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WO2012066911A1 - Liant pour électrode de dispositif électrochimique, ainsi que procédé de fabrication et de conservation de celui-ci - Google Patents

Liant pour électrode de dispositif électrochimique, ainsi que procédé de fabrication et de conservation de celui-ci Download PDF

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Publication number
WO2012066911A1
WO2012066911A1 PCT/JP2011/074636 JP2011074636W WO2012066911A1 WO 2012066911 A1 WO2012066911 A1 WO 2012066911A1 JP 2011074636 W JP2011074636 W JP 2011074636W WO 2012066911 A1 WO2012066911 A1 WO 2012066911A1
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Prior art keywords
electrochemical device
binder
device electrode
electrode
particles
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English (en)
Japanese (ja)
Inventor
恭子 山内
弘一 森田
武志 茂木
達朗 本多
高橋　慎治
一郎 梶原
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JSR Corp
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JSR Corp
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    • 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
    • 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
    • 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
    • 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 binder for an electrochemical device electrode, a method for producing the binder, a method for storing the binder for an electrochemical device electrode, a slurry for an electrochemical device electrode, and an electrochemical device electrode.
  • the binder for an electrochemical device electrode which is a material for obtaining an electrochemical device electrode that has a very low occurrence rate and a high safety such that the separator separating the positive electrode and the negative electrode is damaged, its manufacturing method
  • electrochemical relates to a method for storing a binder for device electrodes, a slurry for electrochemical device electrodes, and an electrochemical device electrode.
  • an electrode active material such as a hydrogen storage alloy or graphite (hereinafter sometimes simply referred to as “active material”), and a thickener such as carboxymethylcellulose
  • active material a hydrogen storage alloy or graphite
  • thickener such as carboxymethylcellulose
  • the binder has a function of improving the adhesion between the electrode layer containing the active material and the current collector.
  • a binder include conjugated dienes.
  • a latex obtained by emulsion polymerization of a monomer containing an aromatic vinyl compound, a (meth) acrylate compound and an ethylenically unsaturated carboxylic acid is known (see Patent Document 1 and Patent Document 2).
  • the binder contains polymer particles that are difficult to swell in the electrolyte solution, have good dispersibility and storage stability when mixed with an active material, and are formed with an electrode layer and a current collector. Performance such as high adhesiveness is required.
  • a binder used for a secondary battery used as a vehicle drive source of a hybrid vehicle or an electric vehicle is required to have higher productivity and safety.
  • compositions (binders) described in Patent Documents 1 and 2 are in a state where organic particles are dispersed in a dispersion medium, aggregates (foreign substances) can be easily formed by processing after production and changes in storage environment. appear. Aggregates thus generated cause a short circuit of the electrode. Specifically, an electrochemical device manufactured using a composition (binder) in which aggregates are generated may cause a problem such as ignition due to an extremely rare defect in the electrode. Therefore, the development of a new binder with reduced foreign matter that can produce an electrode with the least possible occurrence of the above problems has been desired. Furthermore, there has been a demand for the development of a storage method that hardly generates foreign matter.
  • the present invention has been made to solve the above-described problems of the prior art, and has a high safety electrochemical device, specifically, the occurrence rate of defects such as breakage of the separator is extremely small.
  • a binder for an electrochemical device electrode that can be used as a material for forming an electrode of an electrochemical device that hardly causes a problem such as ignition, a method for producing the binder, a slurry for an electrochemical device electrode, and an electrochemical device electrode.
  • the present inventors have found that the binder is removed from the particles having a particle size larger than the thickness of the separator, resulting in the occurrence of defects such as damage to the separator due to the particles. Focusing on the fact that the rate is extremely small, the present inventors have found that the above problem can be achieved by a binder from which particles having a particle size larger than the thickness of the separator are removed, and have completed the present invention.
  • the present invention provides the following binder for an electrochemical device electrode, a method for producing the binder, a method for storing the binder for an electrochemical device electrode, a slurry for an electrochemical device electrode, and an electrochemical device electrode.
  • a binder for an electrochemical device electrode obtained by polymerizing a polymerizable monomer, wherein the number of particles having a particle diameter of 20 ⁇ m or more per mL is 0 when measured with a particle counter.
  • An electrochemical device comprising the binder for an electrochemical device electrode according to any one of the above [1] to [3] (hereinafter sometimes simply referred to as “binder for electrode”) and an electrode active material.
  • Binder for electrode an electrochemical device electrode according to any one of the above [1] to [3]
  • electrode active material an electrode active material.
  • An electrochemical device electrode having a filtration step of polymerizing a polymerizable monomer to obtain a reaction solution containing a polymer and then filtering the obtained reaction solution with a depth-type or pleat-type filter Method for manufacturing binder.
  • Electrochemical device electrode binder containing polymer particles and water stored at a temperature of 2 ° C. or higher and 30 ° C. or lower and filled with the electrochemical device electrode binder for storage
  • the number of particles having a particle diameter of 20 ⁇ m or more per mL when measured with a particle counter is 0, and therefore the separator is damaged by the particles contained in the binder (that is,
  • the separator can be used as a material for forming an electrode constituting an electrochemical device that has a very low defect occurrence rate and high safety.
  • a polymerizable monomer is polymerized to obtain a reaction solution containing a polymer, and then the obtained reaction solution is subjected to a depth type or pleat type filter.
  • the electrode constituting the electrochemical device having a very low safety rate with a very low occurrence rate of defects in which the separator is broken by the particles contained in the binder (that is, the separator is penetrated by the particles).
  • the method for storing the binder for electrochemical device electrodes of the present invention foreign substances such as aggregates are hardly generated during storage of the binder for electrochemical device electrodes, and the yield of the fabricated electrodes can be improved.
  • the separator Since the slurry for an electrochemical device electrode of the present invention contains the binder for an electrochemical device electrode of the present invention, the separator is damaged by the particles contained in the binder (that is, the separator is penetrated by the particles). ) It has an effect that it can be used as a material for forming an electrode constituting an electrochemical device having an extremely low defect occurrence rate and high safety.
  • the electrochemical device electrode of the present invention includes an electrode layer obtained by applying the slurry for an electrochemical device electrode of the present invention to one surface of a current collector, a separator is formed by particles contained in the binder. This produces an effect of constituting an electrochemical device having a very low occurrence rate of defects that are damaged (that is, the separator is penetrated by particles) and that is highly safe.
  • Electrochemical device electrode binder The binder for an electrochemical device electrode of the present invention is obtained by polymerizing a polymerizable monomer. When measured with a particle counter, the number of particles having a particle diameter of 20 ⁇ m or more per mL is 0. Is. In such a binder for an electrochemical device electrode, since the number of particles having a particle diameter of 20 ⁇ m or more per mL when measured with a particle counter is 0, the separator is damaged by the particles contained in the binder (that is, The separator can be used as a material for forming an electrode that constitutes an electrochemical device that has a very low incidence of defects and is highly safe.
  • the conventional binder Since the conventional binder is not operated to remove particles larger than the predetermined particle size, it is considered that particles larger than the predetermined particle size are included. Therefore, if the large particles are charged when an electric current flows, the large particles may be drawn to the electrode side across the separator and may penetrate the separator or cause a crack to penetrate the separator. was there. As described above, the conventional binder may cause a failure in which the separator is damaged (specifically, a failure in which the large particles penetrate the separator or cause a crack to penetrate the separator). It was. When the separator is damaged, the electrochemical device is energized, and thus the electrochemical device may cause a hard short circuit. When the hard short circuit occurs, there is a problem that the electrochemical device ignites in rare cases, for example.
  • the binder for an electrochemical device electrode of the present invention since it does not contain particles (particles larger than a predetermined particle size) that penetrate the separator or cause cracks to penetrate the separator, There is no such problem, and an electrode of an electrochemical device with high safety can be produced.
  • the particles larger than the predetermined particle diameter are specifically particles having a particle diameter of the same size as the thickness of the separator separating the positive electrode and the negative electrode.
  • the thickness of the separator is usually 10 to 30 ⁇ m. If the thickness of the separator is less than 10 ⁇ m, the separator is easily damaged and may cause a failure of the electrochemical device.
  • the binder for an electrochemical device electrode of the present invention is not particularly limited as long as the above conditions are satisfied.
  • the number of particles having a particle diameter of 15 ⁇ m or more and less than 20 ⁇ m per mL when measured with a particle counter. Is preferably 0 to 35000, more preferably 0 to 4000.
  • the number of particles having a particle diameter of more than 10 ⁇ m and less than 15 ⁇ m per mL when measured with a particle counter is more preferably 0 to 500,000, and still more preferably 0 to 200000.
  • the binder tends to be a resistance component, and when this binder is localized, there is a problem that the resistance is likely to increase.
  • the binder is not easily localized. Therefore, there is an advantage that the resistance is hardly increased.
  • the number of particles per mL is measured with a particle counter, and the number of particles is defined for each predetermined particle diameter. That is, the binder for an electrochemical device electrode of the present invention does not contain any particles having a particle diameter of 20 ⁇ m or more per mL.
  • the binder for an electrochemical device electrode of the present invention is obtained by polymerizing a polymerizable monomer.
  • it includes a polymer having a structural unit derived from the polymerizable monomer, and this polymer exhibits a function as a binder.
  • the solid content concentration of the polymer is preferably 20 to 56% by mass, more preferably 23 to 55% by mass, and 25 to 54% by mass. It is particularly preferred.
  • the solid content concentration is within the above range, the polymer particles are stabilized in the binder (exist in a well dispersed state), so that there is an advantage that a binder having excellent long-term stability can be obtained.
  • the solid content concentration is less than 20% by mass, there is a problem that productivity is lowered. That is, when the reaction solution obtained by polymerization is used as a binder as it is, it is necessary to lower the concentration of the polymer obtained by polymerization. Therefore, productivity becomes low.
  • the solid content concentration differs depending on whether it is for the negative electrode or the positive electrode.
  • the solid content concentration of SBR (styrene-butadiene copolymer) which is a negative electrode binder is 40 to 55% by mass.
  • the solid content concentration of the fluoroacrylic emulsion as a binder is 20 to 50% by mass, preferably 27 to 33% by mass.
  • the binder for an electrochemical device electrode of the present invention is not particularly limited as long as it is obtained by polymerizing a polymerizable monomer, and can be used as a binder for a positive electrode or a negative electrode.
  • the binder described in Japanese Patent No. 3999927 can be exemplified.
  • a polymer obtained by polymerizing a polymerizable monomer composed of vinylidene fluoride, a fluorine-containing monomer copolymerizable with vinylidene fluoride, or a hydrocarbon monomer such as ethylene or propylene. can be included.
  • fluorine-containing monomer copolymerizable with vinylidene fluoride examples include vinyl fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether.
  • monomers other than the above-mentioned monomers include unsaturated dibasic acid monoesters, vinylene carbonate, and the like.
  • unsaturated dibasic acid monoesters include maleic acid monomethyl ester, maleic acid monoethyl ester, citraconic acid monomethyl ester, and citraconic acid monoethyl ester.
  • binder for the negative electrode examples include those described in JP 2010-129186 A. Specific examples include those containing a polymer obtained by polymerizing a polymerizable monomer comprising a conjugated diene, an aromatic vinyl compound, a (meth) acrylate compound, an ethylenically unsaturated carboxylic acid, or the like. .
  • conjugated diene examples include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, chloroprene and the like. Of these, 1,3-butadiene is preferred.
  • the proportion of the conjugated diene used in the total amount of the polymerizable monomer is preferably 33 to 48.5% by mass, and more preferably 35 to 45% by mass.
  • the use ratio is less than 33% by mass, the obtained polymer has a high glass transition temperature, and the flexibility of the obtained electrode layer and the adhesion to the current collector tend to be lowered.
  • the content exceeds 48.5% by mass the surface of the obtained electrode layer tends to be sticky, and therefore the workability of the electrode layer sticking to a roll during press working may be inferior. There is.
  • the aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene and the like. Among these, styrene is preferable.
  • the use ratio of the aromatic vinyl compound in the total amount of the polymerizable monomer is preferably 40 to 50% by mass, and more preferably 43 to 48% by mass. When the use ratio is less than 40% by mass, the interaction with the graphite used as the active material is reduced, and as a result, the obtained electrode layer tends to easily lose the active material. On the other hand, when it is more than 50% by mass, the obtained polymer is hard and brittle, and the flexibility of the obtained electrode layer and the adhesion to the current collector tend to be lowered.
  • Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl ( (Meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-hexyl (meth) acrylate, octyl (meth) acrylate, i-nonyl (meth) acrylate, decyl ( Examples include meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and ethylene glycol (meth) acrylate. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate
  • the proportion of the (meth) acrylate compound used in the total amount of the polymerizable monomer is preferably 8 to 12.5% by mass, and more preferably 9 to 12% by mass.
  • the use ratio is less than 8% by mass, the obtained polymer has low affinity with the electrolytic solution, and the binder tends to be an electric resistance component in the electrochemical device. Therefore, the device internal resistance tends to increase.
  • the content is 12.5% by mass, the obtained polymer has excessive absorption of the electrolytic solution, and the binding property is easily lost in the electrochemical device. For this reason, the battery is likely to be deteriorated during high-temperature storage.
  • Examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid and itaconic acid.
  • the use ratio of the ethylenically unsaturated carboxylic acid in the total amount of the polymerizable monomer is preferably 0.1 to 20% by mass, and more preferably 0.2 to 15% by mass.
  • the use ratio is less than 0.1% by mass, the dispersion stability of the polymer particles is insufficient when the slurry for an electrochemical device electrode is prepared, and aggregates are easily generated. Therefore, there is a tendency that problems such as a decrease in the adhesion of the resulting electrode layer to the current collector tend to occur.
  • it exceeds 20% by mass the slurry viscosity increases with time in the storage process after the preparation of the slurry for electrochemical device electrodes, and the slurry tends to be inferior in coatability.
  • polymerizable monomers include, in addition to the above monomers, alkyl amides of ethylenically unsaturated carboxylic acids such as (meth) acrylamide and N-methylol acrylamide; vinyl carboxylates such as vinyl acetate and vinyl propionate.
  • Esters acid anhydrides, monoalkyl esters, monoamides of ethylenically unsaturated dicarboxylic acids; aminoalkyl amides of ethylenically unsaturated carboxylic acids such as aminoethyl acrylamide, dimethylaminomethyl methacrylamide, methylaminopropyl methacrylamide; ) Vinyl cyanide compounds such as acrylonitrile and ⁇ -chloroacrylonitrile.
  • the binder for electrochemical device electrodes of the present invention may contain an emulsifier, a polymerization initiator, a molecular weight regulator, etc. used in the polymerization step described later, in addition to the polymer.
  • the method for producing a binder for an electrochemical device electrode of the present invention is a method for producing the above-described binder for an electrochemical device electrode of the present invention, and a reaction liquid containing a polymer is obtained by polymerizing a polymerizable monomer. Then, the obtained reaction solution is filtered using a depth type or pleat type filter. Since it has such a process, the separator is damaged by the particles contained in the binder (that is, the separator is penetrated by the particles), and the electrode forming the electrochemical device that has a very low incidence of defects and high safety is formed. Thus, a binder for an electrochemical device electrode can be produced.
  • the electrode binder is usually manufactured in a place that is not in a maintained environment such as a clean room.
  • Polymerization step In the method for producing a binder for an electrochemical device electrode of the present invention, a conventionally known method can be adopted as a method for obtaining a reaction solution containing a polymer by polymerizing a polymerizable monomer (polymerization step). .
  • a conventionally known method can be adopted as a method for obtaining a reaction solution containing a polymer by polymerizing a polymerizable monomer (polymerization step).
  • methods described in JP 2010-129186 A, JP 3999927 A, and the like can be mentioned.
  • a reaction liquid containing a polymer is obtained by polymerizing a polymerizable monomer such as vinylidene fluoride by a method such as suspension polymerization, emulsion polymerization, or solution polymerization.
  • a method such as suspension polymerization, emulsion polymerization, or solution polymerization.
  • the method of obtaining can be mentioned.
  • aqueous suspension polymerization and emulsion polymerization are preferable from the viewpoint of ease of post-treatment and the like, and aqueous suspension polymerization is particularly preferable.
  • suspending agent for example, methyl cellulose, methoxylated methyl cellulose, propoxylated methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyethylene oxide, gelatin and the like can be used as a suspending agent.
  • the suspending agent is preferably added in the range of 0.005 to 1.0% by mass, and preferably in the range of 0.01 to 0.4% by mass with respect to the dispersion medium (eg water). Is more preferable.
  • polymerization initiator examples include diisopropyl peroxydicarbonate, dinormalpropyl peroxydicarbonate, dinormalheptafluoropropyl peroxydicarbonate, isobutyryl peroxide, di (chlorofluoroacyl) peroxide, and di (perfluoro). Acyl) peroxide and the like can be used.
  • the amount of the polymerization initiator used is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers. .
  • a chain transfer agent may be added.
  • the chain transfer agent include ethyl acetate, methyl acetate, acetone, ethanol, n-propanol, acetaldehyde, propyl aldehyde, ethyl propionate, tetra
  • examples thereof include carbon chloride.
  • the amount of the chain transfer agent used is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of polymerizable monomers. preferable.
  • the total charged amount of the polymerizable monomers is preferably 1: 1 to 1:10, and preferably 1: 2 to 1: 5 in terms of the total amount of polymerizable monomers: dispersion medium. Is more preferable.
  • the polymerization conditions can be 10 to 50 ° C. and 10 to 100 hours.
  • a method for obtaining a reaction liquid containing a polymer by emulsion polymerization of a polymerizable monomer in an aqueous medium in the presence of an emulsifier, a polymerization initiator, and a molecular weight regulator can be mentioned.
  • anionic surfactants As the emulsifier, anionic surfactants, nonionic surfactants, amphoteric surfactants and the like can be used alone or in combination of two or more.
  • anionic surfactant sulfates of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, sulfates of polyethylene glycol alkyl ethers, and the like can be used.
  • nonionic surfactant an alkyl ester type of polyethylene glycol, an alkyl ether type, an alkylphenyl ether type, or the like can be used.
  • amphoteric surfactants include those in which the anion moiety is a carboxylate salt, sulfate ester salt, sulfonate salt, or phosphate ester salt, and the cation moiety is an amine salt or a quaternary ammonium salt.
  • examples include amino acids such as bentines such as lauryl betaine and stearyl betaine, lauryl- ⁇ -alanine, lauryl di (aminoethyl) glycine, and octyldi (aminoethyl) glycine.
  • the amount of the emulsifier used is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers used.
  • polymerization initiator examples include water-soluble polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate, and oil-soluble polymerization initiators such as benzoyl peroxide, lauryl peroxide, and 2,2′-azobisisobutyronitrile.
  • Redox polymerization initiators in combination with a reducing agent such as sodium bisulfite can be used alone or in combination of two or more.
  • the amount of the polymerization initiator used is preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers.
  • molecular weight modifiers examples include halogenated hydrocarbons such as chloroform and carbon tetrachloride, mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-todecyl mercaptan, t-dotezyl mercaptan and thioglycolic acid, dimethyl Those used in usual emulsion polymerization such as xanthogens such as xanthogen disulfide and diisopropylxanthogen disulfide, terpinolene and ⁇ -methylstyrene dimer can be used.
  • the usage-amount of a molecular weight regulator is 5 mass parts or less normally with respect to 100 mass parts of whole quantity of a polymerizable monomer.
  • the emulsion polymerization may be one-stage, but is preferably a two-stage emulsion polymerization.
  • the first stage emulsion polymerization preferably has a polymerization temperature of, for example, 40 to 80 ° C., a polymerization time of, for example, 2 to 4 hours, and a polymerization conversion rate of 50% or more. It is preferable that it is 60% or more.
  • the polymerization temperature is, for example, 40 to 80 ° C.
  • the polymerization time is, for example, 2 to 6 hours.
  • the polymer in the resulting reaction solution is not particularly limited as long as the electrochemical device electrode binder of the present invention exhibits a function as a binder, but the number average particle diameter is preferably 50 to 400 nm, More preferably, it is 100 to 300 nm.
  • the “number average particle size” in the present specification is a value measured by a concentrated particle size analyzer “FPAR-1000” (trade name) (manufactured by Otsuka Electronics Co., Ltd.).
  • the polymer preferably has a glass transition temperature of ⁇ 50 to + 25 ° C., more preferably ⁇ 30 to + 5 ° C.
  • glass transition temperature means that a polymer film is formed by applying a binder to a glass plate and drying at 120 ° C. for 1 hour. It is a glass transition temperature (Tg) measured using a meter (for example, “differential scanning calorimeter” manufactured by Seiko Denshi Kogyo Co., Ltd.).
  • the depth type filter is a high-precision filtration filter also referred to as a depth filtration or volume filtration type filter.
  • depth type filters include those having a laminated structure in which filtration membranes having a large number of pores are laminated, and those in which fiber bundles are wound up.
  • Specific examples of depth type filters include Profile II, Nexis NXA, Nexis NXT, Polyfine XLD, Ultiplez Profile, etc. (all manufactured by Nippon Pole), depth cartridge filters, wind cartridge filters, etc. (all, Advantech) Co., Ltd.), CP filter, BM filter, etc. (all manufactured by Chisso Corporation), slope pure, diamond, micro-Syria, etc. (all manufactured by Loki Techno Co.), and the like.
  • the depth type filter it is preferable to use a filter having a rated filtration accuracy of 1.0 to 20 ⁇ m, and more preferably 5.0 to 10 ⁇ m.
  • a filter having a rated filtration accuracy within the above range, it is possible to efficiently obtain a filtrate in which the number of particles having a particle diameter of 20 ⁇ m or more per mL when measured with a particle counter is zero. Also, the usable period of the filter is extended because the number of coarse particles trapped in the filter is minimized.
  • the pleated type filter is formed by fold-folding a microfiltration membrane sheet made of non-woven fabric, filter paper, metal mesh, etc., and then forming into a cylindrical shape and sealing the crease seam of the sheet in a liquid-tight manner, and It is a cylindrical high-precision filtration filter obtained by sealing both ends of a cylinder liquid-tightly.
  • a filter having a rated filtration accuracy of 1.0 to 20 ⁇ m is preferably used, and a filter having a rating of 5.0 to 10 ⁇ m is more preferable.
  • a filter having a rated filtration accuracy within the above range it is possible to efficiently obtain a filtrate in which the number of particles having a particle diameter of 20 ⁇ m or more per mL when measured with a particle counter is zero. Also, the usable period of the filter is extended because the number of coarse particles trapped in the filter is minimized.
  • pleat type filters include HDCII, Polyfine II, etc. (all manufactured by Nippon Pole), PP pleated cartridge filter (manufactured by Advantech), Porous Fine (manufactured by Chisso), Sirton Pore, Micropure, etc (All manufactured by Loki Techno Co., Ltd.).
  • the filtration conditions are as follows.
  • a filtrate with 0 particles having a particle diameter of 20 ⁇ m or more per mL is obtained.
  • the differential pressure may be set as appropriate within a range that does not exceed the maximum differential pressure resistance of the filter to be used.
  • the differential pressure is preferably 0.2 to 0.4 MPaG.
  • the liquid temperature is preferably 10 to 50 ° C.
  • the filtration step can be performed using, for example, a filtration device 100 as shown in FIG.
  • the filtration device 100 includes a supply tank 1 for storing and supplying an electrochemical device electrode binder before foreign matter removal, a metering pump 2 for flowing the electrochemical device electrode binder before foreign matter removal at a constant flow rate, and a cartridge filter. (Not shown) and a filter 4 having a housing in which the cartridge filter is housed (mounted), a pulsation preventer 3 located in the middle of the metering pump 2 and the filter 4, a pulsation preventer 3 and a filter 4
  • positioned downstream of the filter 4 are provided.
  • the filtration device 100 includes a return conduit 6 that returns the binder from the filter 4 to the supply tank 1, and a discharge conduit 5 that discharges the binder for an electrochemical device electrode filtered by the filter 4.
  • the reaction solution obtained in the polymerization step is supplied from the supply tank 1 to the pulsation preventer 3 that has been pressurized by the metering pump 2.
  • the pulsation is reduced by the pulsation preventer 3.
  • the reaction liquid discharged from the pulsation preventer 3 is supplied to the filter 4 and removed through the discharge conduit 5 after removing foreign substances.
  • the recovered liquid recovered is an electrochemical device electrode binder.
  • “foreign matter” means particles having a particle diameter of 20 ⁇ m or more.
  • the material of the particles is not particularly limited as long as the particle diameter is 20 ⁇ m or more, and is a metal, a resin, a mixture thereof, or the like.
  • the recovered liquid is returned to the supply tank 1 through the return conduit 6 without returning to the electrochemical device electrode binder, and the filter 4 again. It can also be filtered. Moreover, when the pulsation by the metering pump 2 does not occur, the pulsation preventer 3 may not be disposed. Furthermore, when the viscosity of the reaction solution is high, the viscosity of the reaction solution can be lowered by heating the supply tank, the conduit, or both of them. That is, you may further provide the heating means which can heat a supply tank, a conduit
  • the filtration apparatus 100 is provided with the 1st pressure gauge 7a and the 2nd pressure gauge 7b, you may use the filtration apparatus which is not provided with a pressure gauge. However, by providing the first pressure gauge 7a and the second pressure gauge 7b, the differential pressure generated in the filter can be managed so that the filter functions normally. Moreover, it may replace with the supply tank 1 and may supply the binder for electrochemical device electrodes before foreign material removal directly from the container for conveyance.
  • the filtration apparatus 100 is an example using the single filter 4, a several filter can also be used. When using a some filter, a some filter may be connected in series and you may arrange
  • the method for storing a binder for an electrochemical device electrode of the present invention can store the binder for an electrochemical device electrode containing polymer particles and water well (that is, in a state where no foreign matter is generated) for a long period of time.
  • save method of this invention can be suitably employ
  • the polymer contained in the binder for an electrochemical device electrode contains a polymer that easily aggregates (for example, a fluorine-based polymer), the preservation method of the present invention exhibits a better effect.
  • the electrochemical device electrode binder In the storage method of the present invention, it is essential to store the electrochemical device electrode binder at a temperature of 2 to 30 ° C., preferably 10 to 25 ° C.
  • the upper limit of the above range When the upper limit of the above range is exceeded, polymer particles aggregate at the portion of the interface between the void and the electrochemical device electrode binder that contacts the wall surface of the container during long-term storage, and foreign matter is generated. Therefore, it cannot be stored stably for a long time.
  • polymer particles aggregate in the binder for an electrochemical device electrode, and a gel or foreign matter is generated. Therefore, it cannot be stored stably for a long time.
  • the inner volume of the container is equal to the volume of the void portion excluding the volume occupied by the binder for the electrochemical device electrode from the inner volume of the container filled with the electrochemical device electrode binder. It is essential that the ratio (%) (hereinafter also referred to as “porosity”) is 1 to 20%, preferably 3 to 15%, more preferably 5 to 10%.
  • porosity exceeds the upper limit of the above range, the volatilization amount of water increases when the storage temperature changes, and as a result, the amount of vapor is increased at the gas-liquid interface (the interface between the void and the electrochemical device electrode binder). Aggregation of coalesced particles occurs and foreign matter is generated. Therefore, it cannot be stably stored.
  • the porosity is less than the lower limit of the above range, when the volume of the electrochemical device electrode binder changes due to a change in storage temperature, the container is deformed or the container is ruptured. Therefore, it cannot be stably stored.
  • the oxygen concentration in the void is preferably 1% or less.
  • the binder component the component contained in the binder for electrochemical device electrodes
  • the oxygen concentration is a value obtained by measuring the concentration in the void immediately before sealing the container using an oxygen concentration meter (model number “OXY-1S” manufactured by Jiko Co., Ltd.).
  • the elution rate of metal ions from the container for storing the binder for an electrochemical device electrode is 50 ppm or less.
  • the metal ions are eluted in the electrochemical device electrode binder, the zeta potential balance on the particle surface contributing to the dispersion of the polymer particles in the electrochemical device electrode binder is lost. For this reason, aggregation easily occurs.
  • the polymer particles aggregated in this way are contained, a smooth active material layer cannot be formed, or when producing an electricity storage device, the aggregated polymer particles break through the separator, and the positive electrode and the negative electrode This is not preferable because there is a high possibility of causing a fatal problem such as short-circuiting the circuit.
  • a container made of glass or resin is preferable.
  • a clean container manufactured according to JP-A-59-035043 can be preferably used.
  • the quality of the binder for an electrochemical device electrode hardly changes during storage even if the storage period is sequentially extended to June, December, and 18 months. Moreover, a gel-like thing is not produced. For this reason, the same active material layer can be formed on the same conditions as forming an active material layer using the binder for electrochemical device electrodes immediately after manufacture. Moreover, the effect which can improve the productivity of the binder for electrochemical device electrodes becomes so large that a storage period becomes long in June, December, and 18 months.
  • the slurry for an electrochemical device electrode of the present invention contains the above-mentioned binder for an electrochemical device electrode of the present invention and an electrode active material. Since such a slurry for an electrochemical device electrode contains the binder for an electrochemical device electrode of the present invention, the separator is damaged by the particles contained in the binder (that is, the separator is penetrated by the particles). ) It can be used as a material for forming an electrode constituting an electrochemical device having a very low defect occurrence rate and high safety.
  • the slurry for an electrochemical device electrode of the present invention can be prepared by mixing the binder for an electrochemical device electrode of the present invention and an electrode active material.
  • Electrode active material is not particularly limited. When used for lithium ion secondary battery electrodes, by firing carbon, carbon materials obtained by firing organic polymer compounds such as phenolic resin, polyacrylonitrile, cellulose, etc. The obtained carbon material, artificial graphite, natural graphite and the like can be used. Moreover, when using for an electric double layer capacitor electrode, activated carbon, activated carbon fiber, silica, alumina, etc. can be used. Further, when used for a lithium ion capacitor electrode, a carbon material such as graphite, non-graphitizable carbon, hard carbon, coke, polyacene organic semiconductor (PAS), or the like can be used.
  • PES polyacene organic semiconductor
  • the slurry for electrochemical device electrodes of the present invention includes thickeners, dispersants such as sodium hexametaphosphate, sodium tripolyphosphate, sodium polyacrylate, nonionic or anionic surfactants as latex stabilizers, Additives such as foaming agents may be contained.
  • the solid content in the electrode binder is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the electrode active material. Is more preferably 3 to 3 parts by mass, particularly preferably 0.3 to 3 parts by mass, and most preferably 0.5 to 2 parts by mass.
  • the ratio of the solid content of the electrode binder is too small, good adhesion tends not to be obtained.
  • the ratio of the solid content of the binder for electrodes is excessive, the overvoltage tends to increase and affect the battery characteristics.
  • the favorable adhesiveness of an electrode layer and a collector may not be acquired as the said content rate is less than 0.1 mass part.
  • it exceeds 10 parts by mass it may be difficult to sufficiently improve battery characteristics.
  • the slurry for electrochemical device electrodes of the present invention as means for mixing the binder for electrochemical device electrodes, the electrode active material, and the additive used as necessary, a stirrer, a defoamer, a bead mill, A high-pressure homogenizer can be used.
  • the electrode slurry can be prepared under reduced pressure. By carrying out under reduced pressure, it can prevent that a bubble arises in the electrode layer obtained.
  • Electrochemical device electrode The electrochemical device electrode of the present invention is arranged on a plate-like current collector and one surface side of the current collector, and the above-described slurry for an electrochemical device electrode of the present invention is disposed on one surface of the current collector.
  • An electrode layer obtained by coating Since such an electrochemical device electrode includes an electrode layer obtained by applying the slurry for an electrochemical device electrode of the present invention to one surface of a current collector, a separator is formed by particles contained in the binder. It is possible to construct an electrochemical device that has a very low occurrence rate of defects that are damaged (that is, the separator is penetrated by particles) and that is highly safe.
  • the method for producing an electrochemical device electrode of the present invention is as follows.
  • the above-described slurry for an electrochemical device electrode of the present invention is applied to the surface of a flat plate current collector and dried to form a coating film on the current collector. Form a laminate. Thereafter, the obtained laminate is pressed in the thickness direction. In this way, the electrochemical device electrode of the present invention can be produced.
  • the composition may be applied to the current collector.
  • the current collector As the current collector, a metal foil, an etching metal foil, an expanded metal, or the like can be used. As a material constituting the current collector, a material selected from metal materials such as aluminum, copper, nickel, tantalum, stainless steel, and titanium can be appropriately selected and used according to the type of the target electrochemical device.
  • the current collector has a thickness of 5 to 30 ⁇ m, preferably 8 to 25 ⁇ m, for example, when an electrode for a lithium secondary battery is formed. For example, in the case of constituting an electrode for an electric double layer capacitor, the thickness is 5 to 100 ⁇ m, preferably 10 to 70 ⁇ m, more preferably 15 to 30 ⁇ m.
  • Electrode layer As described above, the electrode layer is disposed on one surface (for example, the surface) side of the current collector, and is obtained by applying the slurry for an electrochemical device electrode of the present invention to one surface of the current collector. is there.
  • a method of applying the slurry for an electrochemical device electrode a conventionally known method can be appropriately employed. For example, a spin coating method (spin coating method), a casting coating method, a roll coating method, a slit & spin coating method, a doctor blade method, a reverse roll method, a comma bar method, a gravure method, an air knife method and the like can be mentioned.
  • the treatment temperature is preferably 20 to 250 ° C., for example, and more preferably 50 to 150 ° C.
  • the treatment time is preferably 1 to 120 minutes, for example, and more preferably 5 to 60 minutes.
  • the electrode layer thus formed has, for example, a thickness of 40 to 100 ⁇ m and a density of 1.3 to 2.0 g / cm 2 .
  • Electrochemical device The electrochemical device electrode obtained as described above can be suitably used as an electrode of an electrochemical device such as a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor. Electrochemical devices are generally formed on the current collector and the surface of the current collector, and are formed on the surface of the current collector and the current collector. And a separator disposed between the positive electrode and the negative electrode, and the thickness of the separator is usually 10 to 10 as described above. 30 ⁇ m. If the thickness of the separator is less than 10 ⁇ m, the separator is easily damaged by vibration or the like, which may cause a failure of the electrochemical device.
  • the separator is made of a porous film, and examples of the material thereof include polypropylene and polyethylene.
  • LiClO 4 LiBF 4, LiI , LiPF 6, LiCF 3 SO 3, LiAsF 6, LiSbF 6, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) 4, LiCH 3 SO 3, LiC 4 F 9 SO 3, Li ( C 4 F 3 SO 2) 2 N, Li [(CO 2) 2] such as 2 B and the like.
  • solvent examples include carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, lactones such as ⁇ -butyrolactone, trimethoxysilane, 1,2-dimethoxyethane, and diethyl ether.
  • carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate
  • lactones such as ⁇ -butyrolactone, trimethoxysilane, 1,2-dimethoxyethane, and diethyl ether.
  • Ethers such as 2-ethoxyethane, tetrahydrofuran and 2-methyltetrahydrofuran, sulfoxides such as dimethyl sulfoxide, oxolanes such as 1,3-dioxolane and 4-methyl-1,3-dioxolane, nitrogen such as acetonitrile and nitromethane Containing compounds, esters such as methyl formate, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, phosphate triester, diglyme, triglyme, tetrag Glymes such as Im, ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, sulfones such as sulfolane, oxazolidinones such as 2-methyl-2-oxazolidinone, 1,3-propane sultone, 4-butane
  • an electrolyte such as tetraethylammonium tetrafluoroborate, triethylmethylammonium tetrafluoroborate, tetraethylammonium hexafluorophosphate is contained in the solvent.
  • a dissolved electrolytic solution is used.
  • the same electrolytic solution as in the case of forming the lithium ion secondary battery can be used.
  • the binder is measured using a dense particle size analyzer “FPAR1000” (manufactured by Otsuka Electronics Co., Ltd.) with an autosampler.
  • FPAR1000 dense particle size analyzer
  • the electrochemical device electrode binder after removing the foreign matter has no change in various properties as a binder (that is, for the electrochemical device electrode). It can be evaluated that the same function as a conventional binder is maintained as a binder.
  • the particle counter is measured using a particle count particle size distribution measuring device “Accurizer 780APS” manufactured by Particle Sizing Systems. Specifically, the number of coarse particles to be measured is “4000 particles / mL (0.56 ⁇ m)” (that is, “4000 particles having a particle diameter larger than 0.56 ⁇ m in 1 mL or less”). Repeat the blank measurement with ultrapure water. Thereafter, 100 mL of a binder (sample) diluted 100 times with ultrapure water is prepared, and this sample is set in the particle size distribution analyzer. After the setting, the sample is automatically diluted to the optimum concentration by the particle size distribution analyzer. Thereafter, the particle size distribution measuring device measures the number of particles per mL of the sample twice, and calculates an average value. This average value is multiplied by 100 to obtain the number of particles per 1 mL of binder.
  • the prepared slurry for electrochemical devices is uniformly applied to the surface of a copper foil current collector (flat current collector) by a doctor blade method so that the film thickness after drying becomes 100 ⁇ m. And a drying treatment at 120 ° C. for 20 minutes to form a dry slurry layer on the surface of the current collector. Thereafter, the current collector on which the dry slurry layer is formed on the surface is pressed with a roll press so that the density of the obtained electrode layer is 1.5 g / cm 3 . In this way, a negative electrode comprising the current collector and the electrode layer formed on the surface (one surface) of the current collector is prepared.
  • the slurry for positive electrode is prepared by stirring and mixing sequentially.
  • the prepared slurry for positive electrode is uniformly applied to the surface of a current collector (flat plate current collector) made of aluminum foil by a doctor blade method so that the film thickness after drying becomes 90 ⁇ m. Drying is carried out at 20 ° C. for 20 minutes to form a dry slurry layer on the surface of the current collector. Thereafter, the current collector with the dry slurry layer formed on the surface thereof is pressed by a roll press so that the density of the obtained electrode layer is 3.8 g / cm 3 . In this way, a positive electrode comprising the current collector and the electrode layer formed on the surface (one surface) of the current collector is produced.
  • a secondary battery composed of a bipolar single-layer laminate cell is manufactured by joining and sealing one unbonded side of the outer package by thermocompression bonding with a heating sealing device.
  • Example 1 In a temperature-controlled reactor equipped with a stirrer, 200 parts of water, 0.1 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite, ⁇ -methylstyrene dimer 0 .2 parts, 0.1 parts of dodecyl mercaptan, 6.0 parts of butadiene as the conjugated diene, 12.5 parts of styrene as the aromatic vinyl compound, 3.5 parts of methyl methacrylate as the (meth) acrylate compound, ethylenically unsaturated carboxylic acid
  • a polymerizable monomer (monomer composition (a)) consisting of 0.5 part of acrylic acid and 2.5 parts of itaconic acid was charged at a temperature of 70 ° C. The temperature was raised and the polymerization reaction was carried out for 2 hours (first stage).
  • the pH of the obtained latex was adjusted to 7.5, residual monomers were removed by steam distillation, and concentrated by vacuum treatment. Thereafter, it was subjected to a Sato-type vibrating screen machine “1200D-1S special type” (manufactured by Koei Sangyo Co., Ltd.) equipped with a 250 mesh filter to obtain a binder for an electrochemical device electrode before foreign matter removal.
  • the obtained binder for an electrochemical device electrode before removing foreign matter had a solid concentration of 48.5% by mass, a pH of 7.8, and a viscosity of 119 mPa ⁇ s.
  • a filtration apparatus 100 shown in FIG. 1 includes a supply tank 1 for storing and supplying an electrochemical device electrode binder before foreign matter removal, and a metering pump 2 for flowing the electrochemical device electrode binder before foreign matter removal at a constant flow rate.
  • a filter 4 having a cartridge filter (not shown) and a housing containing (mounting) the cartridge filter, a pulsation preventer 3 located in the middle of the metering pump 2 and the filter 4, and a pulsation preventer 3
  • a first pressure gauge 7 a disposed between the filter 4 and a second pressure gauge 7 b disposed downstream of the filter 4 is provided.
  • the filtration device 100 includes a return conduit 6 that returns the binder from the filter 4 to the supply tank 1, and a discharge conduit 5 that discharges the binder for an electrochemical device electrode filtered by the filter 4.
  • the filter 4 is one in which a depth type cartridge filter “Profile II” (manufactured by Nippon Pall Co., Ltd., rated filtration accuracy 10 ⁇ m, length 1 inch) is mounted in the housing.
  • the metering pump 2 was an air-driven diaphragm pump, and the differential pressure before and after the filter was 0.34 MPaG.
  • the number average particle diameter in the binder for electrochemical device electrodes after filtration by the filtration apparatus 100 shown in FIG. 1 was 177 nm.
  • the number average particle diameter is a value measured by a concentrated particle size analyzer “FPAR1000” (manufactured by Otsuka Electronics Co., Ltd.) with an autosampler.
  • the binder for an electrochemical device electrode after filtration by the filtration apparatus 100 shown in FIG. The evaluation results are shown in Table 1.
  • the binder for an electrochemical device electrode after filtration by the filtration device 100 is the number of particles having a particle diameter of 20 ⁇ m or more per mL when measured with a particle counter, and the particle diameter is 15 ⁇ m.
  • the number of particles having a particle diameter of less than 20 ⁇ m and the number of particles having a particle diameter of more than 10 ⁇ m and less than 15 ⁇ m were all zero.
  • Example 2 In the same manner as in Example 1, a binder for an electrochemical device electrode before removing foreign matters was obtained. About the obtained binder for electrochemical device electrodes before foreign material removal, it filtered using the filtration apparatus. The filtration device used in this example was replaced with a depth type cartridge filter “Profile II” (manufactured by Nihon Pall Co., Ltd., rated filtration accuracy 10 ⁇ m, length 1 inch) of the filtration device 100 shown in FIG. A type cartridge filter “Profile II” (manufactured by Nippon Pole Co., Ltd., rated filtration accuracy 20 ⁇ m, length 1 inch) was used. The differential pressure before and after the filter was 0.25 MPaG. Moreover, the number average particle diameter in the binder for electrochemical device electrodes after filtration was 177 nm. Said various evaluation was performed about the binder for electrochemical device electrodes after filtration with a filtration apparatus. The evaluation results are shown in Table 2.
  • Example 2 (Comparative Example 2) The above-mentioned various evaluations were carried out in the same manner as in Example 2 with respect to the “binder for electrochemical device electrode before removing foreign matter” before filtration by the filtration device used in Example 2. The evaluation results are shown in Table 2.
  • Example 3 In the same manner as in Example 1, a binder for an electrochemical device electrode before removing foreign matters was obtained.
  • the obtained binder for an electrochemical device electrode before removing the foreign matter was filtered using the filtration apparatus 100 shown in FIG.
  • the differential pressure before and after filtration was set to 0.38 MPaG, and the filtrate was sampled 5 minutes after the start of filtration by the filtration device 100, and the various evaluations were performed.
  • the evaluation results are shown in Table 3.
  • the number average particle diameter in the binder for electrochemical device electrodes after filtration was 177 nm.
  • Example 4 The filtrate (electrochemical device electrode binder after filtration by a filtration device) was sampled in the same manner as in Example 3 except that the filtrate after 10 minutes from the start of filtration was sampled. Said various evaluation was performed about the obtained filtrate. The evaluation results are shown in Table 3. In addition, the number average particle diameter in the binder for electrochemical device electrodes after filtration was 177 nm.
  • Example 5 The filtrate (electrochemical device electrode binder after filtration by a filtration apparatus) was sampled in the same manner as in Example 3 except that the filtrate 15 minutes after the start of filtration was sampled. Said various evaluation was performed about the obtained filtrate. The evaluation results are shown in Table 3. In addition, the number average particle diameter in the binder for electrochemical device electrodes after filtration was 177 nm.
  • Example 3 (Comparative Example 3) The above-mentioned various evaluations were performed in the same manner as in Example 3 with respect to the “binder for electrochemical device electrode before foreign matter removal” before filtration by the filtration device used in Example 3. The evaluation results are shown in Table 3. In addition, the number average particle diameter in the binder for electrochemical device electrodes after filtration was 177 nm.
  • the electrochemical device electrode binders of Examples 1 to 5 were more defective than the electrochemical device electrode binders of Comparative Examples 1 to 3 to break the separator. It was confirmed that the material can be used as a material for constituting an electrode of an electrochemical device having a very low rate and high safety.
  • Example 6 to 10 Comparative Examples 4 to 10
  • JSR TRD2001 manufactured by JSR
  • Example 8 to 10 and Comparative Examples 8 to 10 Table 5
  • each electrochemical device electrode binder produced in Examples 1 to 3 electrochemical device electrode binder after filtration was used to evaluate the presence or absence of hard shorts and the yield rate according to the method described above. did. Furthermore, the [six months storage stability] shown below was evaluated.
  • Table 4 shows the storage temperature (° C.), the ratio of the volume of the void to the internal volume of the container (void ratio (%)), and the oxygen concentration in the gas remaining in the void. , 5 conditions. Then, let stand and store for 6 months. After storage for 6 months, the presence or absence of foreign matter in the binder for electrochemical device electrodes and the container mode are visually observed and evaluated. The evaluation results are shown in Tables 4 and 5. The oxygen concentration was adjusted by placing the electrochemical device electrode binder in a storage container and then blowing high-purity nitrogen into the container to replace the nitrogen.
  • cleaning bottle indicates a 20-liter square can type clean bottle commercially available from Aicello.
  • Wash polycontainer refers to the inside of a commercially available 20-liter square can-type polypropylene container washed in pure room with pure water.
  • Metal can indicates a commercially available metal can.
  • the storage method of the present invention was effective as a storage method capable of preventing the generation of foreign substances such as aggregates. That is, according to the storage method of the present invention, it was confirmed that foreign substances such as aggregates are hardly generated during the storage of the binder for an electrochemical device electrode, and the yield of the manufactured electrode can be improved.
  • the binder for an electrochemical device electrode of the present invention is suitable as a material for an electrode constituting an electrochemical device used as a power source for driving electronic equipment, for example.
  • the slurry for an electrochemical device electrode of the present invention is suitable as a material for an electrode constituting an electrochemical device used as a power source for driving an electronic device, for example.
  • the electrochemical device electrode of the present invention is suitable as an electrode constituting an electrochemical device used as a power source for driving electronic equipment, for example.
  • the method for producing an electrochemical device electrode binder is, for example, a method for producing an electrochemical device electrode binder as an electrode material constituting an electrochemical device used as a power source for driving electronic equipment.
  • the method for preserving the binder for an electrochemical device electrode is suitable as a method for preserving the binder for an electrochemical device electrode that is a material of an electrode constituting an electrochemical device used as a power source for driving an electronic device, for example.
  • 1 supply tank
  • 2 metering pump
  • 3 anti-pulsation device
  • 4 filter
  • 5 discharge conduit
  • 6 return conduit
  • 7a first pressure gauge
  • 7b second pressure gauge
  • 100 filtration device

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Abstract

L'invention concerne un liant pour électrode de dispositif électrochimique pouvant être mis en œuvre en tant que matériau destiné à la formation d'une électrode composant un dispositif électrochimique qui présente une fiabilité élevée, et un très faible risque de défaillance du type rupture de séparateur. Plus précisément, ce liant pour électrode de dispositif électrochimique est obtenu par polymérisation d'un monomère polymérisable, et présente un nombre de particules de diamètre supérieur ou égal à 20μm pour 1mL, mesuré par un compteur de particules, égale à 0.
PCT/JP2011/074636 2010-11-17 2011-10-26 Liant pour électrode de dispositif électrochimique, ainsi que procédé de fabrication et de conservation de celui-ci Ceased WO2012066911A1 (fr)

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