WO2011077939A1 - Batterie secondaire comprenant un fluide ionique - Google Patents

Batterie secondaire comprenant un fluide ionique Download PDF

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Publication number
WO2011077939A1
WO2011077939A1 PCT/JP2010/071877 JP2010071877W WO2011077939A1 WO 2011077939 A1 WO2011077939 A1 WO 2011077939A1 JP 2010071877 W JP2010071877 W JP 2010071877W WO 2011077939 A1 WO2011077939 A1 WO 2011077939A1
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group
anion
electrolyte
secondary battery
current collector
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PCT/JP2010/071877
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English (en)
Japanese (ja)
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晃純 木村
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コニカミノルタホールディングス株式会社
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Priority to JP2011547449A priority Critical patent/JPWO2011077939A1/ja
Publication of WO2011077939A1 publication Critical patent/WO2011077939A1/fr

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    • 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • 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

Definitions

  • the present invention relates to a secondary battery containing an ionic liquid.
  • Non-aqueous electrolyte secondary batteries particularly lithium ion secondary batteries
  • have high voltage and high energy density and have recently been widely used in applications such as portable electronic devices and personal computers.
  • it is also expected to be adapted for large-scale use such as stationary applications at home and automobiles, but it is important to further improve cycle characteristics, particularly to suppress deterioration of cycle characteristics in a high-temperature environment. It has become an issue.
  • a secondary battery containing 0.1 to 10% by volume of vinylene carbonate in an electrolyte is disclosed (for example, see Patent Document 1).
  • an SEI film can be formed on the graphite intercalation compound and the cycle characteristics can be improved.
  • an SEI film is formed on an electrode using a chemical species other than vinylene carbonate for the purpose of improving cycle characteristics.
  • a secondary battery using an electrolyte containing a cyclic sulfonate ester is disclosed.
  • an SEI film is formed on the surface of the positive electrode by sulfur atoms, thereby improving charge / discharge characteristics and storage characteristics (see, for example, Patent Documents 2 and 3).
  • the electrolyte for non-aqueous electrolyte secondary batteries using flammable vinylene carbonate does not have sufficient cycle characteristics, and further improvements are desired.
  • the electrolyte for non-aqueous electrolyte secondary batteries using vinylene carbonate may cause deformation or ignition of the secondary battery cells during abnormal heating of the secondary battery, and further improvement is desired from the viewpoint of safety. It is rare. Since there is no risk of ignition and safety is high, it may be possible to add a little vinylene carbonate to the electrolyte using a flame-retardant ionic liquid, but the SEI film with vinylene carbonate is an electrolyte cycle using an ionic liquid. The characteristics could not be improved greatly.
  • the secondary battery containing a cyclic sulfonate ester in the electrolyte has not enough SEI film formed by the cyclic sulfonate ester, and there is still room for improvement in cycle characteristics.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a secondary battery using an ionic liquid having high safety and cycle characteristics.
  • a further object of the present invention is to provide a secondary battery having high safety and cycle characteristics.
  • the configuration of the present invention is as follows.
  • the electrolyte has one type of supporting electrolyte salt and two types of ionic liquids, and the supporting electrolyte salt and the two types of ionic liquids
  • Each anion is different, and at least one of the anions is an anion that forms a passive film on the current collector, and an anion that forms a passive film on the current collector;
  • at least one is an anion that forms an SEI film on the carbon material on the negative electrode.
  • R represents an alkyl group, cycloalkyl group, aryl group, hydroxyl group, carboxyl group, nitro group, trifluoromethyl group, amide group, carbamoyl group, ester group, carbonyloxy Group, cyano group, halogen atom, alkoxy group, aryloxy group, sulfonyl group, alkylthio group, arylthio group, sulfonamido group, sulfamoyl group, amino group, alkylamino group and arylamino group.
  • X represents an integer from 1 to 5
  • Y represents an integer from 1 to 3.
  • the present invention has found that in an electrolyte containing an ionic liquid, the decomposition of the ionic liquid on the current collector as well as the decomposition of the ionic liquid on the current collector is a cause of poor cycle performance.
  • the anion forming the passive film it was possible to impart high cycle characteristics to the electrolyte having the ionic liquid.
  • SEI film The SEI film (SEI: solid electrolyte interface) in the present invention will be described. Means have been proposed for forming a SEI film (solid electrolyte interface) on the surface of the carbon material on the negative electrode so that the carbon material on the negative electrode does not react directly with an organic solvent. (Hiroyoshi Nakamura et al. “Decompression suppression of electrolyte for lithium battery using electrolyte containing acetate”, Electrochemistry and Industrial Physical Chemistry, Vol. 73, No. 6. pp 429-434 (June 2005)) The film needs to be a film that can transmit lithium ions and has low electron conductivity.
  • the passive film in the present invention will be described. It is a dense and strong film formed on a current collector metal and generated by an anion containing fluorine. This passive film suppresses corrosion of the current collector and decomposition of the electrolyte, which are causes of deterioration of battery performance.
  • the electrolyte of the present invention contains at least one lithium salt and two ionic liquids, and as a combination of anions, (1) When the two anions of the ionic liquid are an anion that can form a passive film on the current collector and an anion that can form an SEI film on the active material (2)
  • the anion of the supporting electrolyte salt is the current collector When an anion capable of forming a passive film on the body and one anion of the ionic liquid is an anion capable of forming an SEI film on the active material (3)
  • the anion of the supporting electrolyte salt is an SEI film on the active material
  • the remaining one anion may be an anion that can form a passive film on the current collector, an anion that can form an SEI film on the active material, or an anion that does not form a passive film.
  • an anion that does not form a dynamic membrane and an SEI coating it can be preferably used because it can be an electrolyte having high decomposition stability and high cycleability.
  • the blending amount of the supporting electrolyte salt in the electrolyte having an anion capable of forming a passive film on the current collector or an anion capable of forming a SEI film on the active material is preferably 5 to 40% by mass, particularly The content is preferably 10 to 30% by mass.
  • the total amount of the supporting electrolyte salt in the electrolyte of the ionic liquid having an anion capable of forming a passive film on the current collector or an anion capable of forming a SEI film on the active material is 10% by mass to 60% by mass. In particular, 15% by mass to 30% by mass is preferable.
  • the secondary battery of the present invention includes a positive electrode, a negative electrode, and an electrolyte, and a separator as necessary. If the electrolyte is sufficiently elastic and there is no fear that the electrodes will contact each other, such as when a solid electrolyte is used, the separator can be omitted.
  • the electrolyte according to the present invention contains at least one supporting electrolyte salt having different anions and two ionic liquids, an anion that can form a passive film on the current collector, and an anion that forms the passive film. Contains an anion capable of forming an SEI film on an active material made of different carbon materials.
  • the electrolyte according to the present invention contains at least one supporting electrolyte salt having different anions and two ionic liquids, and the anion can form a passive film on the current collector, and carbon on the negative electrode.
  • the material contains an anion capable of forming an SEI film.
  • an anion that forms a passive film, an anion that forms a SEI film, or both anions can be present in the electrolyte as an ionic liquid.
  • the amount of anion introduced is not limited because there is no salt precipitation at a low temperature as expected when a solid salt such as a Li salt is contained.
  • an anion capable of forming a passive film, and an anion capable of forming a SEI film in the carbon material on the negative electrode can be contained in the electrolyte in an arbitrary amount.
  • an organic solvent, inorganic fine particles, a polymer, and a polymerizable compound can be appropriately contained depending on the physical properties required for the electrolyte.
  • a separator is unnecessary, which is preferable.
  • the electrolyte according to the present invention is characterized by containing an anion capable of forming a passive film on the current collector and an anion capable of forming an SEI film on the carbon material on the negative electrode.
  • an anion capable of forming a passive film on the current collector and an anion capable of forming an SEI film on the carbon material on the negative electrode.
  • the present invention by forming an SEI film on each of the current collector and the active material, it is possible to prevent the electrolyte from being electrolyzed to the minimum necessary and to prevent the deterioration of the electrolyte, thereby improving the cycle characteristics of the secondary battery.
  • the present invention has been reached.
  • Tetrafluoroborate, hexafluorophosphate, and tris (pentafluoroethyl) trifluorophosphate can be used as the anion that can form a passive film on the current collector.
  • the anion mentioned by (1) and General formula (2) can be used preferably.
  • R represents an alkyl group (methyl, ethyl, i-propyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), a cycloalkyl group (cyclopropyl, cyclohexyl).
  • aryl group phenyl, p-tetradecanyloxyphenyl, o-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.
  • hydroxyl group carboxyl group, nitro group, trifluoromethyl group, amide group (acetamide, Benzamide etc.), carbamoyl group (methylcarbamoyl, butylcarbamoyl, phenylcarbamoyl etc.), ester group (ethyloxycarbonyl, i-propyloxycarbonyl, phenyloxycarbonyl etc.), carbonyloxy group (methylcarbonyloxy) , Propylcarbonyloxy, phenylcarbonyloxy, etc.), cyano group, halogen atom (chlorine, bromine, iodine, fluorine), alkoxy group (methoxy, ethoxy, butoxy, etc.), aryloxy group (
  • bisfluorosulfonylamide or fluorosulfonyl can be used as an anion that can form a SEI film on the active material.
  • the anion capable of forming a passive film on the current collector or the anion capable of forming an SEI film on the active material is not limited to a cation when it is an ionic liquid, but imidazolium (eg, 1-alkyl-3 -Methylimidazolium, 1-allyl-3-alkylimidazolium, 1-alkyl-2,3-dimethylimidazolium, etc.), pyridinium, ammonium, piperidinium, pyrrolidinium, pyrazolium, phosphonium, guanidinium can be used.
  • imidazolium eg, 1-alkyl-3 -Methylimidazolium, 1-allyl-3-alkylimidazolium, 1-alkyl-2,3-dimethylimidazolium, etc.
  • pyridinium ammonium
  • piperidinium pyrrolidinium
  • pyrazolium phosphonium
  • Preferred cations include tetramethylammonium, ethyltrimethylammonium, n-propyltrimethylammonium, diethyldimethylammonium, di-n-propyldimethylammonium, triethylmethylammonium, n-butyldiethylmethylammonium, N, N-diethyl-N-methyl.
  • nonane dimethylimidazole, propylmethylimidazole, butyl Methylimidazole, N, N-dimethylpyrrolidinium, N-methyl-N-ethylpyrrolidinium, N-methyl-N-butylpyrrolidinium, N, -Dimethyl-piperidinium, N-methyl-N-ethyl-piperidinium, N-methyl-N-propyl-piperidinium, N-methyl-N-butyl-piperidinium, tetraethylphosphonium and 5-phosphonia spiro [4.4] nonane Can be preferably used.
  • the supporting electrolyte salt according to the electrolyte of the present invention is a salt that gives ions in the electrolyte composition for secondary batteries, and known supporting electrolyte salts used for batteries can be used.
  • a lithium salt can be preferably used as the supporting electrolyte salt.
  • the anion that does not form a passive film and SEI film includes SCN ⁇ , ClO 4 ⁇ , SbF 6 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (CF 3 CF 2 SO 2 ). 2 N ⁇ , (CF 3 SO 2 ) 3 C ⁇ , CF 3 SO 3 — and the like can be mentioned.
  • An anion capable of forming a passive film on the current collector and an SEI film can be formed on the active material. Any anion is preferably used.
  • the ionic liquid according to the electrolyte of the present invention is not particularly limited as long as it is a salt that is liquid at room temperature, and preferably has a melting point of 80 ° C. or lower, more preferably 60 ° C. or lower, more preferably 30 ° C. or lower. .
  • alkyl ammonium salts pyrrolidinium salts, piperidinium salts, imidazolium salts, pyridinium salts, sulfonium salts, phosphonium salts and the like can be used.
  • An imidazolium salt represented by the following general formula (3) can also be preferably used.
  • R 1 and R 3 represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent
  • R 2 , R 4 and R 5 represent a hydroxyl group, an amino group, respectively.
  • X represents a monovalent anion
  • Either an anion capable of forming a passive film on the current collector and an anion capable of forming a SEI film on the active material are preferably used, but an anion that does not form a passive film and SEI film may be used.
  • the compound represented by the general formula (3) include, for example, ethylmethylimidazole-bisfluoromethylsulfonylamide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium-bisfluorosulfonyl Amide, ethylmethylimidazole-bistrifluorosulfonylamide, N-methyl-N-propylpyrrolidinium-bistrifluorosulfonylamide, 1-isopropyl-2,3-dimethylimidazolium bistrifluoromethanesulfonyl salt, 1-ethyl-2, 3-dimethylimidazolium bistrifluoromethanesulfonyl, 1-butyl-2,3-dimethylimidazolium bistrifluoromethanesulfonyl salt, 1-hexyl-2,3-dimethylimidazolium bistrifluoromethanesulfonyl
  • an ionic liquid that does not form a passive film or SEI film having a viscosity of 100 mPa ⁇ S or less.
  • an ionic liquid that does not contain an organic solvent, and a secondary battery with higher safety can be manufactured.
  • an electrolyte that does not contain an organic solvent is advantageous not only from the viewpoint of safety but also from the viewpoint of improving cycle characteristics because it does not have a volatile component in the electrolyte and can suppress an increase in internal pressure even at high temperatures.
  • ethylmethylimidazole-bisfluoromethylsulfonylamide N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium-bisfluorosulfonylamide, ethylmethylimidazole- Examples include, but are not limited to, bistrifluorosulfonylamide, N-methyl-N-propylpyrrolidinium-bistrifluorosulfonylamide, or 1-ethyl-2,3-dimethylimidazolium bisfluorosulfonyl salt.
  • the content of the ionic liquid in the electrolyte is preferably 10% by mass to 90% by mass, and particularly preferably 40% by mass to 80% by mass.
  • the electrolyte of the present invention contains a lithium salt and an ionic liquid, and an anion that can form a passive film. Therefore, an organic solvent containing vinylene carbonate that may impair flame retardancy is not necessary. However, it can also be contained within a range that does not hinder the effects of the present invention for the purpose of improving the conductivity of the electrolyte or reducing the viscosity.
  • organic solvent applicable to the electrolyte of the present invention examples include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2-di Carbonates such as (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2- Ethers such as methyltetrahydrofuran; Esters such as methyl formate, methyl acetate and ⁇ -butyrolactone; Nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide, N, N-dimethylacetate Amides such as amide; Carbamates such as 3-methyl-2-oxazolid
  • the electrolyte of the present invention can further contain inorganic fine particles, a polymerizable compound, and a polymer. It is also possible to obtain a solid electrolyte by containing a small amount or no use of the organic solvent and containing inorganic fine particles and a polymerizable compound or inorganic fine particles and a polymer in the electrolyte.
  • Examples of the inorganic fine particles related to the electrolyte of the present invention include iron oxide, zirconium oxide, niobium oxide, tantalum oxide, antimony oxide, clay, tin oxide, tungsten oxide, titanium oxide, aluminum phosphate, silicon oxide, zinc oxide, aluminum oxide, These composite oxides can be preferably used.
  • the average particle diameter of the inorganic fine particles is preferably 0.05 to 50 ⁇ m, more preferably 0.1 to 20 ⁇ m from the viewpoint of safety and voltage characteristics.
  • the average particle diameter is a volume average value of the diameter (sphere converted particle diameter) when each particle is converted into a sphere having the same volume, and this value can be evaluated from an electron micrograph. That is, by taking a transmission electron micrograph of the battery composition or particle powder, measuring 200 or more particles in a certain visual field range, obtaining a spherical equivalent particle diameter of each particle, and obtaining an average value thereof. Value.
  • the content of the inorganic fine particles is not particularly limited, but is preferably 0% by mass or more and 100% by mass or less with respect to 100% by mass of the ionic liquid. More preferably, it is 10 mass% or more and 70 mass% or less.
  • Polymerizable compound As the polymerizable compound according to the electrolyte of the present invention, a polymerizable monomer that can be polymerized by polymerization or a polymerizable oligomer can be used.
  • polymerizable monomer examples include radically polymerizable monomers and cationically polymerizable monomers. Although not particularly limited, ethylenically unsaturated monomers shown below are preferably used.
  • ethylenically unsaturated monomers examples include 2-vinylpyrrolidone, acryloylmorpholine, 2-hydroxybutyl vinyl ether, ethylethylene glycol mono (meth) acrylate, propylethylene glycol mono (meth) acrylate, and phenylethylene glycol mono (meth) acrylate.
  • Monofunctional monomer ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxa Modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, Bifunctional monomers such as ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth
  • Trifunctional or higher monomer polyethylene glycol mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate , Poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-teto Ramethylene glycol) mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol-polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate And stearoxy polyethylene glycol mono (meth) acrylate.
  • methoxypolyethylene glycol mono (meth) acrylate is preferably used.
  • polymerizable oligomer examples include epoxy (meth) acrylate, polyester (meth) acrylate, and urethane (meth) acrylate compounds, and urethane (meth) acrylate compounds are preferably used. These polymerizable monomers and polymerizable oligomers can be used in combination.
  • Examples of the method for polymerizing the above monomers include methods using heat, X-rays, ultraviolet rays, visible rays, infrared rays, microwaves, and the like.
  • a polymerization initiator that reacts with ultraviolet rays can be blended in the solid electrolyte composition in order to effectively advance the reaction.
  • Examples of the ultraviolet polymerization initiator include benzoin, benzyl, acetophenone, benzophenone, Michler ketone, biacetyl, benzoyl peroxide and the like. These initiators can be used alone or in combination.
  • thermal polymerization initiator In the case of polymerization by heat, infrared rays, or microwaves, a thermal polymerization initiator can be used.
  • thermal polymerization initiators 1,1-di (tertiarybutylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis- [4,4-di (tertiarybutylperoxycyclohexyl) propane ], 1,1-di (tertiarybutylperoxy) -cyclohexane, tertiarybutylperoxy-3,5,5-trimethylhexanonate, tertiarybutylperoxy-2-ethylhexanoate, benzoyl peroxide And dibenzoyl peroxide.
  • These initiators can be used alone or in combination.
  • the electrolyte according to the present invention can contain a polymer.
  • a battery that can withstand repeated charge and discharge over a long period of time can be stably produced by using a solid electrolyte to which the above-described inorganic fine particles, polymerizable compound and polymer are added.
  • the polymer in the present invention preferably has a polymerization unit (monomer) number average polymerization degree of 1000 or more.
  • polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, poly (meth) acrylate alkyl, Poly (meth) acrylate aryl, polyfluorene, polyamide, polyimide, polyester, polycarbonate, polyurethane and the like are preferably used.
  • alkyl poly (meth) acrylate is preferably used.
  • the blending amount of the above-described polymerizable compound and polymer in the electrolyte is preferably 0 to 40% by mass.
  • it is preferably contained in an amount of 10 to 30% by mass.
  • the electrode according to the secondary battery of the present invention includes a positive electrode in which a positive electrode active material is provided on a current collector, and a negative electrode in which a negative electrode active material is provided on a current collector.
  • Positive electrode active material As the positive electrode active material according to the secondary battery of the present invention, a mixture of an inorganic active material, an organic active material, or both, and an electrode mixture can be used.
  • the positive electrode active material preferably contains at least an inorganic active material because the energy density of the secondary battery can be increased.
  • x is preferably in the range of 0-1.
  • fluorine-based compounds such as FeF 3 , Li 3 FeF 6 , and Li 2 TiF 6
  • metal sulfides such as Li 2 FeS 2 , TiS 2 , MoS 2 , and FeS, and composite oxides of these compounds and lithium can be given.
  • metal oxides and metal phosphorous oxides are preferable, LiFePO 4 , LiCoPO 4 , LiMnPO 4 , Li 2 MPO 4 F, LiMn 0.875 Fe 0.125 PO 4 are more preferable, and LiFePO 4 is most preferable. .
  • organic active material examples include conductive polymers such as polyacetylene, polyaniline, polypyrrole, polythiophene, and polyparaphenylene, organic disulfide compounds, organic sulfur compounds DMcT (2,5-dimercapto-1,3,4-thiadiazole). ), Benzoquinone compound PDBM (poly 2,5-dihydroxy-1,4-benzoquinone-3,6-methylene), carbon disulfide, sulfur-based positive electrode materials such as active sulfur, organic radical compounds, and the like.
  • conductive polymers such as polyacetylene, polyaniline, polypyrrole, polythiophene, and polyparaphenylene
  • organic disulfide compounds organic sulfur compounds DMcT (2,5-dimercapto-1,3,4-thiadiazole).
  • DMcT organic sulfur compounds DMcT (2,5-dimercapto-1,3,4-thiadiazole).
  • Benzoquinone compound PDBM poly 2,5-dihydroxy
  • the surface of the positive electrode active material is coated with an inorganic oxide from the viewpoint of extending the life of the battery.
  • a method of coating the surface of the positive electrode active material is preferable, and examples of the coating method include a method of coating using a surface modifying apparatus such as a hybridizer.
  • inorganic oxides include oxides of group 2 to 16 elements such as magnesium oxide, silicon oxide, alumina, zirconia, and titanium oxide, barium titanate, calcium titanate, lead titanate, ⁇ -LiAlO 2 , LiTiO 3.
  • silicon oxide is preferable.
  • Niobium electrode active material As the negative electrode active material according to the secondary battery of the present invention, a material obtained by applying a mixture of a carbon material and an electrode mixture onto a current collector and drying can be used.
  • the negative electrode active material that has been applied and dried may be formed by pressing.
  • Examples of carbon materials include graphite materials such as various natural graphites, synthetic graphites, and expanded graphites that have been appropriately pulverized, mesocarbon microbeads that have been carbonized, mesophase pitch carbon fibers, and vapor grown carbon. Carbon materials such as fibers, pyrolytic carbon, petroleum coke, pitch coke, and needle coke, and synthetic graphite materials obtained by subjecting these carbon materials to graphitization, or mixtures thereof.
  • the electrode mixture according to the secondary battery of the present invention contains a conductive agent and a binder.
  • a conductive agent As other materials, fillers, lithium salts, aprotic organic solvents and the like may be added.
  • the conductive agent is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in the configured secondary battery.
  • Conductive materials include carbon materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, and conductive materials such as metal powders such as copper, nickel, aluminum, and silver, metal fibers, and polyphenylene derivatives. Can be used as one or a mixture thereof. Among them, a mixture of graphite and acetylene black is particularly preferable.
  • the addition amount of the conductive agent is preferably 1 to 50% by mass, and more preferably 2 to 30% by mass. When using a carbon material, 2 to 15% by mass is particularly preferable.
  • binder used in the electrode mixture according to the present invention examples include polysaccharides, thermoplastic resins, and polymers having rubber elasticity. Specifically, starch, carboxymethyl cellulose, cellulose, diacetyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium alginate, polyacrylic acid, sodium polyacrylate, polyvinyl phenol, polyvinyl methyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylonitrile , Polyacrylamide, polyhydroxy (meth) acrylate, water-soluble polymers such as styrene-maleic acid copolymer, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride -Tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polys
  • carboxymethylcellulose, polytetrafluoroethylene, and polyvinylidene fluoride are more preferable.
  • the binder can be used alone or in combination of two or more.
  • the amount of the binder added is small, the holding power and cohesive force of the electrode mixture are weakened. If the amount is too large, the electrode volume increases and the electrode unit volume or the capacity per unit mass decreases. For this reason, the addition amount of the binder is preferably 1 to 30% by mass, and more preferably 2 to 10% by mass.
  • the filler used in the electrode mixture according to the present invention can be any fibrous material that does not cause a chemical change in the secondary battery of the present invention.
  • olefin polymers such as polypropylene and polyethylene, fibers such as glass and carbon are used.
  • the amount of filler added is not particularly limited, but is preferably 0 to 30% by mass.
  • the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver.
  • aluminum and aluminum alloys are preferable. More preferred.
  • the negative electrode current collector is preferably copper, stainless steel, nickel, or titanium, and more preferably copper or a copper alloy.
  • a film sheet is usually used, but a porous body, a foam, a molded body of a fiber group, and the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • Electrode shape and electrode fabrication method The shape of the electrode and the method for producing the electrode according to the present invention will be described.
  • the shape of the secondary battery of the present invention can be applied to any shape such as a sheet type, a square type, and a cylinder type.
  • the electrode is manufactured by applying a positive electrode active material or a mixture of a negative electrode active material and an electrode mixture on a current collector, drying and then pressing.
  • Examples of the application method of the positive electrode active material or the mixture of the negative electrode active material and the electrode mixture include, for example, a reverse roll method, a direct roll method, a blade method, a knife method, an extrusion method, a curtain method, a gravure method, a bar method, and a dip method.
  • a squeeze method and the like are preferable.
  • the blade method, knife method and extrusion method are preferred.
  • the coating is preferably performed at a speed of 0.1 to 100 m / min. Under the present circumstances, the surface state of a favorable application layer can be obtained by selecting the said application
  • the coating by the above method may be continuous, intermittent or striped.
  • the thickness, length and width of the coating layer are determined by the shape and size of the battery.
  • the thickness of the coating layer on one side is preferably 1 to 2000 ⁇ m in a compressed state after drying.
  • the drying temperature is preferably 80 to 350 ° C, more preferably 100 to 250 ° C.
  • a sheet pressing method a generally adopted method can be used, but a calendar pressing method is particularly preferable.
  • the pressing pressure is not particularly limited, but is preferably 20 to 300 MPa.
  • the press speed of the calendar press method is preferably 0.1 to 50 m / min, and the press temperature is preferably room temperature to 200 ° C.
  • the ratio of the negative electrode sheet width to the positive electrode sheet is preferably 0.9 to 1.1, particularly preferably 0.95 to 1.0.
  • the content ratio of the positive electrode active material and the negative electrode active material varies depending on the compound type and the mixture formulation.
  • the secondary battery 1 was produced according to the following method.
  • a slurry negative electrode active material in which 96% by mass of natural spherical graphite, 4% by mass of polyvinylidene fluoride copolymer and N-methylpyrrolidone are mixed is applied to a thickness of 200 ⁇ m on a copper foil having a thickness of 10 ⁇ m. did. After drying with hot air at 130 ° C. for 5 minutes, a negative electrode was produced by roll pressing.
  • Secondary batteries 2 to 14 were produced in the same manner as in the production of the secondary battery 1 except that the electrolytic solution was changed to the ionic liquid and supporting electrolyte salt shown in Table 1.
  • the fabricated secondary batteries 1 to 14 were evaluated as follows. A battery charged at a voltage of 4.2 V and a charge rate of 0.125 C for 8 hours was discharged at a discharge rate of 0.125 C until the voltage of the secondary battery became 3 V, which was defined as one cycle. This cycle was repeated, and the number of times until the initial discharge capacity fell below 80% was measured.
  • EMIFSA 1-ethyl-3-methylimidazolium bisfluorosulfonylamide
  • EMITFSA 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonylamide
  • P13FSA N-methyl-N-propylpyrrolidinium bisfluorosulfonylamide
  • EMIBF 3 ( CF 2 CF 3 ): 1-ethyl-3-methylimidazolium (pentafluoroethyl) trifluoroborate
  • HNIPTP 1-hexyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate
  • EMIFTA 1-ethyl- 3-Methylimidazolium fluorosulfonyl (trifluoromethylsulfonylamide)
  • EMIBF 4 1-ethyl-3-
  • the secondary battery having an anion that forms a passive film on the current collector and an anion that forms an SEI film on the carbon material on the negative electrode has safety and cycle characteristics. Is apparently high.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une batterie secondaire comprenant une cathode, une anode constituée d'un matériau carboné et un électrolyte. La batterie secondaire est caractérisée en ce que l'électrolyte comprend un type de sel d'électrolyte support et deux types de fluide ionique, les anions du sel d'électrolyte support et les deux types de fluide ionique étant différents, et au moins l'un des types d'anion étant un anion qui forme une couche mince passive sur un collecteur ; et en ce qu'au moins l'un des types d'anion qui diffère de l'anion qui forme une couche mince passive sur le collecteur étant un anion qui forme une couche mince SEI sur le matériau carboné sur l'anode.
PCT/JP2010/071877 2009-12-24 2010-12-07 Batterie secondaire comprenant un fluide ionique WO2011077939A1 (fr)

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JP2012204133A (ja) * 2011-03-25 2012-10-22 National Institute Of Advanced Industrial & Technology 炭素質負極を有する非水電解質リチウムイオン電池
WO2013051302A1 (fr) * 2011-10-05 2013-04-11 国立大学法人東北大学 Batterie secondaire
JP2013084548A (ja) * 2011-09-30 2013-05-09 National Institute Of Advanced Industrial & Technology リチウム二次電池
WO2013069597A1 (fr) * 2011-11-10 2013-05-16 住友電気工業株式会社 Matériau actif d'anode pour batterie au sodium, anode et batterie au sodium
KR20140142705A (ko) * 2012-03-07 2014-12-12 메사추세츠 인스티튜트 오브 테크놀로지 광범위한 온도에서의 작동을 위한 충전식 리튬 배터리
WO2015146265A1 (fr) * 2014-03-28 2015-10-01 Toyota Jidosha Kabushiki Kaisha Électrolyte liquide pour batterie à ions fluorure et batterie à ions fluorure
WO2015163254A1 (fr) * 2014-04-24 2015-10-29 三洋化成工業株式会社 Additif de batterie, électrode, électrolyte et dispositif électrochimique
US20160020462A1 (en) * 2014-07-16 2016-01-21 Prologium Holding Inc. Anode Electrode
KR20170057263A (ko) * 2014-09-25 2017-05-24 바이에리셰 모토렌 베르케 악티엔게젤샤프트 전기 화학 전지, 이의 충전에 적합한 전해질, 이의 제조 방법 및 이의 작동 방법
JP2019091525A (ja) * 2017-11-10 2019-06-13 日立化成株式会社 リチウムイオン二次電池の製造方法
JP2021077608A (ja) * 2019-11-13 2021-05-20 株式会社Ｇｓユアサ 非水電解質、非水電解質蓄電素子及び非水電解質蓄電素子の製造方法
CN113451054A (zh) * 2021-06-28 2021-09-28 鹏盛国能(深圳)新能源集团有限公司 一种锂离子电容电池及其制备方法
WO2024028684A1 (fr) * 2022-08-04 2024-02-08 株式会社半導体エネルギー研究所 Batterie secondaire

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Cited By (22)

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Publication number Priority date Publication date Assignee Title
JP2012204133A (ja) * 2011-03-25 2012-10-22 National Institute Of Advanced Industrial & Technology 炭素質負極を有する非水電解質リチウムイオン電池
JP2013084548A (ja) * 2011-09-30 2013-05-09 National Institute Of Advanced Industrial & Technology リチウム二次電池
JPWO2013051308A1 (ja) * 2011-10-05 2015-07-30 国立大学法人東北大学 二次電池
WO2013051302A1 (fr) * 2011-10-05 2013-04-11 国立大学法人東北大学 Batterie secondaire
WO2013051308A1 (fr) * 2011-10-05 2013-04-11 国立大学法人東北大学 Accumulateur
US9583750B2 (en) 2011-10-05 2017-02-28 Tohoku University Secondary battery
JPWO2013069597A1 (ja) * 2011-11-10 2015-04-02 住友電気工業株式会社 ナトリウム電池用の負極活物質、負極及びナトリウム電池
WO2013069597A1 (fr) * 2011-11-10 2013-05-16 住友電気工業株式会社 Matériau actif d'anode pour batterie au sodium, anode et batterie au sodium
KR20140142705A (ko) * 2012-03-07 2014-12-12 메사추세츠 인스티튜트 오브 테크놀로지 광범위한 온도에서의 작동을 위한 충전식 리튬 배터리
KR102084807B1 (ko) * 2012-03-07 2020-03-04 메사추세츠 인스티튜트 오브 테크놀로지 광범위한 온도에서의 작동을 위한 충전식 리튬 배터리
US10305145B2 (en) 2014-03-28 2019-05-28 Toyota Jidosha Kabushiki Kaisha Liquid electrolyte for fluoride ion battery and fluoride ion battery
WO2015146265A1 (fr) * 2014-03-28 2015-10-01 Toyota Jidosha Kabushiki Kaisha Électrolyte liquide pour batterie à ions fluorure et batterie à ions fluorure
WO2015163254A1 (fr) * 2014-04-24 2015-10-29 三洋化成工業株式会社 Additif de batterie, électrode, électrolyte et dispositif électrochimique
US20160020462A1 (en) * 2014-07-16 2016-01-21 Prologium Holding Inc. Anode Electrode
US10483534B2 (en) * 2014-07-16 2019-11-19 Prologium Holding Inc. Lithium metal anode electrode
JP2017528880A (ja) * 2014-09-25 2017-09-28 バイエリシエ・モトーレンウエルケ・アクチエンゲゼルシヤフト 電気化学セル、電気化学セルの充填に適した電解質、電気化学セルの製造方法、および電気化学セルの動作方法
KR20170057263A (ko) * 2014-09-25 2017-05-24 바이에리셰 모토렌 베르케 악티엔게젤샤프트 전기 화학 전지, 이의 충전에 적합한 전해질, 이의 제조 방법 및 이의 작동 방법
KR102495553B1 (ko) * 2014-09-25 2023-02-02 바이에리셰 모토렌 베르케 악티엔게젤샤프트 전기 화학 전지, 이의 충전에 적합한 전해질, 이의 제조 방법 및 이의 작동 방법
JP2019091525A (ja) * 2017-11-10 2019-06-13 日立化成株式会社 リチウムイオン二次電池の製造方法
JP2021077608A (ja) * 2019-11-13 2021-05-20 株式会社Ｇｓユアサ 非水電解質、非水電解質蓄電素子及び非水電解質蓄電素子の製造方法
CN113451054A (zh) * 2021-06-28 2021-09-28 鹏盛国能(深圳)新能源集团有限公司 一种锂离子电容电池及其制备方法
WO2024028684A1 (fr) * 2022-08-04 2024-02-08 株式会社半導体エネルギー研究所 Batterie secondaire

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