CN113816357A - Preparation method of carbon aerogel - Google Patents
Preparation method of carbon aerogel Download PDFInfo
- Publication number
- CN113816357A CN113816357A CN202111192452.0A CN202111192452A CN113816357A CN 113816357 A CN113816357 A CN 113816357A CN 202111192452 A CN202111192452 A CN 202111192452A CN 113816357 A CN113816357 A CN 113816357A
- Authority
- CN
- China
- Prior art keywords
- carbon aerogel
- preparing
- raw material
- carbon
- material mixed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 125000003010 ionic group Chemical group 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 239000002608 ionic liquid Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- 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 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 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
- 229930003836 cresol Natural products 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 phenolic series compound Chemical class 0.000 claims description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 125000002743 phosphorus functional group Chemical group 0.000 claims description 2
- 125000004354 sulfur functional group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 15
- 239000000203 mixture Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229960000789 guanidine hydrochloride Drugs 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
Abstract
Disclosed is a preparation method of carbon aerogel, which comprises catalyzing raw material mixed liquor to generate sol-gel reaction under the action of continuous current to obtain carbon aerogel precursor, and obtaining the carbon aerogel after the carbon aerogel precursor is subjected to solvent replacement, drying and pyrolysis carbonization, wherein the raw material mixed liquor is added with ionic groups. According to the preparation method of the carbon aerogel, the ionic group is added into the raw material mixed liquid, the ionic group provides heteroatom doping for the carbon aerogel, and meanwhile, the ionic group is used as an electron transport carrier, so that the production rate of the carbon aerogel with heteroatom doping is effectively increased, and convenience is provided for the industrial production of the carbon aerogel. And the reaction regulation of the electrochemical catalysis sol-gel reaction is easy to control.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a preparation method of carbon aerogel.
Background
The carbon aerogel is a novel light nano-porous amorphous solid material, has a unique nano-porous structure, stable physical and chemical properties and excellent conductivity, and has wide application prospects in the fields of catalyst carriers, biological medicines, electrochemistry and the like.
Carbon aerogels are generally prepared by a sol-gel process: in the presence of a catalyst, a three-dimensional network structure is formed by heating for a long time. The sol-gel process is a time-consuming and energy-consuming process, which is one of the main reasons that it is currently difficult to prepare carbon aerogels in large quantities. Simple, low-energy-consumption and mass-production carbon aerogel preparation method still is a great challenge in the field of material synthesis, and is widely concerned by scientific research institutions and enterprises.
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, thereby providing a method for rapidly preparing a carbon aerogel doped with a heteroatom, facilitating industrial production of the carbon aerogel.
According to an aspect of the present invention, there is provided a method for preparing a carbon aerogel, comprising:
mixing at least one phenolic series compound, formaldehyde, an ionic group raw material and a solvent to obtain a raw material mixed solution;
introducing current into the raw material mixed solution, and continuously reacting for the first time to obtain a carbon aerogel precursor;
carrying out solvent replacement on the carbon aerogel precursor, and drying to obtain carbon xerogel;
carbonizing the carbon xerogel to obtain the carbon aerogel.
Optionally, the ionic group source material comprises at least one element of nitrogen, phosphorus, sulfur.
Optionally, the total mass content of nitrogen, phosphorus and sulfur in the carbon aerogel is 0.01-5%.
Optionally, the ionic group raw material is an ionic liquid, and the ionic liquid is at least one of ionic liquids containing nitrogen groups, sulfur groups and phosphorus groups.
Optionally, the ionic liquid includes at least one of imidazole ionic liquid, pyridine ionic liquid, piperidine ionic liquid, pyrrolidine ionic liquid, quaternary ammonium salt ionic liquid, and quaternary phosphonium salt ionic liquid.
Alternatively, the at least one phenolic-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 molar ratio of the at least one phenolic compound to formaldehyde in the raw material mixed solution is 0.2-1: 1, and the solid content of the raw material mixed solution is 10-60%.
Optionally, the current intensity of the current introduced into the raw material mixed liquid is 1-50 milliamperes.
Optionally, the first time is 0.5-12 hours, and the reaction environment is normal temperature and normal pressure.
Optionally, in the step of drying to obtain a carbon xerogel, the ambient pressure is normal pressure.
Optionally, in the step of subjecting the carbon aerogel precursor to solvent replacement, an organic solvent is used for the replacement.
Optionally, the organic solvent is an anhydrous alcohol solvent or an anhydrous ketone solvent.
Optionally, the step of carbonizing the carbon xerogel comprises:
and (3) placing the carbon xerogel in an inert gas environment, and controlling carbonization by temperature programming.
Optionally, the programming includes:
heating to 350-500 ℃ at a heating rate of 1-10 ℃/min, and keeping for 0.5-2 hours;
after keeping for 0.5-2 hours, heating to 700-1100 ℃ at a heating rate of 1-10 ℃/min, and keeping for 0.5-4 hours to finish carbonization, thereby obtaining the carbon aerogel.
Optionally, the current introduced to the raw material mixed liquid is provided by a voltage-stabilizing constant current source.
Optionally, the inert gas is at least one of nitrogen or helium.
Optionally, the carbon aerogel is a three-dimensional network structure.
Optionally, the step of introducing current into the raw material mixed solution includes:
and placing the raw material mixed solution in an electrolytic cell, and continuously providing constant current or constant voltage current through an inert electrode.
Optionally, the inert electrode is a sheet or column electrode.
Optionally, the inert electrode is selected from graphite, platinum or gold.
Optionally, the addition amount of the ionic liquid is 0.05% -10% of the solid content of the raw material mixed liquid.
The preparation method of the carbon aerogel provided by the invention catalyzes the raw material mixed solution to generate sol-gel reaction under the action of continuous current, adds ionic groups into the raw material mixed solution, the ionic group is used as a heteroatom donor and an electron transport carrier, the efficiency of electrochemical catalysis sol-gel reaction is improved, the production rate of the carbon aerogel precursor is improved, the carbon aerogel is obtained after the carbon aerogel precursor is subjected to solvent replacement, drying and pyrolysis carbonization, the heteroatom donor enables the obtained carbon aerogel to have heteroatom doping, namely, the preparation method of the carbon aerogel prepares the carbon aerogel according to an electrochemical method, wherein the raw material solution is added with ionic groups to provide heteroatom doping for the carbon aerogel, meanwhile, the carbon aerogel doped with heteroatoms is used as an electron transmission carrier, so that the production rate of the carbon aerogel doped with heteroatoms is effectively increased, and convenience is provided for industrial production. And the reaction regulation of the electrochemical catalysis sol-gel reaction is easy to control.
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 schematic flow diagram of a method for preparing a carbon aerogel according to an embodiment of the present invention;
fig. 2 shows an electrolytic schematic in the preparation of a carbon aerogel precursor according to the carbon aerogel preparation method of an embodiment of the present invention;
fig. 3 shows an SEM photograph of the carbon aerogel obtained by the method for preparing a carbon aerogel according to the 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 schematic 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: mixing at least one phenol series compound, formaldehyde, an ionic group raw material and a solvent to obtain a raw material mixed solution.
Wherein the phenolic compounds comprise 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.
The ionic group raw material is used to provide at least one of a nitrogen-containing group, a sulfur-containing group, and a phosphorus-containing group, in this embodiment, the ionic group is provided by an ionic liquid (referring to a liquid composed of ions), the ionic group raw material includes at least one of an ionic liquid containing a nitrogen-containing group, a sulfur-containing group, and a phosphorus-containing group, and the ionic liquid includes at least one of an imidazole ionic liquid, a pyridine ionic liquid, a piperidine ionic liquid, a pyrrolidine ionic liquid, a quaternary ammonium salt ionic liquid, and a quaternary phosphonium salt ionic liquid.
The solvent is deionized water, the molar ratio of the phenolic compounds to formaldehyde in the raw material mixed solution is 0.2-1: 1, the solid content of the raw material mixed solution is 10% -60%, the addition amount of the ionic group raw material is confirmed according to requirements, the total mass content of nitrogen, phosphorus and sulfur in the finally obtained carbon aerogel is 0.01% -5%, and correspondingly, the addition amount of the ionic liquid is 0.05% -10% of the solid content of the raw material mixed solution.
Step S02: and (3) introducing current into the raw material mixed liquid, and continuously reacting for the first time to obtain the carbon aerogel precursor.
In this embodiment, the raw material mixture is placed in an electrolytic cell, a constant current or a constant voltage of 1 to 50 milliamperes is supplied to the raw material mixture through an inert electrode of the electrolytic cell, and after the reaction is continued for 0.5 to 12 hours (first time), a carbon aerogel precursor is obtained.
The reaction is carried out in an electrolytic cell, the reaction environment is normal temperature and normal pressure and is easy to control, the inert electrode is a sheet-shaped or columnar electrode, and the electrode material is selected from graphite, platinum or gold.
In the present embodiment, the normal temperature corresponds to 25 degrees celsius, the normal pressure corresponds to a standard atmospheric pressure, and the actual environment has a certain deviation, but the present invention is not particularly affected, and is not particularly limited herein.
Step S03: the solvent solution of the carbon aerogel precursor is replaced and dried to obtain a carbon xerogel.
The carbon xerogel is obtained by replacing the solvent solution of the carbon aerogel precursor with an organic solvent and then drying at atmospheric pressure. In this embodiment, the organic solvent is an anhydrous alcohol solvent or an anhydrous ketone solvent.
Step S04: and carbonizing the carbon xerogel to obtain the carbon aerogel.
In step S04, the carbon xerogel is placed in an inert gas environment and carbonized through temperature programming control to obtain carbon aerogel,
wherein the temperature programming comprises raising the temperature to 350-500 ℃ at a rate of 1-10 ℃/min, keeping the temperature for 0.5-2 hours, raising the temperature to 700-1100 ℃ at a rate of 1-10 ℃/min, keeping the temperature for 0.5-4 hours, and completing carbonization to obtain the carbon aerogel. And after the carbonization is finished, cooling to room temperature so as to take out. The inert gas is, for example, one or a mixture of two of nitrogen and helium.
In the embodiment, the specific surface area of the obtained carbon aerogel is 600-2000 m according to the solid content of the raw material mixed liquid and the intensity of the electrolysis current in the preparation of the carbon aerogel precursor2(ii)/g, specific surface area of mesopores in carbon aerogel to total specific surface area30 to 70 percent of the total weight of the composition.
Fig. 2 shows an electrolytic schematic in the preparation of a carbon aerogel precursor according to the method for preparing a carbon aerogel according to an embodiment of the present invention.
Referring to fig. 2, the electrolytic cell is composed of a cell body 110 and an upper cover 120 to obtain a sealed space, a raw material mixture 101 is disposed in the sealed space, the upper cover 120 is provided with electrodes respectively extending into the raw material mixture in the sealed space and receiving an output current of a power supply 130, and the power supply 130 is a voltage-stabilizing constant current source to continuously provide a current with a stable voltage of 1 to 50 mv.
The electrode of the raw material mixed liquid extending into the closed space is an inert electrode, and the material of the electrode is graphite, platinum, gold and other materials, so that the reaction of the electrode material and the raw material mixed liquid is avoided, and the reliability of the obtained carbon aerogel precursor is guaranteed.
Fig. 3 shows an SEM photograph of the carbon aerogel obtained by the method for preparing a carbon aerogel according to the embodiment of the present invention.
The following shows details of some examples of the preparation method of carbon aerogel and the carbon aerogel obtained thereby according to the embodiments of the present invention.
Example l
In a 100ml electrolytic cell with an inert electrode, 58g of deionized water was added, and then 11g of resorcinol, 16g of formaldehyde (corresponding to a formaldehyde solution concentration of 37%), and 4g of guanidine carbonate (chemical formula of C2H10N6H2CO3) were weighed into 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. Soaking the carbon powder in absolute ethyl alcohol for 8 hours, washing the carbon powder, and drying the carbon powder at 90 ℃ under normal pressure 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 900 ℃ at the heating rate of 5 ℃/min, keeping for 2h, cooling to room temperature, and taking out. The structure schematic diagram of the carbon aerogel precursor preparation electrolytic cell is shown in the attached figure 2, and the microscopic morphology SEM picture is shown in the attached figure 3. The specific surface area of the carbon aerogel sample is 960m2G, density 0.46g/cm3The mesoporous aperture is 4nm, and the content of doping element nitrogen is 2 percent.
Example 2
In a 100ml electrolytic cell with an inert electrode, 58g of deionized water was added, and then 5.5g of resorcinol, 4.5g of phenol, 18g of formaldehyde (corresponding to a concentration of 37% in the formaldehyde solution), and 4g of tributylethylphosphine bis (trifluoromethanesulfonyl) imide salt were weighed into the electrolytic cell, and after magnetic stirring for 30min, 30mA constant current was continuously applied to the electrolytic cell for 10 hours to obtain a carbon aerogel precursor. Soaking the carbon powder in absolute ethyl alcohol for 7 hours, washing the carbon powder, and drying the carbon powder at 85 ℃ under normal pressure to obtain the carbon xerogel. And placing the carbon xerogel in a quartz boat, heating to 360 ℃ at the heating rate of 4 ℃/min in the nitrogen atmosphere, keeping for 0.7h, continuing heating to 950 ℃ at the heating rate of 5 ℃/min, keeping for 3h, cooling to room temperature, and taking out. The specific surface area of the carbon aerogel sample is 900m2A density of 0.51 g/cm/g3The mesoporous aperture is 6nm, the content of doping element nitrogen is 0.1%, the content of phosphorus is 0.05%, and the content of fluorine is 0.08%.
Example 3
In a 100ml electrolytic cell with an inert electrode, 70g of deionized water was added, and then 9.5g of phenol, 16g of formaldehyde (corresponding to a concentration of 37% in the formaldehyde solution), and 4g of guanidine hydrochloride (chemical formula: CH6ClN3) were weighed into the electrolytic cell, and after magnetic stirring for 30min, 40mA constant current was continuously applied to the electrolytic cell for 9 hours to obtain a carbon aerogel precursor. Soaking the carbon powder in absolute ethyl alcohol for 8 hours, washing the carbon powder, and drying the carbon powder at 90 ℃ under normal pressure 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 900 ℃ at the heating rate of 5 ℃/min, keeping for 5h, cooling to room temperature, and taking out. The specific surface area of the carbon aerogel sample is 1000m2The density is 0.39g/cm3, the mesoporous aperture is 4nm, and the content of doping element nitrogen is 1%.
The preparation method of the carbon aerogel catalyzes the raw material mixed solution to generate sol-gel reaction under the action of continuous current, adds ionic groups into the raw material mixed solution, the ionic group is used as a heteroatom donor and an electron transport carrier, the efficiency of electrochemical catalysis sol-gel reaction is improved, the production rate of the carbon aerogel precursor is improved, the carbon aerogel is obtained after the carbon aerogel precursor is subjected to solvent replacement, drying and pyrolysis carbonization, the heteroatom donor enables the obtained carbon aerogel to have heteroatom doping, namely, the preparation method of the carbon aerogel prepares the carbon aerogel according to an electrochemical method, wherein the raw material solution is added with ionic groups to provide heteroatom doping for the carbon aerogel, meanwhile, the carbon aerogel doped with heteroatoms is used as an electron transmission carrier, so that the production rate of the carbon aerogel doped with heteroatoms is effectively increased, and convenience is provided for industrial production. And the reaction regulation of the electrochemical catalysis sol-gel reaction is easy to control.
The electrochemical catalysis sol-gel reaction is convenient to carry out at normal temperature, the current intensity is 1-50 milliamperes, and the overall energy consumption is low.
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 (21)
1. A method for preparing a carbon aerogel, comprising:
mixing at least one phenolic series compound, formaldehyde, an ionic group raw material and a solvent to obtain a raw material mixed solution;
introducing current into the raw material mixed solution, and continuously reacting for the first time to obtain a carbon aerogel precursor;
carrying out solvent replacement on the carbon aerogel precursor, and drying to obtain carbon xerogel;
carbonizing the carbon xerogel to obtain the carbon aerogel.
2. The method of preparing a carbon aerogel according to claim 1,
the ionic group raw material comprises at least one element of nitrogen, phosphorus and sulfur.
3. The method of preparing a carbon aerogel according to claim 2,
the total mass content of nitrogen, phosphorus and sulfur elements in the carbon aerogel is 0.01-5%.
4. The method of preparing a carbon aerogel according to claim 2,
the ionic group raw material is ionic liquid, and the ionic liquid is at least one of ionic liquid containing nitrogen groups, sulfur groups and phosphorus groups.
5. The method of preparing a carbon aerogel according to claim 4,
the ionic liquid comprises at least one of imidazole ionic liquid, pyridine ionic liquid, piperidine ionic liquid, pyrrolidine ionic liquid, quaternary ammonium salt ionic liquid and quaternary phosphonium salt ionic liquid.
6. The method of preparing a carbon aerogel according to claim 1,
the at least one phenolic 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.
7. The method of preparing a carbon aerogel according to claim 1,
the molar ratio of at least one phenolic compound in the raw material mixed liquid to formaldehyde is 0.2-1: 1, and the solid content of the raw material mixed liquid is 10-60%.
8. The method of preparing a carbon aerogel according to claim 1,
the current intensity of the current introduced into the raw material mixed liquid is 1-50 milliamperes.
9. The method of preparing a carbon aerogel according to claim 8,
the first time is 0.5-12 hours, and the reaction environment is normal temperature and normal pressure.
10. The method of preparing a carbon aerogel according to claim 1,
in the step of drying to obtain a carbon xerogel, the ambient pressure is normal pressure.
11. The method of preparing a carbon aerogel according to claim 1,
in the step of replacing the carbon aerogel precursor with the solvent, an organic solvent is used for the replacement.
12. The method of preparing a carbon aerogel according to claim 11,
the organic solvent is an anhydrous alcohol solvent or an anhydrous ketone solvent.
13. The method of preparing the carbon aerogel of claim 1, wherein said carbonizing said carbon xerogel comprises:
and (3) placing the carbon xerogel in an inert gas environment, and controlling carbonization by temperature programming.
14. The method of preparing a carbon aerogel of claim 13, wherein said temperature programming comprises:
heating to 350-500 ℃ at a heating rate of 1-10 ℃/min, and keeping for 0.5-2 hours;
after keeping for 0.5-2 hours, heating to 700-1100 ℃ at a heating rate of 1-10 ℃/min, and keeping for 0.5-4 hours to finish carbonization, thereby obtaining the carbon aerogel.
15. The method of preparing a carbon aerogel according to claim 1,
the current introduced into the raw material mixed liquid is provided by a voltage-stabilizing constant current source.
16. The method of preparing a carbon aerogel according to claim 13,
the inert gas is at least one of nitrogen or helium.
17. The method of preparing a carbon aerogel according to claim 1,
the carbon aerogel is a three-dimensional network structure.
18. The method of preparing a carbon aerogel according to claim 1, wherein the step of supplying an electric current to the raw material mixed liquid comprises:
and placing the raw material mixed solution in an electrolytic cell, and continuously providing constant current or constant voltage current through an inert electrode.
19. The method of preparing a carbon aerogel of claim 18,
the inert electrode is a sheet-shaped or columnar electrode.
20. The method of preparing a carbon aerogel of claim 18,
the inert electrode is selected from graphite, platinum or gold.
21. The method of preparing a carbon aerogel according to claim 4,
the addition amount of the ionic liquid is 0.05-10% of the solid content of the raw material mixed liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111192452.0A CN113816357A (en) | 2021-10-13 | 2021-10-13 | Preparation method of carbon aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111192452.0A CN113816357A (en) | 2021-10-13 | 2021-10-13 | Preparation method of carbon aerogel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113816357A true CN113816357A (en) | 2021-12-21 |
Family
ID=78920330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111192452.0A Withdrawn CN113816357A (en) | 2021-10-13 | 2021-10-13 | Preparation method of carbon aerogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113816357A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113716548A (en) * | 2021-10-13 | 2021-11-30 | 天津晨祥丰凯新材料科技有限公司 | Preparation method of carbon aerogel and precursor thereof |
| CN114852988A (en) * | 2022-04-29 | 2022-08-05 | 东华大学 | Heteroatom-doped carbon aerogel and preparation method and application thereof |
-
2021
- 2021-10-13 CN CN202111192452.0A patent/CN113816357A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113716548A (en) * | 2021-10-13 | 2021-11-30 | 天津晨祥丰凯新材料科技有限公司 | Preparation method of carbon aerogel and precursor thereof |
| CN113716548B (en) * | 2021-10-13 | 2023-03-14 | 天津得瑞丰凯新材料科技有限公司 | Preparation method of carbon aerogel and precursor thereof |
| CN114852988A (en) * | 2022-04-29 | 2022-08-05 | 东华大学 | Heteroatom-doped carbon aerogel and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113816357A (en) | Preparation method of carbon aerogel | |
| CN106229521B (en) | A kind of FeCx@NC catalyst with core-casing structure and preparation method thereof | |
| Xu et al. | Electrochemical synthesis of ammonia using a cell with a Nafion membrane and SmFe 0.7 Cu 0.3− x Ni x O 3 (x= 0− 0.3) cathode at atmospheric pressure and lower temperature | |
| CN105914374B (en) | Composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure and its preparation method and application | |
| CN107170967A (en) | Pre- intercalated layered barium oxide nano material of bivalent metal ion and its preparation method and application | |
| AU2015292008B2 (en) | Use of tungsten-containing material | |
| CN106159239B (en) | A kind of preparation method of manganese sulfide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN105597791A (en) | Molybdenum selenide/porous carbon nanofiber composite material and preparation method and application thereof | |
| CN110052277A (en) | A kind of preparation method of transiting metal group metal sulfide oxygen-separating catalyst | |
| CN111909736B (en) | Electrochemical upgrading method for bio-oil | |
| CN112582658A (en) | Microbial fuel cell constructed by Fe-MOF-GO film anode | |
| CN111229288A (en) | Mo loaded by carbon fiber paperboard2C/NC catalyst, preparation method and application thereof | |
| CN112023951A (en) | Graphene oxide supported nickel-cobalt double-metal selenide oxygen evolution catalyst and preparation and application thereof | |
| CN110492088A (en) | A kind of ZIF-8@redox graphene sulfur loaded composite material and preparation method and lithium-sulphur cell positive electrode and lithium-sulfur cell | |
| CN102617147A (en) | Perovskite structure aluminate-based mixing conductive ceramics and preparation method thereof | |
| CN101483252A (en) | Fuel cell apparatus using NH3 as fuel gas, manufacturing method and using method thereof | |
| CN111545221B (en) | Homologous metal gradient material and preparation method and application thereof | |
| CN112086651B (en) | Synthetic method of WN-rGO nano particles and microbial fuel cell constructed by same | |
| CN114590791A (en) | Carbon aerogel preparation device and preparation method thereof | |
| CN111533110B (en) | Preparation method of nitrogen, sulfur and phosphorus co-doped porous carbon nanotube | |
| CN109592676B (en) | Preparation method of carbon nano composite material derived from carbon nanosheet matrix grown on graphene oxide | |
| Poling et al. | New intermediate temperature proton conductors: Hydrated heavy alkali thio-hydroxogermanates | |
| CN106835191A (en) | A kind of low-temperature protonic conductor solid oxidate electrolytic cell | |
| CN110433843A (en) | A kind of three-dimensional porous elctro-catalyst CoP@NPC and the preparation method and application thereof | |
| CN109360959A (en) | A kind of carbon selenium material and preparation method thereof and the application in energy storage device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220908 Address after: Room 708, Building A3, No. 12, Nanhai Road, Tianjin Economic and Technological Development Zone, Xiqing District, Tianjin, 300457 (Tianjin Yiqi Fighting Business Secretary Co., Ltd. Trustee No. 287) (multiple address information exists) Applicant after: TIANJIN DERUI FENGKAI NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: Plant D1, No.9 Tianyuan Road, Saida Industrial Park, Xiqing Economic and Technological Development Zone, Binhai New Area, Tianjin 300385 Applicant before: TIANJIN CHENXIANG FENGKAI NEW MATERIAL TECHNOLOGY CO.,LTD. |
|
| TA01 | Transfer of patent application right | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20211221 |
|
| WW01 | Invention patent application withdrawn after publication |