Nonaqueous electrolytic solution for electrochemical cells
View Patent ↗The invention relates to the use of an amine oxide as an additive in a nonaqueous electrolytic solution. The electrolytic solution is suitable for use in electrochemical cells such as lithium batteries and lithium ion batteries. Batteries using this electrolyte solution have long life and high capacity retention.
1. A secondary battery comprising
a. an anode,
b. a cathode comprising lithium, and
c. an electrolytic solution comprising
i. a non-aqueous solvent,
ii. a salt, and
iii. an amine oxide having the formula
wherein R 1 and R 2 are independently each a C 6 to C 36 hydrocarbon group, and R 3 is a C 1 to C 36 hydrocarbon group.
2. The secondary battery of claim 1 wherein the hydrocarbon group of at least one of R 1 , R 2 , and R 3 , includes at least one substituent selected from the group consisting of —O—, —S—, —CO—, —CO 2 —, —SO—, —SO 2 —, —NR 4 —, —NR 4 R 5 , —PR 6 —, or —Si(R 7 R 8 )—, wherein R 4 to R 8 are independently selected from the group consisting of hydrogen, halogen, C 1 to C 20 saturated alkyl, C 1 -C 20 alkenyl, phenyl, and combinations thereof.
3. The secondary battery of claim 1 wherein R 1 and R 2 are independently each a C 8 to C 26 hydrocarbon group and R 3 is a C 1 to C 22 hydrocarbon group.
4. The lithium secondary battery of claim 1 wherein the amine oxides are selected from the group consisting of tri(6-aminohexyl)amine oxide, tri(10-aminodecyl)amine oxide, tri(4-cyclohexyl)amine oxide, dioctyl methyl amine oxide, trioctyl amine oxide, didecyl methyl amine oxide, tridecyl amine oxide, didodecyl methyl amine oxide, tridodecyl amine oxide, dihexadecyl methyl amine oxide, trihexadecyl amine oxide, di(coco alkyl)methyl amine oxide, tri(coco alkyl)amine oxide, di(tallow alkyl)methyl amine oxide, tri(tallow alkyl)amine oxide, tri(C 20 -C 22 )amine oxide, and di(C 20 -C 22 alkyl)methyl amine oxide, and combinations thereof.
5. The secondary battery of claim 1 wherein the salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiTaF 6 , LiAlCl 4 , Li 2 B 10 Cl 10 , LiBOB, LiBMB, LiBDFMB, LiMOB, LiDFMOB, LiTOP, LiTDFMP, LiClO 4 , LiCF 3 SO 3 ; LiN(SO 2 C m F 2m+1 )(SO 2 C n F 2n+1 ), and LiC(SO 2 C k F 2k+1 )(SO 2 C m F 2m+1 )(SO 2 C n F 2n+1 ), wherein k=1-10, m=1-10, and n=1-10, respectively; LiN(SO 2 C p F 2p SO 2 ), and LiC(SO 2 C p F 2p SO 2 )(SO 2 C q F 2q+1 ) wherein p=1-10 and q=1-10; and LiPF x (R F ) 6-x and LiBF y (R F ) 4-y , wherein R F represents perfluorinated C 1 -C 20 alkyl groups or perfluorinated aromatic groups, x=0-5, and y=0-3.
6. The secondary battery of claim 1 wherein the non-aqueous solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, acetonitrile, dimethylformamide, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, γ-butyrolactone, 2-methyl-γ-butyrolactone, 3-methyl-γ-butyrolactone, 4-methyl-γ-butyrolactone, β-propiolactone, δ-valerolactone, trimethyl phosphate, triethyl phosphate, tris(2-chloroethyl)phosphate, tris(2,2,2-trifluoroethyl)phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, trihexyl phosphate, triphenyl phosphate, tritolyl phosphate, and combinations thereof.
7. The secondary battery of claim 1 wherein the electrolytic solution comprises:
a. about 20 to about 99 wt % of the non-aqueous solvent,
b. about 1 to about 50 wt % of the salt, and
c. about 0.01 to about 10 wt % of the amine oxide.
8. The secondary battery of claim 1 , wherein the non-aqueous electrolytic solution comprises:
a. ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate;
b. LiPF 6 , and
c. an amine oxide having the formula
wherein R 1 and R 2 are independently each a C 14 -C 24 hydrocarbon group.
9. The secondary battery of claim 1 wherein the non-aqueous electrolytic solution comprises:
a. ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate in a 1:1:1 weight ratio;
b. LiPF 6 in a concentration of about 1.0 M,
c. and wherein, in the amine oxide having the formula
R 1 and R 2 are independently each a C 14 -C 24 hydrocarbon group.
10. A method of making a lithium battery or lithium ion battery comprising:
a. providing an electrolytic solution comprising
i. a non-aqueous solvent,
ii. a lithium containing salt, and
iii. an amine oxide having the formula
wherein R 1 and R 2 are independently each a C 6 to C 36 hydrocarbon group, and R 3 is a C 1 to C 36 hydrocarbon group,
b. laminating and winding a cathode, a first porous separator, an anode, and a second porous separator,
c. placing the wound laminated electrodes and separators in a battery case,
d. infusing the electrolytic solution into the battery case, and
e. sealing the battery case containing the electrodes, electrolytic solution and separators.
11. The method of claim 10 wherein the hydrocarbon group of at least one of R 1 , R 2 , and R 3 includes —O—, —S—, —CO—, —CO 2 —, —SO—, —SO 2 —, —NR 4 —, —NR 4 R 5 , —PR 6 —, or —Si(R 7 R 8 )—, wherein R 4 to R 8 are independently selected from the group consisting of hydrogen, halogen, C 1 to C 20 saturated alkyl, C 1 -C 20 alkenyl, or substituted alkyl, phenyl, or substituted phenyl, or combinations thereof.
12. The method of claim 10 wherein R 1 and R 2 are independently each a C 8 to C 26 hydrocarbon group and R 3 is a C 1 to C 22 hydrocarbon group.
13. The method of claim 10 wherein R 1 and R 2 are independently each a C 10 to C 26 hydrocarbon group and R 3 is a C 1 hydrocarbon group.
14. The method of claim 10 wherein R 1 , R 2 , and R 3 are each the same C 6 to C 36 hydrocarbon group.
15. The method of claim 10 wherein the non-aqueous solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, acetonitrile, dimethylformamide, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, γ-butyrolactone, 2-methyl-γ-butyrolactone, 3-methyl-γ-butyrolactone, 4-methyl-γ-butyrolactone, β-propiolactone, δ-valerolactone, trimethyl phosphate, triethyl phosphate, tris(2-chloroethyl)phosphate, tris(2,2,2-trifluoroethyl)phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, trihexyl phosphate, triphenyl phosphate, tritolyl phosphate, and combinations thereof.
16. The method of claim 10 wherein the lithium containing salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiTaF 6 , LiAlCl 4 , Li 2 B 10 Cl 10 , LiBOB, LiBMB, LiBDFMB, LiMOB, LiDFMOB, LiTOP, LiTDFMP, LiClO 4 , LiCF 3 SO 3 ; LiN(SO 2 C m F 2m+1 )(SO 2 C n F 2n+1 ), and LiC(SO 2 C k F 2k+1 )(SO 2 C m F 2m+1 )(SO 2 C n F 2n+1 ), wherein k=1-10, m=1-10, and n=1-10, respectively; LiN(SO 2 C p F 2p SO 2 ), and LiC(SO 2 C p F 2p SO 2 )(SO 2 C q F 2q+1 ) wherein p=1-10 and q=1-10; and LiPF x (R F ) 6-x and LiBF y (R F ) 4-y , wherein R F represents perfluorinated C 1 -C 20 alkyl groups or perfluorinated aromatic groups, x=0-5, and y=0-3.
17. The method of claim 10 wherein the cathode comprises: a lithium mixed metal oxide selected from the group consisting of LiMnO 2 , LiMn 2 O 4 , LiCoO 2 , Li 2 Cr 2 O 7 , Li 2 CrO 4 , LiNiO 2 , LiFeO 2 , LiNi x Co 1-x O 2 (0<x<1), LiFePO 4 , Li 3 VPO 4 , LiMn 0.5 Ni 0.5 O 2 , LiMn 1/3 Co 1/3 Ni 1/3 O 2 , LiNi x Co y Me z O 2 wherein Me may be one or more of Al, Mg, Ti, B, Ga, or Si and 0<x,y,z<1, and LiMc 0.5 Mn 1.5 O 4 wherein Mc is a divalent metal, and mixtures thereof.
18. The method of claim 10 wherein the anode comprises a material selected from the group consisting of crystalline carbon, lithium metal, LiMnO 2 , LiAl, LiZn, Li 3 Bi, Li 3 Cd, Li 3 Sb, Li 4 Si, Li 4.4 Pb, Li 4.4 Sn, LiC 6 , Li 3 FeN 2 , Li 2.6 Cu 0.4 N, Li 2.6 Cu 0.4 N, Li 4 Ti 5 O 12 , and combinations thereof.