Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
  • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
  • C10B57/045—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing mineral oils, bitumen, tar or the like or mixtures thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/44—Carbon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/44—Carbon
  • C09C1/46—Graphite
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/32—Carbon-based
  • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
• • 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
  • C01P2006/40—Electric properties
• • 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
  • 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
  • Y02E60/30—Hydrogen technology
  • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

• the present invention relates to a raw material oil composition for producing a carbon material for an electric double layer capacitor (hereinafter referred to as EDLC) electrode, and in particular, a carbon material capable of expressing a high capacitance with good reproducibility.
• EDLC electric double layer capacitor
• the present invention relates to a raw material oil composition for producing
• the method of directly activating the raw material pitch has a problem that only EDLC with a capacitance of 20 F / cc can be obtained.
• a high electrostatic capacity can be obtained by the method of activation after dry distillation.
• a method for producing non-porous carbon of ⁇ 0.380 is disclosed (Claim 8), and EDLC using a carbon electrode obtained by this method has a high capacitance of 29 FZcc or higher. Specifically, it uses a carbon material that has been heat-treated (calcined) for 2-4 hours in a nitrogen stream at 650-850 ° C using petroleum-based needle coats or infusibilized pitch as a raw material. .
• JP 2004-182504A measures by X-ray diffraction.
• a method has been proposed in which a pitch having a crystallite thickness Lc (002) in the c-axis direction of 5. Onm or more is carbonized and then activated.
• a raw material pitch having such characteristics is obtained by using a condensed polycyclic hydrocarbon having at least one alkyl substituent, which is preferable for a synthetic pitch, as a raw material in the presence of hydrogen fluoride and boron trifluoride in a range of 100 to 400 °. It has been proposed to add 5% by mass or more of the synthetic pitch to an inexpensive pitch obtained by polymerizing with C and having no alkyl substituent such as naphthalene pitch or anthracene pitch.
• JP 2003-51430 discloses a method of heating raw material coal containing microcrystalline carbon having a layered crystal structure similar to graphite to 600 to 900 ° C. and then performing an activation treatment.
• the interlaminar distance d force obtained by X-ray diffraction is .343 nm or less.
• EDLC having a capacitance of 30 F / cc or more can be obtained by using a raw carbon composition having a crystallite size Lc002 of 3. Onm determined by X-ray diffraction. ing.
• Patent Document 5 states that "it can be obtained by coking heavy hydrocarbons that do not contain impurities such as sulfur and metals and that have appropriate aromaticity under appropriate conditions. . ”([0054]).
• ““ heavy hydrocarbons with moderate aromaticity ” are, for example, bottom oil of fluid catalytic cracking equipment of petroleum heavy oil, residual oil of vacuum distillation equipment, and tar of aromatic compounds. Is mentioned.
• petroleum coke of coking coal can be obtained by using such heavy hydrocarbons and heat-treating them under pressure with a delayed co. There is no discussion about the specific composition. It is a fact.
• An object of the present invention is to find a raw material oil composition having a composition capable of providing a carbon material for an electrode of an electric double layer capacitor capable of exhibiting a high capacitance with good reproducibility without producing a synthetic pitch. It is in.
• a raw material oil composition for producing raw coal includes mainly four components, a saturated component, an aroma component, a resin component, and a fasuart component.
• the present inventors have found that there is an optimum composition range for providing the carbon material for an electrode of an electric double layer capacitor for each component of the raw material oil composition, and have completed the present invention. .
• the present invention is a raw material oil composition for producing a carbon material for an electric double layer capacitor electrode, and is obtained by developing the raw material oil composition by a thin layer chromatography method.
• ingredients aroma components, resin components, and asphaltene components, saturated components
• the present invention relates to a feedstock composition characterized by being 72.
• the present invention includes a raw material carbon composition obtained from this raw material oil composition, a carbon material for an electrode of an electric double layer capacitor obtained by activating the raw material carbon composition, and the carbon material.
• the present invention relates to an electric double layer capacitor.
• a carbon material for an EDLC electrode that expresses a high electrostatic capacity with good reproducibility can be stably obtained without producing a synthetic pitch. This makes it possible to provide an EDLC with a high capacity and capacitance of 30F / cc or higher.
• the composition of the starting oil can be optimized as the carbon material for the EDLC electrode, so that the composition can be easily adjusted.
• the feedstock composition of the present invention is a total of a saturated component, an aroma component, a resin component, and a fasuart component obtained by developing the feedstock composition by thin layer chromatography. 00% by mass of the saturated component is 25% by mass or more, the asphaltene component is 16% by mass or less, the average molecular weight of the feed oil composition is 960 or less, and the aromatic carbon fraction of the feed oil composition A feed oil composition characterized in that (fa) is 0.22 to 0.72.
• the saturated component is preferably 30% by mass or more, and more preferably 35% by mass or more. Further, it is preferable that the asphaltene component is smaller, preferably 12% by mass or less, more preferably 8% by mass or less. Further, fa is preferably 0.25 or more, more preferably 0.30 or more. The average molecular weight is preferably 700 or less, more preferably 600 or less. When the saturated component is less than 25% by mass, the aroma component tends to increase relatively. When the saturated component is excessive, the aromatic carbon fraction (fa) may exceed the above upper limit. In addition, when the resin component increases, the molecular weight increases, and the average molecular weight specified above may be exceeded.
• the aroma component is preferably 35% by mass or more, and preferably 40% by mass or more.
• the aroma component is preferably 70% by mass or less, more preferably 65% by mass or less.
• Examples of the raw material oil include bottom oil in a fluid catalytic cracking apparatus for petroleum heavy oil, residual oil (VR) in a vacuum distillation apparatus, and tar of an aromatic compound.
• a raw material oil composition having a composition defined in the present invention is prepared by appropriately mixing them. For example, after combining appropriately, a part of the sample oil is sampled, and the feed oil that satisfies the conditions specified in the present invention is transferred to the next carbonization treatment process, and the feed oil that does not satisfy the conditions is re-prepared. Only those that satisfy the composition specified in the present invention are used in the next carbonization process.
• the raw oil composition does not contain impurities such as sulfur and metal as much as possible.
• the composition ratio of each component of the feedstock oil is measured by the TLC-FID method.
• the TLC-FID method is a method for saturating a sample by thin layer chromatography (TLC). Divide into Roma, Resin, and Fasuart components, and then detect each component with a Flame Ionization Detector (FID), and use the percentage of each component as a percentage of the total component. Is. For the measurement, “Iatroscan MK-5” (trade name) manufactured by Diatron (currently Mitsubishi Chemical Jatron) was used.
• a sample solution is prepared by dissolving 0.2 g ⁇ 0. Olg of a sample in 10 ml of toluene.
• a microsyringe to spot a thin silica gel rod layer (chroma rod) that has been baked in advance (0.5 cm of the rod holder) using a microsyringe and dry it with a drier.
• 10 chroma rods as a set and develop the sample with a developing solvent.
• developing solvents hexane was used in the first developing tank, hexane / toluene (20:80) was used in the second developing tank, and dichloromethane / methanol (95/5) was used in the third developing tank. Set the developed chroma rod to the Iaguchi scan and measure the amount of each component.
• the average molecular weight of the feedstock is measured by the vapor pressure equilibrium method.
• the outline of the vapor pressure equilibrium method is as follows. Place two thermistors in the saturated vapor of the solvent maintained at the prescribed temperature, and drop the sample solution on one side and the solvent alone on the other. At this time, since the vapor pressure of the sample solution is lower than that of the solvent alone, the vapor in the atmosphere around the thermistor condenses on the sample solution. Since the temperature rises due to the latent heat released at this time, this temperature difference is obtained as the voltage difference ( ⁇ ) of the thermistor, and the relationship between the molar concentration and the voltage difference ( ⁇ ) is obtained using a standard sample with a known molecular weight in advance.
• the aromatic carbon fraction (fa) is determined by the Knight method.
• the carbon distribution is divided into three components (A, A, A) using the 13 C-NMR spectrum of aromatic carbon.
• the raw material oil composition adjusted to a specific composition in this way is then subjected to a raw material charcoal preparation and activation treatment by a known method to prepare a carbon material for an EDLC electrode.
• the raw material oil composition having the predetermined composition is carbonized by a conventionally known method.
• a coking coal composition can be obtained by coking in an autoclave under pressure (for example, lMPa) at a temperature of about 400 to 600 ° C. for several hours.
• the raw material oil composition of the present invention is easily graphitized, and in the coking process, condensed polycyclic aromatics generated by a thermal decomposition reaction are laminated to become raw material coal containing microcrystalline carbon similar to graphite. .
• it is preferable that the graphite-like microcrystalline carbon is included in the raw material carbon composition.
• a carbon material for an EDLC electrode it can be obtained by activating the above raw material carbon composition.
• a conventionally known method can be applied, and examples thereof include an activation reaction with a drug and an activation reaction with a gas.
• An activation reaction using an alkali metal compound is particularly preferable. According to the activation treatment using such an alkali metal compound, the specific surface area of the obtained carbon material is further improved by allowing the alkali metal to enter and react between the layers of the graphite crystals.
• alkali metal compound various carbonates and hydroxides can be used. Specifically, sodium carbonate, potassium carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide, hydroxide Cesium is mentioned. Of these, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are preferred, and potassium hydroxide is particularly preferred. Two or more of these alkali metal compounds may be used in combination (for example, combined use of potassium hydroxide and sodium hydroxide).
• the activation method is usually performed by mixing and heating an activator such as an alkali metal compound and the raw carbon composition.
• the mixing ratio of the raw coal composition and the activator such as alkali metal hydroxide is not particularly limited, but the mass ratio of the two (raw coal composition: activator) is usually 1: 0. A range of 5 to 1: 1: 10 is preferable, and a range of 1 ::! To 1: 5 is more preferable.
• the activation reaction may not proceed sufficiently, and the required surface area may not be obtained.
• the specific surface area increases as the activator increases.
• the cost for activation increases, the activation yield decreases, and the bulk density of the resulting carbon material decreases, resulting in a decrease in capacitance per unit volume.
• the heating temperature in the activation treatment is not particularly limited, but the lower limit is usually 500 ° C, preferably 600 ° C, and the upper limit is usually 1000 ° C, preferably 900 ° C, particularly Preferably 800. C.
• the carbon material for an EDLC electrode is usually obtained through alkali washing, acid washing, water washing, drying and pulverization steps.
• an alkali metal compound used as the activator, the amount of alkali metal remaining in the carbon material should be lower than the level that may adversely affect EDLC (preferably lOOOppm or less).
• the powdering process is carried out by a known method, and it is usually desirable to use a fine powder having an average particle diameter of 0.5 to 50 ⁇ m, preferably about 1 to 20 ⁇ m.
• the EDLC of the present invention is characterized by including an electrode containing the carbon material for an electrode prepared as described above.
• the electrode may be configured by adding, for example, a carbon material for an electrode and a binder, more preferably a conductive agent, and may be an electrode integrated with a current collector.
• binder As the binder used here, known ones can be used. For example, polyolefins such as polyethylene and polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, and fluoroolefin. Fluorinated poly, such as Z butyl ether copolymer cross-linked polymer And celluloses such as carboxymethyl cellulose, vinyl polymers such as polyvinyl pyrrolidone and polyvinyl alcohol, and polyacrylic acid.
• the content of the binder in the electrode is not particularly limited, but is appropriately selected within a range of usually about 0.:! To 30% by mass with respect to the total amount of the carbon material for the electrode and the binder. .
• the conductive agent powders of carbon black, powder graphite, titanium oxide, ruthenium oxide and the like are used.
• the blending amount of the conductive agent in the electrode is appropriately selected depending on the blending purpose, but is usually:! To 50% by mass, preferably with respect to the total amount of the carbon material for the electrode, the binder and the conductive agent. It is appropriately selected within the range of about 2 to 30% by mass.
• a known method is appropriately applied.
• a solvent having a property of dissolving the binder is added to the above components.
• a method in which a slurry is uniformly coated on the current collector, or a method in which the above components are kneaded without adding a solvent and then pressure-molded at room temperature or under heating is employed.
• the current collector a known material and shape can be used, and for example, a metal such as ano-remium, titanium, tantalum, nickel, or an alloy such as stainless steel can be used.
• the unit cell of the EDLC of the present invention generally uses a pair of the above electrodes as a positive electrode and a negative electrode, faces each other through a separator (polypropylene fiber nonwoven fabric, glass fiber nonwoven fabric, synthetic cellulose paper, etc.), and is immersed in an electrolytic solution. Formed by.
• the electrolytic solution a known aqueous electrolytic solution or organic electrolytic solution can be used, but it is more preferable to use an organic electrolytic solution.
• an organic electrolytic solution those used as a solvent for an electrochemical electrolytic solution can be used.
• electrolytic solutions may be mixed and used.
• the supporting electrolyte in the organic electrolytic solution is not particularly limited, but the electrochemical component is not limited.
• Various salts such as salts, acids, alkalis, etc. that are usually used in the field of batteries or batteries can be used, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, and cyclic salts. Quaternary ammonium salts, quaternary phosphonium salts, etc., (CH) NBF,
• (C H) (CH) NBF, (C H) PBF, (C H) (CH) PBF and the like are preferable.
• concentration of these salts in the electrolytic solution is appropriately selected in the range of usually about 0.5 :! to 5 molZl, preferably about 0.5 to 3 mol / l.
• a more specific configuration of the EDLC is not particularly limited.
• a separator is interposed between a pair of thin sheet-like or disk-like electrodes (positive electrode and negative electrode) having a thickness of 10 to 500 zm.
• Examples include a coin type housed in a metal case, a wound type in which a pair of electrodes are wound through a separator, and a stacked type in which a large number of electrode groups are stacked through a separator.
• a raw material carbon composition was obtained by coking a raw material oil having the composition shown in Table 1 below in an autoclave under IMPa at 550 ° C. for 2 hours.
• the activation reaction is allowed to proceed for 1 hour at 750 ° C. in a nitrogen gas atmosphere.
• HC1 the metal potassium remaining in the carbon material was removed and dried to obtain a carbon material for an EDLC electrode.
• Capacitance C [F] ⁇ ⁇ ⁇ / (VI -V2)
• the capacitance [F / g] per mass is calculated by calculating the capacitance C [F] in accordance with F / cc was calculated by multiplying this F / g by the electrode density [g / cc]. The results are shown in Table 1.

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• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Electric Double-Layer Capacitors Or The Like (AREA)
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• 2005
  • 2005-06-21 JP JP2005180637A patent/JP4092344B2/ja not_active Expired - Fee Related
• 2006
  • 2006-06-15 US US11/993,286 patent/US7993619B2/en active Active
  • 2006-06-15 KR KR1020087001104A patent/KR100971669B1/ko active Active
  • 2006-06-15 EP EP06766767.5A patent/EP1894886B1/en active Active
  • 2006-06-15 CN CN2006800222797A patent/CN101203457B/zh active Active
  • 2006-06-15 WO PCT/JP2006/312033 patent/WO2006137323A1/ja not_active Ceased

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