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WO2012029918A1 - Matériau de carbone poreux, condensateur, condensateur hybride, et condensateur au lithium-ion, et électrodes destinées aux dits condensateurs - Google Patents

Matériau de carbone poreux, condensateur, condensateur hybride, et condensateur au lithium-ion, et électrodes destinées aux dits condensateurs Download PDF

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WO2012029918A1
WO2012029918A1 PCT/JP2011/069933 JP2011069933W WO2012029918A1 WO 2012029918 A1 WO2012029918 A1 WO 2012029918A1 JP 2011069933 W JP2011069933 W JP 2011069933W WO 2012029918 A1 WO2012029918 A1 WO 2012029918A1
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Prior art keywords
capacitor
porous carbon
carbon material
electrode
lithium ion
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English (en)
Japanese (ja)
Inventor
貴彦 井戸
知宏 香村
豊浩 碓氷
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Ibiden Co Ltd
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Ibiden Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • 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
    • 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, a capacitor electrode, a hybrid capacitor electrode, a lithium ion capacitor electrode, a capacitor, a hybrid capacitor, and a lithium ion capacitor.
  • capacitors electric double layer capacitors, hybrid capacitors, and lithium ion capacitors (hereinafter simply referred to as “capacitors”) are intended to be used in electric vehicles and the like, taking advantage of their low internal resistance and being able to charge and discharge in a short time. Development) is underway.
  • a porous carbon material made of activated carbon obtained by activating a petroleum coke-based material with alkali or water vapor, a porous carbon material made of activated carbon made of coconut shell or the like, and the like are known. .
  • the porous carbon material made of activated carbon includes pores having a pore diameter of 2 to 50 nm (hereinafter also referred to as mesopores), pores having a pore diameter smaller than 2 nm (hereinafter also referred to as micropores), and Many pores having pore diameters exceeding 50 nm (hereinafter also referred to as macropores) are formed.
  • the macropores include pores having a pore diameter of about 50 to 100 nm. For this reason, when a large number of macropores are formed, the porous carbon material becomes bulky, and in a capacitor electrode using the porous carbon material, the amount of electricity stored per unit volume (hereinafter, also simply referred to as electrode density) decreases. Conceivable.
  • the micropore has a large specific surface area, it is considered that the size of the pore is too small to allow the electrolyte to enter sufficiently. Further, for example, in an electrolytic solution composed of propylene carbonate and tetrabutylammonium ions, it is estimated that the electrolyte ions form a solvation having a diameter of about 0.86 nm. However, since most of the micropores are pores having a pore diameter smaller than 1 nm, the diameter of the electrolyte ions is close to the width of the micropores, and it is considered that the electrolyte ions are not sufficiently adsorbed to the micropores. Therefore, it is considered that the charge / discharge characteristics cannot be said to be sufficiently high in a capacitor electrode using a porous carbon material made of activated carbon in which many micropores and macropores are formed.
  • Patent Document 1 discloses a porous carbon material in which many mesopores are formed.
  • a porous carbon material is obtained by carbonizing a carbon precursor by heating a mixed material of inorganic particles such as silica and a carbon precursor such as phenol resin at 600 to 1500 ° C. Manufactured by etching with acid. The produced porous carbon material is pulverized and processed into carbon powder used for the capacitor electrode.
  • the conventional porous carbon material described in Patent Document 1 is said to be able to obtain many mesopores of a desired size by controlling the particle diameter of the inorganic particles in the production process.
  • Such a porous carbon material has a high specific surface area due to a small number of macropores, and a capacitor electrode using such a porous carbon material is considered to have a high electrode density.
  • the porous carbon material described in Patent Document 1 cannot be said to have a sufficiently high electrical conductivity, and the conductive material increases and the electrode density decreases. Therefore, in order to improve the charge / discharge characteristics of the capacitor electrode, further improvement in electrical conductivity is required.
  • the present inventors have completed the porous carbon material of the present invention having many suitable mesopores and high electrical conductivity.
  • the porous carbon material of the present invention forms pores in the pore diameter range of 2 to 200 nm in the differential pore volume distribution curve obtained by analyzing the adsorption isotherm obtained by the N 2 adsorption method by the BJH method.
  • the total value A of the pore volume included in the range of the pore diameter of 2 to 15 nm occupies 80% or more of the total value B of the pore volume included in the range of the pore diameter of 2 to 200 nm
  • the electrical conductivity is 10.5 Scm ⁇ 1 or more.
  • pores in the pore diameter range of 2 to 200 nm are formed in the differential pore volume distribution curve obtained by analyzing the adsorption isotherm obtained by the N 2 adsorption method by the BJH method. ing. Further, the total value A of differential pore volumes included in the range of pore diameters of 2 to 15 nm accounts for 80% or more of the total value B of differential pore volumes included in the range of pore diameters of 2 to 200 nm. .
  • mesopores with a high specific surface area are formed sufficiently more than macropores with a low specific surface area, the bulk is low, and an electrode for a capacitor using the porous material is The electrode density increases.
  • many mesopores having a size in which the electrolytic solution can easily enter are formed, and such a porous carbon material can be effectively used as an electrode for a capacitor.
  • the total value A may occupy 80% or more of the total value B, and the total value A may occupy 100% of the total value B. That is, the total value A may occupy 80 to 100% of the total value B.
  • the porous carbon material of the present invention has an electric conductivity of 10.5 Scm ⁇ 1 or more, it has a higher electric conductivity than the conventional porous carbon material. Therefore, when the porous carbon material of the present invention is used for a capacitor electrode, it can exhibit high charge / discharge characteristics coupled with the presence of the above-described mesopores. On the other hand, if the electrical conductivity of the porous carbon material is less than 10.5 Scm ⁇ 1 , the electrical conductivity is too low and it is necessary to add a large amount of a conductive material. Decreases.
  • the electric conductivity is desirably 20 to 50 Scm ⁇ 1 .
  • a capacitor electrode using a porous carbon material having an electric conductivity of 20 to 50 Scm ⁇ 1 can exhibit higher charge / discharge characteristics.
  • graphitization proceeds excessively due to the manufacturing method thereof, resulting in fewer mesopores.
  • the porous carbon material of the present invention preferably contains silicon carbide.
  • the silicon carbide content is more preferably 1 to 10% by weight. If the porous carbon material contains 1 to 10% by weight of silicon carbide, it is considered that the porous carbon material is less likely to be crushed into scales. Therefore, the porous carbon material can be easily pulverized, and the particle diameter of the carbon powder can be made more uniform.
  • the silicon carbide content is less than 1% by weight, the silicon carbide content is too small, making it difficult to align the particle diameter of the porous carbon material.
  • the content of silicon carbide exceeds 10% by weight, the electrical conductivity is greatly reduced.
  • the total value B is desirably 0.3 cm 3 / g or more, and the total value B is more desirably 0.4 to 1.2 cm 3 / g.
  • the capacitor electrode using such a porous carbon material can further improve the charge / discharge characteristics.
  • the total value B exceeds 1.2 cm 3 / g, the bulk density (weight per unit volume) of the porous carbon material decreases, and when such a porous carbon material is used, The electrode density is lowered.
  • the capacitor electrode of the present invention is characterized by comprising any one of the porous carbon materials of the present invention.
  • the hybrid capacitor electrode of the present invention is characterized by comprising any one of the porous carbon materials of the present invention.
  • the electrode for lithium ion capacitors of this invention consists of the porous carbon material in any one of this invention, It is characterized by the above-mentioned.
  • a capacitor according to the present invention includes a capacitor electrode made of any one of the porous carbon materials according to the present invention.
  • a hybrid capacitor of the present invention includes a hybrid capacitor electrode made of any one of the porous carbon materials of the present invention.
  • a lithium ion capacitor of the present invention includes a lithium ion capacitor electrode made of any one of the porous carbon materials of the present invention.
  • the porous carbon material of the present embodiment has pores in the pore diameter range of 2 to 200 nm in the differential pore volume distribution curve obtained by analyzing the adsorption isotherm obtained by the N 2 adsorption method by the BJH method. Is formed.
  • the BJH method used here is a method proposed by Barrett, Joyner, Halenda for determining the distribution of mesopores (EP Barrett, LG Joyner and PP Halenda, J. et al. Am. Chem. Soc., 73, 373, (1951)).
  • the total value A of the pore volumes included in the pore diameter range of 2 to 15 nm is equal to the total value B of the pore volumes included in the pore diameter range of 2 to 200 nm. It accounts for over 80%.
  • the electrical conductivity of the porous carbon material of the present embodiment is 10.5 Scm ⁇ 1 or more.
  • the electric conductivity is more preferably 10.5 to 50 Scm ⁇ 1 , and particularly preferably 20 to 50 Scm ⁇ 1 .
  • the electrical conductivity refers to the electrical conductivity obtained by measuring carbon powder prepared from a porous carbon material by a four-terminal method or a four-probe method. Details of the measurement method are described in the Examples.
  • the porous carbon material further contains silicon carbide, and its content is 1 to 10% by weight.
  • the content of silicon carbide contained in the porous carbon material refers to the content of silicon carbide measured using an ICP (Dielectric Coupled Plasma) emission spectrometer. Details of the measurement method are described in the Examples.
  • the total value B of the pore volumes included in the pore diameter range of 2 to 200 nm is 0.3 cm 3 / g or more.
  • the sum B is more desirably is 0.3 ⁇ 1.2cm 3 / g, and particularly desirably 0.4 ⁇ 1.2cm 3 / g.
  • the BET specific surface area is 300 m 2 / g or more.
  • the BET specific surface area is more preferably 350 to 1000 m 2 / g.
  • the BET specific surface area refers to the specific surface area determined by the BET method. Details of the method for measuring the BET specific surface area are described in Examples.
  • the porous carbon material of the present embodiment includes a first composite material in which a modifying group containing a pore source is bonded to the terminal or side chain of a polymer chain constituting the first organic material, or a pore source.
  • the second composite material composed of the inorganic sol or metal alkoxide and the second organic material can be manufactured through a heating step of heating at a temperature not lower than 2200 ° C. and not lower than a temperature at which a part of the pore source is decomposed and vaporized.
  • a modifying group for example, an organosilicon compound included in the first composite material becomes a pore source.
  • a part of silica generated by desorbing an organosilicon compound or the like from the first composite material or a part of the desorbed organosilicon compound is vaporized in the heating step described later. . As a result, it is considered that pores are formed.
  • thermosetting resin is mentioned as a 1st organic material.
  • thermosetting resins include phenolic resins, epoxy resins, polyimide resins, melamine resins, polyamideimide resins, urethane resins, amino resins, unsaturated polyester resins, diallyl phthalate resins, alkyds. Resin, silicon resin and the like.
  • phenol-based resins, epoxy-based resins, polyimide-based resins, melamine-based resins, or polyamide-imide-based resins are preferable, and phenol-based resins or polyimide-based resins having a network skeleton are particularly preferable.
  • the phenolic resin refers to a phenol resin and a resin containing a phenol resin as a main component (for example, a modified phenol resin).
  • the epoxy resin refers to an epoxy resin and a resin mainly composed of an epoxy resin. The same applies to other resins.
  • the modifying group examples include an organosilicon compound.
  • the organosilicon compound has functional groups such as a vinyl group, a methacryl group, an epoxy group, an amino group, a nitrogen-containing group, a sulfur-containing alkyl group, and a hydroxyl group.
  • specific examples of the organosilicon compound include alkoxysilanes (for example, alkoxysilane compounds, alkoxysilane oligomers, polyalkoxysilanes, silane coupling agents, and the like).
  • the organosilicon compound has a reactive functional group such as a vinyl group, a methacryl group, an epoxy group, an amino group, a nitrogen-containing group, a sulfur-containing alkyl group, and a hydroxyl group. Therefore, the first composite material is formed by bonding a modifying group such as an organosilicon compound to the first organic material via these functional groups.
  • alkoxysilane compound examples include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane; trialkoxysilanes; or a polymer thereof.
  • the alkoxysilane compound to be bonded is preferably an alkoxysilane oligomer that is a polymer.
  • tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane or polymers thereof are preferable.
  • alkoxysilane compounds tetramethoxysilane or a polymer thereof is represented by chemical formula (1).
  • R represents a methyl group or a methoxy group.
  • N is an integer of 0 or more.
  • an alkoxysilane oligomer in which n in the chemical formula (1) is 2 to 10 can be used by reducing the polymerization degree of the alkoxysilane compound.
  • the alkoxysilane oligomer can form a large number of bonds with the first organic material such as a phenol resin, and a large number of uniform mesopores can be formed after the heating step.
  • silane coupling agent examples include vinyltriethoxysilane, vinyltrimethoxysilane, tris ( ⁇ -methoxyethoxy) vinylsilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ - (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Trimethoxysilane, (N-phenyl- ⁇ -aminopropyl) trimethoxysilane, ⁇ -ureidopropyltriethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -
  • the silane coupling agent undergoes an addition reaction with the first organic material such as a phenol resin through the functional group to form a first composite material.
  • Silane coupling agents are those in which a hydrolyzable group that easily binds inorganic components and a functional group that easily bonds organic components are bonded to silicon atoms (Si), and are usually used as resin modifiers. It is. By the chemical reaction of the functional group of the silane coupling agent, it bonds with the first organic material, and a crosslinked structure by the silane coupling agent is formed in the first organic material.
  • a phenol resin modified with an alkoxysilane compound hereinafter also referred to as an alkoxysilane-modified phenol resin
  • a polyamideimide resin modified with an alkoxysilane compound hereinafter referred to as an alkoxysilane-modified polyamide
  • the polyimide resin modified with an alkoxysilane compound hereinafter also referred to as an alkoxysilane-modified polyimide resin
  • a phenol resin modified with an alkoxysilane compound can be produced by reacting a phenol resin with an alkoxysilane oligomer that does not have a highly reactive functional group.
  • Chemical formula (2) shows the chemical structure of a phenol resin modified with an alkoxysilane compound.
  • part of a phenol resin and an alkoxysilane compound can be selected arbitrarily.
  • R represents a methyl group or a methoxy group.
  • M is an integer of 1 or more.
  • the phenolic resin modified with the alkoxysilane compound is mixed with a curing reagent and cured by heating at about 170 ° C. for about 30 minutes, at about 100 ° C. for about 30 minutes, at about 220 ° C. for about 120 minutes, etc. You may let them.
  • the curing reaction agent include hexamethylenetetramine, 2-ethyl-4-methyl-imidazole, formaldehyde and the like.
  • Polyamideimide resin modified with alkoxysilane compound is a sol-gel cure (alkoxysilane hydrolysis and condensation reaction) by reacting amide bond of polyamic acid and aromatic carboxylic acid with alkoxysilane (alkoxysilane oligomer). After that, the obtained gel is heat-cured at 120 to 250 ° C.
  • Chemical formula (3) shows the chemical structure of a polyamide-imide resin modified with an alkoxysilane compound. Note that the alkoxysilane compound can be bonded to any part of the polyamideimide resin.
  • X represents an alkyl spacer.
  • M is an integer of 1 or more, and n is an integer of 1 or more.
  • a polyimide resin modified with an alkoxysilane compound is a method for preparing a polyamideimide resin modified with an alkoxysilane compound described above, except that a polyamic acid is used instead of an amide conjugate of a polyamic acid and an aromatic carboxylic acid. It can be prepared by the same method. That is, a polyimide resin modified with an alkoxysilane compound is obtained by performing sol-gel curing (alkoxysilane hydrolysis and condensation reaction) by reacting polyamic acid with alkoxysilane (alkoxysilane oligomer), and then obtained. The gel can be produced by heating at 120 to 430 ° C. for imidization.
  • Chemical formula (4) shows the chemical structure of a polyimide resin modified with an alkoxysilane compound. Note that the alkoxysilane compound can be bonded to any part of the polyimide resin.
  • x is an integer of 1 or more
  • y is an integer of 1 or more
  • n is an integer of 1 or more.
  • a first composite material In order to form a first composite material by reacting an alkoxysilane (alkoxysilane oligomer) with a first organic material such as a phenol resin, an alkoxysilane (alkoxysilane oligomer) is added to the mixture in the sol state.
  • the polysiloxane is bonded to the first organic material by performing a polymerization reaction together with the hydrolysis. Then, for example, heating is performed at a temperature of 100 to 200 ° C. to form a bridge between the first organic materials by a sol-gel reaction, and the sol state is cured to the gel state.
  • an alkoxysilane (alkoxysilane oligomer) can be bonded to an arbitrary portion of the first organic material such as a phenol resin at a uniform interval, and the polysiloxane in the first organic material can be crosslinked and cured. Can be uniformly distributed.
  • the size and quantity of the pores can be controlled by adjusting the molecular weight and bonding point of the polysiloxane bonded in the first organic material such as phenol resin.
  • the first organic material such as phenol resin.
  • the bonding points of alkoxysilane (alkoxysilane oligomer) are increased in the first organic material, a large number of polysiloxane bonds in the first organic material.
  • the bonding points of alkoxysilane (alkoxysilane oligomer) are reduced, the bonding points of polysiloxane are reduced.
  • the fine structure of the carbon obtained by the heating process that is, the pore size and the number of pores are adjusted by the bonding point and bonding amount of the polysiloxane.
  • the structure of the composite may be a structure in which silica particles are dispersed in the phenol resin.
  • a structure dispersed in a phenolic resin cross-linked with (1) can also be considered.
  • sica means not only ceramic silica (SiO 2 ) but also Si—O units in organic materials. The same applies to other inorganic compounds other than silica.
  • the inorganic compound contained in the inorganic sol is vaporized or vaporized after the inorganic compound contained in the second organic material is desorbed. As a result, it is considered that pores are formed.
  • Examples of the inorganic sol include silica sol, alumina sol, magnesia sol, zirconia sol, and titania sol. Among these, silica sol, alumina sol, or magnesia sol is desirable, and silica sol is more desirable from the viewpoint of evaporability.
  • Silica sol includes organosilica sol.
  • the metal alkoxide include alkoxysilanes (eg, alkoxysilane compounds, alkoxysilane oligomers, polyalkoxysilanes, and silane coupling agents). Since the alkoxysilanes are the same as those described in the first composite material, the description thereof is omitted here.
  • alkoxysilanes eg, alkoxysilane compounds, alkoxysilane oligomers, polyalkoxysilanes, and silane coupling agents. Since the alkoxysilanes are the same as those described in the first composite material, the description thereof is omitted here.
  • thermosetting resins include phenolic resins, epoxy resins, polyimide resins, melamine resins, polyamideimide resins, urethane resins, amino resins, unsaturated polyester resins, diallyl phthalate resins, alkyds. Resin, silicon resin and the like. Among these resins, phenol-based resins, epoxy-based resins, polyimide-based resins, melamine-based resins, or polyamide-imide-based resins are preferable, and phenol-based resins or polyimide-based resins having a network skeleton are particularly preferable.
  • the second organic material may be a first composite material.
  • the second composite material having a structure in which inorganic compound particles contained in the inorganic sol are dispersed in the second organic material is a mixture of an inorganic sol such as an organosilica sol and a second organic material such as a phenol resin. And it can produce
  • Heating process a heating process for obtaining a porous carbon material by heating the first composite material or the second composite material containing the pore source at a temperature not lower than 2200 ° C. and not lower than a temperature at which a part of the pore source decomposes and vaporizes will be described. To do.
  • a heating process is performed in inert gas atmosphere, such as nitrogen and argon.
  • the pressure in a heating process is not specifically limited, Usually, it is desirable that it is about a normal pressure.
  • the heating time in the heating step is not particularly limited, but is preferably 1 to 100 hours, and more preferably 2 to 10 hours.
  • the temperature in the heating step is not less than the temperature at which a part of the pore source contained in the first composite material or the second composite material is decomposed and vaporized, and not more than 2200 ° C. Therefore, the temperature in the heating step is appropriately determined according to the type of the first composite material or the second composite material and other heating conditions (temperature rise temperature, heating time, etc.), but exceeds 1500 ° C.
  • the temperature is desirably 2200 ° C.
  • the temperature rising rate in the heating step is usually about 10 to 400 ° C./hour, and preferably about 20 to 200 ° C./hour. Further, it is considered that the pore source can be efficiently vaporized by increasing the CO partial pressure in the heating step.
  • the produced porous carbon material may be subjected to a post-treatment step or a pulverization step described below, if necessary.
  • a post-treatment step of treating the obtained porous carbon material with a base or acid may be performed after the heating step. Residual components can be removed by the post-treatment process.
  • etching is performed using a base such as sodium hydroxide (NaOH) or an acid such as hydrofluoric acid (HF).
  • a base such as sodium hydroxide (NaOH) or an acid such as hydrofluoric acid (HF).
  • HF hydrofluoric acid
  • a carbon powder having a predetermined particle diameter By pulverizing the produced porous carbon material, a carbon powder having a predetermined particle diameter can be obtained.
  • the pulverization of the porous carbon material can be performed using an ultrafine pulverizer, a ball mill, a jet mill or the like.
  • the particle diameter (D50) of the carbon powder after the pulverization step is preferably 0.5 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m. When the particle diameter of the carbon powder is 1 to 5 ⁇ m, a uniform electrode can be formed even when the thickness is small when used as an electrode for a capacitor.
  • the particle size (D50) of the porous carbon material can be obtained by measuring a pulverized carbon powder suspension with a particle size distribution measuring device and a particle size distribution measuring device (laser diffraction type).
  • D50 means that the volume is accumulated from particles having a small particle diameter on a volume basis and becomes 50% of the volume of the entire particle, and the particle diameter (D50) is the particle diameter at D50. Show.
  • a step of pulverizing the obtained porous carbon material (post-heating pulverization step) is performed, and the material obtained by the pulverization step is obtained.
  • the other conditions are the same as those in the heating step except that the material obtained in the post-heating pulverization step is heated at a temperature higher than the temperature in the heating step.
  • the temperature in the additional heating step is preferably from the heating temperature (temperature in the heating step) to 2200 ° C.
  • each condition in the post-processing step is the same as each condition in the post-processing step performed after the heating step.
  • the material containing the pore source is heated at a temperature lower than the temperature in the heating step (preheating step)
  • a step of crushing the material obtained by the preheating step may be performed. After removing a part of the pore source in the preheating step, the obtained material is pulverized, and the pulverized material is heated again, so that the pore source can be reliably removed.
  • the preheating step other conditions are the same as those in the heating step, except that the material including the pore source is heated at a temperature lower than the temperature in the heating step.
  • the temperature in the preheating step is desirably 400 ° C. to heating temperature (temperature in the heating step).
  • each condition in the post-processing step is the same as each condition in the post-processing step performed after the heating step.
  • the capacitor electrode, the capacitor electrode manufacturing method, the capacitor, and the capacitor manufacturing method of this embodiment will be described.
  • a lithium ion capacitor electrode which is a kind of hybrid capacitor electrode will be described as an example of the capacitor electrode
  • a lithium ion capacitor which is a kind of hybrid capacitor will be described as an example of the capacitor.
  • FIG. 1 is a cross-sectional view schematically showing a lithium ion capacitor of the present invention.
  • a lithium ion capacitor 1 according to this embodiment shown in FIG. 1 includes a lithium ion capacitor electrode (a positive electrode is indicated by reference numeral 2 and a negative electrode is indicated by reference numeral 3), a separator 4 and an electrolytic solution (not shown). .
  • the positive electrode 2 and the negative electrode 3 are provided so as to face each other with the separator 4 interposed therebetween.
  • the positive electrode 2 is a polarizable electrode comprising the porous carbon material of the present embodiment described above.
  • the positive electrode 2 includes an electrode composition made of the porous carbon material of the present embodiment, a positive electrode current collector 2a on which the electrode composition is formed, and a positive electrode tab 2b attached to the positive electrode current collector 2a.
  • the positive electrode tab 2b is taken out from the casing 5 to the outside.
  • the thickness of the positive electrode 2 is preferably 30 to 300 ⁇ m, more preferably 40 to 200 ⁇ m, and particularly preferably 50 to 150 ⁇ m.
  • the density of the positive electrode 2 is not particularly limited, but is preferably 0.30 to 10 g / cm 3 , more preferably 0.35 to 5.0 g / cm 3 , and particularly preferably 0.40 to 3.0 g / cm 3 . is there.
  • the positive electrode current collector 2a is made of, for example, metal, carbon, conductive polymer, and the like, and more preferably made of metal.
  • metal for the positive electrode current collector 2a aluminum, platinum, nickel, tantalum, titanium, stainless steel, copper, other alloys, or the like can be used. Among these, it is preferable to use copper, aluminum or an aluminum alloy from the viewpoint of electrical conductivity and voltage resistance.
  • Examples of the shape of the positive electrode current collector 2a include current collectors such as metal foils and metal edged foils, and current collectors having through-holes such as expanded metal, punching metal, and net-like, but reduce diffusion resistance of electrolyte ions.
  • a positive electrode current collector having a through-hole is preferable in that the output density of the lithium ion capacitor can be improved, and among them, expanded metal or punching metal is more preferable in that the electrode strength is further excellent.
  • the ratio of the holes in the positive electrode current collector 2a is preferably 10 to 80 area%, more preferably 20 to 60 area%, and particularly preferably 30 to 50 area%. When the ratio of the penetrating holes is within this range, the diffusion resistance of the electrolytic solution is reduced, and the internal resistance of the lithium ion capacitor is reduced.
  • the hole of a positive electrode electrical power collector should just be provided only in the case of a lithium ion capacitor, and the hole need not be provided in the case of an electric double layer capacitor.
  • the thickness of the positive electrode current collector 2a is preferably 5 to 100 ⁇ m, more preferably 10 to 70 ⁇ m, and particularly preferably 20 to 50 ⁇ m. *
  • the negative electrode 3 is an electrode including a negative electrode active material that can occlude and release lithium ions.
  • the negative electrode 3 is provided with a negative electrode current collector 3a.
  • a negative electrode tab 3b is attached to the negative electrode current collector 3a, and the negative electrode tab 3b is taken out from the casing 5 to the outside.
  • the negative electrode current collector 3b is made of, for example, copper, nickel, stainless steel, and alloys thereof.
  • the negative electrode 3 is preferably preliminarily occluded with lithium ions. Lithium ions can be occluded in the negative electrode by a chemical method or an electrochemical method.
  • Examples of the chemical method include a method of immersing lithium ions by immersing in an electrolytic solution in a state where a negative electrode and a necessary amount of lithium metal are in contact with each other and applying heat.
  • Examples of the electrochemical method include a method in which lithium ions are occluded by making a negative electrode and lithium metal face each other through a separator and charging with constant current in an electrolytic solution.
  • the separator 4 is not particularly limited as long as it can insulate between lithium ion capacitor electrodes and allow ions to pass therethrough.
  • a polyolefin such as polyethylene or polypropylene, a microporous membrane made of rayon or glass fiber, a nonwoven fabric made of rayon or glass fiber, a porous membrane made mainly of pulp (generally called electrolytic capacitor paper), or the like is used. be able to.
  • the thickness of the separator 4 is preferably 1 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, and particularly preferably 20 to 60 ⁇ m.
  • the casing 5 may be formed of a laminate film, a metal case, a resin case, a ceramic case, or the like.
  • the shape is not particularly limited, and may be a coin shape, a cylindrical shape, a square shape, or the like.
  • the electrolytic solution is composed of an electrolyte and a solvent.
  • a lithium salt can be used as the electrolyte. Therefore, lithium ions can be used as cations.
  • As anions PF 6 ⁇ , BF 4 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , N (RfSO 3 ) 2 ⁇ , C (RfSO 3 ) 3 ⁇ , RfSO 3 ⁇ (Rf is 1 to 12 carbon atoms, respectively) F ⁇ , ClO 4 ⁇ , AlCl 4 ⁇ , AlF 4 ⁇ and the like can be used.
  • These electrolytes can be used alone or in combination of two or more.
  • the concentration of the lithium salt as the electrolyte is preferably 0.1 to 2.5 mol / l.
  • a solvent will not be specifically limited if it is a non-aqueous electrolyte solution which can be used for a capacitor or a lithium ion capacitor.
  • Specific examples include carbonates such as propylene boat, ethylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate, and diethyl carbonate; lactones such as ⁇ -butyrolactone; sulfolanes; nitriles such as acetonitrile.
  • These solvents can be used alone or as a mixed solvent of two or more. Of these, carbonates are preferred.
  • the electrode for a lithium ion capacitor of this embodiment can be manufactured through the following steps (1) to (3).
  • Positive electrode composition preparation step A slurry for a positive electrode composition is prepared by mixing a carbon powder made of the porous carbon material of the present embodiment, a conductive material, a binder and water.
  • binder examples include polytetrafluoroethylene, styrene butadiene rubber, polytetrafluoroethylene, styrene butadiene rubber (SBR), and polyvinylidene fluoride (PVDF). These binders can be used alone or in combination of two or more.
  • polytetrafluoroethylene is preferable.
  • the binder is preferably a powder in order to facilitate the moldability.
  • the amount of the binder used is preferably, for example, 1 to 30 parts by weight with respect to 100 parts by weight of the carbon powder.
  • the conductive material is made of particulate carbon that has almost no pores that can form an electric double layer.
  • furnace black acetylene black, and ketjen black (registered by Akzo Nobel Chemicals Bethloten Fennaut Shap) Trade name) and the like.
  • acetylene black and furnace black are preferable.
  • These conductive materials can be used alone or in combination of two or more.
  • the average particle size of the conductive material is preferably smaller than the average particle size of the carbon powder made of the porous carbon material, more preferably 0.001 to 10 ⁇ m, still more preferably 0.05 to 5 ⁇ m, and particularly preferably 0.00. 01 to 1 ⁇ m. When the average particle diameter of the conductive material is within this range, high electrical conductivity can be obtained.
  • the amount of the conductive material is preferably in the range of 0.1 to 50 parts by weight, more preferably 0.5 to 15 parts by weight, and still more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the carbon powder. When the amount of the conductive material is within this range, the capacity of the lithium ion capacitor using the obtained lithium ion capacitor electrode can be increased, and the internal resistance can be decreased.
  • the positive electrode 2 can be produced by such a wet molding method.
  • a method of laminating a positive electrode composition molded into a sheet shape on a positive electrode current collector (kneading sheet molding method), preparing composite particles of the positive electrode composition, forming a sheet on the positive electrode current collector, Examples thereof include a roll press method (dry molding method).
  • a wet molding method and a dry molding method are preferable, and a wet molding method is more preferable.
  • Negative electrode preparation step The negative electrode 3 is prepared by mixing a negative electrode active material, a binder, and a conductive material, adding this to a solvent to prepare a slurry for a negative electrode composition, and applying this slurry to the negative electrode current collector 3a. And dried to form.
  • the negative electrode may be produced by a kneading sheet molding method or a dry molding method.
  • the negative electrode active material may be any material that can reversibly carry lithium ions.
  • electrode active materials used in the negative electrode of lithium ion secondary batteries can be widely used.
  • crystalline carbon materials such as graphite and non-graphitizable carbon, carbon materials such as hard carbon and coke, and polyacene-based substances (PAS) are preferable.
  • These carbon materials and PAS are obtained by carbonizing a phenol resin or the like, activated as necessary, and then pulverized.
  • the same binder and conductive material as the positive electrode can be used.
  • the positive electrode 2 is attached to the upper casing, and the negative electrode 3 is attached to the lower casing.
  • the separator 4 is installed between the positive electrode 2 and the negative electrode 3, and after impregnating with electrolyte solution, a casing is sealed. Thereby, the lithium ion capacitor of this embodiment can be manufactured.
  • the electrode for capacitors the electrode for hybrid capacitors, the electrode for lithium ion capacitors, a capacitor, a hybrid capacitor, and a lithium ion capacitor is described.
  • the porous carbon material of the present embodiment has a fine pore diameter range of 2 to 200 nm in the differential pore volume distribution curve obtained by analyzing the adsorption isotherm obtained by the N 2 adsorption method by the BJH method.
  • the total value A of the differential pore volume included in the pore diameter range of 2 to 15 nm is 80% of the total value B of the differential pore volume included in the pore diameter range of 2 to 200 nm. It accounts for the above. Therefore, in the porous carbon material of this embodiment, the mesopores having a high specific surface area are formed sufficiently more than the macropores having a low specific surface area, the bulk is low, and the electrode for a capacitor using the porous material is used. Increases the electrode density.
  • the porous carbon material of this embodiment has an electric conductivity of 10.5 Scm ⁇ 1 or more, it has a sufficiently high electric conductivity as compared with the conventional porous carbon material. Therefore, when the porous carbon material of this embodiment is used for a capacitor electrode, it can exhibit high charge / discharge characteristics coupled with the presence of the above-described mesopores.
  • the electrical conductivity of the porous carbon material is less than 10.5 Scm ⁇ 1 , the electrical conductivity is too low, and it is necessary to add a large amount of a conductive material. Decreases.
  • the porous carbon material of the present embodiment has an electric conductivity of 20 to 50 Scm ⁇ 1 , a capacitor electrode using this porous carbon material can exhibit higher charge / discharge characteristics. .
  • a porous carbon material having an electric conductivity of more than 50 Scm ⁇ 1 graphitization proceeds excessively due to the manufacturing method thereof, resulting in fewer mesopores.
  • the porous carbon material of this embodiment contains silicon carbide, and its content is 1 to 10% by weight. Since 1 to 10% by weight of silicon carbide is contained in the porous carbon material, it is considered that the porous carbon material is less likely to be crushed into a scaly shape. Therefore, the porous carbon material can be easily pulverized, and the particle diameter of the carbon powder can be made more uniform. On the other hand, if the silicon carbide content is less than 1% by weight, the silicon carbide content is too small, making it difficult to align the particle diameter of the porous carbon material. On the other hand, when the content of silicon carbide exceeds 10% by weight, the electrical conductivity is greatly reduced.
  • the total value B is 0.3 cm 3 / g or more. Since the total value B is 0.3 cm 3 / g or more, there are many mesopores. Therefore, in the capacitor electrode using such a porous carbon material, the charge / discharge characteristics can be further improved. On the other hand, when the total value B exceeds 1.2 cm 3 / g, the bulk density (weight per unit volume) of the porous carbon material decreases, and when such a porous carbon material is used, The electrode density is lowered.
  • the capacitor electrode, the hybrid capacitor electrode, or the lithium ion capacitor electrode of the present embodiment is characterized by being made of any one of the porous carbon materials of the present embodiment.
  • Various capacitors using these electrodes are excellent in charge / discharge characteristics.
  • the capacitor, the hybrid capacitor, or the lithium ion capacitor of the present embodiment includes the capacitor electrode, the hybrid capacitor electrode, or the lithium ion capacitor electrode made of any one of the porous carbon materials of the present embodiment.
  • These capacitors are provided with electrodes having excellent charge / discharge characteristics, they are excellent in charge / discharge characteristics.
  • Example 1 A porous carbon material according to this example was manufactured through the following steps (1) and (2).
  • the adsorption isotherm obtained by the above operation was used to obtain the BET specific surface area by the BET method.
  • the BET specific surface area was 536 m 2 / g.
  • the BET specific surface area was measured by a capacity method and a multipoint method according to JIS Z 8830 (2001).
  • the electrical conductivity of the carbon powder obtained in the step (3) was measured as follows.
  • a powder resistance measurement system (powder resistance measurement system MCP-PD51 type, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used. First, set the carbon powder in the measurement system, gradually apply pressures of 4 kN, 8 kN, 12 kN, 16 kN, and 20 kN, and apply the pressure to the carbon powder. Conductivity was measured. As a result, the electric conductivity of the carbon powder at 20 kN load was 27.7 Scm ⁇ 1 .
  • Example 2 A porous carbon material was produced in the same manner as in Example 1 except that the heating conditions in the step (2) of Example 1 were changed as shown in Table 1 below.
  • Example 5 A polyamide-imide resin modified with an alkoxysilane compound synthesized by introducing siloxane into the basic skeleton of an aromatic polyamide-imide synthesized from trimellitic anhydride and diphenylmethane-4,4′-diisocyanate was used. A film was obtained in the same manner as in Example 1 for the polyamideimide resin modified with the alkoxysilane compound. The obtained film was cut into a predetermined size and heated at 1800 ° C. for 2 hours under heating conditions in an N 2 atmosphere. By passing through the above process, the porous carbon material of Example 5 was manufactured.
  • Example 6 A polyimide resin (HBPI-SiO 2 -A manufactured by Ibiden Resin Co., Ltd.) modified with an alkoxysilane compound was prepared, and a film was obtained in the same manner as in Example 1. The obtained film was cut into a predetermined size, and heated at 2000 ° C. for 2 hours under N 2 atmosphere heating conditions. The porous carbon material of Example 6 was manufactured through the above steps.
  • Example 1 A porous carbon material was produced in the same manner as in Example 1 except that the film was heated at 800 ° C. for 2 hours in an N 2 atmosphere and then treated with 48% hydrofluoric acid (HF aqueous solution) for 24 hours.
  • HF aqueous solution hydrofluoric acid
  • Comparative Example 2 As the porous carbon material of Comparative Example 2, commercially available activated carbon (Calgon Carbon Japan Co., Ltd., Diasorb (registered trademark) F 100D) was used.
  • Example 2 For the porous carbon materials of Examples 2 to 6 and Comparative Examples 1 and 2, similar to Example 1, preparation of differential pore volume distribution curve, measurement of BET specific surface area, measurement of electrical conductivity and carbonization The content of silicon was measured.
  • Table 1 shows the types of resin composites in Examples 2 to 6 and Comparative Examples 1 and 2, heating conditions, and various test results together with the results of Example 1 and the like.
  • the porous carbon materials produced in Examples 1 to 6 pores included in the pore diameter range of 2 to 200 nm were formed, and the pore diameter ranged from 2 to 15 nm.
  • the total value A of the differential pore volume included occupies 80% or more of the total value B of the differential pore volume included in the pore diameter range of 2 to 200 nm.
  • the porous carbon materials produced in Examples 1 to 6 have a total value B of 0.3 cm 3 / g or more. Therefore, the porous carbon materials produced in Examples 1 to 6 are sufficiently low in bulk, and it is considered that the capacitor electrode using the porous carbon material has a high electrode density.
  • porous carbon materials produced in Examples 1 to 6 have an electric conductivity of 10.5 Scm ⁇ 1 or more, which is sufficiently higher than the conventional porous carbon materials shown in Comparative Examples 1 and 2. It has conductivity. Therefore, it is considered that when these porous carbon materials are used for capacitor electrodes, high charge / discharge characteristics can be exhibited. Furthermore, since the porous carbon materials produced in Examples 1 to 6 have a silicon carbide content of 1 to 10% by weight, they are easily pulverized, and it is considered that the particle diameter of the carbon powder can be made more uniform. .
  • the porous carbon material of Comparative Example 1 has an electric conductivity of less than 10.5 Scm ⁇ 1 , and when used for a capacitor electrode, it is considered that the charge / discharge characteristics are lowered. Further, it is considered that no silicon carbide is contained, and the particle diameter of the carbon powder is not more uniform than the carbon particles produced in Examples 1 to 6.
  • the total value A of differential pore volumes included in the range of pore diameters 2 to 15 nm accounts for 69% of the total value B of differential pore volumes included in the range of pore diameters 2 to 200 nm. However, the total value B is less than 0.3 cm 3 / g.
  • the electric conductivity is less than 10.5 Scm ⁇ 1 . Therefore, the capacitor electrode using this porous carbon material is considered to have low charge / discharge characteristics.

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  • Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract

L'invention concerne un matériau de carbone poreux qui est caractéristique en ce que des pores dont le diamètre est compris dans une plage de 2 à 200nm, sont formés sur une courbe de distribution poreuse différentielle qui analyse selon un procédé BJH une isotherme d'adsorption obtenue par un procédé d'adsorption de N2. En outre, une valeur totale (A) de porosité comprise dans une plage de diamètre de pore de 2 à 15nm représente au moins 80% d'une valeur totale (B) de porosité comprise dans une plage de diamètre de pore de 2 à 200nm. Enfin, la conductivité électrique de ce matériau est au moins de 10,5Scm-1.
PCT/JP2011/069933 2010-09-02 2011-09-01 Matériau de carbone poreux, condensateur, condensateur hybride, et condensateur au lithium-ion, et électrodes destinées aux dits condensateurs Ceased WO2012029918A1 (fr)

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JP2013232602A (ja) * 2012-05-01 2013-11-14 Ibiden Co Ltd 蓄電デバイス用電極材料の製造方法、蓄電デバイス用電極、及び、蓄電デバイス
US9312077B2 (en) 2011-12-16 2016-04-12 Calgon Carbon Corporation Double layer capacitors
EP3700875A1 (fr) * 2017-10-27 2020-09-02 Heraeus Battery Technology GmbH Procédé de préparation d'un matériau de carbone poreux à l'aide d'une source de carbone améliorée
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