Introducing a mobile layer of ionic liquid into electrolytes of lithium ion batteries

• US 10,424,814 B2
• Filed: 06/21/2018
• Issued: 09/24/2019
• Est. Priority Date: 04/07/2016
• Status: Active Grant

• Current Assignee: StoreDot Ltd.
• Original Assignee: StoreDot Ltd.
• Inventors: Burshtain, Doron, Kedem, Nir, Aronov, Daniel
• Primary Examiner(s): Gatewood, Daniel S
• Application Number:
  US16/013,969
• Publication Number:
  US 20180301757A1
• Time in Patent Office: 460 Days
• Field of Search: None
• 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 10/0567 characterised by the additives
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/58 of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: H01M 4/5815 Sulfides
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/602 Polymers
• CPC Class Codes: H01M 4/628 Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Electrolytes, anodes, lithium ion cells and methods are provided for preventing lithium metallization in lithium ion batteries to enhance their safety. Electrolytes comprise up to 20% ionic liquid additives which form a mobile solid electrolyte interface during charging of the cell and prevent lithium metallization and electrolyte decomposition on the anode while maintaining the lithium ion mobility at a level which enables fast charging of the batteries. Anodes are typically metalloid-based, for example include silicon, germanium, tin and/or aluminum. A surface layer on the anode bonds, at least some of the ionic liquid additive to form an immobilized layer that provides further protection at the interface between the anode and the electrolyte, prevents metallization of lithium on the former and decomposition of the latter.

Claims

1. A method comprising:

adding, into a carbonate-containing electrolyte of a lithium ion battery, up to 10 percent by volume of at least one ionic liquid, which consists of cations and anions,

forming, during charging of the lithium ion battery and at surfaces of anode material particles thereof, a mobile layer comprising at least some of the cations, and

establishing a gradient of electric charge at the mobile layer during charging of the lithium ion battery, to provide an interphase transition between the electrolyte and the anode material particles, the gradient configured to have a gradual change of parameters which gradually reduces an activation energy of a reduction reaction of lithium ions being charged from the electrolyte into the anode material particles.

2. The method of claim 1, further comprising selecting the cations and/or anions to be at least 50% larger in volume than lithium ions, preventing lithium metallization at the anode material particles by steric hindrance.

3. The method of claim 1, further comprising selecting the cations and anions to have molecular shapes that prevent, by steric hindrance, lithium metallization on the anode material particles.

4. The method of claim 1, further comprising selecting the at least one ionic liquid to have a melting temperature below 0°

C.

5. The method of claim 1, further comprising selecting the cations to comprise at least one piperidinium, substituted or unsubstituted.

6. The method of claim 1, further comprising selecting the anions to comprise at least one sulfonylimide, substituted or unsubstituted.

7. The method of claim 1, wherein the forming is carried out repeatedly during cycling of the lithium ion battery.

8. The method of claim 1, wherein the adding comprises less than percent by volume of the at least one ionic liquid, added into the carbonate-containing electrolyte.

10. The method of claim 1, further comprising producing the anode material particles from Ge, Si and/or Sn.

11. The method of claim 1, further comprising preparing the lithium ion battery with the carbonate-containing electrolyte and anodes made of the anode material particles and operating the prepared lithium ion battery through at least one cycle, to carry out the forming of the mobile layer controllably.

14. The method of claim 1, further comprising coating the anode material particles with a coating that binds at least some of the cations of the mobile layer.

15. The method of claim 14, wherein the coating comprises at least one lithium sulfonate, substituted or unsubstituted.

36. The method of claim 1, further comprising configuring the formed mobile layer to fill in cracks in the anode material particles.

9. A method comprising:

adding, into a carbonate-containing electrolyte of a lithium ion battery, up to 10 percent by volume of at least one ionic liquid, which consists of cations and anions,

forming, during charging of the lithium ion battery and at surfaces of anode material particles thereof, a mobile layer comprising at least some of the cations, and

configuring the formed mobile layer to fill in cracks in the anode material particles.

16. The method of claim 9, wherein the forming is carried out repeatedly during cycling of the lithium ion battery.

17. The method of claim 9, further comprising selecting the cations and/or anions to be at least 50% larger in volume than lithium ions, preventing lithium metallization at the anode material particles by steric hindrance.

18. The method of claim 9, further comprising selecting the cations and anions to have molecular shapes that prevent, by steric hindrance, lithium metallization on the anode material particles.

19. The method of claim 9, further comprising selecting the at least one ionic liquid to have a melting temperature below 0°

C.

20. The method of claim 9, further comprising selecting the cations to comprise at least one piperidinium, substituted or unsubstituted.

21. The method of claim 9, further comprising selecting the anions to comprise at least one sulfonylimide, substituted or unsubstituted.

22. The method of claim 9, further comprising producing the anode material particles from Ge, Si and/or Sn.

23. The method of claim 9, further comprising preparing the lithium ion battery with the carbonate-containing electrolyte and anodes made of the anode material particles and operating the prepared lithium ion battery through at least one cycle, to carry out the forming of the mobile layer controllably.

24. The method of claim 9, further comprising coating the anode material particles with a coating that binds at least some of the cations of the mobile layer.

25. The method of claim 24, wherein the coating comprises at least one lithium sulfonate, substituted or unsubstituted.

34. The method of claim 9, further comprising establishing a gradient of electric charge at the mobile layer during charging of the lithium ion battery, to provide an interphase transition between the electrolyte and the anode material particles, the gradient configured to have a gradual change of parameters which gradually reduces an activation energy of a reduction reaction of lithium ions being charged from the electrolyte into the anode material particles.

12. A method comprising:

adding, into a carbonate-containing electrolyte of a lithium ion battery, up to 10 percent by volume of at least one ionic liquid, which consists of cations and anions,

forming, during charging of the lithium ion battery and at surfaces of anode material particles thereof, a mobile layer comprising at least some of the cations, and

coating the anode material particles with a coating that binds at least some of the cations of the mobile layer.

13. The method of claim 12, wherein the coating comprises at least one lithium sulfonate, substituted or unsubstituted.

26. The method of claim 12, wherein the forming is carried out repeatedly during cycling of the lithium ion battery.

27. The method of claim 12, further comprising selecting the cations and/or anions to be at least 50% larger in volume than lithium ions, preventing lithium metallization at the anode material particles by steric hindrance.

28. The method of claim 12, further comprising selecting the cations and anions to have molecular shapes that prevent, by steric hindrance, lithium metallization on the anode material particles.

29. The method of claim 12, further comprising selecting the at least one ionic liquid to have a melting temperature below 0°

C.

30. The method of claim 12, further comprising selecting the cations to comprise at least one piperidinium, substituted or unsubstituted.

31. The method of claim 12, further comprising selecting the anions to comprise at least one sulfonylimide, substituted or unsubstituted.

32. The method of claim 12, further comprising producing the anode material particles from Ge, Si and/or Sn.

33. The method of claim 12, further comprising preparing the lithium ion battery with the carbonate-containing electrolyte and anodes made of the anode material particles and operating the prepared lithium ion battery through at least one cycle, to carry out the forming of the mobile layer controllably.

35. The method of claim 12, further comprising establishing a gradient of electric charge at the mobile layer during charging of the lithium ion battery, to provide an interphase transition between the electrolyte and the anode material particles, the gradient configured to have a gradual change of parameters which gradually reduces an activation energy of a reduction reaction of lithium ions being charged from the electrolyte into the anode material particles.

37. The method of claim 12, further comprising configuring the formed mobile layer to fill in cracks in the anode material particles.