Lithium metal electrodes and batteries thereof

Patent metadata

Field	Value
Publication number	US-11961975-B2
Application number	US-202117492952-A
Country	US
Kind code	B2
Filing date	Oct 4, 2021
Priority date	Apr 5, 2016
Publication date	Apr 16, 2024
Grant date	Apr 16, 2024

Abstract

The present disclosure is generally related to separators for use in lithium metal batteries, and associated systems and products. Certain embodiments are related to separators that form or are repaired when an electrode is held at a voltage. In some embodiments, an electrochemical cell may comprise an electrolyte that comprises a precursor for the separator.

First claim

What is claimed is:

1. A rechargeable electrochemical cell, comprising:
a first electrode;
a second electrode;
a separator; and
an electrolyte, wherein the electrolyte comprises a salt with a concentration of greater than or equal to 0.01 M, the electrolyte having a portion of a precursor to form the separator, wherein the precursor for the separator is present in the electrolyte at a concentration of greater than or equal to 1 nM and less than or equal to 1 mM; and
wherein the precursor reacts to repair one or more defects in the separator when the first and the second electrodes reach a specific voltage between 0 V and 5 V.

2. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator is capable of healing a defect in the separator.

3. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator comprises a halide anion.

4. The rechargeable electrochemical cell as in claim 3 , wherein the halide anion is one of a fluoride anion, a chloride anion, a bromide anion, or an iodide anion.

5. The rechargeable electrochemical cell of 1 , wherein the precursor for the separator comprises a species that can react to form a halide anion.

6. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator comprises a polyhalide anion.

7. The rechargeable electrochemical cell of claim 6 , wherein the polyhalide anion comprises at least two halogen species.

8. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator comprises a halogen with an oxidation state of 0.

9. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator comprises at least one of a chlorate anion, a perchlorate anion, a nitrate anion, a phosphate anion, a PF 6 − anion, a BF 4 − anion, a bis(fluorosulfonyl)imide anion, or a bis(trifluoromethane)sulfonimide anion.

10. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator comprises a lithium cation.

11. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator comprises an alkaline earth metal cation.

12. The rechargeable electrochemical cell as in claim 11 , wherein the alkaline earth metal cation is Mg 2+ .

13. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator comprises at least two halide anions.

14. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator does not participate in a redox shuttle when the rechargeable electrochemical cell operates at a voltage of greater than or equal to 4 V.

15. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator has a rock salt crystal structure.

16. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator has a fluorite crystal structure.

17. The rechargeable electrochemical cell of claim 1 , wherein the precursor for the separator crystallizes in a R3m crystal structure.

18. The rechargeable electrochemical cell of claim 1 , wherein the electrolyte comprises a solvent with one or more of an ether group, a nitrile group, a cyanoester group, a fluoroester group, a tetrazole group, a fluorosulfonyl group, a chlorosulfonyl group, a nitro group, a carbonate group, a dicarbonate group, a nitrate group, a fluoroamide group, a dione group, an azole group, or a triazine group.

19. The rechargeable electrochemical cell gas in any preceding claim 1 , wherein the electrolyte comprises an alkyl carbonate solvent.

20. The rechargeable electrochemical cell of claim 1 , wherein the electrolyte comprises an additive that increases the solubility of the precursor for the separator in the electrolyte.

21. The rechargeable electrochemical cell of claim 1 , wherein the electrolyte includes an additive comprising one or more of a nitrile group, a fluorosulfonyl group, a chlorosulfonyl group, a nitro group, a nitrate group, a fluoroamide group, or a dione group.

22. The rechargeable electrochemical cell of claim 1 , wherein an ionic conductivity of the separator is greater than or equal to 10 −4 S/cm.

23. The rechargeable electrochemical cell of claim 1 , wherein an area-specific impedance of the separator is less than or equal to 20 Ohm*cm2 2 .

24. The rechargeable electrochemical cell of claim 1 , wherein the separator is stable up to an operating potential of 3.7 V.

25. The rechargeable electrochemical cell of claim 1 , wherein the separator has a shear modulus of greater than or equal to 5 GPa.

26. The rechargeable electrochemical cell as in any of claim 1 , wherein the separator has a shear modulus of greater than or equal to 20 GPa.

27. The rechargeable electrochemical cell of claim 3 , wherein the separator has a coefficient of thermal expansion of less than or equal to 0.0000105 K −1 .

28. The rechargeable electrochemical cell of claim 1 , wherein the separator is a single ion conductor.

29. The rechargeable electrochemical cell of claim 1 , wherein the separator is directly adjacent to the first electrode.

30. The rechargeable electrochemical cell of claim 1 , wherein a thickness of the separator is greater than or equal to 1 nm and less than or equal to 50 microns.

31. The rechargeable electrochemical cell of claim 1 , wherein the separator comprises at least a first layer and a second layer.

32. The rechargeable electrochemical cell of claim 31 , wherein the first layer has a different composition than the second layer.

33. The rechargeable electrochemical cell of claim 31 , wherein the second layer undergoes oxidation at a higher voltage than the first layer.

34. The rechargeable electrochemical cell of claim 31 , wherein the first layer is closer to the first electrode than the second layer.

35. The rechargeable electrochemical cell of claim 31 , wherein the separator comprises at least a third layer.

36. The rechargeable electrochemical cell of claim 1 , wherein a surface of the first electrode comprises a passivation layer.

37. The rechargeable electrochemical cell of claim 36 , wherein the passivation layer has a thickness of greater than or equal to 1 nm and less than or equal to 100 microns.

38. The rechargeable electrochemical cell of claim 36 , wherein the passivation layer comprises a halide anion.

39. The rechargeable electrochemical cell of claim 36 , wherein the passivation layer comprises poly(2-vinyl pyridine).

40. The rechargeable electrochemical cell of claim 1 , wherein a thickness of the first electrode is greater than or equal to 15 microns and less than or equal to 50 microns.

41. The rechargeable electrochemical cell of claim 1 , wherein the second electrode stores a working ion of the rechargeable electrochemical cell at a potential relative to a metal of the working ion that is greater than 2.0 V.

42. The rechargeable electrochemical cell of claim 1 , wherein the second electrode comprises at least one of an intercalation compound, a conversion compound, an oxide, a halide, or a chalcogenide, wherein the second electrode comprises a lithium ion interca

Assignees

• Massachusetts Inst Technology
• Univ Carnegie Mellon
• 24M Tech Inc

Inventors

• Chiang Yet-Ming
• Viswanathan Venkatasubramanian
• Li Linsen
• Pande Vikram
• Krishnamurthy Dilip
• Ahmad Zeeshan
• Woodford William Henry

Classifications

• H01M10/4235 Primary

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• H01M4/134 Primary

  Electrodes based on metals, Si or alloys · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M10/052

  Li-accumulators · CPC title