WO2019167322A1 - バインダー組成物、電極合剤および非水電解質二次電池 - Google Patents

バインダー組成物、電極合剤および非水電解質二次電池 Download PDF

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WO2019167322A1
WO2019167322A1 PCT/JP2018/036676 JP2018036676W WO2019167322A1 WO 2019167322 A1 WO2019167322 A1 WO 2019167322A1 JP 2018036676 W JP2018036676 W JP 2018036676W WO 2019167322 A1 WO2019167322 A1 WO 2019167322A1
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Prior art keywords
binder composition
vinylidene fluoride
electrode mixture
electrode
group
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English (en)
French (fr)
Japanese (ja)
Inventor
壮哉 土肥
勇樹 堺
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Kureha Corp
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Kureha Corp
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Priority to KR1020207025728A priority Critical patent/KR102451851B1/ko
Priority to CN201880087505.2A priority patent/CN111684631B/zh
Publication of WO2019167322A1 publication Critical patent/WO2019167322A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • 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
    • 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 composition used in the production of a nonaqueous electrolyte secondary battery, particularly a lithium ion secondary battery, and an electrode mixture using the same.
  • Nonaqueous electrolyte secondary batteries are also used in hybrid vehicles combining secondary batteries and engines, and electric vehicles powered by secondary batteries, from the viewpoint of global environmental problems and energy saving. Applications are expanding.
  • the electrode for a non-aqueous electrolyte secondary battery has a structure having a current collector and an electrode mixture layer formed on the current collector.
  • the electrode mixture layer is generally formed by applying an electrode mixture containing an electrode active material and a binder composition onto a current collector in a slurry state in which the electrode mixture is dispersed in an appropriate solvent, and volatilizing the solvent.
  • a vinylidene fluoride (VDF) polymer such as polyvinylidene fluoride (PVDF) is mainly used.
  • Patent Document 1 discloses a shear rate of 0 to 1000 in order to control the thickness after coating on a current collector.
  • a mixture slurry prepared such that a flow curve in the range of s ⁇ 1 ] is approximated with a specific correlation coefficient for a specific flow equation is disclosed.
  • the electrode mixture of Patent Document 1 has a problem that an irreversible thickening phenomenon may occur during storage in a slurry state.
  • an electrode mixture containing a binder composition using a VDF / CTFE copolymer has a thixotropic property (viscosity decreases with time when it is subjected to shear stress, and decreases with time when compared with other VDF polymers).
  • thixotropic property viscosity decreases with time when it is subjected to shear stress, and decreases with time when compared with other VDF polymers.
  • the present invention has been made in view of the above-mentioned problems, and its purpose is to suppress a irreversible thickening phenomenon during storage of a slurry-like electrode mixture, and to suppress its thixotropic property. Is to provide.
  • the “electrode” in this specification and the like means that an electrode mixture layer formed from an electrode mixture using the binder composition in the present embodiment is formed on a current collector. It means an electrode of a non-aqueous electrolyte secondary battery.
  • the “battery” in this specification and the like means a nonaqueous electrolyte secondary battery including an “electrode”.
  • “thixotropic property” in the present specification and the like means a property that the viscosity decreases with time when the shear stress is continued, and the viscosity increases when stationary, and OC ⁇ C. Lin “Thixotropic behavior of gel- like systems ”J. Appl. Polym. Sci. Vol.19, 199-214, 1975 can be expressed by the thixotropy coefficient ⁇ . It can be said that the thixotropy is suppressed as the thixotropy coefficient ⁇ is smaller.
  • the binder composition according to this embodiment is an electrode of a battery, and in an electrode in which an electrode mixture layer containing an electrode active material is formed on a current collector, the electrode active material is bound to the current collector. It is used to make it.
  • the binder composition contains a vinylidene fluoride polymer and a specific polymer additive. Moreover, in the binder composition which concerns on this embodiment, as long as the desired effect is not inhibited, another polymer and additive may be included.
  • the vinylidene fluoride polymer according to an aspect of the present invention is a vinylidene fluoride homopolymer in a range that does not inhibit the thickening phenomenon suppressing effect of the vinylidene fluoride copolymer, Or the vinylidene fluoride copolymer which does not contain the structural unit derived from chlorotrifluoroethylene may be included.
  • Examples of the vinylidene fluoride copolymer not containing a structural unit derived from chlorotrifluoroethylene include a VDF / APS copolymer containing a structural unit derived from mono (acryloxypropyl) succinate (APS), hexa VDF / HFP copolymer containing structural units derived from fluoropropylene (HFP), VDF / AA copolymer containing structural units derived from acrylic acid (AA), VDF / HFP / APS copolymer, etc. Can be mentioned.
  • the vinylidene fluoride polymer is a vinylidene fluoride copolymer.
  • the vinylidene fluoride copolymer according to one embodiment of the present invention preferably contains 70% by mole or more of vinylidene fluoride-derived units, more preferably 80% by mole or more, and more preferably 85% by mole or more. It is particularly preferable to contain. Although there is no restriction
  • a silane coupling agent or titanate having both a reactive group and a hydrolyzable group in combination with a vinylidene fluoride polymer such as an amino group or a mercapto group in a solvent that dissolves or swells the vinylidene fluoride polymer.
  • a modified vinylidene fluoride polymer obtained by treatment in a system coupling agent is also used.
  • the effects of the present invention can be suitably achieved by further including a structural unit derived from a monomer component having a carboxyl group.
  • the monomer component having a carboxyl group include acrylic acid, methacrylic acid, monomethyl maleate, 2-carboxyethyl acrylate, methacrylic acid (2-carboxyethyl), succinic acid mono (acryloxyethyl), and succinic acid mono ( Acryloxypropyl), mono (acryloxyethyl) phthalate, mono (methacryloxyethyl) succinate, mono (methacryloxypropyl) succinate, mono (methacryloxyethyl) phthalate, and trifluoroacrylic acid . These may be used individually by 1 type, or may use 2 or more types.
  • the carboxyl group-containing structural unit is contained in an amount of 0.01 to 3 mol%.
  • the content is preferably 0.05 to 1 mol%, and more preferably 0.08 to 0.5 mol%.
  • the functional group amount is less than 0.01 mol%, sufficient adhesion may not be obtained.
  • properties, such as a chemical resistance intrinsic to a fluororesin may be impaired.
  • the abundance of each structural unit can be determined by 1 H NMR or 19 F NMR.
  • methyl cellulose methoxylated methyl cellulose, propoxylated methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyethylene oxide, gelatin and the like can be used.
  • diisopropyl peroxydicarbonate dinormalpropyl peroxydicarbonate, dinormalheptafluoropropyl peroxydicarbonate, isobutyryl peroxide, di (chlorofluoroacyl) peroxide, di (perfluoroacyl) peroxide Oxide, t-butyl peroxypivalate, etc.
  • diisopropyl peroxydicarbonate dinormalpropyl peroxydicarbonate, dinormalheptafluoropropyl peroxydicarbonate, isobutyryl peroxide, di (chlorofluoroacyl) peroxide, di (perfluoroacyl) peroxide Oxide, t-butyl peroxypivalate, etc.
  • the degree of polymerization of the resulting polymer is adjusted by adding a chain transfer agent such as ethyl acetate, methyl acetate, acetone, ethanol, n-propanol, acetaldehyde, propyl aldehyde, ethyl propionate, and carbon tetrachloride. It is also possible.
  • a chain transfer agent such as ethyl acetate, methyl acetate, acetone, ethanol, n-propanol, acetaldehyde, propyl aldehyde, ethyl propionate, and carbon tetrachloride. It is also possible.
  • the binder composition, together with the vinylidene fluoride copolymer includes the following repeating units: -[CH 2 -CHR]-
  • a polymer additive comprising a polymer material having
  • R is a chain or cyclic amide group, a nitrile group, a hydroxy group, an ester-containing group, or an alkyl group having 1 to 4 carbon atoms, and at least one hydrogen atom of the alkyl group is a chain. Or a substituent substituted with a amide group, a nitrile group or a hydroxy group.
  • the “chain or cyclic amide group” has the formula: —CONR 1 R 2 or —NR 1 COR 2 (wherein R 1 and R 2 may be the same or different from each other).
  • Examples of such a chain or cyclic amide group include a 2-pyrrolidone group, an acetamido group, and an N-methylacetamido group.
  • the 2-pyrrolidone group, the acetamide group, and the N-methylacetamide group are monovalent groups in which one hydrogen atom bonded to a carbonyl carbon atom or a nitrogen atom in the corresponding compound is substituted with a bond. Represents a group.
  • the binder composition can suppress thixotropic properties while retaining the effect of suppressing the thickening phenomenon of the slurry when used as an electrode mixture.
  • polymer material examples include polyvinyl pyrrolidone, polyacrylonitrile, polyvinyl alcohol, and the like.
  • polyvinyl alcohol includes polyvinyl alcohol obtained by saponifying polyvinyl acetate and having an acetyl group remaining in a range of 30 mol% or less.
  • the method for producing the polymer material according to one embodiment of the present invention is not particularly limited, and the polymer material can be produced in the same manner as the above-described vinylidene fluoride copolymer.
  • the binder composition according to this embodiment includes a vinylidene fluoride polymer containing the vinylidene fluoride copolymer and a polymer additive.
  • the vinylidene fluoride copolymer may be used alone, or two or more types of vinylidene fluoride copolymers may be used in combination.
  • the polymer additive may be used alone or in combination of two or more polymer materials.
  • the binder composition according to this embodiment may further contain another polymer and various additives as long as the desired effect is not impaired.
  • the content of the vinylidene fluoride copolymer in the binder composition is preferably 2.5% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass.
  • the content of the vinylidene fluoride copolymer is within this range, an irreversible thickening phenomenon during storage can be suppressed when the binder composition is used as an electrode mixture.
  • the content of the polymer additive in the binder composition is preferably 1 to 50% by mass, more preferably 2 to 2% when the total of the vinylidene fluoride polymer and the polymer additive is 100% by mass. 30% by mass, more preferably 2.5 to 10% by mass.
  • the content of the polymer additive is within this range, when the binder composition is used as an electrode mixture, the effect of suppressing an increase in thixotropic properties is further enhanced.
  • the binder composition may further contain a conventional additive as required.
  • the electrode mixture in the present embodiment is obtained by adding an electrode active material and a solvent to a binder composition.
  • An electrode can be produced by applying this electrode mixture on a current collector to form an electrode mixture layer.
  • the electrode mixture is in the form of a slurry and can be adjusted to a desired viscosity by adjusting the amount of the solvent.
  • the electrode mixture can be used as an electrode mixture for the positive electrode or an electrode mixture for the negative electrode by changing the type of the electrode active material according to the type of the current collector to be applied.
  • the electrode mixture in the present embodiment is preferably a positive electrode mixture using a positive electrode active material, that is, a positive electrode active material (positive electrode material).
  • the solvent used in the electrode mixture in the present embodiment is not particularly limited as long as the solvent can dissolve the vinylidene fluoride polymer and the polymer additive.
  • the solvent include N-methyl-2-pyrrolidone (NMP), water, dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide, hexamethylphosphoamide, dioxane, tetrahydrofuran, tetramethylurea, triethyl phosphate. , Trimethyl phosphate, acetone, methyl ethyl ketone, and tetrahydrofuran. These solvents may be used alone or as a mixed solvent in which two or more kinds are mixed.
  • the solvent used in the electrode mixture is preferably a nitrogen-containing organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide, and N-methyl-2-pyrrolidone is preferred. More preferred.
  • the amount of the solvent is preferably 400 to 10000 parts by mass, and more preferably 600 to 8000 parts by mass. Within the range of the amount of the solvent described above, the solution viscosity is moderate and the handling property is excellent.
  • the electrode active material used in the electrode mixture in the present embodiment is an electrode active material for a negative electrode, that is, a negative electrode, when the electrode mixture according to the present embodiment is used as an electrode mixture for a negative electrode.
  • An active material may be used.
  • a positive electrode active material that is, a positive electrode active material may be used.
  • the positive electrode active material examples include a lithium-based positive electrode active material containing lithium.
  • the lithium-based positive electrode active material examples include a composite metal chalcogen compound represented by the general formula LiMY 2 such as LiCoO 2 and LiCo x Ni 1-x O 2 (0 ⁇ x ⁇ 1), or a composite metal oxide, LiMn 2 O And composite metal oxides having a spinel structure such as 4 and olivine type lithium compounds such as LiFePO 4 .
  • M is at least one of transition metals such as Co, Ni, Fe, Mn, Cr and V or Al
  • Y is a chalcogen element such as O and S.
  • the negative electrode active material conventionally known materials including carbon-based materials such as graphite can be used.
  • the electrode active material may be added directly to the binder composition together with the solvent.
  • the electrode active material may be first added to a solvent, and the mixture after stirring may be added to the binder composition. Or you may make it add an electrode active material to the binder solution obtained by mixing a binder composition and a solvent.
  • the electrode mixture in the present embodiment may further contain a conductive aid.
  • the conductive additive is added for the purpose of improving the conductivity of the electrode mixture layer when using an active material having a low electron conductivity such as LiCoO 2 .
  • the conductive assistant for example, carbon black, carbon nanotubes, carbonaceous materials such as graphite fine powder and graphite fiber, and metal fine powder or metal fiber such as nickel and aluminum can be used.
  • the electrode mixture in this embodiment may contain components other than the above-described components.
  • examples of other components include organic acids such as oxalic acid and succinic acid, and conventional additives such as a dispersant.
  • the electrode mixture according to the present embodiment is prepared by mixing the binder composition, the solvent and the electrode active material, and, if necessary, the conductive auxiliary agent and other various components in any order to form a slurry. Can be obtained.
  • a binder solution is prepared by mixing a binder composition and a solvent, an electrode active material is added to the obtained binder solution together with a conductive additive, and the mixture is stirred and mixed to prepare an electrode mixture. Can do.
  • a conductive assistant dispersion is prepared by mixing a conductive assistant and a solvent, and a binder composition, an electrode active material, and the like are added to the obtained conductive assistant dispersion, and the mixture is stirred and mixed to form an electrode.
  • a mixture may be prepared.
  • the electrode mixture may be prepared by preparing the binder solution and the conductive auxiliary agent dispersion, respectively, and stirring and mixing them with an electrode active material or the like.
  • FIG. 1 is a cross-sectional view of an electrode in the present embodiment.
  • the electrode 10 includes a current collector 11 and electrode mixture layers 12 a and 12 b, and electrode mixture layers 12 a and 12 b are formed on the current collector 11.
  • the electrode 10 becomes a positive electrode when the electrode mixture layers 12a and 12b are obtained using the electrode mixture for the positive electrode, and the electrode mixture layers 12a and 12b using the electrode mixture for the negative electrode. Is obtained as a negative electrode.
  • the current collector 11 is a base material for the electrode 10 and a terminal for taking out electricity. Examples of the material of the current collector 11 include iron, stainless steel, steel, copper, aluminum, nickel, and titanium.
  • the shape of the current collector 11 is preferably a foil or a net. When the electrode 10 is a positive electrode, the current collector 11 is preferably an aluminum foil.
  • the thickness of the current collector 11 is preferably 5 to 100 ⁇ m, and more preferably 5 to 20 ⁇ m.
  • the electrode mixture layers 12a and 12b are layers obtained by applying the electrode mixture described above to the current collector 11 and drying it.
  • a method for applying the electrode mixture a known method in the technical field can be used, and a method using a bar coater, a die coater, a comma coater, or the like can be given.
  • the drying temperature for forming the electrode mixture layers 12a and 12b is preferably 50 to 170 ° C.
  • the thickness of the electrode mixture layers 12a and 12b is preferably 10 to 1000 ⁇ m.
  • the electrode 10 has electrode mixture layers 12 a and 12 b formed on both surfaces of the current collector 11.
  • the present invention is not limited to this, and one surface of the current collector 11 is not limited thereto.
  • the electrode mixture layer may be formed only on the surface.
  • the thickness of the electrode mixture layer is usually 20 to 250 ⁇ m, preferably 20 to 150 ⁇ m.
  • the basis weight of the mixture layer is usually 20 to 700 g / m 2 , preferably 30 to 500 g / m 2 .
  • FIG. 2 is an exploded perspective view of the nonaqueous electrolyte secondary battery.
  • the battery 100 includes a positive electrode 1, a negative electrode 2, a separator 3, and a metal casing 5.
  • the battery 100 has a structure in which a power generation element in which a laminated body in which a separator 3 is disposed between a positive electrode 1 and a negative electrode 2 is spirally wound is housed in a metal casing 5.
  • the positive electrode 1 or the negative electrode 2 is the same as the electrode 10 in FIG.
  • the separator 3 a known material such as a porous film of a polymer material such as polypropylene and polyethylene can be used.
  • the battery 100 is illustrated as a cylindrical battery, but the battery 100 in the present embodiment is not limited to this, and may be a coin-shaped, rectangular, or paper-type battery.
  • a binder composition according to an embodiment of the present invention is a binder composition used for binding an electrode active material to a current collector, and the binder composition is a hook composition.
  • a vinylidene fluoride polymer and a polymer additive the vinylidene fluoride polymer includes a vinylidene fluoride copolymer including a structural unit derived from vinylidene fluoride and a structural unit derived from chlorotrifluoroethylene
  • the polymer additive includes the following repeating units: -[CH 2 -CHR]- It is a binder composition which is a polymer material having (In the above repeating unit, R is a chain or cyclic amide group, a nitrile group, a hydroxy group, an ester-containing group, or an alkyl group having 1 to 4 carbon atoms, and at least one hydrogen atom of the alkyl group is Indicates a substituent substituted with a chain or cyclic
  • R is preferably a chain or cyclic amide group, a nitrile group, or a hydroxy group.
  • the polymer additive is preferably polyvinyl pyrrolidone, polyacrylonitrile, or polyvinyl alcohol.
  • the polymer additive may be 1% by mass or more and 50% when the total of the vinylidene fluoride polymer and the polymer additive is 100% by mass. It is preferable that it is contained by mass% or less.
  • the vinylidene fluoride copolymer preferably further includes a structural unit derived from a monomer component having a carboxyl group.
  • An electrode mixture according to an embodiment of the present invention is an electrode mixture including the above-described binder composition, a solvent, and an electrode active material.
  • a nonaqueous electrolyte secondary battery according to an embodiment of the present invention is a nonaqueous electrolyte secondary battery including an electrode mixture layer formed from the above electrode mixture.
  • an electrode mixture was produced using various binder compositions according to the present invention, and a thixotropic coefficient and a gelation evaluation test of the slurry were performed using the mixture.
  • inherent viscosity in the present specification is a value measured by the following method.
  • a vinylidene fluoride copolymer solution is prepared by dissolving 80 mg of vinylidene fluoride copolymer in 20 mL of N, N-dimethylformamide.
  • the viscosity ⁇ of the solution is measured using a Ubbelohde viscometer in a constant temperature bath at 30 ° C.
  • the inherent viscosity ⁇ i is obtained by the following formula using the viscosity ⁇ .
  • ⁇ i (1 / C) ⁇ ln ( ⁇ / ⁇ 0)
  • ⁇ 0 is the viscosity of N, N-dimethylformamide as a solvent
  • C is 0.4 g / dL.
  • Example 1 As a vinylidene fluoride copolymer, vinylidene fluoride (VDF) and chlorotrifluoroethylene (CTFE) (weight ratio 96: 4) are polymerized, and a VDF-CTFE copolymer (inherent viscosity 2.1 dL / g) is used. did. In addition, polyvinyl pyrrolidone (PVP K15) (number average molecular weight 10,000, P0471 manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a polymer additive.
  • PVDF vinylidene fluoride
  • CTFE chlorotrifluoroethylene
  • the above-mentioned vinylidene fluoride copolymer and polymer additive were mixed so that the polymer additive was 5% by mass with respect to the total mass to obtain a binder composition.
  • Lithium-cobalt composite oxide (LCO; LiCoO 2 , Cellseed C10N, manufactured by Nippon Chemical Industry Co., Ltd., average particle size 10 ⁇ m) as an electrode active material 100 parts by mass, carbon black (SP; SuperPal manufactured by Timcal Japan) (Registered trademark) Li, 2 parts by mass of an average particle diameter of 40 nm, specific surface area of 60 m 2 / g) and 2 parts by mass of the binder composition were uniformly dispersed in N-methyl-2-pyrrolidone to form a slurry.
  • An electrode mixture having a total solid content concentration of 76% by mass of the binder composition, the electrode active material, and the conductive additive with respect to the total mass was prepared.
  • the obtained electrode mixture was coated on a 15 ⁇ m-thick aluminum foil as a current collector with a bar coater and dried at 110 ° C. for 30 minutes in a nitrogen atmosphere using a thermostatic bath. Was made.
  • Example 2 As a vinylidene fluoride copolymer, VDF, CTFE and mono (acryloxypropyl) succinate (APS) (weight ratio 96: 4: 1) were polymerized to obtain a VDF-CTFE-APS copolymer (inherent viscosity 2.3 dL). / G) was used in the same manner as in Example 1 except that a binder composition was obtained.
  • the binder composition obtained above in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive is 74% by mass, the electrode mixture and the electrode was made.
  • the binder composition obtained above in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive is 78% by mass, the electrode mixture and the electrode was made.
  • Example 4 As a vinylidene fluoride copolymer, VDF, CTFE and monomethyl maleate (MMM) (weight ratio 98: 2: 0.7) were polymerized to obtain a VDF-CTFE-MMM copolymer (inherent viscosity 2.3 dL / g). A binder composition was obtained in the same manner as in Example 1 except that it was used.
  • an electrode mixture and an electrode were obtained in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive was 75% by mass. Was made.
  • Example 5 A binder composition was obtained in the same manner as in Example 2 except that the polymer additive was 2.5% by mass with respect to the total mass of the binder composition.
  • the binder composition obtained above in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive is 73% by mass, the electrode mixture and the electrode was made.
  • Example 6 A binder composition was obtained in the same manner as in Example 1 except that polyvinyl pyrrolidone (PVP K90) (number average molecular weight 360,000, manufactured by Tokyo Chemical Industry Co., Ltd., P0473) was used as the polymer additive.
  • PVP K90 polyvinyl pyrrolidone
  • an electrode mixture and an electrode were obtained in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive was 75% by mass. Was made.
  • Example 7 A binder composition was obtained in the same manner as in Example 1 except that polyvinyl alcohol (PVA) (manufactured by Nippon Synthetic Chemical Co., Ltd., Gohsenol GH-17) was used as a polymer additive.
  • PVA polyvinyl alcohol
  • an electrode mixture and an electrode were obtained in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive was 75% by mass. Was made.
  • Example 8 A binder composition was obtained in the same manner as in Example 1 except that polyacrylonitrile (PAN) (weight average molecular weight 150,000, manufactured by Sigma-Aldrich, 181315) was used as the polymer additive.
  • PAN polyacrylonitrile
  • the binder composition obtained above in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive is 73% by mass, the electrode mixture and the electrode was made.
  • Example 9 In the same manner as in Example 1, a binder composition was obtained.
  • NCA nickel cobalt lithium aluminum oxide
  • SP carbon black
  • an average particle diameter of 40 nm, 2 parts by mass of a specific surface area of 60 m 2 / g) and 2 parts by mass of the above binder composition were uniformly dispersed in N-methyl-2-pyrrolidone to obtain a total solid of the binder composition, the electrode active material and the conductive assistant.
  • An electrode mixture having a partial concentration of 79% by mass was produced.
  • Example 10 Except for polymerizing VDF, CTFE and APS (weight ratio 96: 4: 1) as a vinylidene fluoride copolymer and using VDF-CTFE-APS copolymer (inherent viscosity 2.3 dL / g) In the same manner as in Example 1, a binder composition was obtained.
  • the binder composition obtained above in the same manner as in Example 9 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive is 74% by mass, the electrode mixture and the electrode was made.
  • an electrode mixture and an electrode were obtained in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive was 68% by mass. Was made.
  • an electrode mixture and an electrode were obtained in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material, and the conductive additive was 70% by mass. Was made.
  • the binder composition obtained above in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive is 73% by mass, the electrode mixture and the electrode was made.
  • Example 5 A binder composition was obtained in the same manner as in Example 1 except that polyethylene glycol (PEG) was used instead of polyvinyl pyrrolidone (PVP K15) which is a polymer additive.
  • PEG polyethylene glycol
  • PVP K15 polyvinyl pyrrolidone
  • the binder composition obtained above in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive is 69% by mass, the electrode mixture and the electrode Was made.
  • Example 6 A binder composition was obtained in the same manner as in Example 1 except that polyacrylic acid (PAA) was used instead of polyvinyl pyrrolidone (PVP K15) which is a polymer additive.
  • PAA polyacrylic acid
  • PVP K15 polyvinyl pyrrolidone
  • an electrode mixture and an electrode were obtained in the same manner as in Example 1 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive was 68% by mass. Was made.
  • the binder composition obtained above in the same manner as in Example 9 except that the total solid concentration of the binder composition, the electrode active material and the conductive additive is 76% by mass, the electrode mixture and the electrode was made.
  • an electrode mixture and an electrode were obtained in the same manner as in Example 9, except that the total solid concentration of the binder composition, the electrode active material and the conductive additive was 78% by mass. Was made.
  • thixotropy coefficient ⁇ of electrode mixture slurry The electrode slurry was measured for 300 seconds at 25 ° C. and a shear rate of 2 s ⁇ 1 using an E-type viscometer (Toki Sangyo Co., Ltd., RE-80).
  • the thixotropy coefficient ⁇ can be obtained from the following equation using the maximum viscosity ⁇ 0 after the start of measurement and the viscosity ⁇ at the time when the change in viscosity over time has disappeared.
  • the difference between the initial shear stress ( ⁇ 0) and the equilibrium shear stress ( ⁇ ) is small, and the thixotropic coefficient ⁇ is 0 to 0.2.
  • the viscosity change accompanying shearing hardly occurred, and the thixotropic property was well suppressed.
  • the electrode mixture slurry did not gel after a certain period of time, and was applied onto an aluminum foil and dried to form a smooth electrode mixture layer.
  • Comparative Examples 1 to 8 did not contain the polymer additive made of the polymer material of the present invention, so that the viscosity change caused by shearing occurred and the thixotropy coefficient showed a high value.

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CN115340624A (zh) * 2022-10-17 2022-11-15 宁德时代新能源科技股份有限公司 聚合物、导电浆料、正极极片、二次电池和用电装置

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KR20230064478A (ko) * 2021-11-03 2023-05-10 주식회사 엘지화학 부착 증진층이 코팅된 양극 집전체 및 그 제조방법, 이를 포함하는 리튬 이차 전지용 양극 및 리튬 이차 전지
WO2025204571A1 (ja) * 2024-03-29 2025-10-02 株式会社クレハ フッ化ビニリデン共重合体、電極用バインダー、電極合剤、電極、および電池
WO2025204572A1 (ja) * 2024-03-29 2025-10-02 株式会社クレハ フッ化ビニリデン共重合体、電極用バインダー、電極合剤、電極、および電池

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