Nonaqueous electrolyte solution and lithium secondary battery using same
View Patent ↗A non-aqueous electrolyte solution including a lithium salt, a non-aqueous solvent, a cyclic carbonate compound having an unsaturated bond and a compound of formula R 21 —S(O) 2 —F in which R 2 is an alkyl group having from 1 to 12 carbon atoms that may be substituted by a fluorine atom or an alkenyl group having from 2 to 12 carbon atoms that may be substituted by a fluorine atom, and the alkyl group or alkenyl group may have an ether linkage within its chain.
1. A non-aqueous electrolyte solution comprising:
a lithium salt;
a non-aqueous solvent;
a cyclic carbonate compound having a carbon-carbon unsaturated bond wherein the concentration of the cyclic carbonate compound with respect to the non-aqueous electrolyte solution is 0.01 weight % to 8 weight %; and
a compound expressed by the following formula (Ib);
wherein R 21 represents an alkyl group having 1-12 carbon atoms or an alkenyl group having 2-12 carbon atoms, wherein the alkyl group or alkenyl group may have an ether linkage within its chain.
2. The non-aqueous electrolyte solution of claim 1 , wherein in the formula (Ib) R 21 is an alkyl group having 1-3 carbon atoms.
3. The non-aqueous electrolyte solution of claim 1 , wherein the cyclic carbonate compound having an unsaturated bond is a compound or a plurality of compounds selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, divinyl ethylene carbonate, vinyl vinylene carbonate and methylene ethylene carbonate.
4. The non-aqueous electrolyte solution of claim 1 , wherein the compound of formula (Ib) is methane sulfonyl fluoride, ethane sulfonyl fluoride, propane sulfonyl fluoride, 2-propane sulfonyl fluoride, butane sulfonyl fluoride, 2-butane sulfonyl fluoride, or any mixture thereof.
5. The non-aqueous electrolyte solution of claim 4 , wherein the compound of formula (Ib) is methane sulfonyl fluoride.
6. The non-aqueous electrolyte solution of claim 4 , wherein the compound of formula (Ib) is ethane sulfonyl fluoride.
7. The non-aqueous electrolyte solution of claim 4 , wherein the compound of formula (Ib) is propane sulfonyl fluoride.
8. The non-aqueous electrolyte solution of claim 4 , wherein the concentration of the compound expressed by the formula (Ib) with respect to the non-aqueous electrolyte solution is 0.1 weight % to 1 weight %.
9. The non-aqueous electrolyte solution of claim 4 , wherein the concentration of the compound expressed by the formula (Ib) with respect to the non-aqueous electrolyte solution is 0.1 weight % to 3 weight %.
10. The non-aqueous electrolyte solution of claim 1 , wherein the concentration of the compound expressed by the formula (Ib) with respect to the non-aqueous electrolyte solution is 0.05 weight % to 3 weight %.
11. The non-aqueous electrolyte solution of claim 1 , wherein the concentration of the compound expressed by the formula (Ib) with respect to the non-aqueous electrolyte solution is 0.05 weight % to 5 weight %.
12. The non-aqueous electrolyte solution of claim 1 , wherein the concentration of the cyclic carbonate compound having an unsaturated bond with respect to the non-aqueous electrolyte solution is 0.1 weight % to 6 weight %.
13. The non-aqueous electrolyte solution of claim 1 , wherein the concentration of the cyclic carbonate compound having an unsaturated bond with respect to the non-aqueous electrolyte solution is 0.5 weight % to 4 weight %.
14. The non-aqueous electrolyte solution of claim 1 , wherein the compound of formula (Ib) is at least one selected from the group consisting of ethene sulfonyl fluoride, 1-propene-1-sulfonyl fluoride, 2-propene-1-sulfonyl fluoride, 2-methoxy-ethane sulfonyl fluoride and 2-ethoxy-ethane sulfonyl fluoride.
15. The non-aqueous electrolyte solution of claim 1 , wherein the cyclic carbonate compound having an unsaturated bond is at least one selected from the group consisting of ethyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4,5-diethyl vinylene carbonate, fluoro vinylene carbonate, trifluoromethyl vinylene carbonate and 4-vinyl vinylene carbonate.
16. The non-aqueous electrolyte solution of claim 1 , wherein R 21 in formula (Ib) is an alkyl group or alkenyl group having an ether linkage in a chain.
17. The non-aqueous electrolyte solution of claim 1 , wherein the cyclic carbonate compound is present in a concentration of from greater than 1 wt % to 4 wt % with respect to the non-aqueous electrolyte solution.
18. The non-aqueous electrolyte solution of claim 1 , wherein the cyclic carbonate compound is present in a concentration of from 2 to 4 wt % with respect to the non-aqueous electrolyte solution.
19. The non-aqueous electrolyte solution of claim 1 , wherein the compound of formula (Ib) is present in an amount of 0.5-2 wt % and the cyclic carbonate compound is present in an amount of greater than 1% to 4 wt % with respect to the non-aqueous electrolyte solution.
20. The non-aqueous electrolyte solution of claim 1 , wherein R 21 contains 1-3 carbon atoms.
21. The non-aqueous electrolyte solution of claim 1 , wherein R 21 contains 1-2 carbon atoms.
22. The non-aqueous electrolyte solution of claim 1 , providing a residual capacity after charging of 95-96%, a residual capacity of 79-82% after high temperature storage, and a gas generation of from 0.60 ml or less when used as an electrolyte in a lithium secondary battery.
23. A lithium secondary battery comprising:
a non-aqueous electrolyte solution; and a positive electrode and a negative electrode capable of absorbing and desorbing lithium ions; wherein the non-aqueous electrolyte solution is the non-aqueous electrolyte solution of claim 1 .