Redox shuttles for lithium ion batteries

Patent metadata

Field	Value
Publication number	US-9293789-B2
Application number	US-201414519347-A
Country	US
Kind code	B2
Filing date	Oct 21, 2014
Priority date	May 25, 2010
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

An electrolyte may include compounds of general Formula IVA or IVB.

where, R 8 , R 9 , R 10 , and R 11 are each independently selected from H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, and alkoxy groups; X and Y are each independently O, S, N, or P; and Z′ is a linkage between X and Y, and at least one of R 8 , R 9 , R 10 , and R 11 is other than H.

First claim

What is claimed is:

1. An electrolyte comprising:
a redox shuttle comprising a compound of Formula IVA or IVB:

R 9 and R 11 are each independently H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, or alkoxy groups;
R 8 and R 10 are each independently alkyl;
X and Y are each independently O, S, N, or P; and
Z′ is a linkage between X and Y.

2. The electrolyte of claim 1 , wherein X and Y are O.

3. The electrolyte of claim 1 , wherein: Z′ is CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 , CH(CH 3 )CH 2 , CH(C 3 )(CH 2 )CH 2 , CH(CH 3 )CH(CH 3 ), CHCH, CCl 2 , C 2 , CF 2 , CH(Cl)CH(Cl), CH(Br)CH(Br), CH(F)CH(F), CH 2 (CF 2 )CH 2 , CH 2 N(Me)CH 2 , CH 2 OCH 2 CH 2 OCH 2 , CH 2 CH 2 OCH 2 OCH 2 CH 2 ; CH 2 CH 2 OCH 2 CH 2 OCH 2 , or CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 .

4. The electrolyte of claim 1 , wherein at least two of R 8 , R 9 , R 10 , and R 11 are independently tertiary alkyl groups.

5. The electrolyte of claim 1 , wherein
X and Y are O; and
Z′ is CH 2 , CH 2 CH 2 , or CHCH.

6. The electrolyte of claim 1 , wherein:
R 8 and R 10 are tert-butyl;
R 9 and R 11 are each independently H, F, Cl, or Br;
X and Y are O; and
Z′ is CH 2 or CHCH.

7. The electrolyte of claim 1 , wherein the compound comprises 5,7-di-tert-butyl-2,3-dibromo-1,4-benzodioxin; 5,7-di-tert-butyl-1,4-benzodioxin; or 4,6-di-tert-butyl-1,3-benzodioxole.

8. The electrolyte of claim 1 , wherein the redox shuttle has a redox potential of from 3 V to 5 V in the electrolyte.

9. The electrolyte of claim 1 , wherein the redox shuttle is present in the electrolyte from 0.0005 wt % to 50 wt %.

10. The electrolyte of claim 1 , further comprising an alkali metal salt.

11. The electrolyte of claim 10 , wherein the alkali metal salt comprises Li[B(C 2 O 4 ) 2 ]; Li[BF 2 (C 2 O 4 )]; LiClO 4 ; LiBF 4 ; LiAsF 6 ; LiPF 6 ; Li[CF 3 S 0 3 ]; Li[N(CF 3 S 0 2 ) 2 ]; Li[C(CF 3 SO 2 ) 3 ]; LiN(SO 2 C 2 F 5 ) 2 ; or a lithium alkyl fluorophosphate.

12. The electrolyte of claim 1 , wherein further comprising a polar aprotic solvent.

13. The electrolyte of claim 12 , wherein the polar aprotic solvent comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dimethyl ether, or γ-butyrolactone.

14. The electrolyte of claim 1 which is substantially non-aqueous.

15. An electrochemical device comprising
a cathode
an anode; and
an electrolyte comprising a compound of Formula IVA or IVB;
the compound of Formula IVA or IVB is:

R 9 and R 11 are each independently H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, or alkoxy groups;
R 8 and R 10 are each independently alkyl;
X and Y are each independently O, S, N, or P; and
Z′ is a linkage between X and Y.

16. The electrochemical device of claim 15 , wherein X and Y are O.

17. The electrochemical device of claim 15 , wherein at least two of R 8 , R 9 , R 11 , and R 11 are independently tertiary alkyl groups.

18. The electrochemical device of claim 15 , wherein: Z′ is CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 , CH(CH 3 )CH 2 , CH(CH 3 )(CH 2 )CH 2 , CH(CH 3 )CH(CH 3 ), CHCH, CCl 2 , CBr 2 , CF 2 , CH(Cl)CH(Cl), CH(Br)CH(Br), CH(F)CH(F), CH 2 (CF 2 )CH 2 , CH 2 N(Me)CH 2 , CH 2 OCH 2 CH 2 OCH 2 , CH 2 CH 2 OCH 2 OCH 2 CH 2 ; CH 2 CH 2 OCH 2 CH 2 OCH 2 , or CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 .

Assignees

• Uchicago Argonne Llc

Inventors

• Weng Wei
• Zhang Zhengcheng
• Amine Khalil

Classifications

• H01M2300/0028

  characterised by the solvent · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• H01G11/64

  characterised by additives · CPC title

• H01M10/052

  Li-accumulators · CPC title

• Y02E60/122

  Cross-Sectional Technologies · mapped topic