NON-AQUEOUS ELECTROLYTIC SOLUTION AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY USING THE SAME
A task of the present invention is to provide a non-aqueous electrolyte secondary battery which exhibits small initial irreversible capacity and high initial efficiency as well as excellent high-temperature cycle characteristics without sacrificing the yield of the battery. The non-aqueous electrolytic solution of the present invention is a non-aqueous electrolytic solution for use in a non-aqueous electrolyte secondary battery which comprises a positive electrode capable of having occluded therein and releasing metal ions, a negative electrode capable of having occluded therein and releasing metal ions, and a non-aqueous electrolytic solution comprising a non-aqueous solvent and an electrolyte dissolved in the non-aqueous solvent, wherein the non-aqueous electrolytic solution contains a compound represented by the general formula (1) in an amount of 0.01 to 4.5% by mass, based on the mass of the non-aqueous electrolytic solution: wherein, in the general formula (1), n represents an integer of 1 to 4, and R 1 to R 3 represent predetermined groups.
1 . A non-aqueous electrolytic solution, comprising:
a non-aqueous solvent,
an electrolyte dissolved in the non-aqueous solvent, and
a compound represented by formula (1) below in an amount of 0.01 to 4.5% by mass, based on a mass of the non-aqueous electrolytic solution,
wherein, when the non-aqueous electrolytic solution comprises propylene carbonate, the non-aqueous electrolytic solution comprises ethylene carbonate and propylene carbonate, and satisfies at least one of the requirements that (A) a volume ratio of the ethylene carbonate and the propylene carbonate be in a range of 99:1 to 40:60, or that (B) a content of the propylene carbonate in the non-aqueous solvent be 10% by volume or less:
wherein, in the formula (1), n represents an integer of 1 to 4; each of R 1 and R 2 independently represents hydrogen, fluorine, or a hydrocarbon group having 1 to 5 carbon atoms and optionally being substituted with fluorine, wherein when n is 2 or more, a plurality of R 1 's are the same or different and a plurality of R 2 's are the same or different, and wherein R 1 and R 2 are optionally bonded together to form a ring; and R 3 represents a carbonyl group, a sulfinyl group, a sulfonyl group, or a group represented by formula (2):
wherein, in the formula (2), R 4 represents fluorine or a hydrocarbon group having 1 to 10 carbon atoms and optionally being substituted with fluorine.
2 . The non-aqueous electrolytic solution according to claim 1 , wherein the compound represented by formula (1) is a compound represented by formula (3):
wherein, in the formula (3), each of R 5 and R 6 independently represents hydrogen, fluorine, or a hydrocarbon group having 1 to 5 carbon atoms and optionally being substituted with fluorine, and R 5 and R 6 are optionally bonded together to form a ring.
3 . The non-aqueous electrolytic solution according to claim 1 , wherein the electrolyte comprises a hexafluorophosphate.
4 . The non-aqueous electrolytic solution according to claim 1 , wherein the solution is suitable for use in a non-aqueous electrolytic secondary battery comprising a negative electrode capable of having occluded therein and releasing metal ions, wherein the negative electrode comprises a carbonaceous material or a material comprising silicon.
5 . The non-aqueous electrolytic solution according to claim 2 , wherein, in the formula (3), R 5 is hydrogen, and R 6 is hydrogen or a methyl group.
6 . The non-aqueous electrolytic solution according to claim 1 , comprising a cyclic carbonate and a linear carbonate as the non-aqueous solvent, wherein a volume ratio of the cyclic carbonate to the linear carbonate) is in a range of 1.5:8.5 to 4:6.
7 . The non-aqueous electrolytic solution according to claim 6 , comprising ethylene carbonate as the cyclic carbonate in the non-aqueous solvent.
8 . The non-aqueous electrolytic solution according to claim 1 , further comprising at least one compound selected from the group consisting of a cyclic carbonate having a fluorine atom, a cyclic carbonate having a carbon-carbon unsaturated bond, a difluorophosphate, a fluorosulfate, a compound having an isocyanate group, a compound having a cyano group, a cyclic sulfonic ester, and a dicarboxylic acid complex salt.
9 . A non-aqueous electrolyte secondary battery comprising a positive electrode capable of having occluded therein and releasing metal ions, a negative electrode capable of having occluded therein and releasing metal ions, and a non-aqueous electrolytic solution,
wherein the non-aqueous electrolytic solution is the non-aqueous electrolytic solution according to claim 1 .
10 . The non-aqueous electrolyte secondary battery according to claim 9 , wherein the negative electrode comprises a carbonaceous material or a material comprising silicon.
11 . The non-aqueous electrolyte secondary battery according to claim 9 , wherein the positive electrode comprises an active material comprising a lithium-manganese composite oxide having a spinel structure.
12 . The non-aqueous electrolytic solution according to claim 1 , comprising propylene carbonate and ethylene carbonate, wherein the volume ratio of the ethylene carbonate and the propylene carbonate is in a range of 99:1 to 40:60.
13 . The non-aqueous electrolytic solution according to claim 1 , comprising propylene carbonate and ethylene carbonate, wherein the content of the propylene carbonate in the non-aqueous solvent is 10% by volume or less.