PROTECTIVE ANODE COATINGS FOR HIGH ENERGY BATTERIES

• US 20190088991A1
• Filed: 03/08/2017
• Published: 03/21/2019
• Est. Priority Date: 03/11/2016
• Status: Active Grant

• Current Assignee: Northwestern University
• Original Assignee: Northwestern University
• Inventors: Hegde, Vinay Ishwar, Snydacker, David H., Wolverton, Christopher M.
• Granted Patent: US 10,833,360 B2
• Time in Patent Office: Days
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Materials for coating a metal anode in a high energy battery, anodes coated with the materials, and batteries incorporating the coated anodes are provided. Also provided are batteries that utilize the materials as electrolytes. The coatings, which are composed of binary, ternary, and higher order metal and/or metalloid oxides, nitrides, fluorides, chlorides, bromides, sulfides, and carbides limit the reactions between the electrolyte and the metal anode in a battery, thereby improving the performance of the battery, relative to a battery that employs a bare anode.

Claims

1. A coated lithium metal anode comprising:

a lithium metal anode; and

a coating on at least a portion of the lithium metal anode, wherein the coating comprises a metal sulfide selected from SrS, CaS, YbS, and combinations thereof.

2. A lithium battery comprising:

the coated lithium metal anode of claim 1;

a cathode in electrical communication with the coated lithium metal anode; and

an electrolyte disposed between the coated lithium metal anode and the cathode.

3. The battery of claim 2, wherein the electrolyte is a sulfide solid electrolyte.

4. A coated lithium metal anode comprising:

a lithium metal anode; and

a coating on at least a portion of the lithium metal anode, wherein the coating comprises a metal oxide selected from rare earth metal oxides, ternary lithium oxides other than Li₃PO₄, quaternary lithium oxides, calcium oxide, or a combination of two or more thereof, and further wherein the metal oxide is stable;

exhibits chemical equilibrium with the lithium metal anode; and

is electrically insulating.

5. The coated lithium metal anode of claim 4, wherein the coating comprises Li₂HfO₃.

6. The coated lithium metal anode of claim 4, wherein the coating comprises Li₇La₃Hf₂O₁₂.

7. The coated lithium metal anode of claim 4, wherein the coating comprises a rare earth metal oxide having the formula R₂O₃, where R is selected from Dy, Er, Gd, Ho, La, Lu, Nd, Pr, Sm, Tm, and Y.

8. The coated lithium metal anode of claim 4, wherein the coating comprises a rare earth metal oxide having the formula LiRO₂, where R is selected from Dy, Er, Gd, Ho, Sc, and Tb.

9. A lithium battery comprising:

the coated lithium metal anode of claim 4;

a cathode in electrical communication with the coated lithium metal anode; and

an electrolyte disposed between the coated lithium metal anode and the cathode.

10. The lithium battery of claim 9, wherein the coating comprises Li₇La₃Hf₂O₁₂ and the electrolyte is a Li₇La₃Zr₂O₁₂ solid electrolyte.

11. A coated lithium metal anode comprising:

a lithium metal anode; and

a coating on at least a portion of the lithium metal anode, wherein the coating comprises a metal halide selected from metal fluorides other than LiF, metal chlorides, and metal bromides, and the metal of the metal halide comprises an alkali metal, an alkaline earth metal, or a rare earth metal, and further wherein metal halide is stable;

exhibits chemical equilibrium with the lithium metal anode; and

is electrically insulating.

12. The coated lithium metal anode of claim 11, wherein the coating comprises a metal halide selected from CaF₂, SrF₂, YbF₂, EuF₂, or a combination thereof.

13. The coated lithium metal anode of claim 11, wherein the coating comprises YbCl₂.

14. The coated lithium metal anode of claim 11, wherein the coating comprises a metal halide selected from YbBr₂, BaBr₂, SrBr₂, EuBr₂, or a combination thereof.

15. The coated lithium metal anode of claim 11, wherein the coating comprises a metal halide selected from LiCl, NaCl, KCl, RbCl, CsCl, or a combination thereof.

16. The coated lithium metal anode of claim 11, wherein the coating comprises a metal halide selected from LiBr, NaBr, KBr, RbBr, CsBr, or a combination thereof.

17. A lithium battery comprising:

the coated lithium metal anode of claim 11;

a cathode in electrical communication with the coated lithium metal anode; and

an electrolyte disposed between the coated lithium metal anode and the cathode.

18. The battery of claim 17, wherein the electrolyte is a sulfide solid electrolyte.

19. A coated lithium metal anode comprising:

a lithium metal anode; and

a coating on at least a portion of the lithium metal anode, wherein the coating comprises a ternary lithium nitride, wherein the ternary lithium nitride is stable;

exhibits chemical equilibrium with the lithium metal anode; and

is electrically insulating.

20. The coated lithium metal anode of claim 19, wherein the ternary lithium nitride has the formula Li_xMN₄, wherein x is 5, 6, or 7 and M is an element selected from Ta, Nb, W, V, Re, and Mo.

21. The coated lithium metal anode of claim 19, wherein the ternary lithium nitride has the formula Li_xMN₂, wherein x is 2 or 3 and further wherein, when x is 2, M is selected from Zr, C, and Si, and when x is 3, M is Sc or B.

22. The coated lithium metal anode of claim 19, wherein the ternary lithium nitride is selected from LiMgN, Li₅Br₂N, Li₁₀BrN₃, Li₄SrN₂, Li₈TeN₂, or a combination thereof.

23. A lithium battery comprising:

the coated lithium metal anode of claim 19;

a cathode in electrical communication with the coated lithium metal anode; and

an electrolyte disposed between the coated lithium metal anode and the cathode.

24. The battery of claim 23, wherein the ternary lithium nitride has the formula Li_xMN₄, wherein x is 5, 6, or 7 and M is an element selected from Ta, Nb, W, V, Re, and Mo, and the electrolyte is an oxide solid electrolyte or a nitride solid electrolyte.

25. The battery of claim 23, wherein the ternary lithium nitride comprises Li₃ScN₂, Li₂ZrN₂, or a combination thereof, and the electrolyte is an oxide solid electrolyte or a nitride solid electrolyte.