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WO1998048429A1 - Electrolyte polymere solide et son utilisation - Google Patents

Electrolyte polymere solide et son utilisation Download PDF

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Publication number
WO1998048429A1
WO1998048429A1 PCT/JP1998/001069 JP9801069W WO9848429A1 WO 1998048429 A1 WO1998048429 A1 WO 1998048429A1 JP 9801069 W JP9801069 W JP 9801069W WO 9848429 A1 WO9848429 A1 WO 9848429A1
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WIPO (PCT)
Prior art keywords
polymer
electrolyte
compound
solid electrolyte
lithium
Prior art date
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Ceased
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PCT/JP1998/001069
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English (en)
Japanese (ja)
Inventor
Masataka Takeuchi
Shuichi Naijo
Koji Tokita
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Resonac Holdings Corp
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Showa Denko KK
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Priority claimed from JP9101927A external-priority patent/JPH10294015A/ja
Application filed by Showa Denko KK filed Critical Showa Denko KK
Publication of WO1998048429A1 publication Critical patent/WO1998048429A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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 uses a mixed solvent of ethylene carbonate and ethyl methyl carbonate, has a high ionic conductivity in a wide temperature range, and has a high electrochemical stability and a high polymer solid electrolyte, particularly a low temperature of 11 ° C. or less. It relates to solid polymer electrolytes that can be used in the field.
  • the present invention relates to a lithium secondary battery using the polymer solid electrolyte, which is excellent in safety and reliability, has high performance, and particularly has good low-temperature characteristics.
  • Lithium primary batteries and lithium (ion) secondary batteries which are typical electrochemical devices, have recently been rapidly mounted on small portable devices due to their high energy density, and have shown rapid growth.
  • Organic solvents used in non-aqueous electrolytes include high dielectric constant, high boiling point cyclic Carbonates (propylene carbonate, ethylene carbonate, butylene carbonate, etc.) and ratatones (two-butyl lactone, etc.), low-viscosity linear carbonates (dimethyl carbonate, getyl carbonate, ethyl methyl carbonate), low-viscosity ether compounds (glyme , Diglyme, THF, dioxolane, etc.) have been studied mainly, and high ionic conductivity has been achieved by increasing the dissociation of the electrolyte salt and making it less viscous.
  • carbonates are widely used because of their wide electrochemical stability range and low reactivity with positive and negative electrode materials (for example, JP-A Nos. 2-10666 and 5-283104). Further, among them, ethylene carbonate is effective for improving the reversibility of a carbon anode such as a graphite anode, and is regarded as an essential solvent for lithium ion batteries currently on the market.
  • a porous film such as a polyolefin nonwoven fabric or a polyolefin microporous film is used as a separator, which is important as a constituent element other than the positive and negative electrodes and the electrolyte in these lithium primary batteries and lithium (ion) secondary batteries.
  • the function of the separator is required to be such that the positive and negative electrodes are electronically isolated from each other so as not to cause a short circuit, and that the ion transfer in the electrolyte between the positive and negative electrodes is not hindered.
  • the battery has the above-described function, it is preferable that the battery be as thin as possible because the energy density of the entire battery is increased.
  • porous thin films are currently used as separators, and film manufacturing and processing costs are high, which is a factor of high cost.
  • Ion conductivity of the solid polymer electrolyte that is generally considered, despite improved to 1 0 _ 4 ⁇ 1 0 _ 5 SZ cm position at that value put in room temperature, when compared to a liquid ion conductive material It is a level lower by two digits or more. Also 0. At low temperatures below C, the ionic conductivity is further reduced. Furthermore, when these solid electrolytes are incorporated into a battery in the form of a thin film, processing techniques such as compounding with electrodes and ensuring contactability were difficult, and there were problems with the manufacturing method.
  • U.S. Pat.No. 4,357,401 states that a polymer solid electrolyte consisting of a crosslinked polymer containing a heteroatom and an ionizable salt reduces the crystallinity of the polymer, lowers the glass transition point, and improves ionic conductivity. However, it was about 10-5 Scm at room temperature, which was still insufficient.
  • US Pat. No. 4,792,504 proposes a solid polymer electrolyte in which an electrolyte comprising a metal salt and a non-protonic solvent is impregnated in a crosslinked network of polyethylene oxide.
  • Japanese Patent Publication No. 3-73081 U.S. Pat. No. 4,908,283 discloses that a polymer comprising an acryloyl-modified polyalkylene oxydono electrolyte salt such as polyethylene glycol diacrylate and an organic solvent is irradiated with an actinic ray such as ultraviolet light to polymer. Methods for forming a solid electrolyte have been disclosed and attempts have been made to reduce the polymerization time. Also, US Pat. No. 4,830,939 and Japanese Patent Application Laid-Open No. 5-109310 (US Pat. No.
  • 5,037,712 disclose a composition comprising a crosslinkable polyethylene unsaturated compound, an electrolyte, an actinic ray inactive solvent, an ultraviolet ray, an electron beam or the like.
  • a similar method for forming a polymer solid electrolyte containing an electrolytic solution by irradiating the same is disclosed. In these systems, the ionic conductivity is improved because the amount of electrolyte in the solid polymer electrolyte is increased, but it is still insufficient, and the membrane strength tends to deteriorate.
  • Japanese Patent Publication No. 6-140052 (W094 / 06165) proposes a solid electrolyte in which a polyalkylene oxide isocyanate crosslinked polymer inorganic oxide composite is impregnated with a non-aqueous electrolytic solution. The strength of the polymer solid electrolyte has been increased.
  • the present inventors have proposed an ionic conduction using a composite comprising a polymer obtained from a (meth) acrylate prepolymer containing an oxyalkylene group having a urethane bond and an electrolyte.
  • a novel solid polymer electrolyte Japanese Patent Publication No. 6-187822 (US Pat. No. 5,597,661) was proposed.
  • the ionic conductivity of this polymer solid electrolyte is at a high level of 10 4 SZ cm (room temperature) without adding a solvent, but becomes 10 3 S / cm or more when a solvent is further added.
  • the film quality was good and improved to the extent that it could be obtained as a self-supporting film.
  • this prepolymer has good polymerizability, and when applied to batteries, there is also a processing merit that it can be polymerized after being assembled into batteries in a prepolymer state and solidified.
  • the present invention provides a solid polymer electrolyte that has good molding process, good strength, easy handling, high ion conductivity over a wide temperature range, stability, low cost, and excellent safety and reliability.
  • the purpose is to do.
  • FIG. 1 is a schematic sectional view of an embodiment of a thin solid state battery according to the present invention. Disclosure of the invention
  • the present inventors have conducted intensive studies in view of the above problems, and as a result, have found that the above problems can be improved by adding a mixed solvent of ethylene carbonate and ethyl methyl carbonate to a polymer solid electrolyte.
  • the low-temperature characteristics can be significantly improved by controlling the amount of ethylene carbonate and ethyl methyl carbonate added in a specific range.
  • the present inventors have developed a lithium secondary battery using the above polymer solid electrolyte, which has a wide operating temperature range, good current characteristics, good cycleability, excellent safety and reliability, and a high processability with shape flexibility. It has been found that it becomes a single-density energy battery.
  • oxyalkylene includes oligooxyalkylenes and polyoxyalkylenes each containing at least one oxyalkylene group.
  • the present invention has achieved the above object by developing the following.
  • a polymer solid electrolyte comprising a polymer, an electrolyte salt, and an organic solvent containing ethylene carbonate and ethyl methyl carbonate.
  • a polymer solid electrolyte comprising a polymer, an electrolyte salt, an organic solvent containing ethylene carbonate and ethyl methyl carbonate, and inorganic fine particles.
  • the total weight of ethylene carbonate and ethyl methyl carbonate is 100% by weight of the polymer. /.
  • the polymer has the general formula (1) or the general formula (2)
  • R 1 and R 2 represent a hydrogen atom or an alkyl group
  • R 3 represents a divalent group having 10 or less carbon atoms.
  • the divalent group may contain a hetero atom, and may have any of a linear, branched, or cyclic structure.
  • X represents 0 or a numerical value from 1 to 10; However, the values of R 2 , R 3 and x in the polymerizable functional group represented by the formula (1) or (2) which are present in plurals in the same molecule are independent of each other and may be the same or different.
  • the negative electrode active material is lithium, a lithium alloy, a carbon material capable of storing and releasing lithium ions, an inorganic oxide capable of storing and releasing lithium ions, and lithium ion.
  • the solid polymer electrolyte of the present invention is characterized in that an organic solvent containing ethylene carbonate (EC) and ethyl methyl carbonate (EMC) is added.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • the mixing ratio (weight) of EC and EMC is usually 3: 1 to 1:15 for EC: EMC. Can be used. If the amount of EC is too large, the deposition temperature of EC at a low temperature becomes high, and particularly in a solid polymer electrolyte, the deposition temperature tends to be even higher. On the other hand, if the amount is too small, the ionic conductivity is reduced and the life of the battery is shortened. Therefore, the preferable mixture ratio (weight) of EC and EMC is EC: EMC is 2: 1 to: 1: 10, 5: 5 to: L: 10 is more preferable, and 4: 6 to 1: 9. Is particularly preferred.
  • the preferable addition amount is in the range of 100% to 1500% by weight of the polymer weight in the polymer solid electrolyte of the present invention, more preferably 200% to 1200% by weight, and more preferably 300% to 1200% by weight. 1000% by weight is particularly preferred.
  • the polymer used in the solid polymer electrolyte of the present invention has good compatibility with EC and EMC, has a high boiling point, has high solubility of the electrolyte salt, and is suitable for the electrochemical element used.
  • a stable one that does not adversely affect is good. That is, a compound having a large dielectric constant, a boiling point of 60 ° C or more, and a wide electrochemical stability range is suitable.
  • Examples of such a solvent include carbonates such as propylene carbonate, dimethyl carbonate, and getyl carbonate; ethers such as 1,2-dimethoxetane, dioxolan, and 2-methyltetrahydrofuran; triethylene dalicol dimethyl ether; Oligoethers, esters such as methyl propionate and methyl methoxypropionate, aromatic nitriles such as benzonitrinole and tolunitrile, dimethylformamide, N-methylpyrrolidone, N-butylpyrrolidone and dimethyl Examples thereof include sulfur compounds such as sulfoxide and sulfolane, and phosphoric esters. Among them, ethers, oligoethers, esters and carbonates are preferable, and esters, Carbonates are particularly preferred.
  • the polymer which is a main component of the polymer solid electrolyte of the present invention must be non-electroconductive and capable of absorbing and retaining various organic polar solvents.
  • high molecules include heteroatoms such as polyalkylene oxide, polyalkyl imine, polyacrylonitrile, poly (meth) acrylate, polyphosphazene, polyfutsudani vinylidene, polyurethane, polyamide, polyester, and polysiloxane.
  • Polar thermoplastic polymer or cross-linked polymer is suitable as the polymer used in the present invention because it has a high strength after absorbing the solvent, has a high solvent retentivity, and is a viscoelastic material.
  • the crosslinks shown here include not only those in which the crosslinks are formed by covalent bonds, those in which the side chains are crosslinked by ionic bonds or hydrogen bonds, and those in which the crosslinks are physically crosslinked via various additives. included.
  • those containing an oxyalkylene perethane structure such as polyalkylene oxide or polyurethane in the molecular structure are preferable because of their good compatibility with various polar solvents and good electrochemical stability.
  • those having a fluorocarbon group such as vinylidene fluoride in the molecular structure are also preferable.
  • R 1 and R 2 represent a hydrogen atom or an alkyl group
  • R 3 represents a divalent group having 10 or less carbon atoms.
  • the divalent group may contain a hetero atom, and may have any of a linear, branched, or cyclic structure.
  • X is 0 or 1-10 Shows the numerical value of.
  • R l in the polymerizable functional group represented by a plurality of the above general formula in the same molecule (1) or (2), the value of R 2, R 3 and x are each independently either the same or different May be.
  • a polymer obtained by curing at least one type of polymerizable compound having the following formulas by heating and irradiating with Z or actinic rays is preferable because it easily forms a film in a state containing a solvent and has good film strength.
  • R 1, R 2 , R 3 and x have the same meaning as in the general formula (1) or (2), and R 4 and R 5 represent an oxyalkylene group and Z or fluorocarbon, It is a divalent group containing oxyfluorocarbon.
  • a polymer obtained by curing at least one polymerizable compound having a polymerizable functional group represented by the formula (1) by heating and / or irradiating with active light is particularly preferable.
  • the method for synthesizing the compound having a functional group represented by the general formula (1) used in the polymer solid electrolyte of the present invention is not particularly limited.
  • an acid chloride and a compound having a hydroxyl group at a terminal For example, it can be easily obtained by reacting with oligooxyalkyleneol.
  • a compound having one functional group represented by the general formula (1) is obtained by reacting an acid chloride with a monoalkyl oligoalkylenedarilicol in a molar ratio of 1: 1 according to the following reaction formula. By doing so, it is easily obtained.
  • CH 2 C (R 1 ) COCI + HO (CH 2 CH (R 6 ) 0) m R 7 ⁇
  • CH 2 C (R 1 ) COO (CH 2 CH (R 6 ) O) m R 7
  • R1 has the same meaning as in the general formula (1)
  • R 6 is H or an alkyl group having 10 or less carbon atoms
  • R 7 is an alkyl group having 10 or less carbon atoms.
  • a compound having two functional groups represented by the general formula (1) can be easily prepared by reacting an acid chloride with an oligoalkylene glycol at a molar ratio of 2: 1 according to the following reaction formula. Is obtained.
  • R1 represents the same meaning as the general formula (1), R 6 is H or an alkyl group having 1 0 carbon atoms. ]
  • the method for synthesizing the compound having a polymerizable functional group represented by the general formula (2) used in the polymer solid electrolyte of the present invention is not particularly limited.
  • CH 2 C (R2) CO [OR 3 ] It can be obtained by reacting xNCO with an oligooxyalkyleneol (wherein, R 2 , R 3 and X each have the same meaning as in the general formula (2)).
  • a compound having one ethylenically unsaturated group is, for example, a methacryloyl isocyanate compound (hereinafter abbreviated as Ml) or an acryloyl isocyanate compound (hereinafter abbreviated as AI).
  • Ml methacryloyl isocyanate compound
  • AI acryloyl isocyanate compound
  • a monoalkyl oligoalkylene glycol in a molar ratio of 1: 1 according to the following reaction formula.
  • R 2 , R 3 and x have the same meaning as in the general formula (2), R 6 is H or an alkyl group having 10 or less carbon atoms, and R 7 is an alkyl group having 10 or less carbon atoms. It is. ]
  • a compound having two ethylenically unsaturated groups can be easily obtained, for example, by reacting Ml or AIs with an oligoalkylene glycol in a molar ratio of 2: 1.
  • Compounds having three ethylenically unsaturated groups include, for example, Ml and / or AIs and a triol obtained by addition-polymerizing a trihydric alcohol such as glycerin with an alkylene oxide. It can be easily obtained by reacting at a molar ratio of
  • the compound having four ethylenically unsaturated groups is, for example, a compound having a molar ratio of 4: 1 between Ml and / or AI and a tetraol obtained by addition-polymerizing an alkylene oxide to a tetrahydric alcohol such as pentaerythritol. It is easily obtained by reacting in a ratio.
  • Compounds having five ethylenically unsaturated groups include, for example, Ml and / or AIs and pentaol obtained by addition polymerization of ⁇ -D-dalcoviranose with alkylene oxide, in a ratio of 5: 1. It can be easily obtained by reacting at a molar ratio of
  • the compound having six ethylenically unsaturated groups is, for example, a compound of the formulas I and ⁇ ⁇ or an AI and a hexanol obtained by addition-polymerizing an alkylene oxide to mannitol in a molar ratio of 6: 1. It is easily obtained by reacting.
  • a method for synthesizing a compound having a polymerizable functional group represented by the general formula (1) or (2) having a fluorocarbon group and a Z or oxyfluorocarbon group is not particularly limited.
  • Has one polymerizable functional group as Compounds are prepared by reacting MIs or AIs with monools such as 2,2,3,3,4,4,4-heptafluoro-1-butanol in a molar ratio of 1: 1 according to the following reaction formula. Can be easily obtained.
  • ⁇ I or AIs and diols such as 2,2,3,3-tetrafluoro-1,4-butanediol. It can be easily obtained by reacting at a molar ratio of 2: 1 according to the following reaction formula.
  • the number of polymerizable functional groups represented by the general formula (1) or (2) contained in one molecule is more preferably three or more.
  • the polymer obtained from the compound having a polymerizable functional group represented by the general formula (2) contains a urethane group, Good properties and high film strength when thinned It is preferred.
  • the polymer which is preferable as a component of the polymer solid electrolyte of the present invention is obtained by polymerizing at least one kind of a compound having a polymerizable functional group represented by the general formula (1) or (2), or It is obtained by polymerization as a polymerization component.
  • the polymer used for the polymer solid electrolyte of the present invention even if it is a homopolymer of a compound having a polymerizable functional group represented by the general formula (1) or the general formula (2), belongs to this category. It may be a copolymer of at least one kind, or a copolymer of at least one kind of the compound and another polymerizable compound.
  • the other polymerizable compound copolymerizable with the compound having a polymerizable functional group represented by the general formula (1) or (2) is not particularly limited.
  • (Meth) acrylamide-based compounds styrene-based compounds such as styrene and para-methylstyrene, N-vinylamide-based compounds such as N-vinylacetamide and N-vinylformamide, and alkyl vinyl ethers such as ethyl-butyl ether Can be mentioned.
  • a general method utilizing the polymerizability of an acryloyl group or a methallyl group in the polymerizable compound can be employed. That is, a radical polymerization catalyst such as azobisisobutyronitrile, benzoyl peroxyside, a CF 3 COOH or the like is added to these monomers alone or a mixture of these monomers and the above-mentioned copolymerizable polymerizable compound.
  • a radical polymerization catalyst such as azobisisobutyronitrile, benzoyl peroxyside, a CF 3 COOH or the like is added to these monomers alone or a mixture of these monomers and the above-mentioned copolymerizable polymerizable compound.
  • Pro Tonsan using BF 3, cationic polymerization catalysts such as Lewis acids a, etc.
  • the polymer used for the polymer solid electrolyte of the present invention preferably contains an oxyalkylene structure.
  • the number of oxyalkylene chains, that is, in R 4 in the general formula (3), or The number of repetitions n of the oxyalkylene group contained in R 5 in the general formula (4) is preferably in the range of 1 to 1,000, particularly preferably in the range of 5 to 100.
  • the polymer used in the polymer solid electrolyte of the present invention may be a homopolymer of a compound having a functional group represented by the general formula (1) or (2) as described above,
  • the copolymer described above may be used, or a copolymer of at least one of these compounds and another polymerizable compound may be used.
  • the polymer used for the polymer solid electrolyte of the present invention is a polymer obtained from at least one compound having a functional group represented by the general formula (1) or (2) and a polymer obtained by combining the polymer and the compound. It may be a mixture of a copolymer as a polymerization component and another polymer.
  • a polymer obtained from at least one compound having a functional group represented by the general formula (1) or (2) and Z or a copolymer having the compound as a copolymer component, polyethylene oxide, and polypropylene oxide The mixture of the present invention with a polymer such as polyacrylonitrile, polybutadiene, polymethacrylic acid (or acrylic) ester, polystyrene, polyphosphazenes, polysiloxane or polysilane, polyvinylidene fluoride, or polytetrafluoroethylene. It may be used for a molecular solid electrolyte.
  • inorganic fine particles to the solid polymer electrolyte of the present invention. This not only improves strength and film thickness uniformity, but also causes fine pores to be formed between the inorganic fine particles and the polymer, and when immersed in an electrolyte solution, the polymer solid electrolyte The free electrolyte is dispersed inside, and the ionic conductivity and mobility can be increased without impairing the strength gap.
  • the addition of the inorganic fine particles increases the viscosity of the polymerizable composition, and has an effect of suppressing the separation even when the compatibility between the polymer and the solvent is insufficient.
  • the inorganic fine particles to be used non-electroconductive and electrochemically stable ones are selected.
  • the inorganic fine particles preferably have a secondary particle structure in which primary particles are aggregated, from the viewpoint of increasing the strength of the polymer solid electrolyte and increasing the amount of retained electrolyte.
  • the inorganic fine particles having such a structure include silica ultrafine particles such as AEROSIL (manufactured by Nippon AEROSIL) and alumina ultrafine particles, and particularly preferred are alumina ultrafine particles in terms of stability and composite efficiency.
  • the specific surface area of the inorganic fine particles is preferably as large as possible.
  • 50 m2 / g or more is more preferable.
  • the crystal particle size of such inorganic fine particles is not particularly limited as long as it can be mixed with the polymerizable composition, but the average particle size is preferably 0.001 / Zm to 10 ⁇ m, and more preferably 0.01 ⁇ m to 1 ⁇ m. m is particularly preferred.
  • various shapes such as a sphere, an egg, a cube, a rectangular parallelepiped, a cylinder or a rod can be used.
  • the amount of addition is preferably 5 Owt% or less, more preferably 0.1 to 30 wt%, based on the solid polymer electrolyte.
  • the (meth) acryloyl-based compound is polymerized and cured by heating and irradiating with Z or actinic light. , Can be recommended.
  • the temperature for the polymerization depends on the type of the polymerizable compound having a polymerizable functional group represented by the general formula (1) or (2) and the type of the initiator, but may be any temperature at which the polymerization occurs. The temperature may be in the range of ° C to 200 ° C.
  • an actinic ray initiator such as benzylmethylketanol or benzophenone may be used, depending on the type of polymerizable compound having a polymerizable functional group represented by the general formula (1) or (2).
  • polymerization can be carried out by irradiating ultraviolet light of several mW or more or an electron beam, a beam or the like.
  • the strength can be improved.
  • the porous film used include a porous polyolefin film such as a mesh-like polyolefin sheet such as a polypropylene nonwoven fabric or a polyethylene net, a polyolefin microporous film such as Celgard (trade name), a nylon nonwoven fabric, and a polyester net.
  • a polyolefin porous film is preferable in terms of stability.
  • the porosity may be about 10 to 90%, but it is preferable that the porosity is as large as possible as long as the strength permits, and the preferable porosity is in the range of 40 to 90%.
  • the method of compounding is not particularly limited, but includes, for example, at least one kind of (meth) atalyloyl-based compound having a polymerizable functional group represented by the general formula (1) or (2), at least one kind of electrolyte salt, and EC and EMC.
  • a porous polymer film After impregnating a porous polymer film with a polymerizable composition comprising a solvent, or a polymerizable composition obtained by adding at least one type of inorganic fine particles thereto, or a polymerizable composition further obtained by adding at least one type of polymerization initiator thereto Polymerizing the (meth) acryloyl compound This method is recommended because the method can be uniformly combined and the film thickness control is simple.
  • the solid polymer electrolyte of the present invention When the solid polymer electrolyte of the present invention is applied to a battery, the solid polymer electrolyte of the present invention has a high electrolytic solution retention property and has no pores, so that liquid leakage and short circuit hardly occur, and the operating temperature range is wide. A non-aqueous battery with high current, long cycle life, and high safety and reliability can be obtained. In addition, since liquid leakage and short circuit hardly occur, the battery can be made thin and a battery with a simple package can be obtained.
  • FIG. 1 shows a schematic cross-sectional view of an example of a thin-film battery as a nonaqueous battery manufactured in this manner.
  • 1 is a positive electrode
  • 2 is a polymer solid electrolyte of the present invention
  • 3 is a negative electrode
  • 4 is a current collector
  • 5 is an insulating resin sealant.
  • the negative electrode active material used in the non-aqueous battery of the present invention one having a low oxidation-reduction potential with an alkali metal ion such as an alkali metal, an alkali metal alloy, a carbon material, a metal oxide or a metal chalcogenide as a carrier is used. It is preferable to use it because a high-voltage, high-capacity battery can be obtained.
  • an alkali metal ion such as an alkali metal, an alkali metal alloy, a carbon material, a metal oxide or a metal chalcogenide as a carrier
  • lithium metal or lithium alloys such as lithium / aluminum alloy, lithium Z lead alloy, and lithium Z antimony alloy are particularly preferable because they have the lowest redox potential.
  • carbon materials are particularly preferable in that they have a low oxidation-reduction potential when they occlude lithium ions, and are stable and safe.
  • the carbon material for lithium ion can occluding and releasing, natural graphite, artificial graphite, vapor grown graphite, petroleum coke, coal co one task, pitch carbon, polyacene, C 6 o, hula etc. c 70; one alkylene ethers And the like.
  • alkali metal salt is required as an electrolyte.
  • the type of alkali metal Shokushio for example, L i CF 3 S 0 3 , L i PF 6, L i C 10 4, L i BF 4, L i SCN, L i A s F 6, L i N (CF 3 SO 2) 2, N a CF 3 S 0 3, L i I, N a PF 6, N a C 10 4, N a I, N a BF 4, Na As F 6, KCF 3 S0 3, KPF 6 and KI can be mentioned.
  • a carbon material negative electrode not only alkali metal ions but also quaternary ammonium Nidium salts, quaternary phosphonium salts, transition metal salts, and various protonic acids can also be used.
  • Such electrolytes (CH 3) 4 NBF 4 , (CH 3 CH 2) 4 NC 10 4 4 Grade Anmoniumu salts such as, transition metal salts such as A g CI 0 4, (CH 3) 4 P BF quaternary Hosuhoniumu salt 4 such as salts of organic San ⁇ Piso such as p-toluenesulfonic acid, hydrochloric acid, and the like inorganic acids such as sulfuric acid.
  • quaternary ammonium salts quaternary phosphonium salts, and metal salts of alkali metal are preferred because of their high output voltage and large dissociation constant.
  • quaternary ammonium salts those having different substituents on the nitrogen of the ammonium ion such as (CH 3 CH 2 ) (CH 3 CH 2 CH 2 CH 2 ) 3 NBF 4 Is preferred because it has a large dissociation constant.
  • a high-voltage, high-capacity battery is obtained by using a positive electrode active material having a high oxidation-reduction potential such as a metal oxide, a metal sulfide, a conductive polymer, or a carbon material for the positive electrode.
  • a positive electrode active material having a high oxidation-reduction potential such as a metal oxide, a metal sulfide, a conductive polymer, or a carbon material for the positive electrode.
  • metal oxides such as dicobalt oxide, manganese oxide, vanadium oxide, nickel oxide, and molybdenum oxide, molybdenum sulfide, and the like have a high packing density and a high volume capacity density.
  • Metal sulfides such as titanium sulfide and vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide and the like are particularly preferable in terms of high capacity and high voltage.
  • the method for producing metal oxides and metal sulfides in this case is not particularly limited, and examples thereof include a general electrolytic method and a general electrolytic method described in “Electrochemistry, Vol. 22, p. 574, 1954”. It is manufactured by a heating method. Further, when used in lithium batteries by these positive electrode active material, during the production of the battery, examples Ebashi 1 ⁇ 0 0 2 Ya L i x Mn0 metal oxide lithium element in the form of 2 like, or metal sulfide It is preferable to use it in a state where it is inserted (composite) into the device.
  • the method for introducing the lithium element is not particularly limited, for example, a method for electrochemically introducing lithium ions, or a method for introducing Li 2 C 3 as described in US Pat. No. 4,357,215. It can be carried out by mixing a metal oxide or the like with a salt and heating the mixture.
  • a conductive polymer is preferable because it is flexible and easily formed into a thin film. Examples of the conductive polymer include polyaniline, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polypyrrole and its derivatives, polychenylene and its derivatives, polypyridinediyl and its derivatives, and polyisothianaphthenile.
  • Polyarylene vinylenes such as polyphenylene vinylene and derivatives thereof, polyfurylene and derivatives thereof, polyselenophene and derivatives thereof, polyparaphenylenevinylene, polychenylenevinylene, polyfurylenevinylene, polynaphthenylenevinylene, polyselenophenvinylene, polypyridinylvinylene and the like And the like.
  • a polymer of an aniline derivative soluble in an organic solvent is particularly preferable.
  • carbon materials include natural graphite, artificial graphite, vapor-grown graphite, petroleum coke, coal coke, fluorinated graphite, pitch-based carbon, and polyacene. No. BEST MODE FOR CARRYING OUT THE INVENTION
  • [X 1 ] is [CH (CH 3 ) CH 20 ] x H, or
  • This photopolymerizable composition was coated on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp (FL20S.BL, manufactured by Sankyo Electric Co., Ltd.) for 10 minutes.
  • ZUA5805 composite film was obtained as a freestanding film of about 30 ⁇ m. 25 ° C for this film, one 20.
  • the photopolymerizable composition was applied and irradiated with light in the same manner as in Example 3, whereby a polymer Z-aluminum oxide C composite film of compound 3 impregnated with an EC / EMC electrolytic solution was converted into a free-standing film of about 30 ⁇ . Obtained. 25 ° C of the film was measured for ionic conductivity in one 20 ° C by an impedance method, respectively, 5.5 X 10- 3, was 1.0 X 10_3SZcm.
  • thermopolymerizable composition was obtained in the same manner as in Example 4 except that benzoyl peroxide (BPO) (0.04 g) was added instead of lucirin T PO (0.005 g) as an initiator.
  • BPO benzoyl peroxide
  • lucirin T PO 0.005 g
  • thermopolymerizable composition was coated on a PET film under an argon atmosphere, coated with a PP film, and heated on a hot plate at 80 ° C for 1 hour.
  • a polymer / aluminum oxide C composite film of compound 3 impregnated with EC / EMC electrolyte was obtained as a free-standing film of about 30 / xm.
  • the ionic conductivity of this film at 25 ° C. and at 20 ° C. was measured by an impedance method to be 5.3 ⁇ 10-3 and 0.8 ⁇ 10-3 sZcm, respectively.
  • a photopolymerizable composition was obtained in the same manner as in Example 4 except that 0.50 g of battery grade Li BF 4 manufactured by Hashimoto Kasei was used instead of Li PF 6 .
  • the water content of this composition (Carno Reisher method) was 50 ppm.
  • the photopolymerizable composition was applied and irradiated with light in the same manner as in Example 4 to obtain an electrolyte-impregnated polymer of compound 3 / aluminum moxide C composite film as a self-supporting film of about 30 / xm.
  • the ionic conductivity of this solid electrolyte at 25 ° C. and 20 ° C. was measured by an impedance method and found to be 4.0 ⁇ 10 3 and 0.3 ⁇ 10 3 SZcm.
  • This photopolymerizable composition was coated on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp for 10 minutes.
  • the copolymer UA5805 composite film of a compound 3 and 5 impregnated with an ECZEMC-based electrolyte solution was obtained as a free-standing film of about 30 ⁇ . 25 ° C of the film was measured for ionic conductivity in one 20 ° C at I impedance method respectively, 6.0 X 1 0- 3, was 0.8 X 1 0-3 S / cm.
  • Compound 8 (0.7 g), Compound 10 (0.3 g), silica heat-treated at 1000 ° C (Aerosil 200, Aerozil Japan, crystal particle size 0.012 / 2 m, average secondary particle size approx.
  • the water content (Karl Fischer method) of this composition was 6 Oppm.
  • This photopolymerizable composition was coated on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp for 10 minutes.
  • the copolymer, a copolymer of Compounds 8 and 10, impregnated with an EC / EMC ZDEC-based electrolyte, 200 composite films were obtained as about 30 zm free standing finolems.
  • 25 ° C of the Fi beam was measured ion Den Shirubedo of one 20 ° C by an impedance method, respectively, 2.0X 1 0- 3, was 0.4 X 1 0-3S / cm.
  • a photopolymerizable composition was obtained in the same manner as in Example 3 except that 0.33 g of magnesium oxide (Micromag 3-150 manufactured by Kyowa Chemical Co., Ltd.) heat-treated at 1000 ° C was added instead of UA5805 as inorganic fine particles. .
  • the water content (Karl Fischer method) of this composition was 35 ppm.
  • the photopolymerizable composition was applied and irradiated with light in the same manner as in Example 3 to obtain a compound 3 polymer / micromag 3-150 composite film impregnated with ECZEMC electrolyte solution as a self-supporting film of about 30 ⁇ m.
  • ECZEMC electrolyte solution as a self-supporting film of about 30 ⁇ m.
  • 25 ° C of this film - was measured ionic conductivity at 20 ° C by an impedance method was respectively 4.3X 10-3, 0.5X 1 0_ 3 SZ cm.
  • Example 3 Example 3 was repeated except that 0.33 g of titanium oxide (Super Titania F-4 manufactured by Showa Denko, crystal particle size 0.028 / m, BET specific surface area 56 m 2 Zg) heat-treated at 1000 ° C was added instead of UA 5805 as inorganic fine particles. In the same manner as in the above, a photopolymerizable composition was obtained. The water content (Karl Fischer method) of this composition was 60 ppm.
  • titanium oxide Super Titania F-4 manufactured by Showa Denko, crystal particle size 0.028 / m, BET specific surface area 56 m 2 Zg
  • MCMB graphite manufactured by Osaka Gas
  • vapor-grown graphite fiber manufactured by Showa Denko KK: average fiber diameter 0.3 ⁇ m, average fiber length 2.0 m, heat treated at 2700 ° C
  • polyvinylidene fluoride An excess N-methylpyrrolidone solution was added to the mixture having a weight ratio of 8.6: 0.4: 1.0 to obtain a gel composition.
  • This composition was applied and molded on a copper foil of about 15 ⁇ m to a thickness of 10 mm ⁇ 10 mm and a thickness of about 250 ⁇ m. Furthermore, it was heated and vacuum-dried at about 100 ° C. for 24 hours to obtain a graphite negative electrode (35 mg).
  • Example 19 Production of lithium ion secondary battery
  • the graphite negative electrode (10 mm x 10 mm) produced in Example 17 was impregnated with electrolyte (1 ML i PF 6 / EC + EMC (3: 7)). Then, the polymer solid electrolyte Z-aluminum oxide C composite film (12 mm ⁇ 12 mm) prepared in Example 4 was laminated on a graphite negative electrode, and the lithium cobaltate positive electrode (lOmmX l O mm) and an electrolyte impregnated with electrolyte (1M Li PF 6 / EC + EMC (3: 7)), seal the battery end with epoxy resin, and use graphite / cobalt oxide lithium ion. A secondary battery was obtained.
  • FIG. 1 shows a cross-sectional view of the obtained battery.
  • This battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C, 25 ° C, and 20 ° C.
  • the maximum discharge capacity was 7.2 mAh, 7.2 mAh, and 6.5 mA, respectively. h.
  • Example 20 Production of lithium ion secondary battery
  • Example 1 was repeated except that the [Compound 3 + 5-based polymer solid electrolyte] / UA5805 film produced in Example 10 was used instead of the compound 3-based polymer solid electrolyte / aluminum oxide C composite film.
  • Example 19 The same procedure as in Example 19 was performed except that the compound 3-based thermopolymerized polymer solid electrolyte Z-aluminum oxide C film prepared in Example 5 was used instead of the compound 3-based polymer solid electrolyte aluminum oxide C film.
  • a lithium ion secondary battery having the cross-sectional view shown in FIG. 1 was manufactured.
  • the graphite anode (10 mm X 10 mm) produced in Example 18 was impregnated with an electrolyte solution (1 ML i PF 6 / EC + EMC (3: 7)).
  • the compound 3 / aluminum oxide C-based photopolymerizable compound prepared in Example 4 was applied to a thickness of 30 / zm, and irradiated with a chemical fluorescent lamp for 10 minutes under an argon atmosphere.
  • a polymer Z-impregnated Z3 aluminum oxide C composite film was formed directly on the graphite negative electrode.
  • Example 1 lithium cobaltate positive electrode prepared in 7 (1 OmmX 1 0 mm) to the electrolytic solution (1M L i PF 6 / EC + EMC (3: 7)) was also impregnated with The end of the battery was sealed with an epoxy resin to obtain a graphite / cobalt oxide lithium ion secondary battery as shown in FIG.
  • the polymer solid electrolyte of the present invention has high ionic conductivity over a wide temperature range and electrochemical stability because it contains EC and an organic solvent containing EMC that is effective in lowering the crystallization temperature of EC as a plasticizer. It can improve current characteristics, temperature characteristics, and life when applied to electrochemical devices such as batteries. In particular, it can be used without problems even at temperatures as low as ⁇ 20 ° C or less.
  • the strength is improved, the handling is facilitated, the diffusion of the electrolyte salt is facilitated, and the current characteristics and cycle characteristics of the electrochemical element are improved. be able to.
  • the fact that a polymerizable compound having a (meth) acrylic group and / or a urethane (meth.,) Acrylic group has excellent curing properties is used, and these compounds and an electrolyte salt are used.
  • the polymerizable composition containing the organic organic solvent or / and the inorganic fine particles is placed on the substrate, the polymer solid electrolyte containing the EC / EMC solvent is applied to the substrate by heating or irradiation with actinic rays such as ultraviolet rays. It became possible to manufacture easily.
  • the solid polymer electrolyte and the negative electrode capable of occluding and releasing lithium ions by using the solid polymer electrolyte and the negative electrode capable of occluding and releasing lithium ions, a high energy density, a large extraction current, a wide operating temperature range, a long cycle life, and a high Leakage, short circuit is less likely to occur, A lithium (ion) secondary battery with excellent safety, long-term reliability, and processability can be obtained.
  • liquid leakage and short-circuiting do not easily occur, a thin lithium ion (ion) secondary battery with a simple package can be obtained.

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Abstract

Electrolyte polymère solide comprenant un solvant organique contenant un polymère, un sel électrolytique, du carbonate d'éthylène et du carbonate d'éthyle-méthyle, et, selon le cas, des particules inorganiques; pile secondaire au lithium fabriquée au moyen de cet électrolyte. Ce dernier présente d'excellentes caractéristiques de moulage, de résistance et de manipulation, une excellente conductivité ionique, une stabilité optimisée, une durée de vie prolongée, d'excellentes caractéristiques de courant et de température dans une plage importante de températures, y compris une plage de températures basses égales ou inférieures à -10 °C. Cette pile secondaire au lithium possède des propriétés excellentes de sécurité, de fiabilité à long terme et de facilité d'utilisation en plus des caractéristiques mentionnées ci-dessus.
PCT/JP1998/001069 1997-04-18 1998-03-13 Electrolyte polymere solide et son utilisation Ceased WO1998048429A1 (fr)

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JP9101927A JPH10294015A (ja) 1997-04-18 1997-04-18 高分子固体電解質及びその用途
JP9/101927 1997-04-18
US5606097P 1997-09-02 1997-09-02
US60/056,060 1997-09-02

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109417196A (zh) * 2017-01-12 2019-03-01 株式会社Lg化学 非水电解液和包括该非水电解液的锂二次电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02172163A (ja) * 1988-12-23 1990-07-03 Bridgestone Corp 非水電解液電池
JPH03129603A (ja) * 1989-10-13 1991-06-03 Matsushita Electric Ind Co Ltd 固体電解質
JPH07109321A (ja) * 1993-08-18 1995-04-25 Shin Etsu Chem Co Ltd 複合固体電解質
JPH0963643A (ja) * 1995-06-14 1997-03-07 Furukawa Battery Co Ltd:The リチウム二次電池
JPH0973907A (ja) * 1995-02-21 1997-03-18 Showa Denko Kk 高分子固体電解質、それを用いた電池及び固体電気二重層コンデンサ、並びにそれらの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02172163A (ja) * 1988-12-23 1990-07-03 Bridgestone Corp 非水電解液電池
JPH03129603A (ja) * 1989-10-13 1991-06-03 Matsushita Electric Ind Co Ltd 固体電解質
JPH07109321A (ja) * 1993-08-18 1995-04-25 Shin Etsu Chem Co Ltd 複合固体電解質
JPH0973907A (ja) * 1995-02-21 1997-03-18 Showa Denko Kk 高分子固体電解質、それを用いた電池及び固体電気二重層コンデンサ、並びにそれらの製造方法
JPH0963643A (ja) * 1995-06-14 1997-03-07 Furukawa Battery Co Ltd:The リチウム二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109417196A (zh) * 2017-01-12 2019-03-01 株式会社Lg化学 非水电解液和包括该非水电解液的锂二次电池
CN109417196B (zh) * 2017-01-12 2021-08-20 株式会社Lg化学 非水电解液和包括该非水电解液的锂二次电池

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