CN114455564A - Carbon aerogel for regulating and controlling density by space limited-area centrifugal force field and method - Google Patents
Carbon aerogel for regulating and controlling density by space limited-area centrifugal force field and method Download PDFInfo
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Abstract
The invention discloses a preparation method of carbon aerogel for regulating and controlling density by a space limited centrifugal field, which comprises the following steps: step 1, uniformly mixing a carbon nano tube, a surfactant and water; step 2, ultrasonically oscillating the mixed solution obtained in the step 1 and standing, and retaining the residual solid matter on the lower layer; step 3, uniformly mixing resorcinol, formaldehyde, sodium carbonate and water; step 4, adding the mixed solution obtained in the step 3 into the residual solid B obtained in the step 2, and uniformly stirring; step 5, preparing wet gel; step 6, preparing alcogel; step 7, carrying out freeze drying treatment on the alcogel obtained in the step 6; and 8, putting the aerogel into a tubular furnace for high-temperature carbonization to obtain the carbon aerogel. The carbon aerogel has the advantages of high porosity, wide density change range, continuous and controllable density and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a carbon aerogel for regulating and controlling density by a space-limited centrifugal force field, and a preparation method of the carbon aerogel for regulating and controlling density by the space-limited centrifugal force field.
Background
The aerogel is a nano porous functional material with a multistage fractal structure. Due to the combination of nano-effect and macroscopic properties, it exhibits many unusual properties different from those of the common condensed state material, such as ultra-high porosity (>99.9%), ultra low density (minimum about 1 kg/m)3) Ultra low refractive index of (<1.0003), ultra low thermal conductivity: (<0.01W/(m.K)), an ultra-low Young's modulus (minimum about 104Pa), and an ultra-low dielectric constant (<1.003), ultra-low speed of sound: (<70m/s), high specific surface area (several thousand m)2The/g) and the ultra-wide adjustable range of physical properties. Aerogels have a wide range of compositions, including chalcogenide aerogels, organic aerogels, carbon-based aerogels, carbide aerogels, and various other classes of aerogels, in addition to conventional oxide aerogels. Due to unique performance and various components, the aerogel is not only considered as a class of materials, but also more considered as a class of structures, and some scholars even classify the aerogel into a new substance condensation state, so that the aerogel has irreplaceable effects on Cerenkov detection, inertial confinement fusion, space high-speed particle capture, super-current helium phase change research and the like.
Carbon aerogel is one of the hot spots that has received wide attention from various researchers in recent years. The carbon aerogel has good conductivity and strong chemical inertia, is widely applied to the fields of energy, environmental protection, chemical production, electronic devices, biological medical treatment and the like by virtue of unique structure and property, particularly has important application value in the aspects of laser equation of state experiments, photocatalysis, energy storage and the like, and in addition, the carbon aerogel has very high specific surface area and is expected to be used for storing hydrogen and removing oil stains.
The development of carbon aerogels dates back to 1989, Pekala et al, Lawrence Levermore laboratories, USA, invented resorcinol-formaldehyde organic aerogels, which were pyrolyzed and carbonized at high temperature to obtain carbon aerogels, after which various carbon aerogels were invented and reported successively. In 2006, Bryning et al prepared single-walled carbon nanotube aerogel for the first time, dispersed single-walled carbon nanotubes in water using a surfactant, and prepared single-walled carbon nanotube aerogel using a sol-gel method. Aliev et al prepared a lamellar carbon nanotube aerogel having superelasticity. Zou et al prepared ultra-low density carbon nanotube aerogels, which could be used for sensors. In 2016, Shen et al prepared carbon nanotube aerogel with different densities by using cheap industrial carbon nanotubes as raw materials and utilizing a centrifugal process and a supercritical drying process.
Li Yuangang et al (national invention patent publication No. CN113117613, published: 2021-07-16) creatively obtain a supramolecular aerogel with a three-dimensional supramolecular network structure by using small organic molecules as a gelling agent raw material, wherein the supramolecular aerogel has the same volume as a bi-component hydrogel and has a lower limit of a density control range of 4mg/cm3The elastic solid material has good reversibility and stimulus responsiveness.
Ma Xiao Jun et al (national invention patent publication No. CN113816356A, Kokai: 2021-12-21) liquefy wood powder and other biomass materials to obtain wood liquefied product precursor, mix with formaldehyde and hexamethylenetetramine, crosslink at a certain temperature to form hydrogel, replace with solvent, and dry to form aerogel. Further, the properties of the aerogel are changed and the pore structure is regulated by combining high-temperature pyrolysis and steam one-step activation technology, so that the loose and porous wood all-component carbon aerogel with ultralow density is prepared.
Chu Zengyong et al (national invention patent publication No. CN113145031A, published: 2021-07-23) mix cellulose and graphene oxide, add to water, stir under liquid to raise temperature, heat under liquid to stir and sonicate; heating, mechanically stirring and foaming, sealing, heating, and adjusting pressure; and pouring the mixture into a mold, cooling the mixture by liquid nitrogen, and freeze-drying the mixture to obtain the cellulose/graphene oxide composite aerogel.
Matricaria championii et al (national invention patent publication No. CN112980044A, published: 2021-06-18) nanocrystallize Kevlar macroscopic fibers to prepare an aramid nanofiber colloidal dispersion; preparing a large aramid nanofiber hydrogel by a solvent exchange phase transition method; by using supercritical CO2And preparing the bulk aramid nanofiber aerogel by drying processes such as normal pressure and the like.
Chengjing et al (national invention patent publication No. CN112265982A, published: 2021-01-26) prepare aerogel based on a method of reduction-freezing-drying to dryness followed by pyrolysis, and then obtain an N-doped graphene/graphene nanoribbon composite absorber with a three-dimensional porous structure in a manner of doping N atoms through high-temperature reaction.
The properties of the carbon aerogel such as conductivity, mechanical modulus, porosity and the like are directly related to the density, and in practical application, special requirements are placed on the density of the carbon aerogel, for example, in a laser equation of state experiment, the required density range of the carbon aerogel is 1000mg/cm of 100-3. However, studies on the wide-range control of carbon aerogel density have been reported to a lesser extent.
Disclosure of Invention
The invention aims to provide carbon aerogel for regulating and controlling density by a space limited centrifugal force field, which has the advantages of high porosity, wide density change range and continuous and controllable density.
The invention also aims to provide a preparation method of the carbon aerogel with the density regulated by the space limited centrifugal force field.
The first technical scheme adopted by the invention is that the preparation method of the carbon aerogel with the density regulated and controlled by the space limited centrifugal force field specifically comprises the following steps:
2, ultrasonically oscillating the mixed solution A obtained in the step 1 for 5-6h, standing at room temperature for 3-4d, and removing supernatant liquid after solid substances are completely separated out from the liquid and deposited at the bottom of the container to obtain a lower-layer residual solid substance B;
step 3, uniformly mixing resorcinol, formalin, sodium carbonate and water, and magnetically stirring for 1-2 hours to form a mixed solution C;
step 4, adding the mixed solution C obtained in the step 3 into the residual solid matter B obtained in the step 2, and uniformly stirring to obtain a mixed solution D;
and 5, transferring the mixed solution D obtained in the step 4 into a plastic centrifuge tube, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 1-2D at room temperature, and then centrifuging to obtain the wet gel.
Step 6, putting the wet gel obtained in the step 5 and a centrifugal tube into a thermostat, soaking and washing for 5-6 days by using tertiary butanol, and replacing the solvent once every 1-2 days to obtain alcogel;
step 7, freezing and drying the alcogel obtained in the step 6 to obtain aerogel;
and 8, putting the aerogel obtained in the step 7 into a tubular furnace, heating the aerogel to the temperature of 850-.
The present invention is also characterized in that,
in the step 1, the carbon nano tube is a multi-wall carbon nano tube, the surfactant is sodium dodecyl benzene sulfonate, and the mass ratio of the carbon nano tube to the surfactant to water is 1:5-10: 150.
In the step 2, the temperature set by ultrasonic oscillation is 45-50 ℃.
In the step 3, the formaldehyde aqueous solution is 38% by mass, and the mass ratio of the resorcinol to the formaldehyde aqueous solution to the sodium carbonate to the water is 1:1.5:0.001-0.01: 3.
In the step 4, the mass ratio of the mixed liquid C to the residual solid B is 1: 1-2.
In the step 5, the volume of the used centrifugal tube is 10-15ml, the rotation speed of the centrifugal machine is 1000-.
In step 6, the temperature of the incubator is set to 45-50 ℃.
And 7, quickly freezing for 3-4h in a freeze dryer, wherein the freeze drying is vacuumizing freeze drying, and the freeze drying time is 24-48 h.
In step 8, the heating rate of the tube furnace is 8-10 ℃/min, and the inert atmosphere is high-purity nitrogen.
The second technical scheme adopted by the invention is that the carbon aerogel with the density regulated and controlled by the space limited centrifugal force field is prepared by adopting the preparation method.
The invention has the beneficial effects that:
(1) the process is simple and easy to operate, and the prepared carbon aerogel is formed by alternately inserting spherical nano particles and tubular nano fibers and stacking the spherical nano particles and the tubular nano fibers together, has the advantages of high porosity, wide density change range, continuous and controllable density and the like, and has important significance in the fields of national defense, aerospace detection, energy conservation, environmental protection and basic physics research.
(2) The invention utilizes the space limited centrifugal field to regulate and control the density of the carbon aerogel, and the adjustable range of the density of the prepared carbon aerogel is 0.1g/cm3～0.5g/cm3。
Drawings
FIG. 1 is a flow chart of the production process of the present invention;
FIG. 2 is an SEM image (scale bar: 1 μm) of a carbon aerogel prepared in example 1 of the present invention;
FIG. 3 is an SEM image (scale: 500nm) of a carbon aerogel prepared in example 1 of the present invention;
FIG. 4 is a TEM image (scale: 200nm) of the carbon aerogel prepared in example 1 of the present invention;
FIG. 5 is a TEM image (scale: 100nm) of the carbon aerogel prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of carbon aerogel for regulating and controlling density by a space limited centrifugal force field, which specifically comprises the following steps as shown in figure 1:
in the step 1, the carbon nano tube is a multi-wall carbon nano tube, the surfactant is sodium dodecyl benzene sulfonate, and the mass ratio of the carbon nano tube to the surfactant to water is 1:5-10: 150.
2, ultrasonically oscillating the mixed solution A obtained in the step 1 for 5-6h, standing at room temperature for 3-4d, and removing supernatant liquid after solid substances are completely separated out from the liquid and deposited at the bottom of the container to obtain a lower-layer residual solid substance B;
in the step 2, the temperature set by ultrasonic oscillation is 45-50 ℃.
Step 3, uniformly mixing resorcinol, formalin, sodium carbonate and water, and magnetically stirring for 1-2 hours to form a mixed solution C;
in the step 3, the formaldehyde aqueous solution is 38% by mass, and the mass ratio of the resorcinol to the formaldehyde aqueous solution to the sodium carbonate to the water is 1:1.5:0.001-0.01: 3.
Step 4, adding the mixed solution C obtained in the step 3 into the residual solid matter B obtained in the step 2, and uniformly stirring to obtain a mixed solution D;
in the step 4, the mass ratio of the mixed liquid C to the residual solid B is 1: 1-2.
And 5, transferring the mixed solution D obtained in the step 4 into a plastic centrifuge tube, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 1-2D at room temperature, and then centrifuging to obtain the wet gel. Transferring the centrifugal tube into a horizontal rotor centrifuge, enabling the bottom of the centrifugal tube to be tightly attached to the maximum diameter position of a centrifuge rotor, and obtaining different centrifugal accelerations by regulating and controlling the rotating speed of the centrifuge, so that the regulation and control of the centrifugal force field size of the spatial position of the bottom of the centrifugal tube are realized, the direction of the centrifugal force is perpendicular to the rotating shaft and faces outwards, and wet gels with different densities can be obtained by centrifuging;
in the step 5, the volume of the used centrifugal tube is 10-15ml, the rotation speed of the centrifugal machine is 1000-.
Step 6, putting the wet gel obtained in the step 5 and a centrifugal tube into a thermostat, soaking and washing for 5-6 days by using tertiary butanol, and replacing the solvent once every 1-2 days to obtain alcogel;
in step 6, the temperature of the incubator is set to 45-50 ℃.
Step 7, freezing and drying the alcogel obtained in the step 6 to obtain aerogel;
and 7, quickly freezing for 3-4h in a freeze dryer, wherein the freeze drying is vacuumizing freeze drying, and the freeze drying time is 24-48 h.
And 8, putting the aerogel obtained in the step 7 into a tubular furnace, heating the aerogel to the temperature of 850-.
In step 8, the heating rate of the tube furnace is 8-10 ℃/min, and the inert atmosphere is high-purity nitrogen.
The invention also provides carbon aerogel for regulating and controlling the density by the space limited centrifugal force field, and the carbon aerogel is prepared by the preparation method.
Example 1
The mass ratio of the carbon nano tube, the surfactant and the water is 1:5:150, the mass ratio of the resorcinol, the formaldehyde, the sodium carbonate and the water is 1:1.5:0.001:3, the mass ratio of the mixed liquid C and the residual solid B is 1:1, and the carbon aerogel is prepared by centrifuging at the rotating speed of 1000r/min for 10 min.
Firstly, uniformly mixing a multi-walled carbon nanotube, sodium dodecyl benzene sulfonate and water according to a mass ratio of 1:5:150, and magnetically stirring for 2 hours to form a mixed solution A;
secondly, ultrasonically oscillating the mixed solution A at 50 ℃ for 5 hours, standing at room temperature for 3 days, and removing supernatant liquid after solid substances are completely separated out from the liquid and deposited at the bottom of the container to obtain a lower-layer residual solid substance B;
thirdly, uniformly mixing resorcinol, a formaldehyde water solution with the mass fraction of 38%, sodium carbonate and water according to the mass ratio of 1:1.5:0.001:3, and magnetically stirring for 2 hours to form a mixed solution C;
fourthly, adding the mixed solution C into the residual solid matter B according to the mass ratio of 1:1 of the mixed solution C to the residual solid matter B, and uniformly stirring to obtain a mixed solution D;
fifthly, transferring the mixed solution D into a plastic centrifuge tube with the volume of 15ml, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 1D at room temperature, transferring the centrifuge tube into a horizontal rotor centrifuge, enabling the bottom of the centrifuge tube to be tightly attached to the maximum diameter position of a rotor of the centrifuge, and centrifuging at the rotating speed of 1000r/min for 10min to obtain wet gel;
sixthly, putting the wet gel and the centrifuge tube into a thermostat with the temperature of 50 ℃, soaking and washing for 5 days by using tert-butyl alcohol, and replacing the solvent once every 1 day to obtain alcogel;
seventhly, transferring the alcogel to a freeze dryer for quick freezing for 3 hours, and starting vacuumizing for 24 hours after the sample is completely solidified to obtain aerogel;
and eighthly, putting the aerogel into a tubular furnace, heating the aerogel to 1050 ℃ from room temperature at the heating rate of 10 ℃/min under the protection of high-purity nitrogen, and maintaining the 1050 ℃ for 4 hours to fully carbonize the sample to obtain the carbon aerogel. FIGS. 2-3 are SEM images of the carbon aerogels prepared according to the present invention, FIGS. 4-5 are TEM images of the carbon aerogels prepared according to the present invention, and it can be seen from FIGS. 2-5 that spherical nanoparticles and tubular nanofibers are alternately inserted and stacked on each other, and the density of the carbon aerogels is measured to be about 0.25g/cm3。
Example 2
The mass ratio of the carbon nano tube, the surfactant and the water is 1:10:150, the mass ratio of the resorcinol, the formaldehyde, the sodium carbonate and the water is 1:1.5:0.001:3, the mass ratio of the mixed liquid C and the residual solid B is 1:1, and the carbon aerogel is prepared by centrifuging at the rotating speed of 1000r/min for 10 min.
Firstly, uniformly mixing a multi-walled carbon nanotube, sodium dodecyl benzene sulfonate and water according to a mass ratio of 1:10:150, and magnetically stirring for 1.5 hours to form a mixed solution A;
secondly, ultrasonically oscillating the mixed solution A at 45 ℃ for 6 hours, standing at room temperature for 4 days, and removing supernatant liquid after solid substances are completely separated out from the liquid and deposited at the bottom of the container to obtain a lower-layer residual solid substance B;
thirdly, uniformly mixing resorcinol, a formaldehyde water solution with the mass fraction of 38%, sodium carbonate and water according to the mass ratio of 1:1.5:0.001:3, and magnetically stirring for 1 hour to form a mixed solution C;
fourthly, adding the mixed solution C into the residual solid matter B according to the mass ratio of 1:2 of the mixed solution C to the residual solid matter B, and uniformly stirring to obtain a mixed solution D;
fifthly, transferring the mixed solution D into a plastic centrifuge tube with the volume of 10ml, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 2D at room temperature, transferring the centrifuge tube into a horizontal rotor centrifuge, enabling the bottom of the centrifuge tube to be tightly attached to the maximum diameter position of a rotor of the centrifuge, and centrifuging for 8min at the rotating speed of 2000r/min to obtain wet gel;
sixthly, putting the wet gel and the centrifuge tube into a thermostat at 45 ℃, soaking and washing for 6 days by using tert-butyl alcohol, and replacing the solvent every 2 days to obtain alcogel;
seventhly, transferring the alcogel to a freeze dryer for quick freezing for 4 hours, starting vacuumizing after the sample is completely solidified, wherein the vacuumizing time is 48 hours, and obtaining the aerogel;
and eighthly, putting the aerogel into a tubular furnace, heating the aerogel to 850 ℃ from room temperature at the heating rate of 8 ℃/min under the protection of high-purity nitrogen, maintaining the high temperature of 850 ℃ for 3 hours, and fully carbonizing the sample to obtain the carbon aerogel.
Example 3
The mass ratio of the carbon nano tube, the surfactant and the water is 1:5:150, the mass ratio of the resorcinol, the formaldehyde, the sodium carbonate and the water is 1:1.5:0.01:3, the mass ratio of the mixed liquid C and the residual solid B is 1:1, and the carbon aerogel is prepared by centrifuging at the rotating speed of 1000r/min for 10 min.
Firstly, uniformly mixing a multi-walled carbon nanotube, sodium dodecyl benzene sulfonate and water according to a mass ratio of 1:5:150, and magnetically stirring for 1 hour to form a mixed solution A;
secondly, ultrasonically oscillating the mixed solution A at 50 ℃ for 5 hours, standing at room temperature for 3 days, and removing supernatant liquid after solid substances are completely separated out from the liquid and deposited at the bottom of the container to obtain a lower-layer residual solid substance B;
thirdly, uniformly mixing resorcinol, a formaldehyde water solution with the mass fraction of 38%, sodium carbonate and water according to the mass ratio of 1:1.5:0.01:3, and magnetically stirring for 2 hours to form a mixed solution C;
fourthly, adding the mixed solution C into the residual solid matter B according to the mass ratio of 1:1 of the mixed solution C to the residual solid matter B, and uniformly stirring to obtain a mixed solution D;
fifthly, transferring the mixed solution D into a plastic centrifuge tube with the volume of 15ml, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 1D at room temperature, transferring the centrifuge tube into a horizontal rotor centrifuge, enabling the bottom of the centrifuge tube to be tightly attached to the maximum diameter position of a rotor of the centrifuge, and centrifuging at the rotating speed of 1000r/min for 10min to obtain wet gel;
sixthly, putting the wet gel and the centrifuge tube into a thermostat with the temperature of 50 ℃, soaking and washing for 5 days by using tert-butyl alcohol, and replacing the solvent once every 1 day to obtain alcogel;
seventhly, transferring the alcogel to a freeze dryer for quick freezing for 3 hours, and starting vacuumizing for 24 hours after the sample is completely solidified to obtain aerogel;
and eighthly, putting the aerogel into a tubular furnace, heating the aerogel to 1000 ℃ from room temperature at the heating rate of 10 ℃/min under the protection of high-purity nitrogen, and maintaining the high temperature of 1000 ℃ for 4 hours to fully carbonize the sample to obtain the carbon aerogel.
Example 4
And the mass ratio of the carbon nano tube, the surfactant and the water is 1:5:150, the mass ratio of the resorcinol, the formaldehyde, the sodium carbonate and the water is 1:1.5:0.001:3, the mass ratio of the mixed liquid C and the residual solid B is 1:2, and the carbon aerogel is prepared by centrifuging at the rotating speed of 1000r/min for 10 min.
Firstly, uniformly mixing a multi-walled carbon nanotube, sodium dodecyl benzene sulfonate and water according to a mass ratio of 1:5:150, and magnetically stirring for 2 hours to form a mixed solution A;
secondly, ultrasonically oscillating the mixed solution A at 50 ℃ for 5 hours, standing for 3 days at room temperature, and removing supernatant liquid after solid substances are completely separated out from the liquid and precipitated at the bottom of the container to obtain a lower-layer residual solid substance B;
thirdly, uniformly mixing resorcinol, a formaldehyde water solution with the mass fraction of 38%, sodium carbonate and water according to the mass ratio of 1:1.5:0.001:3, and magnetically stirring for 2 hours to form a mixed solution C;
fourthly, adding the mixed solution C into the residual solid matter B according to the mass ratio of 1:2 of the mixed solution C to the residual solid matter B, and uniformly stirring to obtain a mixed solution D;
fifthly, transferring the mixed solution D into a plastic centrifuge tube with the volume of 15ml, keeping the loading capacity of the plastic centrifuge tube to be less than one third of the volume of the centrifuge tube, standing for 1D at room temperature, transferring the centrifuge tube into a horizontal rotor centrifuge, enabling the bottom of the centrifuge tube to be tightly attached to the maximum diameter position of a rotor of the centrifuge, and centrifuging for 10min at the rotating speed of 4200r/min to obtain wet gel;
sixthly, putting the wet gel and the centrifuge tube into a thermostat with the temperature of 50 ℃, soaking and washing for 5 days by using tert-butyl alcohol, and replacing the solvent once every 1 day to obtain alcogel;
seventhly, transferring the alcogel to a freeze dryer for quick freezing for 3 hours, and starting vacuumizing for 24 hours after the sample is completely solidified to obtain aerogel;
and eighthly, putting the aerogel into a tubular furnace, heating the aerogel to 1000 ℃ from room temperature at the heating rate of 10 ℃/min under the protection of high-purity nitrogen, and maintaining the high temperature of 1000 ℃ for 4 hours to fully carbonize the sample to obtain the carbon aerogel.
Example 5
The mass ratio of the carbon nano tube, the surfactant and the water is 1:5:150, the mass ratio of the resorcinol, the formaldehyde, the sodium carbonate and the water is 1:1.5:0.001:3, the mass ratio of the mixed liquid C and the residual solid matter B is 1:1, and the carbon aerogel is prepared by centrifuging at the rotating speed of 2000r/min for 10 min.
Firstly, uniformly mixing a multi-walled carbon nanotube, sodium dodecyl benzene sulfonate and water according to a mass ratio of 1:5:150, and magnetically stirring for 2 hours to form a mixed solution A;
secondly, ultrasonically oscillating the mixed solution A at 50 ℃ for 5 hours, standing for 3 days at room temperature, and removing supernatant liquid after solid substances are completely separated out from the liquid and precipitated at the bottom of the container to obtain a lower-layer residual solid substance B;
thirdly, uniformly mixing resorcinol, a formaldehyde water solution with the mass fraction of 38%, sodium carbonate and water according to the mass ratio of 1:1.5:0.001:3, and magnetically stirring for 2 hours to form a mixed solution C;
fourthly, adding the mixed solution C into the residual solid matter B according to the mass ratio of 1:1 of the mixed solution C to the residual solid matter B, and uniformly stirring to obtain a mixed solution D;
fifthly, transferring the mixed solution D into a plastic centrifuge tube with the volume of 15ml, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 1D at room temperature, transferring the centrifuge tube into a horizontal rotor centrifuge, enabling the bottom of the centrifuge tube to be tightly attached to the maximum diameter position of a rotor of the centrifuge, and centrifuging at the rotating speed of 2000r/min for 10min to obtain wet gel;
sixthly, putting the wet gel and the centrifuge tube into a thermostat with the temperature of 50 ℃, soaking and washing for 5 days by using tert-butyl alcohol, and replacing the solvent once every 1 day to obtain alcogel;
seventhly, transferring the alcogel to a freeze dryer for quick freezing for 3 hours, and starting vacuumizing for 24 hours after the sample is completely solidified to obtain aerogel;
and eighthly, putting the aerogel into a tubular furnace, heating the aerogel to 1050 ℃ from room temperature at the heating rate of 10 ℃/min under the protection of high-purity nitrogen, and maintaining the 1050 ℃ for 4 hours to fully carbonize the sample to obtain the carbon aerogel.
Example 6
The mass ratio of the carbon nano tube, the surfactant and the water is 1:5:150, the mass ratio of the resorcinol, the formaldehyde, the sodium carbonate and the water is 1:1.5:0.001:3, the mass ratio of the mixed liquid C and the residual solid B is 1:1, and the carbon aerogel is prepared by centrifuging at the rotating speed of 3000r/min for 10 min.
Firstly, uniformly mixing a multi-walled carbon nanotube, sodium dodecyl benzene sulfonate and water according to a mass ratio of 1:5:150, and magnetically stirring for 2 hours to form a mixed solution A;
secondly, ultrasonically oscillating the mixed solution A at 50 ℃ for 5 hours, standing at room temperature for 3 days, and removing supernatant liquid after solid substances are completely separated out from the liquid and deposited at the bottom of the container to obtain a lower-layer residual solid substance B;
thirdly, uniformly mixing resorcinol, a formaldehyde water solution with the mass fraction of 38%, sodium carbonate and water according to the mass ratio of 1:1.5:0.001:3, and magnetically stirring for 2 hours to form a mixed solution C;
fourthly, adding the mixed solution C into the residual solid matter B according to the mass ratio of 1:1 of the mixed solution C to the residual solid matter B, and uniformly stirring to obtain a mixed solution D;
fifthly, transferring the mixed solution D into a plastic centrifuge tube with the volume of 15ml, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 1D at room temperature, transferring the centrifuge tube into a horizontal rotor centrifuge, enabling the bottom of the centrifuge tube to be tightly attached to the maximum diameter position of a rotor of the centrifuge, and centrifuging for 10min at the rotating speed of 3000r/min to obtain wet gel;
sixthly, putting the wet gel and the centrifuge tube into a thermostat with the temperature of 50 ℃, soaking and washing for 5 days by using tert-butyl alcohol, and replacing the solvent once every 1 day to obtain alcogel;
seventhly, transferring the alcogel to a freeze dryer for quick freezing for 3 hours, and starting vacuumizing for 24 hours after the sample is completely solidified to obtain aerogel;
and eighthly, putting the aerogel into a tubular furnace, heating the aerogel to 1050 ℃ from room temperature at the heating rate of 10 ℃/min under the protection of high-purity nitrogen, and maintaining the 1050 ℃ for 4 hours to fully carbonize the sample to obtain the carbon aerogel.
Example 7
And the mass ratio of the carbon nano tube, the surfactant and the water is 1:5:150, the mass ratio of the resorcinol, the formaldehyde, the sodium carbonate and the water is 1:1.5:0.001:3, the mass ratio of the mixed liquid C and the residual solid B is 1:1, and the carbon aerogel is prepared by centrifuging at the rotating speed of 4200r/min for 10 min.
Firstly, uniformly mixing a multi-walled carbon nanotube, sodium dodecyl benzene sulfonate and water according to a mass ratio of 1:5:150, and magnetically stirring for 2 hours to form a mixed solution A;
secondly, ultrasonically oscillating the mixed solution A at 50 ℃ for 5 hours, standing at room temperature for 3 days, and removing supernatant liquid after solid substances are completely separated out from the liquid and deposited at the bottom of the container to obtain a lower-layer residual solid substance B;
thirdly, uniformly mixing resorcinol, a formaldehyde water solution with the mass fraction of 38%, sodium carbonate and water according to the mass ratio of 1:1.5:0.001:3, and magnetically stirring for 2 hours to form a mixed solution C;
fourthly, adding the mixed solution C into the residual solid matter B according to the mass ratio of 1:1 of the mixed solution C to the residual solid matter B, and uniformly stirring to obtain a mixed solution D;
fifthly, transferring the mixed solution D into a plastic centrifuge tube with the volume of 15ml, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 1D at room temperature, transferring the centrifuge tube into a horizontal rotor centrifuge, enabling the bottom of the centrifuge tube to be tightly attached to the maximum diameter position of a rotor of the centrifuge, and centrifuging for 10min at the rotating speed of 4200r/min to obtain wet gel;
sixthly, putting the wet gel and the centrifuge tube into a thermostat with the temperature of 50 ℃, soaking and washing for 5 days by using tert-butyl alcohol, and replacing the solvent once every 1 day to obtain alcogel;
seventhly, transferring the alcogel into a freeze dryer for quick freezing for 3 hours, starting vacuumizing after the sample is completely solidified, wherein the vacuumizing time is 24 hours, and thus obtaining the aerogel;
and eighthly, putting the aerogel into a tubular furnace, heating the aerogel to 1050 ℃ from room temperature at the heating rate of 10 ℃/min under the protection of high-purity nitrogen, and maintaining the 1050 ℃ for 4 hours to fully carbonize the sample to obtain the carbon aerogel.
Example 8
The mass ratio of the carbon nano tube, the surfactant and the water is 1:5:150, the mass ratio of the resorcinol, the formaldehyde, the sodium carbonate and the water is 1:1.5:0.001:3, the mass ratio of the mixed liquid C and the residual solid matter B is 1:1, and the carbon aerogel is prepared by centrifuging for 5min at the rotating speed of 4200 r/min.
Firstly, uniformly mixing a multi-walled carbon nanotube, sodium dodecyl benzene sulfonate and water according to a mass ratio of 1:5:150, and magnetically stirring for 2 hours to form a mixed solution A;
secondly, ultrasonically oscillating the mixed solution A at 50 ℃ for 5 hours, standing for 3 days at room temperature, and removing supernatant liquid after solid substances are completely separated out from the liquid and precipitated at the bottom of the container to obtain a lower-layer residual solid substance B;
thirdly, uniformly mixing resorcinol, a formaldehyde water solution with the mass fraction of 38%, sodium carbonate and water according to the mass ratio of 1:1.5:0.001:3, and magnetically stirring for 2 hours to form a mixed solution C;
fourthly, adding the mixed solution C into the residual solid matter B according to the mass ratio of 1:1 of the mixed solution C to the residual solid matter B, and uniformly stirring to obtain a mixed solution D;
fifthly, transferring the mixed solution D into a plastic centrifuge tube with the volume of 15ml, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 1D at room temperature, transferring the centrifuge tube into a horizontal rotor centrifuge, enabling the bottom of the centrifuge tube to be tightly attached to the maximum diameter position of a rotor of the centrifuge, and centrifuging for 5min at the rotating speed of 4200r/min to obtain wet gel;
sixthly, putting the wet gel and the centrifuge tube into a thermostat with the temperature of 50 ℃, soaking and washing for 5 days by using tert-butyl alcohol, and replacing the solvent once every 1 day to obtain alcogel;
seventhly, transferring the alcogel to a freeze dryer for quick freezing for 3 hours, and starting vacuumizing for 24 hours after the sample is completely solidified to obtain aerogel;
and eighthly, putting the aerogel into a tubular furnace, heating the aerogel to 1050 ℃ from room temperature at the heating rate of 10 ℃/min under the protection of high-purity nitrogen, and maintaining the 1050 ℃ for 4 hours to fully carbonize the sample to obtain the carbon aerogel.
Claims (10)
1. The preparation method of the carbon aerogel with density regulated and controlled by the space limited centrifugal force field is characterized by comprising the following steps:
step 1, uniformly mixing carbon nanotubes, a surfactant and water, and magnetically stirring for 1-2 hours to form a mixed solution A;
2, ultrasonically oscillating the mixed solution A obtained in the step 1 for 5-6h, standing at room temperature for 3-4d, and removing supernatant liquid after solid substances are completely separated out from the liquid and deposited at the bottom of the container to obtain a lower-layer residual solid substance B;
step 3, uniformly mixing resorcinol, formalin, sodium carbonate and water, and magnetically stirring for 1-2 hours to form a mixed solution C;
step 4, adding the mixed solution C obtained in the step 3 into the residual solid matter B obtained in the step 2, and uniformly stirring to obtain a mixed solution D;
and 5, transferring the mixed solution D obtained in the step 4 into a plastic centrifuge tube, keeping the loading capacity not more than one third of the volume of the centrifuge tube, standing for 1-2D at room temperature, and then centrifuging to obtain the wet gel.
Step 6, putting the wet gel obtained in the step 5 and a centrifugal tube into a thermostat, soaking and washing for 5-6 days by using tertiary butanol, and replacing the solvent once every 1-2 days to obtain alcogel;
step 7, freezing and drying the alcogel obtained in the step 6 to obtain aerogel;
and 8, putting the aerogel obtained in the step 7 into a tube furnace, heating the aerogel to 850-1050 ℃ from room temperature under the protection of inert atmosphere, and maintaining the high temperature of 850-1050 ℃ for 3-4h to fully carbonize the sample, thereby obtaining the carbon aerogel.
2. The preparation method of the carbon aerogel for regulating and controlling the density by the spatially confined centrifugal force field according to claim 1, wherein in the step 1, the carbon nanotubes are multi-walled carbon nanotubes, the surfactant is sodium dodecyl benzene sulfonate, and the mass ratio of the carbon nanotubes to the surfactant to water is 1:5 to 10: 150.
3. The method for preparing carbon aerogel for regulating and controlling density by using a spatially confined centrifugal force field according to claim 1, wherein the temperature set by ultrasonic oscillation in the step 2 is 45-50 ℃.
4. The method for preparing the carbon aerogel for regulating and controlling the density by the spatially confined centrifugal force field according to claim 1, wherein in the step 3, the aqueous formaldehyde solution is 38% by mass, and the mass ratio of the resorcinol to the aqueous formaldehyde solution to the sodium carbonate to the water is 1:1.5:0.001-0.01: 3.
5. The method for preparing carbon aerogel for regulating and controlling density by using a space limited centrifugal force field according to claim 1, wherein in the step 4, the mass ratio of the mixed liquid C to the residual solid B is 1: 1-2.
6. The method for preparing carbon aerogel with density controlled by a spatially confined centrifugal force field according to claim 1, wherein in step 5, the volume of the used centrifugal tube is 10-15ml, the rotation speed of the centrifuge is 1000-.
7. The method for preparing a carbon aerogel having a density controlled by a spatially confined centrifugal force field according to claim 1, wherein in step 6, the temperature of the incubator is set to 45 to 50 ℃.
8. The method for preparing the carbon aerogel with the density regulated by the spatially confined centrifugal force field according to claim 1, wherein in the step 7, the rapid freezing time in a freeze dryer is 3-4 hours, the freeze drying is vacuum-pumping freeze drying, and the freeze drying time is 24-48 hours.
9. The method for preparing carbon aerogel with density regulated by a spatially confined centrifugal force field according to claim 1, wherein in step 8, the temperature rise rate of the tube furnace is 8-10 ℃/min, and the inert atmosphere is high-purity nitrogen.
10. Carbon aerogel with density controlled by a spatially confined centrifugal force field, characterized in that it is prepared by the process according to any one of claims 1 to 9.
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