CN110697705B - Rapid preparation method of asphalt-based activated carbon with hierarchical pore structure - Google Patents

Rapid preparation method of asphalt-based activated carbon with hierarchical pore structure Download PDF

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CN110697705B
CN110697705B CN201910991388.9A CN201910991388A CN110697705B CN 110697705 B CN110697705 B CN 110697705B CN 201910991388 A CN201910991388 A CN 201910991388A CN 110697705 B CN110697705 B CN 110697705B
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activated carbon
asphalt
tube furnace
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CN110697705A (en
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李晨阳
罗英涛
陈开斌
杜娟
张劲斌
王芳平
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Aluminum Corp of China Ltd
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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
    • C01B32/318—Preparation characterised by the starting materials
    • 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
    • C01B32/348—Metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
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    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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    • 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
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Abstract

The invention provides a rapid preparation method of asphalt-based activated carbon with a hierarchical pore structure, which takes coal pitch as a raw material, mixes an activating agent and a pore-forming agent, regulates and controls a temperature rise program, and directly prepares an asphalt-based activated carbon product with a hierarchical pore structure by a carbonization-activation one-step method. The specific surface area of the prepared active carbon is 1600-2Per g, total pore volume of 0.7-1.8cm3The content of micropores is 65-85%, the content of mesopores is 15-33%, and the content of macropores is 0.5-3%. The active carbon prepared by the method can be used for the electrode material of the super capacitor, has excellent super-capacity performance, simple preparation process, low cost and stable product performance, and is suitable for large-scale production.

Description

Rapid preparation method of asphalt-based activated carbon with hierarchical pore structure
Technical Field
The invention relates to a preparation method of asphalt-based activated carbon for a supercapacitor, in particular to a rapid preparation method of asphalt-based activated carbon with a hierarchical pore structure.
Background
Along with the shortage of petrochemical energy and the aggravation of environmental problems, the demand for clean, efficient and environment-friendly new energy materials is more and more urgent. The super capacitor, namely the electrochemical capacitor, is a novel energy storage device between a secondary battery and a traditional capacitor, can provide higher power density than a battery, has the advantages of high charge-discharge rate, long cycle life, low maintenance cost and the like compared with the traditional capacitor, and can be widely applied to the fields of portable equipment, electric automobiles, energy storage systems, military affairs, electronic industry and the like.
The super capacitor can be divided into a double electric layer capacitor and a pseudo capacitor according to an energy storage mechanism, wherein the pseudo capacitor is mainly used for storing energy based on reversible redox reaction on the surface and inside of an electrode; the electric double layer capacitor is based on the reversible electrostatic adsorption of ions in electrolyte on the surface of electrode material with high specific surface area to form electrochemical electric double layer for storing energy.
The electrode material is used as a core component of the super capacitor, and has great influence on the performance and the manufacturing cost of the super capacitor. The activated carbon has rich specific surface area and pore structure, has the advantages of stable chemical performance, low cost, wide source and the like, and becomes the first choice electrode material of the super capacitor. The current research on the active carbon electrode material mainly focuses on improving the specific surface area and adjusting the pore size distribution. In a super capacitor system, micropores of an activated carbon electrode material provide charge storage and specific surface area, and mesopores and macropores provide a transmission and diffusion channel of electrolyte. Therefore, the activated carbon with the hierarchical pore structure is easy to reduce the ion diffusion resistance and the diffusion distance, and simultaneously, the adsorption capacity of electric charges is increased, and the capacity and the charging and discharging efficiency of the super capacitor are effectively improved.
The coal tar pitch is an excellent raw material for preparing the activated carbon as a coking byproduct with high carbon content, low ash content and low cost. Generally, the preparation of the asphalt-based activated carbon needs to undergo a plurality of steps of mixing, oxidizing, acid washing and ash removing, carbonizing, steam activating, secondary chemical activating and the like, and the preparation process is relatively complex (for example, asphalt in patent CN109110758A is subjected to a plurality of steps of mixing, air oxidizing, carbonizing, steam activating and the like to obtain asphalt-based porous carbon, and asphalt in patent CN109019591A is subjected to mixing, spheroidizing, air oxidizing, liquid phase oxidizing, carbonizing and activating to obtain the asphalt-based activated carbon). Therefore, the development of the asphalt-based activated carbon with the hierarchical pore structure, which is prepared by a simple process, is rapid and efficient, can reduce the production cost, maintain the product stability, and is suitable for industrial large-scale production.
Disclosure of Invention
The invention takes coal pitch as raw material, adds activating agent and pore-forming agent, and directly obtains the active carbon product with a hierarchical pore structure by a carbonization-activation one-step method. The active carbon prepared by the method can be used for the electrode material of the super capacitor, has excellent super-capacity performance, simple preparation process and stable product performance, and is suitable for large-scale production.
In order to achieve the purpose, the invention provides the following technical scheme:
a rapid preparation method of asphalt-based activated carbon with a hierarchical pore structure is characterized by comprising the following steps:
(1) respectively crushing the coal tar pitch, the activating agent KOH and the pore-forming agent, sieving the crushed coal tar pitch, the activating agent KOH and the pore-forming agent by a 100-200-mesh sieve, and weighing and uniformly mixing the sieved pitch powder, KOH powder and the pore-forming agent powder according to the mass ratio of 100 (200-300) to (5-20) to obtain a mixture;
(2) putting the mixture obtained in the step (1) into a nickel crucible, transferring the nickel crucible into a high-temperature tube furnace, and introducing inactive gas into the high-temperature tube furnace; directly preparing the activated carbon by adopting a carbonization-activation one-step method, starting a temperature rise program: raising the temperature of the high-temperature tube furnace to 200-300 ℃ at a temperature raising speed of 5-20 ℃/min and keeping the temperature constant for 60-150 min, raising the temperature of the high-temperature tube furnace to 750-900 ℃ at a temperature raising speed of 2-5 ℃/min and keeping the temperature constant for 120-240 min, or raising the temperature of the high-temperature tube furnace to 200-300 ℃ at a temperature raising speed of 5-20 ℃/min and keeping the temperature constant for 60-150 min, raising the temperature of the high-temperature tube furnace to 500-600 ℃ at a temperature raising speed of 5-10 ℃/min and keeping the temperature constant for 60-180 min, and finally raising the temperature of the high-temperature tube furnace to 750-900 ℃ at a temperature raising speed of 2-5 ℃/min and keeping the temperature constant for 120-240 min;
(3) naturally cooling the high-temperature tube furnace to room temperature, and crushing the activated product in the nickel crucible to obtain a crude product of the activated carbon;
(4) and (4) sequentially washing the crude activated carbon obtained in the step (3) with hydrochloric acid, filtering, washing with deionized water until filtrate is neutral to prepare a filter cake, and drying the filter cake in an air drying oven at 110-150 ℃ to constant weight to obtain the asphalt-based activated carbon product with the hierarchical pore structure.
The method for rapidly preparing the asphalt-based activated carbon with the hierarchical pore structure is characterized in that the coal pitch in the step (1) is one or more of low-temperature pitch, medium-temperature pitch and high-temperature pitch.
The method for rapidly preparing the asphalt-based activated carbon with the hierarchical pore structure is characterized in that the pore-forming agent in the step (1) is one or more of urea, ammonium oxalate, ammonium chloride and polyvinyl alcohol.
According to the quick preparation method of the asphalt-based activated carbon with the hierarchical pore structure, the quick preparation method is characterized in that mechanical mixing is adopted when the asphalt powder, the KOH powder and the pore-forming agent powder which are sieved are uniformly mixed in the step (1), and mixing equipment used for mechanical mixing is a three-dimensional mixer, a roller ball mill or a food processor.
The rapid preparation method of the asphalt-based activated carbon with the hierarchical pore structure is characterized in that the inactive gas in the step (2) is high-purity nitrogen or high-purity argon, and the flow rate of the gas is 100mL/min-800mL/min when the inactive gas is introduced into the high-temperature tube furnace.
The invention has the beneficial technical effects that: compared with the prior art, the method selects the coal pitch with low price, high carbon content and low ash content as the raw material, adopts dry mechanical mixing to uniformly mix the coal pitch, the activating agent and the pore-forming agent, directly obtains the activated carbon product with the hierarchical pore structure through a carbonization-activation one-step method, and the specific surface area of the prepared activated carbon product is 1600m2/g-3200m2Per g, total pore volume of 0.7cm3/g-1.8cm3The pore diameter is mainly and intensively distributed between 0.5nm-2nm and 2nm-8nm, obvious multimodal distribution is presented, the microporosity is 65% -85%, the mesoporosity is 15% -33%, and the macroporosity is 0.5% -3%. The invention can be applied to the electrode material of the double electric layer super capacitor, has simple preparation process, high product stability and reasonable pore size distribution, and is suitable for large-scale production.
Drawings
FIG. 1 is an SEM photograph of a pitch-based activated carbon obtained in example 1;
FIG. 2 is a pore size distribution diagram of the pitch-based activated carbon prepared in example 1;
FIG. 3 is a cyclic voltammogram at a scan rate of 5mV/s for an assembled electric double layer supercapacitor of example 2;
fig. 4 is a constant current charge and discharge diagram of the assembled electric double layer supercapacitor of example 2 at a current density of 0.5A/g.
Detailed Description
A rapid preparation method of asphalt-based activated carbon with a hierarchical pore structure comprises the following steps: (1) respectively crushing the coal tar pitch, the activating agent KOH and the pore-forming agent, sieving the crushed coal tar pitch, the activating agent KOH and the pore-forming agent by a 100-mesh 200-mesh sieve, weighing the sieved pitch powder, KOH powder and the pore-forming agent powder according to the mass ratio of 100 to (200-300) to (5-20), and uniformly mixing the sieved pitch powder, KOH powder and the pore-forming agent powder by mechanical mixing to obtain a mixture; the mixing device used for mechanical mixing is a three-dimensional mixer, a roller ball mill or a food processor. The coal pitch is one or more of low-temperature pitch, medium-temperature pitch and high-temperature pitch. The pore-forming agent is one or more of urea, ammonium oxalate, ammonium chloride and polyvinyl alcohol. (2) And (2) loading the mixture obtained in the step (1) into a nickel crucible, transferring the nickel crucible into a high-temperature tube furnace, introducing an inactive gas into the high-temperature tube furnace, wherein the inactive gas is high-purity nitrogen or high-purity argon, and the flow rate of the gas is 100mL/min-800mL/min when the inactive gas is introduced into the high-temperature tube furnace. Directly preparing the activated carbon by adopting a carbonization-activation one-step method, starting a temperature rise program: raising the temperature of the high-temperature tube furnace to 200-300 ℃ at a temperature raising speed of 5-20 ℃/min and keeping the temperature for 60-150 min, raising the temperature of the high-temperature tube furnace to 750-900 ℃ at a temperature raising speed of 2-5 ℃/min and keeping the temperature for 120-240 min, or raising the temperature of the high-temperature tube furnace to 200-300 ℃ at a temperature raising speed of 5-20 ℃/min and keeping the temperature for 60-150 min, raising the temperature of the high-temperature tube furnace to 500-600 ℃ at a temperature raising speed of 5-10 ℃/min and keeping the temperature for 60-180 min, and finally raising the temperature of the high-temperature tube furnace to 750-900 ℃ at a temperature raising speed of 2-5 ℃/min and keeping the temperature for 120-240 min. (3) And naturally cooling the high-temperature tube furnace to room temperature, and crushing the activated product in the nickel crucible to obtain the crude product of the activated carbon. (4) And (4) sequentially washing the crude activated carbon obtained in the step (3) with hydrochloric acid, filtering, washing with deionized water until filtrate is neutral to prepare a filter cake, and drying the filter cake in an air drying oven at 110-150 ℃ to constant weight to obtain the asphalt-based activated carbon product with the hierarchical pore structure. The conditions of the hydrochloric acid washing are as follows: and (3) adjusting the pH value of the washing solution to 2-4 by using 5-10 wt% of hydrochloric acid, heating the washing solution to 50-80 ℃ in a water bath at the rotating speed of 300-550 rpm, and mechanically stirring the washing solution for 60-180 min.
The present invention will be described in detail with reference to examples, but it should be noted that the examples are only a part of the examples of the present invention, and not all of the examples.
Example 1
Respectively crushing the medium-temperature coal pitch, the activating agent KOH and the urea, sieving the crushed medium-temperature coal pitch, the activating agent KOH and the urea by a 200-mesh sieve, weighing the 3 undersize materials according to the mass ratio of 100:300:10, and uniformly mixing the 3 undersize materials by using a three-dimensional mixer to obtain a mixture.
Putting the mixture into a nickel crucible, transferring the nickel crucible into a high-temperature tube furnace, and introducing high-purity nitrogen into the high-temperature tube furnace, wherein the gas flow is 300 mL/min; starting a temperature rise program, firstly rising the temperature to 250 ℃ at the temperature rise speed of 10 ℃/min, and keeping the temperature at the temperature for 60 min; then raising the temperature to 550 ℃ at the temperature raising speed of 5 ℃/min, and keeping the temperature for 90 min; and finally, heating to 850 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 180min, naturally cooling the high-temperature tubular furnace to room temperature, and crushing the activated product in the nickel crucible to obtain the crude product of the activated carbon.
Pouring the crude activated carbon into deionized water, adjusting the pH value of the solution to 2 by using 10 wt% hydrochloric acid, heating the solution to 70 ℃ in a water bath, and mechanically stirring the solution for 120min at the rotating speed of 500 rpm; filtering and washing with deionized water until the filtrate is neutral to prepare a filter cake, and drying the filter cake in an air-blast drying oven at 120 ℃ to constant weight to obtain the asphalt-based activated carbon product with the hierarchical pore structure. The low-temperature nitrogen adsorption-desorption analysis shows that the specific surface area of the activated carbon product is 3051m2(g), total pore volume 1.74cm3In terms of a specific mole ratio, the microporosity was 81%, the mesoporosity was 17.5%, and the macroporosity was 1.5%.
Fig. 1 is an SEM image of the pitch-based activated carbon prepared in example 1, and it can be seen that a large number of macropores of 100nm or more exist on the surface of the activated carbon.
FIG. 2 is a pore size distribution diagram of the pitch-based activated carbon prepared in example 1, and it can be seen that the pore size distribution of the activated carbon shows distinct multiple peaks, mainly concentrated in micropores between 0.5 and 1.8nm and mesopores between 2 and 6 nm.
And (3) electrochemical performance testing: weighing the prepared asphalt-based activated carbon, the adhesive PTFE and the conductive agent acetylene black according to the mass ratio of 75:10:15, adding a proper amount of absolute ethyl alcohol for mixing, magnetically stirring for 30min, drying excessive ethyl alcohol at 100 ℃ to obtain a uniformly mixed viscous material, pressing the viscous material into a flat sheet by using a double-roll machine, cutting the flat sheet into a wafer with the diameter of 10mm, and pressing the wafer onto foamed nickel with the diameter of 16mm under the pressure of 10MPa to prepare the electrode plate. And 6mol/L KOH is adopted as electrolyte, and the button type double electric layer capacitor is assembled in sequence according to the sequence of the pole piece, the diaphragm, the pole piece, the gasket and the elastic sheet. Through tests, the specific capacity of the super capacitor activated carbon electrode material under the current density of 0.5A/g is 298F/g.
Example 2
Respectively crushing the medium-temperature coal tar pitch, the activating agent KOH and the polyvinyl alcohol, sieving the crushed materials by a 200-mesh sieve, weighing the 3 sieved materials according to the mass ratio of 100:300:5, and uniformly mixing the 3 sieved materials by a food processor to obtain a mixture.
Putting the mixture into a nickel crucible, transferring the nickel crucible into a high-temperature tube furnace, and introducing high-purity nitrogen into the high-temperature tube furnace, wherein the gas flow is 300 mL/min; starting a temperature rise program, firstly rising the temperature to 300 ℃ at the temperature rise speed of 10 ℃/min, and keeping the temperature at the temperature for 90 min; then raising the temperature to 900 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 180 min; and naturally cooling the high-temperature tube furnace to room temperature, and crushing the activated product in the nickel crucible to obtain the crude product of the activated carbon.
Dissolving the crude activated carbon in deionized water, adjusting the pH value of the solution to 4 by using 5 wt% hydrochloric acid, heating the solution to 70 ℃ in a water bath, and mechanically stirring the solution for 150min at the rotating speed of 500 rpm; filtering and washing with deionized water until the filtrate is neutral to prepare a filter cake, and drying the filter cake in an air-blast drying oven at 130 ℃ to constant weight to obtain the asphalt-based activated carbon product with the hierarchical pore structure. The low-temperature nitrogen adsorption-desorption analysis shows that the specific surface area of the activated carbon product is 2410m2(g) total pore volume of 1.32cm3The microporosity is 76%, the mesoporosity is 22%, and the macroporosity is 2%.
And (3) electrochemical performance testing: weighing the prepared asphalt-based activated carbon, the adhesive PTFE and the conductive agent acetylene black according to the mass ratio of 75:10:15, adding a proper amount of absolute ethyl alcohol for mixing, magnetically stirring for 30min, drying excessive ethyl alcohol at 100 ℃ to obtain a uniformly mixed viscous material, pressing the viscous material into a flat sheet by using a double-roll machine, cutting the flat sheet into a wafer with the diameter of 10mm, and pressing the wafer onto foamed nickel with the diameter of 16mm under the pressure of 10MPa to prepare the electrode plate. And 6mol/L KOH is adopted as electrolyte, and the button type double electric layer capacitor is assembled in sequence according to the sequence of the pole piece, the diaphragm, the pole piece, the gasket and the elastic sheet. Through tests, the cyclic voltammogram of the super capacitor at the scanning speed of 5mV/s is shown in fig. 3, the constant current charging and discharging diagram of the super capacitor at the current density of 0.5A/g is shown in fig. 4, and the specific capacity of the active carbon electrode material at the current density of 0.5A/g is 286F/g through constant current charging and discharging calculation.
Example 3
Respectively crushing the low-temperature coal tar pitch, the activating agent KOH and the ammonium chloride, sieving the crushed materials by a 100-mesh sieve, weighing the 3 undersize materials according to the mass ratio of 100:200:15, and uniformly mixing the 3 undersize materials by using a three-dimensional mixer to obtain a mixture.
Putting the mixture into a nickel crucible, transferring the nickel crucible into a high-temperature tube furnace, and introducing high-purity argon into the high-temperature tube furnace, wherein the gas flow is 500 mL/min; starting a temperature rise program, firstly raising the temperature to 200 ℃ at a temperature rise speed of 20 ℃/min, and keeping the temperature at the temperature for 90 min; then raising the temperature to 550 ℃ at the temperature rise speed of 5 ℃/min, and keeping the temperature for 90 min; and finally, heating to 800 ℃ at the heating rate of 5 ℃/min, keeping the temperature constant at the temperature for 240min, naturally cooling the high-temperature tube furnace to room temperature, and crushing the activated product in the nickel crucible to obtain the crude product of the activated carbon.
Pouring the crude activated carbon into deionized water, adjusting the pH value of the solution to 2 by using 8 wt% hydrochloric acid, heating the solution to 60 ℃ in a water bath, controlling the rotation speed to be 500rpm, and mechanically stirring the solution for 180 min; filtering, washing with deionized water until the filtrate is neutral to obtain filter cake, and drying the filter cake in 150 deg.C forced air drying oven to constant weight to obtain the final product with multiple stagesA pore structure pitch-based activated carbon product. The low-temperature nitrogen adsorption-desorption analysis shows that the specific surface area of the activated carbon product is 1851m2Per g, total pore volume of 0.84cm3The microporosity is 69%, the mesoporosity is 28%, and the macroporosity is 3%.
And (3) electrochemical performance testing: weighing the prepared asphalt-based activated carbon, the adhesive PTFE and the conductive agent acetylene black according to the mass ratio of 75:10:15, adding a proper amount of absolute ethyl alcohol for mixing, magnetically stirring for 30min, drying excessive ethyl alcohol at 100 ℃ to obtain a uniformly mixed viscous material, pressing the viscous material into a flat sheet by using a double-roll machine, cutting the flat sheet into a wafer with the diameter of 10mm, and pressing the wafer onto foamed nickel with the diameter of 16mm under the pressure of 10MPa to prepare the electrode plate. And 6mol/L KOH is adopted as electrolyte, and the button type double electric layer capacitor is assembled in sequence according to the sequence of the pole piece, the diaphragm, the pole piece, the gasket and the elastic sheet. Through tests, the specific capacity of the super capacitor activated carbon electrode material under the current density of 0.5A/g is 264F/g.
Example 4
Respectively crushing the medium-temperature coal pitch, activating agent KOH and ammonium oxalate, sieving the crushed materials by a 100-mesh sieve, weighing the 3 undersize materials according to the mass ratio of 100:250:10, and uniformly mixing the 3 undersize materials by using a three-dimensional mixer to obtain a mixture.
Putting the mixture into a nickel crucible, transferring the nickel crucible into a high-temperature tube furnace, and introducing high-purity nitrogen into the high-temperature tube furnace, wherein the gas flow is 600 mL/min; starting a temperature rise program, firstly rising the temperature to 250 ℃ at the temperature rise speed of 10 ℃/min, and keeping the temperature at the temperature for 90 min; then raising the temperature to 850 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 180 min; and naturally cooling the high-temperature tube furnace to room temperature, and crushing the activated product in the nickel crucible to obtain the crude product of the activated carbon.
Pouring the crude activated carbon into deionized water, adjusting the pH value of the solution to 2 by using 10 wt% hydrochloric acid, heating the solution to 70 ℃ in a water bath at the rotating speed of 450rpm, and mechanically stirring the solution for 150 min; filtering and washing with deionized water until the filtrate is neutral to prepare a filter cake, and drying the filter cake in an air-blast drying oven at 130 ℃ to constant weight to obtain the asphalt-based activated carbon product with the hierarchical pore structure. The low-temperature nitrogen adsorption-desorption analysis shows that,the specific surface area of the activated carbon product is 2025m2(g) total pore volume of 1.09cm3The microporosity is 79%, the mesoporosity is 20%, and the macroporosity is 1%.
And (3) electrochemical performance testing: weighing the prepared asphalt-based activated carbon, the adhesive PTFE and the conductive agent acetylene black according to the mass ratio of 75:10:15, adding a proper amount of absolute ethyl alcohol for mixing, magnetically stirring for 30min, drying excessive ethyl alcohol at 100 ℃ to obtain a uniformly mixed viscous material, pressing the viscous material into a flat sheet by using a double-roll machine, cutting the flat sheet into a wafer with the diameter of 10mm, and pressing the wafer onto foamed nickel with the diameter of 16mm under the pressure of 10MPa to prepare the electrode plate. And 6mol/L KOH is adopted as electrolyte, and the button type double electric layer capacitor is assembled in sequence according to the sequence of the pole piece, the diaphragm, the pole piece, the gasket and the elastic sheet. Through tests, the specific capacity of the super capacitor activated carbon electrode material under the current density of 0.5A/g is 276F/g.
Example 5
Respectively crushing the high-temperature coal tar pitch, the activating agent KOH and the urea, sieving the crushed materials by a 200-mesh sieve, weighing the 3 undersize materials according to the mass ratio of 100:250:5, and uniformly mixing the 3 undersize materials by using a three-dimensional mixer to obtain a mixture.
Putting the mixture into a nickel crucible, transferring the nickel crucible into a high-temperature tube furnace, and introducing high-purity nitrogen into the high-temperature tube furnace, wherein the gas flow is 350 mL/min; starting a temperature rise program, firstly rising the temperature to 300 ℃ at the temperature rise speed of 10 ℃/min, and keeping the temperature at the temperature for 60 min; then raising the temperature to 550 ℃ at the temperature raising speed of 5 ℃/min, keeping the temperature constant at the temperature for 120min, finally raising the temperature to 850 ℃ at the temperature raising speed of 3 ℃/min, and keeping the temperature constant at the temperature for 180 min; and naturally cooling the high-temperature tube furnace to room temperature, and crushing the activated product in the nickel crucible to obtain the crude product of the activated carbon.
Pouring the crude activated carbon into deionized water, adjusting the pH value of the solution to 2 by using 8 wt% hydrochloric acid, heating the solution to 70 ℃ in a water bath, controlling the rotation speed to be 500rpm, and mechanically stirring the solution for 120 min; filtering and washing with deionized water until the filtrate is neutral to prepare a filter cake, and drying the filter cake in an air-blast drying oven at 150 ℃ to constant weight to obtain the asphalt-based activated carbon product with the hierarchical pore structure. The low-temperature nitrogen adsorption-desorption analysis shows that the activity of the catalyst is highThe specific surface area of the carbon product is 2963m2(g) total pore volume of 1.66cm3In terms of a specific mole ratio, the microporosity is 83%, the mesoporosity is 16.2%, and the macroporosity is 0.8%.
And (3) electrochemical performance testing: weighing the prepared asphalt-based activated carbon, the adhesive PTFE and the conductive agent acetylene black according to the mass ratio of 75:10:15, adding a proper amount of absolute ethyl alcohol for mixing, magnetically stirring for 30min, drying excessive ethyl alcohol at 100 ℃ to obtain a uniformly mixed viscous material, pressing the viscous material into a flat sheet by using a double-roll machine, cutting the flat sheet into a wafer with the diameter of 10mm, and pressing the wafer onto foamed nickel with the diameter of 16mm under the pressure of 10MPa to prepare the electrode plate. And 6mol/L KOH is adopted as electrolyte, and the button type double electric layer capacitor is assembled in sequence according to the sequence of the pole piece, the diaphragm, the pole piece, the gasket and the elastic sheet. Through tests, the specific capacity of the super capacitor activated carbon electrode material under the current density of 0.5A/g is 314F/g.
Example 6
Respectively crushing the medium-temperature coal pitch, the activating agent KOH and the urea, sieving the crushed medium-temperature coal pitch, the activating agent KOH and the urea by a 100-mesh sieve, weighing the 3 sieved materials according to the mass ratio of 100:300:10, and uniformly mixing the 3 sieved materials by using a three-dimensional mixer to obtain a mixture.
Putting the mixture into a nickel crucible, transferring the nickel crucible into a high-temperature tube furnace, and introducing high-purity nitrogen into the high-temperature tube furnace, wherein the gas flow is 500 mL/min; starting a temperature rise program, firstly rising the temperature to 300 ℃ at the temperature rise speed of 20 ℃/min, and keeping the temperature for 120 min; then raising the temperature to 850 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 180 min; and naturally cooling the high-temperature tube furnace to room temperature, and crushing the activated product in the nickel crucible to obtain the crude product of the activated carbon.
Pouring the crude activated carbon into deionized water, adjusting the pH value of the solution to 3 by using 10 wt% hydrochloric acid, heating the solution to 70 ℃ in a water bath at the rotating speed of 500rpm, and mechanically stirring the solution for 150 min; filtering and washing with deionized water until the filtrate is neutral to prepare a filter cake, and drying the filter cake in an air-blast drying oven at 130 ℃ to constant weight to obtain the asphalt-based activated carbon product with the hierarchical pore structure. The low-temperature nitrogen adsorption-desorption analysis shows that the specific surface area of the activated carbon product is 2601m2(g), total pore volume 1.28cm3In terms of a specific mole ratio, the microporosity is 80%, the mesoporosity is 18.5%, and the macroporosity is 1.5%.
And (3) electrochemical performance testing: weighing the prepared asphalt-based activated carbon, the adhesive PTFE and the conductive agent acetylene black according to the mass ratio of 75:10:15, adding a proper amount of absolute ethyl alcohol for mixing, magnetically stirring for 30min, drying excessive ethyl alcohol at 100 ℃ to obtain a uniformly mixed viscous material, pressing the viscous material into a flat sheet by using a double-roll machine, cutting the flat sheet into a wafer with the diameter of 10mm, and pressing the wafer onto foamed nickel with the diameter of 16mm under the pressure of 10MPa to prepare the electrode plate. And 6mol/L KOH is adopted as electrolyte, and the button type double electric layer capacitor is assembled in sequence according to the sequence of the pole piece, the diaphragm, the pole piece, the gasket and the elastic sheet. Through tests, the specific capacity of the super capacitor activated carbon electrode material under the current density of 0.5A/g is 291F/g.
The above description is only a specific embodiment of the present invention, and is made for illustrative purposes, and the implementation form of the present invention is not limited to the above manner, and it should be noted that the method concept and technical solution based on the present invention belong to the protection scope of the present invention through any simple changes and modifications.

Claims (4)

1. A rapid preparation method of asphalt-based activated carbon with a hierarchical pore structure is characterized by comprising the following steps:
(1) respectively crushing the coal tar pitch, the activating agent KOH and the pore-forming agent, sieving the crushed coal tar pitch, the activating agent KOH and the pore-forming agent by a 100-200-mesh sieve, and weighing and uniformly mixing the sieved pitch powder, KOH powder and the pore-forming agent powder according to the mass ratio of 100 (200-300) to (5-20) to obtain a mixture; uniformly mixing the sieved asphalt powder, KOH powder and pore-forming agent powder by adopting a machine, wherein the mixing equipment used for mechanical mixing is a three-dimensional mixer, a roller ball mill or a food processor;
(2) putting the mixture obtained in the step (1) into a nickel crucible, transferring the nickel crucible into a high-temperature tube furnace, and introducing inactive gas into the high-temperature tube furnace; directly preparing the activated carbon by adopting a carbonization-activation one-step method, starting a temperature rise program: raising the temperature of the high-temperature tube furnace to 200-300 ℃ at a temperature raising speed of 5-20 ℃/min and keeping the temperature constant for 60-150 min, raising the temperature of the high-temperature tube furnace to 750-900 ℃ at a temperature raising speed of 2-5 ℃/min and keeping the temperature constant for 120-240 min, or raising the temperature of the high-temperature tube furnace to 200-300 ℃ at a temperature raising speed of 5-20 ℃/min and keeping the temperature constant for 60-150 min, raising the temperature of the high-temperature tube furnace to 500-600 ℃ at a temperature raising speed of 5-10 ℃/min and keeping the temperature constant for 60-180 min, and finally raising the temperature of the high-temperature tube furnace to 750-900 ℃ at a temperature raising speed of 2-5 ℃/min and keeping the temperature constant for 120-240 min;
(3) naturally cooling the high-temperature tube furnace to room temperature, and crushing the activated product in the nickel crucible to obtain a crude product of the activated carbon;
(4) washing the activated carbon crude product obtained in the step (3) with hydrochloric acid, filtering, washing with deionized water in sequence until filtrate is neutral to prepare a filter cake, and drying the filter cake in an air drying oven at 110-150 ℃ to constant weight to obtain an asphalt-based activated carbon product with a hierarchical pore structure; the conditions of the hydrochloric acid washing are as follows: and (3) adjusting the pH value of the washing solution to 2-4 by using 5-10 wt% of hydrochloric acid, heating the washing solution to 50-80 ℃ in a water bath at the rotating speed of 300-550 rpm, and mechanically stirring the washing solution for 60-180 min.
2. The method for rapidly preparing activated carbon based on asphalt with a hierarchical porous structure as defined in claim 1, wherein the coal pitch in step (1) is one or more of low temperature pitch, medium temperature pitch and high temperature pitch.
3. A rapid preparation method of asphalt-based activated carbon with a hierarchical pore structure as defined in claim 1, characterized in that the pore-forming agent in step (1) is one or more of urea, ammonium oxalate, ammonium chloride, and polyvinyl alcohol.
4. The method for rapidly preparing activated carbon based on asphalt with a hierarchical pore structure as set forth in claim 1, characterized in that the inactive gas in step (2) is high purity nitrogen or high purity argon, and the flow rate of the gas when the inactive gas is introduced into the high temperature tube furnace is 100mL/min to 800 mL/min.
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