CN116102010A - High-porosity phenolic resin-based three-dimensional nano-network carbon aerogel and preparation method thereof - Google Patents
High-porosity phenolic resin-based three-dimensional nano-network carbon aerogel and preparation method thereof Download PDFInfo
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 82
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 75
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000004964 aerogel Substances 0.000 claims abstract description 50
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 91
- 238000010438 heat treatment Methods 0.000 claims description 70
- 239000007789 gas Substances 0.000 claims description 51
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 19
- 230000003213 activating effect Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 239000008098 formaldehyde solution Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 31
- 230000004913 activation Effects 0.000 abstract description 17
- 239000012495 reaction gas Substances 0.000 abstract description 13
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 239000000463 material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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Abstract
The invention discloses a high-pore phenolic resin-based three-dimensional nano-network carbon aerogel and a preparation method thereof, which belong to the technical field of nano materials and energy science, and realize the controllable construction of pores by regulating and controlling the pre-carbonization temperature, time and the consumption of reaction gas, thereby obtaining a series of high-pore carbon aerogels with customizable specific surface areas. The pre-carbonization treatment converts the organic aerogel polymer into amorphous carbon to a certain extent, and nitrogen-oxygen reaction gas is introduced to enable the amorphous carbon to react with oxygen to generate carbon dioxide to escape, namely the reaction gas has a certain etching effect on the aerogel to form abundant micropores and small-size mesopores. The invention effectively solves the problems of low porosity, difficult specific surface area regulation, collapse of the three-dimensional nano network structure caused by strong chemical activation pore-forming and the like of the traditional phenolic resin-based carbon aerogel, and is simple, efficient, low in cost and convenient to popularize and use.
Description
Technical Field
The invention relates to the technical field of nano materials and energy science, in particular to a high-pore phenolic resin-based three-dimensional nano network carbon aerogel and a preparation method thereof.
Background
Aerogel is a novel functional material with a nano porous structure, has the performances of ultra-light, high specific surface area, heat insulation, sound insulation, adsorption, catalysis and the like, and has huge application prospects in the fields of aerospace, building energy conservation, military, heat preservation, heat insulation and the like. The phenolic resin-based carbon aerogel has the excellent characteristics of low price, unique three-dimensional nano network structure, high specific surface area, abundant mesopores, high conductivity and the like, so that the phenolic resin-based carbon aerogel plays an irreplaceable role in the fields of gas storage, adsorption and separation, catalysis, energy storage, conversion and the like. However, the specific surface area of the phenolic resin based carbon aerogel obtained by normal pressure drying and high temperature carbonization is generally not high (< 1000 m) 2 And/g), the performance and application expansion of the material are limited, and the material is particularly suitable for application scenes which need developed pores and are rich in specific surface area.
At present, KOH and CO are commonly adopted 2 And water vapor and the like are used as an activating agent to promote the pore structure of the carbon aerogel. However by CO 2 When the pore structure of the carbon aerogel is regulated, the specific surface area of the material is slightly improved (less than 1700 m) 2 /g, as in chinese patent publication No. CN 1891622 A,CN 108862237 B,CN 108854874B). Although KOH activation can generate developed pore structures, three-dimensional network structure collapse is very easy to cause, for example, wang et al (documents Journal of Power Sources and 2008,185,589-594) carry out pore structure adjustment on phenolic resin-based carbon aerogel through KOH, and when the ratio of an activator to a material reaches 5, holes of more than 10nm of the carbon aerogel completely disappear, and the three-dimensional nano-network framework is destroyed. In addition, the chemical activation method also needs acid to neutralize excessive activator and wash to neutrality, and the process is complex and complicated and is not friendly to the environment. Therefore, the development of the preparation method of the phenolic resin-based carbon aerogel with high efficiency, high porosity, customizable specific surface area and nano-network structure retention has important significance for the development of the material. Aiming at the technical problems, the invention provides a high-pore phenolic resin-based three-dimensional nano-network carbon aerogel and a preparation method thereof.
Disclosure of Invention
The invention provides a high-pore phenolic resin-based three-dimensional nano-network carbon aerogel and a preparation method thereof, which effectively solve the technical problems of low specific surface area, poor controllability, collapse of nano-network morphology caused by chemical activation such as KOH and the like of the traditional phenolic resin-based carbon aerogel, and simultaneously provide the phenolic resin-based three-dimensional nano-network carbon aerogel which has good morphology, ultrahigh specific surface area, developed micropore/mesoporous structure and predesigned specific surface area.
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel is characterized by comprising the following steps of:
s1, resorcinol, formaldehyde, water and hexadecyl trimethyl ammonium bromide are used as raw materials to prepare organic aerogel;
s2, grinding the organic aerogel of the S1 into powder, drying, pre-carbonizing in nitrogen flow, heating to 900-950 ℃, introducing nitrogen-oxygen mixed gas, activating for 1-4 h, and cooling to room temperature in the nitrogen flow to obtain the phenolic resin-based three-dimensional nano-network carbon aerogel.
Preferably, in S2, the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixture is 95:5.
Preferably, the flow rate of the nitrogen-oxygen mixture is 30-100 mL/min.
Preferably, in S2, the temperature of the pre-carbonization is 600-900 ℃, and the temperature is kept for 2 hours.
Preferably, in S2, the nitrogen gas flow is 80mL/min.
Preferably, in S2, the temperature rising rate is 5 ℃/min.
Preferably, in S2, the specific surface area of the phenolic resin-based three-dimensional nano-network carbon aerogel is 1179-2924 m 2 /g。
Preferably, in S1, the preparation method of the organic aerogel includes: dissolving resorcinol in formaldehyde, adding water for full dissolution, adding cetyltrimethylammonium bromide, mixing uniformly, and standing in an oil bath at 85 ℃ for 72 hours to obtain the resorcinol.
Preferably, the mass fraction of the formaldehyde solution is 38.5%; the dosage ratio of the resorcinol to the formaldehyde to the water to the hexadecyl trimethyl ammonium bromide is 1g to 1.26mL to 1.46mL to 0.0066-0.026 g.
The high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) The phenolic resin-based organic aerogel is prepared by a sol-gel method, and the customized construction of pores is realized by regulating and controlling the pre-carbonization temperature, the nitrogen-oxygen mixed gas treatment time and the dosage; pre-carbonizing the organic aerogel in nitrogen flow, then heating and treating with nitrogen-oxygen mixture gas to obtain phenolic resin based three-dimensional nano network carbon aerogel with different pore structures, converting the organic aerogel polymer into amorphous carbon to a certain extent by the pre-carbonizing treatment, and introducing nitrogen-oxygen reaction gas to enable the amorphous carbon to react with oxygen to generate CO 2 Escaping, namely, a certain etching effect is generated on the aerogel, so that the aerogel is regulated and controlled to form different micropores and small-size mesoporous structures. The invention effectively solves the problems of low specific surface area, poor controllability, collapse of nano-network morphology caused by chemical activation and the like of the traditional phenolic resin-based carbon aerogel.
(2) The high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel provided by the invention has an ultrahigh specific surface area, and the specific surface area of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel prepared in embodiment 1 is up to 2924m 2 /g。
(3) The preparation method of the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel provided by the invention uses the nitrogen-oxygen mixed gas as the reaction gas, integrates the advantages of chemical activation high-efficiency pore-forming and physical activation nano-structure maintenance, is simple and efficient, has low cost and is convenient to popularize and use.
Drawings
FIG. 1 is a scanning electron microscope image of a high porosity phenolic resin based three dimensional nano network carbon aerogel prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of the high porosity phenolic resin based three dimensional nano network carbon aerogel prepared in example 1 of the present invention;
FIG. 3 is a graph showing isothermal adsorption and desorption of nitrogen gas from the high pore space phenolic resin based three-dimensional nano-network carbon aerogel prepared in example 1 of the present invention;
fig. 4 is a cycle performance chart of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel prepared in example 4 as an electrode material of a supercapacitor.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to specific examples, but the examples are not intended to limit the present invention. The following test methods and detection methods, if not specified, are conventional methods; the reagents and starting materials, unless otherwise specified, are commercially available.
Example 1
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, adding resorcinol with the mass of 10g and formaldehyde solution with the mass fraction of 38.5% of 12.6mL into a 50mL round bottom flask, adding 14.6mL of distilled water, stirring to fully dissolve the resorcinol and formaldehyde solution, adding 0.066g of cetyl trimethyl ammonium bromide, and standing the mixed solution in a water bath at 85 ℃ for reaction for 72 hours to obtain organic aerogel;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 30mL/min, activating for 4 hours, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
Example 2 (differing from example 1 in that the activation time was changed from 4h to 3.75 h)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 30mL/min, activating for 3.75 hours, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin matrix three-dimensional nano-network carbon aerogel.
Example 3 (differing from example 1 in that the activation time was changed from 4h to 3.5 h)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 30mL/min, activating for 3.5 hours, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin matrix three-dimensional nano-network carbon aerogel.
Example 4 (differing from example 1 in that the activation time was changed from 4h to 3 h)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 30mL/min, activating for 3 hours, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin matrix three-dimensional nano-network carbon aerogel.
Example 5 (differing from example 2 in that the activation time was changed from 4h to 1 h)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 30mL/min, activating for 1 hour, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
Example 6 (differing from example 5 in that the flow rate of the nitrogen-oxygen mixture was changed from 30mL/min to 40 mL/min)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 40mL/min, activating for 1 hour, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
Example 7 (differing from example 5 in that the flow rate of the nitrogen-oxygen mixture was changed from 30mL/min to 60 mL/min)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 60mL/min, activating for 1 hour, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
Example 8 (differing from example 5 in that the flow rate of the nitrogen-oxygen mixture was changed from 30mL/min to 90 mL/min)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 90mL/min, activating for 1 hour, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
Example 9 (differing from example 5 in that the flow rate of the nitrogen-oxygen mixture was changed from 30mL/min to 100 mL/min)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 100mL/min, activating for 1 hour, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
Example 10 (differing from example 4 in that the pre-carbonization is at 900 ℃ C. As the activation temperature)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of the S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen flow, preserving heat for 2 hours, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a flow rate of 30mL/min, activating for 3 hours, and cooling to room temperature in the nitrogen flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
Example 11 (differing from example 4 in that the pre-carbonization temperature was reduced from 900 ℃ to 700 ℃)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 700 ℃ at a heating rate of 5 ℃/min in a nitrogen gas flow of 80mL/min, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing a nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 30mL/min, activating for 3 hours, and cooling to room temperature in a nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
Example 12 (differing from example 4 in that the pre-carbonization temperature was changed from 900 ℃ to 600 ℃)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen gas flow of 80mL/min, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing a nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 30mL/min, activating for 3 hours, and cooling to room temperature in a nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
Example 13 (changing parameters of precursor Material)
The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, adding resorcinol with the mass of 10g and formaldehyde solution with the mass fraction of 38.5% in 12.6mL into a 50mL round bottom flask, adding 14.6mL of distilled water, stirring to fully dissolve the resorcinol and formaldehyde solution, adding 0.26g of cetyl trimethyl ammonium bromide, and standing the mixed solution in a water bath at 85 ℃ for reaction for 72h to obtain organic aerogel;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a gas flow rate of 80mL/min, activating for 1 hour, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel.
To further illustrate the effect of the present invention, the present invention provides a comparative example as follows:
comparative example 1 (difference from example 4: preparation of carbon aerogel under nitrogen-oxygen-free mixture) a method for preparing a phenolic resin-based three-dimensional nano-network carbon aerogel, comprising the steps of:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen gas flow of 80mL/min, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen at a gas flow rate of 30mL/min, preserving heat for 3 hours, and cooling to room temperature in nitrogen gas flow of 80mL/min to obtain the phenolic resin-based three-dimensional nano-network carbon aerogel.
Comparative example 2 (preparation of carbon aerogel under Potassium hydroxide)
The preparation method of the phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, preparing organic aerogel according to the step of S1 in the example 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 500 ℃ at a heating rate of 5 ℃/min in a nitrogen gas flow, preserving heat for 3 hours, cooling to room temperature in the nitrogen gas flow of 80mL/min to obtain a pre-carbonized sample, then weighing a certain amount of KOH (2 g) and the pre-carbonized sample (500 mg) respectively, adding a small amount of deionized water into a nickel pot to dissolve KOH completely, adding the sample to be activated into the nickel pot, placing the powder into a magnetic stirrer to be fully mixed and shaken uniformly, drying at 100 ℃ for 24 hours, placing the nickel pot into a carbonization furnace under the protection of 80mL/min of nitrogen gas, heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, and cooling to room temperature in the nitrogen gas flow of 80mL/min to obtain the collapsed carbon aerogel.
Comparative example 3 (Change of activation time: activation 0.5 h)
The preparation method of the phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, the organic aerogel prepared in the embodiment 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen flow of 80mL/min, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a flow rate of 30mL/min, activating for 0.5 hour, and cooling to room temperature in nitrogen flow of 80mL/min to obtain the phenolic resin-based three-dimensional nano-network carbon aerogel.
Comparative example 4 (Change of activation time: activation 4.5 h)
The preparation method of the phenolic resin-based three-dimensional nano-network carbon aerogel comprises the following steps:
s1, the organic aerogel prepared in the embodiment 1;
s2, grinding the organic aerogel of S1 into powder, drying at 100 ℃ for 24 hours, heating to 900 ℃ at a heating rate of 5 ℃/min in nitrogen flow of 80mL/min, preserving heat for 2 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, introducing nitrogen-oxygen mixed gas (the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixed gas is 95:5) at a flow rate of 30mL/min, activating for 4.5 hours, and cooling to room temperature in nitrogen flow of 80mL/min to obtain the phenolic resin-based three-dimensional nano-network carbon aerogel. However, the activation treatment time is too long, the yield of the material is too low, the preparation controllability is too poor, the precursor material is easy to be etched completely, and the accurate specific surface area of the material cannot be provided.
Specific surface areas of the phenolic resin-based three-dimensional nano-network carbon aerogels prepared in the examples 1 to 13 and the comparative examples 1 to 3 are calculated by adopting a BET method, and micropore surface areas and micropore volumes V are calculated by adopting a t-plot method mic The results of the detection are shown in Table 1.
TABLE 1 data sheet of specific surface area, micropore surface area and micropore volume of carbon aerogel of the present invention
| BET specific surface area/m 2 g -1 | Micropore surface area/m 2 g -1 | Micropore volume V mic /cm 3 g -1 | |
| Example 1 | 2924 | 517 | 0.25 |
| Example 2 | 2733 | 753 | 0.31 |
| Example 3 | 2439 | 1351 | 0.61 |
| Example 4 | 1972 | 1189 | 0.55 |
| Example 5 | 1179 | 949 | 0.44 |
| Example 6 | 1255 | 1012 | 0.50 |
| Example 7 | 1579 | 1098 | 0.53 |
| Example 8 | 2089 | 1254 | 0.58 |
| Example 9 | 2318 | 1623 | 0.80 |
| Example 10 | 1843 | 1206 | 0.56 |
| Example 11 | 1978 | 1176 | 0.51 |
| Example 12 | 1987 | 1160 | 0.49 |
| Example 13 | 1301 | 986 | 0.47 |
| Comparative example 1 | 782 | 605 | 0.28 |
| Comparative example 2 | 834 | 564 | 0.26 |
| Comparative example 3 | 901 | 712 | 0.31 |
As can be seen from Table 1, according to the preparation method of the phenolic resin-based three-dimensional nano-network carbon aerogel provided by the invention, the organic aerogel polymer is converted into amorphous carbon to a certain extent through the pre-carbonization treatment, and then the amorphous carbon and oxygen are reacted to generate carbon dioxide to escape through introducing nitrogen-oxygen mixture gas, so that a certain etching effect is generated on the aerogel, and the specific surface area of the obtained phenolic resin-based three-dimensional nano-network carbon aerogel is as high as 2924m 2 And/g. Analysis shows that the strategy has controllability and predictability for construction of material pores. As in examples 1 to 5, comparative examples 1 and 3, it was found that the specific surface area and the reaction gas treatment time thereof satisfy equation (1) at the same gas flow rate and the heat treatment temperature. At this time, the flow rate of the reaction gas is 30mL/min, and the concentration of oxygen in the reaction gas is 5%, so that the oxygen consumption per hour is about 4.02mmol in the reaction gas treatment process, and the consumed oxygen reacts with the same amount of the activated precursor to generate CO 2 Since carbon is in excess during the preparation process, the utilization rate of the introduced oxygen reaches 100%, and the etching amount of carbon per hour based on the utilization rate is consistent with the result observed during the preparation process (the loss amount per hour is about 50-60 mg). Further, by adjusting the flow rate of the reaction gas, it was found that the approximate pore structure (example 4 and example 8) can be obtained by arbitrarily changing the process parameters on the premise of constant oxygen reaction amount, and the specific surface area and the flow rate of the reaction gas satisfy equation (2).
S BET ＝127.6x 2 +833 (1)
S BET ＝0.14y 2 +899 (2)
Wherein S is BET The specific surface area of the material is represented by x, the reaction gas treatment time (h), and y, the flow rate (mL/min) of the reaction gas.
The morphology analysis is carried out on the phenolic resin-based three-dimensional nano-network carbon aerogel prepared in the embodiment 1 of the invention, a prepared sample is fixed on a sample stage by using conductive adhesive, and the structural morphology of the sample is observed by using a Nova field emission scanning electron microscope (FEI) produced in the United states, so that a scanning electron microscope image of the phenolic resin-based three-dimensional nano-network carbon aerogel is shown in figure 1. And (3) taking a small amount of the prepared phenolic resin-based three-dimensional nano-network carbon aerogel powder, placing the powder in absolute ethyl alcohol for ultrasonic dispersion, fishing out a part of samples by using a copper mesh, and observing the structures of the samples by using a transmission electron microscope after the absolute ethyl alcohol volatilizes to obtain a transmission electron microscope image of the phenolic resin-based three-dimensional nano-network carbon aerogel, wherein the transmission electron microscope image is shown in figure 2.
As can be seen from fig. 1, the high-pore phenolic resin-based three-dimensional nano-network carbon aerogel prepared in the embodiment 1 of the present invention is formed by aggregation and connection of nano-spheres of about tens of nanometers, so as to form a three-dimensional network porous skeleton; fig. 2 clearly shows that the phenolic resin-based three-dimensional nano-network carbon aerogel is composed of nano-particles, which are cross-linked with each other to form a three-dimensional network structure. As can be seen from FIG. 3, the samples all show IV type adsorption curves, which are at P/P 0 The trend of sharp rise in the low voltage region of =0-0.1 indicates that there are a large number of micropores in the material, and rise and hysteresis loops occur in the medium-high voltage region, respectively, indicating that there are mesoporous and macroporous structures in the material.
As can be seen from fig. 4, the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel prepared in example 4 of the present invention is used as an electrode material of a supercapacitor, and the capacitor shows excellent specific capacity (114.6F g after 10000 cycles of circulation under the current density of 20A/g -1 ) The capacity retention rate reaches 98%.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The preparation method of the high-porosity phenolic resin-based three-dimensional nano-network carbon aerogel is characterized by comprising the following steps of:
s1, resorcinol, formaldehyde, water and hexadecyl trimethyl ammonium bromide are used as raw materials to prepare organic aerogel;
s2, grinding the organic aerogel of S1 into powder, drying, pre-carbonizing in nitrogen flow, continuously heating to 900-950 ℃, introducing nitrogen-oxygen mixed gas, activating for 1-4 h, and cooling to room temperature in the nitrogen flow to obtain the phenolic resin-based three-dimensional nano-network carbon aerogel.
2. The method according to claim 1, wherein in S2, the volume ratio of nitrogen to oxygen in the nitrogen-oxygen mixture is 95:5.
3. The preparation method according to claim 2, wherein the flow rate of the nitrogen-oxygen mixture is 30-100 mL/min.
4. The method according to claim 1, wherein in S2, the temperature of the pre-carbonization treatment is 600 to 900 ℃, and the heat is preserved for 2 hours.
5. The method according to claim 1, wherein in S2, the nitrogen gas flow is 80mL/min.
6. The method according to claim 1, wherein in S2, the temperature rise rate is 5 ℃/min.
7. The method according to claim 1, wherein in S2, the specific surface area of the phenolic resin-based three-dimensional nano-network carbon aerogel is 1179-2924 m 2 /g。
8. The method according to claim 1, wherein in S1, the method for preparing the organic aerogel comprises: dissolving resorcinol in formaldehyde, adding water for full dissolution, adding cetyltrimethylammonium bromide, mixing uniformly, and standing in an oil bath at 85 ℃ for 72 hours to obtain the resorcinol.
9. The preparation method according to claim 8, wherein the mass fraction of the formaldehyde solution is 38.5%; the dosage ratio of the resorcinol to the formaldehyde to the water to the hexadecyl trimethyl ammonium bromide is 1g to 1.26mL to 1.46mL to 0.0066-0.026 g.
10. A highly porous phenolic resin-based three-dimensional nano-network carbon aerogel prepared by the preparation method of any one of claims 1 to 9.
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