CN114506837B - Method for regulating and controlling pore orientation of carbon aerogel, carbon aerogel and application - Google Patents
Method for regulating and controlling pore orientation of carbon aerogel, carbon aerogel and application Download PDFInfo
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000011148 porous material Substances 0.000 title abstract description 24
- 230000001276 controlling effect Effects 0.000 title abstract description 7
- 230000001105 regulatory effect Effects 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 29
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 14
- 241000233866 Fungi Species 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 amine compound Chemical class 0.000 claims description 16
- 239000004964 aerogel Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- 150000004982 aromatic amines Chemical class 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 229920003235 aromatic polyamide Polymers 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 241000228245 Aspergillus niger Species 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 241000228212 Aspergillus Species 0.000 claims description 2
- 241000228215 Aspergillus aculeatus Species 0.000 claims description 2
- 241000228197 Aspergillus flavus Species 0.000 claims description 2
- 241000228143 Penicillium Species 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 241000235527 Rhizopus Species 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000007710 freezing Methods 0.000 description 9
- 230000008014 freezing Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 239000001963 growth medium Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000001965 potato dextrose agar Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 238000009631 Broth culture Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
Abstract
The application provides a method for regulating and controlling the pore channel orientation of carbon aerogel, the carbon aerogel and application thereof. Adding m-phenylenediamine dispersed in an aqueous solution into a mixed solution of the filamentous fungi by taking the filamentous fungi as an assembly skeleton, stirring by shaking, adding ammonium persulfate to polymerize the m-phenylenediamine to obtain a mycelium-poly m-phenylenediamine compound, then performing cold forming in a cold field, performing freeze drying and demoulding, and finally performing high-temperature heat Jie Cheng carbon aerogel under an inert atmosphere. According to the application, through controlling the orientation of the carbon aerogel channel, the mass transfer resistance of the solution in the material is reduced, and the electric adsorption capacity of the carbon aerogel can be obviously enhanced.
Description
Technical Field
The application belongs to the technical field of inorganic nano porous materials and preparation thereof, and relates to a method for regulating and controlling the pore orientation of carbon aerogel, the carbon aerogel and application thereof.
Background
The Capacitive Deionization (CDI) technology has the advantages of no secondary pollution, simple and convenient operation and the like, is widely applied to the fields of sea water desalination, brackish water purification and the like, and has great application prospect.
Electrode materials are critical in determining CDI performance. Carbon materials, metal oxides, ag/Bi, mxene and the like are widely used for CDI electrodes. However, the conventional electrode preparation method is mainly based on a coating method, the material consumption is small, and the binder can block the pore diameter of the material to reduce the active area, so that the performance of the electrode material is weakened. The preparation of the powder material into the molded body electrode, avoiding the use of the binder and greatly improving the material consumption, has proved to be a feasible method for improving the CDI treatment efficiency.
However, in general, the pores of the molded body electrode are short-range and disordered, and there are closed pores, and the reaction is more likely to occur on the outer surface or accessible mesopores, and most of the material surface is not functional, thus resulting in waste. Particularly, when the porous material is applied to the CDI field, an electric double layer can be rapidly formed on the surface of the material, electrostatic repulsive force can prevent charged substances from migrating from a bulk solution to the surface of an electrode, irregular pore channels can lead to prolonged fluid passing time, and the adsorption balance is slowed down, so that the adsorption rate is influenced. Thus, the irregularities of the channels of the molded body greatly limit its application.
According to the application, hypha and aromatic amine monomers are used as raw materials, and the carbon aerogel formed body electrode with regular pore orientation is constructed through accurate regulation and control of a temperature field, and meanwhile, the influence of the pore orientation of the formed body electrode on CDI performance is examined.
Meanwhile, based on the characteristics of the carbon aerogel with the regular pore orientation, the carbon aerogel can be widely applied to the wider technical field, such as the field of energy battery anode materials or adsorption materials.
Disclosure of Invention
The primary aim of the application is to provide a carbon aerogel with controllable pore channel orientation, wherein the direction of the pore channel inside the material is consistent. The regular pore channels with the same direction can enable the fluid to pass through for a short time, the adsorption balance is fast, the adsorption performance of the material is greatly improved, and the CDI treatment efficiency can be remarkably improved when the material is particularly applied to the CDI field.
The carbon aerogel is a hypha@polyaromatic amine compound obtained by reacting filamentous fungi, aromatic amine monomers and an oxidant, and is obtained by cold field treatment, freeze drying and high-temperature carbonization; the cold field treatment refers to cooling treatment of one flat surface or two opposite flat surfaces on the three-dimensional shape of the material; preferably, the cold source is in direct contact with the flat surface of the three-dimensional shape of the material or in contact with the flat surface through the heat conducting sheet; when the three-dimensional shape of the material is a cylinder, the two bottom surfaces of the cylinder or the whole side surface of the cylinder is subjected to cooling treatment.
The pore diameter of the carbon aerogel material ranges from 5um to 200um.
A second object of the present application is to provide a method for preparing the above carbon aerogel. The preparation is simple, the operation is simple and convenient, the cost is low, and the mass production is convenient, and the preparation method is concretely as follows:
a method for regulating and controlling the pore orientation of carbon aerogel, comprising the following steps:
1) Polymerizing the filamentous hypha, aromatic amine monomer and oxidant to obtain a hypha@polyaromatic amine compound, and molding in a three-dimensional mold;
2) Uniformly contacting one surface, or two opposite surfaces, or two bottom surfaces, or the whole side surface of a cylinder of the mycelium@polyaramid compound in a three-dimensional shape molded by a mold with a cold source, or contacting the whole side surface of the cylinder with a heat-conducting sheet with the cold source;
3) The mycelium@polyaramid compound obtained after the treatment in the step 2) is freeze-dried and dehydrated to obtain mycelium@polyaramid aerogel;
4) And (3) carbonizing the mycelium@polyaromatic amine aerogel at a high temperature under an inert atmosphere to obtain the carbon aerogel.
Further, the temperature of the cold source in the step 2) is-40 to-5 ℃, preferably-25 to-10 ℃, and more preferably-20 to-15 ℃.
The temperature of the cold source is too high, the freezing speed is too slow, the slurry is sunk, and the density is uneven; too low a freezing temperature, too fast a freezing rate, inability of ice crystals to grow, formation of dense layers, and resulting in too small aerogel pores.
Further, the cold source treatment time of the step 2) is 5-20 hours, preferably 2-12 hours, and more preferably 4-6 hours.
The mycelium @ polyaromatic amine compound obtained in the step 1) in the method is preferably molded in a mold to form a three-dimensional material with a flat surface, so that the mycelium @ polyaromatic amine compound is beneficial to contact with a cold source, and the reaction efficiency is improved.
The application can select the cold source to contact with one surface or two opposite surfaces of the three-dimensional shape of the material. For example, when the molding material is a cube, only any one of the planes may be selected, or any two opposite planes may be selected to contact the heat sink. When the three-dimensional shape of the material is a cylinder, the two bottom surfaces of the cylinder or the whole side surface of the cylinder is subjected to cooling treatment. The contact may be via a thermally conductive sheet.
The three-dimensional shape includes: cubes, cylinders, cones, polyhedrons, pyramids, and the like.
The heat-conducting sheet is made of various heat-conducting metals or other heat-conducting materials.
In the method described above, the first step is performed,
the filamentous fungi comprise one or more of aspergillus aculeatus, aspergillus niger, aspergillus flavus, aspergillus rhizogenes and penicillium.
The aromatic amine monomer comprises one or more of aniline, pyrrole and m-phenylenediamine.
The oxidizing agent comprises a persulfate, preferably sodium persulfate or ammonium persulfate.
The mass ratio of the aromatic amine monomer to the dry pure mycelium is 2:1-1:10, preferably 1:1-1:5, further preferably 1:2.
the dry pure mycelium is obtained by breaking up the cultured filamentous fungi, filtering to form cakes, freezing with liquid nitrogen, and freeze-drying for 24 hours until the mycelium is completely dehydrated.
The molar ratio of the oxidant to the aromatic amine monomer is 1:0.5-1:3, preferably 1:1-1:1.5, more preferably 1:1.2.
the concentration of the dispersion of the hypha @ polyaromatic amine complex obtained in step 1) is 5 to 50g/L, preferably 20 to 40g/L, further preferably 25g/L.
The freeze-drying temperature in the step 3) is-20 ℃ to-90 ℃, preferably-60 ℃ to-90 ℃, and further preferably-80 ℃; the time is 12-48 hours, preferably 12-36 hours, more preferably 24 hours.
The carbonization temperature in the step 4) is 400-1100 ℃, the carbonization time is 1-10h, the preferable temperature is 600-800 ℃, and the preferable time is 2-4h.
The inert atmosphere in the step 4) is nitrogen or argon.
The method for regulating and controlling the pore orientation of the carbon aerogel is further optimized as follows:
step one: culturing the filamentous fungi by adopting a liquid phase method; the culture medium is prepared by dissolving 10-50 g of potato dextrose broth powder in 0.5-2L of deionized water, and adding 0.5-2 g of monopotassium phosphate and 0.2-1 g of magnesium sulfate; the temperature of the cultivation of the filamentous fungi is 5-37℃and the shaking is carried out in a shaking environment at a shaking speed of not more than 300rpm, preferably 100-200rpm; the cultivation time is 6-120 hours, preferably 72-96 hours.
Step two: stirring and dispersing the cultured filamentous fungi by an electric stirrer, repeatedly washing with deionized water, filtering, and freeze-drying for later use;
step three: weighing a certain amount of mycelium, adding the mycelium into deionized water to obtain mycelium dispersion liquid, adding aromatic amine monomers, adding a certain amount of oxidant to polymerize the monomers after the precursor is dissolved, repeatedly washing with deionized water to obtain mycelium@polyaromatic amine compound, and preserving at normal temperature;
step four: weighing a certain amount of mycelium@polyaromatic amine compound, adding a certain volume of deionized water to obtain mycelium@polyaromatic amine dispersion liquid, closing a container, and performing ultrasonic dispersion; the concentration of the dispersion liquid is 5-50g/L;
step five: the bottom plane of the container is contacted with a cold source for treatment; the bottom of the container is a heat-conducting sheet, and the rest surface is polytetrafluoroethylene (capable of preserving heat);
step six: freeze-drying until the mycelium is completely dehydrated to obtain mycelium@polyaramid aerogel;
step seven: and (3) carbonizing the mycelium@polyaromatic amine aerogel at high temperature under inert atmosphere to obtain the carbon aerogel.
A third object of the present application is to provide the use of the above carbon aerogel, or of the carbon aerogel obtained by the regulation of the above method. The method is particularly used for preparing an energy battery (air electrode material), a sensor (pressure sensor) or an adsorption material, and is further used for preparing a CDI electrode material.
When used for preparing the adsorption material, for example, the adsorption material can be used for adsorbing: gases, heavy metals or organics; further used for preparing CDI electrode materials.
The beneficial effects of the application are as follows:
(1) The application uses the filamentous fungi as raw materials, and has the advantages of green and environment protection and large surface area;
(2) The method regulates and controls the pore channel orientation of the carbon aerogel through a specific cold conduction means for the first time, is environment-friendly, quick in molding, simple in demolding, and beneficial to mass production, and can be molded in one step compared with the method for preparing the molded body electrode from the powder material in the prior art when being particularly applied to CDI electrode materials.
(3) The carbon aerogel with controllable pore channel orientation prepared by the application has excellent mechanical properties and has wide application prospects in the fields of energy batteries, sensors, adsorption and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the disordered hypha-m-phenylenediamine carbon aerogel of example 3;
FIG. 2 is a scanning electron microscope image of the vertically oriented hypha-m-phenylenediamine carbon aerogel of example 4;
FIG. 3 is a scanning electron microscope image of the horizontally oriented hypha-m-phenylenediamine carbon aerogel of the pore canal of example 5;
FIG. 4 shows the electrosorption performance of various materials measured in example 6.
The application is further illustrated below in conjunction with specific examples. These examples are only for illustrating the present application and are not intended to limit the scope of the present application. Further, after reading the teachings of the present application, those skilled in the art may make various changes or modifications to the present application, which equivalent forms also fall within the scope of the present application as defined in the appended claims.
Example 1
And (5) culturing and producing aspergillus niger on a large scale by adopting a liquid phase method. A potato dextrose broth culture medium is adopted, 25g of potato dextrose broth, 0.5g of anhydrous magnesium sulfate and 1g of dipotassium hydrogen phosphate are added into every 1 liter of deionized water, the mixture is sterilized at the temperature of 121 ℃ for 15 minutes, bacterial spots in the flat culture medium are inoculated into the sterilized liquid culture medium, and the culture medium is placed in a shaking table for culture. The temperature was controlled at 30℃and the oscillation rate at 150rpm. The Aspergillus niger grows to reach a peak value after 3 days.
Pouring the cultured filamentous fungi into a 1000mL blue-mouth bottle, stirring for 5h by adopting an electric stirrer at 1500rpm, and scattering for 3min by adopting a juicer. The dispersion liquid is separated by suction filtration through a G-2 sand core funnel, is respectively rinsed by deionized water and absolute ethyl alcohol, is suction filtered into cakes, is placed into a liquid nitrogen operation basin, is added with liquid nitrogen, and is rapidly frozen. And transferring the mixture into a freeze dryer after the freezing is finished, and freeze-drying the mixture for 24 hours until the mixture is completely dehydrated to obtain dried pure mycelium.
Example 2
The dried pure mycelium obtained in example 1 was taken as 2g, 200mL of deionized water was added thereto and stirred to disperse, and 1g of m-phenylenediamine was further added thereto and stirred at 500rpm for 1 hour. 2.1g of ammonium persulfate is weighed and dissolved in 30ml of deionized water, slowly dripped into the mycelium-m-phenylenediamine suspension, and continuously stirred for 2 hours to obtain the mycelium-poly m-phenylenediamine suspension, and the mycelium-poly m-phenylenediamine suspension is filtered into cakes by suction to obtain the compact mycelium-poly m-phenylenediamine composite material.
Example 3
The hypha-poly (m-phenylenediamine) composite material obtained in the example 2 is placed into an all-aluminum cylindrical mold (the side wall and the bottom of the mold and the upper cover are all made of all-aluminum materials), 30mL of deionized water is added and stirred for 1h, the concentration is 25g/L, ultrasonic dispersion is carried out for 30min, the mold is transferred into a refrigerator with the temperature of-20 ℃ for 4h, a cold field is dispersed in the refrigerator, the temperature is uniform, the frozen aerogel is transferred into a freeze dryer again for freeze drying at the temperature of-80 ℃ for 24h until the aerogel is completely dehydrated, the dehydrated aerogel is placed into a tubular furnace, the heating rate of 2 ℃/min is increased to 800 ℃ for pyrolysis for 2h, and the hypha-poly (m-phenylenediamine) carbon aerogel with disordered internal pore channels is obtained, and a scanning electron microscope image of the aerogel is shown in figure 1.
Example 4
Putting the mycelium-polymetaphenylene diamine compound obtained in the example 2 into a copper bottom, putting the side wall of the cylinder mould with polytetrafluoroethylene (the upper bottom of the mould is covered by a foam plate), adding 30mL of deionized water, stirring for 1h, performing ultrasonic dispersion for 30min, transferring the mould onto a freezing platform, transferring a cold field from the freezing platform (temperature is minus 20 ℃) to the copper bottom, freezing for 4h, transferring the frozen mycelium-polymetaphenylene diamine compound into a freeze dryer, performing freeze drying at minus 80 ℃ for 24h until complete dehydration, putting the dehydrated aerogel into a tubular furnace, performing pyrolysis for 2h at the temperature rising rate of 2 ℃/min to 800 ℃, and obtaining the mycelium-polymetaphenylene diamine carbon aerogel with internal pore channels from bottom to top, wherein a scanning electron microscope image is shown in figure 2.
Example 5
Putting the mycelium-polymetaphenylene diamine compound obtained in the embodiment 2 into a cylindrical mold, adding 30mL of deionized water, stirring for 1h, performing ultrasonic dispersion for 30min, sealing the upper bottom surface and the lower bottom surface of the mold by using heat insulation material polytetrafluoroethylene, transferring the mold into a refrigerator, freezing for 4h (the side surface takes the low temperature inside the refrigerator as a cold source, a cold field can only be conducted from the copper wall around the container to the inside of the container, namely the low temperature field provided by the refrigerator), and because the upper bottom surface and the lower bottom surface are isolated, the cold field at the temperature of-20 ℃ is conducted from the copper wall to the inside, transferring the frozen mycelium @ polymetaphenylene diamine compound into a freeze dryer, performing freeze drying for 24h at the temperature of-80 ℃ until the mycelium is completely dehydrated, putting the dehydrated aerogel into a tubular furnace, performing pyrolysis for 2h at the temperature rising rate of 2 ℃/min to 800 ℃, and obtaining the mycelium-polymetaphenylene diamine carbon aerogel (the inner direction of which is vertical to the side surface of the cylindrical mold) of which is in the horizontal direction (the inner direction is all points to the axis of the cylinder), wherein a scanning electron microscope chart is shown in figure 3.
Example 6
The materials obtained in examples 3, 4 and 5 were placed in a penetrating electric adsorption apparatus, the electric pressure was 1.2V, 500mg/L of chloride ion solution was taken, the solution was injected into the apparatus at a rate of 10mL/min, the adsorption was carried out for 2 hours, 7 samples were taken in total, and the content of chloride ions was measured. The results as in fig. 4 were obtained. From the figure, it can be seen that the adsorption saturation of the longitudinal channel carbon aerogel (example 4) is the fastest, the adsorption capacity is the highest, the rates at which the horizontal channel carbon aerogel (example 5) and the disordered channel carbon aerogel (example 3) reach the adsorption saturation are close, and the adsorption capacity of the non-oriented channel carbon aerogel is the lowest.
Claims (8)
1. A preparation method of carbon aerogel is characterized in that hypha@polyaromatic amine compound obtained by reacting filamentous fungi, aromatic amine monomers and an oxidant is obtained after cold field treatment, freeze drying and high-temperature carbonization; the cold field treatment refers to cooling treatment of one flat surface or two opposite flat surfaces on the three-dimensional shape of the material; the cold source is directly contacted with the flat surface of the three-dimensional shape of the material or contacted with the flat surface through the heat conducting sheet; when the three-dimensional shape of the material is a cylinder, cooling the two bottom surfaces of the cylinder or the whole side surface of the cylinder; the temperature of the cold source is-40 ℃ to-5 ℃; the cold source treatment time is 5-20h.
2. The method of manufacturing according to claim 1, comprising the steps of:
1) Polymerizing the filamentous hypha, aromatic amine monomer and oxidant to obtain a hypha@polyaromatic amine compound, and molding in a three-dimensional mold;
2) Uniformly contacting one surface, or two opposite surfaces, or two bottom surfaces, or the whole side surface of a cylinder of the mycelium@polyaramid compound in a three-dimensional shape molded by a mold with a cold source, or contacting the whole side surface of the cylinder with a heat-conducting sheet with the cold source;
3) The mycelium@polyaramid compound obtained after the treatment in the step 2) is freeze-dried and dehydrated to obtain mycelium@polyaramid aerogel;
4) And (3) carbonizing the mycelium@polyaromatic amine aerogel at a high temperature under an inert atmosphere to obtain the carbon aerogel.
3. The preparation method according to claim 2, wherein the filamentous fungi comprise one or more of aspergillus aculeatus, aspergillus niger, aspergillus flavus, aspergillus rhizopus and penicillium; the aromatic amine monomer comprises one or more of aniline, pyrrole and m-phenylenediamine; the oxidizing agent comprises a persulfate.
4. The preparation method according to claim 2, wherein the mass ratio of the aromatic amine monomer to the dry pure mycelium is 2:1-1:10; the molar ratio of the oxidant to the aromatic amine monomer is 1:0.5-1:3.
5. The method according to claim 2, wherein the concentration of the dispersion of the hypha @ polyaromatic amine complex obtained in step 1) is 5-50g/L.
6. The method according to claim 2, wherein the freeze-drying temperature in step 3) is-20 ℃ to-90 ℃ for 12-48 hours; the carbonization temperature in the step 4) is 400-1100 ℃, the carbonization time is 1-10h, and the inert atmosphere is nitrogen or argon.
7. Use of the carbon aerogel produced by the method of any one of claims 1-6 for producing a negative electrode or an adsorbent material for an energy cell.
8. Use of the carbon aerogel produced by the method of any one of claims 1 to 6 for the production of CDI electrode materials.
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