CN110817835A - Porous carbon material and preparation method thereof - Google Patents
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Abstract
The invention relates to a porous carbon material and a preparation method thereof, wherein the preparation method comprises the following steps: adding a boron source into a mixed solution containing thermosetting resin, an organic solvent and a curing agent by adopting an organic matter polymerization phase separation carbonization method, and heating and curing to obtain a cured product; and placing the obtained cured product in an inert atmosphere, and performing high-temperature treatment at 700-1200 ℃ to obtain the porous carbon material.
Description
Technical Field
The invention relates to a preparation technology of a carbon material, in particular to a preparation method of a porous carbon material, and belongs to the field of preparation of carbon materials.
Background
The porous carbon material is a carbon functional material with excellent pore structure, has the advantages of high specific surface area, good conductivity, high porosity, good chemical stability and the like, and is widely applied to the fields of fuel cells, gas adsorption separation, supercapacitors, prefabricated bodies required by carbide ceramic preparation and the like. The pore structure characteristics determine the effective performance and the application range of the material to a certain extent. Such as: in the preparation of the carbide ceramic with the complex shape by taking the porous carbon as the preform, the pore structure has great influence on the comprehensive performance of the final ceramic part, so that the control of the pore structure and the pore characteristic parameters of the porous carbon has important significance.
At present, the preparation method of the porous carbon material which is commonly used comprises the following steps: (1) physical/chemical activation methods; (2) hard/soft template method; (3) polymerization induced phase separation method. Compared with other two methods, the polymerization-induced phase separation method has the advantages of simple process, low cost, easy industrial production and the like. Among them, U.S. Pat. No. 4, 3859421,1975 (U.S.) used this method to prepare porous carbon from a finished furfuryl alcohol resin as a carbon source. The Wangbun incense (Carbon, 2003,41: 2065-. Chinese patent (application No. 200710018125.7) synthesizes porous carbon by using finished thermosetting phenolic resin (industrial grade 2130#) as a carbon source, and realizes the cutting of the porous carbon pore characteristics by adjusting process parameters. Chinese patent (application No. 201610052368.1) regulates the porous carbon pore characteristics by regulating the molecular structure, viscosity, water content, gelation time and other characteristics of the thermosetting phenolic resin precursor.
Disclosure of Invention
The invention provides a preparation method of a porous carbon material, which comprises the following steps:
adding a boron source into a mixed solution containing thermosetting resin, an organic solvent and a curing agent by adopting an organic matter polymerization phase separation carbonization method, and heating and curing to obtain a cured product (boron-doped organic resin);
and placing the obtained cured product in an inert atmosphere, and performing high-temperature treatment at 700-1200 ℃ to obtain the porous carbon material.
The invention takes thermosetting resin as carbon source, organic solvent as pore former, boron source as complexing agent for the first time, and organic matter is utilized to polymerizeAnd preparing the porous carbon material by an induced phase separation carbonization method. Specifically, the boron source is added into the organic solution of thermosetting resin for heating and curing, and the boron source (such as boric acid and/or borate) and the compound in the thermosetting resin are subjected to crosslinking reaction because the boron source contains B (OH)4 -The root ions exist, the root ions react with the hydroxymethyl in the thermosetting resin to remove a molecule of water, participate in the formation of a polymer, obtain a latticed high polymer with higher molecular weight, increase a solidified solvent-rich phase, and combine with a polymerization induced phase separation method (high-temperature heat treatment at 700-1200 ℃ in an inert atmosphere) to crack the thermosetting resin into carbon to obtain the porous carbon material, and the porous carbon pore characteristics can be regulated and controlled by changing the addition amount of a boron source and other process parameters.
Preferably, the boron source is boric acid and/or a borate, and the borate is at least one of ammonium borate, sodium borate and potassium borate; the thermosetting resin is at least one of phenolic resin, furfuryl alcohol resin, vinyl ester and polyimide resin.
Preferably, the organic solvent is an alcohol, preferably at least one of ethanol, ethylene glycol, polyethylene glycol, diethylene glycol and triethylene glycol.
Preferably, the mass ratio of the thermosetting resin to the organic solvent is (20-70): (80-30). In this ratio range, porous carbon having a stable carbon skeleton can be obtained.
Preferably, the boron source is added in an amount of 0.1 to 10wt%, preferably 0.5 to 5wt%, and more preferably 1.5 to 5wt% of the total mass of the thermosetting resin and the organic solvent. The pore size distribution of the porous carbon can be effectively adjusted in the range, and the porous carbon material with the pore size distribution in the range of 25nm-2754nm is obtained.
Preferably, the addition amount of the curing agent is 2-10% of the total mass of the thermosetting resin and the organic solvent; preferably, the curing agent is at least one of benzene sulfonyl chloride, hexamethylenetetramine, m-diphenylamine and p-toluenesulfonyl chloride.
Preferably, the heat curing regime comprises: firstly, preserving heat for 4-8 hours at 80-100 ℃, then heating to 160-200 ℃ and preserving heat for 6-12 hours; preferably, the rate of temperature rise is 20 ℃ every 2 hours.
Preferably, the inert atmosphere is at least one of nitrogen, argon and helium.
Preferably, the time of the high-temperature treatment is 0.5 to 2 hours.
In another aspect, the invention also provides a porous carbon material prepared according to the preparation method, wherein the average pore diameter of the porous carbon material is 25 nm-5 μm.
The invention adopts an organic matter polymerization induction phase separation carbonization method, and utilizes a boron source (such as boric acid, ammonium borate, sodium borate, potassium borate and the like) to generate a complex effect with thermosetting resin, thereby regulating and controlling the pore characteristics of porous carbon obtained by preparing thermosetting resin (such as phenolic resin and the like), and providing a method for preparing the porous carbon material with controllable pore diameter and pore volume distribution and simple preparation process.
According to the invention, the pore structure characteristics of thermosetting resin-based porous carbon are regulated by adding a boron source (such as boric acid, ammonium borate, sodium borate, potassium borate and the like). Compared with the prior art, the boric acid is used for carrying out a complexing reaction with a compound in the thermosetting resin to participate in the formation of a polymer to form a boron-doped organic resin, so that a high polymer with higher molecular weight is obtained, a latticed structure is more favorably formed, a solvent-rich phase after solidification is increased, the pore characteristics such as the pore size distribution of the cracked porous carbon material and the like are regulated in a large range, the average pore size of the obtained porous carbon material is 25 nm-5 mu m, and the application range of the porous carbon material is widened. The preparation method of the porous carbon material can effectively control the pore size void distribution of the prepared porous carbon material, realizes pore size regulation and pore structure optimization in a larger range, has low requirement on equipment in the preparation process, and has the characteristics of low cost, easy industrial production and the like. Due to the large-range controllability of the pore diameter, massive porous carbon used in the fields of water purification, catalytic adsorption and the like can be prepared, or a prefabricated body of carbide engineering ceramic with a complex shape can be prepared, and the requirements of numerous application fields can be met.
Drawings
FIG. 1 is a microscopic structural view of a porous carbon prepared in example 2 of the present invention;
FIG. 2 is a microscopic structural view of the porous carbon prepared in example 3 of the present invention;
FIG. 3 is a pore size distribution diagram of porous carbons prepared in examples 1 to 5 of the present invention and comparative example 1;
fig. 4 is a microscopic structural view of the porous carbon prepared in comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The invention takes thermosetting resin as a carbon source, an organic solvent as a pore forming agent and a boron source (such as boric acid and the like) as a complexing agent, and obtains the porous carbon material by a phase separation method of complexation reaction and organic polymerization. Specifically, boric acid is added into a thermosetting resin/organic solvent solution, the mixture is uniformly mixed by magnetic stirring, the mixture is heated and cured at a certain temperature and then is subjected to high-temperature heat treatment under the protection of inert atmosphere, a boron source and a compound in the thermosetting resin are subjected to a complexing reaction to participate in the formation of a polymer to form boron-doped organic resin, a high polymer with higher molecular weight is obtained, a grid-shaped structure is more favorably formed, and a solvent-rich phase after curing is increased, so that the pore characteristics such as pore size distribution and the like of the cracked porous carbon material are regulated and controlled in a large range.
In the disclosure, an organic polymer phase separation carbonization method is adopted, and by utilizing the characteristic that a boron source can be crosslinked with a thermosetting resin in a curing stage to generate a grid structure, the separation of the resin from an organic solvent after polymerization is promoted, namely, more alcohol-rich phases are generated in the curing stage, so that the alcohol-rich phases can be volatilized to generate larger pore diameters, and the carbonized porous carbon material can generate larger pore diameters. The following is an exemplary description of the method for preparing the porous carbon material with controllable pore size by using boron source complexation reaction provided by the present invention.
A boron source (e.g., boric acid, ammonium borate, sodium borate, potassium borate, etc.) is added to the mixed solution of the phenol resin and the organic solvent, and uniformly mixed to obtain a mixed solution. In an alternative embodiment, the thermosetting resin is at least one of a phenol resin, a furfuryl alcohol resin, a vinyl ester, and a polyimide resin, and more preferably a phenol resin, a furfuryl alcohol resin, and the like. In an optional embodiment, the addition amount of the curing agent is 2-10% of the total mass of the thermosetting resin and the organic solvent. The curing agent is at least one selected from benzene sulfonyl chloride, hexamethylene tetraethyl amine, m-diphenylamine and p-toluene sulfonyl chloride. In an alternative embodiment, the organic solvent may be an alcohol, preferably at least one of ethanol, ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol. In an optional embodiment, the mass ratio of the phenolic resin to the organic solvent can be 20-70: 80-30 parts. In an alternative embodiment, the added mass of the boron source is 0.1 to 10wt%, preferably 0.5 to 5wt% of the total mass of the thermosetting resin and the organic solvent.
And heating and curing the mixed solution to obtain the boron-doped organic resin. In alternative embodiments, the temperature regime for heat curing is: firstly, heating the mixture to 80-100 ℃, preserving heat for 6 hours, then heating the mixture from 80-100 ℃ to 160-200 ℃, and preserving heat for 6-12 hours. Wherein the temperature is raised from 80-100 ℃ to 160-200 ℃ by a temperature raising mechanism of 20 ℃ every 2 hours.
And carrying out high-temperature treatment on the boron-doped organic resin to obtain the porous carbon material. In an alternative embodiment, the high temperature treatment regimen comprises: heat-treating at 700-1200 deg.C for 0.5-2 hours in inert atmosphere. The inert atmosphere includes nitrogen, argon, helium, and the like.
The average pore diameter of the porous carbon material is measured by a mercury porosimeter. The porous carbon pore structure after pyrolysis can be controlled by controlling the content of the boron source, the distribution density of the complexing points of the boron source (such as boric acid) and the polymerization speed of the thermosetting resin. The boron sources with different contents and the compounds in the thermosetting resin have different degrees of complex reaction, more boron sources enable the molecular weight of the complex product of the thermosetting resin to be higher, the polymerization degree of the thermosetting resin is higher, the corresponding solvent-rich phase generating area is higher, and the higher degree of complex and more solvent-rich phases can obtain larger pore diameter and poresThe volume (for example, it can be 0.28-0.8 cm)3/g)。
According to the invention, through the complexing reaction of the boron source and the thermosetting resin in the curing process, the pore size distribution of the prepared porous carbon material can be effectively controlled, the average pore size of the porous carbon material can be regulated and controlled to be 25 nm-5 mu m, the application range of the porous carbon material is widened, the preparation process has low requirements on equipment, and the porous carbon material has the characteristics of low cost, easiness in industrial production and the like.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Selecting phenolic resin and ethylene glycol, and mixing the following components in percentage by weight: weighing 50 percent of ethylene glycol and 50 percent of boric acid by weight, adding 0.5 percent of boric acid by weight and 8 percent of hexamethylene tetraethyl amine by weight, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. And respectively analyzing the pore size distribution and the microstructure diagram of the scanning electron microscope of the sample. The pore size distribution was measured by mercury porosimetry, resulting in an average pore size of 25nm, and the pore size distribution is shown in FIG. 3.
Example 2
Selecting phenolic resin and ethylene glycol, and mixing the following components in percentage by weight: weighing 50 percent of ethylene glycol and 50 percent of boric acid by weight, adding 1.5 percent of boric acid by weight and 8 percent of hexamethylene tetraethyl amine by weight, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. And respectively analyzing the pore size distribution and the microstructure diagram of the scanning electron microscope of the sample. The pore size distribution was measured by mercury porosimetry, resulting in an average pore size of 642nm, with the pore size distribution shown in FIG. 3; the porous carbon pore structure is obtained by scanning electron microscope microstructure analysis, and as shown in fig. 1, the porous carbon thereof generates three-dimensional interconnected pores.
Example 3
Selecting phenolic resin and ethylene glycol, and mixing the following components in percentage by weight: weighing 50 percent of ethylene glycol, adding 2.5 percent of boric acid and 8 percent of hexamethylene tetraethyl amine, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. And respectively analyzing the pore size distribution and the microstructure diagram of the scanning electron microscope of the sample. The pore size distribution was measured by mercury intrusion porosimetry, resulting in an average pore size of 1552nm and a pore size distribution as shown in FIG. 3. The porous carbon pore structure is obtained by scanning electron microscope microstructure analysis, and as shown in fig. 2, the porous carbon thereof generates three-dimensional interconnected pores.
Example 4
Selecting phenolic resin and ethylene glycol, and mixing the following components in percentage by weight: weighing 50 percent of ethylene glycol and 50 percent of boric acid by weight, adding 3.5 percent of boric acid by weight and 8 percent of hexamethylene tetraethyl amine by weight, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. And respectively analyzing the pore size distribution and the microstructure diagram of the scanning electron microscope of the sample. The pore size distribution was measured by mercury intrusion porosimetry to give an average pore size of 2363nm and the pore size distribution is shown in FIG. 3.
Example 5
Selecting phenolic resin and ethylene glycol, and mixing the following components in percentage by weight: weighing 50 percent of ethylene glycol and 50 percent of boric acid, adding 5 percent of boric acid and 8 percent of hexamethylene tetraethyl amine, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. And respectively analyzing the pore size distribution and the microstructure diagram of the scanning electron microscope of the sample. The pore size distribution was measured by mercury intrusion porosimetry to give an average pore size of 2754nm, and the pore size distribution is shown in FIG. 3.
Example 6
Selecting furfuryl alcohol resin and ethylene glycol according to the following ratio: weighing 50 percent of ethylene glycol and 50 percent of boric acid by weight, adding 1.5 percent of boric acid by weight and 8 percent of hexamethylene tetraethyl amine by weight, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. The average pore diameter of the obtained porous carbon was 745 nm.
Example 7
Selecting phenolic resin and polyethylene glycol (molecular weight is 200), and mixing the following components according to the weight ratio of the phenolic resin: weighing 50 weight percent of polyethylene glycol, adding 1.5 weight percent of boric acid and 8 weight percent of hexamethylene tetraethyl amine, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. The average pore diameter of the porous carbon obtained was 450 nm.
Example 8
Selecting phenolic resin and diethylene glycol, and mixing the following components in percentage by weight: weighing 50 weight percent of diethylene glycol, adding 1.5 weight percent of boric acid and 8 weight percent of hexamethylene tetraethyl amine, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. The average pore diameter of the resulting porous carbon was 250 nm.
Example 9
Selecting phenolic resin and ethylene glycol, and mixing the following components in percentage by weight: weighing 25 percent by weight of ethylene glycol and 75 percent by weight of boric acid, adding 8 percent by weight of hexamethylene tetraethyl amine, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. The average pore diameter of the obtained porous carbon is 1245 nm.
Example 10
Selecting phenolic resin and ethylene glycol, and mixing the following components in percentage by weight: weighing 60 percent by weight of ethylene glycol and 40 percent by weight of boric acid, adding 1.5 percent by weight of hexamethylene tetraethyl amine and 8 percent by weight of hexamethylene tetraethyl amine, and uniformly mixing by magnetic stirring to prepare a colloidal resin mixture. Pouring the obtained mixed solution into a mould, heating the mixture to 100 ℃, and keeping the temperature for 8 hours to perform polycondensation reaction; then raising the temperature from 100 ℃ to 200 ℃, preserving the temperature for 8 hours, and volatilizing and discharging the solvent-rich phase. The temperature rise mechanism adopted for raising the temperature from 100 ℃ to 200 ℃ is that the temperature rises by 20 ℃ every 2 hours. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 1000 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. The porous carbon obtained had a mean pore diameter of 489 nm.
Comparative example 1
According to the following phenolic resin: weighing 50 percent by weight of ethylene glycol, placing the ethylene glycol in a magnetic stirrer, and magnetically stirring the mixture for 30min at the rotating speed of 300r/min to uniformly mix the ethylene glycol and the ethylene glycol. Pouring the obtained solution into a mold, heating and curing at 90 ℃ for 6h, and demolding. And (3) placing the demoulded sample in a graphite crucible, placing the crucible in a graphite furnace, heating to 900 ℃ at the heating rate of 2 ℃/min under the protection of argon atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the porous carbon. And respectively carrying out pore size and pore volume distribution and scanning electron microscope microstructure diagram analysis on the sample. The pore size distribution was measured by mercury porosimetry, the resulting average pore size was 13nm, and the pore size distribution is shown in FIG. 3; the resulting porous carbon microstructure is shown in fig. 4.
Table 1 shows relevant parameters of the porous carbon materials prepared in examples 1 to 10 and comparative example 1 of the present invention:
(Note: the "mass ratio" in Table 1 is the mass ratio of the thermosetting resin and the organic solvent).
Comparative examples 1 to 5 show that: under the condition that other parameters are the same, porous carbon materials obtained by selecting different boric acid addition amounts have different porous characteristics, and the average pore diameter is gradually increased along with the increase of the boric acid content. Comparing examples 2, 7 and 8, it can be seen that: with the other parameters being the same, the average pore size of the resulting carbon material gradually decreases as the molecular weight of the solvent used increases, mainly because the high molecular weight solvent has a greater concentration during curing, making polymerization-induced phase separation more difficult to perform. Comparing examples 2, 9 and 10, it can be seen that: under the condition that other parameters are the same, the average pore diameter and the pore volume of the obtained carbon material are increased along with the reduction of the thermosetting resin, and the content of the phenolic resin is reduced, so that the residual carbon content after high-temperature cracking is reduced, the carbon in the carbon skeleton is reduced, and the porous carbon with larger pore diameter and pore volume is obtained. In general, boric acid and a compound in thermosetting resin are subjected to a complexing reaction to participate in the formation of a polymer to form boron-doped organic resin, so that a high polymer with higher molecular weight is obtained, a latticed structure is more favorably formed, and a solvent-rich phase after solidification is increased, so that the pore characteristics such as the pore size distribution and the like of the cracked porous carbon material are regulated and controlled in a large range.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for producing a porous carbon material, comprising:
adding a boron source into a mixed solution containing thermosetting resin, an organic solvent and a curing agent by adopting an organic matter polymerization phase separation carbonization method, and heating and curing to obtain a cured product;
and placing the obtained cured product in an inert atmosphere, and performing high-temperature treatment at 700-1200 ℃ to obtain the porous carbon material.
2. The method of claim 1, wherein the boron source is boric acid and/or a borate salt, and the borate salt is at least one of ammonium borate, sodium borate, and potassium borate; the thermosetting resin is at least one of phenolic resin, furfuryl alcohol resin, vinyl ester and polyimide resin.
3. The method according to claim 1 or 2, wherein the organic solvent is an alcohol, preferably at least one of ethanol, ethylene glycol, polyethylene glycol, diethylene glycol, and triethylene glycol.
4. The production method according to any one of claims 1 to 3, wherein the mass ratio of the thermosetting resin to the organic solvent is (20 to 70): (80-30).
5. The production method according to any one of claims 1 to 4, wherein the boron source is added in an amount of 0.1 to 10wt%, preferably 0.5 to 5wt%, more preferably 1.5 to 5wt% of the total mass of the thermosetting resin and the organic solvent.
6. The preparation method according to any one of claims 1 to 5, wherein the addition amount of the curing agent is 2 to 10% of the total mass of the thermosetting resin and the organic solvent; preferably, the curing agent is at least one of benzene sulfonyl chloride, hexamethylenetetramine, m-diphenylamine and p-toluenesulfonyl chloride.
7. The production method according to any one of claims 1 to 6, wherein the heat curing system comprises: firstly, preserving heat for 4-8 hours at 80-100 ℃, then heating to 160-200 ℃ and preserving heat for 6-12 hours; preferably, the rate of temperature rise is 20 ℃ every 2 hours.
8. The method according to any one of claims 1 to 7, wherein the inert gas atmosphere is at least one of nitrogen, argon and helium.
9. The method according to any one of claims 1 to 8, wherein the high-temperature treatment is carried out for 0.5 to 2 hours.
10. A porous carbon material produced by the production method according to any one of claims 1 to 9, characterized in that the average pore diameter of the porous carbon material is 25nm to 5 μm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074095A (en) * | 2007-06-26 | 2007-11-21 | 西安交通大学 | Production of porous-carbon material |
| US20150344316A1 (en) * | 2012-09-05 | 2015-12-03 | Toyo Tanso Co., Ltd. | Porous carbon and method of manufacturing same |
| CN105671693A (en) * | 2016-01-25 | 2016-06-15 | 新余学院 | Preparation method of fibrous porous carbon material containing axial macropores |
| CN105776177A (en) * | 2016-03-11 | 2016-07-20 | 北京化工大学 | Laminar boron-doped ordered mesoporous carbon and preparation method thereof |
| CN106589801A (en) * | 2016-12-23 | 2017-04-26 | 昌吉学院 | Synthetic method for high-oxygen index phenolic resin |
| CN107720724A (en) * | 2017-11-16 | 2018-02-23 | 西安交通大学 | A kind of high surface area nano-porous carbon material and preparation method thereof |
-
2018
- 2018-08-14 CN CN201810922755.5A patent/CN110817835A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074095A (en) * | 2007-06-26 | 2007-11-21 | 西安交通大学 | Production of porous-carbon material |
| US20150344316A1 (en) * | 2012-09-05 | 2015-12-03 | Toyo Tanso Co., Ltd. | Porous carbon and method of manufacturing same |
| CN105671693A (en) * | 2016-01-25 | 2016-06-15 | 新余学院 | Preparation method of fibrous porous carbon material containing axial macropores |
| CN105776177A (en) * | 2016-03-11 | 2016-07-20 | 北京化工大学 | Laminar boron-doped ordered mesoporous carbon and preparation method thereof |
| CN106589801A (en) * | 2016-12-23 | 2017-04-26 | 昌吉学院 | Synthetic method for high-oxygen index phenolic resin |
| CN107720724A (en) * | 2017-11-16 | 2018-02-23 | 西安交通大学 | A kind of high surface area nano-porous carbon material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| WANG SHUJUAN ET AL.: "Synthesis and characterization of phenolic resins containing aryl-boron backbone and their utilization in polymeric composites with improved thermal and mechanical properties", 《POLYMERS FOR ADVANCED TECHNOLOGIES》 * |
| 何杨: "嵌段共聚物模板法有序介孔炭的可控制备及其电化学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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