WO2012132396A1 - ポリイミド前駆体溶液、ポリイミド前駆体、ポリイミド樹脂、合剤スラリー、電極、合剤スラリー製造方法、および電極形成方法 - Google Patents
ポリイミド前駆体溶液、ポリイミド前駆体、ポリイミド樹脂、合剤スラリー、電極、合剤スラリー製造方法、および電極形成方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/16—Polyester-imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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 polyimide precursor solution and a polyimide precursor.
- the present invention also relates to a polyimide resin obtained from a polyimide precursor solution or a polyimide precursor.
- the present invention relates to a mixture slurry containing active material particles in a polyimide precursor solution, particularly a mixture slurry for forming a negative electrode.
- the present invention also relates to a method for producing the mixture slurry.
- this invention relates to the electrode (negative electrode) obtained from the mixture slurry.
- the present invention further relates to a method for forming the electrode.
- This monomer type polyimide precursor is mainly composed of a tetracarboxylic acid diester compound and a diamine compound, and forms a porous structure while imidizing and polymerizing by heating, for example.
- the active material particles and the current collector are firmly bound by increasing the molecular weight of the monomer type polyimide precursor, the active material particles can be obtained by adding such a monomer type polyimide precursor to the negative electrode mixture slurry. It is possible to sufficiently suppress the active material layer from peeling off from the negative electrode current collector due to the expansion and contraction. Furthermore, since a strong mold (MOLD) including the active material is formed by forming a porous structure, the active material particles are strongly bound in the pores, and the active material particles expand rapidly. Even if the shrinkage is repeated, the porous structure is maintained without being collapsed. As a result, the charge / discharge cycle of the lithium ion secondary battery or the like can be dramatically improved.
- MOLD strong mold
- An object of the present invention is to provide a polyimide precursor, a polyimide precursor solution capable of binding the active material particles and the current collector more firmly, and charge / discharge cycles such as a lithium ion secondary battery. Another object is to provide a mixture slurry that can be further improved.
- the polyimide precursor solution according to the first aspect of the present invention contains a tetracarboxylic acid ester compound, a diamine compound having an anionic group, and a solvent.
- a tetracarboxylic acid ester compound and a diamine compound are dissolved in the solvent.
- the tetracarboxylic acid ester compound is preferably an aromatic tetracarboxylic acid ester compound.
- the tetracarboxylic acid ester compound is preferably a tetracarboxylic acid diester compound.
- the tetracarboxylic acid ester compound can be obtained very simply by esterifying the corresponding tetracarboxylic dianhydride with alcohol. In addition, it is preferable to esterify tetracarboxylic dianhydride at the temperature of 50 to 150 degreeC.
- Examples of the alcohol for inducing formation of the tetracarboxylic acid ester compound include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2.
- the tetracarboxylic acid ester compound can also be produced by other methods, for example, direct esterification of tetracarboxylic acid.
- 3,3 ′, 4,4′-benzophenone tetracarboxylic acid diester is particularly preferable among the tetracarboxylic acid ester compounds.
- the diamine compound is preferably an aromatic diamine compound.
- the anionic functional group include a carboxyl group, a sulfate ester group, a sulfonic acid group, a phosphate group, and a phosphate ester group. Of these anionic functional groups, a carboxyl group is particularly preferred. Examples of such a diamine compound include 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, metaphenylenediamine 4-sulfonic acid, and the like.
- the polyimide precursor solution according to this aspect may contain a diamine compound having no anionic group as long as the gist of the present invention is not impaired.
- diamine compound having no anionic group examples include paraphenylenediamine (PPD), metaphenylenediamine (MPDA), 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4′-diaminobiphenyl, 3 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 2,2-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3, 3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane (MDA), 2,2-bis- (4-aminophenyl) propane, 3,3'-diaminodiphenylsulfone (33DDS), 4,4'-diaminodiphenyl Sulfone (44DDS), 3,3'-diaminodiphenyl sulf
- the molar ratio of the tetracarboxylic acid ester compound and the diamine compound is usually in the range of 55:45 to 45:55.
- the molar ratio of the tetracarboxylic acid ester compound and the diamine compound can be appropriately changed to a ratio other than the above as long as the gist of the present invention is not impaired.
- Solvent dissolves tetracarboxylic acid ester compound and diamine compound.
- the solvent for example, alcohols for inducing and forming the above-described tetracarboxylic acid esters are preferable.
- N-methyl-2-pyrrolidone, dimethylacetamide, aromatic hydrocarbons and the like may be added to this solvent.
- the polyimide precursor solution may contain a conductive filler, a dispersant and the like.
- the conductive filler functions as a conductive aid.
- conductive fillers include carbon black (oil furnace black, channel black, lamp black, thermal black, ketjen black, acetylene black, etc.), carbon nanotube, carbon nanofiber, fullerene, carbon microcoil, graphite. (Natural graphite, artificial graphite, etc.), carbon black, carbon fiber short fibers (PAN-based carbon short fibers, pitch-based carbon short fibers, etc.) and the like. These conductive fillers may be used alone or in combination. Further, the dispersant is added to uniformly disperse the active material particles in the mixture slurry.
- Examples of such a dispersant include sorbitan monooleate, N, N-dimethyllaurylamine, N, N-dimethylstearylamine, N-cocoalkyl-1,3-diaminopropane, and the like.
- these dispersing agents may be used independently and may be used in combination.
- such a conductive filler-containing polyimide precursor solution has a roll mill, an attritor, a bar mill, a pebble mill, a sand mill, a kedy mill, a mechano-fusion, and a raid so that the conductive filler is uniformly dispersed in the polyimide precursor solution. It is preferable to sufficiently knead with a kneading machine such as a machine.
- active material particles are further contained in the polyimide precursor solution according to the first aspect.
- Examples of the active material particles include silicon (Si) particles, silicon oxide (SiO) particles, silicon alloy particles, and tin (Sn) particles.
- Examples of silicon alloys include solid solutions of silicon and one or more other elements, intermetallic compounds of silicon and one or more other elements, and eutectic alloys of silicon and one or more other elements. It is done.
- Examples of the method for producing the silicon alloy include arc melting, liquid quenching, mechanical alloying, sputtering, chemical vapor deposition, and firing.
- examples of the liquid quenching method include a single roll quenching method, a twin roll quenching method, and various atomizing methods such as a gas atomizing method, a water atomizing method, and a disk atomizing method.
- the active material particles may be core-shell type active material particles in which the above-mentioned active material particles are coated with metal or the like.
- core-shell type active material particles are produced by an electroless plating method, an electrolytic plating method, a chemical reduction method, a vapor deposition method, a sputtering method, a chemical vapor deposition method, or the like.
- the shell portion is preferably formed of the same metal as that forming the current collector. This is because when such active material particles are sintered, the bondability with the current collector is greatly improved, and excellent charge / discharge cycle characteristics can be obtained.
- the active material particles may include particles made of a material alloyed with lithium. Examples of such materials include germanium, tin, lead, zinc, magnesium, sodium, aluminum, gallium, indium, and alloys thereof.
- the active material particles may be surface-treated with a silane coupling agent.
- a silane coupling agent By treating the active material particles in this way, the active material particles can be favorably dispersed in the mixture slurry, and the binding property of the active material to the polyimide resin can be enhanced.
- the active material particles preferably have an average particle size of 0.5 ⁇ m or more and less than 20 ⁇ m, and more preferably 0.5 ⁇ m or more and less than 10 ⁇ m. As the particle diameter of the active material particles is smaller, good cycle characteristics tend to be obtained. In addition, the average particle diameter here is measured by a laser diffraction / scattering method using a particle size distribution measuring apparatus Microtrac MT3100II (manufactured by Nikkiso Co., Ltd.). In addition, when active material particles having a small average particle diameter are used, the absolute amount of volume expansion / contraction of the active material particles accompanying lithium occlusion / release in the charge / discharge reaction is reduced.
- the particle size distribution of the active material particles is preferably as narrow as possible. If the particle size distribution is wide, there will be a large difference in the absolute amount of volume expansion / contraction caused by the insertion / desorption of lithium between active material particles with greatly different particle sizes, resulting in distortion in the active material layer. This is because there is a high possibility that the polyimide resin mold is broken.
- the active material particles are present in a dispersed state in a polyimide precursor varnish mainly composed of a tetracarboxylic acid ester compound, a diamine compound having an anionic group, and a solvent.
- the active material particles according to this aspect are active material particles for a negative electrode of a non-aqueous secondary battery such as a lithium ion secondary battery.
- the polyimide precursor according to the third aspect of the present invention contains a tetracarboxylic acid ester compound and a diamine compound having an anionic group.
- the “tetracarboxylic acid ester compound” and the “diamine compound having an anionic group” are the same as the “tetracarboxylic acid ester compound” and the “diamine compound having an anionic group” described in the first aspect.
- the polyimide precursor may contain the above-described conductive filler, dispersant, and the like. Such a polyimide precursor may be obtained by mixing a “tetracarboxylic acid ester compound” and a “diamine compound having an anionic group”, or obtained by drying the polyimide precursor solution described above. Also good.
- the “tetracarboxylic acid ester compound” and the “diamine compound having an anionic group” may be liquid or powdered.
- the polyimide resin according to the fourth aspect of the present invention is obtained by heating the polyimide precursor solution according to the first aspect or the polyimide precursor according to the third aspect.
- the polyimide resin according to the fifth aspect of the present invention is the polyimide resin according to the fourth aspect, and has a glass transition temperature of 300 ° C. or higher.
- the polyimide resin according to the sixth aspect of the present invention is the polyimide resin according to the fourth aspect or the fifth aspect, and has a molecular weight between crosslinking points of 30 g / mol or less.
- the molecular weight between crosslinking points is more preferably 20 g / mol or less, and further preferably 10 g / mol or less.
- the molecular weight between crosslinking points shows that it has bridge
- the molecular weight between cross-linking points is an important factor for examining the point bonding of the adherend.
- the polyimide resin according to the seventh aspect of the present invention is the polyimide resin according to any one of the fourth to sixth aspects, and has an amide group.
- the electrode according to the eighth aspect of the present invention includes a current collector and an active material layer.
- the current collector is preferably a conductive metal foil.
- a conductive metal foil is formed of, for example, a metal such as copper, nickel, iron, titanium, cobalt, or an alloy obtained by combining these metals.
- the current collector is preferably roughened in order to improve the binding property with the active material layer.
- the current collector may be roughened by providing electrolytic copper or an electrolytic copper alloy on the foil surface. Further, the current collector may be roughened by performing a roughening treatment. Examples of such roughening treatment include a vapor phase growth method, an etching method, and a polishing method. Examples of the vapor phase growth method include a sputtering method, a CVD method, and a vapor deposition method. Examples of the etching method include a physical etching method and a chemical etching method. Examples of the polishing method include polishing by sandpaper and polishing by a blast method.
- an undercoat layer may be formed on the current collector in order to improve the binding property with the active layer.
- the undercoat layer is preferably formed from a resin to which the polyimide resin can be satisfactorily bonded and a conductive filler that imparts conductivity to the undercoat layer.
- the undercoat layer is preferably formed from, for example, a conductive filler dispersed in the monomer type polyimide precursor solution described above or a conductive filler dispersed in a polyamic acid type polyimide precursor solution.
- the conductive filler is not particularly limited.
- carbon black oil furnace black, channel black, lamp black, thermal black, ketjen black, acetylene black, etc.
- carbon nanotube carbon nanofiber
- fullerene carbon Microcoils
- graphite natural graphite, artificial graphite, etc.
- conductive potassium titanate whiskers filamentary nickel, carbon fiber short fibers (PAN-based carbon short fibers, pitch-based carbon short fibers, etc.), whisker fibers, metal particles (copper Particles, tin particles, nickel particles, silver particles, etc.), metal oxides (titanium dioxide, tin dioxide, zinc dioxide, nickel oxide, copper oxide, etc.), metal carbides (titanium carbide, silicon carbide, etc.) Etc.
- These conductive fillers may be used alone or in combination.
- the “polyimide resin solution with conductive filler” for forming the undercoat layer is several tens of minutes at a temperature between 50 ° C. and 100 ° C. It is preferable to apply the above-mentioned mixture slurry after heating. By doing so, the mixture slurry is applied in a state where the undercoat layer is not completely solidified, so that the undercoat layer and the active material layer are well bonded.
- the current collector according to this aspect is a current collector for a negative electrode of a non-aqueous secondary battery such as a lithium ion secondary battery.
- the active material layer is obtained from the above mixture slurry.
- the active material layer covers the current collector. That is, the active material layer is formed on the current collector.
- This active material layer is mainly composed of active material particles and polyimide resin.
- the polyimide resin has a porous structure and functions as a template material including the active material.
- the polyimide resin binds the active material particles in the pores and binds the current collector and the active material particles. It has a role to wear.
- the polyimide resin usually has a porosity of about 20 to 40 parts by volume.
- this polyimide resin has an anionic group as above-mentioned.
- the polyimide resin is mainly formed from a tetracarboxylic acid-derived unit and a diamine-derived unit. And the anionic group is couple
- the above-described mixture slurry may be applied to the current collector or the undercoat layer, and then the coating film may be baked.
- the firing of the coating film is preferably performed, for example, in a non-oxidizing atmosphere such as a vacuum, a nitrogen atmosphere or an argon atmosphere, or in a reducing atmosphere such as a hydrogen atmosphere.
- the firing temperature is preferably equal to or higher than the temperature at which the monomer-type polyimide precursor in the mixture slurry is imidized and becomes sufficiently high molecular weight, and is equal to or lower than the melting points of the current collector and the active material particles.
- the recommended baking temperature of the mixture slurry according to the present invention is a temperature between 100 ° C. and 400 ° C.
- the firing temperature of the mixture slurry is more preferably a temperature between 100 ° C. and 300 ° C., more preferably a temperature between 150 ° C. and 300 ° C., and 200 ° C. More preferably, the temperature is between 1 and 300 degrees C. This is for preventing deterioration of the current collector due to heat and maintaining a crosslinked structure of the polyimide resin.
- the firing method include a method using a normal constant temperature furnace, a discharge plasma sintering method, and a hot press method.
- the coating film may be rolled together with the current collector or may not be rolled, but is preferably not rolled. If the coating film is rolled together with the current collector, the “packing density of the active material particles in the coating film”, “adhesion between the active material particles”, and “adhesion between the active material particles and the current collector” are This is because it becomes too high and the life of the charge / discharge cycle decreases. On the other hand, if not rolled, destruction of the current collector and the mold made of polyimide resin can be prevented, and as a result, good charge / discharge cycle characteristics can be obtained.
- the content of the polyimide resin in the active material layer is preferably 5% by weight or more and 50% by weight or less of the total weight of the active material layer, and is 5% by weight or more and 30% by weight or less. More preferably, it is more preferably 5% by weight or more and 20% by weight or less.
- the volume content of the polyimide resin in the active material layer is preferably 5% by volume or more and 50% by volume or less of the total volume of the active material layer. If the content of the polyimide resin in the active material layer is less than 5% by weight or less than 5% by volume, the adhesion between the active material particles and the adhesion between the active material particles and the current collector may be insufficient. This is because if the content of the polyimide resin in the active material layer is more than 50% by weight or more than 50% by volume, the resistance in the electrode increases and initial charging may be difficult.
- the mixture slurry manufacturing method includes a first mixing step and a second mixing step.
- first mixing step carbon black is mixed with the monomer-type polyimide precursor solution without substantially applying shear stress to prepare a carbon black-added polyimide precursor solution.
- substantially without applying shear stress means that a shear stress that does not destroy the carbon black structure is allowed.
- the monomer-type polyimide precursor solution contains a tetracarboxylic acid ester compound, a diamine compound having an anionic group, and a solvent. Note that a tetracarboxylic acid ester compound and a diamine compound are dissolved in the solvent.
- active material particles are mixed with the carbon black-added polyimide precursor solution to prepare a mixture slurry.
- the solid content of the monomer type polyimide precursor solution is preferably in the range of 5 parts by weight to 11 parts by weight.
- the carbon black is dispersed in the monomer-type polyimide precursor solution without destroying the structure of the carbon black. Therefore, if this mixture slurry manufacturing method is utilized, the electroconductivity of the active material layer obtained from the mixture slurry manufacturing method can be made favorable.
- the electrode forming method includes a coating process and a heating process.
- the application step the above-mentioned mixture slurry is applied onto the current collector, and a mixture slurry coating film is formed on the current collector.
- an undercoat layer may be formed on the current collector in advance.
- the mixture slurry coating film is heated to form a porous active material layer.
- the mixture slurry coating is preferably heated at a temperature of 100 ° C. or higher and lower than 400 ° C., more preferably 150 ° C. or higher and lower than 350 ° C. .
- an active material layer is formed in order to improve the “packing density of active material particles”, “adhesion between active material particles”, and “adhesion between active material particles and current collector”. Is rolled together with the current collector.
- the porous active material layer is formed from the mixture slurry. That is, in this electrode forming method, the active material layer is not rolled.
- the polyimide resin in the active material layer is made porous as described above, the active material particles are included in the porous polyimide resin. For this reason, even if an active material particle repeats intense expansion and contraction, it becomes difficult for the active material particle to fall off from the polyimide resin.
- the mixture slurry coating is heated at a relatively low temperature. For this reason, if this electrode formation method is utilized, a polyimide resin can be made comparatively soft. Therefore, if this electrode forming method is used, the polyimide resin can easily follow the expansion of the active material particles, and the active material particles can be prevented from dropping off from the polyimide resin.
- the polyimide precursor solution and the polyimide precursor according to the present invention can bind the active material particles and the current collector more firmly (particularly the point bonding) than the conventional polyimide precursor solution and the polyimide precursor.
- it is expected to further improve the charge / discharge cycle of the lithium ion secondary battery or the like.
- the polyimide precursor solution and the polyimide precursor according to the present invention are used as a binder for the active material particles, not only the active material particles and the current collector are firmly bonded (particularly point bonding).
- the free carboxyl group is expected to promote the uptake of cations (lithium ions and the like), and as a result, the discharge capacity of lithium ion secondary batteries and the like can be improved.
- Example 2 is a measurement chart by FT-IR (Fourier transform infrared spectroscopy) of polyimide film pieces according to Example 1 and Comparative Example 1 of the present invention. It is a measurement chart of the dynamic viscoelasticity of the polyimide film piece which concerns on Example 1 and Comparative Example 1 of this invention.
- FT-IR Fastier transform infrared spectroscopy
- This negative electrode mixture slurry was applied to one surface (rough surface) of an electrolytic copper foil (thickness 35 ⁇ m) having a rough surface roughness (arithmetic mean roughness) Rz of 4.0 ⁇ m as a current collector, and a thickness after drying of 19 ⁇ m.
- the negative electrode intermediate was prepared by drying.
- the negative electrode intermediate was cut into a circular shape of ⁇ 11 mm, heat-treated (fired) at 300 ° C. for 1 hour in a nitrogen atmosphere, and sintered to produce a negative electrode.
- the counter electrode was produced by cutting out a lithium metal foil having a thickness of 0.5 mm into a circular shape having a diameter of 13 mm.
- LiPF 6 was used a non-aqueous electrolyte solution obtained by dissolving LiPF 6 to be 1 mol / L with respect to solvent were formulated in 1 .
- the lithium ion secondary battery was produced by incorporating the negative electrode, the counter electrode and the nonaqueous electrolyte prepared as described above into a CR2032 type SUS coin cell.
- the positive electrode and the counter electrode were disposed so as to face each other through a polypropylene separator (Celgard 2400: manufactured by Celgard) reinforced with a glass fiber fabric.
- a polypropylene separator (Celgard 2400: manufactured by Celgard) reinforced with a glass fiber fabric.
- the polyimide film piece was set on FTIR-8400 manufactured by Shimadzu Corporation, and FT-IR (Fourier transform-infrared spectroscopic analysis) measurement was performed by a thin film transmission method.
- FT-IR Fastier transform-infrared spectroscopic analysis
- 3350 cm ⁇ 1 and 3100 cm ⁇ 1 of the obtained IR (infrared) spectrum there are peaks attributed to the N—H stretching motion of the unassociated amide group, and the N—H stretching motion of the associated amide group, respectively.
- An attributed peak was confirmed (see FIG. 1). Therefore, it was confirmed that an amide group was present in the polyimide film piece. Therefore, it is presumed that the carboxyl group of diaminobenzoic acid is converted to an amide group by heating.
- Tg glass transition temperature
- this polyimide film piece After setting this polyimide film piece to a dynamic viscoelasticity measuring device EXSTAR6000 made by Seiko Instruments, the storage elastic modulus was measured under the conditions of a measurement frequency of 1 Hz and a temperature increase rate of 2 degrees C / min. A storage modulus curve was obtained. As shown in FIG. 2, the glass transition temperature (Tg) of this polyimide film piece is the “extra tangent of the low-temperature side linear portion of the storage modulus curve” and the “tangential line at the point on the curve of the glass transition region”. Intersection with the tangent line with the maximum gradient. This polyimide film piece had a glass transition temperature (Tg) of 339 degrees C.
- the molecular weight (Mx) between cross-linking points of this polyimide film piece was determined by the following formula (1).
- ⁇ is the density of polyimide (1.3 g / cm 3 )
- T is “absolute temperature at the point where the storage elastic modulus becomes minimum”
- E ′ is “at the minimum point”
- Storage modulus "and R is a gas constant.
- the molecular weight Mx between crosslinking points of this polyimide film piece was 2.9 g / mol (see FIG. 2).
- Mx ⁇ RT / E ′ (1)
- the adhesion strength of the polyimide resin to the copper foil was measured in accordance with “General Rules for Coating Films of Automobile Parts 4.15 Cross Section Adhesion Test Method (JIS D0202 (1998))”.
- As cellophane tape “ASKUL cellophane tape” manufactured by ASKUL Corporation was used.
- the adhesion strength of the above polyimide resin to the copper foil was 28/100.
- a silicon wafer “4-inch silicon wafer surface mirror finish for semiconductor handling” manufactured by Fujimi Fine Technology was polished with “P-2000C-Cw” manufactured by Nihon Kenshi, and then fired on the polished surface of the silicon wafer.
- the monomer type polyimide precursor solution described above was applied so that the film thickness was about 10 ⁇ m to 30 ⁇ m.
- the monomer-type polyimide precursor solution was dried at 100 ° C. for 10 minutes in an air atmosphere, then heated at 220 ° C. for 1 hour under reduced pressure, and at 275 ° C. for 1 hour at 250 ° C. in an air atmosphere. And baked for 1 hour to obtain a test piece.
- the adhesion strength of the polyimide resin to the silicon wafer was measured according to “General Rules for Coating Films of Automobile Parts 4.15 Cross Section Adhesion Test Method (JIS D0202 (1998))”.
- As cellophane tape “ASKUL cellophane tape” manufactured by ASKUL Corporation was used.
- the adhesion strength of the polyimide resin to the silicon wafer was 100/100.
- Charging / discharging cycle test of lithium ion secondary battery The charging / discharging cycle test of the lithium ion secondary battery was done. In the charge / discharge cycle test, the environmental temperature is set to 30 ° C., the charge / discharge rate is set to 0.1C, the cut-off voltage is set to 0.0V for charge, 1.0V for discharge, and the charge / discharge cycle is set to 50 times. The discharge capacity (mAh / g) was measured every time. Further, as a maintenance factor, “a ratio of the discharge capacity of the 30th cycle to the discharge capacity of the second cycle” and “a ratio of the discharge capacity of the 50th cycle to the discharge capacity of the second cycle” were obtained. The capacity density per electrode area of the lithium ion secondary battery was 4.62 mAh / cm 2 (see Table 1).
- the discharge capacity of the first cycle is 4309.6 mAh / g
- the discharge capacity of the second cycle is 3584.8 mAh / g
- the discharge capacity of the 30th cycle is 3115.0 mAh / g
- the cycle discharge capacity was 2689.8 mAh / g.
- a battery was produced in the same manner as in Example 1 except that the negative electrode mixture slurry was applied to one side of an electrolytic copper foil so that the thickness after drying was 14 ⁇ m and then dried to produce a negative electrode intermediate.
- the charge / discharge cycle characteristics of the battery were measured.
- the capacity density per electrode area of this lithium ion secondary battery was 4.70 mAh / cm 2 (see Table 2).
- the discharge capacity of the first cycle is 4194.7 mAh / g
- the discharge capacity of the second cycle is 3470.1 mAh / g
- the discharge capacity of the 30th cycle is 3026.7 mAh / g
- the cycle discharge capacity was 2614.1 mAh / g.
- Example 2 “Negative electrode mixture slurry was applied to one side of an electrolytic copper foil and dried to a thickness of 23 ⁇ m and then dried to produce a negative electrode intermediate” and “Negative electrode intermediate was cut into a circular shape of ⁇ 11 mm, A battery was fabricated in the same manner as in Example 1 except that a negative electrode was produced by heat treatment (firing) at 350 ° C. for 4 hours in a nitrogen atmosphere, and the battery was fabricated in the same manner as in Example 1. Charge / discharge cycle characteristics were measured. In addition, the capacity density per electrode area of the lithium ion secondary battery was 4.75 mAh / cm 2 (see Table 2).
- the discharge capacity of the first cycle is 4238.8 mAh / g
- the discharge capacity of the second cycle is 3500.8 mAh / g
- the discharge capacity of the 30th cycle is 3014.6 mAh / g
- the cycle discharge capacity was 2601.3 mAh / g.
- a negative electrode mixture slurry was applied to one side of an electrolytic copper foil and dried to a thickness of 16 ⁇ m and then dried to produce a negative electrode intermediate” and “a negative electrode intermediate was cut into a circular shape of ⁇ 11 mm, A battery was fabricated in the same manner as in Example 1 except that a negative electrode was produced by heat treatment (firing) at 350 ° C. for 4 hours in a nitrogen atmosphere, and the battery was fabricated in the same manner as in Example 1. Charge / discharge cycle characteristics were measured. In addition, the capacity density per electrode area of the lithium ion secondary battery was 4.80 mAh / cm 2 (see Table 2).
- the discharge capacity of the first cycle is 4121.4 mAh / g
- the discharge capacity of the second cycle is 3414.3 mAh / g
- the discharge capacity of the 30th cycle is 2945.5 mAh / g
- the cycle discharge capacity was 2544.7 mAh / g.
- the negative electrode mixture slurry was applied to one side of the electrolytic copper foil so that the thickness after drying was 15 ⁇ m and then dried to produce a negative electrode intermediate” and “the negative electrode intermediate was cut into a circular shape of ⁇ 11 mm,
- a battery was fabricated in the same manner as in Example 1 except that a negative electrode was produced by heat treatment (firing) at 350 ° C. for 4 hours in a nitrogen atmosphere, and the battery was fabricated in the same manner as in Example 1. Charge / discharge cycle characteristics were measured. The capacity density per electrode area of this lithium ion secondary battery was 4.90 mAh / cm 2 (see Table 2).
- the discharge capacity of the first cycle was 4144.9 mAh / g
- the discharge capacity of the second cycle was 3412.6 mAh / g
- the discharge capacity of the 30th cycle was 2959.5 mAh / g
- the cycle discharge capacity was 2531.3 mAh / g.
- the discharge capacity of the first cycle is 4425.8 mAh / g
- the discharge capacity of the second cycle is 3843.5 mAh / g
- the discharge capacity of the 30th cycle is 3364.5 mAh / g
- the cycle discharge capacity was 3021.8 mAh / g.
- the discharge capacity of the first cycle is 3541.5 mAh / g
- the discharge capacity of the second cycle is 3076.5 mAh / g
- the discharge capacity of the tenth cycle is 3026.4 mAh / g
- the discharge capacity of the cycle was 2803.4 mAh / g
- the discharge capacity of the 50th cycle was 2424.6 mAh / g.
- the discharge capacity of the first cycle is 4700.7 mAh / g
- the discharge capacity of the second cycle is 414.8 mAh / g
- the discharge capacity of the 30th cycle is 3401.5 mAh / g
- the cycle discharge capacity was 2955.6 mAh / g.
- the discharge capacity in the first cycle was 3898.5 mAh / g
- the discharge capacity in the second cycle was 3384.8 mAh / g
- the discharge capacity in the 30th cycle was 2997.9 mAh / g
- the cycle discharge capacity was 2559.5 mAh / g.
- Example 1 “In the production of the negative electrode, 43.3780 g of silicon powder having an average particle size of 0.9 ⁇ m (purity 99.9%) (Fukuda Metal Foil Powder Co., Ltd.)” was used.
- a negative electrode intermediate was prepared by coating on one side so that the thickness after drying was 1 ⁇ m, and then drying the negative electrode intermediate ”and“ cutting the negative electrode intermediate into a circular shape of ⁇ 11 mm, and heat-treating at 350 ° C. for 4 hours in a nitrogen atmosphere
- a battery was produced in the same manner as in Example 1 except that (fired) and sintered to produce a negative electrode, and the charge / discharge cycle characteristics of the battery were measured in the same manner as in Example 1.
- the capacity density per electrode area of the lithium ion secondary battery was 1.77 mAh / cm 2 (see Table 3).
- the discharge capacity of the first cycle is 4282.7 mAh / g
- the discharge capacity of the second cycle is 3748.8 mAh / g
- the discharge capacity of the 30th cycle is 3113.2 mAh / g
- the cycle discharge capacity was 2704.6 mAh / g.
- the discharge capacity of the first cycle is 3714.4 mAh / g
- the discharge capacity of the second cycle is 3231.6 mAh / g
- the discharge capacity of the 30th cycle is 2835.7 mAh / g
- the cycle discharge capacity was 2405.2 mAh / g.
- the discharge capacity of the first cycle is 4424.0 mAh / g
- the discharge capacity of the second cycle is 3873.1 mAh / g
- the discharge capacity of the 30th cycle is 3226.9 mAh / g
- the cycle discharge capacity was 2686.3 mAh / g.
- the discharge capacity of the first cycle is 3870.7 mAh / g
- the discharge capacity of the second cycle is 3391.8 mAh / g
- the discharge capacity of the 30th cycle is 2977.3 mAh / g
- the cycle discharge capacity was 2524.6 mAh / g.
- the discharge capacity of the first cycle is 4448.6 mAh / g
- the discharge capacity of the second cycle is 3820.2 mAh / g
- the discharge capacity of the tenth cycle is 3738.1 mAh / g
- the cycle discharge capacity was 3448.6 mAh / g.
- the charge / discharge cycle was 10 times, and the “ratio of the discharge capacity of the tenth cycle to the discharge capacity of the second cycle” was determined as the maintenance rate. Moreover, the capacity density per electrode area of this lithium ion secondary battery was 1.67 mAh / cm 2 (see Table 4).
- the discharge capacity of the first cycle was 3736.7 mAh / g
- the discharge capacity of the second cycle was 3195.2 mAh / g
- the discharge capacity of the 10th cycle was 3083.1 mAh / g.
- the charge / discharge cycle was 10 times, and the “ratio of the discharge capacity of the tenth cycle to the discharge capacity of the second cycle” was determined as the maintenance rate. Moreover, the capacity density per electrode area of this lithium ion secondary battery was 1.49 mAh / cm 2 (see Table 4).
- the discharge capacity of the first cycle was 4022.2 mAh / g
- the discharge capacity of the second cycle was 3490.8 mAh / g
- the discharge capacity of the 10th cycle was 3441.9 mAh / g.
- the polyimide resin obtained from the monomer-type polyimide precursor solution described above has a glass transition temperature of 308 ° C., a molecular weight between crosslinking points of 181 g / mol, and an adhesion strength to the copper foil of 0/100. there were.
- this polyimide resin had weak adhesion strength, and had already peeled when it was cut into a grid pattern with a cutter knife.
- the monomer-type polyimide precursor solution was dried at 100 ° C. for 10 minutes in an air atmosphere, then heated at 220 ° C. for 1 hour under reduced pressure, and at 275 ° C. for 1 hour at 250 ° C. in an air atmosphere. And baked for 1 hour to obtain a test piece.
- the adhesion strength of the polyimide resin to the silicon wafer was measured according to “General Rules for Coating Films of Automobile Parts 4.15 Cross Section Adhesion Test Method (JIS D0202 (1998))”.
- As cellophane tape “ASKUL cellophane tape” manufactured by ASKUL Corporation was used.
- the adhesion strength of the polyimide resin to the silicon wafer was 100/100.
- the discharge capacity of the first cycle is 3654.3 mAh / g
- the discharge capacity of the second cycle is 2857.9 mAh / g
- the discharge capacity of the 30th cycle is 1645.6 mAh / g
- the cycle discharge capacity was 1224.9 mAh / g.
- the discharge capacity of the first cycle is 3533.4 mAh / g
- the discharge capacity of the second cycle is 2661.4 mAh / g
- the discharge capacity of the 30th cycle is 1453.3 mAh / g
- the cycle discharge capacity was 1067.3 mAh / g.
- the discharge capacity of the first cycle is 3410.2 mAh / g
- the discharge capacity of the second cycle is 2757.5 mAh / g
- the discharge capacity of the 30th cycle is 1207.2 mAh / g
- the cycle discharge capacity was 762.8 mAh / g.
- the discharge capacity of the first cycle is 3780.1 mAh / g
- the discharge capacity of the second cycle is 2709.1 mAh / g
- the discharge capacity of the 30th cycle is 1202.9 mAh / g
- the cycle discharge capacity was 825.3 mAh / g.
- the discharge capacity of the first cycle is 3724.5 mAh / g
- the discharge capacity of the second cycle is 2911.2 mAh / g
- the discharge capacity of the 30th cycle is 1860.4 mAh / g
- the cycle discharge capacity was 1410.8 mAh / g.
- the discharge capacity of the first cycle is 3431.7 mAh / g
- the discharge capacity of the second cycle is 2629.7 mAh / g
- the discharge capacity of the 30th cycle is 1036.1 mAh / g
- the cycle discharge capacity was 746.9 mAh / g.
- the monomer-type polyimide precursor solution according to the present invention can bind the active material particles and the current collector more firmly than the conventional monomer-type polyimide precursor solution. It was revealed that the charge / discharge cycle of the lithium ion secondary battery can be further improved and the discharge capacity of the lithium ion secondary battery can be increased.
- the polyimide precursor solution and polyimide precursor according to the present invention can bind the active material particles and the current collector more firmly than the conventional polyimide precursor solution and polyimide precursor, the lithium ion secondary It is useful as a binder for the active material layer of the negative electrode of a battery.
- the mixture slurry according to the present invention can further improve the charge / discharge cycle of a lithium ion secondary battery or the like and increase the discharge capacity of a lithium ion secondary battery or the like as compared with a conventional mixture slurry. Therefore, it is useful as a negative electrode mixture slurry for forming a negative electrode active material layer of a non-aqueous secondary battery such as a lithium ion secondary battery.
- polyimide precursor solution and polyimide precursor according to the present invention are sufficiently expected to show good adhesion not only to the active material particles and the current collector but also to other adherends, It seems to be useful as a heat-resistant adhesive.
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Abstract
Description
500mLの3つ口フラスコに、ポリテトラフルオロエチレン製の攪拌羽を取り付けた攪拌棒を取り付けて合成容器とした。そして、その合成容器に、ポリイミド前駆体溶液の固形分が28重量%となるように10.19g(0.032mol)の3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物(BTDA)(ダイセル化学工業株式会社製)と、2.91g(0.063mol)のエタノール(上野化学工業株式会社製)とを投入した後、合成容器中の内容物を90度Cで加熱しながら1時間攪拌してBTDAジエステル溶液を調製した。BTDAジエステル溶液を45度C以下に冷却した後、そのBTDAジエステル溶液に4.81g(0.032mol)の3,5-ジアミノ安息香酸(3,5-DABA)(東京化成工業株式会社製)を添加し、再び50度Cに加熱しながら1時間攪拌してモノマー型ポリイミド前駆体溶液を調製した。
(1)負極の作製
上述のモノマー型ポリイミド前駆体溶液を、#300のSUSメッシュでろ過した。この濾過後のモノマー型ポリイミド前駆体溶液から、実施例1と同一の方法でフィルムを作成し、ガラス転移点(Tg)を測定したところ、331度Cであった。濾過前のポリイミド前駆体溶液から作成したフィルムよりTgが下降しているが、不純物が濾過により除去されたため、又は実験誤差のためと考えられる。この濾過した後のモノマー型ポリイミド前駆体溶液 7.3gに、平均粒子径2.1μmのケイ素粉末(純度99.9%)(福田金属箔粉工業株式会社製)39.0gと、一次粒子径39.5nmのケッチェンブラック(福田金属箔粉工業株式会社製)2.4gとを添加した後に遊星式(自公転式)ミキサー(株式会社シンキー製)によりよく混ぜ合わせて、負極合剤スラリーを調製した。
対極は、厚み0.5mmのリチウム金属箔をφ13mmの円形状に切り抜いて作製した。
エチレンカーボネートとジエチルカーボネートとを体積比1:1で調合した溶媒に対してLiPF6が1モル/LとなるようにLiPF6を溶解させた非水電解液を用いた。
上述ようにして作製された負極、対極および非水電解液をCR2032型SUS製コインセル内部に組み込んでリチウムイオン二次電池を作製した。
(1)FT-IR(フーリエ変換-赤外分光分析)によるアミド基の確認
上述のモノマー型ポリイミド前駆体溶液をガラス板上に流延した後、ドクターブレードにより薄く引き延ばし、200度Cで1時間、250度Cで1時間、300度Cで1時間、350度Cで1時間焼成した。その後、ガラス板上に形成されたポリイミドフィルム片をガラス板から引き剥がしてポリイミドフィルム片を得た。
上述のモノマー型ポリイミド前駆体溶液をガラス板上に流延した後、ドクターブレードにより薄く引き延ばし、200度Cで1時間、250度Cで1時間、300度Cで1時間、350度Cで1時間焼成した。その後、ガラス板上に形成されたポリイミドフィルム片をガラス板から引き剥がしてポリイミドフィルム片を得た。
上述のモノマー型ポリイミド前駆体溶液をガラス板上に流延した後、ドクターブレードにより薄く引き延ばし、200度Cで1時間、250度Cで1時間、300度Cで1時間、350度Cで1時間焼成してポリイミドフィルム片を作製した。
Mx=ρRT/E’・・・(1)
福田金属箔粉工業社製の銅箔「CF-T8(膜厚18μm)」を日本研紙製のサンドペーパー「P-2000C-Cw」で研磨した後、その銅箔の研磨面上に、焼成後の膜厚が約10μmから20μmの間の値になるように上述のモノマー型ポリイミド前駆体溶液を塗布した。そして、そのモノマー型ポリイミド前駆体溶液を空気雰囲気下において100度Cで10分間乾燥した後、減圧下において220度Cで1時間加熱し、空気雰囲気下において250度Cで1時間、275度Cで1時間焼成して、試験片を得た。
リチウムイオン二次電池の充放電サイクル試験を行った。充放電サイクル試験は、環境温度を30℃とし、充放電速度を0.1Cとし、カットオフ電圧を充電時0.0V、放電時1.0Vとし、充放電サイクルを50回として行い、1サイクル毎に放電容量(mAh/g)を計測した。また、維持率として、「第2サイクルの放電容量に対する第30サイクルの放電容量の比」および「第2サイクルの放電容量に対する第50サイクルの放電容量の比」を求めた。なお、このリチウムイオン二次電池の電極面積あたりの容量密度は、4.62mAh/cm2であった(表1参照)。
(比較例1)
(参考例1)
(比較例3)
(比較例4)
(比較例5)
(比較例6)
(比較例7)
Claims (14)
- テトラカルボン酸エステル化合物と、
アニオン性基を有するジアミン化合物と、
前記テトラカルボン酸エステル化合物および前記ジアミン化合物を溶解する溶媒と
を含有するポリイミド前駆体溶液。 - 前記アニオン性基は、カルボキシル基である
請求項1に記載のポリイミド前駆体溶液。 - 前記ジアミン化合物は、3,4-ジアミノ安息香酸または3,5-ジアミノ安息香酸である
請求項2に記載のポリイミド前駆体溶液。 - 前記テトラカルボン酸エステル化合物は、3,3’,4,4’-ベンゾフェノンテトラカルボン酸エステルである
請求項1から3のいずれかに記載のポリイミド前駆体溶液。 - テトラカルボン酸エステル化合物と、
アニオン性基を有するジアミン化合物と
を含有するポリイミド前駆体。 - 請求項1から4のいずれかのポリイミド前駆体溶液、または、請求項5に記載のポリイミド前駆体を加熱して得られる
ポリイミド樹脂。 - ガラス転移温度が300度C以上である
請求項6に記載のポリイミド樹脂。 - 架橋点間分子量が30g/mol以下である
請求項6または7に記載のポリイミド樹脂。 - 請求項1から4のいずれかのポリイミド前駆体溶液と、
活物質粒子と
を含有する合剤スラリー。 - 。
集電体と、
請求項9に記載の合剤スラリーから得られ、前記集電体を被覆する活物質層と
を備える、電極。 - 集電体と、
活物質粒子と、前記活物質同士を結着させると共に前記集電体と前記活物質粒子とを結着させるポリイミド樹脂とを有し、前記集電体を被覆する活物質層と
を備え、
前記ポリイミド樹脂は、アニオン性基を有する
電極。 - テトラカルボン酸エステル化合物と、アニオン性基を有するジアミン化合物と、前記テトラカルボン酸エステル化合物および前記ジアミン化合物を溶解する溶媒とを含有するポリイミド前駆体溶液に、カーボンブラックを、実質的にせん断応力を加えることなく混合して、カーボンブラック添加ポリイミド前駆体溶液を調製する第1混合工程と、
前記カーボンブラック添加ポリイミド前駆体溶液に活物質粒子を混合して、合剤スラリーを調製する第2混合工程と
を備える、合剤スラリー製造方法。 - 請求項9に記載の合剤スラリーを集電体上に塗布して、前記集電体上に合剤スラリー塗膜を形成する塗布工程と、
前記合剤スラリー塗膜を加熱して、多孔質活物質層を形成する加熱工程と、
を備える、電極形成方法。 - 前記加熱工程では、前記合剤スラリー塗膜が、100度C以上400度C未満の温度で加熱される
請求項13に記載の電極形成方法。
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US14/006,258 US20140011089A1 (en) | 2011-03-25 | 2012-03-26 | Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method |
EP12765057.0A EP2690123B1 (en) | 2011-03-25 | 2012-03-26 | Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method |
CN201280014529.8A CN103429640B (zh) | 2011-03-25 | 2012-03-26 | 聚酰亚胺前体溶液、聚酰亚胺前体、单体型聚酰亚胺前体溶液、活性物质层形成用粘合剂、聚酰亚胺树脂、合剂浆料、电极、合剂浆料制造方法以及电极形成方法 |
JP2013507175A JP5821137B2 (ja) | 2011-03-25 | 2012-03-26 | 電池電極用バインダー組成物、電池電極用バインダー、電池電極形成用合剤スラリー、電池電極形成用合剤スラリー製造方法、電池電極および電池電極形成方法 |
KR1020137026836A KR101620675B1 (ko) | 2011-03-25 | 2012-03-26 | 폴리이미드 전구체 용액, 폴리이미드 전구체, 폴리이미드 수지, 합제 슬러리, 전극, 합제 슬러리 제조 방법, 및 전극 형성 방법 |
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US15/813,734 Continuation US20180076461A1 (en) | 2011-03-25 | 2017-11-15 | Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method |
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PCT/JP2012/002092 WO2012132396A1 (ja) | 2011-03-25 | 2012-03-26 | ポリイミド前駆体溶液、ポリイミド前駆体、ポリイミド樹脂、合剤スラリー、電極、合剤スラリー製造方法、および電極形成方法 |
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US (2) | US20140011089A1 (ja) |
EP (1) | EP2690123B1 (ja) |
JP (1) | JP5821137B2 (ja) |
KR (1) | KR101620675B1 (ja) |
CN (1) | CN103429640B (ja) |
WO (1) | WO2012132396A1 (ja) |
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Also Published As
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JPWO2012132396A1 (ja) | 2014-07-24 |
CN103429640B (zh) | 2016-03-02 |
US20140011089A1 (en) | 2014-01-09 |
US20180076461A1 (en) | 2018-03-15 |
EP2690123B1 (en) | 2017-03-01 |
KR20130135951A (ko) | 2013-12-11 |
KR101620675B1 (ko) | 2016-05-12 |
EP2690123A1 (en) | 2014-01-29 |
EP2690123A4 (en) | 2014-11-19 |
CN103429640A (zh) | 2013-12-04 |
JP5821137B2 (ja) | 2015-11-24 |
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