CN113185193B - MXene composite fiber reinforced graphene aerogel wave-absorbing material and preparation method thereof - Google Patents
MXene composite fiber reinforced graphene aerogel wave-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of an MXene composite fiber reinforced graphene aerogel wave-absorbing material, which comprises the following steps: preparing MXene composite fibers; preparing a graphene oxide water dispersion solution; adding the MXene composite fiber into the graphene oxide water dispersion solution, adding a reducing agent, and performing high-speed dispersion to obtain the MXene composite fiber-graphene oxide water dispersion solution; placing the MXene composite fiber-graphene oxide aqueous dispersion solution into a reaction kettle, and performing hydrothermal self-assembly reaction to obtain MXene composite fiber reinforced graphene hydrogel; and placing the MXene composite fiber reinforced graphene hydrogel into liquid nitrogen for prefreezing, and then carrying out freeze-drying treatment to obtain the MXene composite fiber reinforced graphene aerogel wave-absorbing material. The wave-absorbing material improves the loss capacity of electromagnetic waves, simultaneously considers impedance matching, and has stronger wave-absorbing loss and wider effective absorption bandwidth.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to an MXene composite fiber reinforced graphene aerogel wave-absorbing material and a preparation method thereof.
Background
With the development of wireless communication technology, related electronic devices and facilities are widely used in the civil and military fields. While bringing convenience to people, the technologies and devices also make the problem of electromagnetic pollution increasingly prominent, and efficient electromagnetic wave absorption and shielding materials are urgently needed to protect people from being injured. In recent years, aerogel wave-absorbing materials draw more and more attention and research due to the characteristics of low density, light weight, wide wave-absorbing frequency band and the like.
The graphene aerogel has a three-dimensional porous structure formed by mutually crosslinking graphene sheet layers, can generate conductive loss under a high-frequency electromagnetic field so as to consume electromagnetic waves, and is proved to be an aerogel wave-absorbing material with development prospect. However, the wave-absorbing performance needs to be further improved due to the single composition and lack of polarization loss mechanism. The graphene composite aerogel with excellent wave-absorbing performance can be obtained by compounding with other materials, such as magnetic nanoparticles, polymer molecules, carbon nanotubes and the like.
The MXene material is a novel two-dimensional material of transition metal carbon and nitride, has the advantages of good conductivity, strong hydrophilicity, adjustable interlayer spacing, rich surface functional groups and the like, and has important application prospects in the fields of batteries, super capacitors, energy storage and conversion, sensors, catalysts, electromagnetic wave absorption and shielding and the like. In particular, in the field of electromagnetic wave absorption, MXene has been demonstrated to have excellent electromagnetic wave loss capability. But at the same time, the higher conductivity of the two-dimensional MXene is not beneficial to impedance matching, and the two-dimensional MXene with high specific surface area can reflect electromagnetic waves at high content, so that impedance mismatch is caused. MXene and graphene aerogel are compounded, and the design of a unique three-dimensional structure is a reasonable solution, so that the achievement in the aspect is less at present, and further intensive research needs to be carried out.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the MXene composite fiber reinforced graphene aerogel wave-absorbing material and the preparation method thereof are provided, the MXene composite fiber and the graphene aerogel are adopted to construct a unique three-dimensional structure, the electromagnetic wave loss capability is improved, and meanwhile impedance mismatch caused by MXene is avoided, so that the aerogel wave-absorbing material with strong electromagnetic wave loss and high impedance matching degree is obtained.
In order to solve the technical problems, an embodiment of the invention provides a preparation method of an MXene composite fiber reinforced graphene aerogel wave-absorbing material, which comprises the following steps:
step 10), preparing MXene composite fibers;
step 20) preparing a graphene oxide water dispersion solution;
step 30) adding the MXene composite fibers into the graphene oxide water dispersion solution, adding a reducing agent, and performing high-speed dispersion to obtain an MXene composite fiber-graphene oxide water dispersion solution;
step 40), placing the MXene composite fiber-graphene oxide aqueous dispersion solution into a reaction kettle, and performing hydrothermal self-assembly reaction to obtain MXene composite fiber reinforced graphene hydrogel;
and step 50), placing the MXene composite fiber reinforced graphene hydrogel into liquid nitrogen for prefreezing, and then performing freeze drying treatment to obtain the MXene composite fiber reinforced graphene aerogel wave-absorbing material.
As a further improvement of the embodiment of the present invention, the step 10) specifically includes:
step 11) preparing MXene aqueous dispersion solution and cellulose aqueous dispersion solution respectively;
and step 12) adding the MXene aqueous dispersion solution into the cellulose aqueous dispersion solution, continuously stirring, and then cleaning, centrifuging and filtering to obtain the MXene composite fiber.
As a further improvement of the embodiment of the invention, MXene in the MXene aqueous dispersion solution comprises Ti3C2Tx、Ti2CTx、Ti3CNTx、Mo2CTx、Mo2TiC2Tx、V2CTx、Nb2CTx、Nb4C3TxThe concentration of the MXene aqueous dispersion solution is 1-10 mg/mL.
As a further improvement of the embodiment of the invention, the cellulose in the cellulose aqueous dispersion solution is carboxymethylated cellulose, the diameter of the cellulose is 1-10 μm, and the concentration of the cellulose aqueous dispersion solution is 0.1-2 mg/mL.
In a further improvement of the embodiment of the invention, in the step 12), the MXene aqueous dispersion solution and the cellulose aqueous dispersion solution are mixed in a solute mass ratio of 1:100 to 1:5, the stirring speed is 200 to 1000rpm, the stirring time is 0.5 to 2 hours, and the mixture is washed with deionized water for 3 to 5 times.
As a further improvement of the embodiment of the invention, the concentration of the graphene oxide aqueous dispersion solution is 2-10 mg/mL.
As a further improvement of the embodiment of the invention, in the step 30), the reducing agent includes one or more of ascorbic acid, sodium ascorbate, sodium bisulfite, sodium sulfide, thiourea, hydrogen iodide, ethylenediamine and hydrazine hydrate, the mass ratio of the reducing agent to graphene oxide is 1: 1-6: 1, and the rotation speed in the high-speed dispersion process is 5000-30000 rpm.
As a further improvement of the embodiment of the invention, in the step 40), the temperature of the hydrothermal self-assembly reaction is 75-95 ℃, and the time of the hydrothermal self-assembly reaction is 6-12 hours.
As a further improvement of the embodiment of the invention, in the step 50), the time for pre-freezing the liquid nitrogen is 6-18 h, the temperature of the freeze drying treatment is-35 to-85 ℃, and the time for freeze drying treatment is 12-48 h.
On the other hand, the embodiment of the invention also provides an MXene composite fiber reinforced graphene aerogel wave-absorbing material prepared by the preparation method.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the MXene composite fibers are arranged in the graphene porous framework, penetrate through pores, are connected with graphene sheet layers and are embedded between the graphene sheet layers. Compared with the existing graphene aerogel, the wave-absorbing material improves the electromagnetic wave loss capability and simultaneously considers impedance matching, and has stronger wave-absorbing loss and wider effective absorption bandwidth. Compared with the traditional powder wave-absorbing material, the wave-absorbing material has the advantages of light density, low thickness and the like.
Drawings
Fig. 1 is an SEM electron micrograph of the MXene composite fiber reinforced graphene aerogel wave-absorbing material prepared in example 1, where (a) is an SEM topography of the MXene composite fiber reinforced graphene aerogel under low magnification, (b) is a local SEM topography of the MXene composite fiber penetrating through pores inside a graphene porous skeleton, (c) is a local SEM topography of the MXene composite fiber connecting graphene sheet layers inside the graphene porous skeleton, and (d) is a local SEM topography of the MXene composite fiber embedding graphene sheet layers inside the graphene porous skeleton;
FIG. 2 is an SEM electron micrograph of MXene composite fibers prepared in example 1 of the invention;
fig. 3 is a change curve of reflection loss values with frequency of the MXene composite fiber reinforced graphene aerogel wave-absorbing material prepared in embodiment 1 of the present invention at different thicknesses.
Detailed Description
The technical solution of the present invention will be explained in detail below.
The embodiment of the invention provides a preparation method of an MXene composite fiber reinforced graphene aerogel wave-absorbing material, which comprises the following steps:
step 10), preparing MXene composite fibers;
step 20) preparing a graphene oxide water dispersion solution;
step 30), adding the MXene composite fiber into the graphene oxide aqueous dispersion solution, adding a reducing agent, and performing high-speed dispersion to obtain an MXene composite fiber-graphene oxide aqueous dispersion solution;
step 40), placing the MXene composite fiber-graphene oxide aqueous dispersion solution into a reaction kettle, and performing hydrothermal self-assembly reaction to obtain MXene composite fiber reinforced graphene hydrogel;
and step 50), placing the MXene composite fiber reinforced graphene hydrogel into liquid nitrogen for prefreezing, and then performing freeze drying treatment to obtain the MXene composite fiber reinforced graphene aerogel wave-absorbing material.
According to the method provided by the embodiment of the invention, a unique three-dimensional structure is constructed by crosslinking the MXene composite fibers and the graphene porous skeleton, and the MXene composite fibers are inserted into pores in the graphene porous skeleton, connected with graphene sheet layers and embedded between the graphene sheet layers. According to the method provided by the embodiment of the invention, in the hydrothermal self-assembly process of the MXene composite fiber and the graphene oxide, the reduced graphene sheet layers are mutually crosslinked to form a graphene porous skeleton due to the combined action of Van der Waals force and a hydrogen bond; meanwhile, the functional groups remained on the surface of the graphene interact with the functional groups on the surface of the MXene composite fiber through hydrogen bond action, so that partial areas of the MXene composite fiber are tightly combined with the graphene sheet layers, and the unique MXene composite fiber reinforced graphene aerogel structure is formed. In the unique three-dimensional structure, the graphene porous skeleton has a complex cross-linked network, which is beneficial to multiple reflections of electromagnetic waves inside, so that the electromagnetic waves are consumed. Meanwhile, the MXene composite fiber forms a path of conductive loss due to the high intrinsic conductivity of the MXene, and the cross-linking of the MXene composite fiber in the graphene three-dimensional framework enables a conductive network structure to be richer and more complex, so that the overall electromagnetic wave loss capability is further enhanced. On the other hand, the MXene composite fiber enables a two-dimensional MXene sheet layer with a high specific surface area to be converted into a one-dimensional structure, and the reflection of electromagnetic waves on the surface of the MXene sheet layer is reduced, so that the overall impedance matching degree is improved. The MXene composite fiber reinforced graphene aerogel has a loose and porous internal structure and is formed by crosslinking an ultra-light two-dimensional graphene sheet layer and light MXene composite fibers, so that the MXene composite fiber reinforced graphene aerogel also has the characteristic of light density. Compared with the existing graphene aerogel, the wave-absorbing material improves the electromagnetic wave loss capability and simultaneously considers impedance matching, and has stronger wave-absorbing loss and wider effective absorption bandwidth. Compared with the traditional powder wave-absorbing material, the wave-absorbing material has the advantages of light density, low thickness and the like.
As a preferred example, the step 10) specifically includes:
step 11) preparing MXene aqueous dispersion solution and cellulose aqueous dispersion solution respectively;
and step 12) adding the MXene aqueous dispersion solution into the cellulose aqueous dispersion solution, continuously stirring, and then cleaning, centrifuging and filtering to obtain the MXene composite fiber.
In the embodiment of the invention, the MXene sheet layer is wrapped on the cellulose to form an MXene composite fiber structure. Compared with pure MXene, the MXene composite fiber enables a two-dimensional MXene sheet layer with a high specific surface area to be converted into a one-dimensional structure, reduces the reflection of electromagnetic waves on the surface of the MXene sheet layer, and improves the impedance matching degree. Meanwhile, MXene composite fibers are easy to be mutually crosslinked to form a conductive network, so that the electromagnetic wave loss capability of the material is enhanced.
As a preferable example, MXene in the MXene aqueous dispersion solution includes Ti3C2Tx、Ti2CTx、Ti3CNTx、Mo2CTx、Mo2TiC2Tx、V2CTx、Nb2CTxAnd Nb4C3TxOne or more of the MXene aqueous dispersion solution, wherein the concentration of the MXene aqueous dispersion solution is 1-10 mg/mL. MXene of this example has a high intrinsic conductivity, facilitating electron transfer throughThe conduction losses dissipate electromagnetic energy. The MXene aqueous dispersion solution in the concentration range can obtain MXene composite fibers uniformly wrapping the MXene, due to the surface limitation of cellulose fibers, the MXene composite fibers cannot be formed at too low concentration, and the MXene cannot be wasted on the contrary because of not increasing the loading capacity at too high concentration.
Preferably, the cellulose in the cellulose aqueous dispersion solution is carboxymethylated cellulose, the diameter of the cellulose is 1-10 μm, and the concentration of the cellulose aqueous dispersion solution is 0.1-2 mg/mL. The surface of the carboxymethylated cellulose has carboxymethyl functional groups compared with the original cellulose, and the MXene sheet layer can be loaded through adsorption. The cellulose with the diameter range in the embodiment facilitates the adsorption of the MXene sheet layer to form uniform MXene composite fibers, and simultaneously facilitates the formation of the mutually cross-linked three-dimensional network in the aerogel. The concentration of the cellulose aqueous dispersion solution is beneficial to the quick and uniform dispersion of MXene solution when the MXene solution is dripped into the cellulose solution.
Preferably, in the step 12), the MXene aqueous dispersion solution and the cellulose aqueous dispersion solution are mixed in a solute mass ratio of 1: 100-1: 5, the mass fraction of MXene in the corresponding MXene composite fiber is 1% -20%, the stirring speed is 200-1000 rpm, the stirring time is 0.5-2 h, and the mixture is washed by deionized water for 3-5 times. Preferably, the MXene aqueous dispersion solution and the cellulose aqueous dispersion solution are mixed according to the solute mass ratio of 1:10, the mass fraction of MXene in the MXene composite fiber is 1%, and the obtained MXene composite fiber has the best performance.
Preferably, the concentration of the graphene oxide aqueous dispersion solution is 2-10 mg/mL. The graphene oxide water dispersion solution with the selected concentration range is beneficial to forming a three-dimensional framework network, an aerogel structure cannot be formed at an excessively low concentration, and MXene composite fibers are unevenly dispersed in the three-dimensional framework to damage the unique structure of the MXene composite fibers at an excessively high concentration.
Preferably, in the step 30), the reducing agent includes one or more of ascorbic acid, sodium ascorbate, sodium bisulfite, sodium sulfide, thiourea, hydrogen iodide, ethylenediamine and hydrazine hydrate, a mass ratio of the reducing agent to graphene oxide is 1: 1-6: 1, and a rotation speed in the high-speed dispersion process is 5000-30000 rpm. The mass ratio of the reducing agent to the graphene oxide is in the range, so that a stable three-dimensional structure can be formed.
Preferably, in the step 40), the temperature of the hydrothermal self-assembly reaction is 75 to 95 ℃, and the time of the hydrothermal self-assembly reaction is 6 to 12 hours. The temperature range and the reaction time range are favorable for the stable, efficient and smooth operation of the hydrothermal self-assembly process.
Preferably, in the step 50), the time for pre-freezing the liquid nitrogen is 6-18 h, the temperature for freeze-drying treatment is-35 to-85 ℃, and the time for freeze-drying treatment is 12-48 h. By adopting the pre-freezing time, the freezing temperature and the processing time, the material is favorably and efficiently freeze-dried, the moisture residue can be caused when the temperature is too low, and the structure of the MXene composite fiber reinforced graphene aerogel can be damaged when the temperature is too high.
The embodiment of the invention also provides the MXene composite fiber reinforced graphene aerogel wave-absorbing material prepared by the preparation method.
The MXene composite fiber reinforced graphene aerogel wave-absorbing material disclosed by the embodiment of the invention is a one-dimensional component and three-dimensional component hybrid structure formed by MXene composite fibers and graphene, and comprises the MXene composite fibers with one dimensional component and a graphene porous skeleton with three dimensional component. The MXene composite fiber has a structure which is inserted into the pores, connected with the graphene sheet layers and embedded between the graphene sheet layers in the graphene porous framework. The mass fraction of the MXene composite fibers in the MXene composite fiber reinforced graphene aerogel wave-absorbing material is 15%.
Experiments prove that the wave-absorbing material prepared by the method provided by the embodiment of the invention has strong electromagnetic wave loss and high impedance matching degree.
Example 1
The MXene composite fiber reinforced graphene aerogel wave-absorbing material is prepared by the following steps:
(1) preparing MXene aqueous dispersion solution, wherein MXene is Ti3C2TxThe concentration is 5 mg/mL; preparing graphene oxide water dispersion solution with the concentration of 2mg/mL(ii) a Preparing an aqueous cellulose dispersion solution, wherein the cellulose is carboxymethylated cellulose, the diameter of the cellulose is about 3 mu m, and the concentration of the cellulose is 1 mg/mL.
(2) Mixing MXene aqueous dispersion solution and cellulose aqueous dispersion solution according to the solute mass ratio of 1:10, and continuously stirring at the stirring speed of 500rpm for 0.5 h; then washing with deionized water for 5 times, centrifuging and filtering to obtain MXene composite fiber, as shown in FIG. 2.
(3) Adding MXene composite fibers into a graphene oxide water dispersion solution, and adding a reducing agent according to the mass ratio of the addition amount of the reducing agent to the graphene oxide of 3:1, wherein the reducing agent is ascorbic acid; and (4) performing high-speed dispersion at the rotating speed of 30000rpm to obtain the MXene composite fiber/graphene oxide aqueous dispersion solution.
(4) Placing the MXene composite fiber/graphene oxide aqueous dispersion solution into a reaction kettle, and performing hydrothermal self-assembly reaction at the temperature of 95 ℃ for 6 hours to obtain the MXene composite fiber reinforced graphene hydrogel.
(5) Placing the MXene composite fiber reinforced graphene hydrogel into liquid nitrogen for pre-freezing for 12 hours; and then carrying out freeze drying treatment at the temperature of-85 ℃ for 24 hours to obtain the MXene composite fiber reinforced graphene aerogel wave-absorbing material.
The prepared MXene composite fiber reinforced graphene aerogel wave-absorbing material is shown in figure 1(a), as shown in figure 1(b), MXene composite fibers are inserted into pores inside a graphene porous framework, as shown in figure 1(c), the MXene composite fibers are connected with graphene sheet layers inside the graphene porous framework, and as shown in figure 1(d), the MXene composite fibers are embedded between the graphene sheet layers inside the graphene porous framework.
And (3) placing the prepared MXene composite fiber reinforced graphene aerogel wave-absorbing material into paraffin in a molten state, cooling and solidifying, taking out the aerogel, and cutting the aerogel into a standard size required by a coaxial method test by using a mold. The complex permeability and dielectric constant of the sample were then determined using the transmission/reflection method of a Ceyear 3656D vector network analyzer.
The test results are shown in fig. 3, and the annotations on the abscissa and ordinate in fig. 3 are modified into chinese, with the abscissa representing frequency and the ordinate representing the reflection loss value. As can be seen from FIG. 3, the wave-absorbing material prepared in example 1 has a good impedance matching degree and wave-absorbing loss, and particularly, the best impedance matching degree is achieved when the thickness is 3mm, and the wave-absorbing material has the best wave-absorbing loss. The corresponding minimum reflection loss value is-58 dB, and meanwhile, the effective absorption bandwidth of 10.5GHz is provided in the frequency range of 9.5-18 GHz, and the whole Ku waveband is covered.
Example 2
The MXene composite fiber reinforced graphene aerogel wave-absorbing material is prepared by the following steps:
(1) preparing MXene aqueous dispersion solution, wherein the MXene is Ti3C2TxThe concentration is 10 mg/mL; preparing a graphene oxide water dispersion solution with the concentration of 5 mg/mL; preparing cellulose aqueous dispersion solution, wherein the used cellulose is carboxymethylated cellulose, the diameter of the cellulose is 5 mu m, and the concentration of the cellulose is 2 mg/mL.
(2) Mixing MXene aqueous dispersion solution and cellulose aqueous dispersion solution according to the solute mass ratio of 1:5, and continuously stirring at the stirring speed of 800rpm for 1 h; and then washing with deionized water for 5 times, centrifuging and filtering to obtain the MXene composite fiber.
(3) Adding MXene composite fibers into a graphene oxide water dispersion solution, and adding a reducing agent according to the mass ratio of the addition amount of the reducing agent to the graphene oxide of 2:1, wherein the reducing agent is sodium bisulfite; and (4) carrying out high-speed dispersion at the rotating speed of 30000rpm to obtain the MXene composite fiber/graphene oxide aqueous dispersion solution.
(4) Placing the MXene composite fiber/graphene oxide aqueous dispersion solution into a reaction kettle, and performing hydrothermal self-assembly reaction at the temperature of 90 ℃ for 12 hours to obtain the MXene composite fiber reinforced graphene hydrogel.
(5) Placing the MXene composite fiber reinforced graphene hydrogel into liquid nitrogen for pre-freezing for 12 hours; and then carrying out freeze drying treatment at the temperature of-85 ℃ for 48 hours to obtain the MXene composite fiber reinforced graphene aerogel.
Example 3
The MXene composite fiber reinforced graphene aerogel wave-absorbing material is prepared by the following steps:
(1) preparing MXene aqueous dispersion solution, wherein MXene is Ti3C2TxThe concentration is 1 mg/mL; preparing a graphene oxide water dispersion solution with the concentration of 10 mg/mL; preparing cellulose aqueous dispersion solution, wherein the used cellulose is carboxymethylated cellulose, the diameter of the cellulose is 1 mu m, and the concentration of the cellulose is 2 mg/mL.
(2) Mixing MXene aqueous dispersion solution and cellulose aqueous dispersion solution according to the solute mass ratio of 1:100, and continuously stirring at the stirring speed of 200rpm for 2 h; and then washing the fiber by using deionized water for 3 times, and centrifuging and filtering the fiber to obtain the MXene composite fiber.
(3) Adding MXene composite fibers into a graphene oxide water dispersion solution, and adding a reducing agent according to the mass ratio of the addition amount of the reducing agent to the graphene oxide of 1:1, wherein the reducing agent is sodium ascorbate; and (4) carrying out high-speed dispersion at the rotating speed of 5000rpm to obtain the MXene composite fiber/graphene oxide water dispersion solution.
(4) Placing the MXene composite fiber/graphene oxide aqueous dispersion solution into a reaction kettle, and performing hydrothermal self-assembly reaction at the temperature of 75 ℃ for 10 hours to obtain the MXene composite fiber reinforced graphene hydrogel.
(5) Placing the MXene composite fiber reinforced graphene hydrogel into liquid nitrogen for pre-freezing for 6 hours; and then carrying out freeze drying treatment at the temperature of-35 ℃ for 30 hours to obtain the MXene composite fiber reinforced graphene aerogel.
Example 4
The MXene composite fiber reinforced graphene aerogel wave-absorbing material is prepared by the following steps:
(1) preparing MXene aqueous dispersion solution, wherein the MXene is Ti3C2TxThe concentration is 10 mg/mL; preparing a graphene oxide water dispersion solution with the concentration of 5 mg/mL; preparing an aqueous dispersion of cellulose, the cellulose beingCarboxymethylated cellulose having a diameter of 10 μm and a concentration of 0.1 mg/mL.
(2) Mixing MXene aqueous dispersion solution and cellulose aqueous dispersion solution according to the solute mass ratio of 1:5, and continuously stirring at the stirring speed of 1000rpm for 1.5 h; and then washing with deionized water for 5 times, centrifuging and filtering to obtain the MXene composite fiber.
(3) Adding MXene composite fibers into a graphene oxide water dispersion solution, and adding a reducing agent into the MXene composite fibers according to the mass ratio of the addition amount of the reducing agent to the graphene oxide of 6:1, wherein the reducing agent is thiourea; and (4) performing high-speed dispersion at the rotating speed of 20000rpm to obtain the MXene composite fiber/graphene oxide aqueous dispersion solution.
(4) Placing the MXene composite fiber/graphene oxide aqueous dispersion solution into a reaction kettle, and performing hydrothermal self-assembly reaction at the temperature of 85 ℃ for 8 hours to obtain the MXene composite fiber reinforced graphene hydrogel.
(5) Placing the MXene composite fiber reinforced graphene hydrogel into liquid nitrogen for pre-freezing for 18 h; and then carrying out freeze drying treatment at the temperature of-50 ℃ for 18h to obtain the MXene composite fiber reinforced graphene aerogel.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to further illustrate the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which is to be protected by the following claims. The scope of the invention is defined by the claims and their equivalents.
Claims (2)
1. A preparation method of an MXene composite fiber reinforced graphene aerogel wave-absorbing material is characterized by comprising the following steps:
step 10) preparing MXene composite fibers;
step 20), preparing a graphene oxide water dispersion solution;
step 30), adding the MXene composite fiber into the graphene oxide aqueous dispersion solution, adding a reducing agent, and performing high-speed dispersion to obtain an MXene composite fiber-graphene oxide aqueous dispersion solution;
step 40) putting the MXene composite fiber-graphene oxide aqueous dispersion solution into a reaction kettle, and performing hydrothermal self-assembly reaction to obtain the MXene composite fiber reinforced graphene hydrogel;
step 50), placing the MXene composite fiber reinforced graphene hydrogel into liquid nitrogen for prefreezing, and then performing freeze drying treatment to obtain the MXene composite fiber reinforced graphene aerogel wave-absorbing material;
the step 10) specifically comprises:
step 11) preparing MXene aqueous dispersion solution and cellulose aqueous dispersion solution respectively;
step 12) adding the MXene aqueous dispersion solution into the cellulose aqueous dispersion solution, continuously stirring, and then cleaning, centrifuging and filtering to obtain MXene composite fibers with one-dimensional structures;
the cellulose in the cellulose aqueous dispersion solution is carboxymethylated cellulose, the diameter of the cellulose is 1-10 mu m, and the concentration of the cellulose aqueous dispersion solution is 0.1-2 mg/mL;
in the MXene composite fiber reinforced graphene aerogel wave-absorbing material, MXene composite fibers are inserted into pores of a graphene porous framework, connected with graphene sheet layers and embedded between the graphene sheet layers;
MXene in the MXene aqueous dispersion solution comprises Ti3C2Tx、Ti2CTx、Ti3CNTx、Mo2CTx、Mo2TiC2Tx、V2CTx、Nb2CTx、Nb4C3Tx, wherein the concentration of the MXene aqueous dispersion solution is 1-10 mg/mL;
in the step 12), mixing the MXene aqueous dispersion solution and the cellulose aqueous dispersion solution according to a solute mass ratio of 1: 100-1: 5, wherein the stirring speed is 200-1000 rpm, the stirring time is 0.5-2 h, and washing with deionized water for 3-5 times;
the concentration of the graphene oxide aqueous dispersion solution is 2-10 mg/mL;
in the step 30), the reducing agent comprises one or more of ascorbic acid, sodium ascorbate, sodium bisulfite, sodium sulfide, thiourea, hydrogen iodide, ethylenediamine and hydrazine hydrate, the mass ratio of the reducing agent to the graphene oxide is 1: 1-6: 1, and the rotating speed in the high-speed dispersion process is 5000-30000 rpm;
in the step 40), the temperature of the hydrothermal self-assembly reaction is 75-95 ℃, and the time of the hydrothermal self-assembly reaction is 6-12 h;
in the step 50), the liquid nitrogen is prefrozen for 6-18 h, the temperature of the freeze drying treatment is-35 to-85 ℃, and the time of the freeze drying treatment is 12-48 h.
2. An MXene composite fiber reinforced graphene aerogel wave-absorbing material which is characterized by being prepared by the preparation method of claim 1.
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