CN115521553A - Preparation method and application of graphene/MXene/polystyrene composite material - Google Patents
Preparation method and application of graphene/MXene/polystyrene composite material Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/28—Nitrogen-containing compounds
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- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a preparation method and application of a graphene/MXene/polystyrene composite material, wherein MXene aqueous dispersion and cationic polystyrene dispersion are mixed, stirred, subjected to solid-liquid separation and vacuum drying to obtain MXene/polystyrene powder; dispersing MXene/polystyrene powder in water to obtain MXene/polystyrene dispersion liquid; mixing the MXene/polystyrene dispersion liquid with the aminated graphene dispersion liquid, stirring, filtering, and carrying out vacuum drying to obtain aminated graphene/MXene/polystyrene composite powder; and carrying out hot-press molding on the aminated graphene/MXene/polystyrene composite powder under a vacuum condition or an inert atmosphere to obtain the graphene/MXene/polystyrene composite material. The graphene/MXene/polystyrene composite material disclosed by the invention has excellent electromagnetic interference shielding performance and thermal conductivity, and is a novel electromagnetic interference shielding material.
Description
Technical Field
The invention relates to a preparation method and application of a graphene/MXene/polystyrene composite material, and belongs to the field of novel functional materials.
Background
The electromagnetic interference shielding material is the key for reducing the electromagnetic radiation generated by the electronic element, and the electromagnetic interference shielding material simultaneously meets the requirements of good heat conductivity and oxidation resistance along with the high frequency and miniaturization of the electronic element; the electromagnetic interference shielding is realized, and meanwhile, the heat can be timely dissipated in an increasingly narrow space of the electronic package for a long time.
Researchers have conducted a great deal of research to achieve high emi shielding performance. However, conventional thermally conductive electromagnetic interference shielding materials, such as metal foils, only exhibit low absorption shielding effectiveness and are susceptible to heavy corrosion. More importantly, due to impedance mismatch, metal-based EMI shielding materials exhibit reflection dominated EMI shielding mechanisms, resulting in secondary radiation contamination. The nano-film constructed of the conductive nano-material shows excellent electromagnetic shielding efficiency, but is not currently suitable for industrial production due to high cost required for manufacturing the nano-film. To address these limitations, polymer nanocomposites have light weight, easy processability, excellent mechanical properties, and strong corrosion resistance, and can effectively build a conductive network in a polymer matrix by adding a small amount of conductive filler to minimize impedance mismatch and conduction loss, and are widely used as a substitute for metals as thermally conductive electromagnetic interference shielding materials. The electromagnetic interference shielding performance of the polymer nanocomposite mainly depends on conductive fillers, and the commonly used conductive fillers comprise metal particles, carbon fibers, carbon black, carbon nanotubes and graphene; however, the direct mixing of the carbon filler with the matrix leads to poor compatibility, which easily leads to serious aggregation of the carbon filler, and leads to large thermal resistance of the filler-interface, thereby greatly limiting the electromagnetic interference shielding performance and the thermal conductivity performance of the polymer nanocomposite. The transition metal carbide/nitride (MXene) has excellent electrical conductivity, thermal conductivity and good dispersibility, so that the MXene can manufacture various MXene-based functional materials, but the MXene is extremely easy to oxidize when exposed to air and water, so that the oxidized MXene loses the nanosheet structure and functional characteristics.
The Chinese patent application CN113329603A discloses a lightweight porous MXene-based composite film electromagnetic shielding material and a preparation method thereof, wherein MXene and GO are respectively dispersed in water to obtain a dispersion liquid of MXene and GO, a cationic surface modifier is added into the MXene dispersion liquid, and after the excessive cationic surface modifier is removed by high-speed centrifugal washing, the positively charged MXene dispersion liquid is prepared, and then the positively charged MXene dispersion liquid and the GO dispersion liquid are mixed to prepare the MXene/GO dispersion liquid; and then, dropwise coating the obtained MXene/GO dispersion liquid on a polymer base sheet, drying at low temperature to remove moisture, then uncovering the sheet to obtain an MXene/GO composite film, and then annealing the obtained MXene/GO composite film to obtain an M/rGO composite film.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide a preparation method of a graphene/MXene/polystyrene composite material with good electromagnetic interference shielding performance and thermal conductivity; the second purpose of the present invention is to provide the application of the graphene/MXene/polystyrene composite material in the field of electromagnetic interference shielding
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a graphene/MXene/polystyrene composite material comprises the following steps:
s1, providing MXene aqueous dispersion with concentration of 1-10mg/mL;
dispersing the cationic polystyrene resin microspheres in water to obtain cationic polystyrene dispersion liquid with the concentration of 1-3 mg/mL;
mixing the MXene aqueous dispersion and the cationic polystyrene dispersion according to the volume ratio of 1-150, stirring at the speed of 300-1000r/min for 45-60min, filtering, and drying in vacuum to obtain MXene/polystyrene powder;
s2, dispersing MXene/polystyrene powder in water to obtain an MXene/polystyrene dispersion liquid with the concentration of 1.5-3 mg/mL;
s3, adding an aminated graphene dispersion liquid into the MXene/polystyrene dispersion liquid to ensure that the mass ratio of MXene to polystyrene to aminated graphene in the obtained mixed liquid is 1-3;
the aminated graphene dispersion liquid is prepared by dispersing aminated graphene in water, and the concentration of the aminated graphene in the aminated graphene dispersion liquid is 1-10mg/mL, further 2-8mg/mL, and further 4-6mg/mL;
s4, carrying out hot-press molding on the aminated graphene/MXene/polystyrene composite powder under a vacuum condition or an inert atmosphere to obtain a graphene/MXene/polystyrene composite material;
wherein the hot-press molding temperature is 150-220 ℃, the hot-press molding pressure is 30-60MPa, and the hot-press molding time is 0.5-3 h.
Thus, the surface of MXene in the MXene aqueous dispersion liquid has negative charges and good flexibility, the surface of cationic polystyrene resin microspheres in the cationic polystyrene dispersion liquid has positive charges, the Mxene can be easily obtained to coat core-shell structure particles on the surface of the cationic polystyrene resin microspheres by mixing the positive charges and the positive charges, the core-shell structure particles are further filtered to promote the free MXene in the solution to be adsorbed on the surface of the cationic polystyrene resin microspheres to obtain a better coating effect, and then the three-dimensional MXene/polystyrene powder with the negative charges on the surface can be obtained by drying; and then dispersing MXene/polystyrene powder in water to form MXene/polystyrene dispersion liquid, mixing the MXene/polystyrene dispersion liquid with the aminated graphene dispersion liquid with positive charges, stirring to coat the aminated graphene on the surfaces of MXene/polystyrene particles to obtain three-dimensional double-layer core-shell structure particles of aminated graphene/MXene @ polystyrene, further performing solid-liquid separation, and drying to obtain the aminated graphene/MXene/polystyrene composite powder with the double-layer core-shell structure. And then, carrying out hot-press molding on the aminated graphene/MXene/polystyrene composite powder under specific conditions, so that the aminated graphene is reduced. Non-carbon elements such as N, H, O and the like form gas under the hot pressing condition to be discharged, so that the interlayer spacing between graphene sheet layers is reduced, the van der Waals force is enhanced, and the graphene sheet layers are tightly combined; meanwhile, nitrogen-containing gas and the like generated in the reduction process cause a capillary effect when being discharged under the action of pressure, so that composite powder particles are combined with each other more tightly, and the integrity, the electromagnetic interference shielding performance and the thermal conductivity of the finally obtained graphene/MXene/polystyrene composite material are improved.
Further, in S1, MXene is Ti 3 C 2 、Ti 2 C、V 4 C 3 、V 2 C、Ti 3 One or more of CN.
Preferably, the MXene is a monolayer MXene, such as a monolayer Ti 3 C 2 Single layer of Ti 2 C. Single layer V 4 C 3 Single layer V 2 C. Single layer of Ti 3 CN, and the like.
Further, the concentration of MXene in the MXene aqueous dispersion is 2 to 8mg/mL, more preferably 4 to 6mg/mL.
Further, the concentration of the cationic polystyrene dispersion is 1.5 to 2.5mg/mL.
Further, in S1, the average particle size of the cationic polystyrene resin microspheres is 250-2000nm, further 250-1000nm, and further 250-500nm.
Further, in S1, the molecular weight (number average molecular weight) of the cationic polystyrene resin microspheres is 50000 to 400000, more preferably 60000 to 350000, still more preferably 70000 to 300000.
Further, in S1, MXene and/or cationic polystyrene resin microspheres are dispersed in water by means of ultrasonic dispersion.
Further, during dispersion, the ultrasonic power is controlled to be 50-100w, the ultrasonic frequency is controlled to be 20-60KHz, the ultrasonic time is 1-20min, and the dispersion is carried out in a cold water bath environment.
Further, in S1 and/or S2, the vacuum drying temperature is 60-90 ℃, further 65-85 ℃, and the drying time is 6-18h, further 8-16h.
Further, in S1 and/or S3, stirring is carried out for 50-55min at the speed of 400-900 r/min.
Further, in S2, the concentration of MXene/polystyrene dispersion was 1.8 to 2.5mg/mL.
Further, the graphene/MXene/polystyrene composite material is in a block shape, and the thickness of the graphene/MXene/polystyrene composite material is 0.5-50mm, further 1-45mm, and further 5-40mm.
Based on the same inventive concept, the invention also provides application of the graphene/MXene/polystyrene composite material prepared by the preparation method in the field of electromagnetic interference shielding.
Compared with the prior art, the invention has the following beneficial effects:
(1) The graphene/MXene/polystyrene composite material is formed by hot-press molding of a graphene/MXene/polystyrene composite material with a double-layer core-shell structure, and the double-layer core-shell structure is connected with each other through graphene to form a three-dimensional conductive network, so that the composite material has excellent electromagnetic interference shielding performance and thermal conductivity, and is a novel electromagnetic interference shielding material.
(2) In the graphene/MXene/polystyrene composite material prepared by the invention, the graphene layer with hydrophobicity is coated on the surface layer of MXene, so that the MXene can be protected, the oxidation resistance of the composite material is improved, and the composite material still has good electromagnetic interference shielding performance even after a long shelf life.
(3) The preparation method disclosed by the invention is simple in process, related raw materials are easy to obtain, the preparation of the graphene/MXene/polystyrene composite material can be completed by using mature means such as ultrasonic, stirring and hot pressing, the preparation cost of the composite material is favorably reduced, and the industrial production of the composite material can be facilitated.
Drawings
FIG. 1 is an EDS diagram of a three-dimensional MXene/polystyrene composite powder obtained in example 1 of the present invention.
Fig. 2 is an EDS diagram of the three-dimensional aminated graphene/MXene/polystyrene composite powder obtained in example 1 of the present invention.
Fig. 3 is an SEM image of the three-dimensional graphene/MXene/polystyrene composite obtained in example 1 of the present invention.
Fig. 4 is a TEM image of the three-dimensional graphene/MXene/polystyrene composite obtained in example 1 of the present invention.
Fig. 5 is an electromagnetic shielding schematic diagram of the three-dimensional graphene/MXene/polystyrene composite material obtained in embodiment 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
A preparation method of a graphene/MXene/polystyrene composite material comprises the following steps:
s1, providing MXene (single-layer Ti) 3 C 2 From Xin En science and technology Co., ltd., fushan city) at a concentration of 1mg/mL;
dispersing cation polystyrene resin microspheres (with the number average molecular weight of 10-30 ten thousand and the average particle size of 250nm, purchased from Xian Ruixi Biotechnology Co., ltd.) in water to obtain a cation polystyrene dispersion liquid with the concentration of 2 mg/mL;
mixing the MXene aqueous dispersion and the cationic polystyrene dispersion according to a volume ratio of 1 to 100, stirring at a speed of 500r/min for 45min, filtering, and performing vacuum drying at 60 ℃ for 12h to obtain three-dimensional MXene/polystyrene powder;
s2, dispersing the MXene/polystyrene powder in deionized water to obtain MXene/polystyrene dispersion liquid with the concentration of 2 mg/mL;
s3, adding an aminated graphene dispersion liquid into the MXene/polystyrene dispersion liquid to ensure that the mass ratio of MXene to polystyrene to aminated graphene in the obtained mixed liquid is 1;
the preparation method comprises the following steps of (1) preparing an aminated graphene dispersion liquid by dispersing aminated graphene (purchased from Nanjing Ginko nanotechnology Co., ltd., product type: JCG-1-150n-NH2, the same below) in water in an ultrasonic mode, wherein the concentration of the aminated graphene in the aminated graphene dispersion liquid is 1mg/mL;
s4, carrying out hot-press molding on 11.2g of the three-dimensional aminated graphene/MXene/polystyrene composite powder in an argon atmosphere to obtain a three-dimensional graphene/MXene/polystyrene composite material with the thickness of 2 mm;
wherein the hot-press molding temperature is 180 ℃, the hot-press molding pressure is 50MPa, and the hot-press molding time is 1h.
In S1, MXene and cationic polystyrene resin microspheres are dispersed in water in an ultrasonic dispersion mode to obtain corresponding dispersion liquid. During dispersion, the ultrasonic power is controlled to be 60w, the ultrasonic frequency is controlled to be 40KHz, the ultrasonic time is 10min, and dispersion is carried out in a cold water bath environment.
The EDS diagram of the three-dimensional MXene/polystyrene composite powder prepared in example 1 is shown in FIG. 1, and it can be seen that the surface of the polystyrene microsphere is rich in Ti, C and O elements, which indicates that MXene is placed on the polystyrene microsphere; the EDS diagram of the obtained three-dimensional aminated graphene/MXene/polystyrene composite powder is shown in figure 2, and the fact that the surface of the polystyrene microsphere is rich in C and O elements and only a small amount of Ti can be seen, which indicates that GO is coated on Ti 3 C 2 An upper layer; an SEM image of the obtained three-dimensional graphene/MXene/polystyrene composite material is shown in FIG. 3, and a better three-dimensional electromagnetic shielding network is formed between microspheres; the TEM image of the obtained three-dimensional graphene/MXene/polystyrene composite material is shown in FIG. 4, and the surface with overlapped nanosheets and ductile fracture can be seen, which shows that graphene and Ti are contained 3 C 2 The coating has good coating property on polystyrene nano microspheres; the electromagnetic shielding of the three-dimensional graphene/MXene/polystyrene composite material is schematically shown in FIG. 5, when an incident electromagnetic wave impacts on the surface of the material, a small part of the electromagnetic wave is reflected, the rest of the electromagnetic wave enters the material, and when the wave passes through the material, ti is used as the wave 3 C 2 And the shell structure of rGO, they will reflect within the shell, its energy will be in conjunction with Ti 3 C 2 And the charges of the rGO are mutually interacted and then dissipated and converted into heat energy, so that the electromagnetic interference shielding performance of the composite material is improved.
The thermal conductivity of the prepared three-dimensional graphene/MXene/polystyrene composite material is 2.53W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 51dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.26W/mK and is reduced by 10.6 percent, and the electromagnetic interference shielding efficiency is 45dB and is reduced by 11.7 percent.
Comparative example 1: three-dimensional Ti 3 C 2 Preparation of polystyrene composite material
Example 1 was repeated with the only difference that: mixing the MXene aqueous dispersion and the cationic polystyrene dispersion in a volume ratio of 2; abandoning the step S3, directly filtering the MXene/polystyrene dispersion liquid obtained in the step S2, drying the mixture for 12 hours in vacuum at the temperature of 60 ℃, and then carrying out hot press molding to obtain three-dimensional Ti with the thickness of 2.04mm 3 C 2 A polystyrene composite material.
Preparing the obtained three-dimensional Ti 3 C 2 The thermal conductivity of the polystyrene composite material is 2.36W/mK, and the electromagnetic interference shielding efficiency in the frequency range of X wave band (8.2-12.4 GHz) is 49dB. Standing at room temperature for 150 days; the heat conductivity is 1.82W/mK and is reduced by 22.8 percent, and the electromagnetic interference shielding efficiency is 37dB and is reduced by 24.4 percent.
Comparative example 2: preparation of three-dimensional graphene/polystyrene composite material
Example 1 was repeated with the only difference that: replacing the MXene aqueous dispersion liquid with an aminated graphene dispersion liquid in S1, and mixing the aqueous dispersion liquid with a cationic polystyrene dispersion liquid according to a volume ratio of 2; and (3) abandoning the step S3, directly filtering the graphene/polystyrene dispersion liquid obtained in the step S2, carrying out vacuum drying at 60 ℃ for 12h, and carrying out hot press molding to obtain the three-dimensional graphene/polystyrene composite material with the thickness of 2.06mm.
The thermal conductivity of the prepared three-dimensional graphene/polystyrene composite material is 1.98/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 39dB. After being placed in a room temperature environment for 150 days, the thermal conductivity is 1.80W/mK and is reduced by 9.1 percent, and the electromagnetic interference shielding efficiency is 35dB and is reduced by 10.2 percent.
Three-dimensional Ti prepared in comparison with comparative example 1 3 C 2 Compared with a polystyrene composite material, the thickness of the three-dimensional graphene/MXene/polystyrene composite material obtained in the embodiment 1 is reduced by 0.04mm, the electromagnetic shielding efficiency is improved by 7.2%, the thermal conductivity is improved by 4%, and the thermal conductivity and the electromagnetic shielding efficiency are improved to some extent; after 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 12.2%, and the retention rate of the thermal conductivity is improved by 12.7%, which shows that the oxidation resistance is obviously improved.
Compared with the three-dimensional graphene/polystyrene composite material prepared in the comparative example 2, the thickness of the three-dimensional graphene/MXene/polystyrene composite material prepared in the example 1 is reduced by 0.06mm, the electromagnetic shielding efficiency is improved by 21.7%, the thermal conductivity is improved by 30.7%, and the thermal conductivity and the electromagnetic shielding efficiency are greatly improved; after 150 days, the retention rate of electromagnetic shielding efficiency and thermal conductivity is slightly low, but the specific numerical values of the electromagnetic shielding effect and the thermal conductivity are obviously higher than those of the three-dimensional GO/polystyrene composite material.
Example 2
Example 1 was repeated with the only difference that: MXene in S1 is single-layer Ti 3 CN。
The thickness of the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 2 is 1.99mm, the thermal conductivity is 2.31W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 47dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.05W/mK and is reduced by 11.2 percent, and the electromagnetic interference shielding efficiency is 42dB and is reduced by 10.6 percent.
Comparative example 3: three-dimensional Ti 3 Preparation of CN/polystyrene composite material
Example 2 was repeated with the only difference that: in S1, mixing the MXene aqueous dispersion and the cationic polystyrene dispersion according to a volume ratio of 2Mixing; step S3 is abandoned, MXene/polystyrene dispersion liquid obtained in step S2 is directly filtered, vacuum drying is carried out for 12 hours at the temperature of 60 ℃, and then hot press molding is carried out to obtain three-dimensional Ti with the thickness of 2.04mm 3 CN/polystyrene composite material.
Preparing the obtained three-dimensional Ti 3 The heat conductivity of the CN/polystyrene composite material is 2.23W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 44dB. Standing at room temperature for 150 days; the thermal conductivity is 1.72W/mK, which is reduced by 22.9%; the electromagnetic interference shielding efficiency is 34dB, and is reduced by 22.7%.
Three-dimensional Ti prepared in comparison with comparative example 3 3 Compared with a CN/polystyrene composite material, the thickness of the three-dimensional graphene/MXene/polystyrene composite material obtained in the embodiment 2 is reduced by 0.05mm, the electromagnetic shielding efficiency is improved by 6.8%, the thermal conductivity is improved by 3.4%, and the thermal conductivity and the electromagnetic shielding efficiency are both improved; after 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 12%, the retention rate of the thermal conductivity is improved by 11.6%, and the oxidation resistance is obviously improved.
Compared with the three-dimensional graphene/polystyrene composite material prepared in the comparative example 2, the three-dimensional graphene/MXene/polystyrene composite material prepared in the example 2 has the advantages that the degree is reduced by 0.07mm, the electromagnetic shielding efficiency is improved by 20.5%, the thermal conductivity is improved by 16.6%, and the thermal conductivity and the electromagnetic shielding efficiency are greatly improved; after 150 days, the electromagnetic shielding efficiency and the retention rate of the thermal conductivity are slightly low, but the specific numerical values of the electromagnetic shielding effect and the thermal conductivity are obviously higher than those of the three-dimensional GO/polystyrene composite material.
Example 3
Example 1 was repeated with the only difference that: MXene in S1 is monolayer V 2 C。
The thickness of the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 3 is 2mm, the thermal conductivity is 2.27W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 45dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.01W/mK and is reduced by 11.4 percent, and the electromagnetic interference shielding efficiency is 39dB and is reduced by 13.3 percent.
Comparative example 4: three-dimensional V 2 Preparation of C/polystyrene composite material
Example of the invention2, the only difference is: mixing the MXene aqueous dispersion and the cationic polystyrene dispersion in a volume ratio of 2; step S3 is abandoned, MXene/polystyrene dispersion liquid obtained in step S2 is directly filtered, vacuum drying is carried out for 12 hours at the temperature of 60 ℃, and then hot press molding is carried out to obtain three-dimensional V with the thickness of 2.05mm 2 C/polystyrene composite material.
Preparing the obtained three-dimensional V 2 The thermal conductivity of the C/polystyrene composite material is 2.18W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 42dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.65W/mK and is reduced by 24.3 percent, and the electromagnetic interference shielding efficiency is 32dB and is reduced by 23.8 percent.
Three-dimensional V prepared in comparative example 4 2 Compared with the C/polystyrene composite material, the thickness of the three-dimensional graphene/MXene/polystyrene composite material obtained in the embodiment 3 is reduced by 0.05mm, the electromagnetic shielding efficiency is improved by 7.1%, and the thermal conductivity is improved by 4.1%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 10.4%, and the retention rate of the thermal conductivity is improved by 12.8%.
Compared with the three-dimensional GO/polystyrene composite material prepared in the comparative example 2, the thickness of the three-dimensional graphene/MXene/polystyrene composite material prepared in the example 3 is reduced by 0.06mm, the electromagnetic shielding efficiency is improved by 15.3%, and the thermal conductivity is improved by 14.6%; after the composite material is placed at room temperature for 150 days, the retention rates of the electromagnetic shielding efficiency and the thermal conductivity are slightly low, but the specific numerical values of the electromagnetic shielding effect and the thermal conductivity are obviously higher than those of the three-dimensional GO/polystyrene composite material.
Comparative example 5
Three-dimensional graphene/Ti of this comparative example 3 C 2 The preparation method of the polystyrene composite material comprises the following steps:
(1) The aminated graphene dispersion, MXene aqueous dispersion and cationic polystyrene dispersion described in example 1 were mixed in a ratio of 1:1, stirring at the speed of 500r/min for 45min, filtering, and performing vacuum drying at 60 ℃ for 12h to obtain three-dimensional graphene/MXene/polystyrene powder;
(2) Carrying out hot-press molding on 11.2g of the three-dimensional graphene/MXene/polystyrene powder in an argon atmosphere to obtain a graphene/MXene/polystyrene composite material with the thickness of 2.02 mm;
wherein the hot-press molding temperature is 180 ℃, the hot-press molding pressure is 50MPa, and the hot-press molding time is 1h.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 5 is 2.03W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 40dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.62W/mK, and is reduced by 20.2 percent; the electromagnetic interference shielding efficiency is 31dB, and is reduced by 22.5%.
Compared with the three-dimensional graphene/MXene/polystyrene composite material obtained in the comparative example 5, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 1 has the advantages that the thickness of the composite material is reduced by 0.02mm, the electromagnetic shielding efficiency is improved by 27.5%, and the thermal conductivity is improved by 39.5%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 10.7%, and the retention rate of the thermal conductivity is improved by 9.5%.
By contrast, the present invention uses a two-step assembly approach, namely: firstly, preparing MXene/polystyrene powder, then forming MXene/polystyrene dispersion liquid, and secondly, further mixing the MXene/polystyrene dispersion liquid with the aminated graphene dispersion liquid, thereby being beneficial to improving the final comprehensive performance of the composite material.
Comparative example 6
Example 1 was repeated with the only difference that: and (2) replacing aminated graphene in S1 with non-aminated graphene (namely common graphene oxide, purchased from Nanjing Jicang nanotechnology Co., ltd., product model number: JCGO-99-1-150 n).
The thickness of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 6 is 2.05mm, the thermal conductivity is 2.26W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 45dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.92W/mK and is reduced by 15.0 percent, and the electromagnetic interference shielding efficiency is 38dB and is reduced by 15.6 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material obtained in the comparative example 6, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 1 has the advantages that the thickness of the composite material is reduced by 0.05mm, the electromagnetic shielding efficiency is improved by 13.3%, and the thermal conductivity is improved by 11.9%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 3.8%, and the retention rate of the thermal conductivity is improved by 4.4%.
By comparison, the aminated graphene is used, so that the final comprehensive performance of the composite material is improved.
Comparative example 7
A preparation method of a graphene/MXene/polystyrene composite material comprises the following steps:
s1, providing MXene (single-layer Ti) 3 C 2 From Xinene science and technology Co., ltd., foshan city) at a concentration of 1mg/mL;
dispersing cationic polystyrene resin microspheres (with the number average molecular weight of 10-30 ten thousand and the average particle size of 250nm, purchased from Sienna Rexi Biotechnology Co., ltd.) in water to obtain a cationic polystyrene dispersion liquid with the concentration of 2 mg/mL;
mixing the MXene aqueous dispersion and the cationic polystyrene dispersion according to a volume ratio of 1;
the preparation method comprises the following steps of (1) preparing an aminated graphene dispersion liquid by ultrasonically dispersing aminated graphene (purchased from Nanjing GmbH nano technology Co., ltd., the model is the same as that of example 1) in water, wherein the concentration of the aminated graphene in the aminated graphene dispersion liquid is 1mg/mL;
s2, carrying out hot-press molding on 11.2g of the three-dimensional aminated graphene/MXene/polystyrene composite powder in an argon atmosphere to obtain a graphene/MXene/polystyrene composite material with the thickness of 2 mm;
wherein the hot-press molding temperature is 180 ℃, the hot-press molding pressure is 50MPa, and the hot-press molding time is 1h.
In S1, MXene and cationic polystyrene resin microspheres are dispersed in water in an ultrasonic dispersion mode to obtain corresponding dispersion liquid. During dispersion, the ultrasonic power is controlled to be 60w, the ultrasonic frequency is controlled to be 40KHz, the ultrasonic time is 10min, and dispersion is carried out in a cold water bath environment.
The thermal conductivity of the graphene/MXene/polystyrene composite material prepared in the comparative example 7 is 2.27W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 45dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.90W/mK, and is reduced by 16.3 percent, and the electromagnetic interference shielding efficiency is 38dB, and is reduced by 15.6 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 7, the three-dimensional graphene/MXene/polystyrene composite material prepared in the example 1 has the advantages that the electromagnetic shielding efficiency is improved by 13.3%, the thermal conductivity is improved by 11.4%, and the thermal conductivity and the electromagnetic shielding efficiency are greatly improved; after 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 3.8%, and the retention rate of the thermal conductivity is improved by 5.6%.
The comparison shows that the MXene/polystyrene powder is prepared after being filtered and dried, then the MXene/polystyrene dispersion liquid is formed, and then the MXene/polystyrene dispersion liquid is further mixed with the aminated graphene dispersion liquid, so that the final comprehensive performance of the composite material is favorably improved.
Example 4
Example 1 was repeated with the only difference that: the hot pressing temperature was 150 ℃. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.06mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 4 is 2.35W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 47dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.07W/mK and is reduced by 11.9 percent, and the electromagnetic interference shielding efficiency is 41dB and is reduced by 12.8 percent.
Comparative example 8
Example 1 was repeated with the only difference that: the hot pressing temperature was 130 ℃. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.14mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 8 is 1.63W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 32dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.24W/mK, the reduction is 24.0 percent, and the electromagnetic interference shielding efficiency is 26dB, and the reduction is 18.8 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 8, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 4 has the advantages that the thickness is reduced by 0.08mm, the electromagnetic shielding efficiency is improved by 46.9%, and the thermal conductivity is improved by 44.2%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 6.0%, and the retention rate of the thermal conductivity is improved by 12.0%.
The comparative example shows that the comprehensive performance of the three-dimensional graphene/MXene/polystyrene composite material is greatly reduced due to the fact that the hot pressing temperature is too low.
Example 5
Example 1 was repeated with the only difference that: the hot pressing temperature was 220 ℃. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 5 is 2.68W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 54dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.49W/mK and is reduced by 7.1 percent, and the electromagnetic interference shielding efficiency is 49dB and is reduced by 9.3 percent.
Comparative example 9
Example 1 was repeated with the only difference that: the hot pressing temperature was 240 ℃. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 9 is 2.68W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 53dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.48W/mK and is reduced by 7.5 percent, and the electromagnetic interference shielding efficiency is 48dB and is reduced by 9.4 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 9, the three-dimensional graphene/MXene/polystyrene composite material prepared in the example 5 has no obvious difference in electromagnetic shielding efficiency, thermal conductivity and oxidation resistance, which indicates that the final performance of the composite material is not greatly influenced by overhigh hot-pressing pressure, and the cost, equipment requirement and other factors are comprehensively considered, so that the overhigh hot-pressing temperature is not necessary.
Example 6
Example 1 was repeated with the only difference that: the hot pressing pressure is 30MPa. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.09mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 6 is 2.39W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 48dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.06W/mK and is reduced by 13.8 percent, and the electromagnetic interference shielding efficiency is 42dB and is reduced by 12.5 percent.
Comparative example 10
Example 1 was repeated with the only difference that: the hot pressing pressure is 20MPa. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.21mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 10 is 1.79W/mK, and the electromagnetic interference shielding efficiency in the frequency range of X waveband (8.2-12.4 GHz) is 36dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.53W/mK, the reduction is 14.5 percent, and the electromagnetic interference shielding efficiency is 31dB, and the reduction is 13.9 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 10, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 6 has the advantages that the thickness is reduced by 0.12mm, the electromagnetic shielding efficiency is improved by 33.3%, and the thermal conductivity is improved by 33.5%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 1.4%, and the retention rate of the thermal conductivity is improved by 0.7%.
The comparison example shows that the comprehensive performance of the three-dimensional graphene/MXene/polystyrene composite material is greatly reduced due to the fact that the hot-pressing pressure is too low, and the comprehensive performance may be related to the factors that the pressure is too low, the generated gas cannot be completely discharged and the like.
Example 7
Example 1 was repeated with the only difference that: the hot pressing pressure is 60MPa. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 1.98mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in example 7 is 2.41W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 52dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.16W/mK and is reduced by 10.3 percent, and the electromagnetic interference shielding efficiency is 47dB and is reduced by 9.6 percent.
Comparative example 11
Example 1 was repeated with the only difference that: the hot pressing pressure is 70MPa. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 1.98mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 11 is 2.41W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 52dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.14W/mK and is reduced by 11.2 percent, and the electromagnetic interference shielding efficiency is 47dB and is reduced by 9.6 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 11, the three-dimensional graphene/MXene/polystyrene composite material prepared in the example 7 has no obvious difference in electromagnetic shielding efficiency, thermal conductivity and oxidation resistance, which shows that the final performance of the composite material is not greatly influenced by the overhigh hot-pressing pressure, and the overhigh hot-pressing pressure is not necessary to be adopted by comprehensively considering the factors such as cost, equipment requirement and the like.
Example 8
Example 1 was repeated with the only difference that: the hot pressing time is 0.5h. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.02mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 8 is 2.46W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 49dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.17W/mK and is reduced by 11.8 percent, and the electromagnetic interference shielding efficiency is 43dB and is reduced by 12.2 percent.
Comparative example 12
Example 1 was repeated with the only difference that: the hot pressing time is 0.3h. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.07mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 12 is 2.14W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 42dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.88W/mK and is reduced by 12.1 percent, and the electromagnetic interference shielding efficiency is 36dB and is reduced by 14.3 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 12, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 8 has the advantages that the thickness is reduced by 0.05mm, the electromagnetic shielding efficiency is improved by 16.7%, and the thermal conductivity is improved by 15.0%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 2.1%, and the retention rate of the thermal conductivity is improved by 0.4%.
The comparative example shows that the comprehensive performance of the three-dimensional graphene/MXene/polystyrene composite material is obviously reduced due to the fact that the hot pressing time is too short.
Example 9
Example 1 was repeated with the only difference that: the hot pressing time is 3h. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in example 9 is 2.54W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 52dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.28W/mK and is reduced by 10.2 percent, and the electromagnetic interference shielding efficiency is 46dB and is reduced by 11.5 percent.
Comparative example 13
Example 1 was repeated with the only difference that: the hot pressing time was 3.2h. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 13 is 2.50W/mK, and the electromagnetic interference shielding efficiency in the frequency range of X waveband (8.2-12.4 GHz) is 51dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.18W/mK and is reduced by 12.8 percent, and the electromagnetic interference shielding efficiency is 45dB and is reduced by 11.8 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 13, the three-dimensional graphene/MXene/polystyrene composite material prepared in the example 9 has no obvious difference in electromagnetic shielding efficiency, thermal conductivity and oxidation resistance, and the comprehensive performance of the material cannot be improved due to the overlong hot pressing time.
Comparative example 14
Example 1 was repeated with the only difference that: so that the mass ratio of MXene, polystyrene and aminated graphene in the mixed solution obtained in S3 is 0.5. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 1.98mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 14 is 2.03W/mK, and the electromagnetic interference shielding efficiency in the frequency range of X waveband (8.2-12.4 GHz) is 40dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.83W/mK, the thermal conductivity is reduced by 9.6 percent, and the electromagnetic interference shielding efficiency is 36dB, and the thermal conductivity is reduced by 10 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 14, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 1 has the advantages that the thickness is increased by 0.02mm, the electromagnetic shielding efficiency is improved by 27.5%, and the thermal conductivity is improved by 24.6%; after being placed at room temperature for 150 days, the retention rate of electromagnetic shielding efficiency and thermal conductivity is slightly low, but the specific values of the electromagnetic shielding effect and the thermal conductivity are obviously higher than those of the composite material prepared in comparative example 14.
The comparative example shows that the comprehensive performance of the three-dimensional graphene/MXene/polystyrene composite material can be obviously reduced due to the fact that the quality of MXene is too small.
Example 10
Example 1 was repeated with the only difference that: so that the mass ratio of MXene, polystyrene and aminated graphene in the mixed solution obtained in S3 is 3. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.07mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in example 10 is 2.76W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 56dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.40W/mK and is reduced by 13.0 percent, and the electromagnetic interference shielding efficiency is 49dB and is reduced by 12.5 percent.
Comparative example 15
Example 1 was repeated with the only difference that: so that the mass ratio of MXene, polystyrene and aminated graphene in the mixed solution obtained in S3 is 3.5. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.08mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 15 is 2.71W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 54dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.26W/mK, the reduction is 16.6 percent, and the electromagnetic interference shielding efficiency is 44dB, and the reduction is 18.5 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 15, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 10 has the advantages that the thickness is reduced by 0.01mm, the electromagnetic shielding efficiency is improved by 3.7%, and the thermal conductivity is improved by 1.8%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 6.0%, and the retention rate of the thermal conductivity is improved by 3.6%.
The comparative example shows that high-quality MXene does not improve the comprehensive performance of the graphene/MXene/polystyrene composite material, but reduces the comprehensive performance of the graphene/MXene/polystyrene composite material.
Example 11
Example 1 was repeated with the only difference that: and (3) making the mass ratio of MXene, polystyrene and aminated graphene in the mixed solution obtained in S3 be 1. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 1.84mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in example 11 is 2.80W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 57dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.68W/mK and is reduced by 4.3 percent, and the electromagnetic interference shielding efficiency is 55dB and is reduced by 3.5 percent.
Comparative example 16
Example 1 was repeated with the only difference that: and (3) making the mass ratio of MXene, polystyrene and aminated graphene in the mixed solution obtained in S3 be 1. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 1.86mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 16 is 2.69W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 54dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.52W/mK and is reduced by 6.3 percent, and the electromagnetic interference shielding efficiency is 51dB and is reduced by 5.6 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 16, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 11 has the advantages that the thickness is reduced by 0.02mm, the electromagnetic shielding efficiency is improved by 5.6%, and the thermal conductivity is improved by 4.1%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 2.0%, and the retention rate of the thermal conductivity is improved by 2.0%.
The comparative example shows that the high-quality aminated graphene does not promote the comprehensive performance of the graphene/MXene/polystyrene composite material, but reduces the comprehensive performance to some extent.
Example 12
Example 1 was repeated with the only difference that: the average grain diameter of the cation polystyrene resin microspheres is 2000nm. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.01mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in example 12 is 2.42W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 48dB. After being placed at room temperature for 150 days, the thermal conductivity is 2.08W/mK and is reduced by 14.1 percent, and the electromagnetic interference shielding efficiency is 42dB and is reduced by 12.5 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 12, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 1 has the advantages that the thickness is reduced by 0.01mm, the electromagnetic shielding efficiency is improved by 6.3%, and the thermal conductivity is improved by 4.5%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 0.7%, and the retention rate of the thermal conductivity is improved by 3.4%.
Comparative example 17
Example 1 was repeated with the only difference that: the average grain diameter of the cation polystyrene resin microspheres is 3000nm. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.03mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 17 is 2.05W/mK, and the electromagnetic interference shielding efficiency in the frequency range of X waveband (8.2-12.4 GHz) is 43dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.68W/mK and is reduced by 18.1 percent, and the electromagnetic interference shielding efficiency is 36dB and is reduced by 16.3 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 17, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 1 has the advantages that the thickness is reduced by 0.03mm, the electromagnetic shielding efficiency is improved by 18.6%, and the thermal conductivity is improved by 23.4%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 4.5%, and the retention rate of the thermal conductivity is improved by 7.4%.
Comparative example 18
Example 1 was repeated with the only difference that: the average grain diameter of the cation polystyrene resin microspheres is 10000nm. Finally, the thickness of the obtained three-dimensional graphene/MXene/polystyrene composite material is 2.07mm.
The thermal conductivity of the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 18 is 1.62W/mK, and the electromagnetic interference shielding efficiency in the X-band frequency range (8.2-12.4 GHz) is 31dB. After being placed at room temperature for 150 days, the thermal conductivity is 1.24W/mK and is reduced by 23.5 percent, and the electromagnetic interference shielding efficiency is 23dB and is reduced by 25.8 percent.
Compared with the three-dimensional graphene/MXene/polystyrene composite material prepared in the comparative example 18, the three-dimensional graphene/MXene/polystyrene composite material prepared in the embodiment 1 has the advantages that the thickness is reduced by 0.07mm, the electromagnetic shielding efficiency is improved by 64.5%, and the thermal conductivity is improved by 56.2%; after the film is placed at room temperature for 150 days, the retention rate of the electromagnetic shielding efficiency is improved by 14.1%, and the retention rate of the thermal conductivity is improved by 12.8%.
Example 1, example 12, comparative example 17 and comparative example 18 illustrate that the electromagnetic shielding efficiency, thermal conductivity and oxidation resistance of the three-dimensional graphene/MXene/polystyrene composite decrease as the average particle size of the cationic polystyrene resin microspheres increases. The smaller the average particle size of the cationic polystyrene resin microspheres is, the more difficult the preparation is, the higher the cost is, and the cationic polystyrene resin microspheres with the average particle size of less than 250nm are difficult to prepare, so that the proper average particle size of the cationic polystyrene resin microspheres needs to be selected in consideration of the comprehensive cost, performance and other factors.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (9)
1. The preparation method of the graphene/MXene/polystyrene composite material is characterized by comprising the following steps:
s1, providing MXene aqueous dispersion with concentration of 1-10mg/mL;
dispersing the cationic polystyrene resin microspheres in water to obtain cationic polystyrene dispersion liquid with the concentration of 1-3 mg/mL;
mixing the MXene aqueous dispersion and the cationic polystyrene dispersion according to a volume ratio of 1-150, stirring at a speed of 300-1000r/min for 45-60min, filtering, and performing vacuum drying to obtain MXene/polystyrene powder;
s2, dispersing MXene/polystyrene powder in water to obtain an MXene/polystyrene dispersion liquid with the concentration of 1.5-3 mg/mL;
s3, adding an aminated graphene dispersion liquid into the MXene/polystyrene dispersion liquid to ensure that the mass ratio of MXene to polystyrene to aminated graphene in the obtained mixed liquid is 1-3;
the aminated graphene dispersion liquid is prepared by dispersing aminated graphene in water, and the concentration of the aminated graphene in the aminated graphene dispersion liquid is 1-10mg/mL;
s4, carrying out hot-press molding on the aminated graphene/MXene/polystyrene composite powder under a vacuum condition or an inert atmosphere to obtain a graphene/MXene/polystyrene composite material;
wherein the hot-press molding temperature is 150-220 ℃, the hot-press molding pressure is 30-60MPa, and the hot-press molding time is 0.5-3 h.
2. The method according to claim 1, wherein MXene is Ti in S1 3 C 2 、Ti 2 C、V 4 C 3 、V 2 C、Ti 3 One or more of CN.
3. The method according to claim 1, wherein the cationic polystyrene resin microspheres in S1 have an average particle size of 250 to 2000nm.
4. The process according to claim 1, wherein the molecular weight of the cationic polystyrene resin microspheres in S1 is 50000 to 400000.
5. The preparation method according to claim 1, wherein in S1, MXene and/or cationic polystyrene resin microspheres are dispersed in water by means of ultrasonic dispersion.
6. The preparation method according to claim 5, wherein the ultrasonic power is controlled to be 50-100w, the ultrasonic frequency is 20-60KHz, the ultrasonic time is 1-20min, and the dispersion is performed in a cold water bath environment.
7. The method according to claim 1, wherein the vacuum drying temperature of S1 and/or S2 is 60-90 ℃ and the drying time is 6-18 hours.
8. The preparation method according to any one of claims 1 to 7, wherein the graphene/MXene/polystyrene composite material is in a block shape and has a thickness of 0.5 to 50mm.
9. The graphene/MXene/polystyrene composite material prepared by the preparation method according to any one of claims 1 to 8 is applied to the field of electromagnetic interference shielding.
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