CN108557799B - High-purity high-conductivity graphene-like hierarchical porous carbon and preparation method thereof - Google Patents
High-purity high-conductivity graphene-like hierarchical porous carbon and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-purity high-conductivity graphene-like hierarchical porous carbon and a preparation method thereof. The preparation method provided by the invention is continuous heating, the steps are tightly connected, the heat loss caused by poor connection of the steps in the conventional method is avoided, and the continuous and large-scale production is easy. The obtained carbon material has the characteristics of high specific surface area, adjustable and controllable aperture and the like, and the carbon skeleton is of a graphene-like structure beneficial to electronic conduction, can give consideration to the dual characteristics of high mass transfer and high conduction, and has the advantages of good thermal shock resistance, strong mechanical strength and the like. Can be applied to the fields of high-efficiency heat dissipation, electrode materials, conductive agents, catalyst carriers and the like.
Description
Technical Field
The invention relates to high-purity high-conductivity graphene-like hierarchical porous carbon and a preparation method thereof, belonging to the field of new materials.
Background
The porous carbon has the characteristics of large specific surface area, adjustable pore structure and interface property, good chemical stability and the like, and the conductivity of the porous carbon can realize the conversion from a semiconductor to a superconductor, and the porous carbon is applied to the fields of new energy, environmental protection, gas separation and storage, drug carriers, catalyst carriers and the like. However, the high porosity and high electronic conductivity of the porous carbon are difficult to be unified on the same porous carbon material. If the conductivity of the commercial activated carbon material with high porosity is about 4us/m, the conductivity of various porous carbon materials reported in the literature is basically less than 100 us/m; and the carbon materials with high conductivity, namely graphene (1u omega.m), carbon nano tubes, graphite electrodes (5.5-9u omega.m), carbon fibers (16-900u omega.m), prebaked anodes (55-60u omega.m), self-baked anodes (70-80u omega.m) and calcined petroleum coke with few pores (about 500u omega.m) basically only contain a few defective pores. In particular fields, such as those requiring convenient particle transport paths and facilitating rapid transfer of electrons, such carbon materials would be insufficient.
To achieve high porosity in carbon materials, more carbon is required to be etched into the pores, at which point the carbon skeleton is weakened. And the electron conductivity of the carbon material is reduced along with the increase of the porosity, and the porous carbon material structure is basically amorphous, so that the structure is not beneficial to the transmission of electrons on the carbon skeleton. The highly conductive carbon material generally has an extremely low porosity, and the elongation of the electron transport path due to the vacancy is impaired. The carbon material with higher conductivity is basically of a graphite structure or a graphite-like structure, the regular structure is convenient for the transmission of electrons, and the two-dimensional sheet structure can construct delocalized pi bonds to improve the transmission rate of the electrons. But the formation of this structure requires graphitization or graphitization.
The porous carbon is graphitized, the graphitization degree of the framework is increased, and the method is a method for effectively improving the conductivity. But the conventional practice is: the porous carbon is prepared firstly, and then graphitizing treatment is carried out, so that the two processes are manually separated, the process flow is increased, and the energy consumption is greatly increased and the operation complexity is greatly reduced. In a preparation method for synthesizing a graphitized porous carbon material by taking activated carbon as a raw material (CN 103318871A), the activated carbon is taken as the raw material, the dispersion of the porous carbon and the complexation of a catalyst are realized in a liquid environment, although the graphitization at a lower temperature is realized, the operation in a solution system is complex, the large-scale production is difficult, and the problem that the catalyst is difficult to remove cleanly is also existed. A method for improving the electric conductivity of activated carbon for purifying petroleum coke-based super capacitors (CN 106744945A) comprises the steps of preparing porous carbon by using petroleum coke as a raw material through a chemical activation method, then further increasing the temperature, gasifying and removing metal impurities with high boiling point, and obtaining the high-purity and high-electric conductivity porous carbon by means of a mechanism of carbide generation-decomposition or dissolution-re-precipitation. However, the method needs high temperature of more than 2000 ℃, has high energy consumption and high equipment requirement, and the reaction process is discontinuous, thereby causing energy consumption waste.
Disclosure of Invention
The invention aims to solve the problem that the high porosity and the high electronic conductivity of a carbon material are difficult to be compatible in the application of the cross field, and provides high-purity high-conductivity graphene-like hierarchical porous carbon which can be produced in a large scale, has the dual characteristics of high mass transfer and high conductivity, and has the advantages of good thermal shock resistance, strong mechanical strength and the like, and a preparation method thereof. Thereby expanding the application field of the novel carbon material and meeting the requirements of special fields on the carbon material.
The technical scheme of the invention is as follows:
a high-purity high-conductivity graphene-like hierarchical porous carbon is prepared by taking a substance with high carbon content as a precursor, and directly performing pore forming, catalytic graphitization and/or aftertreatment to obtain the porous carbon.
A preparation method of high-purity high-conductivity graphene-like hierarchical pore porous carbon comprises the steps of taking a substance with high carbon content as a precursor, adding a pore-forming agent and a catalyst, directly forming pores, carrying out catalytic graphitization and/or aftertreatment, cleaning to be neutral, and drying to obtain the porous carbon.
The high carbon content material is one or more of petroleum coke, pitch coke, coal coke, polyvinyl chloride based carbon, mesocarbon microbeads and carbon fibers.
The mol ratio of the pore-forming agent to the precursor is (0.01-15): 1; the pore-forming agent is sodium hydroxide, potassium oxide, sodium oxide, zinc oxide, potassium salt, sodium salt, zinc salt, or H2O、CO2One or more of them.
The conditions for direct pore forming are as follows: heating to 950 ℃ under the atmosphere A, and keeping the temperature for 0.01 to 10 hours at the heating rate of 0.1 to 50 ℃/min; the atmosphere A is one or more of argon, nitrogen, helium and vacuum.
The molar ratio of the catalyst to the precursor is (0.01-10): 1; the catalyst is one or more of ferric chloride, ferric oxide, ferric nitrate, nickel chloride, nickel oxide, nickel nitrate, nickel carbonate, cobalt chloride, cobalt oxide, cobalt nitrate and cobalt carbonate.
The conditions for catalytic graphitization are as follows: heating to 950-1800 ℃ in the atmosphere B, and keeping the temperature for 0-12h, wherein the heating rate is 0.1-50 ℃/min; the atmosphere B is one or more of argon, nitrogen, helium, chlorine and gaseous silicon tetrachloride.
The post-treatment is one or two of atmosphere heating and solution reaction.
The method for heating the atmosphere comprises the following steps: preserving the heat for 1-3h at the temperature of 950-1800 ℃ in the atmosphere of C; the atmosphere C is one or more of argon, nitrogen, helium, chlorine and gaseous silicon tetrachloride.
The solution reaction method comprises the following steps: acid washing or alkali washing, or acid-alkali alternate immersion washing.
The invention has the beneficial effects that:
according to the method, the high-carbon-content material is used as a precursor, pore-forming and graphitization are realized in the same reactor, the process flow is shortened, meanwhile, the use of the catalyst can reduce the graphitization temperature, and an impurity removal mechanism is constructed. The preparation method provided by the invention is continuous heating, the steps are tightly connected, the heat loss caused by poor connection of the steps in the conventional method is avoided, and the continuous and large-scale production is easy. The method can effectively improve the porosity, the conductivity and the purity of the carbon material, and is a simple and efficient preparation method of the porous carbon with both high porosity and high conductivity.
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. The following examples are intended to illustrate the invention without further limiting it, which can be carried out in any of the ways described in the summary of the invention.
Example 1
Petroleum coke, potassium hydroxide and ferric nitrate are mixed according to a molar ratio of 1: 3: 0.05 percent of the mixture is put into a nickel crucible, then the nickel crucible is put into a high-temperature atmosphere furnace, nitrogen with the volume of 200ccm is introduced, the temperature is raised to 850 ℃ at the speed of 2 ℃/min, the temperature is kept for 1h, then chlorine with the volume of 30ccm is added, the temperature is raised at the speed of 5 ℃/minKeeping the temperature for 4h when the temperature is 1350 ℃, stopping introducing chlorine (continuously introducing nitrogen), naturally cooling to room temperature, immersing the obtained product in 0.05M HCl solution for 1h, taking out the product, cleaning the product to be neutral by deionized water, and drying the product in an oven at 80 ℃ for 8h to obtain the product with the ash content of 0.06%, the conductivity of 10S/cm and the specific surface area of 1370M2Graphene-like hierarchical porous carbon per gram.
Example 2
Mixing asphalt coke, sodium oxide and nickel chloride according to a molar ratio of 1: 3: 0.02 mixing, placing into a nickel crucible, then placing into a high-temperature atmosphere furnace, introducing nitrogen gas of 600ccm, heating to 750 ℃ at the speed of 2 ℃/min, keeping the temperature for 2h, then adding chlorine gas of 60ccm, heating to 1550 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping introducing the chlorine gas (continuously introducing the nitrogen gas), naturally cooling to room temperature, immersing the obtained product into 0.1M HCl solution for 0.5h, taking out, washing to be neutral by deionized water, and drying in a vacuum drying oven at the temperature of 100 ℃ for 4h to obtain the product with the ash content of 0.09%, the Franklin P value of 0.404 and the specific surface area of 1150M2Graphene-like hierarchical porous carbon per gram.
Example 3
Coal coke and nickel chloride are mixed according to a molar ratio of 1: 0.02 mixing, placing into a nickel crucible, placing into a high temperature atmosphere furnace, introducing 600ccm nitrogen and 45ccm CO2Heating to 700 deg.C at a rate of 10 deg.C/min, maintaining for 5 hr, and stopping introducing CO2Adding 20ccm chlorine, heating to 1650 deg.C at 10 deg.C/min, maintaining for 2 hr, stopping introducing chlorine (introducing nitrogen), naturally cooling to room temperature, and soaking the product in 0.5M HNO3Taking out the solution for 0.5h, washing with deionized water to neutrality, and vacuum drying at 100 deg.C for 2h to obtain the final product with ash content of 0.045%, Franklin P value of 0.37, and specific surface area of 850m2Graphene-like hierarchical porous carbon per gram.
Example 4
Petroleum coke, zinc chloride and ferric nitrate are mixed according to a mol ratio of 1: 5: 0.01, placing the mixture into a nickel crucible, then placing the nickel crucible into a high-temperature atmosphere furnace, introducing 60ccm nitrogen, raising the temperature to 950 ℃ at the rate of 2 ℃/min, preserving the heat for 0.5h, then adding 30ccm chlorine, raising the temperature to 1800 ℃ at the rate of 5 ℃/min, preserving the heat for 4h, and stopping introducing the chlorine (continuously introducing the chlorine)Nitrogen gas) and naturally cooled to room temperature, and the resultant was immersed in 1..5M HNO3Taking out the solution for 1h, washing the solution to be neutral by deionized water, and drying the solution in a drying oven at the temperature of 80 ℃ for 8h to obtain the product with the ash content of 0.06%, the conductivity of 15S/cm and the specific surface area of 850m2Graphene-like hierarchical porous carbon per gram.
Example 5
Mixing mesocarbon microbeads, potassium carbonate and ferric nitrate according to a molar ratio of 1: 3: 0.07 mixing, putting into a nickel crucible, then putting into a high-temperature atmosphere furnace, introducing 100ccm nitrogen, heating to 750 ℃ at 10 ℃/min, keeping the temperature for 2h, heating to 1800 ℃ at 5 ℃/min, then introducing 50ccm gaseous silicon tetrachloride, keeping the temperature for 2h, then adding 30ccm chlorine, keeping the temperature for 1h, then stopping introducing the chlorine and the gaseous silicon tetrachloride (continuously introducing the nitrogen), naturally cooling to room temperature, immersing the obtained product into 0.5M HCl solution for 4h, then taking out, washing with deionized water to be neutral, and drying in an oven at 80 ℃ for 8h to obtain the product with the ash content of 0.07%, the conductivity of 20S/cm and the specific surface area of 950M2Graphene-like hierarchical porous carbon per gram.
Example 6
Polyvinyl chloride carbon, potassium hydroxide and cobalt nitrate are mixed according to a molar ratio of 1: 7: 0.03 mixing, putting into a nickel crucible, then putting into a high-temperature atmosphere furnace, introducing 150ccm nitrogen, heating to 850 ℃ at 20 ℃/min, keeping the temperature for 1.5h, adding 30ccm chlorine, heating to 1550 ℃ at 5 ℃/min, keeping the temperature for 6h, stopping introducing the chlorine (continuing introducing the nitrogen), naturally cooling to room temperature, immersing the obtained product into 0.05M HCl solution for 1h, taking out, washing to be neutral by deionized water, and drying in a 110 ℃ oven for 8h to obtain the product with the ash content of 0.045%, the conductivity of 7.6S/cm and the specific surface area of 1870M2Graphene-like hierarchical porous carbon per gram.
Claims (6)
1. A preparation method of high-purity high-conductivity graphene-like hierarchical porous carbon is characterized in that a substance with high carbon content is used as a precursor, a pore-forming agent and a catalyst are added, and after direct pore-forming, catalytic graphitization and/or post-treatment, the porous carbon is cleaned to be neutral and dried to obtain the porous carbon; the high carbon content substance is one or more of petroleum coke, pitch coke, coal coke, polyvinyl chloride based carbon, mesocarbon microbeads and carbon fibers;
the conditions for direct pore forming are as follows: heating to 950 ℃ under the atmosphere A, and keeping the temperature for 0.01 to 10 hours at the heating rate of 0.1 to 50 ℃/min; the atmosphere A is one or more of argon, nitrogen, helium and vacuum; the pore-forming agent is sodium hydroxide, potassium hydroxide, sodium oxide, sodium salt, zinc salt, or H2O、CO2One or more of the above;
the conditions for catalytic graphitization are as follows: heating to 950-1800 ℃ in the atmosphere B, and keeping the temperature for 0-12h, wherein the heating rate is 0.1-50 ℃/min; the atmosphere B is one or more of argon, nitrogen, helium, chlorine and gaseous silicon tetrachloride; the catalyst is one or more of ferric chloride, ferric nitrate, nickel chloride, nickel oxide, nickel nitrate, nickel carbonate, cobalt chloride, cobalt oxide, cobalt nitrate and cobalt carbonate.
2. The preparation method of the high-purity high-conductivity graphene-like hierarchical porous carbon according to claim 1, wherein the molar ratio of the pore-forming agent to the precursor is (0.01-15): 1.
3. the method for preparing the high-purity high-conductivity graphene-like hierarchical porous carbon according to claim 1, wherein the molar ratio of the catalyst to the precursor is (0.01-10): 1.
4. the method for preparing the high-purity high-conductivity graphene-like hierarchical porous carbon according to claim 1, wherein the post-treatment is one or both of atmosphere heating and solution reaction.
5. The method for preparing the high-purity high-conductivity graphene-like hierarchical porous carbon according to claim 4, wherein the method for heating the atmosphere comprises the following steps: preserving the heat for 1-3h at the temperature of 950-1800 ℃ in the atmosphere of C; the atmosphere C is one or more of argon, nitrogen, helium, chlorine and gaseous silicon tetrachloride.
6. The method for preparing the high-purity high-conductivity graphene-like hierarchical porous carbon according to claim 5, wherein the solution reaction method comprises the following steps: acid washing or alkali washing, or acid-alkali alternate immersion washing.
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| CN109850888A (en) * | 2019-01-31 | 2019-06-07 | 西安科技大学 | A kind of method of semicoke sub-prime coproduction porous activated carbon and class graphene aerogel |
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| CN113871590B (en) * | 2021-09-16 | 2023-01-13 | 广东凯金新能源科技股份有限公司 | Layered porous graphite negative electrode material and preparation method thereof |
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