CN111574831A - Polyaniline-barium ferrite-graphene electromagnetic shielding material and preparation method thereof - Google Patents

Polyaniline-barium ferrite-graphene electromagnetic shielding material and preparation method thereof Download PDF

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CN111574831A
CN111574831A CN202010490269.8A CN202010490269A CN111574831A CN 111574831 A CN111574831 A CN 111574831A CN 202010490269 A CN202010490269 A CN 202010490269A CN 111574831 A CN111574831 A CN 111574831A
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向怀珍
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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
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Abstract

The invention relates to the technical field of electromagnetic shielding materials, and discloses a polyaniline-barium ferrite-graphene electromagnetic shielding material which comprises the following formula raw materials and components: cobalt-titanium co-doped barium ferrite, three-dimensional porous graphene, aniline and ammonium persulfate. According to the polyaniline-barium ferrite-graphene electromagnetic shielding material, through a hydrothermal synthesis method and a liquid phase deposition method, a nano cobalt-titanium co-doped barium ferrite has a rich pore structure and higher dielectric constant and saturation magnetization, the magnetic conductivity and magnetic loss performance of the barium ferrite are enhanced, the charge transfer process and the interface polarization effect of the graphene and polyaniline enhanced material improve the dielectric loss performance of the material, absorbed electromagnetic waves are continuously reflected in the rich pore and pore structure of the composite material, and good impedance matching performance is achieved through the magnetic loss performance, the dielectric loss and the steric hindrance reflection effect, so that excellent electromagnetic shielding and wave absorbing performance is shown.

Description

Polyaniline-barium ferrite-graphene electromagnetic shielding material and preparation method thereof
Technical Field
The invention relates to the technical field of electromagnetic shielding materials, in particular to a polyaniline-barium ferrite-graphene electromagnetic shielding material and a preparation method thereof.
Background
The electromagnetic wave is generated by the electric field and the magnetic field which are in the same phase and are vertical to each other, the transmitted shocking particle wave is derived in the space, electromagnetic field transmitted in wave form, electromagnetic wave with electromagnetic radiation characteristic includes radio wave, microwave, infrared ray, visible light, ultraviolet ray, etc. with the wide application of radio technology, electromagnetic radiation pollution, noise pollution, water pollution and air pollution become four public pollution hazards, electromagnetic radiation can interfere the normal operation of precision electronic instrument, medical equipment, aircraft navigation system and other instruments, and the human body is exposed to electromagnetic radiation for a long time, the vision, auditory system, immune system, reproductive system and the like of the human body can be influenced, metabolism disorder and immunity reduction are caused by thermal effect, non-thermal effect and accumulation effect, even cancer is induced, so that the development of novel efficient electromagnetic shielding and wave-absorbing material becomes a research hotspot.
The existing electromagnetic shielding and wave absorbing materials mainly comprise carbon materials such as carbon fibers, graphene, carbon nanotubes and the like; ceramic-based wave-absorbing materials such as silicon carbide and the like; the electromagnetic shielding material can absorb and consume electromagnetic waves through resistance type loss, dielectric loss and magnetic loss, wherein the barium ferrite has high magnetic conductivity, low cost and good demagnetization resistance, and is widely applied to the electromagnetic shielding material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a polyaniline-barium ferrite-graphene electromagnetic shielding material and a preparation method thereof, solves the problem of narrow electromagnetic wave absorption bandwidth of a barium ferrite material, and simultaneously solves the problem that a single barium ferrite wave-absorbing material is difficult to achieve good impedance matching performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the polyaniline-barium ferrite-graphene electromagnetic shielding material comprises the following formula raw materials in parts by weight: 56-75 parts of cobalt-titanium co-doped barium ferrite, 8-15 parts of three-dimensional porous graphene, 5-9 parts of aniline and 12-20 parts of ammonium persulfate.
Preferably, the preparation method of the three-dimensional porous graphene comprises the following steps:
(1) adding distilled water and graphene oxide into a reaction bottle, after uniform ultrasonic dispersion, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the reaction kettle in a heating box, heating to 170-200 ℃ for reaction for 5-10h, cooling the solution to room temperature, adding potassium hydroxide, stirring at a constant speed for 10-18h, vacuum-drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 3-8 ℃/min, carrying out heat preservation treatment at 720-780 ℃ for 1-3h, washing the solid product with distilled water, and fully drying to obtain the three-dimensional porous graphene.
Preferably, the mass ratio of the graphene oxide to the potassium hydroxide is 1: 3-6.
Preferably, the preparation method of the cobalt-titanium co-doped barium ferrite comprises the following steps:
(1) adding distilled water solvent, glucose, barium nitrate, ferric nitrate, cobalt nitrate, tetrabutyl titanate and citric acid serving as a dispersing agent into a reaction bottle, uniformly stirring at a constant speed, adding ammonia water to adjust the pH value of the solution to be neutral, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 170-190 ℃ for reaction for 10-20h, cooling the solution, heating to 90-110 ℃ in an oil bath kettle, uniformly stirring until the solution is in a gel state, fully drying the gel-like mixed product, placing the product in a resistance furnace, heating at the rate of 5-10 ℃/min, heating to 440-480 ℃ for heat preservation treatment for 2-4h, heating to 1000-1100 ℃, and performing heat preservation calcination for 4-6h to obtain a porous nano cobalt-titanium co-doped barium ferrite.
Preferably, the mass ratio of the glucose, the barium nitrate, the ferric nitrate, the cobalt nitrate, the tetrabutyl titanate and the citric acid is 15-25:1:11:0.1-0.6:0.4-0.9:13-18, and the chemical formula of the cobalt-titanium co-doped barium ferrite is BaCo0.1- 0.6Ti0.4-0.9Fe11O19。
Preferably, the preparation method of the polyaniline-barium ferrite-graphene electromagnetic shielding material comprises the following steps:
(1) adding distilled water solvent, 56-75 parts of porous nano cobalt-titanium co-doped barium ferrite and 8-15 parts of three-dimensional porous graphene into a reaction bottle, ultrasonically dispersing uniformly, adding hydrochloric acid to adjust the pH value of the solution to 2-4, then adding 5-9 parts of aniline and 12-20 parts of ammonium persulfate, stirring at a constant speed at 0-5 ℃ to react for 10-18h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline-barium ferrite-graphene electromagnetic shielding material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the polyaniline-barium ferrite-graphene electromagnetic shielding material is prepared by a hydrothermal synthesis method and a liquid phase deposition method, taking carbon nano microspheres generated by glucose as sacrificial templates and then performing a sol-gel method, wherein the cobalt-titanium Co-doped barium ferrite has good nano-morphology and rich pore structure, and Co has rich Co-titanium Co-doped barium ferrite2+、Ti4+By substitution of a portion of Fe3+The crystal lattice reduces the coercive force of the barium ferrite, improves the dielectric constant and the saturation magnetization, and further enhances the magnetic permeability and the magnetic loss performance of the barium ferrite.
The polyaniline-barium ferrite-graphene electromagnetic shielding material is prepared by taking cobalt-titanium co-doped barium ferrite and three-dimensional porous graphene as growth sites through an in-situ polymerization method, the three-dimensional porous graphene and the polyaniline have excellent conductivity, a three-dimensional conductive network is formed among the three, the charge transfer process is promoted, the interfacial polarization effect is enhanced, the dielectric loss performance of the composite material is enhanced, the cobalt-titanium co-doped barium ferrite and the three-dimensional porous graphene have rich pore structures, absorbed electromagnetic waves can be continuously reflected in the pores and the pore structures, and the composite material passes through magnetic loss performance, magnetic loss performance and the like by regulating the content ratio of the cobalt-titanium co-doped barium ferrite, the three-dimensional porous graphene and the polyaniline, Dielectric loss and steric hindrance reflection effect, so that the composite material achieves good impedance matching performance and shows excellent electromagnetic shielding and wave absorbing performance.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the polyaniline-barium ferrite-graphene electromagnetic shielding material comprises the following formula raw materials in parts by weight: 56-75 parts of cobalt-titanium co-doped barium ferrite, 8-15 parts of three-dimensional porous graphene, 5-9 parts of aniline and 12-20 parts of ammonium persulfate.
The preparation method of the three-dimensional porous graphene comprises the following steps:
(1) adding distilled water and graphene oxide into a reaction bottle, after uniform ultrasonic dispersion, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the reaction kettle in a heating box, heating to 170-200 ℃ for reaction for 5-10h, cooling the solution to room temperature, adding potassium hydroxide, wherein the mass ratio of the graphene oxide to the potassium hydroxide is 1:3-6, stirring at a constant speed for 10-18h, vacuum drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace and introducing nitrogen, the heating rate is 3-8 ℃/min, keeping the temperature at 720-780 ℃ for 1-3h, washing the solid product with distilled water, and fully drying to obtain the three-dimensional porous graphene.
The preparation method of the cobalt-titanium co-doped barium ferrite comprises the following steps:
(1) adding distilled water solvent, glucose, barium nitrate, ferric nitrate, cobalt nitrate, tetrabutyl titanate and dispersant citric acid into a reaction bottle, wherein the mass ratio of the six substances is 15-25:1:11:0.1-0.6:0.4-0.9:13-18, uniformly stirring, adding ammonia water to adjust the pH value of the solution to be neutral, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 170 ℃. times, reacting for 10-20h, cooling the solution, heating to 90-110 ℃ in an oil bath kettle, uniformly stirring until the solution forms gel, fully drying the gel mixed product, placing the product in a resistance furnace, heating at the rate of 5-10 ℃/min, heating to 440-, the calcined product is porous nano cobalt-titanium co-doped barium ferrite with a chemical molecular formula of BaCo0.1-0.6Ti0.4-0.9Fe11O19。
The preparation method of the polyaniline-barium ferrite-graphene electromagnetic shielding material comprises the following steps:
(1) adding distilled water solvent, 56-75 parts of porous nano cobalt-titanium co-doped barium ferrite and 8-15 parts of three-dimensional porous graphene into a reaction bottle, ultrasonically dispersing uniformly, adding hydrochloric acid to adjust the pH value of the solution to 2-4, then adding 5-9 parts of aniline and 12-20 parts of ammonium persulfate, stirring at a constant speed at 0-5 ℃ to react for 10-18h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline-barium ferrite-graphene electromagnetic shielding material.
Example 1
(1) Preparing a three-dimensional porous graphene component 1: adding distilled water and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 170 ℃ for reaction for 5 hours, cooling the solution to room temperature, adding potassium hydroxide, wherein the mass ratio of the graphene oxide to the potassium hydroxide is 1:3, stirring at a constant speed for 10 hours, drying the solution in vacuum to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 3 ℃/min, preserving the temperature at 720 ℃ for 1 hour, washing the solid product by using distilled water, and fully drying to prepare the three-dimensional porous graphene component 1.
(2) Preparation of cobalt-titanium co-doped barium ferrite component 1: adding distilled water solvent, glucose, barium nitrate, ferric nitrate, cobalt nitrate, tetrabutyl titanate and dispersant citric acid into a reaction bottle, wherein the mass ratio of the six substances is 15:1:11:0.1:0.9:13, uniformly stirring, adding ammonia water to adjust the pH value of the solution to be neutral, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 170 ℃ for reaction for 10 hours, cooling the solution, heating to 90 ℃ in an oil bath, uniformly stirring to form gel, fully drying the gel mixed product, placing the gel mixed product in a resistance furnace, heating at the rate of 5 ℃/min, heating to 440 ℃ for heat preservation treatment for 2 hours, heating to 1000 ℃, heat preservation and calcination for 4 hours, wherein the calcined product is porous nano cobalt-titanium co-doped barium ferrite component 1, and the chemical formula is BaCo0.1Ti0.9Fe11O19。
(3) Preparing a polyaniline-barium ferrite-graphene electromagnetic shielding material 1: adding a distilled water solvent, 75 parts of porous nano cobalt-titanium co-doped barium ferrite component 1 and 8 parts of three-dimensional porous graphene component 1 into a reaction bottle, ultrasonically dispersing uniformly, adding hydrochloric acid to adjust the pH value of the solution to 4, adding 5 parts of aniline and 12 parts of ammonium persulfate, stirring at a constant speed at 5 ℃ for reaction for 10 hours, vacuum-drying the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline-barium ferrite-graphene electromagnetic shielding material 1.
Example 2
(1) Preparing a three-dimensional porous graphene component 2: adding distilled water and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 170 ℃ for reaction for 10 hours, cooling the solution to room temperature, adding potassium hydroxide, wherein the mass ratio of the graphene oxide to the potassium hydroxide is 1:3, uniformly stirring for 18 hours, drying the solution in vacuum to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 8 ℃/min, preserving the temperature for 1 hour at 780 ℃, washing the solid product by using distilled water, and fully drying to prepare the three-dimensional porous graphene component 2.
(2) Preparation of cobalt-titanium co-doped barium ferrite component 2: adding distilled water solvent, glucose, barium nitrate, ferric nitrate, cobalt nitrate, tetrabutyl titanate and dispersant citric acid into a reaction bottle, wherein the mass ratio of the six substances is 25:1:11:0.2:0.8:14, uniformly stirring, adding ammonia water to adjust the pH value of the solution to be neutral, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 190 ℃ for reaction for 10 hours, cooling the solution, heating to 110 ℃ in an oil bath, uniformly stirring to form gel, fully drying the gel mixed product, placing the gel mixed product in a resistance furnace, heating at the rate of 5 ℃/min, heating to 480 ℃ for heat preservation for 4 hours, heating to 1100 ℃ for heat preservation and calcination for 6 hours, wherein the calcined product is porous nano cobalt-titanium co-doped barium ferrite component 2 with the chemical molecular formula of BaCo0.2Ti0.8Fe11O19。
(3) Preparing a polyaniline-barium ferrite-graphene electromagnetic shielding material 2: adding a distilled water solvent, 69 parts of porous nano cobalt-titanium co-doped barium ferrite component 2 and 10 parts of three-dimensional porous graphene component 2 into a reaction bottle, ultrasonically dispersing uniformly, adding hydrochloric acid to adjust the pH value of the solution to 4, adding 6.5 parts of aniline and 14.5 parts of ammonium persulfate, stirring at a constant speed at 5 ℃ to react for 18 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline-barium ferrite-graphene electromagnetic shielding material 2.
Example 3
(1) Preparing a three-dimensional porous graphene component 3: adding distilled water and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 190 ℃ for reaction for 8 hours, cooling the solution to room temperature, adding potassium hydroxide, wherein the mass ratio of the graphene oxide to the potassium hydroxide is 1:5, stirring at a constant speed for 14 hours, drying the solution in vacuum to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 5 ℃/min, carrying out heat preservation treatment at 760 ℃ for 2 hours, washing the solid product by using distilled water, and fully drying to prepare the three-dimensional porous graphene component 3.
(2) Preparation of cobalt-titanium co-doped barium ferrite component 3: adding distilled water solvent, glucose, barium nitrate, ferric nitrate, cobalt nitrate, tetrabutyl titanate and dispersant citric acid into a reaction bottle, wherein the mass ratio of the six substances is 20:1:11:0.4:0.6:15, uniformly stirring, adding ammonia water to adjust the pH value of the solution to be neutral, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 180 ℃ for reaction for 15h, cooling the solution, heating to 100 ℃ in an oil bath, uniformly stirring to form gel, fully drying the gel mixed product, placing the gel mixed product in a resistance furnace, heating to 460 ℃ at the rate of 8 ℃/min, carrying out heat preservation treatment for 3h, heating to 1050 ℃, carrying out heat preservation calcination for 5h, and obtaining a porous nano cobalt-titanium co-doped barium ferrite component 3 with the chemical formula of BaCo0.4Ti0.6Fe11O19。
(3) Preparing a polyaniline-barium ferrite-graphene electromagnetic shielding material 3: adding a distilled water solvent, 63 parts of porous nano cobalt-titanium co-doped barium ferrite component 3 and 12 parts of three-dimensional porous graphene component 3 into a reaction bottle, ultrasonically dispersing uniformly, adding hydrochloric acid to adjust the pH value of the solution to 3, adding 8 parts of aniline and 17 parts of ammonium persulfate, stirring at a constant speed at 2 ℃ for reaction for 15 hours, vacuum-drying the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline-barium ferrite-graphene electromagnetic shielding material 3.
Example 4
(1) Preparing a three-dimensional porous graphene component 4: adding distilled water and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 200 ℃ for reaction for 10 hours, cooling the solution to room temperature, adding potassium hydroxide, wherein the mass ratio of the graphene oxide to the potassium hydroxide is 1:6, uniformly stirring for 18 hours, drying the solution in vacuum to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 8 ℃/min, keeping the temperature at 780 ℃ for 3 hours, washing the solid product by using distilled water, and fully drying to prepare the three-dimensional porous graphene component 4.
(2) Preparation of cobalt-titanium co-doped barium ferrite component 4: adding distilled water solvent, glucose, barium nitrate, ferric nitrate, cobalt nitrate, tetrabutyl titanate and dispersant citric acid into a reaction bottle, wherein the mass ratio of the six substances is 25:1:11:0.6:0.4:18, uniformly stirring, adding ammonia water to adjust the pH value of the solution to be neutral, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 190 ℃ for reaction for 20 hours, cooling the solution, heating to 110 ℃ in an oil bath, uniformly stirring to form gel, fully drying the gel mixed product, placing the gel mixed product in a resistance furnace, heating to 480 ℃ at the rate of 10 ℃/min, carrying out heat preservation treatment for 4 hours, heating to 1100 ℃ again, carrying out heat preservation calcination for 6 hours, and obtaining a porous nano cobalt-titanium co-doped barium ferrite component 4 with the chemical formula of BaCo0.6Ti0.4Fe11O19。
(3) Preparing a polyaniline-barium ferrite-graphene electromagnetic shielding material 4: adding distilled water solvent, 56 parts of porous nano cobalt-titanium co-doped barium ferrite component 4 and 15 parts of three-dimensional porous graphene component 4 into a reaction bottle, after uniformly dispersing by ultrasonic, adding hydrochloric acid to adjust the pH value of the solution to 2, then adding 9 parts of aniline and 20 parts of ammonium persulfate, stirring at a constant speed at 0 ℃ for reacting for 18 hours, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the polyaniline-barium ferrite-graphene electromagnetic shielding material 4.
Comparative example 1
(1) Preparing a three-dimensional porous graphene comparative component 1: adding distilled water and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 200 ℃ for reaction for 5 hours, cooling the solution to room temperature, adding potassium hydroxide, wherein the mass ratio of the graphene oxide to the potassium hydroxide is 1:3, stirring at a constant speed for 18 hours, drying the solution in vacuum to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 8 ℃/min, keeping the temperature at 740 ℃ for 1 hour, washing the solid product by using distilled water, and fully drying to prepare a three-dimensional porous graphene comparison component 1.
(2) Preparation of cobalt-titanium co-doped barium ferrite comparative component 1: adding distilled water solvent, glucose, barium nitrate, ferric nitrate, cobalt nitrate, tetrabutyl titanate and dispersant citric acid into a reaction bottle, wherein the mass ratio of the six substances is 20:1:11:0.3:0.7:15, uniformly stirring, adding ammonia water to adjust the pH value of the solution to be neutral, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 180 ℃ for reaction for 14h, cooling the solution, heating to 100 ℃ in an oil bath, uniformly stirring to form gel, fully drying the gel mixed product, placing the gel mixed product in a resistance furnace, heating to 460 ℃ at the rate of 8 ℃/min, carrying out heat preservation treatment for 3h, heating to 1060 ℃, carrying out heat preservation calcination for 5h, and obtaining a porous nano cobalt-titanium co-doped barium ferrite contrast component 1 with the chemical formula of BaCo0.3Ti0.7Fe11O19。
(3) Preparing a polyaniline-barium ferrite-graphene electromagnetic shielding contrast material 1: adding a distilled water solvent, 83 parts of porous nano cobalt-titanium co-doped barium ferrite contrast component 1 and 6 parts of three-dimensional porous graphene contrast component 1 into a reaction bottle, ultrasonically dispersing uniformly, adding hydrochloric acid to adjust the pH value of the solution to 3, adding 3 parts of aniline and 8 parts of ammonium persulfate, stirring at a constant speed at 2 ℃ to react for 14 hours, vacuum-drying the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline-barium ferrite-graphene electromagnetic shielding contrast material 1.
Comparative example 2
(1) Preparing a three-dimensional porous graphene comparison component 2: adding distilled water and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 200 ℃ for reaction for 8 hours, cooling the solution to room temperature, adding potassium hydroxide, wherein the mass ratio of the graphene oxide to the potassium hydroxide is 1:4, stirring at a constant speed for 15 hours, drying the solution in vacuum to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 6 ℃/min, carrying out heat preservation treatment at 750 ℃ for 2 hours, washing the solid product by using distilled water, and fully drying to prepare a three-dimensional porous graphene comparison component 2.
(2) Preparation of cobalt-titanium co-doped barium ferrite comparative component 2: adding distilled water solvent, glucose, barium nitrate, ferric nitrate, cobalt nitrate, tetrabutyl titanate and dispersant citric acid into a reaction bottle, wherein the mass ratio of the six substances is 18:1:11:0.5:0.5:16, uniformly stirring, adding ammonia water to adjust the pH value of the solution to be neutral, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, placing the kettle in a heating box, heating to 180 ℃ for reaction for 16h, cooling the solution, heating to 90 ℃ in an oil bath, uniformly stirring until the solution is gelatinous, fully drying a gelatinous mixed product, placing the gelatinous mixed product in a resistance furnace, heating to 460 ℃ at the heating rate of 8 ℃/min, carrying out heat preservation treatment for 3h, heating to 1080 ℃, carrying out heat preservation and calcination for 5h, wherein the calcined product is a porous nano cobalt-titanium co-doped barium ferrite contrast component 2 with the chemical formula of BaCo0.5Ti0.5Fe11O19。
(3) Preparing a polyaniline-barium ferrite-graphene electromagnetic shielding contrast material 2: adding a distilled water solvent, 47 parts of porous nano cobalt-titanium co-doped barium ferrite contrast component 2 and 17 parts of three-dimensional porous graphene contrast component 2 into a reaction bottle, ultrasonically dispersing uniformly, adding hydrochloric acid to adjust the pH value of the solution to 3, adding 11 parts of aniline and 25 parts of ammonium persulfate, stirring at a constant speed at 5 ℃ to react for 15 hours, vacuum-drying the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline-barium ferrite-graphene electromagnetic shielding contrast material 2.
The polyaniline-barium ferrite-graphene electromagnetic shielding material 1-4 and the comparison material 1-2 are subjected to hot press molding to prepare a sheet sample with the thickness of 2mm, and an AV3629 high-performance microwave integrated vector network analyzer is used for testing the wave absorbing performance of the sample, wherein the test standard is GB/T25471.
Figure BDA0002520700430000101
In summary, the polyaniline-barium ferrite-graphene electromagnetic shielding material is prepared by a hydrothermal synthesis method and a liquid phase deposition method, taking carbon nano microspheres generated by glucose as sacrificial templates and a sol-gel method, and the cobalt-titanium Co-doped barium ferrite has good nano-morphology and rich pore structure, and Co has good nano-morphology2+、Ti4+By substitution of a portion of Fe3+The crystal lattice reduces the coercive force of the barium ferrite, improves the dielectric constant and the saturation magnetization, and further enhances the magnetic permeability and the magnetic loss performance of the barium ferrite.
The cobalt-titanium co-doped barium ferrite and the three-dimensional porous graphene are growth sites, and the polyaniline-barium ferrite-graphene composite material is prepared by an in-situ polymerization method, wherein the three-dimensional porous graphene and the polyaniline have excellent conductivity, a three-dimensional conductive network is formed among the three, the charge transfer process is promoted, the interface polarization effect is enhanced, and the dielectric loss performance of the composite material is enhanced, the cobalt-titanium co-doped barium ferrite and the three-dimensional porous graphene both have rich pore structures, absorbed electromagnetic waves can be continuously reflected in the pores and the pore structures, and the composite material can achieve good impedance matching performance through the magnetic loss performance, the dielectric loss and the steric hindrance reflection effect by regulating and controlling the content ratio of the cobalt-titanium co-doped barium ferrite, the three-dimensional porous graphene and the polyaniline, the frequency band with the reflection loss less than or equal to-15 dB is 7.9-14.3GHz, the bandwidth reaches 7.4GHz, the average absorption capacity is 36.4dB at most, and the absorption peak value is-41.6 dB at most, thus showing excellent electromagnetic shielding and wave absorbing performance.

Claims (6)

1. The polyaniline-barium ferrite-graphene electromagnetic shielding material comprises the following formula raw materials in parts by weight: 56-75 parts of cobalt-titanium co-doped barium ferrite, 8-15 parts of three-dimensional porous graphene, 5-9 parts of aniline and 12-20 parts of ammonium persulfate.
2. The polyaniline-barium ferrite-graphene electromagnetic shielding material according to claim 1, wherein: the preparation method of the three-dimensional porous graphene comprises the following steps:
(1) adding graphene oxide into distilled water, after uniform ultrasonic dispersion, transferring the solution into a hydrothermal reaction kettle, heating to 170-200 ℃ for reaction for 5-10h, cooling the solution, adding potassium hydroxide, stirring for 10-18h, removing the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, carrying out heat preservation treatment for 1-3h at 720-780 ℃, washing and drying to prepare the three-dimensional porous graphene.
3. The polyaniline-barium ferrite-graphene electromagnetic shielding material according to claim 2, wherein: the mass ratio of the graphene oxide to the potassium hydroxide is 1: 3-6.
4. The polyaniline-barium ferrite-graphene electromagnetic shielding material according to claim 1, wherein: the preparation method of the cobalt-titanium co-doped barium ferrite comprises the following steps:
(1) adding glucose, barium nitrate, ferric nitrate, cobalt nitrate, tetrabutyl titanate and a dispersant citric acid into a distilled water solvent, uniformly stirring, adding ammonia water to adjust the pH value of the solution to be neutral, transferring the solution into a hydrothermal reaction kettle, heating to 170 ℃ and 190 ℃ for reaction for 10-20h, then heating the solution to 90-110 ℃, stirring until gel is formed, drying, placing the solution into a resistance furnace, heating to 440 ℃ and 480 ℃ for heat preservation treatment for 2-4h, heating to 1000 ℃ and 1100 ℃, and performing heat preservation and calcination for 4-6h, wherein the calcination product is porous nano cobalt-titanium co-doped barium ferrite.
5. The polyaniline-barium ferrite-graphene electromagnetic shielding material according to claim 4, wherein: the mass ratio of the glucose, the barium nitrate, the ferric nitrate, the cobalt nitrate, the tetrabutyl titanate and the citric acid is 15-25:1:11:0.1-0.6:0.4-0.9:13-18, and the chemical formula of the cobalt-titanium co-doped barium ferrite is BaCo0.1-0.6Ti0.4-0.9Fe11O19。
6. The polyaniline-barium ferrite-graphene electromagnetic shielding material according to claim 1, wherein: the preparation method of the polyaniline-barium ferrite-graphene electromagnetic shielding material comprises the following steps:
(1) adding 56-75 parts of porous nano cobalt-titanium co-doped barium ferrite and 8-15 parts of three-dimensional porous graphene into a distilled water solvent, after uniformly dispersing by ultrasonic, adding hydrochloric acid to adjust the pH value of the solution to 2-4, then adding 5-9 parts of aniline and 12-20 parts of ammonium persulfate, reacting for 10-18h at 0-5 ℃, removing the solvent, washing and drying to prepare the polyaniline-barium ferrite-graphene electromagnetic shielding material.
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