Nonaqueous electrolyte solution, electricity storage device using same, and phosphonoformic acid compound used in same
The present invention provides a nonaqueous electrolytic solution capable of suppressing worsening of heat stability of a negative electrode and improving safety of an energy storage device while maintaining high-load charging and discharging cycle properties at a high temperature, an energy storage device using the same, and a phosphonoformic acid compound to be used for the same. The nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent contains 0.001 to 5% by mass of at least one selected from a phosphonoformic acid compound having at least one carbon-carbon unsaturated bond, which is represented by the following general formula (I), and a phosphonoformic acid compound having a carbon-carbon unsaturated bond or two phosphonocarbonyl groups, which is represented by the following general formula (II). In the formula (I), each of R 1 to R 3 is an aliphatic organic group, provided that at least one of R 1 to R 3 represents a carbon-carbon unsaturated bond-containing aliphatic organic group. In the formula (II), each of R 4 and R 5 represents an alkyl group, a cycloalkyl group, or an aryl group, and R 4 and R 5 may be bonded to each other to form a ring structure. m represents 1 or 2; when m is 1, then R 6 represents an aryl group; when m is 2, then R 6 represents an alkylene group, an alkenylene group, or an alkynylene group; and a part of hydrogen atoms of R 4 to R 6 may be substituted with a halogen atom.
1. A nonaqueous electrolytic solution comprising:
an electrolyte salt dissolved in a nonaqueous solvent, and
0.001 to 5% by mass of at least one phosphonoformic acid compound having at least one carbon-carbon unsaturated bond, which is represented by a formula (I):
wherein each of R 1 to R 3 independently represents an aliphatic organic group having 1 to 5 carbon atoms, provided that at least one of R 1 to R 3 represents a 2-propenyl group or a 2-propynyl group.
2. The nonaqueous electrolytic solution according to claim 1 , comprising the phosphonoformic acid compound represented by formula (I), wherein in the formula (I), R 3 is a 2-propenyl group or a 2-propynyl group and each of R 1 and R 2 is independently an alkyl group having 1 to 4 carbon atoms or an alkynyl group having 3 to 5 carbon atoms.
3. The nonaqueous electrolytic solution according to claim 1 , comprising at least one phosphonoformic acid compound represented by the formula (I) selected from the group consisting of 2-propynyl (dimethoxyphosphoryl)formate, 2-propynyl (diethoxyphosphoryl)formate, 2-propynyl (bis(2-propynyloxy)phosphoryl)formate, and 2-propenyl (diethoxyphosphoryl)formate.
4. The nonaqueous electrolytic solution according to claim 1 , wherein the nonaqueous solvent comprises a cyclic carbonate and a linear ester.
5. The nonaqueous electrolytic solution according to claim 4 , wherein the cyclic carbonate comprises one or more carbonates selected from the group consisting of ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, and 2,3-butylene carbonate.
6. The nonaqueous electrolytic solution according to claim 4 , wherein the cyclic carbonate comprises a cyclic carbonate having a fluorine atom or an unsaturated bond.
7. The nonaqueous electrolytic solution according to claim 4 , wherein the linear ester comprises both a symmetric linear carbonate and an asymmetric linear carbonate, and a content of the symmetric linear carbonate is more than a content of the asymmetric linear carbonate.
8. The nonaqueous electrolytic solution according to claim 7 , wherein the asymmetric linear carbonate is one or more carbonates selected from the group consisting of methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, and ethyl propyl carbonate.
9. The nonaqueous electrolytic solution according to claim 1 , further comprising one or more compounds selected from the group consisting of an S(═O) group-containing compound, a fluorinated benzene compound, a carbon-carbon triple bond-containing compound, a carboxylic acid anhydride, a cyclic acetal compound, an isocyanate compound, a nitrile compound, a benzene compound, and a phosphazene compound.
10. The nonaqueous electrolytic solution according to claim 1 , wherein the electrolyte salt comprises one or more lithium salts selected from the group consisting of LiPF 6 , LiBF 4 , LiN(SO 2 CF 3 ) 2 , and LiN(SO 2 F) 2 .
11. The nonaqueous electrolytic solution according to claim 10 , wherein the electrolyte salt further comprises one or more lithium salts selected from the group consisting of an S(═O) 2 O structure-containing lithium salt, a P═O structure-containing lithium salt, and a lithium salt having a boron-containing oxalate complex as an anion.
12. The nonaqueous electrolytic solution according to claim 1 , which is suitable for use in an energy storage device.
13. An energy storage device comprising:
a positive electrode,
a negative electrode, and
a nonaqueous electrolytic solution,
wherein the nonaqueous electrolytic solution comprises an electrolyte salt dissolved in a nonaqueous solvent, and 0.001 to 5% by mass of at least one phosphonoformic acid compound having at least one carbon-carbon unsaturated bond, which is represented by a formula (I):
wherein each of R 1 to R 3 independently represents an aliphatic organic group having 1 to 5 carbon atoms, provided that at least one of R 1 to R 3 represents a 2-propenyl group or a 2-propynyl group.
14. The energy storage device according to claim 13 , wherein an active material of the positive electrode is:
a complex metal oxide comprising lithium and one or more elements selected from the group consisting of cobalt, manganese, and nickel, or
a lithium-containing olivine-type phosphate comprising one or more elements selected from the group consisting of iron, cobalt, nickel, and manganese.
15. The energy storage device according to claim 13 , wherein an active material of the negative electrode comprises one or more members selected from the group consisting of 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.