WO2016043154A1 - 電気化学キャパシタ用電極材料、電気化学キャパシタ用電極塗工液、電気化学キャパシタ用電極および電気化学キャパシタ - Google Patents
電気化学キャパシタ用電極材料、電気化学キャパシタ用電極塗工液、電気化学キャパシタ用電極および電気化学キャパシタ Download PDFInfo
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- WO2016043154A1 WO2016043154A1 PCT/JP2015/075998 JP2015075998W WO2016043154A1 WO 2016043154 A1 WO2016043154 A1 WO 2016043154A1 JP 2015075998 W JP2015075998 W JP 2015075998W WO 2016043154 A1 WO2016043154 A1 WO 2016043154A1
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- Prior art keywords
- electrochemical capacitor
- electrode
- porous carbon
- resin
- carbon material
- Prior art date
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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
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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
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Definitions
- the present invention relates to an electrode material for an electrochemical capacitor, an electrode coating solution for an electrochemical capacitor, an electrode for an electrochemical capacitor, and an electrochemical capacitor.
- Electrochemical capacitors are power storage devices characterized by high-speed charge / discharge characteristics and high-cycle characteristics that greatly exceed secondary batteries.
- an electrode containing activated carbon as a positive electrode and a negative electrode is usually used.
- Charging / discharging is performed by physical adsorption / desorption of electrolyte ions to / from activated carbon. At this time, since no chemical reaction is involved, deterioration is unlikely to occur, and the electric double layer capacitor is characterized by excellent cycle characteristics.
- a lithium ion capacitor an electrode containing activated carbon similar to an electric double layer capacitor is usually used as a positive electrode, and a lithium occlusion carbon material similar to the negative electrode of a lithium ion battery is used as a negative electrode.
- Charging / discharging is performed by absorbing and desorbing electrolyte ions at the positive electrode and inserting and extracting lithium ions at the negative electrode.
- particulate or powdery activated carbon used as an electrode material for electrochemical capacitors is likely to aggregate in the electrode, and the contact area with the electrolyte is limited. Was difficult.
- the flow resistance of the electrolyte increases due to the aggregation of the activated carbon, which has been a negative effect of further improving the high-speed charge / discharge characteristics of the electrochemical capacitor.
- Patent Document 1 discloses a capacitor including an electrode including a porous carbon material in which a pore and a carbonaceous wall constituting an outline of the pore have a three-dimensional network structure.
- the arrangement of voids is determined by the positions of dispersed template particles. Therefore, the uniformity of the porous structure of the porous carbon material is insufficient, and the utilization efficiency of the surface of the porous carbon material is not high.
- the present invention provides an electrode material for an electrochemical capacitor that has high surface utilization efficiency by making the uniformity of the porous structure sufficient, and can contribute to further increase in capacitance and high rate characteristics of the electrochemical capacitor. This is the issue.
- the present invention is an electrode material for an electrochemical capacitor made of a porous carbon material having a co-continuous structure portion having a structural period of 0.002 ⁇ m to 20 ⁇ m in which a carbon skeleton and voids each form a continuous structure.
- the porous carbon material of the present invention has a co-continuous structure portion composed of a carbon skeleton and voids, and has high structural uniformity, so that it has high electrostatic capacity and high rate characteristics as an electrode material for an electrochemical capacitor. It is possible to realize.
- FIG. 2 is a scanning electron micrograph of an electrode material for an electrochemical capacitor of Example 1.
- the electrode material for an electrochemical capacitor of the present invention (hereinafter sometimes simply referred to as “electrode material”) is made of a porous carbon material.
- the porous carbon material used as the electrode material for an electrochemical capacitor of the present invention may be referred to as “the porous carbon material of the present invention” for convenience. Further, the porous carbon material of the present invention may be used in the same meaning as the electrode material for an electrochemical capacitor of the present invention.
- the porous carbon material of the present invention has a co-continuous structure portion in which a carbon skeleton and voids each form a continuous structure.
- a carbon skeleton and voids each form a continuous structure.
- the surface of a sample that was sufficiently cooled in liquid nitrogen was cleaved with tweezers or the like, or the surface of a particulate sample obtained by pulverization with a mortar or the like was observed with a scanning electron microscope (SEM) or the like.
- SEM scanning electron microscope
- the electrolytic solution efficiently penetrates into the voids of the co-continuous structure portion in the electrochemical capacitor application, and the contact area between the electrolytic solution and the electrode material becomes very large. It can contribute to the high capacitance of chemical capacitors.
- the electrolyte ions can move efficiently through the void portion of the co-continuous structure portion, the electrochemical capacitor can be charged and discharged at high speed.
- the carbon skeleton is continuous, the electrical conductivity of the electrode material is increased, so that the internal resistance of the electrochemical capacitor can be reduced.
- the carbon parts supporting each other in the structure for example, a material having great resistance to deformation such as tension and compression during the manufacturing process and use can be obtained. Further, even when the electrode is pressed to reduce the contact resistance of the electrode during cell production, the co-continuous structure portion remains, so that the electrolyte can still enter with high efficiency.
- co-continuous structures include a lattice form and a monolith form, and are not particularly limited.
- a monolithic form is preferable in that the above effect can be exhibited.
- the monolithic form refers to a form in which the carbon skeleton forms a three-dimensional network structure in a co-continuous structure, and is generated by removing aggregated and connected template particles, or a structure in which individual particles are aggregated and connected. It is distinguished from a form having an irregular structure such as a structure formed by a void and a surrounding skeleton.
- the co-continuous structure portion in the porous carbon material of the present invention has a periodic structure.
- having a periodic structure can be confirmed by making X-rays incident on the porous carbon material and having a peak value in the scattering intensity distribution curve.
- the structural period of the porous carbon material of the present invention is 0.002 ⁇ m to 20 ⁇ m.
- the structural period is calculated by the following formula from the scattering angle ⁇ at the position where the X-ray is incident on the electrode material for an electrochemical capacitor of the present invention and the scattering intensity distribution curve has a peak value.
- Structure period L, ⁇ : wavelength of incident X-rays
- the structural period is obtained by X-ray computed tomography (X-ray CT). Specifically, after performing a Fourier transform on a three-dimensional image photographed by X-ray CT, the two-dimensional spectrum is averaged to obtain a one-dimensional spectrum. The characteristic wavelength corresponding to the position of the peak top in the one-dimensional spectrum is obtained, and the structural period is calculated from the reciprocal thereof.
- the structural period of the co-continuous structure portion is 0.002 ⁇ m or more, the electrolytic solution can easily enter the gap, and the flow resistance can be reduced. In addition, electrical conductivity can be improved through the carbon skeleton.
- the structural period is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more. Moreover, a high surface area and physical property can be acquired as a structural period is 20 micrometers or less. The structural period is preferably 10 ⁇ m or less, and more preferably 1 ⁇ m or less.
- the uniformity of the continuous structure of the porous carbon material of the present invention can be determined by the half width of the peak of the scattering intensity when X-rays are incident on the porous carbon material of the present invention.
- the full width at half maximum of the X-ray scattering peak of the porous carbon material of the present invention is preferably 5 ° or less, more preferably 3 ° or less, and particularly preferably 1 ° or less.
- the half width of the peak in the present invention is the peak A at the point A, a straight line parallel to the vertical axis of the graph is drawn from the point A, and the intersection of the straight line and the spectrum baseline is the point B.
- This is the width of the peak at the midpoint (point C) of the line segment connecting points A and B.
- variety of the peak said here is a width
- the portion having no co-continuous structure which will be described later, has no influence on the analysis because the structural period is outside the above range.
- the structure period calculated by the above formula is used as the structure period of the co-continuous structure forming portion.
- the structural period of the co-continuous structure portion can be appropriately adjusted according to the application and use conditions of the electrochemical capacitor.
- the co-continuous structure portion preferably has an average porosity of 10 to 80%.
- the average porosity is an enlargement ratio adjusted to be 1 ⁇ 0.1 (nm / pixel) of a cross section in which an embedded sample is precisely formed by a cross section polisher method (CP method).
- the image is calculated by the following expression from an image observed at a resolution of at least a pixel, where the area of interest required for calculation is set in 512 pixels square, the area of the area of interest is A, and the area of the hole is B.
- Average porosity (%) B / A ⁇ 100
- the average porosity of the co-continuous structure portion is preferably in the range of 15 to 75%, and more preferably in the range of 18 to 70%.
- the carbon skeleton of the porous carbon material of the present invention is preferably derived from polyacrylonitrile.
- polyacrylonitrile is included in the raw material, a porous structure can be formed only by physical phase separation without a polymerization reaction, so that the moldability is improved, the structure is stable, and the structure size is controllable over a wide range. ,preferable.
- the cost is reduced as an electrode material for an electrochemical capacitor.
- the form of the porous carbon material of the present invention is not particularly limited, and examples thereof include a particulate form, a fibrous form, a film form, a powder form, a lump form, a rod form, a flat plate form, and a disc form, and among them, a particulate form or a fibrous form. It is preferable that
- the particulate form can be applied in the electrode manufacturing process for electrochemical capacitors by applying the conventional electrode manufacturing process by applying a coating liquid containing activated carbon, and also when the bending, pulling, and compression occur. Can eliminate distortion.
- the porous carbon material has a portion that does not have a co-continuous structure, which will be described later, if the portion that does not have a co-continuous structure occupies a part of one particle, the electrical conductivity in the particle can be increased. It is possible to expect such effects as increasing the compressive strength of the particles themselves and reducing performance deterioration under high pressure. Therefore, it is preferable that the part not having the co-continuous structure occupies a part of one particle.
- the diameter of the particle is not particularly limited, and can be appropriately selected according to the use.
- a range of 10 nm to 10 mm is preferable because it is easy to handle.
- the thickness is 10 ⁇ m or less, for example, a very smooth solid can be obtained as a solid component for forming the coating liquid. Therefore, it is possible to prevent defects such as peeling and cracking of the coating liquid in a process such as coating.
- the thickness is 0.1 ⁇ m or more, when a composite material with a resin is used, the strength improvement effect as a filler can be sufficiently exhibited, which is preferable.
- the fibrous form is preferable because of high productivity and high handling in the electrochemical capacitor manufacturing process.
- the handleability is high, the degree of freedom of the shape of the electrode to be molded is increased, and it can be filled with a higher density, contributing to space saving of the electrochemical capacitor.
- a porous carbon material having a film shape, a flat plate shape, or a disk shape is preferable in that it can be used as an electrode for an electrochemical capacitor as it is.
- the porous carbon material of the present invention preferably has pores having an average diameter of 0.01 to 10 nm on the surface.
- the surface refers to a contact surface with any outside of the porous carbon material including the surface of the carbon skeleton in the co-continuous structure portion of the porous carbon material.
- the pores can be formed on the surface of the carbon skeleton in the co-continuous structure portion and / or in the portion substantially not having the co-continuous structure described later. It is preferably formed on the surface of the carbon skeleton in at least a portion having a co-continuous structure.
- the average diameter of such pores is preferably 0.01 nm or more, and more preferably 0.1 nm or more. Moreover, it is preferable that it is 5 nm or less, and it is more preferable that it is 2 nm or less.
- the average diameter of the pores is 0.01 nm to 10 nm, the adsorption / desorption function for the electrolyte ions can be improved. From the viewpoint of efficient adsorption of electrolyte ions and the like, the pore diameter is preferably appropriately adjusted to about 1.1 to 2.0 times the diameter of the electrolyte ions.
- the pore volume is preferably 0.1 cm 3 / g or more, more preferably 1.0 cm 3 / g or more, and further preferably 1.5 cm 3 / g or more.
- the upper limit is not particularly limited, but if it exceeds 10 cm 3 / g, the strength of the porous carbon material is lowered, and the bulk density is remarkably lowered, so that the handleability tends to deteriorate, which is not preferable.
- the average diameter of a pore means the measured value by either the BJH method or the MP method. That is, if either one of the measured values by the BJH method or the MP method falls within the range of 0.01 to 10 nm, it is determined that the surface has pores having an average diameter of 0.01 to 10 nm. The same applies to the preferable range of the pore diameter.
- the BJH method and the MP method are widely used as a pore size distribution analysis method, and can be obtained based on a desorption isotherm obtained by adsorbing and desorbing nitrogen on a porous carbon material.
- the BJH method is a method of analyzing the pore volume distribution with respect to the pore diameter assumed to be cylindrical according to the Barrett-Joyner-Halenda standard model, and can be applied mainly to pores having a diameter of 2 to 200 nm. (For details, see J. Amer. Chem. Soc., 73, 373, 1951 etc.).
- the MP method is based on the external surface area and adsorption layer thickness (corresponding to the pore radius because the pore shape is cylindrical) obtained from the change in the tangential slope at each point of the adsorption isotherm.
- the voids in the co-continuous structure portion may affect the pore size distribution and pore volume measured by the BJH method or the MP method. That is, there is a possibility that these measured values may be obtained as values that reflect not only the pores but also the presence of voids. Even in this case, the measured values obtained by these methods are used in the present invention. Assume that the average diameter and the pore volume of the pores. Moreover, if the pore volume measured by MP method is less than 0.05 cm ⁇ 3 > / g, it will be judged that the pore is not formed in the material surface.
- the porous carbon material of the present invention preferably has a BET specific surface area of 20 m 2 / g or more.
- the BET specific surface area is more preferably 100 m 2 / g or more, further preferably 500 m 2 / g or more, and still more preferably 1000 m 2 / g or more.
- the BET specific surface area is 20 m 2 / g or more, the area capable of acting on adsorption / desorption of electrolyte ions is increased, and the performance as an electrochemical capacitor is improved.
- the upper limit is not particularly limited, but if it exceeds 4500 m 2 / g, the strength of the porous carbon material tends to be lowered, the bulk density is remarkably lowered, and the handleability tends to be deteriorated.
- the BET specific surface area in the present invention is calculated according to JIS R 1626 (1996) by measuring the adsorption isotherm by adsorbing and desorbing nitrogen to and from the porous carbon material, and calculating the measured data based on the BET equation. Can do.
- the porous carbon material of the present invention includes a portion that does not substantially have a co-continuous structure (hereinafter, simply referred to as “portion that does not have a co-continuous structure”).
- portion having substantially no co-continuous structure is a portion below the resolution when a cross section formed by the cross section polisher method (CP method) is observed at an enlargement ratio of 1 ⁇ 0.1 (nm / pixel). This means that a part where no clear air gap is observed exists in an area equal to or larger than a square region corresponding to three times the structural period L calculated from the X-ray described later.
- the portion not having the co-continuous structure is densely filled with carbon, the electron conductivity is high and the electrical resistance can be lowered. In addition, since there is a portion that does not have a co-continuous structure, it is possible to increase resistance to compression fracture.
- the ratio of the portion not having the co-continuous structure can be adjusted as appropriate. For example, it is preferable that 5% by volume or more be a portion that does not have a co-continuous structure, because electrical conductivity and thermal conductivity can be maintained at a high level.
- the utilization efficiency of the surface of the porous carbon material when used as an electrode material for an electrochemical capacitor is, for example, a value obtained by dividing the capacitance obtained by a charge / discharge test by the BET specific surface area, that is, the capacitance per BET specific surface area. Is evaluated. The charge / discharge test will be described in detail later in Examples.
- the cell of the electric double layer capacitor has a configuration in which two electrodes as a positive electrode and a negative electrode are arranged via a separator and further immersed in an electrolytic solution.
- the electric double layer capacitor of the present invention includes the electrode containing the porous carbon material of the present invention.
- the electrode preferably further contains a conductive additive, a binder, and a current collector.
- the electrode may contain one or more porous carbon materials other than the porous carbon material of the present invention.
- the cell form of the electrochemical capacitor is not limited at all.
- a coin-type cell, a laminate cell, a cylindrical cell, etc. are mentioned.
- Examples of conductive aids include acetylene black, ketjen black, furnace black, carbon nanotubes, fullerene, and graphene. These may be used alone or in combination.
- binders include hydrophobic binders and hydrophilic binders.
- hydrophobic binder include polytetrafluoroethylene, polyvinylidene fluoride, and styrene-butadiene rubber.
- hydrophilic binder include hydroxymethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol. These binders may be used alone or in combination.
- the binder is preferably combined with the porous carbon material of the present invention, and the form is not particularly limited. A form in which at least a part of the film is attached to the porous carbon material and a form in which at least a part of the fibrillar binder is attached to the porous carbon material can be exemplified.
- a well-known thing can be used as a current collector.
- Aluminum, stainless steel, copper, nickel and the like can be exemplified.
- the current collector is preferably etched on the contact side with the coating solution for the purpose of increasing the contact area with the coating solution and reducing the contact resistance.
- the thickness of the electrode is not particularly limited and can be appropriately changed according to desired characteristics.
- the range of the electrode thickness can be arbitrarily designed in the range of 1 ⁇ m to 10 mm.
- the electrode containing the electrode material of the present invention preferably has an electrode density of 0.3 to 1.0 g / cm 3 . It is preferable that the electrode density is 0.3 g / cm 3 or more because the capacitance per volume increases when used as an electrochemical capacitor.
- the electrode density is more preferably 0.4 g / cm 3 or more.
- the electrode density is 1.0 g / cm 3 or less, when used as an electrochemical capacitor, the electrolyte solution penetrates into the pores of the porous carbon material with high efficiency, enabling high capacity and high-speed charge / discharge. Therefore, it is preferable. More preferably, the electrode density is 0.8 g / cm 3 or less.
- the electrode density in the present invention is calculated by punching an electrode using a punching jig with a known area, measuring its thickness, calculating the volume, and further measuring the weight and dividing by the volume. Value.
- the weight and volume of the current collector portion are not included in the calculation. That is, in the case of an electrode having a current collector, the electrode density is the density of the mixture layer derived from the coating liquid fixed to the current collector.
- a known electrolyte solution can be used, and either an aqueous system or a non-aqueous system may be used.
- the aqueous system include an aqueous sulfuric acid solution, an aqueous sodium sulfate solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonium hydroxide solution, an aqueous potassium chloride solution, and an aqueous potassium carbonate solution.
- electrolytes such as quaternary ammonium salts or quaternary phosphonium salts, ethers such as diethyl ether, dibutyl ether, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether, amides such as formamide and N-methylformamide, And solutions containing sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, dialkyl ketones such as methyl ethyl ketone, and carbonates such as ethylene carbonate and propylene carbonate.
- ethers such as diethyl ether, dibutyl ether, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether, amides such as formamide and N-methylformamide
- amides such as formamide and N-methylformamide
- sulfur-containing compounds such as dimethyl sulfoxide and sulfolane
- dialkyl ketones such as methyl ethyl ketone
- carbonates such as
- a conventionally well-known thing can be used as a separator. It is preferable that electrical insulation is possible and the fluidity of ions is not hindered. Specifically, a separator having a high hole area ratio and a small thickness is preferable.
- the positive electrode of the lithium ion capacitor of the present invention contains the porous carbon material of the present invention, and the preferred embodiment is the same as the electrode for the electric double layer capacitor described above.
- the negative electrode can be manufactured by applying a coating liquid containing an active material, a binder, and a conductive additive to a current collector.
- the negative electrode active material any carbon material that can reversibly absorb and desorb lithium ions can be used.
- the negative electrode is preferably pre-doped with lithium ions, and the pre-doping method is not particularly limited.
- the lithium ion capacitor of the present invention is produced by disposing a positive electrode and a negative electrode through a separator and immersing them in an electrolytic solution.
- the electrolytic solution is not particularly limited, but a non-aqueous organic electrolytic solution in which a lithium salt is dissolved is preferable.
- an organic solvent to be used an aprotic organic solvent is used, the solubility of the electrolyte, the reactivity with the electrode, and the viscosity. It is selected appropriately according to the operating temperature range.
- the electrochemical capacitor of the present invention Since the electrochemical capacitor of the present invention has a high capacitance and can be charged / discharged at high speed, it can be used for efficient power storage, power leveling, etc. in various electronic devices and energy devices.
- renewable energy-related equipment such as solar power generation, wind power generation, geothermal power generation, wave power generation, etc., power supply control base, and backup power sources for hospitals, factories, data centers and the like.
- the electric power generated by the motor during braking is instantaneously applied to the electrochemical capacitor of the present invention.
- the electrochemical capacitor of the present invention can be charged at high speed, and thus is preferably used.
- the time required for charging can be shortened.
- the electrochemical capacitor of the present invention enables power leveling when a momentary overload or voltage drop occurs.
- the secondary battery alone can reduce the load. difficult.
- the electrochemical capacitor of the present invention makes it possible to obtain a device that is small and can withstand a high load. Due to these effects, it is possible to prevent a sudden shutdown due to a voltage drop as compared with the prior art, and a device capable of stable operation can be obtained.
- the electrochemical capacitor of the present invention can be suitably used for electric trains taking advantage of the characteristics of high capacitance and high-speed charging characteristics.
- a train equipped with the electrochemical capacitor of the present invention is preferable because energy loss due to frictional force or the like applied to traveling is small, and regeneration by braking makes it possible to travel with energy saving.
- stable acceleration and deceleration can be performed, which is preferable because it can contribute to stable operation.
- the capacitor when not in use, the capacitor is charged from the main power supply to store the power, and when used, it is warmed up instantaneously and discharged immediately for print output, etc. Therefore, it is preferably used.
- the electrochemical capacitor of the present invention is preferably combined with wind power generation or solar power generation.
- wind power generation the amount of power generation varies greatly with time due to fluctuations in wind power, and conventional secondary batteries cannot follow large voltage fluctuations and cannot store power efficiently.
- the high-speed charge / discharge characteristic of the electrochemical capacitor of the present invention enables highly efficient power storage.
- the charging voltage on the electrochemical capacitor side of the present invention is low, so that it is possible to efficiently store electricity, which is preferable.
- the porous carbon material of the present invention includes, as an example, a step (Step 1) in which 10 to 90% by weight of carbonizable resin and 90 to 10% by weight of disappearing resin are mixed to form a resin mixture,
- the resin mixture can be produced by a production method having a step of separating and immobilizing the resin mixture (step 2) and a step of carbonizing by heating and baking (step 3).
- Step 1 is a step in which 10 to 90% by weight of the carbonizable resin and 90 to 10% by weight of the disappearing resin are mixed to form a resin mixture.
- the carbonizable resin is a resin that is carbonized by firing and remains as a carbon material.
- the carbonizable resin preferably has a carbonization yield of 10% or more, more preferably 40% or more.
- the carbonization yield here is the difference between the weight at room temperature and the weight at 800 ° C. by measuring the change in weight when the temperature is raised at 10 ° C./min in a nitrogen atmosphere by the thermogravimetry (TG) method. Is divided by the weight at room temperature.
- thermoplastic resin examples include polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenol resin, and wholly aromatic polyester.
- thermosetting resins include unsaturated polyester resins, alkyd resins, melamine resins, urea resins, polyimide resins, diallyl phthalate resins, lignin resins, urethane resins, and the like.
- polyacrylonitrile and phenol resin are preferable, and polyacrylonitrile is more preferable.
- polyacrylonitrile is a preferred embodiment because a high specific surface area can be obtained. These may be used alone or in a mixed state.
- a porous carbon material produced by a method for producing a porous carbon material having a step of fixing (Step 2) and a step of carbonizing by heating and firing (Step 3) is particularly preferred.
- the disappearing resin is a resin that can be removed after Step 2 described later, and is preferably a resin that can be removed at least in any stage of the infusibilization treatment, the infusibilization treatment, or the firing. .
- the disappearing resin is preferably a resin having a carbonization yield of less than 10%.
- the removal rate of the disappearing resin is preferably 80% by weight or more, and more preferably 90% by weight or more when finally becoming a porous carbon material.
- the method for removing the lost resin is not particularly limited. A method of chemical removal by depolymerizing with a chemical, a method of removing with a solvent that dissolves the disappearing resin, a method of removing the disappearing resin by reducing the molecular weight by heating and thermal decomposition, etc. are suitably used. . These techniques can be used alone or in combination. When implemented in combination, each may be performed simultaneously or separately.
- a method of hydrolyzing with an acid or alkali is preferable from the viewpoints of economy and handleability.
- the resin that is susceptible to hydrolysis by acid or alkali include polyester, polycarbonate, and polyamide.
- the mixed carbonizable resin and the disappearing resin are continuously supplied with a solvent to dissolve and remove the disappearing resin, or mixed in a batch system.
- a suitable example is a method of dissolving and removing the lost resin.
- the disappearing resin suitable for the method of removing with a solvent include polyolefins such as polyethylene, polypropylene, and polystyrene, acrylic resins, methacrylic resins, polyvinylpyrrolidone, aliphatic polyesters, polycarbonates, and the like.
- polyolefins such as polyethylene, polypropylene, and polystyrene
- acrylic resins methacrylic resins
- polyvinylpyrrolidone aliphatic polyesters
- polycarbonates and the like.
- an amorphous resin is more preferable because of its solubility in a solvent.
- the amorphous resin include polystyrene, methacrylic resin, polycarbonate, and polyvinylpyrrolidone.
- a method of removing the lost resin by reducing the molecular weight by thermal decomposition a method in which the mixed carbonizable resin and the lost resin are heated in a batch manner to thermally decompose, or a continuously mixed carbonized resin and the lost resin are removed.
- a method of heating and thermally decomposing while continuously supplying to a heat source a method in which the mixed carbonizable resin and the lost resin are heated in a batch manner to thermally decompose, or a continuously mixed carbonized resin and the lost resin are removed.
- the disappearing resin is preferably a resin that disappears due to thermal decomposition when carbonizing the carbonizable resin by firing in Step 3 described later.
- the disappearing resin is preferably a resin that does not cause a large chemical change during the infusibilization treatment of the carbonizable resin, which will be described later, and that the carbonization yield after firing is less than 10%.
- Specific examples of such disappearing resins include polyolefins such as polyethylene, polypropylene, and polystyrene, acrylic resins, methacrylic resins, polyacetals, polyvinylpyrrolidones, aliphatic polyesters, aromatic polyesters, aliphatic polyamides, polycarbonates, and the like. Can do. These disappearing resins may be used alone or in a mixed state.
- step 1 the carbonizable resin and the disappearing resin are mixed to form a resin mixture (polymer alloy).
- “Compatibilized” as used herein refers to creating a state in which the phase separation structure of the carbonizable resin and the disappearing resin is not observed with an optical microscope by appropriately selecting the temperature and / or solvent conditions.
- the carbonizable resin and the disappearing resin may be compatible by mixing only the resins, or may be compatible by adding a solvent or the like.
- a system in which a plurality of resins are compatible includes a phase diagram of an upper critical eutectic temperature (UCST) type that is in a phase separation state at a low temperature but has one phase at a high temperature, and conversely, a phase separation state at a high temperature.
- UCT upper critical eutectic temperature
- LCST lower critical solution temperature
- the solvent to be added is not particularly limited, but the absolute value of the difference between the average value of the solubility parameter (SP value) of the carbonizable resin and the disappearing resin, which is a solubility index, is within 5.0. It is preferable. Since it is known that the smaller the absolute value of the difference from the average value of the SP values, the higher the solubility, it is preferable that there is no difference. Further, the larger the absolute value of the difference from the average SP value, the lower the solubility, and it becomes difficult to take a compatible state between the carbonizable resin and the disappearing resin. Therefore, the absolute value of the difference from the average value of SP values is preferably 3.0 or less, and most preferably 2.0 or less.
- carbonizable resins and disappearing resins are polyphenylene oxide / polystyrene, polyphenylene oxide / styrene-acrylonitrile copolymer, wholly aromatic polyester / polyethylene as long as they do not contain solvents.
- examples include terephthalate, wholly aromatic polyester / polyethylene naphthalate, wholly aromatic polyester / polycarbonate.
- combinations of systems containing solvents include polyacrylonitrile / polyvinyl alcohol, polyacrylonitrile / polyvinylphenol, polyacrylonitrile / polyvinylpyrrolidone, polyacrylonitrile / polylactic acid, polyvinyl alcohol / vinyl acetate-vinyl alcohol copolymer, polyvinyl Examples thereof include alcohol / polyethylene glycol, polyvinyl alcohol / polypropylene glycol, and polyvinyl alcohol / starch.
- the method of mixing the carbonizable resin and the disappearing resin is not limited, and various known mixing methods can be adopted as long as uniform mixing is possible. Specific examples include a rotary mixer having a stirring blade, a kneading extruder using a screw, and the like.
- the temperature (mixing temperature) when mixing the carbonizable resin and the disappearing resin is equal to or higher than the temperature at which both the carbonizable resin and the disappearing resin are softened.
- the softening temperature may be appropriately selected as the melting point if the carbonizable resin or disappearing resin is a crystalline polymer, and the glass transition temperature if it is an amorphous resin.
- the mixing temperature is preferably 400 ° C. or lower from the viewpoint of preventing deterioration of the resin due to thermal decomposition and obtaining a precursor of a porous carbon material having excellent quality.
- Step 1 90 to 10% by weight of the disappearing resin is mixed with 10 to 90% by weight of the carbonizable resin. It is preferable that the carbonizable resin and the disappearing resin are within the above-mentioned range since an optimum void size and void ratio can be arbitrarily designed. If the carbonizable resin is 10% by weight or more, it is possible to maintain the mechanical strength of the carbonized material and improve the yield. Further, if the carbonizable material is 90% by weight or less, it is preferable because the lost resin can efficiently form voids.
- the mixing ratio of the carbonizable resin and the disappearing resin can be arbitrarily selected within the above range in consideration of the compatibility of each material. Specifically, in general, the compatibility between resins deteriorates as the composition ratio approaches 1: 1, so when a system that is not very compatible is selected as a raw material, the amount of carbonizable resin is increased. It can also be mentioned as a preferred embodiment that the compatibility is improved by approaching a so-called uneven composition, for example, by reducing it.
- a solvent when mixing the carbonizable resin and the disappearing resin. Addition of a solvent lowers the viscosity of the carbonizable resin and the disappearing resin to facilitate molding, and facilitates compatibilization of the carbonizable resin and the disappearing resin.
- the solvent here is not particularly limited as long as it is a liquid at room temperature that can dissolve and swell at least one of the carbonizable resin and the disappearing resin. If both the carbonizable resin and the disappearing resin are dissolved, it is possible to improve the compatibility of both, which is a more preferable embodiment.
- the addition amount of the solvent should be 20% by weight or more based on the total weight of the carbonizable resin and the disappearing resin from the viewpoint of improving the compatibility between the carbonizable resin and the disappearing resin and reducing the viscosity to improve the fluidity. preferable. On the other hand, from the viewpoint of costs associated with recovery and reuse of the solvent, it is preferably 90% by weight or less based on the total weight of the carbonizable resin and the disappearing resin.
- Step 2 is a step of phase-separating the resin mixture dissolved in Step 1 to form a fine structure and immobilize it.
- the phase separation of the mixed carbonizable resin and the disappearing resin can be induced by various physical and chemical techniques.
- thermally induced phase separation method that induces phase separation by temperature change
- non-solvent induced phase separation method that induces phase separation by adding non-solvent
- flow induced phase separation method that induces phase separation by physical field
- Examples include an orientation-induced phase separation method, an electric field-induced phase separation method, a magnetic field-induced phase separation method, a pressure-induced phase separation method, and a reaction-induced phase separation method that induces phase separation using a chemical reaction.
- a method that does not involve a chemical reaction during phase separation such as a thermally induced phase separation method or a non-solvent induced phase separation method, is preferable in that the porous carbon material of the present invention can be easily produced.
- phase separation methods can be used alone or in combination.
- Specific methods for use in combination include, for example, a method in which non-solvent induced phase separation is caused through a coagulation bath and then heated to cause heat-induced phase separation, or a temperature in the coagulation bath is controlled to control a non-solvent induced phase.
- Examples thereof include a method of causing separation and thermally induced phase separation at the same time, a method of bringing the material discharged from the die into cooling and causing thermally induced phase separation, and then contacting with a non-solvent.
- the primary structure refers to a chemical structure that constitutes a carbonizable resin or a disappearing resin.
- the resin mixture in which the microstructure after phase separation is fixed in Step 2 is subjected to the removal treatment of the lost resin before being subjected to the carbonization step (Step 3), simultaneously with the carbonization step, or both.
- the method for the removal treatment is not particularly limited as long as the disappearing resin can be removed. Specifically, the method of removing the lost resin by chemically decomposing and reducing the molecular weight using acid, alkali or enzyme, the method of removing by dissolving with a solvent that dissolves the lost resin, electron beam, gamma ray, ultraviolet ray, infrared ray A method of decomposing and removing the disappearing resin using radiation such as heat or the like is preferable.
- the heat treatment can be performed at a temperature at which 80% by weight or more of the disappearing resin disappears in advance.
- the lost resin can also be removed by pyrolysis and gasification in the carbonization step (step 3) or infusibilization treatment described later. From the viewpoint of increasing the productivity by reducing the number of steps, it is more preferable to select a method in which the lost resin is thermally decomposed and gasified and removed simultaneously with the heat treatment in the carbonization step (step 3) or infusibilization treatment described later. It is.
- the precursor material which is a resin mixture in which the microstructure after phase separation is fixed in step 2
- the infusible treatment method is not particularly limited, and a known method can be used.
- Specific methods include a method of causing oxidative crosslinking by heating in the presence of oxygen, a method of forming a crosslinked structure by irradiating high energy rays such as electron beams and gamma rays, and impregnating a substance having a reactive group, Examples thereof include a method of forming a crosslinked structure by mixing, and among them, a method of causing oxidative crosslinking by heating in the presence of oxygen is preferable because the process is simple and the production cost can be reduced. These methods may be used singly or in combination, and each may be used simultaneously or separately.
- the heating temperature in the method of causing oxidative crosslinking by heating in the presence of oxygen is preferably 150 ° C. or higher from the viewpoint of efficiently promoting the crosslinking reaction. From the viewpoint of preventing yield deterioration from weight loss due to thermal decomposition, combustion, etc. of the carbonizable resin, the heating temperature is preferably 350 ° C. or lower.
- the oxygen concentration during the treatment is not particularly limited, but it is preferable to supply a gas having an oxygen concentration of 18% or more, particularly air, as it is because manufacturing costs can be kept low.
- the gas supply method is not particularly limited. Examples thereof include a method of supplying air as it is into the heating device and a method of supplying pure oxygen into the heating device using a cylinder or the like.
- the carbonizable resin is irradiated with an electron beam or a gamma ray using a commercially available electron beam generator or gamma ray generator. And a method of inducing cross-linking.
- the lower limit of the irradiation intensity is preferably 1 kGy or more from the efficient introduction of a crosslinked structure by irradiation, and is preferably 1000 kGy or less from the viewpoint of preventing the material strength from being lowered due to the decrease in molecular weight due to cleavage of the main chain.
- a method of forming a crosslinked structure by impregnating and mixing a substance having a reactive group is a method in which a low molecular weight compound having a reactive group is impregnated in a resin mixture, and a crosslinking reaction is advanced by irradiation with heat or high energy rays. And a method in which a low molecular weight compound having a reactive group is mixed in advance and the crosslinking reaction is promoted by heating or irradiation with high energy rays.
- step 3 the resin mixture in which the microstructure after phase separation is fixed in step 2 or, if the disappearing resin has already been removed, the remaining portion made of carbonizable resin is fired and carbonized to form the carbide. It is a process to obtain.
- Calcination is preferably performed by heating to 600 ° C. or higher in an inert gas atmosphere.
- the inert gas refers to one that is chemically inert during heating, and specific examples include helium, neon, nitrogen, argon, krypton, xenon, carbon dioxide, and the like. Of these, nitrogen and argon are preferably used from the economical viewpoint.
- nitrogen and argon are preferably used from the economical viewpoint.
- the carbonization temperature is 1500 ° C. or higher
- argon is preferably used from the viewpoint of suppressing nitride formation.
- the flow rate of the inert gas may be an amount that can sufficiently reduce the oxygen concentration in the heating device, and an optimal value can be selected appropriately depending on the size of the heating device, the amount of raw material supplied, the heating temperature, and the like. preferable.
- the upper limit of the flow rate is not particularly limited. From the standpoint of economy and reducing temperature changes in the heating device, it is preferable to set appropriately according to the temperature distribution and the design of the heating device. Further, if the gas generated during carbonization can be sufficiently discharged out of the system, a porous carbon material excellent in quality can be obtained, which is a more preferable embodiment. From this, the generated gas concentration in the system is 3000 ppm or less. It is preferable to determine the flow rate of the inert gas so that
- the upper limit of the heating temperature is not limited. If it is 3000 degrees C or less, since a special process is not required for an installation, it is preferable from an economical viewpoint. Moreover, in order to raise a BET specific surface area, it is preferable that it is 1500 degrees C or less, and it is more preferable that it is 1000 degrees C or less.
- the heating method in the case of continuously performing carbonization treatment, it is a method to take out the material while continuously supplying the material using a roller, a conveyor, or the like in a heating device maintained at a constant temperature. It is preferable because it can be increased.
- the rate is preferably 1 ° C./min or more.
- the upper limit of the temperature increase rate and the temperature decrease rate is not particularly limited, and is preferably slower than the thermal shock resistance property of the material constituting the heating device.
- the carbide obtained in step 3 can form pores on the surface by further activation treatment.
- the activation method is not particularly limited, such as a gas activation method or a chemical activation method.
- the gas activation method is a method of forming pores by heating at 400 to 1500 ° C., preferably 500 to 900 ° C. for several minutes to several hours, using oxygen, water vapor, carbon dioxide gas, air or the like as an activator.
- the chemical activation method is one or two kinds of activator such as zinc chloride, iron chloride, calcium phosphate, calcium hydroxide, potassium hydroxide, magnesium carbonate, sodium carbonate, potassium carbonate, sulfuric acid, sodium sulfate, potassium sulfate, etc. This is a method of heat treatment for several minutes to several hours using the above, and after washing with water or hydrochloric acid as necessary, the pH is adjusted and dried.
- the BET specific surface area increases and the pore diameter tends to increase by further increasing the activation or increasing the amount of the activator mixed.
- the mixing amount of the activator is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, and further preferably 4 parts by weight or more with respect to the target carbon raw material.
- the upper limit of the mixing amount of the activator is not particularly limited, and is generally 10 parts by weight or less.
- the pore diameter tends to be larger in the chemical activation method than in the gas activation method.
- the chemical activation method is preferably employed because the pore diameter can be increased or the BET specific surface area can be increased.
- a method of activating with an alkaline agent such as calcium hydroxide, potassium hydroxide, potassium carbonate is preferably employed.
- a carbonaceous material carbonized through the step 3 or a porous carbon material optionally subjected to an activation treatment and pulverized into a particulate carbonaceous material is also preferably used as the electrode material of the present invention.
- the pulverization method include a ball mill, a bead mill, and a jet mill.
- the pulverization may be continuous or batch, but is preferably continuous from the viewpoint of production efficiency.
- the filler for filling the ball mill is appropriately selected.
- metal oxides such as alumina, zirconia, and titania, or those coated with nylon, polyolefin, fluorinated polyolefin, etc. with stainless steel, iron, etc. as the core. preferable.
- metals such as stainless steel, nickel, and iron are preferably used.
- the grinding aid is arbitrarily selected from water, alcohol or glycol, ketone and the like.
- alcohol ethanol and methanol are preferable from the viewpoint of availability and cost.
- glycol ethylene glycol, diethylene glycol, propylene glycol and the like are preferable.
- ketone acetone, ethyl methyl ketone, diethyl ketone and the like are preferable.
- the pulverized carbides have a uniform particle size by classification and can stabilize the coating liquid coating process, which can be expected to increase production efficiency and reduce costs.
- About a particle size it is preferable to select suitably according to the use of the carbide
- the electrochemical capacitor of the present invention can be produced by the same method as the conventional electrochemical capacitor except that the electrode using the porous carbon material of the present invention is used. Preferred embodiments are described below.
- the porous carbon material of the present invention when it is in the form of a film, it can be used as it is as an electrode. In that case, it is preferable not to use a current collector from the viewpoint of miniaturization of the electrochemical capacitor.
- the porous carbon material of the present invention is in the form of particles
- the coating liquid can be produced by a dry method or a wet method, which will be described in detail below.
- the method for mixing the porous carbon material of the present invention with other materials is not particularly limited.
- a method of kneading with a twin screw extruder is preferred from the viewpoint of easiness of heating and production efficiency.
- the other materials mentioned here mean binders, conductive assistants and the like. These are appropriately used as necessary.
- the method for producing the coating liquid by a wet method includes a method of preparing a slurry-like electrode coating liquid by mixing the porous carbon material of the present invention, a solvent, and other materials. It is done.
- the other materials mentioned here mean binders, conductive assistants, and the like, and these are used as needed.
- the mixing procedure is not limited, a method in which all materials are charged at the same time, a method in which only the solid content is mixed in advance, or only a component that is soluble in the solvent is mixed with the solvent to prepare a solution in advance. A method of preparing it is conceivable.
- the mixing method is not particularly limited, and a closed rotary stirrer is preferably used from the viewpoint of mixing efficiency.
- the coating method of the electrode coating solution is not particularly limited, and examples thereof include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and brush coating.
- the method for assembling the cell of the electric double layer capacitor of the present invention is not particularly limited and is performed by a generally used method.
- an electrochemical capacitor electrode and an electrolytic solution using the porous carbon material of the present invention are used.
- Electrochemical capacitor electrode is appropriately punched out and sized to match the shape of the cell container by cutting out, etc., and wound, laminated or folded as necessary to put it into the cell container, and then inject the electrolyte into the cell container Can be manufactured by sealing.
- an electrochemical capacitor impregnated with an electrolytic solution in advance may be stored in a cell container.
- it is also a preferable aspect to use a separator, a spacer, or a gasket as necessary when assembling the cell.
- the electrode may be pressed and then incorporated into the cell.
- the porous carbon materials in the electrodes and / or members other than the porous carbon material and the electrodes are pressure-bonded, and a conductive path is formed, thereby reducing the resistance.
- the porous carbon material of the present invention has a communication hole having a co-continuous structure, a gap through which the electrolyte flows is maintained to some extent even when pressing is performed.
- the pressing process may be incorporated in any part of any process related to the production of the electrochemical capacitor, and the pressing may be performed in a state where members other than the electrodes (for example, a separator or the like) are laminated.
- Average porosity (%) B / A ⁇ 100 [BET specific surface area, pore diameter]
- nitrogen adsorption and desorption at a temperature of 77K was measured using liquid nitrogen using the "BELSORP-18PLUS-HT" manufactured by Bell Japan Ltd. using a multipoint method. did.
- the surface area was determined by the BET method, and the pore distribution analysis (pore diameter, pore volume) was performed by the MP method or BJH method.
- the utilization efficiency of the surface of porous carbon material when used as an electrode material for an electrochemical capacitor is a value obtained by dividing the electrostatic capacity obtained by the charge / discharge test described later by the BET specific surface area, that is, the electrostatic capacity per BET specific surface area. The capacity was evaluated.
- Example 1 70 g of polyacrylonitrile (MW 150,000, carbon yield 58%), 70 g of polyvinyl pyrrolidone (MW 40,000) manufactured by Sigma-Aldrich, and 400 g of dimethyl sulfoxide (DMSO) manufactured by Waken Pharmaceutical as a solvent are separated. A uniform and transparent solution was prepared at 150 ° C. while stirring and refluxing for 3 hours. At this time, the concentration of polyacrylonitrile and the concentration of polyvinylpyrrolidone were 13% by weight, respectively.
- DMSO dimethyl sulfoxide
- the solution After cooling the obtained DMSO solution to 25 ° C., the solution is discharged at a rate of 3 ml / min from a 0.6 mm ⁇ 1-hole cap and led to a pure water coagulation bath maintained at 20 ° C., and then 5 m / min.
- the yarn was taken up at a speed and deposited on the bat to obtain a raw yarn. At this time, the air gap was 5 mm, and the immersion length in the coagulation bath was 15 cm.
- the obtained raw yarn was translucent and caused phase separation.
- the obtained yarn is dried for 1 hour in a circulation drier kept at 25 ° C. to dry the moisture on the surface of the yarn, followed by vacuum drying at 25 ° C. for 5 hours. Raw material yarn was obtained.
- the raw material yarn as a precursor material was put into an electric furnace maintained at 240 ° C., and infusible treatment was performed by heating in an oxygen atmosphere for 1 hour.
- the raw yarn that had been infusibilized changed to black.
- Carbon fiber having a co-continuous structure is obtained by carbonizing the obtained infusible raw material under the conditions of a nitrogen flow rate of 1 liter / min, a heating rate of 10 ° C./min, an ultimate temperature of 850 ° C., and a holding time of 1 min. did.
- the fiber diameter was 150 ⁇ m.
- the carbon fiber was pulverized using a ball mill. Thereafter, as an activation treatment, potassium hydroxide was mixed in an amount 4 times that of carbide, and charged into a rotary kiln and heated to 800 ° C. under a nitrogen flow. After the activation treatment for 1 hour and 30 minutes, the temperature was lowered, and then washing was performed using water and dilute hydrochloric acid until the washing solution reached pH7.
- a uniform co-continuous structure was formed as shown in FIG.
- the average porosity of the co-continuous structure portion was 45%, and the structure period was 73 nm. Moreover, it had the structure which included the part which does not have a co-continuous structure in some particle
- the BET specific surface area was 2380 m 2 / g
- the average pore diameter by the MP method was 0.6 nm
- the average pore diameter by the BJH method was 3.3 nm
- the pore volume by the MP method was 1.9 cm 3 / g. It was. The results are summarized in Table 1.
- the resulting porous carbon material was added by 80 parts by weight, 10 parts by weight of acetylene black as a conductive assistant, 10 parts by weight of polyvinylidene fluoride as a binder, and 400 parts by weight of N-methyl-2-pyrrolidone as a solvent.
- An electrode coating solution was obtained by mixing with a Lee mixer. The electrode coating solution was applied to an aluminum foil (thickness 18 ⁇ m) using an applicator (300 ⁇ m), dried at 80 ° C. for 30 minutes, and punched to a diameter of 16 mm to obtain an electrode. The electrode density was 0.43 g / cm 3 . Then, it vacuum-dried at 120 degreeC for 12 hours in the glass container connected with the joint with a vacuum pump and a glass cock, the cock was closed, the tube was removed with the vacuum state maintained, and it put into the glove box as it was.
- FC25CH1 Toray Battery Separator Film Co., Ltd.
- tetraethylammonium tetrafluoroborate / propylene carbonate (1M) was used as an electrolytic solution.
- a coin cell was prepared.
- a charge / discharge test was conducted. Constant current charge / discharge was performed at a current value of 1 mA in a voltage range of 0 to 2.5V. The charge / discharge of 4 cycles was performed, and the electrostatic capacity was calculated from the discharge curve of the 4th cycle.
- the capacitance was 20.2 F / g, and the capacitance per BET specific surface area was 0.85 ⁇ F / cm 2 .
- Table 1 The results are summarized in Table 1.
- Example 2 Although it was the same as that of Example 1 until the carbonization process and grinding
- Example 3 25 g of Wako Pure Chemical Industries, Ltd. polymethyl methacrylate (PMMA) and 100 g of acetone are added to 100 g of a 45 wt% methanol solution of phenol resole (grade: PL2211) manufactured by Gunei Chemical Co., Ltd., and dissolved to dissolve PMMA. did.
- PMMA polymethyl methacrylate
- acetone 100 g of a 45 wt% methanol solution of phenol resole (grade: PL2211) manufactured by Gunei Chemical Co., Ltd., and dissolved to dissolve PMMA. did.
- the prepared solution was poured into a polytetrafluoroethylene dish and dried at room temperature for 4 days. Further, after removing the solvent in a vacuum oven at 23 ° C. for 3 days, the oven temperature was set to 40 ° C. and drying was performed for 2 days in order to completely remove the solvent.
- the obtained sample was carbonized under the conditions of a nitrogen flow rate of 1 liter / min, a temperature rising rate of 10 ° C./min, an ultimate temperature of 700 ° C., and a holding time of 1 hour to obtain a porous carbon material.
- Example 2 Thereafter, pulverization and activation were performed in the same manner as in Example 1 to obtain a particulate porous carbon material.
- a co-continuous structure was formed in the obtained particulate porous carbon material.
- the average porosity of the co-continuous structure portion was 42%, and the structure period was 91 nm. Moreover, it had the structure which included the part which does not have a co-continuous structure in some particle
- the BET specific surface area was 1231 m 2 / g
- the average pore diameter by the MP method was 0.4 nm
- the average diameter of the pores by the BJH method was 20.1 nm
- the pore volume was 1.2 cm 3 / g.
- the obtained porous carbon material was not uniform in pore shape and size in the cross section, and an attempt was made to calculate the structure period, but the obtained scattering intensity distribution curve had no peak, and the structure The uniformity was inferior.
- the BET specific surface area was 1050 m 2 / g
- the average pore diameter by the MP method was 1.2 nm
- the average pore diameter by the BJH method was 2.2 nm
- the pore volume by the MP method was 1.9 cm 3 / g. It was.
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Abstract
Description
〔共連続構造部分〕
本発明の電気化学キャパシタ用電極材料(以下、単に「電極材料」ということがある。)は多孔質炭素材料からなる。本発明の電気化学キャパシタ用電極材料として用いられる多孔質炭素材料は、以下、便宜上「本発明の多孔質炭素材料」ということがある。また、本発明の多孔質炭素材料は、本発明の電気化学キャパシタ用電極材料と同じ意味で使用される場合がある。
ただし構造周期が大きくて小角での散乱が観測できない場合がある。その場合はX線コンピュータ断層撮影(X線CT)によって構造周期を得る。具体的には、X線CTによって撮影した三次元画像をフーリエ変換した後に、その二次元スペクトルの円環平均を取り、一次元スペクトルを得る。その一次元スペクトルにおけるピークトップの位置に対応する特性波長を求め、その逆数より構造周期を算出する。
平均空隙率は、高いほど他素材との複合の際に充填効率を高められ、電解液の流路として圧力損失が小さくなる。一方、平均空隙率は、低いほど圧縮や曲げに強くなるため、取り扱い性や加圧条件での使用に際して有利となる。これらのことを考慮し、共連続構造部分の平均空隙率は15~75%の範囲であることが好ましく、18~70%の範囲がさらに好ましい。
本発明の多孔質炭素材料の形態は特に限定されず、例えば粒子状、繊維状、フィルム状、粉末状、塊状、棒状、平板状、円盤状が挙げられるが、中でも粒子状または繊維状の形態であることが好ましい。
さらに、本発明の多孔質炭素材料は、表面に平均直径0.01~10nmの細孔を有することが好ましい。表面とは、多孔質炭素材料の共連続構造部分における炭素骨格の表面も含め、多孔質炭素材料のあらゆる外部との接触面を指す。細孔は、共連続構造部分における炭素骨格の表面および/または後述する共連続構造を実質的に有しない部分に形成することができる。少なくとも共連続構造を有する部分における炭素骨格の表面に形成することが好ましい。
本発明の多孔質炭素材料は、共連続構造を実質的に有しない部分(以下、単に「共連続構造を有しない部分」という場合がある。)を含んでいることも、好ましい態様である。共連続構造を実質的に有しない部分とは、クロスセクションポリッシャー法(CP法)により形成させた断面を、1±0.1(nm/画素)の拡大率で観察した際に、解像度以下であることにより明確な空隙が観察されない部分が、一辺が後述のX線から算出される構造周期Lの3倍に対応する正方形の領域以上の面積で存在することを意味する。
電気化学キャパシタ用電極材料として使用した際の多孔質炭素材料の表面の利用効率は、たとえば充放電試験により求めた静電容量をBET比表面積で除した値、すなわちBET比表面積あたりの静電容量にて評価される。充放電試験については後に実施例にて詳述する。BET比表面積あたりの静電容量が大きいほど、多孔質炭素材料の表面の利用効率が大きいため、低抵抗での充放電が可能になることから、電気化学キャパシタ用電極材料として高性能であることを意味する。
本発明の電気化学キャパシタの一つの態様である、電気二重層キャパシタの好ましい態様について以下に記述する。電気二重層キャパシタのセルは、正極と負極としての2つの電極がセパレータを介して配置され、さらに電解液に浸漬された構成を有する。本発明の電気二重層キャパシタは当該電極に本発明の多孔質炭素材料を含むものである。また、電極には、好ましくは、さらに導電助剤、バインダー、集電体が含まれる。電極は、本発明の多孔質炭素材料以外の多孔質炭素材料を1種または複数含んでもよい。
本発明の電気化学キャパシタは、高静電容量で、高速充放電が可能であるため、各種電子機器やエネルギーデバイスにおいて、効率的な電力貯蓄や、電力平準化等に活用できる。たとえば、燃料電池自動車、プラグインハイブリッド車、ハイブリッド車、電気自動車、携帯電話、スマートフォン、電車、コピー機、複合機、パソコン、航空機、各種家電、事務機器、工作機器、電動自転車、バイク、フォークリフト、建設機械、クレーン等の各種機械、電子機器に好適である。また、太陽光発電、風力発電、地熱発電、波力発電等の再生エネルギー関連機器や電力供給コントロール基地、さらには病院、工場、データセンター等のバックアップ電源に好適に利用される。
本発明の多孔質炭素材料は、一例として、炭化可能樹脂10~90重量%と消失樹脂90~10重量%とを相溶させて樹脂混合物とする工程(工程1)と、相溶した状態の樹脂混合物を相分離させ、固定化する工程(工程2)、加熱焼成により炭化する工程(工程3)を有する製造方法により製造することができる。
工程1は、炭化可能樹脂10~90重量%と、消失樹脂90~10重量%と相溶させ、樹脂混合物とする工程である。
工程2は、工程1において相溶させた状態の樹脂混合物を相分離させて微細構造を形成し、固定化する工程である。
工程2において相分離後の微細構造が固定化された樹脂混合物は、炭化工程(工程3)に供される前または炭化工程と同時、あるいはその両方で消失樹脂の除去処理を行うことが好ましい。除去処理の方法は特に限定されるものではなく、消失樹脂を除去することが可能であれば良い。具体的には、酸、アルカリや酵素を用いて消失樹脂を化学的に分解、低分子量化して除去する方法や、消失樹脂を溶解する溶媒により溶解除去する方法、電子線、ガンマ線や紫外線、赤外線等の放射線や熱を用いて消失樹脂を分解除去する方法等が好適である。
工程2において相分離後の微細構造が固定化された樹脂混合物である前駆体材料は、炭化工程(工程3)に供される前に不融化処理を行うことが好ましい。不融化処理の方法は特に限定されるものではなく、公知の方法を用いることができる。具体的な方法としては、酸素存在下で加熱することで酸化架橋を起こす方法、電子線、ガンマ線等の高エネルギー線を照射して架橋構造を形成する方法、反応性基を持つ物質を含浸、混合して架橋構造を形成する方法等が挙げられ、中でも酸素存在下で加熱することで酸化架橋を起こす方法が、プロセスが簡便であり製造コストを低く抑えることが可能である点から好ましい。これらの手法は単独もしくは組み合わせて使用しても、それぞれを同時に使用しても別々に使用しても良い。
工程3は、工程2において相分離後の微細構造が固定化された樹脂混合物、あるいは、消失樹脂を既に除去している場合には炭化可能樹脂からなる残存部分を焼成し、炭化して炭化物を得る工程である。
工程3において得た炭化物は、更に賦活処理を行うことで、表面に細孔を形成することができる。賦活の方法としては、ガス賦活法、薬品賦活法等、特に限定するものではない。ガス賦活法とは、賦活剤として酸素や水蒸気、炭酸ガス、空気等を用い、400~1500℃、好ましくは500~900℃にて、数分から数時間、加熱することにより細孔を形成させる方法である。また、薬品賦活法とは、賦活剤として塩化亜鉛、塩化鉄、リン酸カルシウム、水酸化カルシウム、水酸化カリウム、炭酸マグネシウム、炭酸ナトリウム、炭酸カリウム、硫酸、硫酸ナトリウム、硫酸カリウム等を1種または2種以上用いて数分から数時間、加熱処理する方法であり、必要に応じて水や塩酸等による洗浄を行った後、pHを調整して乾燥する。
工程3を経て炭化させた炭化物、あるいは任意に賦活処理を行った多孔質炭素材料を粉砕処理して粒子状とした多孔質炭素材料も、本発明の電極材料として好ましく用いられる。粉砕処理方法の例としては、ボールミル、ビーズミル、ジェットミル等を例示することができる。粉砕処理は、連続式でもバッチ式でも良いが、生産効率の観点から連続式であることが好ましい。ボールミルに充填する充填材は適宜選択される。金属材料の混入が好ましくない用途に対しては、アルミナ、ジルコニア、チタニア等の金属酸化物によるもの、もしくはステンレス、鉄等を芯としてナイロン、ポリオレフィン、フッ化ポリオレフィン等をコーティングしたものを用いることが好ましい。それ以外の用途であればステンレス、ニッケル、鉄等の金属が好適に用いられる。
本発明の電気化学キャパシタは、本発明の多孔質炭素材料を用いた電極を用いてなること以外は、従来の電気化学キャパシタと全く同様の方法によって製造できる。以下に好ましい態様について述べる。
〔共連続構造の有無〕
多孔質炭素材料を乳鉢で粉砕して得た粉末の表面を走査型電子顕微鏡によって表面観察した。その際、炭素骨格とその骨格以外の部分として形成された空隙とがそれぞれ連続しつつ絡み合った構造として観察される部分を有するか否かで、共連続構造の有無を判断した。
多孔質炭素材料を試料プレートに挟み込み、CuKα線光源から得られたX線源から散乱角度10度未満の情報が得られるように、光源、試料及び二次元検出器の位置を調整した。二次元検出器から得られた画像データ(輝度情報)から、ビームストッパーの影響を受けている中心部分を除外して、ビーム中心から動径を設け、角度1°毎に360°の輝度値を合算して、散乱強度分布曲線を得た。得られた曲線においてピーク値を持つかどうかで構造周期を有するかどうか確認した。ピーク値を持つ場合は、ピークを持つ位置の散乱角度2θより、連続構造部分の構造周期を下記の式によって得た。
〔平均空隙率〕
試料を樹脂中に包埋し、その後カミソリ等で多孔質炭素材料の断面を露出させ、日本電子製SM-09010を用いて加速電圧5.5kVにて試料表面にアルゴンイオンビームを照射、エッチングを施す。得られた多孔質炭素材料の断面を走査型二次電子顕微鏡にて材料中心部を1±0.1(nm/画素)となるよう調整された拡大率で、70万画素以上の解像度で観察した画像から、計算に必要な着目領域を512画素四方で設定し、着目領域の面積A、孔部分または消失樹脂部分の面積をBとして、以下の式で算出されたものを言う。
〔BET比表面積、細孔直径〕
試料を300℃で約5時間、減圧脱気した後、日本ベル社製の「BELSORP-18PLUS-HT」を使用し、液体窒素を用いて77Kの温度での窒素吸脱着を多点法で測定した。表面積はBET法、細孔分布解析(細孔直径、細孔容積)はMP法またはBJH法により行った。
電気化学キャパシタ用電極材料として使用した際の多孔質炭素材料の表面の利用効率は、後述する充放電試験により求めた静電容量をBET比表面積で除した値、すなわちBET比表面積あたりの静電容量にて評価した。
70gのポリサイエンス社製ポリアクリロニトリル(MW15万、炭素収率58%)と70gのシグマ・アルドリッチ社製ポリビニルピロリドン(MW4万)、及び、溶媒として400gの和研薬製ジメチルスルホキシド(DMSO)をセパラブルフラスコに投入し、3時間攪拌および還流を行いながら150℃で均一かつ透明な溶液を調整した。このときポリアクリロニトリルの濃度、ポリビニルピロリドンの濃度はそれぞれ13重量%であった。
炭化処理、粉砕までは実施例1と同様としたが、賦活処理以降の工程を実施せず、粒子状の多孔質炭素材料を得た。得られた多孔質炭素材料には共連続構造が形成されていた。共連続構造部分の平均空隙率は45%であり、構造周期は73nmであった。また、共連続構造を有しない部分を粒子の一部に含む構造をしていた。BET比表面積は39m2/gであり、BJH法による細孔の平均直径は12.1nm、MP法による細孔は確認できなかった。
群栄化学(株)社製フェノールレゾール(グレード:PL2211)の45重量%メタノール溶液100gに和光純薬( 株) 社製ポリメチルメタクリレート(PMMA)25g 、アセトン100gを加えて撹拌し、PMMAを溶解した。
ヤシガラを110℃にて24時間の真空乾燥を行い、窒素流量1リットル/分、昇温速度10℃/分、到達温度550℃、保持時間3時間の条件で炭化処理を行い、自然放冷した。次いで、窒素流量1リットル/分、昇温速度10℃/分、到達温度900℃まで昇温し、賦活処理として水蒸気を含んだ窒素を30分通過させた後自然放冷した。得られた粒子状の多孔質炭素材料は、断面内の孔形状、サイズが均一ではなく、構造周期の算出を試みたが、得られた散乱強度分布曲線にはピークが存在せず、構造の均一性に劣るものであった。BET比表面積は1050m2/g、MP法による細孔の平均直径は1.2nm、BJH法による細孔の平均直径は2.2nm、MP法による細孔容積は1.9cm3/gであった。
賦活処理において、水蒸気を含んだ窒素の通過時間を1時間とした以外は比較例1と同様の方法で多孔質炭素材料を得た。得られた粒子状の多孔質炭素材料は、断面内の孔形状、サイズが均一ではなく、構造周期の算出を試みたが、得られた散乱強度分布曲線にはピークが存在せず、構造の均一性に劣るものであった。BET比表面積は1490m2/g、MP法による細孔の平均直径は1.0nm、BJH法による細孔の平均直径は2.1nm、MP法による細孔容積は1.4cm3/gであった。
Claims (15)
- 炭素骨格と空隙とがそれぞれ連続構造をなす構造周期0.002~20μmの共連続構造部分を有する多孔質炭素材料からなる電気化学キャパシタ用電極材料。
- X線を入射して得られる散乱強度のピークの半値幅が5°以下である、請求項1に記載の電気化学キャパシタ用電極材料。
- 前記多孔質炭素材料の炭素骨格がポリアクリロニトリル由来である、請求項1または2に記載の電気化学キャパシタ用電極材料。
- 形態が粒子状である請求項1~3のいずれかに記載の電気化学キャパシタ用電極材料。
- 形態が繊維状である請求項1~3のいずれかに記載の電気化学キャパシタ用電極材料。
- 前記共連続構造部分の平均空隙率が10~80%である、請求項1~5のいずれかに記載の電気化学キャパシタ用電極材料。
- 表面に平均直径0.01~10nmの細孔を有する、請求項1~6のいずれかに記載の電気化学キャパシタ用電極材料。
- 前記細孔が、少なくとも前記共連続構造部分の炭素骨格の表面に形成されている、請求項7に記載の電気化学キャパシタ用電極材料。
- BET比表面積が20m2/g以上である、請求項1~8のいずれかに記載の電気化学キャパシタ用電極材料。
- BJH法またはMP法で計測される前記多孔質炭素材料の細孔容積が0.1cm3/g以上である、請求項1~9のいずれかに記載の電気化学キャパシタ用電極材料。
- 前記多孔質炭素材料がさらに共連続構造を実質的に有しない部分を有する、請求項1~10のいずれかに記載の電気化学キャパシタ用電極材料。
- 請求項1~11のいずれかに記載の電気化学キャパシタ用電極材料と、バインダーとを含む電気化学キャパシタ用電極塗工液。
- 請求項1~11のいずれかに記載の電気化学キャパシタ用電極材料を含む電気化学キャパシタ用電極。
- 電極密度が0.3~1.0g/cm3である請求項13に記載の電気化学キャパシタ用電極。
- 請求項13または請求項14に記載の電気化学キャパシタ用電極を用いてなる電気化学キャパシタ。
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JP2015545963A JPWO2016043154A1 (ja) | 2014-09-17 | 2015-09-14 | 電気化学キャパシタ用電極材料、電気化学キャパシタ用電極塗工液、電気化学キャパシタ用電極および電気化学キャパシタ |
KR1020177009040A KR20170056582A (ko) | 2014-09-17 | 2015-09-14 | 전기 화학 커패시터용 전극 재료, 전기 화학 커패시터용 전극 도공액, 전기 화학 커패시터용 전극 및 전기 화학 커패시터 |
CN201580047090.2A CN106663548B (zh) | 2014-09-17 | 2015-09-14 | 电化学电容器用电极材料、电极涂布液、电极及电化学电容器 |
US15/511,892 US10211000B2 (en) | 2014-09-17 | 2015-09-14 | Electrode material for electrochemical capacitor, electrode coating solution for electrochemical capacitor, electrode for electrochemical capacitor, and electrochemical capacitor |
EP15841206.4A EP3196905A4 (en) | 2014-09-17 | 2015-09-14 | Electrode material for electrochemical capacitor, electrode coating solution for electrochemical capacitor, electrode for electrochemical capacitor, and electrochemical capacitor |
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EP (1) | EP3196905A4 (ja) |
JP (1) | JPWO2016043154A1 (ja) |
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EP3178542B1 (en) * | 2014-07-24 | 2020-08-26 | Toray Industries, Inc. | Carbon film for fluid separation and fluid separation film module |
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CN111235698B (zh) * | 2020-03-24 | 2022-09-23 | 北华大学 | 一种氮掺杂多孔碳纤维材料的制备方法及其应用 |
DE102020119592A1 (de) * | 2020-07-24 | 2022-01-27 | Technische Universität Dresden | Verfahren zur Herstellung poröser Kohlenstofffasern und deren Verwendung |
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US20170323737A1 (en) | 2017-11-09 |
CN106663548B (zh) | 2019-08-02 |
JPWO2016043154A1 (ja) | 2017-06-29 |
EP3196905A4 (en) | 2018-05-30 |
TWI649772B (zh) | 2019-02-01 |
CN106663548A (zh) | 2017-05-10 |
EP3196905A1 (en) | 2017-07-26 |
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