CN115322744A - 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
- Publication number
- CN115322744A CN115322744A CN202211113516.8A CN202211113516A CN115322744A CN 115322744 A CN115322744 A CN 115322744A CN 202211113516 A CN202211113516 A CN 202211113516A CN 115322744 A CN115322744 A CN 115322744A
- Authority
- CN
- China
- Prior art keywords
- nickel
- solution
- carbon composite
- preparation
- dimethylformamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 38
- 238000010521 absorption reaction Methods 0.000 claims abstract description 22
- 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 54
- 239000002244 precipitate Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 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 24
- 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
- 238000000034 method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 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
- 238000005406 washing 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
- 238000000926 separation method Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 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 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011358 absorbing material Substances 0.000 abstract description 16
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005516 engineering process 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- HAZNKDJFOOUKJY-UHFFFAOYSA-N [Ni++].[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ni++].[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HAZNKDJFOOUKJY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- AKWULMNJVXIMRR-UHFFFAOYSA-J nickel(2+);tetraacetate Chemical compound [Ni+2].[Ni+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O AKWULMNJVXIMRR-UHFFFAOYSA-J 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 241000705930 Broussonetia papyrifera Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 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
- 239000002184 metal 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
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
Classifications
-
- 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 framework material, preparing the nickel-carbon composite material and the like. The electromagnetic wave absorbing material can well absorb electromagnetic waves, the maximum reflection loss can reach-40 dB, and the corresponding absorption bandwidth is 2GHz. The preparation method has low cost and is easy to realize industrial production, thereby having good popularization and application prospect.
Description
Technical Field
The present invention belongs to the field of electromagnetic wave absorbing material technology. More particularly, the present invention relates to a nickel-carbon composite material absorbing electromagnetic waves, and a method for preparing the same.
Background
With the development of information technology and the popularization of electronic communication equipment, the phenomenon of electromagnetic wave pollution is seen everywhere. The electromagnetic wave interference not only affects the normal use of the communication equipment, but also causes harm to human bodies. Therefore, there is a need for an efficient, environmentally friendly electromagnetic wave absorbing material to prevent the pollution of electromagnetic waves to the living environment. However, the common electromagnetic wave absorbing material has complex preparation process and unsatisfactory wave absorbing performance, so that the large-scale application of the material is limited. It is an ideal pursuit of people to obtain a material with high-efficiency electromagnetic wave absorption performance and simple preparation process.
Metal-Organic Frameworks (MOFs) materials are commonly used as precursors for certain materials due to their large specific surface area and regular crystal structure, and good Metal-carbon composites can be obtained by combining Metal elements with Organic ligands and carbonizing the combined Metal elements and Organic ligands. 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 wide effective frequency width, 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 electromagnetic wave absorbing nickel-carbon composite material.
Technical scheme
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, preparing the 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 the heat for 8-12 hours at 120-180 ℃ in a reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature, carrying out centrifugal separation, washing the separated precipitate for 2-4 times by using N, N-dimethylformamide, then washing for 2-4 times by using ethanol, and drying the washed precipitate for 22-26 hours at 150-200 ℃ in an oven to obtain the metal organic framework material;
IV, preparing the nickel-carbon composite material
And (4) heating the metal organic framework material prepared in the step (III) in inert gas to 600-900 ℃, and keeping the temperature for 2-4 hours to obtain the nickel-carbon composite material for absorbing the electromagnetic waves.
According to a preferred embodiment of the present 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, the polyvinylpyrrolidone is polyvinylpyrrolidone K30.
According to another preferred embodiment of the present 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, solution B is mixed with solution A with stirring for 8 to 12min.
According to another preferred embodiment of the invention, in step III, when the separated precipitate is washed with N, N-dimethylformamide, the ratio of the precipitate in grams to the N, N-dimethylformamide in milliliters is 1:5 to 20.
According to another preferred embodiment of the present invention, in step III, when the separated precipitate is washed with ethanol, the ratio of the precipitate in grams to the 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 a nickel-oxygen cluster 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 the preparation method, the maximum absorption intensity of the nickel-carbon composite material is-30 dB to 40dB, and the effective absorption bandwidth of the nickel-carbon composite material is 1.9GHz to 2.1GHz.
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
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;
according to the present invention, the primary role of the nickel salt in the preparation of the nickel-carbon composite 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 mclin biochemical technology ltd, and nickel nitrate sold under the trade name nickel nitrate hexahydrate (AR, 98%) by shanghai alatin biochemical technology ltd.
The polyvinylpyrrolidone has the main function of improving the morphological characteristics of the material by a polymer surfactant consisting of a hydrophilic pyrrolidone group and a lipophilic hydrocarbon group in the preparation of the nickel-carbon composite material;
the polyvinylpyrrolidone used in the present invention is polyvinylpyrrolidone K30, which is a product currently marketed, for example, polyvinylpyrrolidone K30 sold under the trade name polyvinylpyrrolidone (K30, 99%) by beijing wauke biotechnology limited.
According to the invention, the weight ratio of nickel salt to polyvinylpyrrolidone is 1:0.3 to 0.5. If the weight ratio of the nickel salt to the polyvinylpyrrolidone is more than 1:0.3, the solution viscosity is too high, so that the solvothermal reaction cannot be effectively carried out; if the weight ratio of nickel salt to polyvinylpyrrolidone is less than 1:0.5, the appearance of the sample cannot be effectively improved by polyvinylpyrrolidone; thus, 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 ratio of the volume of deionized water in ml to the weight of polyvinylpyrrolidone in g is 20 to 40:1. the volume of the deionized water and the weight ratio of the polyvinylpyrrolidone are less than 20:1, polyvinylpyrrolidone can not be completely dissolved; if the volume ratio of the deionized water to the polyvinylpyrrolidone is more than 40:1, the deionized water content is too much, and the flaky appearance cannot be effectively formed; 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 marketed, for example, by Bikinson ultrasonic (Shanghai) Co., ltd., under the trade name Branson ultrasonic apparatus.
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, the main role of terephthalic acid in the preparation of the nickel-carbon composite material of the present invention is to provide ligands for the metal-organic framework;
the main functions of N, N-dimethylformamide in the preparation of the nickel-carbon composite material are terephthalic acid dissolution and deprotonation;
the weight ratio of terephthalic acid to N, N-dimethylformamide was 1:25 to 35. If the weight ratio of terephthalic acid to N, N-dimethylformamide is greater than 1:25, excessive solvent and reagent are wasted, the concentration of reactants is low, and the reaction cannot be effectively carried out; if the weight ratio of terephthalic acid to N, N-dimethylformamide is less than 1:35, the terephthalic acid cannot be effectively dissolved; thus, the weight ratio of terephthalic acid to N, N-dimethylformamide is 1:25 to 35 are suitable, preferably 1:28 to 32;
the terephthalic acid and the N, N-dimethylformamide used in the present invention are commercially available products, for example, terephthalic acid sold under the trade name terephthalic acid by Beijing Vocko Biotechnology Co., ltd, and N, N-dimethylformamide sold under the trade name N, N-dimethylformamide (AR (Shanghai test); 99.5%) by national chemical group Co., ltd.
III, preparing the 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 the heat for 8-12 hours at the temperature of 120-180 ℃ in a reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature, carrying out centrifugal separation, washing the separated precipitate for 2-4 times by using N, N-dimethylformamide, then washing for 2-4 times by using ethanol, and drying the washed precipitate for 22-26 hours at the temperature of 150-200 ℃ in an oven to obtain the metal organic framework material;
according to the invention, the basic reaction of solution A with solution B is as follows:
in this step, solution B and solution A are stirred and mixed for 8-12 min.
According to the invention, the solution A and the solution B react for 8 to 12 hours at a temperature of between 120 and 180 ℃.
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 borne by the reaction kettle, so that danger is easy to occur; therefore, the reaction temperature is reasonable to be 120-180 ℃; preferably 135 to 160 ℃; in the reaction temperature range, if the reaction time is shorter than 8 hours, the reaction is incomplete; if the reaction time is longer than 12 hours, the reaction time is too long, and the crystal growth is too large; therefore, a reaction time of 8 to 12 hours is suitable; preferably 8.8 to 11.2 hours.
In this step, the reaction precipitate of solution B and solution a is separated from the reaction mother liquor using a centrifuge, which is a product currently marketed, for example, by hitachi under the trade name centrifuge (CF 15 RXII).
In this step, the separated precipitate was washed with N, N-dimethylformamide mainly for the purpose of dissolving and washing out the reactant which did not participate in the reaction. The ratio of precipitate in grams to N, N-dimethylformamide in milliliters at the wash was 1:15 to 30. If the ratio of precipitate to N, N-dimethylformamide is less than 1:15, insufficient washing and excessive 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 is appropriate. The main purpose of the separated precipitate washed with ethanol was to wash out the hard-to-volatilize N, N-dimethylformamide. The ratio of precipitate in grams to ethanol in milliliters at the wash 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 waste of the solvent is caused; thus, the ratio of precipitate to ethanol was 1:5 to 20 is suitable.
Then, the washed precipitate is dried in an oven at a temperature of 60-100 ℃ for 22-26 hours. In this step, the drying should be carried out so that the dried precipitate contains less than 0.5% by weight of ethanol.
And performing phase analysis on the dried precipitate by adopting an X-ray powder diffraction analysis method, and determining that the dried precipitate is a metal organic framework material, namely the metal organic framework material formed by combining nickel-oxygen clusters and terephthalic acid as ligands.
IV, preparing the nickel-carbon composite material
And (4) heating the metal organic framework material prepared in the step (III) in inert gas to 600-900 ℃, and keeping the temperature for 2-4 hours to obtain the nickel-carbon composite material for 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 pyrolyse 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 framework material is calcined for 2 to 4 hours at the temperature of 600 to 900 ℃. When the calcination time is within the range, if the calcination temperature is lower than 600 ℃, the material cannot be effectively carbonized; if the calcination temperature is higher than 900 ℃, the reaction temperature is too high, and 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, and 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 analyzed by X-ray diffraction analysis, and the analysis results are shown in FIG. 1.
The X-ray diffraction pattern of FIG. 1 was determined by analysis of JCPDS standard data, and the product obtained in this step was metallic nickel with face-centered cubic structure.
The results are shown in FIG. 2, when observed with an electron microscope. As can be seen from FIG. 2, the calcined product obtained in this step is a petaloid sheet-like structure material.
The invention also relates to the nickel-carbon composite material for absorbing the electromagnetic waves, which is prepared by the preparation method.
The electromagnetic wave absorption performance of the nickel-carbon composite material sample is evaluated according to the transmission line theory by using a vector network analyzer and adopting a coaxial waveguide method (2-18 GHz) to measure the electromagnetic parameters of the sample.
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 invention has the beneficial effects that:
the electromagnetic wave absorbing material is formed by combining nickel and porous carbon, has different micro-morphology structures, and enables the magnetic loss and the dielectric loss of the electromagnetic wave absorbing material to reach impedance matching to a certain extent, thereby improving the electromagnetic wave absorbing performance.
The electromagnetic wave absorbing material can well absorb electromagnetic waves, the maximum reflection loss can reach-40 dB, and the corresponding absorption bandwidth is 2GHz.
The preparation method has low cost and is easy to realize industrial production, thereby having good popularization and application prospect.
Drawings
Fig. 1 is an XRD pattern of the nickel-carbon composite electromagnetic wave absorption material prepared in example 1.
Fig. 2 is an SEM image of the nickel-carbon composite electromagnetic wave absorption material prepared in example 1.
Fig. 3 is an SEM image of a nickel-carbon composite electromagnetic wave absorption 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 graph showing reflection loss of the nickel-carbon composite electromagnetic wave absorption material prepared in example 2.
Fig. 6 is an electromagnetic parameter diagram of a nickel-carbon composite electromagnetic wave absorption material prepared in example 2.
Detailed Description
The invention will be better understood from the following examples.
Example 1: preparation of the electromagnetic wave absorbing nickel-carbon composite material of the invention
The implementation steps of this example are as follows:
I. preparation of solution A
According to the weight ratio of nickel salt to polyvinylpyrrolidone of 1:0.4, adding nickel acetate nickel salt and polyvinylpyrrolidone K30 to deionized water, the ratio of deionized water volume in ml to polyvinylpyrrolidone K30 weight in g being 25:1, ultrasonically dissolving by using ultrasonic equipment to obtain a clear transparent solution A;
II. Preparation of solution B
According to the weight ratio of 1:35, dissolving terephthalic acid in N, N-dimethylformamide, and uniformly stirring and mixing to obtain a solution B;
III, preparing the 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 temperature in a reaction kettle with a polytetrafluoroethylene lining at 120 ℃ for 11 h, cooling to room temperature, performing centrifugal separation, washing the separated precipitate for 3 times by using N, N-dimethylformamide, wherein the ratio of the precipitate in grams to the N, N-dimethylformamide in milliliters is 1:10; and 3 more washes with ethanol, the ratio of precipitate in grams to ethanol in milliliters being 1:5, drying the washed precipitate in an oven at 180 ℃ for 23 hours to obtain the metal organic framework material;
IV, preparing the nickel-carbon composite material
And (3) heating the metal organic framework material prepared in the step (III) to the temperature of 700 ℃ in nitrogen inert gas, and keeping the temperature for 3.4 hours to obtain the nickel-carbon composite material for absorbing the electromagnetic waves.
The maximum absorption intensity of the nickel-carbon composite material measured according to the method described in the specification of the present application was-40 dB, the effective absorption bandwidth thereof was 1.9GHz, the XRD pattern thereof is shown in fig. 1, and fig. 1 shows the (111), (200) and (202) crystal plane peaks of nickel. The SEM spectrum of FIG. 2 shows the micro-morphology of the nickel-carbon composite sample, a petaloid sheet structure material.
Example 2: preparation of the electromagnetic wave absorbing nickel-carbon composite material of the invention
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, adding nickel nitrate nickel salt and polyvinylpyrrolidone K30 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 a clear 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, preparing the 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 hours at the temperature of 140 ℃ in a reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature, carrying out centrifugal separation, washing the separated precipitate for 2 times by using N, N-dimethylformamide, wherein the ratio of the precipitate in grams to the N, N-dimethylformamide in milliliters is 1:15; again washed 2 times with ethanol, the ratio of precipitate in grams to ethanol in milliliters was 1:10, drying the washed precipitate in an oven at the temperature of 200 ℃ for 22 hours to obtain the metal organic framework material;
IV, preparing the nickel-carbon composite material
And (3) heating the metal organic framework material prepared in the step (III) to the temperature of 800 ℃ in nitrogen or argon inert gas, and keeping the temperature for 2.6 hours to obtain the nickel-carbon composite material for absorbing the electromagnetic waves.
The SEM image of the nickel-carbon composite electromagnetic wave absorbing material prepared in this example is shown in fig. 3, and it can be seen from the partially enlarged SEM image that the nickel-carbon composite electromagnetic wave absorbing material has a loose flower-like structure after the solvent concentration is increased, and has a loose porous morphology after being carbonized at a high temperature.
The Raman spectrum of the nickel-carbon composite electromagnetic wave absorbing material prepared in this example, which is measured using a Raman spectrometer, is shown in FIG. 4, and shows the existence state of carbon and the degree of graphitization, as shown in the graph, the Ni/C composite material has a wave number of 1350cm -1 (D band) and 1590cm -1 (GBand) has two peaks indicating successful conversion of the terephthalic acid organic ligand to carbon upon calcination under an inert atmosphere. Where the D band is an sp2 hybridized vibrational band and the G band is an sp3 defect and a disordered vibrational band.
The reflection loss of the nickel-carbon composite electromagnetic wave absorbing material prepared in the embodiment was measured by a coaxial waveguide method, and the reflection loss result is shown in fig. 5, and fig. 5 clearly shows that when the impedance matching thickness is 5mm, the electromagnetic wave absorbing material reaches the maximum reflection loss of-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 in the embodiment is measured by adopting a coaxial waveguide method, the reflection loss result is shown in figure 6, and 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, which indicates that the material has higher dielectric property.
Example 3: preparation of the electromagnetic wave absorbing nickel-carbon composite material of the invention
The implementation steps of this example are as follows:
I. preparation of solution A
According to the weight ratio of nickel salt to polyvinylpyrrolidone of 1:0.4, nickel acetate nickel salt and polyvinylpyrrolidone K30 were added to deionized water in a ratio of volume of deionized water in ml to weight of polyvinylpyrrolidone K30 in g of 35:1, ultrasonically dissolving by using ultrasonic equipment to obtain a clear 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, preparing the 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 temperature for 10 hours at 160 ℃ in a reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature, performing centrifugal separation, washing the separated precipitate for 3 times by using N, N-dimethylformamide, wherein the ratio of the precipitate in grams to the N, N-dimethylformamide in milliliters is 1:20; and washed 4 times with ethanol, the ratio of precipitate in grams to ethanol in milliliters being 1:20, drying the washed precipitate in an oven at the temperature of 150 ℃ for 26 hours to obtain the metal organic framework material;
IV, preparing the nickel-carbon composite material
And (3) heating the metal organic framework material prepared in the step (III) to the temperature of 600 ℃ in nitrogen or argon inert gas, and keeping the temperature for 4.0 hours to obtain the nickel-carbon composite material for absorbing the electromagnetic waves. Its maximum absorption intensity was-35 dB and its effective absorption bandwidth was 2.1GHz, measured according to the method described in the specification of the present application.
Example 4: preparation of the electromagnetic wave absorbing nickel-carbon composite material of the invention
The implementation steps of this example are as follows:
I. preparation of solution A
According to the weight ratio of nickel salt to polyvinylpyrrolidone of 1:0.5, adding nickel nitrate nickel salt and polyvinylpyrrolidone K30 into deionized water, wherein 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 a clear 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, preparing the 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 hours at the temperature of 180 ℃ in a reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature, carrying out centrifugal separation, washing the separated precipitate for 4 times by using N, N-dimethylformamide, wherein the ratio of the precipitate in grams to the N, N-dimethylformamide in milliliters is 1:5; and 3 more washes with ethanol, the ratio of precipitate in grams to ethanol in milliliters being 1:15, drying the washed precipitate in an oven at the temperature of 160 ℃ for 25 hours to obtain the metal organic framework material;
IV, preparing the nickel-carbon composite material
And (3) heating the metal organic framework material prepared in the step (III) to the temperature of 900 ℃ in nitrogen or argon inert gas, and keeping the temperature for 2.0 hours to obtain the nickel-carbon composite material for absorbing the electromagnetic waves. Its maximum absorption intensity was-30 dB and its effective absorption bandwidth was 1.9GHz, measured according to the method described in the specification of the present application.
Claims (10)
1. A preparation method of a nickel-carbon composite material for absorbing electromagnetic waves is characterized by comprising 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, preparing the 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 the heat for 8-12 hours at the temperature of 120-180 ℃ in a reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature, carrying out centrifugal separation, washing the separated precipitate for 2-4 times by using N, N-dimethylformamide, then washing for 2-4 times by using ethanol, and drying the washed precipitate for 22-26 hours at the temperature of 150-200 ℃ in an oven to obtain the metal organic framework material;
IV, preparing the nickel-carbon composite material
And (4) heating the metal organic framework material prepared in the step (III) in inert gas to 600-900 ℃, and keeping the temperature for 2-4 hours to obtain the nickel-carbon composite material for absorbing the electromagnetic waves.
2. The method according to claim 1, wherein in step I, the nickel salt is nickel acetate or nickel nitrate.
3. The method according to claim 1, wherein in step I, the polyvinylpyrrolidone is polyvinylpyrrolidone K30.
4. The method according to claim 1, wherein in step I, the volume ratio of deionized water to polyvinylpyrrolidone is 1-2: 1.
5. the method according to claim 1, wherein in step III, the solution B is mixed with the solution A with stirring for 8 to 12min.
6. The method according to claim 1, wherein in step III, when the separated precipitate is washed with N, N-dimethylformamide, the ratio of the precipitate in grams to the N, N-dimethylformamide in milliliters is 1:5 to 20.
7. The method according to claim 1, wherein in step III, when the separated precipitate is washed with ethanol, the ratio of the precipitate in grams to the ethanol in milliliters is 1:5 to 20.
8. The method according to claim 1, wherein in step III, the metal-organic framework material is a metal-organic framework material in which a nickel-oxygen cluster and terephthalic acid are bound as a ligand.
9. The method according to claim 1, wherein in the step IV, the inert gas is nitrogen or argon.
10. The nickel-carbon composite material for absorbing electromagnetic waves, which is manufactured by the manufacturing method according to any one of claims 1 to 9, is characterized in that the maximum absorption intensity thereof is-30 to-40 dB, and the effective absorption bandwidth thereof is 1.0 to 2.5GHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211113516.8A CN115322744B (en) | 2022-09-14 | 2022-09-14 | Nickel-carbon composite material for absorbing electromagnetic waves and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211113516.8A CN115322744B (en) | 2022-09-14 | 2022-09-14 | Nickel-carbon composite material for absorbing electromagnetic waves and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115322744A true CN115322744A (en) | 2022-11-11 |
| CN115322744B CN115322744B (en) | 2024-03-22 |
Family
ID=83929815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211113516.8A Active CN115322744B (en) | 2022-09-14 | 2022-09-14 | Nickel-carbon composite material for absorbing electromagnetic waves and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115322744B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112961650A (en) * | 2021-02-06 | 2021-06-15 | 安徽理工大学 | Tri-metal organic framework derived iron-nickel alloy/porous carbon ultrathin wave absorber and preparation method thereof |
| CN112980390A (en) * | 2021-02-05 | 2021-06-18 | 安徽理工大学 | Preparation method of bimetal organic frame derived magnetic carbon composite wave-absorbing material |
| CN114520419A (en) * | 2022-01-28 | 2022-05-20 | 广东腐蚀科学与技术创新研究院 | Preparation method of cobalt-based metal organic framework derivative wave absorbing agent with nano composite structure |
| CN114554819A (en) * | 2022-02-25 | 2022-05-27 | 山东大学 | Electromagnetic wave absorber based on iron-based metal organic framework material and preparation method thereof |
-
2022
- 2022-09-14 CN CN202211113516.8A patent/CN115322744B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112980390A (en) * | 2021-02-05 | 2021-06-18 | 安徽理工大学 | Preparation method of bimetal organic frame derived magnetic carbon composite wave-absorbing material |
| CN112961650A (en) * | 2021-02-06 | 2021-06-15 | 安徽理工大学 | Tri-metal organic framework derived iron-nickel alloy/porous carbon ultrathin wave absorber and preparation method thereof |
| CN114520419A (en) * | 2022-01-28 | 2022-05-20 | 广东腐蚀科学与技术创新研究院 | Preparation method of cobalt-based metal organic framework derivative wave absorbing agent with nano composite structure |
| CN114554819A (en) * | 2022-02-25 | 2022-05-27 | 山东大学 | Electromagnetic wave absorber based on iron-based metal organic framework material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115322744B (en) | 2024-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110012656B (en) | Preparation method of nano composite wave-absorbing material | |
| CN112961650B (en) | Three-metal organic framework derived iron-nickel alloy/porous carbon ultrathin wave absorber and preparation method thereof | |
| CN107325787B (en) | Hollow carbon nano-particles and wave-absorbing material prepared from same | |
| CN109705809B (en) | Three-dimensional porous carbon composite wave-absorbing material and preparation method thereof | |
| CN113248725A (en) | Preparation method of electromagnetic wave absorbing material based on MOF derivation and electromagnetic wave absorbing material | |
| CN112251193A (en) | Composite wave-absorbing material based on MXene and metal organic framework and preparation method and application thereof | |
| CN113088252A (en) | Iron-cobalt-nickel alloy/carbon/graphene ultrathin wave-absorbing material and preparation method thereof | |
| CN113258301B (en) | Composite material and preparation method and application thereof | |
| CN111137874B (en) | Method for preparing composite wave-absorbing material by taking HKUST-1 as template | |
| CN110723720B (en) | Light broadband electromagnetic wave absorbing material and preparation method thereof | |
| CN111683512A (en) | Microwave synthesis coal-based carbon/ferromagnetic metal composite electromagnetic absorption material and method | |
| CN112996375B (en) | Cu9S5/C composite material and preparation method and application thereof | |
| CN114395371A (en) | Composite wave absorbing agent derived based on tetrazole copper acetate-iron complex and preparation method thereof | |
| CN115322744B (en) | Nickel-carbon composite material for absorbing electromagnetic waves and preparation method thereof | |
| CN115028847B (en) | CoNi alloy MOF porous material and preparation and application thereof | |
| CN112280533B (en) | Preparation method of ternary composite wave-absorbing material with hollow structure | |
| CN113328262B (en) | Preparation method of manganese oxide @ Ni-Co/graphite carbon nano microwave absorption composite material | |
| CN115074086A (en) | Zn-MOFs derived ZnO/C/Ti 3 C 2 Composite wave-absorbing material and preparation method thereof | |
| CN105668607A (en) | Preparation method of nano-sheet copper sulfide material | |
| CN114875391B (en) | Preparation method of FeCo alloy coated foam nickel wave-absorbing material | |
| CN112165845A (en) | Non-toxic preparation method of self-supporting all-carbon electrode loaded with MOF (Metal organic framework) derived carbon | |
| CN113088075B (en) | Chiral planar spiral PPy/Fe3O4Composite broadband microwave absorbent and preparation method and application thereof | |
| CN113708085B (en) | Preparation method of nano porous carbon coated magnetic nanoparticle compound | |
| CN112250056A (en) | Porous hollow magnetic carbon micro-tube material and preparation method thereof | |
| CN117417727A (en) | Three-dimensional carbon nano tube/ZIF 67 composite wave-absorbing material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |