Nonaqueous electrolytic solution and nonaqeuous-electrolyte secondary battery
View Patent ↗An object of the invention is to provide a nonaqueous electrolytic solution which is capable of bringing about a nonaqueous-electrolyte secondary battery improved in initial charge capacity, input/output characteristics, and impedance characteristics. The invention relates to a nonaqueous electrolytic solution which comprises: a nonaqueous solvent; LiPF 6 ; and a specific fluorosulfonic acid salt, and to a nonaqueous-electrolyte secondary battery containing the nonaqueous electrolytic solution.
1. A nonaqueous electrolytic solution which comprises: a nonaqueous solvent; LiPF 6 ; and a fluorosulfonic acid salt represented by formula (I):
M(FSO 3 ) x
wherein M is a metal atom, N(R) 4 , or P(R) 4 , wherein R is either an organic group having 1-12 carbon atoms or a hydrogen atom, not all of the four R's are hydrogen atoms, the R's may be the same or different, and a part or all of the four R's may form a ring in cooperation with the nitrogen atom or phosphorus atom to which the R's have been bonded;
when M is a metal atom, x indicates the valence of the metal atom M and is an integer of 1 or larger; and when M is N(R) 4 or P(R) 4 , x is 1,
wherein the ratio of the molar content of FSO 3 in the nonaqueous electrolytic solution to the molar content of PF 6 in the nonaqueous electrolytic solution is 0.001-1.2.
2. The nonaqueous electrolytic solution according to claim 1 , wherein the molar content of FSO 3 in the nonaqueous electrolytic solution is 0.0005-0.5 mol/L.
3. The nonaqueous electrolytic solution according to claim 1 , wherein the fluorosulfonic acid salt represented by formula (1) is lithium fluorosulfonate.
4. The nonaqueous electrolytic solution according to claim 1 , which comprises a cyclic carbonate having a fluorine atom.
5. The nonaqueous electrolytic solution according to claim 4 , which comprises the cyclic carbonate having a fluorine atom in the nonaqueous electrolytic solution in an amount of 0.001-85% by mass.
6. The nonaqueous electrolytic solution according to claim 1 , which comprises a cyclic carbonate having a carbon-carbon unsaturated bond.
7. The nonaqueous electrolytic solution according to claim 6 , which comprises the cyclic carbonate having a carbon-carbon unsaturated bond in the nonaqueous electrolytic solution in an amount of 0.001-10% by mass.
8. The nonaqueous electrolytic solution according to claim 1 , which comprises a cyclic sulfonic acid ester.
9. The nonaqueous electrolytic solution according to claim 8 , which comprises the cyclic sulfonic acid ester in the nonaqueous electrolytic solution in an amount of 0.001-10% by mass.
10. The nonaqueous electrolytic solution according to claim 1 , which comprises a compound having a cyano group.
11. The nonaqueous electrolytic solution according to claim 10 , which comprises the compound having a cyano group in the nonaqueous electrolytic solution in an amount of 0.001-10% by mass.
12. The nonaqueous electrolytic solution according to claim 1 , which comprises a diisocyanate compound.
13. The nonaqueous electrolytic solution according to claim 12 , which comprises the diisocyanate compound in the nonaqueous electrolytic solution in an amount of 0.001-5% by mass.
14. The nonaqueous electrolytic solution according to claim 1 , which comprises at least one fluorophosphoric acid lithium salt other than LiPF 6 and lithium imide salts.
15. The nonaqueous electrolytic solution according to claim 1 , which comprises a lithium salt having an oxalic acid group.
16. The nonaqueous electrolytic solution according to claim 14 , wherein the concentration of the at least one fluorophosphoric acid lithium salt other than LiPF 6 and lithium imide salts in the nonaqueous electrolytic solution is 0.0005-0.5 mol/L.
17. The nonaqueous electrolytic solution according to claim 15 , wherein the concentration of the lithium salt having an oxalic acid group in the nonaqueous electrolytic solution is 0.0005-0.5 mol/L.
18. The nonaqueous electrolytic solution according to claim 1 , wherein a ratio of a molar content of FSO 3 to a molar content of PF 6 ([FSO 3 ]/[PF 6 ]) in the nonaqueous electrolytic solution is 0.01-1.2.
19. The nonaqueous electrolytic solution according to claim 1 , which is obtained by adding the LiPF 6 and the fluorosulfonic acid salt represented by formula (1) to the nonaqueous solvent.
20. The nonaqueous electrolytic solution according to claim 1 , which is a nonaqueous electrolytic solution before housing in a case.
21. A nonaqueous-electrolyte secondary battery which comprises: a negative electrode and a positive electrode that are capable of occluding and releasing lithium ions; and the nonaqueous electrolytic solution according to claim 1 .
22. The nonaqueous-electrolyte secondary battery according to claim 21 , wherein the negative electrode comprises a current collector and a negative-electrode active-material layer disposed on the current collector, the negative-electrode active-material layer containing a negative-electrode active material which comprises at least one member selected from an elemental metal, alloys and compounds of silicon, and an elemental metal, alloys and compounds of tin.
23. The nonaqueous-electrolyte secondary battery according to claim 21 , wherein the negative electrode comprises a current collector and a negative-electrode active-material layer disposed on the current collector, the negative-electrode active-material layer containing a negative-electrode active material which comprises a carbonaceous material.
24. The nonaqueous-electrolyte secondary battery according to claim 21 , wherein the negative electrode comprises a current collector and a negative-electrode active-material layer disposed on the current collector, the negative-electrode active-material layer containing a negative-electrode active material which comprises a lithium-titanium composite oxide.
25. The nonaqueous-electrolyte secondary battery according to claim 21 , wherein the positive electrode comprises a current collector and a positive-electrode active-material layer disposed on the current collector, the positive-electrode active-material layer containing one member selected from the group consisting of lithium-cobalt composite oxides, lithium-manganese composite oxides, lithium-cobalt-manganese composite oxides, lithium-nickel composite oxides, lithium-cobalt-nickel composite oxides, lithium-nickel-manganese composite oxides, and lithium-nickel-cobalt-manganese composite oxides.
26. The nonaqueous-electrolyte secondary battery according to claim 21 , wherein the positive electrode comprises a current collector and a positive-electrode active-material layer disposed on the current collector, the positive-electrode active-material layer containing Li x MPO 4 (M is one element selected from the group consisting of the Group-4 to Group-11 transition metals belonging to the fourth period of the periodic table, and x satisfies 0<x<1.2).
27. The nonaqueous electrolytic solution according to claim 1 , wherein the LiPF 6 is present in a molar amount of from 0.5 M to 1.0 M and the fluorosulfonic acid salt is present in an amount of from 0.01 M to 0.5 M.
28. The nonaqueous electrolytic solution of claim 27 , wherein the nonaqueous solvent comprises at least one selected from the group consisting of ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and vinyl carbonate.
29. The nonaqueous-electrolyte secondary battery of claim 21 , having an initial discharge of 139.0-141.8 mAh/g.
30. The nonaqueous-electrolyte secondary battery of claim 21 , having an initial impedance of 0.67 to 0.77 in comparison to a nonaqueous-electrolyte secondary battery that contains an electrolyte containing only LiPF 6 .