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WO2012049967A1 - Mélange d'électrodes négatives pour batteries secondaires à électrolyte non aqueux, électrode négative pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux - Google Patents

Mélange d'électrodes négatives pour batteries secondaires à électrolyte non aqueux, électrode négative pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2012049967A1
WO2012049967A1 PCT/JP2011/072167 JP2011072167W WO2012049967A1 WO 2012049967 A1 WO2012049967 A1 WO 2012049967A1 JP 2011072167 W JP2011072167 W JP 2011072167W WO 2012049967 A1 WO2012049967 A1 WO 2012049967A1
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WIPO (PCT)
Prior art keywords
negative electrode
electrolyte secondary
functional group
sulfur
secondary battery
Prior art date
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PCT/JP2011/072167
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English (en)
Japanese (ja)
Inventor
勇樹 堺
圭介 佐藤
絵美 菅原
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Kureha Corp
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Kureha Corp
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Priority to CN201180048820.2A priority Critical patent/CN103155247B/zh
Priority to KR1020137011754A priority patent/KR101351206B1/ko
Priority to JP2012538621A priority patent/JP5877791B2/ja
Publication of WO2012049967A1 publication Critical patent/WO2012049967A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode mixture for a nonaqueous electrolyte secondary battery, a negative electrode for a nonaqueous electrolyte secondary battery, and a nonaqueous electrolyte secondary battery.
  • Non-aqueous electrolyte secondary batteries using lithium are mainly used as power sources for small electronic devices used in homes such as mobile phones, personal computers, and video camcorders as batteries that can obtain large energy with a small volume and weight. ing.
  • PVDF Polyvinylidene fluoride
  • Binder resin Binder resin
  • PVDF has excellent electrochemical stability, mechanical properties, slurry properties, and the like.
  • PVDF has weak adhesiveness with a copper foil as a current collector. Therefore, a method has been proposed in which a functional group such as a carboxyl group is introduced into PVDF to improve the adhesiveness with the copper foil (see, for example, Patent Documents 1 to 5).
  • the present invention has been made in view of the above-described problems of the prior art, and can be used when producing a negative electrode for a non-aqueous electrolyte secondary battery that has excellent peel strength between the mixture layer and the current collector.
  • An object is to provide a negative electrode mixture for a non-aqueous electrolyte secondary battery.
  • Another object of the present invention is to provide a negative electrode for a non-aqueous electrolyte secondary battery obtained by applying and drying the negative electrode mixture on a current collector.
  • the present invention provides a negative electrode for a nonaqueous electrolyte secondary battery, which is formed from a surface-treated current collector surface-treated with a specific compound and a negative electrode mixture, and has excellent peel strength between the mixture layer and the current collector. With the goal.
  • Another object is to provide a non-aqueous electrolyte secondary battery having the negative electrode.
  • the present inventors have produced a negative electrode for a nonaqueous electrolyte secondary battery containing a specific sulfur-containing organic compound when producing a negative electrode for a nonaqueous electrolyte secondary battery. It has been found that the above problems can be solved by using an agent, and the present invention has been completed. In addition, the present inventors have obtained a nonaqueous electrolyte secondary battery obtained by applying and drying a negative electrode mixture for a nonaqueous electrolyte secondary battery on a surface-treated current collector that has been surface-treated with a specific sulfur-containing organic compound. The negative electrode for use was discovered together that the said subject can be solved.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains a vinylidene fluoride polymer having an acidic functional group, a sulfur-containing organic compound, an electrode active material, and an organic solvent, and the sulfur-containing organic compound is And having at least one functional group containing no sulfur atom.
  • the sulfur-containing organic compound is a sulfur-containing organic compound in which a carbon atom to which a sulfur atom is bonded, or an ⁇ -position or ⁇ -position carbon atom of a carbon atom to which a sulfur atom is bonded, and the functional group are bonded. Is preferred.
  • the sulfur-containing organic compound preferably contains at least one functional group selected from a carbonyl group, a hydroxyl group and an amino group as the functional group.
  • the sulfur-containing organic compound is preferably at least one sulfur-containing organic compound selected from thiourea analogs and thiomalic acid analogs.
  • the acidic functional group of the vinylidene fluoride-containing polymer having an acidic functional group is selected from a carboxyl group (—CO 2 H), a sulfo group (—SO 3 H), and a phosphonic acid group (—PO 3 H 2 ). It is preferably at least one kind of acidic functional group, and more preferably a carboxyl group.
  • a R A 1650-1800 / A 3000-3100 (1)
  • a 1650-1800 is the absorbance of absorption band derived from the carbonyl group is observed in the range of 1650 ⁇ 1800cm -1
  • a 3000-3100 is detected in the range of 3000 ⁇ 3100 cm -1
  • the vinylidene fluoride-based polymer having an acidic functional group is a copolymer of vinylidene fluoride and a monomer having an acidic functional group, and a structural unit derived from a monomer having an acidic functional group in the copolymer.
  • the random rate is preferably 40% or more.
  • the sulfur-containing organic compound is contained in an amount of 0.01 to 5% by mass per 100% by mass of the vinylidene fluoride polymer having an acidic functional group.
  • the electrode active material is preferably 70 to 99.9 parts by mass per 100 parts by mass in total of the electrode active material and the vinylidene fluoride-based polymer having an acidic functional group.
  • the negative electrode for a nonaqueous electrolyte secondary battery of the present invention (first aspect) is obtained by applying and drying the negative electrode mixture for a nonaqueous electrolyte secondary battery on a current collector.
  • the negative electrode for a nonaqueous electrolyte secondary battery of the present invention (second embodiment) is a fluoridation having an acidic functional group on a surface-treated current collector obtained by surface-treating a current collector with a sulfur-containing organic compound.
  • the sulfur-containing organic compound is a sulfur-containing organic compound in which a carbon atom to which a sulfur atom is bonded, or an ⁇ -position or ⁇ -position carbon atom of a carbon atom to which a sulfur atom is bonded, and the functional group are bonded. Is preferred.
  • the sulfur-containing organic compound preferably contains at least one functional group selected from a carbonyl group, a hydroxyl group and an amino group as the functional group.
  • the sulfur-containing organic compound is preferably at least one sulfur-containing organic compound selected from thiourea analogs and thiomalic acid analogs.
  • the nonaqueous electrolyte secondary battery of the present invention has the above-described negative electrode for a nonaqueous electrolyte secondary battery.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention can be used for producing a negative electrode for a non-aqueous electrolyte secondary battery having excellent peel strength between the mixture layer and the current collector. Moreover, since the negative electrode for nonaqueous electrolyte secondary batteries of this invention is obtained by apply
  • the negative electrode for a non-aqueous electrolyte secondary battery according to another aspect of the present invention is obtained by applying a negative electrode mixture for a non-aqueous electrolyte secondary battery to a surface-treated current collector surface-treated with a specific sulfur-containing organic compound. Since it is formed by drying, the peel strength between the mixture layer and the current collector is excellent.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains a vinylidene fluoride polymer having an acidic functional group, a sulfur-containing organic compound, an electrode active material and an organic solvent, and the sulfur-containing organic compound is sulfur. It has at least one functional group containing no atoms. Moreover, the negative electrode for nonaqueous electrolyte secondary batteries of this invention is obtained by apply
  • negative electrode mixture for nonaqueous electrolyte secondary batteries
  • negative electrode mixture the negative electrode for nonaqueous electrolyte secondary batteries
  • negative electrode also simply referred to as “negative electrode”.
  • the negative electrode mixture for non-aqueous electrolyte secondary batteries of the present invention contains a vinylidene fluoride polymer having an acidic functional group as a binder resin (binder).
  • the vinylidene fluoride polymer having an acidic functional group is a polymer containing an acidic functional group in a polymer and obtained using at least vinylidene fluoride as a monomer.
  • the vinylidene fluoride polymer having an acidic functional group is usually a polymer obtained by copolymerizing vinylidene fluoride and an acidic functional group-containing monomer and, if necessary, other monomers.
  • vinylidene fluoride polymer having an acidic functional group one kind may be used alone, or two or more kinds may be used.
  • Examples of the acidic functional group possessed by the vinylidene fluoride polymer having an acidic functional group include a carboxyl group (—CO 2 H), a sulfo group (—SO 3 H), and a phosphonic acid group (—PO 3 H 2 ).
  • a carboxyl group is preferred.
  • the vinylidene fluoride-based polymer having an acidic functional group usually has a structural unit derived from vinylidene fluoride per 100 parts by weight of the polymer, usually 80 parts by weight or more, preferably 85 parts by weight or more, and usually 99.9.
  • the vinylidene fluoride-based polymer having an acidic functional group used in the present invention is usually (1) a method of copolymerizing vinylidene fluoride and an acidic functional group-containing monomer and, if necessary, another monomer (hereinafter referred to as (1) (2), (2) polymerizing vinylidene fluoride or copolymerizing vinylidene fluoride and another monomer, polymerizing vinylidene fluoride polymer and acidic functional group-containing monomer, A method of grafting an acidic functional group-containing polymer onto a vinylidene fluoride polymer using an acidic functional group-containing polymer obtained by copolymerizing an acidic functional group-containing monomer and another monomer (hereinafter, (Also referred to as the method of (2)), (3) after polymerization of vinylidene fluoride or copolymerization of vinylidene fluoride and another monomer to obtain a vinylidene fluoride polymer, the vinylidene fluoride The system
  • the vinylidene fluoride polymer having an acidic functional group used in the present invention has an acidic functional group such as a carboxyl group, the adhesiveness to the current collector is higher than that of polyvinylidene fluoride having no acidic functional group. Improved.
  • the method (1) may be used from the viewpoint of the number of steps and production cost.
  • the vinylidene fluoride polymer having an acidic functional group is preferably a copolymer of vinylidene fluoride and an acidic functional group-containing monomer.
  • the vinylidene fluoride polymer having an acidic functional group used in the present invention contains vinylidene fluoride, usually 80 to 99.9 parts by weight, preferably 95 to 99.7 parts by weight, and an acidic functional group-containing monomer. Usually 0.1 to 20 parts by weight, preferably 0.3 to 5 parts by weight (provided that the total of vinylidene fluoride and acidic functional group-containing monomers is 100 parts by weight) copolymerized vinylidene fluoride It is a polymer.
  • the vinylidene fluoride polymer having an acidic functional group may be a polymer obtained by copolymerizing another monomer in addition to the vinylidene fluoride and the acidic functional group-containing monomer. When other monomers are used, the total amount of the vinylidene fluoride and the acidic functional group-containing monomer is 100 parts by weight, and the other monomer is usually used in an amount of 0.1 to 20 parts by weight.
  • Examples of the acidic functional group-containing monomer include a carboxyl group-containing monomer, a sulfo group-containing monomer, and a phosphonic acid group-containing monomer, which were obtained by applying and drying the negative electrode mixture of the present invention on a current collector. From the viewpoint of peel strength between the mixture layer and the current collector in the negative electrode, a carboxyl group-containing monomer is preferred.
  • carboxyl group-containing monomer unsaturated monobasic acid, unsaturated dibasic acid, monoester of unsaturated dibasic acid and the like are preferable.
  • Examples of the unsaturated monobasic acid include acrylic acid and methacrylic acid.
  • Examples of the unsaturated dibasic acid include maleic acid and citraconic acid.
  • the unsaturated dibasic acid monoester preferably has 5 to 8 carbon atoms, and examples thereof include maleic acid monomethyl ester, maleic acid monoethyl ester, citraconic acid monomethyl ester, and citraconic acid monoethyl ester. Can do.
  • the carboxyl group-containing monomer is preferably at least one monomer selected from unsaturated dibasic acid, unsaturated dibasic acid monoester, acrylic acid and methacrylic acid, maleic acid, citraconic acid, maleic acid monomethyl ester, More preferred is at least one monomer selected from citraconic acid monomethyl ester, acrylic acid, and methacrylic acid.
  • sulfo group-containing monomer examples include vinyl sulfonic acid, 4-sulfophenyl acrylate, 2-acrylamido-4-methylpropene sulfonic acid, and the like.
  • Examples of the phosphonic acid group-containing monomer include vinylphosphonic acid and mono (2-acryloyloxyethyl) acid phosphate.
  • the other monomer that can be copolymerized with the vinylidene fluoride and the acidic functional group-containing monomer means a monomer other than the vinylidene fluoride and the acidic functional group-containing monomer.
  • Examples of the other monomer include vinylidene fluoride.
  • fluorine-based monomer copolymerizable with vinylidene fluoride examples include perfluoroalkyl vinyl ethers typified by vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and perfluoromethyl vinyl ether. be able to.
  • the said other monomer may be used individually by 1 type, and may use 2 or more types.
  • methods such as suspension polymerization, emulsion polymerization, and solution polymerization can be employed. From the viewpoint of ease of post-treatment, aqueous suspension polymerization and emulsion polymerization are preferred, and aqueous suspension is preferred. Turbid polymerization is particularly preferred.
  • suspending agents such as methylcellulose, methoxylated methylcellulose, propoxylated methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyethylene oxide, gelatin, etc.
  • Polyvinylidene fluoride and acidic functional group-containing monomer, other monomer copolymerized as required 100 parts by weight, usually 0.005 to 1.0 part by weight, preferably 0.01 to 0 Add in the range of 4 parts by weight.
  • Polymerization initiators include diisopropyl peroxydicarbonate, dinormalpropyl peroxydicarbonate, dinormalheptafluoropropyl peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyryl peroxide, di (chlorofluoroacyl) peroxide, di (perfluoroacyl) Peroxides can be used.
  • the amount used is usually 0.1 to 5 when the total amount of monomers used for copolymerization (vinylidene fluoride, acidic functional group-containing monomers, and other monomers copolymerized as necessary) is 100 parts by weight. Part by weight, preferably 0.3 to 2 parts by weight.
  • a chain transfer agent such as ethyl acetate, methyl acetate, diethyl carbonate, acetone, ethanol, n-propanol, acetaldehyde, propyl aldehyde, ethyl propionate, carbon tetrachloride, and the resulting fluoride having an acidic functional group
  • the amount used is usually 0.1 when all the monomers used for copolymerization (vinylidene fluoride, acidic functional group-containing monomer, and other monomers copolymerized as required) are 100 parts by weight. 1 to 5 parts by weight, preferably 0.5 to 3 parts by weight.
  • the total amount of monomers used for copolymerization is usually in the weight ratio of the total monomer: water Is 1: 1 to 1:10, preferably 1: 2 to 1: 5, the polymerization is at a temperature of 10 to 80 ° C., the polymerization time is 10 to 100 hours, and the pressure during the polymerization is usually under pressure. Preferably, it is 2.0 to 8.0 MPa-G.
  • vinylidene fluoride is polymerized by polymerizing vinylidene fluoride or copolymerizing vinylidene fluoride and another monomer.
  • a polymer is obtained.
  • the polymerization or copolymerization is usually performed by suspension polymerization or emulsion polymerization.
  • an acidic functional group-containing polymer is obtained by polymerizing an acidic functional group-containing monomer or copolymerizing an acidic functional group-containing monomer and another monomer.
  • the acidic functional group-containing polymer is usually obtained by emulsion polymerization or suspension polymerization.
  • the vinylidene fluoride polymer having an acidic functional group is obtained by grafting the acidic functional group-containing polymer onto the vinylidene fluoride polymer using the vinylidene fluoride polymer and the acidic functional group-containing polymer.
  • the grafting may be performed using a peroxide or may be performed using radiation.
  • a mixture of a vinylidene fluoride polymer and an acidic functional group-containing polymer is added in the presence of the peroxide. This is done by heat treatment.
  • the vinylidene fluoride polymer having an acidic functional group used in the present invention has an inherent viscosity (logarithmic viscosity at 30 ° C. of a solution obtained by dissolving 4 g of a resin in 1 liter of N, N-dimethylformamide. The same applies hereinafter).
  • a value in the range of 0.5 to 5.0 dl / g is preferable, and a value in the range of 1.0 to 4.0 dl / g is more preferable. If it is the viscosity within the said range, it can use suitably for the negative mix for nonaqueous electrolyte secondary batteries.
  • Inherent viscosity ⁇ i is calculated by dissolving 80 mg of vinylidene fluoride polymer having an acidic functional group in 20 ml of N, N-dimethylformamide and using an Ubbelohde viscometer in a constant temperature bath at 30 ° C. It can be carried out.
  • ⁇ i (1 / C) ⁇ ln ( ⁇ / ⁇ 0 )
  • ⁇ is the viscosity of the polymer solution
  • ⁇ 0 is the viscosity of the solvent N, N-dimethylformamide alone
  • C is 0.4 g / dl.
  • the vinylidene fluoride polymer having an acidic functional group has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) usually in the range of 50,000 to 2,000,000, preferably 20 It ranges from 10,000 to 1.5 million.
  • GPC gel permeation chromatography
  • the acidic functional group of the vinylidene fluoride polymer having an acidic functional group is a carboxyl group
  • the absorbance ratio (A R ) represented by 1) is preferably in the range of 0.1 to 2.0, more preferably 0.3 to 1.7.
  • AR is less than 0.1
  • the adhesion to the current collector may be insufficient.
  • a R exceeds 2.0
  • the electrolytic solution resistance of the resulting polymer tends to decrease.
  • the measurement of the infrared absorption spectrum of this polymer is performed by measuring an infrared absorption spectrum about the film manufactured by hot-pressing this polymer.
  • a R A 1650-1800 / A 3000-3100 (1)
  • a 1650-1800 is the absorbance of the absorption band derived from the carbonyl group which is detected in the range of 1650 ⁇ 1800cm -1
  • a 3000-3100 is detected in the range of 3000 ⁇ 3100 cm -1
  • It is the absorbance of the absorption band derived from the CH structure.
  • a R becomes a measure of the abundance of the carbonyl group of the vinylidene fluoride polymer having an acidic functional group, the measure of the abundance of the resulting carboxyl group.
  • the vinylidene fluoride-containing polymer having an acidic functional group is a copolymer of vinylidene fluoride and a monomer having an acidic functional group, and the constitution derived from the monomer having an acidic functional group in the copolymer
  • the unit random rate is preferably 40% or more, and more preferably 60% or more. Although the details are unknown if the random ratio is within the above range, it is preferable because the uniformity of the polymer chain is improved and the acidic functional group interacts with the sulfur-containing organic compound efficiently.
  • the random rate indicates how much of the structural unit derived from the acidic functional group-containing monomer present in the vinylidene fluoride-based polymer having an acidic functional group is dispersed in the polymer chain. It is an indicator. It means that the lower the random rate, the more the structural units derived from the acidic functional group-containing monomer are continuously present. In other words, the acidic functional group-containing monomers tend to have a polymerized chain. On the other hand, the higher the random ratio, the more structural units derived from the acidic functional group-containing monomer exist independently.In other words, the structural units derived from the acidic functional group-containing monomer do not continue and are linked to the structural unit derived from vinylidene fluoride. Tend to.
  • the random ratio of the vinylidene fluoride polymer having an acidic functional group is obtained by dividing the abundance [mol%] of the acidic functional group-containing monomer chain by the abundance [mol%] of the structural unit derived from the acidic functional group-containing monomer.
  • Random rate [%] Abundance of acidic functional group-containing monomer chain [mol%] / Abundance of structural unit derived from acidic functional group-containing monomer [mol%] ⁇ 100).
  • the abundance of the structural unit derived from vinylidene fluoride shall be 100 mol%.
  • the abundance of the acidic functional group-containing monomer chain can be determined by NMR spectrum, and the abundance of the structural unit derived from the acidic functional group-containing monomer can be determined by, for example, a neutralization titration method.
  • the random ratio can be obtained by the following method.
  • a method for producing a vinylidene fluoride-based polymer having an acidic functional group having a random ratio within the above range for example, a method of continuously adding an acidic functional group-containing monomer when performing the aforementioned suspension polymerization or the like Is mentioned.
  • the negative electrode mixture for a nonaqueous electrolyte secondary battery of the present invention contains a sulfur-containing organic compound.
  • the sulfur-containing organic compound contained in the negative electrode mixture of the present invention those having at least one functional group not containing a sulfur atom are used. Since the negative electrode mixture of the present invention contains the sulfur-containing organic compound, it can be used when producing a negative electrode for a non-aqueous electrolyte secondary battery that has excellent peel strength between the mixture layer and the current collector.
  • the sulfur-containing organic compound used in the present invention includes a sulfur atom in which the carbon atom to which the sulfur atom is bonded, or the ⁇ -position or ⁇ -position of the carbon atom to which the sulfur atom is bonded, and the functional group are bonded.
  • An organic compound is preferable, and a sulfur atom-containing organic compound in which the carbon atom to which the sulfur atom is bonded or the carbon atom at the ⁇ -position of the carbon atom to which the sulfur atom is bonded and the functional group is bonded is more preferable, and the sulfur atom is bonded.
  • a sulfur-containing organic compound in which the carbon atom to be bonded to the functional group is particularly preferable. These sulfur-containing organic compounds are preferable because they are easily chemically adsorbed to a current collector such as a copper foil.
  • the said functional group may be contained 1 type in the molecule
  • examples of the functional group include a carbonyl group, a hydroxyl group, and an amino group.
  • the sulfur-containing organic compound preferably contains at least one functional group selected from a carbonyl group, a hydroxyl group and an amino group from the viewpoint of interaction with an acidic functional group in the polymer.
  • the sulfur-containing organic compound is selected from thiourea analogs and thiomalic acid analogs from the viewpoint of the peel strength between the negative electrode mixture layer formed using the negative electrode mixture of the present invention and the current collector. At least one sulfur-containing organic compound is preferred.
  • Examples of the thiourea analogues include compounds represented by the following general formula (1).
  • R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group includes a part of the hydrogen atoms contained in the group, It may be substituted with at least one functional group selected from a carbonyl group, a hydroxyl group and an amino group.
  • R 3 is an atomic group having a molecular weight of 150 or less, including at least two elements selected from hydrogen, carbon, nitrogen, oxygen and sulfur.
  • R 1 and R 2 may be bonded to each other to form a ring, and R 1 and R 3 may be bonded to each other to form a ring.
  • Examples of the thiomalic acid-related compound include compounds represented by the following general formula (4).
  • R 4 is a hydrogen atom, a hydroxyl group, or a hydrocarbon having 1 to 6 carbon atoms, and the hydrocarbon group includes a carbonyl group, a hydroxyl group, It may be substituted with at least one functional group selected from a group and an amino group.
  • R 5 is an atomic group having a molecular weight of 150 or less, containing at least two elements selected from hydrogen, carbon, nitrogen, oxygen and sulfur. R 4 and R 5 may be bonded to each other to form a ring.
  • thiomalic acid analog a compound represented by the formula (5) can be used.
  • the sulfur-containing organic compound used in the present invention usually has a molecular weight of 64 to 500.
  • the negative electrode mixture for a nonaqueous electrolyte secondary battery of the present invention contains an electrode active material.
  • the electrode active material is not particularly limited, and conventionally known electrode active materials for negative electrodes can be used, and specific examples include carbon materials, metal / alloy materials, metal oxides, etc. Material is preferred.
  • the carbon material artificial graphite, natural graphite, non-graphitizable carbon, graphitizable carbon, or the like is used. Moreover, the said carbon material may be used individually by 1 type, or may use 2 or more types.
  • the energy density of the battery can be increased.
  • the artificial graphite can be obtained, for example, by carbonizing an organic material, heat-treating it at a high temperature, pulverizing and classifying it.
  • artificial graphite MAG series (manufactured by Hitachi Chemical Co., Ltd.), MCMB (manufactured by Osaka Gas Chemical), etc. are used.
  • the specific surface area of the electrode active material is preferably 0.3 to 10 m 2 / g, and more preferably 0.5 to 6 m 2 / g.
  • the specific surface area is less than 0.3 m 2 / g, even when a conventional binder is used, it is difficult for the binder to be taken into the active material, and sufficient adhesiveness is ensured. Therefore, the effect of the present invention is small. If the specific surface area exceeds 10 m 2 / g, the amount of decomposition of the electrolytic solution increases and the initial irreversible capacity increases, which is not preferable.
  • the specific surface area of the electrode active material can be determined by a nitrogen adsorption method.
  • the negative electrode mixture for a nonaqueous electrolyte secondary battery of the present invention contains an organic solvent.
  • the organic solvent those having an action of dissolving the vinylidene fluoride-based polymer having the acidic functional group are used, and preferably a solvent having polarity is used.
  • Specific examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoamide, dioxane, tetrahydrofuran, tetramethylurea, triethyl phosphate.
  • N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethyl sulfoxide are preferable.
  • the organic solvent may be used alone or in combination of two or more.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains the vinylidene fluoride polymer having an acidic functional group, a sulfur-containing organic compound, an electrode active material, and an organic solvent.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte having the negative electrode from the viewpoint of peel strength between the negative electrode mixture layer and the current collector formed using the negative electrode mixture of the present invention.
  • the electrode active material is preferably 70 to 99.9 parts by mass, and 80 to 99.5 parts by mass per 100 parts by mass in total of the vinylidene fluoride polymer having an acidic functional group and the electrode active material. More preferably, it is 85 to 99 parts by mass, and the vinylidene fluoride polymer having an acidic functional group is preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass. The amount is more preferably part by mass, and particularly preferably 1 to 15 parts by mass. Further, when the total of the vinylidene fluoride polymer having an acidic functional group and the electrode active material is 100 parts by mass, the organic solvent is preferably 3 to 300 parts by mass, and 4 to 200 parts by mass. Is more preferable.
  • the peel strength between the negative electrode mixture layer formed using the negative electrode mixture of the present invention and the current collector is excellent.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains other components other than the vinylidene fluoride polymer having an acidic functional group, a sulfur-containing organic compound, an electrode active material, and an organic solvent. It may be. As other components, a conductive aid such as carbon black, a pigment dispersant such as polyvinylpyrrolidone, and the like may be included. As said other component, polymers other than the vinylidene fluoride type polymer which has the said acidic functional group may be included.
  • Examples of the other polymer include vinylidene fluoride such as polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, and vinylidene fluoride-perfluoromethyl vinyl ether copolymer.
  • System polymers When the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains another polymer, it is usually 25 parts by mass or less with respect to 100 parts by mass of the vinylidene fluoride polymer having the acidic functional group. Included in quantity.
  • the viscosity of the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention when measured using an E-type viscometer at 25 ° C. and a shear rate of 2 s ⁇ 1 is usually 2000 to 50000 mPa ⁇ s, Preferably, it is 5000 to 30000 mPa ⁇ s.
  • the vinylidene fluoride polymer having an acidic functional group, a sulfur-containing organic compound, an electrode active material, and an organic solvent are made into a uniform slurry. What is necessary is just to mix.
  • the order of mixing is not particularly limited.
  • a method of obtaining a negative electrode mixture for a non-aqueous electrolyte secondary battery by simultaneously mixing all components contained in the negative electrode mixture, a vinylidene fluoride-based polymer having an acidic functional group A non-aqueous electrolyte secondary battery is obtained by dissolving the coalescence in a part of an organic solvent to obtain a binder solution, and adding and mixing the sulfur-containing organic compound, the electrode active material and the remaining organic solvent to the binder solution.
  • the negative electrode for a non-aqueous electrolyte secondary battery of the present invention has two aspects.
  • the negative electrode for nonaqueous electrolyte secondary batteries of the present invention has a current collector and a layer formed from a negative electrode mixture for nonaqueous electrolyte secondary batteries.
  • the negative electrode for a nonaqueous electrolyte secondary battery according to the first aspect is obtained by applying and drying the above-described negative electrode mixture for a nonaqueous electrolyte secondary battery on a current collector.
  • the negative electrode for a nonaqueous electrolyte secondary battery according to the second aspect is a vinylidene fluoride polymer having an acidic functional group on a surface-treated current collector obtained by surface-treating a current collector with a sulfur-containing organic compound.
  • the sulfur-containing organic compound is the same as the sulfur-containing organic compound contained in the above-described negative electrode mixture for nonaqueous electrolyte secondary batteries of the present invention. Things can be used.
  • the negative electrode for nonaqueous electrolyte secondary batteries of the second aspect as the negative electrode mixture for nonaqueous electrolyte secondary batteries, in the negative electrode mixture for nonaqueous electrolyte secondary batteries of the present invention described above, it contains sulfur. The same thing can be used except the organic compound does not need to contain.
  • coating and drying the negative mix for nonaqueous electrolyte secondary batteries to a collector is used as a mixture Marked as layer.
  • the negative electrode for a non-aqueous electrolyte secondary battery of the present invention is excellent in peel strength between the current collector and the mixture layer.
  • the negative electrode for a nonaqueous electrolyte secondary battery according to the first aspect is characterized by using the negative electrode mixture for a nonaqueous electrolyte secondary battery of the present invention, because the negative electrode mixture contains a sulfur-containing organic compound.
  • the peel strength between the current collector and the mixture layer is excellent.
  • a surface-treated current collector obtained by surface-treating a current collector with a sulfur-containing organic compound as a current collector constituting the negative electrode. Even if it is a case where the mixture which does not contain a sulfur-containing organic compound as a negative electrode mixture is used, it is excellent in the peeling strength of a collector and a mixture layer.
  • the surface treatment method is not particularly limited as long as the sulfur-containing organic compound contacts the surface of the current collector.
  • the sulfur-containing organic compound is ethanol, methanol, acetone, or the like. This is carried out by dissolving in an organic solvent and immersing the current collector in the solution.
  • the current collector immersed in the solution is taken out from the solution and then usually dried and used as a surface-treated current collector. Moreover, you may wash
  • the concentration of the sulfur-containing organic compound in the solution is usually 0.1 to 30 wt%, and the time for immersing the current collector in the solution is usually 1 to 180 minutes.
  • the negative electrode for a non-aqueous electrolyte secondary battery of the present invention is excellent in the peel strength between the current collector and the mixture layer is not clear, but the present inventors presume as follows.
  • the sulfur-containing organic compound and a current collector such as a copper foil are in contact.
  • the sulfur-containing organic compound a sulfur-containing organic compound having at least one functional group not containing a sulfur atom is used.
  • a sulfur-containing organic compound having at least one functional group not containing a sulfur atom comes into contact with a current collector such as a copper foil, a self-assembled monolayer is formed on the current collector, and the surface of the current collector is sulfur. It is thought that it coats with the functional group which does not contain an atom.
  • sulfur atoms in the molecule chemisorb to the current collector to form a self-assembled monolayer, and the amino group in the molecule It is thought that it is exposed on the current collector surface.
  • the interaction between the acidic functional group of vinylidene fluoride polymer having acidic functional group and the functional group not containing sulfur atom is the interaction between the current collector such as copper foil and the functional group not containing sulfur atom.
  • the current collector used in the present invention includes, for example, copper, and the shape thereof includes, for example, a metal foil, a metal net, and the like.
  • a copper foil is preferable.
  • the thickness of the current collector is usually 5 to 100 ⁇ m, preferably 5 to 20 ⁇ m.
  • the thickness of the mixture layer is usually 20 to 250 ⁇ m, preferably 20 to 150 ⁇ m.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery is applied to at least one surface, preferably both surfaces of the current collector.
  • the method for coating is not particularly limited, and examples thereof include a method using a bar coater, a die coater, or a comma coater.
  • drying performed after the coating is usually performed at a temperature of 50 to 150 ° C. for 1 to 300 minutes.
  • the pressure at the time of drying is not particularly limited, but it is usually carried out under atmospheric pressure or reduced pressure.
  • heat treatment may be performed after drying. When heat treatment is performed, it is usually performed at a temperature of 100 to 250 ° C. for 1 to 300 minutes. In addition, although the temperature of heat processing overlaps with the said drying, these processes may be a separate process and the process performed continuously.
  • press processing may be performed.
  • it is usually performed at 1 to 200 MPa-G. It is preferable to perform the press treatment because the electrode density can be improved.
  • the negative electrode for nonaqueous electrolyte secondary batteries of the present invention can be produced.
  • a layer structure of the negative electrode for non-aqueous electrolyte secondary batteries when the negative electrode mixture for non-aqueous electrolyte secondary batteries is applied to one surface of the current collector, a two-layer structure of a mixture layer / current collector When the negative electrode mixture for a nonaqueous electrolyte secondary battery is applied to both sides of the current collector, it has a three-layer structure of a mixture layer / current collector / mixture layer.
  • the negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is excellent in the peel strength between the current collector and the mixture layer by using the negative electrode mixture for a non-aqueous electrolyte secondary battery. It is preferable because the electrode is less likely to be cracked or peeled off in the process, etc., leading to improvement in productivity.
  • the negative electrode for a non-aqueous electrolyte secondary battery of the present invention is excellent in the peel strength between the current collector and the mixture layer as described above.
  • the peel strength between the current collector and the mixture layer is According to JIS K6854, it is usually 0.5 to 20 gf / mm, preferably 1 to 15 gf / mm, when measured by a 180 ° peel test.
  • the negative electrode for a non-aqueous electrolyte secondary battery of the present invention is excellent in peel strength between the current collector and the mixture layer.
  • Nonaqueous electrolyte secondary battery The nonaqueous electrolyte secondary battery of the present invention is characterized by having the negative electrode for a nonaqueous electrolyte secondary battery.
  • the non-aqueous electrolyte secondary battery of the present invention is not particularly limited except that the non-aqueous electrolyte secondary battery has the negative electrode.
  • the electrode for a nonaqueous electrolyte secondary battery is usually used as a negative electrode, and conventionally known ones other than the negative electrode, such as a positive electrode and a separator, can be used.
  • a sample for measurement was prepared by adding 20 ml of N, N-dimethylformamide (DMF) to 80 mg of the polymer obtained in each production example and dissolving by heating at 70 ° C. for 2 hours.
  • the inherent viscosity of the measurement sample was measured at 30 ° C. using an Ubbelohde viscometer manufactured by Kusano Kagaku Co., Ltd.
  • the random ratio of the polymers obtained in the following Production Examples 4 to 6 was calculated by calculating the abundance of acidic functional group-containing monomer chains and the abundance of structural units derived from acidic functional group-containing monomers by the following method. did.
  • NMR measurement of the vinylidene fluoride copolymer was performed using a commercially available heavy DMSO as a measurement solvent as it was and using an AVANCE AC 400FT NMR spectrometer manufactured by Bruker.
  • the abundance of the acidic functional group-containing monomer chain is determined by calculating the peak intensity (integrated value) of F adjacent to the acidic functional group-containing monomer appearing in the vicinity of ⁇ 94 ppm in the 19 F-NMR spectrum, and the peak intensity (integrated value) of all F in the spectrum. Value).
  • the polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried at 80 ° C. for 20 hours to obtain a polymer A powder.
  • the polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried at 80 ° C. for 20 hours to obtain a polymer B powder.
  • the polymerization rate was 92%, and the inherent viscosity of the obtained polymer B was 2.2 dl / g.
  • the polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried at 80 ° C. for 20 hours to obtain a polymer C powder.
  • the polymer slurry was heat treated at 95 ° C. for 30 minutes, then dehydrated, washed with water, and further dried at 80 ° C. for 20 hours to obtain a polymer D powder.
  • the polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried at 80 ° C. for 20 hours to obtain a polymer E powder.
  • the polymerization rate is 6%
  • the inherent viscosity of the obtained polymer E is 2.1 dl / g
  • the random rate is 22%.
  • the polymer slurry was heat treated at 95 ° C. for 30 minutes, then dehydrated, washed with water, and further dried at 80 ° C. for 20 hours to obtain a polymer D powder.
  • PAA polyacrylic acid
  • PAA1 Wako Pure Chemical Industries, Ltd., Wako first grade Polyacid Acid, weight average molecular weight (Mw) 250,000
  • PAA2 Wako Pure Chemical Industries, Ltd., Wako first grade Polyacrylic Acid, weight average molecular weight (Mw) 1,000, 000 [Example 1] (Preparation of negative electrode mixture for non-aqueous electrolyte secondary battery) 96 parts by weight of artificial graphite (“MCMB” manufactured by Osaka Gas Chemical Co., Ltd., average particle size 22 ⁇ m, specific surface area 0.9 m 2 / g) as negative electrode active material, 4 parts by weight of polymer A as binder, additive 0.02 parts by weight of thiourea and 5.04 parts by weight of N-methyl-2-pyrrolidone (NMP) as a solvent were mixed to obtain a negative electrode mixture (1) for a non-aqueous electrolyte secondary battery.
  • MCMB artificial graphite
  • NMP N-methyl-2-
  • the negative electrode mixture (1) for a non-aqueous electrolyte secondary battery was applied to one side of a copper foil having a thickness of about 10 ⁇ m using a bar coater at a coating amount of 10 g, dried at 110 ° C. for 30 minutes, and an electrode structure ( 1) was obtained.
  • the obtained electrode structure (1) was pressed at a pressing pressure of 0.8 t / cm 2 to obtain an electrode (1) (mixture layer thickness 130 ⁇ m).
  • the peel strength between the mixture layer and the current collector was measured by a 180 ° peel test in accordance with JIS K6854.
  • Examples 2 to 21 Preparation of negative electrode mixture for non-aqueous electrolyte secondary battery Except that the amounts and types of the negative electrode active material, binder, and additive were changed as described in Tables 1 to 3, the same procedure as in Example 1 was performed, and the negative electrode mixtures for nonaqueous electrolyte secondary batteries (2) to ( 21) was obtained.
  • MAG-D20 means artificial graphite (manufactured by Hitachi Chemical Co., Ltd., “MAG”, average particle size 20 ⁇ m, specific surface area 4.2 m 2 / g).
  • the obtained electrodes (2) to (21) were used as samples, and the peel strength was measured in the same manner as in Example 1.
  • the obtained electrodes (c1) to (c9) were used as samples, and the peel strength was measured in the same manner as in Example 1.
  • Example 2 The same procedure as in Example 1 was conducted except that the negative electrode mixture (1) for nonaqueous electrolyte secondary batteries was changed to the negative electrode mixture (r1) and (r2) for nonaqueous electrolyte secondary batteries, and the electrode (r1) , (R2) was obtained.
  • the obtained electrodes (r1) and (r2) were used as samples, and the peel strength was measured in the same manner as in Example 1.
  • the negative electrode mixture (c10) for a non-aqueous electrolyte secondary battery was applied to one side of an aluminum foil having a thickness of about 15 ⁇ m using a bar coater at a coating amount of 20 g and dried at 110 ° C. for 30 minutes to obtain an electrode (c10). Obtained.
  • the peel strength between the mixture layer and the current collector was measured by a 90 ° peel test in accordance with JIS K6854.
  • the negative electrode mixture (c11) for a non-aqueous electrolyte secondary battery was applied to one side of an aluminum foil having a thickness of about 15 ⁇ m using a bar coater at a coating amount of 20 g and dried at 110 ° C. for 30 minutes to form an electrode (c11). Obtained.
  • the peel strength between the mixture layer and the current collector was measured by a 90 ° peel test in accordance with JIS K6854.
  • Example 22 (Preparation of negative electrode mixture for non-aqueous electrolyte secondary battery) 96 parts by weight of artificial graphite (“MCMB” manufactured by Osaka Gas Chemical Co., Ltd.) as a negative electrode active material, 4 parts by weight of polymer A as a binder, and 5.04 parts by weight of N-methyl-2-pyrrolidone (NMP) as a solvent Were mixed to obtain a negative electrode mixture (22) for a non-aqueous electrolyte secondary battery.
  • MCMB artificial graphite
  • polymer A as a binder
  • NMP N-methyl-2-pyrrolidone
  • a copper foil having a thickness of about 10 ⁇ m was immersed for 60 minutes.
  • the copper foil immersed in the solution was washed with ethanol and dried at 50 ° C. for 10 minutes to obtain a surface-treated copper foil.
  • the negative electrode mixture (22) for a non-aqueous electrolyte secondary battery was applied to one side of a surface-treated copper foil having a thickness of about 10 ⁇ m using a bar coater at a coating amount of 10 g, dried at 110 ° C. for 30 minutes, and an electrode structure Body (22) was obtained.
  • the obtained electrode structure (22) was pressed at a pressing pressure of 0.8 t / cm 2 to obtain an electrode (22) (mixture layer thickness 130 ⁇ m).
  • the peel strength between the mixture layer and the current collector was measured by a 180 ° peel test in accordance with JIS K6854.
  • Example 23 (Production of surface-treated copper foil) A surface-treated copper foil was obtained in the same manner as in Example 22 except that the immersion time was changed from 60 minutes to 10 minutes.
  • An electrode (23) (mixture layer thickness 130 ⁇ m) was obtained in the same manner as in Example 22 except that the surface-treated copper foil obtained by changing the immersion time from 60 minutes to 10 minutes was used.
  • the peel strength between the mixture layer and the current collector was measured by a 180 ° peel test in accordance with JIS K6854.

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Abstract

La présente invention a pour but de procurer une électrode négative pour batteries secondaires à électrolyte non aqueux, dans laquelle la résistance au délaminage entre une couche de mélange et un collecteur de courant est excellente ; et un mélange d'électrodes négatives pour batteries secondaires à électrolyte non aqueux, qui permet la fabrication de l'électrode négative. Cette électrode négative pour batteries secondaires à électrolyte non aqueux peut être fabriquée par application d'un mélange d'électrodes négatives sur un collecteur de courant, puis par séchage du collecteur de courant résultant, le mélange d'électrodes négatives comprenant un polymère de fluorure de vinylidène qui comprend un groupe fonctionnel acide, un composé organique contenant du soufre qui a au moins un groupe fonctionnel ne contenant pas d'atome de soufre, un matériau actif d'électrode et un solvant organique. En variante, cette électrode négative peut être fabriquée par application d'un mélange d'électrodes négatives pour batteries secondaires à électrolyte non aqueux sur un collecteur de courant traité en surface, puis par séchage du collecteur de courant résultant, le collecteur de courant traité en surface étant fabriqué par traitement de la surface d'un collecteur de courant au moyen d'un composé organique contenant du soufre qui comprend au moins un groupe fonctionnel ne contenant pas d'atome de soufre, et le mélange d'électrodes négatives comprenant un polymère de fluorure de vinylidène qui comprend un groupe fonctionnel acide, un matériau actif d'électrode et un solvant organique.
PCT/JP2011/072167 2010-10-14 2011-09-28 Mélange d'électrodes négatives pour batteries secondaires à électrolyte non aqueux, électrode négative pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux Ceased WO2012049967A1 (fr)

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KR1020137011754A KR101351206B1 (ko) 2010-10-14 2011-09-28 비수 전해질 이차 전지용 부극 합제, 비수 전해질 이차 전지용 부극 및 비수 전해질 이차 전지
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JP7098558B2 (ja) 2018-09-19 2022-07-11 株式会社東芝 電極、二次電池、電池パック、車両、及び、定置用電源
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JP2020053385A (ja) * 2018-09-19 2020-04-02 株式会社東芝 電極、二次電池、電池パック、車両、及び、定置用電源
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JP2024508935A (ja) * 2021-03-04 2024-02-28 トンファ エレクトロライト カンパニー リミテッド 二次電池用電解液及びそれを含む二次電池
JP7810715B2 (ja) 2021-03-04 2026-02-03 トンファ エレクトロライト カンパニー リミテッド 二次電池用電解液及びそれを含む二次電池
JP2024519285A (ja) * 2021-04-19 2024-05-10 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． 部分フッ素化ポリマーを製造するための方法
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JPWO2023127432A1 (fr) * 2021-12-27 2023-07-06

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CN103155247A (zh) 2013-06-12
JPWO2012049967A1 (ja) 2014-02-24
KR20130054467A (ko) 2013-05-24
JP5877791B2 (ja) 2016-03-08
KR101351206B1 (ko) 2014-01-14

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