CN113825380A - Cobalt/manganese oxide/porous graphitized carbon wave-absorbing material and preparation method thereof - Google Patents
Cobalt/manganese oxide/porous graphitized carbon wave-absorbing material and preparation method thereof Download PDFInfo
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- 239000011358 absorbing material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title description 6
- 239000010941 cobalt Substances 0.000 title description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 3
- 229910052799 carbon Inorganic materials 0.000 title description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000013118 MOF-74-type framework Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 23
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 16
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 28
- 239000012265 solid product Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- 240000002853 Nelumbo nucifera Species 0.000 description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 3
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910020632 Co Mn Inorganic materials 0.000 description 1
- 229910020678 Co—Mn Inorganic materials 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 102000017946 PGC-1 Human genes 0.000 description 1
- 108700038399 PGC-1 Proteins 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- 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
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Abstract
The invention relates to a preparation method of a Co/MnO/PGC wave-absorbing material, which comprises the steps of firstly mixing cobalt chloride hexahydrate, manganese chloride tetrahydrate and absolute ethyl alcohol, and stirring until the cobalt chloride hexahydrate and the manganese chloride tetrahydrate are completely dissolved to obtain a solution A; adding 2, 5-dihydroxy terephthalic acid into a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide, and uniformly stirring to obtain a solution B; and dropwise adding the solution A into the solution B, quickly stirring, transferring the mixture to a reaction kettle, placing the mixture in an air-blast drying box, heating for reaction, cooling to room temperature after the reaction is finished, centrifugally separating a reaction product, filtering, alternately washing with absolute ethyl alcohol and N-N dimethylformamide, drying to obtain a Co/Mn-MOF-74 precursor, and calcining the precursor under nitrogen to obtain the catalyst. The method has the advantages of simple preparation process, easy operation and control and low production cost, and the prepared composite material has excellent wave-absorbing performance and good application prospect in the field of electromagnetic wave absorption.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a preparation method of a cobalt/manganese oxide/porous graphitized carbon (Co/MnO/PGC) wave-absorbing material.
Background
With the progress of times, the national economic technology is developed at a high speed, and digitalized and high-frequency electromagnetic equipment is changed day by day, and the equipment can generate a large amount of electromagnetic radiation in the use process, so that serious electromagnetic pollution is brought, and the health of human bodies is influenced. Therefore, the research of the wave-absorbing material with strong absorption capacity and wide wave-absorbing frequency band is of great significance.
The electromagnetic wave absorbing material is a material which can enable electromagnetic waves incident to the surface of the wave absorbing material to enter the material, and can attenuate the incident electromagnetic waves in the material through various loss mechanisms, or interference is caused by optical path difference generated between the incident electromagnetic waves and the reflected electromagnetic waves, so that the incident electromagnetic waves and the reflected electromagnetic waves are mutually cancelled.
With the continuous research of the wave-absorbing material, four requirements of thinness, lightness, width and strength are provided for the wave-absorbing material, and the wave-absorbing material in the prior art has the problems of large density and narrow wave-absorbing frequency band and has poor absorption performance on electromagnetic waves. Compared with other types of wave-absorbing materials, the carbon-based material is concerned by the advantages of large specific surface area, low density, good stability, light weight and the like, and the porous structure is beneficial to the absorption of electromagnetic waves, so the porous carbon-based material is selected as the wave-absorbing material, and the development prospect is wide.
Disclosure of Invention
The invention aims to solve the problems of high density and narrow wave-absorbing frequency band of the wave-absorbing material in the prior art, and provides a preparation method of a Co/MnO/PGC wave-absorbing material, which has the characteristics of simple preparation process, easy control and low production cost, and the prepared Co/MnO/PGC wave-absorbing material has the characteristics of light weight, small density, wide effective absorption bandwidth and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a Co/MnO/PGC wave-absorbing material comprises the following steps:
(1) adding cobalt chloride hexahydrate and manganese chloride tetrahydrate into absolute ethyl alcohol, and stirring until the cobalt chloride hexahydrate and the manganese chloride tetrahydrate are completely dissolved to obtain a solution A;
(2) adding 2, 5-dihydroxyterephthalic acid into a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide, and stirring and dissolving to obtain a solution B;
(3) dropwise adding the solution A into the solution B, quickly stirring, transferring the mixed solution to a reaction kettle after dropwise adding is completed, then placing the reaction kettle in a forced air drying box, heating to react, cooling to room temperature after the reaction is completed, taking out the reaction kettle, centrifugally separating reaction products, filtering, alternately washing with anhydrous ethanol and N-N dimethylformamide to obtain a solid product, and drying to obtain a cobalt/manganese-MOF-74 (Co/Mn-MOF-74) precursor;
(4) and calcining the Co/Mn-MOF-74 precursor in a nitrogen atmosphere, and finally cooling to room temperature to obtain the Co/MnO/PGC wave-absorbing material.
Furthermore, in the step (1), the molar ratio of the cobalt chloride hexahydrate to the manganese chloride tetrahydrate is (1-4): 1.
Further, in the step (2), the molar ratio of the 2, 5-dihydroxyterephthalic acid to the total amount of the cobalt chloride hexahydrate and the manganese chloride tetrahydrate is 1: 4.
Further, in the step (2), in the mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide, the volume ratio of distilled water, absolute ethyl alcohol and N-N dimethylformamide is 1:1: 1.
Further, in the step (3), the rotating speed of the rapid stirring is 400-800 r/min, and the time is 6-12 h.
Further, in the step (3), the heating temperature is 130-160 ℃, the heating rate is 5-8 ℃/min, and the reaction time is 12 h.
Further, in the step (3), the rotation speed of centrifugal separation is 8000-10000 r/min, and the time is 5-10 min.
Further, in the step (3), the drying temperature is 60-80 ℃, and the time is 12-14 h.
Further, in the step (4), the heating rate is 2-3 ℃/min, the calcining temperature is 700-800 ℃, and the calcining time is 3-4 h.
The invention has the beneficial effects that:
according to the invention, cobalt chloride hexahydrate and manganese chloride tetrahydrate are used as raw materials, 2, 5-dihydroxyterephthalic acid is used as an organic ligand, a mixed solution of distilled water, absolute ethyl alcohol and N-N dimethylformamide is used as a solvent, and the prepared Co/Mn-MOF-74 precursor is prepared, and has the advantages of unique appearance, large specific surface area, simple preparation process, low cost and repeatable operation. After the Co/Mn-MOF-74 precursor is carbonized, the Co/MnO/PGC wave-absorbing material is obtained, the Co/Mn-MOF-74 precursor is in a symmetrical lotus shape, the weight is light, the filling amount is low, a void structure can generate a large amount of interface polarization, when the matching thickness is 2mm, the filling amount is 20%, the frequency is 15.36GHz, the maximum reflection loss is-47.5 dB, the effective bandwidth is 5.7GHz (12.3GHz-18 GHz), and the Co/MnO/PGC wave-absorbing material is a high-efficiency light broadband wave-absorbing material.
Drawings
FIG. 1 is an XRD pattern of Co/Mn-MOF-74 precursors prepared in examples 1-4;
FIG. 2 is a FT-IR plot of Co/Mn-MOF-74 precursors prepared in examples 1-4;
FIG. 3 is an XRD pattern of Co/MnO/PGC absorbing materials prepared in examples 1-4;
FIG. 4 is an SEM image of the Co/Mn-MOF-74 precursor and the Co/MnO/PGC wave-absorbing material prepared in example 3;
FIG. 5 is a reflection loss curve of the Co/MnO/PGC wave-absorbing material prepared in example 3 under the condition that the thickness is 1.0 mm-5.5 mm.
Detailed Description
In order to make the objects and advantages of the present invention more apparent, the following detailed description of the embodiments of the present invention is provided with reference to the accompanying drawings. It is to be understood that the following text is merely illustrative of one or more specific embodiments of the invention and does not strictly limit the scope of the invention as specifically claimed.
Example 1
A preparation method of a Co/MnO/PGC wave-absorbing material comprises the following steps:
(1) adding 3mmol of cobalt chloride hexahydrate and 3mmol of manganese chloride tetrahydrate into 10mL of absolute ethyl alcohol, and magnetically stirring for 1h until the cobalt chloride and the manganese chloride are completely dissolved to obtain a solution A;
(2) adding 1.5mmol of 2, 5-dihydroxyterephthalic acid into 60mL of a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide (the volume ratio of the distilled water to the absolute ethyl alcohol to the N-N dimethylformamide is 1:1:1), and magnetically stirring for 1.5h until the solution is uniformly dissolved to obtain a solution B;
(3) dropwise adding the solution A into the solution B, rapidly stirring for 9h (the rotating speed is 500r/min), after dropwise adding is completed, transferring the mixed solution to a 100mL reaction kettle, then placing the reaction kettle in a forced air drying oven, heating to 140 ℃ at the heating rate of 6 ℃/min for reaction for 12h, cooling to room temperature after the reaction is completed, taking out the reaction kettle, centrifugally separating the reaction product, filtering, alternately washing with anhydrous ethanol and N-N dimethylformamide for 3 times respectively to obtain a solid product, and placing the solid product in a vacuum drying oven at 60 ℃ for drying for 24h to obtain a Co/Mn-MOF-74 precursor (MOF-74-Co1Mn 1);
(4) and heating the Co/Mn-MOF-74 precursor to 700 ℃ at the speed of 2 ℃/min under a nitrogen atmosphere, calcining for 3h, and finally cooling to room temperature to obtain the Co/MnO/PGC wave-absorbing material (Co/MnO/PGC-1: 1).
Example 2
A preparation method of a Co/MnO/PGC wave-absorbing material comprises the following steps:
(1) adding 4mmol of cobalt chloride hexahydrate and 2mmol of manganese chloride tetrahydrate into 10mL of absolute ethyl alcohol, and magnetically stirring for 1h until the cobalt chloride and the manganese chloride are completely dissolved to obtain a solution A;
(2) adding 1.5mmol of 2, 5-dihydroxyterephthalic acid into 60mL of a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide (the volume ratio of the distilled water to the absolute ethyl alcohol to the N-N dimethylformamide is 1:1:1), and magnetically stirring for 1.5h until the solution is uniformly dissolved to obtain a solution B;
(3) dropwise adding the solution A into the solution B, rapidly stirring for 9h (the rotating speed is 500r/min), after dropwise adding is completed, transferring the mixed solution to a 100mL reaction kettle, then placing the reaction kettle in a forced air drying oven, heating to 140 ℃ at the speed of 6 ℃/min for reaction for 12h, cooling to room temperature after the reaction is completed, taking out the reaction kettle, centrifugally separating the reaction product, filtering, alternately washing with anhydrous ethanol and N-N dimethylformamide for 3 times respectively to obtain a solid product, and placing the solid product in a vacuum drying oven at the temperature of 60 ℃ for drying for 24h to obtain a Co/Mn-MOF-74 precursor (MOF-74-Co2Mn 1);
(4) and heating the Co/Mn-MOF-74 precursor to 700 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, calcining for 3h, and finally cooling to room temperature to obtain the Co/MnO/PGC wave-absorbing material (Co/MnO/PGC-2: 1).
Example 3
A preparation method of a Co/MnO/PGC wave-absorbing material comprises the following steps:
(1) adding 4.5mmol of cobalt chloride hexahydrate and 1.5mmol of manganese chloride tetrahydrate into 10mL of absolute ethanol, and magnetically stirring for 1h until the cobalt chloride and the manganese chloride are completely dissolved to obtain a solution A;
(2) adding 1.5mmol of 2, 5-dihydroxyterephthalic acid into 60mL of a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide (the volume ratio of the distilled water to the absolute ethyl alcohol to the N-N dimethylformamide is 1:1:1), and magnetically stirring for 1.5h until the solution is uniformly dissolved to obtain a solution B;
(3) dropwise adding the solution A into the solution B, rapidly stirring for 9h (the rotating speed is 500r/min), after dropwise adding is completed, transferring the mixed solution to a 100mL reaction kettle, then placing the reaction kettle in a forced air drying oven, heating to 140 ℃ at the speed of 6 ℃/min, reacting for 12h, cooling to room temperature after reaction is completed, taking out the reaction kettle, centrifugally separating the reaction product, filtering, alternately washing with anhydrous ethanol and N-N dimethylformamide for 3 times respectively to obtain a solid product, and placing the solid product in a vacuum drying oven at the temperature of 60 ℃ for drying for 24h to obtain a Co/Mn-MOF-74 precursor (MOF-74-Co3Mn 1);
(4) and heating the Co/Mn-MOF-74 precursor to 700 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, calcining for 3h, and finally cooling to room temperature to obtain the Co/MnO/PGC wave-absorbing material (Co/MnO/PGC-3: 1).
Example 4
A preparation method of a Co/MnO/PGC wave-absorbing material comprises the following steps:
(1) adding 4.8mmol of cobalt chloride hexahydrate and 1.2mmol of manganese chloride tetrahydrate into 10mL of absolute ethanol, and magnetically stirring for 1h until the cobalt chloride hexahydrate and the manganese chloride tetrahydrate are completely dissolved to obtain a solution A;
(2) adding 1.5mmol of 2, 5-dihydroxyterephthalic acid into 60mL of a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide (the volume ratio of the distilled water to the absolute ethyl alcohol to the N-N dimethylformamide is 1:1:1), and magnetically stirring for 1.5h until the solution is uniformly dissolved to obtain a solution B;
(3) dropwise adding the solution A into the solution B, rapidly stirring for 9h (the rotating speed is 500r/min), after dropwise adding is completed, transferring the mixed solution to a 100mL reaction kettle, then placing the reaction kettle in a forced air drying oven, heating to 140 ℃ at the speed of 6 ℃/min for reaction for 12h, cooling to room temperature after the reaction is completed, taking out the reaction kettle, centrifugally separating the reaction product, filtering, alternately washing with anhydrous ethanol and N-N dimethylformamide for 3 times respectively to obtain a solid product, and placing the solid product in a vacuum drying oven at the temperature of 60 ℃ for drying for 24h to obtain a Co/Mn-MOF-74 precursor (MOF-74-Co4Mn 1);
(4) and heating the Co/Mn-MOF-74 precursor to 700 ℃ at the speed of 2 ℃/min under a nitrogen atmosphere, calcining for 3h, and finally cooling to room temperature to obtain the Co/MnO/PGC wave-absorbing material (Co/MnO/PGC-4: 1).
Carrying out phase structure analysis on the precursor and the wave-absorbing material of the embodiment 1-4 by using an X-ray diffractometer (XRD) and a Fourier transform infrared spectrometer (FT-IR); the microstructures of the precursors and the composite materials of examples 1 to 4 were analyzed by a Scanning Electron Microscope (SEM), and the electromagnetic parameters of the samples were analyzed by a Vector Network Analyzer (VNA), and the wave-absorbing properties thereof were calculated. The test results are shown in FIGS. 1-5.
Fig. 1 is an XRD chart of the Co/Mn-MOF-74 precursors prepared in examples 1 to 4, and it can be seen that the Co/Mn-MOF-74 precursors prepared in examples 1 to 4 of the present invention have no impurity phase, sharp peak shape and good crystallinity, and have a diffraction peak at 2 θ ═ 6.7 ° and 11.7 °, respectively, and the two diffraction peaks correspond to crystal planes (110) and (300), respectively, and the results are consistent with the standard cards of Co/Mn related metal-organic frameworks.
FIG. 2 is a FT-IR plot of Co/Mn-MOF-74 precursors prepared in examples 1-4, from which it can be seen that Co/MnO/PGC prepared at different ratios are all at 3430cm-1A significant O-H bond formed by residual water molecules; at 2917cm-1The weak peak at (A) corresponds to the stretching of the C-H bond; 1629cm-1The peak appeared in (A) is attributed to CA ═ C double bond; 1078cm-1The peak is the bending vibration peak of the C-H bond; 572cm-1The characteristic absorption peak is the vibration peak of Mn-O bond. The results are consistent with the XRD results, and prove that the Co/MnO/PGC composite material is successfully synthesized.
FIG. 3 is an XRD pattern of the Co/MnO/PGC absorbing materials prepared in examples 1-4, from which it can be seen that Co/MnO/PGC prepared under different Co-Mn ratios all have the same diffraction peak, and that there is a diffraction peak at 2 θ 44.2 °, 51.5 ° and 75.9 °, corresponding to the (111), (200) and (220) crystal planes of Co (JCPDS NO.15-0806), respectively, indicating that Co is2+Is reduced to metallic Co during the calcination process; the diffraction peaks at 2 θ of 34.91 °, 40.5 °, 58.7 °, 70.2 ° and 73.8 ° respectively correspond to the (111), (200), (220), (311) and (222) crystal planes of MnO (JCPDS No.07-0203), and other peaks are not included. As the Co content increases, the diffraction peak of MnO becomes gradually weaker.
FIG. 4 is an SEM image of Co/Mn-MOF-74 precursor and Co/MnO/PGC absorbing material prepared in example 3, wherein FIG. 3(a) and FIG. 3(b) correspond to an SEM image of the Co/Mn-MOF-74 precursor, and FIG. 3(c) and FIG. 3(d) correspond to an SEM image of Co/MnO/PGC. As can be seen from the figure, the Co/Mn-MOF-74 precursors prepared by adopting 2, 5-dihydroxyterephthalic acid as an organic ligand have similar shapes, are all in symmetrical lotus shapes, and have smooth surfaces and relatively uniform distribution. The Co/MnO/PGC composite material obtained by carbonization still keeps the symmetrical lotus shape of the precursor, but the size is slightly shrunk, and the surface is slightly collapsed.
FIG. 5 is a reflection loss curve of the Co/MnO/PGC wave-absorbing material prepared in example 3 under the condition of thickness of 1.0 mm-5.5 mm, and it can be seen from the graph that when the matching thickness is 2mm, the filling amount is 20%, the frequency is 15.36GHz, the maximum reflection loss is-47.5 dB, the effective bandwidth is 5.7GHz (12.3GHz-18 GHz), and the Co/MnO/PGC wave-absorbing material has excellent electromagnetic wave absorption performance and meets the requirements of the wave-absorbing material on thinness, lightness, width and strength.
The present invention is not limited to the above embodiments, and those skilled in the art can make various equivalent changes and substitutions without departing from the principle of the present invention after learning the content of the present invention, and these equivalent changes and substitutions should be considered as belonging to the protection scope of the present invention.
Claims (9)
1. A preparation method of a Co/MnO/PGC wave-absorbing material is characterized by comprising the following steps:
(1) adding cobalt chloride hexahydrate and manganese chloride tetrahydrate into absolute ethyl alcohol, and stirring until the cobalt chloride hexahydrate and the manganese chloride tetrahydrate are completely dissolved to obtain a solution A;
(2) adding 2, 5-dihydroxyterephthalic acid into a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide, and stirring and dissolving to obtain a solution B;
(3) dropwise adding the solution A into the solution B, quickly stirring, transferring the mixed solution to a reaction kettle after dropwise adding is completed, then placing the reaction kettle in a forced air drying box, heating to 130-160 ℃, cooling to room temperature after reaction is completed, centrifugally separating reaction products, filtering, alternately washing with anhydrous ethanol and N-N dimethylformamide to obtain a solid product, and drying to obtain a Co/Mn-MOF-74 precursor;
(4) and calcining the Co/Mn-MOF-74 precursor in a nitrogen atmosphere to obtain the Co/MnO/PGC wave-absorbing material.
2. The preparation method of the Co/MnO/PGC wave-absorbing material as claimed in claim 1, wherein in the step (1), the molar ratio of cobalt chloride hexahydrate to manganese chloride tetrahydrate is (1-4): 1.
3. The preparation method of Co/MnO/PGC wave-absorbing material according to claim 1, wherein in the step (2), the molar ratio of the 2, 5-dihydroxyterephthalic acid to the total amount of cobalt chloride hexahydrate and manganese chloride tetrahydrate is 1: 4.
4. The preparation method of Co/MnO/PGC wave-absorbing material according to claim 1, wherein in the step (2), the volume ratio of distilled water, absolute ethyl alcohol and N-N dimethylformamide in the mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide is 1:1: 1.
5. The preparation method of the Co/MnO/PGC wave-absorbing material as claimed in claim 1, wherein in the step (3), the rotation speed of the rapid stirring is 400-800 r/min, and the time is 6-12 h.
6. The preparation method of the Co/MnO/PGC wave-absorbing material as claimed in claim 1, wherein in the step (3), the temperature rise rate is 5-8 ℃/min, and the reaction time is 12 h.
7. The preparation method of the Co/MnO/PGC wave-absorbing material as claimed in claim 1, wherein in the step (3), the rotational speed of centrifugal separation is 8000-10000 r/min, and the time is 5-10 min.
8. The preparation method of the Co/MnO/PGC wave-absorbing material according to claim 1, wherein in the step (3), the drying temperature is 60-80 ℃ and the drying time is 12-14 h.
9. The preparation method of Co/MnO/PGC wave-absorbing material according to any one of claims 1 to 8, wherein in the step (4), the temperature rise rate is 2-3 ℃/min, the calcination temperature is 700-800 ℃, and the calcination time is 3-4 h.
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Cited By (5)
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