WO2017219943A1 - Charbon actif à base de coke de pétrole composite et son procédé de préparation, et supercondensateur - Google Patents

Charbon actif à base de coke de pétrole composite et son procédé de préparation, et supercondensateur Download PDF

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WO2017219943A1
WO2017219943A1 PCT/CN2017/088990 CN2017088990W WO2017219943A1 WO 2017219943 A1 WO2017219943 A1 WO 2017219943A1 CN 2017088990 W CN2017088990 W CN 2017088990W WO 2017219943 A1 WO2017219943 A1 WO 2017219943A1
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activated carbon
petroleum coke
gas
preparation
coke
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PCT/CN2017/088990
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English (en)
Chinese (zh)
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赵永彬
张在忠
刘海波
董士光
胡兴华
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山东欧铂新材料有限公司
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Publication of WO2017219943A1 publication Critical patent/WO2017219943A1/fr

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    • 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
    • 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
    • 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
    • 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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • 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
    • 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
    • C01P2006/80—Compositional purity
    • 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 invention belongs to the technical field of activated carbon materials, in particular to a composite petroleum coke-based activated carbon, a preparation method thereof and a super capacitor.
  • Activated carbon also known as activated carbon black, is a black powder or block, granular, honeycomb amorphous carbon, but also has a regular arrangement of crystalline carbon.
  • activated carbon also contains a small amount of hydrogen and oxygen. Some of these elements are derived from the incomplete carbonization of the activated carbon precursor and remain in the activated carbon. The other part is derived from the activation of reagents such as water or sodium hydroxide to form a surface with activated carbon. a group such as a hydroxyl group, a carboxyl group, a carbonyl group or the like.
  • activated carbon also has a part of ash, which is mainly composed of inorganic salts remaining in activated carbon, such as iron salt, sodium salt, potassium salt and the like.
  • Activated carbon can be divided into wood, coal, petroleum coke and resin activated carbon from the raw materials; from the manufacturing method, it is divided into chemical, physical and physical chemical combined activated carbon. These activated carbon precursors form activated carbon in an activation furnace at a high temperature, under a certain pressure, by pyrolysis with an activator, high temperature carbonization and activation reaction. During this activation process, large surface areas and complex pore structures are gradually formed. Activated carbon contains a large number of micropores, has a huge surface area, can effectively remove chromaticity and odor, and can remove most organic pollutants and certain inorganic substances in secondary effluent, including some toxic heavy metals. According to the difficulty of graphitization of activated carbon, it is divided into hard carbon and soft carbon. Generally, lignin and resin are used as raw materials for hard carbon, and petroleum coke is used as raw material for soft carbon.
  • supercapacitors are getting more and more applications. Compared with lithium batteries, supercapacitors have the characteristics of fast charge and discharge speed, high power density, long life, maintenance-free, and environmental protection. Although the energy density is still far lower than that of lithium batteries, they can make up for lithium batteries in terms of power density.
  • the short board has become a powerful complement to lithium batteries and other secondary batteries, and has been successfully applied in many fields such as communications, military, new energy vehicles, national power grids, and port machinery.
  • the storage capacity of supercapacitors depends mainly on the specific surface area and electricity that the electrode material can be used to store electricity.
  • the intensity of the load Theoretically, the larger the surface area of the electrode, the denser the charge and the greater its capacity. Due to its chemical stability and high specific surface area, porous carbon is the most widely used material in the field of supercapacitors, and activated carbon is the most commonly used supercapacitor electrode material.
  • Electrode materials require high specific surface area, reasonable pore size distribution, and good electrical conductivity.
  • the technical problem to be solved by the present invention is to provide a modified composite petroleum coke-based activated carbon, a preparation method thereof, and a super capacitor.
  • the graphene-modified composite petroleum coke-based activated carbon provided by the present invention has a large It has the characteristics of specific surface area, low internal resistance, high capacity, low impurity and low oxygen content, and can be used as a supercapacitor carbon to obtain a supercapacitor with better performance.
  • the invention provides a preparation method of a composite petroleum coke-based activated carbon, comprising the following steps:
  • the activated carbon dispersion obtained in the above step is mixed with a graphene oxide solution, dried, and then heat-treated under a protective gas condition to obtain a composite petroleum coke-based activated carbon.
  • the oxidizing medium comprises one or more of hydrogen peroxide, nitric acid solution, hypochlorous acid solution, perchloric acid solution, potassium ferrate solution, sodium ferrate solution, potassium permanganate solution and potassium manganate solution.
  • hydrogen peroxide hydrogen peroxide
  • nitric acid solution hypochlorous acid solution
  • perchloric acid solution potassium ferrate solution
  • sodium ferrate solution potassium permanganate solution
  • potassium manganate solution potassium manganate solution
  • the petroleum coke includes one or more of a honeycomb coke, a sponge coke, a projectile coke, and a needle coke;
  • the petroleum coke particles have a particle size of 5 to 150 ⁇ m;
  • the treatment time is 2 to 24 hours, and the treatment temperature is 0 to 80 °C.
  • the first gas comprises one or more of air, oxygen, hydrogen, nitrogen, an inert gas, carbon dioxide, and water vapor;
  • the coking temperature is 350 to 700 ° C, and the coking time is 1 to 6 hours.
  • the mass ratio of the activated carbon precursor to the base is 1: (0.5 to 5);
  • the base includes one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide and calcium hydroxide;
  • the base is a particulate alkali, and the granular base has a particle diameter of 10 to 300 ⁇ m.
  • the second gas comprises one or more of air, hydrogen, nitrogen and an inert gas
  • the preactivation temperature is 350 to 500 ° C, and the preactivation time is 1 to 4 hours;
  • the third gas includes one or more of hydrogen, nitrogen, and an inert gas
  • the activation temperature is 700 to 950 ° C, and the activation time is 0.5 to 4 hours.
  • the step C) is specifically:
  • the activated carbon dispersion liquid, the graphene oxide solution and the nitrogen source obtained in the above steps are mixed and dried, and then heat-treated to obtain a composite petroleum coke-based activated carbon;
  • the nitrogen source comprises melamine and/or urea
  • the ratio of the mass of the graphene oxide in the graphene oxide solution to the mass of the activated carbon in the activated carbon dispersion is 0.05% to 1%;
  • the ratio of the mass of the nitrogen source to the mass of the activated carbon in the activated carbon dispersion is from 1% to 5%.
  • the protective gas comprises one or more of hydrogen, ammonia, nitrogen and an inert gas;
  • the heat treatment temperature is 700 to 1000 ° C, and the heat treatment time is 1 to 4 hours.
  • the steps of crushing, screening and magnetic separation are further included;
  • the particle size after the crushing is 6 to 10 ⁇ m.
  • the invention provides a composite petroleum coke-based activated carbon obtained by compounding petroleum coke, graphene oxide and nitrogen source.
  • the present invention also provides a supercapacitor comprising the composite petroleum coke-based activated carbon prepared by any one of the above technical solutions or the composite petroleum coke-based activated carbon according to the above technical solution.
  • the invention provides a preparation method of a composite petroleum coke-based activated carbon, comprising the following steps: First, the petroleum coke particles treated by the oxidizing medium are coked under the condition of the first gas to obtain an activated carbon precursor; then the activated carbon precursor obtained by the above step is mixed with the alkali, and then under the condition of the second gas. Pre-activation, and then activation under the third gas condition, and then washing to obtain activated carbon dispersion; finally, the activated carbon dispersion obtained in the above step is mixed with the graphene oxide solution, dried, and then under protective gas conditions. After the heat treatment, a composite petroleum coke-based activated carbon is obtained.
  • the present invention is mainly directed to micropores, and the pore size distribution is unreasonable; the proportion of alkali used in the preparation process is high; the performance of the prepared activated carbon still cannot meet the capacity requirements; The internal resistance of activated carbon is large and so on.
  • the invention can form an activated active point on the surface of petroleum coke by immersion and coking and pre-activation process of oxidizing medium, which is beneficial to chemical activation of partial pore formation, reduction of alkali usage, increase of mesoporosity, overcoming the surface of petroleum coke, and pore formation.
  • 1 is an electron micrograph of a composite petroleum coke-based activated carbon prepared by the present invention
  • Example 2 is an electron micrograph of a composite petroleum coke-based activated carbon prepared in Example 1 of the present invention
  • Example 3 is a pore size distribution diagram of a composite petroleum coke-based activated carbon prepared in Example 1 of the present invention.
  • All the raw materials of the present invention are not particularly limited in their source, and are commercially available or prepared according to a conventional method well known to those skilled in the art.
  • the purity of all the raw materials of the present invention is not particularly limited, and the present invention preferably employs a conventional purity used in the field of analytically pure or capacitors.
  • the invention provides a preparation method of a composite petroleum coke-based activated carbon, comprising the following steps:
  • the activated carbon dispersion obtained in the above step is mixed with a graphene oxide solution, dried, and then heat-treated under a protective gas condition to obtain a composite petroleum coke-based activated carbon.
  • the petroleum coke particles treated by the oxidizing medium are first coked under the conditions of the first gas to obtain an activated carbon precursor.
  • the specific selection of the petroleum coke of the present invention is not particularly limited, and the petroleum coke which is well known to those skilled in the art can be used, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention
  • the petroleum coke preferably comprises one or more of honeycomb coke, sponge coke, projectile coke and needle coke, more preferably honeycomb coke, projectile coke or needle coke, most preferably needle coke.
  • the quality of the petroleum coke of the present invention is not particularly limited, and the petroleum coke quality known to those skilled in the art can be used. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the petroleum coke is preferably petroleum coke having a carbon content of 90% or more and a sulfur content of 0.5% or less.
  • the particle size of the petroleum coke particles is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the particle size of the petroleum coke particles of the present invention is preferably 5 to 150 ⁇ m. It is more preferably 20 to 120 ⁇ m, still more preferably 40 to 100 ⁇ m, and most preferably 60 to 80 ⁇ m.
  • the specific selection of the oxidizing medium in the present invention is not particularly limited, and the oxidizing medium is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention
  • the oxidizing medium preferably comprises one or more of hydrogen peroxide, nitric acid solution, hypochlorous acid solution, perchloric acid solution, potassium ferrate solution, sodium ferrate solution, potassium permanganate solution and potassium manganate solution.
  • the oxidizing medium in the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality requirements.
  • the specific conditions of the treatment of the present invention are not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the processing time of the present invention is preferably 2-24 hours, more preferably 6 ⁇ 20h, more preferably 10-16h, most preferably 12-14h;
  • the temperature is preferably 0 to 80 ° C, more preferably 10 to 70 ° C, still more preferably 20 to 60 ° C, and most preferably 30 to 50 ° C.
  • the specific manner of the treatment of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the treatment according to the present invention is preferably dipping, immersing, spraying or painting, and Subsequent washing and drying, etc., are more preferably soaking and subsequent washing and drying.
  • the procedures and conditions of the above specific steps of the present invention are not particularly limited, and may be the corresponding processes and conditions well known to those skilled in the art.
  • the first gas is not particularly limited, and the protective gas is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the gas preferably comprises one or more of air, oxygen, hydrogen, nitrogen, an inert gas, carbon dioxide and water vapor, more preferably air, oxygen, hydrogen, nitrogen, an inert gas, carbon dioxide or water vapor.
  • the inert gas of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention is particularly preferably argon gas.
  • the conditions of the coking in the present invention are not particularly limited, and the conditions of petroleum coke coking which are well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention
  • the coking temperature is preferably 350 to 700 ° C, more preferably 400 to 650 ° C, still more preferably 450 to 600 ° C, most preferably 500 to 550 ° C;
  • the coking time is preferably 1 to 6 hours, more preferably 2 to 5 hours, most preferably 3 to 4 hours.
  • the apparatus for the coking of the present invention is not particularly limited, and the petroleum coke coking device well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention
  • the coking unit is preferably a coker.
  • the activated carbon precursor obtained in the above step is mixed with a base, pre-activated under the conditions of the second gas, and then activated under the conditions of the third gas, and then washed to obtain an activated carbon dispersion.
  • the base is not particularly limited in the present invention, and the base for petroleum coke activation well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements, and the alkali of the present invention.
  • it comprises one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide and calcium hydroxide, more preferably potassium hydroxide, sodium hydroxide, lithium hydroxide or calcium hydroxide, more preferably potassium hydroxide, Sodium hydroxide or calcium hydroxide is most preferably potassium hydroxide.
  • the invention does not have the base Other specific restrictions, those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the base is preferably a granular base, and the granular base preferably has a particle diameter of 10 ⁇ 300 ⁇ m, more preferably 50 to 250 ⁇ m, still more preferably 100 to 200 ⁇ m, and most preferably 130 to 170 ⁇ m.
  • the amount of the base to be used in the present invention is not particularly limited, and those skilled in the art can select and adjust according to the actual production conditions, product requirements and quality requirements.
  • the mass ratio of the activated carbon precursor to the base of the present invention is preferably 1: (0.5) ⁇ 5) is more preferably 1: (1 to 4.5), still more preferably 1: (1.5 to 4), and most preferably 1: (2 to 3.5).
  • the present invention is not particularly limited to the mixing, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention preferably mixes with a mixer.
  • the second gas is not particularly limited, and the protective gas is well known to those skilled in the art. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the two gases preferably comprise one or more of air, hydrogen, nitrogen and an inert gas, more preferably air, hydrogen, nitrogen or argon.
  • the pre-activation conditions of the present invention are not particularly limited, and the conditions of pre-activation of petroleum coke which are well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements.
  • the preactivation temperature of the invention is preferably from 350 to 500 ° C, more preferably from 375 to 475 ° C, still more preferably from 400 to 450 ° C, most preferably from 410 to 440 ° C; and the preactivation time is preferably from 1 to 4 hours. It is more preferably 1.5 to 3.5 hours, and most preferably 2 to 3 hours.
  • the third gas is not particularly limited in the present invention, and the protective gas is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the three gases preferably comprise one or more of hydrogen, nitrogen and an inert gas, more preferably hydrogen, nitrogen or argon.
  • the conditions of the activation of the present invention are not particularly limited, and the conditions of petroleum coke activation well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention
  • the activation temperature is preferably 700 to 950 ° C, more preferably 725 to 925 ° C, still more preferably 750 to 900 ° C, most preferably 800 to 850 ° C;
  • the activation time is preferably 0.5 to 4 hours, more preferably It is 1 to 3.5 hours, more preferably 1.5 to 3 hours, and most preferably 2 to 2.5 hours.
  • the apparatus for pre-activation and activation of the present invention is not particularly limited, and the equipment for pre-activation and activation of petroleum coke which is well known to those skilled in the art may be used, and those skilled in the art may select according to actual production conditions, product requirements and quality requirements. And adjustment, this
  • the device for preactivation and activation of the invention is preferably hydrazine.
  • the washing step of the present invention is not particularly limited, and the washing step after the petroleum coke activation is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the specific steps of the washing according to the invention preferably include natural cooling, water washing, pickling and water washing, and more specifically, natural cooling, water washing to neutral, pickling, and washing to neutral.
  • the acid for pickling according to the present invention is preferably one or more of hydrochloric acid, nitric acid and phosphoric acid; the temperature of the washing is preferably from 20 to 100 ° C, more preferably from 40 to 80 ° C, most preferably from 50 to 100 ° C. .
  • the drying step of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality requirements.
  • concentration of the activated carbon dispersion liquid in the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the solid content of the activated carbon dispersion liquid of the present invention is preferably 1% to 10%. % is more preferably 2% to 9%, still more preferably 3% to 8%, and most preferably 5% to 6%.
  • the invention can form an activated active point on the surface of petroleum coke by immersion and coking and pre-activation process of oxidizing medium, which is beneficial to chemical activation of partial pore formation, reduction of alkali usage, increase of mesoporosity, and effective overcoming of petroleum coke surface compaction. It is a difficult problem to make holes.
  • the activated carbon dispersion obtained in the above step is mixed with the graphene oxide solution, dried, and then heat-treated under a protective gas condition to obtain a composite petroleum coke-based activated carbon.
  • the graphene oxide solution of the present invention is preferably a single layer graphene oxide solution, and the monolayer ratio is preferably higher than or equal to 95%.
  • the source of the single-layer graphene oxide solution of the present invention is not particularly limited, and may be commercially available as a source of a single-layer graphene oxide solution well known to those skilled in the art, and may be commercially available or prepared according to a conventional preparation method.
  • the amount of the graphene oxide added in the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the quality of graphene oxide in the graphene oxide solution of the present invention accounts for
  • the proportion of the mass of the activated carbon in the activated carbon dispersion is preferably from 0.05% to 1%, more preferably from 0.1% to 0.9%, still more preferably from 0.3% to 0.7%, most preferably from 0.4% to 0.6%.
  • the chip diameter of the graphene oxide is not particularly limited in the present invention, and the chip diameter of the graphene oxide well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements.
  • the average particle diameter of the graphene oxide of the present invention is preferably from 1 to 50 ⁇ m, more preferably from 5 to 45 ⁇ m, still more preferably from 10 to 40 ⁇ m, and most preferably from 20 to 30 ⁇ m.
  • the mixing of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the mixing according to the present invention is preferably ultrasonic stirring; the mixing time is preferably 0.5 to 2 hours. More preferably, it is 1 to 1.5 hours.
  • the drying of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the drying according to the present invention is preferably spray drying.
  • the protective gas is not particularly limited in the present invention, and the protective gas is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the protection according to the present invention.
  • the gas preferably includes one or more of hydrogen, ammonia, nitrogen, and an inert gas, and more preferably one or both of hydrogen, ammonia, nitrogen, and argon.
  • the heat treatment conditions of the present invention are not particularly limited, and the heat treatment step of preparing activated carbon by petroleum coke well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements.
  • the heat treatment temperature of the invention is preferably 700 to 1000 ° C, more preferably 750 to 950 ° C, still more preferably 800 to 900 ° C, most preferably 830 to 870 ° C; and the heat treatment time is preferably 1 to 4 hours, more It is preferably 1.5 to 3.5 hours, and most preferably 2 to 3 hours.
  • the invention combines and sprays the petroleum coke activated carbon and the graphene oxide to uniformly coat a layer of graphene oxide on the surface of the activated carbon, and reduces the graphene oxide to graphene in the subsequent high-temperature reduction heat treatment, thereby improving the conductance of the activated carbon. Rate, reduce its internal resistance; in addition, high temperature treatment reduces surface functional groups and improves the stability of supercapacitor carbon.
  • the step C) is specifically preferably: mixing the activated carbon dispersion liquid, the graphene oxide solution and the nitrogen source obtained in the above step. After drying, heat treatment is performed to obtain a composite petroleum coke-based activated carbon, that is, a composite petroleum coke-based nitrogen-doped activated carbon.
  • the nitrogen source (nitrogen-containing precursor) of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the nitrogen source of the present invention is preferably a small molecule nitrogen-containing compound. (nitrogen-containing small molecule), more preferably melamine and/or urea, more preferably melamine or urea, most preferably melamine.
  • the amount of the nitrogen source added in the present invention is not particularly limited, and those skilled in the art can select and adjust according to the actual production conditions, product requirements and quality requirements, and the quality of the nitrogen source of the present invention accounts for the activated carbon in the activated carbon dispersion.
  • the proportion of the mass is preferably from 1% to 5%, more preferably from 1.5% to 4.5%, still more preferably from 2% to 4%, most preferably from 2.5% to 3.5%.
  • the invention combines and sprays the petroleum coke activated carbon, graphene oxide and nitrogen source to make the surface of the activated carbon uniformly coat a layer of graphene oxide, and the melamine also enters the activated carbon channel; in the subsequent high temperature reduction heat treatment process, on the one hand
  • the reduction of graphene oxide to graphene improves the electrical conductivity of activated carbon and reduces its internal resistance.
  • melamine is decomposed on the surface of activated carbon to nitrogen doping the activated carbon, while nitrogen doping can greatly improve the functional group distribution on the surface of activated carbon.
  • Improve energy storage efficiency in addition, high temperature treatment reduces surface functional groups and improves the stability of supercapacitor carbon.
  • the heat treatment further preferably includes a crushing, screening and magnetic separation step; the specific process and conditions of the crushing, screening and magnetic separation steps are not particularly limited, and those skilled in the art may
  • the particle size after the crushing according to the present invention is preferably 6 to 10 ⁇ m, and more preferably 7 to 9 ⁇ m, depending on actual production conditions, product requirements, and quality requirements.
  • the invention provides a composite petroleum coke-based activated carbon obtained by compounding petroleum coke, graphene oxide and nitrogen source.
  • the present invention is not particularly limited to the compounding, and may be a composite concept well known to those skilled in the art, and may be one or more of coating, semi-coating, spraying, doping, bonding or embedding.
  • Fig. 1 is an electron micrograph of a composite petroleum coke-based activated carbon prepared by the present invention.
  • the above steps of the present invention provide a composite petroleum coke-based activated carbon and a preparation method thereof.
  • the invention can form an activated active point on the surface of petroleum coke by immersion in an oxidizing medium, coking and pre-activation process, and is beneficial to chemically activated partial pore-forming. , reduce the amount of alkali used, increase the mesoporosity; form a conductive network by graphene modification, reduce the internal resistance of activated carbon; increase the surface nitrogen content by nitrogen source composite high temperature treatment, increase the capacity performance of the capacitor carbon; jointly perform high temperature heat treatment to reduce the surface Functional groups improve the stability of supercapacitor carbon.
  • the composite petroleum coke-based activated carbon prepared by the invention has the advantages of reasonable pore size distribution, large specific surface area, low internal resistance, high capacity, low impurity and low oxygen-containing functional groups, and can be used as a supercapacitor carbon to obtain a supercapacitor with better performance.
  • the experimental results show that the composite petroleum coke-based activated carbon prepared by the invention has a specific surface area of 1800-3500 m 2 /g, a mesoporosity of 55-75%, an average particle diameter of 7-10 ⁇ m, and a nitrogen content of 1.3%-2.5%. , metal impurities ⁇ 100ppm, low resistance, organic mass ratio capacitance up to 220F / g, and good cycle stability.
  • the present invention also provides a supercapacitor comprising the composite petroleum coke-based activated carbon prepared by any one of the above technical solutions or the composite petroleum coke-based activated carbon according to the above technical solution. Pair of the invention
  • the definition of the supercapacitor is not particularly limited, and may be defined by a supercapacitor well known to those skilled in the art.
  • the product was dissolved in water, washed repeatedly to neutral, then refluxed with 6 M hydrochloric acid for 2 h, filtered, washed with deionized water until neutral; deionized water was added to form a 5% aqueous dispersion; solid was added to the dispersion A 0.5 g single layer graphene oxide solution (0.5%, 100 mL) and 0.5 g melamine were ultrasonically stirred for 1 h and spray dried. The obtained solid powder was placed in a rotary kiln, and heated to 800 ° C under a 10% hydrogen-nitrogen mixed gas for 2 h, cooled, and magnetically selected to obtain a supercapacitor carbon.
  • FIG. 2 is an electron micrograph of a composite petroleum coke-based activated carbon prepared in Example 1 of the present invention.
  • FIG. 3 is a pore size distribution diagram of a composite petroleum coke-based activated carbon prepared in Example 1 of the present invention.
  • the composite petroleum coke-based activated carbon prepared in the above Example 1 was tested.
  • the specific surface area of the activated carbon was 1850 m 2 /g, the mesoporosity was 55%, the average particle diameter was 8.6 ⁇ m, the nitrogen content was 2.1%, and the metal impurities were ⁇ 100ppm.
  • the activated carbon and the binders SBR and CMC were mixed and homogenized, uniformly coated on an aluminum foil, and dried, laminated, and punched to assemble into a supercapacitor (organic system, 2.7 V) at a current density of 2 A/g.
  • the mass ratio capacitance is 153F/g.
  • 100 g of high-quality petroleum coke was pulverized into 50-100 ⁇ m particles, 500 mL of 1 M nitric acid was added and refluxed for 6 h, filtered, washed and dried; the material was heated to 350 ° C under air for 60 min, and naturally cooled.
  • 50 g of KOH dissolved in ethanol uniformly mixed and heated to remove the solvent.
  • the mixture was added to a metal nickel crucible, and the temperature was raised to 500 ° C at a rate of 10 to 20 ° C / min under nitrogen atmosphere for 1 h; then, the temperature was raised to 850 ° C at a rate of 10 to 20 ° C / min for 1 h, and naturally lowered to room temperature. .
  • the product was dissolved in water, washed repeatedly to neutral, then refluxed with 6 M hydrochloric acid for 2 h, filtered, washed with deionized water until neutral; deionized water was added to form a 5% aqueous dispersion; solid was added to the dispersion A 0.2 g single layer graphene oxide solution (0.5%, 100 mL) and 2.0 g melamine were ultrasonically stirred for 1 h and spray dried.
  • the obtained solid powder was placed in a rotary kiln, heated to 850 ° C under a mixture of 10% ammonia-argon gas for 1.5 h, cooled, and secondarily pulverized by a ball mill to 8 to 10 ⁇ m to be magnetically selected to obtain a supercapacitor carbon.
  • the composite petroleum coke-based activated carbon prepared in the above Example 2 was tested.
  • the specific surface area of the activated carbon was 1650 m 2 /g, the mesoporosity was 62%, the average particle diameter was 8.5 ⁇ m, the nitrogen content was 2.1%, and the metal impurities were ⁇ 100ppm.
  • the activated carbon and the binders SBR and CMC were mixed and homogenized, uniformly coated on an aluminum foil, and dried, laminated, and punched to assemble into a supercapacitor (organic system, 2.7 V) at a current density of 2 A/g.
  • the mass ratio capacitance is 140F/g.
  • the mixture was added to a metal nickel crucible, and the temperature was raised to 400 ° C at a rate of 10 to 20 ° C / min under nitrogen atmosphere for 3 h; then, the temperature was raised to 800 ° C at a rate of 10 to 20 ° C / min for 1 h, and naturally lowered to room temperature. .
  • the product was dissolved in water, washed repeatedly to neutral, then added with 6 M hydrochloric acid reflux for 2 h, filtered, washed with deionized water Neutral; add deionized water to form a 5% aqueous dispersion; add 0.2g of a single layer graphene oxide solution (0.5%, 100mL) and 1.0g of melamine to the dispersion, ultrasonically stir for 1h, spray dry.
  • the obtained solid powder was placed in a rotary kiln, heated to 800 ° C under a 10% ammonia-nitrogen mixed gas for 2 h, cooled, and secondarily pulverized by a ball mill to 8 to 10 ⁇ m to be magnetically selected to obtain a supercapacitor carbon.
  • the composite petroleum coke-based activated carbon prepared in the above Example 3 was tested.
  • the specific surface area of the activated carbon was 2650 m 2 /g, the mesoporosity was 65%, the average particle diameter was 9.1 ⁇ m, the nitrogen content was 1.4%, and the metal impurities were ⁇ 100ppm.
  • the activated carbon and the binders SBR and CMC were mixed and homogenized, uniformly coated on an aluminum foil, and dried, laminated, and punched to assemble into a supercapacitor (organic system, 2.7 V) at a current density of 2 A/g.
  • the mass ratio capacitance is 186F/g.
  • the mixture was added to a metal nickel crucible, and heated to 450 ° C at a rate of 10 to 20 ° C / min under an argon atmosphere for 3 h; then heated to 760 ° C at a rate of 10 to 20 ° C / min for 3 h, naturally reduced to Room temperature.
  • the product was dissolved in water, washed repeatedly to neutral, then refluxed with 6 M hydrochloric acid for 2 h, filtered, washed with deionized water until neutral; deionized water was added to form a 5% aqueous dispersion; solid was added to the dispersion A 0.7 g single layer graphene oxide solution (0.5%, 100 mL) and 3.0 g melamine were ultrasonically stirred for 1 h and spray dried.
  • the obtained solid powder was placed in a rotary kiln, heated to 780 ° C under a 10% hydrogen-nitrogen mixed gas for 2 h, cooled, and secondarily pulverized by a ball mill to 8 to 10 ⁇ m to be magnetically selected to obtain a supercapacitor carbon.
  • the composite petroleum coke-based activated carbon prepared in the above Example 4 was tested.
  • the specific surface area of the activated carbon was 3150 m 2 /g, the mesoporosity was 70%, the average particle diameter was 9.2 ⁇ m, the nitrogen content was 2.2%, and the metal impurities were ⁇ 100ppm.
  • the activated carbon and the binders SBR and CMC were mixed and homogenized, uniformly coated on an aluminum foil, and dried, laminated, and punched to assemble into a supercapacitor (organic system, 2.7 V) at a current density of 2 A/g.
  • the mass ratio capacitance is 225F/g.

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Abstract

Charbon actif à base de coke de pétrole composite et son procédé de préparation. Des sites actifs activés peuvent être formés sur la surface du coke de pétrole au moyen de l'immersion, la cokéfaction et des processus de pré-activation d'un milieu oxydant, et en conséquence, la formation de pores dans la partie d'activation chimique est facilitée, la quantité d'alcali utilisée est réduite, le taux de mésopores est augmentée, et le problème de difficulté de formation des pores dû à la compacité de la surface du coke de pétrole est résolu. L'oxyde de graphène est réduit en graphène, un réseau conducteur est formé, de sorte que la conductivité du charbon actif est améliorée, et que la résistance interne du charbon actif est réduite. Un traitement thermique à haute température est effectué conjointement, de sorte que les groupes fonctionnels de surface sont réduits, et la stabilité d'un carbone super-condensateur est améliorée. Le charbon actif à base de coke de pétrole composite préparé présente les avantages d'être raisonnable en termes de distribution de la taille des pores, de présenter une grande surface spécifique, une faible résistance interne, une forte capacité, de faibles teneurs en impuretés et en groupe fonctionnel contenant de l'oxygène et peut servir de carbone super-condensateur pour obtenir le supercondensateur présentant de meilleures performances.
PCT/CN2017/088990 2016-06-20 2017-06-19 Charbon actif à base de coke de pétrole composite et son procédé de préparation, et supercondensateur WO2017219943A1 (fr)

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