CN108455604B - Carboxyl asphalt-based porous carbon and preparation method and application thereof - Google Patents
Carboxyl asphalt-based porous carbon and preparation method and application thereof Download PDFInfo
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- CN108455604B CN108455604B CN201810081520.8A CN201810081520A CN108455604B CN 108455604 B CN108455604 B CN 108455604B CN 201810081520 A CN201810081520 A CN 201810081520A CN 108455604 B CN108455604 B CN 108455604B
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Abstract
The invention relates to carboxyl asphalt-based porous carbon and a preparation method and application thereof, wherein the raw material of the carboxyl asphalt-based porous carbon is carboxyl asphaltThe content of the medium carboxyl functional group is more than or equal to 25 percent; the specific surface area of the carboxyl asphalt-based porous carbon is 2249-3295 m2The pore volume is 1.13-1.89 cm3The ratio of the pore diameter of 2-4 nm is 45-80%, and the average particle diameter is 15-35 μm. The carboxyl asphalt-based porous carbon has the characteristics of large specific surface area and high pore volume, is simple in preparation method, and has the characteristics of high specific capacity and good cycle performance when being used as an electrode material of a double electric layer capacitor.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to carboxyl asphalt-based porous carbon and a preparation method and application thereof.
Background
The double-electric-layer capacitor has the advantages of low cost, large specific capacitance, simple charge and discharge, long cycle life and the like, and becomes a novel energy storage element which develops rapidly in recent years. Typical carbon electrode materials are: activated carbon, carbon fibers, carbon nanotubes, and carbon gels. The carbon fiber is high in price, so that the application of the carbon fiber in the field of supercapacitors is limited; the micropore volume of the carbon nano tube is limited, so that the capacitance value is not high; the material density of the carbon gel is low, resulting in a low volumetric capacitance. In contrast, activated carbon is widely available, low in price, good in conductivity, large in specific surface area and good in electrochemical stability, and is the electrode material of the electric double layer capacitor which is most used at present.
The pore size distribution of most activated carbon materials is not optimal because it is difficult to control the pore size during activation, thus limiting the maximum use of the surface area of the material during formation of the electric double layer. Whereas the optimum pore size is different for different electrolytes. Therefore, the reasonably designed pore distribution has important significance for improving the specific capacitance, wherein the micropores mainly store charges by using amount and have larger contribution to the specific capacitance, and the mesopores mainly serve as a transmission channel of ions and have great influence on the rate capability of the material. However, the microporous structure of the activated carbon limits the infiltration of the electrolyte on the inner surface of the micropores, so that the high specific surface area cannot be fully utilized. Therefore, the content of the mesopores is increased, so that the effective specific surface area is increased, and the specific capacitance is increased.
Chinese patent with publication number CN103043663 discloses a sulfonated asphalt-based activated carbon and a preparation method and application thereof, wherein sulfoasphalt is used as a precursor, a three-stage heat treatment mode is adopted, and the specific surface area of the prepared activated carbon can reach 1838-3291 m under the condition that the alkali-carbon ratio is 1-32The ratio of small and medium pores with the pore diameter of 2-5nm is 42.4-97.8%. Chinese patent with application number CN201210179358.6 discloses a method for preparing coal activated carbon with high specific surface area and composite pore structure by using low KOH amount, which uses humus coal as a precursor and adopts a multi-stage heat treatment mode to prepare the activated carbon with micropore-mesopore composite pore structure. Chinese patent with application number CN201010188981.9 discloses 'activated carbon for preparing carbon electrode of super capacitor and preparation method thereof', wherein amphiphilic carbon materials are prepared by taking asphalt with different weights as raw materials, the amphiphilic carbon materials are used as precursors to prepare activated carbon, and the specific surface area of the prepared activated carbon can reach 3000-3400 m under the condition that the alkali-carbon ratio is 2-42The occupancy rate of small and medium pores with the pore diameter of 2-5nm is 25-32%.
The carboxyl asphalt is a carboxylated product of asphalt and is rich in carboxyl functional groups, and the functional groups on the surface of the asphalt not only can increase the wettability of electrolyte, but also can provide pseudocapacitance. At present, no report exists on the preparation of an activated carbon electrode material for an electric double layer capacitor by properly treating carboxyl asphalt.
Disclosure of Invention
The invention provides carboxyl asphalt-based porous carbon, a preparation method and application thereof, wherein the carboxyl asphalt-based porous carbon has the characteristics of large specific surface area and high pore volume, is simple in preparation method, and has the characteristics of high specific capacity and good cycle performance when being used as an electrode material of a double electric layer capacitor.
In order to achieve the purpose, the invention adopts the following technical scheme:
the carboxyl asphalt-based porous carbon is prepared from carboxyl asphalt as a raw material, wherein the content of carboxyl functional groups is more than or equal to 25%; the specific surface area of the carboxyl asphalt-based porous carbon is 2249-3295 m2The pore volume is 1.13-1.89 cm3The ratio of the pore diameter of 2-4 nm is 45-80%, and the average particle diameter is 15-35 μm.
A preparation method of carboxyl asphalt-based porous carbon comprises the following steps:
1) mixing carboxyl asphalt powder with a KOH aqueous solution with the mass concentration of 20-40%, wherein the mass ratio of the carboxyl asphalt powder to the KOH is 1: 0.5-2;
2) fully stirring carboxyl asphalt powder and KOH aqueous solution, placing the mixed solution in a drying oven, and drying at 100-120 ℃ for 6-12 hours to obtain solid powder;
3) putting the solid powder prepared in the step 2) into an activation furnace, and performing segmented heating activation under the nitrogen atmosphere: firstly, heating to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for more than 30min, then heating to 500 ℃ at the speed of 1-3 ℃/min, keeping the temperature for more than 60min, finally heating to 900-1100 ℃ at the speed of 5 ℃/min, and keeping the temperature for 1-2 h;
4) and washing the activated solid for 2-4 h by using boiling water, boiling and washing the activated solid for more than 2h by using a 5% HCl solution, finally washing the activated solid to be neutral by using deionized water, and drying the activated solid for 6-12 h at the temperature of 100-120 ℃ to obtain the carboxyl asphalt-based porous carbon.
A carboxyl pitch-based porous carbon is used as an electrode material of an electric double layer capacitor.
Compared with the prior art, the invention has the beneficial effects that:
1) firstly, carboxyl asphalt is adopted as a raw material to prepare a porous carbon electrode material for a double electric layer capacitor;
2) the carboxyl asphalt is low in cost, rich in functional groups and good in hydrophilicity, can be in contact with a KOH solution in a nanoscale, overcomes mass transfer resistance, reduces concentration gradient, ensures that the activation process is uniformly carried out, reduces the using amount of KOH, avoids an oxidation stabilization process, and is simple to prepare, low in cost and light in pollution;
3) the carboxyl asphalt-based porous carbon has the characteristics of large specific surface area and high pore volume, the preparation method is simple, and electrochemical tests show that the carboxyl asphalt-based porous carbon has the characteristics of high specific capacity and good cycle performance when being used as an electrode material of a double electric layer capacitor.
Drawings
FIG. 1 is a nitrogen adsorption/desorption isotherm diagram of a carboxyasphalt-based porous carbon in example 1 of the present invention.
FIG. 2 is a pore size distribution diagram of the carboxyl pitch-based porous carbon in example 1 of the present invention.
FIG. 3 is a plot of cyclic voltammograms at scan rates of 10mV/s, 20mV/s, 50mV/s, 100mV/s, and 200mV/s for electrodes made from the carboxylated pitch-based porous carbon of example 1 of the present invention in a 6M KOH electrolyte, respectively.
FIG. 4 is a graph of the cycling performance of electrodes made from the carboxy pitch-based porous carbon of invention example 1 in a 6M KOH electrolyte.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
the invention provides carboxyl asphalt-based porous carbon, wherein the raw material of the carboxyl asphalt-based porous carbon is carboxyl asphalt, wherein the content of carboxyl functional groups is more than or equal to 25 percent; the specific surface area of the carboxyl asphalt-based porous carbon is 2249-3295 m2The pore volume is 1.13-1.89 cm3The ratio of the pore diameter of 2-4 nm is 45-80%, and the average particle diameter is 15-35 μm.
A preparation method of carboxyl asphalt-based porous carbon comprises the following steps:
1) mixing carboxyl asphalt powder with a KOH aqueous solution with the mass concentration of 20-40%, wherein the mass ratio of the carboxyl asphalt powder to the KOH is 1: 0.5-2;
2) fully stirring carboxyl asphalt powder and KOH aqueous solution, placing the mixed solution in a drying oven, and drying at 100-120 ℃ for 6-12 hours to obtain solid powder;
3) putting the solid powder prepared in the step 2) into an activation furnace, and performing segmented heating activation under the nitrogen atmosphere: firstly, heating to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for more than 30min, then heating to 500 ℃ at the speed of 1-3 ℃/min, keeping the temperature for more than 60min, finally heating to 900-1100 ℃ at the speed of 5 ℃/min, and keeping the temperature for 1-2 h;
4) and washing the activated solid for 2-4 h by using boiling water, boiling and washing the activated solid for more than 2h by using a 5% HCl solution, finally washing the activated solid to be neutral by using deionized water, and drying the activated solid for 6-12 h at the temperature of 100-120 ℃ to obtain the carboxyl asphalt-based porous carbon.
A carboxyl pitch-based porous carbon is used as an electrode material of an electric double layer capacitor.
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.
[ example 1 ]
Mixing 20g of carboxyl asphalt powder with a KOH aqueous solution with the mass concentration of 40%, wherein the mass ratio of the carboxyl asphalt powder to the KOH is 1:1, fully stirring, placing the mixed solution in a baking oven, and drying for 8 hours at 100 ℃ to obtain solid powder; putting the solid powder into an activation furnace, and carrying out three-stage heating activation under the nitrogen atmosphere: firstly heating to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for 30min, then heating to 500 ℃ at the speed of 2 ℃/min, keeping the temperature for 60min, finally heating to 900 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 h. Washing the activated solid with boiling water for 2h, boiling and washing with 5% HCl solution for 2h, finally washing with deionized water to neutrality, and drying at 110 ℃ for 10h to obtain the carboxyl asphalt-based porous carbon.
The carboxyl asphalt-based porous carbon prepared in the example is ASAP 2020N2The performance of the adsorption apparatus is tested, and the result is shown in figures 1 and 2, and the BET specific surface area is 2249m2G, pore volume of 1.15cm2The ratio of medium pores and micropores with the pore diameter of 2-4 nm is more than 55 percent.
6M KOH is used as electrolyte, and a Tri-electrode system of an electrochemistry workstation LK2005B of Tianjin Lanlix is adopted to respectively test the cyclic voltammetry characteristics and the cyclic performance of the carboxyl asphalt base porous carbon sample. As shown in FIGS. 3 and 4, the test results show that the CV curve of the sample still presents a rectangle when the scan rate reaches 200mV/s, and the specific capacitance can still be kept 219F/g after 3000 cycles at the current density of 1A/g.
[ example 2 ]
Mixing 20g of carboxyl asphalt powder with 30% KOH aqueous solution in a mass ratio of 1:2, fully stirring, placing the mixed solution in a drying oven, and drying at 100 ℃ for 12 hours to obtain solid powder; putting the solid powder into an activation furnace, and carrying out three-stage heating activation under the nitrogen atmosphere: firstly heating to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for 30min, then heating to 500 ℃ at the speed of 3 ℃/min, keeping the temperature for 60min, finally heating to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 h. Washing the activated solid with boiling water for 2h, boiling and washing with 5% HCl solution for 2h, finally washing with deionized water to neutrality, and drying at 110 ℃ for 10h to obtain the carboxyl asphalt-based porous carbon.
The carboxyl asphalt-based porous carbon prepared in the example is ASAP 2020N2The performance test of the adsorption instrument shows that the BET specific surface area is 2847m2G, pore volume of 1.85cm2The ratio of medium pores to micropores with the pore diameter of 2-4 nm is more than 75%.
6M KOH is used as electrolyte, and a Tri-electrode system of an electrochemistry workstation of Tianjin Lanlix LK2005B is adopted to test the cyclic voltammetry characteristics and the cyclic performance of the sample respectively. The test result shows that when the scanning speed reaches 200mV/s, the CV curve of the sample still presents a rectangle, and when the current density is 1A/g, the specific capacitance can still maintain 221F/g after 3000 times of circulation.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (1)
1. The preparation method of the carboxyl asphalt-based porous carbon is characterized in that the carboxyl asphalt-based porous carbon is used as an electrode material of an electric double layer capacitor, the raw material of the carboxyl asphalt-based porous carbon is carboxyl asphalt, wherein the content of carboxyl functional groups is more than or equal to 25 percent; the specific surface area of the carboxyl asphalt-based porous carbon is 2249-3295 m2The pore volume is 1.13-1.89 cm3The ratio of the pore diameter of 2-4 nm is 45-80%, and the average particle diameter is 15-35 mu m;
the preparation method of the carboxyl asphalt-based porous carbon comprises the following steps:
1) mixing carboxyl asphalt powder with a KOH aqueous solution with the mass concentration of 20-40%, wherein the mass ratio of the carboxyl asphalt powder to the KOH is 1: 0.5-2;
2) fully stirring carboxyl asphalt powder and KOH aqueous solution, placing the mixed solution in a drying oven, and drying at 100-120 ℃ for 6-12 hours to obtain solid powder;
3) putting the solid powder prepared in the step 2) into an activation furnace, and performing segmented heating activation under the nitrogen atmosphere: firstly, heating to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for 30min, heating to 500 ℃ at the speed of 1-3 ℃/min, keeping the temperature for 60min, and finally heating to 900-1100 ℃ at the speed of 5 ℃/min, keeping the temperature for 1-2 h;
4) and washing the activated solid for 2-4 h by using boiling water, boiling and washing the activated solid for more than 2h by using a 5% HCl solution, finally washing the activated solid to be neutral by using deionized water, and drying the activated solid for 6-12 h at the temperature of 100-120 ℃ to obtain the carboxyl asphalt-based porous carbon.
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| CN101844765B (en) * | 2010-06-02 | 2012-01-11 | 天津大学 | Active carbon for preparing carbon electrode of super capacitor and preparation method thereof |
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