CN109852344B - Composite wave-absorbing material and preparation method thereof - Google Patents
Composite wave-absorbing material and preparation method thereof Download PDFInfo
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
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Abstract
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a composite wave-absorbing material and a preparation method thereof. The invention provides a preparation method of a composite wave-absorbing material, which comprises the following steps: step 1, dissolving a cobalt source, urea and ammonium fluoride in water, carrying out hydrothermal reaction, cooling and annealing at high temperature to obtain Co3O4(ii) a Step 2, mixing Co3O4Dissolving sodium sulfide in water, carrying out hydrothermal reaction, and then annealing at high temperature to obtain three-dimensional cobalt sulfide; step 3, mixing the three-dimensional cobalt sulfide with a modifier aqueous solution for modification to obtain modified three-dimensional cobalt sulfide; step 4, compounding the modified three-dimensional cobalt sulfide with a graphene oxide aqueous solution to obtain a primary cobalt sulfide/graphene oxide composite material; and 5, heating and reducing the primary cobalt sulfide/graphene oxide composite material, and drying to obtain the composite wave-absorbing material. The preparation method provided by the invention overcomes the technical defects of narrow frequency band, low efficiency and complex preparation process of the traditional graphene-based composite absorbing material.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a composite wave-absorbing material and a preparation method thereof.
Background
In recent years, with the rapid development of science and technology, electronic equipment and communication facilities are visible everywhere and are closely connected with our lives, but serious electromagnetic radiation of the electronic equipment and the communication facilities also becomes a pollution source which cannot be ignored, so that the electronic equipment and the communication facilities not only cause harm to human bodies, but also form a huge obstruction to industrial production and manufacturing. The problem of electromagnetic radiation has become a further pollution problem following water pollution and air pollution. The electromagnetic wave absorbent (wave absorber) is a functional material which can effectively solve electromagnetic pollution, absorb electromagnetic waves and reduce the reflection and transmission of the electromagnetic waves. The ideal electromagnetic wave absorbing material has the characteristics of light weight, small thickness, wide absorption frequency band, stable chemical property and the like. Among various electromagnetic wave absorbing materials, carbon and its composite as a wave absorbing material have been reported to have characteristics of light weight, wide absorption frequency band, and the like, and have a wide application prospect in the field of electromagnetic wave shielding. Typical examples are graphene (RGO) and its complexes.
It is well known that the electromagnetic wave absorption performance of a wave absorbing material is closely related to its structure. For the conventional graphene-based composite wave absorber, graphene is generally used as a substrate to load nanoparticles, however, the conventional graphene-based composite wave absorber has the disadvantages of narrow frequency band, low efficiency, complex preparation process and the like, so that the application range of the conventional graphene-based composite wave absorber is limited to a certain extent.
Disclosure of Invention
In view of the above, the present invention provides a wave-absorbing material with a wide frequency band, high efficiency and a simple preparation process.
The invention provides a preparation method of a composite wave-absorbing material, which is characterized by comprising the following steps:
step 1, dissolving a cobalt source, urea and ammonium fluoride in water, carrying out hydrothermal reaction, cooling and annealing at high temperature to obtain Co3O4；
Step 2, mixing the Co3O4Dissolving sodium sulfide in water, carrying out hydrothermal reaction, and then annealing at high temperature to obtain three-dimensional cobalt sulfide;
step 3, mixing the three-dimensional cobalt sulfide with a modifier aqueous solution for modification to obtain modified three-dimensional cobalt sulfide;
step 4, compounding the modified three-dimensional cobalt sulfide with a graphene oxide aqueous solution to obtain a primary cobalt sulfide/graphene oxide composite material;
and 5, heating and reducing the primary cobalt sulfide/graphene oxide composite material, and drying to obtain the composite wave-absorbing material.
Specifically, the cobalt source is selected from one or more of cobalt dichloride hexahydrate and cobalt nitrate hexahydrate.
Specifically, 3.842g, 3.964g and 0.977g of cobalt dichloride hexahydrate, urea and ammonium fluoride are dissolved in water respectively according to the mass.
More preferably, in step 1, a cobalt source, urea and ammonium fluoride are dissolved in water and ultrasonically stirred to form a dispersion solution, and then hydrothermal reaction is performed. The ultrasonic stirring time is 0.5-1 h.
Preferably, in step 1, the molar ratio of the cobalt source, the urea and the ammonium fluoride is 8: 3: 13;
in the step 1, the temperature of the hydrothermal reaction is 120-160 ℃, and the time of the hydrothermal reaction is 5-10 h;
in the step 1, the high-temperature annealing temperature is 350-500 ℃, and the high-temperature annealing time is 2-6 h.
In step 1, the high-temperature annealing is performed in an inert atmosphere, which may be an argon atmosphere.
More preferably, in the step 1, the temperature of the hydrothermal reaction is 120 ℃, and the time of the hydrothermal reaction is 5 hours; in the step 1, the high-temperature annealing temperature is 350 ℃, and the high-temperature annealing time is 2 hours.
Preferably, in step 2, the Co is3O4And the mass ratio of the sodium sulfide is 1: (3-5).
More preferably, in step 2, Co3O4And sodium sulfide in water through ultrasonic stirring to form a dispersion solution, and carrying out hydrothermal reaction. The ultrasonic stirring time is 0.5-1 h.
Preferably, in the step 2, the temperature of the hydrothermal reaction is 120-180 ℃, and the time of the hydrothermal reaction is 12-24 h;
in the step 2, the high-temperature annealing temperature is 500-700 ℃, and the high-temperature annealing time is 2-6 h.
More preferably, in the step 2, the temperature of the hydrothermal reaction is 120 ℃, and the time of the hydrothermal reaction is 24 hours; in the step 2, the high-temperature annealing temperature is 500 ℃, and the high-temperature annealing time is 2 hours.
Specifically, step 2 is performed by Co3O4After the thermal reaction with sodium sulfide, high-temperature annealing treatment is carried out to obtain the cobalt sulfide with a three-dimensional structureThe specific surface area of cobalt sulfide is larger.
Preferably, in step 3, the aqueous modifier solution is selected from one or more of polyallylamine hydrochloride solution, butenedioic acid solution and polypropylene silicate.
Preferably, in step 3, the mass ratio of the three-dimensional cobalt sulfide to the polyallylamine hydrochloride solution is 50: 1.
in the step 3, 50-100mg of the three-dimensional cobalt sulfide is mixed and modified in the polyallylamine hydrochloride solution, the mixing time is 0.5-1h, and the concentration of the polyallylamine hydrochloride solution is 1 mg/mL.
Specifically, in the step 3, the three-dimensional cobalt sulfide and the modifier aqueous solution are modified, functional groups can be introduced under the modification effect, so that the graphene oxide lamella can be connected with the microspheres of the three-dimensional cobalt sulfide, and the modification treatment does not affect the three-dimensional cobalt sulfide.
Preferably, in step 4, the concentration of the graphene oxide aqueous solution is 0.2 mg/mL. The preparation method of the graphene oxide aqueous solution comprises the steps of dissolving 0.2-1mg of graphene oxide in 100ml of deionized water, and stirring for 0.5-1h to obtain the graphene oxide aqueous solution.
And compounding the modified three-dimensional cobalt sulfide with a graphene oxide aqueous solution, so that the modified three-dimensional cobalt sulfide is wrapped by the graphene oxide, wherein the compounding time is 1-1.5h, and the primary cobalt sulfide/graphene oxide composite material is obtained.
Preferably, in step 5, the heating temperature for the heating reduction is 90 to 110 ℃.
More preferably, in step 5, the time for the heating reduction is 0.5 h.
Preferably, in the step 5, a reducing agent is further included, the primary cobalt sulfide/graphene oxide composite material and the reducing agent are mixed, heated and reduced, and dried to obtain the composite wave-absorbing material.
Specifically, in the step 5, the primary cobalt sulfide/graphene oxide composite material and a reducing agent are mixed, heated and reduced, solid-liquid separation is carried out, the solid is dried in vacuum at the drying condition of 60 ℃ for 6 hours, and the composite wave-absorbing material is obtained.
Preferably, the reducing agent is hydrazine hydrate.
More preferably, the mass fraction of hydrazine hydrate is 80%.
Specifically, in the step 5, a reducing agent is further included, the primary cobalt sulfide/graphene oxide composite material and 0.5-1.5 mL of hydrazine hydrate (mass fraction is 80%) are mixed, heated and reduced, and the composite wave-absorbing material is obtained after drying.
Specifically, the step 4 and the step 5 have the functions of ensuring that the modified three-dimensional cobalt sulfide sheet layer can be in close contact with graphene oxide, the graphene oxide sheet layer can be coated on the surface of the three-dimensional cobalt sulfide reduced by the reducing agent, the compounding is carried out in two steps so as to ensure that the graphene oxide sheet layer can be in close contact with the three-dimensional cobalt sulfide, and the graphene sheet layer reduced by heating can be coated on the surface of the three-dimensional cobalt sulfide.
The invention also provides a composite wave-absorbing material, which is prepared by the preparation method of the composite wave-absorbing material.
According to the invention, the three-dimensional cobalt sulfide is modified, the three-dimensional cobalt sulfide is soaked in the graphene oxide solution, the graphene oxide is attached to the surface of the three-dimensional cobalt sulfide by slow stirring, and the graphene oxide is reduced by heating treatment, so that the coating effect is very good. Graphene, as a novel two-position ultrathin carbon-based material, is formed by tightly stacking single-layer carbon atoms, and the lattice structure of the graphene is very stable. In which the carbon atom is sp2The hybrid rail is arranged, and has the advantages of high specific surface area, aspect ratio, thermal conductivity, electric conductivity, extremely high mechanical strength and the like. The graphene has excellent mechanical properties, and under the action of an external force, due to the self-adaptive distortion of an atomic plane, a C-C bond is not easy to break, and a graphene lattice structure can be kept relatively stable, so that the graphene has high strength in a macroscopic view, and is not easy to break, puncture and tear. The cobalt sulfide belongs to a transition metal sulfide, the cobalt sulfide belongs to a semiconductor functional material, the energy band width is distributed within the range of 1.0-2.0 eV, and the CoS nano material has excellent photoelectron and optical performance. The invention discovers that the composite wave-absorbing material formed by wrapping graphene oxide on the surface of three-dimensional cobalt sulfide is opposite to a graphene-based load materialThe material has better wave-absorbing performance. The graphene introduced into the composite wave-absorbing material can not only reduce the density of the composite, but also fully utilize the huge specific surface area of the graphene and enhance the interface polarization effect of the material, so that the composite wave-absorbing material has wider absorption frequency band, lighter mass and stronger absorption strength.
In conclusion, the preparation method disclosed by the invention has the advantages that the three-dimensional cobalt sulfide is taken as a main body, the redox graphene is adopted for coating to form a binary coating structure, the preparation method mainly adopts a hydrothermal reaction, the operation is simple and easy, and the prepared cobalt sulfide has a special three-dimensional sheet structure which is very beneficial to the wave absorption effect. The binary structure formed by coating the graphene on the surface of the three-dimensional cobalt sulfide structure not only achieves the purpose of effectively absorbing a wide frequency band, but also has a low usage amount, and the composite wave-absorbing material can play a wave-absorbing function by being filled with 20% of the composite wave-absorbing material, so that the requirement on light weight of products is met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows a scanning electron micrograph of three-dimensional cobalt sulfide provided in example 1 of the present invention, at a magnification of 10000 times;
FIG. 2 is an enlarged scanning electron micrograph of the three-dimensional cobalt sulfide of FIG. 1, at a magnification of 80000 times.
Detailed Description
The invention provides a composite wave-absorbing material and a preparation method thereof, which are used for solving the technical defects of narrow frequency band, low efficiency and complex preparation process of the traditional graphene-based composite wave-absorbing material.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Wherein, the followingThe raw materials used in the examples are all commercially available or self-made, cobalt dichloride hexahydrate, urea, ammonium fluoride and Na2S is analytically pure grade.
Example 1
The embodiment of the invention provides a first composite wave-absorbing material, and the preparation method comprises the following steps:
(1) weighing 3.842g, 3.964g and 0.977g of chemical cobalt dichloride hexahydrate, urea and ammonium fluoride which are used as chemical drugs, respectively, adding the chemical drugs into 330mL of distilled water, ultrasonically stirring for 0.5h-1h to form a uniform dispersion solution, transferring the uniform dispersion solution to a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 5h, naturally cooling to room temperature, carrying out heat preservation on the obtained product at 350 ℃ in an argon atmosphere for 2h, and naturally cooling to room temperature to obtain 1.446g of Co3O4；
(2) Mixing Co3O4And 8.640g of Na2S is added into 180mL of aqueous solution, ultrasonic treatment is carried out for 0.5h to 1h to form uniform dispersion solution, hydrothermal reaction is carried out for 24h at 120 ℃, and then annealing is carried out for 2h at 500 ℃ to obtain three-dimensional cobalt sulfide;
(3) transferring the powder of the three-dimensional cobalt sulfide 100mg obtained in the step (2) into a PAH solution (polyallylamine hydrochloride solution) with the concentration of 1mg/mL, slowly stirring for 0.5h, and then obtaining the modified three-dimensional cobalt sulfide through centrifugal separation.
(4) Firstly dispersing 50mg of graphene oxide in 100ml of deionized water, stirring for 0.5h to obtain a graphene oxide aqueous solution, adding 100mg of modified three-dimensional cobalt sulfide into the prepared graphene oxide aqueous solution, and slowly stirring for 1h to obtain the primary cobalt sulfide/graphene oxide composite material.
(5) And (3) adding 10ml of hydrazine hydrate with the mass fraction of 80% into the primary cobalt sulfide/graphene oxide composite material obtained in the step (4), heating and stirring for 0.5h, cooling to room temperature, performing centrifugal separation, and drying at 60 ℃ in vacuum for 6h to obtain the composite wave-absorbing material. The composite wave-absorbing material prepared by the embodiment has an effective frequency bandwidth of-11.2 GHz with a reflection loss value lower than-10 dB and a maximum absorption peak of-52.6 GHz within the frequency range of 2-18 GHz.
And (3) performing electron microscope scanning analysis on the three-dimensional cobalt sulfide obtained in the step (2), wherein the result is shown in fig. 1 and 2, and as can be seen from fig. 1 and 2, the three-dimensional morphology of the three-dimensional cobalt sulfide obtained in the step (2) can be seen from the scanning electron microscope image, the sulfide lamella on the surface of the microsphere is densely distributed, and as can be seen from fig. 2, the lamella has ultrathin thickness. Fig. 1 and 2 show that the three-dimensional ultra-flaky cobalt sulfide has been successfully prepared.
Example 2
The embodiment of the invention provides a second composite wave-absorbing material, and the preparation method comprises the following steps:
(1) weighing 3.842g, 3.964g and 0.977g of chemical cobalt dichloride hexahydrate, urea and ammonium fluoride which are used as chemical drugs, respectively, adding the chemical drugs into 330mL of distilled water, ultrasonically stirring for 0.5h-1h to form a uniform dispersion solution, transferring the uniform dispersion solution to a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 5h, naturally cooling to room temperature, carrying out heat preservation on the obtained product at 350 ℃ in an argon atmosphere for 2h, and naturally cooling to room temperature to obtain 1.446g of Co3O4；
(2) Mixing Co3O4And 8.640g of Na2S is added into 180mL of aqueous solution, ultrasonic treatment is carried out for 0.5h to 1h to form uniform dispersion solution, hydrothermal reaction is carried out for 24h at 150 ℃, and then annealing is carried out for 2h at 500 ℃ to obtain three-dimensional cobalt sulfide;
(3) transferring the powder of the three-dimensional cobalt sulfide 100mg obtained in the step (2) into a PAH solution (polyallylamine hydrochloride solution) with the concentration of 1mg/mL, slowly stirring for 0.5h, and then obtaining the modified three-dimensional cobalt sulfide through centrifugal separation.
(4) Firstly, 80mg of graphene oxide is dispersed in 100ml of deionized water, stirring is carried out for 0.5h to obtain a graphene oxide aqueous solution, 100mg of modified three-dimensional cobalt sulfide is added into the prepared graphene oxide aqueous solution, and stirring is carried out slowly for 1h to obtain the primary cobalt sulfide/graphene oxide composite material.
(5) And (3) adding 10ml of hydrazine hydrate with the mass fraction of 80% into the primary cobalt sulfide/graphene oxide composite material obtained in the step (4), heating and stirring for 0.5h, cooling to room temperature, performing centrifugal separation, and drying at 60 ℃ in vacuum for 6h to obtain the composite wave-absorbing material. The composite wave-absorbing material prepared by the embodiment has an effective frequency bandwidth of-13.2 GHz with a reflection loss value lower than-10 dB and a maximum absorption peak of-45.3 GHz within the frequency range of 2-18 GHz.
Example 3
The embodiment of the invention provides a third composite wave-absorbing material, and the preparation method comprises the following steps:
(1) weighing 3.842g, 3.964g and 0.977g of chemical cobalt dichloride hexahydrate, urea and ammonium fluoride which are used as chemical drugs, respectively, adding the chemical drugs into 330mL of distilled water, ultrasonically stirring for 0.5h-1h to form a uniform dispersion solution, transferring the uniform dispersion solution to a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 5h, naturally cooling to room temperature, carrying out heat preservation on the obtained product at 350 ℃ in an argon atmosphere for 2h, and naturally cooling to room temperature to obtain 1.446g of Co3O4；
(2) Mixing Co3O4And 8.640g of Na2S is added into 180mL of aqueous solution, ultrasonic treatment is carried out for 0.5h to 1h to form uniform dispersion solution, hydrothermal reaction is carried out for 24h at 180 ℃, and then annealing is carried out for 2h at 500 ℃ to obtain three-dimensional cobalt sulfide;
(3) transferring the powder of the three-dimensional cobalt sulfide 100mg obtained in the step (2) into a PAH solution (polyallylamine hydrochloride solution) with the concentration of 1mg/mL, slowly stirring for 0.5h, and then obtaining the modified three-dimensional cobalt sulfide through centrifugal separation.
(4) Firstly, dispersing 100mg of graphene oxide in 100ml of deionized water, stirring for 0.5h to obtain a graphene oxide aqueous solution, adding 100mg of modified three-dimensional cobalt sulfide into the prepared graphene oxide aqueous solution, and slowly stirring for 1h to obtain the primary cobalt sulfide/graphene oxide composite material.
(5) And (3) adding 10ml of hydrazine hydrate with the mass fraction of 80% into the primary cobalt sulfide/graphene oxide composite material obtained in the step (4), heating and stirring for 0.5h, cooling to room temperature, performing centrifugal separation, and drying at 60 ℃ in vacuum for 6h to obtain the composite wave-absorbing material. The composite wave-absorbing material prepared by the embodiment has an effective frequency bandwidth of-10.2 GHz with a reflection loss value lower than-10 dB and a maximum absorption peak of-50.3 GHz within the frequency range of 2-18 GHz.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a composite wave-absorbing material is characterized by comprising the following steps:
step 1, dissolving a cobalt source, urea and ammonium fluoride in water, carrying out hydrothermal reaction, cooling and annealing at high temperature to obtain Co3O4；
Step 2, mixing the Co3O4Dissolving sodium sulfide in water, carrying out hydrothermal reaction, and then annealing at high temperature to obtain three-dimensional cobalt sulfide;
step 3, mixing the three-dimensional cobalt sulfide with a modifier aqueous solution for modification to obtain modified three-dimensional cobalt sulfide; the modifier aqueous solution is selected from polyallylamine hydrochloride solution;
step 4, compounding the modified three-dimensional cobalt sulfide and a graphene oxide aqueous solution to obtain a primary cobalt sulfide/graphene oxide composite material;
and 5, heating and reducing the primary cobalt sulfide/graphene oxide composite material, and drying to obtain the composite wave-absorbing material.
2. The method for preparing the composite wave-absorbing material according to claim 1, wherein in the step 1, the molar ratio of the cobalt source to the urea to the ammonium fluoride is 8: 3: 13;
in the step 1, the temperature of the hydrothermal reaction is 120-160 ℃, and the time of the hydrothermal reaction is 5-10 h;
in the step 1, the high-temperature annealing temperature is 350-500 ℃, and the high-temperature annealing time is 2-6 h.
3. The method for preparing the composite wave-absorbing material according to claim 1, wherein in the step 2, the Co is added3O4And the mass ratio of the sodium sulfide is 1: (3-5);
in the step 2, the temperature of the hydrothermal reaction is 120-180 ℃, and the time of the hydrothermal reaction is 12-24 h;
in the step 2, the high-temperature annealing temperature is 500-700 ℃, and the high-temperature annealing time is 2-6 h.
4. The method for preparing the composite wave-absorbing material according to claim 1, wherein in the step 3, the mass ratio of the three-dimensional cobalt sulfide to the polyallylamine hydrochloride solution is 50: 1.
5. the method for preparing the composite wave-absorbing material according to claim 1, wherein in the step 4, the concentration of the graphene oxide aqueous solution is 0.2 mg/mL.
6. The method for preparing the composite wave-absorbing material according to claim 1, wherein in the step 5, the heating temperature for heating reduction is 90-110 ℃.
7. The method for preparing the composite wave-absorbing material according to claim 1, wherein in the step 5, a reducing agent is further included, the primary cobalt sulfide/graphene oxide composite material and the reducing agent are mixed, heated, reduced and dried to obtain the composite wave-absorbing material.
8. The method for preparing the composite wave-absorbing material according to claim 7, wherein the reducing agent is hydrazine hydrate.
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