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WO2002021618A1 - Additif pour electrode, destine a etre utilise dans une batterie ou un condensateur - Google Patents

Additif pour electrode, destine a etre utilise dans une batterie ou un condensateur Download PDF

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Publication number
WO2002021618A1
WO2002021618A1 PCT/JP2001/007636 JP0107636W WO0221618A1 WO 2002021618 A1 WO2002021618 A1 WO 2002021618A1 JP 0107636 W JP0107636 W JP 0107636W WO 0221618 A1 WO0221618 A1 WO 0221618A1
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Prior art keywords
electrode
aqueous dispersion
fine particles
additive
fluorine
Prior art date
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Ceased
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PCT/JP2001/007636
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English (en)
Japanese (ja)
Inventor
Michio Asano
Kenji Ichikawa
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Daikin Industries Ltd
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Daikin Industries Ltd
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Publication of WO2002021618A1 publication Critical patent/WO2002021618A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • H01G11/30—Electrodes characterised by their material
    • 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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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

  • Electrode additives for batteries or capacitors are Electrode additives for batteries or capacitors
  • the present invention relates to the use of polytetrafluoroethylene fine particles as an additive for molded parts such as general-purpose resins and rubber packings and seals, and in particular for binders for battery electrode sheets made of metal oxide and carbon.
  • the present invention relates to a dispersion type additive containing polytetrafluoroethylene fine particles having an improved dispersion stabilizer composition in order to improve stability of an aqueous paste mixture and physical properties of an electrode when used.
  • polytetrafluoroethylene has properties such as heat resistance, chemical resistance, water and oil repellency, and sliding properties. It is sometimes mixed as an additive as a molded part such as rubber or packing or a seal, or as a binder for battery electrode sheets.
  • a molded part such as rubber or packing or a seal, or as a binder for battery electrode sheets.
  • an aqueous dispersion comprising fine particles of a fluoropolymer such as polytetrafluoroethylene (PTFE) as an additive are as follows.
  • PTFE can be used as a conveyor belt coated on a heat-resistant fiber woven fabric such as glass fiber or carbon fiber, or as a sliding material obtained by coating a mixed paste with a filler such as lead on the surface of a porous steel sheet and firing it.
  • Non-lubricated bearing material Oil seal parts such as automobile power steering, Anti-drip agent added to plastic powder such as poly-carbonate (PC) and PC / AB Salloy to prevent falling off during combustion, It can be applied to various uses such as a soil improver such as chemical fertilizer and lime, and a dust preventive agent that is added to the powder of civil engineering materials such as cement to prevent dust from forming.
  • a soil improver such as chemical fertilizer and lime
  • a dust preventive agent that is added to the powder of civil engineering materials such as cement to prevent dust from forming.
  • batteries such as manganese dioxide, nickel hydroxide, hydrogen storage alloy, lithium oleate, lithium manganate, lithium nickelate and other active materials for electrodes, and conductive agents such as carbon and graphite are used.
  • Fluorine-containing polymers are widely used as materials for binding these electrode mixtures when producing the used primary and secondary battery electrodes.
  • PTFE polytetrafluoroethylene
  • PV d F polyvinylidene fluoride
  • VdF-based copolymers vinylidene fluoride
  • PTFE has a good oxidation resistance due to a perfluoro structure and a fluorine-containing temperature of 327 ° C. It is preferably used because it has characteristics such as high heat resistance due to having the highest melting point among polymers.
  • This PTFE has not only the above-mentioned oxidation resistance and high thermophysical property, but also in terms of battery characteristics, when used as an electrode binder, organic solvents such as PVdF and VdF copolymers. Compared to the case where a solution is used, there is an advantage that the discharge performance is particularly excellent in load characteristics.
  • the reason for this is that when manufacturing an electrode using an electrode composition containing PTFE, especially when rolling the electrode plate, fiberization (fibrillation), which is a unique property of PTFE, occurs, and the PTFE fibers become tertiary. Form the original network structure. Therefore, it is said that the rate of covering the surface of the electrode active material, which is the reaction surface, while binding the electrode mixture is small.
  • a large-capacity capacitor utilizing electric charge accumulated in the electric double layer at the interface between the activated carbon electrode and the electrolyte is widely used as an auxiliary for the secondary battery.
  • a capacitor hereinafter simply referred to as a capacitor
  • it has attracted attention as a short-time backup application for currents of 1 A or more and for electric energy storage devices.
  • PTFE is also preferably used as a binder for an electrode of this capacity.
  • the reason is that, as in the case of the battery described above, it has oxidation resistance, high heat resistance, and an effective binder due to fiber bonding.
  • the only known method of use thereof is an organic solvent dispersion in which PTFE particles are dispersed in an organic solvent, that is, a form in which the PTFE particles are used as a PTF E organosol (Japanese Patent Application Laid-Open No. Hei 329904).
  • aqueous dispersion of PTFE microparticles has higher water repellency and higher specific gravity than hydrocarbon-based polymers such as polystyrene. It is known that it is easy to perform and has poor storage stability. Therefore, in general, an aqueous dispersion of PTFE fine particles obtained by chemical polymerization has not been marketed as it is, but has been marketed after being stabilized.
  • an aqueous dispersion of fine particles of PTFE is mixed with a nonionic surfactant such as polyoxyethylene phenyl, for example, C 8 H 17 C 6 H 4 ⁇ (C 2 H 4 ⁇ )
  • a nonionic surfactant such as polyoxyethylene phenyl, for example, C 8 H 17 C 6 H 4 ⁇ (C 2 H 4 ⁇ )
  • Triton XI 100 trademark
  • the polymer-solid concentration was increased to 40 to 65% by weight by an electroconcentration method or a phase separation method. It is commercially available after shrinking.
  • the appropriate amount of the non-ionic surfactant used in this case is preferably 4 to 12% by weight based on the weight of the solid content of the polymer. When the content is less than 4% by weight, it is known that storage stability is reduced (see Japanese Patent Application Laid-Open No. 240993).
  • Polytetrafluoroethylene is mixed and added for use as an additive, as described above, as molded parts such as general-purpose resins and rubber packings and seals, and as binders for battery electrode sheets, etc.
  • One of the common methods is to use polytetrafluoroethylene fine particles obtained by emulsion polymerization of tetrafluoroethylene in an aqueous medium and particulate materials such as general-purpose resins, rubber, carbon, glass, and metal oxides.
  • Electrode additives it is known to mix activated carbon or conductive carbon with a large surface area, and water-soluble polymers such as carboxymethylcellulose and polyvinyl alcohol as a thickener in an aqueous paste form. . At that time, depending on the mixing conditions, the paste may be greatly thickened, or the paste may be solidified due to the formation of fibrous tetrafluoroethylene.
  • Molded parts obtained by drying and pulverizing the paste obtained in this way and then molding the molded paste include molded articles made of a nonionic surfactant contained in the aqueous polytetrafluoroethylene dispersion.
  • the surfactant Depending on the application, it may be necessary to perform a long-time calcination treatment at a high temperature of 300: or more until the dispersion stabilizer and the stabilizer are decomposed and sublimated. This leads to waste of energy costs required for the dryer and deterioration of the working environment due to decomposition of the surfactant. Therefore, it is desirable not to add a nonionic surfactant as much as possible.
  • the surfactant used for stabilization is the final surfactant.
  • the surfactant used for stabilization is the final surfactant.
  • it remains in the electrode, which is a product, and increases the internal resistance and deteriorates the cycle characteristics. That is, from the viewpoint of battery characteristics, when an aqueous dispersion of PTFE fine particles is used as an electrode additive, it is preferable not to add a surfactant.
  • an aqueous dispersion of PTFE fine particles not stabilized with a non-ionic surfactant has poor dispersion stability, so that the fine particles dispersed during transportation when marketed are used. This is a situation that has hardly ever been marketed, mainly because of the danger of forming aggregates. Further, there is no literature describing use of such an aqueous dispersion as an electrode additive as far as the present inventors know.
  • the present invention improves the paste stability when mixing an aqueous paste with other materials when using an aqueous dispersion of polytetrafluoroethylene fine particles as an additive for molded articles, sheets, and electrodes. It is an object of the present invention to provide an electrode additive suitable for applications that repeatedly require charge and discharge performance such as batteries and capacitors.
  • the present inventors have developed an aqueous dispersion obtained by emulsion polymerization of PTFE, which was conventionally considered to be unfavorable because of easy aggregation, without concentrating or stabilizing the aqueous dispersion. That is, the amount of the nonionic surfactant added to the aqueous dispersion containing the fine particles of PTFE is minimized as much as possible, and it is preferable that the nonionic surfactant is mixed with the electrode mixture as it is, without adding any additional heat. It has been surprisingly found that when used, it can be easily and uniformly mixed with the electrode mixture, and that the resulting electrode has excellent characteristics.
  • the tetrafluoroethylene polymer used in the present invention includes not only PTFE obtained by emulsion polymerization of tetrafluoroethylene in an aqueous medium but also a modified polytetrafluoroethylene modified by copolymerizing a small amount of another co-monomer.
  • Polyethylene (modified PTFE) is also included.
  • this comonomer include hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), perfluoro (alkoxypinyl ether), trifluoroethylene, perfluoroalkyl ethylene, and the like. No.
  • the co-combination ratio of the comonomer varies depending on the type, but is such an amount that the modified PTFE causes fibrillation when the modified PTFE is mixed with other powder materials.
  • the aqueous dispersion of fine particles of the fluorine-containing polymer according to the present invention is preferably an aqueous dispersion of PTFE alone, but may be blended with an aqueous dispersion of another fluorine-containing polymer within a range not to impair the effects of the present invention. May be used. Fluorinated polymers that can be blended
  • PVdF polyvinylidene fluoride
  • VdFHFP vinylidene fluoride Z-hexafluoropropylene copolymer
  • PVdF / TFE vinylidene fluoride notate lafluoroethylene copolymer
  • the PTFE content may be at least 20% by weight, preferably at least 40%
  • the fine particles of the fluoropolymer are fine particles of a tetrafluoroethylene polymer having a fibril forming property and an average particle size of 0.05 to: L "m, preferably 0.1 to 0.3, particularly 0.1 to 0.35 m. Is particularly preferred.
  • the aqueous dispersion of the fine particles of the fluorine-containing polymer according to the present invention is produced by a polymerization method using a corresponding fluorine-containing monomer.
  • a fluorine-containing surfactant is used as a polymerization emulsifier. About 6% by weight can be used.
  • a surfactant may be added.
  • the surfactant used in the aqueous dispersion of the fine particles of the fluorine-containing polymer according to the present invention may be a single commercially available surfactant or a mixture of two or more surfactants.
  • fluorinated surfactant examples include a fluorinated carboxylic acid type having a fluoroalkyl group, particularly a perfluoroalkyl group, or a fluorofluoroalkyl group, particularly a perchlorofluoroalkyl group, or a fluorinated sulfonic acid type.
  • Anionic surfactants are preferably exemplified.
  • Representative compounds include those of formula (2):
  • X is a hydrogen atom, a fluorine atom, or a chlorine atom
  • n is an integer of 3 to 10
  • m is an integer of 0 or 1 to 4
  • A is a carboxyl group, a sulfonic acid group, or an alkali metal or ammonium thereof. And a salt.).
  • Dunidyne DS 101 (trademark) manufactured by Daikin Industries, Ltd., which is an aqueous solution of ammonium perfluorooctanoate. You.
  • the polymerized milking agent used at the time of polymerization of the fluorine-containing polymer or the dispersion stabilizer optionally added after the polymerization is not a nonionic surfactant, Or It is important not to include qualitatively non-ionic surfactants.
  • “substantially free of a nonionic surfactant” means that the total amount of the nonionic surfactant added to the aqueous dispersion is one weight based on the weight of the solid content of the fluoropolymer. %.
  • the aqueous dispersion containing less than the amount required to stabilize the dispersion of the nonionic surfactant (4 to 12% by weight) is used for the battery.
  • the electrode perest tends to start thickening or agglomerate, so that it is preferably less than 0.5% by weight, more preferably less than 0.1% by weight. It is good to do.
  • the tendency of the PTFE fine particles to agglomerate is surprisingly best when they are not added at all.
  • nonionic surfactants include polyoxetylene alkyl ethers, higher alcohol sulfates, and specifically, polyoxyethylene alkyl ether esters (Union Riki Vide Co., Ltd.). Manufactured by: TX-100), polyoxyethylene isotridecyl ether (manufactured by NOF Corporation: Dispanol TOC), polyoxyethyleneoxypropylene tridecyl ether, polyoxyethylene propylene tridecyl ether Polyoxyethylene fatty acid esters, sorbin fatty acid esters, glycerin esters, polyoxyethylene polypropylene propylene block polymer (pronon 104, manufactured by NOF CORPORATION).
  • anionic surfactants that can be used as a polymerization emulsifier or a dispersion stabilizer include higher alcohol sulfates, specifically, sodium lauryl sulfate, and an amphoteric surfactant '14 agent is an amine oxide-based surfactant.
  • an amine oxide-based surfactant There are dihydroxyethylalkylamineoxide, dimethylalkylamineoxide, and dimethylalkylethoxyamineoxide.
  • Commercially available products include, for example, dimethyl lauryl ethoxyamine oxide (Unisafe ALY) manufactured by NOF Corporation.
  • a fluorine-containing surfactant When adding a fluorine-containing surfactant as a dispersion stabilizer, use a non-fluorine surfactant.
  • sexual agents may be used in combination.
  • the ratio of the fluorine-containing surfactant contained in the surfactant is preferably 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by
  • the total amount of the surfactant contained in the aqueous dispersion is about 0.05 to 25% by weight, preferably about 0.17% by weight, more preferably 0.1 to 2% by weight, based on the weight of the fluoropolymer. %, Especially about 0.1 to 1% by weight.
  • an aqueous dispersion of a water-soluble polymer can be used as the dispersion stabilizer.
  • Synthetic polymers include (meth) acrylic acid polymer, polyacrylate (sodium salt, potassium salt, ammonium salt, etc.), polyacrylamide, carboxylated styrene butadiene polymer, carboxylated vinyl polymer, Vinylmethyl-terno maleic anhydride copolymer, polyvinyl alcohol (PVA), polyethylene oxide (PEO), and other inorganic thickeners.
  • Natural substances include guar gum, xanthan gum, alginate, casein, gelatin and derivatives thereof, and cellulosic derivatives. Among these, cellulosic conductors are preferred.
  • Cellulose derivatives include CM C (carboxymethylcellulose sodium salt, carboxymethylcellulose potassium salt, carboxymethylcellulose ammonium salt), carboxymethylcellulose glycolate, cellulose gum, MC (methylcellulose), EC (ethylcellulose), HE C (hydroxyethyl cellulose), EMC (ethyl methyl cellulose), HE EC (hydroxyethyl cellulose), H EMC (hydroxyethyl methyl cellulose), HEPC (hydroxyethyl propyl cellulose), HE CMC (hydroxy (Ethyl carboxymethyl cellulose), cellulose ethanesulfonic acid sodium salt, cyanoethyl cellulose, and vinzyl cellulose.
  • CM C carboxymethylcellulose sodium salt, carboxymethylcellulose potassium salt, carboxymethylcellulose ammonium salt
  • carboxymethylcellulose glycolate cellulose gum
  • MC methylcellulose
  • EMC ethyl methyl cellulose
  • HE EC hydroxyethyl cellulose
  • H EMC hydroxyeth
  • the total amount of the water-soluble polymer as a dispersion stabilizer added to the aqueous dispersion is from 0.1 to 25% by weight, preferably from 0.1 to 25% by weight, based on the solid content of the fluorine-containing polymer. 77% by weight, more preferably 0.1 to 2% by weight.
  • the electrode additive according to the present invention can be used as a binder.
  • Pond electrode mixes include, for example, electrode (positive or negative electrode) active materials such as oxides or hydroxides such as Kono D-reto, nickel, manganese, and lithium, or hydrogen storage alloys, and carbon (graphite, acetylene)
  • electrode active materials such as oxides or hydroxides such as Kono D-reto, nickel, manganese, and lithium, or hydrogen storage alloys
  • carbon graphite, acetylene
  • carbon eg, activated carbon, acetylene black, etc.
  • the additive for an electrode according to the present invention is also useful as a water repellent for an electrode of a battery.
  • the weight of the solid content in the electrode additive of the present invention is about 20 to 60% by weight, preferably 20 to 40% by weight.
  • the electrode additive is obtained by concentrating an aqueous dispersion of a fluorine-containing polymer produced by emulsion polymerization (usually having a solid content of about 20 to 40% by weight) as it is or by removing water by a membrane separation method or the like. It can be produced by adding a predetermined amount of a surfactant, if necessary.
  • the PTFE contained therein may be fibrillated, and the fine particles of the fluorinated polymer containing PTFE may aggregate and precipitate. . Therefore, when a battery additive consisting of an aqueous dispersion of a fluoropolymer is filled into a container after storage and stored or transported, the closed container should be filled with as much of the aqueous dispersion as possible and the percentage of space in the container It is preferable to keep it low.
  • the proportion of the space is preferably 5% by volume or less, more preferably 1% by volume or less.
  • the upper layer is formed in an aqueous dispersion of 1% by volume or more, preferably about 5 to 20% by volume, based on the volume of the aqueous dispersion of the electrode additive.
  • a solvent having a specific gravity lower than that of the aqueous dispersion include aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as hexane, and alicyclic hydrocarbons such as cyclohexane.
  • Solvent layers must be removed 1 "when used, so solvents that mix with water at a constant rate, such as ethyl acetate, ether, butyl alcohol, and tetrahydrofuran, are not suitable.
  • Such a container are not particularly limited, and known containers which can be filled with an electrode additive A closed container can be widely used.
  • the present invention minimizes the amount of a surfactant for stabilizing a fluorine-containing polymer, so that when manufacturing a composition for an electrode, the PTFE fine particles are uniformly dispersed in the electrode mixture without agglomeration.
  • PTFE fine particles are fibrillated to cover the electrode mixture in a mesh-like fashion, and the resulting electrode has an electrode coating with almost no surfactant residue.
  • Emulsion polymerization of the fluoropolymer was performed in a 6-liter stainless steel autoclave according to a conventional method to obtain an aqueous dispersion of fluoropolymer fine particles shown in Table 1.
  • PTFE is a homopolymer of TFE
  • modified PTFE is a TFE copolymer obtained by copolymerizing a small amount of HFP
  • Aqueous dispersions of PT FE, modified PTFE and FEP are used as surfactants derived from polymerization emulsifiers, each with 0.3% or 2.0% by weight of anionic surfactant based on the solid content of the fluoropolymer.
  • Agent C7F15C00NH4 Dunikin DS 101 manufactured by Daikin Industries, Ltd.).
  • a composition for an electrode was produced using an electrode additive composed of aqueous dispersions having different concentrations and concentrations, and an electrode of a coin-type battery was produced to evaluate the battery characteristics.
  • Viscosity is too high to be applied, and viscosity cannot be adjusted
  • the solid content concentration of the aqueous dispersion of the fluoropolymer was all 30% by weight.
  • This positive electrode paste is applied to the surface of an aluminum foil by a doctor blade method
  • NMP N-methyl-2-pyrrolidone
  • This negative electrode paste is applied to the surface of the copper foil by a doctor blade method. It was fabricated and vacuum-dried at 150 ° C for 4 hours to remove the solvent to obtain a negative electrode plate. A component for a 210-coin battery was prepared, and a positive electrode plate and a negative electrode plate previously punched into the same diameter as the inside diameter of the coin-type battery, and a microporous membrane using polypropylene as a separator were prepared.
  • L i PF 6 of the electrolyte 1 mo 1 ⁇ dm- 3 is as an electrolytic solution
  • a 201-coin cell battery was manufactured by using the above components.
  • the current value of the fabricated battery was set so that the current density was 0.5 mA'cm- 2 with respect to the internal geometric area, and the battery was charged and discharged between 4.2 V and 3 V. Was implemented. At this time, the initial capacity is taken as the capacity at the 5th cycle, and by comparing it with the capacity at the 50th cycle, the battery retention depends on whether the capacity retention rate is 90% or more or less than 90%. Was evaluated. Table 3 shows the results.
  • Example 5 ⁇ (good) ⁇
  • Example 7
  • the electrode used for the capacitor was 40 parts by weight of 1% carboxymethylcellulose, 80 parts by weight of activated carbon having a specific surface area of 1500 m 2 / g, 10 parts by weight of acetylene black, and 10 parts by weight of an aqueous dispersion of PTFE fine particles in a solid content. Electrode coating films having such compositions were prepared by a doctor blade method.
  • the electrode additive of Example 16 was capable of forming an electrode coating film, and had good charge / discharge characteristics.
  • a surfactant and liquid paraffin are added to the aqueous dispersion of PTFE fine particles (polymer solid content 30% by weight) obtained by emulsion polymerization in a closed container (about 100 cc) so that the amounts shown in Table 4 are obtained. (Polypin). After that, the dispersion stability was evaluated by shaking with a shaker at a stroke of 180 cycles / min for 10 minutes. The results are shown in Table 4.
  • the degree of etherification is 0.5-0.7
  • the degree of etherification is 0.5-0.7
  • electrode additives comprising the aqueous dispersions of Examples 12 to 15
  • electrodes for coin-type batteries were produced.
  • the positive electrode paste obtained in this manner is applied to the surface of an aluminum foil by a dough plate method, dried at 24 or: for 1 hour, and dried to remove water. It was confirmed that an electrode plate was obtained.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract

L'invention concerne un additif polymère fluoré, destiné notamment à des électrodes, comprenant une dispersion aqueuse de fines particules de polytétrafluoroéthylène, obtenue par polymérisation en émulsion de tétrafluoroéthylène en milieu aqueux. Cette dispersion comporte un émulsifiant, utilisé pour la polymérisation, et éventuellement un stabilisateur de dispersion ajouté après polymérisation. Cet émulsifiant et ce stabilisateur de dispersion ne sont pas des tensioactifs non ioniques ou ils ne contiennent pratiquement pas de tensioactifs non ioniques.
PCT/JP2001/007636 2000-09-04 2001-09-04 Additif pour electrode, destine a etre utilise dans une batterie ou un condensateur Ceased WO2002021618A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2000-267625 2000-09-04
JP2000267625 2000-09-04
JP2001039542A JP2006040543A (ja) 2000-09-04 2001-02-16 電池またはキャパシタに用いる電極用添加剤
JP2001-39542 2001-02-16

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JP5932200B2 (ja) * 2007-05-11 2016-06-08 キヤノン株式会社 水性インク、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置
JP5223282B2 (ja) * 2007-09-28 2013-06-26 日本ケミコン株式会社 電気二重層キャパシタ用電極およびその製造方法並びに電気二重層キャパシタ
JP2009130329A (ja) * 2007-11-28 2009-06-11 Elna Co Ltd 電気化学デバイス用電極およびその製造方法，電気化学デバイスとしての電気二重層キャパシタ
JP2009295405A (ja) * 2008-06-04 2009-12-17 Asahi Glass Co Ltd 蓄電素子電極形成用水性ペーストの製造方法
JP5343977B2 (ja) * 2008-12-08 2013-11-13 ダイキン工業株式会社 電気二重層キャパシタ
JP2018005971A (ja) * 2014-11-13 2018-01-11 旭硝子株式会社 蓄電デバイス用バインダー組成物の製造方法
WO2024004871A1 (fr) * 2022-06-30 2024-01-04 ダイキン工業株式会社 Procédé de production de feuille pour batteries secondaires à semi-conducteurs, liant pour électrodes de batterie secondaire à semi-conducteurs, composition pour former une électrode, mélange d'électrode et électrode
JP7740577B2 (ja) * 2022-12-16 2025-09-17 Ａｇｃ株式会社 水性分散液
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