CN110665442A - Composite activated carbon aerogel and preparation method and application thereof - Google Patents

Composite activated carbon aerogel and preparation method and application thereof Download PDF

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CN110665442A
CN110665442A CN201910927335.0A CN201910927335A CN110665442A CN 110665442 A CN110665442 A CN 110665442A CN 201910927335 A CN201910927335 A CN 201910927335A CN 110665442 A CN110665442 A CN 110665442A
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temperature
cellulose
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cellulose pulp
activation
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CN110665442B (en
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张力平
王天浩
张文涛
张磊
曾志农
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Beijing Forestry University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091Preparation of aerogels, e.g. xerogels
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/34Carbon-based characterised by carbonisation or activation of carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/44Raw materials therefor, e.g. resins or coal
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Carbon And Carbon Compounds (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention relates to the technical field of carbon materials, and particularly relates to a composite activated carbon aerogel and a preparation method and application thereof. The method takes cellulose pulp and carbon nano tubes as raw materials, wherein the weight ratio of the cellulose pulp to the carbon nano tubes is 8-10: 5. The invention adopts cellulose as the carbon aerogel matrix, can realize the renewable utilization of agricultural wastes, reduce the problems of environmental pollution, resource waste and the like, greatly improves the electrochemical performance of the cellulose carbon aerogel by doping the carbon nano tubes, and can be widely applied to the field of super capacitors.

Description

Composite activated carbon aerogel and preparation method and application thereof
Technical Field
The invention relates to the technical field of carbon materials, and particularly relates to a composite activated carbon aerogel and a preparation method and application thereof.
Background
The carbon aerogel has the characteristics of large specific surface area, good chemical stability, rich pore structure, low density and the like, has a developed three-dimensional network structure, and can enable electrolyte to enter the material to achieve the purpose of storing electric energy. These characteristics make the carbon aerogel have huge potential in the fields of energy storage, environmental purification, drug carriers and the like. The traditional carbon aerogel has the disadvantages of complex structure, high price and poor mechanical strength. Compared with the prior art, the biomass carbon aerogel has the advantages of high cost performance, environmental protection and excellent mechanical properties. Therefore, the biomass charcoal aerogel material is currently paid extensive attention in the field of electrode materials of supercapacitors. Among a plurality of biomass raw materials, the cellulose reserves are the most abundant, and the cellulose reserves are also ideal raw materials for preparing the biomass carbon aerogel. However, the cellulose carbon aerogel generally has poor conductivity, which brings obstruction to the application of the cellulose carbon aerogel in the field of supercapacitors.
Disclosure of Invention
Technical problem to be solved
In order to solve the defects in the field, the invention provides a composite activated carbon aerogel and a preparation method and application thereof.
(II) technical scheme
The invention firstly provides a preparation method of composite activated carbon aerogel (a preparation method of cellulose/carbon nanotube activated carbon aerogel), which takes cellulose pulp and carbon nanotubes as raw materials, wherein the weight ratio of the cellulose pulp to the carbon nanotubes is 8-10: 5.
The invention discovers that the conductivity of the cellulose carbon aerogel is improved after the conductive material is added into the cellulose carbon aerogel. However, the addition of some conductive materials solves the problem of conductivity, but it is difficult to achieve compatibility with other aspects of the carbon aerogel material. If graphene is added, the problem that graphene oxide is easy to agglomerate exists, and the dispersion performance of the material is affected. After the carbon nano tubes are added, the specific surface area and the conductivity of the cellulose carbon aerogel are increased, other properties of the carbon aerogel material are not affected, particularly after the carbon nano tubes are added according to the proportion, the conductivity and the properties of the material are well considered, and the integral electrochemical performance of the composite material is improved.
Preferably, the cellulose pulp is a bamboo cellulose pulp.
Compared with other fibers, when the bamboo fiber is applied to the technical scheme of the invention, the mechanical properties of the carbon aerogel and the flexible supercapacitor electrode material are better facilitated. In addition, the bamboo grows rapidly, has good reproducibility, and can be planted sustainably.
As a further preferable scheme, the cellulose content in the bamboo cellulose pulp is not less than 90%, and the lignin content is not less than 1%;
wherein the content of alpha-cellulose in the cellulose is not less than 80%.
Preferably, when the composite sol is prepared, the carbon nano tube and the ionic liquid are mixed to form a cellulose solvent, and then the cellulose pulp is mixed with the cellulose solvent;
in the ionic liquid, cations are one or two of alkyl imidazole ions and alkyl quaternary ammonium ions; and/or, the anion is selected from Cl-、CH3COO-、CF3COO-、CF3SO3 -、BF4 -、(CF3SO2)3C-、PF6 -、(CF3SO2)2N-One or more of; preferably, the cation is an alkylimidazolium ion and the anion is CF3COO-
Aiming at the raw materials with the specific mixture ratio, after the material mixing mode is adjusted and the ionic liquid is further optimized according to the method, the uniformity of the material is improved, and the electrochemical performance of the material is further improved.
Preferably, the mass ratio of the carbon nano tube to the ionic liquid is 1: 10-100, and more preferably 1: 10-50;
and/or the mass ratio of the cellulose pulp to the cellulose solvent is 1: 10-25.
Preferably, the carbon nanotubes and the ionic liquid are mixed and then subjected to ultrasonic treatment at room temperature for 2 hours to form the cellulose solvent.
Preferably, the cellulose pulp and the cellulose solvent are stirred at the speed of 300-700 r/min for 4-12 h at the temperature of 40-70 ℃.
Preferably, the cellulose pulp and the cellulose solvent are stirred at the speed of 400-600 r/min for 5-8 h at the temperature of 50-60 ℃ when being mixed.
As a preferable scheme, the method further comprises an ultrasonic defoaming process after the cellulose pulp and the cellulose solvent are mixed, wherein the ultrasonic defoaming temperature is 30-70 ℃, the power is 150-250W, and the time is 12-30 h;
preferably, the temperature of the ultrasonic defoaming is 50-60 ℃, the power is 180-200W, and the time is 18-24 h.
Aiming at the optimized composite sol material, the invention adaptively adjusts other steps so as to further optimize the performance of the material.
Preferably, the solvent of the composite sol is replaced with t-butanol before drying;
preferably, the composite sol is placed in deionized water to be soaked for 12-36 h, the deionized water is replaced every 4-6 h, then the composite sol is placed in tert-butyl alcohol to be soaked for 12-36 h, and the tert-butyl alcohol is replaced every 4-6 h.
Preferably, the deionized water soaking time is 18-24 hours, the deionized water is replaced every 5-6 hours, the tert-butyl alcohol soaking time is 18-24 hours, and the tert-butyl alcohol is replaced every 5-6 hours.
Preferably, the prepared composite sol is subjected to freeze drying at the temperature of-60 to-20 ℃ and the vacuum degree of 40 to 150 Pa;
preferably, the temperature of the freeze drying is-50 to-30 ℃, and the vacuum degree is 45 to 100 Pa.
Preferably, the composite sol is dried and then is carbonized at high temperature, wherein the temperature of the high-temperature carbonization is 700-1000 ℃, the temperature rising rate is 3-5 ℃/min, the carbonization time is 0.5-2 h, and the temperature reduction rate is 3-5 ℃/min;
preferably, the high-temperature carbonization temperature is 800-900 ℃, the temperature rise rate is 4-5 ℃/min, the carbonization time is 1-2 h, and the temperature reduction rate is 4-5 ℃/min.
Preferably, after the composite sol is carbonized, the method further comprises the step of activation, wherein the activation sequentially comprises KOH activation and high-temperature activation;
preferably, during KOH activation, the mass ratio of carbide to KOH is 1: 1-4, and the activation time is 12-24 h;
preferably, the mass ratio of the carbide to KOH is 1: 2-3, and the activation time is 15-18 h.
Preferably, the high-temperature activation temperature is 700-1000 ℃, the heating rate is 3-5 ℃/min, the activation time is 0.5-2 h, and the cooling rate is 3-5 ℃/min.
Preferably, the high-temperature activation temperature is 800-900 ℃, the temperature rise rate is 4-5 ℃/min, the activation time is 1-2 h, and the temperature reduction rate is 4-5 ℃/min.
The invention provides a preferable scheme, and the method comprises the following steps:
1) mixing the carbon nano tube with ionic liquid to form a cellulose solvent, and stirring the cellulose pulp and the cellulose solvent at the temperature of 50-60 ℃ at the speed of 400-600 r/min for 5-8 h; then placing the mixture at the temperature of 50-60 ℃ and carrying out ultrasonic defoaming for 18-24 h at the power of 180-200W to obtain composite sol (regenerated cellulose/carbon nano tube sol);
wherein, the cation in the ionic liquid solvent is alkyl imidazole ion, and the anion is CF3 COO-; the mass ratio of the carbon nano tube to the ionic liquid is 1: 10-100; the mass ratio of the cellulose pulp to the cellulose solvent is 1: 10-20;
2) carrying out solvent replacement on the regenerated cellulose/carbon nano tube sol, wherein the soaking time of deionized water is 18-24 h, the deionized water is replaced every 5-6 h, the soaking time of tertiary butyl alcohol is 18-24 h, and the tertiary butyl alcohol is replaced every 5-6 h;
then, freeze-drying at the temperature of minus 50 to minus 30 ℃ and the vacuum degree of 45 to 100 Pa;
3) carrying out high-temperature carbonization at the temperature of 800-900 ℃, the temperature rising rate of 4-5 ℃/min, the carbonization time of 1-2 h and the temperature reduction rate of 4-5 ℃/min;
4) activating by KOH, wherein the mass ratio of the carbide to the KOH is 1: 2-3, and the activation time is 15-18 h; and finally, performing high-temperature activation under the conditions that the temperature is 800-900 ℃, the heating rate is 4-5 ℃/min, the activation time is 1-2 h, and the cooling rate is 4-5 ℃/min to obtain the composite carbon aerogel (cellulose/carbon nanotube carbon aerogel).
The third purpose of the invention is to provide the composite carbon aerogel (cellulose/carbon nano tube carbon aerogel) prepared by the method.
The third purpose of the invention is to provide the application of the composite carbon aerogel in the fields of supercapacitors, adsorption and catalyst carriers; preferably in the field of supercapacitors.
(III) advantageous effects
(1) The invention adopts cellulose as the carbon aerogel matrix, can realize the renewable utilization of agricultural wastes, reduce the problems of environmental pollution, resource waste and the like, greatly improves the electrochemical performance of the cellulose carbon aerogel by doping the carbon nano tubes, and can be widely applied to the field of super capacitors.
(2) The cellulose solvent used in the method can dissolve cellulose at a lower temperature, the preparation condition is mild, the flow is simple and convenient, the speed of dissolving the cellulose is high, and the degradation process of the cellulose in the dissolving process can be effectively avoided.
(3) Compared with the traditional carbon aerogel, the composite carbon aerogel (cellulose/carbon nanotube carbon aerogel) provided by the invention has the following advantages: the raw materials belong to agricultural and forestry waste recycling, a solvent used in the preparation process is green and environment-friendly, the energy consumption is low, the specific surface area of a final product is large, the conductivity is good, and the method can be widely applied to the fields of electrode materials of supercapacitors, adsorption, catalyst carriers and the like.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The following examples employ bamboo cellulose pulp from GmbH, Inc.
Example 1
A preparation method of cellulose/carbon nanotube carbon aerogel comprises the following steps:
1) dispersing 2.5g of carbon nano tubes in an ionic liquid solvent to form a cellulose solvent, dissolving 4g of bamboo cellulose pulp in 93.5g of the cellulose solvent, stirring at the speed of 500r/min for 6 hours at the temperature of 55 ℃, and performing ultrasonic defoaming at the power of 200w at the temperature of 55 ℃ for 20 hours to obtain regenerated cellulose/carbon nano tube sol;
wherein the cation in the ionic liquid solvent is alkyl imidazole ion, and the anion is CF3COO-
2) And (3) carrying out solvent replacement on the regenerated cellulose/carbon nano tube sol, wherein the soaking time of deionized water is 20h, the deionized water is replaced every 5h, the soaking time of tertiary butanol is 20h, and the tertiary butanol is replaced every 5 h. Then, freeze-drying was carried out at-45 ℃ under a vacuum of 60 Pa.
3) High-temperature carbonization is carried out under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the carbonization time is 1h, and the cooling rate is 5 ℃/min.
4) Activating by KOH, wherein the mass ratio of carbide to KOH is 1: 3, and the activation time is 16 h. And finally, performing high-temperature activation under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the activation time is 1h, and the cooling rate is 5 ℃/min to obtain the cellulose/carbon nanotube carbon aerogel.
Example 2
A preparation method of cellulose/carbon nanotube carbon aerogel comprises the following steps:
1) dispersing 2.5g of carbon nano tubes in an ionic liquid solvent to form a cellulose solvent, dissolving 6g of bamboo cellulose pulp in 91.5g of the cellulose solvent, stirring at the speed of 500r/min for 6 hours at the temperature of 55 ℃, and performing ultrasonic defoaming at the power of 200w at the temperature of 55 ℃ for 20 hours to obtain regenerated cellulose/carbon nano tube sol;
wherein the cation in the ionic liquid solvent is alkyl imidazole ion, and the anion is CF3COO-
2) And (3) carrying out solvent replacement on the regenerated cellulose/carbon nano tube sol, wherein the soaking time of deionized water is 20h, the deionized water is replaced every 5h, the soaking time of tertiary butanol is 20h, and the tertiary butanol is replaced every 5 h. Then, freeze-drying was carried out at-45 ℃ under a vacuum of 60 Pa.
3) High-temperature carbonization is carried out under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the carbonization time is 1h, and the cooling rate is 5 ℃/min.
4) Activating by KOH, wherein the mass ratio of carbide to KOH is 1: 3, and the activation time is 16 h. And finally, performing high-temperature activation under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the activation time is 1h, and the cooling rate is 5 ℃/min to obtain the cellulose/carbon nanotube carbon aerogel.
Example 3
A preparation method of cellulose/carbon nanotube carbon aerogel comprises the following steps:
1) dispersing 2.5g of carbon nano tubes in an ionic liquid solvent to form a cellulose solvent, dissolving 8g of bamboo cellulose pulp in 89.5g of the cellulose solvent, stirring at the speed of 500r/min for 6 hours at the temperature of 55 ℃, and performing ultrasonic defoaming at the power of 200w at the temperature of 55 ℃ for 20 hours to obtain regenerated cellulose/carbon nano tube sol;
wherein the cation in the ionic liquid solvent is alkyl imidazole ion, and the anion is CF3COO-
2) And (3) carrying out solvent replacement on the regenerated cellulose/carbon nano tube sol, wherein the soaking time of deionized water is 20h, the deionized water is replaced every 5h, the soaking time of tertiary butanol is 20h, and the tertiary butanol is replaced every 5 h. Then, freeze-drying was carried out at-45 ℃ under a vacuum of 60 Pa.
3) High-temperature carbonization is carried out under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the carbonization time is 1h, and the cooling rate is 5 ℃/min.
4) Activating by KOH, wherein the mass ratio of carbide to KOH is 1: 3, and the activation time is 16 h. And finally, performing high-temperature activation under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the activation time is 1h, and the cooling rate is 5 ℃/min to obtain the cellulose/carbon nanotube carbon aerogel.
Comparative example 1
1) Dissolving 4g of bamboo cellulose pulp in 96g of ionic liquid solvent, stirring at the speed of 500r/min for 6h at the temperature of 55 ℃, and performing ultrasonic defoaming at the temperature of 55 ℃ for 20h at the power of 200w to obtain regenerated cellulose sol;
wherein, theIn the ionic liquid solvent, the cation is alkyl imidazole ion and the anion is CF3COO-
2) And (3) carrying out solvent replacement on the regenerated cellulose sol, wherein the soaking time of deionized water is 20h, the deionized water is replaced every 5h, the soaking time of tertiary butanol is 20h, and the tertiary butanol is replaced every 5 h. Then, freeze-drying was carried out at-45 ℃ under a vacuum of 60 Pa.
3) High-temperature carbonization is carried out under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the carbonization time is 1h, and the cooling rate is 5 ℃/min.
4) Activating by KOH, wherein the mass ratio of carbide to KOH is 1: 3, and the activation time is 16 h. And finally, performing high-temperature activation under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the activation time is 1h, and the cooling rate is 5 ℃/min to obtain the cellulose carbon aerogel.
Comparative example 2
1) Dissolving 6g of bamboo cellulose pulp in 94g of ionic liquid solvent, stirring at the speed of 500r/min for 6h at the temperature of 55 ℃, and performing ultrasonic defoaming at the temperature of 55 ℃ for 20h at the power of 200w to obtain regenerated cellulose sol;
wherein the cation in the ionic liquid solvent is alkyl imidazole ion, and the anion is CF3COO-
2) And (3) carrying out solvent replacement on the regenerated cellulose sol, wherein the soaking time of deionized water is 20h, the deionized water is replaced every 5h, the soaking time of tertiary butanol is 20h, and the tertiary butanol is replaced every 5 h. Then, freeze-drying was carried out at-45 ℃ under a vacuum of 60 Pa. High-temperature carbonization is carried out under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the carbonization time is 1h, and the cooling rate is 5 ℃/min. Activating by KOH, wherein the mass ratio of carbide to KOH is 1: 3, and the activation time is 16 h. And finally, performing high-temperature activation under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the activation time is 1h, and the cooling rate is 5 ℃/min to obtain the cellulose carbon aerogel.
Comparative example 3
1) Dissolving 8g of bamboo cellulose pulp in 92g of ionic liquid solvent, stirring at the speed of 500r/min for 6h at the temperature of 55 ℃, and performing ultrasonic defoaming at the temperature of 55 ℃ for 20h at the power of 200w to obtain regenerated cellulose sol;
wherein the cation in the ionic liquid solvent is alkyl imidazole ion, and the anion is CF3COO-
2) And (3) carrying out solvent replacement on the regenerated cellulose sol, wherein the soaking time of deionized water is 20h, the deionized water is replaced every 5h, the soaking time of tertiary butanol is 20h, and the tertiary butanol is replaced every 5 h. Then, freeze-drying was carried out at-45 ℃ under a vacuum of 60 Pa. High-temperature carbonization is carried out under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the carbonization time is 1h, and the cooling rate is 5 ℃/min. Activating by KOH, wherein the mass ratio of carbide to KOH is 1: 3, and the activation time is 16 h. And finally, performing high-temperature activation under the conditions that the temperature is 900 ℃, the heating rate is 5 ℃/min, the activation time is 1h, and the cooling rate is 5 ℃/min to obtain the cellulose carbon aerogel.
Test examples
The carbon aerogels described in examples 1 to 3 and comparative examples 1 to 3 were subjected to a performance test
1. Specific surface area and pore size distribution test:
the samples were degassed by placing them at 200 ℃ for 10 hours to remove volatile materials from the surface of the material before testing. Analysis was performed using a Micommunications ASAP 2460 model automatic specific surface area and pore size Analyzer. The specific surface area and pore size distribution of the porous carbon material were obtained by the BET (Brunauer-Emmett-Teller) theoretical calculation method, and the results are shown in Table 1.
2. Specific capacitance test:
the electrochemical performance of the material was evaluated using CHI 760D electrochemical workstation from CH instruments, USA. The test system is a three-electrode system, wherein the working electrode is a prepared sample, the platinum metal and silver chloride calomel electrode are used as a counter electrode and a reference electrode, and 6M potassium hydroxide solution is selected as electrolyte. The preparation method of the working electrode comprises the following steps: grinding a sample in agate mortar, mixing the ground sample with polyvinylidene fluoride (PVDF) and acetylene black in N-methylpyrrolidone (NMP) to obtain slurry, tabletting the slurry, covering the laminated foam nickel sheet, and drying the laminated foam nickel sheet in an oven for use. The specific capacitance test was performed at a voltage window of 0-0.9V and was obtained by calculating the discharge curve equation C ═ I Δ t/(m Δ V), and the results are shown in table 1.
Wherein C is specific capacitance, F/g; i is a discharge current, A; Δ t is the discharge time, s; Δ V is the operating voltage window, V.
The test results are shown in Table 1 below
TABLE 1
Sample (I) Specific surface area (m)2/g) Average pore diameter (nm) Specific capacitance (F/g)
Example 1 1653.36 2.89 153.1
Example 2 1856.52 2.63 163.6
Example 3 1732.43 2.77 157.6
Comparative example 1 1235.25 3.79 103.5
Comparative example 2 1376.96 3.46 113.5
Comparative example 3 1286.88 3.65 107.8
As can be seen from the data in the table, the specific surface area and the specific capacitance of the carbon aerogel in the embodiments 1 to 3 of the invention are obviously higher than those of the comparative examples 1 to 3, which shows that the specific surface area and the conductivity of the carbon aerogel are effectively improved by adding the carbon nano tube; the great improvement of the specific capacitance also shows that the carbon nano tubes are well dispersed in the carbon aerogel under the system, so that the overall electrochemical performance of the material is improved. Meanwhile, the decrease in the average pore diameter of the carbon aerogel in examples 1 to 3 compared to that in comparative documents 1 to 3 indicates that the pore structure of the carbon aerogel becomes more developed, which facilitates the storage of electric charges, and this may be caused by the interaction of the carbon nanotubes and cellulose at high temperature. In conclusion, after the carbon nano tube is added by the method, the specific surface area and the electrochemical performance of the whole material are effectively improved, and the method can be widely applied to the field of super capacitors.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The preparation method of the composite activated carbon aerogel is characterized by taking cellulose pulp and carbon nano tubes as raw materials, wherein the weight ratio of the cellulose pulp to the carbon nano tubes is 8-10: 5;
preferably, the cellulose pulp is a bamboo cellulose pulp.
2. The method according to claim 1, wherein in the preparation of the composite sol, the carbon nanotubes are mixed with an ionic liquid to form a cellulose solvent, and then the cellulose pulp is mixed with the cellulose solvent;
in the ionic liquid, cations are one or two of alkyl imidazole ions and alkyl quaternary ammonium ions; and/or, the anion is selected from Cl-、CH3COO-、CF3COO-、CF3SO3 -、BF4 -、(CF3SO2)3C-、PF6 -、(CF3SO2)2N-One or more of; preferably, the cation is an alkylimidazolium ion and the anion is CF3COO-
3. The method according to claim 2, wherein the mass ratio of the carbon nanotubes to the ionic liquid is 1: 10 to 100, preferably 1: 10 to 50;
and/or the mass ratio of the cellulose pulp to the cellulose solvent is 1: 10-25.
4. The method according to claim 2 or 3, wherein the cellulose pulp is stirred at a rate of 300 to 700r/min for 4 to 12 hours at a temperature of 40 to 70 ℃ while being mixed with the cellulose solvent;
preferably, after the cellulose pulp and the cellulose solvent are mixed, the ultrasonic defoaming process is also included, wherein the ultrasonic defoaming temperature is 30-70 ℃, the power is 150-250W, and the time is 12-30 h.
5. The method according to any one of claims 2 to 4, wherein a solvent of the composite sol is replaced with t-butanol before drying;
preferably, the composite sol is placed in deionized water to be soaked for 12-36 h, the deionized water is replaced every 4-6 h, then the composite sol is placed in tert-butyl alcohol to be soaked for 12-36 h, and the tert-butyl alcohol is replaced every 4-6 h.
6. The method according to any one of claims 2 to 5, characterized in that the prepared composite sol is freeze-dried at a temperature of-60 ℃ to-20 ℃ and a vacuum degree of 40 Pa to 150 Pa;
preferably, the temperature of the freeze drying is-50 to-30 ℃, and the vacuum degree is 45 to 100 Pa.
7. The method according to any one of claims 2 to 6, characterized in that the composite sol is dried and then subjected to high-temperature carbonization, wherein the temperature of the high-temperature carbonization is 700 to 1000 ℃, the temperature rise rate is 3 to 5 ℃/min, the carbonization time is 0.5 to 2h, and the temperature reduction rate is 3 to 5 ℃/min;
preferably, the high-temperature carbonization temperature is 800-900 ℃, the temperature rise rate is 4-5 ℃/min, the carbonization time is 1-2 h, and the temperature reduction rate is 4-5 ℃/min.
8. The method according to any one of claims 2 to 7, characterized by further comprising the step of activating after the composite sol is carbonized, wherein the activating comprises KOH activation and high-temperature activation in sequence;
preferably, during KOH activation, the mass ratio of carbide to KOH is 1: 1-4, and the activation time is 12-24 h;
preferably, the high-temperature activation temperature is 700-1000 ℃, the heating rate is 3-5 ℃/min, the activation time is 0.5-2 h, and the cooling rate is 3-5 ℃/min.
9. The composite activated carbon aerogel prepared by the method of any one of claims 1 to 8.
10. The use of the composite activated carbon aerogel according to claim 9 in the fields of supercapacitors, adsorption, catalyst supports; preferably in the field of supercapacitors.
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