Nonaqueous electrolytic solution and nonaqueous electrolyte battery
View Patent ↗A nonaqueous electrolytic solution that can provide a battery that is low in gas generation, has a large capacity, and is excellent in storage characteristics and cycle characteristics. The solution contains an electrolyte, a nonaqueous solvent, and one or more compounds represented by Formulae (2) and (3):
1. A nonaqueous electrolytic solution comprising:
an electrolyte,
a nonaqueous solvent, and
a compound represented by at least one formula selected from the group consisting of Formula (2) and Formula (3),
wherein for Formula (2), R 11 and R 12 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, and a group represented by R a —O— in which R a represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group, wherein each of R 11 and R 12 has at most 12 carbon atoms; and R 15 represents an alkyl group having 1 to 12 carbon atoms, optionally substituted by a halogen atom, an alkenyl group having 2 to 12 carbon atoms, optionally substituted by a halogen atom, an aryl group having 6 to 12 carbon atoms, optionally substituted by a halogen atom, or an aralkyl group having 7 to 12 carbon atoms, optionally substituted by a fluorine atom; and
wherein for Formula (3), R 21 to R 24 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, and a group represented by R b —O— in which R b represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group, wherein each of R 21 to R 24 has at most 12 carbon atoms; R 25 represents an alkyl group having 1 to 12 carbon atoms, optionally substituted by a halogen atom, an alkenyl group having 2 to 12 carbon atoms, optionally substituted by a halogen atom, an aryl group having 6 to 12 carbon atoms, optionally substituted by a halogen atom, or an aralkyl group having 7 to 12 carbon atoms, optionally substituted by a halogen atom; and r is an integer of 0 to 6, provided that when both R 21 and R 22 are alkoxy groups, r is an integer of 1 to 6, and at least one of R 23 and R 24 represent a group other than a hydrogen atom.
2. The nonaqueous electrolytic solution according to claim 1 , wherein R 15 is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, an allyl group, a phenyl group, a tolyl group, a xylyl group, a benzyl group, a phenethyl group, a trifluoromethyl group, a trifluoroethyl group, a pentafluoroethyl group, a 2-fluorovinyl group, a 3-fluoro-2-propenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2-fluorobenzyl group, a 3-fluorobenzyl group, a 4-fluorobenzyl group, a 2,4-difluorobenzyl group, and a 3,5-difluorobenzyl group.
3. The nonaqueous electrolytic solution according to claim 1 , wherein R 25 is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, an allyl group, a phenyl group, a tolyl group, a xylyl group, a benzyl group, a phenethyl group, a trifluoromethyl group, a trifluoroethyl group, a pentafluoroethyl group, a 2-fluorovinyl group, a 3-fluoro-2-propenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2-fluorobenzyl group, a 3-fluorobenzyl group, a 4-fluorobenzyl group, a 2,4-difluorobenzyl group, and a 3,5-difluorobenzyl group.
4. The nonaqueous electrolytic solution according to claim 1 , comprising 0.001 to 10 wt % of the compound.
5. The nonaqueous electrolytic solution according to claim 1 , further comprising at least one compound selected from the group consisting of a cyclic carbonate compound having a carbon-carbon unsaturated bond, a cyclic carbonate compound having a fluorine atom, a monofluorophosphate, and a difluorophosphate.
6. The nonaqueous electrolytic solution according to claim 5 , comprising at least one cyclic carbonate compound having a fluorine atom selected from the group consisting of fluoroethylene carbonate, 4,5-difluoro-1,3-dioxolan-2-one, and 4-fluoro-5-methyl-1,3-dioxolan-2-one.
7. The nonaqueous electrolytic solution according to claim 5 , comprising 0.01 to 20 wt % of the cyclic carbonate compound having a fluorine atom.
8. The nonaqueous electrolytic solution according to claim 1 , further comprising at least one cyclic carbonate compound having a carbon-carbon unsaturated bond selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, 4-methyl-4-vinyl ethylene carbonate, and 4,5-divinyl ethylene carbonate.
9. The nonaqueous electrolytic solution according to claim 8 , comprising 0.01 to 8 wt % of the cyclic carbonate compound having a carbon-carbon unsaturated bond.
10. The nonaqueous electrolytic solution according to claim 1 , comprising the compound represented by Formula (2).
11. The nonaqueous electrolytic solution according to claim 1 , comprising the compound represented by Formula (3) wherein r is 0 or 1.
12. The nonaqueous electrolytic solution according to claim 1 , comprising 0.01 to 4 wt % of the compound.
13. The nonaqueous electrolytic solution according to claim 1 , comprising 0.1 to 0.8 wt % of the compound.
14. The nonaqueous electrolytic solution according to claim 1 , further comprising an overcharge protection agent.
15. The nonaqueous electrolytic solution according to claim 14 , comprising 0.1 to 5 wt % of the overcharge protection agent.
16. The nonaqueous electrolytic solution according to claim 1 , wherein the compound is at least one selected from the group consisting of triethyl-2-phosphonopropionate, triethyl-2-phosphonobutyrate, triethyl phosphonofluoroacetate, ethyl(diethylphosphinyl)acetate, and diethyl acetylphosphonate.
17. The nonaqueous electrolytic solution according to claim 16 , comprising 0.001 to 10 wt % of the compound.
18. The nonaqueous electrolytic solution according to claim 16 , further comprising vinylene carbonate.
19. A nonaqueous electrolyte battery comprising the nonaqueous electrolyte solution of claim 1 .