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EP-4293781-B1 - NONAQUEOUS ELECTROLYTIC SOLUTION AND NONAQUEOUS ELECTROLYTIC SOLUTION BATTERY

EP4293781B1EP 4293781 B1EP4293781 B1EP 4293781B1EP-4293781-B1

Inventors

  • NAKAZAWA, EIJI
  • KAWAKAMI, DAISUKE

Dates

Publication Date
20260513
Application Date
20220209

Claims (7)

  1. A nonaqueous electrolytic solution for a nonaqueous electrolytic solution battery including a positive electrode and a negative electrode which are capable of absorbing and releasing metal ions, the nonaqueous electrolytic solution comprising an alkali metal salt, a nonaqueous solvent, a compound represented by General Formula (A), and at least one of a compound represented by General Formula (α) and a compound represented by General Formula (β), wherein the compound represented by General Formula (α) is at least one compound selected from the group consisting of compounds represented by formulas (α1) to (α15): where in General Formula (A), Q 1 and Q 2 each independently represent a C 1 to C 10 alkylene group which may have a substituent; n 1 represents an integer of 0 or 1; and when n 1 is 0, the sulfur atom and the oxygen atom are directly bonded to each other; where in General Formula (α), R 1 and R 2 each independently represent a hydrogen atom, a C 1 to C 12 hydrocarbon group, or a silyl group represented by -SiR 3 R 4 R 5 ; R 3 to R 5 each independently represent a hydrogen atom, a halogen atom, a C 1 to C 12 hydrocarbon group which may have a substituent, or a C 1 to C 12 alkoxy group which may have a substituent; Y represents a hydrogen atom, a halogen atom, a C 1 to C 12 hydrocarbon group which may have a substituent, a group represented by -NR 6 -SiR 7 R 8 R 9 , or a group represented by -NR 10 -R 11 ; R 6 , R 10 , and R 11 each independently represent a hydrogen atom or a C 1 to C 12 hydrocarbon group which may have a substituent; R 7 to R 9 each independently represent a hydrogen atom, a halogen atom, a C 1 to C 12 hydrocarbon group which may have a substituent, or a C 1 to C 12 alkoxy group which may have a substituent; and R 1 or R 2 and Y may be bonded to each other to form a ring; where in General Formula (β), R 21 to R 23 each independently represent a hydrogen atom, a C 1 to C 10 alkyl group which may have a substituent, a C 6 to C 18 aryl group, or a C 7 to C 18 aralkyl group; and Z represents a C 2 to C 10 alkenyl or alkynyl group which may have a substituent;
  2. The nonaqueous electrolytic solution according to claim 1, wherein the content of the compound represented by General Formula (A) is 1.0 × 10 -3 % by mass or more and 10% by mass or less relative to the total amount of the nonaqueous electrolytic solution.
  3. The nonaqueous electrolytic solution according to claim 1 or 2, wherein the content of the compound represented by General Formula (α) or the compound represented by General Formula (β) is 0.01 mass ppm or more and 0.5% by mass or less relative to the total amount of the nonaqueous electrolytic solution.
  4. The nonaqueous electrolytic solution according to any one of claims 1 to 3, wherein the mass ratio of the content of the compound represented by General Formula (A) to the content of the compound represented by General Formula (α) or the compound represented by General Formula (β) in the nonaqueous electrolytic solution is 1.0 or more and 1.0 × 10 4 or less.
  5. A nonaqueous electrolytic solution for a nonaqueous electrolytic solution battery including a positive electrode and a negative electrode which are capable of absorbing and releasing metal ions, the nonaqueous electrolytic solution comprising an alkali metal salt, a nonaqueous solvent, a compound represented by General Formula (AA), and a compound represented by General Formula (αα): where in General Formula (AA), Q 31 and Q 32 each independently represent a C 1 to C 10 alkylene group; the alkylene group may be substituted by a hydrocarbon group, or a hydrogen atom of the alkylene group may be substituted by a halogen atom; n 31 is an integer of 0 or 1; and when n 31 is 0, the sulfur atom and the oxygen atom are directly bonded to each other; where in General Formula (αα), R 31 and R 32 each independently represent a hydrogen atom, a C 1 to C 12 hydrocarbon group, or a silyl group represented by -SiR 33 R 34 R 35 ; R 33 to R 35 each independently represent a hydrogen atom, a halogen atom, a C 1 to C 12 hydrocarbon group which may have a substituent, or a C 1 to C 12 alkoxy group which may have a substituent; Y 31 represents a C 1 to C 12 alkoxy group which may have a substituent; and R 31 or R 32 and Y 31 may be bonded to each other to form a ring; wherein the content of the compound represented by General Formula (αα) is 0.01 mass ppm or more and 0.5% by mass or less relative to the total amount of the nonaqueous electrolytic solution, and the mass ratio of the content of the compound represented by General Formula (AA) to the content of the compound represented by General Formula (αα) in the nonaqueous electrolytic solution is 2.0 or more and 1.0 × 10 4 or less.
  6. The nonaqueous electrolytic solution according to claim 5, wherein the content of the compound represented by General Formula (AA) is 1.0 × 10 -3 % by mass or more and 10% by mass or less relative to the total amount of the nonaqueous electrolytic solution.
  7. A nonaqueous electrolytic solution battery including a positive electrode and a negative electrode which are capable of absorbing and releasing metal ions, and a nonaqueous electrolytic solution, wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution according to any one of claims 1 to 6.

Description

TECHNICAL FIELD The present invention relates to a nonaqueous electrolytic solution and a nonaqueous electrolytic solution battery, and specifically relates to a nonaqueous electrolytic solution containing a specific compound, and a nonaqueous electrolytic solution battery containing this nonaqueous electrolytic solution. BACKGROUND ART Nonaqueous electrolytic solution batteries such as lithium secondary batteries are practically used in broad applications. Examples are power supplies for consumer small apparatuses including mobile phones, such as smartphones and laptop computers, on-vehicle power supplies for electric automobiles, and the like. Many methods have been examined for improving the battery characteristics of nonaqueous electrolytic solution batteries in the field of active materials for positive and negative electrodes and the field of additives for nonaqueous electrolytic solutions. For example, Patent Document 1 discloses examination for improving high-temperature cycle capacity retention and a change in thickness of a battery when stored at a high temperature by adding a cyclic sulfuric acid compound to a nonaqueous electrolytic solution comprising a lithium salt, a specific carbamate compound, and an organic solvent such as a carbonate. Patent Document 2 discloses examination for improving the storage stability of a silyl group-containing compound, improving a cycle capacity retention at a high voltage of 4.9 V, and decreasing the gas generation amount while a battery is operating by adding a trialkylsilyl compound of a protonic acid having phosphorus atom and/or boron atom, a sulfonic acid, or a carboxylic acid and a basic compound or a specific silicon compound to a nonaqueous electrolytic solution. Patent Document 3 discloses a specific non-aqueous electrolyte for a secondary battery, wherein the non-aqueous electrolyte comprises a non-aqueous solvent, a lithium salt, a sulfonate compound, and at least one auxiliary additive selected from an amide compound and an oxazolidine compound. RELATED ART DOCUMENTS PATENT DOCUMENTS Patent Document 1: JP 2016-532989 TPatent Document 2: WO 2015/098471Patent Document 3: KR 10-2015-0024478 A SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION Recently, an increase in capacity of the lithium battery has been accelerated in on-vehicle power supplies for electric automobiles, power supplies for mobile phones including smartphones, and the like, which leads to internal gap reductions from conventional batteries. For this reason, a large amount of gas generation amount in initial conditioning is a fatal defect. An object of the present invention is to provide a nonaqueous electrolytic solution enabling a suppression in gas generation amount during initial conditioning of a nonaqueous electrolytic solution battery. Another object of the present invention is to provide a nonaqueous electrolytic solution battery in which the gas generation amount during initial conditioning is suppressed. MEANS FOR SOLVING PROBLEMS The present inventor, who has conducted extensive research to solve the above problem, has conceived that generation of gas during initial conditioning is suppressed by using a nonaqueous electrolytic solution containing a compound represented by General Formula (A) and at least one of a compound represented by General Formula (α) and a compound represented by General Formula (β), and has completed the present invention. The present invention is as defined in the appended claims. EFFECTS OF INVENTION The present invention can provide a nonaqueous electrolytic solution enabling a significant suppression in gas generation amount during initial conditioning of a nonaqueous electrolytic solution battery, and a nonaqueous electrolytic solution battery in which the gas generation amount during initial conditioning is suppressed. DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments according to the present invention will be specifically described. The embodiments below are one examples (typical examples) of the present invention, and should not be construed as limitations to the present invention. Moreover, the present invention can be optionally modified and be implemented without departing from the scope of the appended claims. [First embodiment] <1-1. Nonaqueous electrolytic solution> The nonaqueous electrolytic solution according to the present invention contains a compound represented by General Formula (A), and at least one of a compound represented by General Formula (α) and a compound represented by General Formula (β) described below. Although the mechanism to suppress the gas generation amount by using such a nonaqueous electrolytic solution containing a compound represented by General Formula (A) and at least one of a compound represented by General Formula (α) and a compound represented by General Formula (β) is not clarified, it is inferred as below. Because the compound represented by General Formula (A) has a cyclic structure hav