CN116004184B - Nano metal oxide/carbon composite wave-absorbing material and preparation method thereof - Google Patents
Nano metal oxide/carbon composite wave-absorbing material and preparation method thereof Download PDFInfo
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- 239000011358 absorbing material Substances 0.000 title claims abstract description 77
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- FAARLWTXUUQFSN-UHFFFAOYSA-N methylellagic acid Natural products O1C(=O)C2=CC(O)=C(O)C3=C2C2=C1C(OC)=C(O)C=C2C(=O)O3 FAARLWTXUUQFSN-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 14
- 239000011148 porous material Substances 0.000 description 13
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
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Abstract
The invention discloses a nano metal oxide/carbon composite wave-absorbing material, which consists of carbon and metal oxide; wherein the mass percentage of carbon is 65-90%, and the mass percentage of metal oxide is 10-35%; the metal oxide is ZnO or CuO. The wave-absorbing material is hollow particles composed of nanospheres. The preparation method of the wave-absorbing material comprises the following steps: firstly, preparing a metal-biomass polyphenol network skeleton; and then heating and carbonizing the metal-biomass polyphenol network skeleton in inert gas, keeping the carbonizing temperature at 600-850 ℃, preserving the heat for 1-3 hours, and then cooling to obtain the nano metal oxide/carbon composite wave-absorbing material. The biomass polyphenol is one or a combination of more of tannic acid, gallic acid and ellagic acid. The metal oxide generated by carbonization and thermal cracking of the metal-polyphenol network can be uniformly distributed in the mesoporous carbon network skeleton and used as a dielectric loss component to regulate and control the impedance matching characteristic of the porous carbon, so that the wave absorbing performance is improved, and the obtained wave absorbing material has good application prospect in the field of electromagnetic stealth.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a nano metal oxide/carbon composite wave-absorbing material and a preparation method thereof.
Background
With the development of advanced radar detection technology, higher and higher requirements are put forward on the stealth capability of military equipment such as armored combat vehicles, ships, airplanes, missiles and the like. The electromagnetic wave absorbing material can effectively reduce the radar reflection section of weapon equipment on the premise of not changing the engine structure position of the weapon, thereby effectively improving the defending capability and the viability of the weapon equipment and becoming a hotspot for military research of various countries. Besides the military stealth field, the electromagnetic wave absorbing material can also reduce electromagnetic signal interference to maintain the normal operation of electronic equipment such as precise instruments and meters, and avoid the problems of instrument test error, signal leakage and the like; the electromagnetic protective clothing and the like can also reduce the harm of electromagnetic radiation energy to human immunity, reproduction, nervous system and the like, and protect the safety of staff. At present, the development of a wave-absorbing material with excellent comprehensive performances such as thin thickness, light weight, wide absorption frequency band, strong reflection loss and the like is a great research direction in the wave-absorbing stealth field. Research shows that the carbon material modified by the magnetic nano particles or the dielectric loss material has better impedance matching characteristic because of absorbing waves through resistance loss and magnetic loss/dielectric loss, can meet the requirement of electromagnetic absorption on wide and strong, can effectively improve the requirement of thin thickness and low density on thin and light, and is expected to replace the traditional stealth materials (carbonyl iron powder, ferrite, barium titanium ore and the like). However, the preparation process of carbon materials such as carbon nanotubes, graphene and carbon fibers is complex, toxic solvents are required to be used, the cost is high, and the preparation method is not beneficial to industrial application when the carbon materials are coated on the surface of a substrate in a large scale.
The biomass is low in price, rich in source and environment-friendly, and the carbon material obtained by carbonizing the biomass serving as a precursor can inherit various pore structures of the biomass material, so that the multiple reflection of incident electromagnetic waves and the loss of interface polarization are increased, the electromagnetic waves are absorbed, and the wave absorbing performance is enhanced. Zhao and the like take shaddock peel as a base material, and convert the shaddock peel into porous carbon nano sheets with a graphite-like lamellar structure through hydrothermal and carbonization processes, so that efficient wave absorption (carbon, 173,2021,501-511) is realized. However, biomass has large individual difference and uneven structure, and poor structural stability after modification and carbonization, and part of the positions can be free from the required wave absorbing effect due to uneven structure when the biomass is coated on a base material for use. Therefore, the technical problems to be solved at present are: the carbon material modified by the magnetic loss/dielectric loss material with uniform and controllable structure and appearance is developed by using a low-cost and green environment-friendly process means, so that the carbon material can realize the broadband strong absorption of incident electromagnetic waves under the condition of low addition quantity.
Disclosure of Invention
Aiming at the technical problem of how to develop the magnetic loss/dielectric loss material modified carbon material with uniform and controllable structure morphology by using low-cost and green environment-friendly process means, the invention provides a nano metal oxide/carbon composite wave-absorbing material and a preparation method thereof.
The nano metal oxide/carbon composite wave-absorbing material provided by the invention consists of carbon and metal oxide. Wherein the mass percentage of carbon is 65-90%, and the mass percentage of metal oxide is 10-35%. The metal oxide is ZnO or CuO.
The nano metal oxide/carbon composite wave-absorbing material is of a hollow nano rod structure.
The specific surface area of the nano metal oxide/carbon composite wave-absorbing material is 300-600 g/cm 3, the minimum reflection loss is-20 to-60 dB when the nano metal oxide/carbon composite wave-absorbing material is used, and the effective wave-absorbing bandwidth is 3-7GHz.
The preparation method of the nano metal oxide/carbon composite wave-absorbing material comprises the following two steps:
step 1, preparing a metal-biomass polyphenol network skeleton precursor, wherein the preparation method comprises the following two steps:
dispersing a surfactant in a mixed solution of water and ethanol, wherein the concentration of the surfactant is 0.5-2%, adding ammonia water to adjust the pH value to 9, adding biomass polyphenol for reaction for 24 hours, adding metal salt for reaction for 12 hours, and centrifuging, washing and drying to obtain the metal-biomass polyphenol network skeleton precursor.
Preferably, the volume ratio of water to ethanol is 4:1 to 8:1, a step of; the mass ratio of biomass polyphenol to the surfactant is 1:2 to 4:1, a step of; the mass of the metal salt and the surfactant is 1: 4-2: 1.
Preferably, the centrifugation speed is 5000-8000 r/min, and the centrifugation time is 3-5 times for 5 minutes each time.
Placing the surfactant, biomass polyphenol and metal salt on a ball mill, ball-milling for 0.5 hour at a high frequency of 20Hz, washing with water and ethanol for three times, and drying to obtain the metal-biomass polyphenol network skeleton precursor.
The raw materials such as the surfactant, biomass polyphenol, metal salt and the like used in the two methods are the same. Wherein the surfactant is one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123, F127 and polyvinylpyrrolidone.
The biomass polyphenol is one or a combination of more of tannic acid, gallic acid and ellagic acid.
The metal salt is zinc salt or copper salt. The zinc salt is preferably one of zinc nitrate, zinc chloride, zinc sulfate and zinc acetate. The copper salt is preferably one of copper nitrate, copper chloride, copper sulfate and copper acetate.
And 2, heating and carbonizing the metal-biomass polyphenol network skeleton precursor in inert gas, preserving heat for 1-3 hours at the carbonization temperature of 600-850 ℃, and then cooling to obtain the nano metal oxide/carbon composite wave-absorbing material.
The inert gas is high-purity nitrogen or high-purity argon, and the heating temperature rising speed is 3-10 ℃/min.
Compared with the prior art, the invention has the following advantages:
(1) The invention prepares a metal-biomass polyphenol network skeleton-based metal oxide/carbon composite material. The metal-biomass polyphenol network is promoted to grow into a uniform nano needle structure through the soft template function of the surfactant. The metal-biomass polyphenol network has rich morphology, regular structure, high specific surface area and rich mesoporous structure. Through pyrolysis carbonization, the metal-biomass polyphenol network is dehydrated and carbonized, and a metal oxide and carbon composite material with rich mesoporous structure is formed. The metal oxide is uniformly distributed in the network skeleton of the porous carbon, so that the interface dipole polarization is effectively increased, the impedance matching characteristic of the porous carbon can be effectively improved by the metal oxide, and the efficient wave absorption is realized.
(2) The metal oxide/carbon composite wave-absorbing material provided by the invention is composed of a carbon skeleton and a metal oxide, and has the characteristics of light weight, high surface area, excellent thermal oxygen stability, abundant porous structures and the like, and the composite material can realize broadband strong absorption of incident electromagnetic waves at a lower addition amount. The broadband strong absorption of the incident electromagnetic wave (the minimum reflection loss is between-20 and-60 dB and the effective bandwidth of wave absorption is between 3 and 7 GHz) can be realized under the condition of lower addition (15 to 30 weight percent).
(3) The metal oxide/carbon composite material provided by the invention has dielectric loss, resistance loss, interface polarization loss and multi-step reflection loss wave absorption characteristics, has moderate resistivity, porosity and impedance matching characteristics, and has a better application prospect in the field of microwave absorption.
(4) The invention can regulate and control the microscopic morphology and size of the metal oxide/carbon composite wave-absorbing material by regulating the conditions of the mixture ratio of the surfactant, the biomass polyphenol, the metal salt, the carbonization temperature, the reaction time and the like. The used reagents such as polyphenol, surfactant, metal salt and the like are low in price, and the used equipment is simple, easy to operate and environment-friendly.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is an XRD spectrum of a ZnO/C composite wave-absorbing material prepared in example 1 of the present invention.
FIG. 2 is an SEM image of a ZnO/C composite wave-absorbing material prepared in example 1 of the present invention.
FIG. 3 is a thermal weight graph of the ZnO/C composite wave-absorbing material prepared in example 1 of the present invention under an air atmosphere.
FIG. 4 is a graph showing the adsorption-desorption of nitrogen by the ZnO/C composite wave-absorbing material prepared in example 1 of the present invention.
FIG. 5 is a schematic wave-absorbing diagram of the ZnO/C composite wave-absorbing material prepared in example 1 of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
Example 1
A preparation method of ZnO/C composite wave-absorbing material comprises the following steps:
Dissolving 0.2g of F127 in a mixed solution of 37mL of deionized water and 8mL of ethanol, dropwise adding ammonia water to adjust the pH value to 9, adding 0.2g of Tannic Acid (TA), stirring for 24 hours at normal temperature to fully polymerize the tannic acid, adding 0.1g of zinc nitrate, stirring for 12 hours again to fully coordinate the tannic acid, washing with water and ethanol in sequence, centrifuging for 3 times in a 6000r/min centrifuge, and drying the centrifuged lower solid product in a vacuum oven at 80 ℃ for 12 hours to obtain the Zn-TA network skeleton precursor.
And secondly, placing the Zn-TA network skeleton precursor in a tube furnace, introducing inert gas high-purity nitrogen, heating the tube furnace to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat at 700 ℃ for 2 hours to obtain the ZnO/C composite wave-absorbing material with the hollow nanorod structure.
The following performance tests were performed on the ZnO/C composite wave-absorbing material prepared in example 1:
(1) The phase of the prepared metal oxide/carbon composite wave-absorbing material is analyzed by using an Shimadzu XRD-6100 type X-ray diffractometer, and the result is shown in figure 1. As can be seen from FIG. 1, the XRD diffraction peak of the ZnO/C composite wave-absorbing material has obvious ZnO (PDF#36-1451) characteristic peak, basically accords with a standard card, has a long and wide peak at 23.6 degrees and corresponds to the peak of the porous C.
(2) Microscopic morphology observation is carried out on the ZnO/C composite wave-absorbing material by adopting an SU-3500 type scanning electron microscope, and the result is shown in figure 2. As can be seen from fig. 2, the composite material has a hollow nanorod structure, and the nanosphere particles form the skeleton of the hollow nanorod.
(3) FIG. 3 is a graph showing the thermal weight loss of the ZnO/C composite wave-absorbing material in an air atmosphere. As can be seen from FIG. 3, the initial decomposition temperature of the ZnO/C composite wave-absorbing material is 400 ℃, and the residual mass is 24wt%. Since C reacts with O 2 in the air and ZnO does not lose weight, the ZnO content in the ZnO/C composite material is 24 weight percent and the C content is 76 weight percent.
(4) The specific surface area was measured by a BrukerAdvance model 400 specific surface analyzer, and the result is shown in fig. 4. As is clear from FIG. 4, the specific surface area of the ZnO/C composite wave-absorbing material was 367m 2/g, and the pore volume was 0.53cm 3/g.
(5) And an N5230A type vector network analyzer is adopted to test electromagnetic parameters of the sample, and the testing method is a coaxial method. Uniformly mixing particles to be tested with paraffin according to a certain proportion, and pressing into a circular ring with the inner diameter of 3mm, the outer diameter of 7mm and the thickness of 2mm. Its electromagnetic parameters were tested in the 2-18GHz range and analyzed by Matlab fitting, etc. The test results are shown in FIG. 5. As can be seen from FIG. 5, the ZnO/C composite wave-absorbing material exhibits excellent wave-absorbing performance, and at an addition of 30wt%, the minimum reflection loss of the wave-absorbing material at a thickness of 3.5mm is-57.8 dB, the effective wave-absorbing bandwidth at a thickness of 3mm is 5.5GHz, the minimum reflection loss at a thickness of 2mm is-55.6 dB, and the effective wave-absorbing bandwidth is 4.4GHz.
Example 2
A preparation method of ZnO/C composite wave-absorbing material comprises the following steps:
Step one, adding 0.2g F127, 0.2g Tannic Acid (TA) and 0.1g zinc nitrate into a ball mill, ball milling for 0.5 hour at the frequency of 20Hz, washing with water for 2 times after ball milling, washing with ethanol for 1 time, and drying for 12 hours in a vacuum oven at 80 ℃ to obtain the Zn-TA network skeleton precursor.
And secondly, placing the Zn-TA network skeleton precursor in a tube furnace, introducing inert gas high-purity nitrogen, heating the tube furnace to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat at 800 ℃ for 2 hours to obtain the ZnO/C composite material with the hollow nanorod structure.
The ZnO content in the ZnO/C composite wave-absorbing material is 15wt% and the C content is 85wt%; the specific surface area is 570m 2/g, and the pore volume is 1.05cm 3/g; the initial decomposition temperature is 380 ℃; at an addition amount of 20wt%, the lowest reflection loss of the composite wave-absorbing material at a thickness of 2mm is-33.0 dB, and the effective wave-absorbing bandwidth is 3.2GHz.
Example 3
A preparation method of ZnO/C composite wave-absorbing material comprises the following steps:
Dissolving 0.2g F127 in a mixed solution of 37mL deionized water and 8mL ethanol, dropwise adding ammonia water to adjust the pH to 9, adding 0.2g Tannic Acid (TA), stirring for 24 hours at normal temperature to fully polymerize the tannic acid, adding 0.1g zinc nitrate, stirring for 12 hours again to fully coordinate the tannic acid, washing with water and ethanol in sequence, centrifuging for 3 times in a 6000r/min centrifuge, and drying the centrifuged lower solid product in a vacuum oven at 80 ℃ for 12 hours to obtain the Zn-TA network skeleton precursor.
And secondly, placing the Zn-TA network skeleton precursor in a tube furnace, introducing inert gas, heating the tube furnace to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat at 800 ℃ for 2 hours to obtain the ZnO/C composite wave-absorbing material with the hollow nano rod structure.
The ZnO content in the ZnO/C composite wave-absorbing material is 22wt% and the C content is 78wt%; the specific surface area is 495m 2/g, and the pore volume is 0.62cm 3/g; the initial decomposition temperature is 405 ℃; when the addition amount is 20wt%, the lowest reflection loss of the composite wave absorbing material is-45.0 dB when the thickness is 1.72mm, and the effective wave absorbing bandwidth is 3.0GHz.
Example 4
A preparation method of ZnO/C composite wave-absorbing material comprises the following steps:
Dissolving 0.2g F127 in a mixed solution of 37mL deionized water and 8mL ethanol, dropwise adding ammonia water to adjust the pH to 9, adding 0.2g Tannic Acid (TA), stirring for 24 hours at normal temperature to fully polymerize the tannic acid, adding 0.2g zinc nitrate, stirring for 12 hours again to fully coordinate the tannic acid, washing with water and ethanol in sequence, centrifuging for 3 times in a 6000r/min centrifuge, and drying the centrifuged lower solid product in a vacuum oven at 80 ℃ for 12 hours to obtain the Zn-TA network skeleton precursor.
And step two, putting the Zn-TA network skeleton precursor into a tube furnace, introducing inert gas, heating the tube furnace to 600 ℃ at a heating rate of 5 ℃/min, and preserving heat at 600 ℃ for 2 hours to obtain the ZnO/C composite material with the hollow nanorod structure.
The ZnO content in the ZnO/C composite wave-absorbing material is 18wt% and the C content is 82wt%; the specific surface area is 356m 2/g, and the pore volume is 0.52cm 3/g; the initial decomposition temperature is 340 ℃; at an addition amount of 30wt%, the lowest reflection loss of the composite wave-absorbing material at a thickness of 2mm is-37.0 dB, and the effective wave-absorbing bandwidth is 3.5GHz.
Example 5
Preparation of ZnO/C composite wave-absorbing material:
Dissolving 0.1g F127 in a mixed solution of 37mL deionized water and 8mL ethanol, dropwise adding ammonia water to adjust the pH to 9, adding 0.2g Ellagic Acid (EA), stirring for 24 hours at normal temperature to fully react the ellagic acid, adding 0.1g zinc nitrate, stirring for 12 hours again to fully coordinate the ellagic acid, washing with water and ethanol in sequence, centrifuging for 3 times in a 6000r/min centrifuge, and drying the centrifuged lower solid product in a vacuum oven at 80 ℃ for 12 hours to obtain the Zn-EA network skeleton precursor.
And secondly, placing the Zn-EA network skeleton precursor in a tube furnace, introducing inert gas high-purity argon, heating the tube furnace to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat at 800 ℃ for 2 hours to obtain the ZnO/C composite wave-absorbing material.
The ZnO content in the ZnO/C composite wave-absorbing material is 24wt% and the C content is 76wt%; the specific surface area is 503m 2/g, and the pore volume is 0.75cm 3/g; the initial decomposition temperature is 368 ℃; at an addition amount of 20wt%, the lowest reflection loss of the composite wave-absorbing material at a thickness of 2mm is-43.6 dB, and the effective wave-absorbing bandwidth is 3.5GHz.
Example 6
Preparation of CuO/C composite wave-absorbing material:
Dissolving 0.2g F127 in a mixed solution of 35mL deionized water and 5mL ethanol, dropwise adding ammonia water to adjust the pH to 9, adding 0.2g Tannic Acid (TA), stirring for 24 hours at normal temperature to fully polymerize the tannic acid, adding 0.2g copper nitrate, stirring for 12 hours again to fully coordinate the tannic acid, washing with water and ethanol in sequence, centrifuging for 3 times in a 8000r/min centrifuge, and drying the centrifuged lower solid product in a vacuum oven at 80 ℃ for 12 hours to obtain the Cu-TA network skeleton precursor.
Step two, placing the Cu-TA network skeleton precursor in a tube furnace, introducing inert gas high-purity argon, heating the tube furnace to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat at 800 ℃ for 2 hours to obtain the CuO/C composite material with the hollow nanorod structure.
The CuO content in the CuO/C composite wave-absorbing material is 35wt% and the C content is 65wt%; the specific surface area is 402m 2/g, and the pore volume is 0.68cm 3/g; the initial decomposition temperature is 385 ℃; at an addition amount of 30wt%, the lowest reflection loss of the composite wave-absorbing material at a thickness of 2mm is-48.2 dB, and the effective wave-absorbing bandwidth is 4.3GHz.
Example 7
Preparation of CuO/C composite wave-absorbing material:
Dissolving 0.2g F127 in a mixed solution of 35mL deionized water and 5mL ethanol, dropwise adding ammonia water to adjust the pH to 9, adding 0.2g Tannic Acid (TA), stirring for 24 hours at normal temperature to fully polymerize the tannic acid, adding 0.1g copper nitrate, stirring for 12 hours again to fully coordinate the tannic acid, washing with water and ethanol in sequence, centrifuging for 3 times in a 8000r/min centrifuge, and drying the centrifuged lower solid product in a vacuum oven at 80 ℃ for 12 hours to obtain the Cu-TA network skeleton precursor.
Step two, placing the Cu-TA network skeleton precursor in a tube furnace, introducing inert gas high-purity argon, heating the tube furnace to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat at 800 ℃ for 2 hours to obtain the CuO/C composite material with the hollow nanorod structure.
The CuO content in the CuO/C composite wave-absorbing material is 16wt% and the C content is 84wt%; the specific surface area is 520m 2/g, and the pore volume is 0.95cm 3/g; the initial decomposition temperature is 397 ℃; when the addition amount is 20wt%, the lowest reflection loss of the composite wave-absorbing material is-35.7 dB when the thickness is 2mm, and the effective wave-absorbing bandwidth is 3.4GHz.
Example 8
Preparation of CuO/C composite wave-absorbing material:
Dissolving 0.2g F127 in a mixed solution of 35mL deionized water and 5mL ethanol, dropwise adding ammonia water to adjust the pH to 9, adding 0.2g Tannic Acid (TA), stirring for 24 hours at normal temperature to fully polymerize the tannic acid, adding 0.05g copper nitrate, stirring for 12 hours again to fully coordinate the tannic acid, washing with water and ethanol in sequence, centrifuging for 3 times in a 8000r/min centrifuge, and drying the centrifuged lower solid product in a vacuum oven at 80 ℃ for 12 hours to obtain the Cu-TA network skeleton precursor.
Step two, placing the Cu-TA network skeleton precursor in a tube furnace, introducing inert gas high-purity argon, heating the tube furnace to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat at 800 ℃ for 2 hours to obtain the CuO/C composite material with the hollow nanorod structure.
The CuO content in the CuO/C composite wave-absorbing material is 10wt% and the C content is 90wt%; the specific surface area is 509m 2/g, and the pore volume is 0.84cm 3/g; the initial decomposition temperature is 403 ℃; when the addition amount is 15wt%, the lowest reflection loss of the composite wave-absorbing material is-28.6 dB when the thickness is 2mm, and the effective wave-absorbing bandwidth is 4.6GHz.
Example 9
Preparation of CuO/C composite wave-absorbing material:
Step one, adding 0.2g F127, 0.2g Tannic Acid (TA) and 0.1g copper nitrate into a ball mill, ball milling for 0.5 hour at the frequency of 20Hz, washing with water for 2 times after ball milling, washing with ethanol for 1 time, and drying for 12 hours in a vacuum oven at 80 ℃ to obtain the Cu-TA network skeleton precursor.
Step two, placing the Cu-TA network skeleton precursor in a tube furnace, introducing inert gas high-purity argon, heating the tube furnace to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat at 800 ℃ for 2 hours to obtain the CuO/C composite material with the hollow nanorod structure.
The CuO content in the CuO/C composite wave-absorbing material is 10wt% and the C content is 90wt%; the specific surface area is 534m 2/g, and the pore volume is 0.95cm 3/g; the initial decomposition temperature is 379 ℃; at an addition amount of 20wt%, the lowest reflection loss of the composite wave-absorbing material at a thickness of 2mm is-47.6 dB, and the effective wave-absorbing bandwidth is 3.9GHz.
Example 10
Preparation of CuO/C composite wave-absorbing material:
Dissolving 0.1g F127 in a mixed solution of 35mL deionized water and 5mL ethanol, dropwise adding ammonia water to adjust the pH value to 9, adding 0.2g Gallic Acid (GA), stirring for 24 hours at normal temperature to fully polymerize the gallic acid, adding 0.1g copper nitrate, stirring for 12 hours again to fully coordinate, washing with water and ethanol in sequence, centrifuging for 3 times in a 8000r/min centrifuge, and drying the centrifuged lower solid product in a vacuum oven at 80 ℃ for 12 hours to obtain the Cu-GA network skeleton precursor.
Step two, placing the Cu-GA network skeleton precursor in a tube furnace, introducing inert GAs high-purity argon, heating the tube furnace to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat at 800 ℃ for 2 hours to obtain the CuO/C composite wave-absorbing material.
The CuO content in the CuO/C composite wave-absorbing material is 19wt% and the C content is 81wt%; the specific surface area is 479m 2/g, and the pore volume is 0.65cm 3/g; the initial decomposition temperature is 375 ℃; at an addition amount of 20wt%, the lowest reflection loss of the composite wave-absorbing material at a thickness of 2mm is-29.4 dB, and the effective wave-absorbing bandwidth is 5.6GHz.
Example 11
Preparation of CuO/C composite wave-absorbing material:
Dissolving 0.1g F127 in a mixed solution of 37mL deionized water and 8mL ethanol, dropwise adding ammonia water to adjust the pH to 9, adding 0.2g Ellagic Acid (EA), stirring for 24 hours at normal temperature to fully react the ellagic acid, adding 0.1g copper nitrate, stirring for 12 hours again to fully coordinate the ellagic acid, washing with water and ethanol in sequence, centrifuging for 3 times in a 8000r/min centrifuge, and drying the centrifuged lower solid product in a vacuum oven at 80 ℃ for 12 hours to obtain the Cu-EA network skeleton precursor.
And secondly, placing the precursor of the Cu-EA network framework in a tube furnace, introducing inert gas high-purity argon, heating the tube furnace to 850 ℃ at a heating rate of 5 ℃/min, and preserving heat at 850 ℃ for 2 hours to obtain the CuO/C composite wave-absorbing material.
The CuO content in the CuO/C composite wave-absorbing material is 32wt% and the C content is 68wt%; the specific surface area is 554m 2/g, and the pore volume is 0.97cm 3/g; the initial decomposition temperature is 375 ℃; when the addition amount is 15wt%, the lowest reflection loss of the composite wave-absorbing material is-37.3 dB when the thickness is 2mm, and the effective wave-absorbing bandwidth is 4.3GHz.
Example 12
A preparation method of ZnO/C composite wave-absorbing material comprises the following steps:
step one, adding 0.2g F127, 0.2g tannic acid, 0.2g ellagic acid and 0.2g zinc nitrate into a ball mill, ball milling for 0.5 hour at 20Hz frequency, washing with water for 2 times after ball milling, washing with ethanol for 1 time, and drying for 12 hours in a vacuum oven at 80 ℃ to obtain the metal Zn-polyphenol composite network skeleton precursor.
And step two, placing a metal Zn-polyphenol composite network skeleton precursor in a tube furnace, introducing inert gas high-purity nitrogen, heating the tube furnace to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat at 800 ℃ for 2 hours to obtain the ZnO/C composite material with the hollow nanorod structure.
The ZnO content in the ZnO/C composite wave-absorbing material is 16wt percent, and the C content is 84wt percent; the specific surface area is 506m 2/g, and the pore volume is 0.89cm 3/g; the initial decomposition temperature is 375 ℃; when the addition amount is 15wt%, the lowest reflection loss of the composite wave-absorbing material is-25.7 dB when the thickness is 2mm, and the effective wave-absorbing bandwidth is 5.8GHz.
In summary, the metal-biomass polyphenol network skeleton is adopted as a precursor, the metal-polyphenol network preparation method is simple and environment-friendly, the morphology is rich, the structure is regular, the porous structure with high specific surface area and rich mesoporous structure is provided, the porous structure reserved after carbonization can increase the electromagnetic wave transmission path and provide active sites for energy dissipation, the interface polarization loss can be increased, and the density and the coating thickness of the wave absorber can be reduced; the metal oxide generated by carbonization and thermal cracking of the metal-polyphenol network can be uniformly distributed in the mesoporous carbon network skeleton and used as a dielectric loss component to regulate and control the impedance matching characteristic of the porous carbon, so that the wave absorbing performance is improved. The wave absorber obtained by the invention has good application prospect in the field of electromagnetic stealth.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalents and modifications can be made to the above-mentioned embodiments without departing from the scope of the invention.
Claims (2)
1. The preparation method of the nano metal oxide/carbon composite wave-absorbing material is characterized by comprising the following two steps:
Step 1, preparing a metal-biomass polyphenol network skeleton precursor; the preparation method is one of the methods A or B:
Method A: dispersing a surfactant in a mixed solution of water and ethanol, adding ammonia water to adjust the pH value to 9, adding biomass polyphenol, reacting for 24 hours, adding metal salt to react for 12 hours, and centrifuging, washing and drying to obtain a metal-biomass polyphenol network skeleton;
Method B: placing a surfactant, biomass polyphenol and metal salt on a ball mill, ball-milling for 0.5 hour at a high frequency of 20Hz, washing with water and ethanol, and drying to obtain a metal-biomass polyphenol network skeleton;
in the method A and the method B, the surfactant is selected from one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymers P123, F127 and polyvinylpyrrolidone; the biomass polyphenol is selected from one or a combination of more of tannic acid, gallic acid and ellagic acid; the metal salt is selected from zinc salt or copper salt;
And 2, heating and carbonizing the metal-biomass polyphenol network skeleton precursor in inert gas, preserving heat for 1-3 hours at the carbonization temperature of 600-850 ℃, and then cooling to obtain the nano metal oxide/carbon composite wave-absorbing material.
2. The method for preparing nano metal oxide/carbon composite wave-absorbing material according to claim 1, wherein in the step 2, the inert gas is high-purity nitrogen or high-purity argon, and the heating rate is 3-10 ℃/min.
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