CN113683075B - Sulfur-doped porous nano carbon electromagnetic wave absorbing material and preparation method thereof - Google Patents

Sulfur-doped porous nano carbon electromagnetic wave absorbing material and preparation method thereof Download PDF

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CN113683075B
CN113683075B CN202110859437.0A CN202110859437A CN113683075B CN 113683075 B CN113683075 B CN 113683075B CN 202110859437 A CN202110859437 A CN 202110859437A CN 113683075 B CN113683075 B CN 113683075B
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nano carbon
sulfur
electromagnetic wave
doped porous
wave absorbing
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CN113683075A (en
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杨烈霁
庄海燕
洪跃辉
叶志民
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725th Research Institute of CSIC
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    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials

Abstract

The sulfur doped porous nano carbon electromagnetic wave absorbing material is black powder, is formed by agglomeration of a plurality of nano carbon particles through electrostatic action, wherein the nano carbon particles are spherical particles with the diameter of 210-230 nm, the surfaces of the nano carbon particles are provided with a plurality of micropores formed by etching hydrogen peroxide, functional groups at the defect positions of the edges of the micropores are combined with sulfur elements in a covalent bond mode, the surfaces of the nano carbon particles are also adsorbed with sulfur elements through electronegativity, and the content of the sulfur elements is 0.5-5% of the total mass of the material. The preparation method comprises the steps of firstly preparing nano carbon, then co-heat treating the nano carbon and hydrogen peroxide to obtain porous nano carbon, and then mixing and calcining the porous nano carbon and thioacetamide. The sulfur element in the material is doped with nano carbon particles in two forms of covalent bond combination and electronegative adsorption, so that the material has a wider effective absorption frequency bandwidth, higher electromagnetic absorption intensity, strong chemical stability, excellent microwave absorption performance, low preparation process cost and simple process.

Description

Sulfur-doped porous nano carbon electromagnetic wave absorbing material and preparation method thereof
Technical Field
The invention relates to the field of electromagnetic wave absorbing materials, in particular to a sulfur-doped porous nano carbon electromagnetic wave absorbing material and a preparation method thereof.
Background
With the development of electromagnetic technology, electromagnetic stealth is increasingly used in industrial and military fields, and the demand for electromagnetic wave absorbing materials is increasing, graphitized carbon-based materials are receiving extensive attention from researchers due to lower density, excellent dielectric properties, and environmental friendly characteristics, and have been reported in great numbers for various types of nano-sized microwave absorbing materials. The development of various existing carbon-based materials is mainly focused on the design of a nano structure and the introduction function of specific elements, and the method is mainly characterized in that on one hand, by adopting a hollow carbon material, lower density and more excellent electromagnetic absorption performance than those of the same type of solid material are obtained, for example, the Xu Hailong subject group of northwest industrial university, the electromagnetic absorption performance of the hollow red cell-shaped carbon sphere prepared by a template method is about 80 percent higher than that of the solid carbon sphere, and the maximum effective absorption bandwidth of a sample in a measured frequency band (2-18 GHz) can reach 3.0GHz; on the other hand, by introducing a pore structure into the carbon material, the electromagnetic wave absorption performance of the material can be effectively improved, for example, ji An subject group of Nanjing aviation aerospace university is synthesized by taking flour as a raw material, and the effective absorption bandwidth of the material is improved to 4.8GHz by introducing the pore structure.
However, there are still a number of problems with the prior art: 1. the existing nano-sized carbon-based material is difficult to ensure the regular shape of the product, so that the improvement of the material performance is limited to a certain extent; 2. the carbon material with pores on the surface has lower conductivity than the non-porous carbon material, and the dielectric loss capability is weakened. The introduction of sulfur element can balance electromagnetic parameters of the material and improve electromagnetic absorption performance, so that the preparation and development of the sulfur-doped porous nano carbon electromagnetic wave absorbing material with regular morphology and uniform size of the prepared product are very necessary.
Disclosure of Invention
The invention aims to provide a sulfur-doped porous nano carbon electromagnetic wave absorbing material and a preparation method thereof, and the defect that the existing nano carbon electromagnetic wave absorbing material is difficult to ensure the appearance of a product and has weak dielectric loss capacity is overcome.
The technical scheme adopted by the invention for solving the technical problems is as follows: the sulfur-doped porous nano carbon electromagnetic wave absorbing material is black powder, and is formed by agglomeration of a plurality of nano carbon particles through electrostatic action, wherein the nano carbon particles are spherical particles with the diameter of 210-230 nm, the surfaces of the nano carbon particles are provided with a plurality of micropores formed through hydrogen peroxide etching, functional groups at the defect positions of the edges of the micropores are combined with sulfur elements in a covalent bond mode, the surfaces of the nano carbon particles are also adsorbed with sulfur elements through electronegativity, and the content of the sulfur elements is 0.5-5% of the total mass of the material.
The preparation method of the sulfur-doped porous nano carbon electromagnetic wave absorbing material comprises the following steps:
step 1, placing nano SiO 2 Adding 500-1000 ml of ethanol, 20-50 ml of formaldehyde and 2-4 g of resorcinol into a container, adding a proper amount of ammonia water to adjust the mixed solution to be alkaline, uniformly stirring and reacting for 18-24 h, performing centrifugal separation, performing high-temperature carbonization treatment on the powder obtained by the centrifugal separation under the protection of nitrogen, and then etching with sodium hydroxide solution to remove nano SiO 2 Obtaining a nano carbon material with the particle diameter of 210-230 nm;
step 2, uniformly mixing the nano carbon material obtained in the step 1 with 100-500 ml of hydrogen peroxide, and then performing co-heat treatment to obtain a porous nano carbon material;
and 3, mixing the porous nano carbon material obtained in the step 2 with thioacetamide in a mass ratio of 1:0.5-1:2, heating to 200-300 ℃ at a heating rate of 2-5 ℃/min for presintering, heating to 500-700 ℃ at a heating rate of 2-5 ℃/min for calcination for 1-2 hours, and cooling to obtain the sulfur-doped porous nano carbon electromagnetic wave absorbing material.
Preferably, in step 1, the high temperature carbonization treatment is performed at a temperature of 700 ℃.
According to the technical scheme, the invention has the beneficial effects that:
the sulfur-doped porous nano carbon electromagnetic wave absorbing material provided by the invention has uniform size and regular shape of nano particles, sulfur element is doped with nano carbon particles in two forms of covalent bond combination and electronegative adsorption, has strong chemical stability, has wider effective absorption frequency band width and higher electromagnetic absorption strength under ultralow filling degree and low thickness as an electromagnetic wave absorbent, has excellent microwave absorption performance, does not adopt a highly toxic organic solvent in the preparation process of the sulfur-doped porous nano carbon electromagnetic wave absorbing material, has low cost and simple process, can be used for large-scale industrial production, has excellent weather resistance, can be applied to electromagnetic protection of various civil equipment under normal temperature conditions, and has wide application market and economic prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern of sulfur-doped porous nanocarbon;
FIG. 2 is an elemental signature of sulfur-doped porous nanocarbon C;
FIG. 3 is an elemental species map of sulfur-doped porous nanocarbon;
fig. 4 is a scanning electron microscope picture of sulfur-doped porous nanocarbon C
FIG. 5 is an infrared absorption spectrum picture of sulfur-doped porous nanocarbon;
FIG. 6 is a graph of electromagnetic parameters of sulfur-doped porous nanocarbon;
FIG. 7 is a graph of reflection loss of sulfur-doped porous nanocarbon A;
FIG. 8 is a graph of reflection loss of sulfur-doped porous nanocarbon B;
FIG. 9 is a graph of reflection loss of sulfur-doped porous nanocarbon C;
fig. 10 is a graph of selected thickness reflection loss for sulfur-doped porous nanocarbon C.
Detailed Description
The sulfur-doped porous nano carbon electromagnetic wave absorbing material is black powder, and is formed by agglomeration of a plurality of nano carbon particles through electrostatic action, wherein the nano carbon particles are spherical particles with the diameter of 210-230 nm, the surfaces of the nano carbon particles are provided with a plurality of micropores formed through hydrogen peroxide etching, functional groups at the defect positions of the edges of the micropores are combined with sulfur elements in a covalent bond mode, the surfaces of the nano carbon particles are also adsorbed with sulfur elements through electronegativity, and the content of the sulfur elements is 0.5-5% of the total mass of the material.
The preparation method of the sulfur-doped porous nano carbon electromagnetic wave absorbing material comprises the following steps:
step 1, placing nano SiO 2 Adding 500-1000 ml of ethanol, 20-50 ml of formaldehyde and 2-4 g of resorcinol into a container, adding a proper amount of ammonia water to adjust the mixed solution to be alkaline, stirring at a constant speed for reacting for 18-24 h, performing centrifugal separation, and obtaining the product by centrifugal separationThe powder is carbonized at 700 ℃ under the protection of nitrogen, and then etched by sodium hydroxide solution to remove nano SiO 2 Obtaining the nano carbon material with the particle diameter of 210-230 nm.
And 2, uniformly mixing the nano carbon material obtained in the step 1 with 100-500 ml of hydrogen peroxide, and then performing co-heat treatment to obtain the porous nano carbon material.
And 3, mixing the porous nano carbon material obtained in the step 2 with thioacetamide in a mass ratio of 1:0.5-1:2, heating to 200-300 ℃ at a heating rate of 2-5 ℃/min for presintering, heating to 500-700 ℃ at a heating rate of 2-5 ℃/min for calcination for 1-2 hours, and cooling to obtain the sulfur-doped porous nano carbon electromagnetic wave absorbing material.
Example 1
The invention relates to a sulfur-doped porous nano carbon electromagnetic wave absorbing material and a preparation method thereof, comprising the following steps:
step 1, preparing a nano carbon material by using a template etching method: siO with the grain diameter of 200-300 nm is added into a container 2 And absolute ethyl alcohol, adding formaldehyde and resorcinol with a molar ratio of 2 to 1 after stirring and dispersing uniformly, then dripping a small amount of ammonia water until the solution is alkaline, stirring at a constant speed for reacting for 18-24 hours, centrifuging, separating, carbonizing at a high temperature, and etching with sodium hydroxide solution to remove nano SiO 2 And obtaining the nano carbon.
And 2, performing co-heat treatment on the nano carbon obtained in the step 1 and hydrogen peroxide to obtain the porous nano carbon.
And 3, weighing 100mg of the porous nano carbon material obtained in the step 2, weighing 50mg of thioacetamide according to the mass ratio of 1 to 0.5, mixing and grinding the materials for 20 minutes until the materials are uniform, transferring the mixture into a crucible, covering and integrally sealing the crucible by using tinfoil, placing the container into a tube furnace, introducing nitrogen for protection, setting a program, firstly heating to 200 ℃ at the heating rate of 2-5 ℃/min and preserving heat for ten minutes, then heating to 600 ℃ at the heating rate of 2-5 ℃/min and preserving heat for 2 hours, and naturally cooling to obtain the black powdery sulfur-doped porous nano carbon A.
Example 2
Step 1, same as in example 1.
Step 2, same as in example 1.
And 3, weighing 100mg of the porous nano carbon material obtained in the step 1, weighing 100mg of thioacetamide according to the mass ratio of 1 to 1, mixing and grinding the materials for 20 minutes until the materials are uniform, transferring the mixture into a crucible, covering and integrally sealing the crucible by using tinfoil, placing the container into a tubular furnace, introducing nitrogen for protection, heating the container to 200 ℃ at the heating rate of 2-5 ℃/min and preserving heat for ten minutes, heating the container to 600 ℃ at the heating rate of 2-5 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain the black powdery sulfur-doped porous nano carbon B.
Example 3
Step 1, same as in example 1.
Step 2, same as in example 1.
And 3, weighing 100mg of the porous nano carbon material obtained in the step 1, weighing 200mg of thioacetamide according to the mass ratio of 1 to 1, mixing and grinding the two materials for 20 minutes until the mixture is uniform, transferring the mixture into a crucible, covering and integrally sealing the crucible by using tinfoil, placing the container into a tubular furnace, introducing nitrogen for protection, heating the container to 200 ℃ at the heating rate of 2-5 ℃/min and preserving heat for ten minutes, heating the container to 600 ℃ at the heating rate of 2-5 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain black powdery sulfur-doped porous nano carbon C.
The powder samples synthesized in examples 1-3 were mixed with paraffin wax in a ratio of 5:95 and pressed into a circular ring with an inner diameter of 3.04mm and an outer diameter of 7.00mm, and electromagnetic parameter test was performed using a vector network analyzer, and reflection loss performance parameters were obtained through calculation, wherein the sulfur-doped porous nanocarbon of example 3 had the best electromagnetic absorption performance, exhibited excellent electromagnetic absorption performance at a filling ratio as low as 5wt%, and the minimum reflection loss value could reach-57 dB, while the effective absorption bandwidth could exceed 6 GHz at a sample thickness below 2 mm.
The carbon spheres prepared by the template method and thioacetamide in examples 1-3 realize sulfur doping in a high-temperature treatment mode, and the results show that the synthesized sulfur doped porous nano carbon with different doping amounts has similar diffraction peaks through X-ray diffraction characterization, and two obvious diffraction peaks are respectively (002) crystal faces and (101) crystal faces corresponding to carbon materials in the measured range, as shown in figure 1.
The invention relates to a preparation principle of a sulfur-doped porous nano carbon electromagnetic wave absorbing material, which is characterized in that a large number of unsaturated bonds exist on the surface of a porous nano carbon material prepared by using a template etching method, thioacetamide is taken as a sulfur source, the thioacetamide is decomposed at high temperature, sulfur element is captured and fixed by the carbon material in a covalent bond mode in a closed environment, the amount of doped sulfur can be regulated and controlled by changing the dosage of the thioacetamide, and the introduction of the sulfur element can improve the impedance matching of the material and greatly improve the dielectric loss performance. The elemental characteristic test results of the sulfur-doped porous nanocarbon C shown in FIG. 2 show that the elemental content analysis results of the sulfur-doped porous nanocarbon of FIG. 3 show that the elemental content of the sulfur-doped porous nanocarbon of FIG. 3 is 0.52wt%,1.2wt% and 2.16wt%, respectively, while the elemental content of carbon and elemental oxygen in the material are also shown as the curves in FIG. 3, which demonstrates the successful introduction of elemental sulfur.
The sulfur-doped porous nano carbon electromagnetic wave absorbing material is synthesized into porous nano carbon by a template etching method, and sulfur elements are co-thermally doped at high temperature. In the sulfur doped porous nano carbon electromagnetic wave absorbing material, the doping and content control of sulfur element can regulate the influence of the pore structure in the material on electromagnetic parameters, balance impedance matching and enhance dielectric loss, so that the material can show excellent electromagnetic absorption performance when the filling ratio is as low as 5wt%, the minimum reflection loss value can reach-57 dB, and the effective absorption bandwidth can exceed 6 GHz when the sample thickness is lower than 2 mm.
The electromagnetic wave absorption performance of the sulfur-doped porous nano carbon electromagnetic wave absorption material is mainly derived from dielectric loss of the carbon material and dipole polarization caused by sulfur element doping, and the impedance matching and attenuation performance of the material are balanced through sulfur doping regulation and control, so that the electromagnetic wave attenuation capability of the material is improved. The ultra-low density and low filling ratio of the porous material can reduce the production cost of the material in practical application, and can be produced in large scale to meet the application requirement.
As shown in a scanning electron microscope picture of the sulfur-doped porous nano carbon C in fig. 4, the single particle size of the sulfur-doped porous nano carbon C is 210nm-230nm, micropores are randomly distributed on the surface of a spherical shell, and larger broken holes on the surface of the spherical body are due to the effect of template etching on the structure, so that the spherical structure of the particles can be basically maintained.
In the sulfur-doped porous nano carbon electromagnetic wave absorbing material of the invention, part of sulfur element is combined with nano carbon in a chemical bond form, such as an infrared absorption spectrum of the sulfur-doped porous nano carbon shown in figure 5, wherein an S-C, S-O bond stretching vibration absorption peak appears at 700cm -1 About, the S=O bond stretching vibration absorption peak appears at 1050cm -1 The sulfur element is fixed in a chemical bond form instead of being physically mixed, so that the sulfur doped porous nano carbon electromagnetic wave absorbing material synthesized by the invention has a certain chemical stability.
According to the sulfur-doped porous nano carbon electromagnetic wave absorbing material, the doping amount of sulfur element is regulated, and along with the improvement of the sulfur doping amount, the real part and the imaginary part of electromagnetic parameters of a corresponding sample are increased, as shown in fig. 6, and the electromagnetic absorption performance is changed due to the change of the parameters, as shown in reflection loss maps of fig. 7, 8 and 9, and the minimum reflection loss of the sample is not more than-10 dB under the condition of low thickness. Under the condition that the filling proportion is 5wt%, the matching thickness of the sulfur-doped porous nano carbon B is 1.95 mm, and when the frequency is 16 GHz, the effective absorption frequency band width is 2.6 GHz, and the absorption frequency band range corresponds to 15.4-18 GHz. Under the condition that the filling proportion is 5wt%, the matching thickness of the sulfur-doped porous nano carbon C is 1.95 and mm, the effective absorption frequency band width is 6.3 GHz, and the absorption frequency band range corresponds to 11.7-18.0 GHz.
The sulfur-doped porous nano carbon electromagnetic wave absorbing material is controlled by adjusting the doping amount, so that a sample with the best relative performance under a system is finally obtained, and as shown in a reflection loss spectrum of the sulfur-doped porous nano carbon C with the selected thickness in the figure 10, the minimum reflection loss can reach-57 dB when the matching thickness is 2.2 mm and the frequency is 12.5 GHz under the condition that the filling proportion is 5 wt%. The sample with the doping amount has the widest corresponding effective absorption bandwidth, so that the sample has the optimal electromagnetic absorption performance.

Claims (2)

1. A sulfur-doped porous nano carbon electromagnetic wave absorbing material is characterized in that: the material is black powder, and is formed by agglomeration of a plurality of nano carbon particles through electrostatic action, wherein the nano carbon particles are spherical particles with the diameter of 210-230 nm, the surfaces of the nano carbon particles are provided with a plurality of micropores formed through hydrogen peroxide etching, functional groups at the defect positions of the edges of the micropores are combined with sulfur elements in a covalent bond mode, the surfaces of the nano carbon particles are also adsorbed with sulfur elements through electronegativity, and the content of the sulfur elements is 0.5-5% of the total mass of the material;
which comprises the following steps: step 1, placing nano SiO 2 Adding 500-1000 ml of ethanol, 20-50 ml of formaldehyde and 2-4 g of resorcinol into a container, adding a proper amount of ammonia water to adjust the mixed solution to be alkaline, uniformly stirring and reacting for 18-24 h, performing centrifugal separation, performing high-temperature carbonization treatment on the powder obtained by the centrifugal separation under the protection of nitrogen, and then etching with sodium hydroxide solution to remove nano SiO 2 Obtaining a nano carbon material with the particle diameter of 210-230 nm;
step 2, uniformly mixing the nano carbon material obtained in the step 1 with 100-500 ml of hydrogen peroxide, and then performing co-heat treatment to obtain a porous nano carbon material;
and 3, mixing the porous nano carbon material obtained in the step 2 with thioacetamide in a mass ratio of 1:0.5-1:2, heating to 200-300 ℃ at a heating rate of 2-5 ℃/min for presintering, heating to 500-700 ℃ at a heating rate of 2-5 ℃/min for calcination for 1-2 hours, and cooling to obtain the sulfur-doped porous nano carbon electromagnetic wave absorbing material.
2. The sulfur-doped porous nanocarbon electromagnetic wave absorbing material according to claim 1, wherein: in step 1, the high-temperature carbonization treatment temperature is 700 ℃.
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