CN115322744B - Nickel-carbon composite material for absorbing electromagnetic waves and preparation method thereof - Google Patents
Nickel-carbon composite material for absorbing electromagnetic waves and preparation method thereof Download PDFInfo
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- CN115322744B CN115322744B CN202211113516.8A CN202211113516A CN115322744B CN 115322744 B CN115322744 B CN 115322744B CN 202211113516 A CN202211113516 A CN 202211113516A CN 115322744 B CN115322744 B CN 115322744B
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 129
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 56
- 239000002244 precipitate Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 26
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 26
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000012621 metal-organic framework Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 150000002815 nickel Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011358 absorbing material Substances 0.000 abstract description 22
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Abstract
The invention relates to a nickel-carbon composite material for absorbing electromagnetic waves and a preparation method thereof. The preparation method of the nickel-carbon composite material comprises the steps of preparing a solution A, preparing a solution B, preparing a metal organic frame material, preparing a nickel-carbon composite material and the like. The electromagnetic wave absorbing material can absorb electromagnetic waves well, the maximum reflection loss can reach-40 dB, and the corresponding absorption bandwidth is 2GHz. The preparation method of the invention has low cost and is easy to realize industrial production, thus having good popularization and application prospect.
Description
Technical Field
The invention belongs to the technical field of electromagnetic wave absorbing materials. More particularly, the invention relates to a nickel-carbon composite material for absorbing electromagnetic waves and a preparation method of the nickel-carbon composite material for absorbing electromagnetic waves.
Background
With the development of information technology and the popularization of electronic communication equipment, electromagnetic wave pollution phenomenon is everywhere visible. Electromagnetic wave interference not only affects normal use of communication equipment, but also causes harm to human body. Therefore, there is a need for an efficient, green and environment-friendly electromagnetic wave absorbing material to prevent pollution of electromagnetic waves to the living environment of people. However, the conventional electromagnetic wave absorbing material has complex preparation process and unsatisfactory wave absorbing performance, so that the large-scale application of the electromagnetic wave absorbing material is limited. It is an ideal pursuit of people how to obtain a material with high-efficiency electromagnetic wave absorption performance and simple preparation process.
Since Metal-organic framework (Metal-Organic Frameworks, MOFs) materials have a large specific surface area and a regular crystal structure, they are generally used as precursors for certain materials, and good Metal-carbon composites can be obtained by combining Metal elements with organic ligands and carbonizing. The MOFs material can be used for effectively combining the metal compound with the carbon material, so that the electromagnetic wave absorbing material with excellent wave absorbing performance is prepared.
Therefore, the MOFs material can be used for preparing the electromagnetic wave absorbing material with good wave absorbing performance and effective bandwidth, and the preparation process is simple, easy to produce and low in cost, and is beneficial to large-scale preparation.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a nickel-carbon composite material for absorbing electromagnetic waves.
Another object of the present invention is to provide a method for preparing the nickel-carbon composite material for absorbing electromagnetic waves.
Technical proposal
The invention is realized by the following technical scheme.
The invention relates to a preparation method of a nickel-carbon composite material for absorbing electromagnetic waves.
The preparation method comprises the following preparation steps:
I. preparation of solution A
According to the weight ratio of nickel salt to polyvinylpyrrolidone of 1:0.3 to 0.5, adding nickel salt and polyvinylpyrrolidone into deionized water, and ultrasonically dissolving by using ultrasonic equipment to obtain a clear and transparent solution A;
II. Preparation of solution B
According to the weight ratio of terephthalic acid to N, N-dimethylformamide of 1: 25-35, dissolving terephthalic acid in N, N-dimethylformamide, and uniformly stirring and mixing to obtain a solution B;
III, preparation of Metal organic framework Material
Pouring the solution B obtained in the step II into the solution A obtained in the step I, stirring and mixing uniformly, then preserving heat for 8-12 hours at the temperature of 120-180 ℃ in a reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature, centrifugally separating, washing separated precipitate with N, N-dimethylformamide for 2-4 times, washing the separated precipitate with ethanol for 2-4 times, and then drying the washed precipitate in an oven at the temperature of 150-200 ℃ for 22-26 hours to obtain the metal organic frame material;
IV, preparing nickel-carbon composite material
And (3) heating the metal organic frame material prepared in the step (III) to 600-900 ℃ in inert gas, and keeping the temperature for 2-4 hours to obtain the nickel-carbon composite material absorbing the electromagnetic waves.
According to a preferred embodiment of the invention, in step I, the nickel salt is nickel acetate or nickel nitrate.
According to another preferred embodiment of the present invention, in step I, said polyvinylpyrrolidone is polyvinylpyrrolidone K30.
According to another preferred embodiment of the invention, in step I, the volume ratio of deionized water to polyvinylpyrrolidone is 1 to 2:1.
according to another preferred embodiment of the present invention, in step III, the solution B is mixed with the solution A with stirring for 8 to 12 minutes.
According to another preferred embodiment of the invention, in step III, when the separated precipitate is washed with N, N-dimethylformamide, the ratio of precipitate in grams to N, N-dimethylformamide in milliliters is 1:5 to 20.
According to another preferred embodiment of the invention, in step III, when the separated precipitate is washed with ethanol, the ratio of precipitate in grams to ethanol in milliliters is 1:5 to 20.
According to another preferred embodiment of the present invention, in step III, the metal organic framework material is a metal organic framework material formed by combining nickel oxide clusters and terephthalic acid as ligands.
According to another preferred embodiment of the present invention, in step IV, the inert gas is nitrogen or argon.
The invention relates to a nickel-carbon composite material for absorbing electromagnetic waves, which is prepared by adopting the preparation method, wherein the maximum absorption intensity is-30-40 dB, and the effective absorption bandwidth is 1.9-2.1 GHz.
The present invention will be described in more detail below.
The invention relates to a preparation method of a nickel-carbon composite material for absorbing electromagnetic waves.
The preparation method comprises the following preparation steps:
I. preparation of solution A
The weight ratio of the nickel salt to polyvinylpyrrolidone is 1:0.3 to 0.5, adding nickel salt and polyvinylpyrrolidone into deionized water, and ultrasonically dissolving by using ultrasonic equipment to obtain a clear and transparent solution A;
according to the present invention, the primary role of the nickel salt in the preparation of the nickel-carbon composite material of the present invention is to provide a source of nickel metal;
the nickel salt used in the present invention is nickel acetate or nickel nitrate, which are currently commercially available products such as nickel acetate sold under the trade name nickel acetate tetrahydrate (AR, 99.5%) by Shanghai microphone Biochemical technology Co., ltd, and nickel nitrate sold under the trade name nickel nitrate hexahydrate (AR, 98%) by Shanghai Alding Biochemical technology Co., ltd.
The main function of polyvinylpyrrolidone in preparing the nickel-carbon composite material is to improve the morphological characteristics of the material by a polymer surfactant composed of hydrophilic pyrrolidone groups and lipophilic hydrocarbon groups;
the polyvinylpyrrolidone used in the present invention is polyvinylpyrrolidone K30, which is a product currently commercially available, for example polyvinylpyrrolidone K30 sold under the trade name polyvinylpyrrolidone (K30, 99%) by the biotechnology company of beijing wokawa.
According to the invention, the weight ratio of nickel salt to polyvinylpyrrolidone is 1:0.3 to 0.5. If the weight ratio of nickel salt to polyvinylpyrrolidone is greater than 1:0.3, the solution viscosity is too great to allow the solvothermal reaction to proceed effectively; if the weight ratio of nickel salt to polyvinylpyrrolidone is less than 1:0.5, polyvinylpyrrolidone cannot effectively improve the morphology of the sample; therefore, the weight ratio of nickel salt to polyvinylpyrrolidone is 1:0.3 to 0.5 is reasonable; preferably 1:0.38 to 0.42;
in this step, the weight ratio of deionized water volume in ml to polyvinylpyrrolidone in g is 20 to 40:1. the weight ratio of the volume of deionized water to polyvinylpyrrolidone is less than 20:1, polyvinylpyrrolidone cannot be completely dissolved; if the volume ratio of deionized water to polyvinylpyrrolidone is greater than 40:1, the deionized water content is excessive, and the flaky morphology may not be formed effectively; therefore, the volume ratio of the deionized water to the polyvinylpyrrolidone is 20-40: 1 is appropriate;
the ultrasonic apparatus used in the present invention is a product currently on the market, such as an ultrasonic apparatus sold under the trade name Branson sonicator by the company Shanghai, inc.
II. Preparation of solution B
According to the weight ratio of terephthalic acid to N, N-dimethylformamide of 1: 25-35, dissolving terephthalic acid in N, N-dimethylformamide, and uniformly stirring and mixing to obtain a solution B;
according to the present invention, terephthalic acid has a primary role in the preparation of the nickel-carbon composite material of the present invention in providing ligands for the metal-organic framework;
the main role of N, N-dimethylformamide in the preparation of the nickel-carbon composite material of the present invention is to dissolve terephthalic acid and deprotonate;
terephthalic acid and N, N-dimethylformamide weight ratio 1:25 to 35. If the weight ratio of terephthalic acid to N, N-dimethylformamide is greater than 1:25, the excessive solvent waste and the low concentration of the reactant can not effectively occur; if the weight ratio of terephthalic acid to N, N-dimethylformamide is less than 1:35, terephthalic acid is not effectively dissolved; thus, the weight ratio of terephthalic acid to N, N-dimethylformamide is 1:25 to 35 are suitable, preferably 1: 28-32;
terephthalic acid and N, N-dimethylformamide used in the present invention are commercially available products, such as terephthalic acid sold under the trade name terephthalic acid by Beijing Walker biotechnology Co., ltd, and N, N-dimethylformamide sold under the trade name N, N-dimethylformamide (AR (Shanghai test),. Gtoreq.99.5%) by national pharmaceutical systems chemical reagent Co., ltd.
III, preparation of Metal organic framework Material
Pouring the solution B obtained in the step II into the solution A obtained in the step I, stirring and mixing uniformly, then preserving heat for 8-12 hours at the temperature of 120-180 ℃ in a reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature, centrifugally separating, washing separated precipitate with N, N-dimethylformamide for 2-4 times, washing the separated precipitate with ethanol for 2-4 times, and then drying the washed precipitate in an oven at the temperature of 150-200 ℃ for 22-26 hours to obtain the metal organic frame material;
according to the invention, the basic reaction of solution A with solution B is as follows:
in this step, the solution B and the solution A are stirred and mixed for 8 to 12 minutes.
According to the invention, the solution A and the solution B are reacted at a temperature of 120-180 ℃ for 8-12 hours.
In the reaction time range, if the reaction temperature is lower than 120 ℃, the reaction temperature is too low, and the reaction cannot be effectively carried out; if the reaction temperature is higher than 180 ℃, the reaction temperature is too high and exceeds the temperature born by the reaction kettle, so that danger is easy to occur; therefore, the reaction temperature is reasonable to be 120-180 ℃; preferably 135-160 ℃; in the reaction temperature range, if the reaction time is shorter than 8 hours, the reaction is not thorough; if the reaction time is longer than 12 hours, the reaction time is too long, and the crystal growth is too large; therefore, the reaction time is suitably 8 to 12 hours; preferably 8.8 to 11.2 hours.
In this step, the reaction precipitate of the solution B and the solution A is separated from the reaction mother liquor using a centrifuge, which is a product currently commercially available, for example, a centrifuge product sold under the trade name of centrifuge (CF 15 RXII) by Hitachi.
In this step, the isolated precipitate is washed with N, N-dimethylformamide primarily for the purpose of dissolving and washing out reactants that do not participate in the reaction. The ratio of precipitate in grams to N, N-dimethylformamide in milliliters at the time of washing was 1: 15-30. If the ratio of precipitate to N, N-dimethylformamide is less than 1:15, insufficient washing and more impurities; if the ratio of precipitate to N, N-dimethylformamide is greater than 1:30, waste is caused; thus, the ratio of precipitate to N, N-dimethylformamide was 1:15 to 30 are suitable. The main purpose of the washing of the separated precipitate with ethanol is to wash out the poorly volatile N, N-dimethylformamide. The ratio of precipitate in grams to ethanol in milliliters at the time of washing was 1:5 to 20. If the ratio of precipitate to ethanol is greater than 1:5, residual N, N-dimethylformamide cannot be completely washed out; if the ratio of precipitate to ethanol is less than 1:20, the solvent is wasted; thus, the ratio of precipitate to ethanol was 1:5 to 20 are suitable.
The washed precipitate is then dried in an oven at a temperature of 60 to 100℃for 22 to 26 hours. In this step, the drying should be such that the dried precipitate contains ethanol in an amount of 0.5% by weight or less.
The dried precipitate is subjected to phase analysis by adopting an X-ray powder diffraction analysis method, and the dried precipitate is determined to be a metal organic framework material, namely, the metal organic framework material is formed by combining nickel oxide clusters and terephthalic acid serving as ligands.
IV, preparing nickel-carbon composite material
And (3) heating the metal organic frame material prepared in the step (III) to 600-900 ℃ in inert gas, and keeping the temperature for 2-4 hours to obtain the nickel-carbon composite material absorbing the electromagnetic waves.
In this step, the main purpose of the calcination of the metal-organic framework material in an inert gas is to pyrolyze the metal-organic framework material to form a Ni/C composite.
According to the invention, the inert gas is nitrogen or argon.
The metal organic frame material is calcined for 2 to 4 hours at the temperature of 600 to 900 ℃. When the calcination time is within the above range, if the calcination temperature is lower than 600 ℃, the material cannot be effectively carbonized; if the calcining temperature is higher than 900 ℃, the reaction temperature is too high, so that energy waste is caused; accordingly, a calcination temperature of 600 to 900 ℃ is appropriate, preferably 660 to 840 ℃, more preferably 700 to 780 ℃; when the calcination temperature is within the above range, if the calcination time is shorter than 2 hours, the carbonization time is too short and the reaction is insufficient; if the calcination time is longer than 4 hours, the reaction time is too long, so that energy waste is caused; accordingly, a calcination time of 2 to 4 hours is suitable, preferably 2.4 to 3.6 hours, more preferably 2.8 to 3.2 hours;
preferably, the metal organic framework material is calcined at a temperature of 660-840 ℃ for 2.4-3.6 hours.
More preferably, the metal organic framework material is calcined at a temperature of 700 to 780 ℃ for 2.8 to 3.2 hours.
The product obtained in this step was examined and analyzed by an X-ray diffraction analysis method, and the analysis results are shown in FIG. 1.
The X-ray diffraction pattern of figure 1 is determined according to JCPDS standard data analysis, and the product obtained by the step is metallic nickel with a face-centered cubic structure.
The results are shown in FIG. 2, which are observed by electron microscopy. As can be seen from FIG. 2, the calcined product obtained in this step is a petal-like sheet-like structure material.
The invention also relates to the nickel-carbon composite material for absorbing electromagnetic waves, which is prepared by adopting the preparation method.
And measuring electromagnetic parameters of the sample by using a vector network analyzer and adopting a coaxial waveguide method (2-18 GHz), and evaluating the electromagnetic wave absorption performance of the nickel-carbon composite material sample according to the transmission line theory.
According to the transmission line theory, the maximum absorption intensity of the product prepared by the preparation method is-30-40 dB, and the effective absorption bandwidth is 1.9-2.1 GHz.
Advantageous effects
The beneficial effects of the invention are as follows:
the electromagnetic wave absorbing material is formed by combining nickel and porous carbon and has different microstructure structures, so that the magnetic loss and dielectric loss of the electromagnetic wave absorbing material are matched with each other to a certain extent, and the electromagnetic wave absorbing performance is improved.
The electromagnetic wave absorbing material can absorb electromagnetic waves well, the maximum reflection loss can reach-40 dB, and the corresponding absorption bandwidth is 2GHz.
The preparation method of the invention has low cost and is easy to realize industrial production, thus having good popularization and application prospect.
Drawings
Fig. 1 is an XRD pattern of the nickel-carbon composite electromagnetic wave absorbing material prepared in example 1.
Fig. 2 is an SEM image of the nickel-carbon composite electromagnetic wave absorbing material prepared in example 1.
Fig. 3 is an SEM image of the nickel-carbon composite electromagnetic wave absorbing material prepared in example 2.
FIG. 4 is a Raman spectrum of the nickel-carbon composite electromagnetic wave absorbing material prepared in example 2.
Fig. 5 is a reflection loss diagram of the nickel-carbon composite electromagnetic wave absorbing material prepared in example 2.
Fig. 6 is an electromagnetic parameter chart of the nickel-carbon composite electromagnetic wave absorbing material prepared in example 2.
Detailed Description
The invention will be better understood by the following examples.
Example 1: preparation of the Nickel-carbon composite material for absorbing electromagnetic waves
The implementation steps of this embodiment are as follows:
I. preparation of solution A
According to the weight ratio of nickel salt to polyvinylpyrrolidone of 1:0.4, nickel acetate and polyvinylpyrrolidone K30 are added into deionized water, and the weight ratio of the volume of the deionized water in ml to the polyvinylpyrrolidone K30 in g is 25:1, ultrasonically dissolving by using ultrasonic equipment to obtain clear and transparent solution A;
II. Preparation of solution B
According to the weight ratio of terephthalic acid to N, N-dimethylformamide of 1:35, dissolving terephthalic acid in N, N-dimethylformamide, and uniformly stirring and mixing to obtain a solution B;
III, preparation of Metal organic framework Material
Pouring the solution B obtained in the step II into the solution A obtained in the step I, stirring and mixing for 10min, then preserving heat for 11 h at the temperature of 120 ℃ in a reaction kettle provided with a polytetrafluoroethylene lining, cooling to room temperature, centrifugally separating, washing the separated precipitate for 3 times by using N, N-dimethylformamide, wherein the ratio of the precipitate to the N, N-dimethylformamide in terms of gram is 1:10; the precipitate was washed 3 more times with ethanol in grams and the ratio of ethanol in milliliters was 1:5, drying the washed precipitate in an oven at 180 ℃ for 23 hours to obtain the metal organic frame material;
IV, preparing nickel-carbon composite material
And (3) heating the metal organic frame material prepared in the step (III) to 700 ℃ in nitrogen inert gas, and keeping the temperature for 3.4 hours to obtain the nickel-carbon composite material absorbing electromagnetic waves.
The maximum absorption intensity of the nickel-carbon composite material is-40 dB, the effective absorption bandwidth is 1.9GHz, the XRD patterns of the composite material are shown in figure 1, and the figure 1 shows (111), (200) and (202) crystal plane peaks of nickel. The SEM spectrogram of figure 2 shows the microscopic morphology of the nickel-carbon composite sample and the petal-shaped sheet-like structural material.
Example 2: preparation of the Nickel-carbon composite material for absorbing electromagnetic waves
The implementation steps of this embodiment are as follows:
I. preparation of solution A
According to the weight ratio of nickel salt to polyvinylpyrrolidone of 1:0.3, nickel nitrate and polyvinylpyrrolidone K30 are added into deionized water, wherein the weight ratio of the volume of the deionized water in ml to the polyvinylpyrrolidone K30 in g is 30:1, ultrasonically dissolving by using ultrasonic equipment to obtain clear and transparent solution A;
II. Preparation of solution B
According to the weight ratio of terephthalic acid to N, N-dimethylformamide of 1:25, dissolving terephthalic acid in N, N-dimethylformamide, and uniformly stirring and mixing to obtain a solution B;
III, preparation of Metal organic framework Material
Pouring the solution B obtained in the step II into the solution A obtained in the step I, stirring and mixing for 8min, then preserving the heat for 12 h at the temperature of 140 ℃ in a reaction kettle provided with a polytetrafluoroethylene lining, cooling to room temperature, centrifugally separating, washing the separated precipitate for 2 times by using N, N-dimethylformamide, wherein the ratio of the precipitate to the N, N-dimethylformamide in terms of gram is 1:15; the precipitate was washed with ethanol 2 more times and the ratio of precipitate in grams to ethanol in milliliters was 1:10, drying the washed precipitate in an oven at 200 ℃ for 22 hours to obtain the metal organic frame material;
IV, preparing nickel-carbon composite material
And (3) heating the metal organic frame material prepared in the step (III) to 800 ℃ in nitrogen or argon inert gas, and keeping the temperature for 2.6 hours to obtain the nickel-carbon composite material absorbing electromagnetic waves.
The example was used to observe the preparation of a nickel-carbon composite electromagnetic wave absorbing material using a scanning electron microscope, the SEM image of which is shown in fig. 3, and it can be seen from the enlarged partial SEM image that the nickel-carbon composite electromagnetic wave absorbing material exhibits a loose flower-like structure after the concentration of the solvent is increased, and a loose porous morphology after carbonization at high temperature.
The preparation of the nickel-carbon composite electromagnetic wave absorbing material of this example was measured using a Raman spectrometer, the Raman spectrum of which is shown in FIG. 4, and the Raman spectrum shows the presence of carbon and the degree of graphitization, as shown in the figure, the Ni/C composite material was prepared at a wavenumber of 1350cm -1 (D band) and 1590cm -1 (G band) has two peaks, indicating successful conversion of terephthalic acid organic ligand to carbon by calcination under an inert atmosphere. Wherein the D band is an sp2 hybridized vibrational band and the G band is an sp3 defective and disordered vibrational band.
The reflection loss of the nickel-carbon composite electromagnetic wave absorbing material prepared by the embodiment is measured by adopting a coaxial waveguide method, the reflection loss result is shown in figure 5, and figure 5 clearly shows that when the impedance matching thickness is 5mm, the maximum reflection loss of the electromagnetic wave absorbing material reaches-40 dB at 6.8GHz, and the effective absorption bandwidth is 2.8GHz.
The reflection loss of the nickel-carbon composite electromagnetic wave absorbing material prepared by the embodiment is measured by adopting a coaxial waveguide method, the reflection loss result is shown in figure 6, figure 6 clearly shows that the real part of the complex dielectric constant fluctuates within the range of 5-6.5, and the imaginary part fluctuates within the range of 1-3, thus indicating that the material has higher dielectric property.
Example 3: preparation of the Nickel-carbon composite material for absorbing electromagnetic waves
The implementation steps of this embodiment are as follows:
I. preparation of solution A
According to the weight ratio of nickel salt to polyvinylpyrrolidone of 1:0.4, nickel acetate and polyvinylpyrrolidone K30 are added into deionized water, and the weight ratio of the volume of the deionized water in ml to the polyvinylpyrrolidone K30 in g is 35:1, ultrasonically dissolving by using ultrasonic equipment to obtain clear and transparent solution A;
II. Preparation of solution B
According to the weight ratio of terephthalic acid to N, N-dimethylformamide of 1:32, dissolving terephthalic acid in N, N-dimethylformamide, and uniformly stirring and mixing to obtain a solution B;
III, preparation of Metal organic framework Material
Pouring the solution B obtained in the step II into the solution A obtained in the step I, stirring and mixing for 12min, then preserving the heat for 10 h at 160 ℃ in a reaction kettle provided with a polytetrafluoroethylene lining, cooling to room temperature, centrifugally separating, washing the separated precipitate for 3 times by using N, N-dimethylformamide, wherein the ratio of the precipitate to the N, N-dimethylformamide in terms of gram is 1:20, a step of; the precipitate was washed with ethanol 4 more times and the ratio of precipitate in grams to ethanol in milliliters was 1:20, drying the washed precipitate in an oven at 150 ℃ for 26 hours to obtain the metal organic frame material;
IV, preparing nickel-carbon composite material
And (3) heating the metal organic frame material prepared in the step (III) to 600 ℃ in nitrogen or argon inert gas, and keeping the temperature for 4.0 hours to obtain the nickel-carbon composite material absorbing electromagnetic waves. Its maximum absorption strength is-35 dB and its effective absorption bandwidth is 2.1GHz, as measured by the method described in the specification.
Example 4: preparation of the Nickel-carbon composite material for absorbing electromagnetic waves
The implementation steps of this embodiment are as follows:
I. preparation of solution A
According to the weight ratio of nickel salt to polyvinylpyrrolidone of 1:0.5, nickel nitrate and polyvinylpyrrolidone K30 are added into deionized water, and the weight ratio of the volume of the deionized water in ml to the polyvinylpyrrolidone K30 in g is 40:1, ultrasonically dissolving by using ultrasonic equipment to obtain clear and transparent solution A;
II. Preparation of solution B
According to the weight ratio of terephthalic acid to N, N-dimethylformamide of 1:28, dissolving terephthalic acid in N, N-dimethylformamide, and uniformly stirring and mixing to obtain a solution B;
III, preparation of Metal organic framework Material
Pouring the solution B obtained in the step II into the solution A obtained in the step I, stirring and mixing for 10min, then preserving the heat for 8 h at the temperature of 180 ℃ in a reaction kettle provided with a polytetrafluoroethylene lining, cooling to room temperature, centrifugally separating, washing the separated precipitate for 4 times by using N, N-dimethylformamide, wherein the ratio of the precipitate to the N, N-dimethylformamide in terms of gram is 1:5, a step of; the precipitate was washed 3 more times with ethanol in grams and the ratio of ethanol in milliliters was 1:15, drying the washed precipitate in an oven at 160 ℃ for 25 hours to obtain the metal organic frame material;
IV, preparing nickel-carbon composite material
And (3) heating the metal organic frame material prepared in the step (III) to 900 ℃ in nitrogen or argon inert gas, and keeping the temperature for 2.0 hours to obtain the nickel-carbon composite material absorbing electromagnetic waves. Its maximum absorption strength is-30 dB and its effective absorption bandwidth is 1.9GHz, as measured by the method described in the specification.
Claims (8)
1. The preparation method of the nickel-carbon composite material for absorbing electromagnetic waves is characterized by comprising the following preparation steps of:
I. preparation of solution A
According to the weight ratio of nickel salt to polyvinylpyrrolidone of 1:0.3 to 0.5, adding nickel salt and polyvinylpyrrolidone into deionized water, and ultrasonically dissolving by using ultrasonic equipment to obtain clear and transparent solution A, wherein the nickel salt is nickel acetate or nickel nitrate;
II. Preparation of solution B
According to the weight ratio of terephthalic acid to N, N-dimethylformamide of 1: 25-35, dissolving terephthalic acid in N, N-dimethylformamide, and uniformly stirring and mixing to obtain a solution B;
III, preparation of Metal organic framework Material
Pouring the solution B obtained in the step II into the solution A obtained in the step I, stirring and mixing uniformly, then preserving heat for 8-12 hours at the temperature of 120-180 ℃ in a reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature, centrifugally separating, washing separated precipitate with N, N-dimethylformamide for 2-4 times, washing the separated precipitate with ethanol for 2-4 times, and then drying the washed precipitate in an oven at the temperature of 150-200 ℃ for 22-26 hours to obtain the metal organic frame material;
IV, preparing nickel-carbon composite material
And (3) heating the metal organic frame material prepared in the step (III) to 600-900 ℃ in inert gas, and keeping the temperature for 2-4 hours, wherein the inert gas is nitrogen or argon, so as to obtain the nickel-carbon composite material absorbing electromagnetic waves.
2. The method according to claim 1, wherein in step I, the polyvinylpyrrolidone is polyvinylpyrrolidone K30.
3. The method according to claim 1, wherein in the step I, the volume ratio of deionized water to polyvinylpyrrolidone is 1 to 2:1.
4. the preparation method according to claim 1, wherein in step III, the solution B and the solution A are mixed with stirring for 8 to 12 minutes.
5. The process according to claim 1, wherein in step III, the ratio of the isolated precipitate in grams to the N, N-dimethylformamide in milliliters is 1:5 to 20.
6. The process according to claim 1, wherein in step III, the ratio of the isolated precipitate in grams to the ethanol in milliliters is 1:5 to 20.
7. The method of claim 1, wherein in step III, the metal organic framework material is a metal organic framework material formed by combining nickel oxide clusters and terephthalic acid as ligands.
8. The nickel-carbon composite material for absorbing electromagnetic waves prepared by the preparation method according to any one of claims 1 to 7, which is characterized in that the maximum absorption intensity is-30 to-40 dB and the effective absorption bandwidth is 1.0 to 2.5GHz.
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| CN112143460A (en) * | 2020-09-25 | 2020-12-29 | 同济大学 | Composite wave-absorbing material based on metal organic framework material and preparation method and application thereof |
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