CN111269694B - Magnetoelectric composite nano porous wave-absorbing material and preparation method thereof - Google Patents
Magnetoelectric composite nano porous wave-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a magnetoelectric composite nano porous wave-absorbing material and a preparation method thereof, wherein the wave-absorbing material comprises the following components in percentage by mass in the total amount of the wave-absorbing material: 15% -45% of CoO, 10% -40% of Co and 40% -55% of porous carbon. Solid raw materials of dodecyl trimethyl ammonium bromide and Co (NO) 3 ) 2 Mixing cobalt acetate and 1-benzyl-2-methylimidazole, dissolving in water, stirring, and standing to obtain a purple precursor mixed solution; and centrifuging and collecting the purple centrifugation product; washing and drying to obtain Co (OH) 2 @ ZIF-67 complex precursor; the precursor is carbonized in a protective atmosphere to obtain the magnetoelectric composite nano porous wave-absorbing material which has larger reflection loss and absorption bandwidth and can be applied to human body electromagnetic wave protection and radar electromagnetic wave absorption coatings.
Description
Technical Field
The invention belongs to the technical field of functional materials, relates to a wave-absorbing material and a preparation method thereof, and particularly relates to a magnetoelectric composite nano porous wave-absorbing material and a preparation method thereof.
Background
With the more serious electromagnetic radiation pollution in the current society, the requirements of people on electromagnetic protection are more and more stringent. The light and high-efficiency electromagnetic wave absorption material can play an effective role in attenuating electromagnetic waves. However, it is often difficult to achieve the requirements of light weight, high efficiency and wide frequency with a single magnetic loss or dielectric loss material. Therefore, it is an effective method to solve this problem to prepare a composite absorbent having a synergistic effect of magnetic loss and dielectric loss. The magnetoelectric composite nano porous wave-absorbing material contains a large amount of mesoporous pores, so that electromagnetic wave energy can more easily enter the material. The dielectric loss of the material is mainly derived from the porous carbon. When electromagnetic waves are incident into the material, part of electrons can be accumulated on the mesoporous pore wall to form interface polarization, and the dielectric loss capacity of the material is enhanced through interface polarization relaxation loss.
Disclosure of Invention
The invention aims to provide a magnetoelectric composite nano porous wave-absorbing material for improving the defects of the prior art, which has larger reflection loss and absorption bandwidth; another object of the present invention is to provide a process for the preparation of the above-mentioned materials, which is simple, inexpensive in raw materials and good in reproducibility.
The technical scheme of the invention is as follows: aiming at the technical requirement that the wave-absorbing material needs to reach light weight, high efficiency and porosity, a nanometer needle-shaped precursor is introduced, and after carbonization, the magnetic oxide and nanometer porous carbon are compounded; firstly, the ZIF-67 derived porous carbon material has excellent wave absorbing performance, and in the invention, the ZIF-67 is tried to be respectively compounded with a material cobalt oxide phase with good magnetic loss characteristic, so that the magnetic loss capability of the MOFs derived porous carbon is further improved, and the electromagnetic loss composite wave absorbing material is obtained. CoO itself is also a good microwave absorber because of its high saturation magnetization, magnetic loss and large anisotropy field. Therefore, the magnetic oxide CoO is selected to be compounded with the ZIF-67 in the invention.
The specific technical scheme of the invention is as follows: a magnetoelectric composite nano porous wave-absorbing material is characterized in that the components of the wave-absorbing material and the mass percentages of the components in the total amount of the wave-absorbing material are respectively as follows: 15-45% of CoO, 10-40% of Co and 40-55% of porous carbon.
The invention also provides a method for preparing the magnetoelectric composite nano porous wave-absorbing material, which comprises the following steps:
weighing solid raw materials according to the components and the proportion of the solid raw materials, mixing, dissolving in water, stirring, and standing to obtain a purple precursor mixed solution;
(II) centrifuging the purple precursor mixed solution and collecting a purple centrifugal product; washing with deionized water, and drying to obtain Co (OH) 2 @ ZIF-67 complex precursor;
(III) mixing Co (OH) 2 @ ZIF-67 compound precursor is carbonized in protective atmosphere at the temperature of 500-600 ℃ and carbonThe reaction time is 2 to 3 hours.
The solid raw material components and the mass percentages of the components in the total amount of the solid raw materials are respectively as follows: dodecyl trimethyl ammonium bromide 1.4-3.6 wt% and Co (NO) 3 ) 2 (Co (NO) is preferred 3 ) 2。 6H 2 3.6 to 4.4 percent of O), 18.5 to 21.2 percent of cobalt acetate (preferably cobalt acetate (II) tetrahydrate) and 73 to 74 percent of 1-benzyl-2-methylimidazole.
Preferably, the centrifugal rotating speed is 8000-10000 r/min; the centrifugation time is 3-5 min.
Preferably, the protective atmosphere is nitrogen, argon or helium.
The saturation magnetization intensity of the magnetoelectric composite nano porous wave-absorbing material prepared by the invention is 21.6-39.5 emu/g, the coercive force is 650-1200 Koe, and the specific surface area of a sample is 204-282 m 2 Per g, the total pore volume is 0.15-0.25 cm 3 /g。
When the thickness of the magnetoelectric composite nano porous wave-absorbing material is 1.5-2.5 mm, the minimum reflection loss is-33.93 to-31.81 dB, and the effective bandwidth reaches 3.72-5.8 GHz.
In the invention, needle-shaped Co (OH) is synthesized in situ 2 And carrying out carbonization on the/ZIF-67 precursor in nitrogen or argon or helium atmosphere to obtain the CoO/Co/porous carbon composite material. CoO and Co particles are embedded into the porous carbon, so that the magnetic loss capacity of the material is improved, the impedance matching of the material is optimized, and the nano particles show good microwave absorption performance. Firstly, in-situ synthesis of Co (OH) 2 And calcining the/ZIF-67 precursor in nitrogen or argon or helium atmosphere to obtain the CoO/Co/porous carbon material.
Has the advantages that:
the magnetoelectric composite nano porous wave-absorbing material prepared by the invention has larger reflection loss and absorption bandwidth; the preparation method is simple, the raw materials are cheap, and the repeatability is good.
Drawings
FIG. 1 is a graph of reflection loss at different thicknesses of the product of example 1, a complex of cobalt oxide and ZIF-67 at 500 deg.C;
FIG. 2 is a graph of the reflection loss at different thicknesses for the product of cobalt oxide and ZIF-67 composite of example 2 at 550 deg.C;
FIG. 3 graph of reflection loss of the cobalt oxide and ZIF-67 composite at 600 deg.C for different thicknesses of the resulting product of example 3;
FIG. 4 is a graph of the reflection loss of the resulting product of comparative example 1 cobalt oxide with ZIF-67 composite at 650 deg.C at various thicknesses.
Detailed Description
Example 1
Ten 0.06g of dialkyltrimethylammonium bromide, 0.18g of Co (NO) 3 ) 2 ·6H 2 O, 0.88g of cobalt (II) acetate tetrahydrate (98%) and 3.04g of 1-benzyl-2-methylimidazole are dissolved in 30ml of deionized water, and the mixed solution is stirred at room temperature for 5 hours and then stands for 24 hours to obtain a purple precursor mixed solution. The purple precursor mixed solution was centrifuged (10000 r/min,5 min) and washed 3 times with deionized water. Drying the wet product in a vacuum drying oven at 80 ℃ for 2h, and then performing pyrolysis at 500 ℃ for 3h in a nitrogen atmosphere to obtain a CoO/Co/porous carbon composite wave-absorbing material; wherein CoO accounts for 45%, co accounts for 15%, and porous carbon accounts for 40%, as shown in FIG. 1, when the thickness is 1.5-2.5 mm, the minimum Reflection Loss (RL) is-32.48 dB, and the effective width is 3.72GHz; as shown in Table I, the saturation magnetization was 21.6emu/g, and the specific surface area of the sample having a coercive force of 960Koe was 204.97m 2 Per g, total pore volume of 0.1518cm 3 /g。
Example 2
0.14g of dodecyltrimethylammonium bromide, 0.144g of Co (NO) 3 ) 2 ·6H 2 O, 0.74g of cobalt (II) acetate tetrahydrate (98%) and 2.88g of 1-benzyl-2-methylimidazole are dissolved in 30ml of deionized water, the mixed solution is stirred for 5 hours at room temperature and then stands for 24 hours to obtain a purple precursor mixed solution, and the purple precursor mixed solution is subjected to centrifugal separation (10000 r/min,3 min) and washed 3 times with deionized water. And drying the wet product in a vacuum drying oven at 80 ℃ for 2h, and then performing pyrolysis at 550 ℃ for 3h in the nitrogen atmosphere to obtain the CoO/Co/porous carbon composite wave-absorbing material. Wherein CoO accounts for 35%, co accounts for 20%, and porous carbon accounts for 45%, as shown in FIG. 2, when it is thickWhen the degree is 1.5-2.5 mm, the minimum Reflection Loss (RL) is-33.93 dB, and the effective width is 5.8GHz; as shown in Table I, the sample having a saturation magnetization of 24.8emu/g and a coercive force of 1220Koe had a specific surface area of 204.93m 2 Per g, total pore volume of 0.1831cm 3 /g。
Example 3
0.1g of dodecyltrimethylammonium bromide, 0.168g of Co (NO) 3 ) 2 ·6H 2 O, 0.8g of cobalt (II) acetate tetrahydrate (98 percent) and 2.92g of 1-benzyl-2-methylimidazole are dissolved in 30ml of deionized water, the mixed solution is stirred for 5 hours at room temperature and then stands for 24 hours to obtain a purple precursor mixed solution, and the purple precursor mixed solution is subjected to centrifugal separation (8000 r/min,5 min) and washed for 2 times by the deionized water. And drying the wet product in a vacuum drying oven at 70 ℃ for 3h, and then carrying out 600 ℃ pyrolysis for 2h in a nitrogen atmosphere to obtain the CoO/Co/porous carbon composite wave-absorbing material. Wherein CoO accounts for 20%, co accounts for 33%, and porous carbon accounts for 47%, as shown in FIG. 3, when the thickness is 1.5-2.5 mm, the minimum Reflection Loss (RL) is-31.81 dB, and the effective width is 4.0GHz; as shown in Table I, the sample having a saturation magnetization of 30.4emu/g and a coercive force of 650Koe had a specific surface area of 207.17m 2 Per g, total pore volume of 0.2362cm 3 /g。
Comparative example 1
0.12g of dodecyltrimethylammonium bromide, 0.16g of Co (NO) 3 ) 2 ·6H 2 O, 0.76g of cobalt (II) acetate tetrahydrate (98 percent) and 2.96g of 1-benzyl-2-methylimidazole are dissolved in 30ml of deionized water, the mixed solution is stirred for 5 hours at room temperature and then stands for 24 hours to obtain a purple precursor mixed solution, and the purple precursor mixed solution is subjected to centrifugal separation (10000 r/min,3 min) and washed for 3 times by the deionized water. And drying the wet product in a vacuum drying oven at 80 ℃ for 2h, and then carrying out pyrolysis at 650 ℃ for 2h in a nitrogen atmosphere to obtain the CoO/Co/porous carbon composite wave-absorbing material. Wherein CoO accounts for 10%, co accounts for 35%, and porous carbon accounts for 55%, as shown in FIG. 4, when the thickness is 1.5-2.5 mm, the magnetoelectric composite nano porous wave-absorbing material has no wave-absorbing performance; as shown in Table I, the saturation magnetization was 39.3emu/g, and the specific surface area of the sample having a coercive force of 700Koe was 281.99m 2 Per g, total pore volume 0.2479cm 3 /g。
When electromagnetic waves enter the wave-absorbing material, the energy of the electromagnetic waves is lost by generating oscillation current, and most of the electromagnetic waves are guided to enter the wave-absorbing material on the surface of the wave-absorbing material so as to reduce reflection.
And (3) testing electromagnetic parameters of products obtained at different calcining temperatures, and simulating the wave-absorbing performance of the products by calculation. The calcination temperature was 500, 550, and the absorption bandwidth of the sample at 600 ℃ was 3.72GHz,5.80GHz, and 4.0GHz, respectively, when the thickness was 2 mm. In these samples, the calcination temperature of 550 ℃ showed the best performance because of having closer values of dielectric loss and magnetic loss, i.e., having excellent impedance matching. In conclusion, the sample with the calcination temperature of 550 ℃ has the best wave-absorbing performance in all samples, and when the thickness is only 2mm, the maximum reflection loss is-33.93 dB, and the effective absorption bandwidth can reach 5.8GHz (9.68 GHz-15.48 GHz). This is based on acicular Co (OH) as compared to the prepared pure ZIF-67 derived porous carbon material 2 The wave absorbing performance of the CoO/Co/porous carbon composite material of the/ZIF-67 is greatly improved.
The saturation magnetization, coercive force, specific surface area and total pore volume of the surface-magnetoelectric composite nano porous wave-absorbing material are shown.
Claims (5)
1. A magnetoelectric composite nano porous wave-absorbing material is characterized in that the wave-absorbing material comprises the following components in percentage by mass in the total amount of the wave-absorbing material: 15% -45% of CoO, 10% -40% of Co and 40% -55% of porous carbon; the preparation method comprises the following steps:
according to the components of the solid raw materials and the mass percentage of each component in the total amount of the solid raw materials: dodecyl trimethyl ammonium bromide 1.4-3.6 wt% and Co (NO) 3 ) 2 3.6 to 4.4 percent of cobalt acetate, 18.5 to 21.2 percent of cobalt acetate, 73 to 74 percent of 1-benzyl-2-methylimidazoleMixing and dissolving solid raw materials in water, stirring and standing to obtain a purple precursor mixed solution;
(II) centrifuging the purple precursor mixed solution and collecting a purple centrifugal product; washing with deionized water and drying to obtain Co (OH) 2 @ ZIF-67 complex precursor;
(III) mixing Co (OH) 2 The @ ZIF-67 compound precursor is carbonized in protective atmosphere, the carbonization temperature is 500-600 ℃, and the carbonization time is 2-3 hours.
2. The magnetoelectric composite nano porous wave-absorbing material according to claim 1, characterized in that the centrifugal rotation speed is 8000 to 10000r/min; the centrifugation time is 3-5 min.
3. The magnetoelectric composite nano-porous wave-absorbing material according to claim 1, characterized in that the protective atmosphere is nitrogen, argon or helium.
4. The magnetoelectric composite nano-porous wave-absorbing material according to claim 1, characterized in that the saturation magnetization of the prepared magnetoelectric composite nano-porous wave-absorbing material is 21.6-39.5 emu/g, the coercive force is 650-1200 Koe, and the specific surface area of the sample is 204-282 m 2 Per g, the total pore volume is 0.15-0.25 cm 3 /g。
5. The magnetoelectric composite nano-porous wave-absorbing material according to claim 1, characterized in that when the thickness of the prepared magnetoelectric composite nano-porous wave-absorbing material is 1.5-2.5 mm, the minimum reflection loss is-33.93-31.81 dB, and the effective bandwidth reaches 3.72-5.8 GHz.
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| CN112371189A (en) * | 2020-11-11 | 2021-02-19 | 浙江工业大学 | Hydroxide-coated ZIF (zinc-oxygen-doped organic framework) MOFs (metal-organic frameworks) heterogeneous catalyst and preparation and application thereof |
| CN113511640B (en) * | 2021-05-26 | 2022-03-22 | 中国人民解放军国防科技大学 | Metal nanocrystalline-amorphous carbon composite wave-absorbing particle and preparation method thereof |
| CN113801631B (en) * | 2021-11-09 | 2024-02-02 | 西北大学 | MnCo 2 O 4 ZIF-67/Ni wave-absorbing material and preparation method thereof |
| CN115141031B (en) * | 2022-05-18 | 2023-07-04 | 安徽大学 | Electromagnetic wave absorption composite material and preparation method and application thereof |
| CN116315732B (en) * | 2023-05-24 | 2023-09-05 | 陕西煤业化工技术研究院有限责任公司 | Nano hollow heterogeneous double-shell structure electromagnetic wave absorbing material and preparation method thereof |
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