Additive for enhancing the performance of electrochemical cells

• US 7,172,834 B1
• Filed: 07/24/2003
• Issued: 02/06/2007
• Est. Priority Date: 07/29/2002
• Status: Expired due to Fees

• Current Assignee: United States Of America As Represented By The Secretary Of The Army (Government of the United States of America)
• Original Assignee: The United States Of America As Represented By The Secretary Of The Army
• Inventors: Xu, Kang, Jow, T. Richard, Zhang, Shengshui
• Primary Examiner(s): Cantelmo; Gregg
• Application Number:
  US10/625,686
• Time in Patent Office: 1,293 Days
• Field of Search: 252/519.2, 429/188, 429/199, 429/329, 429/332
• US Class Current: 429/188
• 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 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A lithium battery includes an electrolyte comprised of a non-aqueous solvent, and a salt mixture. The salt mixture includes an alkali metal electrolyte salt and an additive salt having an anion of a mixed anhydride of oxalic acid and boric acid. Specific additive salts include lithium bis(oxalato) borate and lithium oxalyldifluoroborate. Particular electrolyte salts comprise LiPF₆ and LiBF₄. The additive salt is present in an amount of 0.1–60 mole percent of the total of the additive salt and electrolyte salt content of the electrolyte. Also disclosed is a method for enhancing the performance characteristics of a lithium battery through the use of the electrolyte composition. Also disclosed is the compound lithium oxalyldifluoroborate.

Claims

1. An electrolyte for a battery, said electrolyte comprising:

a non-aqueous solvent; and

a salt mixture, said salt mixture comprising an alkali metal electrolyte salt and an additive salt combination comprising a first additive salt having a first additive anion of bis(oxalato) borate and a second additive salt having a second additive anion of oxalyldifluoroborate.

2. The electrolyte of claim 1, wherein said additive salt combination is present in an amount of 0.1–

60 mole percent of the total of said salt mixture.

3. The electrolyte of claim 1, wherein said first additive salt is lithium bis(oxalato) borate, and said second additive salt is lithium oxalyldifluoroborate.

4. The electrolyte of claim 1, wherein said alkali metal electrolyte salt comprises a member selected from the group consisting of:

LiPF₆, LiBF₄, LiClO₄, LiC(SO₂CF₃)₃, LiN(SO₂CF₃)₂, LiO₃SCF₂CF₃, LiO₃SC₆F₅, LiO₂CCF₃, LiB(C₆H₅)₄, LiCF₃SO₃, LiB(C₂O₄)₂, LiBF₂C₂O₄ and combinations thereof.

5. The electrolyte of claim 1, wherein said first additive salt is lithium bis(oxalato) borate and present from 0.5 to 5 mole percent.

6. The electrolyte of claim 1, wherein said electrolyte salt comprises a member selected from the group consisting of:

LiPF₆, LiBF₄, and combinations thereof.

7. The electrolyte of claim 1, wherein said non-aqueous solvent includes a carbonic acid ester.

8. The electrolyte of claim 7, wherein said carbonic acid ester comprises a member selected of the group consisting of:

ethylene carbonate, butylene carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, and mixtures thereof.

9. The electrolyte of claim 1, wherein said non-aqueous solvent includes at least one alkyl ester.

10. The electrolyte of claim 9, wherein said at least one alkyl ester comprises a member selected from the group consisting of:

methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, and mixtures thereof.

11. The electrolyte of claim 1, wherein said solvent includes at least one cyclic ester or cyclic amide.

12. The electrolyte of claim 1, including at least one member selected from the group consisting of:

γ

-butyrolactone, N-methylpyrrolidinone, and mixtures thereof.

13. The electrolyte of claim 1, wherein said salt mixture is present in an amount of 0.3–

1.5 moles per liter.

14. The electrolyte of claim 1, wherein said solvent comprises, on a weight basis:

0–

60% propylene carbonate;

0–

60% γ

-butyrolactone;

10–

60% ethylene carbonate; and

0–

80% of a member selected from the group consisting of;

dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, methyl acetate, methyl propionate, methyl butyrate, and combinations thereof.