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 dissolving the electrolyte, 0.001 vol % to 5 vol % of a compound represented by Formula (1), and further contains at least one compound selected from the group consisting of cyclic carbonate compounds having carbon-carbon unsaturated bonds, cyclic carbonate compounds having fluorine atoms, monofluorophosphates, and difluorophosphates. In Formula (1), R 1 to R 3 each independently represent an alkyl group having 1 to 12 carbon atoms, optionally substituted by a halogen atom; and n is an integer of 0 to 6.
1. A nonaqueous electrolytic solution comprising:
an electrolyte;
a nonaqueous solvent;
at least one compound selected from the group consisting of (a), (b), (c) and (d):
(a) 0.01 wt % to 8 wt % of a cyclic carbonate compound having a carbon-carbon unsaturated bond,
(b) 0.01 wt % to 20 wt % of a cyclic carbonate compound having a fluorine atom,
(c) a monofluorophosphate, and
(d) a difluorophosphate,
wherein, if both the cyclic carbonate compound having a carbon-carbon unsaturated bond and the cyclic carbonate compound having a fluorine atom are present, then a total amount of the cyclic carbonate compound having a carbon-carbon unsaturated bond and the cyclic carbonate compound having a fluorine atom is at most 20 wt %, and
wherein, if the monofluorophosphate, the difluorophosphate, or both, are present, then a total amount of the monofluorophosphate and the difluorophosphate is 0.001 wt % to 5 wt %; and
the nonaqueous electrolytic solution further comprises 0.001 vol % to 5 vol % of a compound of Formula (1),
wherein R 1 to R 3 each independently represent an alkyl group having 1 to 12 carbon atoms, the alkyl group optionally substituted by a halogen atom; and n is an integer of 0 to 6.
2. The nonaqueous electrolytic solution according to claim 1 , wherein the alkyl group of Formula (1) has 1 to 8 carbon atoms.
3. A nonaqueous electrolyte battery comprising (i) the nonaqueous electrolytic solution according to claim 2 , and (ii) negative and positive electrodes that can absorb and desorb lithium ions.
4. The nonaqueous electrolytic solution according to claim 2 , wherein R 1 to R 3 are each independently selected from the group consisting of a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, and a cyclohexyl group.
5. A nonaqueous electrolyte battery comprising (i) the nonaqueous electrolytic solution according to claim 4 , and (ii) negative and positive electrodes that can absorb and desorb lithium ions.
6. The nonaqueous electrolytic solution according to claim 1 , comprising at least one cyclic carbonate compound (a) 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.
7. A nonaqueous electrolyte battery comprising (i) the nonaqueous electrolytic solution according to claim 6 , and (ii) negative and positive electrodes that can absorb and desorb lithium ions.
8. The nonaqueous electrolytic solution according to claim 6 , wherein the cyclic carbonate compound (a) having a carbon-carbon unsaturated bond is vinylene carbonate.
9. A nonaqueous electrolyte battery comprising (i) the nonaqueous electrolytic solution according to claim 8 , and (ii) negative and positive electrodes that can absorb and desorb lithium ions.
10. The nonaqueous electrolytic solution according to claim 1 , comprising at least one cyclic carbonate compound (b) 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.
11. The nonaqueous electrolytic solution according to claim 1 , comprising 0.01 to 20 wt % of the cyclic carbonate compound (b) having a fluorine atom.
12. The nonaqueous electrolytic solution according to claim 1 , wherein the compound of Formula (1) is selected from the group consisting of triethyl phosphonoformate, triethyl phosphonoacetate, and triethyl-3-phosphonopropionate.
13. A nonaqueous electrolyte battery comprising (i) the nonaqueous electrolytic solution according to claim 12 , and (ii) negative and positive electrodes that can absorb and desorb lithium ions.
14. A nonaqueous electrolyte battery comprising (i) the nonaqueous electrolytic solution according to claim 1 , and (ii) negative and positive electrodes that can absorb and desorb lithium ions.
15. The nonaqueous electrolytic solution according to claim 1 , comprising 0.001 vol % to 3 vol % of the compound of Formula (1).
16. The nonaqueous electrolytic solution according to claim 1 , comprising 0.001 vol % to 2 vol % of the compound of Formula (1).
17. The nonaqueous electrolytic solution according to claim 1 , comprising 0.001 vol % to 1 vol % of the compound of Formula (1).
18. The nonaqueous electrolytic solution according to claim 1 , comprising 0.001 vol % to 0.8 vol % of the compound of Formula (1).
19. The nonaqueous electrolytic solution according to claim 1 , comprising 0.01 wt % to 4 wt % of the cyclic carbonate compound (a) having a carbon-carbon unsaturated bond.
20. The nonaqueous electrolytic solution according to claim 1 , comprising 0.01 wt % to 3 wt % of the cyclic carbonate compound (a) having a carbon-carbon unsaturated bond.