JP2017118136A - Polarizable electrode for double layer capacitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode for double layer capacitor, capable of achieving high energy density even at a high voltage and little time degradation of a capacitance or a resistor, that is, excellent long-term reliability.SOLUTION: The electrode for double layer capacitor includes: a polarizable electrode material containing porous carbon particles, conductive auxiliary material, tungsten oxide powder and binder; conductive adhesive containing conductive material and poly-N-vinyl acetamide (PNVA) system binder; a sheet-like collector.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a polarizable electrode for an electric double layer capacitor with improved voltage resistance for the purpose of improving energy density and long-term reliability.

  An electric double layer capacitor is a power storage element that utilizes the capacitance of an electric double layer formed by adsorption / desorption of electrolyte ions at the interface between a pair of positive and negative polarizable electrodes and an electrolyte solution.

  Electric double layer capacitors can be used for small capacity types such as for memory backup, medium power types and large capacity types such as auxiliary power sources for electric vehicles, auxiliary power sources for solar cells, auxiliary power sources for wind power generation and instantaneous power failure compensation devices. Has been widely studied. In particular, in recent years, in automobiles and construction machinery, etc., studies have been made on further reducing fuel consumption by utilizing regenerative energy, and electric double layer capacitors have been studied as devices capable of rapid charge / discharge.

  Characteristics to be evaluated of the electric double layer capacitor include capacitance (C), operating voltage (V), energy density (E), internal resistance, service life, and the like. Improvement of both characteristics is important, but recently, especially the improvement of energy density, which is a disadvantage of electric double layer capacitors, and further extension of the service life (improvement of long-term reliability) are the small capacity mentioned above. It is also required for applications from types to large capacity types.

Patent Document 1 provides a polarizable electrode material containing tungsten oxide powder. As a result, a polarizable electrode material for a high withstand voltage type electric double layer capacitor having a high energy density and little deterioration of capacitance and resistance with time, that is, excellent long-term reliability, and electricity using the same A double layer capacitor is realized.
The polarizable electrode material for the electric double layer capacitor is joined to the current collector with a conductive adhesive based on water glass.

In Patent Document 1, an electric double layer capacitor having a high energy density and little deterioration with time of capacitance and resistance, that is, excellent long-term reliability, is obtained by tungsten oxide contained in the electrode material. . The reason why high effect is recognized by including tungsten oxide is not clear, but is considered as follows. Inside the electric double layer capacitor, there are residual moisture in the electrolyte solution and moisture mixed during assembly. Further, physically adsorbed water and chemically bonded adsorbed water exist on the surface and inside of the activated carbon, conductive additive, binder and separator used for the electrode layer. These waters are desorbed as water during repeated charging and discharging, and are electrolyzed by applying a voltage to generate gas and generate OH ^{− and the} like. In addition, these waters may cause decomposition of the electrolyte (solution). Especially when it is an organic electrolyte and contains fluorine as the electrolyte anion, the reaction of the residual water in the electric double layer capacitor with the electrolyte Since hydrofluoric acid (HF) is generated, corrosion of the current collector is severe. In addition, these decomposition products coat the surface of the activated carbon or block the pores of the activated carbon, thereby reducing the surface area of the activated carbon and causing a decrease in capacitance. These decomposition products also cause an increase in resistance by closing the opening of the separator. The increase in internal resistance decreases the energy that can be discharged over time. In Patent Document 1, it is considered that tungsten oxide contained in the electrode material adsorbs and removes moisture and decomposition products, thereby preventing the pores of the porous carbon particles and the opening of the separator from being blocked.

Patent Document 2 discloses a conductive material and a poly-N-vinylacetamide-based binder as a conductive adhesive for joining a polarizable electrode layer, which is a component of an electrode for an electric double layer capacitor, and a sheet-like current collector. An electrically conductive adhesive is provided. Thereby, the heat-resistant adhesive which can make the drying process for a water | moisture content removal 250 degreeC or more is provided to the conductive adhesive.
In Patent Document 2, there is no description about using this adhesive as a conductive adhesive for joining an electrode material containing tungsten oxide and a sheet-like current collector.

JP2011-233845A JP 2009-277783 A

  According to Patent Documents 1 and 2 described above, an electric double layer capacitor having excellent long-term reliability has been developed. However, an electric double layer capacitor having further improved long-term reliability is demanded. In particular, under conditions of high voltage exceeding 3.0V, which is a severe condition, deterioration with time of the electric double layer capacitor (degradation of capacitance with time, increase of internal resistance with time) is likely to accelerate. There is a strong demand for an electric double layer capacitor that further enhances long-term reliability below.

  The present invention provides an electrode for an electric double layer capacitor that has a high energy density and little deterioration with time of capacitance and resistance even at a high voltage of 3.0 V or more, that is, excellent long-term reliability. With the goal.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have contributed to an increase in the internal resistance of the electric double layer capacitor over time when used in an electric double layer capacitor at a high voltage of 3.0 V or higher. It was found that the bonding state between the electrode material and the current collector was poor. The failure of this bonded state, HF generated by decomposition of water and electrolytes in the electric double layer capacitor, OH ^- or the like by the corrosion of the conventional operating voltage (approximately 2.5-2.7V) the effect was less current collector / This is probably due to the significant peeling of the electrode. As a result, the interface resistance between the current collector and the electrode material increases.

The inventors of the present invention provide an electrode for an electric double layer capacitor comprising an electrode material containing tungsten oxide, a conductive adhesive containing a poly-N vinylacetamide (PNVA) binder, and a sheet-like current collector. , even at high voltage exceeding 3.0 V, the electrode material and the sheet-like current collector can be firmly adhered, whereby, HF generated by decomposition of moisture and electrolytes, OH ^- or the like current collector and the electrode It has been found that corrosion of the current collector / exfoliation of the electrode material can be suppressed because it does not intrude into the material. As a result, the electrode for the electric double layer capacitor has high energy density and little deterioration with time of capacitance and internal resistance even at a high voltage exceeding 3.0 V, that is, has long-term reliability. Also in Patent Document 1, long-term reliability at a high voltage is obtained. However, in the present invention, long-term reliability is further improved, and in particular, suppression of increase in internal resistance is remarkably improved.

  Thus, according to the present invention, the following (1) to (7) are provided.

  (1) Polarizable electrode material including porous carbon particles, conductive additive, tungsten oxide powder, and binder, conductive adhesive including conductive material and poly-N-vinylacetamide (PNVA) binder, and sheet-like An electrode for an electric double layer capacitor, comprising: a current collector.

  (2) The electrode for an electric double layer capacitor according to (1), wherein the polarizable electrode material, the conductive adhesive, and the sheet-like current collector are laminated in this order.

  (3) In (1) or (2), the poly-N-vinylacetamide-based binder is selected from the group consisting of N-vinylacetamide homopolymers and N-vinylacetamide copolymers. The electrode for electrical double layer capacitors as described.

  (4) The electric double layer capacitor electrode according to (3), wherein the N-vinylacetamide copolymer is a copolymer of poly-N-vinylacetamide and sodium acrylate.

  (5) The electric double layer capacitor electrode according to (4), wherein the polymerization ratio of the poly-N-vinylacetamide and the sodium acrylate is 9/1 to 5/5.

  (6) The electric double layer capacitor electrode according to any one of (1) to (5), wherein the conductive material contains carbon black.

  (7) The electrode for an electric double layer capacitor according to any one of (1) to (6), wherein the sheet-like current collector comprises a plain aluminum foil.

By using an electrode for an electric double layer capacitor comprising an electrode material containing tungsten oxide, a conductive adhesive containing a poly-N vinylacetamide (PNVA) binder, and a sheet-like current collector of the present invention, The electrode material and the sheet-like current collector can be firmly bonded, so that HF, OH ^{− and the} like generated by the decomposition of moisture and electrolyte do not enter between the current collector and the electrode material. Further, tungsten oxide contained in the electrode material can adsorb and remove HF, OH ^{− and the} like generated by the decomposition of moisture and electrolyte. Therefore, corrosion of the current collector / detachment of the electrode material can be suppressed, and even at a high voltage exceeding 3.0 V, the energy density is high and the capacitance and internal resistance are less deteriorated with time, that is, long-term reliability is achieved. The electric double layer capacitor is obtained. Also in Patent Document 1, long-term reliability at a high voltage is obtained. However, in the present invention, long-term reliability is further improved, and in particular, suppression of increase in internal resistance is remarkably improved.

FIG. 1 is an enlarged schematic cross-sectional view showing an example of an electrode for an electric double layer capacitor of the present invention. FIG. 2 is an enlarged schematic cross-sectional view showing an example of an electrode for an electric double layer capacitor of the present invention (in which an electrode layer is bonded to both sides of a current collector). FIG. 3 is a schematic plane view showing a method of punching electrodes produced in Examples and Comparative Examples. FIG. 4 is a schematic perspective view showing a configuration in which the electrode member of the present invention and a separator are combined. FIG. 5 is a schematic diagram showing the structure of three types of electrodes with different positions of tungsten oxide.

  An electrode for an electric double layer capacitor according to the present invention includes a polarizable electrode material containing porous carbon particles, a conductive additive, tungsten oxide powder, and a binder, and a conductive material and a poly-N-vinylacetamide (PNVA) binder. It includes a conductive adhesive and a sheet-like current collector.

  Each element which comprises the electrode for electric double layer capacitors by this invention is demonstrated below.

The porous carbon particles contained in the polarizable electrode material are not particularly limited as long as they are carbonaceous substances that can form an electric double layer, and activated carbon or the like can be used. Activated carbon having a BET specific surface area of 500 m ² / g or more, preferably 1000 m ² / g or more, and 3000 m ² / g or less, preferably 2500 m ² / g or less can be used. There is no restriction | limiting in particular as a raw material of activated carbon. Specific examples include plant-based wood, coconut husk, pulp waste liquor, fossil fuel-based coal, heavy petroleum oil, coal pyrolyzed, petroleum-based pitch, coke, synthetic resin phenol resin, furan resin Various materials such as a polyvinyl chloride resin and a polyvinylidene chloride resin can be used.

  As the activation method of activated carbon, various methods such as gas activation and chemical activation can be applied. Water, carbon dioxide, oxygen, chlorine, sulfur dioxide, sulfur vapor, etc. can be used as the gas used for gas activation. As chemicals used for chemical activation, zinc chloride, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, phosphoric acid, calcium chloride, potassium sulfide and the like can be used.

  The activated carbon can be pulverized by various methods such as a ball mill, a jet mill, and a hammer mill. If the target particle size cannot be adjusted by pulverization, the particle size may be adjusted by classification.

  The porous carbon may be graphite-like microcrystalline carbon produced by subjecting a carbon material to activation treatment. This microcrystalline carbon forms an electric double layer when ions or the like enter between crystal layers when a voltage is applied, and can be obtained, for example, according to the technique disclosed in JP-A-11-317333.

  The conductive material contained in the polarizable electrode material is a graphite that has high conductivity due to the presence of delocalized π electrons; a spherical aggregate in which several layers of graphitic carbon microcrystals gather to form a turbulent structure. Certain carbon blacks (acetylene black, ketjen black, other furnace blacks, channel blacks, thermal lamp blacks, etc.); hydrocarbons such as methane, propane, acetylene, etc. are vapor-phase pyrolyzed to form a thin film on graphite as a substrate And pyrolytic graphite formed by precipitation. Among them, artificial graphite, particularly high-purity artificial graphite, has a relatively small particle size and has a relatively good conductivity in that the metal impurity content is low and high conductivity can be ensured. Ketjen black and acetylene black are preferable. Here, “high purity” means that the ash content is 0.5 mass% or less.

  The blending amount of the conductive additive is preferably 10 parts by mass or less, where the total mass of the porous carbon particles, the conductive additive, and the binder, which are the main components of the polarizable electrode material, is 100 parts by mass. The said total mass is a dry mass after removing the shaping | molding adjuvant used when mix | blending those main components. The conductive additive is used to lower the contact resistance between the porous carbon particles, and a conventional polarizable electrode layer (in this specification, unless otherwise specified, an electrode layer is a layer composed of an electrode material, Or the layer comprised from the mixture of an electrode material and a conductive adhesive is pointed out, and a current collector is not included. However, when the amount of the conductive additive is increased, the workability of the polarizable electrode layer is deteriorated, and problems such as cracks, cracks, and deterioration in rollability occur. In addition, since the size of the particles is smaller than that of the activated carbon, if the particles are not uniformly dispersed, the inter-particle voids of the polarizable electrode layer are filled, and there is a problem that the diffusion of the electrolyte solution is hindered.

  With the tungsten oxide powder contained in the polarizable electrode material, it is possible to obtain an electric double layer capacitor having high energy density and little deterioration of capacitance and resistance with time, that is, excellent long-term reliability. The reason why the high effect is recognized by including the tungsten oxide powder is not clear, but it is considered to prevent the porous carbon particles and the pores of the separator from being blocked by adsorbing and removing moisture and decomposition products.

  As the addition amount of the tungsten oxide powder, the total mass of the porous carbon particles, the conductive additive, and the binder, which are the main components of the polarizable electrode material, is 100 parts by mass (the total mass is a combination of these main components) The dry mass after removing the molding aid used at the time is preferably a ratio of 2 to 40 parts by mass, more preferably 4 to 30 parts by mass. When the addition amount is less than 2 parts by mass, the effect of removing moisture and decomposition products by adsorption is insufficient, and the effect is not sufficient. On the other hand, as the added amount of tungsten oxide powder increases, the ratio of the porous carbon particles per volume of the electrode material decreases, so the initial capacitance of the capacitor cell decreases. When the addition amount is 4 parts by mass or more and 30 parts by mass or less, the effect of adsorbing and removing moisture and decomposition products is remarkable, and at the same time the initial capacitance can be secured, which is more preferable.

  Regarding the particle diameter of the tungsten oxide powder, any particle diameter can be used as long as it does not affect the thickness of the electrode layer when forming the electrode layer for an electric double layer capacitor. Actually, it is preferable that the particle diameter of the tungsten oxide powder is about 0.1 μm to 50 μm because it does not affect the thickness of the electrode layer and the pulverization / classification process does not cost much.

  Tungsten oxide powder is generally commercially available with a particle size of several tens of μm. For those having a particle size smaller than this particle size, steps such as pulverization and classification are required. As the particle size is reduced, the pulverization time becomes longer and the yield decreases, resulting in higher costs. For this reason, about 0.1 micrometer is considered to be the minimum particle diameter which can be used industrially. The electrode layer for an electric double capacitor usually has a thickness of about 0.01 to 5 mm. For this reason, it is necessary to keep the particle size of the tungsten oxide powder to be added below the thickness of the electrode layer, but considering the particle size of commercially available tungsten oxide, the maximum particle size is practically about 30 μm. it is conceivable that.

  The tungsten oxide powder can be pulverized by various methods such as ball milling, jet milling, hammer milling, etc. as in the case of pulverizing activated carbon. If the target particle size cannot be adjusted by pulverization, the particle size may be adjusted by classification. Moreover, as a mixing method of tungsten oxide and porous carbon particles, there is no limitation on the mixing method for uniformly dispersing, for example, solid (body) in which tungsten oxide and porous carbon particles are mixed in a solid state. -It is also possible to use a solid dispersion or a slurry dispersion in which at least one of them is previously dispersed in a liquid such as water or an organic solvent. Furthermore, in order to improve dispersibility at the time of mixing these, it is also possible to mix using ultrasonic mixing or a water flow.

  The binder contained in the polarizable electrode material binds the porous carbon particles, the conductive additive, and the tungsten oxide powder contained in the polarizable electrode material. As the binder, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE), polypropylene (PP), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), or the like can be used.

  The blending amount of the binder is preferably 1 to 30 parts by mass, more preferably 3 to 100 parts by mass, with the total mass of the porous carbon particles, the conductive additive, and the binder as the main components of the polarizable electrode material being 100 parts by mass. 20 parts by mass. The said total mass is a dry mass after removing the shaping | molding adjuvant used when mix | blending those main components. When the blending amount of the binder is less than 1 part by mass, it becomes difficult to hold the porous carbon particles on the polarizable electrode material. On the other hand, when the blending amount exceeds 30 parts by mass, the energy density of the electric double layer capacitor is lowered and the internal resistance is increased.

  Each component of the polarizable electrode material, that is, the porous carbon particles that are the material for forming the electric double layer, the conductive auxiliary agent for ensuring conductivity, and the binder for binding them, the forming auxiliary agent [water , Alcohol (methanol, ethanol, etc.), oil (petroleum, other oils, etc.)] are added and mixed, and this is formed into a sheet shape by rolling, extruding, or coating (coating). The polarizable electrode layer having a desired average pore diameter and porosity can be obtained. For example, when ethanol is used as the molding aid, the mixing ratio is 3 to 15 parts by mass of the carbon material, 5 to 15 parts by mass of the binder, and 100 parts by mass of the electric double layer forming material. The above polarizable electrode layer can be obtained by roll extrusion at a temperature of 50 to 100 ° C .: 50 to 300 parts by mass. In some cases, a conductive adhesive may be mixed with each element of the polarizable electrode material to form a polarizable electrode layer.

  The average pore diameter of the polarizable electrode layer is preferably from 0.1 μm to 5 μm, and more preferably from 0.5 μm to 3 μm. If the average pore diameter is less than the above range, the conductive adhesive may not easily enter the pores of the polarizable electrode layer. On the other hand, if the average pore diameter exceeds the above range, the conductive adhesive may be in the polarizable electrode layer. The conductive adhesive that penetrates deep into the pores and remains at the interface between the current collector and the polarizable electrode layer may become very thin and the bonding strength may be reduced. In addition, when the porous carbon particles of the polarizable electrode layer are made of activated carbon, the pores of the activated carbon are covered with the conductive adhesive component, so that the capacitor performance may be deteriorated. In addition, the average pore diameter referred to in the present specification is a value measured using a mercury intrusion porosimeter (“Pore Sizer 9310” manufactured by Micrometrics).

  The porosity of the polarizable electrode layer is preferably 40% or more and 90% or less, and more preferably 60% or more and 80% or less. If the porosity is below the above range, a sufficient amount of electrolyte may not be retained when used in a capacitor, and the internal resistance may increase. In addition, since the conductive adhesive that can enter the pores of the polarizable electrode layer is reduced, the anchor effect and the internal resistance reduction effect may not be sufficiently ensured. On the other hand, if the porosity exceeds the above range, if the amount of the conductive adhesive is insufficient, there will be a lot of pores into which the conductive adhesive has not entered, and again the anchor effect May be insufficient. In addition, it may remain as a void portion (in the case of a capacitor, an electrolytic solution is injected to become a liquid phase portion), and the internal resistance reduction effect may not be sufficiently ensured. Conversely, when the amount of the conductive adhesive is too large, the conductive adhesive enters deeply into the pores of the polarizable electrode layer. Therefore, when activated carbon is used for the polarizable electrode layer, most of the pores of the activated carbon are covered with an adhesive, which reduces the specific surface area of the activated carbon and may cause a decrease in capacitor performance. is there.

Here, the porosity (%) referred to in the present specification is a value obtained as a ratio [(V ₀ / V) × 100] of the pore volume (V ₀ ) to the volume (V) of the entire polarizable electrode layer. Say. The pore volume can be obtained by the following equation by measuring the true density (ρ) of the polarizable electrode layer and the mass (W) of the polarizable electrode layer.
V ₀ = V− (W / ρ)
The porosity and average pore diameter of the polarizable electrode layer can be adjusted by the type of the electric double layer forming material that is a constituent material of the polarizable electrode layer, the amount of binder, the roll pressure at the time of preparing the polarizable electrode layer, and the like. The thickness of the polarizable electrode layer is generally 0.05 to 1 mm, and more preferably 0.08 to 0.5 mm.

  As a poly-N-vinylacetamide (PNVA) binder contained in the conductive adhesive, the following formula (1):

(In the formula, R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. A polymer containing a repeating structural unit having an amide structure represented by a bond, an ester bond, a thioether bond or an amide bond is preferred. R ¹ and R ² are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a t-butyl group, or a methoxymethyl group, and further R ¹ is a hydrogen atom. More preferably, it is an atom and R ² is a methyl group or an ethyl group.

Moreover, as a polymer containing the repeating structural unit which has an amide structure, the compound represented by following formula (2):

(In the formula, R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. A polymer obtained by polymerizing a bond, a thioether bond or an amide bond) is preferably used. R ¹ and R ² are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a t-butyl group, or a methoxymethyl group, and further R ¹ is a hydrogen atom. More preferably, it is an atom and R ² is a methyl group or an ethyl group.

Among them, the polymer of N-vinylacetamide (in the case of R ¹ = H and R ² = CH _{3 in} the general formula (2)) stabilizes the aqueous solution irrespective of the pH (hydrogen ion concentration) of acid, alkali, etc. It is preferably used because it can be absorbed in

The N-vinylacetamide-based binder has not only heat resistance but also high coating properties and dispersibility. Since the applicability is high, the adhesion to the current collector is not a point adhesion but a surface adhesion, and the electrode material layer and the current collector can be uniformly adhered. Therefore, no gap is formed between the current collector and the electrode material layer, and moisture or decomposition products (OH ⁻ , HF, etc.) do not enter the gap, and the current collector is corroded / electrode material layer and the current collector. Detachment from the body is suppressed. In particular, sufficient adhesion to a sheet-like current collector such as a plain aluminum foil having a smooth surface and long-term durability resulting therefrom can be maintained. Further, since the dispersibility is high, the conductive material can be uniformly dispersed in the conductive adhesive. Therefore, the conductivity of the conductive adhesive is increased, resulting in low resistance.

  In the present invention, the N-vinylacetamide-based binder refers to an N-vinylacetamide homopolymer and an N-vinylacetamide copolymer. Monomers copolymerizable with N-vinylacetamide include (meth) acrylic acid or a salt thereof such as sodium acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate. Butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylic acid monomers such as polyoxyalkylene glycol mono (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (meth) Acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid or a salt thereof (Meth) acrylamide monomers such as N-isopropyl (meth) acrylamide; vinyl ester monomers such as vinyl acetate, vinyl butyrate and vinyl valerate; styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, Styrenic monomers such as m-chlorostyrene; vinyl ether monomers such as methyl vinyl ether, butyl vinyl ether, vinyl benzyl ether; maleic anhydride, maleic acid or salt thereof, fumaric acid or salt thereof, maleic acid dimethyl ester, fumaric acid diethyl ester Examples include dicarboxylic acid monomers such as allyl monomers such as allyl alcohol, allyl phenyl ether, and allyl acetate, and monomers such as (meth) acrylonitrile, vinyl chloride, ethylene, and propylene. It is also possible to copolymerize a combination of two or more of the above exemplary monomers.

By using an N-vinylacetamide copolymer, the properties of the copolymer component can be added to the basic properties (heat resistance, coating properties, dispersibility) of N-vinylacetamide. Among the N-vinylacetamide copolymers, a copolymer of poly-N-vinylacetamide and sodium acrylate is preferable in terms of improving the swelling resistance against the electrolyte solution (solvent). When the bonded portion swells as a whole, generally, the adhesiveness between the electrode material layer and the current collector is lowered, peeling is likely to occur, and the peeled portion does not become a conductive path, resulting in an increase in internal resistance. In addition, if the electrolyte solution partially penetrates and only a part of the adhesive part swells, a gap is generated due to a difference in swelling with the surrounding adhesive part, and the conductive path is reduced. Furthermore, moisture and decomposition are generated in the gap. Objects (OH ⁻ , HF, etc.) invade, and corrosion of the current collector is promoted, resulting in an increase in internal resistance. Since the copolymer of poly-N-vinylacetamide and sodium acrylate has high swelling resistance to the electrolyte solution (solvent), peeling between the electrode material layer and the current collector can be suppressed.

  The proportion of these copolymerizable monomers used is generally 60% by mass or less, preferably 50% by mass or less, preferably 40% by mass or less, so as not to impair the target performance of the present invention with respect to the total amount of polymerizable monomers. More preferably, it is 30 mass% or less.

  When defined by the polymerization ratio, the polymerization ratio of poly-N-vinylacetamide and sodium acrylate is preferably 9/1 to 5/5. The higher the sodium acrylate content, the better the swelling resistance to the electrolyte solution (solvent) and the resulting adhesive strength, but the lower the poly-N-vinylacetamide content, the higher the heat resistance. , Dispersibility and applicability deteriorate. For electric double layer capacitor applications, it is preferable to set the polymerization ratio within the above range in consideration of the balance between durability (caused by adhesion) and processability (caused by dispersibility and applicability).

  In the present invention, the N-vinylacetamide polymer is a three-dimensional crosslinked product containing a three-dimensional crosslinked structure. N-vinylacetamide is a N-vinyl acetate in the presence of a crosslinking agent having two or more polymerizable double bonds in one molecule. A method in which vinylacetamide is polymerized and cross-linked with the above-mentioned other comonomer as necessary, or a precursor polymer that is not cross-linked is previously produced, and this is reacted with a functional group in the polymer to form a chemical bond, For example, it is produced by a method of crosslinking with radiation or peroxide.

  The crosslinking agent having two or more polymerizable double bonds in one molecule used for crosslinking here is tetraallyloxyethane, pentaerythritol tetraallyl ether, pentaerythritol triallyl ether, trimethylolpropane triallyl ether. A polyallyl ether derived from a compound having two or more hydroxyl groups in one molecule, such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, diallyl ether, monosaccharide, disaccharide, polysaccharide and cellulose; Polyaryls derived from compounds having two or more carboxyl groups in one molecule such as triallyl trimelliate, triallyl citrate, diallyl oxalate, diallyl succinate, diallyl adipate, diallyl maleate Esters; compounds having two or more allyl groups in one molecule such as diallylamine and triallyl isocyanurate; divinyl oxalate, divinyl malonate, divinyl succinate, divinyl glutarate, divinyl adipate, divinyl maleate, divinyl fumarate , Compounds having two or more vinyl ester structures in one molecule such as trivinyl citrate; N, N′-butylenebis (N-vinylacetamide), N, N′-diacetyl-N, N′-divinyl-1,4 -Bis (N-vinylcarboxylic acid amide) compounds such as bisaminomethylcyclohexane; N, N'-methylenebisacrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Trimethylol group Compounds having a plurality of acrylamide structures such as lopantri (meth) acrylate and pentaerythritol tri (meth) acrylate and (meth) acrylic groups; all known cross-linking agents such as divinylbenzene, divinyl ether and allyl (meth) acrylate It can be used. These crosslinking agents can be used alone or in combination of two or more.

  10 mass% or less is suitable with respect to the polymerizable monomer whole quantity containing N-vinyl acetamide, and, as for the usage-amount of the said crosslinking agent, 6 mass% or less is more preferable.

  As a crosslinking agent that can generate a chemical bond by reacting with a functional group (for example, a hydroxyl group, an amino group, a carboxyl group, etc.) in an uncrosslinked precursor polymer, polyglycidyl ether, poly Examples include isocyanurates, polyamines, polyols, and polycarboxylic acids. The amount of these crosslinking agents used is preferably such that the ratio of polymer: crosslinking agent is 90:10 to 99.999: 0.001 in terms of mass ratio based on the total amount of the crosslinked precursor polymer. The range of ˜99.995: 0.005 is more preferable.

  The molecular weight of the N-vinylacetamide polymer is preferably 5000 or more, more preferably 5000 or more and 10 million or less, further preferably 30,000 or more and 10 million or less, and particularly preferably 100,000 or more and 5 million or less. If the molecular weight is too small, the heat resistant adhesiveness is lowered and the mechanical strength is also reduced, which is not preferable. If the molecular weight is too high, the liquid viscosity of the produced conductive adhesive becomes too high, which is not preferable.

  Specific examples of the polymer of N-vinylacetamide of the present invention include poly-N-vinylacetamide manufactured by Showa Denko. For example, crosslinked NA-150F, NA-010F, NA-010S, non-crosslinked GE -191, GE-191LH, GE-191L, GE-191LL, GE-191L34, and GE-167 (sodium acrylate copolymer), GE-167L, GE-163LM, and XGC-330 (co-vinyl acetate) Polymer) and XGC-265 (acrylamide copolymer).

  As the conductive material contained in the conductive adhesive, the same conductive material as that contained in the polarizable electrode material can be used. Specifically, graphite having high conductivity due to the presence of delocalized π electrons; carbon black (acetylene black, which is a spherical aggregate in which several layers of graphitic carbon microcrystals gather to form a turbulent structure. Ketjen black, other furnace blacks, channel blacks, thermal lamp blacks, etc.); hydrocarbons such as methane, propane, acetylene, etc. are vapor-phase pyrolyzed and deposited in the form of a thin film on the substrate graphite Examples thereof include graphite. Among these, carbon black is preferable because it has a relatively small particle size and relatively good conductivity. In addition, artificial graphite, particularly high-purity artificial graphite, is preferable in that the content of metal impurities is low and high conductivity can be ensured. Here, “high purity” means that the ash content is 0.5 mass% or less.

  Note that the conductive material contained in the conductive adhesive can be the same as the conductive aid contained in the polarizable electrode material. However, in this specification, there is no particular notice in order to avoid confusion of terms. As long as the material is included in the polarizable electrode material, it is referred to as “conductive aid”, and the material included in the conductive adhesive is referred to as “conductive material”.

  In order to facilitate the coexistence of the low internal resistance and the heat resistant adhesiveness of the conductive adhesive, it is preferable to use two or more types of conductive materials having different particle diameters in combination. For example, a mixture of high-purity artificial graphite powder and acetylene black can be suitably used.

  A case where carbon black such as acetylene black and high-purity artificial graphite are used as the conductive material will be described. The particle diameter of acetylene black is usually about 10 to 50 nm as an average particle diameter (primary particle diameter). Moreover, it is preferable to use a high purity artificial graphite having an average particle diameter of 0.5 to 20 μm, and more preferably 1 to 10 μm. By including a conductive material in which the conductive adhesive is a combination of high-purity artificial graphite having such an average particle size and acetylene black, the conductivity of the conductive adhesive itself is increased, and the pores of the polarizable electrode material layer A part of the conductive adhesive can be allowed to enter to obtain a so-called anchor effect, and an excellent bonding strength and internal resistance reduction effect can be ensured.

  Thus, the use of carbon black such as acetylene black and artificial graphite as the conductive material, from the diffraction intensity curve obtained by the X-ray diffraction method for the cross section of the electrode, particularly the conductive adhesive portion, Since a crystalline diffraction line shape based on artificial graphite and an amorphous diffraction line shape based on carbon black are observed, it can be confirmed.

  The mixing ratio of acetylene black and high-purity artificial graphite is preferably 1:10 to 1: 1 by mass ratio, and more preferably 1: 3 to 1: 1. By setting it as such a mixing ratio, sufficient adhesiveness and the high internal resistance reduction effect can be ensured simultaneously.

  The average particle size of the high-purity artificial graphite is a value measured by a laser particle size distribution measuring device (“SALD-2000” manufactured by Shimadzu Corporation). Moreover, what is necessary is just to select the acetylene black whose average particle diameter is in the said range according to the nominal value of the manufacturer of acetylene black.

  These conductive materials are preferably 0.5% or less in ash regardless of the type. When an electrode using a carbon material having such a low ash content is applied to an electric double layer capacitor, the life of the capacitor can be extended.

  The amount of the total conductive material in the conductive adhesive is preferably 3% by mass or more and 30% by mass or less. More preferably, it is 5 mass% or more and 15 mass% or less. When the amount of the conductive material is less than the above range, the conductivity of the conductive adhesive may be insufficient. On the other hand, when the above range is exceeded, the amount balance with the binder (poly-N-vinylacetamide binder) for forming the conductive adhesive is lost, and the adhesiveness tends to be lowered.

  In addition, the amount of the poly-N-vinylacetamide binder in the conductive adhesive is preferably 15% by mass or less, and more preferably 10% by mass or less. When the amount of the poly-N-vinylacetamide binder exceeds the above range, the internal resistance may increase excessively. In addition, from the viewpoint of sufficiently securing the adhesiveness with the conductive adhesive, the amount of the poly-N-vinylacetamide binder in the conductive adhesive is preferably 0.5% by mass or more, and preferably 2% by mass or more. More preferably.

  In addition, the conductive adhesive of the present invention has a small particle size conductive material that can enter the pores of the polarizable electrode layer by adopting a configuration containing two or more types of conductive materials having different particle sizes ( For example, a conductive material having a large particle size (for example, high-purity artificial graphite) can be contained together with carbon black such as acetylene black. Therefore, since the conductive adhesive having good conductivity can be formed while reducing the conductive material having a small particle size, the surface of the poly-N-vinylacetamide binder particles in the dispersion medium is reduced to the conductive material having a small particle size. It is possible to prevent the resin from being covered with, and when the conductive adhesive is used, good heat-resistant adhesiveness can be secured.

  Metal materials such as aluminum, titanium, tantalum, nickel, iron, stainless steel, and copper can be used for the sheet-like current collector that is a component of the electrode for the electric double layer capacitor, but aluminum is excellent in electrical conductivity. It is particularly preferable because of its high stability (it does not dissolve and precipitate in the electrolyte) and its cost is low. These metals can be used in any shape of foil, plate and sheet.

  The sheet-shaped current collector may be a sheet-shaped current collector such as a plain aluminum foil having a smooth surface, although the surface may be roughened so that irregularities are formed on the surface. Also good. When the surface of the sheet-like current collector is roughened, the method is not particularly limited, and known methods such as sand blasting and etching (electrolytic etching, chemical etching, etc.) can be employed. Among these, chemical etching using chemicals is preferable because the pores and irregularities formed on the surface of the sheet-like current collector can be easily controlled to a shape suitable for the anchor effect of the adhesive. The unevenness formed on the surface is easy to cause the anchor effect of the adhesive, and has the advantages of improved adhesion and low resistance. On the other hand, a sheet-like current collector such as a plain aluminum foil having a smooth surface does not require a roughening treatment and is low in cost. According to the present invention, when the sheet-shaped current collector is a plain aluminum foil, even if a void portion exists due to point contact between the sheet-shaped current collector and the polarizable electrode material, the void portion is a conductive adhesive. (The void portion disappears), and the conductive adhesive can penetrate into the pores of the polarizable electrode material and maintain sufficient adhesiveness. That is, according to the present invention, even when the sheet-like current collector includes a plain aluminum foil, it is possible to maintain sufficient adhesiveness and long-term durability resulting from this, and to realize cost reduction. Can do.

  The thickness of the current collector (when the surface is roughened, the thickness before the treatment) is generally 10 to 100 μm, and more preferably 20 to 50 μm.

The electrode for an electric double layer capacitor of the present invention is assembled using each of the above constituent elements. The electrode for an electric double layer capacitor of the present invention includes an electrode material containing tungsten oxide, a conductive adhesive containing a poly-N vinylacetamide (PNVA) binder, and a sheet-like current collector. Poly N vinylacetamide (PNVA) -based binder, even at high voltage, strongly adheres the electrode material and the sheet-like current collector, and suppresses peeling of the electrode material, so that HF generated by decomposition of moisture and electrolyte, There is no room for OH ⁻ or the like to enter, and corrosion of the current collector due to HF, OH ⁻ or the like is suppressed. Also, if HF, OH ^- or the like when close to the current collector, HF, OH ^- since such is adsorbed and removed by the tungsten oxide, HF, OH ^- or the like is prevented to react in contact with the current collector Further, corrosion of the current collector is further suppressed. Suppression of corrosion leads to suppression of peeling of the electrode material, and the low resistance of the electric double layer capacitor can be maintained over a long period of time. That is, according to the present invention, corrosion of the current collector / debonding of the electrode material can be suppressed, the energy density is high even at high voltage, and the capacitance and internal resistance are less deteriorated with time, that is, have long-term reliability. An electric double layer capacitor is obtained.

  A polarizable electrode material can be made into a polarizable electrode layer by producing it in layers by a sheet manufacturing method, a coating method (coating method) or the like. In the sheet manufacturing method, a sheet of electrode material (electrode layer) may be formed in advance and then adhered to a sheet-like current collector via a conductive adhesive. Moreover, after mixing an electrode material and a conductive adhesive to form a sheet (electrode layer), it may be adhered to a sheet-like current collector. The coating method (coating method) is a production method in which a polarizable electrode material is coated on a current collector to form an electrode layer. In the coating method, a conductive adhesive may be applied to the current collector, and then the polarizable electrode material may be coated. Alternatively, a conductive adhesive and a polarizable electrode material may be mixed and the current collector may be coated with the mixture.

  In the case of the sheet manufacturing method, for example, after adjusting the particle size of the porous carbon particles obtained by the above-described method so that the average particle size D50 is about 5 to 200 μm, the conductive auxiliary agent, tungsten oxide powder, It can be kneaded by adding a binder, and rolled to form a sheet. In kneading, liquid auxiliaries such as water, ethanol and acetonitrile may be used alone or in combination as appropriate. When the same activated carbon is used as the porous carbon particles of the polarizable electrode material for rolling treatment, the sheet manufacturing method is easier to consolidate the activated carbon than the coating method. It is done.

  In the case of the coating method, a stirrer obtained by adding a conductive adhesive and, if necessary, a dispersion medium (for example, water, ethanol, etc.) to a mixture containing porous carbon particles, a conductive auxiliary agent, and tungsten oxide. It is good also as a coating liquid by mixing using. The coating liquid is applied to a current collector using a roll coater, and then the coated current collector is placed in an oven to evaporate and remove the dispersion medium from the coating liquid layer. A layer can be obtained.

The conductive adhesive is applied to the surface (bonding surface) of the sheet-like current collector and / or polarizable electrode layer. The application surface may be a joint surface of either the sheet-like current collector or the polarizable electrode layer, but may be applied to both. The coating amount of the conductive adhesive, the amount of dried (i.e., the conductive adhesive component amounts) with is preferably to 2 to 15 g / ^{m 2,} and more preferably set to 2 to 10 g / ^{m 2.}

  The polarizable electrode material, the conductive adhesive, and the sheet-like current collector may be laminated in this order. The polarizable electrode material and the sheet current collector are laminated so that the conductive adhesive is interposed between the polarizable electrode material and the sheet current collector. The laminating method may be simply superimposing, but it is preferable to compress and compress after superimposing. By making it like the latter, while joining more reliably, a part of conductive adhesive can be reliably press-fitted in the hole of a polarizable electrode layer. In addition, since the polarizable electrode layer is compressed and densified, it is possible to increase the capacity of the polarizable electrode layer. Although the pressurization method is not particularly limited, for example, a method of passing between a pair of rolls is relatively simple. At this time, the clearance between the rolls with respect to the total thickness of the laminate is preferably, for example, 30 to 90%, and more preferably 50 to 70%. By setting it as such clearance, the increase in capacity | capacitance of a polarizable electrode layer can be achieved. If the clearance is less than the above range, the current collector may be deformed and the polarizable electrode layer may be peeled off.

  When the polarizable electrode material and the sheet current collector are laminated so that the conductive adhesive is interposed between the polarizable electrode material and the sheet current collector, the polarizable electrode material and the conductive adhesive are mixed. Thus, the increase in internal resistance is suppressed as compared with the case where the sheet-shaped current collector is joined. The reason for this is not limited by a specific theory, but when tungsten oxide contained in the polarizable electrode material comes into direct contact with the sheet-like current collector, the tungsten oxide acts as a catalyst to cause the corrosion reaction of the current collector. It may be possible to promote.

  After combining the polarizable electrode material, the conductive adhesive, and the sheet-like current collector, if a volatile component (such as a dispersion medium) is contained in the conductive adhesive, it is removed. Although the removal method is not particularly limited, for example, induction heating, far-infrared heating, and hot air drying are suitable. The drying temperature is preferably around the boiling point of the dispersion medium. After removal of the dispersion medium, an electric double layer capacitor electrode as shown in FIG. 1 is obtained as an example of the electric double layer capacitor electrode of the present invention. In FIG. 1, an electrode 10 is made of a constituent material including, on the upper surface of a current collector 11, porous carbon particles that are an electric double layer forming material, a conductive aid for ensuring conductivity, tungsten oxide, and a binder. A polarizable electrode material layer 12 is bonded via a conductive adhesive layer 13. As shown in FIG. 1, the polarizable electrode material layer 12 made of the above-described constituent material is a porous body, and a part of the conductive adhesive layer 13 enters the pores 12a.

  Hereinafter, the present invention will be described in detail based on examples. However, the following examples are not intended to limit the present invention, and all modifications made without departing from the spirit of the preceding and following descriptions are included in the technical scope of the present invention.

<Production of electric double layer capacitor>
The electric double layer capacitors used in Examples and Comparative Examples were produced by the following procedure.

[Polarizable electrode material]
80 parts by mass of steam activated activated coconut shell activated carbon (“YP-50F” manufactured by Kuraray Chemical Co., Ltd.) having a specific surface area of about 1700 m ² / g by BET method as porous carbon particles, and acetylene black powder (Electrochemical Industry) as a conductive auxiliary agent 10 parts by mass of “Denka Black powder product” manufactured by Co., Ltd., 10 parts by mass of polytetrafluoroethylene powder (“Teflon 6J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) as a binder, and tungsten trioxide (oxidized by Kanto Chemical Co., Inc.) 30 parts by mass of ethanol was added to a mixture composed of 10 parts by mass of tungsten (deer grade 1 average particle size 30 μm), kneaded, and then paste extruded into a tape shape. Thereafter, the obtained tape-like material is rolled and rolled three times to form a sheet, and further dried at 150 ° C. for 1 hour to remove ethanol to obtain a sheet of polarizable electrode material having a width of 100 mm and a thickness of 150 μm. It was.

[Conductive adhesive]
As conductive materials, high-purity artificial graphite having an average particle size of 8 μm (“SP-270” manufactured by Nippon Graphite Industry Co., Ltd.) and average particle size (primary particle size): 35 nm of acetylene black (“DENKA BLACK” manufactured by Denki Kagaku Kogyo Co., Ltd.) ) Was used. As poly N-vinylacetamide (PNVA) binder, polyN-vinylacetamide ("PNVA GE191-203" manufactured by Showa Denko KK) or sodium acrylate copolymer ("PNVA GE167-103" manufactured by Showa Denko KK) Was used to obtain a conductive adhesive.
In the comparative example, synthetic rubber (SBR (styrene butadiene rubber)) was used instead of PNVA.

[Current collector]
As the current collector, a plain aluminum foil (“A1N30H-H18” manufactured by Nihon Foil Co., Ltd.) having a width of 150 mm and a thickness of 30 μm was used.

[Manufacture of electrodes]
A conductive adhesive was applied to both sides of the current collector using an application roll. The coating amount was 12 g / m ² per side (about 2 g / m ² after drying). After application, a long polar electrode layer was layered on the conductive adhesive application surface (both sides) of the current collector, and a laminated sheet was formed through a compression roll (clearance: 70%). The laminated sheet was passed through a dryer set at a temperature of 150 ° C. in 3 minutes, and the dispersion medium was removed from the conductive adhesive to obtain a long electrode shown in FIG. As shown in FIG. 3, in this laminated sheet, the dimension of the portion where the polarizable electrode material sheet is laminated is 3 cm square, and the lead portion (the portion where the polarizable electrode is not laminated on the current collector) is 1 A square-shaped polarizable electrode was punched out in a shape of × 5 cm.

[Manufacture of electric double layer capacitors]
Two polarizable electrodes are used as a positive electrode and a negative electrode, and a porous PTFE sheet (“BSP070080-2” manufactured by Japan Gore Co., Ltd.) with a thickness of 80 μm and a 3.5 cm square is inserted as a separator between them. Cover the electrodes and separator with two 5 x 10 cm aluminum laminates ("PET12 / A120 / PET12 / CPP30 dry laminate" manufactured by Showa Denko Packaging Co., Ltd.) and heat-melt the three sides including the lead The aluminum pack cell was made by sealing by wearing. (FIG. 4 shows the electric double layer capacitor before the aluminum laminate material is heat-sealed.) At the time of heat-sealing, a part of the lead portion is led out of the aluminum pack cell, and the lead portion and the aluminum pack cell The joint portion was sealed by thermal fusion between the lead portion and the aluminum laminate material. This aluminum pack cell was vacuum-dried at 150 ° C. for 24 hours, and then brought into a glove box that maintained a dew point of −60 ° C. or lower in an argon atmosphere, and the opening (unsealed side) faced upward. 4 mL of a propylene carbonate solution of 1.5 mol / L triethylmethylammonium tetrafluoroborate (1.5 mol / L TEMA / PC) was poured into an aluminum pack as an electrolyte solution, and allowed to stand for 10 minutes under a reduced pressure of -0.05 MPa. The gas inside the electrode was replaced with an electrolyte solution. Finally, a single-layer electric double layer capacitor was fabricated by fusing and sealing the opening of the aluminum pack. This electric double layer capacitor was stored at 40 ° C. for 24 hours, and the electrolyte solution was aged to the inside of the electrode. Thereafter, the capacitor was sandwiched between 5 × 5 cm and 5 mm thick SUS plates, and pressurized at 1 MPa from the surface direction.

  The following evaluation was performed on the electric double layer capacitors of the above-described Examples and Comparative Examples.

<Durability evaluation test>
The produced electric double layer capacitor was operated at a voltage higher than 2.7V. At the start of operation and after approximately 1000 hours of operation, the capacitance and internal resistance were measured and compared to evaluate how much capacity was maintained and how much the internal resistance increased.

More specific measurement items are as follows.
[Capacitance density]
For the electric double layer capacitor, an operation of charging for 1500 seconds under the conditions of 10 mA / cm ² and 3.0 V and discharging until reaching 0 V under the condition of 10 mA / cm ² is defined as one cycle, and this is continuously performed for 10 cycles. The discharge curve from the start of the discharge at the 10th cycle to 0 V was integrated to obtain the capacitance of the electric double layer capacitor at the time of the 10th charge, and this was divided by the electrode volume. The capacitance density was calculated.

[DC internal resistance]
It calculated | required by calculating using a formula "V = IR" at the time of the said capacitance density measurement.

[Capacitance maintenance rate]
Operation for discharging the electric double layer capacitor at 60 ° C. or 70 ° C. under conditions of 10 mA / cm ² and 3.0 V for 100 hours and then discharging until 0 V under the condition of 10 mA / cm ² This cycle was repeated for 1 cycle. The capacitance at the first cycle and the cycle at the time when a predetermined time (1000 hours) has elapsed is obtained by the method described above for the capacitance density, and the result is the static value at the time when the predetermined time has elapsed from the start of measurement (the first cycle). The capacitance retention rate was evaluated by the capacitance retention rate [100 × (capacitance of the cycle when a predetermined time elapses) / (capacitance at the first cycle)] (%).

[Internal resistance increase rate]
At the time of measuring the capacitance maintenance rate, the DC internal resistance was also measured, and the internal resistance increase rate was evaluated by (internal resistance after a predetermined time) / (initial internal resistance) × 100.

The results are shown in Table 1.

From Table 1, it can be seen that when PNVA is used, the rate of increase in internal resistance is small compared to when SBR is used, and durability is high even at a high voltage of 3.0V. Among PNVA, it can be seen that when a PNVA copolymer is used, the rate of increase in internal resistance is further small and durability is high even at a high voltage of 3.0V.

<Electrolytic solution immersion peel test (heat resistance test)>
The electrode was prepared by changing the adhesive component in the conductive adhesive (PNVA, PNVA copolymer (polymerization ratio 9/1), SBR). These electrodes were immersed in a simulated electrolyte at 100 ° C. and a propylene carbonate solution of 1.5 mol / L triethylmethylammonium tetrafluoroborate (1.5 mol / L TEMA / PC) for a predetermined time (1, 5, The peeling state of the electrode layer portion after 10 and 24 hours) was observed.
The results are shown in Table 2.

  From Table 2, it can be seen that by using PNVA as an adhesive component of the conductive adhesive, peeling is suppressed, that is, the adhesiveness is improved, by using PNVA. Especially, the remarkable improvement of adhesive force was seen in the PNVA copolymer.

  About the PNVA copolymer with high adhesive force, the polymerization ratio was changed, electrodes were prepared, and a peel test of these electrodes was performed. The polymerization ratio was PNVA / sodium acrylate: 9/1, 7/3, 5/5. Moreover, in order to accelerate peeling, the simulation electrolyte solution was 200 degreeC. The results are shown in Table 3.

  From Table 3, it can be seen that as the sodium acrylate content increases, peeling is suppressed, that is, the adhesiveness is improved.

When the viscosity of the conductive adhesive using these copolymers was also measured, the following results were obtained. The viscosity was measured using a BL type viscometer. The measurement temperature was 25 ° C., and the rotation speed of the rotor was 30 rpm.
9/1: 12000 mPa · s
7/3: 20000 mPa · s or more 5/5: 20000 mPa · s or more (PNVA alone: 9000 mPa · s)
From the viewpoint of electrode production, a polymerization ratio having good dispersibility and coating properties is preferred. An appropriate polymerization ratio can be selected in consideration of both adhesiveness and processability.

<Effect of the location of tungsten oxide on durability>
Based on the above electrodes, three types of electrodes called <electrode surface side>, <adhesive layer side>, and <uniform dispersion> were prepared as shown in FIG. The electrode referred to as <electrode surface side> has an activated carbon sheet sandwiched between an electrode material containing a conductive adhesive and tungsten oxide so that tungsten oxide exists on the surface side of the electrode, that is, tungsten oxide is a current collector. It was made to keep away from. The electrode referred to as <adhesive layer side> is obtained by stacking an electrode material containing tungsten oxide on the adhesive layer, and further overlaying an activated carbon sheet thereon, so that tungsten oxide is present on the adhesive layer side (not on the electrode surface side). That is, tungsten oxide is brought close to the current collector. The activated carbon sheet thickness and the electrode material thickness at <electrode surface side> and <adhesion layer side> are each 100 μm, and the tungsten oxide concentration in the electrode material is 10 parts by mass (the total mass of the electrode material is 100 parts by mass). It was. The electrode referred to as <uniform dispersion> is obtained by uniformly dispersing tungsten oxide contained in the electrode material up to the activated carbon sheet used in <electrode surface side> and <adhesion layer side>. Thereby, the total thickness of the electrode and the amount of tungsten oxide are made uniform among the three types of electrodes.
Here, in order to clarify how much the location of tungsten oxide affects the durability performance of the capacitor, an SBR binder was used as an adhesive component of the conductive adhesive.

  These three types of electrodes were subjected to the durability performance evaluation test described above. The operating conditions of the capacitor were 3.0 V, 70 ° C., 1000 hours, and 1.5 mol / L of propylene carbonate solution of triethylmethylammonium tetrafluoroborate (1.5 mol / L TEMA / PC) was used as the electrolyte. It was. The results are shown in Table 4.

  From Table 4, it can be seen that the closer the tungsten oxide is to the current collector, the lower the effect of improving durability, and the higher the rate of resistance increase. In the case of uniform dispersion, the effect of improving the durability was the highest.

DESCRIPTION OF SYMBOLS 9 Current collection terminal 10 Electric double layer capacitor electrode 11 Current collector 12 Polarization electrode layer 12a Hole 13 Conductive adhesive layer 15 Separator 16 Aluminum laminate material

Claims (7)

  Polarizable electrode material including porous carbon particles, conductive additive, tungsten oxide powder, and binder, conductive adhesive including conductive material and poly-N-vinylacetamide (PNVA) binder, and sheet-like current collector And an electrode for an electric double layer capacitor.   The electrode for an electric double layer capacitor according to claim 1, wherein the polarizable electrode material, the conductive adhesive, and the sheet-like current collector are laminated in this order.   The electric double layer according to claim 1 or 2, wherein the poly-N-vinylacetamide-based binder is selected from the group consisting of an N-vinylacetamide homopolymer and an N-vinylacetamide copolymer. Capacitor electrode.   The electrode for an electric double layer capacitor according to claim 3, wherein the N-vinylacetamide copolymer is a copolymer of poly-N-vinylacetamide and sodium acrylate.   The electrode for an electric double layer capacitor according to claim 4, wherein a polymerization ratio of the poly-N-vinylacetamide and the sodium acrylate is 9/1 to 5/5.   The electrode for an electric double layer capacitor according to any one of claims 1 to 5, wherein the conductive material contains carbon black.   The electrode for an electric double layer capacitor according to any one of claims 1 to 6, wherein the sheet-like current collector comprises a plain aluminum foil.

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