WO2004011371A1 - 活性炭、その製造方法、分極性電極および電気二重層キャパシタ - Google Patents
活性炭、その製造方法、分極性電極および電気二重層キャパシタ Download PDFInfo
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- WO2004011371A1 WO2004011371A1 PCT/JP2003/008464 JP0308464W WO2004011371A1 WO 2004011371 A1 WO2004011371 A1 WO 2004011371A1 JP 0308464 W JP0308464 W JP 0308464W WO 2004011371 A1 WO2004011371 A1 WO 2004011371A1
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- 150000002596 lactones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Classifications
-
- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
-
- 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
Definitions
- the present invention relates to an activated carbon, a method for producing the same, a polarizable electrode and an electric double layer:
- the activated carbon of the present invention is used for cleaning, purifying, recovering, storing gas, decoloring, etc., utilizing its light absorbing and adsorbing performance, and also for electric devices utilizing characteristics of low content of alkali metal and / or heavy metals. It is particularly suitable as an electrode for a secondary battery or an electric double layer capacitor.
- Activated carbon is widely used in the food, chemical, pharmaceutical, and other industries.Specifically, activated carbon is used for water purification, air purification, solvent recovery, flue gas desulfurization / denitration, decolorization, Examples of applications include water treatment, sewage treatment, human waste treatment, industrial wastewater treatment, sugar use, nuclear power use (adsorption of radioactive substances), methane storage, and hydrogen storage. These mainly utilize the adsorption performance of activated carbon, and activated carbon as an adsorbent having further excellent adsorption performance is being pursued.
- activated carbons free of alkali metals and heavy metals are desired. Therefore, conventionally, in a method for producing activated carbon, the carbonaceous material is activated by a gas activation treatment or a chemical activation treatment, for example, after an activation treatment using an alkali metal hydroxide as an activation aid. In order to remove alkali metals and heavy metals from the treated material, washing with a strong acid such as hydrochloric acid, nitric acid or sulfuric acid is generally performed.
- the alkali metal hydroxide is strongly oxidizing, so that the heating furnace body utilized during the activation treatment is corroded, and the activated material is activated.
- the activated products are washed with hydrochloric acid or nitric acid, it is extremely difficult to produce activated carbon from which heavy metals have been completely removed.
- activated carbon containing heavy metals is used as a raw material for polarizable electrodes of electronic devices, for example, electric double layer capacitors, as described above, heavy metals dendriticized on the separators of electric double layer capacitors by reduction precipitation of heavy metals Particles are formed and problems such as puncturing of the separator may occur, which may cause short-circuits and other obstacles.
- alkali metal derived from the alkali metal hydroxide used as the activator may remain in the activated carbon. If such activated carbon is used as a raw material for the polarizing electrode of an electric double layer capacitor, the leakage current increases. However, there was also a problem that the charging efficiency was lowered and the energy efficiency was lowered (in other words, the self-discharge holding ratio was lowered).
- Japanese Patent Application Laid-Open No. 2002-43090 discloses an electric double layer capacitor which can adopt an alkali activation method and is manufactured by washing with water, an acid solution or an alkali solution after activation. Discloses activated carbon for polarizable electrodes, and describes that self-discharge can be reduced by reducing the amount of Ni. However, an electric double layer capacitor with the intended performance cannot be constructed only by reducing the amount of Ni.
- an object of the present invention is to prevent the occurrence of dendrite phenomena due to the reduction and precipitation of aluminum and heavy metals when used as a raw material for electronic devices, to prevent short-circuits and other failures, and to provide high self-discharge.
- An object of the present invention is to provide an activated carbon exhibiting a retention rate and suitable for use in electronic devices and the like. Disclosure of the invention
- the present inventors have found that the above-mentioned problem in the conventional technology is caused by the fact that the total content of alkali metal and / or heavy metal contained in the activated carbon is too large, so that the above-mentioned problem does not occur. To achieve this, it has been found that it is effective to adjust the total content of alkali metal and z or heavy metal in the activated carbon to a specific value or less.
- the present inventors believe that the total content of alkali metal and / or heavy metal in activated carbon is too large because activated carbon (or activated material) has high affinity with activated carbon when washed with strong acid, Heavy metals that remain in a form such as alkali metal salts and / or hydroxides with relatively low solubility in water (eg, nickel hydroxide, It has been found that it is difficult to remove copper hydroxide, zinc hydroxide, etc.) from activated carbon, and that alkali metals and / or many such heavy metals remain in activated carbon.
- activated carbon or activated material
- Heavy metals that remain in a form such as alkali metal salts and / or hydroxides with relatively low solubility in water (eg, nickel hydroxide, It has been found that it is difficult to remove copper hydroxide, zinc hydroxide, etc.) from activated carbon, and that alkali metals and / or many such heavy metals remain in activated carbon.
- the present inventors have found that (i) by removing the alkali metal in the activated carbon by carbonating the alkali metal with carbonic acid, thereby reducing the affinity between the alkali metal and the activated carbon and increasing the water solubility.
- the heavy metal in the activated carbon can be complexed with a basic substance, thereby reducing the affinity between the heavy metal and the activated carbon and increasing the water solubility to remove the heavy metal; ii i)
- the heavy metal can be removed by washing the activated material with an acidic aqueous solution containing an oxidizing agent, and (iv) the activated material is washed with hot water as compared with washing with normal temperature water.
- the first invention provides an activated carbon obtained by activating a carbonaceous material, wherein the activated carbon has a total content of Al-Li metal of 100 ppm or less. Further, the first present invention provides a method for producing activated carbon, which comprises activating a carbonaceous material and washing the obtained activated substance with a liquid containing carbon dioxide to obtain activated carbon. provide.
- a second aspect of the present invention provides an activated carbon obtained by activating a carbonaceous material, wherein the activated carbon has a total content of heavy metals of 20 ppm or less. Further, the second invention provides a method for producing activated carbon, comprising activating a carbonaceous material and washing the obtained activated substance with a liquid containing a basic substance to obtain activated carbon. I will provide a.
- the third aspect of the present invention specifies the carbonaceous material in the second aspect of the present invention as an easily graphitizable carbonaceous material, specifies the activation treatment as an alkali activation treatment, and further enhances the effect of the invention.
- Activated carbon obtained by alkali activation of a carbonized material Provided is an activated carbon characterized by having a total genus content of less than 200 ppm and a total content of aluminum alloy of less than 200 ppm.
- a third aspect of the present invention is to obtain an activated carbon by subjecting a graphitizable carbonaceous material to an alkali activation treatment and washing the obtained activation treatment with an oxidizing aqueous solution containing an oxidizing agent.
- the third invention provides an alkali-activated graphitizable carbonaceous material, and washing the obtained activated material with hot water, hot hydrochloric acid and water in this order, or hot water, Activated carbon can be obtained by washing in the order of water, hot hydrochloric acid, ammonia water and hot water, or by washing in the order of hot water, carbonated water, hot hydrochloric acid, ammonia water, hot hydrochloric acid and hot water.
- a method for producing activated carbon is provided.
- a fourth invention provides a polarizable electrode formed by mixing the activated carbon of the first, second, and third inventions with at least a binder and a conductive material, and a polarizable electrode thereof. And an electric double layer capacitor using the same.
- FIG. 1 is a schematic sectional view showing an example of the electric double layer capacitor of the present invention.
- the activated carbon of the first aspect of the present invention is obtained by activating a carbonaceous material.
- the activated carbon of the present invention has a total content of Alkyri metal of 100 ppm or less. This is because, when the total content of alkali metals exceeds 100 ppm, when activated carbon is used as a raw material for electron deposition, dendritic formation of the metal due to reduction precipitation occurs, causing short-circuiting and other problems, This is because ions may cause a decrease in the capacitance retention rate.
- examples of the alkali metal species that can be contained in the activated carbon include lithium, sodium, potassium, and cesium. Usually the content is high Is sodium and Z or potassium, so it is important to control their content.
- the alkali metal may be present in the activated carbon as a metal alkali, but is usually present as an oxide, a hydroxide, a chloride or the like.
- the content of the alkali metal in the activated carbon can be measured by atomic absorption spectrometry.
- the means for reducing the total alkali metal content of the activated carbon of the first invention to 100 ppm or less includes repeating washing with ion-exchanged water or a strongly acidic aqueous solution. Applying the method for producing activated carbon of the present invention, characterized by washing with a liquid containing carbonic acid.
- the raw material of the carbonaceous material used in the first aspect of the present invention is not particularly limited as long as it can be activated carbon by carbonization and Z or activation, and examples thereof include wood, sawdust, coconut shell, and tarmi shell.
- Minerals such as fruit husk (charcoal), fruit seed (charcoal), plant systems such as lignin, peat, peat, lignite, lignite, bituminous coal, anthracite, coatas, coal tar, coal pitch, petroleum distillation residue, petroleum pitch Natural materials such as cotton, cotton and rayon, and synthetic materials such as phenol, acrylic and vinylon.
- the activation treatment is not particularly limited, and a conventionally known gas activation treatment method and drug activation treatment method can be applied.
- the activated carbon of the first invention described above can be preferably produced by the method for producing the activated carbon of the first invention described below.
- an activated carbon is obtained by activating a carbonaceous material and washing the obtained activated material with a liquid containing carbonic acid (carbonic acid washing treatment). Is the way.
- carbonic acid washing treatment By subjecting the activated material to a carbonic acid washing treatment, the alkali metal contained therein becomes alkali carbonate exhibiting high water solubility, so that the alkali metal content remaining in the activated carbon can be reduced to 100 ppm or less.
- the “liquid containing carbonic acid” used in the carbonic acid washing treatment is preferably a carbonic acid Water.
- concentration of carbonic acid in the carbonated water is not particularly limited, it is usually 0.1% by weight to 10% by weight.
- the amount of the “liquid containing carbonic acid” used in the carbonic acid washing treatment is not particularly limited, and practically, 1 to 100 parts by weight per 1 part by weight of the activated material to be washed.
- the content is more preferably 2 to 50 parts by weight, and particularly preferably 5 to 20 parts by weight.
- the temperature during the carbonic acid washing treatment is not particularly limited, but if it is too high, the concentration of carbonic acid in the ⁇ liquid containing carbonic acid '' decreases, and the efficiency of removing the alkali metal is too low.
- the reaction temperature is preferably 0 to 50 ° C, more preferably 0 to 45 ° C, since the removal efficiency of the alkali metal decreases in reaction rate.
- the number of times the activated material is washed with the “liquid containing carbonic acid” is not particularly limited, but the amount of alkali metal remaining on the activated carbon and the target alkali metal concentration level Usually 1-3 times, depending on.
- the pressure at which the activated material is cleaned with the “liquid containing carbonic acid” is not particularly limited, but if it is too high, a special pressure applying means must be installed in the cleaning device. Therefore, the pressure is preferably from atmospheric pressure to IMPa, more preferably from atmospheric pressure to 0.5 MPa.
- activated material is washed (carbonated washing treatment) with the “liquid containing carbonic acid” to obtain activated carbon
- heavy metals contained in trace amounts in the activated carbon for example, In order to remove nickel, copper, dumbbell, etc., it is preferable to further perform a hydrochloric acid cleaning treatment.
- the concentration of hydrochloric acid used in the hydrochloric acid washing treatment is not particularly limited, and a concentration of generally available hydrochloric acid is sufficient. Therefore, the concentration of hydrochloric acid used is preferably from 0.01 to 37% by weight, particularly preferably from 0.1 to 30% by weight in consideration of operability and safety, and from 0.5 to 2% by weight. 5% by weight is particularly preferred.
- the temperature at which the hydrochloric acid cleaning treatment is performed is not particularly limited. Hydrochloric acid is easily volatilized when it is cut off, and heavy metal removal efficiency may be reduced if it is too low. Therefore, the temperature is preferably in the range of 10 to 90 ° C, more preferably 20 to 90 ° C.
- the number of times of the hydrochloric acid washing treatment is not particularly limited, but is usually 1 to 3 times, depending on the amount of the alkali metal remaining on the activated carbon and the target alkali metal concentration level.
- the activated carbon washed with hydrochloric acid is preferably subsequently washed with distilled water or ion-exchanged water.
- Activated carbon obtained by performing a carbonic acid washing treatment without performing a hydrochloric acid washing treatment may be immediately subjected to a water purification washing treatment.
- the amount of distilled water or ion-exchanged water used in the clean water cleaning treatment is not particularly limited, but it is preferable to wash until no chlorine ions are detected. Specifically, although it depends on the water purification system to be described later, usually 1 to 100 parts by weight is preferable for 1 part by weight of activated carbon, and 1 to 100 parts by weight in consideration of economy and operability.
- Examples of the clean water washing method include a method of stirring and washing using a stirring tank and a method of washing by flowing a liquid under reduced pressure or pressure using a filter.
- Activated carbon obtained by washing with a liquid containing carbon dioxide, and, if necessary, activated carbon obtained by washing with hydrochloric acid and / or washing with purified water, are dried under heating and Z or reduced pressure to obtain activated carbon in a dry state. It becomes.
- a conventional carbonization treatment for example, 400 to 80 ° may be performed according to the type of the carbonaceous material.
- the carbonaceous material is subjected to an activation treatment, but the treatment method is not particularly limited, and a conventionally known gas activation treatment method or chemical activation treatment method is applied. Can be.
- the gas activation treatment includes an activation treatment method using steam, carbon dioxide, oxygen, propane combustion exhaust gas, or a mixed gas thereof.
- the activation treatment include an activation treatment method using agents such as zinc chloride, calcium chloride, phosphoric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide.
- an alkali metal hydroxide is used as an activation aid, so that alkali metal remains in the activated carbon. Since there is a tendency to become easier, the production method of the first aspect of the present invention can be preferably applied when performing a general alkali activation treatment.
- the activated carbon of the second aspect of the present invention is obtained by activating a carbonaceous material, and has a total heavy metal content of 20 ppm or less. This is because if the total content of heavy metals exceeds 20 ppm, when activated carbon is used as a raw material for electronic devices, reductive precipitation of heavy metals will cause dendrite phenomena, causing short-circuiting and other problems, and self-discharge retention. This is because, if the rate is reduced, or if used as an adsorbent in the production of purified water, for example, heavy metals continue to elute, albeit very slightly, in the purified water obtained.
- examples of heavy metal species that can be contained in activated carbon include nickel, copper, zinc, iron, silver, and the like.
- nickel, copper, zinc, and iron usually have high contents, and it is important to control these contents.
- the content of heavy metals in activated carbon can be measured by inductively coupled plasma emission spectroscopy (ICP).
- ICP inductively coupled plasma emission spectroscopy
- Means for reducing the total content of heavy metals in the activated carbon of the second invention to 20 ppm or less includes repeating washing with ion-exchanged water or a strongly acidic aqueous solution.
- a base described below is used. Washing with a liquid containing a volatile substance Applying a method for producing light activated carbon.
- the raw material of the carbonaceous material used in the second present invention is as described in the first present invention.
- the activation treatment is not particularly limited, and a conventionally known gas activation treatment method and drug activation treatment method can be applied.
- the activated carbon of the second invention described above can be preferably produced by the method for producing the activated carbon of the second invention described below.
- the carbonaceous material is subjected to a gas activation treatment or a chemical activation treatment, and the obtained activation treatment is washed with a liquid containing a basic substance (basic washing treatment).
- a liquid containing a basic substance basic washing treatment
- the “liquid containing a basic substance” used in the basic washing treatment preferably includes an aqueous solution in which ammonia, organic amine, ammonium carbonate, a mixture thereof, or the like is dissolved in water as the basic substance.
- the basic substance is preferably ammonia, an organic amine or a mixture thereof from the viewpoint of easy removal of the basic substance from the activated carbon.
- the organic amine include methylamine, ethylamine, propylamine, dimethylamine, getylamine, dipropynoleamine, trimethylamine, and triethylamine.
- the basic substance concentration in the "liquid containing a basic substance” is not particularly limited, but is usually from 0.1 to 1 0 weight 0/0.
- the amount of the “liquid containing a basic substance” used in the basic washing treatment is not particularly limited, and practically, 1 to 10 parts by weight based on 1 part by weight of the activated material to be washed. It is preferably 0 parts by weight, particularly preferably 2 to 50 parts by weight, particularly preferably 5 to 20 parts by weight in consideration of operability and alkali metal removal efficiency.
- the temperature during the basic washing treatment is not particularly limited, but if it is too high, The basic substance is easily volatilized from the ⁇ liquid containing the basic substance '', and if it is too low, the efficiency of removing heavy metals decreases in reaction rate, so it is preferably from 10 to 60 ° C, preferably from 10 to 60 ° C. 20 to 50 ° C.
- the number of times the activated material is washed with the “liquid containing a basic substance” in the basic washing process is not particularly limited, but the amount of heavy metal remaining on the activated carbon and the target heavy metal concentration level Usually 1-3 times, depending on.
- the pressure for cleaning the activated material with the ⁇ liquid containing a basic substance '' is not particularly limited, but if it is too high, a special pressure applying means is installed in the cleaning device. Therefore, the pressure is preferably from atmospheric pressure to IMPa, more preferably from atmospheric pressure to 0.5 MPa.
- the activated material is washed with a “liquid containing a basic substance” (basic washing treatment) to obtain activated carbon, and then, if necessary, further removed to remove the basic substance. Washing with hydrochloric acid is preferred.
- the concentration of hydrochloric acid used in the hydrochloric acid washing treatment is not particularly limited, and a concentration of generally available hydrochloric acid is sufficient. Therefore, the concentration of hydrochloric acid used is preferably from 0.01 to 37% by weight, particularly preferably from 0.1 to 30% by weight in consideration of operability and safety, and from 0.5 to 2%. 5% by weight is particularly preferred.
- the temperature at which the hydrochloric acid washing treatment is performed is not particularly limited. However, if the temperature is too high, hydrochloric acid is easily volatilized, and if the temperature is too low, the efficiency of removing heavy metals may decrease. The temperature is in the range of 90 ° C, more preferably 20 to 90 ° C. Although the number of times of the hydrochloric acid washing treatment is not particularly limited, it is usually 1 to 3 times, depending on the type and concentration level of the basic substance remaining on the activated carbon.
- the activated carbon washed with hydrochloric acid is preferably subsequently washed with distilled water or ion-exchanged water.
- Activated carbon obtained by a basic washing treatment without a hydrochloric acid washing treatment may be immediately subjected to a clean water washing treatment.
- the amount of distilled water or ion-exchanged water used in the water purification process is particularly limited. However, it is preferable to wash until chloride ions or basic substances are no longer detected. Specifically, although it depends on the water purification system to be described later, it is usually preferably 1 to 100 parts by weight with respect to 1 part by weight of activated carbon, and 1 to 100 parts in consideration of economy and operability. 100 parts by weight is more preferred.
- Examples of the clean water washing method include a method of stirring and washing using a stirring tank and a method of washing by flowing a liquid under reduced pressure or pressure using a filter.
- Activated carbon obtained by washing with a liquid containing a basic substance, and, if necessary, activated carbon obtained by washing with hydrochloric acid and / or washing with purified water, are dried under heating and / or reduced pressure, and dried. Activated carbon.
- a conventional carbonization treatment for example, 400 to 80 may be performed depending on the type of the carbonaceous material.
- the graphitizable carbonaceous material is also subjected to a gas activation treatment or a chemical activation treatment, but the treatment method is not particularly limited, and the gas activation treatment in the first invention of the present invention is not particularly limited.
- a treatment method or a drug activation treatment method can be applied.
- the gas activation treatment includes an activation treatment method using steam, carbon dioxide, oxygen, propane combustion exhaust gas, or a mixed gas thereof.
- the chemical activation treatment includes zinc chloride, calcium chloride, and phosphorus.
- An activation treatment method using a chemical such as an acid, sulfuric acid, sodium hydroxide, potassium hydroxide, magnesium hydroxide, or calcium hydroxide can be given.
- a general alkali activation treatment using potassium hydroxide or sodium hydroxide as a chemical is performed, alkali metal remains in the activated carbon because an alkali metal hydroxide is used as an activation aid. Because of this tendency, the production method of the second aspect of the present invention can be preferably applied when performing a general alkali activation treatment.
- the activated carbon of the third aspect of the present invention specifies the carbonaceous material in the second aspect of the present invention as an easily graphitizable carbonaceous material, specifies the activation treatment as an alkali activation treatment, and further enhances the effect of the invention. It is obtained by subjecting an easily graphitizable carbonaceous material to an alkali activation treatment.
- the activated carbon of the third aspect of the present invention has a heavy metal content of 20 ppm or less.
- the content of heavy metal exceeds 20 ppm
- the content of Alkyri metal is 200 ppm or less. This is because, when the content of the alkali metal exceeds 200 ppm, the leakage current increases, the charging efficiency decreases, the energy efficiency decreases, and the self-discharge retention rate decreases.
- examples of heavy metal species that can be contained in the activated carbon include nickel, iron, zinc, tin, silver, silver, and the like.
- the content is high at least one of nickel, iron and zinc, and it is important to control the content.
- the content of heavy metals in activated carbon can be measured by inductively coupled plasma emission spectroscopy (ICP).
- ICP inductively coupled plasma emission spectroscopy
- examples of the alkali metal species that can be contained in the activated carbon include lithium, sodium, potassium, and cesium. Usually, the contents are high in sodium and / or potassium, so it is important to control these contents.
- the alkali metal may be present in the activated carbon as a metal alkali, but is usually present as an oxide, a hydroxide, a chloride, a carbonate or the like. As described above, the content of the alkali metal in the activated carbon can be measured by atomic absorption spectrometry.
- the carbon content extracted by hydrocarbons such as benzene, toluene, xylene, mesitylene, and mixtures thereof is preferably not more than 0.2% by weight. If the carbon content exceeds 0.2% by weight, the pores of the activated carbon are blocked, the capacitance is reduced, and the durability is deteriorated.
- the extraction operation 5 to 50 parts by weight of hydrocarbon is mixed with 1 part by weight of activated carbon at a temperature higher than the boiling point of the hydrocarbon to be used and mixed for 1 hour or more, then the activated carbon is separated by filtration and dried Can be exemplified.
- the calculation of the carbon content extracted by hydrocarbons is performed by comparing the weight before and after the extraction operation. In the first and second activated carbons of the present invention as well, the carbon content extracted by the hydrocarbon is preferably 0.2% by weight or less.
- Means for reducing the total content of heavy metals in the activated carbon of the third invention to 20 ppm or less may include repeating washing with ion-exchanged water or a strongly acidic aqueous solution.
- the method is described below. Washing with an acidic aqueous solution containing an agent is applied to the method for producing activated carbon of the present invention, which is characterized by the following.
- a temperature of about room temperature is used as a means for not only reducing the content of heavy metals in the activated carbon of the third invention to 20 ppm or less, but also reducing the content of aluminum alloy to 200 ppm or less at the same time.
- Washing with ion-exchanged water or a strongly acidic aqueous solution may be repeated, but preferably, the method for producing activated carbon of the present invention, which is described later and is characterized by washing with at least hot water and hot hydrochloric acid, is applied. It is mentioned.
- the carbonaceous material used in the third aspect of the present invention is an easily graphitizable carbonaceous material that forms activated carbon upon activation, such as petroleum coatas, petroleum pitch, synthetic mesophase pitch, polychlorinated vinyl, polyimide, A carbonaceous material starting from polyacrylonitrile or the like can be used.
- mesophase pitch-based carbon fibers can be preferably used.
- mesophase pitch-based carbon fiber conductive From the viewpoint of excellent properties, those containing 50% by volume or more, preferably 80% by volume or more of an optically anisotropic phase are desirable.
- the mesophase pitch-based carbon fiber is obtained by melt-spinning a synthetic mesophase pitch or a mesophase pitch derived from petroleum or coal, then infusibilizing the material, and then carbonizing. is there. It is preferable to use a synthetic mesophase pitch in consideration of the operability of melt spinning, the productivity, the operability during activation, and the capacitance of the obtained activated carbon.
- the infusibilization treatment is a treatment necessary for activation (heating) treatment while maintaining the form of the melt-spun pitch fiber.
- the melt-spun pitch fiber is treated with oxygen for 1 to 20 times. This is a process of heating to about 100 to 350 ° C.
- the carbonization treatment following the infusibilization treatment is a treatment in which the infusibilized material is carbonized by heating the infusibilized material in an inert gas atmosphere. If the heating temperature is too low, the carbon crystal structure is undeveloped and over-activation tends to occur, and the density tends to decrease too much. If the heating temperature is too high, the crystallization of the carbon fiber progresses too much and the activation hardly progresses Therefore, the temperature is preferably 500 to 100 ° C, more preferably 600 to 900 ° C.
- the carbonaceous material is preferably used after being pulverized. It is preferable to use one having a maximum length in the direction of 500 ⁇ or less, more preferably 200 ⁇ or less. The maximum length in the long axis direction can be confirmed, for example, by observing an electron micrograph of a pulverized material of a randomly extracted carbonaceous material. Pulverization can be performed by a known pulverizer such as a cone crusher, a double rono crusher, a disk crusher, a rotary crusher, a Ponole mill, a centrifugal roller mill, a ring roll mill, a centrifugal ball mill, and a turbo mill.
- a known pulverizer such as a cone crusher, a double rono crusher, a disk crusher, a rotary crusher, a Ponole mill, a centrifugal roller mill, a ring roll mill, a centrifugal ball mill, and a turbo mill.
- the activated carbon of the third aspect of the present invention described above can be preferably produced by the method for producing activated carbon of the third aspect of the present invention described below.
- an activated carbon is obtained by subjecting a graphitizable carbonaceous material to an alkali activation treatment, and washing the obtained activation treatment with an acidic aqueous solution containing an oxidizing agent. Is the way. By washing with an acidic aqueous solution containing an oxidizing agent, heavy metals contained in the activated material move to the washing liquid side. Therefore, the content of heavy metals remaining in the activated carbon can be reduced to 20 ppm or less.
- the graphitizable carbonaceous material is subjected to an alkali activation treatment to obtain an activation treated product.
- the graphitizable carbonaceous material is mixed with an alkali metal hydroxide as an activation aid in a conventional manner, and the resulting mixture is heated in an atmosphere of an inert gas such as nitrogen gas. It is activated by
- alkali metal hydroxide examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.
- sodium hydroxide is required to obtain activated carbon having a large capacitance.
- a hydroxylating rim it is preferable to use a hydroxylating rim. These may be used alone or as a mixture. It can also be used in the form of a powder or a concentrated aqueous solution.
- the amount of the alkali metal hydroxide used in the graphitizable carbonaceous material if the latter is too small, the activation treatment becomes difficult to be performed uniformly and sufficiently, and the properties of the target activated carbon may vary, and conversely. If the amount is too high, not only is it not economical, but the activation may proceed too much, and the capacitance per weight tends to increase, but the capacitance per volume decreases. Therefore, the amount of alkali metal hydroxide to be used in the carbonaceous material is preferably 30 to 500 parts by weight with respect to 100 parts by weight of the carbonaceous material in consideration of economy, operability, and safety. , Particularly preferably 50 to 3 100 parts by weight.
- the heating temperature condition for activating the graphitizable carbonaceous material mixed with Al-Kyri metal hydroxide if the heating temperature is too low, the activation is not sufficient, and if it is too high, the obtained activated carbon is crystallized. Progresses, not only does the capacitance decrease when used as an electrode of an electric double layer capacitor, but also increases the danger due to the alkali metal generated from the alkali metal hydroxide used. Even if a nickel-based material that has high resistance to alkali metals is used, intergranular corrosion accompanying the crystallization of the material (furnace material) is promoted, and the incorporation of heavy metal particles into the activated carbon significantly increases.
- the heating temperature (activation temperature) for activation is preferably 400 ° C. to 100 ° C., and more preferably 450 ° C. to 900 ° C. Considering the accompanying economics, the temperature is particularly preferably from 470 ° C to 850 ° C.
- the rate of temperature rise up to the activation temperature is preferably 0.2 ° C to 10 ° C / min, avoiding rapid temperature increase in consideration of the above-mentioned problem of grain boundary crystallization of the activation vessel. Preferably it is 0.3 to 8 ° C / min.
- the holding time at the activation temperature is not particularly limited as long as the calorific value is sufficiently transmitted to the activated carbon, but is usually 30 minutes to 5 hours, and considering the progress of crystallization together with the holding, it is 45 minutes to 4 minutes. Time.
- the cooling rate from the activation temperature is important to avoid grain boundary crystallization of the activation furnace body. That is, since rapid cooling promotes metal crystallization, the cooling rate is preferably:! To 50 ° C / min, more preferably 1 to 30 ° C / min.
- the activated material obtained by the alkali activation treatment of the graphitizable carbonaceous material is washed with an ⁇ oxidizing agent-containing aqueous acidic solution '' (oxidizing agent cleaning treatment).
- an oxidizing agent By cleaning the activated material with an oxidizing agent, the heavy metal mixed in from the furnace body that has been oxidized during the alkaline activation process using metal hydroxide and has undergone intergranular corrosion can be effectively removed from the activated material. Can be removed.
- the activated material should be washed with warm water in advance. Is preferred. By this washing, alkali metal hydroxides, alkali metal carbonates and the like remaining in the activated material can be removed.
- the amount of the ⁇ oxidizing aqueous solution containing an oxidizing agent '' is reduced by removing as much as possible a substance that can react with the acidic aqueous solution from the activated material by hot water washing.
- the temperature and amount of the hot water are not limited, but usually at a temperature of 30 ° C. to 90 ° C., preferably 3 to 50 parts by weight per 1 part by weight of the activated material to be washed, Considering the washing efficiency and the volumetric efficiency of the reactor, it is more preferably used in an amount of 5 to 45 parts by weight.
- the oxidizing agent used in the “acidic aqueous solution containing an oxidizing agent” includes inorganic oxidizing agents such as hydrogen peroxide and persulfuric acid, and organic peracids such as peracetic acid and formic acid. And organic peroxides such as t-butyl hydroperoxide. Among them, hydrogen peroxide is most preferable in consideration of stability in an acidic aqueous solution, availability, safety, and influence on carbon materials.
- the concentration of the oxidizing agent in such an "acidic aqueous solution containing an oxidizing agent" is preferably 0.1 to 10% by weight, and more preferably 0.1 to 10% by weight in consideration of the economy and the effect on the carbon material.
- an organic acid aqueous solution such as formic acid and acetic acid
- an inorganic acid aqueous solution such as hydrochloric acid, sulfuric acid, and nitric acid
- inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid are preferable from the viewpoint of the effect of reducing the amount of residual metal
- the use of hydrochloric acid is most preferable in consideration of the remaining acidic roots in the carbonaceous material. It is good.
- the concentration of the acid is preferably 0.1 to 5N, taking into account the effect on metal removability and the carbon material, and more preferably 0.2 to 4N, taking into account economy and operability.
- the ratio is 0.5 to 3.
- the amount of the ⁇ acid solution containing an oxidizing agent '' to be used for the activated material is preferably 3 to 5 parts by weight with respect to 1 part by weight of the activated material to be washed, taking into account operability and economics. More preferably 4 to 30 parts by weight, particularly preferably 5 to 20 parts by weight is there.
- the cleaning temperature in the oxidizing agent cleaning process is not particularly limited. However, if the temperature is too high, not only the decomposition of the oxidizing agent peroxide may be caused, but also the oxidation of the carbon material may proceed. If it is too low, the effect of the oxidizing agent tends to decrease. Therefore, it is preferably 0: to 50, more preferably 0 to 45 ° C.
- the number of oxidizing agent cleaning treatments is not particularly limited, and is usually 1 to 3 times, although it depends on the amount of metal remaining in the activated material and the target residual metal level of activated carbon. There are many.
- the pressure at which the activated material is washed with the “acid solution containing the oxidizing agent” is not particularly limited, but if it is too high, a special device is required.
- the pressure is from atmospheric pressure to IMPa, preferably from atmospheric pressure to 0.5 MPa.
- Activated carbon can be obtained by subjecting the activated material to an oxide cleaning treatment.
- the obtained activated carbon is preferably further washed with distilled water or ion-exchanged water (clean water cleaning treatment).
- the amount of distilled water or ion-exchanged water to be used in the water purification treatment is not particularly limited, but it is preferable to wash until chlorine ions are no longer detected.
- it is preferably 1 part by weight to 100 parts by weight with respect to 1 part by weight of activated carbon, and more preferably 1 part by weight to 10 parts by weight in consideration of economy and operability, although it depends on the washing method. 0 parts by weight.
- Examples of the clean water washing method include a method of stirring and washing using a stirring tank and a method of washing by flowing a liquid under reduced pressure or pressure using a filter.
- Activated carbon obtained by washing with an “acidic aqueous solution containing an oxidizing agent” and, if necessary, activated carbon obtained by washing with hydrochloric acid and / or washing with purified water, are dried under heating and / or reduced pressure, and dried. Activated carbon.
- the third present invention produces activated carbon having not only a total heavy metal content of 20 ppm or less but also a total alkali metal content of 200 ppm or less.
- the graphitizable carbonaceous material is alkali-activated, and the obtained activated material is washed with hot water, hot hydrochloric acid and water in this order, or By washing in the order of water, carbonated water, hot hydrochloric acid, ammonia water and hot water, or 3 by washing in the order of hot water, carbonated water, hot hydrochloric acid, ammonia water, hot hydrochloric acid and hot water
- a method for producing activated carbon is provided.
- the solubility of alkali metal compounds such as alkali metal hydroxides and alkali metal carbonates in hot water is much higher than the solubility in water.
- the reactivity of heavy metals with hot hydrochloric acid is much higher than the reactivity with hydrochloric acid at about room temperature, and therefore, by washing the activated material with hot hydrochloric acid, heavy metals contained in the activated material can be obtained. Can be easily converted into a water-soluble chloride. Therefore, the activated material is washed with hot water and subsequently with hot hydrochloric acid to reduce the content of heavy metals remaining in the activated carbon to 20 ppm or less and the content of aluminum alloy to 200 ppm or less. can do.
- the water for washing and the hydrochloric acid may be heated, activated carbon can be produced at a high yield without greatly modifying a conventional alkali activation treatment facility. .
- the activated material obtained by the alkali activation treatment of the carbonaceous material is first washed with hot water (hot water washing), and then washed with hot hydrochloric acid. (Wash with hot hydrochloric acid) and wash with water (wash with water).
- hot water washing can remove substances that can react with the acidic aqueous solution in the subsequent hot hydrochloric acid washing, and can not only enhance the effect of hot hydrochloric acid but also reduce the amount of the acidic aqueous solution used.
- the temperature and amount of hot water are not limited, but the temperature is preferably 30 to 95 ° C, more preferably 60 to 90 ° C. It is preferably used in an amount of 3 to 50 parts by weight, more preferably 5 to 45 parts by weight in consideration of washing efficiency and volumetric efficiency of the reactor, per 1 part by weight of the activated material to be activated.
- the activated material washed with hot water is washed with hot hydrochloric acid. If the concentration of hydrochloric acid is too low, the removal efficiency may be reduced by causing immobilization of heavy metals.If the concentration is too high, activated carbon to be treated is chlorinated. More preferably, it is carried out within the range of 0.5 to 2.5.
- hot hydrochloric acid in the temperature range of 60 ° C to 90 ° C.
- the amount of hot hydrochloric acid is preferably 3 to 50 parts by weight per 1 part by weight of the activated material to be washed, more preferably 4 to 30 parts by weight in consideration of operability and economic efficiency, particularly It is preferably 5 to 20 parts by weight.
- activated carbon is obtained. Since activated carbon is easily affected by residual metals contained in the water used, it is preferable to use clean water such as ion-exchanged water, distilled water, or membrane permeated water as the washing water.
- the amount of washing water is not particularly limited, but it is preferable to wash until no chloride ions are detected. Depending on the method of washing, usually 1 part by weight to 100 parts by weight per 1 part by weight of activated carbon, 1 part by weight to 100 parts by weight in consideration of economy and operability It may be used in the range of parts.
- washing method a method of stirring and washing using a stirring tank and a method of washing by flowing a liquid under reduced pressure or under pressure using a filter can be used.
- the pressure at the time of performing hot water washing, hot hydrochloric acid washing, and water washing is not particularly limited, but if it is too high, a special device is required.
- the pressure is from atmospheric pressure to IMPa, preferably from atmospheric pressure to 0.5 MPa.
- the activated material obtained by the activation treatment of the raw material is first washed with hot water (hot water washing), washed with carbonated water (carbonated water washing), washed with hot hydrochloric acid (hot hydrochloric acid washing), Wash with ammonia water (wash with ammonia water), and wash with hot water (wash with hot water).
- the differences from the procedure 1 are the carbonated water cleaning, the ammonia water cleaning, and the final hot water cleaning.
- the carbonated water washing operation is an operation for removing the alkali metal in the activated material as a carbonate, and can be performed in the same manner as the case described in the first production method of the present invention.
- ammonia water washing operation is an operation for removing heavy metals from the activated material as an ammonia complex, and can be performed in the same manner as in the case of the second production method of the present invention.
- the last hot water washing operation can be performed in the same manner as the hot water washing operation in step 1.
- the activated material obtained by the alkali activation treatment of the carbonaceous material is first washed with hot water (hot water washing), (Wash with carbonated water), wash with hot hydrochloric acid (wash with hot hydrochloric acid), wash with ammonia water (wash with ammonia water), wash with hot hydrochloric acid again, and wash with hot water
- This hot hydrochloric acid washing is as described above, and it becomes possible to remove ammonia-derived substances (residues and metal complexes) in the activated material by this washing operation.
- the activated carbon obtained by the production method of the third aspect of the present invention described above is dried under heating and heat or under reduced pressure to obtain dry activated carbon.
- the activated carbon of the first, second and third inventions described above is useful as a material of a polarizable electrode particularly suitable for an electric double layer capacitor. Therefore, the fourth invention provides a polarizable electrode formed by mixing the activated carbon of the first, second or third invention with at least a binder and a conductive material, and an electric double layer using the same. Ki provide.
- the polarizable electrode according to the fourth aspect of the present invention is characterized in that the activated carbon according to the first, second or third aspect of the present invention comprises at least a binder such as polyvinylidene orifice, a binder such as polytetrafluoroethylene and carbon black. These conductive materials are mixed and molded. Mixing a conductive material can reduce the resistance of the electrode, which is effective in reducing the internal resistance of the polarizing electrode.
- a polarizable electrode suitable for such an electric double layer capacitor a generally known method can be applied.
- commercially available materials such as polyvinylidene V denfluoride, polytetrafluoroethylene, etc., which are known as binders, and conductive materials such as carbon black are added to a few percent if necessary, and then kneaded. It can be formed into an electrode by putting it in a mold and pressing it, or rolling it into a sheet and punching it into the required shape. Alternatively, the kneaded material may be applied to a current collector to form a coated electrode.
- an organic compound such as alcohol or dimethylpyrrolidone, a solvent such as water, a dispersant, or various additives may be used as necessary. Heat can also be applied within a range that does not impair the effects of the invention.
- the polarizable electrode described above is useful as an electrode of the fourth electric double layer capacitor of the present invention as shown in FIG. 1 (schematic sectional view). Each component constituting the capacitor of FIG. 1 can have the same configuration as a known electric double layer capacitor except that the polarizable electrode according to the present invention is used.
- a current collecting member made of aluminum or the like, 3 and 4 are polarizable electrodes made of the activated carbon of the present invention
- 5 is a separator made of a polypropylene nonwoven fabric or the like
- 6 is polypropylene, polyethylene, polyamide, polyamide imide
- 7 shows a case made of a material such as stainless steel.
- tetraethylammonium tetrafluoroporate and tetramethylammonium tetra may be used, for example, carbonates such as ethylene carbonate, dimethyl carbonate, getyl carbonate, and propylene carbonate; -tolyls such as acetonitrile; ⁇ -butyl mouth ratatone; It is necessary to enclose an electrolytic solution dissolved in a solvent such as lactones, sulfoxides such as dimethylsnolefoxide, and amides such as dimethylformamide.
- Mettler softening point obtained by heat treatment of petroleum cracking residue 285 Using a nozzle with an optically anisotropic pitch of 285 ° C and a spinning hole with a diameter of 0.2 mm and a spinning hole of 0.2 mm in a slit with a width of 2 mm Then, the mixture was melt-blown, infusibilized and carbonized to produce mesophase pitch carbon fiber.
- the granulated product was dehydrated under a reduced pressure of 1.5 Torr at a heating rate of 2 ° C. to 300 ° C. for 5 hours.
- 24 g of the obtained dehydrated granules were placed in a 2-inch horizontal nickel reactor equipped with a thermometer, and the system was purged with nitrogen. The temperature was raised to 0 ° C at 200 ° C / hour. After reaching 700 ° C, the temperature was maintained for 1 hour, and then cooled to room temperature over 2 hours. After flowing nitrogen through a distilled water bubbler for 1 hour, 150 ml of water was added.
- Activated carbon was obtained by repeating the same operation as in Example A1 except that washing with carbonated water was not performed in Example A1.
- Example A1 5.9 g of activated carbon was obtained by repeating the same operation as in Example A1 except that 50 g of a fuynol resin carbide obtained by pulverizing a carbon material to 20 ⁇ or less in Example A1.
- Activated carbon was obtained by repeating the same operation as in Example A2, except that washing with carbonated water was not performed in Example A2.
- each of the obtained activated carbons of Examples A1 to A2 and Comparative Examples A1 to A2 was further pulverized to an average particle size of 5 to 20 ⁇ to obtain powdered activated carbon, and the powdered activated carbon 80 weight 0 / 0 , conductive carbon 10 weight 0 /. And 10% by weight of polytetrafluoroethylene (Teflon (registered trademark) 6J, Mitsui 'Dupont Chemical Co., Ltd.).
- Teflon registered trademark
- 6J Mitsui 'Dupont Chemical Co., Ltd.
- the obtained kneaded material is formed into a sheet having a thickness of 300 ⁇ by roll rolling, punched into a circular shape having a diameter of 2 cm using a punch, and dried under reduced pressure at 150 ° C for 4 hours to form a sheet.
- a polar electrode was produced.
- the obtained polarizable electrode is placed in a stainless steel case, as shown in Fig. 1, in a glove box with a dew point of 80 ° C or less, a current collector, a polarizable electrode sheet, a polypropylene non-woven cloth, and a polarizable electrode sheet.
- the polarizable electrode is impregnated with a propylene carbonate solution containing 1 mol of tetraethylammonium tetrafluoroborate, and the step is performed using a polypropylene insulating gasket.
- An electric double layer capacitor was fabricated by sealing the upper lid of the stainless steel case.
- the obtained electric double-layer capacitor was charged at a constant current of 2 mA / cm2 per electrode surface area at room temperature to an ultimate voltage of 2.5 V using an electric double-layer capacitor evaluation device manufactured by Hioki Electric. and auxiliary charging at 30 minutes low voltage V, performed 10 times charge-discharge cycle test of performing constant current discharge at 2 mA / cm 2 after supplemental charging completion, from 1.2 at that time 1. to 0 V
- the initial capacitance was determined from the discharge curve by a standard method. Table 1 shows the obtained results.
- the electric double layer capacitors made from the activated carbons of Examples A1 and A2 having a total alkali metal content of 100 ppm or less had a self-discharge retention of 100%. %, Showing excellent performance as an electric double layer capacitor.
- the electric double-layer capacitors made from the activated carbons of Comparative Examples A1 and A2 in which the total content of Al-Li metal exceeds 100 ppm have a self-discharge retention of less than 90%, and The performance was not sufficient as a double layer capacitor.
- An optically anisotropic pitch with a Mettler softening point of 285 ° C obtained by heat treatment of petroleum cracking residue has 100 mm spinning holes with a diameter of 0.2 mm in a slit with a width of 2 mm Melt blow spinning using a nozzle, infusibilization treatment and carbonization treatment A carbon fiber was manufactured.
- the granulated product was dehydrated under a reduced pressure of 1.5 Torr at a temperature rising rate of 2 ° CZ to 300 ° C. for 5 hours.
- 24 g of the obtained dehydrated granules are placed in a 2-inch horizontal nickel reactor equipped with a thermometer, and the system is purged with nitrogen.Then, at 700 ° C under a nitrogen stream of 10 OmL / min. Until 200 ° CZ. After the temperature reached 700 ° C, the temperature was maintained for 1 hour, and then cooled to room temperature over 2 hours. After flowing nitrogen through a distilled water bubbler for 1 hour, the mixture was charged into 15 OmL of water.
- Activated carbon was obtained by repeating the same operation as in Example B1 except that washing with ammonia water was not performed in Example B1.
- Activated carbon was obtained by repeating the same operation as in Example B1 except that 50 g of a phenol resin carbide obtained by pulverizing a carbon material to 20 ⁇ or less in Example B1. 5.9 g were obtained.
- Activated carbon was obtained by repeating the same operation as in Example B2, except that washing with ammonia water was not performed in Example B2.
- Each of the obtained activated carbons of Examples B1 and B2 and Comparative Examples B1 and B2 was further pulverized to an average particle size of 5 to 20 ⁇ to obtain powdered activated carbon.
- Teflon (registered trademark) 6J Mitsui 'Dupont Chemical Co., Ltd.
- the obtained kneaded material is formed into a sheet having a thickness of 300 / zm by roll rolling, punched into a circular shape having a diameter of 2 cm using a punch, and then dried under reduced pressure at 150 ° C for 4 hours.
- a sheet-shaped polarizable electrode was produced.
- the obtained polarizable electrode was placed in a stainless steel case, as shown in Fig. 1, in a glove box with a dew point of _80 ° C or less, a current collecting member, a polarizable electrode sheet, a polypropylene non-woven cloth, and a polarizable electrode.
- the polarizable electrode is impregnated with a propylene carbonate solution containing 1 mol of tetraethylammonium tetrafluoroporate, and a stainless steel case using a polypropylene insulating gasket.
- An electric double-layer capacitor was fabricated by sealing the upper lid.
- the obtained electric double layer capacitor was evaluated using a Hioki Electric Double Layer Capacitor Evaluation Apparatus at room temperature up to an ultimate voltage of 2.5 V and 2 mA / electrode surface area.
- Charge / discharge cycle test constant current charge at cm2, supplementary charge at 2.5 V for 30 minutes under low voltage, and constant current discharge at 2 mA / cm2 after completion of supplementary charge. From the discharge carp from 1.2 to 1.0V, the initial capacitance was determined by a standard method. Table 2 shows the obtained results.
- the electric double layer capacitor for which the capacitance was determined was charged at a constant current of 2 mA / cm2 per electrode surface area at room temperature up to the ultimate voltage of 2.5 V, and supplementary charged at a low voltage of 2.5 V for 30 minutes. After charging, leave the battery open for 50 hours, discharge at a constant current of 2 mA / cm 2 , calculate the capacitance after leaving the capacitor from the discharge carp from 1.2 V to 1.0 V by the standard method, The self-discharge holding ratio (%) was obtained by dividing the above by the initial capacitance obtained earlier. Table 2 shows the obtained results. 2 tables
- Examples B 1 and 20 having a total metal content of 20 ppm or less The electric double layer capacitor produced from the activated carbon of Example B2 exhibited a self-discharge holding ratio of 90% or more, and exhibited excellent performance as an electric double layer capacitor.
- the electric double-layer capacitors made from the activated carbons of Comparative Example B1 and Comparative Example B2 with a total heavy metal content of more than 20 ppm have a self-discharge retention of less than 90% and an electric double-layer capacitor. As was not enough performance.
- Anisotropic pitch with a Mettler softening point of 285 ° C obtained by heat treatment of petroleum cracking residue, and a nozzle with 1000 spinning holes of 0.2 mm diameter in a slit of 2 mm width
- the mixture was melt blow-spun using, and subjected to infusibilization treatment and carbonization treatment to produce mesophase pitch carbon fiber.
- the obtained mesophase pitch carbon fiber was powder-framed to 0.02 mm, and 100 g of the obtained pulverized product was mixed with 200 g of 95% hydrogen hydroxide, and the mixture was fitted with a nitrogen inlet tube and an off-gas line.
- the reaction tube was set in a cylindrical heating furnace, and the temperature was raised to 700 ° C at a rate of 3.3 ° C / min while flowing nitrogen at 1 ° 0 ml (mL) / min. For 1 hour. Then, it was cooled to room temperature at a rate of 5 ° CZ to obtain an activated material.
- the obtained activated material was filled in a pressure filter having a diameter of 3 cm and washed with 2 liters (L) of ion-exchanged water at 60 ° C. under a pressure of 0.2 MPa.
- 2 L of 1N hydrochloric acid containing 1% by weight of hydrogen peroxide was used, and washed at a temperature of 40 ° C. and a pressure of 0.2 MPa.
- 4 L of ion-exchanged water washing was performed at a temperature of 60 ° C and a pressure of 0.2 MPa to obtain activated carbon.
- the obtained activated carbon was heated at 100 ° C. for 3 hours, subsequently, heated at a pressure of 0.1 IMP a for 8 hours, and dried under reduced pressure to obtain a dried activated carbon.
- Example C 2 Activated carbon was produced in the same manner as in Example C1, except that 1N hydrochloric acid containing 2% by weight of hydrogen peroxide was used as the acidic aqueous solution to be used.
- Activated carbon was produced in the same manner as in Example C1, except that hydrochloric acid containing no hydrogen peroxide was used as the acidic aqueous solution to be used.
- the obtained polarizable electrode was placed in a stainless steel case, as shown in Fig. 1, in a glove box with a dew point of 180 ° C or less, a current collector, a polarizable electrode sheet, a polypropylene non-woven cloth, and a polarizable electrode.
- the polarizable electrode is impregnated with a propylene carbonate solution containing 1 mol of tetraethylammonium tetrafluoroborate, and a polypropylene insulating gasket is used.
- An electric double layer capacitor was fabricated by caulking and sealing the stainless steel case top cover.
- the electric double layer capacitor made from the activated carbon of Comparative Example C1 having a total heavy metal content of more than 20 ppm has a self-discharge retention of less than 90%, which is not sufficient performance as an electric double layer capacitor.
- An optically anisotropic pitch with a Mettler softening point of 285 ° C obtained by heat-treating petroleum cracking residue is used as a nozzle with 100 mm spinning holes of 0.2 mm diameter in a 2 mm wide slit.
- the mixture was melt blow-spun using a fiber, infusibilized and carbonized to produce mesophase pitch carbon fibers (manufactured by Petro Materials).
- the obtained mesophase pitch carbon fiber is pulverized to 0.02 mm, and 100 g of the obtained pulverized product is mixed with 200 g of 95% hydrogen hydroxide, and the mixture is mixed with a nitrogen inlet tube and an off-gas line. It was charged in a 4-inch nickel reaction tube. The reaction tube was set in a cylindrical heating furnace, and the temperature was raised to 700 ° C at a rate of 3.3 ° C / min while flowing nitrogen at 100 milliliter (mL) / min. For 1 hour. Then, it was cooled to room temperature at a rate of 5 ° CZ to obtain an activated material.
- the obtained activated material was filled in a pressure filter having a diameter of 3 cm and washed with 2 liters (L) of ion-exchanged water at 80 ° C under a pressure of 0.2 MPa. Next, 2 L of 1N hydrochloric acid at 80 ° C. was used, and washing was performed at a pressure of 0.2 MPa. Further, using 4 L of ion-exchanged water, washing was performed at a temperature of 60 ° C and a pressure of 0.2 MPa to obtain activated carbon. The obtained activated carbon was heated at 100 ° C. for 3 hours, subsequently, heated at a pressure of 0.1 IMP a for 8 hours, and dried under reduced pressure to obtain a dried activated carbon.
- Activated carbon was produced in the same manner as in Example D1, except that 2N hydrochloric acid was used instead of 1N hydrochloric acid in Example D1.
- Example D 3 Activated carbon was produced in the same manner as in Example D1, except that the amount of ion-exchanged water at 80 ° C was changed from 2 L to 1 L in Example D1.
- Activated carbon was produced in the same manner as in Example D1, except that washing with 1N hydrochloric acid at 80 ° C was performed at 20 ° C in Example D1.
- Activated carbon was produced in the same manner as in Example D1, except that 4N hydrochloric acid was used instead of 1N hydrochloric acid in Example D1.
- Activated carbon was produced in the same manner as in Example D1, except that washing with ion-exchanged water at 80 ° C was performed at 20 ° C in Example D1.
- the obtained polarizable electrode is placed in a stainless steel case, as shown in Fig. 1, in a glove box with a dew point of 80 ° C or less, a current collector, a polarizable electrode sheet, a polypropylene non-woven cloth, and a polarizable electrode sheet.
- the polarizable electrode is impregnated with a propylene carbonate solution containing 1 mol of tetraethylammonium tetrafluoroborate, and a stainless steel case gasket is formed using a polypropylene insulating gasket.
- An electric double layer capacitor was fabricated by caulking and sealing the top lid.
- the battery After supplemental charging at a constant voltage of 7 V, and after leaving the supplementary charge for 50 hours, the battery was left open for 2 hours, and then discharged at a constant current of 2 mAZcm 2 to determine the capacitance after standing. Then, the self-discharge holding ratio (%) was obtained by dividing the capacitance after the standing by the previously obtained initial capacitance. Table 4 shows the obtained results.
- the electric double layer capacitors made from the activated carbons of Examples D1 to D3 having a heavy metal content of 20 ppm or less and an alkali metal content of 200 ppm or less have a self-discharge holding property.
- the ratio was over 90%, indicating excellent performance as an electric double layer capacitor.
- Comparative Examples D1 to D2 in which the metal content does not exceed 200 ppm but the heavy metal content exceeds 20 ppm, and the heavy metal content does not exceed 20 ppm but the alkali metal content is 200 ppm.
- the electric double layer capacitor made from the activated carbon of Comparative Example D3 exceeding pm had a self-discharge retention of less than 90% and did not have sufficient performance as an electric double layer capacitor.
- Example D4
- the activated material obtained in the same manner as in Example Dl was filled in a pressure filter having a diameter of 3 cm and washed with 2 liters (L) of ion-exchanged water at 80 ° C under a pressure of 0.2 MPa. did. Next, it was washed with 1 L of carbonated water having a carbonic acid concentration of 1% by weight at 20 ° C under a pressure of 0.2 MPa. Subsequently, the substrate was washed with 2 L of 1N hydrochloric acid at 80 ° C. under a pressure of 0.2 MPa. Next, washing was performed at 30 ° C. and 5% aqueous ammonia 0.5 under a pressure of 0.2 MPa. Finally, activated carbon was obtained by washing with 3 L of ion exchanged water at 60 ° C and drying.
- the activated material obtained in the same manner as in Example D 1 was filled in a pressure filter having a diameter of 3 cm and washed with 2 liters (L) of ion-exchanged water at 80 ° C under a pressure of 0.2 MPa. . Next, it was washed with 1 L of carbonated water having a carbonic acid concentration of 1% by weight at 20 ° C under a pressure of 0.2 MPa. Subsequently, the substrate was washed with 2 L of 1N hydrochloric acid at 80 ° C. under a pressure of 0.2 MPa.
- Example D5 using the obtained activated carbons of Examples D4 and D5, an electric double layer capacitor was produced in the same manner as in Example D1, and the initial capacitance (FZc c) was measured. The capacitance (F / cc) and the self-discharge holding ratio (%) were evaluated. Table 5 shows the obtained results.
- the extracted carbon content of the activated carbon obtained in Examples D4 and D5 was measured as shown below. That is, in a 1.5-L glass three-necked flask equipped with a stirrer, a cooling condenser, and a thermometer and containing 700 g of toluene, 70 g of the activated carbon obtained in Example D4 or D5 was placed. Then, the mixture was stirred and dispersed, and heated and refluxed at 115 ° C. for 1 hour to perform a carbon content extraction treatment. After cooling the mixture to room temperature, the mixture is filtered, and the filtered activated carbon is heated at 100 ° C for 3 hours, followed by drying under reduced pressure (pressure 0, IMP a, heating for 8 hours). Activated carbon in a state was obtained. The weight loss of the extraction was determined by comparing the weight of the activated carbon before and after the extraction treatment. Table 5 shows the obtained results.
- the activated carbon of the first aspect of the present invention has a total alkali metal content of 100 ppm or less. Therefore, when used as a raw material for electronic devices, it is difficult to cause the phenomenon of dendrite formation due to the reduction and precipitation of alkali metals, it is unlikely to cause short-circuits and other obstacles, and it has a good self-discharge retention rate.
- the elution of alkali metals into purified water can be greatly suppressed, making it suitable for use in the production of foods and pharmaceuticals, the production of purified water, electronic devices, and the like.
- the second and third inventions have a total heavy metal content of 20 ppm or less, when used as a raw material for an electronic device, the dendrite phenomenon due to the reduction and precipitation of heavy metals is less likely to occur, It is hard to cause troubles such as short-circuit, and shows a good self-discharge holding ratio.
- the activated carbon according to the third aspect of the present invention since the content of Al-Li metal is 200 Ppm or less, when used as a raw material for an electronic device, reduction precipitation of Al-Li metal or heavy metal It is difficult to cause dendrite phenomena due to heat and hardly causes troubles such as short-circuit, and shows a good self-discharge holding ratio. Therefore, it is suitable as a raw material for electric and electronic devices such as electric double layer capacitors.
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- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003246253A AU2003246253B8 (en) | 2002-07-30 | 2003-07-03 | Activated carbon, method for production thereof, polarized electrode and electrical double layer capacitor |
EP03738657A EP1526114A4 (en) | 2002-07-30 | 2003-07-03 | ACTIVE CHARCOAL, PROCESS FOR PRODUCING THE SAME, POLARIZED ELECTRODE AND DOUBLE LAYER CAPACITOR |
JP2004524104A JP4238830B2 (ja) | 2002-07-30 | 2003-07-03 | 活性炭、その製造方法、分極性電極および電気二重層キャパシタ |
US10/519,399 US7759289B2 (en) | 2002-07-30 | 2003-07-03 | Activated carbon, method for production thereof, polarizing electrode and electrical double layer capacitor |
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JP2002-221796 | 2002-07-30 | ||
JP2002221796 | 2002-07-30 | ||
JP2002221793 | 2002-07-30 | ||
JP2002-221793 | 2002-07-30 | ||
JP2002-263708 | 2002-09-10 | ||
JP2002263684 | 2002-09-10 | ||
JP2002-263684 | 2002-09-10 | ||
JP2002263708 | 2002-09-10 |
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WO2004011371A1 true WO2004011371A1 (ja) | 2004-02-05 |
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PCT/JP2003/008464 WO2004011371A1 (ja) | 2002-07-30 | 2003-07-03 | 活性炭、その製造方法、分極性電極および電気二重層キャパシタ |
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US (1) | US7759289B2 (ja) |
EP (1) | EP1526114A4 (ja) |
JP (3) | JP4238830B2 (ja) |
KR (1) | KR100984989B1 (ja) |
CN (1) | CN100380547C (ja) |
AU (1) | AU2003246253B8 (ja) |
WO (1) | WO2004011371A1 (ja) |
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Also Published As
Publication number | Publication date |
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US20050266990A1 (en) | 2005-12-01 |
CN1671621A (zh) | 2005-09-21 |
AU2003246253A1 (en) | 2004-02-16 |
EP1526114A4 (en) | 2011-09-07 |
US7759289B2 (en) | 2010-07-20 |
JP2008297201A (ja) | 2008-12-11 |
KR20050026066A (ko) | 2005-03-14 |
EP1526114A1 (en) | 2005-04-27 |
JP2008297200A (ja) | 2008-12-11 |
KR100984989B1 (ko) | 2010-10-04 |
JP5041164B2 (ja) | 2012-10-03 |
CN100380547C (zh) | 2008-04-09 |
AU2003246253B2 (en) | 2009-12-03 |
JP4238830B2 (ja) | 2009-03-18 |
JPWO2004011371A1 (ja) | 2005-12-15 |
AU2003246253B8 (en) | 2010-01-07 |
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