Lithium salt compound, nonaqueous electrolyte solution using same, lithium ion secondary battery and lithium ion capacitor
The present invention is concerned with (1) a lithium salt compound including a lithium cation including, as a ligand, at least one ether compound selected from 2,5,8,11-tetraoxadodecane and 2,5,8,11,14-pentaoxapentadecane and a difluorophosphate anion; (2) a nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution containing the aforementioned lithium salt compound; (3) a lithium ion secondary battery including a positive electrode, a negative electrode, and the aforementioned nonaqueous electrolytic solution; (4) a lithium ion capacitor using the aforementioned nonaqueous electrolytic solution; and (5) a production method of the aforementioned lithium salt compound, including bringing the aforementioned ether compound and lithium difluorophosphate into contact with each other. The nonaqueous electrolytic solution of the present invention is excellent in high-temperature cyclic property and output characteristics after high-temperature cycles and is capable of suppressing metal elution from a positive electrode or the like.
1. A nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution comprising a lithium salt compound comprising a lithium cation including, as a ligand, at least one ether compound selected from 2,5,8,11-tetraoxadodecane and 2,5,8,11,14-pentaoxapentadecane and a difluorophosphate anion,
wherein, in the lithium cation, a molar ratio of the ether compound to a lithium ion (Li + ) is from 0.25-0.55;
wherein the lithium salt compound is bis(difluorophosphoryl)(2,5,8,11-tetraoxadodecane) dilithium or bis(difluorophosphoryl)(2,5,8,11,14-pentaoxapentadecane) dilithium: and
wherein a content of the lithium salt compound in the nonaqueous electrolytic solution is from 0.1 to 10% by mass.
2. The nonaqueous electrolytic solution according to claim 1 , wherein a content of the lithium salt compound in the nonaqueous electrolytic solution is from 0.2 to 8% by mass.
3. The nonaqueous electrolytic solution according to claim 1 , further comprising, as an additive, at least one selected from the group consisting an SO 2 group-containing compound, an aromatic compound, a carbon-carbon triple bond-containing compound, a lithium-containing ionic compound, a cyclic acetal compound, and a phosphazene compound.
4. The nonaqueous electrolytic solution according to claim 3 , wherein the additive is at least one selected from ala SO 2 group-containing compound, a carbon-carbon triple bond-containing compound, a lithium-containing ionic compound, and a cyclic acetal compound.
5. The nonaqueous electrolytic solution according to claim 3 , wherein the content of the additive in the nonaqueous electrolytic solution is from 0.001 to 5% by mass.
6. The nonaqueous electrolytic solution according to claim 1 , comprising a nonaqueous solvent comprising at least one selected from a cyclic carbonate and a linear carbonate.
7. The nonaqueous electrolytic solution according to claim 4 , wherein the additive is at least one SO 2 group-containing compound selected from the group consisting of 1,3-propanesultone, 1,3-butanesultone, 2,4-butanesultone, 1,4-butanesultone, 1,3-propenesultone, 2,2-dioxide-1,2-oxathiolane-4-yl acetate, ethylene sulfate, propylene sulfate, butane-1,4-diyl dimethanesulfonate, and methylene methanesulfonate.
8. The nonaqueous electrolytic solution according to claim 4 , wherein the additive is at least one carbon-carbon triple bond-containing compound selected from the group consisting of methyl 2-propynyl carbonate, 2-propynyl methanesulfonate, 2-propynyl vinylsulfonate, di(2-propynyl) oxalate, ethynyl ethylene carbonate, 2-propynyl 2-oxo-1,3-dioxolane-4-carboxylate, and 2-butyne-1,4-diyl dimethanesulfonate.
9. The nonaqueous electrolytic solution according to claim 4 , wherein the additive is at least one lithium-containing ionic compound selected from the group consisting of lithium difluorophosphate, lithium fluorosulfonate, lithium difluorobis[oxalate-O,O′]phosphate, lithium tetrafluoro[oxalate-O,O′]phosphate, lithium bis[oxalate-O,O′]borate, lithium difluoro[oxalate-O,O′]borate, lithium methyl sulfate, lithium ethyl sulfate, and lithium 2,2,2-trifluoroethyl sulfate.
10. The nonaqueous electrolytic solution according to claim 4 , wherein the additive is at least one cyclic acetal compound selected from the group consisting of 1.3-dioxolane, 1,3-dioxane, and 1,3,5-trioxane.
11. A lithium ion secondary battery, comprising:
a positive electrode;
a negative electrode; and
a nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution being the nonaqueous electrolytic solution according to claim 1 .
12. The lithium ion secondary battery according to claim 11 , wherein the negative electrode comprises, as a negative electrode active material, one or more selected from the group consisting of a lithium metal, a lithium alloy, a carbon material capable of absorbing and releasing lithium, tin, a tin compound, silicon, a silicon compound, and a lithium titanate compound.
13. A lithium ion capacitor comprising the nonaqueous electrolytic solution according to claim 1 .