with aluminum, the method comprising
providing garnet precursors at predetermined combination; optionally drying the precursors for about 10 minutes to about 10 hours at about 80° C.-to about 200° C.; milling the combination for 5 to 10 hours; calcining the combination in vessels at about 500° C. to about 1200° C. for about 4 to about 10 hours to form a garnet phase; milling the formed garnet until the d 50 particle size is between 100 and 1000 nm; mixing the milled forming garnet with a binder to form a slurry optionally comprising a at least one member selected from the group consisting of a plasticizer, a dispersant, garnet chemical precursors, and combinations thereof; optionally filtering the slurry; optionally providing green films of the slurry; sintering the slurry or sintering the green film; wherein sintering comprises:
applying pressure to the slurry with setting plates;
heating the slurry under flowing gas between 140° C. and 1200° C. for about 15 minutes to about 6 hours;
and either heat sintering or field assisted sintering for about 10 minutes to about 10 hours.

40 . The method of claim 39 , wherein the garnet precursor are selected from LiOH, Li 2 O, Li 2 CO 3 , La 2 O 3 , ZrO 2 and Al(NO 3 ) 3 .9H 2 O.

41 . The method of claim 39 or 40 , wherein calcining the combination is in vessels at 900° C. for 6 hours or less.

42 . The method of any one of claims 39 - 41 , wherein the calcining comprises using Alumina vessels.

43 . The method of claim 39 , wherein the milling the formed garnet is until the d 50 particle size is 400 nm.

44 . The method of any one of claims 39 - 43 , wherein the mixing the milled forming garnet with a binder to form a slurry comprises about 4% w/w binder.

45 . The method of any one of claims 39 - 44 , wherein the binder is polyvinyl butyral.

46 . The method of claim 39 , wherein the filtering the slurry comprises filtering with an 80 mesh sieve.

48 . The method of claim 39 , wherein the applying pressure to the slurry with setting plates comprises applying a pressure of 3 metric tons.

49 . The method of claim 39 , wherein the setter plates are Pt setter plates.

50 . The method of claim 39 , wherein the flowing gas is an Argon gas flowing at a flow rate of 315 sccm.

51 . The method of any one of claims 39 - 50 , wherein the heating the slurry under flowing inert gas comprises separate dwells at 160° C. to 200° C. and 330° C. to 600° C. for 2 to 4 hours (hrs) each un

Assignees

• Quantumscape Corp

Inventors

• Holme Tim
• Donnelly Niall

Classifications

• H01M2300/0071

  Oxides · CPC title

• C04B2235/3215

  Barium oxides or oxide-forming salts thereof · CPC title

• C04B35/486

  Fine ceramics · CPC title

• C04B2235/3258

  Tungsten oxides, tungstates, or oxide-forming salts thereof · CPC title

• C04B2235/3205

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