WO2012029618A1 - 電池又は電気二重層キャパシタ集電体コート用導電性組成物、電池又は電気二重層キャパシタ集電体、電池および電気二重層キャパシタ - Google Patents
電池又は電気二重層キャパシタ集電体コート用導電性組成物、電池又は電気二重層キャパシタ集電体、電池および電気二重層キャパシタ Download PDFInfo
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- WO2012029618A1 WO2012029618A1 PCT/JP2011/069120 JP2011069120W WO2012029618A1 WO 2012029618 A1 WO2012029618 A1 WO 2012029618A1 JP 2011069120 W JP2011069120 W JP 2011069120W WO 2012029618 A1 WO2012029618 A1 WO 2012029618A1
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- Prior art keywords
- battery
- current collector
- electric double
- group
- layer capacitor
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/74—Terminals, e.g. extensions of current collectors
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/624—Electric conductive 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/668—Composites of electroconductive material and synthetic resins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a conductive composition for coating a battery or an electric double layer capacitor current collector, a battery coated with the same or an electric double layer capacitor current collector, a battery including the battery or the electric double layer capacitor current collector, and an electric battery.
- the present invention relates to a multilayer capacitor.
- chargeable / dischargeable batteries have been put to practical use as power sources for mobile devices such as mobile phones and notebook computers.
- lithium ion secondary batteries that are lightweight, have a high voltage and a large capacity, and electric double layer capacitors with good charge / discharge rate characteristics are often used.
- a conductive coat layer is provided on the metal current collector, and an active material layer is formed on the surface of the conductive coat layer, thereby reducing the resistance at the interface between the metal current collector and the active material layer.
- Patent Document 5 a method of coating a conductive composition for coating a battery or an electric double layer capacitor current collector after treating the current collector surface in advance with a silane coupling agent or the like has been devised.
- polyvinyl alcohol, a silane coupling agent, a current collector metal surface, a hydroxyl group of polyvinyl alcohol, a silanol group of the silane coupling agent, and a polycarboxylic acid that bonds these with an ester bond, and conductivity The inventor has devised a method of using a conductive composition for coating a battery or an electric double layer capacitor current collector blended with an auxiliary agent (Patent Document 6).
- Patent Documents 3 and 4 cannot achieve charge / discharge cycle characteristics at a practically sufficient high rate for batteries for power applications such as in-vehicle use. This was insufficient for preventing the deterioration of the battery or electric double layer capacitor characteristics during the process.
- the method using the polycarboxylic acid of Patent Document 6 can further improve the adhesion of the active material layer to the current collector, compared to the conventional method using only polyvinyl alcohol or the method using silanol group-modified polyvinyl alcohol, Although the charge / discharge characteristics at a high rate can be further improved, it is not sufficient in preventing deterioration of battery or electric double layer capacitor characteristics after long-term multi-cycle charge / discharge or when left at high temperature in a charged state.
- the present invention improves a battery or electric double layer capacitor characteristics (cycle life and float life) by improving the adhesion (peeling resistance) between the battery or electric double layer capacitor current collector and the active material layer.
- Conductive composition for capacitor current collector coating, battery or electric double layer capacitor current collector using battery or electric double layer capacitor current collector, and battery or electric double layer capacitor current collector It is an object to provide a battery and an electric double layer capacitor having high characteristics (cycle life and float life).
- a conductive composition for a battery or an electric double layer capacitor current collector coating comprising a vinylsilane copolymer, a polycarboxylic acid (excluding the vinylsilane copolymer) and a conductive auxiliary agent
- the vinylsilane copolymer is represented by the following formula (1):
- U represents the following formula (2):
- R 2 to R 4 are independently -OR 5
- R 5 is a group selected from the group consisting of H, a C 1 -C 6 alkyl group and a group derived from a cation capable of constituting an electrolyte of a battery or an electric double layer capacitor
- V is a unit derived from a vinyl monomer having at least an active hydrogen group (provided that U is excluded);
- R 21 to R 23 are independently H or a C 1 -C 6 al
- a ratio of m to n (m / n) is 0.0001 to 1]
- a conductive composition for a battery or an electric double layer capacitor current collector coating comprising a vinyl carboxylate copolymer, a polycarboxylic acid (excluding the vinyl carboxylate copolymer) and a conductive auxiliary agent
- the vinyl carboxylate copolymer is a copolymer of a vinyl carboxylate monomer and a vinylsilane monomer
- the vinylsilane monomer is selected from the group consisting of vinylalkyldialkoxysilane, ⁇ - (meth) acryloxypropyltrialkoxysilane, ⁇ - (meth) acryloxypropylalkyldialkoxysilane, and vinyltris ( ⁇ -methoxyethoxy) silane.
- a conductive composition for coating a battery or an electric double layer capacitor current collector wherein the conductive composition is one or more kinds of compounds, (3)
- the present invention relates to a battery or an electric double layer capacitor including the battery or the electric double layer capacitor current collector.
- a battery or an electric battery that improves adhesion of the battery or electric double layer capacitor current collector and the active material layer (peeling resistance) and improves battery or electric double layer capacitor characteristics (cycle life and float life).
- Conductive composition for current collector coating for double layer capacitor, battery or electric double layer capacitor current collector using the same or conductive composition for current collector coating for electric double layer capacitor, and battery or electric double layer capacitor current collector A battery using an electric body or a battery and an electric double layer capacitor having high electric double layer capacitor characteristics (cycle life and float life) can be provided.
- the subject of the present invention is, for example, the conductivity of the current collector used to improve the battery or electric double layer capacitor characteristics by increasing the adhesion between the battery current collector and the active material layer.
- the coating agent has a sufficiently low resistance value for practical use, and when it is used after being charged and discharged for a long period of time or when it is left at a high temperature in a charged state, it is peeled off by electrochemical decomposition, and the battery The characteristic is that the characteristics of the fall significantly.
- the present inventor has examined the above-mentioned problems of the prior art, and the deterioration of the battery or electric double layer capacitor characteristics occurs because the conventional binder has a structure in which the hydrogen of the hydroxyl group of polyvinyl alcohol is replaced with Si. It turns out that it is because it has. That is, the following formula (B): As described above, since the structure (siloxane bond) in which the hydrogen of the hydroxyl group of polyvinyl alcohol is substituted with Si is easily broken electrochemically, the coating layer is easily peeled off during charging and discharging, which is the battery or It was found that it causes deterioration of the characteristics of the electric double layer capacitor.
- the present invention relates to a copolymer of a vinyl silane monomer and a vinyl monomer having active hydrogen (preferably a vinyl carboxylate copolymer in which Si is directly bonded to the skeleton carbon of the vinyl carboxylate copolymer), a polycarboxylic acid,
- a copolymer of a vinyl silane monomer and a vinyl monomer having active hydrogen preferably a vinyl carboxylate copolymer in which Si is directly bonded to the skeleton carbon of the vinyl carboxylate copolymer
- a polycarboxylic acid preferably a vinyl carboxylate copolymer in which Si is directly bonded to the skeleton carbon of the vinyl carboxylate copolymer
- the conductive composition for coating a battery or an electric double layer capacitor current collector of the present invention includes, for example, an active hydrogen present on the surface of a metal current collector and a vinylsilane copolymer (preferably a carboxylic acid). Since the silicon element of the acid vinyl copolymer) is substituted and chemically bonded, it has high adhesion to the metal current collector and is easily decomposed electrochemically with respect to the main chain “—C—O— Since the “Si—” bond structure is not formed, an advantage that an electrochemically stable coat layer can be formed is utilized.
- the conductive coat layer on the battery or electric double layer capacitor current collector using the conductive composition for the battery or electric double layer capacitor current collector of the present invention further comprises a conductive coat layer and an active material layer.
- the battery or electric double layer capacitor of the present invention has a low internal resistance, excellent charge / discharge cycle characteristics, a large charge / discharge capacity, and a battery or electric double layer capacitor current collector of an electrode active material after long-term multi-cycle charge / discharge Detachment from the body hardly occurs and has a long life.
- the conductive composition for the battery or electric double layer capacitor current collector coating of the first aspect of the present invention comprises a vinylsilane copolymer, a polycarboxylic acid (excluding the vinylsilane copolymer), a conductive A conductive composition for a battery or an electric double layer capacitor current collector coating comprising a property aid,
- the vinylsilane copolymer is represented by the following formula (1): [In the formula, U represents the following formula (2): (Where X represents a single bond or a bond chain (excluding oxygen), R 2 to R 4 are independently -OR 5 (R 5 is a group selected from the group consisting of H, a C 1 -C 6 alkyl group and a group derived from a cation capable of constituting an electrolyte of a battery or an electric double layer capacitor), A unit selected from the group consisting of a C 1 -C 6 alkyl group and a halogen group, V is a unit derived from a
- the conductive composition for the battery or electric double layer capacitor current collector coating of the second aspect of the present invention comprises a vinyl carboxylate copolymer, a polycarboxylic acid (however, excluding the vinyl carboxylate copolymer), A conductive composition for a battery or an electric double layer capacitor current collector coating containing a conductive auxiliary agent,
- the vinyl carboxylate copolymer is a copolymer of a vinyl carboxylate monomer and a vinylsilane monomer
- the vinylsilane monomer is selected from the group consisting of vinylalkyldialkoxysilane, ⁇ - (meth) acryloxypropyltrialkoxysilane, ⁇ - (meth) acryloxypropylalkyldialkoxysilane, and vinyltris ( ⁇ -methoxyethoxy) silane. It is characterized by being 1 or more types of compounds.
- the preferred embodiment of the vinylsilane copolymer in the conductive composition for the battery or electric double layer capacitor current collector coating of the first aspect of the present invention is the battery or electric double layer capacitor current collector of the second aspect of the present invention.
- a vinyl carboxylate copolymer in a conductive composition for body coating The definitions and preferred embodiments of the polycarboxylic acid and the conductive auxiliary in the conductive composition for the battery or electric double layer capacitor current collector coating of the first and second aspects of the present invention are excluded from the parentheses for the polycarboxylic acid. Common. Therefore, unless otherwise specified, the conductive composition for the battery or the electric double layer capacitor current collector coating according to the first aspect of the present invention will be described below.
- the conductive composition for coating a battery or an electric double layer capacitor current collector of the first aspect of the present invention is also referred to as a conductive composition for coating a battery or an electric double layer capacitor current collector.
- the polycarboxylic acid in the present invention is a concept including polycarboxylic acid and an acid anhydride derived from the polycarboxylic acid.
- the polycarboxylic acid is collectively referred to as polycarboxylic acid, or referred to as polycarboxylic acid (derived from polycarboxylic acid). Of the acid anhydride).
- Vinylsilane copolymer The vinylsilane copolymer in the present invention (hereinafter also referred to as vinylsilane copolymer) is represented by the above formula (1).
- the unit represented by the formula (2) is also referred to as a unit derived from a vinylsilane monomer.
- the vinyl silane copolymer is a conductive composition for coating a battery or an electric double layer capacitor current collector containing polycarboxylic acid (excluding the vinyl silane copolymer) and a conductive auxiliary agent.
- Carboxylic acid serves as a crosslinking agent, and serves as a binder together with polycarboxylic acid. That is, when the battery or the electric double layer capacitor current collector coating conductive composition is thermally cured, the vinyl silane copolymer is a vinyl monomer having at least an active hydrogen group in the vinyl silane copolymer (hereinafter referred to as vinyl).
- the active hydrogen group of the unit derived from (also referred to as a system monomer) crosslinks with the polycarboxylic acid through a dehydration condensation polymerization reaction (for example, ester bond formation reaction).
- a dehydration condensation polymerization reaction for example, ester bond formation reaction.
- the crosslinking reaction can be started only by evaporating (it is considered that the intermolecular distance between the vinylsilane copolymer and the polycarboxylic acid approaches in the solvent), and the crosslinking reaction can be promoted by further heating.
- the promotion of the crosslinking reaction by heating is preferably in the range of 40 to 250 ° C., and more preferably in the range of 100 to 180 ° C. from the balance between the crosslinking rate and the thermal deterioration of the adherend.
- the active hydrogen group of the unit derived from the vinyl monomer is preferably a hydroxy group (—OH), a carboxyl group (—COOH), an amino group from the viewpoint of stability during production and electrolysis resistance.
- R 6 to R 10 are each independently a hydrogen atom, a C 1 to C 8 alkyl group, a hydroxyl group, an acyl group, a carboxyl group, an amino group, a vinyl group, or an allyl group). And an aryl group, a halogen, a metal, etc.), and a hydroxy group, an amino group, and a sulfo group are more preferable.
- the active hydrogen group of the unit derived from the vinyl monomer in the vinyl silane copolymer is the active hydrogen group of the unit derived from another vinyl monomer in the vinyl silane copolymer, or other vinyl silane copolymer. It can form dipolar interactions and hydrogen bonds with the active hydrogen groups of the vinyl monomer units in the coalescence, and can generate a dehydration-condensation reaction with the polycarboxylic acid. It can crosslink with active hydrogen groups on the body surface.
- the vinyl monomer from which the unit of the vinyl monomer is derived is preferably a vinyl carboxylate monomer or an acrylic monomer from the viewpoint of stability during production and anti-electrolytic properties, but a vinyl carboxylate monomer is more preferred. preferable.
- the vinyl silane copolymer in the case where the vinyl monomer is a vinyl carboxylate monomer is also referred to as a vinyl carboxylate copolymer (the second battery or the conductive composition for coating an electric double layer capacitor current collector of the present invention).
- vinyl carboxylate monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, Examples include vinyl piperate, vinyl octylate, vinyl monochloroacetate, vinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, and vinyl cinnamate.
- the unit V derived from the vinyl carboxylate monomer is preferably the following formula (4): (Wherein R 1 is a group selected from the group consisting of H, an organic group derived from a carboxylic acid, and a group derived from a cation capable of constituting an electrolyte of a battery or an electric double layer capacitor). It is a monomer-derived unit, preferably a cation-derived group constituting an electrolyte of a battery or an electric double layer capacitor that is adapted as a source of ionic species that becomes an irreversible capacity at the time of charge and discharge. Li is preferred, and Na is preferred for sodium ion batteries.
- the unit derived from a vinyl carboxylate monomer when R 1 is H or an organic group derived from a carboxylic acid is preferably It can be obtained by saponifying a vinyl carboxylate copolymer obtained by vinyl polymerization of a vinyl carboxylate monomer.
- the proportion of the organic group derived from the carboxylic acid is It is preferably 30% or less (that is, the degree of saponification is 70% or more), More preferably, it is 20% or less (that is, the degree of saponification is 80% or more), More preferably, it is 10% or less (that is, the degree of saponification is 90% or more), that is, It is preferably 0% or more and 30% or less (that is, the degree of saponification is 70% or more and 100% or less), More preferably, it is 0% or more and 20% or less (that is, the degree of saponification is 80% or more and 100% or less), More preferably, it is 0% or more and 10% or less (that is, the degree of saponification is is
- the organic group R 1 derived from carboxylic acid is A hydrocarbon group which may be substituted with a halogen (preferably a C 1 to C 17 linear or branched alkyl group (for example, a methyl group, an ethyl group, a propyl group, a pentyl group, a heptyl group, a nonyl group, an undecanyl group, Tridecanyl group, pentadecanyl group, heptadecanyl group, monochloromethyl group, 1-ethyl-pentyl group), C 3 -C 6 cycloalkyl group (eg cyclohexyl group, cyclopentyl group), aromatic group (eg phenyl group)), Or -CO-R 41 , wherein R 41 is a C 1 to C 17 linear or branched alkyl group (for example, a methyl group, an ethyl group, a propyl group, a pentyl group
- R 1 is a group derived from a cation capable of constituting an electrolyte of a battery or an electric double layer capacitor
- a cation that can constitute an electrolyte of a battery or an electric double layer capacitor from the viewpoint of irreversible capacity, It can be an alkaline metal other than Li, such as Na or K, an alkaline earth metal, such as Be, Mg, Ca, Sr, or a lithium, or a tetraalkylammonium, such as tetraethylammonium, triethylmethylammonium, etc.
- a cation-derived group constituting the electrolyte of the electric double layer capacitor is preferable.
- the cation that can constitute the electrolyte of the battery or the electric double layer capacitor may be any cation of an electrolyte that can be used as the electrolyte of the battery or the electric double layer capacitor, but the battery or the electric double layer capacitor current collector coat of the present invention. Particularly preferred is an electrolyte cation of a battery or an electric double layer capacitor using the electroconductive composition.
- lithium in the case of a lithium ion secondary battery tetraalkylammonium in the case of an electric double layer capacitor (tetraethylammonium in the case of a capacitor using tetraethylammonium tetrafluoroborate, triethylmethylammonium bis (trifluoromethane) In the case of a capacitor using sulfonyl) imide, it is triethylmethylammonium).
- R 2 to R 4 independently represent a unit represented by a group selected from the group consisting of —OR 5 , C 1 to C 6 alkyl group and halogen group, and R 5 represents , H, C 1 -C 6 alkyl group and a group selected from the group consisting of a group derived from a cation capable of constituting an electrolyte of a battery or an electric double layer capacitor.
- R 2 to R 4 are preferably —OCH 3 and / or —CH 3 from the viewpoints of stability during production and electrolysis resistance, -OCH 3 is more preferred.
- R 5 is preferably a cation-derived group constituting the electrolyte of the battery or electric double layer capacitor to be applied.
- R 5 is a cation-derived group capable of constituting an electrolyte of a battery or an electric double layer capacitor
- the cation that can constitute the electrolyte of the battery or the electric double layer capacitor is an alkali metal excluding Li such as Na and K, an alkaline earth metal such as Be, Mg, Ca, and Sr, or lithium, Alternatively, it may be tetraalkylammonium such as tetraethylammonium or triethylmethylammonium, and the like, and is preferably a group derived from a cation constituting an electrolyte of a battery or an electric double layer capacitor to be applied.
- the cation that can constitute the electrolyte of the battery or the electric double layer capacitor may be an cation of an electrolyte that can be used as the electrolyte of the battery or the electric double layer capacitor.
- an electrolyte cation of a battery or an electric double layer capacitor using the conductive composition for body coating is particularly preferred.
- lithium in the case of a lithium ion secondary battery tetraalkylammonium in the case of an electric double layer capacitor (tetraethylammonium in the case of a capacitor using tetraethylammonium tetrafluoroborate, triethylmethylammonium bis (trifluoromethane) In the case of a capacitor using sulfonyl) imide, it is triethylmethylammonium).
- substitution rate is 100% when all of R 5 is substituted with a group derived from a cation that can constitute the electrolyte of the battery or electric double layer capacitor, the battery or electricity
- the substitution rate of the group derived from the cation that can constitute the electrolyte of the double layer capacitor is preferably 5% or more, and more preferably 20% or more.
- a conductive composition for a battery or an electric double layer capacitor current collector coat binds a vinylsilane copolymer (preferably a vinyl carboxylate copolymer) having a silanol group chemically bonded to a hydroxyl group present on a metal surface. Since it is used as an adhesive, it has high adhesion, and since silicon atoms are directly bonded to the main chain carbon of the vinyl carboxylate copolymer, it is difficult to decompose electrochemically.
- the silanols are being preserved. Condensation to increase the viscosity, and adhesion does not decrease. Since sodium hydroxide is used when saponifying the vinyl acetate portion, Na is substituted for R 1 and / or R 5 (Patent Document 6).
- a battery or an electric double layer capacitor collection substituted with Na ions When the conductive composition for electric conductor coating is applied to a lithium ion secondary battery, it prevents ion conduction during charging / discharging of the battery, leads to deterioration of battery or electric double layer capacitor characteristics, and reduces charge / discharge capacity.
- a lithium ion secondary battery it is more preferable to saponify with lithium hydroxide and replace R 1 and / or R 5 with Li.
- the conductive composition for battery or electric double layer capacitor current collector coating is a lithium ion secondary battery or electric double layer It is preferable as a conductive composition for capacitor current collector coating.
- the lithium ion secondary battery or the conductive composition for electric double layer capacitor current collector coating is obtained by substituting at least part of hydrogen and hydroxy group of the silanol group with lithium, and deterioration due to condensation between silanols, It becomes an ion source for the depletion of lithium ions due to parasitic capacity when it is built in and charged into a lithium ion secondary battery, and can contribute to the improvement of charge and discharge capacity.
- R 5 is a C 1 -C 6 alkyl group
- Preferred is a C 1 -C 6 linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, n-propyl, and n-butyl, and more preferred is an ethyl group.
- M in the formula (2) is from the viewpoint of stability during production and electrolysis resistance, 1 to 10,000, preferably 5 to 1,000, and more preferably 10 to 500.
- N in the formula (2) is From the viewpoint of stability during production and electrolysis resistance, 20 to 100,000, preferably 200 to 20,000, and more preferably 300 to 1,000.
- the ratio of m to n (m / n) in equation (2) is From the viewpoint of stability during production and electrolysis resistance, 0.0001 to 1, 0.005 to 0.5 is preferable, and 0.01 to 0.1 is more preferable.
- X in Formula (2) is a single bond or a bond chain (excluding oxygen).
- the bond chain is a group that connects the main chain of the vinylsilane copolymer and the silane structure,
- hydrocarbons having 1 to 18 carbon atoms such as alkylene, alkenylene, alkynylene, phenylene, or naphthylene (these hydrocarbons may be substituted with halogen such as fluorine, chlorine, bromine, etc.),-( CH 2 O) m -, - (CH 2 O) mCH 2 -, - CO -, - COCO -, - CO (CH 2) m CO -, - CO (C 6 H 4) CO -, - S-, —CS—, —SO—, —SO 2 —, —NR—, —CONR—, —NRCO—, —CSNR—, —NRCS—, —NRNR—, —HPO 4 —, —Si (OR)
- each R is independently an arbitrary substituent, preferably a hydrogen atom or an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms), m is a natural number, preferably 1 to 10).
- the group selected can be illustrated. From the viewpoint of ensuring that the siloxane bond in the formula (2) is electrochemically stable and ensuring the peel resistance of the coating layer at the time of charge / discharge of the battery or electric double layer capacitor X is most preferably a single bond in terms of thermal stability or structural stability under high temperature / acidic conditions, but even if it is a range that does not inhibit the effects of the present invention, X may be a bonded chain. Good.
- the bonding chain is not particularly limited, but for example, a hydrocarbon having 1 to 18 carbon atoms such as alkylene, alkenylene, alkynylene, phenylene, or naphthylene (these hydrocarbons are substituted with halogen such as fluorine, chlorine, or bromine).
- a hydrocarbon having 1 to 18 carbon atoms such as alkylene, alkenylene, alkynylene, phenylene, or naphthylene (these hydrocarbons are substituted with halogen such as fluorine, chlorine, or bromine).
- each R is independently an arbitrary substituent, hydrogen atom, alkyl group (especially carbon Preferably an alkyl group of 1 to 4)
- the m is a natural number, preferably 1 to 10.
- an alkylene group having 6 or less carbon atoms, particularly a methylene group, or —CH 2 OCH 2 — is a preferable bonding chain in terms of stability during production or use.
- Vinyl carboxylate copolymer As vinylsilane copolymer, From the viewpoint of stability during production and electrolysis resistance, A vinyl carboxylate copolymer in which the vinyl monomer is a vinyl carboxylate monomer is preferred.
- the unit V is represented by the above formula (4), the unit U is R 21 to R 23 are all H, X is a single bond, and R 2 to R 4 are all —OR. 5 (represented as OR 31 to R 33 , respectively):
- OR 31 to R 33 the following formula (6): It is preferable that it is a copolymer represented by these.
- R 31 to R 33 independently take the above-described preferred embodiment of R 5 .
- the vinyl carboxylate copolymer a copolymer obtained by reacting vinyl acetate and vinyltriethoxysilane can be exemplified (unit V is —COOCH 3 group (ie, R 1 is methyl group). And R 2 to R 4 have a —OC 2 H 5 group (that is, R 31 to R 33 have an ethyl group).
- the vinyl acetate part of this copolymer is saponified with sodium hydroxide or the like to form a hydroxy group (the unit V has an —OH group or an —ONa group (ie, R 1 is H or Na), and R 2 to R 4 can be an —OH group or an —ONa group (ie, when R 31 to R 33 have H as Na).
- the saponification degree is preferably 50% or more (that is, 50 to 100%) from the viewpoint of the resistance to electrolytic solution, more preferably 70% or more (that is, 70 to 100%), and 80% or more (that is, 80 to 100%). ), More preferably 90% or more (that is, 90 to 100%).
- Replacing the active hydrogen of the hydrolyzed vinyl carboxylate copolymer with a cation-derived group that can constitute the electrolyte of a battery or electric double layer capacitor such as Na specifically, R 1 and R 2 to R 4 It is preferable to introduce a cation-derived group capable of constituting an electrolyte of a battery such as Na or an electric double layer capacitor into the battery.
- the battery has a substitution rate of 100%.
- the substitution rate of a group derived from a cation that can constitute the electrolyte of the battery or the electric double layer capacitor is preferably 5% or more, and particularly preferably 20% or more.
- vinyl acetate vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl piperate
- vinyl octylate vinyl monochloroacetate, vinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate and vinyl cinnamate, but vinyl acetate is used from the viewpoint of price and availability.
- vinylalkyldialkoxysilanes such as vinyltrimethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane; ⁇ - (meth) acryloxy ⁇ - (meth) acryloxypropyltrialkoxysilane such as propyltrimethoxysilane and ⁇ - (meth) acryloxypropyltriethoxysilane; ⁇ - (meth) acryloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloxypropyl It is preferable to use ⁇ - (meth) acryloxypropylalkyldialkoxysilane such as methyldiethoxysilane; vinyltris ( ⁇ -methoxyethoxy) silane, etc., but from the viewpoint of stability during production and electrolysis resistance, Triethoxysilane are more preferable
- vinyl silane copolymer a copolymer obtained by copolymerizing a specific functional group-containing monomer together with the above-described vinyl monomer having an active hydrogen group (preferably a vinyl carboxylate monomer) and a vinyl silane monomer, It is preferable at the point from which the outstanding adhesiveness and electrochemical stability are acquired.
- Specific functional group-containing monomers include, for example, glycidyl (meth) acrylate, glycidyl (meth) allyl ether, 3,4-epoxycyclohexyl (meth) acrylate, triallyloxyethylene, diallyl maleate, triallyl cyanurate, Monomers having two or more allyl groups such as allyl isocyanurate and tetraallyloxyethane, allyl glycidyl ether, allyl acetate, vinyl acetoacetate, allyl acetoacetate, allyl diacetacetate, acetoacetoxyethyl (meth) acrylate, aceto Acetoacetoxyalkyl (meth) acrylates such as acetoxypropyl (meth) acrylate; acetoacetoxy such as acetoacetoxyethyl crotonate and acetoacetoxypropyl crotonate Alkyl cro
- (Meth) acrylate trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydro Shibuchiru (meth) acrylate the alkyl group with a carbon number of 1 to 10 such as, and the like, especially hydroxyalkyl (meth) acrylates having 1 to 6.
- these specific functional group containing monomers can be used individually or in combination of 2 or more types.
- nitrile monomers such as (meth) acrylonitrile can be used as functional group-containing monomers other than the specific functional group-containing monomers.
- the total amount of the specific functional group-containing monomer and the functional group-containing monomer other than the specific functional group-containing monomer is 0.01 to 10% by weight of the entire copolymerizable monomer. It is preferably 0.05 to 5% by weight, more preferably 0.1 to 5% by weight, still more preferably 0.1 to 1% by weight.
- a copolymerizable monomer other than the specific functional group-containing monomer can be used in combination as long as the object of the present invention is not impaired.
- styrene such as styrene and ⁇ -methylstyrene is used.
- Monomers such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl carboxylate such as vinyl laurate, vinyl monomers such as alkyl vinyl ether such as methyl vinyl ether; olefins such as ethylene, propylene, 1-butene, isobutene, vinyl chloride, Olefinic monomers such as halogenated olefins such as vinylidene chloride, vinyl fluoride and vinylidene fluoride, ethylene sulfonic acid; and butadiene-1,3,2-methylbutadiene, 1,3 or 2,3-dimethylbutadiene-1, 3 Diene monomers such as 2-chloro-1,3 and the like.
- nitrile monomers such as (meth) acrylonitrile can be used as functional group-containing monomers other than the specific functional group-containing monomers.
- the polycarboxylic acid in the present invention has 2 or more carboxylic acids in one molecule, preferably 2 to 1000, more preferably 3 to 100, in terms of reactivity and crosslink density, and a molecular weight of 100,000 or less, preferably 30000.
- polycarboxylic acids having a molecular weight of 20000 or less are more preferable.
- Aromatic carboxylic acids are preferable from the viewpoint of reactivity, and those in which three or more carboxylic acids are substituted in one molecule are preferable from the viewpoint of reactivity and crosslinking density.
- Citric acid Citric acid, butanetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, hexahydrophthalic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, methylbicyclo [2.2 .1] Heptane-2,3-dicarboxylic acid, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, aspartic acid, pyromellitic acid, melittic acid, phosphorus-containing ester group tetracarboxylic acid, phenylethynylphthal
- the conductive auxiliary agent in the present invention may be conductive particles, fillers, or ionic liquids.
- Examples of conductive particles or fillers include Ag, Cu, Au, Al, Mg, Rh, W, Mo, Co, Ni, Pt, Pd, Cr, Ta, Pb, V, Zr, Ti, In, Fe, Metal powders and flakes such as Zn, or colloids; Sn—Pb, Sn—In, Sn—Bi, Sn—Ag, Sn—Zn alloy powders and flakes; acetylene black, furnace black, channel black, etc.
- the size of the particles constituting the conductive particles or the conductive fillers is preferably in the range of 0.001 to 100 ⁇ m, more preferably in the range of 0.01 to 10 ⁇ m from the viewpoint of conductivity and liquidity. .
- the size of these particles is the average particle diameter obtained by averaging the diameters of the circles having the area of the planar image of each particle measured with an electron microscope for all the measured particles.
- the liquid having ionicity may be a liquid in which ions are dissolved or an ionic liquid.
- liquid ions in which ions are dissolved include sodium chloride, potassium chloride, lithium chloride and the like when the solvent is water, and lithium hexafluorophosphate and the like when the solvent is an organic substance such as dimethyl carbonate.
- ionic liquids examples include imidazo such as 1,3-dimethylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide, 1-ethyl-3-methylimidazolium bromide, etc.
- Pyridinium salt derivatives such as 3-methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide; tetrabutylammonium heptadeca Examples thereof include alkylammonium derivatives such as fluorooctane sulfonate and tetraphenylammonium methanesulfonate; phosphonium salt derivatives such as tetrabutylphosphonium methanesulfonate and the like. These ionic liquids can be used in combination with conductive particles.
- the conductive composition for the battery or the electric double layer capacitor current collector coat is a vinylsilane copolymer (hereinafter also referred to as component A), Polycarboxylic acid (however, excluding the vinylsilane copolymer) (hereinafter also referred to as component B); A conductive assistant (hereinafter also referred to as component C (also referred to as liquid other than ions in the case of a liquid in which ions are dissolved)).
- component A vinylsilane copolymer
- component B Polycarboxylic acid
- component B A conductive assistant
- component C also referred to as liquid other than ions in the case of a liquid in which ions are dissolved
- Component A and Component B are stable as binders in order to enhance the adhesion (peeling resistance) between the battery current collector and the active material layer by the conductive composition for the battery or electric double layer capacitor current collector coating.
- From the viewpoint of functioning as Component B is based on 100 parts by weight of Component A (preferably vinyl carboxylate copolymer). 1 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 10 to 200 parts by weight, further preferably 10 to 100 parts by weight, further preferably 20 to 100 parts by weight. Is more preferable.
- Component C is based on 100 parts by weight of Component A (preferably vinyl carboxylate copolymer), The content is preferably 10 to 9900 parts by weight, more preferably 20 to 4900 parts by weight, and still more preferably 50 to 1900 parts by weight.
- Component A preferably vinyl carboxylate copolymer
- the total amount of components A, B and C is 50 to 100% by weight is preferred, More preferably, it is 80 to 100% by weight, More preferably, it is 90 to 100% by weight.
- the conductive composition for the battery or electric double layer capacitor current collector coating may be a solid such as a powder or flake, or a liquid such as a paste, solution or suspension, as long as the components A, B and C are included. But you can. However, when the conductive composition for coating a battery or an electric double layer capacitor current collector is coated on the battery current collector as a coating, it is preferably used in the form of a liquid such as a paste, solution or suspension. If the conductive composition for the electric double layer capacitor current collector coating is in a solid state, it is mixed with a solvent to form a liquid when used, and the conductive composition for the battery or electric double layer capacitor current collector coating is in a paste form. If it is present, it is preferable to make it a liquid with a viscosity or properties that are easy to use by mixing with a solvent as it is.
- the conductive composition for the battery or the electric double layer capacitor current collector coating can be added with a solvent described later in accordance with the coating device in an arbitrary ratio for viscosity adjustment.
- a viscosity of 1 to 10000 mPa ⁇ s is preferred, a viscosity of 10 to 1000 mPa ⁇ s is more preferred, and a viscosity of 100 to 500 mPa ⁇ s is particularly preferred.
- a conductive composition for a battery or an electric double layer capacitor current collector coat is obtained as a paste, solution, suspension, or the like by mixing and stirring components A, B, and C, and if necessary, optional components described below.
- Stirring can be performed by appropriately selecting various stirring devices such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, a homogenizer for emulsification, and an ultrasonic homogenizer. Moreover, it can also be preferably made into said suitable viscosity range by stirring, heating or cooling as needed.
- various stirring devices such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, a homogenizer for emulsification, and an ultrasonic homogenizer.
- it can also be preferably made into said suitable viscosity range by stirring, heating or cooling as needed.
- the conductive composition for a battery or an electric double layer capacitor current collector coat may contain various solvents in order to adjust the liquidity centered on the viscosity.
- Solvents include hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, amylbenzene, turpentine oil, pinene, etc.), halogenated hydrocarbons (chlorinated) Methyl, chloroform, carbon tetrachloride, ethylene chloride, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene, fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc.), alcohol (methanol, ethanol, n-propanol, (Isopropanol, n-amyl alcohol, isoamyl alcohol, n-hex
- JP-A 2010-146726 discloses other binders other than the vinyl copolymer.
- the curable organic component and inorganic component described in 1) can be used as appropriate.
- an organic component in addition to various epoxy compounds, siloxane compounds, etc., prepolymers such as curable monomers and oligomers can be used, and these can be melted in a polymer state or dissolved in a solvent. It can also be used, or a fine powder having fluidity can be used.
- thermoplastic resins include vinyl acetate, vinyl alcohol, vinyl butyral, vinyl chloride, methacrylate, acrylic acid, methacrylic acid, styrene, ethylene, amide, cellulose, isobutylene, vinyl ether, polyvinylidene fluoride, polyester, and the like.
- thermosetting resin examples include urea, melamine, phenol, resorcinol, epoxy, oxetane, episulfide, isocyanate, a mixture of chitosan and carboxylic acid, a prepolymer composed of imide and the like, a polymer, and a derivative. These compounds can be used alone or in combination of two or more.
- the conductive composition for a battery or an electric double layer capacitor current collector coating may further contain a coupling agent.
- a coupling agent include (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane as a fluorine-based silane coupling agent and Shin-Etsu as an epoxy-modified silane coupling agent.
- Coupling agent manufactured by Kagaku Kogyo Co., Ltd. (trade name: KBM-403), coupling agent manufactured by Toagosei Co., Ltd.
- oxetane-modified silane coupling agent (trade name: conductive composition for coating of current collector of TESOX battery), or , Vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -chloropropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- (trimethoxysilyl) propyl succinic anhydride, ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltri Toxisilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -methacryloxypropylpropyltrimethoxysilane, ⁇ Silane coupling agents
- a titanium coupling agent or a silane coupling agent is preferable.
- active hydrogen contained in the conductive composition for the battery or electric double layer capacitor current collector coat for example, hydrogen It is possible to react with a substituent having a binding functional group) to further improve the cross-linking density, and for the element constituting the current collector and the element constituting the current composition for the battery or the electric double layer capacitor current collector coating Mutual substitution reaction can be further suppressed.
- a crosslinking reaction caused by a titanium coupling agent or a silane coupling agent can improve the crosslinking rate, improve the adhesion strength, and the electrochemical strength.
- a conductive composition for a battery or an electric double layer capacitor current collector coat it is possible to prevent the formation of an excessively insulating modified layer at the interface, thereby increasing the interface resistance. It can be suppressed.
- a compound having active hydrogen for example, a hydrogen bonding functional group
- a coupling agent are heated in advance before adding a polycarboxylic acid. After the reaction, the conductive composition for coating a battery or an electric double layer capacitor current collector may be produced.
- the conductive composition for a battery or an electric double layer capacitor current collector coat can contain various surfactants in order to control wetting.
- surfactants include soaps, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate.
- amphoteric surfactants include alkyl diaminoethyl glycine hydrochloride, 2 -Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, fatty acid alkyl betaine, sulfobetaine, amidoxide, etc.
- Nonionic (nonionic) surfactants include polyethylene glycol alkyl ester compounds, alkyl ether compounds such as triethylene glycol monobutyl ether, ester compounds such as polyoxysorbitan esters, alkylphenol compounds, and fluorine compounds. Examples thereof include silicone compounds and silicone type compounds. These compounds can be used alone or in combination of two or more.
- Insulating filler In order to improve the mechanical strength and thermal characteristics of the conductive composition for the battery or the electric double layer capacitor current collector coating, various insulating fillers can be used as long as necessary without impairing the necessary conductivity. Can be blended. Insulating fillers include powders of metal oxides such as alumina, silica, zirconia and titania, sols such as colloidal silica, titania sol and alumina sol, clay minerals such as talc, kaolinite and smectite, and carbides such as silicon carbide and titanium carbide.
- metal oxides such as alumina, silica, zirconia and titania
- sols such as colloidal silica, titania sol and alumina sol
- clay minerals such as talc, kaolinite and smectite
- carbides such as silicon carbide and titanium carbide.
- Nitrides such as silicon nitride, aluminum nitride and titanium nitride, borides such as boron nitride, titanium boride and boron oxide, complex oxides such as mullite, hydroxides such as aluminum hydroxide and magnesium hydroxide, batteries, etc. Or the barium titanate etc. which can raise the dielectric constant of the electrically conductive composition for electrical double layer capacitor collector coatings are mentioned.
- the conductive composition for the battery or the electric double layer capacitor current collector coating may further contain a stabilizer as appropriate, if necessary.
- stabilizers include 2,6-di-tert-butyl-phenol, 2,4-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-ethyl- Phenol-based antioxidants exemplified by phenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-anilino) -1,3,5-triazine Agent, alkyldiphenylamine, N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N'-isopropyl-p-phenylenediamine, etc.
- Aromatic amine antioxidants exemplified by dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, bis Trisulfide hydroperoxide decomposer exemplified by [2-methyl-4- ⁇ 3-n-alkylthiopropionyloxy ⁇ -5-tert-butyl-phenyl] sulfide, 2-mercapto-5-methyl-benzimidazole, etc.
- (Isodecyl) phosphite phenyl diisooctyl phosphite, diphenyl isooctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate diethyl ester, Phosphorus hydroperoxide decomposers exemplified by sodium bis (4-tert-butylphenyl) phosphate, salicylate series exemplified by phenyl salicylate, 4-tert-octylphenyl salicylate, etc.
- Stabilizer benzophenone light stabilizer exemplified by 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole
- Benzotriazole-based light stabilizers exemplified by 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol]
- Hindered amine light stabilizers exemplified by phenyl-4-piperidinyl carbonate, bis- [2,2,6,6-tetramethyl-4-piperidinyl] sebacate and the like, [2,2′-thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel- (II)
- Agents, cyanoacrylate-based light stabilizer may be mentioned oxalic acid anilide-
- the conductive composition for the battery or the electric double layer capacitor current collector coat may contain, in addition to the component A, the component B, and the component C, as necessary, a solvent, other fixing agents, a coupling agent ( Hereinafter, it may also include a component D), a surfactant (hereinafter also referred to as component E), an insulating filler (hereinafter also referred to as component F), and a stabilizer (hereinafter also referred to as component G).
- a component D a surfactant
- component F an insulating filler
- stabilizer hereinafter also referred to as component G
- the conductive composition for coating a battery or an electric double layer capacitor current collector contains component D (coupling agent) and component A (preferably vinyl carboxylate).
- the polymer) is preferably contained in an amount of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and still more preferably 0.3 to 3 parts by weight with respect to 100 parts by weight.
- the battery or electric double layer capacitor current collector conductive composition Preferably contains 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight of component E (surfactant) per 100 parts by weight of component A (preferably vinyl carboxylate copolymer). More preferably, it is contained in an amount of 1 to 10 parts by weight.
- component E surfactant
- component A preferably vinyl carboxylate copolymer
- the battery or electric double layer capacitor current collector coating preferably contains 0.001 to 10 parts by weight of component F (insulating filler) with respect to 100 parts by weight of component A (preferably vinyl carboxylate copolymer). 5 parts by weight is more preferable, and 0.1 to 2 parts by weight is still more preferable.
- component F insulating filler
- the conductive composition for the battery or electric double layer capacitor current collector coating contains component G (stabilizer), It is preferably contained in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 1 part by weight per 100 parts by weight of A (preferably vinyl carboxylate copolymer). It is more preferable to include.
- the K value defines the curing shrinkage stress generated when the thermosetting resin component in the conductive composition is cured, and the conductive assistant in the conductive resin composition (acetylene in the examples) is determined by this shrinkage stress. Since the black particles) break down the surface oxide layer of the current collector (aluminum foil) and reach the metal layer, the resistance is lowered. Therefore, the effect of pressing the conductive auxiliary agent on the current collector when the shrinkage stress specified by the K value is larger This is advantageous in producing an electrode having a high resistance and a low resistance.
- the battery or the electric double layer capacitor current collector coat conductive composition is absorbed with a 15 ml glass pipette, and Teflon having an inner diameter of 5 mm is used. Inject into a (registered trademark) sex tube.
- the conductive composition for coating a battery or an electric double layer capacitor current collector injected into a Teflon tube is subjected to vacuum evaporation of the solvent at room temperature (preferably 20 to 30 ° C.) and then into the Teflon tube.
- the battery or electric double layer capacitor current collector coating conductive composition injected into the Teflon tube is gradually evaporated in a solvent at room temperature (preferably 20 to 30 ° C.) so as not to cause bubbles.
- the length of the conductive composition for coating a battery or an electric double layer capacitor current collector injected into the Teflon tube is Ymm.
- the conductive composition for coating the battery or the electric double layer capacitor current collector is actually cured in an oven by the oven.
- Heat at temperature and time preferably 40 to 280 ° C., 0.1 to 200 minutes, more preferably 60 to 250 ° C., 0.2 to 100 minutes, still more preferably 80 to 220 ° C., 0.4 to 50 minutes.
- thermosetting is performed until the contraction of the length of the conductive composition for the battery or electric double layer capacitor current collector coating in the Teflon tube stops, and the length Lmm in the Teflon tube after thermosetting is measured.
- the volume shrinkage S v (%) is calculated by the following formula.
- the conductive composition for the battery or the electric double layer capacitor current collector coating is a solid such as a powder or flake
- the volume before and after heat curing of the molded product obtained by high-pressure press molding can be used.
- the powder and flakes are formed into pellets having a total weight of 5 tons and a diameter of 19 to 21 mm and a thickness of 9 to 11 mm, and the volume is determined from the diameter and thickness of the prepared pellets before heating, and then heated (preferably 40-280 ° C., 0.1-200 minutes, more preferably 60-250 ° C., 0.2-100 minutes, still more preferably 80-220 ° C., 0.4-50 minutes) By calculating from the thickness, the volume shrinkage can be calculated.
- the conductive composition for the battery or electric double layer capacitor current collector coating was in the form of a solution, and the heating conditions were 160 ° C. and 80 seconds.
- the present invention improves the battery or electric double layer capacitor characteristics (cycle life and float life) by improving the adhesion (peeling resistance) between the battery current collector and the active material layer as compared with the prior art. It is an object of the present invention to provide a conductive composition for coating a capacitor current collector.
- the present invention provides a battery or an electric double layer capacitor current collector coating comprising a vinyl silane copolymer, a polycarboxylic acid (excluding the vinyl silane copolymer) and a conductive auxiliary agent as a basis for solving the problem.
- An electrically conductive composition was employed.
- the K value of the conductive composition for the battery or electric double layer capacitor current collector coating is preferably Is from 3 to 90, more preferably from 3.2 to 20, and even more preferably from 3.5 to 10.
- the current is prevented by the insulation property of the hydroxide film or oxide film on the surface of the current collector with a sufficiently low resistance. While the material layer and the current collector may not be in close contact with each other, if the K value of the conductive composition for coating a battery or an electric double layer capacitor current collector is within the above preferred range, the battery or The conductive auxiliary agent contained in the conductive composition for the current collector coating of the double layer capacitor is subjected to water on the surface of the metal current collector due to the stress when the battery or the conductive composition for current collector coating is thermally cured and contracted. By pushing and breaking through an oxide layer or an insulating layer made of an oxide layer (for example, FIGS. 2 and 3), the resistance value is sufficiently low in practical use.
- Condensation reaction is preferred as a curing reaction that increases volume shrinkage, and has a vinylsilane monomer and active hydrogen from the viewpoint of adhesion to the metal current collector so that the conductive resin layer does not float off the current collector due to curing stress.
- Use of a vinyl monomer copolymer and polycarboxylic acid as a binder is highly effective.
- a compound having 4 or more substituents in one molecule is preferable from the viewpoint of volume shrinkage upon curing and an elastic modulus after curing, and the combination of a tetrafunctional or higher alcohol and a tetrafunctional or higher carboxylic acid is a curing stress.
- the compound having an active hydrogen equivalent having 4 or more active hydrogens of 500 (g / mol) or less and a carboxylic acid having 4 or more carboxylic acids is preferable.
- a compound having an acid equivalent of 500 (g / mol) or less is more preferable because the volumetric shrinkage increases and the elastic modulus increases in proportion to the amount of the condensation reaction per unit volume.
- the conductive composition for the battery or electric double layer capacitor current collector coating is further formed into a conductive coating agent by using a binder and a conductive agent that have sufficiently high adhesion to the metal current collector and large cure shrinkage.
- a practically low resistance value can be obtained by pushing and breaking through the conductive auxiliary agent contained in the insulating layer consisting of a hydroxide layer or oxide layer on the surface of the metal current collector with the stress when the thermosetting resin shrinks.
- the coat layer shown can be formed.
- the present invention further prevents the occurrence of conductive chipping when slitting the electrode because the secondary conductive coating layer enhances the adhesion with the active material layer, and can prevent accidents resulting from short-circuits during use. .
- the battery current collector of the present invention coated with a conductive composition for coating a battery or an electric double layer capacitor current collector is a battery or electric double layer formulated using the above materials. It can be produced by coating a battery or an electric double layer capacitor current collector with a conductive composition for coating a capacitor current collector.
- the battery or electric double layer capacitor current collector include metals such as gold, silver, copper, aluminum, nickel, iron and cobalt, and composite materials having conductivity such as carbon fiber nonwoven fabric and metal composite materials, and lithium.
- an aluminum foil is used for the positive electrode, a copper foil is used for the negative electrode, and an aluminum foil or an aluminum etching foil is used in the electric double layer capacitor.
- a gravure coater, slit die coater, spray coater, dipping, etc. can be used.
- the thickness of the coat layer is preferably in the range of 0.01 to 100 ⁇ m from the viewpoint of stably securing the opportunity and area where the conductive auxiliary agent and the battery current collector are in contact with each other and ensuring a low resistance value stably.
- a range of 0.05 to 5 ⁇ m is more preferable from the viewpoint of electrical characteristics and adhesion.
- the battery of the present invention As the battery of the present invention (hereinafter also referred to as a battery) to which the battery current collector of the present invention can be applied, From the viewpoint of the high effect of preventing electrochemical deterioration due to the high charge potential, Lithium ion secondary battery, sodium ion secondary battery, potassium ion secondary battery, magnesium ion secondary battery are preferred, A lithium ion secondary battery is more preferable. Among lithium ion secondary batteries, the effect on iron olivine-based lithium ion secondary batteries having high internal resistance is even higher.
- the battery can be produced by a known method.
- the adhesion between the current collector and the active material layer is improved, it is possible to prevent deterioration of the battery or electric double layer capacitor characteristics due to peeling during use.
- the resistance between the current collector and the active material layer can be reduced, charging and discharging can be performed at a high rate.
- the conductive assistant breaks through the insulating oxidation and / or hydroxide film on the current collector surface, the electrode is not pressed by a roll press or the like after the electrode is manufactured, or the press pressure is lowered. Can also reduce the resistance of the electrode. As a result, since the active material layer is not crushed and the electrolyte is impregnated and ions are easily moved, a battery that can be charged and discharged at a high rate can be manufactured.
- an electrochemically stable interfacial bond state can be formed, so that a battery or an electric double layer accompanying electrolysis when repeated for a long period of multi-cycle charge / discharge or left in a charged state at a high temperature It is possible to prevent deterioration of capacitor characteristics.
- the battery of the present invention has a low internal resistance and is unlikely to peel between the current collector and the active material layer, so that a large current can flow and rapid charging / discharging is possible.
- the vinylsilane copolymer (preferably vinyl carboxylate copolymer) of the present invention forms a covalent bond with a polar substituent (such as a hydroxyl group in the case of a metal) present on the current collector surface.
- the conventional conductive composition for a battery or an electric double layer capacitor current collector coat has a siloxane structure because the bond is easily broken electrochemically, so that a battery with excellent long-term reliability cannot be produced.
- silicon is bonded to the main chain of a vinylsilane copolymer (preferably vinyl carboxylate copolymer) via a carbon atom, the bond is electrochemically stable and excellent in long-term stability.
- the polycarboxylic acid in the coating agent has substituents (preferably hydroxyl groups) having active hydrogen in the vinylsilane copolymer (preferably vinyl carboxylate copolymer) or active hydrogen on the surface of the current collector.
- the conductive auxiliary agent in the coating agent interacts with the surface of the current collector to reduce the interface resistance value.
- a metal current collector an insulating oxide film or hydroxide film exists on the surface, but when conductive particles are used, the conductive particles are insulative due to shrinkage stress during drying and solidification. The resistance value can be reduced by breaking through the film.
- the conductive particles in order for the conductive particles to break through the oxide film or the hydroxide film, it is necessary to have a high adhesion force that is large enough to antagonize the contraction stress.
- the electrochemical stability of the interface is also required so that the adhesive force is maintained to such an extent that the state in which the conductive particles have penetrated the insulating film can be maintained even after the charge / discharge test. Further, when an ionic liquid is used, the resistance value can be reduced by soaking into the defects of these insulating films.
- Example 1 In Example 1, a battery comprising a vinylsilane copolymer, polycarboxylic acid, and a conductive auxiliary agent or a current collector coated with a conductive composition for coating an electric double layer capacitor current collector on both the positive electrode and the negative electrode was used. A method for producing a lithium ion secondary battery will be described.
- the above dispersion was dispersed using a bead mill with a cooling jacket.
- 0.5 mm zirconia balls are added at a filling rate of 80%, stirred at a peripheral speed of 7 m while cooling so that the liquid temperature does not exceed 30 ° C., and conductive for coating a battery or an electric double layer capacitor current collector A coating liquid as a composition was obtained.
- Example 2 In Example 2, a battery comprising a vinylsilane copolymer, polycarboxylic acid, and a conductive auxiliary agent or a current collector coated with a conductive composition for coating an electric double layer capacitor current collector on a positive electrode was used. A method for manufacturing a battery will be described.
- a lithium ion battery was produced in the same manner as in Example 1 except that the conductive coating layer was not formed on the negative electrode.
- Example 3 In Example 3, a battery comprising a vinylsilane copolymer, a polycarboxylic acid and a conductive auxiliary agent or a current collector coated on the negative electrode with a conductive composition for coating an electric double layer capacitor current collector was used as a lithium ion secondary. A method for manufacturing a battery will be described.
- a lithium ion battery was produced in the same manner as in Example 1 except that the conductive coating layer was not formed on the positive electrode.
- Example 4 a conductive composition for a battery or an electric double layer capacitor current collector coating comprising a vinylsilane copolymer, a polycarboxylic acid and a conductive auxiliary agent, in which the ratio of m is increased from that in Example 1 and the silicon content is increased.
- a method for producing a lithium ion secondary battery using the coated current collector will be described.
- the obtained copolymer contains 2.5 mol% of vinylsilane units, and 99% of the vinyl carboxylate portion is saponified. I understood that.
- Example 5 In Example 5, a current collector coated with a conductive composition for coating a battery or an electric double layer capacitor current collector comprising a vinylsilane copolymer having a saponification degree reduced from that of Example 1, a polycarboxylic acid, and a conductive auxiliary agent. A method of manufacturing a lithium ion secondary battery using the body will be described.
- Example 6 a method for producing a lithium ion secondary battery by removing acetylene black blended in the positive electrode will be described. Electron conduction is assisted by the interaction between the acetylene black contained in the active material layer and the current collector, but the capacity of the battery is reduced because it is necessary to remove the active material by the amount of acetylene black. .
- the conductive composition for a battery or an electric double layer capacitor current collector coating of the present invention the exchange of electrons with the current collector is performed by the conductive composition for the battery or electric double layer capacitor current collector coating of the present invention. Since things are in charge, it is possible to increase the amount of active material by removing acetylene black from the active material. In the comparative example, when the acetylene black in the active material was removed in the absence of the conductive composition for the battery or the electric double layer capacitor current collector coating of the present invention, the result showed that the charge / discharge characteristics were remarkably lowered.
- a lithium ion battery was produced in the same manner as in Example 1 except that the positive electrode from which the acetylene black in the obtained active material was removed was used.
- Example 7 a conductive composition for coating a battery or an electric double layer capacitor current collector comprising a vinylsilane copolymer in which sodium in the vinylsilane copolymer is substituted with lithium, a polycarboxylic acid, and a conductive auxiliary agent.
- a method for producing a lithium ion secondary battery using a current collector coated on both the positive electrode and the negative electrode will be described.
- Lithium ions were obtained in the same manner as in Example 1 except that the conductive composition for coating a battery or an electric double layer capacitor current collector was prepared by replacing the vinylsilane copolymer with the obtained Li-type vinylsilane copolymer. A battery was produced.
- Example 8 a conductive composition for a battery or electric double layer capacitor current collector coating comprising a vinylsilane copolymer using ⁇ -acryloxypropyltrimethoxysilane as a vinylsilane monomer, a polycarboxylic acid, and a conductive auxiliary agent
- a method for producing a lithium ion secondary battery using a current collector in which both the positive electrode and the negative electrode are coated will be described.
- the obtained white gel is pulverized and washed with methanol to remove unreacted ⁇ -acryloxypropyltrimethoxysilane and then dried to obtain a vinylsilane copolymer of ⁇ -acryloxypropyltrimethoxysilane type. It was.
- the obtained copolymer contained 1 mol% of ⁇ -acryloxypropyltrimethoxysilane unit, and 90% of the vinyl carboxylate portion was contained. It turns out that it is saponified.
- Example 9 a current collector in which both a positive electrode and a negative electrode were coated with a conductive composition for coating a battery or electric double layer capacitor current collector comprising limonene oxide, a vinylsilane copolymer, polycarboxylic acid and a conductive auxiliary agent.
- limonene oxide limonene oxide
- vinylsilane copolymer vinylsilane copolymer
- polycarboxylic acid a conductive auxiliary agent
- a method for producing a lithium ion secondary battery using a battery will be described.
- polycarboxylic acid and a hydroxyl group carry out dehydration condensation, since it becomes an ester bond, two functional groups having hydrogen bonding properties are reduced (A).
- Example 10 a battery comprising sodium 2-acrylamido-2-methylpropanesulfonate (a specific functional group-containing monomer), a vinylsilane copolymer composed of a vinylsilane monomer and vinyl acetate, a polycarboxylic acid and a conductive auxiliary agent, or A method for producing a lithium ion secondary battery using a current collector obtained by coating a conductive composition for coating an electric double layer capacitor current collector on both the positive electrode and the negative electrode will be described.
- the obtained copolymer contained 1.5 mol% vinyl silane units and 1 mol% sulfonic acid units. It was found that 99% was saponified.
- Example 2 Manufacture of lithium ion secondary batteries
- the obtained vinylsilane copolymer was changed to the vinylsilane copolymer having the sulfonic acid unit to produce a conductive composition for coating a battery or an electric double layer capacitor current collector.
- a lithium ion battery was prepared.
- Example 11 an electric double layer type capacitor was formed using a battery comprising a vinylsilane copolymer, polycarboxylic acid and a conductive auxiliary agent or a current collector coated with a conductive composition for coating an electric double layer capacitor current collector. A manufacturing method will be described.
- the above coating solution was applied to a rolled aluminum foil having a width of 300 mm and a thickness of 20 ⁇ m at a width of 200 mm and a thickness of 10 ⁇ m, and dried for 30 seconds in a 180 ° C. hot air oven.
- the coating film thickness after drying was 1 ⁇ m.
- the electrode was cut at 40 mm ⁇ 50 mm so as to include a region having no 10 mm active material layer on the short side, and an aluminum tab was joined to the exposed portion of the metal by resistance welding.
- a separator manufactured by Celguard; # 2400 is cut to a width of 45 mm and a length of 120 mm, folded back into three, and sandwiched so that the two electrodes face each other, and this is an aluminum laminate cell with a width of 50 mm and a length of 100 mm Was sandwiched between two parts, and the sealant was sandwiched between the portions where the tabs hit, and the sealant portion and the side perpendicular to it were heat laminated to form a bag.
- Example 12 a battery comprising a vinyl silane copolymer in which a part of sodium in the vinyl silane copolymer is substituted with tetraethylammonium, a polycarboxylic acid, and a conductive auxiliary agent, or a conductive coating for a current collector coating of an electric double layer capacitor.
- a method for producing an electric double layer capacitor using a current collector coated with a conductive composition will be described.
- a conductive composition for coating a battery or an electric double layer capacitor current collector was produced in the same manner as in Example 1 except that a tetraethylammonium type vinylsilane copolymer was used as the vinylsilane copolymer. did.
- Example 1 A lithium ion secondary battery was produced in the same manner as in Example 1 except that the current collector not coated with the battery or the conductive composition for coating the electric double layer capacitor current collector was used.
- Comparative Example 2 In Comparative Example 2, a conductive composition for coating a battery or an electric double layer capacitor current collector comprising partially saponified polyvinyl alcohol and a conductive auxiliary agent was coated on both the positive electrode and the negative electrode instead of the vinylsilane copolymer. A method for producing a lithium ion secondary battery using a current collector will be described.
- 0.5 mm zirconia balls are charged at a filling rate of 80%, stirred at a peripheral speed of 7 m while cooling so that the liquid temperature does not exceed 30 ° C., and conductive for battery or electric double layer capacitor current collector coating.
- a coating liquid as a composition was obtained.
- a lithium ion secondary battery was produced in the same manner as in Example 1 except that the current collector was coated with the conductive composition for coating a battery or an electric double layer capacitor current collector.
- Comparative Example 3 In Comparative Example 3, a conductive composition for coating a battery or an electric double layer capacitor current collector comprising a partially saponified polyvinyl alcohol, a polycarboxylic acid and a conductive auxiliary agent instead of a vinylsilane copolymer was used for the positive electrode and the negative electrode. A method for producing a lithium ion secondary battery using a current collector coated on both will be described.
- 0.5 mm zirconia balls are charged at a filling rate of 80%, stirred at a peripheral speed of 7 m while cooling so that the liquid temperature does not exceed 30 ° C., and conductive for battery or electric double layer capacitor current collector coating.
- a coating liquid as a composition was obtained.
- a lithium ion secondary battery was produced in the same manner as in Example 1 except that the current collector was coated with the conductive composition for coating a battery or an electric double layer capacitor current collector.
- Comparative Example 4 In Comparative Example 4, a conductive composition for coating a battery or an electric double layer capacitor current collector comprising a partially saponified polyvinyl alcohol, a polycarboxylic acid, a conductive auxiliary agent and a silane coupling agent instead of the vinylsilane copolymer A method for producing a lithium ion secondary battery using a current collector in which both the positive electrode and the negative electrode are coated will be described.
- acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd .; Denka Black HS-100
- acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd .
- Denka Black HS-100 Denka Black HS-100
- the dispersion was dispersed using a bead mill with a cooling jacket.
- 0.5 mm zirconia balls are added at a filling rate of 80%, and stirred at a peripheral speed of 7 m while cooling so that the liquid temperature does not exceed 30 ° C.
- Conductive composition for battery or electric double layer capacitor current collector coating The thing was produced.
- a lithium ion secondary battery was produced in the same manner as in Example 1 except that the current collector was coated with the conductive composition for coating a battery or an electric double layer capacitor current collector.
- Comparative Example 5 a lithium ion secondary battery was prepared using the battery obtained by removing the polycarboxylic acid of Example 1 or the current collector in which the conductive composition for coating an electric double layer capacitor current collector was coated on both the positive electrode and the negative electrode. A manufacturing method will be described.
- the above dispersion was dispersed using a bead mill with a cooling jacket.
- 0.5 mm zirconia balls are added at a filling rate of 80%, stirred at a peripheral speed of 7 m while cooling so that the liquid temperature does not exceed 30 ° C., and conductive for coating a battery or an electric double layer capacitor current collector A coating liquid as a composition was obtained.
- a lithium ion secondary battery was produced in the same manner as in Example 1 except that the current collector was coated with the conductive composition for coating a battery or an electric double layer capacitor current collector.
- Comparative Example 6 In Comparative Example 6, a method for producing a lithium ion secondary battery using a current collector surface-treated with a silane coupling agent will be described.
- a lithium ion secondary battery was produced in the same manner as in Example 1 except that the current collector coated with the silane coupling agent was used.
- Comparative Example 7 a method of producing a lithium ion secondary battery by using a current collector not coated with a battery or a conductive composition for coating an electric double layer capacitor current collector, and further removing acetylene black blended with the positive electrode. explain.
- a lithium ion secondary battery was produced in the same manner as in Example 6 except that a current collector that was not coated with the battery or the conductive composition for coating an electric double layer capacitor current collector was used.
- Comparative Example 8 In Comparative Example 8, a method for producing an electric double layer type capacitor using a current collector not coated with a battery or a conductive composition for coating an electric double layer capacitor current collector will be described.
- An electric double layer type capacitor was produced in the same manner as in Example 8, except that a current collector that was not coated with a conductive composition for coating a battery or an electric double layer capacitor current collector was used.
- Comparative Example 9 In Comparative Example 9, a method of manufacturing an electric double layer type capacitor using an etching foil will be described.
- An electric double layer type capacitor was produced in the same manner as in Example 8, except that an aluminum etching foil for an electric double layer type capacitor (width 300 mm, thickness 20 ⁇ m) was used as the current collector.
- the cell after measuring the initial capacity was set to a potential of 4.3 V, and the impedance of 1 kHz was measured with a voltage change of ⁇ 10 mV around the potential.
- the discharge rate was determined from the initial capacity, and the discharge capacity for each discharge rate was measured.
- the charge was increased to 4.3V with a constant current over 10 hours each time, and then charged with a 4.3V constant voltage for 2 hours. Then, it discharged until it became 3V with a constant current over 10 hours, and the discharge capacity at this time was made into the discharge capacity of 0.1C.
- the battery was discharged at a current value at which discharge was completed in 1 hour from the discharge capacity determined at 0.1 C, and the discharge capacity at that time was determined and used as the discharge capacity at 1 C.
- the discharge capacity at 3C, 10C, and 30C was obtained, and the capacity retention rate was calculated when the discharge capacity at 0.1C was 100%.
- Electrode peeling test after endurance test The battery was subjected to a 1000 cycle endurance charge / discharge test under the above cycle life conditions, and it was confirmed by disassembling the battery whether the active material layer was detached from the positive electrode and the negative electrode after the endurance test.
- the evaluation criteria were as follows. ⁇ : No desorption at all ⁇ : Partial desorption is observed, but the current collector is not exposed ⁇ : Desorption proceeds, and a part of the current collector is exposed ⁇ : Active material layer is completely detached
- the cell after measuring the initial capacity was set to a potential of 2 V, and an impedance of 1 kHz was measured with a voltage change of ⁇ 10 mV around the potential.
- the discharge rate was determined from the initial capacity, and the discharge capacity for each discharge rate was measured. Charging was performed by increasing the voltage to 2 V at a constant current every hour for 1 hour. Then, it discharged until it became 0V with a constant current over 1 hour, and the discharge capacity at this time was made into the discharge capacity of 1C. Next, after discharging in the same manner, discharging was performed at a current value at which discharge was completed in 0.1 hours from the discharging capacity determined at 1C, and the discharging capacity at that time was determined to be the discharging capacity at 10C. Similarly, the discharge capacities at 30C, 100C, and 300C were obtained, and the capacity retention rate when the discharge capacity at 1C was 100% was calculated.
- Electrode peeling test after endurance test The battery was subjected to an endurance float test for 3000 hours under the above-mentioned float life conditions, and it was confirmed by disassembling the electric double layer type capacitor whether the active material layer was detached from the electrode current collector after the endurance test.
- the evaluation criteria were as follows. ⁇ : No desorption at all ⁇ : Partial desorption is observed, but the current collector is not exposed ⁇ : Desorption proceeds, and a part of the current collector is exposed ⁇ : Active material layer is completely detached
- VTES uses vinyltriethoxysilane
- ⁇ APTMES represents ⁇ -acryloxypropyltrimethoxysilane.
- the internal resistance is low and the electrochemical durability is better than the conventional one. Can be provided.
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Abstract
Description
上記のように、電池として十分な特性を発揮できない一つの理由として、金属集電体と活物質層間の抵抗値が高く、また、金属集電体と活物質層間の密着力が不十分だったことを挙げることができる。
ビニルシラン系共重合体と、ポリカルボン酸(但し、前記ビニルシラン系共重合体は除く)と、導電性助剤とを含む電池又は電気二重層キャパシタ集電体コート用導電性組成物であって、
前記ビニルシラン系共重合体が、下記式(1):
Xは単結合または結合鎖(但し、酸素を除く)を示し、
R2~R4は、独立して、
-OR5(R5は、H、C1~C6アルキル基及び電池又は電気二重層キャパシタの電解質を構成し得るカチオンに由来する基からなる群から選択される基である)、
C1~C6アルキル基、及び
ハロゲン基からなる群から選択される基である)で表される単位を表し、
Vは、少なくとも活性水素基を有するビニル系モノマーに由来する単位(但し、前記Uは除く)であり、
R21~R23は、独立して、H又はC1~C6アルキル基
mは1~10000の数、nは20~100000の数であり、
mとnの比率(m/n)が、0.0001~1である〕で表わされることを特徴とする電池又は電気二重層キャパシタ集電体コート用導電性組成物、
(2)カルボン酸ビニル共重合体と、ポリカルボン酸(但し、前記カルボン酸ビニル共重合体は除く)と、導電性助剤とを含む電池又は電気二重層キャパシタ集電体コート用導電性組成物であって、
前記カルボン酸ビニル共重合体が、カルボン酸ビニルモノマーとビニルシラン系モノマーとの共重合体であり、
前記ビニルシラン系モノマーが、ビニルアルキルジアルコキシシラン、γ-(メタ)アクリロキシプロピルトリアルコキシシラン、γ-(メタ)アクリロキシプロピルアルキルジアルコキシシラン及びビニルトリス(β-メトキシエトキシ)シランからなる群から選択される1種以上の化合物であることを特徴とする電池又は電気二重層キャパシタ集電体コート用導電性組成物、
(3)前項(1)又は(2)記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物でコートした電池又は電気二重層キャパシタ集電体、及び
(4)前項(3)記載の電池又は電気二重層キャパシタ集電体を含む電池又は電気二重層キャパシタに関する。
本発明の第1の態様の電池又は電気二重層キャパシタ集電体コート用導電性組成物は、ビニルシラン系共重合体と、ポリカルボン酸(但し、前記ビニルシラン系共重合体は除く)と、導電性助剤とを含む電池又は電気二重層キャパシタ集電体コート用導電性組成物であって、
前記ビニルシラン系共重合体が、下記式(1):
Xは単結合または結合鎖(但し、酸素を除く)を示し、
R2~R4は、独立して、
-OR5(R5は、H、C1~C6アルキル基及び電池又は電気二重層キャパシタの電解質を構成し得るカチオンに由来する基からなる群から選択される基である)、
C1~C6アルキル基、及び
ハロゲン基からなる群から選択される基である)で表される単位を表し、
Vは、少なくとも活性水素基を有するビニル系モノマーに由来する単位(但し、前記Uは除く)であり、
R21~R23は、独立して、H又はC1~C6アルキル基、好ましくはH又はメチル基、より好ましくはHであり、
mは1~10000の数、nは20~100000の数であり、
mとnの比率(m/n)が、0.0001~1である〕で表わされることを特徴とする。
前記カルボン酸ビニル共重合体が、カルボン酸ビニルモノマーとビニルシラン系モノマーとの共重合体であり、
前記ビニルシラン系モノマーが、ビニルアルキルジアルコキシシラン、γ-(メタ)アクリロキシプロピルトリアルコキシシラン、γ-(メタ)アクリロキシプロピルアルキルジアルコキシシラン及びビニルトリス(β-メトキシエトキシ)シランからなる群から選択される1種以上の化合物であることを特徴とする。
本発明の第1及び第2の態様の電池又は電気二重層キャパシタ集電体コート用導電性組成物におけるポリカルボン酸と導電性助剤の定義と好適態様はポリカルボン酸についての括弧書きを除いて共通する。
そこで、以下では、特に断らない限り、本発明の第1の態様の電池又は電気二重層キャパシタ集電体コート用導電性組成物について説明し、その説明は、ビニルシラン系共重合体をカルボン酸ビニル共重合体に置き換えれば、本発明の第2の態様の電池又は電気二重層キャパシタ集電体コート用導電性組成物にも適用されるものとする。
以下では、本発明の第1の態様の電池又は電気二重層キャパシタ集電体コート用導電性組成物を電池又は電気二重層キャパシタ集電体コート用導電性組成物ともいう。
また、本発明におけるポリカルボン酸は、ポリカルボン酸とそのポリカルボン酸由来の酸無水物も含む概念であり、以下では、まとめてポリカルボン酸というか、又は、ポリカルボン酸(ポリカルボン酸由来の酸無水物を含む)という。
本発明におけるビニルシラン系共重合体(以下、ビニルシラン系共重合体ともいう)は、前記式(1)で示される。なお、以下、式(2)で表される単位をビニルシラン系モノマー由来の単位ともいう。
即ち、電池又は電気二重層キャパシタ集電体コート用導電性組成物を熱硬化させる際に、ビニルシラン系共重合体は、ビニルシラン系共重合体中の少なくとも活性水素基有するビニル系モノマー(以下、ビニル系モノマーともいう)由来の単位の活性水素基がポリカルボン酸と脱水縮重合反応(例えば、エステル結合生成反応)をすることで架橋する。
また、電池又は電気二重層キャパシタ集電体コート用導電性組成物を熱硬化させる際に電池又は電気二重層キャパシタ集電体コート用導電性組成物を、溶媒に溶解して使用すると、溶媒を蒸散させるだけ架橋反応を開始させる事ができ(溶媒中で、ビニルシラン系共重合体とポリカルボン酸の分子間距離が近づくためと考えられる)、さらに加熱することで架橋反応を促進できる。
加熱による架橋反応の促進は40~250℃の範囲が好ましく、架橋速度と被着体の熱劣化のバランスから100~180℃の範囲がより好ましい。
ビニル系モノマー由来の単位が有する活性水素基は、具体的には、製造時の安定性や耐電気分解特性の観点から、好ましくは、ヒドロキシ基(-OH)、カルボキシル基(-COOH)、アミノ基(-NH2、-NHR6)、ヒドラジド基(R7R8NN(R9)C(=O)R10)、ヒドロキシルアミノ基(-NHOH)、スルホ基(-SO3H)、チオール基(-SH)(前記式中、R6~R10はそれぞれ独立して、水素原子、C1~C8のアルキル基、ヒドロキシル基、アシル基、カルボキシル基、アミノ基、ビニル基、アリル基、アリール基、ハロゲン、金属などである)などを例示する事ができ、ヒドロキシ基、アミノ基、スルホ基がより好ましい。
カルボン酸ビニルモノマーがビニル重合したカルボン酸ビニル共重合体をケン化して得ることができる。
この場合、すなわち、R1がカルボン酸に由来する有機基である場合、
耐電解液性や集電体への密着性の観点及び、
ポリカルボン酸との反応に伴う硬化収縮応力による導電助剤の集電体への圧接効果を強める観点から、カルボン酸に由来する有機基の割合が、
30%以下(すなわちケン化度が70%以上)であることが好ましく、
20%以下(すなわちケン化度が80%以上)であることがより好ましく、
10%以下(すなわちケン化度が90%以上)であることが更に好まし、即ち、
0%以上30%以下(すなわちケン化度が70%以上100%以下)であることが好ましく、
0%以上20%以下(すなわちケン化度が80%以上100%以下)であることがより好ましく、
0%以上10%以下(すなわちケン化度が90%以上100%以下)であることが更に好ましい。
ハロゲンで置換されてもよい炭化水素基(好ましくはC1~C17直鎖又は分岐鎖のアルキル基(例えば、メチル基、エチル基、プロピル基、ペンチル基、ヘプチル基、ノニル基、ウンデカニル基、トリデカニル基、ペンタデカニル基、ヘプタデカニル基、モノクロロメチル基、1-エチル-ペンチル基)、C3~C6シクロアルキル基(例えば、シクロヘキシル基、シクロペンチル基)、芳香族基(例えば、フェニル基))、又は、
-CO-R41で表され、R41はハロゲンで置換されてもよいC1~C17直鎖又は分岐鎖のアルキル基(例えば、メチル基、エチル基、プロピル基、ペンチル基、ヘプチル基、ノニル基、ウンデカニル基、トリデカニル基、ペンタデカニル基、ヘプタデカニル基、モノクロロメチル基、1-エチル-ペンチル基)、C3~C6シクロアルキル基(例えば、シクロヘキシル基、シクロペンチル基)、芳香族基(例えば、フェニル基)であり得る。
電池又は電気二重層キャパシタの電解質を構成し得るカチオンとしては、不可逆容量の観点から、
NaやKなどのLiを除くアルカリ金属、Be、Mg、Ca、Srなどのアルカリ土類金属、又は、リチウム、又はテトラエチルアンモニウム、トリエチルメチルアンモニウムなどのテトラアルキルアンモニウム等などで有り得、適応する電池又は電気二重層キャパシタの電解質を構成するカチオン由来の基であることが好ましい。
ビニルシラン系モノマー由来の単位は前記式(2)で表される。
-OCH3がより好ましい。
電池又は電気二重層キャパシタの電解質を構成し得るカチオンとしては不可逆容量の観点から、NaやKなどのLiを除くアルカリ金属、Be、Mg、Ca、Srなどのアルカリ土類金属、又は、リチウム、又はテトラエチルアンモニウム、トリエチルメチルアンモニウムなどのテトラアルキルアンモニウム等などで有り得、適応する電池又は電気二重層キャパシタの電解質を構成するカチオン由来の基であることが好ましい。
好ましくはC1~C6の直鎖又は分岐鎖のアルキル基であり、例えば、メチル基、エチル基、n-プロピル、n-ブチルが挙げられ、より好ましくはエチル基である。
1~10000であり、5~1000が好ましく、10~500がより好ましい。
製造時の安定性や耐電気分解特性の観点から、
20~100000であり、200~20000が好ましく、300~1000がより好ましい。
製造時の安定性や耐電気分解特性の観点から、
0.0001~1であり、0.005~0.5が好ましく、0.01~0.1がより好ましい。
ここで、結合鎖とは、ビニルシラン共重合体の主鎖とシラン構造とをつなぐ基であり、
炭素数1~18の、アルキレン、アルケニレン、若しくはアルキニレン、フェニレン、又はナフチレン等の炭化水素(これらの炭化水素はフッ素、塩素、臭素等のハロゲン等で置換されていても良い)の他、-(CH2O)m-、-(CH2O)mCH2-、-CO-、-COCO-、-CO(CH2)mCO-、-CO(C6H4)CO-、-S-、-CS-、-SO-、-SO2-、-NR-、-CONR-、-NRCO-、-CSNR-、-NRCS-、-NRNR-、-HPO4-、-Si(OR)2-、-Ti(OR)2-、-Al(OR)-、等(Rは各々独立して任意の置換基であり、水素原子、アルキル基(特に炭素数1~4のアルキル基)が好ましく、またmは自然数であり、好ましくは1~10である)からなる群から選択される基が例示できる。
式(2)中のシロキサン結合が電気化学的に安定で、電池又は電気二重層型キャパシタの充放電時にコート層の耐剥離性を確保する観点から、
Xは、熱安定性の点や高温下/酸性条件下での構造安定性の点で単結合であるものが最も好ましいが、本発明の効果を阻害しない範囲であれば結合鎖であってもよい。かかる結合鎖としては特に限定されないが、例えば炭素数1~18の、アルキレン、アルケニレン、若しくはアルキニレン、フェニレン、又はナフチレン等の炭化水素(これらの炭化水素はフッ素、塩素、臭素等のハロゲン等で置換されていても良い)の他、-(CH2O)m-、-(CH2O)mCH2-、-CO-、-COCO-、-CO(CH2)mCO-、-CO(C6H4)CO-、-S-、-CS-、-SO-、-SO2-、-NR-、-CONR-、-NRCO-、-CSNR-、-NRCS-、-NRNR-、-HPO4-、-Si(OR)2-、-Ti(OR)2-、-Al(OR)-、等(Rは各々独立して任意の置換基であり、水素原子、アルキル基(特に炭素数1~4のアルキル基)が好ましく、またmは自然数であり、好ましくは1~10である)が挙げられる。中でも製造時あるいは使用時の安定性の点で炭素数6以下のアルキレン基、特にメチレン基、あるいは-CH2OCH2-が好ましい結合鎖である。
ビニルシラン系共重合体としては、
製造時の安定性や耐電気分解特性の観点から、
ビニル系モノマーがカルボン酸ビニルモノマーであるカルボン酸ビニル共重合体が好ましい。
なお、式(5)及び(6)中、R31~R33は独立にR5の上述の好適態様をとる。
酢酸ビニルの代わりに、プロピロン酸ビニル、酪酸ビニル、カプロン酸ビニル、カプリル酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ミリスチン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、シクロヘキサンカルボン酸ビニル、ピパリン酸ビニル、オクチル酸ビニル、モノクロロ酢酸ビニル、アジピン酸ビニル、メタクリル酸ビニル、クロトン酸ビニル、ソルビン酸ビニル、安息香酸ビニル、桂皮酸ビニルなどを例示できるが、価格や入手の容易さの観点で酢酸ビニルを使用することが好ましく、
ビニルトリエトキシシランの代わりに、例えば、ビニルトリメトキシシラン、ビニルトリプロポキシシラン、ビニルトリブトキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン等のビニルアルキルジアルコキシシラン;γ-(メタ)アクリロキシプロピルトリメトキシシラン、γ-(メタ)アクリロキシプロピルトリエトキシシラン等のγ-(メタ)アクリロキシプロピルトリアルコキシシラン;γ-(メタ)アクリロキシプロピルメチルジメトキシシラン、γ-(メタ)アクリロキシプロピルメチルジエトキシシラン等のγ-(メタ)アクリロキシプロピルアルキルジアルコキシシラン;ビニルトリス(β-メトキシエトキシ)シラン等を使用すること好ましいが、製造時の安定性や耐電気分解特性の観点でビニルトリエトキシシランがより好ましい。
ビニルシラン系共重合体として、上記の活性水素基を有するビニル系モノマー(好ましくは、カルボン酸ビニルモノマー)及びビニルシラン系モノマーと共に、特定の官能基含有モノマーを共重合したものが、集電体との優れた密着性や電気化学的な安定性が得られる点で好ましい。
なお、これらの特定の官能基含有モノマーは、単独でもしくは2種以上のものを組み合わせて使用することができる。
本発明におけるポリカルボン酸は、1分子中にカルボン酸を2個以上、反応性や架橋密度の観点から好ましくは2~1000個、より好ましくは3~100個有する分子量100000以下、好ましくは分子量30000以下、より好ましくは分子量20000以下のポリカルボン酸(ポリカルボン酸由来の酸無水物も含む)である。
芳香族カルボン酸が反応性の観点で好ましく、カルボン酸が1分子中に3以上置換されているものが反応性や架橋密度の観点で好ましい。
ポリカルボン酸としては、
クエン酸、ブタンテトラカルボン酸、3,3’,4,4’-ビフェニルテトラカルボン酸、ヘキサヒドロフタル酸、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸、メチルビシクロ[2.2.1]ヘプタン-2,3-ジカルボン酸、ビシクロ[2.2.1]ヘプタン-2,3-ジカルボン酸、アスパラギン酸、ピロメリット酸、メリト酸、含リンエステル基テトラカルボン酸、フェニルエチニルフタル酸及びオキシジフタル酸からなる群から選択される1種以上の化合物並びに/若しくはこれらの化合物由来の酸無水物、及び/又は、
エチレングリコールビスアンヒドロトリメリテート(酸無水物)、1,3,3a,4,5,9b-ヘキサヒドロ-5(テトラヒドロ-2,5-ジオキソ-3-フラニル)ナフト[1,2-c]フラン-1,3-ジオン(酸無水物)、グリセリンビスアンヒドロトリメリテートモノアセテート(酸無水物)、エチレングリコールビスアンヒドロトリメリテート(酸無水物)からなる群から選択される1種以上の化合物を例示できる。
本発明における導電性助剤は、導電性を有する、粒子若しくはフィラー、又はイオン性を有する液体であり得る。
なお、これらの粒子の大きさは、電子顕微鏡で測定された各粒子の平面画像の面積を有する円の直径を、測定した全粒子について平均した値を平均粒子径としたものある。
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、上述したように
ビニルシラン系共重合体(以下、成分Aともいう)と、
ポリカルボン酸(但し、前記ビニルシラン系共重合体を除く)(以下、成分Bともいう)と、
導電性助剤(以下、成分C(イオンが溶解した液体の場合はイオン以外の液体は除く)ともいう)とを含む。
成分Bは、成分A(好ましくはカルボン酸ビニル共重合体)100重量部に対して、
1~300重量部含むことが好ましく、5~200重量部含むことがより好ましく、10~200重量部含むことが更に好ましく、10~100重量部含むことが更に好ましく、20~100重量部含むことが更に好ましい。
成分Cは、成分A(好ましくはカルボン酸ビニル共重合体)100重量部に対して、
10~9900重量部含むことが好ましく、20~4900重量部含むことがより好ましく、50~1900重量部含むことが更に好ましい。
電池又は電気二重層キャパシタ集電体コート用導電性組成物の不揮発成分中、成分A、B及びCの合計量が、
50~100重量%であることが好ましく、
80~100重量%であることがより好ましく、
90~100重量%であることが更に好ましい。
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、成分A、B及びCを含めば、粉末状、フレーク状等の固体でもよいし、ペースト、溶液又は懸濁液等の液状体でもよい。
但し、電池又は電気二重層キャパシタ集電体コート用導電性組成物を電池集電体上に被膜としてコートする場合はペースト、溶液又は懸濁液等の液状で使用することが好ましいので、電池又は電気二重層キャパシタ集電体コート用導電性組成物が固形状であれば使用する際に溶媒と混合して液状にし、電池又は電気二重層キャパシタ集電体コート用導電性組成物がペースト状であればそのまま、又は、さらに溶媒と混合して、使用しやすい粘度又は性状の液状にすることが好ましい。
(電池又は電気二重層キャパシタ集電体コート用導電性組成物の製造方法)
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、成分A、B及びC、必要に応じて、後述する任意成分を混合し撹拌することによってペースト、溶液又は懸濁液等として得ることができる。撹拌は、プロペラ式ミキサー、プラネタリーミキサー、ハイブリッドミキサー、ニーダー、乳化用ホモジナイザー、超音波ホモジナイザー等の各種撹拌装置を適宜選択して行うことができる。また、必要に応じて加熱又は冷却しながら撹拌して好ましくは上記の好適粘度範囲にすることもできる。
(溶媒)
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、粘度を中心とする液性を調整するために、各種溶媒を含むことができる。溶媒としては、炭化水素(プロパン、n-ブタン、n-ペンタン、イソヘキサン、シクロヘキサン、n-オクタン、イソオクタン、ベンゼン、トルエン、キシレン、エチルベンゼン、アミルベンゼン、テレビン油、ピネン等)、ハロゲン系炭化水素(塩化メチル、クロロホルム、四塩化炭素、塩化エチレン、臭化メチル、臭化エチル、クロロベンゼン、クロロブロモメタン、ブロモベンゼン、フルオロジクロロメタン、ジクロロジフルオロメタン、ジフルオロクロロエタン等)、アルコール(メタノール、エタノール、n-プロパノール、イソプロパノール、n-アミルアルコール、イソアミルアルコール、n-ヘキサノール、n-ヘプタノール、2-オクタノール、n-ドデカノール、ノナノール、シクロヘキサノール、グリシドール等)、エーテル、アセタール(エチルエーテル、ジクロロエチルエーテル、イソプロピルエーテル、n-ブチルエーテル、ジイソアミルエーテル、メチルフェニルエーテル、エチルベンジルエーテル、フラン、フルフラール、2-メチルフラン、シネオール、メチラール)、ケトン(アセトン、メチルエチルケトン、メチル-n-プロピルケトン、メチル-n-アミルケトン、ジイソブチルケトン、ホロン、イソホロン、シクロヘキサノン、アセトフェノン等)、エステル(ギ酸メチル、ギ酸エチル、ギ酸プロピル、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸-n-アミル、酢酸メチルシクロヘキシル、酪酸メチル、酪酸エチル、酪酸プロピル、ステアリン酸ブチル等)、多価アルコールとその誘導体(エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテル、メトキシメトキシエタノール、エチレングリコールモノアセテート、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、プロピレングリコール、プロピレングリコールモノエチルエーテル等)、脂肪酸及びフェノール(ギ酸、酢酸、無水酢酸、プロピオン酸、無水プロピオン酸、酪酸、イソ吉草酸、フェノール、クレゾール、o-クレゾール、キシレノール等)、窒素化合物(ニトロメタン、ニトロエタン、1-ニトロプロパン、ニトロベンゼン、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジアミルアミン、アニリン、モノメチルアニリン、o-トルイジン、o-クロロアニリン、ジクロヘキシルアミン、ジシクロヘキシルアミン、モノエタノールアミン、ホルムアミド、N,N-ジメチルホルムアミド、アセトアミド、アセトニトリル、ピリジン、α-ピコリン、2,4-ルチジン、キノリン、モルホリン等)、硫黄、リン、その他化合物(二硫化炭素、ジメチルスルホキシド、4,4-ジエチル-1,2-ジチオラン、ジメチルスルフィド、ジメチルジスルフィド、メタンチオール、プロパンスルトン、リン酸トリエチル、リン酸トフェニル、炭酸ジエチル、炭酸エチレン、ホウ酸アミル等)、無機溶剤(液体アンモニア、シリコーンオイル等)、水等の液体を例示することができる。
前記ビニル共重合体以外のその他の結着剤として、特開2010-146726公報
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、さらに、カップリング剤を含むことができる。
このようなカップリング剤としては、具体的にはフッ素系のシランカップリング剤として、(トリデカフルオロ-1,1,2,2-テトラヒドロオクチル)トリエトキシシラン、エポキシ変性シランカップリング剤として信越化学工業株式会社製カップリング剤(商品名:KBM-403)、オキセタン変性シランカップリング剤として東亞合成株式会社製カップリング剤(商品名:TESOX電池集電体コート用導電性組成物)、あるいは、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ-クロロプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、3-(トリメトキシシリル)プロピル無水コハク酸、γ-アミノプロピルトリエトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルトリメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルメチルジメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、β-グリシドキシプロピルメチルジメトキシシラン、γ-メタクリロキシキシプロピルトリメトキシシラン、γ-メタクリロキシキシプロピルメチルジメトキシシラン、γ-メルカプトプロピルトリメトキシシラン等のシランカップリング剤や、トリエタノールアミンチタネート、チタニウムアセチルアセトネート、チタニウムエチルアセトアセテート、チタニウムラクテート、チタニウムラクテートアンモニウム塩、テトラステアリルチタネート、イソプロピルトリクミルフェニルチタネート、イソプロピルトリ(N-アミノエチル-アミノエチル)チタネート、ジクミルフェニルオキシアセテートチタネート、イソプロピルトリオクタイノルチタネート、イソプロピルジメタクリイソステアロイルチタネート、チタニウムラクテートエチルエステル、オクチレングリコールチタネート、イソプロピルトリイソステアロイルチタネート、トリイソステアリルイソプロピルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、テトラ(2-エチルヘキシル)チタネート、ブチルチタネートダイマー、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリ(ジオクチルホスフェート)チタネート、イソプロピルトリス(ジオクチルパイロホスフェート)チタネート、テトライソプロピルビス(ジオクチルホスファイト)チタネート、テトラオクチルビス(ジトリデシルホスファイト)チタネート、テトラ(2,2-ジアリルオキシメチル-1-ブチル)ビス(ジ-トリデシル)ホスファイトチタネート、ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート、ビス(ジオクチルパイロホスフェート)エチレンチタネート、テトラ-i-プロピルチタネート、テトラ-n-ブチルチタネート、ジイソステアロイルエチレンチタネート等のチタン系カップリング剤を挙げることができる。
これらの化合物は、1種類、又は2種類以上を適宜組み合わせて使用することができる。
カップリング剤としては、チタン系カップリング剤又はシランカップリング剤が好ましい。
カップリング剤を電池又は電気二重層キャパシタ集電体コート用導電性組成物に配合することにより、電池又は電気二重層キャパシタ集電体コート用導電性組成物中に含まれる活性水素(例えば、水素結合性官能基)を有する置換基と反応させ更に架橋密度を向上させる事ができ、電池又は電気二重層キャパシタ集電体コート用導電性組成物を構成する元素と集電体を構成する元素の相互置換反応を更に抑制できる。
特に、チタン系カップリング剤やシランカップリング剤による架橋反応が起きることで、架橋速度を向上させたり密着力や強度電気化学的な耐性を向上させたりできる。
また、電池又は電気二重層キャパシタ集電体コート用導電性組成物中に配合して用いることで界面に過度な絶縁性の改質層を形成することを防ぐことが出来、界面抵抗の増大を抑える事が出来る。
また、特開2010-146726公報の実施例7に記載したように、例えばポリカルボン酸を添加する前に活性水素(例えば、水素結合性官能基)を有する化合物とカップリング剤とをあらかじめ加熱して反応させておいてから電池又は電気二重層キャパシタ集電体コート用導電性組成物を作製してもよい。
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、ぬれを調節するために、各種界面活性剤を含有することができる。
このような界面活性剤としては、アニオン界面活性剤として、石ケン、ラウリル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテルリン酸、ポリオキシエチレンアルキルフェニルエーテルリン酸、N-アシルアミノ酸塩、α-オレフィンスルホン酸塩、アルキル硫酸エステル塩、アルキルフェニルエーテル硫酸エステル塩、メチルタウリン酸塩等が挙げられ、両性界面活性剤としては、塩酸アルキルジアミノエチルグリシン、2-アルキル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタイン、ラウリルジメチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルベタイン、脂肪酸アルキルベタイン、スルホベタイン、アミオキサイド等が挙げられ、非イオン(ノニオン)型界面活性剤としては、ポリエチレングリコールのアルキルエステル型化合物、トリエチレングリコールモノブチルエーテル等のアルキルエーテル型化合物、ポリオキシソルビタンエステル等のエステル型化合物、アルキルフェノール型化合物、フッ素型化合物、シリコーン型化合物等が挙げられる。これらの化合物は、1種類、又は2種類以上を適宜組み合わせて使用することができる。
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、機械的強度や熱的特性を向上させるために、必要に応じて、各種の絶縁性フィラーを必要な導電性を損なわない範囲で配合することができる。絶縁性フィラーとしてはアルミナ、シリカ、ジルコニア、チタニア等の金属酸化物の粉末や、コロイダルシリカやチタニアゾル、アルミナゾル等のゾル、タルク、カオリナイト、スメクタイト等の粘土鉱物、炭化ケイ素、炭化チタン等の炭化物、窒化ケイ素、窒化アルミニウム、窒化チタン等の窒化物、窒化ホウ素、ホウ化チタン、酸化ホウ素等のホウ化物、ムライト等の複合酸化物、水酸化アルミニウム、水酸化マグネシウム等の水酸化物等、電池又は電気二重層キャパシタ集電体コート用導電性組成物の誘電率を上げる事が出来るチタン酸バリウム等が挙げられる。
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、さらに必要に応じて、安定剤を適宜選択して含むことができる。
このような安定剤としては、具体的には2,6-ジ-tert-ブチル-フェノール、2,4-ジ-tert-ブチル-フェノール、2,6-ジ-tert-ブチル-4-エチル-フェノール、2,4-ビス-(n-オクチルチオ)-6-(4-ヒドロキシ-3,5-ジ-tert-ブチル-アニリノ)-1,3,5-トリアジン等によって例示されるフェノール系酸化防止剤、アルキルジフェニルアミン、N,N’-ジフェニル-p-フェニレンジアミン、6-エトキシ-2,2,4-トリメチル-1,2-ジヒドロキノリン、N-フェニル-N’-イソプロピル-p-フェニレンジアミン等によって例示される芳香族アミン系酸化防止剤、ジラウリル-3,3’-チオジプロピオネート、ジトリデシル-3,3’-チオジプロピオネート、ビス[2-メチル-4-{3-n-アルキルチオプロピオニルオキシ}-5-tert-ブチル-フェニル]スルフィド、2-メルカプト-5-メチル-ベンゾイミダゾール等によって例示されるサルファイド系ヒドロペルオキシド分解剤、トリス(イソデシル)ホスファイト、フェニルジイソオクチルホスファイト、ジフェニルイソオクチルホスファイト、ジ(ノニルフェニル)ペンタエリトリトールジホスファイト、3,5-ジ-tert-ブチル-4-ヒドロキシ-ベンジルホスファートジエチルエステル、ナトリウムビス(4-tert-ブチルフェニル)ホスファート等によって例示されるリン系ヒドロペルオキシド分解剤、フェニルサリチラート、4-tert-オクチルフェニルサリチラート等によって例示されるサリチレート系光安定剤、2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン-5-スルホン酸等によって例示されるベンゾフェノン系光安定剤、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2,2’-メチレンビス[4-(1,1,3,3-テトラメチルブチル)-6-(2N-ベンゾトリアゾール-2-イル)フェノール]等によって例示されるベンゾトリアゾール系光安定剤、フェニル-4-ピペリジニルカルボナート、セバシン酸ビス-[2,2,6,6-テトラメチル-4-ピペリジニル]等によって例示されるヒンダードアミン系光安定剤、[2,2’-チオ-ビス(4-t-オクチルフェノラート)]-2-エチルヘキシルアミン-ニッケル-(II)によって例示されるNi系光安定剤、シアノアクリレート系光安定剤、シュウ酸アニリド系光安定剤等を挙げることができる。
これらの化合物は、1種類又は2種類以上を適宜組み合わせて使用することができる。
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、上述したように、成分A、成分B及び成分Cの他に、必要に応じて、溶媒、その他の決着剤、カップリング剤(以下、成分Dともいう)、界面活性剤(以下、成分Eともいう)、絶縁性フィラー(以下、成分Fともいう)及び安定剤(以下、成分Gともいう)を含むことができる。
電池又は電気二重層キャパシタ集電体コート用導電性組成物は、体積収縮率Sv及び弾性率GPaに対して、式(3)
K≡Sv×GPa (3)
で定義されるKの値(以下、K値ともいう)が3~90であることが好ましい。
電池又は電気二重層キャパシタ集電体コート用導電性組成物が溶液状の場合、電池又は電気二重層キャパシタ集電体コート用導電性組成物を15mlガラス製ピペットで吸液し、内径5mmのテフロン(登録商標)性チューブに注入する。
なお、テフロン性チューブに注入された電池又は電気二重層キャパシタ集電体コート用導電性組成物が、溶媒を室温(好ましくは、20~30℃)で真空蒸散させた後、前記テフロン性チューブ内の長さでYmm(ただし、Yは9~13mmの範囲)になるように、テフロン性チューブに注入する前の電池又は電気二重層キャパシタ集電体コート用導電性組成物中の溶媒量及び電池又は電気二重層キャパシタ集電体コート用導電性組成物の吸液量を調整する。
前記テフロン性チューブに注入された電池又は電気二重層キャパシタ集電体コート用導電性組成物を、室温(好ましくは、20~30℃)で、泡をかまないように溶媒を徐々に真空蒸散させ、前記テフロン性チューブに注入された電池又は電気二重層キャパシタ集電体コート用導電性組成物の長さをYmmにする。
前記テフロン性チューブ内で長さYmmとなった電池又は電気二重層キャパシタ集電体コート用導電性組成物をオーブンにより実際に電池又は電気二重層キャパシタ集電体コート用導電性組成物を硬化させる温度と時間(好ましくは40~280℃、0.1~200分、より好ましくは60~250℃、0.2~100分、更に好ましくは80~220℃、0.4~50分)で加熱してテフロンチューブ内の電池又は電気二重層キャパシタ集電体コート用導電性組成物の長さの収縮が停止するまで熱硬化させ、熱硬化後の前記テフロン性チューブ内の長さLmmを測定する。体積収縮率Sv(%)を以下の式で算出する。
Sv=100×(Y-L)/Y
また、電池又は電気二重層キャパシタ集電体コート用導電性組成物が粉末状、フレーク状等の固体である場合、高圧プレス成型した成型物の加熱硬化前後の体積を用いることができる。この場合、該粉末及びフレークを総加重5トンで直径19~21mm、厚さ9~11mmのペレット状に形成し、作製後のペレットの加熱前の直径と厚みから体積を求め、次いで加熱(好ましくは40~280℃、0.1~200分、より好ましくは60~250℃、0.2~100分、更に好ましくは80~220℃、0.4~50分)後のペレットの体積も直径と厚みから求めることで、体積収縮率を算出できる。
なお、後述する実施例においては、電池又は電気二重層キャパシタ集電体コート用導電性組成物は、いずれも溶液状であり、加熱条件は160℃、80秒で行った。
熱硬化後の前記テフロン性チューブ内の長さLmmの電池又は電気二重層キャパシタ集電体コート用導電性組成物硬化体を、テフロンチューブを切開して前記テフロン性チューブから取り出し、JIS K 7113に準拠した方法で測定された引っ張り弾性率を弾性率GPaとする。
本発明は、その解決手段の基礎として、ビニルシラン系共重合体とポリカルボン酸(但し、前記ビニルシラン系共重合体は除く)と導電性助剤とを含む電池又は電気二重層キャパシタ集電体コート用導電性組成物を採用した。
密着性(耐剥離性)と高め電池又は電気二重層キャパシタ特性(サイクル寿命及びフロート寿命)を向上する観点から、電池又は電気二重層キャパシタ集電体コート用導電性組成物のK値は、好ましくは3~90、より好ましくは 3.2~20、更に好ましくは3.5~10である。
また、1分子中に4以上の置換基を有する化合物が硬化に伴う体積収縮と硬化後の弾性率の観点から好ましく、4官能以上のアルコールと4官能以上のカルボン酸との組み合わせは、硬化応力を大きくするための組み合わせとして好ましく、体積収縮と弾性率を向上させるために前記4以上の活性水素を有する活性水素当量が500(g/mol)以下の化合物と、4以上のカルボン酸を有するカルボン酸当量が500(g/mol)以下の化合物が単位体積あたりの縮合反応の量に比例して体積収縮率が大きくなり弾性率が高くなるため更に好ましい。
(電池又は電気二重層キャパシタ集電体)
電池又は電気二重層キャパシタ集電体コート用導電性組成物でコートされた本発明の電池集電体(以下、電池集電体ともいう)は、上記材料を用いて配合した電池又は電気二重層キャパシタ集電体コート用導電性組成物を電池又は電気二重層キャパシタ集電体にコートすることで製造できる。
電池又は電気二重層キャパシタ集電体としては、金、銀、銅、アルミ、ニッケル、鉄、コバルト、などの金属やカーボン繊維不織布、金属複合材料などの導電性を有する複合材料を例示でき、リチウムイオン二次電池においては正極用にアルミ箔、負極用に銅箔、電気二重層キャパシタにおいてはアルミ箔やアルミのエッチング箔が用いられている。
コーティングはグラビアコーターやスリットダイコーター、スプレーコーター、ディッピングなどを利用することが出来る。
導電性助剤と電池集電体とが接触する機会や面積を安定に確保して、低抵抗値を安定に確保する観点から、コート層の厚さは0.01~100μmの範囲が好ましく、電気特性及び密着性の観点から0.05~5μmの範囲が更に好ましい。
本発明の電池集電体を適用できる本発明の電池(以下、電池ともいう)としては、
充電電位の高さに伴う電気化学的な劣化を防ぐ効果の高さの観点から、
リチウムイオン二次電池、ナトリウムイオン二次電池、カリウムイオン二次電池、マグネシウムイオン二次電池が好ましく、
リチウムイオン二次電池がより好ましい。リチウムイオン二次電池の中では、内部抵抗が高い鉄オリビン系のリチウムイオン二次電池への効果が更に高い。
電池の製造は、公知の方法によって行うことができる。
また、集電体表面に化学的に強固に結合するため、界面の劣化に伴う抵抗値の増大を抑えることが出来、充放電試験や保存試験など長期信頼性試験後の電池又は電気二重層キャパシタ特性の低下が小さい。
特に、本発明のビニルシラン系共重合体(好ましくはカルボン酸ビニル共重合体)は、集電体表面に存在する極性置換基(例えば金属の場合は水酸基など)と共有結合を形成するため、密着力とその密着力の電気化学的な耐久性に優れる。
従来の電池又は電気二重層キャパシタ集電体コート用導電性組成物では、結合が電気化学的に切れやすいためシロキサン構造を有するため、長期信頼性に十分優れる電池を製造できないが、本発明によれば、ケイ素がビニルシラン系共重合体(好ましくはカルボン酸ビニル共重合体)の主鎖に炭素原子を介して結合しているので結合が電気化学的に安定であり、長期安定性に優れる。
また、コート剤中のポリカルボン酸は、ビニルシラン系共重合体(好ましくはカルボン酸ビニル共重合体)中の活性水素を有する置換基(好ましくは水酸基)同士や集電体表面の活性水素を有する置換基(好ましくは水酸基)との間を架橋することで電気化学的に分解しにくくする効果を有する。
このような電気化学的に堅牢な結合は、集電体が電気化学的にその他の電池構成材料と相互マイグレーションを起す事を防ぎ、抵抗の高い合金層の形成や空隙の発生による抵抗値の増大や機械的な強度の低下を防ぐ効果がある。
また、コート剤中の導電性助剤が集電体表面と相互作用することで界面の抵抗値も下げる。例えば、金属集電体の場合表面には絶縁性の酸化膜や水酸化膜が存在するのだが、導電性粒子を使った場合、乾燥固化時の収縮応力により該導電性粒子がそれら絶縁性の膜を突き破ることで抵抗値を低減させることができる。
このように、導電性粒子が該酸化膜や水酸化膜を突き破るためには、収縮応力が大きくかつ収縮応力に拮抗できるだけの密着力の高さが必要になる。
また、この導電性粒子が絶縁性の膜を突き破りめり込んだ状態が充放電試験後も保持できる程度に密着力が保持されるよう、界面の電気化学的な安定性も必要である。
また、イオン性液体を用いた場合それら絶縁性の膜の欠損に染み込むことで抵抗値を低減させることができる。
実施例1ではビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極と負極の両方にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
冷却機付き10L三つ口フラスコに、
メタノール1000部、酢酸ビニル1400部、ビニルトリエトキシシラン50部、
を加え攪拌しながらドライアルゴン置換を行い60℃まで温度を上げた。
そこへ、3.5%の2,2’-アゾビスイソブチロニトリルのメタノール溶液1200部を滴下した。
ビニルトリエトキシシランの10%メタノール溶液100部を5時間かけて滴下しながら重合を行った。
メタノール蒸気を導入することで未反応の酢酸ビニル単量体を除去した。
ここに水酸化ナトリウムの10%メタノール溶液100部を40℃で攪拌しながら滴下した。
得られた白色ゲルを粉砕しメタノールで洗浄して未反応のビニルトリエトキシシランを除去し、次いで乾燥させることでビニルシラン系共重合体を得た。
得られた共重合体は(Inductively Coupled Plasma Atomic Emission Spectroscopy:ICP-AES)による元素分析の結果ビニルシラン単位が1モル%含有されており、カルボン酸ビニル部の99%がケン化されていることが分かった。
分子量はGPC(Gel Permeation Chromatography)で測定し、
m/n=0.01、m=10、n=990であった。
10Lのビーカーに水1000部と水酸化ナトリウム5部を加え均一になるまで攪拌した。そこへ、上記ビニルシラン系共重合体を20部加え80℃で6時間均一になるまで攪拌した。そこへ、ピロメリット酸を10部加え60℃で4時間均一になるまで攪拌した。そこへアセチレンブラック(電気化学工業社製;デンカブラックHS-100)を25部加え概ね均一になるまで攪拌し分散液を得た。
幅300mm、厚さ20μmの圧延アルミ箔(正極用)及び幅300mm、厚さ15μmの圧延銅箔(負極用)に幅200mm、厚さ10μmで上記塗工液を塗布し、180℃温風炉で30秒乾燥させた。乾燥後の塗工膜厚はそれぞれ1μmであった。
冷却ジャケット付きの10Lプラネタリーミキサーに、PVdFの15%NMP溶液(株式会社クレハ製;クレハKFポリマー#1120)600部、コバルト酸リチウム(日本化学工業株式会社製;C-5H)1000部、アセチレンブラック(電気化学工業株式会社製;デンカブラックHS-100)100部、NMP5000部を加え液温が30℃を超えないように冷却しながら均一になるまで攪拌した。これを、前記導電コート層を形成した集電体に幅180mm、厚さ200μmで塗工し、160℃温風炉で20秒乾燥させた。これを線圧500kgf/cmでロールプレスした。プレス後の正極活物質層の厚みは20μmであった。
冷却ジャケットつきの10Lプラネタリーミキサーに、PVdFの15%NMP溶液(株式会社クレハ製;クレハKFポリマー#9130)600部、グラファイト(日本黒鉛株式会社製;CGB-200)1100部、NMP4000部を加え液温が30℃を超えないように冷却しながら均一になるまで攪拌した。これを、前記導電コート層を形成した集電体に幅180mm、厚さ200μmで塗工し、120℃温風炉で2分間乾燥させた。これを線圧500kgf/cmでロールプレスした。プレス後の負極活物質層の厚みは25μmであった。
正極及び負極を短辺に10mm活物質層が無い領域が含まれるように40mm×50mmでカットし、金属がむき出しになっている部分に正極はアルミのタブを、負極にニッケルのタブを抵抗溶接で接合した。セパレーター(セルガード株式会社製;#2400)を幅45mm、長さ120mmにカットし、3つに折り返してその間に正極及び負極が対向するように挟み込み、これを幅50mm長さ100mmのアルミラミネートセルを二つ折りにしたもので挟み、タブが当たる部分にシーラントを挟み込んだ上でシーラント部分とそれに直行する辺を熱ラミネートして袋状にした。これを100℃の真空オーブンに12時間入れて真空乾燥させ、次いでドライブローブボックス中で6フッ化リン酸リチウム/EC:DEC=1:1 1M電解液(キシダ化学株式会社製;LBG-96533)を注入し、真空含侵した後、余った電解液を扱き出し、真空シーラーで接合密封して、リチウムイオン電池を製造した。
実施例2ではビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
負極には前記導電性コート層を形成しなかったこと以外は実施例1と同じようにリチウムイオン電池を作製した。
実施例3ではビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を負極にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
正極には前記導電性コート層を形成しなかったこと以外は実施例1と同じようにリチウムイオン電池を作製した。
実施例4ではmの比率を実施例1より増やしケイ素含有率を上げたビニルシラン共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物をコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
冷却機付き10L三つ口フラスコに、
メタノール1200部、酢酸ビニル1400部、ビニルトリエトキシシラン200部、
を加え攪拌しながらドライアルゴン置換を行い60℃まで温度を上げた。
そこへ、3.7%の2,2’-アゾビスイソブチロニトリルのメタノール溶液1300部を滴下した。
ビニルトリエトキシシランの10%メタノール溶液200部を5時間かけて滴下しながら重合を行った。
メタノール蒸気を導入することで未反応の酢酸ビニル単量体を除去した。ここに水酸化ナトリウムの10%メタノール溶液150部を40℃で攪拌しながら滴下した。
得られた白色ゲルを粉砕しメタノールで洗浄して未反応のビニルトリエトキシシランを除去し、次いで乾燥させることでビニルシラン系共重合体を得た。
得られた共重合体は(Inductively Coupled Plasma Atomic Emission Spectroscopy:ICP-AES)による元素分析の結果ビニルシラン単位が2.5モル%含有されており、カルボン酸ビニル部の99%がケン化されていることが分かった。
分子量はGPC(Gel Permeation Chromatography)で測定し、
m/n=0.026、m=25、n=975であった。
得られたm/n=0.026のビニルシラン系共重合体をm/n=0.01のビニルシラン系共重合体に変えて電池又は電気二重層キャパシタ集電体コート用導電性組成物を作製したこと以外は実施例1と同じようにリチウムイオン電池を作製した。
実施例5ではケン化度を実施例1より減らしたビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物をコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
冷却機付き10L三つ口フラスコに、
メタノール1000部、酢酸ビニル1400部、ビニルトリエトキシシラン50部
を加え攪拌しながらドライアルゴン置換を行い60℃まで温度を上げた。
そこへ、3.5%の2,2’-アゾビスイソブチロニトリルのメタノール溶液1200部を滴下した。
ビニルトリエトキシシランの10%メタノール溶液100部を5時間かけて滴下しながら重合を行った。
メタノール蒸気を導入することで未反応の酢酸ビニル単量体を除去した。
ここに水酸化ナトリウムの10%メタノール溶液60部を40℃で攪拌しながら滴下した。
得られた白色ゲルを粉砕しメタノールで洗浄して未反応のビニルトリエトキシシランを除去し、次いで乾燥させることでビニルシラン系共重合体を得た。
得られた共重合体は(Inductively Coupled Plasma Atomic Emission Spectroscopy:ICP-AES)による元素分析の結果ビニルシラン単位が1モル%含有されており、カルボン酸ビニル部の75%がケン化されていることが分かった。
分子量はGPC(Gel Permeation Chromatography)で測定し、
m/n=0.01、m=10、n=990であった。
得られた75%ケン化のビニルシラン系共重合体を99%ケン化のビニルシラン系共重合体に変えて電池又は電気二重層キャパシタ集電体コート用導電性組成物を作製したこと以外は実施例1と同じようにリチウムイオン電池を作製した。
実施例6では正極に配合したアセチレンブラックを抜いてリチウムイオン二次電池を製造する方法を説明する。
なお、活物質層に含有されるアセチレンブラックと集電体との間の相互作用によって、電子伝導がアシストされるが、アセチレンブラックを入れる分だけ活物質を抜く必要があるため電池の容量が減る。本発明の電池又は電気二重層キャパシタ集電体コート用導電性組成物を使用すると、集電体との間の電子のやり取りは本発明の電池又は電気二重層キャパシタ集電体コート用導電性組成物が受け持つため、活物質中のアセチレンブラックを抜いて活物質の量を増やすころができる。比較例では、本発明の電池又は電気二重層キャパシタ集電体コート用導電性組成物が無い状態で活物質中のアセチレンブラックを抜くと著しく充放電特性が落ちる結果を示した。
冷却ジャケット付きの10Lプラネタリーミキサーに、PVdFの15%NMP溶液(株式会社クレハ製;クレハKFポリマー#1120)600部、コバルト酸リチウム(日本化学工業株式会社製;C-5H)1000部、NMP4700部を加え液温が30℃を超えないように冷却しながら均一になるまで攪拌した。これを、前記導電コート層を形成した集電体に幅180mm、厚さ200μmで塗工し、160℃温風炉で20秒乾燥させた。これを線圧500kgf/cmでロールプレスした。プレス後の正極活物質層の厚みは20μmであった。
得られた活物質中のアセチレンブラックを抜いた正極を用いたこと以外は、実施例1と同じようにリチウムイオン電池を作製した。
実施例7ではビニルシラン系共重合体中のナトリウムがリチウムで置換されたビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極と負極の両方にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
冷却機付き10L三つ口フラスコに、
メタノール1000部、酢酸ビニル1400部、ビニルトリエトキシシラン50部、
を加え攪拌しながらドライアルゴン置換を行い60℃まで温度を上げた。
そこへ、3.5%の2,2’-アゾビスイソブチロニトリルのメタノール溶液1200部を滴下した。
ビニルトリエトキシシランの10%メタノール溶液100部を5時間かけて滴下しながら重合を行った。
メタノール蒸気を導入することで未反応の酢酸ビニル単量体を除去した。
ここに水酸化リチウムの5%メタノール溶液250部を40℃で攪拌しながら滴下し、滴化終了後60℃で5時間攪拌した。
得られた白色ゲルを粉砕しメタノールで洗浄して未反応のビニルトリエトキシシランを除去し、次いで乾燥させることでLiタイプのビニルシラン系共重合体を得た。
得られた共重合体は(Inductively Coupled Plasma Atomic Emission Spectroscopy:ICP-AES)による元素分析の結果リチウムが5重量%含有されており、ビニルシラン単位が1モル%含有されており、カルボン酸ビニル部の98%がケン化されていることが分かった。
分子量はGPC(Gel Permeation Chromatography)で測定し、
m/n=0.01、m=10、n=990であった。
ビニルシラン系共重合体を得られたLiタイプのビニルシラン系共重合体に変えて電池又は電気二重層キャパシタ集電体コート用導電性組成物を作製したこと以外は実施例1と同じようにリチウムイオン電池を作製した。
[実施例8]
実施例8ではビニルシラン系モノマーとしてγ-アクリロキシプロピルトリメトキシシランを用いたビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極と負極の両方にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
冷却機付き10L三つ口フラスコに、
メタノール1000部、酢酸ビニル1400部、γ-アクリロキシプロピルトリメトキシシラン120部、
を加え攪拌しながらドライアルゴン置換を行い60℃まで温度を上げた。
そこへ、3.6%の2,2’-アゾビスイソブチロニトリルのメタノール溶液1200部を滴下した。
メタノール蒸気を導入することで未反応の酢酸ビニル単量体を除去した。
ここに水酸化ナトリウムの5%メタノール溶液200部を40℃で攪拌しながら滴下し、滴化終了後60℃で5時間攪拌した。
得られた白色ゲルを粉砕しメタノールで洗浄して未反応のγ-アクリロキシプロピルトリメトキシシランを除去し、次いで乾燥させることでγ-アクリロキシプロピルトリメトキシシランタイプのビニルシラン系共重合体を得た。
得られた共重合体は(Inductively Coupled Plasma Atomic Emission Spectroscopy:ICP-AES)による元素分析の結果γ-アクリロキシプロピルトリメトキシシラン単位が1モル%含有されており、カルボン酸ビニル部の90%がケン化されていることが分かった。
分子量はGPC(Gel Permeation Chromatography)で測定し、
m/n=0.01、m=10、n=990であった。
ビニルシラン系共重合体を得られたγ-アクリロキシプロピルトリメトキシシランタイプのビニルシラン系共重合体に変えて電池又は電気二重層キャパシタ集電体コート用導電性組成物を作製したこと以外は実施例1と同じようにリチウムイオン電池を作製した。
実施例9ではリモネンオキシドとビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極と負極の両方にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
なお、ポリカルボン酸と水酸基とが脱水縮合をした場合、エステル結合になるため、水素結合性を有する官能基が2つ減る(A)。
(ビニルシラン系共重合体の合成方法)
冷却機付き10L三つ口フラスコに、
メタノール1200部、酢酸ビニル1400部、ビニルトリエトキシシラン200部、
リモネンオキシド100部を加え攪拌しながらドライアルゴン置換を行い60℃まで温度を上げた。
そこへ、3.7%の2,2’-アゾビスイソブチロニトリルのメタノール溶液1300部を滴下した。
ビニルトリエトキシシランの10%メタノール溶液200部を5時間かけて滴下しながら重合を行った。
メタノール蒸気を導入することで未反応の酢酸ビニル単量体を除去した。ここに水酸化ナトリウムの10%メタノール溶液150部を40℃で攪拌しながら滴下した。
得られた白色ゲルを粉砕しメタノールで洗浄して未反応のビニルトリエトキシシランを除去し、次いで乾燥させることでビニルシラン系共重合体を得た。
得られた共重合体は(Inductively Coupled Plasma Atomic Emission Spectroscopy:ICP-AES)による元素分析の結果ビニルシラン単位が2.2モル%、リモネンオキシド単位が1.3モル%含有されており、カルボン酸ビニル部の99%がケン化されていることが分かった。
分子量はGPC(Gel Permeation Chromatography)で測定し、
m/n=0.022、m=24、n=1076であった。
得られたビニルシラン系共重合体をm/n=0.01のビニルシラン系共重合体に変えて電池又は電気二重層キャパシタ集電体コート用導電性組成物を作製したこと以外は実施例1と同じようにリチウムイオン電池を作製した。
実施例10では2-アクリルアミド-2-メチルプロパンスルホン酸ナトリウム(特定の官能基含有モノマー)とビニルシラン系モノマーと酢酸ビニルからなるビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極と負極の両方にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
(ビニルシラン系共重合体の合成方法)
冷却機付き10L三つ口フラスコに、酢酸ビニル1000部、ビニルトリメトキシシラン10部、メタノール2500部、2-アクリルアミド-2-メチルプロパンスルホン酸ナトリウム3部を加え、ドライアルゴン置換を行い60℃まで温度を上げた。そこへ、3.7%の2,2’-アゾビスイソブチロニトリルのメタノール溶液400部を滴下した。ビニルトリエトキシシランの10%メタノール溶液200部を5時間かけて滴下しながら重合を行った。メタノール蒸気を導入することで未反応の酢酸ビニル単量体を除去した。ここに水酸化ナトリウムの10%メタノール溶液150部を40℃で攪拌しながら滴下した。得られた白色ゲルを粉砕しメタノールで洗浄して未反応のビニルトリエトキシシランを除去し、次いで乾燥させることでビニルシラン系共重合体を得た。得られた共重合体は(Inductively Coupled Plasma Atomic Emission Spectroscopy:ICP-AES)による元素分析の結果ビニルシラン単位が1.5モル%、スルホン酸単位が1モル%含有されており、カルボン酸ビニル部の99%がケン化されていることが分かった。分子量はGPC(Gel Permeation Chromatography)で測定し、m/n=0.01、m=15、n=1485であった。
得られたビニルシラン系共重合体を上記スルホン酸単位を有するビニルシラン系共重合体に変えて電池又は電気二重層キャパシタ集電体コート用導電性組成物を作製したこと以外は実施例1と同じようにリチウムイオン電池を作製した。
実施例11ではビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物をコートした集電体を用いて電気二重層型キャパシタを製造する方法を説明する。
電池又は電気二重層キャパシタ集電体コート用導電性組成物は実施例1と同じ方法で作製した。
幅300mm、厚さ20μmの圧延アルミ箔に幅200mm、厚さ10μmで上記塗工液を塗布し、180℃温風炉で30秒乾燥させた。乾燥後の塗工膜厚は1μmであった。
冷却ジャケット付きの10Lプラネタリーミキサーに、PVdFの15%NMP溶液(株式会社クレハ製;クレハKFポリマー#1120)3000部、活性炭(クラレケミカル株式会社製;クラレコールRP-20)1500部、NMP2500部を加え液温が30℃を超えないように冷却しながら均一になるまで攪拌した。これを、前記導電コート層を形成した集電体に幅180mm、厚さ200μmで塗工し、160℃温風炉で20秒乾燥させた。これを線圧500kgf/cmでロールプレスした。プレス後の電極活物質層の厚みは20μmであった。
電極を短辺に10mm活物質層が無い領域が含まれるように40mm×50mmでカットし、金属がむき出しになっている部分にアルミのタブを抵抗溶接で接合した。セパレーター(セルガード株式会社製;#2400)を幅45mm、長さ120mmにカットし、3つに折り返してその間に2枚の電極が対向するように挟み込み、これを幅50mm長さ100mmのアルミラミネートセルを二つ折りにしたもので挟み、タブが当たる部分にシーラントを挟み込んだ上でシーラント部分とそれに直行する辺を熱ラミネートして袋状にした。これを100℃の真空オーブンに12時間入れて真空乾燥させ、次いでドライブローブボックス中でホウフッ化テトラエチルアンモニウム/PC 1M電解液(キシダ化学株式会社製;CPG-00005)を注入し、真空含侵した後、余った電解液を扱き出し、真空シーラーで接合密封して、電気二重層型キャパシタを製造した。
実施例12ではビニルシラン系共重合体中のナトリウムの一部がテトラエチルアンモニウムに置換されたビニルシラン系共重合体とポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物をコートした集電体を用いて電気二重層型キャパシタを製造する方法を説明する。
実施例1で作製したビニルシラン系共重合体100部をイオン交換水9900部に80℃×12時間加熱溶解し、その後室温まで冷却した。そこへ、テトラエチルアンモニウムクロリド5部を加え30分攪拌した。そこへ、イオン交換性樹脂(三菱化学株式会社製;AMP01)500部を加え、更に12時間攪拌した。イオン交換性樹脂を取り除いた後、減圧蒸留で水分を取り除くことでテトラエチルアミンタイプのビニルシラン系共重合体を得た。ビニルシラン系共重合体中のナトリウムの70%がテトラエチルアンモニウムに置換されていた。
ビニルシラン系共重合体としてテトラエチルアンモニウムタイプのビニルシラン系共重合体を用いたこと以外は実施例1と同じ方法で電池又は電気二重層キャパシタ集電体コート用導電性組成物を製造し塗工液とした。
上記塗工液を用いたこと以外は、実施例8と同じ方法で製造した。
上記同コート層を形成した集電体を用いたこと以外は、実施例8と同じ方法で製造した。
上記電極を用いたこと以外は、実施例9と同じ方法で電気二重層型キャパシタを製造した。
電池又は電気二重層キャパシタ集電体コート用導電性組成物をコートしていない集電体を用いたこと以外は実施例1と同じ方法で、リチウムイオン二次電池を製造した。
比較例2ではビニルシラン系共重合体の代わりに部分ケン化型のポリビニルアルコールと導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極と負極の両方にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
10Lのビーカーに水1100部と部分ケン化型のポリビニルアルコール(株式会社クラレ製;クラレポバールPVA235(ケン化度87~89%))を20部加え80℃で6時間均一になるまで攪拌した。そこへアセチレンブラック(電気化学工業社製;デンカブラックHS-100)を25部加え概ね均一になるまで攪拌し分散液を得た。上記分散液を冷却ジャケットつきのビーズミルを用いて分散した。分散には0.5mmのジルコニアボールを充填率80%で入れ、周速7mで液温が30℃以上にならないように冷却しながら攪拌し、電池又は電気二重層キャパシタ集電体コート用導電性組成物である塗工液を得た。
上記電池又は電気二重層キャパシタ集電体コート用導電性組成物を集電体にコートしたこと以外は、実施例1と同じ方法でリチウムイオン二次電池を作製した。
比較例3ではビニルシラン系共重合体の代わりに部分ケン化型のポリビニルアルコールとポリカルボン酸と導電性助剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極と負極の両方にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
10Lのビーカーに水1000部と部分ケン化型のポリビニルアルコール(株式会社クラレ製;クラレポバールPVA235)を20部加え80℃で6時間均一になるまで攪拌した。そこへ、ピロメリット酸を10部加え60℃で4時間均一になるまで攪拌した。そこへアセチレンブラック(電気化学工業社製;デンカブラックHS-100)を25部加え概ね均一になるまで攪拌し分散液を得た。上記分散液を冷却ジャケットつきのビーズミルを用いて分散した。分散には0.5mmのジルコニアボールを充填率80%で入れ、周速7mで液温が30℃以上にならないように冷却しながら攪拌し、電池又は電気二重層キャパシタ集電体コート用導電性組成物である塗工液を得た。
上記電池又は電気二重層キャパシタ集電体コート用導電性組成物を集電体にコートしたこと以外は、実施例1と同じ方法でリチウムイオン二次電池を作製した。
比較例4ではビニルシラン系共重合体の代わりに部分ケン化型のポリビニルアルコールとポリカルボン酸と導電性助剤とシランカップリング剤から成る電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極と負極の両方にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
10Lのビーカーに水1000部と部分ケン化型のポリビニルアルコール(株式会社クラレ製;クラレポバールPVA235)を20部とシランカップリング剤(信越化学工業株式会社製;KBM-403)1部を加え80℃で6時間均一になるまで攪拌した。そこへ、ピロメリット酸を10部加え60℃で4時間均一になるまで攪拌した。そこへアセチレンブラック(電気化学工業社製;デンカブラックHS-100)を25部加え概ね均一になるまで攪拌し分散液を得た。上記分散液を冷却ジャケットつきのビーズミルを用いて分散した。分散には0.5mmのジルコニアボールを充填率80%で入れ、周速7mで液温が30℃以上にならないように冷却しながら攪拌し電池又は電気二重層キャパシタ集電体コート用導電性組成物を作製した。
上記電池又は電気二重層キャパシタ集電体コート用導電性組成物を集電体にコートしたこと以外は、実施例1と同じ方法でリチウムイオン二次電池を作製した。
サイクル寿命は80cycとなった。これを更に500cyc充放電すると、電極表面から集電体コート用電池又は電気二重層キャパシタ集電体コート用導電性組成物の層がアルミ箔から脱落した。これは、集電体コート用電池又は電気二重層キャパシタ集電体コート用導電性組成物とアルミ箔間の密着力がまったく無い状態になった為である。
剥離試験後に、アルミ集電体側の剥離面及び導電性コート側の剥離面について、電池又は電気二重層キャパシタ集電体コート用導電性組成物PSを用いてケイ素の量を測定したところ、アルミ集電体側にはケイ素が検出されたが導電性コート側にはほとんど検出されなかった。このことから、式(B)の切断反応が起きることで剥離したことが示された。
比較例5では実施例1のポリカルボン酸を抜いた電池又は電気二重層キャパシタ集電体コート用導電性組成物を正極と負極の両方にコートした集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
10Lのビーカーに水1100部と水酸化ナトリウム5部を加え均一になるまで攪拌した。そこへ、実施例1の方法で作製したビニルシラン系共重合体を20部加え80℃で6時間均一になるまで攪拌した。そこへアセチレンブラック(電気化学工業社製;デンカブラックHS-100)を25部加え概ね均一になるまで攪拌し分散液を得た。
上記電池又は電気二重層キャパシタ集電体コート用導電性組成物を集電体にコートしたこと以外は、実施例1と同じ方法でリチウムイオン二次電池を作製した。
比較例6ではシランカップリング剤で表面処理した集電体を用いてリチウムイオン二次電池を製造する方法を説明する。
幅300mm、厚さ20μmの圧延アルミ箔及び幅300mm、厚さ15μmの圧延銅箔に幅200mm、厚さ10μmでシランカップリング剤(信越化学工業株式会社製;KBM-403)のメタノール1%溶液を塗布し、180℃温風炉で30秒乾燥させた。乾燥後の塗工膜厚はおよそ0.2μmであった。
上記シランカップリング剤をコートした集電体を用いたこと以外は、実施例1と同じ方法でリチウムイオン二次電池を作製した。
比較例7では電池又は電気二重層キャパシタ集電体コート用導電性組成物をコートしていない集電体を用い、更に正極に配合したアセチレンブラックを抜いてリチウムイオン二次電池を製造する方法を説明する。
電池又は電気二重層キャパシタ集電体コート用導電性組成物をコートしてない集電体を用いたこと以外は、実施例6と同じ方法でリチウムイオン二次電池を作製した。
比較例8では電池又は電気二重層キャパシタ集電体コート用導電性組成物をコートしていない集電体を用いて電気二重層型キャパシタを製造する方法を説明する。
電池又は電気二重層キャパシタ集電体コート用導電性組成物をコートしていない集電体を用いたこと以外は、実施例8と同じ方法で電気二重層型キャパシタを作製した。
比較例9ではエッチング箔を用いて電気二重層型キャパシタを製造する方法を説明する。
集電体として電気二重層型キャパシタ用のアルミエッチング箔(幅300mm、厚さ20μm)を用いたこと以外は、実施例8と同じ方法で電気二重層型キャパシタを作製した。
上記の実施例及び比較例で製造したについて、下記の特性を測定した。
初期容量を出すために0.01mAの定電流で電圧が4.3Vになるまで充電し、次いで4.3Vの定電圧で2時間充電した。その後、0.01mAの定電流で電圧が3Vになるまで放電した。これを3回繰り返し、3回目の放電容量を初期容量とした。
初期内部抵抗として、初期容量を測定した後のセルを4.3Vの電位にし、その電位をセンターに±10mVの電圧変化で1kHzのインピーダンスを測定した。
初期容量から放電レートを求めて、放電レート別の放電容量を測定した。充電は毎回10時間かけて定電流で4.3Vまで電圧を上げた後、4.3V定電圧で2時間充電した。その後、10時間かけて定電流で3Vになるまで放電し、このときの放電容量を0.1Cの放電容量とした。次に同様に充電した後0.1Cで求めた放電容量から1時間で放電が完了する電流値で放電しそのときの放電容量を求め1Cのときの放電容量とした。同様に、3C、10C、30Cのときの放電容量を求め、0.1Cの時の放電容量を100%としたときの容量維持率を算出した。
1Cで4.3Vまで充電し、4.3Vの定電圧で2時間充電したあと1Cで放電する充放電試験を実施した。このとき、放電容量が最初の1回目の放電に対して何%になるかを計算し容量が80%をきったときの充放電回数を寿命とした。
60℃で0.1Cで4.3Vまで充電し、4.3Vの定電圧でのインピーダンス変化をおよそ1日おきに測定した。抵抗値が2倍になった時間を寿命とした。
電池を上記サイクル寿命条件で1000サイクル耐久充放電試験を行い、耐久試験後の正極及び負極から活物質層の脱離がないかを電池を分解して確認した。
評価基準は以下の通りであった。
◎:全く脱離は見られない
○:一部脱離は見られるが、集電体は剥き出しになっていない
△:脱離が進行し、集電体の一部が剥き出しになっている
×:活物質層が完全に脱離している
上記の実施例及び比較例で製造した電気二重層型キャパシタについて、下記の特性を測定した。
初期容量を出すために0.01mAの定電流で電圧が2Vになるまで充電した。その後、0.01mAの定電流で電圧が0Vになるまで放電した。これを3回繰り返し、3回目の放電容量を初期容量とした。
初期内部抵抗として、初期容量を測定した後のセルを2Vの電位にし、その電位をセンターに±10mVの電圧変化で1kHzのインピーダンスを測定した。
初期容量から放電レートを求めて、放電レート別の放電容量を測定した。充電は毎回1時間かけて定電流で2Vまで電圧を上げ充電した。その後、1時間かけて定電流で0Vになるまで放電し、このときの放電容量を1Cの放電容量とした。次に同様に充電した後1Cで求めた放電容量から0.1時間で放電が完了する電流値で放電しそのときの放電容量を求め10Cのときの放電容量とした。同様に、30C、100C、300Cのときの放電容量を求め、1Cの時の放電容量を100%としたときの容量維持率を算出した。
1Cで2Vまで充電したあと1Cで0Vまで放電する充放電試験を実施した。このとき、放電容量が最初の1回目の放電に対して何%になるかを計算し容量が80%を切ったときの充放電回数を寿命とした。
60℃、1Cで2.8Vまで充電し、2.8Vの定電圧でのインピーダンス変化をおよそ1日おきに測定した。抵抗値が2倍になった時間を寿命とした。
電池を上記フロート寿命条件で3000時間耐久フロート試験を行い、耐久試験後の電極集電体からの活物質層の脱離がないかを電気二重層型キャパシタを分解して確認した。
評価基準は以下の通りであった。
◎:全く脱離は見られない
○:一部脱離は見られるが、集電体は剥き出しになっていない
△:脱離が進行し、集電体の一部が剥き出しになっている
×:活物質層が完全に脱離している
VTESはビニルトリエトキシシランを、
γAPTMESはγ-アクリロキシプロピルトリメトキシシランを表す。
1:活物質層
2:電池又は電気二重層キャパシタ集電体コート用導電性組成物のコート層
3.電池集電体
Claims (12)
- ビニルシラン系共重合体と、ポリカルボン酸(但し、前記ビニルシラン系共重合体は除く)と、導電性助剤とを含む電池又は電気二重層キャパシタ集電体コート用導電性組成物であって、
前記ビニルシラン系共重合体が、下記式(1):
Xは単結合または結合鎖(但し、酸素を除く)を示し、
R2~R4は、独立して、
-OR5(R5は、H、C1~C6アルキル基及び電池又は電気二重層キャパシタの電解質を構成し得るカチオンに由来する基からなる群から選択される基である)、
C1~C6アルキル基、及び
ハロゲン基からなる群から選択される基である)で表される単位を表し、
Vは、少なくとも活性水素基を有するビニル系モノマーに由来する単位(但し、前記Uは除く)であり、
R21~R23は、独立して、H又はC1~C6アルキル基
mは1~10000の数、nは20~100000の数であり、
mとnの比率(m/n)が、0.0001~1である〕で表わされることを特徴とする電池又は電気二重層キャパシタ集電体コート用導電性組成物。 - Xが、単結合又は炭素数6以下のアルキレンもしくはアルケニレンもしくはアルキニレンもしくはフェニレンもしくはナフチレンとこれらの水素がフッ素に置換された構造、-CH2OCH2-、-(OCH2)m、-(CH2O)mCH2-、-CO-、-COCO-、-CO(CH2)mCO-、-CO(C6H4)CO-、-S-、-CS-、-SO-、-SO2-、-NR-、-CONR-、-NRCO-、CSNR-、-NRCS-、-NRNR-及び-HPO4-(Rは各々独立して水素原子、炭素数6以下のアルキレン基であり、mは自然数)からなる群から選択される基である請求項1記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物。
- 前記活性水素基が、ヒドロキシ基(-OH)、カルボキシル基(-COOH)、アミノ基(-NH2、-NHR6)、ヒドラジド基(R7R8NN(R9)C(=O)R10)、ヒドロキシルアミノ基(-NHOH)、スルホ基(-SO3H)及びチオール基(-SH)(前記式中、R6~R10はそれぞれ独立して、水素原子、C1~C8のアルキル基、ヒドロキシル基、アシル基、カルボキシル基、アミノ基、ビニル基、アリル基、アリール基、ハロゲン及び金属からなる群から選ばれる基である請求項1記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物。
- 前記ビニル系モノマーが、カルボン酸ビニルモノマーである請求項1記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物。
- 電池又は電気二重層キャパシタの電解質を構成し得るカチオン由来の基が、アルカリ金属、アルカリ土類金属、リチウム及びテトラアルキルアンモニウムからなる群から選択される少なくとも1種の化合物由来の基である、請求項1記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物。
- カルボン酸ビニル共重合体と、ポリカルボン酸(但し、前記カルボン酸ビニル共重合体は除く)と、導電性助剤とを含む電池又は電気二重層キャパシタ集電体コート用導電性組成物であって、
前記カルボン酸ビニル共重合体が、カルボン酸ビニルモノマーとビニルシラン系モノマーとの共重合体であり、
前記ビニルシラン系モノマーが、ビニルアルキルジアルコキシシラン、γ-(メタ)アクリロキシプロピルトリアルコキシシラン、γ-(メタ)アクリロキシプロピルアルキルジアルコキシシラン及びビニルトリス(β-メトキシエトキシ)シランからなる群から選択される1種以上の化合物であることを特徴とする電池又は電気二重層キャパシタ集電体コート用導電性組成物。 - 前記ポリカルボン酸の分子量が1000以下である請求項1又は6記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物。
- 前記ポリカルボン酸が、
クエン酸、ブタンテトラカルボン酸、3,3’,4,4’-ビフェニルテトラカルボン酸、ヘキサヒドロフタル酸、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸、メチルビシクロ[2.2.1]ヘプタン-2,3-ジカルボン酸、ビシクロ[2.2.1]ヘプタン-2,3-ジカルボン酸、アスパラギン酸、ピロメリット酸、メリト酸、含リンエステル基テトラカルボン酸、フェニルエチニルフタル酸及びオキシジフタル酸からなる群から選択される1種以上の化合物並びに/若しくはこれらの化合物由来の酸無水物、及び/又は、
エチレングリコールビスアンヒドロトリメリテート、1,3,3a,4,5,9b-ヘキサヒドロ-5(テトラヒドロ-2,5-ジオキソ-3-フラニル)ナフト[1,2-c]フラン-1,3-ジオン、グリセリンビスアンヒドロトリメリテートモノアセテート、エチレングリコールビスアンヒドロトリメリテートからなる群から選択される1種以上の化合物である請求項1又は5記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物。 - さらに、チタン系カップリング剤及びシランカップリング剤からなる群から選択される少なくとも1種のカップリング剤を含む、請求項1又は6記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物。
- 前記電池又は電気二重層キャパシタ集電体コート用導電性組成物の体積収縮率Sv及び弾性率GPaに対して、式(3)
K≡Sv×GPa (3)
で定義されるKの値が3~90である請求項1又は6記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物。 - 請求項1又は6記載の電池又は電気二重層キャパシタ集電体コート用導電性組成物でコートした電池集電体。
- 請求項11記載の電池又は電気二重層キャパシタ集電体を含む電池又は電気二重層キャパシタ。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013229187A (ja) * | 2012-04-25 | 2013-11-07 | Showa Denko Kk | カーボンコート箔塗工液用バインダー、カーボンコート箔塗工液、カーボンコート箔、リチウムイオン二次電池用電極、および、リチウムイオン二次電池 |
JP2015079708A (ja) * | 2013-10-18 | 2015-04-23 | 協立化学産業株式会社 | 電池又は電気二重層キャパシタ集電体用コート剤組成物、電池又は電気二重層キャパシタ集電体、電池及び電気二重層キャパシタ |
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JP2017115019A (ja) * | 2015-12-24 | 2017-06-29 | 関西ペイント株式会社 | 顔料ペースト及び塗工材 |
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KR20190139981A (ko) * | 2017-06-13 | 2019-12-18 | 아테크 가부시키가이샤 | 수성도료 조성물, 공기 정화기구 및 공기 정화방법 |
Families Citing this family (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103081192B (zh) * | 2010-08-31 | 2016-01-06 | 协立化学产业株式会社 | 电池或双电层电容器集电体涂布用导电性组合物、电池或双电层电容器集电体、电池及双电层电容器 |
EP2679637B1 (en) | 2011-02-23 | 2017-05-10 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Aqueous liquid composition, aqueous coating, functional coating film, and composite material |
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US20160104918A1 (en) * | 2013-05-24 | 2016-04-14 | Joyce Wang | Gel polymer electrolyte and lithium ion batteries employing the gel polymer electrolyte |
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US10497939B2 (en) | 2013-10-29 | 2019-12-03 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Cation-conductive conformal ultrathin polymer electrolytes |
KR102201317B1 (ko) | 2014-02-24 | 2021-01-11 | 삼성전자주식회사 | 이차전지용 음극 및 이를 포함하는 이차전지 |
US10269504B2 (en) * | 2014-07-10 | 2019-04-23 | The United States Of America As Represented By The Secretary Of The Army | Supercapacitor having holes formed in carbonaceous electrodes for increasing the frequency of operation |
JP5729797B1 (ja) * | 2014-08-25 | 2015-06-03 | スリーエステクノ株式会社 | 導電性塗料および導電性塗料を用いた面状発熱体 |
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US20170214037A1 (en) * | 2014-09-30 | 2017-07-27 | Gs Yuasa International Ltd. | Negative electrode for nonaqueous electrolyte energy storage device, nonaqueous electrolyte energy storage device, and energy storage apparatus |
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CN106374080A (zh) * | 2015-07-24 | 2017-02-01 | 东莞力朗电池科技有限公司 | 一种圆柱锂离子电池正极极片材料及制备方法 |
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US10991936B2 (en) | 2015-12-23 | 2021-04-27 | Robert Bosch Gmbh | Anode composition, method for preparing anode and lithium ion battery |
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KR101984723B1 (ko) * | 2016-09-07 | 2019-05-31 | 주식회사 엘지화학 | 리튬 전극용 다공성 집전체 및 이를 포함하는 리튬 전극 |
US11387047B2 (en) * | 2016-10-18 | 2022-07-12 | KYOCERA AVX Components Corporation | Solid electrolytic capacitor with improved performance at high temperatures and voltages |
CN110268559A (zh) * | 2017-02-08 | 2019-09-20 | 凸版印刷株式会社 | 碱性二次电池用正极及碱性二次电池 |
JP6747577B2 (ja) * | 2017-03-14 | 2020-08-26 | 株式会社村田製作所 | リチウムイオン二次電池 |
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US20190379010A1 (en) * | 2018-06-08 | 2019-12-12 | Cyberx Engineering Inc. | Flexible batteries |
US20200115564A1 (en) | 2018-10-16 | 2020-04-16 | Dupont Electronics, Inc. | Stretchable conductive fluoroelastomer paste composition |
TWI718931B (zh) | 2020-04-14 | 2021-02-11 | 國立勤益科技大學 | 具二氧化矽微球之超級電容器電極及其製備方法 |
CN111916758B (zh) * | 2020-07-28 | 2022-05-31 | 福建巨电新能源股份有限公司 | 一种改性三维编织网状集流体及其改性方法和锂离子电池 |
WO2022104213A1 (en) * | 2020-11-16 | 2022-05-19 | Novelis Inc. | Covalently bonded coatings for foils used as current collectors in energy storage devices |
CN113793936B (zh) * | 2021-08-24 | 2023-04-11 | 广州市乐基智能科技有限公司 | 一种用于固态锂电池的复合粘结剂及其制备方法和应用 |
JP2023075573A (ja) * | 2021-11-19 | 2023-05-31 | 日本電気硝子株式会社 | 蓄電デバイス用部材の製造方法 |
US20230317956A1 (en) * | 2022-03-31 | 2023-10-05 | Samsung Sdi Co., Ltd. | Electrode for non-aqueous electrolyte rechargeable battery and non-aqueous electrolyte rechargeable battery |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63121265A (ja) * | 1986-11-08 | 1988-05-25 | Asahi Chem Ind Co Ltd | 二次電池 |
JPH07201362A (ja) * | 1993-12-29 | 1995-08-04 | Tdk Corp | リチウム二次電池 |
JPH09237625A (ja) * | 1996-02-27 | 1997-09-09 | Dainippon Printing Co Ltd | 非水電解液二次電池用電極板及びその製造方法 |
JP2008153053A (ja) * | 2006-12-18 | 2008-07-03 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池用正極板の製造方法および非水電解質二次電池 |
JP2010146726A (ja) * | 2007-11-30 | 2010-07-01 | Kyoritsu Kagaku Sangyo Kk | 導電性組成物 |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3729438A (en) * | 1970-03-30 | 1973-04-24 | Union Carbide Corp | Latex polymers of vinylacetate and a silane |
JPS58164604A (ja) | 1982-03-25 | 1983-09-29 | Kuraray Co Ltd | ケイ素を含有する変性ポリビニルアルコ−ルの製造方法 |
JPS6417485A (en) | 1987-07-10 | 1989-01-20 | Mitsubishi Electric Corp | Image sensing element |
JP3530544B2 (ja) * | 1992-09-14 | 2004-05-24 | キヤノン株式会社 | 二次電池 |
CA2110097C (en) | 1992-11-30 | 2002-07-09 | Soichiro Kawakami | Secondary battery |
EP0662728B1 (en) | 1993-12-29 | 1998-04-29 | TDK Corporation | Lithium secondary cell |
JPH0997602A (ja) * | 1995-09-29 | 1997-04-08 | Mitsubishi Chem Corp | 非水系二次電池 |
JPH0997625A (ja) * | 1995-09-29 | 1997-04-08 | Seiko Instr Inc | 非水電解質二次電池およびその製造方法 |
JPH11144735A (ja) * | 1997-11-05 | 1999-05-28 | Fujitsu Ltd | 電 池 |
JPH11238503A (ja) * | 1998-02-20 | 1999-08-31 | Yuasa Corp | 非水電解質二次電池 |
JPH11238502A (ja) * | 1998-02-24 | 1999-08-31 | Shin Kobe Electric Mach Co Ltd | 蓄電池 |
JP3973003B2 (ja) * | 1998-04-13 | 2007-09-05 | Tdk株式会社 | シート型電気化学素子 |
KR100276966B1 (ko) * | 1998-07-31 | 2001-02-01 | 이병길 | 2차전지용 금속 알루미늄과 구리 집전체의 전처리 방법 |
TW200410439A (en) | 2002-11-22 | 2004-06-16 | Kureha Chemical Ind Co Ltd | Binder composition for electrode of nonaqueous electrolyte battery, and use thereof |
JP3789427B2 (ja) | 2002-11-29 | 2006-06-21 | 本田技研工業株式会社 | 電気二重層コンデンサ用電極体 |
US6917094B2 (en) | 2002-11-29 | 2005-07-12 | Honda Motor Co., Ltd | Electrode for electric double layer capacitor |
KR100490543B1 (ko) * | 2002-12-14 | 2005-05-17 | 삼성에스디아이 주식회사 | 음극 및 리튬 전지의 제조방법 |
DE602004025758D1 (de) * | 2003-01-23 | 2010-04-15 | Kuraray Co | Polyvinylacetal und dessen Verwendung |
KR101179378B1 (ko) | 2005-02-10 | 2012-09-03 | 쇼와 덴코 가부시키가이샤 | 이차전지용 집전기, 이차전지 양극, 이차전지 음극, 이차전지 및 그들의 제조 방법 |
JP4593488B2 (ja) * | 2005-02-10 | 2010-12-08 | 昭和電工株式会社 | 二次電池用集電体、二次電池用正極、二次電池用負極、二次電池及びそれらの製造方法 |
US9144824B2 (en) * | 2006-11-10 | 2015-09-29 | The Regents Of The University Of California | Atmospheric pressure plasma-induced graft polymerization |
KR101252941B1 (ko) * | 2008-06-02 | 2013-04-12 | 다이니치 세이카 고교 가부시키가이샤 | 도공액, 전극판 제조용 도공액, 언더코트제 및 그 사용 |
JP5359074B2 (ja) * | 2008-07-11 | 2013-12-04 | 東洋インキScホールディングス株式会社 | 水系炭素材料組成物及びそれを用いた電池用組成物 |
JP4646160B2 (ja) | 2009-03-30 | 2011-03-09 | ソニー株式会社 | 伝送装置および方法 |
US8501348B2 (en) * | 2009-12-07 | 2013-08-06 | Nanotek Instruments, Inc. | Submicron-scale and lower-micron graphitic fibrils as an anode active material for a lithium ion battery |
CN103081192B (zh) * | 2010-08-31 | 2016-01-06 | 协立化学产业株式会社 | 电池或双电层电容器集电体涂布用导电性组合物、电池或双电层电容器集电体、电池及双电层电容器 |
-
2011
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63121265A (ja) * | 1986-11-08 | 1988-05-25 | Asahi Chem Ind Co Ltd | 二次電池 |
JPH07201362A (ja) * | 1993-12-29 | 1995-08-04 | Tdk Corp | リチウム二次電池 |
JPH09237625A (ja) * | 1996-02-27 | 1997-09-09 | Dainippon Printing Co Ltd | 非水電解液二次電池用電極板及びその製造方法 |
JP2008153053A (ja) * | 2006-12-18 | 2008-07-03 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池用正極板の製造方法および非水電解質二次電池 |
JP2010146726A (ja) * | 2007-11-30 | 2010-07-01 | Kyoritsu Kagaku Sangyo Kk | 導電性組成物 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013229187A (ja) * | 2012-04-25 | 2013-11-07 | Showa Denko Kk | カーボンコート箔塗工液用バインダー、カーボンコート箔塗工液、カーボンコート箔、リチウムイオン二次電池用電極、および、リチウムイオン二次電池 |
JP2015079669A (ja) * | 2013-10-17 | 2015-04-23 | 協立化学産業株式会社 | 集電体用コート剤組成物 |
JP2015079708A (ja) * | 2013-10-18 | 2015-04-23 | 協立化学産業株式会社 | 電池又は電気二重層キャパシタ集電体用コート剤組成物、電池又は電気二重層キャパシタ集電体、電池及び電気二重層キャパシタ |
JP2017115019A (ja) * | 2015-12-24 | 2017-06-29 | 関西ペイント株式会社 | 顔料ペースト及び塗工材 |
KR20190139981A (ko) * | 2017-06-13 | 2019-12-18 | 아테크 가부시키가이샤 | 수성도료 조성물, 공기 정화기구 및 공기 정화방법 |
KR102306766B1 (ko) | 2017-06-13 | 2021-09-30 | 아테크 가부시키가이샤 | 수성도료 조성물, 공기 정화기구 및 공기 정화방법 |
JP2019102185A (ja) * | 2017-11-29 | 2019-06-24 | 株式会社Gsユアサ | 極板、電極体及び蓄電素子 |
JP7073689B2 (ja) | 2017-11-29 | 2022-05-24 | 株式会社Gsユアサ | 極板、電極体及び蓄電素子 |
Also Published As
Publication number | Publication date |
---|---|
EP2613386A4 (en) | 2017-01-04 |
KR20130107291A (ko) | 2013-10-01 |
KR101731671B1 (ko) | 2017-05-11 |
EP2613387B1 (en) | 2017-10-11 |
KR101594661B1 (ko) | 2016-02-24 |
EP2613386B1 (en) | 2018-01-24 |
CN103155068B (zh) | 2015-11-25 |
CN103081192A (zh) | 2013-05-01 |
US20130164614A1 (en) | 2013-06-27 |
EP2613386A1 (en) | 2013-07-10 |
US20130157129A1 (en) | 2013-06-20 |
US9315680B2 (en) | 2016-04-19 |
US9181439B2 (en) | 2015-11-10 |
JP5834008B2 (ja) | 2015-12-16 |
CN103155068A (zh) | 2013-06-12 |
JPWO2012029858A1 (ja) | 2013-10-31 |
WO2012029858A1 (ja) | 2012-03-08 |
EP2613387A1 (en) | 2013-07-10 |
JPWO2012029618A1 (ja) | 2013-10-28 |
TWI473865B (zh) | 2015-02-21 |
KR20130055004A (ko) | 2013-05-27 |
TW201224084A (en) | 2012-06-16 |
TW201224085A (en) | 2012-06-16 |
CN103081192B (zh) | 2016-01-06 |
TWI550036B (zh) | 2016-09-21 |
JP5507696B2 (ja) | 2014-05-28 |
EP2613387A4 (en) | 2017-01-11 |
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