Processes and materials for casting and sintering green garnet thin films

Patent metadata

Field	Value
Publication number	US-12084387-B2
Application number	US-202016734196-A
Country	US
Kind code	B2
Filing date	Jan 3, 2020
Priority date	Jul 21, 2015
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

Set forth herein are processes and materials for making ceramic thin films by casting ceramic source powders and precursor reactants, binders, and functional additives into unsintered thin films and subsequently sintering the thin films under controlled atmospheres and on specific substrates.

First claim

What is claimed is:

1. A method for sintering a green tape, the method comprising:
(a) providing at least one source powder;
wherein the at least one source powder is a lithium-stuffed garnet powder;

(b) modifying the at least one source powder to prepare a modified source powder using an aprotic solvent;
(c) providing a slurry of the modified source powder;
(d) casting the slurry to form a green tape;
wherein the green tape comprises the modified source powder, an aprotic solvent, a binder, and a dispersant;
and
wherein the amount of source powder in the green tape is at least 75%, 80%, 85%, or 90% by weight; and
wherein modified source powder has a particle size distribution having a d 50 of 50 nm to 5 μm;

(e) drying the green tape;
(f) stress relieving the green tape; and
(g) sintering the green tape.

2. The method of claim 1 , wherein the amount of source powder in the green tape is at least 85% by weight.

3. The method of claim 1 , wherein the at least one source powder is Li x Zr 2 La 3 O 12 yAl 2 O 3 ; wherein x ranges from 5 to 9; and y ranges from 0 to 1.

4. The method of claim 1 , wherein the modifying the at least one source powder comprises modifying the particle size distribution of the at least one source powder.

5. The method of claim 4 , wherein the particle size distribution, after the modifying step, has a d 50 of about 100 nm, 200 nm, 300 nm, 400 nm, 1 μm, 2 μm, 3 μm, or 4 μm.

6. The method of claim 1 , wherein the surface area of the at least one source powder is increased to at least 5 m 2 /g during the modifying the at least one source powder.

7. The method of claim 6 , wherein the surface area of the at least one source powder is increased to at least 8 m 2 /g and less than 15 m 2 /g during the modifying the at least one source powder.

8. The method of claim 1 , wherein the modifying the at least one source powder comprises decreasing an average particle size of particles of the at least one source powder.

9. The method of claim 1 , further comprising laminating more than one green tape together.

10. The method of claim 1 , further comprising laminating one green tape on to a second green tape.

11. The method of claim 1 , wherein the at least one source powder is a Li-stuffed garnet compound characterized by the formula Li x La y Zr z O t ·qAl 2 O 3 , wherein 4<x<10, 1<y<4, 1<z<3, 6<t<14, and 0≤q≤1.

12. The method of claim 1 , wherein the at least one source powder is a Li-stuffed garnet compound characterized by the formula Li 7-x La 3 Zr 2 O 12 ·qAl 2 O 3 , wherein q is 0, 0.3, 0.35, 0.5, 0.75, or 1.0 and 0≤x≤1.

13. The method of claim 1 , wherein providing the slurry comprises formulating the slurry by mixing at least two or more of:
a solvent selected from the group consisting of methanol, MEK, ethanol, propanol, isopropanol (IPA), acetone, cyclohexanol, toluene, acetic acid, benzene, and a combination thereof;
a binder selected from the group consisting of fish oil, PVB, KD1, an acrylic acid, triton, phosphate esters, derivatives thereof, and combinations thereof;
a plasticizer selected from the group consisting of a benzyl butyl phthalate and di-butyl phthalate;
a pH modifier;
a sintering aid; and
a source powder selected from a lithium-stuffed garnet.

14. The method of claim 1 , wherein the modifying comprises classifying the at least one source powder based on a particle size.

15. The method of claim 1 , wherein the slurry, when dried, has about 80% w/w source powder.

16. The method of claim 1 , wherein the slurry, when dried, has about 10-25% w/w organic content, wherein the organic content refers to slurry components other than the source powder.

17. The method of claim 1 , wherein the slurry, when dried, has about 10-25% w/w organic content, wherein the organic content refers to slurry components other than the source powder wherein the source powder is a lithium-stuffed garnet.

18. The method of claim 1 , wherein the amount of binder and plasticizer in the slurry is about 10-25% w/w organic content, wherein the organic content refers to slurry components other than the source powder wherein the source powder is a lithium-stuffed garnet.

19. The method of claim 1 , wherein the source powder is characterized by the formula Li 7.1 Zr 2 La 3 O 12 +0.5Al 2 O 3 , as batched.

20. A green tape, comprising:
a source powder, wherein the source powder is a lithium-stuffed garnet powder;
an aprotic solvent;
a binder;
a pH modifier selected from citric acid or ammonia hydroxide; and
a dispersant;
wherein the amount of source powder in the green tape is at least 75%, 80%, 85%, or 90% by weight; and
wherein the modified source powder has a particle size distribution having a d 50 of 50 nm to 5 μm.

21. The green tape of claim 20 , further comprising a member selected from a plasticizer, and a sintering aid.

22. The green tape of claim 20 , comprising a sintering aid selected from MgO, Al 2 O 3 , and combinations thereof.

23. The green tape of claim 20 , wherein the solvent is an azeotrope.

24. The green tape of claim 20 , wherein the solvent further comprises a member selected from methyl ethyl ketone (MEK), tetrahydrofuran, toluene, acetone, 1-butanol, 2-butanol, cyclohexane, cyclohexanol, ethanol, isopropanol, methanol, 1-propanol, propylene carbonate, hexane, m-xylene, pentane, and combinations thereof.

25. The green tape of claim 24 , wherein the solvent comprises methyl-ethyl ketone (MEK).

26. The green tape of claim 25 , wherein the solvent further comprises isopropanol (IPA).

27. The green tape of claim 20 , wherein the solvent further comprises cyclohexanone.

28. The green tape of claim 27 , wherein the amount of cyclohexanone is about 10-25% by weight.

29. The green tape of claim 26 , wherein the ratio of MEK:IPA is 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, or 2:8 w/w.

30. The green tape of claim 20 , comprising a source powder of a lithium-stuffed garnet having a density of 4 g/cm 3 , and a solvent further comprising MEK and IPA.

31. The green tape of claim 20 , comprising a source powder of a lithium-stuffed garnet having a density of 4 g/cm 3 , and a solvent further comprising MEK, IPA, and cyclohexanone.

Assignees

• Quantumscape Battery Inc

Inventors

• Karpenko Oleh
• Xu Gengfu
• Donnelly Niall
• Iyer Sriram
• Holme Tim

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2300/0068

  inorganic · CPC title

• C04B2237/562

  made of alumina or aluminates · CPC title

• C04B2237/346

  Titania or titanates · CPC title

• C04B2237/343

  Alumina or aluminates · CPC title