WO2013002322A1 - Binder composition for secondary cell negative electrode, slurry composition for secondary cell negative electrode, negative electrode for secondary cell, and secondary cell - Google Patents
Binder composition for secondary cell negative electrode, slurry composition for secondary cell negative electrode, negative electrode for secondary cell, and secondary cell Download PDFInfo
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- WO2013002322A1 WO2013002322A1 PCT/JP2012/066524 JP2012066524W WO2013002322A1 WO 2013002322 A1 WO2013002322 A1 WO 2013002322A1 JP 2012066524 W JP2012066524 W JP 2012066524W WO 2013002322 A1 WO2013002322 A1 WO 2013002322A1
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- negative electrode
- secondary battery
- active material
- binder
- electrode active
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a binder composition for a negative electrode of a secondary battery, and particularly relates to a binder composition for a negative electrode of a lithium ion secondary battery.
- the present invention also relates to a slurry composition, a negative electrode and a secondary battery using such a secondary battery negative electrode binder.
- portable terminals such as notebook personal computers, mobile phones, and PDAs (Personal Digital Assistants) have been widely used.
- a nickel hydrogen secondary battery, a lithium ion secondary battery, and the like are frequently used.
- Mobile terminals are required to have more comfortable portability, and are rapidly becoming smaller, thinner, lighter, and higher in performance.
- mobile terminals are used in various places.
- the battery is required to be smaller, thinner, lighter, and higher in performance as in the case of the portable terminal.
- a conductive carbonaceous material is used as a negative electrode active material because of its light weight and high energy density, and the binder is used for shape retention of the electrode active material layer and adhesion to the current collector.
- a polymer hereinafter sometimes referred to as “polymer binder”.
- This polymer binder is required to have adhesion with an electrode active material, resistance to a polar solvent used as an electrolyte, and stability in an electrochemical environment. From such required characteristics, fluorine-based polymers such as polyvinylidene fluoride are used. However, the fluorine-based polymer has problems such as impeding conductivity when the electrode active material layer is formed and insufficient adhesive strength between the current collector and the electrode active material layer. Furthermore, when a fluorine-based polymer is used for the negative electrode which is a reduction condition, there are problems such as insufficient stability and deterioration of the cycle characteristics of the secondary battery.
- Patent Document 1 Japanese Patent Laid-Open No. 11-25899
- Patent Document 2 Japanese Patent Laid-Open No. 2010-140684
- an ethylenically unsaturated acid monomer such as (meth) acrylic acid and a conjugated material such as butadiene
- a polymer binder obtained by copolymerizing a diene and an aromatic vinyl such as styrene is disclosed. According to such a polymer binder, a battery having high adhesion between the current collector and the electrode active material layer and high cycle characteristics can be obtained.
- various studies have been made to improve the characteristics by blending various additives with the polymer binder.
- Patent Documents 3 to 5 teach that an alkenyl group-containing compound is added to the electrolytic solution for the purpose of preventing deterioration of the electrolytic solution.
- the present invention is excellent in adhesion between a current collector after charging and discharging and an electrode active material layer, and can be used for secondary battery negative electrodes that can contribute to improvement of cycle characteristics and low-temperature output characteristics of secondary batteries at high temperatures.
- An object is to provide a binder composition.
- the inventors of the present invention have continually studied to solve the above-mentioned problems.
- the polymer binder used for the negative electrode active material layer and the specific compound are used in combination, whereby the current collector and the electrode active material layer after charging and discharging are used.
- the present inventors have found that a secondary battery having improved cycle characteristics at low temperatures and improved low-temperature output characteristics can be obtained.
- a binder composition for a secondary battery negative electrode comprising a binder and a propargyl group-containing compound, wherein the content of the propargyl group-containing compound is 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder.
- binder composition for secondary battery negative electrodes as described in (1) or (2) in which the binder contains an ethylenically unsaturated carboxylic acid monomer unit.
- a secondary battery negative electrode slurry composition comprising the secondary battery negative electrode binder composition according to any one of (1) to (4) above and a negative electrode active material.
- a negative electrode for a secondary battery comprising a negative electrode active material layer comprising the negative electrode binder composition for a secondary battery and the negative electrode active material according to any one of (1) to (4) above on a current collector.
- a secondary battery comprising a positive electrode, a negative electrode, an electrolytic solution, and a separator, wherein the negative electrode is a negative electrode for a secondary battery according to any one of (7) to (9).
- the adhesion between the current collector and the electrode active material layer is improved, and in particular, the high temperature cycle characteristics and the low temperature output characteristics are improved.
- a secondary battery is obtained.
- Such an action mechanism of the present invention is not necessarily clear.
- the present inventors presume the mechanism by which the above effect is achieved as follows. That is, by adding a propargyl group-containing compound to the negative electrode active material layer, the propargyl group-containing compound is adsorbed on the negative electrode active material surface, and a thin layer called SEI (Solid Electrolyte Interface) coating is formed on the negative electrode active material surface. Will be promoted.
- SEI Solid Electrolyte Interface
- Secondary battery negative electrode binder composition contains a binder and a propargyl group-containing compound.
- the binder used in the present invention is not particularly limited, and various polymer compounds that have been conventionally used as binders for negative electrode active material layers such as fluoropolymers, diene polymers, and nitrile polymers can be used. Used. Among these, a polymer compound that can be easily synthesized in an aqueous system and easily obtained in the form of an aqueous latex is preferable. Examples of such a polymer compound include a polymer compound containing an ethylenically unsaturated acid monomer unit, preferably an ethylenically unsaturated carboxylic acid monomer unit.
- the polymer compound containing an ethylenically unsaturated carboxylic acid monomer unit preferably contains an aliphatic conjugated diene monomer unit as a comonomer, and, if necessary, other monomers that can be copolymerized with these monomers. Units derived from the mer may be included. Furthermore, it is particularly preferable to contain these monomer units in a specific ratio from the viewpoint of the durability, flexibility, adhesiveness, and the like of the binder.
- the binder particularly preferably used in the present invention comprises an ethylenically unsaturated carboxylic acid monomer unit, an aliphatic conjugated diene monomer unit, and other monomer units copolymerizable therewith, Those containing monomer units in a specific ratio are preferred.
- the ethylenically unsaturated carboxylic acid monomer unit is a polymer repeating unit obtained by polymerizing an ethylenically unsaturated carboxylic acid monomer
- the aliphatic conjugated diene monomer unit is an aliphatic conjugated diene type. It is a polymer repeating unit obtained by polymerizing monomers, and other monomer units copolymerizable with these are polymer repeating units obtained by polymerizing other copolymerizable monomers. is there.
- Examples of the ethylenically unsaturated carboxylic acid monomer include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Can be used. Among these, acrylic acid, methacrylic acid, and itaconic acid are preferable, and itaconic acid is particularly preferable in terms of excellent adhesion to the current collector.
- a polymer binder is used in combination with a propargyl group-containing compound described later, the dispersibility of the binder composition in water increases as the amount of the propargyl group-containing compound increases (hereinafter, sometimes abbreviated as water dispersibility). May decrease. However, water dispersibility is improved by introducing a unit containing a carboxylic acid into the polymer binder. In particular, when itaconic acid, which is a dicarboxylic acid, is introduced, the affinity between the binder and water increases.
- Aliphatic conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted Examples thereof include linear conjugated pentadienes, substituted and side chain conjugated hexadienes, and one or more kinds can be used. In particular, 1,3-butadiene is preferred.
- Other monomers copolymerizable with these include aromatic vinyl monomers, vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, and unsaturated monomers containing hydroxyalkyl groups. Body, unsaturated carboxylic acid amide monomer, etc., and these can be used alone or in combination.
- an aromatic vinyl monomer is preferable from the viewpoint that swelling with respect to the electrolytic solution can be suppressed.
- aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, vinyltoluene, divinylbenzene and the like, and one or more kinds can be used.
- styrene is particularly preferable in that swelling with respect to the electrolytic solution can be suppressed.
- vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like, and one or more can be used. In particular, acrylonitrile and methacrylonitrile are preferable.
- unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate, Examples thereof include monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate and the like, and one or more can be used. Particularly preferred is methyl methacrylate.
- Examples of unsaturated monomers containing a hydroxyalkyl group include ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl Examples include methacrylate, di- (ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, etc. More than one species can be used. In particular, ⁇ -hydroxyethyl acrylate is preferred.
- Examples of the unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N, N-dimethylacrylamide, and the like, and one or more can be used. Particularly preferred are acrylamide and methacrylamide.
- any of the monomers used in ordinary emulsion polymerization such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, can be used.
- the ratio of each monomer unit of the binder in the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and more preferably 1 to ethylenically unsaturated carboxylic acid monomer units.
- the aliphatic conjugated diene monomer unit is preferably 20 to 80% by mass, more preferably 25 to 70% by mass, and even more preferably 30 to 60% by mass.
- the other polymerizable monomer units are preferably 5 to 79.9% by mass, more preferably 10 to 70% by mass, and more preferably 20 to 60% by mass.
- the stability of the binder composition and the slurry composition is improved, and sufficient adhesion between the negative electrode active material and the current collector in the negative electrode for a secondary battery is obtained. Sex can be obtained. As a result, durability of the obtained secondary battery, in particular, high temperature cycle characteristics is improved, which is preferable.
- the flexibility of the negative electrode for secondary battery and the adhesion between the negative electrode active material and the current collector are highly balanced, which is preferable.
- the durability of the obtained secondary battery, in particular, the high temperature cycle characteristics is improved, which is preferable.
- the flexibility of the negative electrode for a secondary battery and the adhesion between the negative electrode active material and the current collector are highly balanced, which is preferable.
- the durability of the obtained secondary battery, in particular, the high temperature cycle characteristics is improved, which is preferable.
- the glass transition temperature (Tg) of the binder is preferably ⁇ 60 to 40 ° C., more preferably ⁇ 50 to 30 ° C., and particularly preferably ⁇ 40 to 20 ° C.
- Tg of the binder is within the above range, characteristics such as flexibility, binding and winding properties of the negative electrode, and adhesion between the negative electrode active material and the current collector are highly balanced, which is preferable.
- hydrogenation may be performed on the diene unit after polymerization.
- the method for hydrogenation is not particularly limited, and a normal method can be used.
- the binder composition for a secondary battery negative electrode of the present invention contains a specific amount of a propargyl group-containing compound with respect to 100 parts by mass (in terms of solid content) of the binder.
- a specific amount of a propargyl group-containing compound when containing a specific amount of a propargyl group-containing compound, propargyl is brought into contact with the negative electrode active material. It is considered that the group-containing compound forms an SEI film in the vicinity of the active point of the negative electrode active material.
- the SEI coating prevents the components of the electrolytic solution from coming into contact with the active points, so that the decomposition of the electrolytic solution in the battery is suppressed.
- the increase in the electrolyte viscosity due to the decomposition of the electrolyte and the increase in the internal resistance of the secondary battery are suppressed, so that the high-temperature storage characteristics, the high-temperature cycle characteristics, and the low-temperature output characteristics of the secondary battery are improved.
- swelling of the negative electrode active material layer due to the decomposition product of the electrolyte component is prevented, the peel strength is maintained, and the high temperature cycle characteristics and the low temperature output characteristics can be further improved.
- the content of the propargyl group-containing compound in the binder composition is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the binder (in terms of solid content). Part.
- the content of the propargyl group-containing compound is too small, the formation of the SEI coating becomes insufficient, the electrolytic solution component is easily decomposed, and the battery cycle characteristics and output characteristics may be deteriorated.
- the content of the propargyl group-containing compound is too large, the stability of the slurry prepared using the binder composition is impaired, and the viscosity of the slurry tends to increase. As a result, it becomes difficult to apply the slurry, the uniformity of the obtained negative electrode is lowered, and the output characteristics may be lowered.
- the propargyl group-containing compound used in the present invention has one or more propargyl groups (HC—C—CH 2 —) in the molecule.
- the number of propargyl groups is not particularly limited. However, when the number of propargyl groups is increased, the dispersibility in water may be reduced, and a uniform aqueous slurry may not be obtained. Therefore, the number of propargyl groups per molecule of the propargyl group-containing compound is preferably 2 or less, particularly preferably 1. Accordingly, monopropargyl group-containing compounds are particularly preferably used in the present invention.
- propargyl group-containing compound examples include monopropargyl group-containing compounds such as propargyl benzenesulfonate, propargyl acrylate, propargyl methacrylate, and propargyl acetate; Examples include dipropargyl group-containing compounds such as dipropargyl carbonate.
- the binder composition for secondary battery negative electrode of the present invention may contain a dispersion medium for dispersing these components in addition to the binder and the propargyl group-containing compound.
- the dispersion medium may be either water or an organic solvent.
- a hydrophilic solvent may be mixed with water as the dispersion medium. Examples of the hydrophilic solvent include methanol, ethanol, N-methylpyrrolidone and the like, and it is preferably 5% by mass or less based on water.
- a reaction solvent at the time of preparing the binder described later may be used as a dispersion medium as it is, or the solvent may be replaced after preparing the binder.
- the total solid concentration of the binder and the propargyl group-containing compound is not particularly limited, but about 20 to 60% by mass is appropriate.
- the binder composition may contain various dispersants used at the time of preparing the binder.
- the binder composition may further contain an antiaging agent, an antiseptic, and the like as long as the dispersibility of the composition is not impaired.
- antioxidant examples include amine-based antioxidants, phenol-based antioxidants, quinone-based antioxidants, organic phosphorus-based antioxidants, sulfur-based antioxidants, and phenothiazine-based antioxidants.
- preservative examples include isothiazoline compounds and pyrithione compounds.
- a monomer composition containing the above monomer is polymerized in an aqueous solvent to prepare an aqueous dispersion containing a binder (a binder having a binding force).
- a solution or dispersion in which a binder as a coalesced particle is dissolved or dispersed in an aqueous solvent), and a specific amount of a propargyl group-containing compound and other optional components are added to and mixed with an aqueous dispersion containing the binder.
- the method for producing the binder composition is not limited to this.
- a propargyl group-containing compound, an anti-aging agent, or an antiseptic may be blended in advance in the monomer composition, and then polymerization may be performed. Good. Moreover, you may mix
- the ratio of each monomer in the monomer composition in the step of obtaining an aqueous dispersion containing a binder is preferably 0.1 to 20% by mass, more preferably 0. 5 to 15% by mass, more preferably 1.0 to 10% by mass, and aliphatic conjugated diene monomer is preferably 20 to 80% by mass, more preferably 25 to 70% by mass, and more preferably 30 to 30% by mass.
- the amount of the other monomer copolymerizable with these is preferably 5 to 79.9% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass.
- the aqueous solvent is not particularly limited as long as it can disperse the binder, and is usually selected from dispersion media having a boiling point of 80 to 350 ° C., preferably 100 to 300 ° C. at normal pressure.
- the number in parentheses after the name of the following exemplified dispersion medium is a boiling point (unit: ° C) at normal pressure, and a value after the decimal point is rounded off or rounded down.
- glycol ethers include propylene glycol monomethyl ether (120), methyl cellosolve (124), ethyl cellosolve (136), ethylene glycol tertiary butyl ether (152) Butyl cellosolve (171), 3-methoxy-3-methyl-1-butanol (174), ethylene glycol monopropyl ether (150), diethylene glycol monobutyl pyrute (230), triethylene glycol monobutyl ether (271), dipropylene glycol monomethyl ether (188); ethers include 1,3-dioxolane (75), 1,4-dioxolane (101), and tetrahydrofuran (
- water is most preferable from the viewpoint that it is not flammable and a binder dispersion is easily obtained.
- water may be used as the main solvent, and an aqueous solvent other than the above-described water may be mixed and used within a range in which the dispersion state of the binder can be ensured.
- the polymerization method is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used.
- Examples of the polymerization reaction include ionic polymerization, radical polymerization, and living radical polymerization. Manufacturing efficiency, such as easy to obtain high molecular weight, obtained in a state where the polymer is dispersed in water as it is, no redispersion treatment is required, and can be used as it is for slurry composition preparation for secondary battery negative electrode From the viewpoint of the above, the emulsion polymerization method is most preferable.
- the emulsion polymerization method is a conventional method, for example, the method described in “Experimental Chemistry Course” Vol. 28, (Publisher: Maruzen Co., Ltd., edited by The Chemical Society of Japan), that is, water in a sealed container with a stirrer and a heating device.
- Add additives such as dispersants, emulsifiers and crosslinkers, initiators and monomers to the prescribed composition, stir to emulsify the monomers in water, start the polymerization by increasing the temperature while stirring Is the method. Or after emulsifying the said composition, it is the method of starting reaction similarly in an airtight container.
- Emulsifiers, dispersants, polymerization initiators and the like are those generally used in these polymerization methods, and the amount used thereof may be generally used.
- seed particles can be employed (seed polymerization).
- the polymerization temperature and polymerization time can be arbitrarily selected depending on the polymerization method and the type of polymerization initiator used, but the polymerization temperature is usually about 30 ° C. or higher and the polymerization time is about 0.5 to 30 hours.
- Additives such as amines can also be used as polymerization aids.
- an aqueous dispersion of polymer particles obtained by these methods is mixed with an alkali metal (Li, Na, K, Rb, Cs) hydroxide, ammonia, an inorganic ammonium compound (NH 4 Cl, etc.), an organic amine compound (ethanol).
- a basic aqueous solution in which amine, diethylamine, etc.) are dissolved can be added to adjust the pH to 5 to 10, preferably 5 to 9.
- the pH adjustment with the alkali metal hydroxide is preferable because the binding property (peel strength) between the binder composition, the current collector and the active material is improved.
- the above-mentioned binder may be composite polymer particles composed of two or more kinds of polymers.
- the composite polymer particles can also be obtained by a method (two-stage polymerization method) in which at least one monomer component is polymerized by a conventional method, and then at least one other monomer component is added and polymerized by a conventional method. Can do.
- polymerization initiator used for the polymerization examples include lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 3,3,5-trimethylhexanoyl peroxide, and the like.
- a chain transfer agent may be added.
- the chain transfer agent is preferably an alkyl mercaptan, specifically, n-butyl mercaptan, t-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan.
- N-stearyl mercaptan N-stearyl mercaptan.
- n-octyl mercaptan and t-dodecyl mercaptan are preferable from the viewpoint of good polymerization stability.
- chain transfer agents may be used in combination with the alkyl mercaptan.
- chain transfer agents that may be used in combination include terpinolene, allyl alcohol, allylamine, sodium allyl sulfonate (potassium), and sodium methallyl sulfonate (potassium).
- the amount of the serial transfer agent used is not particularly limited as long as the effect of the present invention is not hindered.
- the number average particle size of the binder in the aqueous dispersion is preferably 50 to 500 nm, and more preferably 70 to 400 nm. When the number average particle diameter of the binder is in the above range, the strength and flexibility of the obtained negative electrode are improved.
- the presence of the polymer particles can be easily measured by a transmission electron microscope method, a Coulter counter, a laser diffraction scattering method, or the like.
- the binder may be a binder composed of polymer particles having a core-shell structure obtained by polymerizing the above monomers stepwise.
- the method of adding and mixing the propargyl group-containing compound and other optional components to the aqueous dispersion containing the binder is not particularly limited.
- the mixing method include a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type.
- a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, a planetary mixer, and a planetary kneader can be used.
- an additive may be added to the obtained binder composition for a negative electrode of the secondary battery of the present invention in order to improve applicability and charge / discharge characteristics.
- additives include cellulose polymers such as carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, polyacrylates such as sodium polyacrylate, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, acrylic acid-vinyl alcohol copolymer, Examples thereof include methacrylic acid-vinyl alcohol copolymer, maleic acid-vinyl alcohol copolymer, modified polyvinyl alcohol, polyethylene glycol, ethylene-vinyl alcohol copolymer, and partially saponified polyvinyl acetate.
- these additives can also be added to the slurry composition for a secondary battery negative electrode of the present invention described later.
- the secondary battery negative electrode slurry composition of the present invention comprises the above secondary battery negative electrode binder composition and a negative electrode active material. Below, the aspect which uses the slurry composition for secondary battery negative electrodes of this invention as a slurry composition for lithium ion secondary battery negative electrodes is demonstrated.
- the negative electrode active material used in the present invention is a material that transfers electrons in the negative electrode for a secondary battery.
- Examples of the negative electrode active material for a lithium ion secondary battery include a carbon material-based active material and an alloy-based active material.
- the carbon material-based active material refers to an active material having carbon as a main skeleton into which lithium can be inserted, and specifically includes a carbonaceous material and a graphite material.
- the carbonaceous material generally indicates a carbon material having a low graphitization (low crystallinity) obtained by heat-treating (carbonizing) a carbon precursor at 2000 ° C. or less, and the graphitic material is a graphitizable carbon at 2000 ° C.
- a graphitic material having high crystallinity close to that of the graphite obtained by heat treatment as described above will be shown.
- Examples of the carbonaceous material include graphitizable carbon that easily changes the carbon structure depending on the heat treatment temperature, and non-graphitic carbon having a structure close to an amorphous structure typified by glassy carbon.
- graphitizable carbon examples include carbon materials made from tar pitch obtained from petroleum and coal, such as coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fibers, pyrolytic vapor-grown carbon fibers, etc. Is mentioned.
- MCMB is a carbon fine particle obtained by separating and extracting mesophase spherules produced in the process of heating pitches at around 400 ° C.
- mesophase pitch-based carbon fiber is a mesophase pitch obtained by growing and coalescing the mesophase spherules. Is a carbon fiber made from a raw material.
- non-graphitizable carbon examples include phenol resin fired bodies, polyacrylonitrile-based carbon fibers, pseudo-isotropic carbon, and furfuryl alcohol resin fired bodies (PFA).
- Examples of the graphite material include natural graphite and artificial graphite.
- Examples of artificial graphite include artificial graphite heat-treated at 2800 ° C or higher, graphitized MCMB heat-treated MCMB at 2000 ° C or higher, and graphitized mesophase pitch carbon fiber heat-treated at 2000 ° C or higher. It is done.
- a graphite material is preferable.
- the alloy-based active material used in the present invention refers to an active material containing an element capable of inserting lithium in the structure and having a theoretical electric capacity per mass of 500 mAh / g or more when lithium is inserted.
- Lithium metal, a single metal forming a lithium alloy and an alloy thereof, and oxides, sulfides, nitrides, silicides, carbides, phosphides, and the like thereof are used.
- Examples of single metals and alloys forming lithium alloys include compounds containing metals such as Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, and Zn. Is mentioned. Among these, silicon (Si), tin (Sn) or lead (Pb) simple metals, alloys containing these atoms, or compounds of these metals are used.
- the alloy-based active material used in the present invention may further contain one or more nonmetallic elements.
- SiC, SiO x C y (hereinafter referred to as “Si—O—C”) (0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 5), Si 3 N 4 , Si 2 N 2 O, Examples thereof include SiO x (0 ⁇ x ⁇ 2), SnO x (0 ⁇ x ⁇ 2), LiSiO, LiSnO, etc.
- SiO x C y capable of inserting and releasing lithium at a low potential is preferable.
- SiO x C y can be obtained by firing a polymer material containing silicon.
- the range of 0.8 ⁇ x ⁇ 3 and 2 ⁇ y ⁇ 4 is preferably used in view of the balance between capacity and cycle characteristics.
- oxides, sulfides, nitrides, silicides, carbides, and phosphides examples include oxides, sulfides, nitrides, silicides, carbides, and phosphides of elements into which lithium can be inserted.
- Oxides are particularly preferred. Specifically, an oxide such as tin oxide, manganese oxide, titanium oxide, niobium oxide, vanadium oxide, or a lithium-containing metal composite oxide material containing a metal element selected from the group consisting of Si, Sn, Pb, and Ti atoms is used. It has been.
- the silicon oxide include materials such as silicon carbide (Si—O—C).
- a lithium titanium composite oxide represented by Li x Ti y M z O 4 (0.7 ⁇ x ⁇ 1.5, 1.5 ⁇ y ⁇ 2.3, 0 ⁇ z ⁇ 1.6, M includes Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb), among which Li 4/3 Ti 5/3 O 4 , Li1Ti 2 O 4 and Li 4/5 Ti 11/5 O 4 are used.
- silicon-containing materials materials containing silicon
- Si—O—C materials containing carbon
- insertion / extraction of Li to / from Si (silicon) occurs at a high potential and C (carbon) at a low potential, and expansion / contraction is suppressed as compared with other alloy-based active materials.
- the negative electrode active material a graphite material and a silicon-containing material are preferable, and natural graphite and Si—O—C are particularly preferable.
- an SEI film is formed by contact with a propargyl group-containing compound, the active sites at the edge portion are easily deactivated, and decomposition of the electrolyte component can be effectively prevented.
- the present invention is effective for an electrode containing a carbon material-based active material.
- a negative electrode active material may be used individually by 1 type, and may use 2 or more types together.
- a combination of a graphite material and a silicon-containing material is preferred.
- the blending ratio (graphitic material / silicon-containing material) is preferably 99/1 to 40/60, more preferably 95/5 to 45/55, by weight.
- the shape of the negative electrode active material is preferably a granulated particle. When the shape of the particles is spherical, a higher density electrode can be formed during electrode molding.
- the volume average particle diameter of the negative electrode active material is appropriately selected in consideration of other constituent elements of the battery, but is usually 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m, more preferably 5 to 20 ⁇ m. Further, the 50% volume cumulative diameter of the negative electrode active material is usually 1 to 50 ⁇ m, preferably 15 to 30 ⁇ m, from the viewpoint of improving battery characteristics such as initial efficiency, load characteristics, and cycle characteristics.
- the volume average particle diameter is determined by measuring the particle size distribution by laser diffraction.
- the 50% volume cumulative diameter is a 50% volume average particle diameter calculated by measuring with a laser diffraction particle size distribution analyzer (SALD-3100; manufactured by Shimadzu Corporation).
- the tap density of the negative electrode active material is not particularly limited, but 0.6 g / cm 3 or more is preferably used.
- the BET specific surface area of the negative electrode active material is preferably 3 to 20 m 2 / g, more preferably 3 to 15 m 2 / g, and particularly preferably 3 to 10 m 2 / g.
- the BET specific surface area of the negative electrode active material is in the above range, the active points on the surface of the negative electrode active material are increased, so that the low-temperature output characteristics of the secondary battery are excellent.
- the total content of the negative electrode active material and the binder composition in the secondary battery negative electrode slurry composition of the present invention is preferably 10 to 90 parts by mass, more preferably 30 parts, relative to 100 parts by mass of the slurry composition. ⁇ 80 parts by mass.
- the content of the binder composition relative to the total amount of the negative electrode active material is preferably 0.1 to 5 parts by mass, more preferably 0.005 parts by mass with respect to 100 parts by mass of the total amount of the negative electrode active material. 5 to 2 parts by mass.
- the viscosity of the obtained slurry composition for secondary battery negative electrode is optimized, and the coating is smoothly performed.
- sufficient adhesion strength can be obtained without increasing the resistance of the obtained negative electrode.
- peeling of the negative electrode active material layer from the current collector in the electrode plate pressing step can be suppressed.
- water is preferably used as a dispersion medium for the slurry.
- a mixture of water and a hydrophilic solvent may be used as a dispersion medium.
- the hydrophilic solvent include methanol, ethanol, N-methylpyrrolidone and the like, and it is preferably 5% by mass or less based on water.
- the slurry composition for secondary battery negative electrodes of this invention it is preferable to contain a electrically conductive agent.
- a electrically conductive agent conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube can be used.
- the content of the conductive agent in the slurry composition is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material.
- thickener In the slurry composition for secondary battery negative electrodes of this invention, it is preferable to contain a thickener.
- thickeners include cellulose polymers such as carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, and ammonium salts and alkali metal salts thereof; (Modified) poly (meth) acrylic acid and ammonium salts and alkali metal salts thereof; (Modified) Polyvinyl alcohols such as polyvinyl alcohol, a copolymer of acrylic acid or acrylate and vinyl alcohol, maleic anhydride or a copolymer of maleic acid or fumaric acid and vinyl alcohol; Examples include polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, modified polyacrylic acid, oxidized starch, phosphate starch, casein, and various modified starches.
- the blending amount of the thickener is preferably 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the negative electrode active material. When the blending amount of the thickener is within the above range, the coating property and the adhesion with the current collector are good.
- (modified) poly means “unmodified poly” or “modified poly”
- (meth) acryl means “acryl” or “methacryl”.
- the slurry composition for secondary battery negative electrode may further contain other components such as a reinforcing material, a leveling agent, and an electrolyte additive having a function of inhibiting electrolyte decomposition, It may be contained in a negative electrode for a secondary battery described later. These are not particularly limited as long as they do not affect the battery reaction.
- the reinforcing material various inorganic and organic spherical, plate-like, rod-like or fibrous fillers can be used.
- a reinforcing material By using a reinforcing material, a tough and flexible negative electrode can be obtained, and excellent long-term cycle characteristics can be exhibited.
- the content of the reinforcing material in the slurry composition is usually 0.01 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material. By being included in the above range, high capacity and high load characteristics are exhibited.
- the leveling agent examples include surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants.
- the content of the leveling agent in the slurry composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material.
- the productivity, smoothness, and battery characteristics during the production of the negative electrode are excellent.
- the surfactant By containing the surfactant, the dispersibility of the negative electrode active material and the like in the slurry composition can be improved, and the smoothness of the negative electrode can be improved.
- the electrolytic solution additive used in the slurry composition and the electrolytic solution vinylene carbonate or the like can be used.
- the content of the electrolytic solution additive in the slurry composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material.
- the cycle characteristics and the high temperature characteristics are excellent.
- Other examples include nanoparticles such as fumed silica and fumed alumina. By mixing the nanoparticles, the thixotropy of the slurry composition can be controlled, and the leveling property of the negative electrode can be improved.
- the content of the nanoparticles in the slurry composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material. When the nanoparticles are in the above range, the slurry stability and productivity are excellent, and high battery characteristics are exhibited.
- the slurry composition for a secondary battery negative electrode of the present invention can contain a water-soluble polymer in addition to the binder composition.
- the water-soluble polymer include ethylenically unsaturated carboxylic acid monomer units of 20 to 60% by mass, (meth) acrylic acid ester monomer units of 20 to 80% by mass and other monomer units copolymerizable therewith.
- a water-soluble polymer consisting of 0 to 20% by mass is preferred.
- the water-soluble polymer in the present invention refers to a polymer having a 1% aqueous solution viscosity of 0.1 to 100,000 mPa ⁇ s at pH 12.
- Examples of the ethylenically unsaturated carboxylic acid monomer include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Can be used.
- the ratio of these ethylenically unsaturated carboxylic acid monomer units is more preferably 25 to 55% by mass, particularly preferably 30 to 50% by mass.
- (Meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2- Acrylic acid alkyl esters such as ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate , Pentyl methacrylate, hexyl methacrylate, heptyl meth
- Other monomers that can be copolymerized include carboxylic acid ester monomers having two or more carbon-carbon double bonds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate; styrene, chlorostyrene, Styrene monomers such as vinyl toluene, t-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, ⁇ -methyl styrene, divinylbenzene; acrylamide, N-methylol aqua amide, Amide monomers such as acrylamide-2-methylpropanesulfonic acid; ⁇ , ⁇ -unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; Olefins such as ethylene and propylene; Halogen atom-containing monomers such as vinyl chloride and vinyl
- ⁇ , ⁇ -unsaturated nitrile compounds and styrene monomers are preferable, and ⁇ , ⁇ -unsaturated nitrile compounds are particularly preferable.
- the ratio of these copolymerizable monomer units is more preferably 0 to 10% by mass, particularly preferably 0 to 5% by mass.
- Examples of the method for producing a water-soluble polymer include a method in which a monomer composition containing the above monomer is polymerized in an aqueous solvent to obtain a water-dispersible polymer and alkalized to pH 7-13. About an aqueous solvent and the polymerization method, it is the same as that of the above-mentioned binder composition for secondary battery negative electrodes.
- the method for alkalinizing to pH 7 to 13 is not particularly limited, but alkaline earth solutions such as an aqueous alkali metal solution such as an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution, an aqueous calcium hydroxide solution, and an aqueous magnesium hydroxide solution.
- alkaline earth solutions such as an aqueous alkali metal solution such as an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution, an aqueous calcium hydroxide solution, and an aqueous magnesium hydroxide solution.
- alkaline earth solutions such as an aqueous alkali metal solution such as an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution, an aqueous calcium hydroxide solution, and an aqueous magnesium hydroxide solution.
- examples include
- the slurry composition for a secondary battery negative electrode is obtained by mixing the binder composition, the negative electrode active material, and a conductive agent used as necessary.
- the mixing method is not particularly limited, and examples thereof include a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type.
- a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, a planetary mixer, and a planetary kneader can be used.
- Negative electrode for secondary battery comprises the binder composition and the negative electrode active material, and specifically, the slurry composition for secondary battery negative electrode of the present invention is collected. It is obtained by applying and drying on an electric body.
- the method for producing the negative electrode for secondary battery of the present invention is not particularly limited.
- a method of forming the negative electrode active material layer by applying and drying the slurry composition on at least one surface, preferably both surfaces of the current collector. can be mentioned.
- the method for applying the slurry composition onto the current collector is not particularly limited.
- Examples of the method include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
- drying method examples include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
- the drying time is usually 5 to 30 minutes, and the drying temperature is usually 40 to 180 ° C.
- the porosity of the negative electrode active material layer is lowered by pressure treatment using a die press or a roll press after applying and drying the slurry composition on the current collector. It is preferable to have the process to do.
- a preferable range of the porosity is 5 to 30%, more preferably 7 to 20%. If the porosity is too high, charging efficiency and discharging efficiency are deteriorated. When the porosity is too low, it is difficult to obtain a high volume capacity, and the negative electrode active material layer is liable to be peeled off from the current collector, resulting in a defect.
- the thickness of the negative electrode active material layer in the negative electrode for secondary battery of the present invention is usually 5 to 300 ⁇ m, preferably 30 to 250 ⁇ m. When the thickness of the negative electrode active material layer is in the above range, both load characteristics and cycle characteristics are high.
- the content ratio of the negative electrode active material in the negative electrode active material layer is preferably 85 to 99% by mass, more preferably 88 to 97% by mass.
- the density of the negative electrode active material layer of the negative electrode for a secondary cell preferably 1.6 ⁇ 1.9g / cm 3, more preferably 1.65 ⁇ 1.85g / cm 3.
- the density of the negative electrode active material layer is in the above range, a high-capacity battery can be obtained.
- the current collector used in the present invention is not particularly limited as long as it is an electrically conductive and electrochemically durable material.
- a metal material is preferable because it has heat resistance.
- iron, copper, aluminum Nickel, stainless steel, titanium, tantalum, gold, platinum and the like are particularly preferable as the current collector used for the negative electrode for the secondary battery.
- the shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 to 0.5 mm is preferable.
- the current collector is preferably used after roughening in advance. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
- an abrasive cloth paper with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used. Further, an intermediate layer may be formed on the current collector surface in order to increase the adhesive strength and conductivity with the negative electrode active material layer.
- the secondary battery of the present invention is a secondary battery comprising a positive electrode, a negative electrode, a separator and an electrolytic solution, and the negative electrode is the negative electrode for a secondary battery.
- the positive electrode is formed by laminating a positive electrode active material layer containing a positive electrode active material and a secondary battery positive electrode binder composition on a current collector.
- Positive electrode active material an active material that can be doped and dedoped with lithium ions is used, and the positive electrode active material is roughly classified into an inorganic compound and an organic compound.
- Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides of lithium and transition metals, and the like.
- Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.
- Transition metal oxides include MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O. 5 , V 6 O 13 and the like. Among them, MnO, V 2 O 5 , V 6 O 13 and TiO 2 are preferable from the viewpoint of cycle stability and capacity.
- the lithium-containing composite metal oxide include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure.
- lithium-containing composite metal oxide having a layered structure lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), Co—Ni—Mn lithium composite oxide, Ni—Mn—Al lithium
- lithium-containing cobalt oxide (LiCoO 2 ) lithium-containing nickel oxide (LiNiO 2 ), Co—Ni—Mn lithium composite oxide, Ni—Mn—Al lithium
- examples thereof include composite oxides and lithium composite oxides of Ni—Co—Al.
- the lithium-containing composite metal oxide having a spinel structure include lithium manganate (LiMn 2 O 4 ) and Li [Mn 3/2 M 1/2 ] O 4 in which a part of Mn is substituted with another transition metal (wherein M may be Cr, Fe, Co, Ni, Cu or the like.
- Li X MPO 4 (wherein, M is Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Li X MPO 4 as the lithium-containing composite metal oxide having an olivine structure)
- An olivine type lithium phosphate compound represented by at least one selected from Si, B, and Mo, 0 ⁇ X ⁇ 2) may be mentioned.
- a conductive polymer such as polyacetylene or poly-p-phenylene can be used.
- An iron-based oxide having poor electrical conductivity may be used as an electrode active material covered with a carbon material by allowing a carbon source material to be present during reduction firing. These compounds may be partially element-substituted.
- the positive electrode active material for the secondary battery may be a mixture of the above inorganic compound and organic compound.
- the volume average particle diameter of the positive electrode active material is usually 0.01 to 50 ⁇ m, preferably 0.05 to 30 ⁇ m.
- the volume average particle diameter is in the above range, the amount of the binder composition for the positive electrode when preparing the slurry composition for the positive electrode described later can be reduced, the decrease in the capacity of the battery can be suppressed, and for the positive electrode It becomes easy to prepare the slurry composition to have a viscosity suitable for application, and a uniform electrode can be obtained.
- the content ratio of the positive electrode active material in the positive electrode active material layer is preferably 90 to 99.9% by mass, more preferably 95 to 99% by mass.
- the binder composition for the secondary battery positive electrode is not particularly limited and a known one can be used.
- resins such as polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, polyacrylonitrile derivatives, acrylic soft heavy
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- polyacrylic acid derivatives polyacrylonitrile derivatives
- acrylic soft heavy A soft polymer such as a polymer, a diene soft polymer, an olefin soft polymer, or a vinyl soft polymer can be used. These may be used alone or in combination of two or more.
- the positive electrode may further contain other components such as an electrolyte additive having a function of suppressing the above-described electrolyte decomposition. These are not particularly limited as long as they do not affect the battery reaction.
- the current collector used in the above-described negative electrode for a secondary battery can be used, and there is no particular limitation as long as the material has electrical conductivity and is electrochemically durable.
- Aluminum is particularly preferred for the secondary battery positive electrode.
- the thickness of the positive electrode active material layer is usually 5 to 300 ⁇ m, preferably 10 to 250 ⁇ m. When the thickness of the positive electrode active material layer is in the above range, both load characteristics and energy density are high.
- the positive electrode can be produced in the same manner as the above-described negative electrode for secondary battery.
- the separator is a porous substrate having pores
- usable separators include (a) a porous separator having pores, and (b) a porous separator in which a polymer coat layer is formed on one or both sides. Or (c) a porous separator in which a porous resin coat layer containing an inorganic ceramic powder is formed.
- Non-limiting examples of these include high-grade polypropylene, polyethylene, polyolefin, or aramid porous separators, polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride hexafluoropropylene copolymers.
- Examples include a separator having a molecular film and a coat layer, or a separator coated with a porous film layer made of an inorganic filler or a dispersant for inorganic filler.
- the electrolytic solution used in the present invention is not particularly limited.
- a solution obtained by dissolving a lithium salt as a supporting electrolyte in a non-aqueous solvent can be used.
- the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and other lithium salts.
- LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferably used. These can be used alone or in admixture of two or more.
- the amount of the supporting electrolyte is usually 1% by mass or more, preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, with respect to the electrolytic solution. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity is lowered and the battery charging and discharging characteristics are lowered.
- the solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
- Alkyl carbonates such as carbonate (BC) and methyl ethyl carbonate (MEC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane; tetrahydrofuran; sulfolane and dimethyl sulfoxide Sulfur-containing compounds are used.
- dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate are preferable because high ion conductivity is easily obtained and the use temperature range is wide. These can be used alone or in admixture of two or more. Moreover, it is also possible to use an electrolyte containing an additive. Moreover, as an additive, carbonate type compounds, such as vinylene carbonate (VC), are preferable, and vinylene carbonate is more preferable especially. By including vinylene carbonate in the electrolytic solution, the propargyl-containing compound and vinylene carbonate can promote decomposition on the negative electrode active material and suppress decomposition of the electrolytic solution itself. The content of vinylene carbonate in the electrolytic solution is preferably 0.01 to 8% by volume.
- Examples of the electrolytic solution other than the above include a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide and polyacrylonitrile with an electrolytic solution, and an inorganic solid electrolyte such as lithium sulfide, LiI, and Li 3 N.
- the manufacturing method of the secondary battery of the present invention is not particularly limited.
- the above-described negative electrode and positive electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery and placed in the battery container, and the electrolytic solution is injected into the battery container and sealed.
- an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate and the like can be inserted to prevent an increase in pressure inside the battery and overcharge / discharge.
- the shape of the battery may be any of a laminated cell type, a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, and the like.
- ⁇ Adhesion strength peel strength of negative electrode active material layer>
- the negative electrode for a secondary battery manufactured in Examples and Comparative Examples was cut into a rectangle having a length of 100 mm and a width of 10 mm to obtain a test piece, and a cellophane tape (in JIS Z1522 2009) was formed on the surface of the negative electrode active material layer with the negative electrode active material layer side down. Then, stress was measured when one end of the current collector was pulled in a vertical direction at a pulling speed of 50 mm / min and peeled off (the cellophane tape was fixed to a test stand). The measurement was performed three times, and the average value was obtained and used as the peel strength. The higher the peel strength, the greater the binding force of the negative electrode active material layer to the current collector, that is, the higher the adhesion strength.
- ⁇ Durability: High-temperature cycle characteristics> Using a negative electrode for a lithium ion secondary battery produced in the examples and comparative examples, a lithium ion secondary battery of a laminate type cell was prepared and left to stand in an environment of 25 ° C. for 24 hours. After that, under an environment of 25 ° C., charge / discharge operation of charging to 4.2 V and discharging to 3.0 V was performed by a constant current method of 0.1 C, and an initial capacity C0 was measured. Furthermore, in a 60 ° C. environment, charging / discharging of charging to 4.2 V and discharging to 3.0 V was repeated by a constant current method of 0.1 C, and the capacity C2 after 100 cycles was measured. The high-temperature cycle characteristics were evaluated by a capacity change rate represented by ⁇ C C2 / C0 ⁇ 100 (%). Higher values indicate better high temperature cycle characteristics.
- a lithium ion secondary battery of a laminate type cell was prepared and left at 25 ° C. for 24 hours.
- the charging / discharging operation of charging to 4.2V and discharging to 3.0V was performed by the constant current method.
- the battery was charged to a 50% charged state (SOC 50%) by a constant current method of 0.1 C under an environment of 25 ° C., and a voltage V 0 (V) was measured.
- the battery was discharged from the voltage V 0 (V) at a discharge rate of 0.1 C in an environment of ⁇ 25 ° C., and the voltage V 10 after 10 seconds of discharge was measured.
- Example 1 Manufacture of binder composition
- a 5 MPa pressure vessel equipped with a stirrer 33 parts of 1,3-butadiene, 4 parts of itaconic acid, 63 parts of styrene, 4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water, and potassium persulfate 0.5 as a polymerization initiator
- a portion was added and stirred sufficiently, and then heated to 50 ° C. to initiate polymerization.
- the reaction was stopped by cooling to obtain an aqueous dispersion containing a binder.
- the glass transition temperature of the binder was 10 ° C.
- aqueous sodium hydroxide solution After adding 5% aqueous sodium hydroxide solution to the aqueous dispersion containing the binder and adjusting the pH to 8, the unreacted monomer is removed by heating under reduced pressure, and then cooled to 30 ° C. or lower to obtain a binder solid.
- a propargyl group-containing compound 3 parts of propargyl benzenesulfonate was added to 100 parts per minute to obtain a binder composition.
- the above mixture was mixed with 1 part of the binder (based on solid content) and ion-exchanged water, adjusted to a final solid content concentration of 42%, and further mixed for 10 minutes. This was defoamed under reduced pressure to obtain a slurry composition for a secondary battery negative electrode having good fluidity.
- the dispersion stability of the slurry was evaluated as described above.
- the secondary battery negative electrode slurry composition was applied on a copper foil having a thickness of 20 ⁇ m with a comma coater so that the film thickness after drying was about 150 ⁇ m, heat-treated at 60 ° C. for 1 minute, and then 120 An electrode raw material was obtained by heat treatment at 0 ° C. for 1 minute.
- the raw electrode was rolled with a roll press to obtain a negative electrode for a secondary battery having a negative electrode active material layer thickness of 80 ⁇ m.
- a positive electrode active material 100 parts of LiFePO 4 having a volume average particle diameter of 0.5 ⁇ m and an olivine crystal structure is used, and a 1% aqueous solution of carboxymethyl cellulose (CMC, “BSH-12” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is used as a dispersant.
- CMC carboxymethyl cellulose
- a planetar such that a 40% aqueous dispersion of a copolymer obtained by emulsion polymerization of a monomer mixture containing% by mass is 5 parts in terms of solids and the total solids concentration is 40% with ion-exchanged water.
- a slurry for a positive electrode composition layer was prepared by mixing with a Lee mixer.
- the secondary battery positive electrode slurry composition was applied onto a 20 ⁇ m thick copper foil with a comma coater so that the film thickness after drying was about 200 ⁇ m, and heat-treated at 60 ° C. for 1 minute, and then 120 A positive electrode for a secondary battery was obtained by heat treatment at 0 ° C. for 1 minute.
- a single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 ⁇ m, manufactured by a dry method, porosity 55%) was cut into a circle having a diameter of 18 mm.
- the obtained positive electrode for a lithium ion secondary battery was disposed such that the current collector surface was in contact with the aluminum packaging exterior.
- a separator was disposed on the surface of the positive electrode on the positive electrode active material layer side.
- the negative electrode for a lithium ion secondary battery obtained above was placed on the separator so that the surface on the negative electrode active material layer side faces the separator.
- the electrolyte was poured into the packaging material so that no air remained. Furthermore, in order to seal the opening of the aluminum packaging material, heat sealing at 150 ° C. was performed to close the aluminum exterior, and a lithium ion secondary battery was manufactured.
- the obtained negative electrode and secondary battery were evaluated for adhesion strength, durability, and low-temperature output characteristics as described above.
- Example 2 The same procedure as in Example 1 was performed except that the amount of propargyl benzenesulfonate was 7 parts with respect to 100 parts of binder solid content. The results are shown in Table 1.
- Example 3 The amount of propargyl benzenesulfonate added was the same as in Example 1 except that the amount was 15 parts with respect to 100 parts of binder solid content. The results are shown in Table 1.
- Example 4 The same procedure as in Example 1 was conducted except that propargyl acrylate was used instead of propargyl benzenesulfonate as the propargyl group-containing compound. The results are shown in Table 1.
- Example 5 The same procedure as in Example 1 was conducted except that propargyl methacrylate was used instead of propargyl benzenesulfonate as the propargyl group-containing compound. The results are shown in Table 1.
- Example 6 The same procedure as in Example 1 was performed except that methacrylic acid was used in place of itaconic acid as a comonomer at the time of preparing the binder. The results are shown in Table 1.
- Example 7 As the negative electrode active material, natural graphite having a BET specific surface area of 8 m 2 / g (average particle diameter: 22 ⁇ m) was used instead of natural graphite having a BET specific surface area of 5 m 2 / g (average particle diameter: 24.5 ⁇ m). Same as Example 1. The results are shown in Table 1.
- Example 8 As the negative electrode active material, natural graphite having a BET specific surface area of 15 m 2 / g (average particle diameter: 15 ⁇ m) was used instead of natural graphite having a BET specific surface area of 5 m 2 / g (average particle diameter: 24.5 ⁇ m). Same as Example 1. The results are shown in Table 1.
- Example 9 As the negative electrode active material, natural graphite (average particle size: 24.5 ⁇ m) of a BET specific surface area of 5 m 2 / g natural graphite (average particle size: 24.5 ⁇ m) of a BET specific surface area of 5 m 2 / g instead of 80 parts and The procedure was the same as Example 1 except that 20 parts of SiOC (average particle size: 10 ⁇ m) having a BET specific surface area of 6.5 m 2 / g was used. The BET specific surface area of the negative electrode active material was 5.2 m 2 / g. The results are shown in Table 1.
- Example 10 As the negative electrode active material, natural graphite (average particle size: 24.5 ⁇ m) of a BET specific surface area of 5 m 2 / g BET specific instead of surface area 5.0 m 2 / g natural graphite (average particle size: 24.5 ⁇ m) 50 Parts and a BET specific surface area of 6.5 m 2 / g of SiOC (average particle size: 10 ⁇ m) were used in the same manner as in Example 1 except that 50 parts were used. The BET specific surface area of the negative electrode active material was 5.8 m 2 / g. The results are shown in Table 1.
- Example 11 The same procedure as in Example 1 was performed except that dipropargyl carbonate was used as the propargyl group-containing compound instead of propargyl benzenesulfonate. The results are shown in Table 1.
- Example 12 The same procedure as in Example 1 was conducted except that itaconic acid was not used as a comonomer for preparing the binder.
- the glass transition temperature of the binder was 7 ° C. The results are shown in Table 1.
- Example 1 The procedure was the same as Example 1 except that the propargyl group-containing compound was not blended in the binder composition. The results are shown in Table 1.
- Example 1 (Comparative Example 4) Example 1 was repeated except that methyl 2-octanoate was used in place of propargyl benzenesulfonate. The results are shown in Table 1.
- the adhesion between the current collector and the electrode active material layer was improved, and in particular, a secondary battery with improved cycle characteristics and low-temperature output characteristics was obtained. .
Abstract
Description
しかしながら、特許文献1、2に記載のポリマーバインダーでは、充放電後の集電体と電極活物質層との間の密着性が低下したり、得られる二次電池の、サイクル特性、特に高温におけるサイクル特性や低温出力特性が低下したりする問題があり、さらなる改善が望まれていた。
そこで、本発明は、充放電後の集電体と電極活物質層との間の密着性に優れ、二次電池の高温におけるサイクル特性、低温出力特性の向上に寄与しうる二次電池負極用バインダー組成物を提供することを目的とする。 By using the polymer binder described in Patent Documents 1 and 2 for the electrode active material layer, a battery with high adhesion between the current collector and the electrode active material layer and high cycle characteristics can be obtained. However, secondary batteries are constantly required to have higher functionality and longer life. Specifically, improvement in cycle characteristics, low-temperature output characteristics, and the like, and improvement in adhesion between the current collector after charging and discharging and the electrode active material layer are also required.
However, in the polymer binders described in Patent Documents 1 and 2, the adhesion between the current collector after charging and discharging and the electrode active material layer is reduced, or the cycle characteristics of the resulting secondary battery, particularly at high temperatures, are reduced. There has been a problem that cycle characteristics and low-temperature output characteristics deteriorate, and further improvement has been desired.
Therefore, the present invention is excellent in adhesion between a current collector after charging and discharging and an electrode active material layer, and can be used for secondary battery negative electrodes that can contribute to improvement of cycle characteristics and low-temperature output characteristics of secondary batteries at high temperatures. An object is to provide a binder composition.
(1)バインダー及びプロパルギル基含有化合物を含有し、前記プロパルギル基含有化合物の含有量が、前記バインダー100質量部に対して0.1~20質量部である、二次電池負極用バインダー組成物。 That is, the gist of the present invention aimed at solving the above problems is as follows.
(1) A binder composition for a secondary battery negative electrode, comprising a binder and a propargyl group-containing compound, wherein the content of the propargyl group-containing compound is 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder.
本発明の二次電池負極用バインダー組成物は、バインダーと、プロパルギル基含有化合物とを含有する。 (1) Secondary battery negative electrode binder composition The secondary battery negative electrode binder composition of the present invention contains a binder and a propargyl group-containing compound.
本発明で使用されるバインダーは、特に限定はされず、フッ素系重合体、ジエン系重合体、ニトリル系重合体等の従来より負極活物質層のバインダーとして用いられてきた種々の高分子化合物が用いられる。これらの中でも、水系での合成が容易であり、簡便に水系ラテックスの形態で得られる高分子化合物が好ましい。このような高分子化合物としては、エチレン性不飽和酸単量体単位、好ましくはエチレン性不飽和カルボン酸単量体単位を含む高分子化合物が挙げられる。 (binder)
The binder used in the present invention is not particularly limited, and various polymer compounds that have been conventionally used as binders for negative electrode active material layers such as fluoropolymers, diene polymers, and nitrile polymers can be used. Used. Among these, a polymer compound that can be easily synthesized in an aqueous system and easily obtained in the form of an aqueous latex is preferable. Examples of such a polymer compound include a polymer compound containing an ethylenically unsaturated acid monomer unit, preferably an ethylenically unsaturated carboxylic acid monomer unit.
本発明の二次電池負極用バインダー組成物には、上記のバインダー100質量部(固形分換算)に対し、特定量のプロパルギル基含有化合物が含まれる。何ら理論的に制限されるものではないが、本発明の二次電池負極用バインダー組成物によれば、特定量のプロパルギル基含有化合物を含有することで、負極活物質と接触した際に、プロパルギル基含有化合物が、負極活物質の活性点近傍でSEI被膜を形成すると考えられる。SEI被膜によって、電解液の成分が活性点に接触することが防止されるため、電池内での電解液の分解が抑制される。その結果、電解液の分解による電解液粘度の上昇と二次電池の内部抵抗の上昇とが抑制されるため、二次電池の高温保存特性、高温サイクル特性、低温出力特性が向上する。また、電解液成分の分解物による負極活物質層の膨潤が防止され、ピール強度が維持され、高温サイクル特性及び低温出力特性をさらに向上できる。 (Propargyl group-containing compound)
The binder composition for a secondary battery negative electrode of the present invention contains a specific amount of a propargyl group-containing compound with respect to 100 parts by mass (in terms of solid content) of the binder. Although not theoretically limited at all, according to the binder composition for a negative electrode of a secondary battery of the present invention, when containing a specific amount of a propargyl group-containing compound, propargyl is brought into contact with the negative electrode active material. It is considered that the group-containing compound forms an SEI film in the vicinity of the active point of the negative electrode active material. The SEI coating prevents the components of the electrolytic solution from coming into contact with the active points, so that the decomposition of the electrolytic solution in the battery is suppressed. As a result, the increase in the electrolyte viscosity due to the decomposition of the electrolyte and the increase in the internal resistance of the secondary battery are suppressed, so that the high-temperature storage characteristics, the high-temperature cycle characteristics, and the low-temperature output characteristics of the secondary battery are improved. Further, swelling of the negative electrode active material layer due to the decomposition product of the electrolyte component is prevented, the peel strength is maintained, and the high temperature cycle characteristics and the low temperature output characteristics can be further improved.
ジプロパルギルカーボネート等のジプロパルギル基含有化合物があげられる。 Specific examples of the propargyl group-containing compound include monopropargyl group-containing compounds such as propargyl benzenesulfonate, propargyl acrylate, propargyl methacrylate, and propargyl acetate;
Examples include dipropargyl group-containing compounds such as dipropargyl carbonate.
本発明の二次電池負極用バインダー組成物には、バインダーおよびプロパルギル基含有化合物に加え、これら成分を分散するための分散媒が含まれていてもよい。分散媒は、水、有機溶媒の何れであってもよく、バインダー組成物の分散安定性を損なわない範囲であれば、分散媒として水に親水性の溶媒を混合してもよい。親水性の溶媒としては、メタノール、エタノール、N-メチルピロリドンなどがあげられ、水に対して5質量%以下であることが好ましい。また、後述するバインダー調製時の反応溶媒をそのまま分散媒としてもよく、バインダー調製後に溶媒置換してもよい。 (Other ingredients)
The binder composition for secondary battery negative electrode of the present invention may contain a dispersion medium for dispersing these components in addition to the binder and the propargyl group-containing compound. The dispersion medium may be either water or an organic solvent. As long as the dispersion stability of the binder composition is not impaired, a hydrophilic solvent may be mixed with water as the dispersion medium. Examples of the hydrophilic solvent include methanol, ethanol, N-methylpyrrolidone and the like, and it is preferably 5% by mass or less based on water. In addition, a reaction solvent at the time of preparing the binder described later may be used as a dispersion medium as it is, or the solvent may be replaced after preparing the binder.
本発明の二次電池負極用バインダー組成物を製造する方法としては、上記単量体を含む単量体組成物を、水系溶媒中で重合してバインダーを含む水分散液(結着力を有する重合体粒子であるバインダーが水系溶媒に溶解又は分散された溶液又は分散液)を得、バインダーを含む水分散液に特定量のプロパルギル基含有化合物及びその他の任意成分を添加・混合する方法が挙げられる。ただし、バインダー組成物の製造方法がこれに限定されることはなく、たとえば、単量体組成物にプロパルギル基含有化合物、老化防止剤あるいは防腐剤等を予め配合し、その後に重合を行ってもよい。また、重合中あるいは重合後の任意の段階でこれらをバインダー組成物に配合してもよい。 (Method for producing binder composition for secondary battery negative electrode)
As a method for producing a binder composition for a secondary battery negative electrode of the present invention, a monomer composition containing the above monomer is polymerized in an aqueous solvent to prepare an aqueous dispersion containing a binder (a binder having a binding force). A solution or dispersion in which a binder as a coalesced particle is dissolved or dispersed in an aqueous solvent), and a specific amount of a propargyl group-containing compound and other optional components are added to and mixed with an aqueous dispersion containing the binder. . However, the method for producing the binder composition is not limited to this. For example, a propargyl group-containing compound, an anti-aging agent, or an antiseptic may be blended in advance in the monomer composition, and then polymerization may be performed. Good. Moreover, you may mix | blend these with a binder composition in the arbitrary steps during superposition | polymerization or after superposition | polymerization.
本発明の二次電池負極用スラリー組成物は、上記二次電池負極用バインダー組成物及び負極活物質を含有してなる。以下においては、本発明の二次電池負極用スラリー組成物を、リチウムイオン二次電池負極用スラリー組成物として用いる態様について説明する。 (2) Slurry composition for secondary battery negative electrode The secondary battery negative electrode slurry composition of the present invention comprises the above secondary battery negative electrode binder composition and a negative electrode active material. Below, the aspect which uses the slurry composition for secondary battery negative electrodes of this invention as a slurry composition for lithium ion secondary battery negative electrodes is demonstrated.
本発明に用いる負極活物質は、二次電池用負極内で電子の受け渡しをする物質である。 (Negative electrode active material)
The negative electrode active material used in the present invention is a material that transfers electrons in the negative electrode for a secondary battery.
これら炭素系活物質の中でも黒鉛質材料が好ましい。 Examples of the graphite material include natural graphite and artificial graphite. Examples of artificial graphite include artificial graphite heat-treated at 2800 ° C or higher, graphitized MCMB heat-treated MCMB at 2000 ° C or higher, and graphitized mesophase pitch carbon fiber heat-treated at 2000 ° C or higher. It is done.
Among these carbon-based active materials, a graphite material is preferable.
本発明では、スラリーの分散媒として水を用いることが好ましい。本発明においては、バインダー組成物の分散安定性を損なわない範囲であれば、分散媒として水に親水性の溶媒を混ぜたものを使用してもよい。親水性の溶媒としては、メタノール、エタノール、N-メチルピロリドンなどがあげられ、水に対して5質量%以下であることが好ましい。 (Dispersion medium)
In the present invention, water is preferably used as a dispersion medium for the slurry. In the present invention, as long as the dispersion stability of the binder composition is not impaired, a mixture of water and a hydrophilic solvent may be used as a dispersion medium. Examples of the hydrophilic solvent include methanol, ethanol, N-methylpyrrolidone and the like, and it is preferably 5% by mass or less based on water.
本発明の二次電池負極用スラリー組成物においては、導電剤を含有することが好ましい。導電剤としては、アセチレンブラック、ケッチェンブラック、カーボンブラック、グラファイト、気相成長カーボン繊維、およびカーボンナノチューブ等の導電性カーボンを使用することができる。導電剤を含有することにより、負極活物質同士の電気的接触を向上させることができ、二次電池に用いる場合に放電レート特性を改善することができる。スラリー組成物における導電剤の含有量は、負極活物質100質量部に対して、好ましくは1~20質量部、より好ましくは1~10質量部である。 (Conductive agent)
In the slurry composition for secondary battery negative electrodes of this invention, it is preferable to contain a electrically conductive agent. As the conductive agent, conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube can be used. By containing a conductive agent, the electrical contact between the negative electrode active materials can be improved, and the discharge rate characteristics can be improved when used in a secondary battery. The content of the conductive agent in the slurry composition is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material.
本発明の二次電池負極用スラリー組成物においては、増粘剤を含有することが好ましい。増粘剤としては、カルボキシメチルセルロース、メチルセルロース、ヒドロキシプロピルセルロースなどのセルロース系ポリマーおよびこれらのアンモニウム塩並びにアルカリ金属塩;
(変性)ポリ(メタ)アクリル酸およびこれらのアンモニウム塩並びにアルカリ金属塩;
(変性)ポリビニルアルコール、アクリル酸又はアクリル酸塩とビニルアルコールとの共重合体、無水マレイン酸又はマレイン酸もしくはフマル酸とビニルアルコールとの共重合体などのポリビニルアルコール類;
ポリエチレングリコール、ポリエチレンオキシド、ポリビニルピロリドン、変性ポリアクリル酸、酸化スターチ、リン酸スターチ、カゼイン、各種変性デンプンなどが挙げられる。 (Thickener)
In the slurry composition for secondary battery negative electrodes of this invention, it is preferable to contain a thickener. Examples of thickeners include cellulose polymers such as carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, and ammonium salts and alkali metal salts thereof;
(Modified) poly (meth) acrylic acid and ammonium salts and alkali metal salts thereof;
(Modified) Polyvinyl alcohols such as polyvinyl alcohol, a copolymer of acrylic acid or acrylate and vinyl alcohol, maleic anhydride or a copolymer of maleic acid or fumaric acid and vinyl alcohol;
Examples include polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, modified polyacrylic acid, oxidized starch, phosphate starch, casein, and various modified starches.
本発明の二次電池負極用スラリー組成物は、上記バインダー組成物に加え、水溶性ポリマーを含むことができる。水溶性ポリマーとしては、エチレン性不飽和カルボン酸単量体単位20~60質量%、(メタ)アクリル酸エステル単量体単位20~80質量%およびこれらと共重合可能な他の単量体単位0~20質量%からなる水溶性ポリマーが好ましい。二次電池負極用スラリー組成物に上記水溶性ポリマーを含ませることで、二次電池用負極の密着性及び耐久性が向上するため、ピール強度を向上させることができる。本発明における水溶性ポリマーとは、pH12において、1%水溶液粘度が0.1~100000mPa・sである重合体をいう。 (Water-soluble polymer)
The slurry composition for a secondary battery negative electrode of the present invention can contain a water-soluble polymer in addition to the binder composition. Examples of the water-soluble polymer include ethylenically unsaturated carboxylic acid monomer units of 20 to 60% by mass, (meth) acrylic acid ester monomer units of 20 to 80% by mass and other monomer units copolymerizable therewith. A water-soluble polymer consisting of 0 to 20% by mass is preferred. By including the water-soluble polymer in the slurry composition for a secondary battery negative electrode, the adhesion and durability of the secondary battery negative electrode are improved, so that the peel strength can be improved. The water-soluble polymer in the present invention refers to a polymer having a 1% aqueous solution viscosity of 0.1 to 100,000 mPa · s at pH 12.
二次電池負極用スラリー組成物は、上記バインダー組成物、負極活物質および必要に応じ用いられる導電剤等を混合して得られる。 (Production of slurry composition for secondary battery negative electrode)
The slurry composition for a secondary battery negative electrode is obtained by mixing the binder composition, the negative electrode active material, and a conductive agent used as necessary.
本発明の二次電池用負極は、上記のバインダー組成物および負極活物質を含んでなり、具体的には、本発明の二次電池負極用スラリー組成物を集電体上に塗布、乾燥して得られる。 (3) Negative electrode for secondary battery The negative electrode for secondary battery of the present invention comprises the binder composition and the negative electrode active material, and specifically, the slurry composition for secondary battery negative electrode of the present invention is collected. It is obtained by applying and drying on an electric body.
本発明の二次電池用負極の製造方法は、特に限定されないが、例えば、上記スラリー組成物を集電体の少なくとも片面、好ましくは両面に塗布、乾燥し、負極活物質層を形成する方法が挙げられる。 (Method for producing secondary battery negative electrode)
The method for producing the negative electrode for secondary battery of the present invention is not particularly limited. For example, a method of forming the negative electrode active material layer by applying and drying the slurry composition on at least one surface, preferably both surfaces of the current collector. Can be mentioned.
本発明で用いる集電体は、電気導電性を有しかつ電気化学的に耐久性のある材料であれば特に制限されないが、耐熱性を有するため金属材料が好ましく、例えば、鉄、銅、アルミニウム、ニッケル、ステンレス鋼、チタン、タンタル、金、白金などが挙げられる。中でも、二次電池用負極に用いる集電体としては銅が特に好ましい。集電体の形状は特に制限されないが、厚さ0.001~0.5mm程度のシート状のものが好ましい。集電体は、負極活物質層との接着強度を高めるため、予め粗面化処理して使用するのが好ましい。粗面化方法としては、機械的研磨法、電解研磨法、化学研磨法などが挙げられる。機械的研磨法においては、研磨剤粒子を固着した研磨布紙、砥石、エメリバフ、鋼線などを備えたワイヤーブラシ等が使用される。また、負極活物質層との接着強度や導電性を高めるために、集電体表面に中間層を形成してもよい。 (Current collector)
The current collector used in the present invention is not particularly limited as long as it is an electrically conductive and electrochemically durable material. However, a metal material is preferable because it has heat resistance. For example, iron, copper, aluminum Nickel, stainless steel, titanium, tantalum, gold, platinum and the like. Among these, copper is particularly preferable as the current collector used for the negative electrode for the secondary battery. The shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 to 0.5 mm is preferable. In order to increase the adhesive strength with the negative electrode active material layer, the current collector is preferably used after roughening in advance. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. In the mechanical polishing method, an abrasive cloth paper with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used. Further, an intermediate layer may be formed on the current collector surface in order to increase the adhesive strength and conductivity with the negative electrode active material layer.
本発明の二次電池は、正極、負極、セパレーター及び電解液を備えてなる二次電池であって、負極が、上記二次電池用負極である。 (4) Secondary battery The secondary battery of the present invention is a secondary battery comprising a positive electrode, a negative electrode, a separator and an electrolytic solution, and the negative electrode is the negative electrode for a secondary battery.
正極は、正極活物質及び二次電池正極用バインダー組成物を含む正極活物質層が、集電体上に積層されてなる。 (Positive electrode)
The positive electrode is formed by laminating a positive electrode active material layer containing a positive electrode active material and a secondary battery positive electrode binder composition on a current collector.
正極活物質は、リチウムイオンをドープ及び脱ドープ可能な活物質が用いられ、無機化合物からなるものと有機化合物からなるものとに大別される。 (Positive electrode active material)
As the positive electrode active material, an active material that can be doped and dedoped with lithium ions is used, and the positive electrode active material is roughly classified into an inorganic compound and an organic compound.
二次電池正極用バインダー組成物としては、特に制限されず公知のものを用いることができる。例えば、ポリエチレン、ポリテトラフルオロエチレン(PTFE)、ポリフッ化ビニリデン(PVDF)、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体(FEP)、ポリアクリル酸誘導体、ポリアクリロニトリル誘導体などの樹脂や、アクリル系軟質重合体、ジエン系軟質重合体、オレフィン系軟質重合体、ビニル系軟質重合体等の軟質重合体を用いることができる。これらは単独で使用しても、これらを2種以上併用してもよい。 (Binder composition for secondary battery positive electrode)
The binder composition for the secondary battery positive electrode is not particularly limited and a known one can be used. For example, resins such as polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, polyacrylonitrile derivatives, acrylic soft heavy A soft polymer such as a polymer, a diene soft polymer, an olefin soft polymer, or a vinyl soft polymer can be used. These may be used alone or in combination of two or more.
正極は、前述の二次電池用負極と同様に製造することができる。 The thickness of the positive electrode active material layer is usually 5 to 300 μm, preferably 10 to 250 μm. When the thickness of the positive electrode active material layer is in the above range, both load characteristics and energy density are high.
The positive electrode can be produced in the same manner as the above-described negative electrode for secondary battery.
セパレーターは気孔部を有する多孔性基材であって、使用可能なセパレーターとしては、(a)気孔部を有する多孔性セパレーター、(b)片面または両面に高分子コート層が形成された多孔性セパレーター、または(c)無機セラミック粉末を含む多孔質の樹脂コート層が形成された多孔性セパレーターが挙げられる。これらの非制限的な例としては、ポリプロピレン系、ポリエチレン系、ポリオレフィン系、またはアラミド系多孔性セパレーター、ポリビニリデンフルオリド、ポリエチレンオキシド、ポリアクリロニトリルまたはポリビニリデンフルオリドヘキサフルオロプロピレン共重合体などの高分子フィルム、さらにコート層を有するセパレーター、または無機フィラー、無機フィラー用分散剤からなる多孔膜層がコートされたセパレーターなどがある。 (separator)
The separator is a porous substrate having pores, and usable separators include (a) a porous separator having pores, and (b) a porous separator in which a polymer coat layer is formed on one or both sides. Or (c) a porous separator in which a porous resin coat layer containing an inorganic ceramic powder is formed. Non-limiting examples of these include high-grade polypropylene, polyethylene, polyolefin, or aramid porous separators, polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride hexafluoropropylene copolymers. Examples include a separator having a molecular film and a coat layer, or a separator coated with a porous film layer made of an inorganic filler or a dispersant for inorganic filler.
本発明に用いられる電解液は、特に限定されないが、例えば、非水系の溶媒に支持電解質としてリチウム塩を溶解したものが使用できる。リチウム塩としては、例えば、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLiなどのリチウム塩が挙げられる。特に溶媒に溶けやすく高い解離度を示すLiPF6、LiClO4、CF3SO3Liは好適に用いられる。これらは、単独、または2種以上を混合して用いることができる。支持電解質の量は、電解液に対して、通常1質量%以上、好ましくは5質量%以上、また通常は30質量%以下、好ましくは20質量%以下である。支持電解質の量が少なすぎても多すぎてもイオン導電度は低下し電池の充電特性、放電特性が低下する。 (Electrolyte)
The electrolytic solution used in the present invention is not particularly limited. For example, a solution obtained by dissolving a lithium salt as a supporting electrolyte in a non-aqueous solvent can be used. Examples of the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and other lithium salts. In particular, LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferably used. These can be used alone or in admixture of two or more. The amount of the supporting electrolyte is usually 1% by mass or more, preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, with respect to the electrolytic solution. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity is lowered and the battery charging and discharging characteristics are lowered.
本発明の二次電池の製造方法は、特に限定されない。例えば、上述した負極と正極とをセパレーターを介して重ね合わせ、これを電池形状に応じて巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口する。さらに必要に応じてエキスパンドメタルや、ヒューズ、PTC素子などの過電流防止素子、リード板などを入れ、電池内部の圧力上昇、過充放電の防止をすることもできる。電池の形状は、ラミネートセル型、コイン型、ボタン型、シート型、円筒型、角形、扁平型などいずれであってもよい。 (Method for manufacturing secondary battery)
The manufacturing method of the secondary battery of the present invention is not particularly limited. For example, the above-described negative electrode and positive electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery and placed in the battery container, and the electrolytic solution is injected into the battery container and sealed. Further, if necessary, an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate and the like can be inserted to prevent an increase in pressure inside the battery and overcharge / discharge. The shape of the battery may be any of a laminated cell type, a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, and the like.
実施例および比較例で製造する二次電池負極用バインダー組成物について、スラリー調製時の粘度への影響を以下のように評価した。
バインダー組成物を添加する前のスラリー粘度η0(mPa・s)とバインダー組成物を添加した後のスラリー粘度η1(mPa・s)を、25℃の環境下で、B型粘度計(60rpm、ローターNo.4)にて測定し、バインダー添加前後のスラリー粘度変化η1/η0×100(%)を算出し、分散安定性の評価指針とした。この数値が小さいほど、分散安定性に優れていることを示す。 <Dispersion stability of slurry>
About the binder composition for secondary battery negative electrodes manufactured by an Example and a comparative example, the influence on the viscosity at the time of slurry preparation was evaluated as follows.
The slurry viscosity η0 (mPa · s) before adding the binder composition and the slurry viscosity η1 (mPa · s) after adding the binder composition were measured in a B-type viscometer (60 rpm, rotor) in an environment of 25 ° C. No. 4) was measured and the change in slurry viscosity η1 / η0 × 100 (%) before and after addition of the binder was calculated and used as an evaluation guideline for dispersion stability. The smaller this value, the better the dispersion stability.
実施例および比較例で製造する二次電池用負極を長さ100mm、幅10mmの長方形に切り出して試験片とし、負極活物質層面を下にして負極活物質層表面にセロハンテープ(JIS Z1522 2009に規定されるもの)を貼り付け、集電体の一端を垂直方向に引張り速度50mm/分で引張って剥がしたときの応力を測定した(なお、セロハンテープは試験台に固定されている。)。測定を3回行い、その平均値を求めてこれをピール強度とした。ピール強度が大きいほど負極活物質層の集電体への結着力が大きい、すなわち密着強度が大きいことを示す。 <Adhesion strength: peel strength of negative electrode active material layer>
The negative electrode for a secondary battery manufactured in Examples and Comparative Examples was cut into a rectangle having a length of 100 mm and a width of 10 mm to obtain a test piece, and a cellophane tape (in JIS Z1522 2009) was formed on the surface of the negative electrode active material layer with the negative electrode active material layer side down. Then, stress was measured when one end of the current collector was pulled in a vertical direction at a pulling speed of 50 mm / min and peeled off (the cellophane tape was fixed to a test stand). The measurement was performed three times, and the average value was obtained and used as the peel strength. The higher the peel strength, the greater the binding force of the negative electrode active material layer to the current collector, that is, the higher the adhesion strength.
実施例および比較例で製造するリチウムイオン二次電池用負極を用いて、ラミネート型セルのリチウムイオン二次電池を作製し、25℃の環境下で24時間静置した。その後に、25℃の環境下で、0.1Cの定電流法によって、4.2Vまで充電し、3.0Vまで放電する充放電の操作を行い、初期容量C0を測定した。さらに、25℃の環境下で、4.2Vに充電し、60℃、7日間保存した後、0.1Cの定電流法によって、4.2Vまで充電し、3.0Vまで放電する充放電の操作を行い、高温保存後の容量C1を測定した。高温保存特性は、ΔC=C1/C0×100(%)で示す容量変化率にて評価した。この値が高いほど高温保存特性に優れることを示す。 <Durability: High temperature storage characteristics>
Using a negative electrode for a lithium ion secondary battery produced in the examples and comparative examples, a lithium ion secondary battery of a laminate type cell was prepared and left to stand in an environment of 25 ° C. for 24 hours. After that, under an environment of 25 ° C., charge / discharge operation of charging to 4.2 V and discharging to 3.0 V was performed by a constant current method of 0.1 C, and an initial capacity C0 was measured. Furthermore, after charging to 4.2 V in an environment of 25 ° C., storing at 60 ° C. for 7 days, charging to 4.2 V and discharging to 3.0 V by a constant current method of 0.1 C The operation was performed, and the capacity C1 after high temperature storage was measured. The high-temperature storage characteristics were evaluated by the capacity change rate represented by ΔC = C1 / C0 × 100 (%). Higher values indicate better high temperature storage characteristics.
実施例および比較例で製造するリチウムイオン二次電池用負極を用いて、ラミネート型セルのリチウムイオン二次電池を作製し、25℃の環境下で24時間静置した。その後に、25℃の環境下で、0.1Cの定電流法によって、4.2Vまで充電し、3.0Vまで放電する充放電の操作を行い、初期容量C0を測定した。さらに、60℃環境下で、0.1Cの定電流法によって、4.2Vまで充電し、3.0Vまで放電する充放電を繰り返し、100サイクル後の容量C2を測定した。高温サイクル特性は、ΔC=C2/C0×100(%)で示す容量変化率にて評価した。この値が高いほど高温サイクル特性に優れることを示す。 <Durability: High-temperature cycle characteristics>
Using a negative electrode for a lithium ion secondary battery produced in the examples and comparative examples, a lithium ion secondary battery of a laminate type cell was prepared and left to stand in an environment of 25 ° C. for 24 hours. After that, under an environment of 25 ° C., charge / discharge operation of charging to 4.2 V and discharging to 3.0 V was performed by a constant current method of 0.1 C, and an initial capacity C0 was measured. Furthermore, in a 60 ° C. environment, charging / discharging of charging to 4.2 V and discharging to 3.0 V was repeated by a constant current method of 0.1 C, and the capacity C2 after 100 cycles was measured. The high-temperature cycle characteristics were evaluated by a capacity change rate represented by ΔC = C2 / C0 × 100 (%). Higher values indicate better high temperature cycle characteristics.
上記の高温サイクル特性試験後の負極について、極板の膨らみ率を下記の式から算出した。この値が低いほど耐久性が高いことを意味している。
数1
極板の膨らみ率=|試験前の負極活物質層の厚み-試験後の負極活物質層の厚み|/試験前の負極活物質層の厚み×100 <Durability: Swelling rate of electrode plate after high-temperature cycle characteristics test>
About the negative electrode after said high temperature cycling characteristic test, the swelling rate of the electrode plate was computed from the following formula. The lower the value, the higher the durability.
Number 1
Swelling rate of electrode plate = | thickness of negative electrode active material layer before test−thickness of negative electrode active material layer after test | / thickness of negative electrode active material layer before test × 100
実施例および比較例で製造するリチウムイオン二次電池用負極を用いて、ラミネート型セルのリチウムイオン二次電池を作製し、25℃の環境下で、24時間静置した後に、0.1Cの定電流法により、4.2Vまで充電し、3.0Vまで放電する充放電の操作を行った。その後、25℃の環境下で、0.1Cの定電流法により50%充電状態(SOC50%)まで充電し、電圧V0(V)を測定した。次いで、-25℃の環境下で、電圧V0(V)から放電レート0.1Cで放電し、放電10秒後の電圧V10を測定した。低温出力特性は、ΔV=V0-V10(V)で示す電圧変化にて評価し、この値が小さいほど低温出力特性に優れることを示す。 <Low temperature output characteristics>
Using a negative electrode for a lithium ion secondary battery produced in Examples and Comparative Examples, a lithium ion secondary battery of a laminate type cell was prepared and left at 25 ° C. for 24 hours. The charging / discharging operation of charging to 4.2V and discharging to 3.0V was performed by the constant current method. Thereafter, the battery was charged to a 50% charged state (SOC 50%) by a constant current method of 0.1 C under an environment of 25 ° C., and a voltage V 0 (V) was measured. Next, the battery was discharged from the voltage V 0 (V) at a discharge rate of 0.1 C in an environment of −25 ° C., and the voltage V 10 after 10 seconds of discharge was measured. The low temperature output characteristic is evaluated by a voltage change represented by ΔV = V 0 −V 10 (V), and the smaller this value is, the better the low temperature output characteristic is.
(バインダー組成物の製造)
攪拌機付き5MPa耐圧容器に、1,3-ブタジエン33部、イタコン酸4部、スチレン63部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム4部、イオン交換水150部及び重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、50℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、バインダーを含む水系分散液を得た。なお、バインダーのガラス転移温度は10℃であった。 Example 1
(Manufacture of binder composition)
In a 5 MPa pressure vessel equipped with a stirrer, 33 parts of 1,3-butadiene, 4 parts of itaconic acid, 63 parts of styrene, 4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water, and potassium persulfate 0.5 as a polymerization initiator A portion was added and stirred sufficiently, and then heated to 50 ° C. to initiate polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain an aqueous dispersion containing a binder. The glass transition temperature of the binder was 10 ° C.
ディスパー付きのプラネタリーミキサーに、負極活物質としてBET比表面積5m2/gの天然黒鉛(平均粒子径:24.5μm)を100部、カルボキシメチルセルロース(日本製紙ケミカル社製、MAC350HC)1%水溶液を固形分相当量で1部をそれぞれ加え、イオン交換水で固形分濃度55%に調整した後、25℃で60分混合した。次に、イオン交換水で固形分濃度52%に調整した後、さらに25℃で15分混合し混合液を得た。 (Production of slurry composition for secondary battery negative electrode)
In a planetary mixer with a disper, 100 parts of natural graphite (average particle size: 24.5 μm) having a BET specific surface area of 5 m 2 / g as a negative electrode active material and a 1% aqueous solution of carboxymethyl cellulose (manufactured by Nippon Paper Chemical Co., Ltd., MAC350HC) 1 part was added in an amount corresponding to the solid content, adjusted to a solid content concentration of 55% with ion-exchanged water, and then mixed at 25 ° C. for 60 minutes. Next, after adjusting the solid content concentration to 52% with ion-exchanged water, the mixture was further mixed at 25 ° C. for 15 minutes to obtain a mixed solution.
上記二次電池負極スラリー組成物を、コンマコーターで、厚さ20μmの銅箔の上に、乾燥後の膜厚が150μm程度になるように塗布し、60℃で1分間加熱処理し、次いで120℃で1分間加熱処理して電極原反を得た。この電極原反をロールプレスで圧延して負極活物質層の厚みが80μmの二次電池用負極を得た。 (Manufacture of batteries)
The secondary battery negative electrode slurry composition was applied on a copper foil having a thickness of 20 μm with a comma coater so that the film thickness after drying was about 150 μm, heat-treated at 60 ° C. for 1 minute, and then 120 An electrode raw material was obtained by heat treatment at 0 ° C. for 1 minute. The raw electrode was rolled with a roll press to obtain a negative electrode for a secondary battery having a negative electrode active material layer thickness of 80 μm.
ベンゼンスルホン酸プロパルギルの添加量を、バインダー固形分100部に対し7部とした以外は、実施例1と同様とした。結果を表1に示す。 (Example 2)
The same procedure as in Example 1 was performed except that the amount of propargyl benzenesulfonate was 7 parts with respect to 100 parts of binder solid content. The results are shown in Table 1.
ベンゼンスルホン酸プロパルギルの添加量を、バインダー固形分100部に対し、15部とした以外は、実施例1と同様とした。結果を表1に示す。 (Example 3)
The amount of propargyl benzenesulfonate added was the same as in Example 1 except that the amount was 15 parts with respect to 100 parts of binder solid content. The results are shown in Table 1.
プロパルギル基含有化合物として、ベンゼンスルホン酸プロパルギルに代えてアクリル酸プロパルギルを用いた以外は、実施例1と同様とした。結果を表1に示す。 (Example 4)
The same procedure as in Example 1 was conducted except that propargyl acrylate was used instead of propargyl benzenesulfonate as the propargyl group-containing compound. The results are shown in Table 1.
プロパルギル基含有化合物として、ベンゼンスルホン酸プロパルギルに代えてメタアクリル酸プロパルギルを用いた以外は、実施例1と同様とした。結果を表1に示す。 (Example 5)
The same procedure as in Example 1 was conducted except that propargyl methacrylate was used instead of propargyl benzenesulfonate as the propargyl group-containing compound. The results are shown in Table 1.
バインダー調製時のコモノマーとして、イタコン酸に代えてメタアクリル酸を用いた以外は、実施例1と同様とした。結果を表1に示す。 (Example 6)
The same procedure as in Example 1 was performed except that methacrylic acid was used in place of itaconic acid as a comonomer at the time of preparing the binder. The results are shown in Table 1.
負極活物質として、BET比表面積5m2/gの天然黒鉛(平均粒子径:24.5μm)に代えてBET比表面積8m2/gの天然黒鉛(平均粒子径:22μm)を用いた以外は、実施例1と同様とした。結果を表1に示す。 (Example 7)
As the negative electrode active material, natural graphite having a BET specific surface area of 8 m 2 / g (average particle diameter: 22 μm) was used instead of natural graphite having a BET specific surface area of 5 m 2 / g (average particle diameter: 24.5 μm). Same as Example 1. The results are shown in Table 1.
負極活物質として、BET比表面積5m2/gの天然黒鉛(平均粒子径:24.5μm)に代えてBET比表面積15m2/gの天然黒鉛(平均粒子径:15μm)を用いた以外は、実施例1と同様とした。結果を表1に示す。 (Example 8)
As the negative electrode active material, natural graphite having a BET specific surface area of 15 m 2 / g (average particle diameter: 15 μm) was used instead of natural graphite having a BET specific surface area of 5 m 2 / g (average particle diameter: 24.5 μm). Same as Example 1. The results are shown in Table 1.
負極活物質として、BET比表面積5m2/gの天然黒鉛(平均粒子径:24.5μm)に代えてBET比表面積5m2/gの天然黒鉛(平均粒子径:24.5μm)を80部およびBET比表面積6.5m2/gのSiOC(平均粒子径:10μm)を20部用いた以外は、実施例1と同様とした。なお、負極活物質のBET比表面積は、5.2m2/gであった。結果を表1に示す。 Example 9
As the negative electrode active material, natural graphite (average particle size: 24.5μm) of a BET specific surface area of 5 m 2 / g natural graphite (average particle size: 24.5μm) of a BET specific surface area of 5 m 2 / g instead of 80 parts and The procedure was the same as Example 1 except that 20 parts of SiOC (average particle size: 10 μm) having a BET specific surface area of 6.5 m 2 / g was used. The BET specific surface area of the negative electrode active material was 5.2 m 2 / g. The results are shown in Table 1.
負極活物質として、BET比表面積5m2/gの天然黒鉛(平均粒子径:24.5μm)に代えてBET比表面積5.0m2/gの天然黒鉛(平均粒子径:24.5μm)を50部およびBET比表面積6.5m2/gのSiOC(平均粒子径:10μm)を50部用いた以外は、実施例1と同様とした。なお、負極活物質のBET比表面積は、5.8m2/gであった。結果を表1に示す。 (Example 10)
As the negative electrode active material, natural graphite (average particle size: 24.5μm) of a BET specific surface area of 5 m 2 / g BET specific instead of surface area 5.0 m 2 / g natural graphite (average particle size: 24.5μm) 50 Parts and a BET specific surface area of 6.5 m 2 / g of SiOC (average particle size: 10 μm) were used in the same manner as in Example 1 except that 50 parts were used. The BET specific surface area of the negative electrode active material was 5.8 m 2 / g. The results are shown in Table 1.
プロパルギル基含有化合物として、ベンゼンスルホン酸プロパルギルに代えてジプロパルギルカーボネートを用いた以外は、実施例1と同様とした。結果を表1に示す。 (Example 11)
The same procedure as in Example 1 was performed except that dipropargyl carbonate was used as the propargyl group-containing compound instead of propargyl benzenesulfonate. The results are shown in Table 1.
バインダー調製時のコモノマーとして、イタコン酸を用いなかった以外は、実施例1と同様とした。なお、バインダーのガラス転移温度は7℃であった。結果を表1に示す。 Example 12
The same procedure as in Example 1 was conducted except that itaconic acid was not used as a comonomer for preparing the binder. The glass transition temperature of the binder was 7 ° C. The results are shown in Table 1.
バインダー組成物にプロパルギル基含有化合物を配合しなかった以外は、実施例1と同様とした。結果を表1に示す。 (Comparative Example 1)
The procedure was the same as Example 1 except that the propargyl group-containing compound was not blended in the binder composition. The results are shown in Table 1.
バインダー組成物にプロパルギル基含有化合物を配合しなかった以外は、実施例10と同様とした。結果を表1に示す。 (Comparative Example 2)
The procedure was the same as Example 10 except that the propargyl group-containing compound was not blended in the binder composition. The results are shown in Table 1.
ベンゼンスルホン酸プロパルギルの添加量を、バインダー固形分100部に対し、25部とした以外は、実施例1と同様とした。結果を表1に示す。 (Comparative Example 3)
The amount of propargyl benzenesulfonate added was the same as in Example 1 except that the amount was 25 parts with respect to 100 parts of binder solid content. The results are shown in Table 1.
ベンゼンスルホン酸プロパルギルに代えて2-オクチン酸メチルを用いた以外は、実施例1と同様とした。結果を表1に示す。 (Comparative Example 4)
Example 1 was repeated except that methyl 2-octanoate was used in place of propargyl benzenesulfonate. The results are shown in Table 1.
Claims (11)
- バインダー及びプロパルギル基含有化合物を含有し、前記プロパルギル基含有化合物の含有量が、前記バインダー100質量部に対して0.1~20質量部である、二次電池負極用バインダー組成物。 A binder composition for a secondary battery negative electrode containing a binder and a propargyl group-containing compound, wherein the content of the propargyl group-containing compound is 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder.
- 前記プロパルギル基含有化合物が、モノプロパルギル基含有化合物である請求項1に記載の二次電池負極用バインダー組成物。 The binder composition for a secondary battery negative electrode according to claim 1, wherein the propargyl group-containing compound is a monopropargyl group-containing compound.
- 前記バインダーが、エチレン性不飽和カルボン酸単量体単位を含む請求項1または2に記載の二次電池負極用バインダー組成物。 The binder composition for a secondary battery negative electrode according to claim 1 or 2, wherein the binder contains an ethylenically unsaturated carboxylic acid monomer unit.
- 前記バインダーのガラス転移温度が、-60℃~40℃である請求項1~3のいずれかに記載の二次電池負極用バインダー組成物。 4. The binder composition for a secondary battery negative electrode according to claim 1, wherein the binder has a glass transition temperature of −60 ° C. to 40 ° C.
- 請求項1~4のいずれかに記載の二次電池負極用バインダー組成物および負極活物質を含有してなる二次電池負極用スラリー組成物。 A secondary battery negative electrode slurry composition comprising the secondary battery negative electrode binder composition according to any one of claims 1 to 4 and a negative electrode active material.
- 前記負極活物質のBET比表面積が、3~20m2/gである請求項5に記載の二次電池負極用スラリー組成物。 The slurry composition for secondary battery negative electrode according to claim 5, wherein the negative electrode active material has a BET specific surface area of 3 to 20 m 2 / g.
- 請求項1~4のいずれかに記載の二次電池用負極バインダー組成物および負極活物質を含んでなる負極活物質層を集電体上に有する二次電池用負極。 A negative electrode for a secondary battery comprising a negative electrode active material layer comprising the negative electrode binder composition for a secondary battery according to any one of claims 1 to 4 and a negative electrode active material on a current collector.
- 前記負極活物質のBET比表面積が、3~20m2/gである請求項7に記載の二次電池用負極。 The negative electrode for a secondary battery according to claim 7, wherein the negative electrode active material has a BET specific surface area of 3 to 20 m 2 / g.
- 前記負極活物質が、炭素材料系活物質である請求項7または8に記載の二次電池用負極。 The negative electrode for a secondary battery according to claim 7 or 8, wherein the negative electrode active material is a carbon material-based active material.
- 正極、負極、電解液、並びにセパレーターを備えるリチウムイオン二次電池であって、前記負極が請求項7~9のいずれかに記載の二次電池用負極である二次電池。 A secondary battery comprising a positive electrode, a negative electrode, an electrolytic solution, and a separator, wherein the negative electrode is a negative electrode for a secondary battery according to any one of claims 7 to 9.
- 前記電解液が、ビニレンカーボネートを含む請求項10に記載の二次電池。 The secondary battery according to claim 10, wherein the electrolytic solution contains vinylene carbonate.
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JP2013522935A JP6115468B2 (en) | 2011-06-29 | 2012-06-28 | Secondary battery negative electrode binder composition, secondary battery negative electrode slurry composition, secondary battery negative electrode and secondary battery |
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CN109461884A (en) * | 2018-12-08 | 2019-03-12 | 广东维都利新能源有限公司 | A kind of lithium battery that can be worked at high temperature and save |
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CN113614975A (en) * | 2018-12-13 | 2021-11-05 | 株式会社Lg新能源 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
CN113614975B (en) * | 2018-12-13 | 2024-03-29 | 株式会社Lg新能源 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
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JPWO2013002322A1 (en) | 2015-02-23 |
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