Electrolytes with ionic liquid additives for lithium ion batteries

• US 10,096,859 B2
• Filed: 03/02/2017
• Issued: 10/09/2018
• 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:
  US15/447,889
• Publication Number:
  US 20170294681A1
• Time in Patent Office: 586 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. An electrolyte for a lithium ion battery having an anode made of anode material particles and a cathode, said electrolyte consisting of carbonate containing electrolyte, at least one lithium salt and an additive present in an amount up to 10 volume percent of the electrolyte, the additive consisting of at least one ionic liquid which consists of cations and anions, wherein, while operating the battery:

during charging of the battery, at least the cations form, upon application of an electric field in a vicinity of the anode, a mobile layer at surfaces of the anode material particles, which accommodates expansion of the anode material particles by rearrangement of at least the cations,

during discharging of the battery, at least the cations diffuse into the carbonate-containing electrolyte; and

wherein the anions comprise at least one sulfonylimide, substituted or unsubstituted, and the cations comprise at least one piperidinium, substituted or unsubstituted, wherein the at least one ionic liquid is further selected to have a melting temperature below 10°

C.

2. The electrolyte of claim 1, wherein the additive is present in an amount up to about 5 volume percent of the electrolyte.

3. The electrolyte of claim 1, wherein the additive is present in an amount of 0.1-2 volume percent of the electrolyte.

4. The electrolyte of claim 1, wherein the cations comprise a positively charged nitrogen atom and/or the anions comprise a negatively charged nitrogen atom.

5. The electrolyte of claim 1, wherein the additive has a melting temperature below 0°

C.

6. The electrolyte of claim 1, wherein the additive has a melting temperature below −

4°

C.

7. The electrolyte of claim 1, wherein the additive has a melting temperature below −

20°

C.

8. The electrolyte of claim 1, wherein said additive comprises a plurality of ionic liquids, together present in an amount up to 10% of the electrolyte.

9. The electrolyte of claim 1, wherein the cations and/or anions are at least 50% larger in volume than lithium ions, preventing metallization at the anode by steric hindrance.

10. The electrolyte of claim 1, wherein the additive is selected to establish 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.

11. The electrolyte of claim 10, wherein the additive comprises at least one of:

1-butyl-1-methylpyrrolidinium;

bis(trifluoromethanesulfonyl)imide;

butyl-3-methylimidazolium;

bis(trifluoromethanesulfonyl)imide;

1-butyl-3-methylimidazolium;

bis(fluorosulfonyl)imide;

N,N-Diethyl-N-methyl-N-propylammonium;

bis(fluorosulfonyl)imide;

N-propyl-N-methylpiperidinium;

bis(trifluoromethanesulfonyl)imide, or any combination thereof, which species may be substituted or unsubstituted.

12. A lithium ion cell comprising:

an anode comprising a metalloid selected from the group consisting of Si, Sn, Ge, Al, and combinations thereof;

a cathode, and

the electrolyte of claim 1.

13. The lithium ion cell of claim 12, wherein the anode comprises metalloid active material nanoparticles partly or completely coated with particles selected from the group consisting of B₄C, WC, VC and TiN.

14. The lithium ion cell of claim 12, wherein the anode comprises metalloid active material nanoparticles partly or completely coated with a polymer containing lithium.

15. The lithium ion cell of claim 12, wherein the anode comprises metalloid active material nanoparticles partly or completely coated with a borate salt, a phosphate salt, or a combination thereof.

16. A lithium ion cell comprising a graphite-based anode, a cathode, and the electrolyte of claim 1.

21. The electrolyte of claim 1, wherein the anode active material particles comprise LTO (lithium titanate).

17. An electrolyte for a lithium ion battery having an anode made of anode material particles and a cathode, said electrolyte consisting of carbonate containing electrolyte, at least one lithium salt and an additive present in an amount up to 10 volume percent of the electrolyte, the additive consisting of at least one ionic liquid which consists of cations and anions, wherein the at least one ionic liquid consists of at least one sulfonylimide, substituted or unsubstituted, and at least one piperidinium, substituted or unsubstituted, selected to have a melting temperature below 10°

C.

18. The electrolyte of claim 17, wherein the at least one ionic liquid comprises cations and/or anions at least 50% larger in volume than lithium ions, preventing metallization at the anode by steric hindrance.

19. The electrolyte of claim 17, wherein at least one the ionic liquid comprises at least one of:

1-butyl-1-methylpyrrolidinium;

bis(trifluoromethanesulfonyl)imide;

butyl-3-methylimidazolium;

bis(trifluoromethanesulfonyl)imide;

1-butyl-3-methylimidazolium;

bis(fluorosulfonyl)imide;

N,N-Diethyl-N-methyl-N-propylammonium;

bis(fluorosulfonyl)imide;

N-propyl-N-methylpiperidinium;

bis(trifluoromethanesulfonyl)imide, or any combination thereof, which species may be substituted or unsubstituted.

20. A lithium ion cell comprising:

an anode comprising a metalloid selected from the group consisting of Si, Sn, Ge, Al, and combinations thereof;

a cathode; and

the electrolyte of claim 17.