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EP-3772130-B1 - ADDITIVE FOR NON-AQUEOUS ELECTROLYTE SOLUTIONS, NON-AQUEOUS ELECTROLYTE SOLUTION, AND ELECTRICITY STORAGE DEVICE

EP3772130B1EP 3772130 B1EP3772130 B1EP 3772130B1EP-3772130-B1

Inventors

  • KONO, YUKI
  • TAKAI, YASUYUKI
  • FUJITA, KOJI

Dates

Publication Date
20260506
Application Date
20190122

Claims (10)

  1. An additive for nonaqueous electrolyte solutions, comprising a compound represented by the following formula (1a) or (1b), in Formulae (1a) and (1b), X represents an alkylene group having 3 to 7 carbon atoms, which may be substituted with a halogen atom, or an alkenylene group having 3 to 7 carbon atoms, which may be substituted with a halogen atom, each of which constitutes a cyclic structure together with the sulfur atom of a sulfonyl group, n represents an integer of 1 to 7, Z represents a monovalent group represented by Formula (2a), (2b), or (2c), and m represents 0 or 1, (A) when the compound is represented by the formula (1a), R 2a represents: • an alkyl group having 1 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkenyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryl group which may be substituted with a halogen atom or with an alkyl group having 1 to 3 carbon atoms; • an alkoxy group having 1 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkenyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryloxy group which may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or with a halogen atom; • a hydroxyl group; • a lithium alcoholate group; or • a lithium atom, R 2b represents: • an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, or a trifluoromethyl group, each of which may be substituted with a halogen atom; • an alkenyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • a tolyl group, a xylyl group, or a naphthyl group, each of which may be substituted with a halogen atom or an alkyl group having 1 to 3 carbon atoms; • an alkoxy group having 1 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkenyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryloxy group which may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; • a hydroxyl group; • a lithium alcoholate group; or • a lithium atom, R 2c represents: • an alkyl group having 1 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkenyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryl group which may be substituted with a halogen atom or an alkyl group having 1 to 3 carbon atoms; • a methoxy group, an n-propoxy group or an n-butoxy group, each of which may be substituted with a halogen atom; • an alkenyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryloxy group which may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; • a hydroxyl group; • a lithium alcoholate group; or • a lithium atom, wherein two R 2c 's in the same molecule may be the same as or different from each other, (B) when the compound is represented by the formula (1b) and m is 0, R 2a , R 2b and R 2c each independently represent: • an alkyl group having 1 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkenyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryl group which may be substituted with a halogen atom or an alkyl group having 1 to 3 carbon atoms; • an alkoxy group having 1 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkenyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryloxy group which may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; • a hydroxyl group; • a lithium alcoholate group; or • a lithium atom, wherein two R 2c 's in the same molecule may be the same as or different from each other, and (C) when the compound is represented by the formula (1b) and m is 1, R 2a and R 2c each independently represent: • an alkyl group having 1 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkenyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryl group which may be substituted with a halogen atom or an alkyl group having 1 to 3 carbon atoms; • an alkoxy group having 1 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkenyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryloxy group which may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; • a hydroxyl group; • a lithium alcoholate group; or • a lithium atom, wherein two R 2c 's in the same molecule may be the same as or different from each other, and R 2b represents: • an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, or a trifluoromethyl group, each of which may be substituted with a halogen atom; • an alkenyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • a tolyl group, a xylyl group, or a naphthyl group, each of which may be substituted with a halogen atom or an alkyl group having 1 to 3 carbon atoms; • a methoxy group, an n-propoxy group, or an n-butoxy group, each of which may be substituted with a halogen atom; • an alkenyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an alkynyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom; • an aryloxy group which may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom; • a hydroxyl group; • a lithium alcoholate group; or • a lithium atom.
  2. The additive for nonaqueous electrolyte solutions according to claim 1, wherein X in Formulae (1a) and (1b) is an alkylene group having 3 to 7 carbon atoms.
  3. The additive for nonaqueous electrolyte solutions according to claim 2, wherein X in Formulae (1a) and (1b) is an alkylene group having 4 carbon atoms.
  4. The additive for nonaqueous electrolyte solutions according to any one of claims 1 to 3, wherein Z in Formulae (1a) and (1b) is a monovalent group represented by Formula (2a).
  5. A nonaqueous electrolyte solution comprising: (i) an additive for nonaqueous electrolyte solutions comprising a compound represented by the following formula (1a) or (1b), in Formulae (1a) and (1b), X represents an alkylene group having 3 to 7 carbon atoms, which may be substituted with a halogen atom, or an alkenylene group having 3 to 7 carbon atoms, which may be substituted with a halogen atom, each of which constitutes a cyclic structure together with the sulfur atom of a sulfonyl group, n represents an integer of 1 to 7, Z represents a monovalent group represented by Formula (2a), (2b), or (2c), and m represents 0 or 1, in Formulae (2a), (2b), and (2c), R 2a , R 2b , and R 2c each independently represent an alkyl group having 1 to 4 carbon atoms, which may be substituted with a halogen atom, an alkenyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom, an alkynyl group having 2 to 4 carbon atoms, which may be substituted with a halogen atom, an aryl group which may be substituted with a halogen atom or with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, which may be substituted with a halogen atom, an alkenyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom, an alkynyloxy group having 2 to 4 carbon atoms, which may be substituted with a halogen atom, an aryloxy group which may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or with a halogen atom, a hydroxyl group, a lithium alcoholate group, or a lithium atom, and two R 2c 's in the same molecule may be the same as or different from each other; (ii) a nonaqueous solvent; and (iii) an electrolyte.
  6. The nonaqueous electrolyte solution according to claim 5, wherein the nonaqueous solvent includes a cyclic carbonate and a chained carbonate.
  7. The nonaqueous electrolyte solution according to claim 5 or 6, wherein the electrolyte includes a lithium salt.
  8. An electricity storage device comprising: the nonaqueous electrolyte solution according to any one of claims 5 to 7; a positive electrode; and a negative electrode.
  9. A lithium ion battery comprising: the nonaqueous electrolyte solution according to any one of claims 5 to 7; a positive electrode; and a negative electrode.
  10. A lithium ion capacitor comprising: the nonaqueous electrolyte solution according to any one of claims 5 to 7; a positive electrode; and a negative electrode.

Description

Technical Field The present invention relates to an additive for nonaqueous electrolyte solutions. The present invention further relates to a nonaqueous electrolyte solution containing the additive for nonaqueous electrolyte solutions and an electricity storage device using the nonaqueous electrolyte solution. Background Art In recent years, along with an increase in attention to solving environmental problems and establishing a sustainable recycling-based society, nonaqueous electrolyte solution secondary batteries typified by lithium ion batteries and electricity storage devices such as an electric double layer capacitor have been widely studied. Among those, the lithium ion batteries are used as power sources for laptops, mobile phone, or the like from the viewpoint that they have high working voltages and energy densities. These lithium ion batteries are expected as a new power source from the viewpoint that they have higher energy densities than lead batteries and nickel-cadmium batteries, and a higher capacity of batteries is realized therewith. However, the lithium ion batteries have a problem in that the capacity of the batteries is reduced over time in charge/discharge cycles. As a method for suppressing a reduction in the capacity of a battery over time in charge/discharge cycles, a method in which various additives are added to an electrolyte solution has been examined. The additives are decomposed during a first charge/discharge to form a film called a solid electrolyte interface (SEI) on a surface of an electrode. Since the SEI is formed during the first cycle of the charge/discharge cycles, electricity is not consumed for decomposition of a solvent and the like in the electrolyte solution, the lithium ions can be transferred between electrodes through the SEI. That is, formation of the SEI prevents the deterioration of electricity storage devices such as a nonaqueous electrolyte solution secondary battery in a case where the charge/discharge cycles are repeated, and thus contributes to an improvement of battery characteristics, storage characteristics, load characteristics, or the like. For example, Patent Literature 1 discloses that charge/discharge cycle characteristics of a lithium secondary battery are improved by addition of 1,3-propanesultone (PS) into an electrolyte solution that forms SEI as an additive. Further, Patent Literature 2 discloses that the self-discharge rate of a nonaqueous electrolyte secondary battery is reduced by addition of a 1,3,2-dioxaphospholane-2-dioxide derivative or PS as an additive into an electrolyte solution. Patent Literature 3 discloses that discharge characteristics and the like of a lithium secondary battery are improved by adding a derivative of vinylene carbonate (VC) as an additive. Patent Literatures 4 to 8 all refer to non-aqueous electrolytic solutions for electrochemical devices, comprising an electrolyte salt dissolved in a non-aqueous organic solvent, in admixture with a substituted sulfolane compound as additive or co-solvent. Citation List Patent Literature [Patent Literature 1] Japanese Unexamined Patent Publication No. S63-102173[Patent Literature 2] Japanese Unexamined Patent Publication No. H10-50342[Patent Literature 3] Japanese Unexamined Patent Publication No. H05-074486[Patent Literature 4] US 2017/271715 A1[Patent Literature 5] WO 2017/043576 A1[Patent Literature 6] JP 2012 056925 A[Patent Literature 7] WO 2018/016195 A1[Patent Literature 8] JP 2017 208322 A Summary of Invention Technical Problem However, even with use of those additives, sufficient performance has not been obtained and there has been a desire for development of novel additives for further improving battery characteristics of electricity storage devices. In addition, the electrolyte solution in which a derivative of VC is used as an additive as described in Patent Literature 3 generates gases including carbon dioxide upon decomposition of the derivative of VC on an electrode, which thus leads to a reduction in battery performance. An object of the present invention is to provide an additive for nonaqueous electrolyte solutions, which makes it possible to suppress initial resistance, improve cycle characteristics over a long period of time, and suppress gas generation in a case where the additive for nonaqueous electrolyte solutions is used in an electricity storage device such as a nonaqueous electrolyte solution secondary battery. In addition, another object of the present invention is to provide a nonaqueous electrolyte solution using the additive for nonaqueous electrolyte solutions and an electricity storage device using the nonaqueous electrolyte solution. Solution to Problem The subject-matter of the present invention is defined in the appended claims. Preferred embodiments are presented in the subclaims. In an aspect of the present invention, an additive for nonaqueous electrolyte solutions, including a compound represented by the following Formula (1a) or Form