WO2015166839A1 - エネルギー貯蔵デバイスの電極用多孔質炭素材料およびその製造方法 - Google Patents
エネルギー貯蔵デバイスの電極用多孔質炭素材料およびその製造方法 Download PDFInfo
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- WO2015166839A1 WO2015166839A1 PCT/JP2015/062103 JP2015062103W WO2015166839A1 WO 2015166839 A1 WO2015166839 A1 WO 2015166839A1 JP 2015062103 W JP2015062103 W JP 2015062103W WO 2015166839 A1 WO2015166839 A1 WO 2015166839A1
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
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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
- Y02E60/13—Energy storage using capacitors
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a porous carbon material for energy storage devices that is effective for improving durability, suppressing gas generation, and improving withstand voltage, and a method for producing the same.
- Electric double layer capacitors one of the energy storage devices, are superior in output characteristics and life characteristics compared to batteries. Therefore, using these characteristics, backup of various memories, power assist for automobiles and trains, UPS, etc. It has been developed and put to practical use for storage power applications such as (Uninterruptible Power Supply). In recent years, electric double layer capacitors have attracted attention as auxiliary power sources for electric vehicles (EV) and hybrid vehicles (HV) and for regenerative energy storage because of the above-described excellent characteristics. Such automotive energy storage devices are used under harsh usage conditions compared to consumer applications and not only require higher energy density, but also have longer-term capacity retention characteristics and higher durability Sex is required.
- a power storage method using an electric double layer does not involve a chemical reaction, in principle, it has excellent temperature characteristics and durability.
- gas is generated due to decomposition of the electrolytic solution, the electrolyte, etc., and durability and capacity decrease occur.
- the cause is not clear, but water is present on the surface of carbon materials such as activated carbon used in energy storage devices, and the water is not sufficiently desorbed and removed during drying at the time of electrode production.
- degradation is prominent when reductive decomposition generates H 2 gas and OH ⁇ , and further activation of hydrolysis of a solvent such as an electrolytic solution and electrolyte by OH ⁇ .
- electrolytes and electrolytes are electrochemically oxidized and decomposed, resulting in polymerization and fluorination, which affects durability.
- Patent Document 1 is based on activated carbon having a specific oxygen atom / carbon atom ratio, which is considered to react with oxygen in the activated carbon and solute in the electrolyte when the amount of oxygen in the activated carbon is large.
- An electric double layer capacitor in which a decrease in discharge capacity is suppressed has been proposed.
- This document describes heat treatment at a temperature of 500 to 1100 ° C. in order to obtain activated carbon having a specific oxygen atom / carbon atom ratio.
- Patent Document 2 discloses an activated carbon that suppresses deterioration over time by heat treatment at 500 to 1000 ° C. when producing activated carbon obtained from mesophase-based soft carbon that has particularly large gas generation and large capacity reduction.
- a manufacturing method and a manufacturing apparatus therefor have been proposed.
- Patent Document 3 discloses that as a negative electrode active material of a Li ion type power storage device, a fine particle activated carbon having a spherical and submicron average particle diameter in which siloxane is supported on the surface and pores using an organic solvent is used. It is disclosed that an increase in capacity and durability of the device can be achieved. However, since the siloxane itself supported on the activated carbon surface becomes an insulator and a resistor between particles, there is a possibility that the input / output characteristics may be deteriorated.
- Patent Document 4 a silane compound or a silazane compound is used as a surface modifier, and the alkoxy group in the silane compound or the silazane compound is eliminated and bonded to the surface of the activated carbon, thereby improving the wettability with the electrolytic solution.
- an electric double layer capacitor having good life characteristics by smoothly absorbing and desorbing ions. Although this method suppresses the decrease in capacity, no consideration has been given to gas generation, which is one of the practical problems. Further, when the added surface modifier remains in an unreacted state, there is a possibility that the cause of gas generation or the deterioration of the electrolyte solution is promoted. Furthermore, since the surface modifier used in the present invention has a low flash point, there is a concern that attention must be paid when the electrode is dried.
- Patent Document 5 by attaching a silicon or metal oxide to at least a part of the surface of the activated carbon and hydrolyzing it, the active sites are covered to suppress the decomposition of the electrolytic solution, and the withstand voltage of the cell is improved. It is disclosed.
- the metal oxide described in the same document becomes an insulator or a resistor like the siloxane described in Patent Document 3, and the resistance increases, which may adversely affect the input / output characteristics.
- the metal may be deposited during charging / discharging due to decomposition of the metal oxide, which may cause a short circuit or promote deterioration.
- Patent Document 6 discloses that either an insulating oxide or an electrochemically reactive oxide capable of causing a reversible electrochemical reaction with an electrolytic solution is applied to a substrate having pores by a method such as a supercritical coating method. By coating, the substrate surface including the inside of the pores is uniformly coated (quantitatively speaking, 90% or more of the surface area), and direct contact between the electrolyte and the substrate is avoided, and the electrolyte is decomposed. It is disclosed that by suppressing it, an excellent charge / discharge cycle can be provided. However, the oxide described in the same document becomes an insulator or a resistor like the siloxane described in Patent Document 3, and the resistance increases, which may adversely affect the input / output characteristics. In addition, the performance may be deteriorated due to deterioration due to oxidation / reduction of the oxide itself.
- An object of the present invention has been made in view of the above circumstances, and is a porous carbon material for an electrode of an energy storage device, which is effective in improving durability, suppressing gas generation, and improving withstand voltage, and a method for producing the same. Is to provide.
- the present inventors have studied the porous carbon material for an electrode of an energy storage device and the production method thereof in detail, and have reached the present invention.
- the present invention includes the following preferred embodiments.
- Porous carbon material 0.5 to 5 parts by mass of an insulating material having a boiling point of 150 ° C. or higher with respect to 100 parts by mass of the porous carbon material, and 1300 to 2050 m, containing 0.25 to 15 parts by mass of a conductive additive with respect to 100 parts by mass of the insulating material, and carrying the insulating material and the conductive additive together on the porous carbon material.
- a porous carbon material for an electrode of an energy storage device having a BET specific surface area of 2 / g.
- porous carbon material for an electrode of an energy storage device according to any one of [1] to [4], further comprising a polymer compound supported thereon.
- a method for producing a porous carbon material for an electrode of an energy storage device having a BET specific surface area of 1300 to 2050 m 2 / g, the porous carbon material comprising 100 parts by mass of the porous carbon material A production method of carrying 0.5 to 5 parts by mass of an insulating material having a boiling point of 150 ° C. or higher, and 0.25 to 15 parts by mass of a conductive additive with respect to 100 parts by mass of the insulating material.
- the porous carbon material for an electrode of the energy storage device of the present invention When used for an electrode, durability such as a performance maintenance rate of the energy storage device is improved, gas generation is suppressed, and a withstand voltage is improved.
- This is not only suitable for use as an electrode for electric double layer capacitors and lithium ion capacitors that require high durability, but is also suitable as a positive electrode additive for lithium ion batteries. Although this principle is unknown, it is considered that not only the adsorption of water to the porous carbon material is suppressed, but also the deterioration and decomposition of the electrolyte solution of the energy storage device are suppressed.
- the porous carbon material for an electrode of the energy storage device of the present invention is formed when the electrode is molded from the porous carbon material for an electrode of the present invention, or the porous carbon material for an electrode of the present invention is used as another positive electrode material.
- the electrode is formed by addition, a conductive path is formed between the porous carbon materials for electrodes, and it is considered that the performance maintenance ratio is excellent by suppressing an increase in resistance due to the addition of the insulating material.
- the specific surface area of the porous carbon material for electrodes or the porous carbon material used as the base material of the porous carbon material for electrodes, the electrostatic capacity per volume of the electrode in the 25 ° C. measurement after the durability test, and 1 Hz and 1000 Hz It is a figure which shows the relationship with the difference of resistance value in.
- the specific surface area of the porous carbon material for electrodes or the porous carbon material used as the base material of the porous carbon material for electrodes, the electrostatic capacity per volume of the electrode in the measurement at ⁇ 30 ° C. after the durability test, and 1 Hz It is a figure which shows the relationship with the difference of the resistance value in 1000 Hz.
- the porous carbon material for an electrode of the energy storage device of the present invention has a BET specific surface area of 1300 to 2050 m 2 / g, and is 0.5 to 5 with respect to 100 parts by mass of the porous carbon material and the porous carbon material. 0.25 to 15 parts by mass of a conductive additive with respect to 100 parts by mass of the insulating material and 100 parts by mass of the insulating material, and the porous carbon material carries the insulating material and the conductive auxiliary together It is characterized by being a porous carbon material for electrodes.
- the porous carbon material for an electrode of the energy storage device of the present invention is 1300 to 2050 m 2 / g, preferably 1320 to 2000 m 2 / g, more preferably 1400 to 2000 m 2 / g, still more preferably 1340 to 1950 m 2 / g. And most preferably has a BET specific surface area of 1500-1950 m 2 / g. If the BET specific surface area is too small, ions in the electrolytic solution are difficult to move, and the capacitance per unit mass is reduced. Moreover, when a BET specific surface area is too large, the bulk density of the electrode using the porous carbon material for electrodes of this invention will fall, and the electrostatic capacitance per volume will fall.
- the BET specific surface area is calculated by a nitrogen adsorption method, and can be measured by, for example, the method described in Examples.
- the porous carbon material for an electrode of the energy storage device of the present invention comprises a porous carbon material, 0.5 to 5 parts by mass of an insulating material and 100 parts by mass of the insulating material with respect to 100 parts by mass of the porous carbon material. On the other hand, it contains 0.25 to 15 parts by mass of a conductive additive.
- the porous carbon material is not particularly limited, and examples thereof include charcoal, activated carbon, carbon nanotubes, carbon nanohorns, mesoporous carbon prepared using an inorganic porous material as a template, and carbon aerogel obtained by drying and carbonizing an organic wet gel.
- the porous carbon material is preferably activated carbon.
- Specific examples of activated carbon include, for example, plant-based activated carbon obtained by carbonizing and activating wood, sawdust, charcoal, fruit shells such as coconut shells and walnut shells, fruit seeds, pulp production by-products, lignin, and molasses. Mineral activated carbon, phenol, saran, acrylic resin, etc.
- the activation method include gas activation for treatment with high-temperature steam or carbon dioxide gas, and chemical activation for treatment with chemicals such as phosphoric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, and any activation method is used. I do not care.
- the porous carbon material these porous carbon materials may be used alone, or two or more kinds may be used in combination.
- activated carbon activated carbon derived from coconut shell is preferable from the viewpoint of availability, price, and quality, and activated carbon obtained by gas-activating the coconut shell is more preferable.
- the porous carbon material is preferably a porous carbon material from which impurities are removed as much as possible.
- the impurities include metals such as alkali metals, alkaline earth metals, nickel, and iron.
- a porous carbon material from which such impurities have been removed by washing with water or a washing solution such as an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid may be used as the porous carbon material in the present invention.
- the porous carbon material may contain impurities (for example, silicon) that cannot be removed by washing with the above-described aqueous solution of an inorganic acid.
- a porous carbon material from which impurities such as silicon are removed by washing with an aqueous solution of an alkali metal hydroxide such as sodium hydroxide may be used as the porous carbon material in the present invention.
- the cleaning may be performed once or a plurality of times with one type of cleaning liquid, or may be performed a plurality of times by combining two or more cleaning liquids.
- the porous carbon material from the viewpoint of obtaining an electrode for the porous carbon material of the present invention having the above predetermined BET specific surface area, preferably 1300 ⁇ 2400m 2 / g, more preferably 1400 ⁇ 2300m 2 / g, more preferably It has a BET specific surface area of 1420 to 2300 m 2 / g, more preferably 1450 to 2200 m 2 / g, and most preferably 1520 to 2200 m 2 / g. If the BET specific surface area of the porous carbon material is too small, in the energy storage device including the electrode manufactured using the porous carbon material for electrodes, ions in the electrolytic solution are difficult to move, and the electrostatic capacity per unit mass Becomes smaller. Moreover, when the BET specific surface area of a porous carbon material is too large, the bulk density of the electrode using the porous carbon material for electrodes will fall, and the electrostatic capacitance per volume will fall.
- the porous carbon material for an electrode of the present invention includes 0.5 to 5 parts by mass of an insulating material having a boiling point of 150 ° C. or higher with respect to 100 parts by mass of the porous carbon material.
- the insulating material is not particularly limited as long as it has a boiling point of 150 ° C. or higher, a high dielectric breakdown voltage, and a low dielectric loss.
- paraffinic or naphthenic hydrorefined mineral oil For example, paraffinic or naphthenic hydrorefined mineral oil; Hydrocarbon synthetic oils such as olefins, alkylbenzenes, alkylnaphthalenes, alkyldiphenylalkanes; oxygen-containing synthetic oils such as diesters, polyol esters, polyoxyalkylene glycols, polyphenyl ethers; dimethyl silicones, methyl phenyl silicones, methyl hydrogen silicones, Silicone oil such as cyclic dimethyl silicone (siloxane compound having a siloxane unit in the main chain); fluorocarbon compound such as perfluoroalkyl ether, perfluoropolyether, hydrochlorofluorocarbon; rapeseed oil Esterified products due to grade alcohol.
- Hydrocarbon synthetic oils such as olefins, alkylbenzenes, alkylnaphthalenes, alkyldiphenylalkanes
- silicone oil (a siloxane compound having a siloxane unit in the main chain) is preferable from the viewpoint of high dielectric breakdown voltage and electrochemical stability, and dimethyl silicone is more preferable from the viewpoint of availability and price. preferable.
- these insulating materials may be used alone or in combination of two or more as the insulating material.
- the porous carbon material for an electrode of the present invention is 0.5 to 5 parts by mass, preferably 0.7 to 4.5 parts by mass, more preferably 1 to 4 parts by mass with respect to 100 parts by mass of the porous carbon material. Insulation material is included. When the amount of the insulating material is lower than the predetermined amount, in the energy storage device including the electrode manufactured using the porous carbon material for an electrode of the present invention, the effect of suppressing the gas generation due to the decomposition of the electrolytic solution and the performance maintenance rate and Energy density improvement effect is not enough.
- the amount of the insulating material exceeds 5 parts by mass with respect to 100 parts by mass of the porous carbon material, the effect of suppressing gas generation is saturated and does not improve, while the pores of the porous carbon material are blocked to save energy.
- the ability may decrease.
- the kinematic viscosity at 25 ° C. of the insulating material is preferably 1 to 1000 mm 2 / s, more preferably 1 from the viewpoint of obtaining a sufficient effect even when the insulating material is thinly and uniformly supported to obtain a sufficient effect and energy storage capacity. 0.5 to 500 mm 2 / s, more preferably 2 to 300 mm 2 / s. If the kinematic viscosity is too low, the boiling point of the insulating material is relatively low, and when the porous carbon material for an electrode of the present invention is produced or dried before or after electrode preparation, the porous carbon material for an electrode of the present invention is used.
- the insulating material is volatilized and the amount of the insulating material carried decreases, and the effect may be reduced. If the kinematic viscosity is too high, it is difficult to carry it thinly and uniformly because the viscosity is high, and the carrying amount necessary to achieve a sufficient effect may increase. Moreover, the pores of the porous carbon material are blocked, and the energy storage capacity may be reduced.
- the kinematic viscosity can be measured at 25 ° C. based on JIS-K2283 (2000).
- the boiling point of the insulating material is 150 ° C. or higher, preferably 200 ° C. or higher.
- the boiling point of the insulating material is 150 ° C. or higher, preferably 200 ° C. or higher.
- the insulating material volatilizes, the amount of the insulating material carried decreases, and the effect may be reduced. Further, there is a risk of ignition when performing heat treatment or drying.
- the upper limit of the boiling point of the insulating material is not particularly limited.
- the pour point of the insulating material is preferably ⁇ 30 ° C. or lower, more preferably ⁇ 40 ° C. or lower. If the pour point is too high, the kinematic viscosity rapidly increases in a low temperature environment such as a cold region, and the insulating material solidifies, which may reduce the energy storage capacity.
- a pour point depressant may be added. By adding the pour point depressant, the interfacial tension is lowered, and it can be supported thinly and uniformly in the pores of the porous carbon material. It does not specifically limit as a pour point depressant to add, A well-known additive can be used.
- pour point depressants include polyalkyl acrylate, polyvinyl acetate, polyalkyl styrene, polybutene, ethylene propylene copolymer, polyalkyl methacrylate, chlorinated paraffin and condensate of naphthalene or phenol. From these pour point depressants, effective ones can be appropriately selected and used. When a pour point depressant is added, the amount of pour point depressant added may be appropriately selected depending on the type of insulating material to be added, but from the viewpoint of obtaining the effect of lowering the fluidity, 100 parts by mass of the insulating material is added. On the other hand, it is preferable that it is 0.01 mass part or more. In addition, from the viewpoint of low possibility of affecting the pores of the porous carbon material when adhering to the porous carbon material, the amount is 0.3 parts by mass or less with respect to 100 parts by mass of the insulating material. Is preferred.
- the porous carbon material for an electrode of the present invention comprises 0.5 to 5 parts by mass of an insulating material having a boiling point of 150 ° C. or higher with respect to 100 parts by mass of the porous carbon material, and 100 parts by mass of the insulating material. 0.25 to 15 parts by mass of a conductive additive.
- the conductive aid is not particularly limited as long as it can exist chemically and electrochemically stably in the energy storage device, and for example, a particulate or fibrous conductive aid can be used.
- the particulate conductive additive include carbon black such as acetylene black and furnace black, natural graphite, artificial graphite, titanium nitride particles, and the like, and those subjected to surface modification are also preferably used. it can.
- the conductive additive it is preferable to use a particulate conductive additive from the viewpoint of availability and cost, and it is more preferable to use carbon black such as acetylene black.
- the fibrous conductive additive include carbon fibers such as vapor grown carbon fiber (VGCF).
- VGCF vapor grown carbon fiber
- one type of conductive additive may be used alone, or two or more conductive additives may be used in combination.
- the primary particle size of the particulate conductive aid is preferably 20 nm or more, more preferably 30 nm or more, from the viewpoint of dispersibility.
- the primary particle diameter of the particulate conductive additive is preferably 100 nm or less, more preferably 50 nm or less, from the viewpoint of increasing the number of conductive paths and enhancing the effect of suppressing the increase in resistance caused by the addition of the insulating material.
- a primary particle diameter is an average value of the particle diameter measured using the electron microscope.
- the porous carbon material for an electrode of the present invention includes a porous carbon material, an insulating material, and a conductive additive.
- the amount of the conductive additive is 0.25 to 15 parts by mass, preferably 0.5 to 12.5 parts by mass, more preferably 1 to 12.5 parts by mass with respect to 100 parts by mass of the insulating material.
- the amount of the conductive additive is lower than the predetermined range, the effect of suppressing the increase in resistance due to the addition of the insulating material is not sufficiently exhibited.
- the amount of the conductive additive exceeds the predetermined range, the effect of suppressing an increase in resistance due to the addition of the insulating material is reduced. Although the cause is not clear, this is considered to be because the dispersibility of the conductive additive is lowered.
- the porous carbon material for an electrode of the energy storage device of the present invention includes a porous carbon material, an insulating material, and a conductive additive, and the insulating material and the conductive additive are carried together on the porous carbon material. It is the porous carbon material for electrodes made.
- the conductive aid carried together suppresses the increase in resistance associated with the addition of insulating material, resulting in performance It is possible to obtain a porous carbon material for an electrode of an energy storage device that is excellent in durability such as a maintenance rate, has a small amount of gas generation, and can be used at a high potential.
- Examples of the state in which the insulating material and the conductive additive are supported together on the porous carbon material include, for example, a state in which the insulating material and the conductive auxiliary material exist as a mixture on the surface of the porous carbon material, It is conceivable that the conductive auxiliary material is embedded or dispersed in the insulating material spread on the surface of the material.
- the porous carbon material for an electrode of the energy storage device includes 0.5 to 5 parts by mass of an insulating material with respect to 100 parts by mass of the porous carbon material and 100 parts by mass of the insulating material. And 0.25 to 15 parts by mass of a conductive additive can be supported.
- the amount of the insulating material to be supported is preferably 0.7 to 4.5 parts by mass, more preferably 1 to 4 parts by mass with respect to 100 parts by mass of the porous carbon material.
- the amount of the conductive additive to be supported is preferably 0.5 to 12.5 parts by mass, more preferably 1 to 12.5 parts by mass with respect to 100 parts by mass of the porous carbon material.
- the supporting method is not particularly limited.
- an insulating material and a conductive additive are simultaneously added to and supported on a porous carbon material, or a mixture containing an insulating material and a conductive aid is added to and supported on a porous carbon material.
- a method in which a porous carbon material is immersed and supported in a mixture containing an insulating material and a conductive additive For example, it can be carried out by the following method using the stock solution or the solution.
- An insulating material stock solution or an insulating material diluted with a solvent and a conductive additive are simultaneously added to the porous carbon material, for example, by spraying, spraying, or the like. Add, stir and mix.
- An insulating material and a conductive additive are mixed in advance to prepare a mixed solution (adhesive stock solution), and the mixed solution is sprayed onto the porous carbon material, or the mixed solution is applied to the porous carbon material. In addition, stirring and mixing.
- a mixed solution adheresive stock solution
- Insulating material stock solution or an adding solution obtained by diluting an insulating material with a solvent and an adding solution obtained by diluting a conductive additive with a solvent are simultaneously added to the porous carbon material by, for example, spraying or the like.
- a spray may be used as the spraying device.
- the conductive additive may be added by spraying on the porous carbon material.
- a device for spraying for example, a powder coating device made of air blast or air spray, an electrostatic coating device, or the like may be used.
- a mixing / stirring device such as a double cone mixer, horizontal cylindrical mixer, rocking and rotating mixer, concrete mixer, etc. You can do it.
- spraying and spraying can be performed in an apparatus capable of stirring and heating such as a rotary kiln and then drying.
- the porous carbon material When soaking the stock solution or the stock solution, the porous carbon material may be added and soaked in the stock solution or the stock solution, and the solid may be separated and dried as necessary. From the viewpoint of ease of processing and the coexistence probability of the insulating material and the conductive additive, it is preferable to use the methods (2) and (4).
- the porous carbon material for electrodes of the energy storage device of the present invention can be manufactured by adding and loading an additive stock solution made of an insulating material and a conductive additive to the porous carbon material. It is also possible to dilute the adhering stock solution by mixing it with a solvent or a solvent containing a polymer compound described below and add it to the porous carbon material to carry it.
- the insulating material and conductive additive are dispersed to a certain degree uniformly in the mixed solution. This is preferable because it can be uniformly supported on the carbonaceous material.
- the mixed solution is made into an emulsion, or a polymer compound described below is added to the mixed solution.
- preparation of the mixed solution immediately before adding or spraying the porous material, or re-stirring immediately before adding or spraying, etc. may increase dispersion.
- the solvent is preferably removed by a drying treatment at 100 to 330 ° C.
- a solvent examples include water, alcohols such as ethanol, methanol, propanol, and butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, and cyclohexane.
- a solvent one type of solvent may be used alone, or two or more types may be used in combination. Among these, it is preferable to use water as a solvent from the viewpoint of the global environment and manufacturing safety.
- the method of dispersing the conductive additive in the adhering stock solution or the insulating material constituting the additive solution is not particularly limited as long as the conductive aid can be dispersed, and various dispersing devices can be used.
- a high-speed mixer that stirs with a high-speed rotating impeller, a roll mill that kneads between two or three rollers, a bead mill, a ball mill, or a material that exerts an effect by moving a hard ball in a predetermined container
- High-speed rotary shearing stirrer that simultaneously pulverizes and disperses
- high-pressure jet disperser that applies high pressure to the target suspension and performs dispersion emulsification by collision between liquids, ultrasonic emulsification disperser using ultrasonic waves, etc.
- These devices can be suitably used for dispersion and mixing of the insulating material and the conductive additive, and dispersion and mixing of the insulating material and / or the conductive additive and the solvent. It is also possible to use one type or two or more types of devices.
- a polymer compound can be added.
- the polymer compound is not particularly limited as long as it can exist chemically and electrochemically stably in the energy storage device, and can increase the dispersion of the insulating material and the conductive additive, or can increase the viscosity.
- cellulose derivatives sodium salt or ammonium salt of carboxymethyl cellulose (CMC)
- polyacrylic acid and polyacrylate polyethylene oxide and derivatives thereof.
- the polymer compound one of these may be used alone, or two or more may be used in combination.
- carboxymethylcellulose is preferable from the viewpoint of use in electrode materials.
- the amount of the polymer compound varies depending on the polymer compound to be used and is not particularly limited. However, considering the influence on the pores of a porous carbon material such as activated carbon, for example, as a solid content with respect to 100 parts by mass of the porous carbon material. The amount is preferably less than 5 parts by mass, and more preferably less than 2 parts by mass.
- the porous carbon material for an electrode of the energy storage device of the present invention may further carry a polymer compound together.
- the polymer compound is an additive that does not contribute to the storage capacity, it is preferable that the polymer compound is not supported. However, from the viewpoint of improving and maintaining the dispersibility of the conductive additive, it is together. It may be supported.
- the amount of the polymer compound in the porous carbon material for electrodes of the energy storage device of the present invention is based on 100 parts by mass of the porous carbon material in consideration of the influence on the pores of the porous carbon material such as activated carbon.
- the solid content is preferably less than 5 parts by mass, and more preferably less than 2 parts by mass.
- the porous carbon material for an electrode of the energy storage device of the present invention can be produced by drying the porous carbon material after supporting the insulating material and the conductive additive on the porous carbon material. Drying is an operation for removing moisture adsorbed on the porous carbon material or a solvent used when diluting the stock solution, for example, by heating the porous carbon material, It is possible to remove the water adsorbed on the solvent and the solvent used when diluting the stock solution. In addition to heating or instead of heating, for example, when drying by means such as reduced pressure, reduced pressure heating, freezing, etc., to dilute the moisture adsorbed on the porous carbon material and the adhering stock solution The solvent to be removed may be removed.
- Drying is preferably performed by heating at a temperature of 100 to 330 ° C., preferably for 0.1 to 24 hours.
- the drying temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and further preferably 120 ° C. or higher from the viewpoint of removing moisture adsorbed on the porous carbon material.
- the drying temperature is preferably 330 ° C. or lower, more preferably 300 ° C. or lower, and further preferably 250 ° C. or lower from the viewpoint of preventing the insulating material from being decomposed and volatilized by heating the insulating material. preferable.
- the drying time depends on the drying temperature employed, but is preferably 0.1 hours or more, more preferably 0.5 hours or more from the viewpoint of removing moisture adsorbed on the porous carbon material. More preferably, it is 1 hour or more. In terms of economy, it is preferably 24 hours or shorter, more preferably 12 hours or shorter, and even more preferably 6 hours or shorter.
- Drying can be performed under normal pressure or a reduced pressure atmosphere.
- it is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas or in an air atmosphere with a dew point of ⁇ 20 ° C. or lower.
- the porous carbon material for electrodes of the energy storage device of the present invention suppresses the adsorption of water and the decomposition of the electrolytic solution, suppresses the amount of gas generation, and has an excellent performance maintenance ratio and withstand voltage. Therefore, the porous carbon material for an electrode of the present invention can be suitably used as an electrode for an electric double layer capacitor or a lithium ion capacitor that requires high durability.
- the porous carbon material for an electrode of the present invention is used as an electrode, for example, the porous carbon material for an electrode of the present invention is pulverized so as to have an appropriate center particle diameter, and the pulverized porous carbon material for an electrode is used as a binder.
- the porous carbon material for an electrode of the present invention can be used as an additive for a positive electrode of a lithium ion battery, for example.
- the porous carbon material for an electrode of the present invention is used as an additive for an electrode, for example, it is pulverized to have an appropriate center particle diameter, and the pulverized porous carbon material for an electrode is used as a member constituting a lithium ion battery.
- the positive electrode can be manufactured by adding, mixing and molding.
- As the binder polytetrafluoroethylene “6J” manufactured by Mitsui DuPont Co., Ltd.
- a conductive adhesive 2 “HITASOL GA-703” manufactured by Hitachi Chemical Co., Ltd. was applied to an etching aluminum foil 3 obtained from Hosen Co., Ltd. so as to have a coating thickness of 100 ⁇ m.
- the tab 4 with the sealant 5 made from aluminum obtained from Hosen Co., Ltd. was welded to the etching aluminum foil 3 using an ultrasonic welding machine. After welding, vacuum drying was performed at 120 ° C. to obtain a polarizable electrode 6 including an aluminum current collector.
- an aluminum laminated resin sheet manufactured by Hosen Co., Ltd. is cut into a rectangle (length 200 mm ⁇ width 60 mm), folded in two, and one side ((1) in FIG. 4) remains by thermocompression bonding.
- a bag-shaped exterior sheet 7 having two open sides was prepared.
- an electrolyte solution was injected in a dry box in an argon atmosphere (dew point ⁇ 90 ° C. or less).
- an electrolytic solution a 1.5 mol / L triethylmethylammonium tetrafluoroborate propylene carbonate solution manufactured by Toyo Gosei Kogyo Co., Ltd. was used.
- the laminate was impregnated with the electrolyte in the exterior sheet 7, the remaining one side ((3) in FIG. 5) of the exterior sheet 7 was thermocompression bonded to produce the electric double layer capacitor 8 shown in FIG. .
- Resistance measurement was performed using an electrochemical measurement device (VSP manufactured by BioLogic). At 25 ° C and -30 ° C, a constant voltage alternating current impedance measurement method was used to give an amplitude range of 5 mV centered on 0 V, and a frequency of 4 mHz to 1 MHz. Measurement was carried out to obtain a Board-Plot (FIG. 6) showing the relationship between frequency and impedance. The difference in resistance value at 1 Hz and 1000 Hz in this Plot was determined as the resistance related to charge transfer (electrode reaction and ion adsorption / desorption), and the resistance values were compared. The results are shown in Table 3.
- the amount of gas generated is measured by measuring the dry weight of the measuring electrode cell and the weight in water, obtaining the cell volume from the generated buoyancy and water density, and calculating the gas volume calculated from the change in cell volume before and after the durability test. It was corrected by the temperature difference and obtained. That is, the amount of generated gas was determined by the following equation (2).
- the cell weight A represents the cell weight (g) in the air
- the cell weight W represents the cell weight (g) in the water.
- Example 1 Dimethyl silicone oil “KF-96-100CS”, one of siloxane compounds (manufactured by Shin-Etsu Chemical Co., Ltd., boiling point: 200 ° C. or more, volatile content at 150 ° C./24 h of 0.5 or less, kinematic viscosity: 100 mm 2 / s ) 2.00 parts by mass, Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd.) 0.02 parts by mass (corresponding to 1 part by mass with respect to 100 parts by mass of the insulating material) are mixed, and the thin film swirl type high-speed mixer The mixture was stirred with "40-40 type" (manufactured by Primex).
- siloxane compounds manufactured by Shin-Etsu Chemical Co., Ltd., boiling point: 200 ° C. or more, volatile content at 150 ° C./24 h of 0.5 or less, kinematic viscosity: 100 mm 2 / s ) 2.00 parts
- the obtained porous carbon material for an electrode was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then an electrode composition 1 was obtained according to the method for producing an electrode described above. Using this electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced according to the method for producing a measurement electrode cell described above. Various measurements were performed using the obtained electric double layer capacitor 8. Tables 1 to 3 show various physical property values of the obtained porous material for electrodes and measurement results of the obtained electric double layer capacitor.
- Example 2 Dimethyl silicone oil “KF-96-100CS” (2.00 parts by mass) and Denka Black 0.02 parts by mass (corresponding to 1 part by mass with respect to 100 parts by mass of the insulating material) were added to CMC “Serogen 7A” (Daiichi Kogyo Seiyaku). It was mixed with 0.50 part by mass of a 2% by weight aqueous solution (manufactured by Co., Ltd.) and stirred with a thin film swirl type high speed mixer “Filmix 40-40 type”. Furthermore, it mixed with ion-exchange water and stirred so that it might become 30.00 mass parts as a whole, and the addition liquid was prepared.
- Example 3 1.50 parts by weight of dimethyl silicone oil “KF-96-100CS”, Softener sill 10 which is an emulsion of dimethyl silicone oil (kinematic viscosity 100 mm 2 / s) (manufactured by Shin-Etsu Chemical Co., Ltd., nonvolatile content 30%, of which 2% is a mixture) 1.79 parts by mass and Denka Black 0.02 parts by mass (corresponding to 1 part by mass with respect to 100 parts by mass of the insulating material) were stirred with a thin film swirl type high-speed mixer “Filmix 40-40”. Further, the emulsion solution was prepared by mixing and stirring with ion-exchanged water so that the total amount was 40.00 parts by mass.
- Dimethyl silicone oil “KF-96-100CS”
- Softener sill 10 which is an emulsion of dimethyl silicone oil (kinematic viscosity 100 mm 2 / s) (manufactured by Shin-Etsu Chemical Co., Ltd.
- Example 4 A porous carbon material for an electrode was obtained in the same manner as in Example 2 except that the amount of dimethyl silicon oil was changed to 1.00 parts by mass (the amount of the conductive auxiliary material was 2 parts by mass with respect to 100 parts by mass of the insulating material). Equivalent to).
- the porous carbon material for electrodes after spraying and drying was 101.03 parts by mass.
- the obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. .
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 5 A porous carbon material for an electrode was obtained in the same manner as in Example 2 except that the amount of dimethylsilicone oil was changed to 3.00 parts by mass (the amount of conductive additive was 0.67 parts by mass with respect to 100 parts by mass of the insulating material). Part)).
- the porous carbon material for electrodes after spraying and drying was 103.03 parts by mass.
- the obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. .
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 6 A porous carbon material for an electrode was obtained in the same manner as in Example 2 except that the amount of dimethyl silicon oil was changed to 5.00 parts by mass (the amount of conductive auxiliary was 0.40 parts by mass with respect to 100 parts by mass of the insulating material). Part)).
- the porous carbon material for an electrode after spraying and drying was 105.03 parts by mass.
- the obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. .
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 7 A porous carbon material for electrodes was obtained in the same manner as in Example 1 except that dimethyl silicone oil “KF96-100CS” was changed to “KF96L-2CS” (boiling point: 230 ° C., kinematic viscosity: 2 mm 2 / s). .
- the porous carbon material for electrodes after spraying and drying was 102.02 parts by mass.
- the obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. .
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 8 Example 1 except that dimethyl silicone oil “KF96-100CS” was changed to “KF96-50CS” (boiling point: 200 ° C. or higher, volatile content at 150 ° C./24 h of 0.5 or lower, kinematic viscosity: 50 mm 2 / s) Similarly, a porous carbon material for an electrode was obtained. In Example 8, the porous carbon material for an electrode after spraying and drying was 102.06 parts by mass. The obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. . Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 9 Except for changing dimethyl silicone oil “KF-96-100CS” to “KF-96-1000CS” (boiling point: 200 ° C. or more, volatile content 0.5 or less at 150 ° C./24 h, kinematic viscosity: 1000 mm 2 / s)
- an electrode porous carbon material was obtained.
- the porous carbon material for electrodes after spraying and drying was 102.02 parts by mass.
- the obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. .
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 10 A porous carbon material for electrodes was obtained in the same manner as in Example 2 except that the amount of Denka black was changed to 0.05 parts by mass (corresponding to 2.5 parts by mass with respect to 100 parts by mass of the insulating material).
- the porous carbon material for an electrode after spraying and drying was 102.06 parts by mass.
- the obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. .
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 11 A porous carbon material for electrodes was obtained in the same manner as in Example 2 except that the amount of Denka black was changed to 0.20 parts by mass (corresponding to 10 parts by mass with respect to 100 parts by mass of the insulating material).
- the porous carbon material for an electrode after spraying and drying was 102.21 parts by mass.
- the obtained porous carbon material was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1.
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 12 A porous carbon material for an electrode was obtained in the same manner as in Example 1 except that the coconut shell granular activated carbon manufactured by Kuraray Chemical Co., Ltd. was changed to one having a BET specific surface area of 1450 m 2 / g.
- the porous carbon material for electrodes after spraying and drying was 102.02 parts by mass.
- the obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. .
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 13 A porous carbon material for an electrode was obtained in the same manner as in Example 1 except that the coconut shell granular activated carbon manufactured by Kuraray Chemical Co., Ltd. was changed to one having a BET specific surface area of 1862 m 2 / g.
- the porous carbon material for an electrode after spraying and drying was 102.02 parts by mass.
- the obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. .
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 14 A porous carbon material for an electrode was obtained in the same manner as in Example 1 except that the coconut shell granular activated carbon manufactured by Kuraray Chemical Co., Ltd. was changed to one having a BET specific surface area of 2069 m 2 / g.
- the porous carbon material for electrodes after spraying and drying was 102.02 parts by mass.
- the obtained porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1. .
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 15 In the same manner as in Example 2, a porous carbon material for electrodes and a polarizable electrode 6 were obtained. In place of the 1.5 mol / L triethylmethylammonium tetrafluoroborate propylene carbonate solution as the electrolytic solution, 1.0 mol / L tetraethylammonium tetrafluoroborate acetonitrile solution “LIPASTE” manufactured by Toyama Pharmaceutical Co., Ltd. An electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced in the same manner as in Example 1 except that “-AN / EAF1” was used. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 16 In the same manner as in Example 11, a porous carbon material for electrodes and a polarizable electrode 6 were obtained. In place of the 1.5 mol / L triethylmethylammonium tetrafluoroborate propylene carbonate solution as the electrolytic solution, 1.0 mol / L tetraethylammonium tetrafluoroborate acetonitrile solution “LIPASTE” manufactured by Toyama Pharmaceutical Co., Ltd. An electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced in the same manner as in Example 1 except that “-AN / EAF1” was used. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 1 The electrode composition 1 and the polarizable electrode were used in the same manner as in Example 1, using the pulverized coconut shell granular activated carbon produced in Kuraray Chemical Co., Ltd. used in Example 1 without spraying the impregnating solution on the activated carbon. 6 and electric double layer capacitor 8 were produced. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 2 Using Kuraray Chemical Co., Ltd., the coconut shell granular activated carbon was changed to one with a BET specific surface area of 1290 m 2 / g, and pulverized coconut shell granular activated carbon was used as it was without spraying the additive liquid on the activated carbon. In the same manner as in Example 1, an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 3 Using Kuraray Chemical Co., Ltd., the coconut shell granular activated carbon was changed to one with a BET specific surface area of 1450 m 2 / g, and pulverized coconut shell granular activated carbon was used as it was without spraying the impregnating liquid on the activated carbon. In the same manner as in Example 1, an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Reference example 4 Example: Using Kuraray Chemical Co., Ltd., coconut shell granular activated carbon with a BET specific surface area of 1862 m 2 / g, and pulverizing coconut shell granular activated carbon as it is without spraying the adsorbent on the activated carbon.
- an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced.
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 1 Using Kuraray Chemical Co., Ltd., the coconut shell granular activated carbon was changed to one with a BET specific surface area of 2069 m 2 / g. In the same manner as in Example 1, an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Example 6 Using Kuraray Chemical Co., Ltd., coconut shell granular activated carbon with a BET specific surface area of 2224 m 2 / g, and pulverizing coconut shell granular activated carbon as it is without spraying the adsorbent on the activated carbon. In the same manner as in Example 1, an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Comparative Example 1 A porous carbon material for an electrode was obtained in the same manner as in Example 1 except that Denka black was omitted.
- the electrode porous carbon material after spraying and drying was 102.00 parts by mass.
- the porous carbon material for electrodes was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then the electrode composition 1, the polarizable electrode 6 and the electric double layer capacitor 8 were produced in the same manner as in Example 1.
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Comparative Example 2 A porous carbon material for an electrode was obtained in the same manner as in Example 2 except that the amount of dimethyl silicon oil “KF-96-100CS” was changed to 0.30 parts by mass (the amount of conductive auxiliary material was 100 mass of insulating material). Equivalent to 6.67 parts by weight).
- the electrode porous carbon material after spraying and drying was 100.33 parts by mass.
- the obtained porous carbon material for an electrode was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced in the same manner as in Example 1.
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Comparative Example 3 A porous carbon material for an electrode was obtained in the same manner as in Example 2 except that the amount of dimethyl silicon oil was changed to 7.00 parts by mass (the amount of conductive auxiliary was 0.29 parts by mass with respect to 100 parts by mass of the insulating material). Part)).
- the electrode porous carbon material after spraying and drying was 107.03 parts by mass.
- the obtained porous carbon material for an electrode was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced in the same manner as in Example 1.
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Comparative Example 4 In the same manner as in Example 1, except that dimethyl silicon oil “KF-96-100CS” was changed to “KF-96L-0.65CS” (boiling point: 100 ° C., kinematic viscosity: 0.65 mm 2 / s). A porous carbon material was obtained. In Comparative Example 3, the electrode porous carbon material after spraying and drying was 100.42 parts by mass. The obtained porous carbon material for an electrode was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced in the same manner as in Example 1. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Comparative Example 5 A porous carbon material for electrodes was obtained in the same manner as in Example 2 except that the amount of Denka black was changed to 0.002 parts by mass (corresponding to 0.1 parts by mass with respect to 100 parts by mass of the insulating material). In Comparative Example 5, the porous carbon material for electrodes after spraying and drying was 102.12 parts by mass. The obtained porous carbon material for an electrode was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced in the same manner as in Example 1. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Comparative Example 6 A porous carbon material for electrodes was obtained in the same manner as in Example 2 except that the amount of Denka black was changed to 0.40 parts by mass (corresponding to 20 parts by mass with respect to 100 parts by mass of the insulating material). In Comparative Example 6, the electrode porous carbon material after spraying and drying was 102.41 parts by mass. The obtained porous carbon material for an electrode was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced in the same manner as in Example 1. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Comparative Example 7 A porous carbon material for an electrode was obtained in the same manner as in Example 1 except that the coconut shell granular activated carbon manufactured by Kuraray Chemical Co., Ltd. was changed to one having a BET specific surface area of 2224 m 2 / g.
- the electrode porous carbon material after spraying and drying was 102.02 parts by mass.
- the obtained porous carbon material for an electrode was finely pulverized so as to have a center particle diameter of 6 ⁇ m, and then an electrode composition 1, a polarizable electrode 6 and an electric double layer capacitor 8 were produced in the same manner as in Example 1.
- Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- Comparative Example 8 A porous carbon material for electrode, electrode composition 1 and polarizable electrode 6 were obtained in the same manner as in Example 2 except that Denka black was removed. Then, an electric double layer capacitor was obtained in the same manner as in Example 1 except that 1.0 mol / L tetraethylammonium tetrafluoroborate acetonitrile solution “LIPASTE-AN / EAF1” manufactured by Toyama Pharmaceutical Co., Ltd. was used as the electrolyte. 8 was produced. Various measurements were performed in the same manner as in Example 1. The measurement results are shown in Tables 1 to 3.
- the deterioration of the capacitor is caused by deterioration of the constituent members (electrode, electrolyte, binder, etc.) of the capacitor due to an electrochemical reaction.
- the following reactions can be considered.
- (3) SEI (Solid electrolyte interface) coating at electrode interface Changes in pore diameter or pore closure due to the formation of (4) decomposition of residual moisture, oxidation of surface functional groups contained in the porous carbon material, and generation of gas due to deterioration of the electrolyte solution.
- the deterioration of the capacitor is caused such as an increase in the capacitance, a decrease in the capacitance, and expansion of the cell due to gas generation.
- the viscosity of the electrolyte increases due to the low temperature, and electrode material, electrode interface degradation and / or electrolyte degradation, etc. It is thought that it is reflected remarkably.
- an endurance test 60 ° C, 3V load for a predetermined time
- the subsequent deterioration state is evaluated at -30 ° C. Compared to the center.
- the electric double layer capacitor produced by the polarizable electrode using the porous carbon material for an electrode of the present invention has a porous carbon material and an insulating material as a base material for the porous carbon material for an electrode. Compared with an electric double layer capacitor produced using a porous carbon material for electrodes containing only the material, it has an initial capacitance equal to or higher than that at 25 ° C. and ⁇ 30 ° C. When an insulating material is supported on the porous carbon material, the pores of the porous carbon material are blocked by the insulating material, and the capacitance is reduced.
- the electric double layer capacitor manufactured by the polarizable electrode using the porous carbon material for an electrode of the present invention hardly has such a decrease in capacitance. Furthermore, a high capacity retention rate is exhibited even after the durability test, and the generation of gas is also suppressed. Moreover, as shown in Table 3, the electric double layer capacitor produced from the polarizable electrode using the porous carbon material for an electrode of the present invention has an increase in resistance and is greatly improved in durability. From these facts, it is clear that when the porous carbon material for an electrode of the present invention is used for an electrode, an energy storage device having excellent durability can be obtained.
- FIG. 6 shows the relationship between the frequency and the resistance value of the porous carbon material for an electrode and the porous carbon material used as the substrate of the porous carbon material for an electrode in constant voltage AC impedance measurement at ⁇ 30 ° C. Represent (Bode-Plot diagram).
- charge transfer electrowetting reaction and ion adsorption / desorption
- the difference between 1 Hz and 1000 Hz was determined as the resistance related to charge transfer.
- the interface resistance electrical resistance
- Example 1 when Comparative Example 1 and Example 1 containing the same amount of insulating material and conductive additive in the test electrode are compared, since Example 1 has a smaller resistance than Comparative Example 1, it is porous. It can be seen that the increase in resistance is suppressed when the porous carbon material for an electrode contains the insulating material and the conductive additive, rather than adding the conductive additive after the insulating material is supported on the carbon material.
- FIGS. 7 and 8 show the specific surface area of the electrode porous carbon material or the porous carbon material used as the base material for the electrode, and the volume of the electrode measured at 25 ° C. or ⁇ 30 ° C. after the durability test. The relationship between the per-capacitance and the difference in resistance component at 1 Hz and 1000 Hz is shown.
- the plots related to the electrode porous carbon material are Example 12, Example 1, Example 13, Example 14, in order from the one with the lowest specific surface area of the electrode porous carbon material. This corresponds to Comparative Example 7.
- the plot regarding porous carbon material (unsupported) is the reference example 2, the reference example 3, the reference example 1, the reference example 4, the reference example 5, and the reference example 6 in an order from the thing with the low specific surface area of a porous carbon material. It corresponds to.
- the porous carbon material (the insulating material and the conductive auxiliary material are not carried) included in the porous carbon material for electrodes of the above-described Example 12, Example 1, Example 13, Example 14, and Comparative Example 7 was used.
- the electrodes prepared in this manner correspond to Reference Example 3, Reference Example 1, Reference Example 4, Reference Example 5, and Reference Example 6, respectively. 7 and 8, when the specific surface area of the porous carbon material is less than 1300 m 2 / g, the capacitance is rapidly decreased.
- the retention rate of the capacitance increases as the specific surface area of the porous carbon material for electrodes increases, but from FIG. 7, when the specific surface area exceeds 2050 m 2 / g, 25 ° C.
- the electrostatic capacity is reduced, and further, the effect of supporting the insulating material and the conductive additive is not obtained. From these facts, it is understood that when the specific surface area is less than 1300 m 2 / g, sufficient capacity cannot be obtained due to clogging of the pores, and when it exceeds 2050 m 2 / g, the effect of increasing the electrostatic capacity cannot be obtained. .
- the amount of the insulating material when the amount of the insulating material is 0.5 to 5 parts by mass with respect to 100 parts by mass of the porous carbon material, a high performance maintenance rate and a gas generation amount suppressing effect can be obtained. Can do. If the amount of the insulating material is lower than 0.5 parts by mass with respect to 100 parts by mass of the porous carbon material, the effect of suppressing gas generation, the performance maintaining rate, and the effect of suppressing increase in resistance are not sufficient. On the other hand, if the amount of the insulating material is more than 5 parts by mass with respect to 100 parts by mass of the porous carbon material, the gas generation suppression effect is saturated, while the pores of the porous carbon material are blocked, resulting in electrostatic capacitance. In addition, the performance maintenance rate decreases.
- Comparative Example 4 having the lowest kinematic viscosity shown in FIGS. 12 and 13 is a comparative example using an insulating material having a boiling point of less than 150 ° C.
- Examples 1 and 7 to 9 using an insulating material having a boiling point of 150 ° C. or higher a high performance maintenance ratio and an effect of suppressing gas generation can be obtained. From FIG. 12 and FIG. 13, when the boiling point is less than 150 ° C., the amount of the insulating material carried by the insulating material is volatilized by the temperature of drying or the like when the electrode is produced using the porous carbon material for an electrode. Decrease, the effect is reduced.
- the kinematic viscosity is preferably 1000 mm 2 / s or less because the viscosity can be supported thinly and uniformly without being too high, and a high capacitance can be obtained without blocking the pores of the porous carbon material. I understand that.
- the amount of the conductive additive is lower than 0.25 parts by mass with respect to 100 parts by mass of the insulating material added at the same time, the number of conductive paths cannot be increased, and the effect of suppressing increase in resistance is not exhibited. If the amount of the conductive additive is more than 15 parts by mass with respect to 100 parts by mass of the insulating material added at the same time, the ratio of the conductive additive is increased and the dispersibility is lowered, so that a sufficient effect cannot be obtained.
- the present invention provides 0.5 to 5 parts by mass of an insulating material having a boiling point of 150 ° C. or higher with respect to 100 parts by mass of the porous carbon material, and 0 to 100 parts by mass of the insulating material.
- Energy storage having a BET specific surface area of 1300 to 2050 m 2 / g, comprising 25 to 15 parts by mass of a conductive additive, the insulating material and the conductive additive being supported together on the porous carbon material
- the conductive additive carried together suppresses the increase in resistance caused by the addition of insulating material, has excellent durability such as performance maintenance rate, has low gas generation, and can be used at high potential. A storage device can be obtained.
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Abstract
Description
本発明は、耐久性の向上、ガス発生の抑制および耐電圧の向上に有効なエネルギー貯蔵デバイス用多孔質炭素材料およびその製造方法に関する。
〔1〕多孔質炭素材料、
該多孔質炭素材料100質量部に対して0.5~5質量部の、150℃以上の沸点を有する絶縁材、および、
該絶縁材100質量部に対して0.25~15質量部の導電助材
を含み、該多孔質炭素材料に、該絶縁材および該導電助材が一緒になって担持された、1300~2050m2/gのBET比表面積を有する、エネルギー貯蔵デバイスの電極用多孔質炭素材料。
〔2〕前記絶縁材の25℃における動粘度が1~1000mm2/sである、前記〔1〕に記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料。
〔3〕前記絶縁材の流動点は-30℃以下である、前記〔1〕または〔2〕に記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料。
〔4〕前記絶縁材は主鎖にシロキサン単位を有するシロキサン化合物である、前記〔1〕~〔3〕のいずれかに記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料。
〔5〕さらに高分子化合物が一緒になって担持された、前記〔1〕~〔4〕のいずれかに記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料。
〔6〕1300~2050m2/gのBET比表面積を有する、エネルギー貯蔵デバイスの電極用多孔質炭素材料の製造方法であって、多孔質炭素材料に、該多孔質炭素材料100質量部に対して0.5~5質量部の、150℃以上の沸点を有する絶縁材、および、該絶縁材100質量部に対して0.25~15質量部の導電助材を担持させる、製造方法。
〔7〕多孔質炭素材料に絶縁材および導電助材を添加して担持させる、前記〔6〕に記載の製造方法。
〔8〕多孔質炭素材料に絶縁材および導電助材を含む混合物を添加して担持させる、前記〔6〕に記載の製造方法。
〔9〕多孔質炭素材料を絶縁材および導電助材を含む混合物に浸漬させて担持させる、前記〔6〕に記載の製造方法。
〔10〕前記混合物はさらに高分子化合物を含有する、前記〔8〕または〔9〕に記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料の製造方法。
(1)絶縁材の添着原液または絶縁材を溶媒で希釈した添着液と、導電助材とを、多孔質炭素材料に対して例えば噴霧、吹付け等により同時に添加するか、多孔質炭素材料に添加して撹拌・混合する方法。
(2)絶縁材および導電助材を予め混合して混合液(添着原液)を調製し、該混合液を多孔質炭素材料に対して噴霧するか、または、該混合液を多孔質炭素材料に加えて撹拌・混合する方法。
(3)絶縁材の添着原液または絶縁材を溶媒で希釈した添着液と、導電助材を溶媒で希釈した添着液とを、多孔質炭素材料に対して例えば噴霧等により同時に添加するか、多孔質炭素材料に添加して撹拌・混合するか、または多孔質炭素材料を所定量の絶縁材を溶媒で希釈した添着液および所定量の導電助材を溶媒で希釈した添着液の混合物に浸漬させる方法。なお、溶媒は、必要に応じて乾燥させてよい。
(4)絶縁材、導電助材および溶媒を予め混合して得た添着液を、多孔質炭素材料に対して噴霧等により添加するか、多孔質炭素材料に添加して撹拌・混合するか、または該添着液に多孔質炭素材料を浸漬させる方法。なお、必要に応じて溶媒を乾燥させてよい。
これらの装置は絶縁材と導電助材との分散、混合、および、絶縁材および/または導電助材と溶媒等との分散、混合に好適に使用することが可能である。1種または2種以上の装置を利用することも可能である。
日本ベル株式会社製のBELSORP-miniを使用し、活性炭または炭素材料を窒素気流下(窒素流量:50mL/分)にて120℃で3時間加熱した後、77Kにおける活性炭および炭素材料の窒素吸着等温線を測定した。得られた吸着等温線からBET式により多点法による解析を行い、得られた曲線の相対圧p/p0=0.01~0.1の領域での直線から比表面積を算出した。
JIS K2283(2000年)に基づいて、25℃で測定した。測定装置としては、ウベローデ粘度計を使用した。
電極構成部材である電極用多孔質炭素材料、バインダーおよび導電助材を、事前に120℃、減圧(0.1KPa以下)の雰囲気にて16時間以上減圧乾燥を行い使用した。
電極用多孔質炭素材料、導電助材およびバインダーを、(電極用多孔質炭素材料に含まれる多孔質炭素材料および絶縁材の質量):(電極用多孔質炭素材料に含まれる導電助材の質量+電極作成時に添加した導電助材の質量):バインダーの質量の比が81:9:10となるように秤量し、混錬した。上記バインダーとしては、三井・デュポン株式会社製のポリテトラフルオロエチレン「6J」を使用し、上記導電助材としては、電気化学工業株式会社製の導電性カーボンブラック「デンカブラック粒状」を使用した。混錬した後、さらに均一化を図る為、1mm角以下のフレーク状にカットし、コイン成形機にて400Kg/cm2の圧力を与え、コイン状の二次成形物を得た。得られた二次成形物をロールプレス機により160μm±5%の厚みのシート状に成形した後、所定の大きさ(3cm×3cm)に切り出し、図1に示すような電極組成物1を作製した。そして、得られた電極組成物1を120℃、減圧雰囲気下で16時間以上乾燥した後、重量、シート厚みおよび寸法を計測し、以下の測定に用いた。なお、電極用多孔質炭素材料の作成については、それぞれの実施例および比較例について後述する。また、表1に電極用多孔質材料の組成を示す。
図2に示すように、宝泉株式会社より入手したエッチングアルミニウム箔3に日立化成工業株式会社製の導電性接着剤2「HITASOL GA-703」を塗布厚が100μmになるように塗布した。そして、図3に示すように、導電性接着剤2が塗布されたエッチングアルミニウム箔3と先にカットしておいたシート状の電極組成物1とを接着した。そして、宝泉株式会社より入手したアルミニウム製のシーラント5付きタブ4をエッチングアルミニウム箔3に超音波溶接機を用いて溶接した。溶接後、120℃で真空乾燥し、アルミニウム製の集電体を備える分極性電極6を得た。
得られた電気二重層キャパシタ8を菊水電子工業株式会社製の「CAPACITOR TESTER PFX2411」を用いて、25℃および-30℃において、到達電圧3.0Vまで、電極表面積あたり200mAで定電流充電し、さらに、3.0Vで30分、定電圧下補充電し、補充電完了後、25mAで放電した。得られた放電曲線データをエネルギー換算法で算出し静電容量(F)とした。具体的には、充電の後電圧がゼロになるまで放電し、このとき放電した放電エネルギーから静電容量(F)を計算した。そして、電極体積あたりで割った静電容量(F/cc)を求めた。その結果を表2に示す。
耐久性試験は先に記述した静電容量測定後、60℃の恒温槽中にて3.0Vの電圧を印加しながら400時間保持した後で、上記と同様にして25℃および-30℃において静電容量測定を行った。耐久試験前後の静電容量から、次の式(1)に従いそれぞれの温度についての容量維持率を求めた。60℃の恒温槽中にて3.0Vの電圧を印加しながら400時間保持する前を耐久試験前とし、400時間保持した後を耐久試験後とした。その結果を表2に示す。
抵抗測定は電気化学測定装置(BioLogic社製 VSP)を用い、25℃および-30℃において、定電圧交流インピ-ダンス測定法にて0Vを中心に5mVの振幅幅を与え、4mHzから1MHzの周波数にて測定を実施し、周波数とインピーダンスの関係を示すBode-Plot(図6)を得た。本Plotにおける1Hzおよび1000Hzにおける抵抗値の差を電荷移動(電極反応およびイオン吸脱着)にかかわる抵抗として求め、抵抗値を比較した。その結果を表3に示す。
発生したガス量は、測定電極セルの乾燥重量と水中の重量を測り、発生した浮力および水の密度からセル体積を求め、耐久試験前後のセル体積の変化から算出したガス体積量を測定時の温度差で補正し、求めた。すなわち、発生したガス量は以下の式(2)で求めた。なお、式(2)中、セル重量Aとは空気中でのセル重量(g)を表し、セル重量Wとは水中でのセル重量(g)を表す。
シロキサン化合物の1種であるジメチルシリコンオイル「KF-96-100CS」(信越化学工業株式会社製、沸点:200℃以上、150℃/24hにおける揮発分0.5以下、動粘度:100mm2/s)2.00質量部、デンカブラック(電気化学工業株式会社製)0.02質量部(絶縁材100質量部に対して1質量部に相当する)を混合し、薄膜旋回型高速ミキサー「フィルミックス40-40型」(プライミクス社製)にて攪拌した。さらに、1時間超音波振動を与えて均一分散させ、添着液を調製した。
この添着液を、クラレケミカル株式会社製の椰子殻粒状活性炭(BET比表面積:1630m2/g、粒径:10メッシュのふるいを通過し、60メッシュのふるいを通過しない活性炭が98重量%以上、強熱残分:0.17%)100質量部に、スプレーを使用して噴霧した。その後得られた炭素材料を120℃で16時間乾燥し、102.02質量部の電極用多孔質炭素材料を得た。得られた電極用多孔質炭素材料を用い各種物性を測定した。
ジメチルシリコンオイル「KF-96-100CS」2.00質量部、デンカブラック0.02質量部(絶縁材100質量部に対し1質量部に相当する)を、CMC「セロゲン7A」(第一工業製薬株式会社製)2質量%水溶液0.50質量部と混合し、薄膜旋回型高速ミキサー「フィルミックス40-40型」にて攪拌した。さらに全体で30.00質量部となるようイオン交換水と混合、攪拌し、添着液を調製した。この溶液を、実施例1と同様に椰子殻粒状活性炭100質量部に噴霧した。その後、得られた炭素材料を120℃、減圧雰囲気下で16時間以上真空乾燥し、102.03質量部の電極用多孔質炭素材料を得た。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
ジメチルシリコンオイル「KF-96-100CS」1.50質量部、ジメチルシリコンオイル(動粘度100mm2/s)のエマルジョンであるソフナーシル10(信越化学工業株式会社製、不揮発分30%、うち混合物2%と記載)1.79質量部、デンカブラック0.02質量部(絶縁材100質量部に対し1質量部に相当する)を、薄膜旋回型高速ミキサー「フィルミックス40-40型」にて攪拌し、さらに全体で40.00質量部となるようイオン交換水と混合、攪拌し、エマルジョン溶液を調製した。この溶液を、実施例1と同様に椰子殻粒状活性炭100質量部に噴霧した。その後得られた炭素材料を120℃で16時間乾燥し、102.06質量部の電極用多孔質炭素材料を得た。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
ジメチルシリコンオイルの量を1.00質量部に変更した以外は、実施例2と同様にして電極用多孔質炭素材料を得た(導電助材量は絶縁材100質量部に対し2質量部に相当する)。実施例4において、噴霧、乾燥後の電極用多孔質炭素材料は101.03質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
ジメチルシリコンオイルの量を3.00質量部に変更した以外は実施例2と同様にして、電極用多孔質炭素材料を得た(導電助材量は絶縁材100質量部に対し0.67質量部に相当する)。実施例5において、噴霧、乾燥後の電極用多孔質炭素材料は103.03質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
ジメチルシリコンオイルの量を5.00質量部に変更した以外は実施例2と同様にして、電極用多孔質炭素材料を得た(導電助材量は絶縁材100質量部に対し0.40質量部に相当する)。実施例6において、噴霧、乾燥後の電極用多孔質炭素材料は105.03質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
ジメチルシリコンオイル「KF96-100CS」を「KF96L-2CS」(沸点:230℃、動粘度:2mm2/s)に変更した以外は実施例1と同様にして、電極用多孔質炭素材料を得た。実施例7において、噴霧、乾燥後の電極用多孔質炭素材料は102.02質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
ジメチルシリコンオイル「KF96-100CS」を「KF96-50CS」(沸点:200℃以上、150℃/24hにおける揮発分0.5以下、動粘度:50mm2/s)に変更した以外は実施例1と同様にして、電極用多孔質炭素材料を得た。実施例8において、噴霧、乾燥後の電極用多孔質炭素材料は102.06質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
ジメチルシリコンオイル「KF-96-100CS」を「KF-96-1000CS」(沸点:200℃以上、150℃/24hにおける揮発分0.5以下、動粘度:1000mm2/s)に変更した以外は実施例1と同様にして、電極用多孔質炭素材料を得た。実施例9において、噴霧、乾燥後の電極用多孔質炭素材料は102.02質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
デンカブラックの量を0.05質量部(絶縁材100質量部に対し2.5質量部に相当する)に変更した以外は実施例2と同様にして、電極用多孔質炭素材料を得た。実施例10において、噴霧、乾燥後の電極用多孔質炭素材料は102.06質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
デンカブラックの量を0.20質量部(絶縁材100質量部に対し10質量部に相当する)に変更した以外は実施例2と同様にして、電極用多孔質炭素材料を得た。実施例11において、噴霧、乾燥後の電極用多孔質炭素材料は102.21質量部であった。得られた多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
クラレケミカル株式会社製の椰子殻粒状活性炭をBET比表面積が1450m2/gのものに変更した以外は、実施例1と同様にして電極用多孔質炭素材料を得た。実施例12において、噴霧、乾燥後の電極用多孔質炭素材料は102.02質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
クラレケミカル株式会社製の椰子殻粒状活性炭をBET比表面積が1862m2/gのものに変更した以外は実施例1と同様にして、電極用多孔質炭素材料を得た。実施例13において、噴霧、乾燥後の電極用多孔質炭素材料は102.02質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
クラレケミカル株式会社製の椰子殻粒状活性炭をBET比表面積が2069m2/gのものに変更した以外は実施例1と同様にして、電極用多孔質炭素材料を得た。実施例14において、噴霧、乾燥後の電極用多孔質炭素材料は102.02質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
実施例2と同様にして、電極用多孔質炭素材料および分極性電極6を得た。そして電解液として、1.5mol/Lのトリエチルメチルアンモニウム・テトラフルオロボレートのプロピレンカーボネート溶液に代えて、富山薬品工業株式会社製の1.0mol/Lのテトラエチルアンモニウム・テトラフルオロボレートのアセトニトリル溶液「LIPASTE-AN/EAF1」を用いた以外は実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
実施例11と同様にして、電極用多孔質炭素材料および分極性電極6を得た。そして電解液として、1.5mol/Lのトリエチルメチルアンモニウム・テトラフルオロボレートのプロピレンカーボネート溶液に代えて、富山薬品工業株式会社製の1.0mol/Lのテトラエチルアンモニウム・テトラフルオロボレートのアセトニトリル溶液「LIPASTE-AN/EAF1」を用いた以外は実施例1と同様にして、電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
活性炭に添着液を噴霧することなく、実施例1で用いたクラレケミカル株式会社製の椰子殻粒状活性炭を粉砕したものをそのまま用いて、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
クラレケミカル株式会社製の椰子殻粒状活性炭をBET比表面積が1290m2/gのものに変更し、活性炭に添着液を噴霧することなく、椰子殻粒状活性炭を粉砕したものをそのまま用いて、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
クラレケミカル株式会社製の椰子殻粒状活性炭をBET比表面積が1450m2/gのものに変更し、活性炭に添着液を噴霧することなく、椰子殻粒状活性炭を粉砕したものをそのまま用いて、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
クラレケミカル株式会社製の椰子殻粒状活性炭をBET比表面積が1862m2/gのものに変更し、活性炭に添着液を噴霧することなく、椰子殻粒状活性炭を粉砕したものをそのまま用いて、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
クラレケミカル株式会社製の椰子殻粒状活性炭をBET比表面積が2069m2/gのものに変更し、活性炭に添着液を噴霧することなく、椰子殻粒状活性炭を粉砕したものをそのまま用いて、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
クラレケミカル株式会社製の椰子殻粒状活性炭をBET比表面積が2224m2/gのものに変更し、活性炭に添着液を噴霧することなく、椰子殻粒状活性炭を粉砕したものをそのまま用いて、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
参考例1と同様にして、電極組成物1および分極性電極6を得た。そして電解液として、1.5mol/Lのトリエチルメチルアンモニウム・テトラフルオロボレートのプロピレンカーボネート溶液に代えて、富山薬品工業株式会社製の1.0mol/Lのテトラエチルアンモニウム・テトラフルオロボレートのアセトニトリル溶液「LIPASTE-AN/EAF1」を用いたこと以外は実施例1と同様にして、電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
デンカブラックを除いたこと以外は実施例1と同様にして、電極用多孔質炭素材料を得た。比較例1において、噴霧、乾燥後の電極用多孔質炭素材料は102.00質量部であった。この電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
ジメチルシリコンオイル「KF-96-100CS」の量を0.30質量部に変更した以外は実施例2と同様にして、電極用多孔質炭素材料を得た(導電助材量は絶縁材100質量部に対し6.67質量部に相当する)。比較例2において、噴霧、乾燥後の電極用多孔質炭素材料は100.33質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
ジメチルシリコンオイルの量を7.00質量部に変更した以外は実施例2と同様にして、電極用多孔質炭素材料を得た(導電助材量は絶縁材100質量部に対し0.29質量部に相当する)。比較例3において、噴霧、乾燥後の電極用多孔質炭素材料は107.03質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。測定結果を表1~3に示す。
ジメチルシリコンオイル「KF-96-100CS」を「KF-96L-0.65CS」(沸点:100℃、動粘度:0.65mm2/s)に変更した以外は実施例1と同様にして、電極用多孔質炭素材料を得た。比較例3において、噴霧、乾燥後の電極用多孔質炭素材料は100.42質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
デンカブラックの量を0.002質量部(絶縁材100質量部に対し0.1質量部に相当する)に変更した以外は実施例2と同様にして、電極用多孔質炭素材料を得た。比較例5において、噴霧、乾燥後の電極用多孔質炭素材料は102.012質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
デンカブラックの量を0.40質量部(絶縁材100質量部に対し20質量部に相当する)に変更した以外は、実施例2と同様にして電極用多孔質炭素材料を得た。比較例6において、噴霧、乾燥後の電極用多孔質炭素材料は102.41質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
クラレケミカル株式会社製の椰子殻粒状活性炭をBET比表面積が2224m2/gのものに変更した以外は実施例1と同様にして、電極用多孔質炭素材料を得た。比較例7において、噴霧、乾燥後の電極用多孔質炭素材料は102.02質量部であった。得られた電極用多孔質炭素材料を中心粒径が6μmになるように微粉砕した後、実施例1と同様にして電極組成物1、分極性電極6および電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
デンカブラックを除いたこと以外は実施例2と同様にして、電極用多孔質炭素材料、電極組成物1および分極性電極6を得た。そして電解液として富山薬品工業株式会社製の1.0mol/Lのテトラエチルアンモニウム・テトラフルオロボレートのアセトニトリル溶液「LIPASTE-AN/EAF1」を用いた以外は実施例1と同様にして、電気二重層キャパシタ8を作製した。そして実施例1と同様の方法で各種測定を実施した。各測定結果を表1~3に示す。
キャパシタの性能評価として耐久性の評価を行う場合、一般的には、常温(25℃)での容量や抵抗の評価を加速試験の前後で行い、その変化を測定する。しかしながら常温での評価では劣化現象を確認する為に長期にわたる加速試験を必要とする(たとえば60℃の電圧負荷試験であれば2000時間程度)。低温下で容量や抵抗の評価を行うことにより、常温で評価を行う場合と比較して、劣化現象を早期に比較・確認することが可能である。ここで、キャパシタの劣化は、キャパシタの構成部材(電極、電解液、バインダー等)が電気化学的反応により劣化することで引き起こされる。
具体的には以下のような反応が考えられる。
(1)電解液の分解
(2)多孔質炭素材料および/または電解液中に残留する水分の分解に伴うフッ化水素酸の生成と副反応
(3)電極界面におけるSEI(Solid electrolyte interface)被膜の生成による、細孔径の変化あるいは細孔の閉塞
(4)残留水分の分解や、多孔質炭素材料に含まれる表面官能基の酸化および電解液の劣化に伴うガスの発生
これらの現象により、抵抗の増加、静電容量の低下やガス発生に伴うセルの膨張といったキャパシタの劣化が引き起こされると考えられる。
特に、低温下で測定比較を行う場合には、低温であるために電解液の粘性が増加し、電極材、電極界面の劣化および/または電解液の劣化などが、容量や抵抗等の評価により顕著に反映されると考えられる。このような観点から本発明においては、劣化現象を明確に比較、検討するため、耐久試験(60℃、3Vの負荷を所定時間)を実施し、その後の劣化状態を-30℃での評価を中心に比較した。
図7および図8において、多孔質炭素材料の比表面積が1300m2/g未満の場合、静電容量は急激に低下している。
2 導電性接着剤
3 エッチングアルミニウム箔
4 タブ
5 シーラント
6 分極性電極
7 外装シート
8 電気二重層キャパシタ
Claims (10)
- 多孔質炭素材料、
該多孔質炭素材料100質量部に対して0.5~5質量部の、150℃以上の沸点を有する絶縁材、および、
該絶縁材100質量部に対して0.25~15質量部の導電助材
を含み、該多孔質炭素材料に、該絶縁材および該導電助材が一緒になって担持された、1300~2050m2/gのBET比表面積を有する、エネルギー貯蔵デバイスの電極用多孔質炭素材料。 - 前記絶縁材の25℃における動粘度が1~1000mm2/sである、請求項1に記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料。
- 前記絶縁材の流動点は-30℃以下である、請求項1または2に記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料。
- 前記絶縁材は主鎖にシロキサン単位を有するシロキサン化合物である、請求項1~3のいずれかに記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料。
- さらに高分子化合物が一緒になって担持された、請求項1~4のいずれかに記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料。
- 1300~2050m2/gのBET比表面積を有する、エネルギー貯蔵デバイスの電極用多孔質炭素材料の製造方法であって、多孔質炭素材料に、該多孔質炭素材料100質量部に対して0.5~5質量部の、150℃以上の沸点を有する絶縁材、および、該絶縁材100質量部に対して0.25~15質量部の導電助材を担持させる、製造方法。
- 多孔質炭素材料に絶縁材および導電助材を添加して担持させる、請求項6に記載の製造方法。
- 多孔質炭素材料に絶縁材および導電助材を含む混合物を添加して担持させる、請求項6に記載の製造方法。
- 多孔質炭素材料を絶縁材および導電助材を含む混合物に浸漬させて担持させる、請求項6に記載の製造方法。
- 前記混合物はさらに高分子化合物を含有する、請求項8または9に記載のエネルギー貯蔵デバイスの電極用多孔質炭素材料の製造方法。
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CN111146417A (zh) * | 2019-12-24 | 2020-05-12 | 中国科学院山西煤炭化学研究所 | 一种快充型锂离子电池球形石墨负极材料及其制备方法 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008037682A (ja) * | 2006-08-03 | 2008-02-21 | Toyota Motor Corp | 活性炭の処理方法と、処理済み活性炭と、処理済み活性炭を使用している蓄電装置 |
JP2011049231A (ja) * | 2009-08-25 | 2011-03-10 | Nippon Zeon Co Ltd | 電気化学素子用電極の製造方法、電気化学素子用電極及び電気化学素子 |
WO2013128776A1 (ja) * | 2012-02-29 | 2013-09-06 | 日本ゼオン株式会社 | 電気化学素子電極用複合粒子、電気化学素子電極用複合粒子の製造方法、電気化学素子電極材料及び電気化学素子電極 |
JP2014042063A (ja) * | 2013-10-31 | 2014-03-06 | Nippon Zeon Co Ltd | 電気化学素子用電極の製造方法、電気化学素子用電極及び電気化学素子 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04296332A (ja) | 1991-03-26 | 1992-10-20 | Nitto Denko Corp | フッ素樹脂薄肉チューブ |
JPH0963905A (ja) | 1995-08-29 | 1997-03-07 | Matsushita Electric Ind Co Ltd | 電気二重層キャパシタおよびその製造方法 |
JPH10116755A (ja) | 1996-10-11 | 1998-05-06 | Toyota Central Res & Dev Lab Inc | 電気二重層キャパシタ用電極 |
JP4296332B2 (ja) | 1999-05-07 | 2009-07-15 | 株式会社豊田中央研究所 | 電気二重層キャパシタ及びその製造方法 |
JP4392223B2 (ja) | 2003-10-31 | 2009-12-24 | Jfeケミカル株式会社 | 活性炭の製造方法およびその製造装置 |
JP5336752B2 (ja) * | 2007-03-30 | 2013-11-06 | 住友化学株式会社 | 炭素粒子フィルム、積層電極、および電気二重層キャパシタの製造方法 |
CN101388291B (zh) | 2008-10-31 | 2012-10-31 | 中国科学院上海硅酸盐研究所 | 含硼多孔碳电极材料及其制备方法 |
CN101604580B (zh) | 2009-04-03 | 2011-10-05 | 中国科学院上海硅酸盐研究所 | 单源化合物一步分解法制备多孔碳电极材料的方法 |
WO2011115349A1 (ko) * | 2010-03-17 | 2011-09-22 | 경상대학교산학협력단 | 튜브형 구조의 생체 삽입 전지 |
JP5531902B2 (ja) | 2010-10-08 | 2014-06-25 | マツダ株式会社 | 蓄電装置用活性炭含有活物質、その製造方法、及び同活物質を有する蓄電装置 |
JP2012124388A (ja) | 2010-12-09 | 2012-06-28 | Mitsubishi Electric Corp | 電気二重層キャパシタ及び電気二重層キャパシタ用電極の製造方法 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008037682A (ja) * | 2006-08-03 | 2008-02-21 | Toyota Motor Corp | 活性炭の処理方法と、処理済み活性炭と、処理済み活性炭を使用している蓄電装置 |
JP2011049231A (ja) * | 2009-08-25 | 2011-03-10 | Nippon Zeon Co Ltd | 電気化学素子用電極の製造方法、電気化学素子用電極及び電気化学素子 |
WO2013128776A1 (ja) * | 2012-02-29 | 2013-09-06 | 日本ゼオン株式会社 | 電気化学素子電極用複合粒子、電気化学素子電極用複合粒子の製造方法、電気化学素子電極材料及び電気化学素子電極 |
JP2014042063A (ja) * | 2013-10-31 | 2014-03-06 | Nippon Zeon Co Ltd | 電気化学素子用電極の製造方法、電気化学素子用電極及び電気化学素子 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111146417A (zh) * | 2019-12-24 | 2020-05-12 | 中国科学院山西煤炭化学研究所 | 一种快充型锂离子电池球形石墨负极材料及其制备方法 |
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US20170047173A1 (en) | 2017-02-16 |
CN106233408A (zh) | 2016-12-14 |
KR20160146754A (ko) | 2016-12-21 |
CN106233408B (zh) | 2018-09-07 |
JPWO2015166839A1 (ja) | 2017-04-20 |
US10297398B2 (en) | 2019-05-21 |
JP6491644B2 (ja) | 2019-03-27 |
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