CN116209231B - Carbon-based composite wave-absorbing material and preparation method and application thereof - Google Patents
Carbon-based composite wave-absorbing material and preparation method and application thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000011358 absorbing material Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 98
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000003763 carbonization Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 238000004729 solvothermal method Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- -1 aldehyde compound Chemical class 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 150000002989 phenols Chemical class 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 230000005670 electromagnetic radiation Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000004873 anchoring Methods 0.000 abstract description 3
- 239000000696 magnetic material Substances 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 28
- 235000019441 ethanol Nutrition 0.000 description 25
- 238000005406 washing Methods 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 7
- 239000005011 phenolic resin Substances 0.000 description 7
- 229920001568 phenolic resin Polymers 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 5
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical class O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate 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
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- YARHBRUWMYJLHY-UHFFFAOYSA-Q triazanium;iron(3+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YARHBRUWMYJLHY-UHFFFAOYSA-Q 0.000 description 1
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
Abstract
The invention belongs to the technical field of wave-absorbing materials, and provides a carbon-based composite wave-absorbing material, and a preparation method and application thereof. According to the invention, the concave hollow carbon cube is taken as a matrix, alloy nano particles are grown in the concave hollow carbon cube, and the anchoring growth of the alloy nano particles containing magnetic components in the concave hollow carbon cube solves the problem that magnetic materials are easy to stack and agglomerate due to large surface activity, so that stable wave absorbing effect is convenient to realize, and meanwhile, a large number of heterogeneous interfaces formed when the alloy nano particles are contacted with the carbon components can induce abundant interface polarization loss effect, so that the effective absorption bandwidth of the composite wave absorbing material is widened. The results of the embodiment show that when the fitting thickness of the carbon-based composite wave-absorbing material provided by the invention is 2.4mm, the Reflection Loss (RL) value can reach-48.27 dB, and the effective absorption bandwidth of RL < -10dB is up to 5.76GHz (5.60-11.36 GHz).
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a carbon-based composite wave-absorbing material, and a preparation method and application thereof.
Background
The performance improvement of communication equipment and the widening of electromagnetic wave frequency bands bring convenience to the life of people and also bring increasingly serious electromagnetic pollution problems. Under such realistic conditions, on the one hand, the application requirements of electromagnetic compatibility and electromagnetic protection in the civilian field are becoming urgent; on the other hand, with the great development of military stealth technology by the country, the traditional electromagnetic wave absorbing material cannot meet the requirements of national defense weapon update iteration. Therefore, there is a need in the current society to develop high performance wave absorbing materials with the characteristics of light, thin, wide, and strong applications to throttle the increasingly serious electromagnetic pollution problem and realize stealth revolution of weaponry.
The carbon material has excellent composite characteristic and adjustable electric loss capacity, and has wide application and considerable development prospect in the field of electromagnetic wave absorption. However, the single loss mode exhibited by the carbon component and the significant frequency dispersion effect at high frequencies limit further improvement of the wave absorbing effect. Therefore, the comprehensive optimization of the electrical matching characteristics of carbon components from the aspects of component compounding and structural design is a mainstream research trend. In practical work, at the microstructure construction level, scholars are devoted to designing and developing hollow carbon materials to improve the overall impedance matching effect. Ji An et al (Jietal. Research Progression nanostructural design and composition requirements, carbon,2022,189,617-633) system integrates the wave-absorbing properties of nano-sized solid carbon spheres, hollow porous carbon spheres, corresponding composites and the like, and illustrates the positive value of the construction of hollow cavities in carbon materials for improving the wave-absorbing effect. However, the absorption bandwidth that can be realized by the wave-absorbing material is only 3.9GHz (8.3-12.2 GHz). Therefore, how to widen the absorption bandwidth of the wave-absorbing material is a technical problem to be solved in the art.
Disclosure of Invention
The invention aims to provide a carbon-based composite wave-absorbing material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a carbon-based composite wave-absorbing material, which comprises a concave hollow carbon cube and alloy nano particles growing on the inner side of the concave hollow carbon cube; the elemental composition of the alloy nanoparticle includes two or more of Fe, co, ni, zn, mn, mo, cu, cr, zr, V and Ti, and contains at least one of Fe, co, and Ni.
Preferably, the edge length of the concave hollow carbon cube is 50-300 nm, and the wall thickness is 15-30 nm.
Preferably, the mass of the alloy nano particles is 8-35% of the mass of the concave hollow carbon cubes.
The invention provides a preparation method of the carbon-based composite wave-absorbing material, which comprises the following steps:
(1) Mixing the multi-metal MOF nano particles with water, ethanol and an alkaline catalyst to obtain a mixed solution containing the multi-metal MOF nano particles;
(2) Mixing the mixed solution containing the multi-metal MOF nano particles obtained in the step (1) with a phenolic compound and an aldehyde compound, and performing copolycondensation reaction to obtain multi-metal MOF@PR nano particles;
(3) Dispersing the multi-metal MOF@PR nano particles obtained in the step (2) in a mixed solvent, and performing solvothermal reaction to obtain a precursor of the concave hollow PR cube/alloy nano particles;
(4) Carbonizing the precursor of the concave hollow PR cube/alloy nano particle obtained in the step (3) to obtain the carbon-based composite wave-absorbing material.
Preferably, the alkaline catalyst in the step (1) comprises one or more of ammonia water, sodium hydroxide, barium hydroxide and sodium carbonate.
Preferably, the ratio of the amount of the multi-metal MOF nanoparticle in step (1), the basic catalyst in step (1), the phenolic compound in step (2) and the aldehyde compound in step (2) is (0.02 to 0.06) g: (1.5-4) mL (0.13-0.17) g: (0.18-0.24) mL.
Preferably, the temperature of the copolycondensation reaction in the step (2) is 10-45 ℃, and the time of the copolycondensation reaction is 5-10 h.
Preferably, the temperature of the solvothermal reaction in the step (3) is 170-210 ℃, and the time of the solvothermal reaction is 8-18 h.
Preferably, the carbonization temperature in the step (4) is 550-900 ℃, and the carbonization time is 4-10 h.
The invention also provides application of the carbon-based composite wave-absorbing material prepared by the technical scheme or the preparation method of the technical scheme in electromagnetic radiation protection, electronic communication and radar stealth.
The invention provides a carbon-based composite wave-absorbing material, which comprises a concave hollow carbon cube and alloy nano particles growing on the inner side of the concave hollow carbon cube; the elemental composition of the alloy nanoparticle includes two or more of Fe, co, ni, zn, mn, mo, cu, cr, zr, V and Ti, and contains at least one of Fe, co, and Ni. According to the invention, the concave hollow carbon cube is taken as a matrix, alloy nano particles are grown in the concave hollow carbon cube, the anchoring growth of the alloy nano particles containing magnetic components in the concave hollow carbon cube solves the problem that magnetic materials are easy to stack and agglomerate due to large surface activity, so that stable wave absorbing effect is convenient to realize, and meanwhile, a large number of heterogeneous interfaces formed when the alloy nano particles are contacted with the carbon components can induce abundant interface polarization loss effect, so that the effective absorption bandwidth of the composite wave absorbing material is widened; in addition, the specific surface area of the surface concave cube is larger than that of a conventional cube, the large-scale reflection loss effect is easier to realize, and the complex cavity structure in the carbon cube can also capture electromagnetic waves, so that the reflection and scattering attenuation efficiency is improved. The results of the embodiment show that when the fitting thickness of the carbon-based composite wave-absorbing material provided by the invention is 2.4mm, the Reflection Loss (RL) value can reach-48.27 dB, and the effective absorption bandwidth of RL < -10dB is up to 5.76GHz (5.60-11.36 GHz).
Drawings
FIG. 1 is a schematic view of the crystal structure of NiFePBA cubic nanoparticles prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of NiFe nanoparticles prepared in example 1 of the present invention;
FIG. 3 is a TEM image of the C-CNF-1 wave-absorbing material prepared in example 1 of the present invention;
FIG. 4 is a TEM image of the C-CNF-2 wave-absorbing material prepared in example 2 of the present invention;
FIG. 5 is a TEM image of the C-CNF-3 wave-absorbing material prepared in example 3 of the present invention;
FIG. 6 is a TEM image of the C-CNF-4 wave-absorbing material prepared in example 4 of the present invention;
FIG. 7 is a graph showing the reflection loss of the C-CNF-1 wave-absorbing material prepared in example 1 of the present invention in 2-18 GHz;
FIG. 8 is a graph showing the reflection loss of the C-CNF-2 wave-absorbing material prepared in example 2 of the present invention in 2-18 GHz;
FIG. 9 is a graph showing the reflection loss of the C-CNF-3 absorbing material prepared in example 3 of the present invention in 2-18 GHz;
FIG. 10 is a graph showing the reflection loss of the C-CNF-4 absorbing material prepared in example 4 of the present invention in 2-18 GHz.
Detailed Description
The invention provides a carbon-based composite wave-absorbing material, which comprises a concave hollow carbon cube and alloy nano particles growing on the inner side of the concave hollow carbon cube; the elemental composition of the alloy nanoparticle includes two or more of Fe, co, ni, zn, mn, mo, cu, cr, zr, V and Ti, and contains at least one of Fe, co, and Ni.
The carbon-based composite wave-absorbing material provided by the invention comprises a concave hollow carbon cube. The invention takes the concave hollow carbon cube as a matrix, the specific surface area of the surface concave cube is larger than that of the conventional cube, the large-scale reflection loss effect is easier to realize, and the complex cavity structure in the carbon cube can also capture electromagnetic waves, thereby improving the reflection, scattering and attenuation efficiency.
In the invention, the edge length of the concave hollow carbon cube is preferably 50-300 nm, more preferably 50-150 nm; the wall thickness of the concave hollow carbon cube is preferably 15 to 30nm, more preferably 15 to 25nm.
The carbon-based composite wave-absorbing material provided by the invention also comprises alloy nano particles growing on the inner side of the concave hollow carbon cube. In the present invention, the elemental composition of the alloy nanoparticle includes two or more of Fe, co, ni, zn, mn, mo, cu, cr, zr, V and Ti, and contains at least one of Fe, co, and Ni.
In the present invention, the mass of the alloy nanoparticle is preferably 8 to 35% of the mass of the hollow carbon cube, more preferably 8 to 30%.
According to the invention, the concave hollow carbon cube is taken as a matrix, alloy nano particles are grown in the concave hollow carbon cube, the anchoring growth of the alloy nano particles containing magnetic components in the concave hollow carbon cube solves the problem that magnetic materials are easy to stack and agglomerate due to large surface activity, so that stable wave absorbing effect is convenient to realize, and meanwhile, a large number of heterogeneous interfaces formed when the alloy nano particles are contacted with the carbon components can induce abundant interface polarization loss effect, so that the effective absorption bandwidth of the composite wave absorbing material is widened; in addition, the specific surface area of the surface concave cube is larger than that of a conventional cube, the large-scale reflection loss effect is easier to realize, and the complex cavity structure in the carbon cube can also capture electromagnetic waves, so that the reflection and scattering attenuation efficiency is improved.
The invention provides a preparation method of the carbon-based composite wave-absorbing material, which comprises the following steps:
(1) Mixing the multi-metal MOF nano particles with water, ethanol and an alkaline catalyst to obtain a mixed solution containing the multi-metal MOF nano particles;
(2) Mixing the mixed solution containing the multi-metal MOF nano particles obtained in the step (1) with a phenolic compound and an aldehyde compound, and performing copolycondensation reaction to obtain multi-metal MOF@PR nano particles;
(3) Dispersing the multi-metal MOF@PR nano particles obtained in the step (2) in a mixed solvent, and performing solvothermal reaction to obtain a precursor of the concave hollow PR cube/alloy nano particles;
(4) Carbonizing the precursor of the concave hollow PR cube/alloy nano particle obtained in the step (3) to obtain the carbon-based composite wave-absorbing material.
In the present invention, all raw materials are commercially available products unless otherwise specified.
According to the invention, the multi-metal MOF nano particles are mixed with water, ethanol and an alkaline catalyst to obtain a mixed solution containing the multi-metal MOF nano particles.
In the present invention, the ethanol is preferably absolute ethanol; the water is preferably deionized water.
The operation of mixing the multi-metal MOF nanoparticles with water, ethanol and a basic catalyst is not particularly limited, and a solid-liquid mixing mode well known to those skilled in the art is adopted.
In the present invention, the mixing of the multi-metal MOF nanoparticles with water, ethanol and a basic catalyst is preferably: the multi-metal MOF nano particles are firstly mixed with part of ethanol, then water and the rest of ethanol are added for ultrasonic dispersion, and then an alkaline catalyst is added. In the present invention, the mode of mixing the multi-metal MOF nanoparticles with a portion of ethanol is preferably pulverization; the device for crushing is preferably a cell crusher; the pulverizing time is preferably 30 to 40 minutes. In the present invention, the partial ethanol is preferably 40 to 50% of the total volume of ethanol. In the invention, the equipment used for ultrasonic dispersion is preferably an ultrasonic cleaner; the time of the ultrasonic dispersion is preferably 25 to 30 minutes.
In the present invention, the alkaline catalyst preferably includes one or more of ammonia, sodium hydroxide, barium hydroxide and sodium carbonate, more preferably one or more of ammonia, sodium hydroxide and sodium carbonate. In the present invention, the mass percentage concentration of the ammonia water is preferably 25 to 28%. The alkaline catalyst is used for catalyzing the condensation polymerization reaction of phenolic resin.
In the present invention, the ratio of the amount of the multi-metal MOF nanoparticle, water and ethanol is preferably (0.02 to 0.06) g: (20-50) mL: (60-80) mL, more preferably (0.03-0.04) g: (30-40) mL: (60-70) mL.
In the present invention, the multi-metal MOF nanoparticles preferably comprise NiFePBA nanoparticles. In the invention, the preparation method of the NiFePBA nanoparticle is preferably as follows: mixing ferricyanide with water to obtain a solution A; mixing a nickel source, a complexing agent and water to obtain a solution B; and mixing the solution A and the solution B, stirring to obtain a solution C, and aging to obtain the NiFePBA nano particles.
In the present invention, ferricyanide is preferably mixed with water to give solution a.
The operation of mixing the ferricyanide and water is not particularly limited, and a solid-liquid mixing method well known to those skilled in the art may be adopted.
In the present invention, the ferricyanide preferably includes potassium ferricyanide, sodium ferricyanide or ammonium ferricyanide, more preferably potassium ferricyanide.
In the present invention, the ratio of the mass of ferricyanide to the volume of water is preferably (1-2) g:200mL.
The present invention preferably mixes the nickel source, complexing agent and water to obtain solution B.
The operation of mixing the nickel source, the complexing agent and the water is not particularly limited, and a solid-liquid mixing mode well known to those skilled in the art is adopted.
In the present invention, the nickel source preferably comprises nickel chloride hexahydrate NiCl 2 ·6H 2 Nickel nitrate hexahydrate Ni (NO) 3 ) 2 ·6H 2 Nickel sulfate hexahydrate, niSO 4 ·6H 2 O and Nickel acetate tetrahydrate Ni (CH) 3 COO) 2 ·4H 2 One or more of O, more preferably nickel chloride hexahydrate NiCl 2 ·6H 2 O。
In the present invention, the complexing agent preferably comprises one or more of citrate, formate, acetate, succinate, tartrate and glycolate, more preferably citrate. In the present invention, the citrate is preferably trisodium citrate dihydrate.
After obtaining the solution A and the solution B, the invention preferably mixes the solution A and the solution B, stirs to obtain the solution C, and then aging to obtain the NiFePBA nano-particles.
In the present invention, the mixing mode of the solution a and the solution B is preferably: solution B was added to solution a.
In the present invention, fe in the solution C 3+ 、Ni 2+ The ratio of the amount of the substance to the complexing agent is preferably (0.05 to 0.95): (0.05-0.95): (1-3).
In the present invention, the stirring time is preferably 1 to 2 minutes. The present invention preferably controls the stirring time within the above range, and too long stirring time will affect the uniformity of initial nucleation of the multi-metal MOF nanoparticles. In the present invention, the stirring means is preferably magnetic stirring.
In the present invention, the aging temperature is preferably 15 to 30 ℃, more preferably 25 ℃; the aging time is preferably 18 to 36 hours, more preferably 24 hours. The aging time in the invention affects the sufficiency and uniformity of the growth of the nano particles, the too short time can lead to the failure of the formation of the microcosmic cube shape of the nano particles, the uneven particle size, and the too long time can lead to the sedimentation of the nano particles at the bottom of the container or the overlapping and adhesion of the nano particles.
After the mixed solution containing the multi-metal MOF nano particles is obtained, the mixed solution containing the multi-metal MOF nano particles is mixed with a phenolic compound and an aldehyde compound to carry out copolycondensation reaction, so that the multi-metal MOF@PR nano particles are obtained.
In the present invention, the mixing of the mixed solution containing the multi-metal MOF nanoparticle with the phenolic compound and the aldehyde compound is preferably: phenolic compounds are added into mixed liquid containing the multi-metal MOF nano particles, and then aldehyde compounds are added. In the present invention, the time for adding the aldehyde compound and the time for adding the phenol compound are preferably spaced from each other by 20 to 40 minutes, more preferably 30 minutes. According to the invention, the thickness of the PR layer can be regulated and controlled by controlling the adding time of the aldehyde compound.
In the present invention, the phenolic compound preferably includes benzene ring derivatives in which a dihydroxy group exists in the ortho, meta or para position, more preferably resorcinol.
In the present invention, the aldehyde compound preferably includes one or more of formaldehyde, acetaldehyde and furfural, more preferably formaldehyde.
In the present invention, the ratio of the amount of the multi-metal MOF nanoparticle, the basic catalyst, the phenolic compound and the aldehyde compound is preferably (0.02 to 0.06) g: (1.5-4) mL (0.13-0.17) g: (0.18 to 0.24) mL, more preferably (0.03 to 0.04) g: (3-4) mL: (0.15-0.16) g: (0.21-0.23) mL.
In the present invention, the temperature of the copolycondensation is preferably 10 to 45 ℃, more preferably 10 to 30 ℃. The temperature of the copolycondensation reaction affects the polymerization reaction speed and the initial generation site of the phenolic resin, the reaction speed is uncontrollable due to the fact that the temperature of the copolycondensation reaction is too high, the phenolic resin is unevenly coated on the multi-metal MOF nano particles, the synthetic raw materials are self-nucleated in the solution, the reaction speed is too low due to the fact that the temperature of the copolycondensation reaction is too low, or the polymerization degree of the generated phenolic resin is low, and the coating process efficiency is low.
In the present invention, the time of the copolycondensation is preferably 5 to 10 hours, more preferably 5 to 7 hours. The time of the copolycondensation reaction affects the sufficiency of the polymerization reaction and the coating condition of the phenolic resin, the insufficient polymerization reaction and poor coating effect can be caused by the too short time, and the excessive polymerization reaction and the external adhesion of product particles can be caused by the too long time.
After finishing the copolycondensation, the product of the copolycondensation is preferably washed and dried in sequence. The washing and drying operation is not particularly limited in the present invention, and washing and drying techniques well known to those skilled in the art may be employed. In the present invention, the washing is preferably water washing and alcohol washing. In the present invention, the reagent used for the water washing is preferably deionized water; the number of water washes is preferably three. In the present invention, the reagent used for the alcohol washing is preferably absolute ethanol; the number of times of the alcohol washing is preferably three. In the present invention, the drying temperature is preferably 55 to 75 ℃; the drying time is preferably from drying to constant weight.
After the multi-metal MOF@PR nano particles are obtained, the multi-metal MOF@PR nano particles are dispersed in a mixed solvent, and a solvothermal reaction is carried out to obtain the precursor of the concave hollow PR cube/alloy nano particles.
In the present invention, the process of dispersing the multi-metal mof@pr nanoparticles in the mixed solvent is preferably: firstly, crushing and dispersing for 20-80 min, and then, performing ultrasonic dispersion for 15-40 min; more preferably: firstly crushing and dispersing for 30-50 min, and then performing ultrasonic dispersion for 25-35 min.
In the present invention, the mixed solvent is preferably a mixed solution of water and an alcohol reagent; the alcohol reagent preferably comprises ethanol, methanol or isopropanol, more preferably ethanol. The alcohol reagent is used for regulating and controlling the polarity of the solvent.
In the invention, the volume ratio of water to alcohol reagent in the mixed solvent is preferably 1: (0 to 0.2), more preferably 1:0.05. in the present invention, the total volume of the mixed solvent is preferably 80% of the volume capacity of the inner container of the hydrothermal kettle, depending on the capacity of the inner container of the hydrothermal kettle.
In the invention, the dosage ratio of the multi-metal MOF@PR nano particles, water and alcohol reagent is preferably (0.08-0.15) g: (66-80) mL: (0-14) mL, more preferably 0.1g:76mL:4mL.
In the present invention, the temperature of the solvothermal reaction is preferably 170 to 210 ℃, more preferably 180 to 210 ℃. The temperature of the solvothermal reaction influences the efficiency and the specific morphology of PR (PR) layer indent, the depolymerization and fracture of the PR layer can be caused by the too high temperature, the indent degree of the PR layer is uncontrollable, the etching of the internal multi-metal MOF nano particles can not be effectively realized due to the too low temperature, and the indent effect of the PR layer can not be further generated.
In the present invention, the time of the solvothermal reaction is preferably 8 to 18 hours, more preferably 12 to 18 hours. The time of solvothermal reaction influences the actual concave appearance of the PR layer, the etching efficiency of the multi-metal MOF nano particles is low due to the fact that the time is too short, the PR layer cannot achieve sufficient concave in a high-temperature high-pressure environment, and uncontrollable shape change of the PR layer can be induced due to the fact that the time is too long.
After the solvothermal reaction is finished, the product of the solvothermal reaction is preferably washed and dried sequentially. The washing and drying operation is not particularly limited in the present invention, and washing and drying techniques well known to those skilled in the art may be employed. In the present invention, the washing is preferably water washing and alcohol washing. In the present invention, the reagent used for the water washing is preferably deionized water; the number of water washes is preferably three. In the present invention, the reagent used for the alcohol washing is preferably absolute ethanol; the number of times of the alcohol washing is preferably three. In the present invention, the drying temperature is preferably 55 to 75 ℃; the drying time is preferably from drying to constant weight.
After the precursor of the concave hollow PR cube/alloy nano particle is obtained, the precursor of the concave hollow PR cube/alloy nano particle is carbonized to obtain the carbon-based composite wave-absorbing material.
The carbonization operation is not particularly limited, and may be performed by carbonization techniques known to those skilled in the art.
In the present invention, the carbonization temperature is preferably 550 to 900 ℃, more preferably 650 to 850 ℃. The carbonization temperature in the invention affects the sufficiency of carbonization of the phenolic resin layer, namely the graphitization degree of the phenolic derivative carbon, and the too high temperature can cause the graphitization degree to be too high, thereby affecting the overall impedance matching characteristic of the wave-absorbing material, and the too low temperature can generate insignificant graphitization degree and cause the reduction of the electric loss capacity of the wave-absorbing agent.
In the present invention, the carbonization time is preferably 4 to 10 hours, more preferably 4 to 6 hours. The carbonization time in the invention affects the carbonization efficiency and effect, the carbonization is insufficient due to the too short time, the performance advantage of the carbon component can not be exerted, and the high efficiency of the carbonization process can be damaged due to the too long time.
In the present invention, the rate of heating to the carbonization temperature is preferably 5 to 8 ℃/min.
In the present invention, the carbonization is preferably performed in a nitrogen atmosphere; the equipment used for the carbonization is preferably a tube furnace.
The preparation method provided by the invention realizes the construction of the cavity structure by utilizing the solvothermal method, solves the problem that template components and acid and alkali etchants are required to be introduced in the traditional hard template etching method, reduces the generation of synthesis byproducts, and effectively ensures the phase purity of the product; in addition, the generation of alloy particles and the carbonization of phenolic resin are realized in the same process, so that the synthesis efficiency is greatly improved.
The invention also provides application of the carbon-based composite wave-absorbing material prepared by the technical scheme or the preparation method of the technical scheme in electromagnetic radiation protection, electronic communication and radar stealth.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The carbon-based composite wave-absorbing material consists of a concave hollow carbon cube and alloy nano particles growing on the inner side of the concave hollow carbon cube; the alloy nano particles are NiFe nano particles, the edge length of the concave hollow carbon cube is 270nm, the wall thickness is 23nm, and the mass of the alloy nano particles is 15% of the mass of the concave hollow carbon cube.
The preparation process comprises the following steps:
(1) Preparation of NiFePBA cube nanoparticles
Will be 1.32gK 3 [Fe(CN) 6 ]Dissolving in 200mL of deionized water to obtain solution A; will be 0.95g NiCl 2 ·6H 2 O and 2.32g sodium citrate dihydrate were dissolved in 200mL deionized water to give solution B; rapidly adding the solution B into the magnetically stirred solution A, and uniformly stirring for 1min to obtain solution C (Fe in solution C) 3+ 、Ni 2+ And sodium citrate dihydrate in an amount of 0.5:0.5: 1) And then standing and aging the solution C for 24 hours at room temperature, collecting a precipitate at the bottom of a reaction container after the reaction is finished, centrifugally washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and drying the washed precipitate in a drying oven at 65 ℃ to obtain NiFePBA cubic nano particles.
(2) Preparation of NiFePBA@PR nanocubes
Adding 0.03g of NiFePBA cubic nano particles prepared in the step (1) into 20mL of absolute ethyl alcohol, crushing and dispersing for 30min by using a cell crusher, taking out the suspension, transferring into a 250mL single-neck flask, adding 40mL of absolute ethyl alcohol and 30mL of deionized water in a supplementary manner, then placing the single-neck flask and the internal suspension into an ultrasonic cleaner for ultrasonic dispersion for 25min, then taking out the single-neck flask, placing the single-neck flask on a stirring table for uniform magnetic stirring, adding 3mL of ammonia water with the mass percentage concentration of 25%, and continuously stirring for 15min to enable the ammonia water to be fully dispersed;
then adding 0.15g of resorcinol into the system for 30min, then adding 0.21mL of formaldehyde into the system, performing copolycondensation reaction for 7h at room temperature, after the reaction is finished, respectively centrifugally washing the obtained reaction liquid for three times by using deionized water and absolute ethyl alcohol, and placing the washed precipitate into a drying oven at 65 ℃ to dry the solvent, thereby obtaining NiFePBA@PR nano particles.
(3) Preparation of concave hollow PR cube/NiFePBA nanoparticle
Uniformly dispersing 0.10g of NiFe PBA@PR nanocubes in a mixed solvent consisting of 76mL of deionized water and 4mL of absolute ethyl alcohol by using the same crushing dispersion process and ultrasonic dispersion process in the step (2), transferring into a polytetrafluoroethylene inner liner with the capacity of 100mL, further sealing in a stainless steel shell, placing a sealed hydrothermal kettle in an oven, reacting for 10 hours at 180 ℃, after the reaction is finished, centrifugally washing the reaction solution with deionized water and absolute ethyl alcohol for three times respectively, and placing the washed precipitate in an oven at 65 ℃ to dry the solvent, thereby obtaining the concave hollow PR cubes/NiFePBA nanoparticles.
(4) Preparation of concave hollow carbon cubes/NiFe nanoparticles
Placing the concave hollow PR cube/NiFePBA nano particles obtained in the step (3) into a tube furnace, carbonizing at 650 ℃ for 6 hours in a nitrogen atmosphere, and obtaining the final product concave hollow carbon cube/NiFe nano particles, namely C-CNF-1 wave-absorbing material, wherein the temperature rising rate from room temperature to target temperature is 5 ℃/min, and the density of the C-CNF-1 wave-absorbing material is 1.16g/cm by adopting a density tester 3 。
FIG. 1 is a schematic view of the crystal structure of NiFePBA cubic nanoparticles prepared in example 1 of the present invention. As can be seen from fig. 1, ni in NiFePBA is +2 valent, fe is +3 valent, ni and N, fe are bound to C by single bonds, and C and N are bound by triple bonds.
FIG. 2 is an XRD pattern for NiFe nanoparticles prepared in example 1 of the present invention. As can be seen from fig. 2, niFe alloy particles of high crystallinity are produced during high temperature carbonization.
The microscopic morphology and the internally complex cavity structure of the C-CNF-1 absorbing material prepared in example 1 were observed by a high-power transmission electron microscope (TEM, JEM-2100), and the results are shown in FIG. 3. As can be seen from fig. 3, after 10h solvothermal reaction, the six surfaces of the hollow carbon cubes achieved regular indent towards the body-form center of the cubes, but due to the limitation of reaction time, only slight rupture and outflow of NiFePBA could be achieved, resulting in insignificant cavities in the microstructure of the final C-CNF-1 wave-absorbing material.
Example 2
The preparation procedure is essentially the same as in example 1, except that: the solvothermal reaction time is prolonged to 12 hours, and finally the C-CNF-2 wave-absorbing material is prepared, and the density of the C-CNF-2 wave-absorbing material is 1.04g/cm by adopting a density tester 3 。
FIG. 4 is a TEM image of the C-CNF-2 absorbent material prepared in example 2. As can be seen from comparing fig. 3 and fig. 4, the concave of six surfaces of the hollow carbon cubes in the composite wave-absorbing material prepared in example 2 is more obvious, the hollow cavities with the shape similar to the cubes in the hollow carbon cubes are more clear after the hollow carbon cubes are treated at high temperature, and the dimension (namely the edge length) is about 128-135 nm.
Example 3
The preparation procedure is essentially the same as in example 1, except that: the solvothermal reaction time is prolonged to 14 hours, and finally the C-CNF-3 wave-absorbing material is prepared, and the density of the C-CNF-3 wave-absorbing material is tested to be 0.99g/cm by a density tester 3 。
FIG. 5 is a TEM image of the C-CNF-3 absorbent material prepared in example 3. As can be seen from comparing fig. 4 and fig. 5, the composite wave-absorbing material prepared in example 3 has more sufficient concave recesses on six surfaces of the hollow carbon cube, so that the volume of the formed internal cavity is significantly reduced, and the size (i.e., the edge length) is about 77-90 nm.
Example 4
The preparation procedure is essentially the same as in example 1, except that: the solvothermal reaction time is prolonged to 16 hours, and finally the C-CNF-4 wave-absorbing material is prepared, and the density of the C-CNF-4 wave-absorbing material is tested to be 0.93g/cm by a density tester 3 。
FIG. 6 is a TEM image of the C-CNF-4 absorbent material prepared in example 4. As can be seen from comparing fig. 5 and fig. 6, the concave of the six surfaces of the hollow carbon cube in the composite wave-absorbing material prepared in example 4 is more perfect, and the volume of the internal cavity formed by extrusion is continuously reduced, and the size (i.e. the edge length) is about 56-64 nm. In addition, since the morphological change of the hollow cube requires basic conditions of high temperature and high pressure, the more remarkable the surface deformation has occurred, the more severe the subsequent deformation conditions are required. According to the solvothermal conditions in the invention, the surface of the C-CNF-4 wave-absorbing material in the embodiment 4 is concave to a limit state, the reaction time is prolonged, and the microscopic morphology of the wave-absorbing material is not additionally changed.
Performance test:
the carbon-based composite wave absorbing materials prepared in examples 1 to 4 were respectively mixed with molten paraffin according to the following ratio 1:1 (weight ratio of the wave absorber is 50 wt%) and pressing in a metal mould to form a standard coaxial test ring with 3.04mm inner diameter, 7mm outer diameter and 2mm thickness, and using a vector network analyzer (model: agilent PNA-N5244A) to test electromagnetic wave absorption characteristics of the wave absorbing material in the frequency range of 2-18 GHz by using a coaxial method.
The wave-absorbing properties of the C-CNF-1 wave-absorbing material prepared in example 1 are shown in FIG. 7. As can be seen from FIG. 7, when the matching thickness is 3.0mm, the maximum reflection loss RL value of the C-CNF-1 wave-absorbing material in the frequency range of 2-18 GHz is-36.85 dB, and the effective absorption bandwidth is 4.16GHz (6.64 GHz-10.80 GHz).
The wave-absorbing properties of the C-CNF-2 wave-absorbing material prepared in example 2 are shown in FIG. 8. As can be seen from FIG. 8, when the matching thickness is 2.4mm, the maximum reflection loss RL value of the C-CNF-2 wave-absorbing material in the frequency range of 2-18 GHz is-48.27 dB, and the effective absorption bandwidth is 5.76GHz (5.60 GHz-11.36 GHz).
The wave-absorbing properties of the C-CNF-3 wave-absorbing material prepared in example 3 are shown in FIG. 9. As can be seen from FIG. 9, when the matching thickness is 2.8mm, the maximum reflection loss RL value of the C-CNF-3 wave-absorbing material in the frequency range of 2-18 GHz is-41.77 dB, and the effective absorption bandwidth is 4.0GHz (6.16 GHz-10.16 GHz).
The wave-absorbing properties of the C-CNF-4 wave-absorbing material prepared in example 4 are shown in FIG. 10. As can be seen from FIG. 10, when the matching thickness is 3.1mm, the maximum reflection loss RL value of the C-CNF-4 wave-absorbing material in the frequency range of 2-18 GHz is-30.79 dB, and the effective absorption bandwidth is 4.40GHz (6.24 GHz-10.64 GHz).
As can be seen from the above examples, the carbon-based composite wave-absorbing material provided by the invention has excellent impedance matching characteristics and high-efficiency absorption capacity in a test range of 2-18 GHz, and when the fitting thickness is 2.4mm, the reflection loss (ReflectionLoss, RL) value can reach-48.27 dB, and the effective absorption bandwidth of RL < -10dB is up to 5.76GHz (5.60-11.36 GHz).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A carbon-based composite wave-absorbing material comprises a concave hollow carbon cube and alloy nano particles growing on the inner side of the concave hollow carbon cube; the elemental composition of the alloy nanoparticle includes two or more of Fe, co, ni, zn, mn, mo, cu, cr, zr, V and Ti, and contains at least one of Fe, co, and Ni.
2. The carbon-based composite wave absorbing material according to claim 1, wherein the edge length of the concave hollow carbon cube is 50-300 nm, and the wall thickness is 15-30 nm.
3. The carbon-based composite wave absorbing material according to claim 1 or 2, wherein the mass of the alloy nano particles is 8-35% of the mass of the hollow carbon cubes.
4. A method for producing the carbon-based composite wave-absorbing material according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing the multi-metal MOF nano particles with water, ethanol and an alkaline catalyst to obtain a mixed solution containing the multi-metal MOF nano particles;
(2) Mixing the mixed solution containing the multi-metal MOF nano particles obtained in the step (1) with a phenolic compound and an aldehyde compound, and performing copolycondensation reaction to obtain multi-metal MOF@PR nano particles;
(3) Dispersing the multi-metal MOF@PR nano particles obtained in the step (2) in a mixed solvent, and performing solvothermal reaction to obtain a precursor of the concave hollow PR cube/alloy nano particles;
(4) Carbonizing the precursor of the concave hollow PR cube/alloy nano particle obtained in the step (3) to obtain a carbon-based composite wave-absorbing material;
the multi-metal MOF nanoparticles include NiFe PBA nanoparticles.
5. The method according to claim 4, wherein the basic catalyst in the step (1) comprises one or more of ammonia water, sodium hydroxide, barium hydroxide and sodium carbonate.
6. The method according to claim 4, wherein the ratio of the amount of the multi-metal MOF nanoparticles in the step (1), the basic catalyst in the step (1), the phenolic compound in the step (2) and the aldehyde compound in the step (2) is (0.02 to 0.06) g: (1.5-4) mL (0.13-0.17) g: (0.18-0.24) mL.
7. The process according to claim 4, wherein the temperature of the copolycondensation in the step (2) is 10 to 45℃and the time of the copolycondensation is 5 to 10 hours.
8. The method according to claim 4, wherein the solvothermal reaction in the step (3) is carried out at a temperature of 170 to 210℃for a period of 8 to 18 hours.
9. The method according to claim 4, wherein the carbonization temperature in the step (4) is 550 to 900 ℃ and the carbonization time is 4 to 10 hours.
10. Use of the carbon-based composite wave-absorbing material according to any one of claims 1 to 3 or the carbon-based composite wave-absorbing material prepared by the preparation method according to any one of claims 4 to 9 in electromagnetic radiation protection, electronic communication and radar stealth.
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| CN115491177A (en) * | 2022-08-26 | 2022-12-20 | 南京航空航天大学 | MOF-derived carbon-based magnetic nanocomposite electromagnetic wave absorption material and preparation method thereof |
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| CN114975937A (en) * | 2022-06-06 | 2022-08-30 | 浙江理工大学 | Cobalt chloride packaged nitrogen-doped carbon hollow cubic nano box composite material and preparation and application thereof |
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