Non-aqueous liquid electrolyte, electricity storage device using same, and phosphorus compound used therein

1. A nonaqueous electrolytic solution, comprising an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution comprising a lithium phosphate of formula (I), in which a polar group (X 1 ) is bound directly to a phosphorus atom (P):

wherein, R 20 is an organic group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, in each of which a part of hydrogen atoms may be substituted with a halogen atom, or a lithium atom; and X 1 is a polar group (i) containing a —C(═O) group, a —P(═O) group, or an —S(═O) 2 group.

2. The nonaqueous electrolytic solution according to claim 1 , wherein the lithium phosphate is at least one lithium phosphate of any of formulae (I-II) to (I-IV):

wherein, R 1 and R 2 are each independently synonymous with R 20 ,

wherein, R 1 , R 3 , and R 4 are each independently synonymous with R 20 , and

wherein, R 1 and R 5 are each independently synonymous with R 20 .

3. An energy storage device comprising a positive electrode, a negative electrode, and the nonaqueous electrolytic solution according to claim 1 .

4. The energy storage device according to claim 3 , wherein the electrolyte salt comprises at least one selected from the group consisting of LiPF 6 , LiBF 4 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , and LiN(SO 2 F) 2 in a concentration of 0.3 M or more and 2.5 M or less.

5. The energy storage device according to claim 3 , which comprises a complex metal oxide comprising lithium and at least one selected from the group consisting of cobalt, manganese, and nickel and/or a lithium-containing olivine-type phosphate comprising at least one selected from the group consisting of iron, cobalt, nickel, and manganese, as a positive electrode active material.

6. The energy storage device according to claim 3 , which comprises at least one selected from the group consisting of metal lithium, 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, as a negative electrode active material.

7. The nonaqueous electrolyte solution according to claim 1 , wherein the lithium phosphate is any one of formulae (I-V) to (I-VII), in which a polar group is bound directly to a phosphorus atom (P):

wherein, R 11 and R 12 are each independently synonymous with R 20 , provided that at least one of R 11 and R 12 is an alkynyl group having 3 to 6 carbon atoms,

wherein, R 11 , R 13 , and R 14 are each independently synonymous with R 20 , provided that the case where all of R 11 , R 13 , and R 14 are a lithium atom is excluded, and

wherein, R 11 and R 15 are each independently synonymous with R 20 .

8. A nonaqueous electrolytic solution, comprising an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution comprising a compound of formula (II), in which a cyclic polar group (X 2 ) is bound directly to a phosphorus atom (P):

wherein, R 10 and R 20 are each independently an organic group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, in each of which a part of hydrogen atoms may be substituted with a halogen atom, or a lithium atom; and X 2 is a 4- to 7-membered ring polar group (iii) containing a —C(═O)—O— group or a —C(═O)—N— group, provided that when X 2 is a 4- to 7-membered ring polar group containing a —C(═O)—N— group, at least one of R 10 and R 20 is a lithium atom.

9. The nonaqueous electrolytic solution according to claim 8 , wherein in formula (II), at least of R 10 and R 20 is a lithium atom.

10. The nonaqueous electrolytic solution according to claim 8 , wherein the compound of formula (II) is at least one compound of any of formulae (II-I) to (II-VI), in which a cyclic polar group is bound directly to a phosphorus atom (P):

wherein, R 21 is synonymous with R 20 ; and p 21 and q 21 each independently represent an integer of 0 to 2 and satisfy a relation: 1≤(p 21 +q 21 )≤3, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent represented by the following general formula (I-VII),

wherein, R 22 is synonymous with R 20 ; and p 22 and q 22 each independently represent an integer of 0 to 3 and satisfy a relation: 1≤(p 22 +q 22 )≤4, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (II-VII),

wherein, R 23 is synonymous with R 20 ; and p 23 and q 23 each independently represent an integer of 0 to 2 and satisfy a relation: 1≤(p 23 +q 23 )≤3, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (II-VII),

wherein, R 24 is synonymous with R 20 ; Y 24 represents an —NH— group or an —O— group; p 24 represents an integer of 0 to 1; q 24 represents an integer of 1 to 4; and p 24 and q 24 satisfy a relation: 2≤(p 24 +q 24 )≤4, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (II-VII),

wherein, R 25 is synonymous with R 20 , provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (II-VII),

wherein, R 26 is synonymous with R 20 ; Y 26 represents an —NH— group or an —O— group; p 26 represents an integer of 0 to 1; q 26 represents an integer of 1 to 4; and p 26 and q 26 satisfy a relation 2≤(p 26 +q 26 )≤4, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent represented of formula (II-VII), and

wherein, R 27 and R 28 are each independently synonymous with R 20 ; and * represents a site binding to the cyclic polar group.

11. The nonaqueous electrolytic solution according to claim 8 , wherein the compound of formula (II) is at least one selected from the group consisting of compounds of any of formulae (V-I) to (V-III), in which a cyclic polar group is bound directly to a phosphorus atom (P):

wherein, R 61 and R 62 are each independently an organic group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, in each of which a part of hydrogen atoms may be substituted with a halogen atom; and p 61 and q 61 each independently represent an integer of 0 to 2 and satisfy a relation: 1≤(p 61 +q 61 )≤3, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (V-IV),

wherein, R 63 and R 64 are each independently synonymous with R 61 and R 62 , respectively; and p 62 and q 62 each independently represent an integer of 0 to 3 and satisfy a relation: 1≤(p 62 +q 62 )≤4, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (V-IV),

wherein, R 65 and R 66 are each independently synonymous with R 61 and R 62 , respectively; and p 63 and q 63 each independently represent an integer of 0 to 2 and satisfy a relation: 1≤(p 63 +q 63 )≤3, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (V-IV), and

wherein, R 71 and R 72 are each independently synonymous with R 61 and R 62 , respectively.

12. An energy storage device comprising a positive electrode, a negative electrode, and the nonaqueous electrolytic solution according to claim 8 .

13. The energy storage device according to claim 12 , wherein the electrolyte salt comprises at least one selected from the group consisting of LiPF 6 , LiBF 4 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , and LiN(SO 2 F) 2 in a concentration of 0.3 M or more and 2.5 M or less.

14. The energy storage device according to claim 12 , which comprises a complex metal oxide comprising lithium and at least one selected from the group consisting of cobalt, manganese, and nickel and/or a lithium-containing olivine-type phosphate comprising at least one selected from the group consisting of iron, cobalt, nickel, and manganese, as a positive electrode active material.

15. The energy storage device according to claim 12 , which comprises at least one selected from the group consisting of metal lithium, 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, as a negative electrode active material.

16. A nonaqueous electrolytic solution, comprising an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution comprising a compound of formula (III), in which a polar group (X 3 ) is bound to a phosphorus atom (P):

wherein, R 20 is an organic group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, in each of which a part of hydrogen atoms may be substituted with a halogen atom, or a lithium atom; and X 3 is a polar group containing a —C(═O) group, a —P(═O) group, an —S(═O) 2 group, a —CN group, or an alkyl group having 1 to 6 carbon atoms, in which a part of hydrogen atoms is substituted with a fluorine atom.

17. The nonaqueous electrolytic solution according to claim 16 , wherein the compound of formula (III) is at least one compound of any of formulae (III-1) to (III-7):

wherein, A 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an alkoxy group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an —OC(═O)R 113 group, an —OC(═O)—OR 114 group, an —S(═O) 2 R 115 group, or an —S(═O) 2 OR 116 group; R 111 , R 114 , and R 116 each independently represent an organic group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, in each of which a part of hydrogen atoms may be substituted with a halogen atom, or a lithium atom; R 112 , R 113 , and R 115 each represent an organic group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, in each of which a part of hydrogen atoms may be substituted with a halogen atoms; and n 1 represents an integer of 0 to 2,

wherein, A 2 represents an alkoxy group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an —OC(═O)R 123 group, an —OC(═O)—OR 124 group, an —S(═O) 2 R 125 group, or an —S(═O) 2 OR 126 group; R 121 , R 122 , R 124 , and R 126 are each independently synonymous with R 20 ; R 123 and R 125 are each independently synonymous with R 113 and R 115 , respectively; and n 2 represents an integer of 0 to 2,

wherein, A 3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an alkoxy group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an —OC(═O)R 134 group, an —OC(═O)—OR 135 group, an —S(═O) 2 R 136 group, or an —S(═O) 2 OR 137 group; R 131 , R 132 , R 133 , R 135 , and R 137 are each independently synonymous with R 20 ; R 134 and R 136 are each independently synonymous with R 113 and R 115 , respectively; and n 3 represents an integer of 0 to 2,

wherein, A 4 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an alkoxy group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an —OC(═O)R 143 group, an —OC(═O)—OR 144 group, an —S(═O) 2 R 145 group, or an —S(═O) 2 OR 146 group; R 141 , R 144 , and R 146 are each independently synonymous with R 20 ; R 142 , R 143 , and R 145 are each independently synonymous with R 113 and R 115 , respectively; and n 4 represents an integer of 0 to 2,

wherein, A 5 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an alkoxy group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an —OC(═O)R 153 group, an —OC(═O)—OR 154 group, an —S(═O) 2 R 155 group, or an —S(═O) 2 OR 156 group; R 151 , R 152 , R 154 , and R 156 are each independently synonymous with R 20 ; R 153 and R 155 are each independently synonymous with R 113 and R 115 , respectively; and n 5 represents an integer of 0 to 2,

wherein, A 6 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an alkoxy group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an —OC(═O)R 162 group, an —OC(═O)—OR 163 group, an —S(═O) 2 R 164 group, or an —S(═O) 2 OR 165 group; R 161 , R 163 , and R 165 are each independently synonymous with R 20 ; R 162 and R 164 are each independently synonymous with R 113 and R 115 , respectively; and n 6 represents an integer of 0 to 2, and

wherein, R 172 represents an alkyl group having 1 to 6 carbon atoms, in which a part of hydrogen atoms are substituted with a fluorine atom; A 7 represents an alkoxy group having 1 to 8 carbon atoms, in which a part of hydrogen atoms may be substituted with a halogen atom, an —OC(═O)R 173 group, an —OC(═O)—OR 174 group, an —S(═O) 2 R 175 group, or an —S(═O) 2 OR 176 group; R 171 , R 174 , and R 176 are each independently synonymous with R 20 ; R 173 and R 175 are each independently synonymous with R 113 and R 115 , respectively; and n 7 represents an integer of 0 to 2.

18. An energy storage device comprising a positive electrode, a negative electrode, and the nonaqueous electrolytic solution being the nonaqueous electrolytic solution according to claim 16 .

19. The energy storage device according to claim 18 , wherein the electrolyte salt comprises at least one selected from the group consisting of LiPF 6 , LiBF 4 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , and LiN(SO 2 F) 2 in a concentration of 0.3 M or more and 2.5 M or less.

20. The energy storage device according to claim 18 , which comprises a complex metal oxide comprising lithium and at least one selected from the group consisting of cobalt, manganese, and nickel and/or a lithium-containing olivine-type phosphate comprising at least one selected from the group consisting of iron, cobalt, nickel, and manganese, as a positive electrode active material.

21. The energy storage device according to claim 18 , which comprises at least one selected from the group consisting of metal lithium, 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, as a negative electrode active material.

22. A lithium phosphate of any one of formulae (IV-I) to (IV-VI), in which a cyclic polar group is bound directly to a phosphorus atom (P):

wherein, R 41 is an organic group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, in each of which a part of hydrogen atoms may be substituted with a halogen atom, or a lithium atom; and p 41 and q 41 each independently represent an integer of 0 to 2 and satisfy a relation: 1≤(p 41 +q 41 )≤3, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (IV-VII),

wherein, R 42 is synonymous with R 41 ; and p 42 and q 42 each independently represent an integer of 0 to 3 and satisfy a relation: 1≤(p 42 +q 42 )≤4, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (IV-VII),

wherein, R 43 is synonymous with R 41 ; and p 43 and q 43 each independently represent an integer of 0 to 2 and satisfy a relation: 1≤(p 43 +q 43 )≤3, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (IV-VII),

wherein, R 44 is synonymous with R 41 ; Y 44 represents an —NH— group or an —O— group; p 44 represents an integer of 0 to 1; q 44 represents an integer of 1 to 4; and p 44 and q 44 satisfy a relation: 2≤(p 44 +q 44 )≤4, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (IV-VII),

wherein, R 45 is synonymous with R 41 , provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (IV-VII),

wherein, R 46 is synonymous with R 41 ; Y 46 represents an —NH— group or an —O— group; p 46 represents an integer of 0 to 1; q 46 represents an integer of 1 to 4; and p 46 and q 46 satisfy a relation: 2≤(p 46 +q 46 )≤4, provided that in the cyclic polar group, a part of hydrogen atoms may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or a substituent of formula (IV-VII), and

wherein, R 47 and R 48 are each independently synonymous with R 41 ; and * represents a site binding to the cyclic polar group.