CN111547721A - Preparation method of mesoporous activated carbon for supercapacitor - Google Patents
Preparation method of mesoporous activated carbon for supercapacitor Download PDFInfo
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- 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
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
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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
- C01B32/348—Metallic compounds
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- 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
- H01G11/24—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
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- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- 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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- 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
Abstract
The invention discloses a preparation method of mesoporous activated carbon for a supercapacitor, and relates to the field of activated carbon material preparation. The method takes coal tar pitch and gel as raw materials and prepares the active carbon for the supercapacitor after the steps of modification treatment, pretreatment, homogenization treatment, activation and post-treatment. The prepared active carbon has the mesoporous rate of 24-41 percent and the specific surface area of 1600-2420m2(ii) in terms of/g. The invention takes the gel as the framework, realizes the structure of the crosslinked three-dimensional structure formed by the gel and the coal tar pitch in the carbonization and activation process, has the characteristic of easy regulation of pore size distribution, and is used for the super capacitor at presentCompared with the activated carbon of the device, the activated carbon of the device has higher mesoporous rate, and the electrochemical performance of the activated carbon under large current is greatly improved.
Description
Technical Field
The invention relates to the field of activated carbon material preparation, in particular to a preparation method of mesoporous activated carbon for a supercapacitor.
Background
The super capacitor is used as a novel energy storage device between a traditional capacitor and a battery, and has the characteristics of high energy density, high power density, long service life, wide service temperature range and the like. Due to the unique advantages, the method is widely applied to various fields of new energy, electronic products, wind power generation, rail transit, military, aerospace and the like. With the continuous expansion of the application field, higher requirements are provided for the specific capacity of the super capacitor, the cycle life under the condition of large-current charge and discharge and the rate capability.
The activated carbon as a commercial key material for the super capacitor has great influence on the performance of the capacitor. Important factors affecting the electrochemical properties of activated carbon are specific surface area, pore size distribution, pore shape and structure, electrical conductivity, surface chemical properties, and the like. Of these, the specific surface area and pore size distribution are the two most important factors affecting the electrochemical performance of carbon materials. It is generally believed that micropores in the activated carbon can adsorb electrolyte particles, and mesopores function to transport ions. Therefore, the specific capacity and the cycle life of the capacitor are improved by improving the specific surface area and the mesoporous rate of the activated carbon, and the important way for improving the performance of the super capacitor under high current density is achieved.
Currently, activated carbon for commercial grade supercapacitors is generally obtained by KOH activation. However, the activated carbon generally has micropores as the main component and contains a small amount of mesopores, and the proportion of the mesopores is about 15%. Under the condition of large current, the specific surface area of the activated carbon cannot be effectively utilized, and the migration of electrolyte ions to the surfaces of micropores is limited due to few mesopores, so that the problem of poor rate capability exists, and the application field of the super capacitor under the condition of large current is limited. Therefore, the condition of higher specific surface area is further maintained, the mesoporous rate of the activated carbon for the supercapacitor is improved, and the rate performance of the activated carbon under high current density is improved. CN110127692A provides a preparation method for preparing mesoporous heat-resistant activated carbon by taking coal pitch as a raw material and performing the processes of crushing, mixing, heating, crosslinking, screening and the like, and the method is mainly used for preparing the activated carbon with high mesoporous rate by using a magnesium oxide template with the particle size of 80nm and is mainly used in the field of activated carbon for adsorption tubes; CN110697705A provides a method for preparing asphalt-based activated carbon with a hierarchical pore structure by using a pore-forming agent and coal pitch as raw materials through a carbonization and activation one-step method; the above patents all adopt a template method and a pore-forming agent to prepare the mesoporous carbon, so that the template agent has the characteristic of high price, and the application effect in the field of supercapacitors is not proposed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of mesoporous activated carbon for a supercapacitor, which can solve the rate capability problem of a carbon material for the supercapacitor under high current density by regulating and controlling the pore size distribution of the activated carbon and increasing the mesoporous ratio in the activated carbon.
The invention adopts the following technical scheme:
a preparation method of mesoporous activated carbon for a supercapacitor is characterized by comprising the following steps:
(1) crushing, modifying, filtering and drying the coal tar pitch;
(2) adding the coal tar pitch obtained by the treatment in the step (1) into a gel solution for pretreatment to obtain a coal tar pitch compound, wherein the pretreatment process conditions are as follows: the pretreatment temperature is 60-80 ℃, and the pretreatment time is 1-3 h;
(3) adding an activating agent KOH into the coal tar pitch compound, and homogenizing the coal tar pitch compound and the activating agent to obtain a coal tar pitch composite material, wherein the process conditions of homogenization treatment are as follows: the homogenization temperature is 50-100 ℃, and the homogenization time is 1-6 h;
(4) the coal tar pitch composite material is activated and then is subjected to acid washing, soaking, water washing and drying to obtain the activated carbon.
The method according to the above, wherein the coal pitch is modified in the step (1) to have a particle size of less than 0.15 mm.
According to the method, the reagent used in the modification treatment in the step (1) is a mixture of concentrated sulfuric acid and hydrogen peroxide, and the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 100: (1-10), and the time of modification treatment is 2-24 h.
The method is characterized in that the gel solution in the step (2) is one or more of carboxymethyl cellulose solution, starch solution or polyvinyl alcohol solution, and the concentration of the gel solution is 1-6%.
The method is characterized in that the mass ratio of the coal tar pitch compound to the activating agent in the homogenization treatment in the step (3) is 1: (1-4); the homogenization treatment employs mechanical stirring, ultrasound or wet milling.
The method is characterized in that the process conditions for activating the coal tar pitch composite in the step (4) are as follows: the heating speed is 1-10 ℃/min, the activation temperature is 750-950 ℃, and the activation time is 1-4 h.
Compared with the prior art, the invention has the beneficial technical effects that:
1) compared with the active carbon used for the super capacitor at present, the active carbon prepared by the method has higher mesoporous rate, can improve the pore size distribution of the active carbon, and obviously improves the proportion of the mesoporous volume to the total pore volume, wherein the mesoporous range is 24-41%.
2) The invention takes the gel as a framework, forms a cross-linked three-dimensional structure with the coal pitch in the carbonization and activation process, not only utilizes the escape of volatile components of the coal pitch to manufacture pores, but also utilizes the combination activation of an activating agent KOH and water in the gel to form the activated carbon with reasonable pore size distribution, and the obtained activated carbon has uniform pore size distribution and is easy to regulate and control.
3) The active carbon prepared by the invention has higher specific capacity, can greatly improve the rate capability of a super capacitor under large current, the specific capacity of the active carbon reaches 290-335F/g under the current density of 1A/g, and the cycle life reaches 99.1-100% after 10000 circles.
4) The raw material of the active carbon used in the invention has wide source and low price, can improve the added value of the biomass material, and has wide application space.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention;
FIG. 2 is an adsorption isotherm of activated carbon prepared by the process of the present invention;
FIG. 3 is a graph showing the distribution of pore diameters of activated carbon produced by the method of the present invention;
FIG. 4 is a charge-discharge curve of the activated carbon prepared by the method of the present invention with a current density of 1A/g;
FIG. 5 shows SEM morphology of activated carbon prepared by the method of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
Referring to fig. 1, the preparation method of mesoporous activated carbon for a supercapacitor of the invention comprises the following steps: (1) crushing, modifying, filtering and drying the coal tar pitch to obtain the coal tar pitch with the oxygen-containing functional group mass percentage of 2.7-35.3%. The particle size of the coal pitch is crushed to be less than 0.15mm during modification treatment. The reagent used for modification treatment is a mixture of concentrated sulfuric acid and hydrogen peroxide, and the concentrated sulfuric acid and the hydrogen peroxide are used for oxidation modification treatment, so that the oxygen-containing functional groups of the coal pitch are increased, the hydrophilicity of the coal pitch is improved, and the coal pitch and a gel solution are bridged to form a larger molecular structure. The volume ratio of concentrated sulfuric acid to hydrogen peroxide is 100: (1-10), and the time of modification treatment is 2-24 h. (2) Adding the coal tar pitch obtained by the treatment in the step (1) into a gel solution for pretreatment, realizing the crosslinking of the coal tar pitch and the gel, and obtaining a coal tar pitch compound, wherein the pretreatment process conditions are as follows: the pretreatment temperature is 60-80 ℃, and the pretreatment time is 1-3 h; the gel solution is one or more of carboxymethyl cellulose solution, polyvinyl alcohol solution or starch solution, the concentration of the gel solution is 1-6%, and preferably, the concentration of the gel solution is 2-6%. (3) Adding an activating agent KOH into the coal tar pitch compound, and homogenizing the coal tar pitch compound and the activating agent to obtain a coal tar pitch composite material, wherein the process conditions of homogenization treatment are as follows: the homogenization temperature is 50-100 ℃, the homogenization time is 1-6 h, and preferably, the homogenization treatment is carried outThe technological conditions of the chemical treatment are as follows: the homogenization temperature is 60-80 ℃, and the homogenization time is 1-4 h. The mass ratio of the coal tar pitch compound to the activating agent in the homogenization treatment is 1: (1-4), preferably, the mass ratio of the coal tar pitch complex to the activating agent in the homogenization treatment is 1: (2-3); the homogenization treatment employs mechanical stirring, ultrasound or wet milling. (4) Activating the coal tar pitch composite material, and then carrying out acid washing, soaking, water washing and drying to obtain the activated carbon, wherein the prepared activated carbon has a mesoporous range of 24-41 percent and a specific surface area of 1600m2/g-2420m2(ii)/g, the average pore diameter is 2.4202nm-2.6714 nm. The process conditions for activating the coal tar pitch composite material are as follows: the heating rate is 1-10 ℃/min, the activation temperature is 750-900 ℃, the activation time is 1-4 h, and the preferable process conditions for activating the coal asphalt composite material are as follows: the heating speed is 2 ℃/min to 5 ℃/min, the activation temperature is 750 ℃ to 850 ℃, and the activation time is 2h to 3 h. FIGS. 2 to 5 are respectively an adsorption isotherm of the activated carbon prepared by the method of the present invention, a pore size distribution diagram of the activated carbon prepared by the method of the present invention, a charge-discharge curve of the activated carbon prepared by the method of the present invention at a current density of 1A/g, and an SEM morphology of the activated carbon prepared by the method of the present invention.
Example 1
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 10mL of hydrogen peroxide, wherein the modification treatment time is 24h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 35.3%. And adding the coal pitch treated under the conditions into a 2% carboxymethyl cellulose solution, and carrying out pretreatment at 60 ℃ for 2h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 2:1, the homogenization treatment temperature is 60 ℃, and the homogenization treatment time is 3 hours. And after the homogenization treatment is finished, directly activating the coal asphalt composite material, wherein the activation treatment temperature is 750 ℃, the activation treatment time is 2h, and the heating rate is 5 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The resulting porous activated carbon had a specific surface area of 2104m2Per g, total pore volume of1.5005m3A pore volume of 1.0512m3The ratio of mesopores to the total pore volume is 29.94%, and the average pore diameter is 2.6714 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 335F/g, and the capacity retention rate reaches 99.8 percent after 10000 cycles of circulation.
Example 2
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 10mL of hydrogen peroxide, wherein the modification treatment time is 24h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 35.3%. And adding the coal pitch treated under the conditions into a 2% carboxymethyl cellulose solution, and carrying out pretreatment at 70 ℃ for 2h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 2:1, the homogenization treatment temperature is 60 ℃, and the homogenization treatment time is 3 hours. And after the homogenization treatment is finished, directly activating the coal asphalt composite material, wherein the activation treatment temperature is 750 ℃, the activation treatment time is 2h, and the heating rate is 5 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The resulting porous activated carbon had a specific surface area of 2104m2(g) total pore volume of 1.5125m3A pore volume of 1.0584m3The ratio of mesopores to the total pore volume is 30.02%, and the average pore diameter is 2.6632 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 329F/g, and the capacity retention rate reaches 99.6 percent after 10000 cycles of circulation.
Example 3
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 8mL of hydrogen peroxide, wherein the modification treatment time is 16h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 28.1%. And adding the coal pitch treated under the conditions into a 2% carboxymethyl cellulose solution, and carrying out pretreatment at 80 ℃ for 3h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound for homogenization treatment to obtain a coal tar pitch composite material, wherein the activating agent KOH and the coal tar pitch areThe mass ratio of the green composite is 3:1, the homogenization temperature is 60 ℃, and the homogenization time is 2 h. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, the activation treatment temperature is 850 ℃, the activation treatment time is 3h, and the heating rate is 2 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The specific surface area of the obtained porous activated carbon is 2420m2(g) total pore volume of 1.5034m3A pore volume of 1.1426m3The ratio of mesopores to the total pore volume is 24.00%, and the average pore diameter is 2.5211 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 313F/g, and the capacity retention rate reaches 99.2 percent after 10000 cycles of circulation.
Example 4
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 6mL of hydrogen peroxide, wherein the modification treatment time is 10h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 20.4%. And adding the coal pitch treated under the conditions into a 4% carboxymethyl cellulose solution, and carrying out pretreatment at 60 ℃ for 1h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 2:1, the homogenization treatment temperature is 80 ℃, and the homogenization treatment time is 2 hours. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, the activation treatment temperature is 800 ℃, the activation treatment time is 2h, and the heating rate is 3 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The specific surface area of the obtained porous activated carbon was 1840m2(g) total pore volume of 1.4125m3A pore volume of 0.9888m3The ratio of mesopores to the total pore volume was 29.99%, and the average pore diameter was 2.4202 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 308F/g, and the capacity retention rate reaches 99.6 percent after 10000 cycles of circulation.
Example 5
Crushing coal tar pitch to below 0.15mm, and feeding the crushed coal tar pitch with 100mL of concentrated sulfuric acid and 1mL of hydrogen peroxideCarrying out oxidation modification treatment, wherein the time of the modification treatment is 2h, and the oxygen-containing functional group of the coal pitch after the oxidation modification treatment is 2.7%. And adding the coal pitch treated under the conditions into 6% carboxymethyl cellulose solution, and carrying out pretreatment at 80 ℃ for 2h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 3:1, the homogenization treatment temperature is 80 ℃, and the homogenization treatment time is 3 hours. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, the activation treatment temperature is 850 ℃, the activation treatment time is 2h, and the heating rate is 4 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 1600m2(g) total pore volume of 1.2279m3A pore volume of 0.9332m3The ratio of mesopores to the total pore volume is 23.98%, and the average pore diameter is 2.6325 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 303F/g, and the capacity retention rate reaches 100% after 10000 cycles of circulation.
Example 6
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 3mL of hydrogen peroxide, wherein the modification treatment time is 4h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 6.5%. And adding the coal pitch treated under the conditions into 6% carboxymethyl cellulose solution, and carrying out pretreatment at 60 ℃ for 2h to obtain the coal pitch compound. Adding an activating agent KOH into the coal-tar pitch compound, and carrying out homogenization treatment to obtain the coal-tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal-tar pitch compound is 3:1, the homogenization treatment temperature is 80 ℃, the homogenization treatment time is 2h, and the heating rate is 5 ℃/min. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, the activation treatment temperature is 800 ℃, and the activation treatment time is 2 hours. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 1720m2(g) total pore volume of 1.3256m3A pore volume of 0.9976m3The ratio of mesopores to the total pore volume was 25.72%, and the average pore diameter was 2.5202 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 298F/g, and the capacity retention rate reaches 99.4% after 10000 cycles of circulation.
Example 7
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 6mL of hydrogen peroxide, wherein the modification treatment time is 8h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 9.4%. And adding the coal pitch treated under the conditions into 6% carboxymethyl cellulose solution, and carrying out pretreatment at 80 ℃ for 3h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 3:1, the homogenization treatment temperature is 80 ℃, and the homogenization treatment time is 2 hours. And after the homogenization treatment is finished, directly activating the coal asphalt composite material, wherein the activation treatment temperature is 850 ℃, the activation treatment time is 2h, and the heating rate is 3 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The specific surface area of the obtained porous activated carbon was 1830m2(g) total pore volume of 1.4101m3A pore volume of 0.8602m3The ratio of mesopores to the total pore volume is 39.00%, and the average pore diameter is 2.4746 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 307F/g, and the capacity retention rate reaches 99.1 percent after 10000 cycles of circulation.
Example 8
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 6mL of hydrogen peroxide, wherein the modification treatment time is 15h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 14.1%. And adding the coal pitch treated under the conditions into a 5% carboxymethyl cellulose solution, and carrying out pretreatment at 60 ℃ for 1h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound for homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is3:1, wherein the homogenization treatment temperature is 80 ℃, the homogenization treatment time is 1h, and the temperature rise speed is 2 ℃/min. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, the activation treatment temperature is 800 ℃, and the activation treatment time is 3 hours. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The specific surface area of the obtained porous activated carbon was 2008m2(g) total pore volume of 1.4337m3A pore volume of 0.8541m3The ratio of mesopores to the total pore volume was 40.12%, and the average pore diameter was 2.5103 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 317F/g, and the capacity retention rate reaches 100 percent after 10000 cycles.
Example 9
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 3mL of hydrogen peroxide, wherein the modification treatment time is 15h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 16.7%. And adding the coal pitch treated under the conditions into a carboxymethyl cellulose solution with the concentration of 5%, and pretreating at 80 ℃ for 1h to obtain the coal pitch composite. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 3:1, the homogenization treatment temperature is 80 ℃, and the homogenization treatment time is 2 hours. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, wherein the activation treatment temperature is 800 ℃, the activation treatment time is 2h, and the heating rate is 4 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 1994m2(g) total pore volume of 1.5016m3A pore volume of 0.9495m3The ratio of mesopores to the total pore volume was 36.77%, and the average pore diameter was 2.4674 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 309F/g, and the capacity retention rate reaches 100% after 10000 cycles.
Example 10
Crushing coal tar pitch to be less than 0.15mm, carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 8mL of hydrogen peroxide,the time of the modification treatment is 12 hours, and the oxygen-containing functional group of the coal pitch after the oxidation modification treatment is 13.5 percent. And adding the coal tar pitch treated under the conditions into a polyvinyl alcohol solution with the concentration of 6%, and carrying out pretreatment at 80 ℃ for 1h to obtain the coal tar pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 3:1, the homogenization treatment temperature is 80 ℃, and the homogenization treatment time is 1 h. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, the activation treatment temperature is 850 ℃, the activation treatment time is 2h, and the heating rate is 4 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 1896m2(g) total pore volume of 1.4936m3A pore volume of 0.9041m3The ratio of mesopores to the total pore volume was 39.47%, and the average pore diameter was 2.5567 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 311F/g, and the capacity retention rate reaches 100% after 10000 cycles.
Example 11
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 8mL of hydrogen peroxide, wherein the time of the modification treatment is 12h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 12.6%. And adding the coal tar pitch treated under the conditions into a starch solution with the concentration of 6%, and carrying out pretreatment at 80 ℃ for 1h to obtain the coal tar pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 3:1, the homogenization treatment temperature is 80 ℃, and the homogenization treatment time is 3 hours. And after the homogenization treatment is finished, directly activating the coal asphalt composite material, wherein the activation treatment temperature is 850 ℃, the activation treatment time is 2h, and the heating rate is 5 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 1911m2(g) total pore volume of 1.5136m3A pore volume of 0.9026m3The ratio of mesopores to the total pore volume was 40.37%, and the average pore diameter was 2.6673 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 301F/g, and the capacity retention rate reaches 100% after 10000 cycles of circulation.
Example 12
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 8mL of hydrogen peroxide, wherein the modification treatment time is 12h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 15.4%. Adding the coal pitch processed under the conditions into a mixed solution formed by 6% of starch and carboxymethyl cellulose, wherein the mass ratio of the starch to the carboxymethyl cellulose is 1:1, carrying out pretreatment at 80 ℃ for 2h to obtain the coal-tar pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 3:1, the homogenization treatment temperature is 80 ℃, and the homogenization treatment time is 2 hours. And after the homogenization treatment is finished, directly activating the coal asphalt composite material, wherein the activation treatment temperature is 850 ℃, the activation treatment time is 2h, and the heating rate is 3 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 1943m2(g) total pore volume of 1.6125m3A pore volume of 1.0415m3The ratio of mesopores to the total pore volume is 35.41%, and the average pore diameter is 2.6024 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 322F/g, and the capacity retention rate reaches 100% after 10000 cycles of circulation.
Example 13
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 8mL of hydrogen peroxide, wherein the modification treatment time is 16h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 20.7%. Adding the coal tar pitch processed under the conditions into a mixed solution formed by 6% of starch, carboxymethyl cellulose and polyvinyl alcohol, wherein the mass ratio of the starch to the carboxymethyl cellulose to the polyvinyl alcohol is 1: 1:1, carrying out pretreatment at 80 ℃ for 2h to obtain the coal-tar pitch compound.Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 3:1, the homogenization treatment temperature is 80 ℃, and the homogenization treatment time is 2 hours. And after the homogenization treatment is finished, directly activating the coal asphalt composite material, wherein the activation treatment temperature is 850 ℃, the activation treatment time is 2h, and the heating rate is 5 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 2310m2(g) total pore volume of 1.5714m3A pore volume of 1.0951m3The ratio of mesopores to the total pore volume was 30.31% and the average pore diameter was 2.6024 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 316F/g, and the capacity retention rate reaches 100% after 10000 cycles of circulation.
Example 14
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 8mL of hydrogen peroxide, wherein the modification treatment time is 10h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 18.4%. And adding the coal pitch treated under the conditions into 6% carboxymethyl cellulose solution, and carrying out pretreatment at 80 ℃ for 2h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 3:1, the homogenization treatment temperature is 50 ℃, and the homogenization treatment time is 2 hours. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, the activation treatment temperature is 850 ℃, the activation treatment time is 2h, and the heating rate is 1 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 2001m2(g) total pore volume of 1.4727m3A pore volume of 1.1016m3The ratio of mesopores to the total pore volume is 25.2%, and the average pore diameter is 2.4324 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 290F/g, and the capacity retention rate reaches 99.1 percent after 10000 cycles.
Example 15
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 8mL of hydrogen peroxide, wherein the modification treatment time is 10h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 18.4%. And adding the coal pitch treated under the conditions into 6% carboxymethyl cellulose solution, and carrying out pretreatment at 60 ℃ for 2h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 3:1, the homogenization treatment temperature is 100 ℃, and the homogenization treatment time is 2 hours. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, the activation treatment temperature is 850 ℃, the activation treatment time is 2h, and the heating rate is 2 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 2041m2(per gram), total pore volume of 1.4670m3A pore volume of 1.1047m3The ratio of mesopores to the total pore volume was 24.7%, and the average pore diameter was 2.4311 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 294F/g, and the capacity retention rate reaches 99.5 percent after 10000 cycles of circulation.
Example 16
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 10mL of hydrogen peroxide, wherein the modification treatment time is 22h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 35.3%. And adding the coal pitch treated under the conditions into a 2% carboxymethyl cellulose solution, and carrying out pretreatment at 70 ℃ for 2h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 1:1, the homogenization treatment temperature is 60 ℃, and the homogenization treatment time is 3 hours. And after the homogenization treatment is finished, directly activating the coal asphalt composite material, wherein the activation treatment temperature is 750 ℃, the activation treatment time is 2h, and the heating rate is 5 ℃/min. The product after the activation treatment is subjected to acid washing, soaking, water washing and dryingObtaining the porous activated carbon product. The resulting porous activated carbon had a specific surface area of 1610m2(g) total pore volume of 1.3477m3A pore volume of 0.8976m3The ratio of mesopores to the total pore volume was 33.4%, and the average pore diameter was 2.6526 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 291F/g, and the capacity retention rate reaches 99.8 percent after 10000 cycles of circulation.
Example 17
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 10mL of hydrogen peroxide, wherein the modification treatment time is 22h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 35.3%. And adding the coal pitch treated under the conditions into a 2% carboxymethyl cellulose solution, and carrying out pretreatment at 70 ℃ for 2h to obtain the coal pitch compound. Adding an activating agent KOH into the coal tar pitch compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch compound is 1:4, the homogenization treatment temperature is 60 ℃, and the homogenization treatment time is 3 hours. And after the homogenization treatment is finished, directly activating the coal asphalt composite material, wherein the activation treatment temperature is 850 ℃, the activation treatment time is 2h, and the heating rate is 8 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 2332m2(g) total pore volume of 1.8143m3A pore volume of 1.3716m3The ratio of mesopores to the total pore volume was 24.4%, and the average pore diameter was 2.4635 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 280F/g, and the capacity retention rate reaches 99.5 percent after 10000 cycles of circulation.
Example 18
Crushing the coal tar pitch to be less than 0.15mm, and carrying out oxidation modification treatment on the crushed coal tar pitch by using 100mL of concentrated sulfuric acid and 10mL of hydrogen peroxide, wherein the modification treatment time is 22h, and the oxygen-containing functional group of the coal tar pitch after the oxidation modification treatment is 35.3%. And adding the coal pitch treated under the conditions into a 2% carboxymethyl cellulose solution, and carrying out pretreatment at 80 ℃ for 2h to obtain the coal pitch compound. Mixing coal pitchAnd adding an activating agent KOH into the compound, and carrying out homogenization treatment to obtain the coal tar pitch composite material, wherein the mass ratio of the activating agent KOH to the coal tar pitch composite material is 1:4, the homogenization treatment temperature is 60 ℃, and the homogenization treatment time is 3 hours. After the homogenization treatment is finished, the coal asphalt composite material is directly subjected to activation treatment, wherein the activation treatment temperature is 950 ℃, the activation treatment time is 2h, and the heating rate is 10 ℃/min. And (4) pickling, soaking, washing and drying the product after the activation treatment to obtain a porous activated carbon product. The obtained porous activated carbon had a specific surface area of 2413m2(g) total pore volume of 1.7843m3A pore volume of 1.3364m3The ratio of mesopores to the total pore volume was 25.1%, and the average pore diameter was 2.4341 nm. Under the current density of 1A/g, the specific capacity of the prepared active carbon reaches 297F/g, and the capacity retention rate reaches 99.1% after 10000 cycles.
Claims (6)
1. A preparation method of mesoporous activated carbon for a supercapacitor is characterized by comprising the following steps:
(1) crushing, modifying, filtering and drying the coal tar pitch;
(2) adding the coal tar pitch obtained by the treatment in the step (1) into a gel solution for pretreatment to obtain a coal tar pitch compound, wherein the pretreatment process conditions are as follows: the pretreatment temperature is 60-80 ℃, and the pretreatment time is 1-3 h;
(3) adding an activating agent KOH into the coal tar pitch compound, and homogenizing the coal tar pitch compound and the activating agent to obtain a coal tar pitch composite material, wherein the process conditions of homogenization treatment are as follows: the homogenization temperature is 50-100 ℃, and the homogenization time is 1-6 h;
(4) the coal tar pitch composite material is activated and then is subjected to acid washing, soaking, water washing and drying to obtain the activated carbon.
2. The method according to claim 1, wherein the coal pitch treated in the step (1) is modified to have a particle size of less than 0.15 mm.
3. The method according to claim 3, wherein the reagent used in the modification treatment in step (1) is a mixture of concentrated sulfuric acid and hydrogen peroxide, and the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 100: (1-10), and the time of modification treatment is 2-24 h.
4. The method of claim 1, wherein the gel solution in step (2) is one or more of a carboxymethyl cellulose solution, a starch solution or a polyvinyl alcohol solution, and the concentration of the gel solution is 1% -6%.
5. The method of claim 2, wherein the mass ratio of the coal tar pitch complex to the activating agent in the homogenizing treatment in the step (3) is 1: (1-4); the homogenization treatment employs mechanical stirring, ultrasound or wet milling.
6. The method according to claim 1, wherein the process conditions for activating the coal tar pitch composite in step (4) are as follows: the heating speed is 1-10 ℃/min, the activation temperature is 750-950 ℃, and the activation time is 1-4 h.
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