WO2019009242A1 - Composition de liant, mélange d'électrode, électrode, batterie secondaire à électrolyte non aqueux, et dispersant - Google Patents

Composition de liant, mélange d'électrode, électrode, batterie secondaire à électrolyte non aqueux, et dispersant Download PDF

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Publication number
WO2019009242A1
WO2019009242A1 PCT/JP2018/025054 JP2018025054W WO2019009242A1 WO 2019009242 A1 WO2019009242 A1 WO 2019009242A1 JP 2018025054 W JP2018025054 W JP 2018025054W WO 2019009242 A1 WO2019009242 A1 WO 2019009242A1
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Prior art keywords
carbon atoms
group
binder composition
electrode
dispersant
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PCT/JP2018/025054
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English (en)
Japanese (ja)
Inventor
佳余子 岡田
正太 小林
達 宮崎
卓 村田
泰輔 小関
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株式会社クレハ
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Publication of WO2019009242A1 publication Critical patent/WO2019009242A1/fr

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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
    • 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, an electrode mixture, an electrode, and a non-aqueous electrolyte secondary battery, and a dispersant. More specifically, the present invention relates to a binder composition, an electrode mixture using the binder composition, an electrode and a non-aqueous electrolyte secondary battery, and a dispersant used in the binder composition.
  • Nonaqueous electrolyte secondary batteries represented by lithium ion secondary batteries and the like are widely used as batteries having high energy density.
  • a non-aqueous electrolyte secondary battery as a power source for hybrid cars, electric cars and the like, and its practical use has been started.
  • a resin composition called a binder is used to bind an electrode active material to a current collector.
  • the electrode is manufactured by applying a slurry-like electrode mixture in which the binder and the electrode active material are mixed to a current collector and drying it.
  • a binder having high adhesion performance that can reduce the compounding amount as much as possible is desired so that the compounding amount of the active material can be increased.
  • polyvinylidene fluoride As a means to improve the adhesiveness of a binder, the method of using polyvinylidene fluoride for binder resin is known, for example, and various things are proposed also as polyvinylidene fluoride. For example, copolymerizing a vinylidene fluoride copolymer having an intrinsic viscosity of more than 2.0 dl / g (see, for example, Patent Document 1), a vinylidene fluoride and a monoester of an unsaturated dibasic acid such as maleic acid monomethyl ester. And a vinylidene fluoride copolymer (see, for example, Patent Document 3) obtained by copolymerizing vinylidene fluoride and an acrylic acid compound. Proposed.
  • a vinylidene fluoride copolymer having an intrinsic viscosity of more than 2.0 dl / g see, for example, Patent Document 1
  • Japanese Patent Publication Japanese Patent Application Laid-Open No. 9-289023 (disclosed on November 4, 1997)” Japanese Patent Publication "Japanese Patent Application Laid-Open No. 6-172452 (published on June 21, 1994)” Japanese Patent Publication "Tokukai 2010-525124 (July 22, 2010 published)"
  • the electrode mixture using the binder as described above has a high viscosity.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a binder composition capable of reducing the viscosity of an electrode mixture while having high adhesion performance.
  • the binder composition concerning one mode of the present invention is a binder composition used in order to bind an electrode active material to a current collection object, and adhesive resin and a dispersing agent are used.
  • the dispersant is a compound represented by the following formula (I) or (II):
  • X 6 independently represents a hydrogen atom or a methyl group
  • X 1 represents a methylene group
  • X 2 and X 3 independently represent H, —NH 2
  • m is an integer of 1 to 50
  • a 3 is an alkylene group having 2 to 4 carbon atoms
  • R 2 and R 3 are each independently H, an alkyl group having 1 to 18 carbon atoms or 1 carbon atom Represents an aminoalkyl group of -18.
  • the dispersant according to one aspect of the present invention is a dispersant for being added to a binder composition used to bind an electrode active material to a current collector, and the binder composition has an adhesive property. It is a binder composition containing resin, and is a dispersing agent which contains a compound represented by the following formula (I) or (II) as a main component.
  • X 6 independently represents a hydrogen atom or a methyl group
  • X 1 represents a methylene group
  • X 2 and X 3 independently represent H, —NH 2
  • m is an integer of 1 to 50
  • a 3 is an alkylene group having 2 to 4 carbon atoms
  • R 2 and R 3 are each independently H, an alkyl group having 1 to 18 carbon atoms or 1 carbon atom Represents an aminoalkyl group of -18.
  • a binder composition capable of reducing the viscosity of the electrode mixture when it is used as an electrode mixture while having high adhesion performance.
  • an electrode mixture layer formed of an electrode mixture using the binder composition of the present embodiment is formed on a current collector, unless otherwise specified.
  • the "battery" in this specification means the nonaqueous electrolyte secondary battery provided with the "electrode.”
  • the binder composition which concerns on this embodiment is used in order to bind an electrode active material to a collector in the electrode in which the electrode mixture layer containing an electrode active material is formed on a collector.
  • the binder composition contains an adhesive resin and a dispersant.
  • the binder composition may contain a solvent in addition to the adhesive resin and the dispersant.
  • the binder composition may further contain a conductive aid.
  • the binder composition may further contain an additive as an optional component.
  • the adhesive resin contained in the binder composition according to this embodiment is not particularly limited as long as the electrode active material can be bound to the current collector, and a vinylidene fluoride resin, an acrylic resin, and a synthetic rubber Etc. can be used.
  • a vinylidene fluoride-based resin is a resin containing a constituent unit derived from vinylidene fluoride as a main component, and a homopolymer of vinylidene fluoride and a monomer copolymerizable with vinylidene fluoride Both copolymers with vinylidene fluoride are included.
  • "Containing a constitutional unit derived from vinylidene fluoride as a main component” is intended to mean that the constitutional unit derived from vinylidene fluoride in the polymer exceeds 50% by mole.
  • the constituent unit derived from vinylidene fluoride is 90 mol% or more, more preferably 95 mol% or more.
  • Other monomer components copolymerizable with vinylidene fluoride include hydrocarbon monomers such as ethylene and propylene; trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropyrene, vinyl fluoride, and perfluoro Monomers containing fluorine other than vinylidene fluoride such as perfluoroalkyl vinyl ether represented by methyl vinyl ether; unsaturated dibasic acids such as maleic acid and citraconic acid or monoalkyl esters thereof; and (meth) acrylic acid Examples thereof include alkyl (meth) acrylate compounds represented by methyl (meth) acrylate.
  • acryloyloxyethyl succinic acid methacryloyloxyethyl succinic acid, acryloyloxy propyl succinic acid, methacryloyloxy propyl succinic acid, acryloyloxy ethyl phthalic acid, methacryloyloxy ethyl phthalic acid, 2-carboxyethyl acrylate, And 2-carboxyethyl methacrylate may be used.
  • An acrylic resin is a resin containing a structural unit of (meth) acrylic acid, (meth) acrylic acid ester, or (meth) acrylonitrile as a main component, and poly (meth) acrylic acid or poly (meth) acrylic acid Methyl, poly (meth) acrylonitrile, polyacrylamide, copolymers of (meth) acrylic acid and (meth) acrylonitrile, and copolymers of (meth) acrylic acid ester and (meth) acrylonitrile, etc. are mentioned, among them , Polyacrylic acid or polyacrylonitrile is preferred.
  • Examples of synthetic rubbers include styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, (meth) acrylic acid ester-butadiene rubber, butadiene rubber, chloroprene rubber, isoprene rubber, peptyl rubber, ethylene propylene rubber, nitrile rubber, silicone rubber, fluorine Examples thereof include rubber, acrylic rubber, urethane rubber, polysulfide rubber, chlorinated butyl rubber, and shrimp chlorohydrin rubber. Among these, styrene-butadiene rubber (SBR) is preferable. These synthetic rubbers are preferably in the form of a water dispersible latex or emulsion in order to facilitate preparation of the mixture, and thickeners may be mixed and used.
  • SBR styrene-butadiene rubber
  • SBR acrylonitrile-butadiene rubber
  • acrylic acid ester-butadiene rubber butadiene rubber
  • cellulose compounds such as carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose, ammonium salts or alkali metal salts of the cellulose compounds, poly (meth) acrylic acid and modified poly (meth) acrylics
  • Polycarboxylic acids such as acids, alkali metal salts of the polycarboxylic acids, polyvinyl alcohols, modified polyvinyl alcohols and polyvinyl alcohol (co) polymers such as ethylene-vinyl alcohol copolymers, (meth) acrylic acid, maleic acid and Examples thereof include unsaturated carboxylic acids such as fumaric acid and water-soluble polymers such as cationized guar gum.
  • carboxymethyl cellulose and its salts are preferable.
  • a vinylidene fluoride resin is preferable as the adhesive resin.
  • the content of the adhesive resin is preferably 10 to 99.7 parts by mass, more preferably 15 to 99 parts by mass, and still more preferably 20 to 98 parts by mass with respect to 100 parts by mass of the binder composition. is there.
  • the total amount of the adhesive resin, the dispersant and the additive is 100 parts by mass.
  • the dispersant contained in the binder composition according to the present embodiment is a compound represented by the following formula (I) or a compound represented by the following formula (II).
  • a plurality of X 6 each independently represent a hydrogen atom or a methyl group
  • X 1 represents a methylene group
  • X 2 and X 3 independently represent H , -NH 2 , a hydrocarbon group having 1 to 8 carbon atoms,-(A 1 O) 1 R 1 or -A 2 NX 4 X 5 .
  • the hydrocarbon group having 1 to 8 carbon atoms at X 2 and X 3 is preferably an aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and 3 to 8 carbon atoms.
  • a cycloalkenyl group of Examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group and n-butyl group, and branched alkyl groups such as isopropyl group, isobutyl group and tert-butyl group.
  • alkyl groups an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is more preferable.
  • alkenyl group an alkenyl group having 2 to 6 carbon atoms is preferable, and alkenyl having 2 to 4 carbon atoms is more preferable.
  • a cycloalkyl group having 3 to 6 carbon atoms is preferable, a cycloalkyl group having 5 or 6 carbon atoms is more preferable, and a cyclohexyl group is more preferable.
  • a cycloalkenyl group having 3 to 6 carbon atoms is preferable, a cycloalkenyl group having 5 or 6 carbon atoms is more preferable, and a cyclohexenyl group is more preferable.
  • the hydrocarbon group having 1 to 8 carbon atoms in X 2 and X 3 an aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group and a cyclohexenyl group are more preferable.
  • a 1 in 1 represents an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group.
  • l is an integer of 1 to 5, preferably an integer of 1 to 4, and more preferably an integer of 1 or 2.
  • - (A 1 O) R 1 in the l R 1 is H or an alkyl group having 1 to 8 carbon atoms, preferably H or an alkyl group having 1 to 4 carbon atoms, more preferably H or a carbon number 1 Or an alkyl group of 2.
  • a 2 in -A 2 NX 4 X 5 represents an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 1 or 2 carbon atoms.
  • X 4 and X 5 in -A 2 NX 4 X 5 independently represent H or a hydrocarbon group having 1 to 4 carbon atoms.
  • Preferred as -A 1 NX 4 X 5 is an aminoethyl group (-C 2 H 4 NH 2 ).
  • m is an integer of 1 to 50
  • a 3 represents an alkylene group having 2 to 4 carbon atoms
  • R 2 and R 3 independently represent H, an alkyl group having 1 to 18 carbon atoms Or an aminoalkyl group having 1 to 18 carbon atoms.
  • M in the formula (II) is preferably 1 to 20, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 or 2.
  • the alkylene group having 2 to 4 carbon atoms in A 3 is preferably an ethylene group.
  • the alkyl group having 1 to 18 carbon atoms in R 2 and R 3 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or It is an ethyl group.
  • the aminoalkyl group having 1 to 18 carbon atoms in R 2 and R 3 is preferably an aminoalkyl group having 1 to 6 carbon atoms, more preferably an aminoalkyl group having 1 to 4 carbon atoms, and still more preferably It is an aminomethyl group or an aminoethyl group.
  • X 1 is NH or O
  • X 3 is H
  • —NH 2 a hydrocarbon group having 1 to 6 carbon atoms
  • —C 2 H 4 OH a hydrocarbon group having 1 to 6 carbon atoms
  • —C 2 H 4 OH a hydrocarbon group having 1 to 6 carbon atoms
  • Compounds which are C 2 H 4 NH 2 are preferred.
  • the compound whose R ⁇ 2 > and R ⁇ 3 > is H, a methyl group, an ethyl group, or an aminoethyl group independently is preferable.
  • particularly preferred compounds as dispersants are morpholine, 4-methylmorpholine, 4-ethylmorpholine, 4- (2-hydroxyethyl) morpholine, 4- (1-cyclohexenyl) morpholine 4- (2-aminoethyl) morpholine, 4-aminomorpholine, piperazine, 1-methylpiperazine, N- (2-aminoethyl) piperazine, and 1- (2-hydroxyethyl) piperazine.
  • particularly preferred compounds as dispersants are monoethanolamine, N-methylethanolamine, N-ethylethanolamine and 2- (2-aminoethylamino) ethanol.
  • the binder composition only one type of dispersant may be used, or a plurality of dispersants may be mixed and used.
  • the content of the dispersant is preferably 0.1 to 80 parts by mass, more preferably 0.2 to 70 parts by mass, and still more preferably 0.3 to 80 parts by mass with respect to 100 parts by mass of the binder composition. 60 parts by mass.
  • the total amount of the adhesive resin, the dispersant and the additive is 100 parts by mass.
  • the form of the composition which contains the compound represented by Formula (I) or the compound represented by Formula (II) as a main component may also be sufficient.
  • the additive represented by Formula (III) shown next is included in a binder composition
  • the compound represented by Formula (I) or the compound represented by Formula (II) as a main component is included.
  • the dispersant as a composition may be an embodiment in which the additive represented by Formula (III) is contained.
  • the binder composition according to the present embodiment can contain additives in addition to the adhesive resin and the dispersant described above.
  • the additive is a compound represented by the following formula (III).
  • n is an integer of 1 to 100
  • R 4 is a hydrocarbon group having 1 to 18 carbon atoms
  • R 5 is H or an alkyl group having 1 to 4 carbon atoms
  • a 4 is 2 to 4 carbon atoms It is an alkylene group.
  • n is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4.
  • n may be 1 to 100, preferably 1 to 50, and more preferably 1 to 12, from the viewpoint of the peel strength of the adhesive mixture layer finally obtained. It is more preferable that it is ⁇ 3.
  • n is 1 to 100, the peel strength of the finally obtained adhesive mixture layer can be improved.
  • R 4 is preferably a phenyl group or an alkyl group having 1 to 18 carbon atoms.
  • the alkyl group is more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
  • R 5 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group.
  • a 4 is an ethylene group, a propylene group or a butylene group, preferably an ethylene group or a propylene group, more preferably a propylene group.
  • R 4 and R 5 are independently an alkyl group having 1 to 4 carbon atoms, and A 4 is an ethylene group or It is a compound which is a propylene group.
  • the content of the additive is preferably 1 to 80 parts by mass, and more preferably 3 to 70 parts by mass with respect to 100 parts by mass of the binder composition.
  • the total amount of the adhesive resin, the dispersant and the additive is 100 parts by mass.
  • the binder composition may contain a solvent.
  • the solvent used for the binder composition may be a non-aqueous solvent or water as long as it can dissolve or disperse the binder composition.
  • the non-aqueous solvent for example, N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoamide, dioxane, tetrahydrofuran, tetramethylurea, Triethyl phosphate, trimethyl phosphate, acetone, methyl ethyl ketone, cyclohexanone and the like can be mentioned.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-dimethylformamide
  • N N-dimethylacetamide
  • dimethylsulfoxide hexamethylphosphoamide
  • dioxane tetrahydrofuran
  • tetramethylurea Trieth
  • the inherent viscosity is not particularly limited, but is preferably 1 dl / g or more and 5 dl / g or less, and 1.5 dl / g. It is more preferably g or more and 4 dl / g or less, and still more preferably 1.7 dl / g or more and 3.5 dl / g or less.
  • the inherent viscosity is 1 dl / g or more, the adhesion of the binder composition becomes better.
  • the inherent viscosity is 5 dl / g or less, the decrease in the slurry solid content is further suppressed, and the productivity is further improved.
  • the binder composition may be prepared, for example, by mixing an adhesive resin, a dispersant, a conductive auxiliary agent, an additive, a solvent, and the like by an existing method so as to be a uniform binder composition.
  • the order of mixing is not particularly limited.
  • a dispersant may be directly added to the adhesive resin, or the adhesive resin and the dispersant may be mixed.
  • a method of mixing a solution in which an adhesive resin is dissolved or dispersed in a solvent and a dispersing agent a method of mixing a solution in which an adhesive resin is dissolved or dispersed in a solvent and a solution in which a dispersing agent is dissolved
  • the adhesive resin or the solution thereof may be mixed with the dispersing agent or the solution thereof, respectively, in the production of
  • the binder composition according to the present embodiment can obtain low shear viscosity, that is, high dispersibility, by including the above-described dispersant. Thereby, it can suppress that an aggregate produces on an electrode surface by forming an electrode using electrode mixture containing a binder constituent concerning this embodiment. Therefore, in the battery finally obtained, it is possible to suppress the deterioration of the battery performance due to the aggregates.
  • the electrode mixture in the present embodiment contains a binder composition and an electrode active material.
  • the electrode mixture may further contain a solvent.
  • An electrode can be manufactured by apply
  • the electrode mixture is in the form of slurry and can be adjusted to a desired viscosity by adjusting the amount of solvent.
  • 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 electrode active material or the like according to the type of the current collector to be coated.
  • the solvent used in the electrode mixture in the present embodiment is not particularly limited as long as it can dissolve or disperse the binder composition described above, and may be a non-aqueous solvent, or water It may be As the non-aqueous solvent, for example, N-methyl-2-pyrrolidone (NMP), dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide, hexamethylphosphoamide, dioxane, tetrahydrofuran, tetramethylurea, triethyl phosphate Trimethyl phosphate, acetone, methyl ethyl ketone, tetrahydrofuran and the like.
  • NMP N-methyl-2-pyrrolidone
  • dimethylformamide N, N-dimethylacetamide, N, N-dimethylsulfoxide
  • hexamethylphosphoamide dioxane
  • tetrahydrofuran tetramethylurea
  • solvents may be used alone or as a mixed solvent of two or more kinds.
  • nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide and N, N-dimethylacetamide are preferable, and N-methyl- More preferred is 2-pyrrolidone (NMP).
  • the content of the solvent is preferably 15 to 300 parts by mass, and 20 to 250 parts by mass, based on 100 parts by mass of the binder composition, the electrode active material, and the other components in the electrode mixture. It is more preferable that Within the range of the amount of the solvent mentioned above, the solution viscosity becomes appropriate and the handling property is excellent.
  • the electrode active material used in the electrode mixture according to the present embodiment is, as described above, the electrode active material for the negative electrode, ie, the negative electrode, when the electrode mixture according to the present embodiment is used as the electrode mixture for the negative electrode.
  • An active material may be used, and when the electrode mixture according to the present embodiment is used as an electrode mixture for a positive electrode, an electrode active material for a positive electrode, that is, a positive electrode active material may be used.
  • lithium type positive electrode active material containing lithium is mentioned, for example.
  • lithium-based positive electrode active materials include complex metal chalcogen compounds represented by the general formula LiMY 2 such as LiCoO 2 and LiCo x Ni 1 -x O 2 (0 ⁇ x ⁇ 1), or complex metal oxides, LiMn 2 O composite metal oxides taking a spinel structure such as 4 and LiFePO 4 olivine-type lithium compounds such like.
  • M is at least one of transition metals such as Co, Ni, Fe, Mn, Cr and V
  • 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 mixture in this embodiment may further contain a conductive aid.
  • a conductive additive is added for the purpose of improving the conductivity of the electrode mixture layer when using an olivine-type lithium compound such as LiFePO 4 or an active material having a small electron conductivity such as LiCoO 2 as an electrode active material It is.
  • the conductive additive for example, carbon black materials such as carbon black, carbon nanotubes, graphite fine powder and graphite fiber, and metal fine powder or metal fiber such as nickel and aluminum can be used.
  • the conductive aid may be contained in the binder composition as described above, in addition to being contained in the electrode mixture.
  • the same materials as described above can also be used when included in the binder composition.
  • the electrode mixture in this embodiment may contain other components other than the components described above.
  • examples of other components include pigment dispersants such as polyvinyl pyrrolidone and the like.
  • the method for producing the electrode mixture according to this embodiment may be, for example, mixing the binder composition, the electrode active material, the solvent, and the conductive auxiliary agent so as to form a uniform slurry, and the order of mixing is particularly limited I will not.
  • the electrode active material may be added directly to the binder composition, or alternatively, the electrode active material may first be added to a solvent, and a mixture obtained by stirring and mixing may be added to the binder composition.
  • an electrode active material or the like may be added before the solvent is added to the adhesive resin.
  • an electrode active material or the like may be added to the adhesive resin or the solution or the dispersant or the solution thereof.
  • the electrode in the non-aqueous electrolyte secondary battery in the present embodiment is formed by providing an electrode mixture layer formed of the above-mentioned electrode mixture on a current collector.
  • the electrode mixture layer may be formed on at least one surface of the current collector, and may be formed on both surfaces of the current collector.
  • a current collector used for the electrode in the present embodiment a current collector generally used in the technical field can be used.
  • the current collector for the negative electrode include copper and the like
  • examples of the current collector for the positive electrode include aluminum and the like.
  • a shape of a collector metal foil, a metal mesh, etc. are mentioned. However, the present invention is not limited to these, and the type and shape may be appropriately selected according to the application and the like.
  • the electrode mixture layer is a layer obtained by applying the electrode mixture described above to a current collector and drying it.
  • a known method such as a bar coater, a die coater, or a comma coater can be used.
  • the thickness of the electrode mixture layer is not particularly limited, but is usually 20 to 250 ⁇ m, and preferably 20 to 150 ⁇ m.
  • the weight per unit area of the electrode mixture layer is not particularly limited, but is usually 20 to 700 g / m 2 and preferably 30 to 500 g / m 2 .
  • the drying temperature and drying time for forming the electrode mixture layer are usually 1 to 300 minutes at a temperature of 50 to 150 ° C.
  • the pressure at the time of drying is not particularly limited, but the drying is usually performed under atmospheric pressure or reduced pressure.
  • a pressing process may be further performed, and when the pressing process is performed, the pressure is usually 1 to 200 MPa-G.
  • the electrode in the present embodiment is formed using an electrode mixture having a low shear viscosity, ie, high dispersibility, containing the binder composition according to the present embodiment, it is an electrode with less aggregates. Therefore, by using the electrode in this embodiment, it is possible to suppress the decrease in the performance of the battery due to the aggregates. Since the electrode in the present embodiment is formed using the electrode mixture containing the binder composition according to the present embodiment, high adhesion between the electrode mixture layer and the current collector, that is, high peel strength is obtained. Can. By this, peeling of the electrode mixture layer from the current collector can be suppressed, and deterioration of the performance of the battery due to peeling of the electrode mixture layer can be suppressed.
  • Non-aqueous electrolyte secondary battery in the present embodiment includes the above-described electrode.
  • the non-aqueous electrolyte secondary battery according to the present embodiment also includes, for example, a polymer battery containing a gel electrolyte. It does not specifically limit about the other member (for example, separator) in a non-aqueous electrolyte secondary battery, For example, the member used conventionally can be used.
  • non-aqueous electrolyte secondary battery in the present embodiment includes the electrode formed of the electrode mixture containing the binder composition according to the present embodiment, the decrease in battery performance is suppressed.
  • the present invention includes the following.
  • a binder composition used to bind an electrode active material to a current collector comprising: an adhesive resin and a dispersant, wherein the dispersant is a compound represented by the following formula (I) or (II) It is a composition.
  • X 6 independently represents a hydrogen atom or a methyl group
  • X 1 represents a methylene group
  • X 2 and X 3 independently represent H, —NH 2
  • m is an integer of 1 to 50
  • a 3 is an alkylene group having 2 to 4 carbon atoms
  • R 2 and R 3 are each independently H, an alkyl group having 1 to 18 carbon atoms or 1 carbon atom Represents an aminoalkyl group of -18.
  • X 1 is NH or O
  • X 3 is H, -NH 2 , a hydrocarbon group having 1 to 6 carbon atoms, -C 2 H 4 OH or- it is preferably a compound which is a C 2 H 4 NH 2.
  • the compound represented by the above formula (II) is a compound wherein R 2 and R 3 are independently H, or an alkyl group having 1 to 2 carbon atoms or an aminoalkyl group, and m is 1 or 2. Is preferred.
  • the above dispersants are morpholine, 4-methylmorpholine, 4-ethylmorpholine, 4- (2-hydroxyethyl) morpholine, 4- (1-cyclohexenyl) morpholine, 4- (2-aminoethyl) morpholine, 4 -Aminomorpholine, piperazine, 1-methylpiperazine, N- (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) piperazine, monoethanolamine, N-methylethanolamine, N-ethylethanolamine, and 2- Preferably, it is at least one selected from the group consisting of (2-aminoethylamino) ethanol.
  • the above-mentioned binder composition further contains the additive represented by following formula (III).
  • n is an integer of 1 to 100
  • R 4 is a hydrocarbon group having 1 to 18 carbon atoms
  • R 5 is H or an alkyl group having 1 to 4 carbon atoms
  • a 4 is 2 to 4 carbon atoms
  • the additive is a compound in which n is 1 to 4 and A 4 is an ethylene group or a propylene group.
  • the additive is preferably ethylene glycol dimethyl ether, ethylene glycol monophenyl ether, dipropylene glycol dimethyl ether or diethylene glycol diethyl ether.
  • the adhesive resin is preferably a vinylidene fluoride resin, an acrylic resin, or a synthetic rubber.
  • the adhesive resin is preferably polyvinylidene fluoride, polyacrylic acid, polyacrylonitrile, or styrene butadiene rubber.
  • the electrode mixture which concerns on 1 aspect of this invention contains the above-mentioned binder composition and an electrode active material.
  • a mixture layer formed of the above-mentioned electrode mixture is provided on a current collector.
  • a non-aqueous electrolyte secondary battery according to an aspect of the present invention includes the above-described electrode.
  • the dispersant according to one aspect of the present invention is a dispersant for being added to a binder composition used to bind an electrode active material to a current collector, and the binder composition has an adhesive property. It is a binder composition containing resin, and is a dispersing agent which contains a compound represented by the following formula (I) or (II) as a main component.
  • X 6 independently represents a hydrogen atom or a methyl group
  • X 1 represents a methylene group
  • X 2 and X 3 independently represent H, —NH 2
  • m is an integer of 1 to 50
  • a 3 is an alkylene group having 2 to 4 carbon atoms
  • R 2 and R 3 are each independently H, an alkyl group having 1 to 18 carbon atoms or 1 carbon atom Represents an aminoalkyl group of -18.
  • An electrode mixture was prepared as described below, and the dispersion properties were evaluated and the shear viscosity was measured. Moreover, the electrode was produced using electrode mixture agent, electrode property evaluation and peeling strength test were done.
  • Example 1-1 (Preparation of electrode mixture) LiFePO 4 (manufactured by Takasen Co., Ltd.), conductive carbon black (manufactured by TIMCAL, SUPER C65), and vinylidene fluoride copolymer (manufactured by Kureha, KF) as an adhesive resin so as to obtain the composition shown in Table 1 below.
  • Polymer # 9700, inherent viscosity 2.5 dl / g) was dispersed in N-methyl-2-pyrrolidone (NMP), and morpholine was added as a dispersing agent to obtain an electrode mixture.
  • NMP N-methyl-2-pyrrolidone
  • the obtained electrode mixture was coated on a 15 ⁇ m thick Al foil with a bar coater and dried at 130 ° C. for 30 minutes to produce a single-sided coated electrode having a single-sided basis weight of 200 g / m 2 .
  • Example 1-2 The same procedure as in Example 1-1 was repeated, except that the dispersant was changed to 4-methylmorpholine.
  • Example 1-3 The same procedure as in Example 1-1 was repeated, except that 4-ethylmorpholine was used as the dispersant.
  • Example 1-4 The same procedure as in Example 1-1 was repeated, except that the dispersing agent was changed to 4- (2-hydroxyethyl) morpholine.
  • Example 1-5 The same procedure as in Example 1-1 was repeated, except that the dispersant was changed to 4- (2-aminoethyl) morpholine.
  • Example 1-6 The same procedure as in Example 1-1 was repeated, except that the dispersant was changed to 4-aminomorpholine.
  • Example 1-7 The same procedure as in Example 1-1 was repeated except that piperazine was used as the dispersant.
  • Example 1-8 The same procedure as in Example 1-1 was repeated, except that 1-methylpiperazine was used as the dispersant.
  • Example 1-9 The same procedure as in Example 1-1 was repeated, except that the dispersant was N- (2-aminoethyl) piperazine.
  • Example 1-10 The same procedure was performed as in Example 1-1 except that 2- (methylamino) ethanol was used as the dispersant.
  • Example 1-11 The same procedure was performed as in Example 1-1 except that 2- (ethylamino) ethanol was used as the dispersant.
  • Example 1-12 The same procedure as in Example 1-1 was repeated, except that the dispersant was monoethanolamine.
  • Example 2 The same procedure as in Example 1-1 was repeated except that the adhesive resin was changed to a vinylidene fluoride copolymer (Kureha, KF polymer # 9400, inherent viscosity 2.1 dl / g).
  • Example 3 The same procedure as in Example 1-1 was repeated, except that the adhesive resin was changed to vinylidene fluoride homopolymer (Kureha, KF polymer # 7300, inherent viscosity: 3.1 dl / g).
  • Example 4 The same procedure as in Example 1-1 was repeated except that the adhesive resin was changed to polyacrylonitrile (manufactured by Sigma-Aldrich).
  • Example 5 The same procedure as in Example 1-1 was repeated except that the adhesive resin was changed to polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.).
  • Example 7 The same procedure as in Example 6 was performed except that the adhesive resin was polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and the solvent was NMP. Dispersion property evaluation, preparation of an electrode and shear viscosity measurement were performed in the same manner as in Example 6. The results are shown in Table 4.
  • Example 8-1 (Preparation of electrode mixture) The same procedure as in Example 1-1 was carried out except that 0.5 parts by mass of ethylene glycol dimethyl ether (hereinafter, additive 1) was further added as an additive. The results of the dispersion property evaluation and the shear viscosity measurement are shown in Table 5.
  • An electrode was produced from the obtained electrode mixture in the same manner as in Example 1-1, and electrode property evaluation and peel strength test were performed. The results are shown in Table 5.
  • Example 8-2 The same procedure as in Example 8-1 was performed except that the proportion of the additive was 5 parts by mass.
  • Example 8-3 The same procedure as in Example 1-1 was carried out except that 0.5 parts by mass of ethylene glycol monophenyl ether (hereinafter, additive 2) as an additive was further added to the electrode mixture.
  • additive 2 ethylene glycol monophenyl ether
  • Example 8-4 The same procedure as in Example 1-1 was carried out except that 0.5 parts by mass of diethylene glycol dimethyl ether (hereinafter, additive 3) as an additive was further added to the electrode mixture.
  • additive 3 diethylene glycol dimethyl ether
  • Example 8-5 The same procedure as in Example 1-1 was conducted, except that 0.5 parts by mass of dipropylene glycol dimethyl ether (hereinafter, additive 4) as an additive was further added to the electrode mixture.
  • additive 4 dipropylene glycol dimethyl ether
  • Example 8-6 The same procedure as in Example 1-1 was conducted, except that 0.5 parts by mass of diethylene glycol diethyl ether (hereinafter, additive 5) as an additive was further added to the electrode mixture.
  • additive 5 diethylene glycol diethyl ether
  • Example 8-7 The electrode mixture, wherein as an additive: CH 3 (CH 2) 17 - (OCH 2 CH 2) a compound represented by 50 -OCH 3 (hereinafter, the additive 6) except for adding 0.5 part by weight Further Were carried out in the same manner as in Example 1-1.
  • Comparative Example 1 The same procedure as in Example 1-1 was repeated except that no dispersant was added.
  • the present invention can be used as a binder composition used to bond a current collector and an electrode active material in a non-aqueous electrolyte secondary battery.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une composition de liant qui a une viscosité réduite tout en conservant ses performances de liaison pendant la production d'une électrode. Une composition de liant, qui peut être utilisée pour lier un matériau actif d'électrode à un collecteur de courant, est caractérisée en ce qu'elle contient une résine adhésive et un dispersant, le dispersant étant un composé représenté par la formule (I) ou (II).
PCT/JP2018/025054 2017-07-05 2018-07-02 Composition de liant, mélange d'électrode, électrode, batterie secondaire à électrolyte non aqueux, et dispersant WO2019009242A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116895759A (zh) * 2023-08-01 2023-10-17 深圳市皓飞新型材料有限公司 一种正极材料分散剂组合物及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10188991A (ja) * 1996-12-27 1998-07-21 Nippon Zeon Co Ltd リチウムイオン二次電池電極用バインダー組成物、電極、および電池
JP2012033364A (ja) * 2010-07-30 2012-02-16 Furukawa Battery Co Ltd:The リチウムイオン二次電池の電極製造方法及びリチウムイオン二次電池の製造方法
JP2012164521A (ja) * 2011-02-07 2012-08-30 Unitika Ltd 二次電池電極のバインダー用樹脂組成物、及びこれを用いてなるバインダー液、二次電池電極、二次電池
JP2013012357A (ja) * 2011-06-28 2013-01-17 Nippon Zeon Co Ltd 二次電池用負極、二次電池、負極用スラリー組成物及び二次電池用負極の製造方法
JP2013089528A (ja) * 2011-10-20 2013-05-13 Panasonic Corp 電池用電極板および電池
JP2014135275A (ja) * 2012-12-14 2014-07-24 Toyo Ink Sc Holdings Co Ltd 蓄電デバイス電極形成用組成物、蓄電デバイス電極、及び蓄電デバイス
JP2015030777A (ja) * 2013-08-01 2015-02-16 東洋インキＳｃホールディングス株式会社 カーボンブラック分散液およびその利用
JP2017513198A (ja) * 2014-04-01 2017-05-25 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． リチウムイオン蓄電デバイス用の水性バインダー組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10188991A (ja) * 1996-12-27 1998-07-21 Nippon Zeon Co Ltd リチウムイオン二次電池電極用バインダー組成物、電極、および電池
JP2012033364A (ja) * 2010-07-30 2012-02-16 Furukawa Battery Co Ltd:The リチウムイオン二次電池の電極製造方法及びリチウムイオン二次電池の製造方法
JP2012164521A (ja) * 2011-02-07 2012-08-30 Unitika Ltd 二次電池電極のバインダー用樹脂組成物、及びこれを用いてなるバインダー液、二次電池電極、二次電池
JP2013012357A (ja) * 2011-06-28 2013-01-17 Nippon Zeon Co Ltd 二次電池用負極、二次電池、負極用スラリー組成物及び二次電池用負極の製造方法
JP2013089528A (ja) * 2011-10-20 2013-05-13 Panasonic Corp 電池用電極板および電池
JP2014135275A (ja) * 2012-12-14 2014-07-24 Toyo Ink Sc Holdings Co Ltd 蓄電デバイス電極形成用組成物、蓄電デバイス電極、及び蓄電デバイス
JP2015030777A (ja) * 2013-08-01 2015-02-16 東洋インキＳｃホールディングス株式会社 カーボンブラック分散液およびその利用
JP2017513198A (ja) * 2014-04-01 2017-05-25 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． リチウムイオン蓄電デバイス用の水性バインダー組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116895759A (zh) * 2023-08-01 2023-10-17 深圳市皓飞新型材料有限公司 一种正极材料分散剂组合物及其制备方法和应用

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