WO2020017656A1 - Composé, dispersant, composition de dispersion pour batterie, électrode et batterie - Google Patents

Composé, dispersant, composition de dispersion pour batterie, électrode et batterie Download PDF

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WO2020017656A1
WO2020017656A1 PCT/JP2019/028564 JP2019028564W WO2020017656A1 WO 2020017656 A1 WO2020017656 A1 WO 2020017656A1 JP 2019028564 W JP2019028564 W JP 2019028564W WO 2020017656 A1 WO2020017656 A1 WO 2020017656A1
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group
dispersant
electrode
dispersion
carbon material
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PCT/JP2019/028564
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Japanese (ja)
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智彦 星野
秋生 日水
友明 枡岡
岡　直人
雄 森田
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東洋インキＳｃホールディングス株式会社
トーヨーカラー株式会社
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Publication of WO2020017656A1 publication Critical patent/WO2020017656A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • 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 disclosure relates to a compound, a dispersant, a dispersion composition for a battery, an electrode, and a battery.
  • Patent Literature 1 and Patent Literature 2 a dispersion of a carbon material is prepared using a polymer dispersant such as polyvinylpyrrolidone and polyvinyl butyral and used as a battery composition.
  • a polymer dispersant such as polyvinylpyrrolidone and polyvinyl butyral
  • Such a polymer dispersant itself has viscosity. Therefore, particularly when a dispersant is used for a carbon material having a high specific surface area, such as carbon nanotubes (CNT), which is known as a highly conductive material, the amount of the required dispersant increases, and the viscosity of the dispersion liquid increases. Will be higher. As a result, the coatability of the dispersion is reduced, and it is difficult to obtain a good electrode.
  • CNT carbon nanotubes
  • a method of increasing the energy density there is a method of increasing the ratio of the active material in the mixture composition.
  • a carbon nanotube having a small average outer diameter when used, a conductive network can be efficiently formed with a small amount. Therefore, the amount of the conductive material contained in the positive electrode and the negative electrode for the lithium ion secondary battery can be reduced, and the energy density can be increased.
  • carbon nanotubes having a small average outer diameter have a strong cohesive force and are difficult to disperse. Therefore, it is difficult to obtain a dispersion liquid of carbon nanotubes having sufficient dispersibility.
  • multi-walled carbon nanotubes having an outer diameter of 10 nm to several tens of nm are carbon materials that are difficult to disperse, but are becoming relatively inexpensive and are expected to be put to practical use in lithium-ion battery applications.
  • a carbon nanotube having a small average outer diameter is used, a conductive network can be efficiently formed with a small amount, and it is expected that the amount of a conductive material contained in an electrode of a lithium ion battery can be reduced.
  • carbon nanotubes having a small average outer diameter also have strong cohesive force, it is difficult to obtain a carbon nanotube dispersion having sufficient dispersibility.
  • Patent Document 3 proposes dispersion in N-methylpyrrolidone (NMP) using a water-soluble polymer polyvinylpyrrolidone (hereinafter, PVP).
  • Patent Literature 4 describes dispersion using a nonionic resin-type dispersant represented by PVP.
  • the resin-type dispersant in the battery easily absorbs the electrolyte and swells.
  • the contact state between the carbon materials or between the carbon material and the active material or the current collector is broken.
  • the appropriately formed conductive path is cut off, causing problems such as deterioration of battery resistance and reduction of cycle life.
  • a low molecular dispersant may be used.
  • the molecules of the dispersant itself change during storage of the battery under high-temperature conditions, which may adversely affect battery characteristics.
  • a dispersant that has excellent dispersibility and can form a dispersion having excellent storage stability is desired. Further, a battery electrode mixture layer having uniform and good coating film properties and low electrode plate resistance is desired. Further, batteries that are excellent in use at high temperatures are desired.
  • the present disclosure is excellent in dispersibility as compared with the related art, and can form a dispersion composition that can realize more excellent coating film properties, and in particular, a dispersant that can be suitably used in battery applications. provide.
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a dispersion composition using a dispersant containing a triazine derivative having a specific structure can form a good conductive path.
  • the inventors have found that not only a reduction in resistance but also excellent battery characteristics can be realized, and the present invention has been completed.
  • embodiments of the present invention will be described, but the present invention is not limited to the following embodiments and includes various embodiments.
  • One embodiment relates to a compound represented by the following general formula (1).
  • X 1 to X 5 each independently represent a hydrogen atom, a carboxyl group, or an alkyl group which may be substituted, or two adjacent substituents are combined to form a benzimidazole ring, a benzoindole ring, a benzopyrazole Form a ring or a benzimidazolone ring. However, it has a benzimidazole ring, a benzoindole ring, a benzopyrazole ring, or a benzimidazolone ring in which at least one adjacent two substituents are combined.
  • X 6 to X 10 each independently represent a hydrogen atom, a carboxyl group, or a substituted or unsubstituted alkyl group. However, at least one is a carboxyl group.
  • One embodiment relates to a dispersant represented by the following general formula (2).
  • R 1 represents a group represented by Y 1 -Z 1 .
  • Y 1 represents an arylene group which may have a substituent selected from an alkyl group, a halogen group, a nitro group, a carboxyl group, and an alkoxy group.
  • Z 1 represents a carboxyl group or a phosphate group.
  • One embodiment relates to a dispersant comprising the compound of the above embodiment.
  • One embodiment further relates to the dispersant of the above embodiment further comprising at least one of an amine and an inorganic base.
  • One embodiment relates to a dispersion composition including a pigment or a carbon material, the dispersant of the above embodiment, and a solvent.
  • One embodiment relates to a dispersion composition further comprising a polymer dispersant in the dispersion composition of the above embodiment.
  • One embodiment relates to the dispersion composition of the above embodiment, wherein the polymer dispersant has a hydroxyl group.
  • One embodiment relates to the dispersion composition of the above embodiment, wherein the polymer dispersant includes at least one of a polyvinyl alcohol-based resin and a cellulose-based resin.
  • One embodiment relates to the dispersion composition of the above embodiment, wherein the carbon material includes a carbon nanotube.
  • One embodiment relates to a composition for an electrode using the dispersion composition of the above embodiment.
  • One embodiment relates to the electrode composition of the above embodiment, further comprising a binder.
  • One embodiment further relates to the electrode composition of the above embodiment further including an active material.
  • One embodiment relates to an electrode having a mixture layer formed on the current collector from the electrode composition of the above embodiment.
  • One embodiment relates to a battery including the electrode of the above embodiment and a non-aqueous electrolyte.
  • the present invention it is possible to provide a dispersant having good dispersibility and capable of forming a dispersion composition capable of realizing excellent coating properties.
  • the dispersion composition constituted by using this dispersant can be suitably used for battery applications, and can realize excellent battery characteristics.
  • FIG. 1 is a 1 H-NMR chart of the triazine derivative A.
  • Triazine derivative represented by the general formula (1).
  • One embodiment relates to a triazine derivative represented by the general formula (2).
  • the triazine derivatives represented by these general formulas (1) and (2) can be suitably used as a dispersant.
  • X 1 to X 5 each independently represent a hydrogen atom, a carboxyl group, a substituted or unsubstituted alkyl group, or two adjacent groups are combined with each other to form a benzimidazole ring, benzoindole Forms a ring, a benzopyrazole ring, or a benzimidazolone ring.
  • X 1 to X 5 form at least one benzimidazole ring, benzoindole ring, benzopyrazole ring, or benzimidazolone ring formed by combining two adjacent ones.
  • the benzene ring structure in the benzimidazole ring, benzoindole ring, benzopyrazole ring, and benzimidazolone ring is derived from the benzene ring to which each of X 1 to X 5 is bonded.
  • X 6 to X 10 are each independently a hydrogen atom, a carboxyl group, or a substituted or unsubstituted alkyl group. However, at least one is a carboxyl group.
  • two of X 1 to X 5 which are adjacent to each other are preferably combined with each other to form one benzimidazolone ring. It is preferable that the remaining three of X 1 to X 5 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. In this embodiment, X 1 and X 5 are more preferably each independently a hydrogen atom or a substituted or unsubstituted alkyl group.
  • X 6 to X 10 are each independently a hydrogen atom or a carboxyl group, and the number of carboxyl groups is preferably one or two. Specific examples of such triazine derivatives include derivatives A to E and F described later in Examples.
  • R 1 represents a group represented by Y 1 -Z 1 .
  • Y 1 represents an arylene group, and the arylene group may have a substituent selected from an alkyl group, a halogen group, a nitro group, a carboxyl group, and an alkoxy group.
  • Z 1 represents a carboxyl group or a phosphate group. In one embodiment, Z 1 is preferably a carboxyl group.
  • the “substituents” of the optionally substituted arylene group represented by Y 1 may be the same or different. Specific examples of the substituent include a carboxyl group, a phosphoric acid group, a halogen group such as fluorine, chlorine, and bromine, a nitro group, an alkyl group, and an alkoxyl group. Further, the arylene group may have a plurality of substituents.
  • substituents include the following structures (a) to (j).
  • the symbol * represents a bonding portion with a benzene ring (phenyl group).
  • the above structures (a) to (j) may be present at any of the ortho, meta, and para positions starting from the bond between the phenyl group and the nitrogen atom. In one embodiment, the above structures (a) to (d) are preferably present at the meta position and the para position, and the above structures (e) to (j) are more preferably present at the meta position or the para position.
  • R2 is a benzimidazole group
  • specific examples of such a triazine derivative include a derivative X described later in Examples.
  • examples of the substituent include an alkyl group such as a methyl group.
  • Specific examples of such a triazine derivative include derivatives Y, Z, AA, AB, AC, and AD described later in Examples.
  • X 1 to X 5 are united with each other to form one benzimidazolone ring;
  • the remaining three of X 1 to X 5 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group;
  • X 6 to X 10 are each independently a hydrogen atom or a carboxyl group;
  • a form in which the number of carboxyl groups is one or two is preferred.
  • the triazine derivative represented by the general formula (1) or (2) described above (hereinafter, referred to as a triazine derivative) is preferably used in combination with an amine and / or an inorganic base. Accordingly, one embodiment relates to a dispersant comprising a triazine derivative represented by the general formula (1) or (2) and an amine, an inorganic base, or a combination of an amine and an inorganic base.
  • Examples of the amine used in combination with the triazine derivative include primary, secondary and tertiary amines having 1 to 40 carbon atoms.
  • the amine may have an ether group or a hydroxyl group in the molecule.
  • the amine is preferably a primary, secondary or tertiary alkylamine having 1 to 40 carbon atoms.
  • the alkyl group in the alkylamine may have either a straight-chain structure or a branched structure.
  • the primary amine having 1 to 40 carbon atoms include alkylamines such as propylamine, butylamine, isobutylamine, octylamine, 2-ethylhexylamine, laurylamine, stearylamine, and oleylamine; 2-aminoethanol; -Aminopropanol, 3-ethoxypropylamine, and 3-lauryloxypropylamine.
  • Examples of the secondary amine having 1 to 40 carbon atoms include alkylamines such as dibutylamine, diisobutylamine, N-methylhexylamine, dioctylamine, and distearylamine, and 2-methylaminoethanol.
  • tertiary amine having 1 to 40 carbon atoms examples include triethylamine, tributylamine, N, N-dimethylbutylamine, N, N-diisopropylethylamine, dimethyloctylamine, trioctylamine, dimethyldecylamine, dimethyllaurylamine, and dimethylmyristylamine.
  • alkylamines such as dimethylpalmitylamine, dimethylstearylamine, and dilaurylmonomethylamine, triethanolamine, and 2- (dimethylamino) ethanol.
  • amines exemplified above primary, secondary and tertiary alkylamines having 1 to 30 carbon atoms are preferred. Primary, secondary or tertiary alkylamines having 1 to 20 carbon atoms are more preferred.
  • the amount of the amine to be added is not particularly limited, but is preferably 0.1 mol equivalent or more and 5 mol equivalent or less relative to 1 mol equivalent of the triazine derivative represented by the general formula (1). More than 3 molar equivalents and less than 2 molar equivalents are more preferable.
  • the above amine can be added at the time of producing a dispersant and / or at the time of producing a dispersion composition described later.
  • inorganic base examples include an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal phosphate, Examples include alkaline earth metal phosphates.
  • alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • alkaline earth metal hydroxide examples include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and the like.
  • alkali metal carbonate examples include lithium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like.
  • alkaline earth metal carbonate examples include magnesium carbonate, calcium carbonate, strontium carbonate, and barium carbonate.
  • alkali metal phosphate examples include lithium phosphate, trisodium phosphate, disodium hydrogenphosphate, tripotassium phosphate, dipotassium hydrogenphosphate, and the like.
  • alkaline earth metal phosphates include magnesium phosphate, calcium phosphate, strontium phosphate, and barium phosphate.
  • the amount of the inorganic base to be added is not particularly limited, but those having a monovalent cation with respect to 1 mol of the triazine derivative represented by the general formula (1) or (2) may be 0.1 to 0.1. 1 mol or more and 2.0 mol or less are preferable, and 0.3 mol or more and 1.0 mol or less are more preferable. Those having a divalent cation are preferably at least 0.05 mol and at most 1.0 mol, more preferably at least 0.15 mol and at most 0.5 mol. Those having a trivalent cation are preferably at least 0.03 mol and at most 0.7 mol, more preferably at least 0.1 mol and at most 0.4 mol.
  • the inorganic base can be added at the time of producing a dispersant and / or at the time of producing a dispersion composition described later.
  • the dispersant of the above embodiment can be suitably used particularly as a dispersant for carbon materials such as carbon black used in applications such as batteries, capacitors, and capacitors. However, it can be used not only as a carbon material but also as a dispersant for a pigment used in a coloring composition such as various inks, paints, and color filter resists.
  • the dispersant containing the triazine derivative of the above embodiment may be used in combination with other dispersants known in the art for the purpose of adjusting film formability and film strength and controlling rheology.
  • a triazine derivative may be used in combination with one or more compounds known in the art as a polymer dispersant (polymer dispersant).
  • the dispersant may include a triazine derivative and a polymer dispersant.
  • polymer dispersant Specific examples of usable polymer dispersants include polyvinyl alcohol, functional groups other than hydroxyl groups, for example, acetyl group, sulfo group, carboxyl group, carbonyl group, and amino group, modified polyvinyl alcohol, and polyvinyl salts modified with various salts. Examples thereof include polyvinyl alcohol-based resins modified by acetal (acetoacetal-modified or butyral-modified) with alcohols, other anion- or cation-modified polyvinyl alcohols, and aldehydes.
  • various (meth) acrylic polymers, polymers derived from ethylenically unsaturated hydrocarbons, various cellulosic polymers, and the like, and copolymers thereof can be used. However, it is not limited to these.
  • the average degree of polymerization of the polymer dispersant is preferably from 50 to 3,000, more preferably from 100 to 2,000, and still more preferably from 200 to 1,000.
  • polyvinyl alcohol-based resin those having a saponification rate of 60 mol% or more to a hydroxyl group are preferable, and those having a saponification rate of 75 mol% or more are more preferable, and 80 mol are used in order to have a suitable affinity for a dispersoid, a dispersion solvent, and an electrolyte solution. % Or more is more preferable.
  • polyvinyl alcohol-based resins included in the above range of the amount of hydroxyl groups include the following. Kuraray Povar (Kuraray polyvinyl alcohol resin), Gohsenol, and Gohsenex (Nippon Synthetic Chemical Industry Co., Ltd. polyvinyl alcohol resin), Denka Povar (Denka Corporation polyvinyl alcohol resin), and J-Povar (Nippon Vinegar And various grades can be obtained. Also, modified polyvinyl alcohol having various functional groups can be obtained in the same manner.
  • a modified polyvinyl alcohol is synthesized and used, generally, in a solution such as methanol, together with vinyl acetate, a (meth) acrylic monomer such as (meth) acrylic acid, a vinyl ester monomer, and an ⁇ , ⁇ -unsaturated monomer. It is known that a copolymer having a saturated bond and a functional group is copolymerized and then subjected to a saponification reaction to obtain a modified polyvinyl alcohol having a controlled modification rate.
  • a modified polyvinyl alcohol-based resin can be obtained by a method in which an acid anhydride is added to the polyvinyl alcohol-based resin or an esterification reaction is performed.
  • polyvinyl acetal resins for example, various grades can be obtained under trade names such as Mobital (polyvinyl butyral resin manufactured by Kuraray Co., Ltd.) and Eslek (polyvinyl acetal or polyvinyl butyral manufactured by Sekisui Chemical Co., Ltd.). May be used in order to obtain the above preferred amount of hydroxyl groups.
  • Mobital polyvinyl butyral resin manufactured by Kuraray Co., Ltd.
  • Eslek polyvinyl acetal or polyvinyl butyral manufactured by Sekisui Chemical Co., Ltd.
  • a polyvinyl acetal resin controlled to a predetermined degree of acetalization can be obtained by reacting polyvinyl alcohol with an aldehyde. Further, by changing the carbon number of the aldehyde, the carbon number of the acetal group can be arbitrarily selected.
  • cellulose or a resin in which a part of the hydroxyl group of cellulose is modified to an alkyl group, a hydroxyalkyl group, or a carboxyalkyl group or a salt thereof can be used.
  • Metrolose Metalcellulose manufactured by Shin-Etsu Chemical Co., Ltd.
  • mecelose water-soluble cellulose ether, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, methylcellulose, manufactured by Tomoe Industries
  • sunrose carboxymethylcellulose sodium, manufactured by Nippon Paper Industries
  • ethocell ethyl cellulose manufactured by Dow Chemical Company
  • Daicel CMC Carboxy methylcellulose sodium manufactured by Daicel FineChem.
  • methyl cellulose and ethyl cellulose are preferable from the viewpoint of solubility in an electrolytic solution and swelling.
  • the polymer dispersant can be used in the range of 0.01 to 25% by mass based on the entire dispersion composition described below.
  • ⁇ Dispersion composition> One embodiment relates to a dispersion composition containing a dispersant, a pigment or a carbon material, and a solvent, and containing, as the dispersant, a triazine derivative represented by the general formula (1) or (2). Another embodiment includes a triazine derivative represented by the general formula (1) or (2) as a dispersant, including a dispersant, a pigment or a carbon material, and a solvent, and a polymer dispersant described above. And a dispersion composition comprising: Although not particularly limited, when a carbon material is used in the above-described dispersion composition, a composition that can be suitably used for battery applications such as electrodes can be formed. Hereinafter, the composition for an electrode will be described more specifically.
  • the electrode composition may be a carbon material dispersion containing a dispersant containing a triazine derivative, a carbon material, and a solvent.
  • the composition for an electrode may be a carbon material dispersed varnish including a dispersant including a triazine derivative, a polymer dispersant, a carbon material, and a solvent.
  • the electrode composition of the above embodiment may be a mixture paste further including a binder and an active material.
  • the carbon material is not particularly limited, but when used as a carbon material for a battery, graphite, carbon black, carbon nanotube, carbon nanofiber, carbon fiber, graphene, fullerene, etc. may be used alone or in combination of two or more. It is preferable to use the above in combination. From the viewpoints of conductivity, availability, and cost, it is more preferable to use carbon black or carbon nanotube.
  • the carbon black commercially available various products such as furnace black, channel black, thermal black, acetylene black, and Ketjen black can be used alone or in combination of two or more. Further, carbon black or hollow carbon after the oxidation treatment which is usually performed can be used.
  • the particle size of the carbon black is preferably 0.01 to 1 ⁇ m, more preferably 0.01 to 0.2 ⁇ m. Here, the particle size indicates an average primary particle size measured by an electron microscope. These physical property values are generally used to express physical properties of carbon black.
  • the carbon nanotube is a carbon material having a shape obtained by winding graphene into a cylindrical shape.
  • the diameter determined by observing with an electron microscope is about several nm to 100 nm, and the length is about several nm to 1 mm.
  • the diameter of the carbon nanotube is preferably 50 nm or less, particularly preferably 20 nm or less, from the viewpoint of exhibiting semiconductor properties, transparency of the coating film, and the like.
  • the length of the carbon nanotube is preferably from 100 nm to 1 mm, particularly preferably from 500 nm to 1 mm.
  • the carbon nanotube has a single-layer structure or a multi-layer structure, but may have any structure. Further, carbon materials having a fiber diameter of about 100 nm to about 1 ⁇ m, which are classified as carbon nanofibers and observed by an electron microscope, can also be used.
  • the above-mentioned graphene is a monoatomic thin film constituting graphite, is a carbon material in which carbon atoms are arranged in a honeycomb lattice (hexagon) on a plane, and includes a multi-layer graphene that is laminated.
  • the multi-layer graphene one having 2 to 50 graphene layers can be used.
  • solvent As the solvent, one of an aprotic polar solvent, a water-soluble polar solvent, and water may be used alone, or two or more may be used as a mixture.
  • an amide solvent is preferable, and particularly, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2 -Use of amide aprotic solvents such as pyrrolidone and hexamethyl phosphate is preferred.
  • water-soluble polar solvent alcohol-based, ester-based, ether-based, glycol-based, glycol ester-based, and glycol ether-based solvents are preferred.
  • Water may be used alone, or a small amount of a water-soluble polar solvent having a low surface tension may be used in combination in order to improve the wettability and coatability of the carbon material, particularly, propylene glycol monoethyl ether and ethylene. It is preferably used in combination with glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, propylene glycol monopropyl ether, or N-methyl-2-pyrrolidone.
  • the binder is not particularly limited, but ethylene, propylene, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, styrene, vinyl butyral, vinyl acetal, and vinyl Polymer or copolymer containing pyrrolidone or the like as a constituent unit, polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, acrylic resin, formaldehyde resin, silicon resin, fluorine resin, Cellulose resins such as carboxymethylcellulose; rubbers such as styrene-butadiene rubber and fluorine rubber; and conductive resins such as polyaniline and polyacetylene. Further, modified resins and copolymers of these resins may be used.
  • a polymer compound containing a fluorine atom in the molecule for example, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene, etc. from the viewpoint of resistance.
  • These binders can be used alone or in combination of two or more.
  • water it is preferable to use these polymer compounds containing a fluorine atom and an emulsion such as styrene-butadiene rubber in combination with carboxymethyl cellulose which also functions as a thickener.
  • the binder can be used in the range of 0.001 to 50% by mass based on the entire dispersion composition.
  • the active material is a substance that stores or discharges electricity along with an oxidation-reduction reaction in a battery.
  • Specific examples of the active material include a positive electrode active material used for a positive electrode and a negative electrode active material used for a negative electrode.
  • the positive electrode active material is not particularly limited as long as it functions as an active material for a battery.
  • a metal compound such as a metal oxide or metal sulfide capable of doping or intercalating lithium ions, a conductive polymer, or the like can be used.
  • a lithium manganese composite oxide for example, Li x Mn 2 O 4 or Li x MnO 2
  • a lithium nickel composite oxide for example, Li x NiO 2
  • a lithium cobalt composite oxide Li x CoO 2
  • lithium nickel cobalt composite oxide e.g., Li x Ni 1-y Co y O 2
  • lithium manganese cobalt composite oxides e.g., Li x Mn y Co 1-y O 2
  • lithium nickel manganese cobalt composite oxide e.g., Li composite oxide powder of lithium and a transition metal, such as x Ni y Co z Mn 1-yz O 2
  • a spinel-type lithium manganese nickel composite oxide eg, Li x Mn 2-y Ni y O 4
  • olivine lithium phosphorus oxide powder having a structure (e.g., Li x FePO 4, Li x Fe 1-y Mn PO 4, etc.
  • Li x CoPO 4 Li x CoPO 4
  • manganese oxide iron oxide, copper oxide, nickel oxide, vanadium oxide (e.g. V 2 O 5, V 6 O 13)
  • a transition metal oxide powder such as titanium oxide, iron sulfate (Fe 2 (SO 4 ) 3 ), TiS 2 , and a transition metal sulfide powder such as FeS.
  • x, y, and z are numbers, and 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, and 0 ⁇ y + z ⁇ 1.
  • conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. These positive electrode active materials can be used alone or in combination of two or more.
  • the negative electrode active material is not particularly limited. For example, doping of lithium ions or capable of intercalating metals Li, or alloys thereof, tin alloy, silicon alloy negative electrode, Li X TiO 2, Li X Fe 2 O 3, Li X Fe 3 O 4, Li X WO 2 or the like Metal oxides, conductive polymers such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, and carbonaceous materials such as natural graphite Carbon-based materials such as powder, carbon black, mesophase carbon black, resin-fired carbon material, gas-phase grown carbon fiber, and carbon fiber are used.
  • x is a number, and 0 ⁇ x ⁇ 1.
  • the dispersion composition (composition for an electrode) is a dispersion of a carbon material containing the above-described dispersant, carbon material, and solvent. It is a dispersion varnish.
  • the above-mentioned dispersion composition can be used in various fields such as printing inks, paints, plastics, toners, color filter resist inks, and batteries which require uniform and good coating film properties.
  • the dispersion composition can provide a uniform and good coating film property and a coating film suitable for an electrode layer having a low surface resistance, it can be suitably used for forming an electrode of a battery. it can.
  • the dispersion composition may be used as a constituent material of a base layer provided between the current collector and the mixture layer.
  • the dispersion of the carbon material which is one embodiment of the dispersion composition, can be produced by mixing the dispersant, the carbon material, and the solvent. Further, the dispersion varnish of the carbon material can be manufactured by mixing the above-mentioned dispersant, the carbon material, the solvent, and the polymer dispersant.
  • the order of addition of each component is not limited. For example, as for the dispersion liquid of the carbon material, (1) a method of collectively mixing and dispersing all the components, and (2) a method of dispersing the carbon material in a solvent in which a dispersant is dispersed and dissolved in advance are exemplified.
  • dispersion varnish of the carbon material (1) a method of mixing, dispersing, and dissolving all the components at once, (2) a method of mixing and dissolving a binder powder after preparing a carbon material dispersion in advance, and (3) A) a method of preparing a carbon material dispersion in advance and then mixing the binder solution. Further, the solvent described above may be further added as necessary.
  • a disperser generally used for pigment dispersion or the like can be used.
  • mixers such as disperser, homomixer, and planetary mixer, homogenizers (such as “Clearmix” manufactured by M Technique, Inc., “Fillmix” manufactured by PRIMIX, and “Abramix” manufactured by Silverson), paint conditioners ( Red Devil Co., Ltd., colloid mills ("PUC colloid mill” manufactured by PUC, “colloid mill MK” manufactured by IKA), cone mills ("corn mill MKO” manufactured by IKA, etc.), ball mills, sand mills (Shinmaru Enterprises Co., Ltd.) "Dino Mill", etc.), Attritor, Pearl Mill (e.g., "DCP Mill”, etc.), Media Type Disperser such as Koball Mill, Wet Jet Mill ("Genus PY”, manufactured by Genus, “Starburst”, manufactured by Sugino Machine) , Nanomizer
  • a disperser that has been subjected to a treatment for preventing metal from mixing from the disperser.
  • a metal contamination prevention treatment for example, when using a media type disperser, a method using a ceramic or resin disperser in which the agitator and the vessel are made of ceramic, a method of spraying tungsten carbide or resin coating on the surface of the metal agitator and the vessel are used. It is preferable to use a disperser that has been subjected to the above processing.
  • the medium it is preferable to use glass beads or ceramic beads such as zirconia beads or alumina beads.
  • a roll mill it is preferable to use a ceramic roll. Only one type of disperser may be used, or a plurality of types of apparatuses may be used in combination.
  • the electrode composition of the above embodiment preferably has a composition obtained by further adding an active material and a binder to the dispersion composition containing the dispersant, the carbon material, the solvent, and the polymer dispersant.
  • the electrode composition having such a composition can be suitably used as a material for forming a mixture layer of an electrode (hereinafter, referred to as “mixture paste”).
  • This mixture paste can be produced by mixing the above-mentioned dispersion composition, a binder, and an active material.
  • the order of addition of each component is not limited. For example, a method in which all the components are mixed at once, a method in which the remaining components are added to and mixed with the dispersion of the carbon material prepared in advance by the above method, and an active material in the carbon material dispersion varnish prepared in advance by the method described above A method of charging and mixing is exemplified. Further, the solvent described above may be further added as necessary.
  • the same apparatus as that used for producing the above-described dispersion composition of the present invention can be used.
  • the composition for an electrode of the present invention can be particularly used for an electrode of a lithium ion secondary battery.
  • a lithium ion secondary battery will be described, but an electrode using the electrode composition of the present invention is not limited to a lithium ion secondary battery.
  • Lithium ion secondary batteries include a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on a current collector, and a non-aqueous electrolyte composed of an electrolyte containing lithium. .
  • the material and shape of the current collector used are not particularly limited, and as the material, metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel are used. Copper is preferably used as the material.
  • a flat foil is generally used, but a roughened surface, a perforated foil, and a mesh can also be used.
  • a conductive base layer may be provided on the current collector for the purpose of improving contact resistance and adhesion (peeling strength) between the current collector and the mixture layer.
  • the mixture layer can be formed by directly applying the mixture paste on a current collector and drying the paste.
  • the thickness of the mixture layer is generally 1 ⁇ m or more and 1 mm or less, preferably 100 ⁇ m or more and 500 ⁇ m or less.
  • the application method is not particularly limited, and a known method can be used. Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method. After the application, a rolling process using a lithographic press or a calender roll may be performed.
  • an electrolytic solution constituting the lithium ion secondary battery a solution obtained by dissolving an electrolyte containing lithium in a non-aqueous solvent is used.
  • the electrolyte include LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , and Li (CF 3 SO 2 ) 3 C. , LiI, LiBr, LiCl, LiAlCl, LiHF 2 , LiSCN, LiBPh 4 (where Ph is a phenyl group) and the like, but is not limited thereto.
  • the non-aqueous solvent is not particularly limited, but carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -octanoic lactone Lactones, such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolan, 4-methyl-1,3-dioxolan, 1,2-methoxyethane, 1,2-ethoxyethane, 1,2-dibutoxyethane, etc.
  • carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -octanoic lactone Lactones, such as tetrahydrofuran, 2-methyl
  • esters such as methyl formate, methyl acetate and methyl propionate
  • sulfoxides such as dimethyl sulfoxide and sulfolane
  • nitriles such as acetonitrile
  • N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone.
  • These solvents may be used alone or in combination of two or more.
  • a mixture of ethylene carbonate and other solvents having a high dielectric constant and a high dissolving power of the electrolyte is preferable, and as other solvents, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and linear carbonates such as diethyl carbonate are preferable.
  • a system solvent is more preferred.
  • the above-mentioned electrolytic solution may be held in a polymer matrix to form a gelled polymer electrolyte.
  • the polymer matrix include, but are not limited to, an acrylate resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, and a polysiloxane having a polyalkylene oxide segment.
  • the structure of the battery using the composition of the present invention is not particularly limited, but is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary, and is paper-type, cylindrical-type, square-type, button-type, and laminated. It can be formed into various shapes such as a mold and a wound mold according to the purpose of use.
  • a dispersion composition comprising a dispersant, a carbon material, and a solvent
  • a ⁇ carbon material dispersion '' comprising a dispersant, a carbon material, a solvent, and a polymer dispersant.
  • the dispersion composition is referred to as “carbon material dispersion varnish”, and the battery dispersion composition including the dispersant, the carbon material, the solvent, the polymer dispersant, the binder, and the active material is referred to as “mixture paste”.
  • NMP N-methyl-2-pyrrolidone used as a solvent
  • mass% is abbreviated as “%”.
  • the structures of the triazine derivatives BA to BD used in Comparative Examples are shown below.
  • the method for producing the triazine derivatives BA to BD used in Comparative Examples is not particularly limited, and a known method can be applied.
  • the method described in JP-A-2004-217842 can be applied.
  • the disclosures in the above publications are incorporated herein by reference.
  • Denka Black HS100 manufactured by Denka Corporation: acetylene black, the average primary particle diameter determined by observing with an electron microscope is 48 nm, the specific surface area determined by the S-BET equation from the nitrogen adsorption amount is 39 m 2 / g, hereinafter “HS100” Abbreviated.
  • super-P manufactured by TIMCAL: furnace black, the average primary particle diameter determined by observing with an electron microscope is 40 nm, and the specific surface area determined by the S-BET equation from the nitrogen adsorption amount is 62 m 2 / g.
  • Monarch 800 (manufactured by Cabot Corporation): furnace black, average primary particle diameter determined by observing with an electron microscope is 17 nm, specific surface area determined by S-BET equation from nitrogen adsorption amount is 210 m 2 / g, hereinafter referred to as “M800”.
  • M800 specific surface area determined by S-BET equation from nitrogen adsorption amount
  • EC-300J manufactured by Lion Specialty Chemicals: Ketjen black, the average primary particle diameter determined by observation with an electron microscope is 40 nm, and the specific surface area determined by the S-BET equation from the amount of adsorbed nitrogen is 800 m 2 / g. .
  • Carbon nanotubes multi-walled carbon nanotubes (Flotube7010, manufactured by Cano), fiber diameter: 7 to 11 ⁇ m, hereinafter abbreviated as “FT7010”.
  • VGCF manufactured by Showa Denko KK: carbon nanofiber, fiber diameter 150 nm, fiber length 10 to 20 ⁇ m determined by observation with an electron microscope.
  • PVDF polyvinylidene fluoride
  • PVA-103 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol, saponification degree 98.0 to 99.0 mol%, average polymerization degree 300 PVA-403 (manufactured by Kuraray): polyvinyl alcohol, saponification degree 78.5 to 81.5 mol%, average polymerization degree 300 KL-506 (manufactured by Kuraray): anion-modified polyvinyl alcohol, saponification degree 74.0 to 80.0 mol%, polymerization degree 600
  • GOHSENX L-3266 (manufactured by Nippon Gosei Kagaku): Sulfonic acid-modified polyvinyl alcohol, saponification degree 86.5 to 89.0 mol% (hereinafter abbreviated as L-3266)
  • GOHSENX K-434 (manufactured by Nippon Synthetic Chemical Company): cation-modified polyvinyl alcohol, saponification degree 85.5 to 88.0
  • Ethocel-10 manufactured by Dow Chemical Company
  • Ethyl cellulose viscosity of 5% toluene / ethanol (8/2) solution at 25 ° C. 9.0 to 11.0 mPa ⁇ s
  • PVP manufactured by Nippon Shokubai Co., Ltd.
  • PVB-A polymer dispersant obtained according to the following synthesis example (synthesis example) A 10% aqueous solution of PVA-103 was prepared, and 0.2 parts by mass of hydrochloric acid and 2 parts by mass of butyraldehyde were added dropwise to 100 parts by mass of the aqueous solution while stirring. Subsequently, the temperature was raised to 80 ° C. and maintained for 1 hour, followed by cooling. This was dried and pulverized to obtain PVB-A having a degree of acetalization of 15 mol%.
  • ⁇ Viscosity measurement of carbon material dispersion The viscosity of the dispersion of the carbon material is determined by allowing the dispersion of the carbon material to stand in a constant temperature bath at 25 ° C. for 1 hour or more, stirring the dispersion sufficiently, and then using a viscometer (TOKISANGYO CO. LTD, VISCOMTER, MODEL). BL) at a stirring speed of 60 rpm.
  • ⁇ Volume resistivity of electrode film> The positive electrode mixture paste was applied on an aluminum foil using an applicator so that the weight per unit of the electrode was 20 mg / cm 2, and then, in an electric oven at 120 ° C. ⁇ 5 ° C. for 25 minutes. The coating was dried. Thereafter, the surface resistivity ( ⁇ / ⁇ ) of the dried coating film was measured using Loresta GP, MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd. After the measurement, the volume resistivity ( ⁇ ⁇ cm) of the electrode film was multiplied by the thickness of the electrode mixture layer formed on the aluminum foil.
  • the thickness of the electrode mixture layer was calculated by subtracting the thickness of the aluminum foil from the average value measured at three points in the electrode film using a film thickness meter (manufactured by NIKON, DIGIMICRO MH-15M). The volume resistivity ( ⁇ ⁇ cm) was used.
  • the laminated lithium secondary battery was set in a constant temperature room at 25 ° C., and charge / discharge measurement was performed using a charge / discharge device (SM-8, manufactured by Hokuto Denko Corporation). After performing constant-current constant-voltage charging (cut-off current 0.6 mA) at a charging end voltage of 4.3 V at a charging current of 12 mA (0.2 C), constant-current discharging is performed at a discharging end voltage of 3 V at a discharging current of 12 mA. went.
  • SM-8 charge / discharge device
  • a constant current constant voltage charge (cutoff current 0.6 mA) was performed at a charge end voltage of 4.3 V with a charge current of 12 mA (0.2 C), and a discharge current of 12 mA (0.2 C). And a constant current discharge was performed at 120 mA (2 C) until the discharge end voltage reached 3.0 V, and the discharge capacity was determined.
  • the rate characteristic is a ratio between the 0.2 C discharge capacity and the 2 C discharge capacity, and can be expressed by the following equation 1.
  • Rate characteristics ⁇ 2C discharge capacity / 0.2C discharge capacity ⁇ ⁇ 100 ⁇ (%)
  • the laminate type lithium ion secondary battery was set in a constant temperature room at 25 ° C., and charge / discharge measurement was performed using a charge / discharge device (SM-8, manufactured by Hokuto Denko). After performing constant-current constant-voltage charging (cut-off current 0.6 mA) at a charging end voltage of 4.3 V at a charging current of 12 mA (0.2 C), a discharging end voltage of 3 V at a discharging current of 12 mA (0.2 C). At a constant current. This operation was repeated three times, and the third discharge capacity was set to 0.2 C discharge capacity at 25 ° C.
  • SM-8 charge / discharge device
  • constant-current and constant-voltage charging (cut-off current: 0.6 mA) was performed at a charging end voltage of 4.3 V with a charging current of 12 mA (0.2 C), and stored in a constant temperature room set at 55 ° C. for 7 days.
  • a constant current discharge was performed at a discharge current of 12 mA (0.2 C) at a discharge end voltage of 3 V to determine a discharge capacity.
  • the high-temperature storage characteristics are the ratio of the 0.2 C discharge capacity at 25 ° C. to the 0.2 C discharge capacity after storage at 55 ° C. for 7 days, and can be expressed by the following formula 2.
  • a positive electrode active material manufactured by BASF Toda Battery Materials GK, HED (registered trademark) NCM-111 1100
  • acetylene black manufactured by Denka Corporation, Denka Black (registered trademark) HS100
  • PVDF (stock) 3 parts by mass of Kureha KF Polymer W # 1300 manufactured by Kureha Battery Materials Japan Co., Ltd
  • Examples 1-2 to 1-64, Comparative Examples 1-1 to 1-4 The carbon material dispersions (A2) to (A57) and (B1) to (B1) were prepared in the same manner as in Example 1-1, except that the amount of the triazine derivative, inorganic base or amine listed in Table 1 was changed. B4) was obtained.
  • Table 1 shows the evaluation results of the carbon material dispersions prepared in Examples 1-1 to 1-64 and Comparative Examples 1-1 to 1-4.
  • the unit of the viscosity described in Table 1 is mPa ⁇ s.
  • Example 2-2 to 2-64 Comparative Examples 2-1 to 2-4
  • the mixture pastes (A2) to (A64) and (B1) to (B1) were prepared in the same manner as in Example 2-1 except that the carbon material dispersion A1 was changed to each of the carbon material dispersions listed in Table 2. B4) was obtained.
  • Example 3-2 to 3-64 The electrode films (A2) to (A64) and (B1) to (B4) were produced in the same manner as in Example 3-1 except that the mixture paste (A1) was changed to each of the mixture pastes listed in Table 3. I got
  • Table 4 shows the evaluation results of the electrode films manufactured in Examples 3-1 to 3-64 and Comparative examples 3-1 to 3-4.
  • the conductivity was evaluated according to the following criteria. (Evaluation criteria) ++++ (best): volume resistivity ( ⁇ ⁇ cm) of the electrode film is less than 5 +++ (excellent): volume resistivity ( ⁇ ⁇ cm) of the electrode film is 5 or more and less than 10 ++ (good): volume of the electrode film
  • the resistivity ( ⁇ ⁇ cm) is 10 or more and less than 20 + (OK):
  • the volume resistivity ( ⁇ ⁇ cm) of the electrode film is 20 or more and less than 100-(impossible): The volume resistivity of the electrode film ( ⁇ ⁇ cm) ) Is 100 or more
  • Example 3A-1 Production and evaluation of positive electrode (Example 3A-1)
  • the electrode film (A1) was rolled by a roll press (3t hydraulic roll press manufactured by Sank Metal Co., Ltd.) to produce a positive electrode having a mixture layer density of 3.1 g / cm 3 .
  • Examples 3A-2 to 3A-64, Comparative Examples 3A-1 to 3A-4) A positive electrode was produced in the same manner as in Example 3A-1, except that the electrode film (A1) was changed to each of the electrode films listed in Table 5.
  • Example 4-1 The positive electrode (A1) and the standard negative electrode were punched into 45 mm ⁇ 40 mm and 50 mm ⁇ 45 mm, respectively. These and a separator (porous polypropylene film) inserted therebetween were inserted into an aluminum laminate bag, and dried at 60 ° C. for 1 hour in an electric oven. Then, in a glove box filled with argon gas, LiPF 6 was added at a concentration of 1 M to a mixed solvent of an electrolytic solution (a mixture of ethylene carbonate, dimethyl carbonate, and diethyl carbonate at a ratio of 1: 1: 1 (volume ratio)). After injecting 2 mL of the dissolved non-aqueous electrolyte, the aluminum laminate was sealed and a laminated lithium ion secondary battery (A1) was produced.
  • LiPF 6 a mixture of ethylene carbonate, dimethyl carbonate, and diethyl carbonate at a ratio of 1: 1: 1 (volume ratio)
  • Example 4-2 to 4-64 Comparative Examples 4-1 to 4-4.
  • the laminated lithium ion secondary batteries (A2) to (A64) and (B1) to (B1) were manufactured in the same manner as in Example 4-1 except that the positive electrode (A1) was changed to the positive electrode listed in Table 6. B4) was prepared.
  • Table 7 shows the evaluation results of the laminated lithium secondary batteries produced in Examples 4-1 to 4-64 and Comparative examples 4-1 to 4-4.
  • the evaluation criteria for each characteristic are as follows. (Rate characteristics) +++ (excellent): the rate characteristic is 80% or more ++ (good): the rate characteristic is 70% or more and less than 80% + (acceptable): the rate characteristic is 60% or more and less than 70%-(impossible): the rate characteristic is 60 % (High temperature storage characteristics) +++ (excellent): high-temperature storage characteristics of 80% or more ++ (good): high-temperature storage characteristics of 70% or more and less than 80% + (acceptable): high-temperature storage characteristics of 60% or more and less than 70%-(impossible): high-temperature storage characteristics Is less than 60%
  • Table 8 shows the evaluation results of the laminated lithium ion secondary batteries manufactured using the carbon material dispersions used in Examples 1-1 to 1-64 and Comparative Examples 1-1 to 1-4.
  • the overall evaluation was based on the sum of the numbers of “+” in the evaluation of the rate characteristics and the high-temperature storage characteristics of the laminated lithium ion secondary battery, and was evaluated in five steps according to the following criteria. 5 (best): the sum of the number of “+” is 6 or more 4 (excellent): the sum of the number of “+” is 5 3 (good): the sum of the number of “+” is 4 2 (acceptable) : The sum of the numbers of "+” is 3 1 (impossible): When the evaluation includes "-"
  • the laminated lithium secondary batteries of Examples 4-1 to 4-64 using the triazine derivatives A to AD were the same as those of Comparative Examples 2-1 to 2-4 using the triazine derivatives BA to BD. It was much better than a laminated lithium secondary battery. Therefore, it has been clarified that the present invention can provide a lithium secondary battery having excellent characteristics that cannot be achieved by a conventional dispersant.
  • Examples 5-1 to 5-5, Comparative examples 5-1 to 5-5 According to the materials and compositions of the carbon material dispersion shown in Table 9, the carbon material dispersion varnish shown in Table 10, and the positive electrode mixture paste shown in Table 11, the carbon material dispersion was prepared in the same manner as in Example 1-1. A material-dispersed varnish, a mixture paste, an electrode, and a positive electrode were respectively manufactured, a laminated lithium secondary battery was assembled, and rate characteristics and high-temperature characteristics were evaluated. The amount of the dispersant was appropriately determined according to each carbon material.
  • Table 12 shows the evaluation results of the rate characteristics and the high-temperature storage characteristics in Examples 5-1 to 5-5 and Comparative examples 5-1 to 5-5.
  • Table 14 shows the results of the viscosity evaluation of the dispersions obtained in Examples 6-1 to 6-4 and Comparative Example 6-1.
  • Table 16 shows the evaluation results of the rate characteristics and high-temperature characteristics of Examples 7-1 to 7-11 and Comparative example 7-1.
  • Example 7-1 to 7-11 the same rate characteristics and high-temperature storage characteristics as those obtained when the polymer dispersant was not used were obtained.
  • Comparative Example 7-1 had the same rate characteristics and high-temperature storage characteristics as when no polymer dispersant was used. Further, the same tendency was confirmed when other dispersants of the present invention (triazine derivatives other than triazine derivative A) were used.
  • Example 8-1 ⁇ Preparation of negative electrode mixture paste> (Example 8-1)
  • a plastic container having a capacity of 150 cm 3 the carbon material dispersion prepared in Example 6-1, CMC, and water were added. Thereafter, the mixture was stirred at 2000 rpm for 30 seconds using a rotation / revolution mixer (manufactured by Shinkey, Nawataro Awari, ARE-310) to obtain a carbon material dispersed varnish C1. Thereafter, the active material was added, and the mixture was stirred at 2000 rpm for 150 seconds using a rotation / revolution mixer (manufactured by Shinky Inc., Awatori Naritaro, ARE-310).
  • Example 8-2 to 8-4 Comparative Example 8-1
  • the carbon material-dispersed varnishes C2 to C4 the comparative carbon material-dispersed varnish D1
  • the negative electrode mixture paste (mixture slurry) C2 To C4 and D1 were obtained.
  • all the electrode films using the carbon material-dispersed varnish of the present invention had good conductivity.
  • the conductivity of the electrode film was evaluated according to the following criteria.
  • volume resistivity ( ⁇ ⁇ cm) of the electrode film is less than 0.3 + (good): volume resistivity ( ⁇ ⁇ cm) of the electrode film is 0.3 or more and less than 0.5 ⁇ (poor) ): Volume resistivity ( ⁇ ⁇ cm) of electrode film is 0.5 or more
  • Example 10-1 to 10-4 Laminated lithium secondary batteries C1 to C4 and D1 were produced in the same manner as in Example 4-1 except that a standard positive electrode was used as the positive electrode and the negative electrodes listed in Table 19 were used as the negative electrodes.
  • Table 19 shows the evaluation results of the rate characteristics and the high-temperature storage characteristics.
  • the evaluation criteria are as follows. (Rate characteristics) +++ (excellent): the rate characteristic is 80% or more. +++ (good): the rate characteristic is 70% or more and less than 80%. + (Acceptable): the rate characteristic is 60% or more and less than 70%. % (High temperature storage characteristics) +++ (excellent): high-temperature storage characteristics of 80% or more ++ (good): high-temperature storage characteristics of 70% or more and less than 80%, + (Possible): high-temperature storage characteristics of 60% or more and less than 70%-(impossible): high-temperature storage characteristics of less than 60%
  • the laminated lithium secondary batteries of Examples 10-1 to 10-4 using the triazine derivatives A to D are the laminated lithium secondary batteries of Comparative Example 10-1 using the triazine derivative BD.
  • the rate characteristics and the high-temperature storage characteristics were very excellent. From this, it is clear that according to the present invention, it is possible to provide a lithium secondary battery having excellent characteristics that cannot be achieved by a conventional dispersant.

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Abstract

Ce dispersant comprend un dérivé de triazine représenté par la formule générale (1) ou (2), et une amine ou une base inorganique. Cette composition de dispersion comprend le dispersant, un matériau carboné et un solvant. La composition de dispersion comprend en outre un liant. Dans la présente invention, une composition d'électrode comprend en outre un matériau actif dans la composition de dispersion.
PCT/JP2019/028564 2018-07-20 2019-07-19 Composé, dispersant, composition de dispersion pour batterie, électrode et batterie WO2020017656A1 (fr)

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JP7362989B2 (ja) 2021-09-23 2023-10-18 関西ペイント株式会社 導電性顔料ペースト、合材ペースト、及びリチウムイオン電池用電極
JP7453487B1 (ja) 2022-09-19 2024-03-19 関西ペイント株式会社 導電性顔料ペースト、合材ペースト、及びリチウムイオン電池用電極
WO2024063003A1 (fr) * 2022-09-19 2024-03-28 関西ペイント株式会社 Pâte pigmentaire électroconductrice, pâte de mélange et électrode pour batteries au lithium-ion

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