CN108178141B - Preparation method of microporous carbon with high conductivity, high tap density and high specific surface area - Google Patents
Preparation method of microporous carbon with high conductivity, high tap density and high specific surface area Download PDFInfo
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- CN108178141B CN108178141B CN201810044728.2A CN201810044728A CN108178141B CN 108178141 B CN108178141 B CN 108178141B CN 201810044728 A CN201810044728 A CN 201810044728A CN 108178141 B CN108178141 B CN 108178141B
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Abstract
The invention provides a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area, and the prepared material can be used for a super capacitor, but is not limited to the application in the fields of molecular adsorption, pressure swing adsorption separation, membrane separation and the like. The carbon source and the copper salt are uniformly mixed, the copper salt is reduced to CuCl with low melting point and simple substance copper in situ in the high-temperature heat treatment process, and the conductivity of the material is improved by utilizing the template action of the CuCl for pore forming and the catalytic graphitization action of the copper. In addition, the metal copper is a good electronic conductor, and the residual copper in the carbon material can improve the conductivity of the material on one hand and improve the tap density of the material without influencing the pore structure on the other hand. The preparation method is simple to operate and easy to implement industrially and produce in large scale.
Description
Technical Field
The invention belongs to the technical field of porous carbon preparation, and relates to a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area.
Background
Carbon materials are widely used as supercapacitor electrode materials due to their characteristics of high electrochemical conductivity, high thermal stability, controllable pore structure, adjustable surface chemistry, and the like. The super capacitor made of the carbon-based material mainly stores energy by means of an electric double layer generated by an electrode/electrolyte interface, so that the super capacitor can realize quick charge and discharge, has high power density and is low in specific capacity. Much research is currently being undertaken around designing high capacity electrode materials to increase their energy density. The ideal electrode material needs to have various properties for promoting the performance improvement of the capacitor, such as large specific surface area providing active sites for forming an electric double layer, pore structure matched with electrolyte ions for realizing the maximization of electric double layer capacitance, good conductivity for effectively improving charge and discharge performance and power density under the condition of large current, various active groups for improving the surface wettability of the material and contributing to pseudocapacitance, and high packing density for improving the volume energy density of the capacitor. However, the factors are mutually restricted, and it is urgently needed to prepare a new material which can balance the influence of the factors and optimize the energy density and the power density of the new material.
According to the double-layer capacitance energy storage mechanism, micropores are the main active sites for adsorbing electrolyte ions, so that the carbon material with high specific surface area is the first choice of the electrode material of the super capacitor. Theoretically, the larger the specific surface area of the material, the higher the specific capacitance should be. However, it has been found that the specific capacitance does not increase linearly when the specific surface area of the material is raised to a certain extent. And the specific surface area of the material is too high, so that the electric conductivity and the packing density of the material are inevitably reduced, which is not favorable for the capacitive energy of the material. Further studies have indicated that submicron pore structured electrode materials exhibit high energy storage densities. The proposition of this theory has attracted the attention of numerous researchers to the development of electrode materials with submicron pore structures. The existing method for preparing microporous carbon mainly comprises an activation method and a template method, wherein an activating agent in the activation method is randomly distributed in a carbon precursor, and pores are formed from outside to inside mainly by means of interaction between the activating agent and the carbon precursor in the activation process, so that the generated pore channel structure is irregular, and the pore connectivity is poor. When the material is used as an electrode material of a super capacitor, electrolyte ions are not easy to enter the irregular micropores, so that the effective utilization rate of the surface of the electrode material is reduced. The molecular sieve is taken as the template to prepare the carbon material with large specific surface area and concentrated micropore size distribution, but the template needs to be synthesized in advance, and the yield of the material prepared by the method is low, so that the method is not beneficial to realizing the large-scale preparation of the material. Therefore, it is necessary to develop a microporous carbon material with a large specific surface area and a concentrated pore size distribution, which is easy to prepare.
In order to achieve better electric double layer capacitor performance, an ideal electrode material should have a large number of micropores and diffusion of electrolyte ions inside the micropores is not limited. And heteroatom is introduced into the microporous carbon material, the surface chemistry of the carbon material is directionally modified, the wettability of the material is improved, the utilization rate of micropores is improved, and the conductivity of the material can be improved by doping the heteroatom, so that the rate capability of the material can be improved. Generally, a high carbonization temperature is required for the carbon material to transform from an amorphous structure to a graphitized structure by improving the conductivity of the material, and the increase of the carbonization temperature inevitably causes the sharp reduction of the heteroatoms or the collapse of the microporous structure, which is not beneficial to improving the specific capacity of the material. And metal ions are introduced into the material, and the crystallinity and the conductivity of the material can be improved by utilizing the catalytic graphitization of the metal. In addition, improving the volume specific capacitance of the material without affecting the mass specific capacitance of the material is a great challenge for researchers. Mechanical compaction of carbon materials is an effective method for increasing tap density, but this method only reduces macropores to a certain extent and does not reduce mesopores that do not contribute to capacity. The mesopores can store a large amount of electrolyte, further increasing the quality of the whole device. In another method, the tap density of the material is improved by utilizing the sheet polymerization of graphene oxide prepared by a chemical oxidation method during subsequent drying treatment. However, the preparation process of the method is complex and is not beneficial to realizing industrial production. Therefore, it is necessary to develop a method for simply preparing a highly conductive carbon material having a high skeleton density and being porous.
Based on the above, the invention provides a preparation method for synthesizing microporous carbon with high conductivity, high tap density and high specific surface area, which comprises the steps of mixing a carbon precursor with copper chloride, using CuCl molten salt formed in situ in the heat treatment process as a pore-forming agent to promote the formation of micropores, reducing CuCl into elemental copper by carbon heat with the rise of carbonization temperature, and preparing the material with high conductivity due to the catalytic graphitization of copper. In addition, the density of the simple substance copper is obviously higher than that of the carbon material, the simple substance copper is a good electronic conductor, and the residual part of copper after acid cleaning can not only improve the bulk density of the material, but also improve the conductivity of the material. In addition, if the carbon precursor contains functional groups such as amino groups and carboxyl groups, the functional groups can coordinate with copper ions, and the coordination can reduce the loss of nitrogen during the heat treatment.
Disclosure of Invention
The invention aims to provide microporous carbon with high conductivity, high tap density and high specific surface area and a preparation method thereof. The method is simple and easy to implement, and the prepared carbon material has high conductivity, large tap density and pore size matched with electrolyte ions, and is an ideal electrode material of the super capacitor.
The technical scheme of the invention is as follows:
a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area comprises the following steps:
mixing the carbon precursor with copper salt, and carrying out heat treatment and acid washing on the obtained mixture in an inert atmosphere to obtain the microporous carbon with high specific surface area, high tap density and high conductivity.
The mass ratio of the carbon precursor to the copper salt is 1: 0.2 to 20.
The copper salt is copper chloride.
The carbon precursor is one or more than two of coal pitch, petroleum coke, glucose, sucrose, cellulose, amino acid, polyacrylonitrile, phenolic resin, epoxy resin, styrene resin and ion exchange resin which can pyrolyze the carbon residue in inert atmosphere.
The amino acid is one or more of glutamic acid, aspartic acid, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine and threonine.
The inert atmosphere is nitrogen or argon atmosphere; the heat treatment temperature is 450-1000 ℃, and the heat treatment time is 0.1-4 h.
Mixing the carbon precursor with copper chloride in a mixing mode including dry mixing and wet mixing; dry mixing is to mix the carbon precursor with copper chloride by grinding or ball milling; the wet mixing is to dissolve the carbon precursor and the copper chloride in water, ethanol and/or methanol respectively, and then stir and mix the two solutions; or dissolving one of the carbon precursor and the copper chloride in a certain solvent, and adding the other substance into the solution to be stirred and mixed; the concentration of the carbon precursor in the wet mixing is 0.001-0.1g mL-1，CuCl2The concentration is 0.001-1g mL-1。
The invention has the beneficial effects that: the invention is creatively realized in that the carbon material prepared by the one-step method can realize integration of a plurality of functions, namely high specific surface area, aperture matched with electrolyte ions, high tap density and high conductivity. According to the invention, a carbon precursor and copper chloride are mixed, and after CuCl formed by reduction in the heat treatment process reaches a melting point (426 ℃), a molten salt medium is formed and is uniformly mixed with a carbide intermediate, so that the microporous carbon material with concentrated pore size distribution is synthesized. In addition, Cu species are reduced into elemental copper by carbon heat in the heat treatment processThe catalytic graphitization of which promotes sp2The production of char. And the part of copper coated by the carbon layer is not easy to remove in the pickling process, and the part of copper can promote the improvement of the conductivity and tap density of the material. And the method is simple and feasible and is suitable for large-scale production.
Drawings
FIG. 1 is a nitrogen adsorption curve of the carbon material prepared in example 1 of the present invention.
FIG. 2 shows the carbon material prepared in example 1 of this embodiment in an amount of 6mol L-1The specific capacitance of the KOH electrolyte three-electrode system is changed under different current densities.
Detailed Description
The following examples are further illustrative of the present invention and do not limit the scope of the invention.
Example 1
The embodiment provides a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area, and a complex formed by coordination of L-glutamic acid rich in amino and carboxyl functional groups and copper chloride is used as a carbon precursor. The highly dispersed copper species are thermally reduced into CuCl and elementary copper by in-situ carbon under the high-temperature carbonization condition, and the nitrogen-doped microporous carbon with high conductivity, high tap density and high specific surface area is formed after acid washing. The specific operation steps are as follows:
mixing L-glutamic acid and CuCl with the mass ratio of 1:3.62Respectively dissolving the two solutions in deionized water, uniformly stirring and mixing the two solutions, removing the solvent, and drying to obtain the carbon precursor.
And (3) placing the dried carbon precursor into a high-temperature furnace, heating to 900 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, keeping the temperature for 2 hours at the temperature, and carrying out acid pickling to obtain the carbon material. Fig. 1 is a nitrogen adsorption isotherm of the material, and the curve shows type i distribution, indicating that the material contains a large number of micropores. The specific surface area is as high as 2051m2g-1. The nitrogen content is 3.19% by element analysis, and the tap density is 0.35g cm by tap density tester-3. This example also analyzes the supercapacitor performance of this material. FIG. 2 shows that the amount of microporous carbon material is 6mol L-1Multiple in three electrode system in KOH electrolyteRate capability. At a current density of 0.5A g-1Its specific capacitance value is 273F g-1Current density of 50Ag-1Its specific capacitance value is 188F g-1The capacity retention rate was 69%.
Example 2
The embodiment provides a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area, and a complex formed by coordination of L-glutamic acid rich in amino and carboxyl functional groups and copper chloride is used as a carbon precursor. The highly dispersed copper species are thermally reduced into CuCl and elementary copper by in-situ carbon under the high-temperature carbonization condition, and the nitrogen-doped microporous carbon with high conductivity, high tap density and high specific surface area is formed after acid washing. The specific operation steps are as follows:
mixing L-glutamic acid and CuCl with the mass ratio of 1:1.82Respectively dissolving the two solutions in ethanol, uniformly stirring and mixing the two solutions, removing the solvent and drying to obtain the carbon precursor.
And (3) placing the dried carbon precursor into a high-temperature furnace, heating to 900 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, keeping the temperature for 2 hours at the temperature, and carrying out acid pickling to obtain the nitrogen-doped microporous carbon material. The material has abundant microporous structure, and specific surface area of 1358m2g-1The pore size distribution is concentrated at 0.5nm, 0.8nm, 1.2-1.5 nm. Tap density of 0.45g cm-3.
Example 3
The embodiment provides a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area, and a complex formed by coordination of L-glutamic acid rich in amino and carboxyl functional groups and copper chloride is used as a carbon precursor. The highly dispersed copper species are thermally reduced into CuCl and elementary copper by in-situ carbon under the high-temperature carbonization condition, and the nitrogen-doped microporous carbon with high conductivity, high tap density and high specific surface area is formed after acid washing. The specific operation steps are as follows:
mixing L-glutamic acid and CuCl with the mass ratio of 1:9.12Dissolving in deionized water, mixing the two solutions, and drying.
Placing the dried carbon precursor in a high-temperature furnace, and heating at a temperature rise rate of 5 ℃/min in an argon atmosphereRaising the rate to 900 ℃, keeping the temperature for 2 hours at the temperature, and obtaining the nitrogen-doped microporous carbon material after acid washing. The specific surface area of the material is 3266m2g-1Pore volume of 2.30cm3g-1。
Example 4
The embodiment provides a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area for a supercapacitor, wherein a mixture formed by grinding and mixing lysine and copper chloride is used as a carbon precursor. Under the condition of high-temperature carbonization, copper species are thermally reduced into CuCl and elementary copper in situ, and nitrogen-doped microporous carbon with high conductivity, high tap density and high specific surface area is formed after acid washing. The specific operation steps are as follows:
weighing lysine and CuCl with corresponding mass according to the mass ratio of 1:3.62Grinding and mixing, then placing the obtained mixture in a high-temperature furnace, heating to 900 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, keeping the temperature for 2 hours at the temperature, and carrying out acid pickling to obtain the nitrogen-doped microporous carbon material. The specific surface area is 1169m2g-1。
Example 5
The embodiment provides a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area, and a complex formed by coordination of L-glutamic acid rich in amino and carboxyl functional groups and copper chloride is used as a carbon precursor. The highly dispersed copper species are thermally reduced into CuCl and elementary copper by in-situ carbon under the high-temperature carbonization condition, and the nitrogen-doped microporous carbon with high conductivity, high tap density and high specific surface area is formed after acid washing. The specific operation steps are as follows:
mixing L-glutamic acid and CuCl with the mass ratio of 1:1.82Dissolving in deionized water, mixing the two solutions, and drying.
And (3) placing the dried carbon precursor into a high-temperature furnace, heating to 550 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, keeping the temperature for 2 hours at the temperature, and carrying out acid pickling to obtain the nitrogen-doped microporous carbon material. The specific surface area is 982m2g-1Tap density of 0.57g cm-3.
Example 6
The embodiment provides a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area, wherein phenolic resin and CuCl are weighed according to the mass ratio of 1:42·2H2And (3) ball-milling and mixing for 2h, placing the obtained mixture in a high-temperature furnace, heating to 900 ℃ at the heating rate of 5 ℃/min in an argon atmosphere, keeping the temperature for 2h, and carrying out acid pickling to obtain the microporous carbon material.
The specific operation steps are as follows:
mixing phenolic resin and CuCl in a mass ratio of 1:42·2H2And (3) performing ball milling and mixing on the mixture for 2h, then carbonizing the mixture, heating the mixture to 900 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and keeping the temperature for 2h under the temperature condition to obtain the microporous carbon material. Its specific surface area is 1696m2g-1Pore volume of 0.70cm3g-1。
Example 7
The embodiment provides a preparation method of microporous carbon with high conductivity, high tap density and high specific surface area, and a complex formed by coordination of L-glutamic acid rich in amino and carboxyl functional groups and copper chloride is used as a carbon precursor. The highly dispersed copper species are thermally reduced into CuCl and elementary copper by in-situ carbon under the high-temperature carbonization condition, and the nitrogen-doped microporous carbon with high conductivity, high tap density and high specific surface area is formed after acid washing. The specific operation steps are as follows:
mixing L-glutamic acid and CuCl with the mass ratio of 1:0.92Dissolving in deionized water, mixing the two solutions, and drying.
And (3) placing the dried carbon precursor into a high-temperature furnace, heating to 900 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and keeping the temperature for 2 hours under the temperature condition to obtain the nitrogen-doped microporous carbon material. The specific surface area of which is 527m2g-1The tap density is 0.58g cm-3。
Comparative example 1
This example was heat-treated with glutamic acid as a carbon source in the same manner as in the above example to obtain a nitrogen-doped carbon material. The nitrogen adsorption result shows that the specific surface area is only 39m2g-1。
Comparative example 2
This example uses a phenol resin as a carbon source, and heat-treats it in the same manner as in the above example to obtain a carbon material. The nitrogen adsorption result showed that the specific surface area was 613m2g-1。
Claims (6)
1. A preparation method of microporous carbon with high conductivity, high tap density and high specific surface area is characterized by comprising the following steps:
mixing a carbon precursor with copper salt, and carrying out heat treatment and acid washing on the obtained mixture in an inert atmosphere to obtain the microporous carbon with high specific surface area, high tap density and high conductivity;
the carbon precursor is amino acid or phenolic resin; the copper salt is copper chloride; the heat treatment temperature is 450-1000 ℃, and the heat treatment time is 0.1-4 h.
2. The preparation method according to claim 1, wherein the mass ratio of the carbon precursor to the copper salt is 1: 0.2 to 20.
3. The method according to claim 1, wherein the amino acid is one or a mixture of two or more of glutamic acid, aspartic acid, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine and threonine.
4. The method according to claim 1, 2 or 3, wherein the inert gas atmosphere is nitrogen or argon.
5. The production method according to claim 1, 2 or 3, wherein the carbon precursor is mixed with copper chloride in a manner including dry mixing and wet mixing; dry mixing is to mix the carbon precursor with copper chloride by grinding or ball milling; the wet mixing is to dissolve the carbon precursor and the copper chloride in water, ethanol and/or methanol respectively, and then stir and mix the two solutionsCombining; or dissolving one of the carbon precursor and the copper chloride in a certain solvent, and adding the other substance into the solution to be stirred and mixed; the concentration of the carbon precursor in wet mixing is 0.001-0.1 g/mL-1，CuCl2The concentration is 0.001-1 g/mL-1。
6. The production method according to claim 4, wherein the carbon precursor is mixed with copper chloride in a manner including dry mixing and wet mixing; dry mixing is to mix the carbon precursor with copper chloride by grinding or ball milling; the wet mixing is to dissolve the carbon precursor and the copper chloride in water, ethanol and/or methanol respectively, and then stir and mix the two solutions; or dissolving one of the carbon precursor and the copper chloride in a certain solvent, and adding the other substance into the solution to be stirred and mixed; the concentration of the carbon precursor in wet mixing is 0.001-0.1 g/mL-1，CuCl2The concentration is 0.001-1 g/mL-1。
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