CN117384594A - CoSe/MnSe@nitrogen doped carbon composite wave-absorbing material and preparation method thereof - Google Patents
CoSe/MnSe@nitrogen doped carbon composite wave-absorbing material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 239000011358 absorbing material Substances 0.000 title claims abstract description 60
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 229920001690 polydopamine Polymers 0.000 claims abstract description 25
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- 238000005406 washing Methods 0.000 claims abstract description 11
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 10
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 10
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims abstract description 10
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 description 16
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- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
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- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal selenide Chemical class 0.000 description 3
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a CoSe/MnSe@nitrogen doped carbon composite wave-absorbing material and a preparation method thereof, wherein polyvinylpyrrolidone and manganese acetate tetrahydrate are dissolved in a mixture of deionized water and ethanol to obtain a solution A, and potassium cobalt cyanide is dissolved in the deionized water to obtain a solution B; then, dropwise adding the solution B into the solution A while magnetically stirring, continuously stirring after the dropwise adding is finished, aging at room temperature, and filtering, washing and drying to obtain a CoMn-PBA composite material; adding the CoMn-PBA composite material into a Tris buffer solution, then adding dopamine hydrochloride, and continuously stirring; then filtering, washing and drying to obtain the CoMn-PBA@polydopamine composite material; uniformly mixing CoMn-PBA@PDA and selenium powder, placing the mixture into a tube furnace, calcining the mixture under the protection of nitrogen, and cooling the mixture along with the furnace to obtain the CoSe/MnSe@NC composite material. The material prepared by the invention has the characteristics of simple preparation process, wide frequency band and thin matching thickness, and can be used as a good wave-absorbing material.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a CoSe/MnSe@nitrogen doped carbon composite wave-absorbing material and a preparation method thereof.
Background
In recent years, with the continuous development of communication technology and the wide application of various electronic devices, electromagnetic radiation and interference generated at the same time of bringing convenience to people become a new social problem, which not only affects the use of precision instruments, but also endangers human health. Electromagnetic wave absorbing materials can absorb electromagnetic energy with high efficiency and convert the electromagnetic energy into heat energy or other forms of energy to be dissipated, so that the development of high-performance wave absorbing materials is significant in reducing electromagnetic pollution. In addition, the development of electromagnetic stealth combat technology is particularly important for improving national defense reality, so that the microwave absorbing material with strong attenuation capability, wide frequency, light weight and thin thickness is very important for human health and military safety. Magnetic metal/carbon composites are a typical combination of magnetically lossy and dielectrically lossy dielectrics, which have been widely studied as high performance metal-based composites over the past few years due to their synergistic loss mechanisms. In recent years, metal-organic frameworks (MOFs) have become an attractive precursor for magnetic carbon-based functional materials because of their periodic arrangement of metal sites and organic ligands, which has been very beneficial in creating good chemical uniformity in composite materials, and this unique advantage has stimulated the explosive development of magnetic carbon-based wave absorbing materials to some extent. Prussian Blue Analogues (PBA) are used as a subclass of MOFs materials, have the characteristics of rich pore structures, large specific surface areas, and various structures and functions, and are widely applied to the field of electromagnetic wave absorption. However, the pure PBA material is not favorable for realizing good impedance matching when being used for absorbing electromagnetic waves, the effective absorption bandwidth is narrow, dielectric loss and magnetic loss can be effectively regulated through structural design and compounding of the multi-component magnetoelectric material, the impedance matching is improved, the effective absorption bandwidth is widened, and the purpose of improving the electromagnetic wave absorption performance is achieved. Since the transition metal selenide has proper conductivity, excellent electrochemical activity and adjustable morphology, more and more researchers use the transition metal selenide for preparing electromagnetic wave absorbing materials. However, it should be noted that the microstructure of the magnetic carbon-based wave-absorbing material may collapse during the pyrolysis process, and the chemical composition of the magnetic carbon-based wave-absorbing material depends too much on the precursor thereof, which is generally difficult to control. These difficulties mean that by rational design of the PBA precursors it is still possible to further improve their microwave absorption properties. Polymeric carbons have been of great interest because of their superior properties and simple preparation methods. It is worth mentioning that the dopamine monomer can self-polymerize under aerobic alkaline condition, and can form a film with adhesion capability on almost any substrate, so that the problem of structural collapse of the material at high temperature can be solved.
The researches have proposed a plurality of modification strategies aiming at the problem of narrow absorption frequency band of the magnetic carbon-based material derived from MOFs, and on one hand, morphology of the MOFs is regulated, so that electromagnetic parameters and electromagnetic wave absorption performance are effectively regulated. On the other hand, the composite material is compounded with other dielectric materials, so that a loss mechanism is increased, and the attenuation capability on electromagnetic waves is enhanced. According to research, the existing preparation method is long in time consumption and complex in preparation process, so that the preparation of the composite material by adopting a simple and controllable method is an effective strategy for enhancing electromagnetic wave absorption capacity.
Disclosure of Invention
The invention aims at solving the problems of thick matching thickness and narrow wave-absorbing frequency band of a transition metal selenide wave-absorbing material, and provides a preparation method of a CoSe/MnSe@NC composite wave-absorbing material, which is simple in preparation process, easy to control and low in production cost, and the prepared CoSe/MnSe@NC wave-absorbing material has the advantages of thin matching thickness, strong absorption and wider effective absorption bandwidth.
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of a CoSe/MnSe@nitrogen doped carbon composite wave absorbing material comprises the following steps:
s1, dissolving polyvinylpyrrolidone and manganese acetate tetrahydrate in a mixture of deionized water and ethanol to obtain a solution A, and dissolving potassium cobalt cyanide in the deionized water to obtain a solution B;
s2, dropwise adding the solution B into the solution A while magnetically stirring, continuously stirring after the dropwise adding is completed, aging at room temperature, and filtering, washing and drying to obtain a CoMn-Prussian Blue Analogue (PBA) composite material;
s3, adding the CoMn-Prussian Blue Analogue (PBA) composite material into a Tris buffer solution, then adding dopamine hydrochloride, and continuously stirring;
s4, filtering, washing and drying to obtain the CoMn-PBA@polydopamine (PDA) composite material;
s5, uniformly mixing the CoMn-PBA@PDA and selenium powder, placing the mixture into a tube furnace, calcining the mixture under the protection of nitrogen, and cooling the calcined mixture along with the furnace to obtain the CoSe/MnSe@NC composite material.
Preferably, in step S1, the molar ratio of the cobalt potassium cyanide to the manganese acetate tetrahydrate is 1: (1-2).
Preferably, in step S1, the volume ratio of deionized water to ethanol is 1: (2-4).
Preferably, in the step S2, the magnetic stirring speed is 600-800 r/min, the stirring time is 10-15 min, and the aging time is 20-24 h.
Preferably, in step S2, the drying temperature is 60-80 ℃ and the time is 12-14 h.
Preferably, in step S3, the mass ratio of the CoMn-prussian blue analog to the dopamine hydrochloride is 1: (0.5-1).
Preferably, in step S3, the stirring time is 20 to 24 hours.
Preferably, in step S5, the mass ratio of the CoMn-pba@pda composite material to the selenium powder is 1: (2-3).
The invention also provides the CoSe/MnSe@nitrogen doped carbon composite wave-absorbing material prepared by the preparation method of the CoSe/MnSe@nitrogen doped carbon composite wave-absorbing material, and the prepared wave-absorbing material can effectively improve the effective absorption bandwidth of the material and reduce the matching thickness, and has a certain development prospect.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, coMn-PBA is taken as a nucleation site, and dopamine is polymerized on the surface of the nucleation site to prepare a core-shell CoMn-PBA@PDA nanocube; mixing the precursor with selenium powder, and performing high-temperature pyrolysis to convert the precursor into the CoSe/MnSe@NC composite wave-absorbing material with a core-shell structure; in the method, the preparation process of the precursor is simple, the appearance is unique, the cost is low, and the operation can be repeated; the PDA coating therein helps to inhibit microstructure collapse of the CoMn-PBA during pyrolysis, thereby forming a unique core-shell structure. The carbon shell optimizes the electromagnetic parameters of the composite material, so that the dielectric loss is obviously enhanced, and the attenuation capability of the composite material to incident electromagnetic waves is improved.
2. In the invention, the precursor is converted into the ideal magnetic carbon-based composite material through high-temperature selenization pyrolysis, so that the effective absorption bandwidth of the material can be effectively improved, the matching thickness can be reduced, when the matching thickness is 1.8mm, the filling amount is 40%, and when the frequency is 17.52GHz, the minimum reflection loss (RL min ) A value of-27.38 dB and an Effective Absorption Bandwidth (EAB) value of 3.36GHz (14.64-18.00 GHz); when the matching thickness is 2.2mm, the EAB value reaches 7.68GHz (9.68-17.36 GHz), and the wave-absorbing material is a wave-absorbing material with low thickness and wide frequency band and has a certain development prospect.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
In the drawings:
FIG. 1 is an X-ray diffraction pattern of a CoSe/MnSe@NC composite wave absorbing material prepared in embodiment 2 of the present invention;
FIG. 2 is a scanning electron microscope image of the CoSe/MnSe@NC composite wave-absorbing material prepared in example 2 of the present invention;
FIG. 3 is a graph showing the reflection loss of the CoSe/MnSe@NC composite wave absorbing material prepared in example 1 of the present invention at a thickness of 1.0-5.5 mm;
FIG. 4 is a graph showing the reflection loss of the CoSe/MnSe@NC composite wave absorbing material prepared in example 2 of the present invention at a thickness of 1.0-5.5 mm;
FIG. 5 is a graph showing the reflection loss of the CoSe/MnSe@NC composite wave absorbing material prepared in example 3 of the present invention at a thickness of 1.0 to 5.5 mm.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
The invention provides a preparation method of a CoSe/MnSe@nitrogen doped carbon composite wave-absorbing material, which comprises the following steps:
s1, dissolving polyvinylpyrrolidone and manganese acetate tetrahydrate into a mixture of deionized water and ethanol to obtain a solution A, wherein the molar ratio of potassium cobalt cyanide to manganese acetate tetrahydrate is 1: (1-2); dissolving cobalt potassium cyanide in deionized water to obtain a solution B, wherein the volume ratio of deionized water to ethanol is 1: (2-4);
s2, dropwise adding the solution B into the solution A while magnetically stirring, wherein the magnetic stirring speed is 600-800 r/min, the stirring time is 10-15 min, and the aging time is 20-24 h; continuously stirring after the dripping is finished, aging at room temperature, and then filtering, washing and drying to obtain the CoMn-Prussian Blue Analogue (PBA) composite material, wherein the drying temperature is 60-80 ℃ and the time is 12-14 h;
s3, adding the CoMn-Prussian Blue Analog (PBA) composite material into a Tris buffer solution, wherein the mass ratio of the CoMn-Prussian blue analog to the dopamine hydrochloride is 1: (0.5-1); adding dopamine hydrochloride, and continuously stirring for 20-24 h;
s4, filtering, washing and drying to obtain the CoMn-PBA@polydopamine (PDA) composite material;
s5, uniformly mixing the CoMn-PBA@PDA and selenium powder, wherein the mass ratio of the CoMn-PBA@PDA composite material to the selenium powder is 1: (2-3); placing the mixture into a tube furnace, calcining under the protection of nitrogen, and cooling along with the furnace to obtain the CoSe/MnSe@NC composite material.
The invention also provides the CoSe/MnSe@nitrogen doped carbon composite wave-absorbing material prepared by the preparation method of the CoSe/MnSe@nitrogen doped carbon composite wave-absorbing material, and the prepared wave-absorbing material can effectively improve the effective absorption bandwidth of the material and reduce the matching thickness, and has a certain development prospect.
Example 1
A preparation method of a CoSe/MnSe@NC composite wave-absorbing material comprises the following steps:
(1) 1.5g of polyvinylpyrrolidone and 0.22 g of manganese acetate tetrahydrate are dissolved in 90mL of deionized water and ethanol mixture (1:2v/v) to form solution A, 0.16g of potassium cobalt cyanide is dissolved in 60mL of deionized water to form solution B, then the solution B is dropwise added into the solution A while magnetically stirring, stirring is continued for 10 minutes after the dropwise addition is completed, after aging for 24 hours at room temperature, the reaction product is alternately washed three times with absolute ethyl alcohol and distilled water, a white solid product is obtained after filtering, and the CoMn-PBA composite material is obtained after drying at 60 ℃ for 12 hours.
(2) 0.2g of CoMn-PBA composite was added to 150mL of Tris buffer, sonicated and stirred for 0.5h, 0.1g of dopamine hydrochloride was added and stirring was continued for 24h. Washing and filtering after stirring is completed, and placing the mixture in a vacuum drying oven for drying to obtain the CoMn-PBA@PDA composite material. Uniformly mixing 0.2g of CoMn-PBA@PDA composite material with 0.6g of selenium powder, placing the mixture in a tube furnace, heating to 800 ℃ at a speed of 5 ℃/min under nitrogen atmosphere, calcining for 3 hours, and cooling to room temperature to obtain the CoSe/MnSe@NC composite wave-absorbing material, which is marked as CMC-0.5.
Example 2
A preparation method of a CoSe/MnSe@NC composite wave-absorbing material comprises the following steps:
(1) 1.5g of polyvinylpyrrolidone and 0.22 g of manganese acetate tetrahydrate are dissolved in 90mL of deionized water and ethanol mixture (1:2v/v) to form solution A, 0.16g of potassium cobalt cyanide is dissolved in 60mL of deionized water to form solution B, then the solution B is dropwise added into the solution A while magnetically stirring, stirring is continued for 10 minutes after the dropwise addition is completed, after aging for 24 hours at room temperature, the reaction product is alternately washed three times with absolute ethyl alcohol and distilled water, a white solid product is obtained after filtering, and the CoMn-PBA composite material is obtained after drying at 60 ℃ for 12 hours.
(2) 0.2g of CoMn-PBA composite was added to 150mL of Tris buffer, sonicated and stirred for 0.5h, 0.15g of dopamine hydrochloride was added and stirring was continued for 24h. Washing and filtering after stirring is completed, and placing the mixture in a vacuum drying oven for drying to obtain the CoMn-PBA@PDA composite material. Uniformly mixing 0.2g of CoMn-PBA@PDA composite material with 0.6g of selenium powder, placing the mixture in a tube furnace, heating to 800 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere, calcining for 3 hours, and cooling to room temperature to obtain the CoSe/MnSe@NC composite wave-absorbing material, which is marked as CMC-0.75.
Example 3
A preparation method of a CoSe/MnSe@NC composite wave-absorbing material comprises the following steps:
(1) 1.5g of polyvinylpyrrolidone and 0.22 g of manganese acetate tetrahydrate are dissolved in 90mL of deionized water and ethanol mixture (1:2v/v) to form solution A, 0.16g of potassium cobalt cyanide is dissolved in 60mL of deionized water to form solution B, then the solution B is dropwise added into the solution A while magnetically stirring, stirring is continued for 10 minutes after the dropwise addition is completed, after aging for 24 hours at room temperature, the reaction product is alternately washed three times with absolute ethyl alcohol and distilled water, a white solid product is obtained after filtering, and the CoMn-PBA composite material is obtained after drying at 60 ℃ for 12 hours.
(2) 0.2g of CoMn-PBA composite was added to 150mL of Tris buffer, sonicated and stirred for 0.5h, 0.2g of dopamine hydrochloride was added and stirring was continued for 24h. Washing and filtering after stirring is completed, and placing the mixture in a vacuum drying oven for drying to obtain the CoMn-PBA@PDA composite material. Uniformly mixing 0.2g of CoMn-PBA@PDA composite material with 0.6g of selenium powder, placing the mixture in a tube furnace, heating to 800 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere, calcining for 3 hours, and cooling to room temperature to obtain the CoSe/MnSe@NC composite wave-absorbing material, which is marked as CMC-1.
Performance test:
1. and carrying out phase structure analysis on the CoSe/MnSe@NC composite wave-absorbing material by using an X-ray diffractometer.
FIG. 1 is an X-ray diffraction pattern of the CoMn-PBA and CoSe/MnSe@NC composite absorbing material prepared in example 2, and as shown in FIG. 1 (a), diffraction peaks of CoMn-PBA at 2θ=17.0°, 24.1 °, 34.4 °, 38.6 °, 49.4 °, 55.8, 64.4 ° and 67.2 ° are attributed to standard PDF cards (JCPDS No. 89-3735) of CoMn-PBA, with crystal plane indices of (200), (220), (400), (420), (440), (620), (640) and (642), respectively. In fig. 1 (b), diffraction peaks appearing at 32.7 °, 47.0 °, 58.4 °, 68.6 ° and 78.2 ° of the main diffraction peak are attributed to standard PDF cards of MnSe (jcpdsno. 11-0683) with crystal plane indices (200), (220), (222), (400) and (420), respectively. In addition, diffraction peaks appearing at the main diffraction peaks at 33.1 °, 44.8 °, 50.3 °, 61.6 ° and 69.6 ° are assigned to standard PDF cards of CoSe (JCPDS No. 70-2870) with crystal plane indices (101), (102), (110), (201) and (202), respectively, and graphitized carbon formation is demonstrated at the diffraction peaks of 26 °, which analysis shows that the CoSe/mnse@nc composite wave-absorbing material was successfully prepared.
2. The microstructure of the CoSe/MnSe@NC composite wave-absorbing material prepared in example 2 was analyzed by a scanning electron microscope. FIG. 2 is a scanning electron microscope image of the CoSe/MnSe@NC composite wave-absorbing material prepared in example 2, wherein FIG. 2 (a) is a scanning electron microscope image of CoMn-PBA, and the CoMn-PBA has an intact crystal form, a regular cubic shape, a smooth surface, uniform dispersion and a grain size of about 1 μm. FIG. 2 (b) is a scanning electron micrograph of CoMn-PBA@PDA, showing a significant increase in thickness and a roughened surface. FIG. 2 (c) is a scanning electron microscope image of CoSe/MnSe@NC, after high temperature selenization, the obtained CoSe/MnSe@NC well inherits the morphology of the precursor with slight collapse, because the introduction of the PDA layer helps to maintain the cube structure, and a small amount of carbon spheres are generated nearby, because the PDA is formed after high temperature carbonization. More heterogeneous interfaces can be generated between CoSe/MnSe, so that interface polarization loss can be promoted, a carbon network formed by NC provides a channel for electrons to move, the conductivity loss of the material is improved, and the attenuation of electromagnetic waves is facilitated.
3. And analyzing electromagnetic parameters of the sample by means of a vector network analyzer, and further calculating the wave absorbing performance of the sample.
FIG. 3 shows the thickness of the CoSe/MnSe@NC composite wave-absorbing material prepared in example 1A reflection loss curve with the degree of 1.0-5.5 mm; FIG. 4 is a reflection loss curve of the CoSe/MnSe@NC composite wave absorbing material prepared in example 2 at a thickness of 1.0-5.5 mm; FIG. 5 is a reflection loss curve of the CoSe/MnSe@NC composite wave absorbing material prepared in example 3 at a thickness of 1.0-5.5 mm. As can be seen from FIG. 3, CMC-0.5 (CoSe/MnSe@NC composite wave absorbing material prepared in example 1) RL at a thickness of 2.50mm min The value was-13.53 dB (14.00 GHz), and the EAB value was 3.76GHz (16.08-12.32 GHz).
As can be seen from FIG. 4, RL of CMC-0.75 (CoSe/MnSe@NC composite wave-absorbing material prepared in example 2) min And EAB values significantly improved over CMC-0.5, RL at a matching thickness of 1.80mm min The value is-27.38 dB at 17.52GHz, and the EAB value is 3.36GHz (14.64-18.00 GHz); when the matching thickness is 2.20mm, the EAB value reaches 7.68GHz, and the absorption bandwidth is obviously improved. The improvement in the wave-absorbing performance is attributed to strong electromagnetic attenuation and good impedance matching characteristics. The special core-shell structure increases the interface polarization of the material and improves the impedance matching characteristic of the material, and moderate conductivity provides stronger conductivity loss and remarkably dissipates electromagnetic waves.
As can be seen from FIG. 5, the CMC-1 (CoSe/MnSe@NC composite wave-absorbing material prepared in example 3) had significantly decreased wave-absorbing performance with increasing PDA addition, and RL when the matching thickness was 1.50mm min And EAB values of-20.24 dB (16.96 GHz) and 3.6GHz (14.40-18.00 GHz), respectively; the maximum EAB value was 4.88GHz (9.60-14.48 GHz) when the matching thickness was 2.00 mm. Clearly, RL of the sample min And EAB values show a tendency to increase and decrease as the amount of PDA added increases. This is due to the dielectric loss and impedance matching of the material that is affected when the PDA addition is too high; in contrast, when the addition amount is too low, the dielectric constant of the sample is low, and high electromagnetic attenuation cannot be generated. Therefore, the addition amount of the PDA has a great influence on electromagnetic parameters, and the moderate addition amount is beneficial to obtaining good wave absorbing performance. The CoSe/MnSe@NC composite material has excellent electromagnetic wave absorption performance, and the requirements of the wave absorbing material on thinness, lightness, width and strength are met.
Finally, it should be noted that: the foregoing is merely a preferred example of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the CoSe/MnSe@nitrogen doped carbon composite wave absorbing material is characterized by comprising the following steps of:
s1, dissolving polyvinylpyrrolidone and manganese acetate tetrahydrate in a mixture of deionized water and ethanol to obtain a solution A, and dissolving potassium cobalt cyanide in the deionized water to obtain a solution B;
s2, dropwise adding the solution B into the solution A while magnetically stirring, continuously stirring after the dropwise adding is completed, aging at room temperature, and filtering, washing and drying to obtain the CoMn-Prussian blue analogue composite material;
s3, adding the CoMn-Prussian blue analogue composite material into a Tris buffer solution, then adding dopamine hydrochloride, and continuously stirring;
s4, filtering, washing and drying to obtain the CoMn-PBA@polydopamine (PDA) composite material;
s5, uniformly mixing the CoMn-PBA@PDA and selenium powder, placing the mixture into a tube furnace, calcining the mixture under the protection of nitrogen, and cooling the calcined mixture along with the furnace to obtain the CoSe/MnSe@NC composite material.
2. The method for preparing the CoSe/MnSe@nitrogen doped carbon composite wave absorbing material is characterized by comprising the following steps of: in the step S1, the molar ratio of the cobalt potassium cyanide to the manganese acetate tetrahydrate is 1: (1-2).
3. The method for preparing the CoSe/MnSe@nitrogen doped carbon composite wave absorbing material is characterized by comprising the following steps of: in step S1, the volume ratio of deionized water to ethanol is 1: (2-4).
4. The method for preparing the CoSe/MnSe@nitrogen doped carbon composite wave absorbing material is characterized by comprising the following steps of: in the step S2, the magnetic stirring speed is 600-800 r/min, the stirring time is 10-15 min, and the aging time is 20-24 h.
5. The method for preparing the CoSe/MnSe@nitrogen doped carbon composite wave absorbing material is characterized by comprising the following steps of: in the step S2, the drying temperature is 60-80 ℃ and the drying time is 12-14 h.
6. The method for preparing the CoSe/MnSe@nitrogen doped carbon composite wave absorbing material is characterized by comprising the following steps of: in step S3, the mass ratio of the CoMn-prussian blue analog to the dopamine hydrochloride is 1: (0.5-1).
7. The method for preparing the CoSe/MnSe@nitrogen doped carbon composite wave absorbing material is characterized by comprising the following steps of: in the step S3, the stirring time is 20-24 hours.
8. The method for preparing the CoSe/MnSe@nitrogen doped carbon composite wave absorbing material is characterized by comprising the following steps of: in the step S5, the mass ratio of the CoMn-PBA@PDA composite material to the selenium powder is 1: (2-3).
9. A CoSe/mnse@nitrogen doped carbon composite wave-absorbing material prepared based on the preparation method of the CoSe/mnse@nitrogen doped carbon composite wave-absorbing material of claims 1-8.
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