WO2020054274A1 - 電極合剤、電極合剤の製造方法、および電極の製造方法 - Google Patents

電極合剤、電極合剤の製造方法、および電極の製造方法 Download PDF

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WO2020054274A1
WO2020054274A1 PCT/JP2019/031096 JP2019031096W WO2020054274A1 WO 2020054274 A1 WO2020054274 A1 WO 2020054274A1 JP 2019031096 W JP2019031096 W JP 2019031096W WO 2020054274 A1 WO2020054274 A1 WO 2020054274A1
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vinylidene fluoride
electrode mixture
based polymer
electrode
active material
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PCT/JP2019/031096
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English (en)
French (fr)
Japanese (ja)
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民人 五十嵐
泰史 池山
正太 小林
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株式会社クレハ
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Priority to CN201980053494.0A priority Critical patent/CN112567550B/zh
Priority to KR1020217009978A priority patent/KR102377091B1/ko
Priority to JP2020546766A priority patent/JP6883150B2/ja
Publication of WO2020054274A1 publication Critical patent/WO2020054274A1/ja

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    • 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
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

  • the present invention relates to an electrode mixture and its use. More specifically, the present invention relates to an electrode mixture, a method for producing an electrode mixture, and a method for producing an electrode.
  • Vinylidene fluoride-based polymers mainly containing repeating units derived from vinylidene fluoride are widely used as binder resins for batteries such as lithium ion secondary batteries.
  • the binder resin is used for bonding the electrode active material to the current collector.
  • Patent Document 1 discloses an aqueous mixture containing a polyvinylidene fluoride-based polymer and a method for producing an electrode using the same. According to this technique, it is described that an excellent electrode can be manufactured without using a large amount of an organic solvent.
  • Patent Document 2 discloses a vinylidene fluoride-based polymer powder having excellent solubility in an aprotic polar solvent such as NMP. Also disclosed is a vinylidene fluoride polymer powder dispersed in NMP at 23 ° C.
  • Patent Document 3 discloses that a heat-treated vinylidene fluoride-based polymer is subjected to a heat treatment at a temperature at which the polymer powder has a temperature of 125 ° C. or higher and a crystal melting temperature (Tm) or lower. A method for producing a polymer powder is disclosed. Also disclosed is a vinylidene fluoride polymer powder dispersed in NMP at 23 ° C.
  • an electrode mixture can be prepared without using a large amount of an organic solvent.
  • a large amount of water since a large amount of water is used, there is a problem that the active material is easily deteriorated when a strongly alkaline active material is used.
  • an aluminum foil is used as the current collector, corrosion of the current collector occurs, and it is necessary to consider optimizing the composition of the dispersion medium. There are problems such as the need to study conditions and the difficulty in recycling the dispersion medium. Therefore, development of an electrode mixture in which the amount of a solvent such as water is reduced is desired.
  • a binder a mixture of vinylidene fluoride-based polymer powder dispersed in NMP disclosed in Patent Documents 2 and 3, a solution in which vinylidene fluoride-based polymer powder is dissolved in NMP is used.
  • the amount of the organic solvent used for adjusting the viscosity of the electrode mixture to be constant can be reduced as compared with the case where the binder is used as a binder.
  • the viscosity of the electrode mixture may increase, or the viscosity of the electrode mixture may be compensated to keep the viscosity of the electrode mixture constant. Therefore, the use amount of the dispersion medium may increase.
  • an object of the present invention is to suppress the dissolution of a vinylidene fluoride-based polymer powder in a dispersion medium when the vinylidene fluoride-based polymer powder is dispersed in an electrode mixture and to reduce the amount of a diluting solvent used.
  • An object of the present invention is to provide an electrode mixture that can reduce the amount and suppress the increase in the viscosity of the electrode mixture during manufacturing.
  • an electrode mixture according to one embodiment of the present invention is an electrode mixture including a vinylidene fluoride-based polymer, a dispersion stabilizer, an active material, and a dispersion medium,
  • a median diameter determined by a laser diffraction scattering method is 500 ⁇ m or less
  • the maximum melting peak temperature Tm1 at the first temperature rise in the differential scanning calorimetry is 130 ° C. or more;
  • the complex viscosity is measured at an angular frequency of 10 rad -1 while heating the electrode mixture from 25 ° C. to 80 ° C.
  • the complex viscosity at 30 ° C. Assuming that the temperature at which the complex viscosity reaches 10-fold is TC10, the electrode mixture has a TC10 of 40 ° C. or more and 80 ° C. or less.
  • the electrode mixture according to the embodiment is a vinylidene fluoride-based polymer powder, a dispersion stabilizer, an active material, and a dispersion medium, and an electrode mixture,
  • the median diameter determined by a laser diffraction scattering method is 500 ⁇ m or less
  • the maximum melting peak temperature Tm1 at the first temperature rise in the differential scanning calorimetry is 130 ° C. or more;
  • the complex viscosity is measured at an angular frequency of 10 rad -1 while heating the electrode mixture from 25 ° C. to 80 ° C.
  • the complex viscosity at 30 ° C. Assuming that the temperature at which the complex viscosity reaches 10-fold is TC10, the TC10 is 40 ° C. or higher and 80 ° C. or lower.
  • An electrode can be produced by applying and drying the electrode mixture on the current collector to form an electrode mixture layer.
  • the electrode mixture in the present embodiment is preferably an electrode active material for a positive electrode, that is, an electrode mixture for a positive electrode using a positive electrode active material (a positive electrode material).
  • vinylene fluoride-based polymer refers to a homopolymer of vinylidene fluoride and a copolymer of vinylidene fluoride and a monomer copolymerizable with vinylidene fluoride. (Copolymer).
  • the monomer copolymerizable with vinylidene fluoride can be appropriately selected from, for example, known monomers.
  • the vinylidene fluoride unit be contained in an amount of 90 mol% or more, and it is particularly preferable that the vinylidene fluoride unit be contained in an amount of 95 mol% or more.
  • ⁇ Monomer> As the monomer, (i) vinylidene fluoride alone or (ii) a mixture of vinylidene fluoride and a monomer copolymerizable with vinylidene fluoride can be used.
  • Examples of monomers copolymerizable with vinylidene fluoride include fluorine-containing compounds such as vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoroalkylvinyl ether. Further, as the monomer containing no fluorine, ethylene, maleic acid and its ester, (meth) acrylic acid and its ester, allyl glycidyl ether, and the like can be used.
  • the vinylidene fluoride-based polymer powder has a median diameter determined by a laser diffraction scattering method of 500 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 50 ⁇ m or less, and 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more. , More preferably 1 ⁇ m or more.
  • the median diameter of the vinylidene fluoride-based polymer powder is defined as a particle diameter (D50) at an integrated value of 50% in a volume-based particle size distribution obtained by a wet method in a laser diffraction scattering method. When it is within the above range, it is suitable as a raw material for an electrode mixture.
  • the median diameter of the vinylidene fluoride-based polymer powder is preferably equal to or less than the thickness of the coated electrode mixture layer before drying, and is preferably equal to or less than the particle diameter of the active material. More preferred.
  • the measurement by the laser diffraction scattering method can be performed, for example, using a Microtrac MT3300EXII (measurement range: 0.02 to 2000 ⁇ m) manufactured by Microtrac Bell and an automatic sample circulator, and using water as a dispersion medium.
  • a dispersion liquid which has been wetted with ethanol in advance and then dispersed in water using a wetting agent aqueous solution can be used.
  • the TC10 of the electrode mixture is 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 55 ° C. or higher.
  • the upper limit temperature of TC10 is 80 ° C. or lower, preferably 70 ° C. or lower, more preferably 62 ° C. or lower.
  • TC10 measures the complex viscosity at an angular frequency of 10 rad -1 while heating the electrode mixture from 25 ° C. to 80 ° C. at a rate of 5 ° C./min using a parallel plate rheometer. The temperature at which the complex viscosity reaches 10 times the complex viscosity at 30 ° C.
  • TC10 When TC10 is in the above-mentioned temperature range, an increase in the viscosity of the electrode mixture, particularly around room temperature, is suppressed, and thus there are effects such as a reduction in the amount of a solvent such as a dispersion medium in the electrode mixture.
  • a solvent such as a dispersion medium in the electrode mixture.
  • the vinylidene fluoride-based polymer powder in the mixture dissolves to increase the viscosity of the electrode mixture, and the electrode mixture exhibits adhesiveness.
  • the above complex viscosity can be adjusted, for example, by subjecting vinylidene fluoride-based polymer powder to heat treatment near the melting point.
  • the vinylidene fluoride polymer powder used in the present embodiment has a viscosity X and Y defined below in a dispersion obtained by dispersing the powder in N-methylpyrrolidone, and a ratio of Y to X (Y / X). Is preferably 5 or more. Further, it is more preferably 50 or more, and further preferably 100 or more.
  • X Viscosity of a dispersion obtained by dispersing vinylidene fluoride-based polymer powder in N-methylpyrrolidone at a concentration of 6% by weight at 25 ° C. at a shear rate of 100 s ⁇ 1 at 25 ° C.
  • Y Vinylidene fluoride-based polymer powder A solution prepared by dissolving a solution of 6% by weight in N-methylpyrrolidone at 70 ° C. at a shear rate of 100 s ⁇ 1 at 25 ° C. was measured. An effect such as an increase in the viscosity of the electrode mixture in the vicinity is suppressed, and the amount of solvent used in the electrode mixture is reduced.
  • Y / X can be increased, for example, by changing the heat treatment temperature and heat treatment time near the melting point and the cooling conditions to increase the crystallinity.
  • ⁇ X is preferably from 2 to 3000 mPa ⁇ s, more preferably from 2 to 500 mPa ⁇ s, and still more preferably from 3 to 100 mPa ⁇ s.
  • ⁇ Y / X is preferably from 5 to 5,000, more preferably from 10 to 1,000, even more preferably from 50 to 500.
  • the maximum melting peak temperature Tm1 at the first temperature rise in the differential scanning calorimetry is preferably 130 ° C. or higher, more preferably 145 ° C. or higher, and preferably 155 ° C. or higher. More preferred.
  • the content is within the above range, a more crystalline vinylidene fluoride-based polymer powder is obtained, and the increase in the viscosity of the electrode mixture at around room temperature is suppressed, so that a solvent such as a dispersion medium in the electrode mixture is used. The effect of reducing the amount is exhibited.
  • the maximum melting peak temperature is the temperature at the top of the melting peak having the highest peak intensity.
  • RH of the vinylidene fluoride polymer powder used in the present embodiment is preferably from 0.3 to 3, more preferably from 0.5 to 2, and even more preferably from 0.6 to 1.5.
  • rH is the ratio of ⁇ H2 to ⁇ H1 ( ⁇ H2 / ⁇ H1).
  • ⁇ H1 is the peak area on the lower side of the maximum melting peak temperature Tm2 at the second heating in the differential scanning calorimetry in the differential scanning calorimetry curve obtained by the first heating in the differential scanning calorimetry. is there.
  • ⁇ H2 is the peak area on the higher temperature side than Tm2.
  • FIG. 1 is a reference diagram showing ⁇ H1 and ⁇ H2 in differential scanning calorimetry.
  • a baseline is drawn before and after the melting peak, and is subtracted from the heat flux.
  • the differential scanning calorimetry curve from which the baseline is subtracted is sectioned at Tm2.
  • the area on the low temperature side from Tm2 is set to ⁇ H1
  • the area on the high temperature side from Tm2 is set to ⁇ H2.
  • rH can be adjusted, for example, by subjecting particles of vinylidene fluoride-based polymer to heat treatment. For example, by changing the heat treatment temperature, heat treatment time, and cooling conditions near the melting point, rH can be set within a desired range.
  • Tm1 and Tm2 are preferably Tm2-10 ° C ⁇ Tm1 ⁇ Tm2 + 20 ° C, more preferably Tm2-5 ° C ⁇ Tm1 ⁇ Tm2 + 15 ° C, and preferably Tm2 + 2 ° C ⁇ Tm1 ⁇ Tm2 + 10 ° C. More preferred.
  • Tm1 and Tm2 are within the above-mentioned temperature range, effects such as containing more stable crystalline components can be obtained.
  • the vinylidene fluoride polymer powder used in the present embodiment preferably has a weight average molecular weight in terms of polystyrene of 100,000 to 10,000,000, and preferably 200,000 to 5,000,000 as determined by gel permeation chromatography (GPC). Is more preferable, and more preferably 500,000 to 2,000,000.
  • GPC gel permeation chromatography
  • the electrode mixture according to the present embodiment includes the above-mentioned vinylidene fluoride-based polymer powder, so that the electrode mixture is applied to a current collector and dried by heating with a hot air drying furnace or an IR heater.
  • the vinylidene fluoride-based polymer powder dissolves or swells in the electrode mixture due to the temperature rise. Then, the viscosity of the electrode mixture increases, and adhesiveness is imparted.
  • the method for producing the vinylidene fluoride-based polymer powder includes, for example, a preparation step of preparing an untreated vinylidene fluoride-based polymer powder that has not been heat-treated, and, at a temperature of 140 ° C. or more, the untreated vinylidene fluoride-based polymer powder.
  • a heat treatment step of performing a heat treatment includes, for example, a preparation step of preparing an untreated vinylidene fluoride-based polymer powder that has not been heat-treated, and, at a temperature of 140 ° C. or more.
  • the untreated vinylidene fluoride-based polymer powder may be a commercially available one, or may be prepared using a known means.
  • a vinylidene fluoride-based polymer may be micronized by freeze-pulverization or classification, or a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a microsuspension polymerization method, or the like may be used. It can also be performed in combination.
  • ⁇ Heat treatment step> In the heat treatment step, preferably at a temperature of 140 ° C or more, more preferably 150 ° C or more, further preferably 155 ° C or more, and preferably 230 ° C or less, more preferably 200 ° C or less, and still more preferably 180 ° C or less, The untreated vinylidene fluoride polymer is heated.
  • the stability of the crystal of the vinylidene fluoride-based polymer powder can be improved by restructuring the crystal. Further, by performing the heat treatment in the above temperature range, the majority of the crystals of the vinylidene fluoride-based polymer powder are melted, and the crystals are recrystallized at a high temperature, so that more stable crystals can be formed. . In the former case, the heat treatment is performed at a temperature lower than the melting point to stabilize the unmelted crystal component, and in the latter case, the ratio of the melted component is increased while recrystallizing at a high temperature. More stable crystal components can be formed. By using a vinylidene fluoride-based polymer powder containing a large amount of highly stable crystal components, an electrode mixture having a low viscosity even at high temperatures can be obtained.
  • the heat treatment time is not particularly limited, but is preferably 10 seconds to 72 hours, more preferably 1 minute to 20 hours, and even more preferably 10 minutes to 5 hours.
  • the heat treatment time is as described above, more stable and more stable crystal components can be formed.
  • the untreated vinylidene fluoride-based polymer powder may be heated while standing, the polymer may be heated with stirring, or may be heated under high shear.
  • the heat treatment may be performed using a hot air circulation furnace, a conical blender dryer, a Henschel mixer, a ribbon blender, a fluidized bed heat treatment furnace, or the like.
  • the heat treatment of the vinylidene fluoride-based polymer powder can also be performed by dispersing the vinylidene fluoride-based polymer in a poor solvent.
  • an aqueous suspension of vinylidene fluoride-based polymer obtained by suspension polymerization or an aqueous emulsion of vinylidene fluoride-based polymer obtained by emulsion polymerization may be heated under pressure using an autoclave.
  • the heated vinylidene fluoride-based polymer powder is preferably cooled in order to promote crystallization of the amorphous phase.
  • the cooling may be a rapid cooling condition or a slow cooling condition, but by cooling under a slow cooling condition, more stable crystal components can be formed.
  • it may be cooled rapidly using a refrigerant, or may be cooled at a rate of 0.1 ° C. to 60 ° C./min.
  • slow cooling it is not necessary to slowly cool to room temperature. At this time, it is preferable to gradually cool to 150 ° C., and it is more preferable to gradually cool to 140 ° C.
  • drying can be performed by a common drying method such as a tray dryer, a conical dryer, a fluidized bed dryer, a flash dryer, and a spray dryer.
  • the vinylidene fluoride-based polymer powder after the heat treatment may be crushed or pulverized before being dispersed or mixed in a dispersion medium, for example.
  • the electrode mixture according to the present embodiment may include a dispersion stabilizer.
  • the dispersion stabilizer is a polymer used in a state of being dissolved in a dispersion medium in an electrode mixture, and is different from the above-mentioned vinylidene fluoride-based polymer powder used in a state of being dispersed in a dispersion medium.
  • the dispersion stabilizer is at least one dispersion selected from the group consisting of polyvinylidene fluoride, polyacrylonitrile, nitrile rubber, poly (meth) acrylic acid and esters thereof, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, and cellulose ether.
  • it is a stabilizer.
  • the use of polyvinylidene fluoride as a dispersion stabilizer can provide both the function as a dispersion stabilizer and the function as a binder, and is particularly preferable.
  • the dispersion stabilizer is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and more preferably 0.3 to 2 parts by weight. More preferably, it is contained.
  • the amount of the dispersion stabilizer indicates the amount of the resin component.
  • the total amount of the vinylidene fluoride-based polymer powder and the dispersion stabilizer is preferably 0.2 to 20 parts by weight, more preferably 0.4 to 10 parts by weight. More preferably, the content is 0.6 to 4 parts by weight.
  • the weight ratio between the vinylidene fluoride polymer powder and the dispersion stabilizer is preferably from 10:90 to 99: 1, and from 25:75 to 95: 5. Is more preferable, and the ratio is more preferably from 40:60 to 90:10.
  • the vinylidene fluoride-based polymer powder or dispersion stabilizer is preferably a vinylidene fluoride-based polymer containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo group, and an amide group. Further, the functional group is preferably contained in an amount of 0.03 to 5 mol%, more preferably 0.05 to 3 mol%, and further preferably 0.1 to 2 mol%.
  • the vinylidene fluoride-based polymer powder or dispersion stabilizer is preferably a (meth) acrylic acid-modified vinylidene fluoride-based polymer or a carboxyl group-containing (meth) acrylate-modified vinylidene fluoride-based polymer powder.
  • the viscosity of the dispersion medium can be appropriately adjusted, and the stability of the electrode mixture, the applicability to the current collector, and the like can be improved.
  • the electrode mixture can be made into an electrode mixture for a positive electrode or an electrode mixture for a negative electrode by changing the type of the active material and the like according to the type of the current collector to be applied.
  • a lithium composite metal oxide is typically used as the positive electrode active material.
  • lithium composite metal oxides for example, LiMnO 2, LiMn 2 O 4 , LiCoO 2, LiNiO 2, LiNi x Co 1-x O 2 (0 ⁇ x ⁇ 1), LiNi x Co y Mn 1-x-y O 2 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), LiFePO 4 and the like.
  • a conventionally known material such as a carbon-based material such as graphite can be used.
  • the active material is preferably a positive electrode active material from the viewpoint that the effects of the present invention can be sufficiently exhibited.
  • the particle size of the active material is preferably 0.5 to 50 ⁇ m, more preferably 1 to 25 ⁇ m, and further preferably 2 to 15 ⁇ m.
  • the dispersion medium preferably contains 10 to 100 parts by weight, more preferably 20 to 75 parts by weight, and even more preferably 25 to 50 parts by weight.
  • the dispersion medium may be any liquid that can disperse the vinylidene fluoride polymer powder and can be dissolved by heating at room temperature or below the melting point of the vinylidene fluoride polymer powder.
  • the dispersion medium contains an aprotic polar solvent.
  • the dispersion medium is not particularly limited as long as the solvent can dissolve the vinylidene fluoride-based polymer powder.
  • As the dispersion medium one type of solvent or a mixed solvent of two or more types may be used. However, it is preferable to use one type of solvent, and it is possible to suppress the cost of solvent recovery or repurification.
  • the aprotic polar solvent may be any solvent as long as the vinylidene fluoride-based polymer powder can be dissolved by heating.
  • a good solvent or a latent solvent for the vinylidene fluoride-based polymer powder can be used.
  • the relative dielectric constant is preferably 15 or more, more preferably 22 or more, and still more preferably 30 or more.
  • aprotic polar solvents examples include N-methylpyrrolidone (NMP), dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N, N-dimethylsulfoxide (DMSO), ⁇ -butyrolactone, propylene carbonate, And cyclohexanone.
  • the aprotic polar solvent is preferably a good solvent for the vinylidene fluoride-based polymer powder. Specifically, it is preferable to use NMP, DMF, DMAc, or DMSO.
  • the aprotic polar solvent is preferably contained in an amount of 65 parts by weight or more, more preferably 80 parts by weight or more, even more preferably 90 parts by weight or more.
  • the electrode mixture according to the present embodiment may contain other components as long as the effects of the present invention are not impaired.
  • Other components include, for example, a conductive aid and a pigment dispersant.
  • the conductive assistant is added for the purpose of improving the conductivity of the electrode mixture layer when using an active material having low electron conductivity such as LiCoO 2 .
  • the conductive assistant for example, carbonaceous substances such as carbon black, carbon nanotubes, graphite fine powder and graphite fiber, and fine metal powder or metal fiber such as nickel and aluminum can be used.
  • a nitrogen compound such as a phosphorus compound, a sulfur compound, an organic acid, an amine compound, and an ammonium compound
  • an organic ester such as a silane-based, titanium-based and aluminum-based coupling agents; Can be used.
  • the electrode mixture according to this embodiment uses an aprotic polar solvent such as NMP as a main component of the dispersion medium, and does not need to use water as the dispersion medium, and may also contain a highly alkaline active material. it can.
  • a good solvent or a latent solvent can be used alone, and there is no need to consider optimizing the solvent composition, and setting of drying conditions after application of the electrode mixture to the current collector and Recycling of the solvent is also facilitated.
  • the electrode mixture according to the present embodiment contains the above-mentioned vinylidene fluoride-based polymer powder as a binder, thereby having a shear viscosity suitable for application to a current collector and an electrode mixture having a high solid content.
  • the agent can be adjusted.
  • the electrode mixture according to the present embodiment is, for example, by mixing a binder composition prepared by dispersing the above-mentioned vinylidene fluoride-based polymer powder in a dispersion medium, with an active material or a dispersion containing the active material. Can be prepared.
  • Method of manufacturing electrode Hereinafter, an example of a method for manufacturing an electrode will be specifically described, but the method for manufacturing an electrode according to the present embodiment is not limited to the following method.
  • the method for producing an electrode according to the present embodiment includes a preparation step of preparing an electrode mixture, and a coating step of applying the electrode mixture to a current collector,
  • the preparation step includes a mixing step of mixing the vinylidene fluoride-based polymer powder with the active material or the active material and the dispersion medium, From the mixing step to the coating step, the temperature of the electrode mixture is maintained at TC10 or lower.
  • electrode in the present specification and the like refers to a battery electrode in which an electrode mixture layer formed from the electrode mixture in the present embodiment is formed on a current collector, unless otherwise specified. means.
  • ⁇ Preparation process of electrode mixture In the preparation process of the electrode mixture, it is selected from the group consisting of polyvinylidene fluoride, polyacrylonitrile, nitrile rubber, poly (meth) acrylic acid and its ester, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, and cellulose ether. Preferably, at least one dispersion stabilizer is added to the electrode mixture.
  • the preparation step includes a mixing step of mixing the vinylidene fluoride-based polymer powder or the binder composition with an active material and a dispersion medium.
  • the preparation step it is preferable to mix a dispersion in which vinylidene fluoride-based polymer powder is dispersed in a dispersion medium in advance with the active material or a dispersion containing the active material.
  • the preparation step it is preferable to mix the active material or the dispersion containing the active material with vinylidene fluoride-based polymer powder.
  • a conventional vinylidene fluoride-based polymer powder when mixed with an active material in the form of a powder and a dispersion medium is added, or when mixed with a dispersion containing the active material, the heat of the electrode mixture is increased due to shear heat generation in the kneading step. The temperature rises. Then, the vinylidene fluoride-based polymer powder gradually dissolves in the electrode mixture to increase the viscosity of the electrode mixture, making it difficult to adjust the viscosity of the electrode mixture to a constant.
  • the vinylidene fluoride-based polymer powder dissolves in the dispersion medium, so that it was necessary to adjust the viscosity of the mixture to a desired value by adding a large amount of a diluting solvent.
  • the vinylidene fluoride-based polymer powder is mixed with the active material in the form of a powder and further mixed by adding a dispersion medium or when mixed with a dispersion containing the active material. A change in viscosity due to dissolution of the polymer powder in the dispersion medium is suppressed. Therefore, since the viscosity of the electrode mixture is kept at a low value, the amount of the diluting solvent added can be suppressed, and the cost can be reduced and the productivity can be improved in the electrode manufacturing process.
  • the electrode mixture is applied to the current collector.
  • the electrode is a positive electrode when an electrode mixture layer is obtained using an electrode mixture for a positive electrode, and a negative electrode when an electrode mixture layer is obtained using an electrode mixture for a negative electrode.
  • the current collector is a base material of the electrode and a terminal for extracting electricity.
  • Examples of the material of the current collector include iron, stainless steel, steel, copper, aluminum, nickel, and titanium.
  • the shape of the current collector is preferably a foil or a net.
  • the current collector is preferably an aluminum foil.
  • the thickness of the current collector is preferably from 1 ⁇ m to 100 ⁇ m, more preferably from 3 to 20 ⁇ m.
  • the electrode mixture layer is a layer obtained by applying the above-mentioned electrode mixture to a current collector and drying the same.
  • a method for applying the electrode mixture a method known in the art can be used, and a method using a bar coater, a die coater, a comma coater, or the like can be used.
  • the drying temperature for forming the electrode mixture layer is preferably from 60 ° C. to 200 ° C., and more preferably from 80 ° C. to 150 ° C. When the drying temperature is in this range, the dissolution of the vinylidene fluoride-based polymer powder can be promoted by an increase in the temperature of the mixture in the drying step, and an electrode having high peel strength can be obtained.
  • the electrode mixture layer may be formed on both surfaces of the current collector, or may be formed on only one of the surfaces.
  • the thickness of the electrode mixture layer is usually 30 to 600 ⁇ m, preferably 70 to 350 ⁇ m per one side.
  • the density may be increased by pressing the electrode mixture layer.
  • the basis weight of the electrode mixture layer is usually 50 to 1000 g / m 2 , preferably 100 to 500 g / m 2 .
  • the temperature of the electrode mixture is preferably set to TC10 or lower, more preferably TC10-5 ° C or lower, still more preferably TC10-10 ° C or lower, and preferably a dispersion medium.
  • the temperature is maintained at or above the melting point of the largest constituent component, more preferably at or above 0 ° C, and even more preferably at or above 5 ° C.
  • the electrode according to the present embodiment can be used, for example, as a positive electrode of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.
  • the electrode mixture according to the present embodiment is a vinylidene fluoride-based polymer, a dispersion stabilizer, an active material, and a dispersion medium, the electrode mixture,
  • a median diameter determined by a laser diffraction scattering method is 500 ⁇ m or less
  • the maximum melting peak temperature Tm1 at the first temperature rise in the differential scanning calorimetry is 130 ° C. or more;
  • the complex viscosity at 30 ° C. Assuming that the temperature at which the complex viscosity is ten times as high as TC10 is TC10, TC10 is 40 ° C. or more and 80 ° C. or less.
  • X represents the viscosity of a dispersion obtained by dispersing the vinylidene fluoride-based polymer in N-methylpyrrolidone at a concentration of 6% by weight at 25 ° C. at a shear rate of 100 s ⁇ 1 at 25 ° C.
  • Y the viscosity of a solution of the vinylidene fluoride polymer dissolved in N-methylpyrrolidone at a concentration of 6% by weight and 70 ° C. at 25 ° C. at a shear rate of 100 s ⁇ 1
  • the ratio of Y to X is preferably 5 or more.
  • the dispersion stabilizer is at least one selected from the group consisting of polyvinylidene fluoride, polyacrylonitrile, nitrile rubber, poly (meth) acrylic acid and esters thereof, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, and cellulose ether. And two dispersion stabilizers, which are used in a state of being dissolved in a dispersion medium.
  • the vinylidene fluoride-based polymer of the present invention used in a state of being dispersed in a dispersion medium or polyvinylidene fluoride used as the dispersion stabilizer is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo group, and an amide group. It is preferable that the vinylidene fluoride-based polymer contains a functional group in an amount of from 0.03 mol% to 5 mol%.
  • the vinylidene fluoride-based polymer or the dispersion stabilizer is a (meth) acrylic acid-modified vinylidene fluoride-based polymer or a carboxyl group-containing (meth) acrylate-modified vinylidene fluoride-based polymer.
  • the active material preferably contains lithium composite metal oxide particles as a main component.
  • the dispersion medium contains an aprotic polar solvent, and the aprotic polar solvent is a good solvent for the vinylidene fluoride-based polymer.
  • the method for producing an electrode mixture according to this embodiment includes a step of heat-treating an untreated vinylidene fluoride-based polymer that has not been heat-treated at a temperature of 140 ° C. or higher to obtain a vinylidene fluoride-based polymer.
  • the method for producing an electrode mixture according to the present embodiment further includes a step of preparing the untreated vinylidene fluoride-based polymer by polymerizing the mixture by an emulsion polymerization method.
  • the method for manufacturing an electrode according to the embodiment of the present invention A preparation step of preparing the electrode mixture, An application step of applying the electrode mixture to a current collector,
  • the preparation step includes a mixing step of mixing the vinylidene fluoride-based polymer powder with the active material or the active material and the dispersion medium, From the mixing step to the coating step, the temperature of the electrode mixture is maintained at TC10 or lower.
  • the preparing step further includes a step of mixing a dispersion in which the vinylidene fluoride-based polymer is dispersed in the dispersion medium in advance with the active material or a dispersion containing the active material.
  • the method for producing an electrode according to the present embodiment includes a step of mixing the active material or a dispersion containing the active material with the vinylidene fluoride-based polymer.
  • the obtained untreated vinylidene fluoride polymer powder had a weight average molecular weight of 1.1 million, a median diameter (D50) of 194 ⁇ m, and a Tm1 of 175.7 ° C.
  • Mod-PVDF1 An untreated vinylidene fluoride-based polymer powder Mod-PVDF1 was prepared by the following procedure.
  • the amount of AES introduced was measured by 1 H NMR measurement according to the following procedure.
  • Apparatus manufactured by Bruker, AVANCE AC 400FT NMR spectrometer Measurement conditions Frequency: 400 MHz Measurement solvent: DMSO-d 6 Measurement temperature: 25 ° C
  • VDF obtained based on the integrated intensity of the signal mainly observed at 4.19 ppm derived from AES and the signals mainly observed at 2.24 ppm and 2.87 ppm derived from vinylidene fluoride in the 1 H NMR spectrum.
  • the amount (mol%) (VDF amount) of the structural unit derived from vinylidene fluoride contained in the / AES polymer was 99.64 mol%. Further, the amount (mol%) of the structural unit derived from acryloyloxyethyl succinic acid (AES amount) was 0.36 mol%.
  • PVDF powder (trade name kynar (registered trademark) HSV900) manufactured by Arkema Corporation was used.
  • the weight average molecular weight was 660,000, the median diameter (D50) was 5 ⁇ m, and Tm1 was 161.0 ° C.
  • sPVDF1 was used as it was, and in the production of the vinylidene fluoride-based polymer powder 17, heat treatment, cooling treatment, and post-treatment were performed using sPVDF1 as the untreated vinylidene fluoride-based polymer powder. .
  • ⁇ Heat treatment> On a stainless steel vat having a width of 30 cm, a length of 21 cm and a height of 2 cm, 8 g of untreated vinylidene fluoride-based polymer powder was spread uniformly on the bottom surface of the stainless steel vat. Next, the stainless steel bat was covered with aluminum foil, placed in a hot-air circulating furnace (HISPEC HT210S, manufactured by Kusumoto Kasei Co., Ltd.) adjusted to a temperature of 162 ° C., and held for 1 hour.
  • HISPEC HT210S manufactured by Kusumoto Kasei Co., Ltd.
  • the vinylidene fluoride-based polymer obtained by the heat treatment was taken out of the hot-air circulation furnace while being placed on the stainless steel vat, and quenched on a steel plate at room temperature. At this time, the temperature of the vinylidene fluoride-based polymer had reached 80 ° C. 30 seconds later. It was allowed to cool to 30 ° C. in a room temperature atmosphere. 4 g of the cooled vinylidene fluoride polymer was placed in a mortar, and crushed with a pestle. The crushed vinylidene fluoride polymer was dispersed in ethanol, and sieved while flowing the ethanol through a sieve having an opening of 45 ⁇ m to remove dust. Ethanol was volatilized by holding at 60 ° C. for 5 hours to obtain vinylidene fluoride-based polymer powder 1.
  • vinylidene fluoride polymer powders 2 to 18 were produced in the same procedure as vinylidene fluoride polymer powder 1 by the heat treatment conditions, cooling methods, and post-treatment methods (crushing or pulverization) shown in Table 1. . Cooling by slow cooling was performed by cooling to 100 ° C. at a rate of 0.5 ° C./min, and then allowing the mixture to cool at room temperature. In the post-treatment method (pulverization), pulverization was carried out using a refrigeration pulverizer JFC-300 manufactured by JASCO. About 0.8 g of heat-treated vinylidene fluoride-based polymer powder and tungsten carbide steel balls were placed in a sample container, and the lid was closed.
  • Freezing and pulverization were performed using liquid nitrogen as a refrigerant under the conditions of pre-cooling for 10 minutes, pulverization time of 15 minutes, and number of reciprocating motions of 1450 rpm, to obtain a heat-treated vinylidene fluoride-based polymer powder which had been subjected to freeze pulverization. This was repeated 5 times, and the obtained freeze-ground heat-treated vinylidene fluoride-based polymer powder was dispersed in ethanol and mixed. Ethanol was volatilized by holding at 60 ° C. for 5 hours to obtain a heat-treated vinylidene fluoride-based polymer powder.
  • a G2 rheometer manufactured by TA Instruments was used, and the distance between the gaps was set to 0.5 mm using a 50 mm parallel plate. Then, the viscosity was measured at 25 ° C. for 30 seconds at a shear rate of 100 s ⁇ 1 to determine the viscosity of the 6% NMP dispersion. Further, when the vinylidene fluoride-based polymer powder was dissolved in the sample preparation operation to form a solution, the measurement was performed by the same procedure. The viscosity measured at 25 ° C. at a shear rate of 100 s ⁇ 1 was defined as X.
  • the viscosity of a solution dissolved in NMP at 70 ° C. measured at 25 ° C. at a shear rate of 100 s ⁇ 1 was defined as Y.
  • the molecular weight of the vinylidene fluoride polymer powder is determined by gel permeation chromatography (manufactured by JASCO Corporation; GPC-900) of an N-methylpyrrolidone solution in which the vinylidene fluoride polymer powder is dissolved at a concentration of 0.1% by weight. And a Shodex KD-806M column at a temperature of 40 ° C.) to determine the weight average molecular weight in terms of polystyrene.
  • the mixture was introduced into a standard sample circulator, and the median diameter (D50) was determined.
  • D50 median diameter
  • the particle permeability was set to the transmission mode
  • the particle shape was set to the non-spherical mode
  • the particle refractive index was set to 1.42
  • the solvent refractive index was set to 1.333.
  • DSC measurement [Differential scanning calorimetric analysis (DSC measurement)] The DSC measurement of the untreated vinylidene fluoride-based polymer powder that has not been subjected to the heat treatment and the heat-treated vinylidene fluoride-based polymer powder were performed according to JIS K7122-1987 using DSC1 manufactured by METTLER TOLEDO.
  • Table 2 shows the results of each evaluation.
  • the vinylidene fluoride polymers 1 to 13 and 18 which were subjected to the heat treatment at a temperature equal to or higher than the melting point of the untreated vinylidene fluoride polymer had a Y / X of 5 or more.
  • the vinylidene fluoride polymers 14 and 15 that were not subjected to the heat treatment had a Y / X of 1.
  • the heat-treated vinylidene fluoride polymer 17 had a Y / X of 5 or more, but had a large D50 value, poor electrode smoothness as shown in Table 3, and a raw material for the electrode mixture. Was not suitable.
  • the vinylidene fluoride polymer having a median diameter of 50 ⁇ m or less obtained by performing the heat treatment at a temperature equal to or higher than the melting point has a Y / X of 5 or more and has a large number of highly crystalline crystalline phases.
  • the vinylidene fluoride-based polymer does not dissolve in the solvent at around room temperature but dissolves in the solvent at a high temperature range, so that when used as a raw material of the electrode mixture, it is possible to suppress the viscosity of the electrode mixture. I knew I could do it.
  • the vinylidene fluoride polymer powders 14, 15 and 16 were heated and stirred at 70 ° C. for 5 hours in NMP at a concentration of 6% to form a solution, and then allowed to cool and used.
  • PVDF a binder composition obtained by dispersing the above vinylidene fluoride-based polymer powder 1 in NMP at a concentration of 20% is used, and as a dispersion stabilizer, a binder solution in which Mod-PVDF1 is dissolved in NMP at a concentration of 6% It was used.
  • the remaining dispersion stabilizer (2.22 g of a 6% NMP solution of Mod-PVDF1), and 3.1 g of NMP were added.
  • the non-volatile content concentration became 74%.
  • kneading was performed for 2 minutes at 800 rpm using Awatake Neritaro to obtain an electrode mixture (secondary kneading step).
  • the sample temperature after kneading was 28 ° C.
  • the electrode mixture was stored at 25 ° C.
  • each material is set so that the dispersion stabilizer type and the mixing ratio of the vinylidene fluoride-based polymer powder to the dispersion stabilizer described in Table 3 are satisfied.
  • the nonvolatile content of the slurry was adjusted to the N.V. V.
  • the procedure was performed in the same manner as in Production Example 3 except that the amount of NMP added was adjusted so as to obtain a value.
  • the sample temperature after the addition of the binder and the composition was 25 ° C. or more and less than 30 ° C.
  • vinylidene fluoride-based polymer 4 vinylidene fluoride-based polymer powder was used in place of the binder composition, and the non-volatile content of the slurry in the secondary kneading step was as shown in Table 3. V. A mixture was prepared in the same manner as in Production Example 3, except that the amount of NMP added was adjusted so as to obtain a value. The sample temperature after the addition of the vinylidene fluoride-based polymer powder was 25 ° C or higher and lower than 30 ° C.
  • Electrode Each of the electrode mixtures obtained in Production Examples 3, 3-1 and 3-2 was applied to a 15 ⁇ m aluminum foil using a coater dryer GT-3 made of Sank Metal and dried. Thus, an electrode was obtained.
  • the drying furnace was composed of three zones with a furnace length of 1 m, and the temperature in each drying furnace was 110 ° C. Coating was performed by a converse method at a coating speed of 0.6 m / min, a coating width of 60 mm, a coating length of 30 cm, and intermittent coating of a plurality of electrodes by changing the gap distance.
  • the electrode of the first pattern which is the start of coating, was discarded.
  • An electrode having a basis weight of 200 ⁇ 20 g / m 2 on one side was used as an electrode for evaluation. Both ends of the electrode were cut off to have a width of 50 mm.
  • the peel strength of the coated electrode after the above-mentioned drying is determined by a 90 ° peel strength test according to JIS K 65-14-1 by laminating the electrode coating surface and a thick plastic plate (made of acrylic resin, thickness 5 mm) with a double-sided tape. Asked by. The test speed was 10 mm per minute.
  • Table 3 shows the evaluation results of the binder composition, the electrode mixture, and the electrode.
  • N.V indicates a nonvolatile content concentration.
  • ND indicates that the temperature at which the value of the complex viscosity at 30 ° C. becomes 10 times the complex viscosity was not reached in the test range.
  • peel strength indicates that the evaluation was not performed.
  • TC10 of the electrode mixture using vinylidene fluoride-based polymer powders 1 to 11 was as high as 50 ° C. or higher.
  • the temperature in the test range did not reach a temperature at which the value of the complex viscosity at 30 ° C became 10 times the value of the complex viscosity.
  • the TC10 of the electrode mixture using the vinylidene fluoride-based polymer powders 12 to 13 was 48 ° C. or lower.
  • TC10 was 59.7 ° C., but the value of D50 of the vinylidene fluoride polymer powder was large, and the smoothness of the obtained electrode was 20% or more. (Poor), which proved not to be excellent as an electrode mixture.
  • TC10 was as high as 50 ° C. or higher for electrode mixtures 19 and 20 using a mixed solvent of NMP and DMF as a dispersion medium.
  • the vinylidene fluoride polymer 18 is treated in the same manner as the vinylidene fluoride polymers 8 to 11, but does not contain a dispersion stabilizer in the electrode mixture. Since the slurry is separated during the measurement of the viscosity of the electrode mixture, the viscosity of the mixture is excessively low, the linearity of the end of the coated electrode is poor, and the smoothness of the coated electrode is poor. Therefore, it was found that the composition of the electrode mixture was not suitable.
  • the present invention can be used as an electrode mixture applied to a current collector in the production of an electrode for a lithium ion secondary battery.
PCT/JP2019/031096 2018-09-11 2019-08-07 電極合剤、電極合剤の製造方法、および電極の製造方法 WO2020054274A1 (ja)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022114039A1 (ja) 2020-11-30 2022-06-02 株式会社クレハ フッ化ビニリデン重合体組成物およびその製造方法、樹脂組成物、電極合剤、ならびにこれらを含む電極およびその製造方法
JP2023505931A (ja) * 2020-06-12 2023-02-14 アルケマ フランス 電池電極用組成物
WO2024045504A1 (zh) * 2022-08-30 2024-03-07 宁德时代新能源科技股份有限公司 粘结剂、制备方法、正极极片、二次电池及用电装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010074041A1 (ja) * 2008-12-26 2010-07-01 株式会社クレハ 非水電解質二次電池用負極合剤、非水電解質二次電池用負極および非水電解質二次電池
JP2012064542A (ja) * 2010-09-17 2012-03-29 Toyota Motor Corp 電池用活物質ペースト、電池用活物質ペーストの分散性評価方法、電池用活物質ペーストの分散性の管理方法、及び、電極板の製造方法
JP2013170203A (ja) * 2012-02-20 2013-09-02 Nippon Shokubai Co Ltd ポリエーテル共重合体

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3966570B2 (ja) * 1997-03-14 2007-08-29 株式会社クレハ 電池用バインダー溶液およびその製造方法
CN101207193B (zh) * 2006-12-21 2010-11-17 比亚迪股份有限公司 一种电极浆料的制备方法
WO2010138647A1 (en) * 2009-05-29 2010-12-02 Arkema Inc. Aqueous polyvinylidene fluoride composition
KR101413864B1 (ko) 2009-10-30 2014-06-30 가부시끼가이샤 구레하 열처리가 끝난 불화 비닐리덴계 중합체 분말의 제조 방법 및 불화 비닐리덴계 중합체 용액의 제조 방법
JP5766120B2 (ja) * 2009-10-30 2015-08-19 株式会社クレハ フッ化ビニリデン系重合体粉末およびフッ化ビニリデン系重合体溶液
KR20130096314A (ko) * 2011-01-06 2013-08-29 미쯔비시 레이온 가부시끼가이샤 폴리불화비닐리덴용 개질제, 전지용 결합제 수지 조성물, 이차 전지용 전극 및 전지
JP5701131B2 (ja) * 2011-04-05 2015-04-15 株式会社クレハ フッ化ビニリデン系共重合体、および該共重合体の用途
KR101993811B1 (ko) * 2014-04-02 2019-06-27 니폰 제온 가부시키가이샤 이차전지용 정극, 이차전지용 정극의 제조방법 및 이차전지

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010074041A1 (ja) * 2008-12-26 2010-07-01 株式会社クレハ 非水電解質二次電池用負極合剤、非水電解質二次電池用負極および非水電解質二次電池
JP2012064542A (ja) * 2010-09-17 2012-03-29 Toyota Motor Corp 電池用活物質ペースト、電池用活物質ペーストの分散性評価方法、電池用活物質ペーストの分散性の管理方法、及び、電極板の製造方法
JP2013170203A (ja) * 2012-02-20 2013-09-02 Nippon Shokubai Co Ltd ポリエーテル共重合体

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023505931A (ja) * 2020-06-12 2023-02-14 アルケマ フランス 電池電極用組成物
WO2022114039A1 (ja) 2020-11-30 2022-06-02 株式会社クレハ フッ化ビニリデン重合体組成物およびその製造方法、樹脂組成物、電極合剤、ならびにこれらを含む電極およびその製造方法
WO2024045504A1 (zh) * 2022-08-30 2024-03-07 宁德时代新能源科技股份有限公司 粘结剂、制备方法、正极极片、二次电池及用电装置

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