WO2015186814A1 - 電極の製造方法 - Google Patents
電極の製造方法 Download PDFInfo
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- WO2015186814A1 WO2015186814A1 PCT/JP2015/066278 JP2015066278W WO2015186814A1 WO 2015186814 A1 WO2015186814 A1 WO 2015186814A1 JP 2015066278 W JP2015066278 W JP 2015066278W WO 2015186814 A1 WO2015186814 A1 WO 2015186814A1
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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
- H01M4/139—Processes of manufacture
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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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
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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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- 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 method for producing an electrode of an electrochemical element such as a lithium ion secondary battery.
- the present invention relates to a method for producing an electrode using a binder made of polyamic acid.
- lithium ion secondary batteries Since lithium ion secondary batteries have high energy density and high capacity, they are widely used as driving power sources for mobile information terminals. In recent years, use in industrial applications such as mounting on electric / hybrid vehicles that require large capacity is becoming widespread, and studies for higher capacity and higher performance are being made.
- One of the attempts is to increase the charge / discharge capacity by using silicon or tin having a large amount of lithium occlusion per unit volume or an alloy containing these as the negative electrode active material.
- Patent Document 1 describes that, in a lithium secondary battery, when a polyimide resin is used as a binder for a negative electrode, the battery capacity is hardly reduced even if the charge / discharge cycle is repeated, and the cycle life is prolonged.
- the electrode is manufactured by heat treatment at 350 ° C. for 2 hours.
- Patent Document 2 describes a binder resin composition for an electrode comprising a specific polyamic acid and a solvent, which has a low degree of swelling with respect to an electrolytic solution and has excellent toughness (large breaking elongation and breaking energy).
- Patent Document 3 describes a resin composition for an electrode of a lithium ion secondary battery containing a polyimide resin having a carboxyl group and an epoxy resin.
- Patent Document 4 discloses a polyimide that is dissolved in an aqueous solvent together with imidazoles having two or more alkyl groups as substituents at 1.6 times mol or more with respect to the tetracarboxylic acid component of polyamic acid. An electrode manufacturing method using the aqueous precursor composition is described.
- Non-Patent Document 1 shows that the smaller the degree of swelling of the binder resin for electrodes with respect to the electrolytic solution, the higher the discharge capacity retention rate associated with the charge / discharge cycle, which is preferable.
- the object of the present invention is to use water as a solvent, heat treatment at a relatively low temperature of 200 ° C. or lower and a relatively short time, a low degree of swelling even in a battery environment, and excellent adhesion and toughness. It is an object of the present invention to propose a method of manufacturing an electrode that can easily obtain an electrode for a high-performance lithium secondary battery that can be maintained and has good environmental adaptability.
- an electrode containing a polyimide precursor aqueous solution composition obtained by dissolving a polyamic acid having a specific chemical structure in a water solvent together with a specific imidazole, and a specific cross-linking agent By using the mixture composition, even if an electrode is produced by heat treatment at a relatively low temperature of 200 ° C. or lower and for a relatively short time, the degree of swelling is small even in a battery environment, and excellent adhesion and toughness are achieved.
- the inventors have found that an electrode for a high-performance lithium secondary battery that can be maintained can be easily obtained, and have reached the present invention.
- the present invention relates to the following items.
- At least an electrode active material and a polyamic acid having a repeating unit represented by the following chemical formula (1) are used as a substituent of 1.6 times mole or more with respect to the tetracarboxylic acid component of the polyamic acid.
- An electrode mixture layer comprising an electrode precursor composition comprising an aqueous polyimide precursor solution composition dissolved in an aqueous solvent together with imidazoles having two or more alkyl groups, and a crosslinking agent having a carbodiimide group or an oxazoline group And then heat treatment to remove the solvent and perform imidization reaction of the polyamic acid.
- A consists of one or more tetravalent groups selected from the group consisting of the following chemical formula (2), the following chemical formula (3), and the following chemical formula (4)
- B is the following chemical formula: (5), one or more divalent groups selected from the group consisting of the following chemical formula (6), the following chemical formula (7), the following chemical formula (8), and a divalent saturated hydrocarbon group having 4 to 10 carbon atoms.
- X is a direct bond, oxygen atom, sulfur atom, methylene group, carbonyl group, sulfoxyl group, sulfone group, 1,1′-ethylidene group, 1,2-ethylidene group, 2,2′- Isopropylidene group, 2,2′-hexafluoroisopropylidene group, cyclohexylidene group, phenylene group, 1,3-phenylenedimethylene group, 1,4-phenylenedimethylene group, 1,3-phenylenediethylidene group, 1,4-phenylenediethylidene group, 1,3-phenylenedipropylidene group, 1,4-phenylenedipropylidene group, 1,3-phenylenedioxy group, 1,4-phenylenedioxy group, biphenylenedioxy Group, methylene diphenoxy group, ethylidene diphenoxy group, propylidene
- Y is a direct bond, oxygen atom, sulfur atom, methylene group, carbonyl group, sulfoxyl group, sulfone group, 1,1′-ethylidene group, 1,2-ethylidene group, 2,2′- Isopropylidene group, 2,2′-hexafluoroisopropylidene group, cyclohexylidene group, phenylene group, 1,3-phenylenedimethylene group, 1,4-phenylenedimethylene group, 1,3-phenylenediethylidene group, 1,4-phenylenediethylidene group, 1,3-phenylenedipropylidene group, 1,4-phenylenedipropylidene group, 1,3-phenylenedioxy group, 1,4-phenylenedioxy group, biphenylenedioxy Group, methylene diphenoxy group, ethylidene diphenoxy group, propylidene di
- Imidazoles having two or more alkyl groups as substituents include 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, and 1-methyl-4-ethylimidazole.
- Item 2. The method for producing an electrode according to Item 1, which is an imidazole selected from the group consisting of: 3. Item 3. The method for producing an electrode according to Item 1 or 2, wherein the electrode active material is carbon powder, silicon powder, tin powder, or an alloy powder containing silicon or tin. 4). Item 4. The method for producing an electrode according to any one of Items 1 to 3, wherein the electrode active material is a lithium transition metal oxide. 5. Item 5. The method for producing an electrode according to any one of Items 1 to 4, wherein an electrode for a lithium ion secondary battery is obtained.
- a heat treatment at a relatively low temperature of 200 ° C. or less and for a relatively short time a high degree of swelling and low adhesion can be maintained even in a battery environment using polyimide as a binder.
- An electrode for a lithium secondary battery can be easily obtained.
- an aqueous solvent is used, environmental adaptability is also good.
- the electrode production method of the present invention can particularly suitably produce electrodes (negative electrode and positive electrode) of lithium secondary batteries.
- electrodes negative electrode and positive electrode
- the electrode production method of the present invention demonstrates based on the manufacturing method of the electrode for lithium secondary batteries especially.
- the current collector is preferably a conductive metal foil usually used in batteries.
- the conductive metal foil include a metal foil having conductivity such as copper, aluminum, nickel, stainless steel (iron), titanium, and cobalt, or an alloy foil made of a combination thereof.
- a foil made of copper or a copper alloy having a thickness of about 5 to 100 ⁇ m is used as the negative electrode current collector, and an aluminum foil having a thickness of about 5 to 100 ⁇ m is used as the positive electrode current collector. It is suitable because it is easy to process, inexpensive, and easily improves the performance of the electrode.
- the current collector has a surface roughness controlled as required, and may have a shape other than foil, such as a flat plate shape, a mesh shape, a net shape, a lath shape, a punching metal shape, and an embossed shape.
- An electrode mixture composition (electrode mixture paste) used in the present invention is a polyimide precursor aqueous solution composition obtained by dissolving a polyamic acid having at least an electrode active material and a specific repeating unit together with a specific imidazole in an aqueous solvent. And a crosslinking agent having a carbodiimide group or an oxazoline group.
- the electrode active material of the electrode mixture composition used in the present invention is not limited as long as it is usually used in a battery. In the case of the negative electrode, any substance that can electrochemically insert and desorb lithium can be used.
- carbon powder such as graphite, cokes, carbon black, pyrolytic carbon, silicon powder, tin powder, or silicon Or the alloy powder containing tin can be mentioned.
- the alloy powder is preferably an intermetallic compound of silicon or tin and a metal element, and the metal element is preferably a transition metal such as nickel, titanium, iron, cobalt, copper, zircon, or manganese.
- any material that has lithium element and can electrochemically desorb and insert lithium may be used.
- Preferable examples include lithium transition metal oxides such as Co 0.2 Mn 0.1 O 2 .
- a polyamic acid having a repeating unit of the chemical formula (1) is used.
- This polyamic acid can be easily prepared by reacting a tetracarboxylic acid component and a diamine component at a low temperature in order to suppress the imidization reaction.
- the tetracarboxylic acid component is a tetracarboxylic acid, that is, a tetracarboxylic acid, its acid dianhydride, its esterified compound, or the like, preferably a dianhydride.
- the tetravalent group represented by A is selected from the group consisting of the chemical formula (2), the chemical formula (3), and the chemical formula (4) described above. One or more types are used.
- Such a tetravalent group is derived from a tetracarboxylic acid.
- the tetracarboxylic acid that is the base of such a tetravalent group is referred to as a “tetracarboxylic acid component”.
- the tetracarboxylic acid component constituting the polyamic acid used in the present invention is preferably selected from the group consisting of 4,4′-oxydiphthalic acids, 3,3 ′, 4,4′-biphenyltetracarboxylic acids, and pyromellitic acids.
- One or more kinds of tetracarboxylic acids preferably 3,3 ′, 4,4′-biphenyltetracarboxylic acids or 4,4′-oxydiphthalic acids and 3,3 ′, 4,4′-biphenyltetra It is a mixture comprising a combination of carboxylic acids and / or pyromellitic acids.
- the mixture is composed of 10 to 90 mol%, further 20 to 60 mol% of 4,4′-oxydiphthalic acid, and 90 to 10 mol%, further 80 to 40 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic acid. And / or a mixture composed of a combination with pyromellitic acids.
- the divalent group represented by B As the divalent group represented by B, the chemical formula (5), chemical formula (6), chemical formula (7), chemical formula (8) and One or more selected from the group consisting of divalent saturated hydrocarbon groups having 4 to 10 carbon atoms are used.
- a divalent group is derived from a diamine.
- the diamine that is the source of such a divalent group is referred to as a “diamine component”.
- the diamine component constituting the polyamic acid used in the present invention preferably contains one or more diamines selected from aromatic diamines having 1 to 4 aromatic rings and aliphatic diamines having 4 to 10 carbon atoms.
- aromatic diamines having 1 to 4 aromatic rings include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,4-bis ( ⁇ -amino-tert-butyl) toluene, 1 aromatic such as bis-p- (1,1-dimethyl-5-amino-pentyl) benzene, 1-isopropyl-2,4-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine Aromatic diamine having a ring, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3′-dichlorobenzidine, 4,4′-diaminodiphenyl sulfide, 3, 3'-diaminodiphenyl sulfone, 1,5-dia
- aromatic diamine which has four aromatic rings
- the aromatic diamine represented by following Chemical formula (8) can be mentioned suitably.
- X is a direct bond, oxygen atom, sulfur atom, methylene group, carbonyl group, sulfoxyl group, sulfone group, 1,1′-ethylidene group, 1,2-ethylidene group, 2, 2'-isopropylidene group, 2,2'-hexafluoroisopropylidene group, cyclohexylidene group, phenylene group, 1,3-phenylenedimethylene group, 1,4-phenylenedimethylene group, 1,3-phenylenediene Ethylidene group, 1,4-phenylenediethylidene group, 1,3-phenylenedipropylidene group, 1,4-phenylenedipropylidene group, 1,3-phenylenedioxy group, 1,4-phenylenedioxy group, Bipheny
- Examples of the aliphatic diamine having 4 to 10 carbon atoms include 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane (hexamethylenediamine), 1,7- Preferable examples include diamines such as diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane.
- the diamine component constituting the polyamic acid used in the present invention is 50 to 99 mol%, preferably 70 to 97 mol, of one or more kinds of diamines selected from the above-mentioned aromatic diamines having 1 to 4 aromatic rings. %, More preferably 80 to 95 mol%.
- the diamine component constituting the polyamic acid used in the present invention further contains 1 to 50 mol%, preferably 3 to 30 mol%, more preferably 5 to 20 mol% of a diamine having a polar group.
- the diamine having a polar group an aromatic diamine having a polar group having reactivity with an epoxy resin such as a hydroxyl group or a carboxyl group in the molecule is suitable.
- aromatic diamines having polar groups include diaminophenol compounds such as 2,4-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4′-diamino.
- Hydroxybiphenyl such as -3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-2,2 ', 5,5'-tetrahydroxybiphenyl
- 3,3′-diamino-4,4′-dihydroxydiphenylmethane 4,4′-diamino-3,3′-dihydroxydiphenylmethane
- 4,4′-diamino-2,2′-dihydroxydiphenylmethane 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphene] L] propane, 2,2-bis
- benzenecarboxylic acids such as 3,5-diaminobenzoic acid and 2,4-diaminobenzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3 ′
- Carboxybiphenyl compounds such as dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxybiphenyl, 3,3 '-Diamino-4,4'-dicarboxydiphenylmethane, 4,4'-diamino-3,3'-dicarboxydiphenylmethane, 4,4'-diamino-2,2'-dicarboxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4
- Y is a direct bond, oxygen atom, sulfur atom, methylene group, carbonyl group, sulfoxyl group, sulfone group, 1,1′-ethylidene group, 1,2-ethylidene group, 2,2′- Isopropylidene group, 2,2′-hexafluoroisopropylidene group, cyclohexylidene group, phenylene group, 1,3-phenylenedimethylene group, 1,4-phenylenedimethylene group, 1,3-phenylenediethylidene group, 1,4-phenylenediethylidene group, 1,3-phenylenedipropylidene group, 1,4-phenylenedipropylidene group, 1,3-phenylenedioxy group, 1,4-phenylenedioxy group, biphen
- the diamine component constituting the polyamic acid used in the present invention is, in particular, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis.
- the molar ratio [tetracarboxylic acid component / diamine component] of the tetracarboxylic acid component and the diamine component constituting the polyamic acid used in the present invention is approximately equimolar, specifically 0.95 to 1.05, preferably 0.97. It is important to set it to ⁇ 1.03. Outside the range of this molar ratio, the toughness of the resulting polyimide resin may be reduced.
- the imidazoles (compounds) having two or more alkyl groups as substituents used in the present invention are preferably compounds represented by the following chemical formula (11).
- X 1 to X 4 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and at least two of X 1 to X 4 have 1 to 5 carbon atoms. 5 alkyl groups.
- imidazoles having two or more alkyl groups as substituents are highly soluble in water, a polyimide precursor composition can be easily produced by using them.
- these imidazoles 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 1-methyl-4-ethylimidazole and the like are preferable.
- the amount of imidazoles having two or more alkyl groups as substituents used in the present invention is preferably relative to the carboxyl group of the polyamic acid produced by the reaction of the raw material tetracarboxylic dianhydride and diamine. 0.8 times equivalent or more, More preferably, it is 1.0 times equivalent or more, More preferably, it is 1.2 times equivalent or more. If the amount of imidazole used is less than 0.8 equivalents relative to the carboxyl group of the polyamic acid, it may not be easy to obtain a uniformly dissolved polyimide precursor aqueous solution composition.
- the upper limit of the usage-amount of imidazoles is not specifically limited, Usually, it is less than 10 times equivalent, Preferably it is less than 5 times equivalent, More preferably, it is less than 3 times equivalent. If the amount of imidazole used is too large, it may be uneconomical and the storage stability of the composition may be deteriorated.
- the equivalent to the carboxyl group of the polyamic acid that defines the amount of imidazoles is the number (number of molecules) of imidazoles in one carboxyl group forming the amic acid group of the polyamic acid. Indicates whether to use.
- the amount of the imidazoles used in the present invention is preferably 1.6 times mol or more, more preferably 2 with respect to the tetracarboxylic acid component of the polyamic acid, that is, with respect to the raw material tetracarboxylic dianhydride. It is 0.0 times mol or more, More preferably, it is 2.4 times mol or more. Moreover, the upper limit of the amount used is usually less than 20 times mol, preferably less than 10 times mol, more preferably less than 6 times mol.
- the characteristics of imidazoles used in the present invention are not only to increase the solubility in water by forming a salt with a carboxyl group of polyamic acid, but also when imidizing the polyimide precursor (dehydration ring closure) into a polyimide, It has an extremely high catalytic action.
- an aromatic polyimide having extremely high physical properties can be easily obtained, for example, by a heat treatment at a lower temperature for a shorter time.
- the polyimide precursor aqueous solution composition used in the present invention is: (i) Polyamic acid obtained by reacting a tetracarboxylic acid component with a diamine component using an organic solvent as a reaction solvent is poured into water to obtain a polyamic acid powder, and the polyamic acid powder is imidazoles in an aqueous solvent.
- a water-soluble polyimide precursor is obtained by reacting a tetracarboxylic acid component and a diamine component in the presence of imidazoles (preferably imidazoles having two or more alkyl groups) using an organic solvent as a reaction solvent, A method of dissolving it in an aqueous solvent after separating it, or (iii) A polycarboxylic acid is obtained by reacting a tetracarboxylic acid component and a diamine component using an organic solvent as a reaction solvent, and the polyamic acid is converted into an imidazole (preferably two or more alkyl groups) using the organic solvent as a reaction solvent.
- a water-soluble polyimide precursor is obtained by reacting with an imidazole having a solvent, and is separated and then dissolved in an aqueous solvent.
- the aqueous polyimide precursor solution composition used in the present invention preferably reacts a tetracarboxylic acid component and a diamine component in the presence of imidazoles having two or more alkyl groups as substituents using water as a reaction solvent. Therefore, it is possible to manufacture very simply (directly).
- This reaction is carried out at a relatively low temperature of 100 ° C. or less, preferably 80 ° C. or less, in order to suppress the imidization reaction, using approximately equimolar amounts of the tetracarboxylic acid component and the diamine component.
- the normal reaction temperature is 25 ° C. to 100 ° C., preferably 40 ° C. to 80 ° C., more preferably 50 ° C.
- reaction time is about 0.1 to 24 hours, preferably Is preferably about 2 to 12 hours.
- the reaction may be carried out in an air atmosphere, but usually it is suitably carried out in an inert gas, preferably a nitrogen gas atmosphere.
- the polyimide precursor aqueous solution composition used in the present invention uses a water solvent, but a known organic solvent other than water used when preparing polyamic acid is 50% by mass or less, preferably 30% by mass or less, More preferably, you may use in the ratio of 10 mass% or less.
- an organic solvent other than water may be used in a proportion of 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less in the total solvent.
- the organic solvent referred to here does not include tetracarboxylic acid components such as tetracarboxylic dianhydride, diamine components, polyimide precursors such as polyamic acid, and imidazoles.
- organic solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [ 2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane, dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole, m-cresol, phenol, ⁇ -butyrolactone, etc. .
- the reaction solvent is preferably a solvent having an organic solvent content of less than 5%, and an organic solvent other than water. It is particularly preferable that the water solvent does not contain.
- the composition of the reaction solvent can be appropriately selected according to the desired solvent composition of the polyimide precursor aqueous solution composition to be produced, and may be preferably the same as the desired solvent composition of the polyimide precursor aqueous solution composition. .
- the polyimide precursor aqueous solution composition used in the present invention is not limited in the solid content concentration due to the polyimide precursor (substantially polyamic acid), it is preferably 5 with respect to the total amount of the polyimide precursor and the solvent. It is suitable that the content is from mass% to 45 mass%, more preferably from 7 mass% to 40 mass%, still more preferably from 9 mass% to 30 mass%. If the solid content concentration is lower than 5% by mass, the productivity may be remarkably deteriorated, and if it is higher than 45% by mass, the fluidity of the solution may be lost.
- the solution viscosity of the polyimide precursor aqueous solution composition of the present invention at 30 ° C.
- the handling is preferably 3 to 200 Pa ⁇ sec. If the solution viscosity exceeds 1000 Pa ⁇ sec, the fluidity is lost, so that uniform application to metal or glass becomes difficult, and if it is lower than 0.5 Pa ⁇ sec, it may sag during application to metal or glass. Since cissing and the like occur, it is not preferable, and it may be difficult to obtain an aromatic polyimide having high characteristics.
- the aqueous polyimide precursor solution composition used in the present invention can usually obtain an aromatic polyimide by removing an aqueous solvent by heat treatment and imidizing (dehydrating ring closure).
- the heat treatment conditions are not particularly limited, but are generally 100 ° C. or higher, preferably 120 ° C. to 600 ° C., more preferably 150 ° C. to 500 ° C., 0.01 hours to 30 hours, preferably 0.01 to 10 hours. is there.
- the characteristics of the aromatic polyimide obtained by using the aqueous polyimide precursor solution of the present invention are as follows: a normal organic solvent can be obtained by heating at a relatively low temperature (for example, 150 ° C. to 300 ° C., preferably 200 ° C. to 280 ° C.). Compared with the polyimide precursor (polyamic acid) solution composition used, it is possible to exhibit excellent characteristics such as high adhesiveness to metals, for example.
- the electrode mixture composition used in the present invention contains an electrode active material and a polyimide precursor aqueous solution composition, and further contains a crosslinking agent having a carbodiimide group or an oxazoline group. This is preferable because a decrease in the adhesive strength between the layer and the current collector can be suppressed.
- the crosslinking agent having a carbodiimide group include carbodiimide group-containing resins such as polycarbodiimide.
- Examples of the crosslinking agent having an oxazoline group include 1,3-phenylenebisoxazoline and oxazoline group-containing resin.
- the addition amount of the crosslinking agent is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass with respect to the polyamic acid.
- the electrode mixture composition used in the present invention can further contain a pyridine compound, can further reduce the degree of swelling of the resulting polyimide binder with respect to the electrolytic solution, and can increase the elongation at break and the energy at break. Furthermore, it is preferable because the heat treatment time for obtaining the electrode can be shortened and the heat treatment temperature can be further reduced.
- the pyridine compound is a compound having a pyridine skeleton in its chemical structure. For example, pyridine, 3-pyridinol, quinoline, isoquinoline, quinoxaline, 6-tert-butylquinoline, acridine, 6-quinolinecarboxylic acid, 3,4 Preferred examples include lutidine, pyridazine and the like. These pyridine compounds may be used alone or in combination of two or more.
- the addition amount of the pyridine compound is not limited, but is preferably 0.05 to 2.0 molar equivalents, more preferably 0.8, relative to the amic acid structure of the polyamic acid (per mole of the amic acid structure). 1 to 1.0 molar equivalent.
- the addition amount is outside this range, the swelling degree of the resin with respect to the electrolytic solution is made smaller, the breaking elongation and breaking energy of the resulting polyimide binder are made larger, and further the heat treatment temperature for obtaining the electrode is kept lower. It may be difficult to obtain the effect of adding a pyridine compound.
- the electrode mixture composition used in the present invention suitably contains additives such as surfactants, viscosity modifiers (thickeners), conductive assistants (conductive agents), etc., which are contained in ordinary electrode mixture compositions. Can be contained.
- additives such as surfactants, viscosity modifiers (thickeners), conductive assistants (conductive agents), etc.
- the electrode mixture composition used in the present invention is preferably in a slurry state by sufficiently kneading the polyimide precursor aqueous solution composition with the addition of the crosslinking agent, the electrode active material and other components as required. can get.
- the amount of the electrode active material in the electrode mixture composition is not particularly limited, but is usually 0.1 to 1000 times, preferably 1 to 1000 times on a mass basis with respect to the solid content mass caused by the polyamic acid. More preferably, it is 5 to 1000 times, and further preferably 10 to 1000 times. If the amount of the electrode active material is too small, an inactive portion increases in the electrode mixture layer formed on the current collector, and the function as an electrode may be insufficient.
- the electrode mixture composition of the present invention is preferably mixed so that the solid content resulting from the polyamic acid is 1 to 15% by mass in the total solid content. Outside this range, the electrode performance may deteriorate.
- an electrode mixture composition (paste) containing at least an electrode active material, a polyimide precursor aqueous solution composition, and a crosslinking agent is applied and cast on the surface of the current collector.
- a laminate in which an electrode mixture layer is formed on the surface of the current collector is obtained.
- the electrode mixture layer is usually adjusted to a thickness of about 10 to 300 ⁇ m after drying.
- the electrode mixture layer is formed on one side or both sides of the current collector.
- the laminate in which the electrode mixture layer is formed on the surface of the current collector is heat-treated to remove the solvent and convert the polyamic acid amic acid structure into an imide structure.
- This heat treatment step is preferably performed in a temperature range of 80 ° C. to 200 ° C., preferably 90 ° C. to 180 ° C., more preferably 100 ° C. to 170 ° C.
- heat processing temperature is 80 degrees C or less, imidation reaction may not fully advance or the physical property of an electrode molded object may fall.
- it exceeds 200 degreeC there exists a possibility that a collector may deteriorate.
- the heat treatment may be performed by a method in which the temperature is raised stepwise in multiple stages in order to prevent foaming and powdering.
- the heat treatment time is preferably in the range of 10 minutes to 48 hours. 48 hours or longer is not preferable from the viewpoint of productivity, and if it is shorter than 10 minutes, imidation reaction or solvent removal may be insufficient. During this time, most of the solvent is removed and the polyamic acid is substantially converted to polyimide by the imidization reaction.
- the heat treatment can be suitably performed under reduced pressure conditions or under an inert gas flow condition.
- substantially becoming polyimide means that the amic acid structure may remain in the polyimide, and is 70% or more, preferably 80% or more, more preferably 90% or more of the amic acid structure. May be imidized. It is not always easy to completely imidize the amic acid structure by heat treatment at such a low temperature.
- the binder binder before the addition of the electrode active material
- the binder comprising the polyamic acid composed of the repeating unit composed of the specific tetracarboxylic acid component and the diamine component of the present invention and the crosslinking agent (heat treatment at such a low temperature)
- the degree of swelling is small even in a battery environment (the rate of mass increase due to swelling when immersed in dimethyl carbonate at 25 ° C.
- the 90 ° peel strength with the current collector was 0.5 N / mm or more, more preferably 0.7 N / mm or more before being immersed in dimethyl carbonate, and was immersed in dimethyl carbonate at 25 ° C. for 24 hours.
- the subsequent 90 ° peel strength retention is 80% or more, more preferably 85% or more, and still more preferably 90% or more.
- the peeling was less than 5%, and the peeling after being immersed in dimethyl carbonate for 24 hours at 25 ° C. was also less than 5%
- the excellent properties required as a binder for high-performance batteries that can maintain toughness is preferably 2% by mass or less, more preferably 1% by mass or less) and excellent adhesion
- the electrode obtained by the method for producing an electrode of the present invention can suitably produce a battery according to a known method.
- the obtained positive electrode and negative electrode are wound into a cylindrical shape, for example, while sandwiching a separator such as a polyolefin porous body in accordance with a normal method, and this cylindrical electrode body is
- the battery can be suitably obtained by inserting the electrode body and the nonaqueous electrolytic solution into the exterior body while remaining in the shape or being crushed into a flat shape.
- a binder (binder resin composition) comprising an aromatic polyamic acid having a repeating unit represented by the chemical formula (1), which is a feature of the present invention, was heat-treated at a low temperature of 200 ° C. or lower. Even in the case, it shows that the characteristics required as a binder resin for electrodes are sufficiently satisfied.
- ⁇ Solution stability> The sample solution was stored in an atmosphere adjusted to a temperature of 25 ° C., and a change in solution viscosity after 1 month was within ⁇ 10%, and a sample with a change exceeding ⁇ 10% was rated as x.
- ⁇ DMC swelling test> A sample obtained by cutting an electrode composed of a copper foil and an electrode mixture layer into a 5 cm square is used as a sample, and the mass of the electrode mixture layer alone is determined by subtracting the mass of the copper foil by calculation.
- ⁇ Adhesion test (cross-cut method)> The adhesion test was conducted according to JIS K 5600-5-6. The evaluation was visually indicated as classification 0 to classification 5 (the smaller the number, the stronger the adhesion) based on the evaluation standard (3). The adhesion test was performed on samples before and after the swelling test with a dimethyl carbonate solution.
- the 90 ° peel strength test was measured using a universal testing machine (RTC-1225A manufactured by Orientec Co., Ltd.) in accordance with IPC-TM650.
- ODPA 4,4′-oxydiphthalic dianhydride
- s-BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
- PPD p-phenylenediamine
- ODA 4,4′-diaminodiphenyl ether
- HMD hexamethylenediamine
- 3,5-DABA 3,5-diaminobenzoic acid
- MBAA 4,4′-diamino-3,3′-dicarboxydiphenylmethane
- 1,3-PBO 1,3-phenylenebisoxazoline
- 1,2-DMZ 1,2-Dimethylimidazole
- Example 1 450 g of water as a solvent was added to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 18.40 g (0.092 mol) of ODA and 3,5-DABA of ODA were added thereto. 1.55 g (0.010 mol) and 24.54 g of 1,2-DMZ (1.25 equivalents relative to the carboxyl group) were added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 30.04 g (0.102 mol) of s-BPDA was added and stirred at 70 ° C.
- the copper foil coated with the electrode binder resin composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. Then, a heat treatment was performed at 170 ° C. for 1 hour to form a binder resin film having a thickness of 25 ⁇ m.
- a DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. Further, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with a dimethyl carbonate solution.
- the electrode binder composition (electrode) was prepared by kneading 8.3 g of the binder resin composition for electrodes (solid content mass after imidization 0.8 g) and 9.2 g of silicon powder of 325 mesh pass so as to be ground in a mortar.
- a mixture paste was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
- the copper foil coated with the paste was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 1 hour at 170 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 ⁇ m.
- a DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
- Example 2 Various tests were performed in the same manner as in Example 1 except that 1% by mass of 1,3-PBO was added to the electrode binder resin composition instead of the carbodiimide resin. These results are shown in Table 1.
- Example 3 450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 17.91 g (0.089 mol) of ODA and 2.85 g of MBAA ( 0.010 mol) and 23.89 g of 1,2-DMZ (1.25 equivalents relative to the carboxyl group) were added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 29.24 g (0.099 mol) of s-BPDA was added and stirred at 70 ° C. for 6 hours to obtain a solid content concentration of 9.5% by mass, a solution viscosity of 3.4 Pa ⁇ s, and a logarithmic viscosity of 0.21.
- a polyamic acid solution was obtained.
- 1 mass% carbodiimide resin (Nisshinbo Chemical Co., Ltd. polycarbodiimide) was added with respect to the polyamic acid to the obtained polyamic-acid solution, and the binder resin composition for electrodes was obtained.
- the copper foil coated with the electrode binder resin composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. Then, a heat treatment was performed at 170 ° C. for 1 hour to form a binder resin film having a thickness of 25 ⁇ m.
- a DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. Further, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with a dimethyl carbonate solution.
- the electrode binder composition (electrode) was prepared by kneading 8.4 g of the binder resin composition for an electrode (solid content after imidization: 0.8 g) and 9.2 g of 325 mesh pass silicon powder in a mortar. A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod. The copper foil coated with the paste was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 1 hour at 170 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 ⁇ m. A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution. These results are shown in Table 1.
- Example 4 Various tests were conducted in the same manner as in Example 3 except that 1% by mass of 1,3-PBO was added to the electrode binder resin composition instead of the carbodiimide resin. These results are shown in Table 1.
- Example 5 450 g of water was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, to which 12.16 g (0.105 mol) of HMD and 3,5-DABA were added. 1.77 g (0.012 mol) and 27.95 g of 1,2-DMZ (1.25 equivalents relative to the carboxyl group) were added and stirred at 25 ° C. for 1 hour to dissolve. 36.07 g (0.116 mol) of ODPA was added to this solution, and the mixture was stirred at 70 ° C.
- the copper foil coated with the electrode binder resin composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. Then, a heat treatment was performed at 170 ° C. for 1 hour to form a binder resin film having a thickness of 25 ⁇ m.
- a DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. Further, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with a dimethyl carbonate solution.
- the electrode binder composition (electrode) was prepared by kneading 8.7 g of the binder resin composition for electrodes (solid content mass after imidization 0.8 g) and 9.2 g of silicon powder of 325 mesh pass so as to be ground in a mortar.
- a mixture paste was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod.
- the copper foil coated with the paste was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 1 hour at 170 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 ⁇ m.
- a DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution.
- Example 6 Various tests were conducted in the same manner as in Example 5 except that 1% by mass of 1,3-PBO was added to the electrode binder resin composition instead of the carbodiimide resin. These results are shown in Table 1.
- Example 7 450 g of water was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge pipe, and 11.79 g (0.101 mol) of HMD and 3.23 g of MBAA were added thereto. 0.011 mol) and 27.10 g of 1,2-DMZ (1.25 equivalents relative to the carboxyl group) were added and stirred at 25 ° C. for 1 hour to dissolve. To this solution, 34.98 g (0.113 mol) of ODPA was added and stirred at 70 ° C.
- the copper foil coated with the electrode binder resin composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. Then, a heat treatment was performed at 170 ° C. for 1 hour to form a binder resin film having a thickness of 25 ⁇ m.
- a DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. Further, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with a dimethyl carbonate solution.
- Example 8 Various tests were conducted in the same manner as in Example 7 except that 1% by mass of 1,3-PBO was added to the electrode binder resin composition instead of the carbodiimide resin. These results are shown in Table 1.
- Example 9 450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 2.26 g (0.021 mol) of PPD and 14.63 g of ODA ( 0.073 mol) and 1.59 g (0.010 mol) of 3,5-DABA and 25.08 g of 1,2-DMZ (1.25 times equivalent to the carboxyl group) were added at 25 ° C. Stir for 1 hour to dissolve. To this solution, 15.35 g (0.052 mol) of s-BPDA and 16.18 g (0.052 mol) of ODPA were added and stirred at 70 ° C. for 6 hours to obtain a solid content concentration of 9.7% by mass.
- a polyamic acid solution having a viscosity of 4.1 Pa ⁇ s and a logarithmic viscosity of 0.42 was obtained.
- 1 mass% carbodiimide resin (Nisshinbo Chemical Co., Ltd. polycarbodiimide) was added with respect to the polyamic acid to the obtained polyamic-acid solution, and the binder resin composition for electrodes was obtained.
- the copper foil coated with the electrode binder resin composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. Then, a heat treatment was performed at 170 ° C. for 1 hour to form a binder resin film having a thickness of 25 ⁇ m.
- a DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. Further, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with a dimethyl carbonate solution.
- the electrode binder composition (electrode) was prepared by kneading 8.2 g of the binder resin composition for electrodes (solid content after imidization: 0.8 g) and 9.2 g of 325 mesh pass silicon powder in a mortar. A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod. The copper foil coated with the paste was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 1 hour at 170 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 ⁇ m. A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution. These results are shown in Table 1.
- Example 10 Various tests were conducted in the same manner as in Example 9 except that 1% by mass of 1,3-PBO was added to the electrode binder resin composition instead of the carbodiimide resin. These results are shown in Table 1.
- Example 11 450 g of water was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 2.20 g (0.020 mol) of PPD and 14.23 g of ODA ( 0.071 mol) and 2.91 g (0.010 mol) of MBAA and 24.40 g of 1,2-DMZ (1.25 times equivalent to the carboxyl group) were added and stirred at 25 ° C. for 1 hour. , Dissolved. To this solution, 14.93 g (0.051 mol) of s-BPDA and 15.74 g (0.051 mol) of ODPA were added and stirred at 70 ° C. for 6 hours to obtain a solid content concentration of 9.5% by mass.
- a polyamic acid solution having a viscosity of 3.6 Pa ⁇ s and a logarithmic viscosity of 0.38 was obtained.
- 1 mass% carbodiimide resin (Nisshinbo Chemical Co., Ltd. polycarbodiimide) was added with respect to the polyamic acid to the obtained polyamic-acid solution, and the binder resin composition for electrodes was obtained.
- the copper foil coated with the electrode binder resin composition was fixed on a substrate, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. Then, a heat treatment was performed at 170 ° C. for 1 hour to form a binder resin film having a thickness of 25 ⁇ m.
- a DMC swelling test was performed using a binder resin film formed on the copper foil as a sample. Further, an adhesion test and a 90 ° peel strength measurement were performed on the samples before and after the swelling test with a dimethyl carbonate solution.
- the electrode binder composition (electrode) was prepared by kneading 8.4 g of the binder resin composition for an electrode (solid content after imidization: 0.8 g) and 9.2 g of 325 mesh pass silicon powder in a mortar. A mixture paste) was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod. The copper foil coated with the paste was fixed on the substrate, defoamed and pre-dried at 25 ° C. for 30 minutes under reduced pressure, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere for 1 hour at 170 ° C. Heat treatment was performed to produce an electrode with an electrode mixture layer thickness of 100 ⁇ m. A DMC swelling test was performed using the obtained electrode as a sample. Moreover, the adhesion test was done about the sample before and behind the swelling test in a dimethyl carbonate solution. These results are shown in Table 1.
- Example 12 Various tests were conducted in the same manner as in Example 11 except that 1% by mass of 1,3-PBO was added to the electrode binder resin composition instead of the carbodiimide resin. These results are shown in Table 1.
- Example 2 Various tests were performed in the same manner as in Example 1 except that 1% by mass of an epoxy resin was added to the electrode binder resin composition instead of the carbodiimide resin. These results are shown in Table 2.
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Abstract
Description
特許文献2には、電解液に対する膨潤度が小さく、優れた靱性(大きな破断伸度及び破断エネルギー)を有する、特定のポリアミック酸と溶剤とからなる電極用バインダー樹脂組成物が記載されている。また、電極を製造する際にはイミド化反応が十分に進行するよう、比較的高い温度での加熱処理が必要であることが記載されている。
特許文献3には、カルボキシル基を有するポリイミド樹脂とエポキシ樹脂とを含有するリチウムイオン二次電池の電極用樹脂組成物が記載されている。
また、近年、電池用の集電体(銅箔など)は極薄化が進んで厚さが10μm以下のものが使用されるようになり、電極製造工程で集電体が高温に曝されると機械強度が大幅に低下するなどの問題が生じることから、200℃以下の比較的低温で熱処理することが望まれている。
さらに、電極製造工程における有機溶媒の使用は環境への影響が懸念されるため、有機溶媒を使用しない環境適応性が良好である製造プロセスが望まれている。
1. 集電体の表面に、少なくとも電極活物質と、下記化学式(1)で表される繰返し単位を有するポリアミド酸を前記ポリアミド酸のテトラカルボン酸成分に対して1.6倍モル以上の置換基として2個以上のアルキル基を有するイミダゾール類と共に水溶媒中に溶解してなるポリイミド前駆体水溶液組成物と、カルボジイミド基又はオキサゾリン基を有する架橋剤とを含有する電極合剤組成物によって電極合剤層を形成し、次いで加熱処理して溶媒を除去するとともにポリアミド酸のイミド化反応を行うことを特徴とする電極の製造方法。
2. 置換基として2個以上のアルキル基を有するイミダゾール類が、1,2-ジメチルイミダゾール、2-エチル-4-メチルイミダゾール、4-エチル-2-メチルイミダゾール、及び1-メチル-4-エチルイミダゾールからなる群から選択されるイミダゾール類であることを特徴とする項1に記載の電極の製造方法。
3. 電極活物質が、炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末であることを特徴とする項1又は2に記載の電極の製造方法。
4. 電極活物質が、リチウム遷移金属酸化物であることを特徴とする項1~3のいずれかに記載の電極の製造方法。
5. リチウムイオン二次電池用電極を得ることを特徴とする項1~4のいずれかに記載の電極の製造方法。
集電体は、必要に応じて表面粗さが制御され、例えば平板状、メッシュ状、ネット状、ラス状、パンチングメタル状、エンボス状などの箔以外の形状であっても構わない。
本発明で用いる電極合剤組成物の電極活物質は、電池で通常用いられるものであれば限定されるものではない。負極の場合は、リチウムを電気化学的に挿入、脱離することができる物質であればよく、例えば黒鉛、コークス類、カーボンブラック、熱分解炭素などの炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末を挙げることができる。合金粉末はケイ素若しくはスズと金属元素との金属間化合物であることが好ましく、金属元素としてはニッケル、チタン、鉄、コバルト、銅、ジルコン、マンガンなどの遷移金属であることが好ましい。正極の場合は、リチウム元素を有し、リチウムを電気化学的に脱離、挿入することができる物質であればよく、例えばLiCoO2、LiNiO2、LiMnO2,LiCo0.5Mn0.5O2,LiNi0.7Co0.2Mn0.1O2などのリチウム遷移金属酸化物を好適に挙げることができる。
このポリアミド酸は、溶媒中でテトラカルボン酸成分とジアミン成分とをイミド化反応を抑制するために低温で反応させることによって容易に調製することができる。
テトラカルボン酸成分は、テトラカルボン酸類すなわちテトラカルボン酸、その酸二無水物及びそのエステル化化合物などであり、好ましくは二無水物である。
本発明において、イミダゾール類の量を規定するポリアミド酸のカルボキシル基に対する倍当量とは、ポリアミド酸のアミド酸基を形成するカルボキシル基1個に対して何個(何分子)の割合でイミダゾール類を用いるかを表す。なお、ポリアミド酸のアミド酸基を形成するカルボキシル基の数は、原料のテトラカルボン酸成分1分子当たり2個のカルボキシル基を形成するものとして計算される。
したがって、本発明で用いるイミダゾール類の使用量は、ポリアミド酸のテトラカルボン酸成分に対して、つまり原料のテトラカルボン酸二無水物に対して、好ましくは1.6倍モル以上、より好ましくは2.0倍モル以上、さらに好ましくは2.4倍モル以上である。また、使用量の上限は、通常は20倍モル未満、好ましくは10倍モル未満、より好ましくは6倍モル未満である。
(i) 有機溶媒を反応溶媒とし、テトラカルボン酸成分とジアミン成分とを反応して得られたポリアミド酸を水中に投入してポリアミド酸粉末を得、そのポリアミド酸粉末を水溶媒中でイミダゾール類(好ましくは2個以上のアルキル基を有するイミダゾール類)と共に混合溶解して水溶液組成物を得る方法、
(ii) 有機溶媒を反応溶媒とし、イミダゾール類(好ましくは2個以上のアルキル基を有するイミダゾール類)の存在下にテトラカルボン酸成分とジアミン成分とを反応して水溶性ポリイミド前駆体を得、それを分離後、水溶媒に溶解する方法、或いは、
(iii) 有機溶媒を反応溶媒とし、テトラカルボン酸成分とジアミン成分とを反応してポリアミド酸を得、そのポリアミド酸を、有機溶媒を反応溶媒として、イミダゾール類(好ましくは2個以上のアルキル基を有するイミダゾール類)と反応して水溶性ポリイミド前駆体を得、それを分離後、水溶媒に溶解する方法
などでも得ることができる。但し、前述の通り、有機溶媒の含有量が極めて少ない、さらには有機溶媒を含まないポリイミド前駆体水溶液組成物を得るためには、ポリイミド前駆体を有機溶媒中で調製することは好ましくない。
溶液粘度が1000Pa・secを超えると、流動性がなくなるため金属やガラスなどへの均一な塗布が困難となり、また、0.5Pa・secよりも低いと、金属やガラスなどへの塗布時にたれやハジキなどが生じるので好ましくなく、また高い特性の芳香族ポリイミドを得ることが難しくなることがある。
本発明のポリイミド前駆体水溶液を用いて得られる芳香族ポリイミドの特性は、比較的低温(例えば150℃~300℃、好ましくは200℃~280℃)で加熱処理しただけで、通常の有機溶媒を用いたポリイミド前駆体(ポリアミド酸)溶液組成物に較べて遜色なく、好適には、例えば金属類などとの接着性が高いというような優れた特性を発揮することができる。
ピリジン類化合物は、化学構造中にピリジン骨格を有する化合物のことであり、例えばピリジン、3-ピリジノール、キノリン、イソキノリン、キノキサリン、6-tert-ブチルキノリン、アクリジン、6-キノリンカルボン酸、3,4-ルチジン、ピリダジンなどを好適に挙げることができる。これらのピリジン系化合物は、単独または2種以上併用して使用しても差し支えない。
加熱処理温度が80℃以下の場合、イミド化反応が十分に進行しなかったり、電極成形体の物性が低下したりすることがある。また、200℃を超えると集電体が劣化する恐れがある。加熱処理は発泡や粉末化を防ぐために多段で段階的に昇温させる方法で行ってもよい。加熱処理時間は10分~48時間の範囲が好ましい。48時間以上は生産性の点から好ましくなく、10分よりも短いとイミド化反応や溶媒の除去が不十分となることがある。
この間に、ほとんどの溶媒が除かれ、且つポリアミド酸はイミド化反応によって実質的にポリイミドになる。加熱処理は、効率よく溶媒を除くために、減圧下条件下や不活性ガス流条件下で好適に行うことができる。
<固形分濃度>
試料溶液(その質量をw1とする)を、熱風乾燥機中120℃で10分間、250℃で10分間、次いで350℃で30分間加熱処理して、加熱処理後の質量(その質量をw2とする)を測定する。固形分濃度[質量%]は、次式によって算出した。
固形分濃度[質量%]=(w2/w1)×100
試料溶液を、固形分濃度に基づいて濃度が0.5g/dl(溶媒はNMP)になるように希釈した。この希釈液について、30℃にて、キャノンフェンスケNo.100を用いて流下時間(T1)を測定した。対数粘度は、ブランクのNMPの流下時間(T0)を用いて、次式から算出した。
対数粘度={ln(T1/T0)}/0.5
試料溶液を、トキメック社製E型粘度計を用いて30℃で測定した。
試料溶液を、25℃の温度に調整された雰囲気中に保管し、1ヶ月後の溶液粘度変化が±10%以内のものを○、±10%を超えたものを×とした。
銅箔と電極合剤層からなる電極を5cm角に切り出したものを試料とし、電極合剤層単独の質量は計算によって銅箔の質量を減じることによって求めることとし、以下のジメチルカーボネート溶液での膨潤試験によって電極合剤層の膨潤度Sを測定した。すなわち、25℃で24時間真空乾燥後の電極合剤層の質量を乾燥質量(Wd)とし、ジメチルカーボネート(DMC)溶液に25℃で24時間浸漬後の電極合剤層の質量を膨潤質量(Ww)とし、次式により膨潤度Sを計算した。
S[質量%]=(Ww-Wd)/Ww×100
付着性試験は、JIS K 5600-5-6に準拠して行った。なお、評価は目視により、評価基準(3)に準拠した分類0~分類5(数字が小さいほど強固に付着している)で示した。
なお、付着性試験は、ジメチルカーボネート溶液での膨潤試験前後の試料について、それぞれ行った。
90°ピール強度試験は、万能試験機(オリエンテック社製RTC-1225A)を用いて、IPC-TM650に準拠して測定した。
ジメチルカーボネート溶液での膨潤試験前後の試料について、90°ピール強度を測定し、次式により90°ピール強度の保持率を算出した。
90°ピール強度保持率[%]
=浸漬後の90°ピール強度/浸漬前の90°ピール強度×100
ODPA:4,4’-オキシジフタル酸二無水物、
s-BPDA:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、
PPD:p-フェニレンジアミン、
ODA:4,4’-ジアミノジフェニルエーテル、
HMD:ヘキサメチレンジアミン、
3,5-DABA:3,5-ジアミノ安息香酸
MBAA:4,4’-ジアミノ-3,3’-ジカルボキシジフェニルメタン
1,3-PBO:1,3-フェニレンビスオキサゾリン
1,2-DMZ:1,2-ジメチルイミダゾール
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにODAの18.40g(0.092モル)及び3,5-DABAの1.55g(0.010モル)と、1,2-DMZの24.54g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs-BPDAの30.04g(0.102モル)を加え、70℃で6時間撹拌して、固形分濃度9.6質量%、溶液粘度4.2Pa・s、対数粘度0.27のポリアミド酸溶液を得た。
得られたポリアミド酸溶液に、ポリアミド酸に対して1質量%のカルボジイミド樹脂(日清紡ケミカル社製ポリカルボジイミド)を添加し電極用バインダー樹脂組成物を得た。
銅箔上に形成したバインダー樹脂フィルムを試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験及び90°ピール強度測定を行った。
これらの結果を表1に示した。
ペーストを塗布した銅箔を基板上に固定し、減圧下25℃で30分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、170℃で1時間加熱処理して、電極合剤層の厚みが100μmの電極を作製した。
得られた電極を試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表1に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりに1,3-PBOを1質量%添加した以外は実施例1と同様にして各種試験を行った。
これらの結果を表1に示した。
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにODAの17.91g(0.089モル)及びMBAAの2.85g(0.010モル)と、1,2-DMZの23.89g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs-BPDAの29.24g(0.099モル)を加え、70℃で6時間撹拌して、固形分濃度9.5質量%、溶液粘度3.4Pa・s、対数粘度0.21のポリアミド酸溶液を得た。
得られたポリアミド酸溶液に、ポリアミド酸に対して1質量%のカルボジイミド樹脂(日清紡ケミカル社製ポリカルボジイミド)を添加し電極用バインダー樹脂組成物を得た。
銅箔上に形成したバインダー樹脂フィルムを試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験及び90°ピール強度測定を行った。
これらの結果を表1に示した。
ペーストを塗布した銅箔を基板上に固定し、減圧下25℃で30分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、170℃で1時間加熱処理して、電極合剤層の厚みが100μmの電極を作製した。
得られた電極を試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表1に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりに1,3-PBOを1質量%添加した以外は実施例3と同様にして各種試験を行った。
これらの結果を表1に示した。
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにHMDの12.16g(0.105モル)及び3,5-DABAの1.77g(0.012モル)と、1,2-DMZの27.95g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にODPAの36.07g(0.116モル)を加え、70℃で6時間撹拌して、固形分濃度9.2質量%、溶液粘度0.1Pa・s、対数粘度0.27のポリアミド酸溶液を得た。
得られたポリアミド酸溶液に、ポリアミド酸に対して1質量%のカルボジイミド樹脂(日清紡ケミカル社製ポリカルボジイミド)を添加し電極用バインダー樹脂組成物を得た。
銅箔上に形成したバインダー樹脂フィルムを試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験及び90°ピール強度測定を行った。
これらの結果を表1に示した。
ペーストを塗布した銅箔を基板上に固定し、減圧下25℃で30分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、170℃で1時間加熱処理して、電極合剤層の厚みが100μmの電極を作製した。
得られた電極を試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表1に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりに1,3-PBOを1質量%添加した以外は実施例5と同様にして各種試験を行った。
これらの結果を表1に示した。
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにHMDの11.79g(0.101モル)及びMBAAの3.23g(0.011モル)と、1,2-DMZの27.10g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にODPAの34.98g(0.113モル)を加え、70℃で6時間撹拌して、固形分濃度9.4質量%、溶液粘度0.1Pa・s、対数粘度0.20のポリアミド酸溶液を得た。
得られたポリアミド酸溶液に、ポリアミド酸に対して1質量%のカルボジイミド樹脂(日清紡ケミカル社製ポリカルボジイミド)を添加し電極用バインダー樹脂組成物を得た。
銅箔上に形成したバインダー樹脂フィルムを試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験及び90°ピール強度測定を行った。
これらの結果を表1に示した。
ペーストを塗布した銅箔を基板上に固定し、減圧下25℃で30分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、170℃で1時間加熱処理して、電極合剤層の厚みが100μmの電極を作製した。
得られた電極を試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表1に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりに1,3-PBOを1質量%添加した以外は実施例7と同様にして各種試験を行った。
これらの結果を表1に示した。
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの2.26g(0.021モル)、ODAの14.63g(0.073モル)及び3,5-DABAの1.59g(0.010モル)と、1,2-DMZの25.08g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs-BPDAの15.35g(0.052モル)及びODPAの16.18g(0.052モル)を加え、70℃で6時間撹拌して、固形分濃度9.7質量%、溶液粘度4.1Pa・s、対数粘度0.42のポリアミド酸溶液を得た。
得られたポリアミド酸溶液に、ポリアミド酸に対して1質量%のカルボジイミド樹脂(日清紡ケミカル社製ポリカルボジイミド)を添加し電極用バインダー樹脂組成物を得た。
銅箔上に形成したバインダー樹脂フィルムを試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験及び90°ピール強度測定を行った。
これらの結果を表1に示した。
ペーストを塗布した銅箔を基板上に固定し、減圧下25℃で30分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、170℃で1時間加熱処理して、電極合剤層の厚みが100μmの電極を作製した。
得られた電極を試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表1に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりに1,3-PBOを1質量%添加した以外は実施例9と同様にして各種試験を行った。
これらの結果を表1に示した。
攪拌機、窒素ガス導入・排出管を備えた内容積500mLのガラス製の反応容器に、溶媒として水の450gを加え、これにPPDの2.20g(0.020モル)、ODAの14.23g(0.071モル)及びMBAAの2.91g(0.010モル)と、1,2-DMZの24.40g(カルボキシル基に対して1.25倍当量)とを加え25℃で1時間攪拌し、溶解させた。この溶液にs-BPDAの14.93g(0.051モル)及びODPAの15.74g(0.051モル)を加え、70℃で6時間撹拌して、固形分濃度9.5質量%、溶液粘度3.6Pa・s、対数粘度0.38のポリアミド酸溶液を得た。
得られたポリアミド酸溶液に、ポリアミド酸に対して1質量%のカルボジイミド樹脂(日清紡ケミカル社製ポリカルボジイミド)を添加し電極用バインダー樹脂組成物を得た。
銅箔上に形成したバインダー樹脂フィルムを試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験及び90°ピール強度測定を行った。
これらの結果を表1に示した。
ペーストを塗布した銅箔を基板上に固定し、減圧下25℃で30分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、170℃で1時間加熱処理して、電極合剤層の厚みが100μmの電極を作製した。
得られた電極を試料としてDMC膨潤試験を行った。またジメチルカーボネート溶液での膨潤試験前後の試料について付着性試験を行った。
これらの結果を表1に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりに1,3-PBOを1質量%添加した以外は実施例11と同様にして各種試験を行った。
これらの結果を表1に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂を添加しない以外は実施例1と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりにエポキシ樹脂を1質量%添加した以外は実施例1と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂を添加しない以外は実施例3と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりにエポキシ樹脂を1質量%添加した以外は実施例3と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂を添加しない以外は実施例5と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりにエポキシ樹脂を1質量%添加した以外は実施例5と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂を添加しない以外は実施例7と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりにエポキシ樹脂を1質量%添加した以外は実施例7と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂を添加しない以外は実施例9と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりにエポキシ樹脂を1質量%添加した以外は実施例9と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂を添加しない以外は実施例11と同様にして各種試験を行った。
これらの結果を表2に示した。
電極用バインダー樹脂組成物にカルボジイミド樹脂の代わりにエポキシ樹脂を1質量%添加した以外は実施例11と同様にして各種試験を行った。
これらの結果を表2に示した。
Claims (5)
- 集電体の表面に、少なくとも電極活物質と、下記化学式(1)で表される繰返し単位を有するポリアミド酸を前記ポリアミド酸のテトラカルボン酸成分に対して1.6倍モル以上の置換基として2個以上のアルキル基を有するイミダゾール類と共に水溶媒中に溶解してなるポリイミド前駆体水溶液組成物と、カルボジイミド基又はオキサゾリン基を有する架橋剤とを含有する電極合剤組成物によって電極合剤層を形成し、次いで加熱処理して溶媒を除去するとともにポリアミド酸のイミド化反応を行うことを特徴とする電極の製造方法。
- 置換基として2個以上のアルキル基を有するイミダゾール類が、1,2-ジメチルイミダゾール、2-エチル-4-メチルイミダゾール、4-エチル-2-メチルイミダゾール、及び1-メチル-4-エチルイミダゾールからなる群から選択されるイミダゾール類であることを特徴とする請求項1に記載の電極の製造方法。
- 電極活物質が、炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末であることを特徴とする請求項1又は2に記載の電極の製造方法。
- 電極活物質が、リチウム遷移金属酸化物であることを特徴とする請求項1~3のいずれかに記載の電極の製造方法。
- リチウムイオン二次電池用電極を得ることを特徴とする請求項1~4のいずれかに記載の電極の製造方法。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3273513A1 (en) * | 2016-07-22 | 2018-01-24 | Samsung Electronics Co., Ltd. | Binder, method of preparing the binder, and anode and lithium battery including the binder |
CN107641484A (zh) * | 2016-07-22 | 2018-01-30 | 三星电子株式会社 | 粘合剂、制备该粘合剂的方法、以及包括该粘合剂的电极和锂电池 |
WO2018062383A1 (ja) * | 2016-09-29 | 2018-04-05 | 日本電気株式会社 | 耐熱絶縁層付電極 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102443793B1 (ko) * | 2014-04-18 | 2022-09-19 | 유비이 가부시키가이샤 | 전극의 제조 방법 |
JP2018193410A (ja) * | 2015-10-01 | 2018-12-06 | 日清紡ケミカル株式会社 | 樹脂添加剤、並びにそれを用いたマスターバッチ及び樹脂組成物 |
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CN115997300A (zh) * | 2020-06-25 | 2023-04-21 | Ube株式会社 | 全固态二次电池用电极、全固态二次电池以及全固态二次电池的制造方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002060489A (ja) * | 2000-08-07 | 2002-02-26 | Saehan Ind Inc | ポリアミド酸及びポリイミドの製造方法、並びにこれらを用いて得られた接着テープ |
JP2012036382A (ja) * | 2010-07-14 | 2012-02-23 | Ube Industries Ltd | ポリイミド前駆体水溶液組成物 |
WO2012165609A1 (ja) * | 2011-06-03 | 2012-12-06 | 日本電気株式会社 | リチウム二次電池用電極結着剤、これを用いたリチウム二次電池用負極、リチウム二次電池、自動車、リチウム二次電池用電極結着剤の製造方法、及びリチウム二次電池の製造方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3311402B2 (ja) | 1992-11-19 | 2002-08-05 | 三洋電機株式会社 | 二次電池 |
CN1117113A (zh) | 1994-06-29 | 1996-02-21 | 中国矿业大学 | 石门揭煤动力现象预测方法及装置 |
DE19819752A1 (de) * | 1998-05-04 | 1999-11-11 | Basf Ag | Für elektrochemische Zellen geeignete Zusammensetzungen |
CN1117113C (zh) * | 2000-03-14 | 2003-08-06 | 世韩米克罗尼克斯株式会社 | 用作粘合剂的聚胺酸及聚酰亚胺树脂的制造方法 |
CN102484254B (zh) | 2009-09-30 | 2015-02-11 | 宇部兴产株式会社 | 电极用粘合剂树脂组合物、电极合剂糊剂及电极 |
JP5740103B2 (ja) * | 2009-10-19 | 2015-06-24 | 日東電工株式会社 | 熱伝導部材、及びそれを用いた組電池装置 |
CN103097463B (zh) * | 2010-07-14 | 2014-11-19 | 宇部兴产株式会社 | 聚酰亚胺前体水溶液组合物,及制备聚酰亚胺前体水溶液组合物的方法 |
JP5419226B2 (ja) | 2010-07-29 | 2014-02-19 | 日東電工株式会社 | フリップチップ型半導体裏面用フィルム及びその用途 |
JP5338924B2 (ja) * | 2010-11-30 | 2013-11-13 | 東レ株式会社 | リチウムイオン電池電極用バインダー、リチウムイオン電池負極用ペーストおよびリチウムイオン電池負極の製造方法 |
JP5920337B2 (ja) * | 2011-03-11 | 2016-05-18 | 宇部興産株式会社 | ポリイミド前駆体及びポリイミド |
JP2013020875A (ja) | 2011-07-13 | 2013-01-31 | Dic Corp | リチウムイオン二次電池の電極用樹脂組成物及びリチウムイオン二次電池 |
JP5596641B2 (ja) * | 2011-08-29 | 2014-09-24 | 大日精化工業株式会社 | 塗工液、導電性塗工膜、蓄電装置用電極板及び蓄電装置 |
JP5834930B2 (ja) | 2011-09-09 | 2015-12-24 | 宇部興産株式会社 | ポリイミド前駆体水溶液組成物、及びポリイミド前駆体水溶液組成物の製造方法 |
TWI583723B (zh) | 2012-01-20 | 2017-05-21 | Asahi Kasei E-Materials Corp | Multilayer printed circuit boards |
JP2013229263A (ja) * | 2012-04-27 | 2013-11-07 | Toyo Ink Sc Holdings Co Ltd | 電気化学素子用組成物および電気化学素子用電極 |
JP6031935B2 (ja) * | 2012-10-11 | 2016-11-24 | 宇部興産株式会社 | 電極用バインダー樹脂組成物、電極合剤ペースト、及び電極 |
-
2015
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002060489A (ja) * | 2000-08-07 | 2002-02-26 | Saehan Ind Inc | ポリアミド酸及びポリイミドの製造方法、並びにこれらを用いて得られた接着テープ |
JP2012036382A (ja) * | 2010-07-14 | 2012-02-23 | Ube Industries Ltd | ポリイミド前駆体水溶液組成物 |
WO2012165609A1 (ja) * | 2011-06-03 | 2012-12-06 | 日本電気株式会社 | リチウム二次電池用電極結着剤、これを用いたリチウム二次電池用負極、リチウム二次電池、自動車、リチウム二次電池用電極結着剤の製造方法、及びリチウム二次電池の製造方法 |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3273513A1 (en) * | 2016-07-22 | 2018-01-24 | Samsung Electronics Co., Ltd. | Binder, method of preparing the binder, and anode and lithium battery including the binder |
CN107641484A (zh) * | 2016-07-22 | 2018-01-30 | 三星电子株式会社 | 粘合剂、制备该粘合剂的方法、以及包括该粘合剂的电极和锂电池 |
US10756350B2 (en) | 2016-07-22 | 2020-08-25 | Samsung Electronics Co., Ltd. | Binder, method of preparing the binder, and anode and lithium battery including the binder |
CN107641484B (zh) * | 2016-07-22 | 2021-09-24 | 三星电子株式会社 | 粘合剂、制备该粘合剂的方法、以及包括该粘合剂的电极和锂电池 |
WO2018062383A1 (ja) * | 2016-09-29 | 2018-04-05 | 日本電気株式会社 | 耐熱絶縁層付電極 |
CN109804488A (zh) * | 2016-09-29 | 2019-05-24 | 日本电气株式会社 | 具有耐热绝缘层的电极 |
JPWO2018062383A1 (ja) * | 2016-09-29 | 2019-07-11 | 日本電気株式会社 | 耐熱絶縁層付電極 |
US11233231B2 (en) | 2016-09-29 | 2022-01-25 | Nec Corporation | Electrode with heat-resistant insulating layer |
JP7070421B2 (ja) | 2016-09-29 | 2022-05-18 | 日本電気株式会社 | 耐熱絶縁層付電極 |
CN109804488B (zh) * | 2016-09-29 | 2023-03-10 | 日本电气株式会社 | 具有耐热绝缘层的电极 |
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