CN113862706A - Preparation method of carbon aerogel and precursor thereof - Google Patents
Preparation method of carbon aerogel and precursor thereof Download PDFInfo
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- CN113862706A CN113862706A CN202111191757.XA CN202111191757A CN113862706A CN 113862706 A CN113862706 A CN 113862706A CN 202111191757 A CN202111191757 A CN 202111191757A CN 113862706 A CN113862706 A CN 113862706A
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000007833 carbon precursor Substances 0.000 title description 2
- 239000002243 precursor Substances 0.000 claims abstract description 54
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 239000005539 carbonized material Substances 0.000 claims description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- -1 phenol series compound Chemical class 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000002848 electrochemical method Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000005406 washing Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical group [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/29—Coupling reactions
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The preparation method of the carbon aerogel and the precursor thereof is characterized in that current is provided for raw material mixed liquid, the raw material mixed liquid is catalyzed by an electrochemical method to carry out sol-gel reaction, and inorganic salt in the raw material mixed liquid is used as an electron transmission carrier, so that the catalysis effect is greatly improved, the sol-gel reaction speed is improved, the production speed of the carbon aerogel precursor is improved, the preparation speed of the carbon aerogel is further improved, and convenience is provided for the industrial production of the carbon aerogel. And the inorganic salt is also used as a pore-forming agent, so that the specific surface area of the obtained carbon aerogel is improved, and the performance of the carbon aerogel is improved. The inorganic salt enables the obtained carbon aerogel precursor to be in a super-salt environment, the mechanical strength is high, the carbon aerogel precursor can be directly dried under a normal pressure environment conveniently, and the production efficiency is improved.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a preparation method of carbon aerogel and a precursor thereof.
Background
The porous carbon material has developed pore diameter, not only has strong adsorption capacity, but also has a series of excellent performances such as good conductivity, heat resistance, high temperature resistance and the like, is rapidly developed in recent years, and is widely applied to various fields such as chemical industry, environmental protection, medicine, national defense and the like.
In recent years, carbon aerogels have attracted extensive attention in academia and industry due to their advantages such as high specific surface area, abundant and controllable three-dimensional pore canals, and the like. The carbon aerogel has the advantages of high conductivity, high surface area, high porosity and the like, and the characteristics enable the carbon aerogel to become a popular application material in the fields of energy storage, medicine, chemical industry, environmental protection and the like.
The preparation method of the conventional carbon aerogel comprises a sol-gel method, and the conventional sol-gel method has long polymerization and aging time and large energy consumption, and is not suitable for industrial production.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for preparing a carbon aerogel and a precursor thereof, which can increase the reaction rate of obtaining a carbon aerogel precursor by a sol-gel reaction, increase the production efficiency, and facilitate the industrial production of the carbon aerogel.
According to an aspect of the present invention, there is provided a method for preparing a carbon aerogel precursor, comprising:
placing the raw material mixed solution in an electrolytic cell;
supplying current to the raw material mixed liquid through the electrolytic cell, and continuously reacting for a first time to obtain a carbon aerogel precursor, wherein,
the raw material mixed liquid comprises at least one phenolic compound, formaldehyde and inorganic salt.
Optionally, the phenol series compound comprises at least one of resorcinol and its homologues, catechol and its homologues, phenol and its homologues, bisphenol a and its homologues, and cresol and its homologues.
Optionally, the inorganic salt comprises at least one of sodium chloride, zinc chloride, calcium chloride, magnesium chloride, potassium chloride.
Optionally, the ratio of formaldehyde to inorganic salt to at least one phenolic compound in the raw material mixture is 1-10 g: 1-15 g: 0.1-5.0 g.
Optionally, the intensity of the current provided is 1-50 milliamperes.
Optionally, the intensity of the current provided is 20-30 milliamperes.
Optionally, the current is provided by a regulated constant current source.
Optionally, the first time is 0.5-8 hours.
Optionally, the electrodes of the electrolytic cell are inert electrodes.
Optionally, the electrode material of the inert electrode comprises at least one of platinum, gold, and a conductive carbon material.
According to another aspect of the present invention, there is provided a method for preparing a carbon aerogel, comprising:
a carbon aerogel precursor obtained according to the method for preparing a carbon aerogel precursor of the present invention;
and drying the carbon aerogel precursor, then pyrolyzing the dried carbon aerogel precursor, and removing impurities in the carbonized material obtained by pyrolysis to obtain the carbon aerogel.
Optionally, the pyrolyzing comprises:
and placing the dried carbon aerogel precursor in an inert gas environment, and preserving the heat at the first temperature for a second time to obtain the carbonized material.
Optionally, the first temperature is 700-1100 ℃, and the second time is 1-5 hours.
Optionally, the first temperature is 800-950 ℃, and the second time is 2-3 hours.
Optionally, the dry gas pressure at which the carbon aerogel precursor is dried is atmospheric pressure.
Optionally, the specific surface area of the obtained carbon aerogel is 1500-3000 m2/g。
According to the preparation method of the carbon aerogel precursor, provided by the invention, current is supplied to the raw material mixed liquid, the sol-gel reaction of the raw material mixed liquid is catalyzed by adopting an electrochemical method, and the inorganic salt is used as a carrier for electron transmission, so that the rate of the sol-gel reaction is greatly increased, the preparation speed of the carbon aerogel precursor is increased, and the preparation speed of the carbon aerogel is further increased. And the inorganic salt is also used as a pore-forming agent, so that the pore diameter of pore-forming can be improved, and the specific surface area can be improved.
The preparation method of the carbon aerogel provided by the invention adopts the preparation method of the carbon aerogel precursor to prepare the carbon aerogel precursor, the carbon aerogel precursor is dried and pyrolyzed according to the carbon aerogel precursor to obtain the carbon aerogel, the inorganic salt enables the carbon aerogel precursor to be in a super-salt environment, the mechanical strength is high, the drying operation is directly performed under normal pressure, the operation is convenient, the production efficiency is improved conveniently, no air pressure control equipment is needed, and the cost is low. The pore-forming agent is inorganic salt, inorganic salt impurities removed by the pore-forming agent can be conveniently removed by washing, and the pore-forming agent does not need to be activated after pyrolysis and carbonization and is convenient to use.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent from the following description of the embodiments of the present invention with reference to the accompanying drawings, in which:
fig. 1 shows a flow diagram of a method for preparing a carbon aerogel according to an embodiment of the present invention.
Detailed Description
Various embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Like elements in the various figures are denoted by the same or similar reference numerals. For purposes of clarity, the various features in the drawings are not necessarily drawn to scale.
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples.
Fig. 1 shows a flow diagram of a method for preparing a carbon aerogel according to an embodiment of the present invention.
Referring to fig. 1, a method for preparing a carbon aerogel according to an embodiment of the present invention includes:
step S01: and placing the raw material mixed liquor in an electrolytic cell.
The raw material mixed liquid comprises at least one phenolic compound, formaldehyde, inorganic salt and deionized water, and is uniformly stirred after being mixed to obtain the raw material mixed liquid, wherein the solid content of the raw material mixed liquid is adjusted by adjusting the amount of the deionized water, and in the embodiment, the mass ratio of the main solid component in the raw material mixed liquid to the deionized water is 2-9: 1.
In this embodiment, the phenol-series compound is at least one of resorcinol and its homologues, catechol and its homologues, phenol and its homologues, bisphenol a and its homologues, and creosol and its homologues. The inorganic salt includes at least one of sodium chloride, zinc chloride, calcium chloride, magnesium chloride and potassium chloride (further, zinc chloride), and has a low melting point, so that the pores can be conveniently removed from the inorganic salt in the subsequent activating and pore-forming step.
The ratio of the formaldehyde to the inorganic salt to the phenol compound in the raw material mixture is 1-10 g: 1-15 g: 0.1-5.0 g.
Step S02: and supplying current to the raw material mixed liquor through an electrolytic cell, and continuously reacting for the first time to obtain the carbon aerogel precursor.
In this embodiment, the electrodes of the electrolytic cell are inert electrodes to avoid the electrodes participating in the reaction of the raw material mixture, and to ensure the reliability of the sol-gel reaction of the raw material mixture under the action of the current. The electrode material of the inert electrode is, for example, an inert conductive material such as platinum, gold, a conductive carbon material, and the like.
In this embodiment, a voltage-stabilizing constant current source is used to provide current, the intensity of the provided current is 1 to 50 milliamperes (further, 20 to 30mA), and the current is continuously provided for 0.5 to 80 hours (first time), so as to ensure the sufficient progress of the sol-gel reaction and the quality of the obtained carbon aerogel precursor.
Step S03: and pyrolyzing the carbon xerogel to obtain a carbonized material, and removing pore-forming agents in the carbonized material to obtain the carbon aerogel.
In step S03, the step of drying the carbon aerogel precursor includes: the carbon aerogel precursor is dried (the solvent in the voids is removed while maintaining the structure of the gel) at a temperature of 50 degrees celsius under normal pressure (one standard atmospheric pressure, having a certain deviation according to the actual experimental environment, but having no particular influence on the practice of the present invention, and the specific range thereof is not particularly limited, for example, the structural characteristics of the obtained carbon xerogel can be ensured even when the deviation reaches ± 20%), to obtain the carbon xerogel.
And (3) pyrolyzing (carbonizing) the carbon xerogel, cooling the carbon xerogel to room temperature after pyrolysis is finished, washing the obtained carbonized material to be neutral to remove impurities (mainly inorganic salt serving as a pore-forming agent) in the carbonized material, washing the carbonized material with water, and drying the washed carbonized material to obtain the target carbon aerogel. The specific surface area of the finally obtained carbon aerogel is 1500-3000 m2/g。
In this embodiment, the pyrolysis carbonization operation includes: and (3) placing the carbon xerogel in an inert gas environment, heating to a first temperature and keeping for a second time to obtain a carbonized material, wherein the first temperature is 700-1100 ℃, and the second time is 1-5 hours (further, the first temperature is 800-950 ℃, and the second time is 2-3 hours). Wherein the inert gas is at least one of nitrogen and helium.
The preparation method of the carbon aerogel in the embodiment of the invention adopts an electrochemical method to catalyze the sol-gel reaction, and uses the inorganic salt as a carrier for electron transmission, so that the preparation speed of the carbon aerogel precursor is improved, the power supply current of electrolytic catalysis is small, and the energy consumption is low.
The inorganic salt is used as a pore-forming agent, the preparation environment of the carbon aerogel is a super-salt environment, the mechanical strength of the obtained carbon aerogel precursor is high, direct drying under normal pressure is facilitated, and the operation is convenient.
The inorganic salt can be effectively removed by washing with deionized water after the carbon xerogel is pyrolyzed and carbonized, subsequent treatments such as activation and the like are not needed after carbonization, and the obtained carbon aerogel has high purity and is particularly suitable for the fields of electrochemistry, medicine, environmental protection and the like.
The properties of the carbon aerogel obtained by the method for producing a carbon aerogel according to the embodiment of the present invention will be described below with reference to examples 1 to 4.
Example l
In a 100ml electrolytic cell with inert electrode, 60g of deionized water was added, followed by weighing 11g of m-xylylenePhenol, 16g of formaldehyde (corresponding to a concentration of 37% in the formaldehyde solution), and 6g of sodium chloride were added to the electrolytic cell, and after magnetic stirring for 30min, 10mA constant current was continuously applied to the electrolytic cell for 8 hours to obtain a carbon aerogel precursor. Drying at normal pressure and 50 ℃ to obtain the carbon xerogel. And placing the carbon xerogel in a quartz boat, heating to 350 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping for 0.5h, continuing heating to 1000 ℃ at the heating rate of 5 ℃/min, keeping for 2h, cooling to room temperature, and taking out. And washing the carbonized sample to be neutral by using deionized water, and drying at 120 ℃ to obtain the porous carbon aerogel with high specific surface area. The specific surface area of the carbon aerogel sample is 2000m2G, density 0.29g/cm3The aperture of the material is 2 nm.
Example 2
70g of deionized water is added into a 100ml electrolytic cell with an inert electrode, then 9.5g of phenol, 18g of formaldehyde (corresponding to the concentration of the formaldehyde solution being 37 percent) and 12g of zinc chloride are weighed into the electrolytic cell, after magnetic stirring is carried out for 30min, 50mA constant current is continuously introduced into the electrolytic cell for 4 hours, and the carbon aerogel precursor is obtained. Drying at 60 ℃ under normal pressure to obtain the carbon xerogel. And placing the carbon xerogel on a quartz boat, heating to 350 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping for 0.5h, continuously heating to 1000 ℃ at the heating rate of 5 ℃/min, keeping for 5h, cooling to room temperature, and taking out. And washing the carbonized sample to be neutral by using deionized water, and drying at 120 ℃ to obtain the porous carbon aerogel with high specific surface area. The specific surface area of the carbon aerogel sample is 2500m2G, density 0.20g/cm3The aperture of the material is 1.9 nm.
Example 3
70g of deionized water is added into a 100ml electrolytic cell with an inert electrode, then 5.5g of resorcinol, 4.5g of phenol, 25g of formaldehyde (corresponding to the concentration of the formaldehyde solution being 37%) and 10g of potassium chloride are weighed into the electrolytic cell, after magnetic stirring is carried out for 30min, 30mA constant current is continuously introduced into the electrolytic cell for 8 hours, and the carbon aerogel precursor is obtained. Drying at 55 ℃ under normal pressure to obtain carbon xerogel. Placing the carbon xerogel in a quartz boat, heating to 350 ℃ at a heating rate of 5 ℃/min in the nitrogen atmosphere, keeping for 0.5h, and continuously heating to 900 ℃ at a heating rate of 5 ℃/minKeeping for 4h, cooling to room temperature and taking out. And washing the carbonized sample to be neutral by using deionized water, and drying at 120 ℃ to obtain the porous carbon aerogel with high specific surface area. The specific surface area of the carbon aerogel sample is 2600m2G, density 0.21g/cm3The aperture of the material is 2.1 nm.
Example 4
70g of deionized water is added into a 100ml electrolytic cell with an inert electrode, then 5.5g of resorcinol, 6.0g of mixed cresol, 26g of formaldehyde (corresponding to the concentration of the formaldehyde solution being 37%) and 12g of zinc chloride are weighed into the electrolytic cell, after magnetic stirring is carried out for 30min, 50mA constant current is continuously introduced into the electrolytic cell for 4 hours, and the carbon aerogel precursor is obtained. Drying at 60 ℃ under normal pressure to obtain the carbon xerogel. And (3) placing the carbon xerogel in a quartz boat, heating to 400 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping for 0.5h, continuing heating to 1000 ℃ at the heating rate of 5 ℃/min, keeping for 5h, cooling to room temperature, and taking out. And washing the carbonized sample to be neutral by using deionized water, and drying at 120 ℃ to obtain the porous carbon aerogel with high specific surface area. The specific surface area of the carbon aerogel sample is 2400m2G, density 0.27g/cm3The aperture of the material is 1.8 nm.
According to the embodiments 1 to 4, the specific surface area of the carbon aerogel obtained by the preparation method of the carbon aerogel in the embodiment of the invention reaches 2000m2The pore diameter is mainly 0-10 nanometers and is between the pore diameter range of micropores and mesopores.
The preparation method of the carbon aerogel precursor provided by the invention adopts an electrochemical method to catalyze the sol-gel reaction of the raw material mixed solution, and takes the inorganic salt as the carrier of electron transmission, so that the rate of the sol-gel reaction is greatly increased, the preparation speed of the carbon aerogel precursor is increased, and the preparation speed of the carbon aerogel is further increased. And the inorganic salt is also used as a pore-forming agent, so that the pore diameter of pore-forming can be improved, and the specific surface area can be improved.
Further, the inorganic salt is selected from chlorate, and the chlorate has low melting point, so that the filling of the chlorate to the pore-forming is conveniently released in the pyrolysis step in the preparation of the carbon aerogel.
The preparation method of the carbon aerogel provided by the invention adopts the preparation method of the carbon aerogel precursor to prepare the carbon aerogel precursor, and the carbon aerogel is obtained by drying and pyrolyzing the carbon aerogel precursor. The pore-forming agent is inorganic salt, inorganic salt impurities removed by the pore-forming agent can be simply removed by washing, and the pore-forming agent does not need to be activated after pyrolysis and carbonization and is convenient to use.
While embodiments in accordance with the invention have been described above, these embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments described. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated. The invention is limited only by the claims and their full scope and equivalents.
Claims (16)
1. A method of preparing a carbon aerogel precursor, comprising:
placing the raw material mixed solution in an electrolytic cell;
supplying current to the raw material mixed liquid through the electrolytic cell, and continuously reacting for a first time to obtain a carbon aerogel precursor, wherein,
the raw material mixed liquid comprises at least one phenolic compound, formaldehyde and inorganic salt.
2. The method of preparing a carbon aerogel precursor of claim 1,
the phenol series compound comprises at least one of resorcinol and its homologues, catechol and its homologues, phenol and its homologues, bisphenol A and its homologues, and cresol and its homologues.
3. The method of preparing a carbon aerogel precursor of claim 1,
the inorganic salt comprises at least one of sodium chloride, zinc chloride, calcium chloride, magnesium chloride and potassium chloride.
4. The method of preparing a carbon aerogel precursor of claim 1,
the ratio of formaldehyde to inorganic salt to at least one phenolic compound in the raw material mixture is 1-10 g: 1-15 g: 0.1-5.0 g.
5. The method of preparing a carbon aerogel precursor of claim 1, wherein said electrical current is provided at an intensity of 1 to 50 milliamps.
6. The method of preparing a carbon aerogel precursor of claim 5, wherein said electrical current is provided at an intensity of 20 to 30 milliamps.
7. The method of preparing a carbon aerogel precursor of claim 1,
the current is supplied by a regulated constant current source.
8. The method of preparing a carbon aerogel precursor of claim 1,
the first time is 0.5-8 hours.
9. The method of preparing a carbon aerogel precursor of claim 1,
the electrodes of the electrolytic cell are inert electrodes.
10. The method of preparing a carbon aerogel precursor of claim 9,
the electrode material of the inert electrode comprises at least one of platinum, gold and a conductive carbon material.
11. A method for preparing a carbon aerogel, comprising:
a carbon aerogel precursor obtained by the method for preparing a carbon aerogel precursor of any of claims 1 to 10;
and drying the carbon aerogel precursor, then pyrolyzing the dried carbon aerogel precursor, and removing impurities in the carbonized material obtained by pyrolysis to obtain the carbon aerogel.
12. The method of preparing a carbon aerogel of claim 11, wherein said pyrolyzing comprises:
and placing the dried carbon aerogel precursor in an inert gas environment, and preserving the heat at the first temperature for a second time to obtain the carbonized material.
13. The method of preparing a carbon aerogel according to claim 12,
the first temperature is 700-1100 ℃, and the second time is 1-5 hours.
14. The method of preparing a carbon aerogel according to claim 13,
the first temperature is 800-950 ℃, and the second time is 2-3 hours.
15. The method of preparing a carbon aerogel according to claim 11,
the dry gas pressure for drying the carbon aerogel precursor is normal pressure.
16. The method of preparing the carbon aerogel of claim 11, wherein the obtained carbon aerogel has a specific surface area of 1500 to 3000m2/g。
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