CN109922548B - Carbon-based electrothermal film and preparation method thereof - Google Patents
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Abstract
The invention relates to a carbon-based electrothermal film and a preparation method thereof, belongs to the technical field of carbon nano materials, and relates to preparation of a carbon film and application of the carbon film in the field of electric heating. The carbon-based electric heating film taking the graphitized microcrystal as the cross-linking agent is finally obtained by using the three-dimensional graphene as a framework unit, filling polyacrylonitrile, hot pressing, pre-oxidation and high-temperature carbonization. Different from the anisotropy and the stacking effect of graphene sheets brought by the traditional layer-by-layer self-assembly structure, the electrical and thermal properties of the film retain the isotropy of three-dimensional graphene to a certain extent. Meanwhile, the film has low working voltage and high heating rate, and is one of the reported film materials with the optimal electrothermal performance.
Description
Technical Field
The invention relates to a carbon-based electrothermal film and a preparation method thereof, belongs to the technical field of carbon nano materials, and relates to preparation of a carbon film and application of the carbon film in the field of electric heating.
Background
Coal heating is a long-term main heating mode in China, inevitably produces more pollutants and carbon dioxide, and brings a serious environmental pollution problem to China. The electric energy is clean and environment-friendly energy and plays a significant role in the field of future heating. The commonly used electric heating system mainly comprises materials such as resistance wires and metal nets, and takes nichrome as an example, so that the electric heating system is expensive, high in density, heavy in mass, low in electric heating conversion efficiency and difficult to process. Therefore, there is an urgent need to develop an electrothermal material with low density, good flexibility and high efficiency.
The graphene has excellent mechanical, electrical and thermal properties, low density, easy processing and corrosion resistance. These excellent physical properties make them of great potential in the field of electrocaloric materials. At present, there are two preparation methods for the graphene electrothermal film, one is to obtain the transparent graphene electrothermal film on a transparent substrate, such as glass, PET, etc., by a chemical vapor deposition method, and the method is mainly used in the fields of automobile glass defogging, etc. However, this method is costly, not resistant to bending and not suitable for large-area production. The other method is to mix the high molecular resin and the graphene powder into slurry and form a film by printing, spraying and other methods. The electric heating film has poor structural uniformity, nonuniform heating and low electric heating conversion efficiency, and can not embody the intrinsic thermoelectric property of the graphene film. The super-advanced people invent an interlayer graphene electrothermal film, the working voltage is higher, the electrothermal conversion efficiency is lower, and the temperature rise and fall speed is slower. Liu Juan et al invented a 36V operating voltage's graphite alkene electric heat membrane, and operating voltage is on the high side, and does not give the electric heat conversion performance parameter of electric heat membrane.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the carbon-based electrothermal film takes three-dimensional graphene as a framework unit, polyacrylonitrile as filling, and finally obtains the carbon-based electrothermal film taking graphitized microcrystals as a cross-linking agent through hot pressing, pre-oxidation and high-temperature carbonization. Meanwhile, the working voltage is low, the heating rate is high, the temperature can reach 235 ℃ under the voltage of 1.75V, and the film is one of the film materials with the optimal electrothermal performance reported at present. In addition, the excellent electrical heating cycle performance in the bent state enables it to operate in harsh environments.
The technical solution of the invention is as follows:
a carbon-based electrothermal film is prepared from three-dimensional graphene and polyacrylonitrile, wherein the three-dimensional graphene is a skeleton unit, and the polyacrylonitrile is filled in the skeleton of the three-dimensional graphene;
the carbon-based electrothermal film comprises three-dimensional graphene and graphite microcrystals, wherein the three-dimensional graphene and the graphite microcrystals are in a cross-linked structure;
the thickness of the carbon-based electrothermal film is 10-500 mu m;
the carbon-based electrothermal film has good tensile property and bending property;
the carbon-based electrothermal film has a high specific heating rate which is not lower than 213 ℃ s-1V-1;
the carbon-based electrothermal film has low working voltage and can work below 10V.
A preparation method of a carbon-based electrothermal film comprises the following steps:
firstly, mixing graphene oxide and a first organic solvent, stirring, uniformly stirring to obtain a uniform solution, and then carrying out a solvothermal reaction on the obtained solution in a high-pressure reaction kettle;
secondly, performing solvent exchange on the product obtained in the first step and water, and performing freeze drying after the solvent exchange is finished;
thirdly, heating the product obtained in the second step in an inert atmosphere or under a vacuum condition to obtain a three-dimensional porous graphene skeleton structure;
fourthly, mixing polyacrylonitrile long-chain molecules with a second organic solvent, and stirring to obtain a uniform solution;
fifthly, adding the three-dimensional porous graphene skeleton structure obtained in the third step into the solution obtained in the fourth step to enable polyacrylonitrile long-chain molecules to be filled in the three-dimensional graphene pores, and drying after filling is completed to obtain a graphene/polyacrylonitrile composite material;
sixthly, carrying out hot pressing on the graphene/polyacrylonitrile composite material obtained in the fifth step in a mould to obtain a graphene/polyacrylonitrile composite material film;
and seventhly, pre-oxidizing the graphene/polyacrylonitrile composite material film obtained in the sixth step in a tubular furnace, and further carbonizing in Ar protective atmosphere to obtain the carbon-based electrothermal film.
In the first step, the first organic solvent is ethanol, acetone, tetrahydrofuran or N, N-dimethylformamide, the concentration of the graphene oxide is 0.375-10 mg/mL, and the solvothermal reaction temperature is 130-250 ℃.
The advantages of using the first organic solvent to disperse the graphene oxide are as follows: the three-dimensional graphene prepared by taking the organic solvent as the dispersion liquid has few stacked graphene units in a microstructure, is a network structure formed by crosslinking single-layer or few-layer graphene sheets by chemical bonds, and ensures the intrinsic structure and performance of the graphene.
In the third step, the heating treatment temperature is 200-1000 ℃, and the heating treatment time is 30-300 min;
in the fourth step, the second organic solvent is one or more than two of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethylene carbonate and N-methylpyrrolidone which are mixed according to any proportion; the molecular weight of polyacrylonitrile long-chain molecules is 5-20 ten thousand;
in the fifth step, the mass ratio of the three-dimensional porous graphene skeleton structure to the polyacrylonitrile long chain molecule is 10: 10-90; the advantages are that: the graphite microcrystal of the polyacrylonitrile with higher molecular weight after carbonization has larger grain size and less defects; the polyacrylonitrile can completely fill the pores of the three-dimensional graphene on one hand, and can form a cross-linked structure with the three-dimensional graphene after carbonization on the other hand to form a three-dimensional electric conduction and heat conduction channel;
in the sixth step, the hot pressing temperature is 25-150 ℃, and the hot pressing pressure is 19-500 Pa; the mold is a circular mold with the diameter of 10-100 mm. According to different requirements, the die can be made into any shape such as rectangle, square and the like. The advantages of different hot pressing pressures and temperatures are: the thermoplasticity of the polyacrylonitrile precursor can be ensured, and the compactness of the polyacrylonitrile precursor and the three-dimensional graphene composite material is further ensured;
in the seventh step, the pre-oxidation temperature is 250-320 ℃, and the carbonization temperature is 800-3000 ℃.
In the third step, the obtained three-dimensional graphene as a starting material for preparing the electric heating film has the advantages that: compared with the traditional layer-by-layer self-assembly preparation method, the three-dimensional graphene effectively prevents the stacking effect in the graphene film forming process, and the electrical and thermal properties of the film maintain the isotropy of the three-dimensional graphene to a certain extent.
Advantageous effects
(1) The carbon-based electric heating film taking the graphitized microcrystal as the cross-linking agent is finally obtained by using the three-dimensional graphene as a framework unit, filling polyacrylonitrile, hot pressing, pre-oxidation and high-temperature carbonization. Different from the anisotropy and the stacking effect of graphene sheets brought by the traditional layer-by-layer self-assembly structure, the electrical and thermal properties of the film retain the isotropy of three-dimensional graphene to a certain extent. Meanwhile, the film has low working voltage and high heating rate, and is one of the reported film materials with the optimal electrothermal performance.
(2) The electrothermal film disclosed by the invention is low in working voltage, high in heating rate and good in flexibility, and can be used in a severe environment. The energy-saving heating device can be used in the fields of household heating, building heating, aircraft deicing and the like, and has the effects of cleanness, environmental protection and energy conservation.
Drawings
FIG. 1a is a tensile stress-strain curve of an electrothermal film;
FIG. 1b shows the resistance change rate of the electrothermal film under different curvature radii;
FIG. 2 shows the bending cycle stability of the electrothermal film under a certain curvature radius and a voltage of 1V;
fig. 3 is a temperature curve diagram of the carbon-based electrothermal film with temperature rise under the voltage of 0.88V,1.13V,1.30V and 1.61V and temperature drop after power failure.
Detailed Description
The present invention is further described with reference to the following specific embodiments, but the scope of the present invention is not limited to the embodiments described in the following embodiments.
Example 1
60mg of graphene oxide is weighed and dispersed in 60mL of ethanol, the mixture is stirred for 1 hour and uniformly dispersed, and the obtained dispersion liquid is poured into a 100mL polytetrafluoroethylene reaction kettle and reacts for 12 hours at the temperature of 150 ℃.
And (3) carrying out solvent replacement on the obtained graphene product, completely replacing all ethanol with water, and then carrying out freeze drying.
The dried graphene skeleton was placed in a tube furnace and annealed at a temperature of 800 ℃ for 1 hour.
Weighing 20mg of polyacrylonitrile with the molecular weight of 15 ten thousand in 10ml of N, N-dimethylformamide, heating to 50 ℃, stirring to dissolve, and putting 20mg of three-dimensional graphene into the solution to uniformly mix. Drying to obtain the polyacrylonitrile/graphene compound.
The above-mentioned composite was placed in a round stainless steel mold having a diameter of 40mm and hot-pressed for 3 hours under a pressure of 100Pa and at a temperature of 100 ℃.
And (3) placing the hot-pressed film into a tube furnace, and pre-oxidizing for 6 hours in an air atmosphere at the pre-oxidation temperature of 270 ℃. And further carbonizing for 6 hours in Ar atmosphere at 800 ℃ to finally obtain the carbon-based electrothermal film. The film thickness was 16 μm and the density was 0.92mg/cm3。
The obtained carbon-based electrothermal film is subjected to bending property and electrothermal property tests, and the results are shown in fig. 1a, fig. 1b, fig. 2 and fig. 3, and as can be seen from fig. 1, the tensile strength of the electrothermal film is 50MPa, and the electrothermal film shows very small resistance change when the curvature radius is 10-26 mm, so that the tensile property and the bending property of the film are shown. It can be seen from fig. 2 that the electrothermal performance shows good bending cycle stability under the voltage of 1V. It can be known from fig. 3 that as the voltage increases, the saturation temperature of the electric heating film gradually increases, and the electric heating film can rapidly increase to the saturation temperature under different voltages.
Example 2
Weighing 60mg of graphene oxide, dispersing the graphene oxide in 60mL of ethanol, stirring for 1 hour, uniformly dispersing, pouring the obtained dispersion liquid into a 100mL of polytetrafluoroethylene reaction kettle, and reacting for 12 hours at 180 ℃.
And (3) carrying out solvent replacement on the obtained graphene product, completely replacing all ethanol with water, and then carrying out freeze drying.
The dried graphene skeleton was placed in a tube furnace and annealed at a temperature of 1000 ℃ for 1 hour.
Weighing 30mg of polyacrylonitrile with the molecular weight of 15 ten thousand in 10ml of N, N-dimethylformamide, heating to 50 ℃, stirring to dissolve, and putting 20mg of three-dimensional graphene into the solution to uniformly mix. Drying to obtain the polyacrylonitrile/graphene compound.
The above-mentioned composite was placed in a round stainless steel mold having a diameter of 40mm and hot-pressed for 3 hours under a pressure of 120Pa and at a temperature of 150 ℃.
And (3) placing the hot-pressed film into a tube furnace, and pre-oxidizing for 6 hours in an air atmosphere at the pre-oxidation temperature of 270 ℃. And further carbonizing for 6 hours in Ar atmosphere at 800 ℃ to finally obtain the carbon-based electrothermal film. The film thickness is 20um, and the density is 0.95mg/cm3。
Example 3
Weighing 90mg of graphene oxide, dispersing in 60mL of ethanol, stirring for 1 hour, uniformly dispersing, pouring the obtained dispersion into a 100mL polytetrafluoroethylene reaction kettle, and reacting at 150 ℃ for 12 hours.
And (3) carrying out solvent replacement on the obtained graphene product, completely replacing all ethanol with water, and then carrying out freeze drying.
The dried graphene skeleton was placed in a tube furnace and annealed at a temperature of 800 ℃ for 1 hour.
Weighing 50mg of polyacrylonitrile with the molecular weight of 15 ten thousand in 10ml of N, N-dimethylformamide, heating to 50 ℃, stirring to dissolve, and putting 20mg of three-dimensional graphene into the solution to uniformly mix. Drying to obtain the polyacrylonitrile/graphene compound.
The above-mentioned composite was placed in a round stainless steel mold having a diameter of 40mm and hot-pressed for 3 hours under a pressure of 120Pa and at a temperature of 150 ℃.
And (3) placing the hot-pressed film into a tube furnace, and pre-oxidizing for 6 hours in an air atmosphere at the pre-oxidation temperature of 270 ℃. And further carbonizing for 6 hours in Ar atmosphere at 800 ℃ to finally obtain the carbon-based electrothermal film. The film thickness is 20um, and the density is 1.02mg/cm3。
Example 4
Weighing 90mg of graphene oxide, dispersing in 60mL of ethanol, stirring for 1 hour, uniformly dispersing, pouring the obtained dispersion into a 100mL polytetrafluoroethylene reaction kettle, and reacting at 180 ℃ for 12 hours.
And (3) carrying out solvent replacement on the obtained graphene product, completely replacing all ethanol with water, and then carrying out freeze drying.
The dried graphene skeleton was placed in a tube furnace and annealed at a temperature of 1000 ℃ for 1 hour.
Weighing 20mg of polyacrylonitrile with the molecular weight of 15 ten thousand in 10ml of N, N-dimethylformamide, heating to 50 ℃, stirring to dissolve, and putting 20mg of three-dimensional graphene into the solution to uniformly mix. Drying to obtain the polyacrylonitrile/graphene compound.
The above-mentioned composite was placed in a round stainless steel mold having a diameter of 40mm and hot-pressed for 3 hours under a pressure of 100Pa and at a temperature of 100 ℃.
And (3) placing the hot-pressed film into a tube furnace, and pre-oxidizing for 6 hours in an air atmosphere at the pre-oxidation temperature of 300 ℃. And further carbonizing for 6 hours in Ar atmosphere at 1000 ℃ to finally obtain the carbon-based electrothermal film. The film thickness is 16um, and the density is 0.87mg/cm3。
Example 5
30mg of graphene oxide is weighed and dispersed in 60mL of ethanol, the mixture is stirred for 1 hour and uniformly dispersed, and the obtained dispersion liquid is poured into a 100mL polytetrafluoroethylene reaction kettle and reacts for 12 hours at 180 ℃.
And (3) carrying out solvent replacement on the obtained graphene product, completely replacing all ethanol with water, and then carrying out freeze drying.
The dried graphene skeleton was placed in a tube furnace and annealed at a temperature of 800 ℃ for 1 hour.
Weighing 30mg of polyacrylonitrile with the molecular weight of 15 ten thousand in 10ml of N, N-dimethylformamide, heating to 50 ℃, stirring to dissolve, and putting 20mg of three-dimensional graphene into the solution to uniformly mix. Drying to obtain the polyacrylonitrile/graphene compound.
The above-mentioned composite was placed in a round stainless steel mold having a diameter of 40mm and hot-pressed for 3 hours under a pressure of 120Pa and at a temperature of 150 ℃.
And (3) placing the hot-pressed film into a tube furnace, and pre-oxidizing for 6 hours in an air atmosphere at the pre-oxidation temperature of 300 ℃. And further carbonizing for 6 hours in Ar atmosphere at 1000 ℃ to finally obtain the carbon-based electrothermal film. The thickness of the film is 15um, and the density is 0.84mg/cm3。
Example 6
30mg of graphene oxide is weighed and dispersed in 60mL of ethanol, the mixture is stirred for 1 hour and uniformly dispersed, and the obtained dispersion liquid is poured into a 100mL polytetrafluoroethylene reaction kettle and reacts for 12 hours at the temperature of 200 ℃.
And (3) carrying out solvent replacement on the obtained graphene product, completely replacing all ethanol with water, and then carrying out freeze drying.
The dried graphene skeleton was placed in a tube furnace and annealed at a temperature of 1000 ℃ for 1 hour.
Weighing 50mg of polyacrylonitrile with the molecular weight of 15 ten thousand in 10ml of N, N-dimethylformamide, heating to 50 ℃, stirring to dissolve, and putting 20mg of three-dimensional graphene into the solution to uniformly mix. Drying to obtain the polyacrylonitrile/graphene compound.
The above-mentioned composite was placed in a round stainless steel mold having a diameter of 40mm and hot-pressed for 3 hours under a pressure of 120Pa and at a temperature of 150 ℃.
And (3) placing the hot-pressed film into a tube furnace, and pre-oxidizing for 6 hours in an air atmosphere at the pre-oxidation temperature of 300 ℃. And further carbonizing for 6 hours in Ar atmosphere at 1000 ℃ to finally obtain the carbon-based electrothermal film. The thickness of the film is 17um, and the density is 0.89mg/cm3。
Example 7
300mg of graphene oxide is weighed and dispersed in 60mL of ethanol, the mixture is stirred for 1 hour and uniformly dispersed, and the obtained dispersion liquid is poured into a 100mL polytetrafluoroethylene reaction kettle and reacts for 12 hours at 180 ℃.
And (3) carrying out solvent replacement on the obtained graphene product, completely replacing all ethanol with water, and then carrying out freeze drying.
The dried graphene skeleton was placed in a tube furnace and annealed at a temperature of 800 ℃ for 1 hour.
Weighing 20mg of polyacrylonitrile with the molecular weight of 15 ten thousand in 10ml of N, N-dimethylformamide, heating to 50 ℃, stirring to dissolve, and putting 20mg of three-dimensional graphene into the solution to uniformly mix. Drying to obtain the polyacrylonitrile/graphene compound.
The above-mentioned composite was placed in a round stainless steel mold having a diameter of 40mm and hot-pressed for 3 hours under a pressure of 100Pa and at a temperature of 100 ℃.
And (3) placing the hot-pressed film into a tube furnace, and pre-oxidizing for 6 hours in an air atmosphere at the pre-oxidation temperature of 300 ℃. And further carbonizing for 6 hours in Ar atmosphere at 1500 ℃ to finally obtain the carbon-based electrothermal film. The film thickness is 14um, and the density is 0.81mg/cm3。
Example 8
300mg of graphene oxide is weighed and dispersed in 60mL of ethanol, the mixture is stirred for 1 hour and uniformly dispersed, and the obtained dispersion liquid is poured into a 100mL polytetrafluoroethylene reaction kettle and reacts for 12 hours at 180 ℃.
And (3) carrying out solvent replacement on the obtained graphene product, completely replacing all ethanol with water, and then carrying out freeze drying.
The dried graphene skeleton was placed in a tube furnace and annealed at a temperature of 1000 ℃ for 1 hour.
Weighing 30mg of polyacrylonitrile with the molecular weight of 15 ten thousand in 10ml of N, N-dimethylformamide, heating to 50 ℃, stirring to dissolve, and putting 20mg of three-dimensional graphene into the solution to uniformly mix. Drying to obtain the polyacrylonitrile/graphene compound.
The above-mentioned composite was placed in a round stainless steel mold having a diameter of 40mm and hot-pressed for 3 hours under a pressure of 120Pa and at a temperature of 150 ℃.
And (3) placing the hot-pressed film into a tube furnace, and pre-oxidizing for 6 hours in an air atmosphere at the pre-oxidation temperature of 300 ℃. And further carbonizing for 6 hours in Ar atmosphere at 1500 ℃ to finally obtain the carbon-based electrothermal film. The thickness of the film is 15um, and the density is 0.84mg/cm3。
Example 9
300mg of graphene oxide is weighed and dispersed in 60mL of ethanol, the mixture is stirred for 1 hour and uniformly dispersed, and the obtained dispersion liquid is poured into a 100mL polytetrafluoroethylene reaction kettle and reacts for 12 hours at the temperature of 200 ℃.
And (3) carrying out solvent replacement on the obtained graphene product, completely replacing all ethanol with water, and then carrying out freeze drying.
The dried graphene skeleton was placed in a tube furnace and annealed at a temperature of 1000 ℃ for 1 hour.
Weighing 50mg of polyacrylonitrile with the molecular weight of 15 ten thousand in 10ml of N, N-dimethylformamide, heating to 50 ℃, stirring to dissolve, and putting 20mg of three-dimensional graphene into the solution to uniformly mix. Drying to obtain the polyacrylonitrile/graphene compound.
The above-mentioned composite was placed in a round stainless steel mold having a diameter of 40mm and hot-pressed for 3 hours under a pressure of 120Pa and at a temperature of 150 ℃.
And (3) placing the hot-pressed film into a tube furnace, and pre-oxidizing for 6 hours in an air atmosphere at the pre-oxidation temperature of 300 ℃. And further carbonizing for 6 hours in Ar atmosphere at 1500 ℃ to finally obtain the carbon-based electrothermal film. The thickness of the film is 15um, and the density is 0.92mg/cm3。
Parts of the invention not described in detail are within the common general knowledge of a person skilled in the art.
Claims (1)
1. A carbon base electric heat membrane which characterized in that: the carbon-based electrothermal film comprises three-dimensional graphene and polyacrylonitrile, wherein the three-dimensional graphene is a skeleton unit, and the skeleton of the three-dimensional graphene is filled with the polyacrylonitrile;
the thickness of the carbon-based electrothermal film is 10-500 mu m;
the preparation method of the carbon-based electrothermal film comprises the following steps:
firstly, mixing graphene oxide and a first organic solvent, stirring, uniformly stirring to obtain a uniform solution, and then carrying out a solvothermal reaction on the obtained solution in a high-pressure reaction kettle;
secondly, performing solvent exchange on the product obtained in the first step and water, and performing freeze drying after the solvent exchange is finished;
thirdly, heating the product obtained in the second step in an inert atmosphere or under a vacuum condition to obtain a three-dimensional porous graphene skeleton structure;
fourthly, mixing polyacrylonitrile and a second organic solvent, and stirring to obtain a solution;
step five, adding the three-dimensional porous graphene skeleton structure obtained in the step three into the solution obtained in the step four, and drying to obtain a graphene/polyacrylonitrile composite material;
sixthly, carrying out hot pressing on the graphene/polyacrylonitrile composite material obtained in the fifth step to obtain a graphene/polyacrylonitrile composite material film;
seventhly, sequentially pre-oxidizing and carbonizing the graphene/polyacrylonitrile composite material film obtained in the sixth step in a tubular furnace to obtain a carbon-based electrothermal film;
in the first step, the first organic solvent is ethanol, acetone, tetrahydrofuran or N, N-dimethylformamide, the concentration of the graphene oxide is 0.375-10 mg/mL, and the solvothermal reaction temperature is 130-250 ℃;
in the third step, the heating treatment temperature is 200-1000 ℃, and the heating treatment time is 30-300 min;
in the fourth step, the second organic solvent is one or more than two of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethylene carbonate and N-methylpyrrolidone which are mixed according to any proportion; the molecular weight of polyacrylonitrile is 5-20 ten thousand;
in the fifth step, the mass ratio of the three-dimensional porous graphene skeleton structure to polyacrylonitrile is 10: 10-90;
in the sixth step, the hot pressing temperature is 25-150 ℃, and the hot pressing pressure is 19-500 Pa;
in the seventh step, the pre-oxidation temperature is 250-320 ℃, and the carbonization temperature is 800-3000 ℃.
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