Polyether-functionalized redox shuttle additives for lithium ion batteries
Compounds may have general Formula I, II, or III: where R 1 , R 2 , R 3 , and R 4 are independently H, F, Cl, Br, CN, NO 2 , a alkyl group, a haloalkyl group, a phosphate group, a polyether group; or R 1 and R 2 , or R 3 and R 4 , or R 2 and R 3 (in the case of Formula II) may join together to form a fused ring on the benzene ring; and X and Z are independently a group of Formula A: where R 5 and R 6 and R 7 are independently H, F, Cl, Br, CN, NO 2 , a alkyl group, a haloalkyl group, a phosphate group, or a polyether group; R 7 is H, F, Cl, Br, CN, NO 2 , a alkyl group, a haloalkyl group, a phosphate group, or a polyether group; n is an integer from 1 to 8; and m is an integer from 1 to 13. Such compounds may be used as redox shuttles in electrolytes for use in electrochemical cells, batteries and electronic devices.
1. A compound represented by Formula I, II, or III:
wherein:
R 1 is n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl;
R 2 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether, or R 1 and R 2 join together to form a ring;
R 3 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether; or
where the compound is represented by Formula II, R 1 and R 2 , or R 2 and R 3 join together to form a ring;
R 4 is n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl; and
X and Z are independently a group of Formula A:
wherein:
R 5 and R 6 are independently H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether;
R 7 is alkyl, haloalkyl, phosphate, or polyether;
n is an integer from 1 to 8; and
m is an integer from 1 to 13.
2. The compound of claim 1 , wherein R 2 and R 3 are hydrogen.
3. The compound of claim 1 represented by Formula I.
4. The compound of claim 3 , wherein:
R 2 and R 3 are independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, or a polyether group having from 2 to 20 carbon atoms;
R 5 and R 6 at each occurrence are individually H, a C 1 -C 4 alkyl, a C 1 -C 4 haloalkyl, H, Cl, Br, or I;
R 7 is alkyl;
n is 1 or 2; and
m is 1 to 8.
5. The compound of claim 1 represented by Formula II.
6. The compound of claim 1 represented by Formula III.
7. The compound of claim 6 , wherein:
R 1 and R 4 are tert-butyl;
R 2 and R 3 are H;
R 5 and R 6 at each occurrence are individually H or methyl;
R 7 is methyl, or ethyl;
n is 1 or 2; and
m is 1 to 8.
8. The compound of claim 1 , wherein R 7 is C 1 -C 4 alkyl.
9. A compound which is 1,4-bis(2-(2-methoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; 1,4-bis(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; or 1,4-bis(2-(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene.
10. An electrolyte comprising:
an alkali metal salt;
a polar aprotic solvent; and
a redox shuttle comprising a compound represented by Formula I, II, or III:
wherein:
R 1 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether;
R 2 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether, or R 1 and R 2 join together to form a ring;
R 3 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether; or where the compound is represented by Formula II, R 1 and R 2 , or R 2 and R 3 join together to form a ring;
R 4 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether; or R 3 and R 4 join together to form a ring; and
X and Z are independently a group of Formula A:
wherein:
R 5 and R 6 are independently H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether;
R 7 is H, alkyl, haloalkyl, phosphate, or polyether;
n is an integer from 1 to 8;
m is an integer from 1 to 13; and
wherein the electrolyte solution is substantially non-aqueous.
11. An electrochemical device comprising
a cathode
an anode; and
a substantially non-aqueous electrolyte comprising:
an alkali metal salt;
a polar aprotic solvent; and
a compound represented by Formula I, II, or III;
wherein:
Formula I, II, and III are:
R 1 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether;
R 2 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether, or R 1 and R 2 join together to form a ring;
R 3 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether; or where the compound is represented by Formula II, R 1 and R 2 , or R 2 and R 3 join together to form a ring;
R 4 is H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether; or R 3 and R 4 join together to form a ring; and
X and Z are independently a group of Formula A:
R 5 and R 6 are independently H, F, Cl, Br, CN, NO 2 , alkyl, haloalkyl, phosphate, or polyether;
R 7 is H, alkyl, haloalkyl, phosphate, or polyether;
n is an integer from 1 to 8; and
m is an integer from 1 to 13.
12. The electrolyte of claim 10 , wherein R 1 , R 2 , R 3 , and R 4 are independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, or a polyether having from 2 to 20 carbon atoms.
13. The electrolyte of claim 10 , wherein R 1 and R 4 are individually H, alkyl or haloalkyl, and R 2 and R 3 are hydrogen.
14. The electrolyte of claim 10 , wherein R 1 and R 4 are individually H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl, and R 2 and R 3 are H.
15. The electrolyte of claim 10 represented by Formula III.
16. The electrolyte of claim 15 , wherein:
R 1 and R 4 are individually H, alkyl or haloalkyl;
R 2 and R 3 are hydrogen;
R 5 and R 6 at each occurrence are individually H or methyl;
R 7 is H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl;
n is 1 or 2;
m is 1 to 8.
17. The electrolyte of claim 15 , wherein:
R 1 and R 4 are tert-butyl;
R 2 and R 3 are H;
R 5 and R 6 at each occurrence are individually H or methyl;
R 7 is H, methyl, or ethyl;
n is 1 or 2; and
m is 1 to 8.
18. The electrolyte of claim 10 , wherein the compound is 1-nitro-3-tert-butyl-2,5-di-oligo(ethylene glycol)benzene; 1-cyano-3-tert-butyl-2,5-di-oligo(ethylene glycol)benzene; 1,4-di-tert-butyl-2,3-di-oligo(ethylene glycol)benzene; 5-tert-butyl-1,3-dinitro-2,4-di-oligo(ethylene glycol)benzene; 1-(benzyloxy)-4-bromo-2,3-di-oligo(ethylene glycol)benzene; 1,3,5-tri-tert-butyl-2,4-di-oligo(ethylene glycol)benzene; 2-methyl-1,4-di-oligo(ethylene glycol)benzene; 2,3-dimethyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-dimethyl-1,4-di-oligo(ethylene glycol)benzene; 2,6-dimethyl-1,4-di-oligo(ethylene glycol)benzene; 2,3,6-trimethyl-1,2-di-oligo(ethylene glycol)benzene; 2,3,5,6-tetramethyl-1,4-di-oligo(ethylene glycol)benzene; 4-methyl-1,2-di-oligo(ethylene glycol)benzene; 2-ethyl-1,4-di-oligo(ethylene glycol)benzene; 2,3-diethyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-diethyl-1,4-di-oligo(ethylene glycol)benzene; 2,6-diethyl-1,4-di-oligo(ethylene glycol)benzene; 2,3,6-triethyl-1,2-di-oligo(ethylene glycol)benzene; 2,3,5,6-tetraethyl-1,4-di-oligo(ethylene glycol)benzene; 4-ethyl-1,2-di-oligo(ethylene glycol)benzene; 2,5-diisopropyl-1,4-di-oligo(ethylene glycol)benzene; 2-tert-butyl-1,4-di-oligo(ethylene glycol)benzene; 2,3-di-tert-butyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-butyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-pentyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-butyl-3,6-di-nitro-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-butyl-3,6-di-cyano-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-butyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-dicyclohexyl-1,4-di-oligo(ethylene glycol)benzene; 4-tert-butyl-1,2-di-oligo(ethylene glycol)benzene; 4,5-di-tert-butyl-1,2-di-oligo(ethylene glycol)benzene; 4,5-di-tert-pentyl-1,2-di-oligo(ethylene glycol)benzene; 4,5-di-tert-butyl-1,2-diethoxybenzene; 9,10-di-oligo(ethylene glycol)-1,4:5,8-dimethano-1,2,3,4,5,6,7,8-octahydroanthracene; 9,10-di-oligo(ethylene glycol)-1,4:5,8-diethano-1,2,3,4,5,6,7,8-octahydroanthracene; 1,4-bis(2-(2-methoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; 1,4-bis(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; or 1,4-bis(2-(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene.
19. The electrolyte of claim 10 , wherein the compound is 1,4-bis(2-(2-methoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; 1,4-bis(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; or 1,4-bis(2-(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene.
20. The electrochemical device of claim 11 , wherein the compound is 1-nitro-3-tert-butyl-2,5-di-oligo(ethylene glycol)benzene; 1-cyano-3-tert-butyl-2,5-di-oligo(ethylene glycol)benzene; 1,4-di-tert-butyl-2,3-di-oligo(ethylene glycol)benzene; 5-tert-butyl-1,3-dinitro-2,4-di-oligo(ethylene glycol)benzene; 1-(benzyloxy)-4-bromo-2,3-di-oligo(ethylene glycol)benzene; 1,3,5-tri-tert-butyl-2,4-di-oligo(ethylene glycol)benzene; 2-methyl-1,4-di-oligo(ethylene glycol)benzene; 2,3-dimethyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-dimethyl-1,4-di-oligo(ethylene glycol)benzene; 2,6-dimethyl-1,4-di-oligo(ethylene glycol)benzene; 2,3,6-trimethyl-1,2-di-oligo(ethylene glycol)benzene; 2,3,5,6-tetramethyl-1,4-di-oligo(ethylene glycol)benzene; 4-methyl-1,2-di-oligo(ethylene glycol)benzene; 2-ethyl-1,4-di-oligo(ethylene glycol)benzene; 2,3-diethyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-diethyl-1,4-di-oligo(ethylene glycol)benzene; 2,6-diethyl-1,4-di-oligo(ethylene glycol)benzene; 2,3,6-triethyl-1,2-di-oligo(ethylene glycol)benzene; 2,3,5,6-tetraethyl-1,4-di-oligo(ethylene glycol)benzene; 4-ethyl-1,2-di-oligo(ethylene glycol)benzene; 2,5-diisopropyl-1,4-di-oligo(ethylene glycol)benzene; 2-tert-butyl-1,4-di-oligo(ethylene glycol)benzene; 2,3-di-tert-butyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-butyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-pentyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-butyl-3,6-di-nitro-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-butyl-3,6-di-cyano-1,4-di-oligo(ethylene glycol)benzene; 2,5-di-tert-butyl-1,4-di-oligo(ethylene glycol)benzene; 2,5-dicyclohexyl-1,4-di-oligo(ethylene glycol)benzene; 4-tert-butyl-1,2-di-oligo(ethylene glycol)benzene; 4,5-di-tert-butyl-1,2-di-oligo(ethylene glycol)benzene; 4,5-di-tert-pentyl-1,2-di-oligo(ethylene glycol)benzene; 4,5-di-tert-butyl-1,2-diethoxybenzene; 9,10-di-oligo(ethylene glycol)-1,4:5,8-dimethano-1,2,3,4,5,6,7,8-octahydroanthracene; 9,10-di-oligo(ethylene glycol)-1,4:5,8-diethano-1,2,3,4,5,6,7,8-octahydroanthracene; 1,4-bis(2-(2-methoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; 1,4-bis(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; or 1,4-bis(2-(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene.
21. The electrochemical device of claim 11 , wherein the compound is 1,4-bis(2-(2-methoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; 1,4-bis(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene; or 1,4-bis(2-(2-(2-(2-methoxy)ethoxy)ethoxy)ethoxy)ethoxy-2,5-di-tert-butyl-benzene.