LITHIUM LANTHANUM ZIRCONATE THIN FILMS

• US 20200131643A1
• Filed: 10/31/2019
• Published: 04/30/2020
• Est. Priority Date: 10/31/2018
• Status: Active Grant

• Current Assignee: Arizona Board of Regents (University of Arizona)
• Original Assignee: Arizona Board of Regents (University of Arizona)
• Inventors: Chan, Candace, Weller, Jon Mark
• Granted Patent: US 11,268,196 B2
• Time in Patent Office: Days
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/45555 applied in non-semiconductor technology
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: C23C 18/1216 Metal oxides C23C18/1212 takes precedence
• CPC Class Codes: C23C 18/1254 Sol or sol-gel processing
• CPC Class Codes: C23C 18/1295 with after-treatment of the deposited inorganic material
• CPC Class Codes: C23C 22/05 using aqueous solutions
• CPC Class Codes: C23C 22/70 using melts
• CPC Class Codes: C23C 28/042 including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 2300/0077 based on zirconium oxide
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Forming a lithium lanthanum zirconate thin film includes disposing zirconium oxide on a substrate to yield a zirconium oxide coating, contacting the zirconium oxide coating with a solution including a lithium salt and a lanthanum salt, heating the substrate to yield a dried salt coating on the zirconium oxide coating, melting the dried salt coating to yield a molten salt mixture, reacting the molten salt mixture with the zirconium oxide coating to yield lithium lanthanum zirconate, and cooling the lithium lanthanum zirconate to yield a lithium lanthanum zirconate coating on the substrate. In some cases, the zirconium oxide coating is contacted with an aqueous molten salt mixture including a lithium salt and a lanthanum salt, the molten salt mixture is reacted with the zirconium oxide coating to yield lithium lanthanum zirconate, and the lithium lanthanum zirconate is cooled to yield a lithium lanthanum zirconate coating on the substrate.

Claims

1. A method of coating a substrate, the method comprising:

disposing zirconium oxide on a substrate to yield a zirconium oxide coating on the substrate;

contacting the zirconium oxide coating with a solution comprising a lithium salt and a lanthanum salt;

heating the substrate to yield a dried salt coating on the zirconium oxide coating;

melting the dried salt coating to yield a molten salt mixture;

reacting the molten salt mixture with the zirconium oxide coating to yield lithium lanthanum zirconate; and

cooling the lithium lanthanum zirconate to yield a lithium lanthanum zirconate coating on the substrate.

2. The method of claim 1, wherein disposing zirconium oxide on the substrate comprises atomic layer deposition or plasma-enhanced atomic layer deposition of zirconium oxide on the substrate.

3. The method of claim 2, wherein disposing the zirconium oxide on the substrate further comprises disposing additional zirconium oxide on the zirconium oxide coating with a chemical vapor deposition or sol-gel process.

4. The method of claim 2, wherein the zirconium oxide used to form the zirconium oxide coating is in the form of zirconium oxide nanoparticles.

5. The method of claim 1, wherein the zirconium oxide coating is amorphous.

6. The method of claim 1, wherein the solution is homogeneous.

7. The method of claim 1, wherein the lithium salt comprises lithium nitrate.

8. The method of claim 1, wherein the lanthanum salt comprises lanthanum nitrate.

9. The method of claim 1, wherein the solution further comprises a zirconium salt.

10. The method of claim 9, wherein the zirconium salt comprises a nitrate salt.

11. The method of claim 1, wherein contacting the solution with the zirconium oxide coating comprises spraying the solution on the zirconium oxide coating.

12. The method of claim 1, wherein contacting the solution with the zirconium oxide coating comprises drop casting the solution on the zirconium oxide coating.

13. The method of claim 1, wherein heating the substrate comprises removing liquid from the solution.

14. The method of claim 1, wherein melting the dried salt coating comprises heating the substrate to at least 400°

C., at least 450°

C., at least 800°

C. or at least 900°

C.

15. The method of claim 1, wherein contacting the solution with the zirconium oxide coating comprises wetting the zirconium oxide coating with the solution.

16. The method of claim 1, wherein the substrate is planar.

17. The method of claim 1, wherein the substrate comprises protrusions and recessions.

18. The method of claim 1, wherein the lithium lanthanum zirconate coating is polycrystalline or nanocrystalline.

19. The method of claim 1, wherein a thickness of the lithium lanthanum zirconate coating is in a range of 1 micron to 10 microns.

20. The method of claim 1, wherein the solution comprises a polar solvent.

21. The method of claim 20, wherein the polar solvent comprises water.

22. The method of claim 20, wherein the polar solvent comprises an organic solvent.

23. The method of claim 22, wherein the organic solvent comprises methanol.

24. A method of coating a substrate, the method comprising:

disposing zirconium oxide on a substrate to yield a zirconium oxide coating on the substrate;

heating an aqueous mixture comprising a lithium salt and a lanthanum salt to yield a molten salt mixture;

contacting the zirconium oxide coating with the molten salt mixture;

reacting the molten salt mixture with the zirconium oxide coating to yield lithium lanthanum zirconate; and

cooling the lithium lanthanum zirconate to yield a lithium lanthanum zirconate coating on the substrate.

25. The method of claim 24, wherein contacting the substrate with the molten salt mixture comprises immersing the substrate in the molten salt mixture.

26. The method of claim 24, wherein the aqueous mixture further comprises a zirconium salt.