WO2012111335A1 - Agent de formation d'un film de protection d'électrode - Google Patents

Agent de formation d'un film de protection d'électrode Download PDF

Info

Publication number
WO2012111335A1
WO2012111335A1 PCT/JP2012/001019 JP2012001019W WO2012111335A1 WO 2012111335 A1 WO2012111335 A1 WO 2012111335A1 JP 2012001019 W JP2012001019 W JP 2012001019W WO 2012111335 A1 WO2012111335 A1 WO 2012111335A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
electrode
protective film
compound
forming agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/001019
Other languages
English (en)
Japanese (ja)
Inventor
文平 吉田
剛史 大高
敦史 若月
拓馬 竹田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanyo Chemical Industries Ltd
Original Assignee
Sanyo Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sanyo Chemical Industries Ltd filed Critical Sanyo Chemical Industries Ltd
Priority to JP2012557845A priority Critical patent/JPWO2012111335A1/ja
Publication of WO2012111335A1 publication Critical patent/WO2012111335A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to an electrode protective film forming agent, an electrode and an electrolytic solution particularly useful for a lithium secondary battery or a lithium ion capacitor.
  • Non-aqueous electrolyte secondary batteries such as lithium secondary batteries are characterized by high voltage and high energy density, so they are widely used in the field of portable information equipment, and the demand is rapidly expanding.
  • a position as a standard battery for mobile information devices such as mobile phones and notebook computers has been established.
  • higher performance for example, higher capacity and higher energy density
  • various methods such as higher density by improving the filling rate of electrodes, improvement of the depth of use of current active materials (especially negative electrodes), development of new high-capacity active materials, etc. have been carried out. Yes.
  • the capacity of the non-aqueous electrolyte secondary battery is reliably increased by these methods.
  • a cobalt composite oxide which is an active material of a non-aqueous electrolyte secondary battery having an operating voltage of 4.2 V class, has a charge capacity of about 155 mAh / g when charged to 4.3 V based on the current Li standard.
  • LiCoO 2 cobalt composite oxide
  • the utilization rate of a positive electrode active material becomes large by the improvement of a charging voltage.
  • Patent Document 1 by adding an aromatic sulfide such as methylphenyl sulfide or diphenyl sulfide, the aromatic sulfide is preferentially oxidized on the surface of the positive electrode over the electrolyte, and the oxidation product is converted into the negative electrode. It is disclosed that by repeating the reaction of diffusion and reduction to return to the original sulfide body, the oxidative decomposition of the solvent is suppressed, and the storage characteristics, charge / discharge cycle characteristics and the like are improved.
  • an aromatic sulfide such as methylphenyl sulfide or diphenyl sulfide
  • Patent Document 2 by adding a sulfide compound having an aryl group or a heterocyclic group as a substituent, this sulfide compound is preferentially applied to strongly oxidizing chemical species such as active oxygen generated on the surface of the positive electrode. It has been disclosed to suppress a decrease in discharge capacity due to repeated charge and discharge by reacting and suppressing oxidative decomposition of the solvent. Furthermore, it is disclosed that a part of the oxidized material adheres to the positive electrode, is reduced during discharge, returns to the original state, and a part is diffused to the negative electrode.
  • JP 7-320779 A Japanese Patent Laid-Open No. 10-64591
  • An object of this invention is to provide the electrode or electrolyte solution for lithium secondary batteries or lithium ion capacitors which is high voltage, high capacity
  • the present invention includes an alkenyl ether group (X) represented by the general formula (1) and a group (L) having at least one atom selected from oxygen, fluorine, silicon, phosphorus and sulfur, and an ether.
  • T 1 to T 3 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the electrode protective film forming agent (B) of the present invention can suppress the decomposition of the electrolytic solution on the electrode surface under a high voltage, and can improve the charge / discharge cycle characteristics and the high temperature storage characteristics.
  • a high-voltage, high-capacity lithium secondary battery or lithium-ion capacitor can be obtained, and under these high voltages.
  • the charge / discharge cycle performance and high-temperature storage characteristics can be improved.
  • the electrode protective film forming agent (B) of the present invention includes an alkenyl ether group (X) represented by the general formula (1) and a group having at least one atom selected from oxygen, fluorine, silicon, phosphorus and sulfur ( L) and a compound (A) having an ether group concentration of 0.1 to 9.0 meq / g.
  • alkenyl ether group (X) represented by the general formula (1) and a group having at least one atom selected from oxygen, fluorine, silicon, phosphorus and sulfur ( L) and a compound (A) having an ether group concentration of 0.1 to 9.0 meq / g.
  • T 1 , T 2 and T 3 in the general formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, n-propyl group and isopropyl group).
  • alkenyl ether group (X) examples include a vinyl ether group, a 1-propenyl ether group, and a 2-methyl-1-propenyl ether group. Of these, vinyl ether groups and 1-propenyl ether groups are preferred from the viewpoint of charge / discharge cycle characteristics.
  • the number of alkenyl ether groups (X) contained in the compound (A) is 1 to 5, preferably 2 to 4, more preferably 2 or 3, from the viewpoint of charge / discharge cycle characteristics.
  • the group (L) possessed by the compound (A) is a group having at least one atom selected from oxygen, fluorine, silicon, phosphorus and sulfur, preferably groups represented by the following (a) to (g) A group having at least one group selected from the group consisting of and a hydrocarbon group having 1 to 20 carbon atoms.
  • a group having at least one group selected from the group consisting of and a hydrocarbon group having 1 to 20 carbon atoms (A): carbonate group (b): fluorinated hydrocarbon group having 1 to 20 carbon atoms (c): sulfino group (d): sulfo group (E): Phosphate ester group (f): Siloxane group (g): Silylene group
  • fluorinated hydrocarbon group (b) having 1 to 20 carbon atoms a linear or branched fluorinated hydrocarbon group [perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoro 2 -Methylpropyl group, perfluoropentyl group, perfluoro-2-methylbutyl group, perfluoro2,2-dimethylpropyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, perfluorododecyl group, perfluorotridecyl group Decyl group, perfluorotetradecyl group, perfluoropentadecyl group, perfluorooctadecyl group, perfluoroeicosyl group, perfluoromethylene group, perfluoroethylene group, perfluoropropylene group, perfluorobutylene
  • Examples of the phosphate ester group (e) include an alkyl phosphate ester group. Specific examples of (e) include a methyl phosphate group, an ethyl phosphate group, a butyl phosphate group, and a hexyl phosphate group.
  • Examples of the siloxane group (f) include alkylsiloxane groups.
  • Specific examples of the alkylsiloxane group include a dimethylsiloxane group, a diethylsiloxane group, a dibutylsiloxane group, and a dihexylsiloxane group.
  • Examples of the silylene group (g) include a dialkylsilylene group.
  • Examples of the dialkylsilylene group include a dimethylsilylene group, a diethylsilylene group, a dibutylsilylene group, and a dihexylsilylene group.
  • hydrocarbon group having 1 to 20 carbon atoms examples include linear or branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, and aromatic hydrocarbon groups.
  • the ether group concentration of the compound (A) is 0.1 to 9.0 meq / g, preferably 0.1 to 7.5 meq / g.
  • the ether group concentration is 0.1 to 9.0 milliequivalent / g, oxidative decomposition of the electrode protective film can be suppressed, and charge / discharge cycle characteristics and high-temperature storage characteristics can be improved. If the ether group concentration exceeds 9.0 milliequivalent / g, oxidation stability is inferior, which is not preferable.
  • the compound (A) is preferably a compound (A1) represented by the general formula (2) and a compound (A2) represented by the general formula (3).
  • R 1 is an aliphatic hydrocarbon group having a linear or aliphatic hydrocarbon group or a cyclic structure having from 5 to 12 carbon atoms having 1 to 6 carbon atoms branched, plurality is R 1 May be the same or different, and T 1 , T 2 and T 3 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is a number from 1 to 10. ]
  • X is an alkenyl ether group represented by the general formula (1);
  • Y is a mono- to tetra-valent fluorinated hydrocarbon group having 1 to 20 carbon atoms;
  • n represents an integer of 1 to 4.
  • the linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms includes a methylene group, an ethylene group, a trimethylene group, an ethylidene group, a tetramethylene group, a 1-methyltrimethylene group, 2 -Methyltrimethylene group, 1-ethylethylene group, 1,1-dimethylethylene group, ethylmethylmethylene group, propylmethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1 -Dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 1-ethyltrimethylene group, 1,1,2-trimethylethylene group, Diethylmethylene group, 1-propylethylene group, butylmethylene group, hexamethylene group, 1-methylpentamethylene group, , 1-dimethyltetramethylene group
  • examples of the aliphatic hydrocarbon group having a cyclic structure having 5 to 12 carbon atoms include 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group 1,4-cyclohexylene group, a residue obtained by removing two hydroxyl groups from 1,3-cyclohexanedimethanol, a residue obtained by removing two hydroxyl groups from 1,4-cyclohexanedimethanol, 1-hydroxy- Residue obtained by removing two hydroxyl groups from 3-hydroxymethylcyclohexane, residue obtained by removing two hydroxyl groups from 1-hydroxy-4-hydroxymethylcyclohexane, and two hydroxyl groups removed from 1,4-cyclohexanediethanol
  • Examples thereof include a residue and a residue obtained by removing two hydroxyl groups from 1,4-cyclohexanedipropanol.
  • an aliphatic hydrocarbon group having a cyclic structure having 5 to 12 carbon atoms is preferable from the viewpoint of cycle characteristics, and more preferable is the removal of two hydroxyl groups from 1,4-cyclohexanedimethanol. Residue.
  • examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • n is a number of 1 to 10, and preferably 1 to 4 from the viewpoint of cycle characteristics.
  • a fluorinated hydrocarbon group in which 1 to 4 fluorine atoms of a linear, branched, or cyclic perfluoroalkane having 1 to 20 carbon atoms are removed A compound in which a divalent linear or branched alkylene group (K) having 1 to 10 carbon atoms is bonded to an alkenyl ether group (X), and is shortest between the fluorinated hydrocarbon group and the alkenyl ether group. In which the number of covalent bonds intervening in is 2 to 5.
  • the 1 to 4 valent fluorinated hydrocarbon group (Y) having 1 to 20 carbon atoms is a group in which 1 to 4 fluorine atoms of a linear, branched or cyclic perfluoroalkane having 1 to 20 carbon atoms are removed. From the viewpoint of charge / discharge cycle characteristics, a group from which 1 to 3 fluorine atoms have been removed is preferred, and a group from which 2 to 3 fluorine atoms have been removed is more preferred.
  • the mono- to tetra-valent fluorinated hydrocarbon group (Y) having 1 to 20 carbon atoms is a linear or branched fluorinated hydrocarbon group (Y1) [perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, Perfluorobutyl group, perfluoro 2-methylpropyl group, perfluoropentyl group, perfluoro 2-methylbutyl group, perfluoro 2,2-dimethylpropyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, Perfluorododecyl group, perfluorotridecyl group, perfluorotetradecyl group, perfluoropentadecyl group, perfluorooctadecyl group, perfluoroeicosyl group, perfluoromethylene group, perfluoroethylene group, perfluoropropylene group, perfluoroprop
  • Examples of the divalent linear or branched alkylene group (K) having 1 to 10 carbon atoms include methylene group, ethylene group, propylene group, 2-methylpropylene group, 2,2-dimethylpropylene group, butylene group, and cyclopentylene. Cyclohexylene group and 2-methylbutylene group.
  • Examples of the compound (A) include a compound (A21) in which a linear or branched fluorinated hydrocarbon group (Y1) is bonded to an alkenyl ether group (X) through an alkylene group (K), and a cyclic fluorinated hydrocarbon group ( Examples thereof include compound (A22) in which Y2) is bonded to alkenyl ether group (X) through alkylene group (K).
  • a compound in which a linear fluorinated hydrocarbon group is bonded via a linear alkylene group having 1 to 3 carbon atoms is preferable from the viewpoint of cycle characteristics.
  • Examples of (A21) include compounds having a monoalkenyl ether group, compounds having a dialkenyl ether group, and compounds having a trialkenyl ether group.
  • monovinyl ether [3,3,4,4,4-pentafluorobutanol vinyl ether, 3,3,4,4,5,5,5-heptafluoropentanol vinyl ether, 3,3,4 , 4,5,5,6,6,6-nonafluorohexanol vinyl ether, 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptanol vinyl ether, and 4, 4,5,5,6,6,7,7,8,8,8-undecafluorooctanol vinyl ether and the like]; mono (1-propenyl) ether [3,3,4,4,4-pentafluorobutanol ( 1-propenyl) ether, 3,3,4,4,5,5,5-heptafluoropentanol (1-propenyl) ether, 3,3,4,4,5,5,6,6,6-nonaflu Lohexanol (1-propenyl) ether and 4,4,5,5,6,6,7,7,8,
  • Examples of the compound (A22) include a compound having a monoalkenyl ether group, a compound having a dialkenyl ether group, and a compound having a trialkenyl ether group.
  • the compound (A) functions as a positive electrode protective film forming agent. That is, compound (A) is polymerized on the surface of the positive electrode active material to form a film by containing compound (A) in the electrode or electrolyte and applying a voltage to the electrode.
  • This film serves as a protective film that suppresses the decomposition of the electrolytic solution on the electrode surface under a high voltage, and improves the charge / discharge cycle characteristics.
  • the protective film is formed during the initial charge.
  • An electrode in which a polymer film of the compound (A) is formed on the (positive electrode active material surface) can also be used.
  • Compound (A) in the present invention can be synthesized by an ordinary method.
  • the compound represented by the general formula (2) the compound can be synthesized by transesterification of a monoalcohol having an alkenyloxy group and the diol having R 1 with a chain carbonate in the presence of a basic catalyst. it can.
  • the compound represented by the general formula (3) it can be synthesized by reacting the corresponding alcohol with allyl chloride in the presence of a basic catalyst to form an allyl ether, followed by propenyl transfer reaction of this allyl ether. it can.
  • Examples of the basic catalyst include sodium metal, sodium hydroxide, sodium methoxide, sodium tert-butoxide, metal potassium, potassium hydroxide, potassium methoxide and potassium tert-butoxide.
  • Examples of monoalcohol having an alkenyloxy group include ethylene glycol monovinyl ether, ethylene glycol monopropenyl ether, propylene glycol monovinyl ether, propylene glycol monopropenyl ether, 1-hydroxymethyl-4- (vinyloxymethyl) cyclohexane and 1-hydroxymethyl. -4- (propenyloxymethyl) cyclohexane and the like.
  • Examples of the diol having R 1 include ethylene glycol, propylene glycol, and 1,4-bis (hydroxymethyl) cyclohexane.
  • Examples of the chain carbonate include dimethyl carbonate, diethyl carbonate, and diphenyl carbonate.
  • the electrode protective film forming agent (B) of the present invention can further contain a negative electrode protective film forming agent (C).
  • C negative electrode protective film forming agent
  • Examples of the negative electrode protective film forming agent (C) include vinylene carbonate, fluoroethylene carbonate, chloroethylene carbonate, ethylene sulfite, propylene sulfite, and ⁇ -bromo- ⁇ -butyrolactone. Among these, vinylene carbonate is preferable from the viewpoint of cycle characteristics.
  • the content of the compound (A) in the electrode protective film forming agent (B) is preferably 10 to 100% by weight, more preferably 50 to 100% by weight, based on the weight of (B).
  • the content of the negative electrode protective film forming agent (C) in the electrode protective film forming agent (B) is preferably 0 to 90% by weight, more preferably 0 to 50% by weight, based on the weight of (B). It is.
  • the electrode of the present invention contains an electrode protective film forming agent (B), an active material (D), and a binder (E).
  • the active material (D) examples include a negative electrode active material (D1), a positive electrode active material (D2) for a lithium secondary battery, and a positive electrode active material (D3) for a lithium ion capacitor.
  • a negative electrode active material (D1) graphite, amorphous carbon, a polymer compound fired body (for example, those obtained by firing and carbonizing a phenol resin, a furan resin, etc.), cokes (for example, pitch coke, needle coke, and petroleum coke), And carbon fibers, conductive polymers (for example, polyacetylene and polypyrrole), tin, silicon, and metal alloys (for example, lithium-tin alloy, lithium-silicon alloy, lithium-aluminum alloy, and lithium-aluminum-manganese alloy).
  • Examples of the positive electrode active material (D2) for the lithium secondary battery include composite oxides of lithium and transition metals (for example, LiCoO 2 , LiNiO 2 , LiMnO 2 and LiMn 2 O 4 ), transition metal oxides (for example, MnO 2 and V 2). O 5 ), transition metal sulfides (eg, MoS 2 and TiS 2 ), and conductive polymers (eg, polyaniline, polyvinylidene fluoride, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene, and polycarbazole).
  • Examples of the positive electrode active material (D3) for the lithium ion capacitor include activated carbon, carbon fiber, and conductive polymer (for example, polyacetylene and polypyrrole).
  • binder (E) examples include polymer compounds such as starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, and polypropylene.
  • the electrode of the present invention can further contain a Lewis base (F).
  • a Lewis base F
  • the storage stability of the compound (A) is improved.
  • the Lewis base (F) include triazole derivatives (1,2,3-benzotriazole, 5-methyl-1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, 1 2,4-triazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methyl-1,2,4-triazole, 3, -Amino-5-ethyl-1,2,4-triazole, 3-amino-5-propyl-1,2,4-triazole and 3-amino-5-butyl-1,2,4-triazole) It is done. These can be obtained commercially. Of these, 3-amino-1,2,4-triazole is preferable from the viewpoint of charge / discharge cycle characteristics.
  • the electrode of the present invention can further contain a conductive additive (G).
  • a conductive additive examples include graphite (for example, natural graphite and artificial graphite), carbon blacks (for example, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black) and metal powder (for example, Aluminum powder and nickel powder), conductive metal oxides (for example, zinc oxide and titanium oxide), and the like.
  • each of electrode protective film forming agent (B), active material (D), binder (E), Lewis base (F) and conductive additive (G) based on the total weight of the electrode is preferred.
  • the content is as follows.
  • the content of the electrode protective film forming agent (B) is preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight, from the viewpoint of charge / discharge cycle characteristics, battery capacity and high storage characteristics.
  • the content of the active material (D) is preferably 70 to 98% by weight, more preferably 90 to 98% by weight, from the viewpoint of charge / discharge cycle characteristics.
  • the content of the binder (E) is preferably 0.5 to 29% by weight, more preferably 1 to 10% by weight, from the viewpoint of charge / discharge cycle characteristics.
  • the content of the Lewis base (F) is preferably 0 to 7.5% by weight, more preferably 0.5 to 3% by weight, from the viewpoint of battery capacity, battery output and charge / discharge cycle characteristics.
  • the content of the conductive auxiliary agent (G) is preferably 0 to 29% by weight, more preferably 0 to 10% by weight, from the viewpoint of battery output.
  • an electrode protective film forming agent (B), an active material (D), a binder (E), and, if necessary, a Lewis base (F) and a conductive additive (G) are added to water or a solvent.
  • a slurry dispersed at a concentration of ⁇ 60% by weight is applied to the current collector with a coating device such as a bar coater, then dried to remove the solvent, and if necessary, obtained by pressing with a press. It is done.
  • a positive electrode for a lithium secondary battery is obtained by using a positive electrode active material (D2) for a lithium secondary battery as the active material (D), and a positive electrode active material for a lithium ion capacitor (D3) as the active material (D).
  • the negative electrode for lithium secondary batteries is obtained by using the negative electrode active material (D1) as the active material (D), and the negative electrode for lithium ion capacitors is obtained by doping lithium into the negative electrode for lithium secondary batteries. It is done.
  • Examples of the solvent include 1-methyl-2-pyrrolidone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, N, N-dimethylaminopropylamine, and tetrahydrofuran.
  • Examples of the current collector include copper, aluminum, titanium, stainless steel, nickel, baked carbon, conductive polymer, and conductive glass.
  • the electrolytic solution of the present invention contains an electrode protective film forming agent (B), an electrolyte (H) and a nonaqueous solvent (I), and is particularly useful as an electrolytic solution for lithium secondary batteries and lithium ion capacitors.
  • non-aqueous solvent (I) those used in ordinary electrolytic solutions can be used, for example, lactone compounds, cyclic or chain carbonates, chain carboxylates, cyclic or chain ethers, phosphoric acid. Esters, nitrile compounds, amide compounds, sulfones, sulfolanes, and the like and mixtures thereof can be used.
  • lactone compound examples include 5-membered rings (such as ⁇ -butyrolactone and ⁇ -valerolactone) and 6-membered lactone compounds (such as ⁇ -valerolactone).
  • Examples of the cyclic carbonate include propylene carbonate, ethylene carbonate and butylene carbonate.
  • Examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate.
  • chain carboxylic acid esters include methyl acetate, ethyl acetate, propyl acetate, and methyl propionate.
  • cyclic ether examples include tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,4-dioxane and the like.
  • chain ether examples include dimethoxymethane and 1,2-dimethoxyethane.
  • phosphate esters include trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, tripropyl phosphate, tributyl phosphate, tri (trifluoromethyl) phosphate, tri (trichloromethyl) phosphate, Tri (trifluoroethyl) phosphate, tri (triperfluoroethyl) phosphate, 2-ethoxy-1,3,2-dioxaphosphoran-2-one, 2-trifluoroethoxy-1,3,2- Examples include dioxaphospholan-2-one and 2-methoxyethoxy-1,3,2-dioxaphosphoran-2-one.
  • Nonaqueous solvent (I) may be used individually by 1 type, and may use 2 or more types together.
  • lactone compounds Of the non-aqueous solvents (I), lactone compounds, chain carbonates, chain carbonates and phosphates are preferred from the viewpoint of battery output and charge / discharge recycling characteristics, and more preferred are lactone compounds and chain carbonates.
  • Esters particularly preferred are lactone compounds, especially preferred are 5- or 6-membered lactone compounds, and most preferred are 5-membered lactone compounds.
  • the electrolytic solution of the present invention can further contain the Lewis base (F).
  • the storage stability of the compound (A) is improved.
  • Preferred contents or concentrations of the electrode protective film forming agent (B), the electrolyte (H), the non-aqueous solvent (I) and the Lewis base (F) in the electrolytic solution of the present invention are as follows.
  • the content of (B) is preferably 0.01 to 10% by weight, more preferably 0.05 to 1% by weight, based on the weight of the electrolyte, from the viewpoints of charge / discharge cycle characteristics, battery capacity and high storage characteristics. It is.
  • the content of (F) is preferably 0 to 10% by weight, more preferably 0.01 to 10% by weight, particularly preferably from the viewpoint of battery capacity, battery output and charge / discharge cycle characteristics. Is 0.05 to 1% by weight.
  • the concentration of the electrolyte (H) in the electrolytic solution is preferably 0.01 to 3 mol / L, more preferably 0.05 to 1 based on the capacity of the electrolytic solution from the viewpoint of battery output and charge / discharge cycle characteristics. 0.5 mol / L.
  • the content of the non-aqueous solvent (I) is preferably 70 to 99% by weight and more preferably 93 to 99% by weight based on the weight of the electrolytic solution from the viewpoint of battery output and charge / discharge cycle characteristics.
  • the electrolytic solution of the present invention may further contain additives such as an overcharge inhibitor, a dehydrating agent and a capacity stabilizer.
  • additives such as an overcharge inhibitor, a dehydrating agent and a capacity stabilizer.
  • the overcharge preventing agent include biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, aromatic compounds such as cyclohexylbenzene, t-butylbenzene and t-amylbenzene.
  • the amount of the overcharge inhibitor used is usually 0 to 5% by weight, preferably 0 to 3% by weight, based on the total weight of the electrolyte.
  • the dehydrating agent examples include zeolite, silica gel and calcium oxide.
  • the amount of the dehydrating agent used is usually 0 to 5% by weight, preferably 0 to 3% by weight, based on the total weight of the electrolytic solution.
  • the capacity stabilizer examples include fluoroethylene carbonate, succinic anhydride, 1-methyl-2-piperidone, heptane and fluorobenzene.
  • the amount of the capacity stabilizer used is usually 0 to 5% by weight, preferably 0 to 3% by weight, based on the total weight of the electrolytic solution.
  • the lithium secondary battery of the present invention seals the battery can by injecting the electrolyte into the battery can containing the positive electrode, the negative electrode and the separator, the electrode of the present invention (the positive electrode is a lithium secondary battery). Positive electrode), the electrolytic solution of the present invention is used as the electrolytic solution, or a combination thereof is used.
  • a separator in a lithium secondary battery As a separator in a lithium secondary battery, a microporous film made of polyethylene or polypropylene film, a multilayer film of porous polyethylene film and polypropylene, a nonwoven fabric made of polyester fiber, aramid fiber, glass fiber, etc., and silica on these surfaces, The thing to which ceramic fine particles, such as an alumina and a titania, were made to adhere is mentioned.
  • the battery can in the lithium secondary battery, metal materials such as stainless steel, iron, aluminum and nickel-plated steel can be used, but plastic materials can also be used depending on the battery application. Further, the battery can be formed into a cylindrical shape, a coin shape, a square shape, or any other shape depending on the application.
  • the lithium ion capacitor of the present invention can be obtained by replacing the positive electrode with a positive electrode for a lithium ion capacitor and replacing the battery can with a capacitor can in the basic configuration of the lithium secondary battery of the present invention.
  • Examples of the material and shape of the capacitor can include the same as those exemplified for the battery can.
  • reaction product was purified by an alumina column [150 mesh, Blockman 1, standard grade, manufactured by Sigma-Aldrich] using hexane as a solvent, and 1-hydroxymethyl-4- (propenyloxy) 9.0 parts (48.6 mmol parts) of methyl) cyclohexane were obtained (yield 71%).
  • reaction product was purified by an alumina column [150 mesh, Blockman 1, standard grade, manufactured by Sigma-Aldrich] using hexane as a solvent, and bis [ ⁇ 4- (propenyloxy 352 parts (893 mmol parts) of (methyl) cyclohexyl ⁇ methyl] carbonate (A-1) were obtained (yield 89%, ether group concentration: 5.4 meq / g).
  • reaction was carried out for 5 hours while distilling off the ethanol produced. After removing residual ethanol under reduced pressure (2.5 kPa), the reaction product was purified by an alumina column [150 mesh, Blockman 1, standard grade, manufactured by Sigma-Aldrich] using hexane as a solvent, and 109 parts of compound (A-3) was obtained. (0.21 mol part) was obtained (yield 21%, ether group concentration: 3.8 meq / g). The value of n calculated by 1H-NMR measurement of the compound (A-3) was 2.4.
  • the temperature was raised to 65 ° C. over 2 hours and further stirred for 4 hours to carry out an etherification reaction and a rearrangement reaction. After allowing to cool, 200 parts of water was added and the aqueous layer was separated. Further, the organic layer was washed with 200 parts of water. After removing toluene at 80 ° C.
  • reaction product was purified by an alumina column [150 mesh, Blockman 1, standard grade, Sigma-Aldrich] using hexane as a solvent, and 2, 2, 3, 3, 4 , 4-hexafluoro-1,5-pentanediol di (1-propenyl) ether (A-4) (14.2 parts, 48.6 mmol) was obtained (yield 71%, ether group concentration: 6.8 mm). Equivalent / g).
  • the organic layer was washed with 200 parts of saturated brine. After removing THF by reduced pressure (2.5 kPa) at 30 ° C., the reaction product was purified by an alumina column using hexane as a solvent, and tris [ ⁇ 4- (propenyloxymethyl) cyclohexyl ⁇ methyl] phosphate (A-9) 25. 3 parts (44.3 mmol) were obtained (yield 65%, ether group concentration: 5.2 meq / g).
  • a negative electrode to which an electrode protective film forming agent (B) and a Lewis base (F) were added based on the formulations shown in Tables 1 and 2 was produced by the following method. 92.5 parts of graphite powder having an average particle size of about 8 to 12 ⁇ m, 7.5 parts of polyvinylidene fluoride, 200 parts of 1-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] and the parts shown in Tables 1 and 2 (B) and (F) were sufficiently mixed in a mortar to obtain a slurry. The obtained slurry was applied to one side of a copper foil having a thickness of 20 ⁇ m, dried at 100 ° C. for 15 minutes to evaporate the solvent, punched to 16.15 mm ⁇ , and made 30 ⁇ m in thickness with a press machine. To 18 and Comparative Examples 1 to 5 were prepared.
  • a positive electrode to which an electrode protective film forming agent (B) and a Lewis base (F) were added was produced by the following method.
  • Activated carbon powder 90.0 parts, Kechen Black [Sigma-Aldrich Co.] 5.0 parts, Polyvinylidene fluoride [Sigma-Aldrich Co.] 5.0 parts, and (B) and ( F) was thoroughly mixed in a mortar, 70.0 parts of 1-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] was added, and further mixed well in a mortar to obtain a slurry.
  • the obtained slurry was applied to one side of an aluminum electrolytic foil having a thickness of 20 ⁇ m using a wire bar in the atmosphere, dried at 100 ° C. for 15 minutes, and further under reduced pressure (10 mmHg) at 80 ° C. for 5 minutes. It was dried and punched out to 15.95 mm ⁇ to produce positive electrodes for lithium ion capacitors of Examples 19 to 36 and Comparative Examples 6 to 10.
  • a negative electrode to which the electrode protective film forming agents (B) and (F) were added based on the formulations shown in Tables 3 and 4 was produced by the following method. 92.5 parts of graphite powder having an average particle size of about 8 to 12 ⁇ m, 7.5 parts of polyvinylidene fluoride, 200 parts of 1-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.] and the number of parts shown in Tables 3 and 4 (B) and (F) were sufficiently mixed in a mortar to obtain a slurry. The obtained slurry was applied to one side of a 20 ⁇ m thick copper foil, dried at 100 ° C.
  • a positive electrode for a lithium ion battery of Comparative Example 11 was produced in the same manner as in Example 1 except that 1.5 parts of methylsulfone was added instead of the electrode protective film forming agent (B) and the Lewis base (F).
  • a negative electrode for a lithium ion battery of Comparative Example 11 was produced in the same manner as in Example 1 except that the electrode protective film forming agent (B) and the Lewis base (F) were not added.
  • ⁇ Comparative Example 12> A positive electrode for a lithium ion battery of Comparative Example 12 in the same manner as in Example 1 except that 1.5 parts of 1,3-propane sultone was added instead of the electrode protective film forming agent (B) and Lewis base (F). Was made.
  • a negative electrode for a lithium ion battery of Comparative Example 12 was produced in the same manner as in Example 1 except that the electrode protective film forming agent (B) and the Lewis base (F) were not added.
  • a positive electrode for a lithium ion capacitor of Comparative Example 13 was produced in the same manner as in Example 18, except that 1.5 parts of dimethyl sulfone was added instead of the electrode protective film forming agent (B) and the Lewis base (F).
  • a negative electrode for a lithium ion capacitor of Comparative Example 13 was produced in the same manner as in Example 13, except that the electrode protective film forming agent (B) and the Lewis base (F) were not added.
  • ⁇ Comparative example 14> A positive electrode for a lithium ion capacitor of Comparative Example 14 in the same manner as in Example 18 except that 1.5 parts of 1,3-propane sultone was added instead of the electrode protective film forming agent (B) and Lewis base (F). Was made.
  • a negative electrode for a lithium ion capacitor of Comparative Example 14 was produced in the same manner as in Example 18 except that the electrode protective film forming agent (E) and the Lewis base (F) were not added.
  • the positive and negative electrodes of Examples 1 to 18 and Comparative Examples 1 to 5, 11 and 12 are arranged on both ends of a 2032 type coin cell so that the coated surfaces face each other.
  • a separator polypropylene nonwoven fabric
  • the mixture was sealed in a cell in which an electrolytic solution in which LiPF 6 was dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate (volume ratio 1: 1) at a rate of 1 mol / L was prepared, and a high voltage charge / discharge cycle was performed by the following method.
  • Tables 5 and 6 show the results of evaluation of characteristics and high-temperature storage characteristics.
  • Examples 37 to 50 and Comparative Examples 15 to 22 [Creation of electrolyte] Compound (A), (F), (C) and non-aqueous solvent (I) are blended in the weight ratios shown in Tables 7 and 8, and LiPF 6 as an electrolyte is added thereto so as to have a concentration of 1 mol / L.
  • the electrolytes of Examples 37 to 50 and Comparative Examples 15 to 19 were prepared by dissolution.
  • the negative electrode obtained as described above was doped with lithium as follows.
  • the negative electrode and lithium metal foil were sandwiched between separators (polypropylene nonwoven fabric) and set in a beaker cell, and a predetermined amount of lithium ions was occluded in the negative electrode over about 10 hours.
  • the doping amount of lithium was about 75% of the negative electrode theoretical capacity.
  • Capacitor cell assembly A separator (polypropylene non-woven fabric) is inserted between the positive electrode and the negative electrode obtained as described above, and impregnated with an electrolytic solution. A lithium ion capacitor was produced by sealing in a case.
  • the electrode and electrolyte using the electrode protective film forming agent (B) of the present invention are excellent in cycle characteristics under high voltage and high-temperature storage stability, the electrode for lithium secondary batteries or lithium ion capacitors is particularly used. In addition, it is useful as an electrolyte solution and suitable for an electric vehicle.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention concerne un agent de formation d'un film de protection d'électrode présentant une tension élevée et une grande capacité et pouvant augmenter les propriétés de stockage à haute température et les propriétés de cycle de charge/de décharge d'une batterie secondaire au lithium ou d'un condensateur au lithium-ion. L'invention concerne également une électrode et une solution d'électrolyte comprenant le film de protection d'électrode. La présente invention concerne un agent (B) de formation d'un film de protection d'électrode, ledit agent contenant un composé (A) présentant un groupe alcényle éther (X) représenté par la formule générale (1) et un groupe (L) présentant au moins un type d'atome choisi parmi l'oxygène, le fluore, le silicium, le phosphore et le soufre, et le composé présente une concentration de groupe éther de 0,1-9,0 mEq/g.
PCT/JP2012/001019 2011-02-18 2012-02-16 Agent de formation d'un film de protection d'électrode Ceased WO2012111335A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012557845A JPWO2012111335A1 (ja) 2011-02-18 2012-02-16 電極保護膜形成剤

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-033460 2011-02-18
JP2011033460 2011-02-18
JP2011-082613 2011-04-04
JP2011082613 2011-04-04

Publications (1)

Publication Number Publication Date
WO2012111335A1 true WO2012111335A1 (fr) 2012-08-23

Family

ID=46672279

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/001019 Ceased WO2012111335A1 (fr) 2011-02-18 2012-02-16 Agent de formation d'un film de protection d'électrode

Country Status (2)

Country Link
JP (1) JPWO2012111335A1 (fr)
WO (1) WO2012111335A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014073378A1 (fr) * 2012-11-07 2014-05-15 三洋化成工業株式会社 Agent formateur de pellicule protectrice d'électrode, électrode, électrolyte, accumulateur au lithium, condensateur lithium-ion et procédé de production de pellicule protectrice d'électrode
WO2015037486A1 (fr) * 2013-09-12 2015-03-19 新神戸電機株式会社 Solution d'électrolyte pour condensateurs lithium-ion et condensateur lithium-ion
CN113809401A (zh) * 2021-10-26 2021-12-17 远景动力技术(江苏)有限公司 锂离子电池非水电解液及其应用
JP2022543538A (ja) * 2019-07-12 2022-10-13 ハネウェル・インターナショナル・インコーポレーテッド リチウムイオンセル用の電解質溶液
JP2024152720A (ja) * 2023-04-13 2024-10-25 星歐光學股▲ふん▼有限公司 ポリマー、電解質及び電池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004363031A (ja) * 2003-06-06 2004-12-24 Japan Storage Battery Co Ltd 非水電解質二次電池
JP2010086954A (ja) * 2008-09-03 2010-04-15 Sanyo Chem Ind Ltd 電解液用添加剤
JP2010165667A (ja) * 2008-12-18 2010-07-29 Sanyo Chem Ind Ltd 電解液用添加剤
WO2011096450A1 (fr) * 2010-02-03 2011-08-11 宇部興産株式会社 Solution électrolytique non aqueuse, élément électrochimique utilisant celle-ci, et composé alcynyle utilisé pour celle-ci
WO2011129053A1 (fr) * 2010-04-12 2011-10-20 三洋化成工業株式会社 Agent de formation d'un film protecteur d'électrode et solution électrolytique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004363031A (ja) * 2003-06-06 2004-12-24 Japan Storage Battery Co Ltd 非水電解質二次電池
JP2010086954A (ja) * 2008-09-03 2010-04-15 Sanyo Chem Ind Ltd 電解液用添加剤
JP2010165667A (ja) * 2008-12-18 2010-07-29 Sanyo Chem Ind Ltd 電解液用添加剤
WO2011096450A1 (fr) * 2010-02-03 2011-08-11 宇部興産株式会社 Solution électrolytique non aqueuse, élément électrochimique utilisant celle-ci, et composé alcynyle utilisé pour celle-ci
WO2011129053A1 (fr) * 2010-04-12 2011-10-20 三洋化成工業株式会社 Agent de formation d'un film protecteur d'électrode et solution électrolytique

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014073378A1 (fr) * 2012-11-07 2014-05-15 三洋化成工業株式会社 Agent formateur de pellicule protectrice d'électrode, électrode, électrolyte, accumulateur au lithium, condensateur lithium-ion et procédé de production de pellicule protectrice d'électrode
KR20150068462A (ko) * 2012-11-07 2015-06-19 산요가세이고교 가부시키가이샤 전극 보호막 형성제, 전극, 전해액, 리튬 2 차 전지, 리튬 이온 캐패시터, 및, 전극 보호막의 제조 방법
JPWO2014073378A1 (ja) * 2012-11-07 2016-09-08 三洋化成工業株式会社 電極保護膜形成剤、電極、電解液、リチウム二次電池、リチウムイオンキャパシタ、および、電極保護膜の製造方法
CN104737340B (zh) * 2012-11-07 2016-12-14 三洋化成工业株式会社 电极保护膜形成剂、电极、电解液、锂二次电池、锂离子电容器和电极保护膜的制造方法
KR101692172B1 (ko) 2012-11-07 2017-01-02 산요가세이고교 가부시키가이샤 전극 보호막 형성제, 전극, 전해액, 리튬 2 차 전지, 리튬 이온 캐패시터, 및, 전극 보호막의 제조 방법
WO2015037486A1 (fr) * 2013-09-12 2015-03-19 新神戸電機株式会社 Solution d'électrolyte pour condensateurs lithium-ion et condensateur lithium-ion
JP2022543538A (ja) * 2019-07-12 2022-10-13 ハネウェル・インターナショナル・インコーポレーテッド リチウムイオンセル用の電解質溶液
JP7343684B2 (ja) 2019-07-12 2023-09-12 ハネウェル・インターナショナル・インコーポレーテッド リチウムイオンセル用の電解質溶液
CN113809401A (zh) * 2021-10-26 2021-12-17 远景动力技术(江苏)有限公司 锂离子电池非水电解液及其应用
CN113809401B (zh) * 2021-10-26 2024-01-30 远景动力技术(江苏)有限公司 锂离子电池非水电解液及其应用
JP2024152720A (ja) * 2023-04-13 2024-10-25 星歐光學股▲ふん▼有限公司 ポリマー、電解質及び電池

Also Published As

Publication number Publication date
JPWO2012111335A1 (ja) 2014-07-03

Similar Documents

Publication Publication Date Title
JP6842557B2 (ja) 硫酸ホウ素リチウム化合物、リチウム二次電池用添加剤、電池用非水電解液、及びリチウム二次電池
CN105103361B (zh) 电池用非水电解液、化合物、高分子电解质和锂二次电池
KR101055144B1 (ko) 아미드 화합물을 포함하는 전해질 및 이를 구비한 전기화학소자
TWI518975B (zh) 電極保護膜形成劑、電極、電解液、鋰二次電池、鋰離子電容器、電雙層電容器以及電極保護膜的製造方法
WO2013002186A1 (fr) Agent de formation d'un film de protection d'électrode, électrode, solution d'électrolyte, cellule secondaire au lithium, condensateur lithium-ion et procédé de formation d'un film de protection d'électrode
WO2021166771A1 (fr) Solution électrolytique d'une cellule secondaire contenant un ester d'acide phosphorique cyclique
WO2014073378A1 (fr) Agent formateur de pellicule protectrice d'électrode, électrode, électrolyte, accumulateur au lithium, condensateur lithium-ion et procédé de production de pellicule protectrice d'électrode
JPWO2011129053A1 (ja) 電極保護膜形成剤及び電解液
CN104072533B (zh) 一类含低聚氧化乙烯单元的硅腈类化合物及其制备方法、在锂电池中的应用
JP2015225689A (ja) 電池用添加剤
CN100483840C (zh) 有机电解液及采用它的锂电池
TW202122378A (zh) 組成物
WO2012111335A1 (fr) Agent de formation d'un film de protection d'électrode
CN114300747A (zh) 一种电解液及含该电解液的锂离子电池
JP6284772B2 (ja) 電極保護膜形成剤
KR20090111327A (ko) 비수전해액 및 비수전해액 2차 전지
JP2013026180A (ja) 電極保護膜形成剤
JP2014137843A (ja) 電極保護膜形成剤
JP6957179B2 (ja) 電池用非水電解液及びリチウム二次電池
JP7120507B2 (ja) ホウ酸リチウム組成物、リチウム二次電池用添加剤、ホウ酸リチウム組成物の製造方法、リチウム二次電池用非水電解液、リチウム二次電池
JP6326255B2 (ja) 電池用添加剤
JP2013012442A (ja) 電極保護膜形成剤
WO2013031045A1 (fr) Additif pour électrode, et électrode
JP2012256515A (ja) 電極保護膜形成剤
JP2015207392A (ja) 電池用添加剤

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12747655

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012557845

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12747655

Country of ref document: EP

Kind code of ref document: A1