CN113831599B - Magnetoelectric coupling type electromagnetic shielding film and preparation method and application thereof - Google Patents
Magnetoelectric coupling type electromagnetic shielding film and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electromagnetic shielding materials, and discloses a ternary composite conductive filler made of magnetic Fe3O4The nano particles are loaded on the surface of the silver nanowire intercalated graphene composite material to obtain the nano particles; discloses a magnetoelectric coupling type electromagnetic shielding film, which is formed by casting and drying slurry consisting of ternary composite conductive filler, polyvinyl alcohol and water; a process for preparing the magnetoelectric coupled electromagnetic shielding film includes such steps as in-situ synthesizing to coat polydopamine on the surface of one-dimensional silver nanowire to form a core-shell structure, compounding with laminated graphene to obtain the composite Ag nanowire-intercalated graphene material, and adding Fe3O4The nano particles are loaded on the surface of the composite material to obtain the ternary composite conductive filler, and then the ternary composite conductive filler is added into the polyvinyl alcohol aqueous solution and is subjected to casting to obtain the magnetoelectric coupling type electromagnetic shielding film. The magnetoelectric coupling type electromagnetic shielding film disclosed by the invention has good flexible electromagnetic shielding performance and has good application prospect in the field of flexible electromagnetic shielding.
Description
Technical Field
The invention relates to the technical field of electromagnetic shielding materials, in particular to a magnetoelectric coupling type electromagnetic shielding film, a preparation method and application thereof.
Background
The rapid development of modern electronic technology brings great convenience to social life and brings serious electromagnetic interference, the development trend of light weight and high integration of modern electronic equipment puts higher and higher requirements on electromagnetic shielding materials, and polymers play an important role in the field of electromagnetic shielding films due to unique characteristics such as viscoelasticity, corrosion resistance, good processing performance and the like.
The molecular chain of polyvinyl alcohol (PVA) contains a large number of hydroxyl groups, so that the PVA has good water solubility and film-forming property, has good compatibility with inorganic filler, belongs to an environment-friendly high polymer material, can be completely biodegraded in the environment, and cannot cause secondary pollution to the environment after being discarded. However, the polyvinyl alcohol has poor conductivity and is not beneficial to electromagnetic shielding, so that the electromagnetic shielding performance of the film can be obviously improved by mixing the conductive filler and the polyvinyl alcohol to form the conductivity of the polyvinyl alcohol matrix.
The one-dimensional silver nanowires have high conductivity and large length-diameter ratio, and can form a conductive network structure in a polymer matrix, so that the conductive network structure is beneficial to reflection, absorption and attenuation of electromagnetic waves, and the one-dimensional silver nanowires are widely applied to electromagnetic shielding materials. However, when silver nanowires are contacted with each other, huge contact resistance is generated, so that the conductivity is reduced, the application of the silver nanowires in electromagnetic shielding materials is severely limited, and the surface modification of the silver nanowires is expected to reduce the contact resistance of the silver nanowires. In addition, the impedance matching can greatly improve the shielding effectiveness of the electromagnetic shielding material, and when the impedance of the surface of the material is close to the characteristic impedance of the free space, the ideal optimal impedance matching is achieved, and the incident electromagnetic wave can enter the material as much as possible to be lost. The combination of the filler with high conductivity and stronger magnetism is expected to improve the electromagnetic performance and impedance matching characteristic of the conductive filler, thereby improving the electromagnetic shielding performance of the composite material.
Therefore, it is an urgent need to solve the problems in the art to provide a magnetoelectric coupling type electromagnetic shielding film and a method for preparing the same.
Disclosure of Invention
In view of the above, the invention provides a magnetoelectric coupling type electromagnetic shielding film, a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a ternary composite conductive filler, which is prepared from magnetic Fe3O4The nano particles are loaded on the surface of the silver nanowire intercalated graphene composite material to obtain the nano particles; the silver nanowire intercalated graphene composite material consists of graphene nanosheets and a core-shell composite material intercalated between the graphene nanosheets; the core-shell composite material is composed of one-dimensional silver nanowires and polydopamine coated on the surfaces of the one-dimensional silver nanowires.
The beneficial effects of the preferred technical scheme are as follows: the polydopamine is coated on the silver nanowires to form a core-shell structure, so that the contact resistance between the silver nanowires can be effectively reduced, and the conductivity of the material is increased; the modified silver nanowires are intercalated into graphene with excellent conductivity to form a multi-layer composite structure, so that the conductivity of the composite material is further improved; introduction of Fe3O4The impedance matching characteristic of the ternary composite conductive filler is enhanced by the nano particles.
The invention also provides a magnetoelectric coupling type electromagnetic shielding film which is obtained by casting and drying slurry, wherein the slurry comprises the ternary composite conductive filler, polyvinyl alcohol and water; the mass ratio of the silver nanowire intercalated graphene composite filler to the polyvinyl alcohol is less than or equal to 50%, and the mass ratio of the polyvinyl alcohol to the deionized water is 5-15%.
Preferably, the molecular weight of the polyvinyl alcohol is 10000-200000, and the alcoholysis degree is more than or equal to 98%.
The beneficial effects of the preferred technical scheme are as follows: the magnetoelectric coupling type electromagnetic shielding film disclosed by the invention adopts polyvinyl alcohol as a matrix, the polyvinyl alcohol film has good flexibility and mechanical strength, when the film is used as a shielding material, the film has little influence on external force action such as external stretching, compression, bending and the like, and a large amount of hydroxyl active groups in a polyvinyl alcohol molecular chain ensure that the film has good compatibility with the obtained conductive filler; the polydopamine-coated silver nanowires and the shell structure form a conductive network structure in a polyvinyl alcohol matrix, so that the reflection and absorption of electromagnetic waves in the material are promoted, and the electromagnetic shielding performance of the composite film is improved; the silver nanowires are intercalated into the layered graphene with good conductivity, so that gaps among graphene sheet layers are increased, an effective place is provided for multiple reflection of electromagnetic waves, and the attenuation of the electromagnetic waves is enhanced; introduction of magnetic particles Fe3O4The combination of the two layers is beneficial to the magnetic loss of electromagnetic waves, optimizes the impedance matching characteristic, further promotes the attenuation of the electromagnetic waves, and greatly improves the electromagnetic shielding performance of the film.
The preparation method of the magnetoelectric coupling type electromagnetic shielding film comprises the following steps:
(1) adding silver nanowires into a Tris-HCl buffer solution, uniformly stirring, adding dopamine hydrochloride, and reacting in a dark environment to obtain a mixed solution;
(2) adding graphene nanosheets into the mixed solution, continuing to react, then centrifugally separating out precipitates, and washing and drying the precipitates to obtain the silver nanowire intercalated graphene composite filler;
(3) the silver nanowire intercalation graphene composite filler and magnetic Fe3O4Adding the nano particles into deionized water, carrying out ultrasonic treatment, filtering and drying to obtain a ternary composite conductive filler;
(4) and adding the ternary composite conductive filler and polyvinyl alcohol into deionized water, reacting under the stirring condition until the polyvinyl alcohol is completely dissolved to obtain slurry, and carrying out tape casting and drying on the slurry to obtain the magnetoelectric coupling type electromagnetic shielding film.
The beneficial effects of the preferred technical scheme are as follows: the method comprises the steps of synthesizing polydopamine on the surface of a silver nanowire in situ to form a core-shell coating structure, then compounding the polydopamine with graphene to obtain a multilayer composite material, then loading Fe3O4 nanoparticles on the obtained composite material to obtain a conductive filler, and finally adding the conductive filler into a polyvinyl alcohol aqueous solution and carrying out casting to obtain the magnetoelectric coupling type electromagnetic shielding film. The obtained composite film is ensured to have good flexible electromagnetic shielding performance, and has good application prospect in the field of flexible electromagnetic shielding.
Preferably, the pH of the Tris-HCl buffer solution in the step (1) is 8.0-9.0, and the mass ratio of the silver nanowires to the dopamine hydrochloride to the Tris-HCl buffer solution is 1: (20-50): 2000; the stirring speed is 200-500 r/min; the reaction time is 5 hours, and the reaction temperature is 15-35 ℃.
The beneficial effects of the preferred technical scheme are as follows: the dopamine hydrochloride is enabled to be self-polymerized to form poly-dopamine to be coated on the silver nanowires, and the surfaces of the silver nanowires are functionalized to reduce the contact resistance between the silver nanowires.
Preferably, the mass ratio of the graphene nanosheets to the dopamine hydrochloride in the step (2) is (1-3): (2-5).
The beneficial effects of the preferred technical scheme are as follows: the graphene is grafted to the functionalized silver nanowire to form a graphene/functionalized silver nanowire composite structure, so that the conductivity of the composite filler is further improved. The graphene lamellar structure is introduced to be combined with a network structure formed by the functionalized silver nanowires, so that the absorption and attenuation of electromagnetic waves are facilitated.
Preferably, the reaction in the step (2) is carried out under the condition of keeping out of the sun, the reaction temperature is 15-35 ℃, and the reaction time is 1 h; the centrifugal rotating speed is more than 3000 rpm; the washing times are 5-8 times; the drying temperature is 60-80 ℃.
The beneficial effects of the preferred technical scheme are as follows: dopamine hydrochloride is extremely easy to oxidize when meeting light, and the oxidation of dopamine in the self-polymerization process can be improved through reaction in a light-shading environment; and removing the Tris-HCl buffer solution through centrifugation and washing to obtain the composite conductive filler.
Preferably, the silver nanowire intercalated graphene composite filler and the magnetic Fe in the step (3)3O4The ratio of the nano particles to the deionized water is 1: 2: (100-400);
the ultrasonic time is 1-2 h, and the ultrasonic power is 500W;
the aperture of the filter membrane used for filtering is 0.45 mu m; the drying temperature is 60-80 ℃.
The beneficial effects of the preferred technical scheme are as follows: magnetic Fe3O4The particles are loaded on the conductive silver nanowire intercalated graphene composite filler, so that the magnetic property of the conductive filler can be improved, the magnetic loss of electromagnetic waves can be increased, the impedance matching characteristic of the filler can be enhanced, the electromagnetic waves can be absorbed by the interior of the thin film more, and the electromagnetic shielding property of the thin film is further improved.
Preferably, the mass ratio of the ternary composite conductive filler, the polyvinyl alcohol and the deionized water in the step (4) is (2-5): 10: 100, respectively; the reaction temperature is 70-90 ℃, the rotating speed is less than 100r/min, and the time is 1-2 h;
the casting temperature is 70-80 ℃; the drying temperature is 40-50 ℃.
The beneficial effects of the preferred technical scheme are as follows: the water-soluble polyvinyl alcohol is used as a base material, and is compounded with the obtained magnetoelectric coupling type filler to obtain the polymer-based electromagnetic shielding film through tape casting, and the obtained film not only has good electromagnetic shielding performance, but also has excellent mechanical property and flexibility.
The invention also provides application of the magnetoelectric coupling type electromagnetic shielding film in flexible electromagnetic shielding.
According to the technical scheme, compared with the prior art, the invention discloses and provides the magnetoelectric coupling type electromagnetic shielding film, the preparation method and the application, and the magnetoelectric coupling type electromagnetic shielding film has the following beneficial effects:
(1) in the present inventionIn the disclosed ternary composite conductive filler, polydopamine containing rich active functional groups has good conductivity and firm adhesion to almost all types of surfaces, and is functionalized on the surfaces of silver nanowires, so that the polydopamine is coated on the silver nanowires to form a core-shell structure, the contact resistance among the silver nanowires can be effectively reduced, and the conductivity of the material is increased; the modified silver nanowires are intercalated into graphene with excellent conductivity to form a multi-layer composite structure, so that the conductivity of the composite material is further improved; introduction of Fe3O4The nano particles enhance the impedance matching characteristic of the composite filler, so that the impedance of the surface of the material is close to the characteristic impedance of a free space, the ideal optimal impedance matching is achieved, and incident electromagnetic waves enter the material as much as possible to be lost; simultaneously introducing graphene with high conductivity and Fe with stronger magnetism3O4The conductivity, magnetism and impedance matching characteristics of the conductive filler can be improved, and the electromagnetic shielding performance of the composite material is further improved.
(2) The magnetoelectric coupling type electromagnetic shielding film disclosed by the invention has flexibility and electromagnetic shielding performance, and has good electromagnetic shielding property in an X wave band. The polyvinyl alcohol is used as a matrix, so that the flexibility and the mechanical strength are good, when the shielding material is used as a shielding material, the influence on external force action such as external stretching, compression, bending and the like is small, and a large number of hydroxyl active groups in a polyvinyl alcohol molecular chain enable the polyvinyl alcohol molecular chain to have good compatibility with the obtained conductive filler; the polydopamine-coated silver nanowire and the shell structure form a conductive network structure in a polyvinyl alcohol matrix, so that the reflection and absorption of electromagnetic waves in the material are promoted, and the electromagnetic shielding performance of the composite film is improved; the silver nanowires are intercalated into the layered graphene with good conductivity, so that gaps among graphene sheet layers are increased, an effective place is provided for multiple reflection of electromagnetic waves, and the attenuation of the electromagnetic waves is enhanced; introduction of magnetic particles Fe3O4The combination of the two layers is beneficial to the magnetic loss of electromagnetic waves, optimizes the impedance matching characteristic, further promotes the attenuation of the electromagnetic waves, and greatly improves the electromagnetic shielding performance of the film.
(3) The preparation method disclosed by the invention adopts an in-situ polymerization method to perform surface modification on the silver nanowires to obtain a polydopamine-coated silver nanowire core-shell structure, then intercalates the silver nanowires in graphene nanosheets to form a multilayer composite structure, and then intercalates Fe3O4The nano particles are loaded on the obtained composite material to obtain the high-performance ternary composite conductive filler. The whole method has simple step operation, mild reaction process and easy control, and is beneficial to industrialized popularization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is an SEM picture of a core-shell structure of a poly-dopamine coated silver nanowire.
FIG. 2 is Fe3O4SEM picture of/graphene/modified silver nanowire ternary composite conductive filler.
Fig. 3 shows electromagnetic shielding effectiveness of the magnetoelectric coupling type electromagnetic shielding film prepared based on example 5 in the X band.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a ternary composite conductive filler which is prepared from magnetic Fe3O4The nano particles are loaded on the surface of the silver nanowire intercalated graphene composite material to obtain the nano particles; the silver nanowire intercalation graphene composite material is prepared from graphene nanosheets and graphene nanoparticlesCore-shell composite material intercalated between the sheets; the core-shell composite material consists of one-dimensional silver nanowires and polydopamine coated on the surfaces of the one-dimensional silver nanowires.
The invention also provides a magnetoelectric coupling type electromagnetic shielding film which is obtained by casting and drying slurry, wherein the slurry comprises the ternary composite conductive filler, polyvinyl alcohol and water; the mass ratio of the silver nanowire intercalated graphene composite filler to the polyvinyl alcohol is less than or equal to 50%, and the mass ratio of the polyvinyl alcohol to the deionized water is 5-15%. Wherein the molecular weight of the polyvinyl alcohol is 10000-200000, and the alcoholysis degree is more than or equal to 98%.
The preparation method of the magnetoelectric coupling type electromagnetic shielding film comprises the following steps:
(1) adding silver nanowires into a Tris-HCl buffer solution, uniformly stirring, adding dopamine hydrochloride, and reacting in a dark environment to obtain a mixed solution; the pH value of the Tris-HCl buffer solution is 8.0-9.0, and the mass ratio of the silver nanowires to the dopamine hydrochloride to the Tris-HCl buffer solution is 1: (20-50): 2000; the stirring speed is 200-500 r/min; the reaction time is 5h, and the reaction temperature is 15-35 ℃;
(2) according to the mass ratio of the graphene nanosheets to the dopamine hydrochloride of (1-3): (2-5) adding graphene nanosheets into the mixed solution, continuing to react for 1h, then centrifugally separating out precipitates, washing and drying the precipitates to obtain the silver nanowire intercalated graphene composite filler; the reaction is carried out under the condition of keeping out of the sun, the temperature of the reaction is 15-35 ℃, and the reaction time is 1 h; the centrifugal rotating speed is more than 3000 rpm; the washing times are 5-8 times; the drying temperature is 60-80 ℃;
(3) the silver nanowire intercalation graphene composite filler and magnetic Fe3O4Adding the nano particles into deionized water, carrying out ultrasonic treatment for 1-2 h, filtering (by adopting a filter membrane with the aperture of 0.45 mu m), and drying to obtain a ternary composite conductive filler; wherein, the silver nanowire intercalation graphene composite filler and the magnetic Fe3O4The ratio of the nano particles to the deionized water is 1: 2: (100-400); the power of the ultrasonic wave is 500W; filtering with a micro-nano filter membrane; drying at a temperature of60～80℃；
(4) The weight ratio of the ternary composite conductive filler to the polyvinyl alcohol to the deionized water is (2-5): 10: adding the ternary composite conductive filler and polyvinyl alcohol into deionized water, stirring and reacting until the polyvinyl alcohol is completely dissolved to obtain slurry, and carrying out tape casting and drying on the slurry to obtain the magnetoelectric coupling type electromagnetic shielding film; wherein the stirring reaction temperature is 70-90 ℃, the rotating speed is less than 100r/min, and the time is 1-2 h; the casting temperature is 70-80 ℃; the drying temperature is 40-50 ℃.
Example 1
The embodiment 1 of the invention provides a preparation method of a magnetoelectric coupling type electromagnetic shielding film, which specifically comprises the following steps:
(1) dissolving 5g of Tris (hydroxymethyl) aminomethane in 100mL of deionized water, and then dropwise adding 0.1mol/L hydrochloric acid to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution;
(2) adding 100mg of silver nanowires into Tris-HCl buffer solution, uniformly stirring at the rotating speed of 300r/min, and then adding 3g of dopamine hydrochloride to react for 5 hours in a dark environment at room temperature to obtain a mixed solution;
(3) adding 2g of graphene nanosheets into the obtained mixed solution, continuously reacting for 1h, then centrifugally separating out precipitates, washing the precipitates for 5 times by using deionized water, and drying at 80 ℃ to obtain the modified silver nanowire intercalated graphene composite filler;
(4) the obtained silver nanowire intercalation graphene composite filler and Fe3O4Carrying out ultrasonic treatment on the nanoparticles in deionized water at a mass ratio of 1:2 for 1h at a power of 500W, filtering (by using a filter membrane with a pore diameter of 0.45 mu m), and drying (at a drying temperature of 80 ℃) to obtain a ternary composite conductive filler;
(5) adding 2g of ternary composite conductive filler and 10g of polyvinyl alcohol into 100g of deionized water, reacting at 80 ℃ at a stirring speed of 100r/min for 2h until the polyvinyl alcohol is completely dissolved, casting at room temperature, and drying at 45 ℃ to obtain the magnetoelectric coupling type electromagnetic shielding film.
Example 2
The embodiment 2 of the invention provides a preparation method of a magnetoelectric coupling type electromagnetic shielding film, which specifically comprises the following steps:
(1) dissolving 5g of Tris (hydroxymethyl) aminomethane in 100mL of deionized water, and then dropwise adding 0.1mol/L hydrochloric acid to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution;
(2) adding 100mg of silver nanowires into Tris-HCl buffer solution, uniformly stirring at the rotating speed of 300r/min, and then adding 3g of dopamine hydrochloride to react for 5 hours in a dark environment at room temperature to obtain a mixed solution;
(3) adding 2g of graphene nanosheets into the obtained mixed solution, continuously reacting for 1h, then centrifugally separating out precipitates, washing the precipitates for 5 times by using deionized water, and drying at 80 ℃ to obtain the silver nanowire intercalated graphene composite filler;
(4) the obtained silver nanowire intercalation graphene composite filler and Fe3O4Carrying out ultrasonic treatment on the nanoparticles in deionized water at a mass ratio of 1:2 for 1h at a power of 500W, filtering (by using a filter membrane with a pore diameter of 0.45 mu m), and drying (at a drying temperature of 80 ℃) to obtain a ternary composite conductive filler;
(5) adding 4g of ternary composite conductive filler and 10g of polyvinyl alcohol into 100g of deionized water, reacting at 80 ℃ at a stirring speed of 100r/min for 2h until the polyvinyl alcohol is completely dissolved, casting at room temperature, and drying at 45 ℃ to obtain the magnetoelectric coupling type electromagnetic shielding film.
Example 3
Embodiment 3 of the present invention provides a method for preparing a magnetoelectric coupling type electromagnetic shielding film, which specifically includes the following steps:
(1) dissolving 5g of Tris (hydroxymethyl) aminomethane in 100mL of deionized water, and then dropwise adding 0.1mol/L hydrochloric acid to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution;
(2) adding 100mg of silver nanowires into Tris-HCl buffer solution, uniformly stirring at the rotating speed of 300r/min, and then adding 3g of dopamine hydrochloride to react for 5 hours in a dark environment at room temperature to obtain a mixed solution;
(3) adding 2g of graphene nanosheets into the obtained mixed solution, continuously reacting for 1h, then centrifugally separating out precipitates, washing the precipitates for 5 times by using deionized water, and drying at 80 ℃ to obtain the silver nanowire intercalated graphene composite filler;
(4) the obtained silver nanowire intercalation graphene composite filler and Fe3O4Carrying out ultrasonic treatment on the nanoparticles in deionized water at a mass ratio of 1:2 for 1h at a power of 500W, filtering (by using a filter membrane with a pore diameter of 0.45 mu m), and drying (at a drying temperature of 80 ℃) to obtain a ternary composite conductive filler;
(5) adding 6g of ternary composite conductive filler and 10g of polyvinyl alcohol into 100g of deionized water, reacting at 80 ℃ at a stirring speed of 100r/min for 2h until the polyvinyl alcohol is completely dissolved, casting at room temperature, and drying at 45 ℃ to obtain the magnetoelectric coupling type electromagnetic shielding film.
Example 4
Embodiment 4 of the present invention provides a method for preparing a magnetoelectric coupling type electromagnetic shielding film, which specifically includes the following steps:
(1) dissolving 5g of Tris (hydroxymethyl) aminomethane in 100mL of deionized water, and then dropwise adding 0.1mol/L hydrochloric acid to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution;
(2) adding 100mg of silver nanowires into Tris-HCl buffer solution, uniformly stirring at the rotating speed of 300r/min, and then adding 3g of dopamine hydrochloride to react for 5 hours in a dark environment at room temperature to obtain a mixed solution;
(3) adding 3g of graphene nanosheets into the obtained mixed solution, continuously reacting for 1h, then centrifugally separating out precipitates, washing the precipitates for 5 times by using deionized water, and drying at 80 ℃ to obtain the silver nanowire intercalated graphene composite filler;
(4) the obtained silver nanowire intercalation graphene composite filler and Fe3O4Carrying out ultrasonic treatment on the nano particles in deionized water at a mass ratio of 1:2 for 1h at a power of 500W, filtering (by adopting a filter membrane with the aperture of 0.45 mu m), and drying (at a drying temperature of 80 ℃) to obtain a ternary composite conductive filler;
(5) adding 6g of ternary composite conductive filler and 10g of polyvinyl alcohol into 100g of deionized water, reacting at 80 ℃ at a stirring speed of 100r/min for 2h until the polyvinyl alcohol is completely dissolved, casting at room temperature, and drying at 45 ℃ to obtain the magnetoelectric coupling type electromagnetic shielding film.
Example 5
Embodiment 5 of the present invention provides a method for preparing a magnetoelectric coupling type electromagnetic shielding film, which specifically includes the following steps:
(1) dissolving 5g of Tris (hydroxymethyl) aminomethane in 100mL of deionized water, and then dropwise adding 0.1mol/L hydrochloric acid to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution;
(2) adding 100mg of silver nanowires into Tris-HCl buffer solution, uniformly stirring at the rotating speed of 300r/min, and then adding 3g of dopamine hydrochloride to react for 5 hours in a dark environment at room temperature to obtain a mixed solution;
(3) adding 4g of graphene nanosheets into the obtained mixed solution, continuously reacting for 1h, then centrifugally separating out precipitates, washing the precipitates for 5 times by using deionized water, and drying at 80 ℃ to obtain the silver nanowire intercalated graphene composite filler;
(4) silver nanowire intercalation graphene composite filler and Fe3O4Carrying out ultrasonic treatment on the nanoparticles in deionized water at a mass ratio of 1:2 for 1h at a power of 500W, filtering (by using a filter membrane with a pore diameter of 0.45 mu m), and drying (at a drying temperature of 80 ℃) to obtain a ternary composite conductive filler;
(5) adding 6g of ternary composite conductive filler and 10g of polyvinyl alcohol into 100g of deionized water, reacting at 80 ℃ at a stirring speed of 100r/min for 2h until the polyvinyl alcohol is completely dissolved, casting at room temperature, and drying at 45 ℃ to obtain the magnetoelectric coupling type electromagnetic shielding film.
Effect verification
1. The micro morphology of the polydopamine-coated silver nanowire is characterized by adopting a Zeiss scanning electron microscope SIGMA300, the core-shell composite material of the polydopamine-coated silver nanowire prepared in the example 1 is detected, and an SEM picture is obtained and is shown in figure 1.
2. The micro-morphology of the ternary composite conductive filler is characterized by a Zeiss scanning electron microscope SIGMA300, the ternary composite conductive filler prepared in example 2 is detected, and the obtained SEM picture is shown in figure 2.
3. The vector network analyzer CEYEAR3672A-S was used to test the electromagnetic shielding performance of the magnetoelectric coupling type electromagnetic shielding film, and the electromagnetic shielding performance in the X band was tested using the magnetoelectric coupling type electromagnetic shielding film prepared in example 5, and the results are shown in fig. 3.
From the above results, it can be known that the functionalized nanocomposite electromagnetic shielding film prepared in example 5 has excellent electromagnetic shielding performance in the X-band, and the shielding performance can reach as high as 43 dB.
4. The electromagnetic shielding performance of the magnetoelectric coupling type electromagnetic shielding films obtained in examples 1 to 5 in the X band was measured, and the results are shown in table 1.
TABLE 1 average shielding effectiveness of the electromagnetic shielding film obtained in the example in X-band
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The ternary composite conductive filler is characterized by comprising magnetic Fe3O4The nano particles are loaded on the surface of the silver nanowire intercalated graphene composite material to obtain the nano particles; the silver nanowire intercalated graphene composite material is prepared from graphene nanoThe graphene nano-sheets are intercalated by core-shell composite materials; the core-shell composite material is composed of one-dimensional silver nanowires and polydopamine coated on the surfaces of the one-dimensional silver nanowires.
2. A magnetoelectric coupling type electromagnetic shielding film is characterized by being obtained by casting and drying slurry, wherein the slurry comprises the ternary composite conductive filler according to claim 1, polyvinyl alcohol and water; the mass ratio of the silver nanowire intercalated graphene composite filler to the polyvinyl alcohol is less than or equal to 50%, and the mass ratio of the polyvinyl alcohol to the deionized water is 5-15%.
3. The magnetoelectric coupling type electromagnetic shielding film according to claim 2, wherein the polyvinyl alcohol has a molecular weight of 10000 to 200000 and an alcoholysis degree of 98% or more.
4. A method for preparing a magnetoelectric coupling type electromagnetic shielding film according to claim 2 or 3, comprising the steps of:
(1) adding silver nanowires into a Tris-HCl buffer solution, uniformly stirring, adding dopamine hydrochloride, and reacting in a dark environment to obtain a mixed solution;
(2) adding graphene nanosheets into the mixed solution, continuing to react, then centrifugally separating out precipitates, and washing and drying the precipitates to obtain the silver nanowire intercalated graphene composite filler;
(3) the silver nanowire intercalation graphene composite filler and magnetic Fe3O4Adding the nano particles into deionized water, carrying out ultrasonic treatment, filtering and drying to obtain a ternary composite conductive filler;
(4) and adding the ternary composite conductive filler and polyvinyl alcohol into deionized water, reacting under the stirring condition until the polyvinyl alcohol is completely dissolved to obtain slurry, and carrying out tape casting and drying on the slurry to obtain the magnetoelectric coupling type electromagnetic shielding film.
5. The method for preparing the magnetoelectric coupling type electromagnetic shielding film according to claim 4, wherein the pH of the Tris-HCl buffer solution in the step (1) is 8.0 to 9.0, and the mass ratio of the silver nanowires to the dopamine hydrochloride to the Tris-HCl buffer solution is 1: (20-50): 2000; the stirring speed is 200-500 r/min; the reaction time is 5 hours, and the reaction temperature is 15-35 ℃.
6. The preparation method of the magnetoelectric coupling type electromagnetic shielding film according to claim 4, wherein the mass ratio of the graphene nanoplatelets to the dopamine hydrochloride in step (2) is (1-3): (2-5).
7. The preparation method of the magnetoelectric coupling type electromagnetic shielding film according to claim 4 or 6, wherein the reaction in the step (2) is carried out under a dark condition, the temperature of the reaction is 15 to 35 ℃, and the reaction time is 1 hour; the centrifugal rotating speed is more than 3000 rpm; the washing times are 5-8 times; the drying temperature is 60-80 ℃.
8. The method for preparing the magnetoelectric coupling type electromagnetic shielding film according to claim 4, wherein the silver nanowire intercalation graphene composite filler and magnetic Fe in the step (3)3O4The mass ratio of the nano particles to the deionized water is 1: 2: (100-400);
the ultrasonic time is 1-2 h, and the ultrasonic power is 500W;
the aperture of the filter membrane used for filtering is 0.45 mu m; the drying temperature is 60-80 ℃.
9. The preparation method of the magnetoelectric coupling type electromagnetic shielding film according to claim 4, wherein the mass ratio of the ternary composite conductive filler, the polyvinyl alcohol and the deionized water in step (4) is (2-5): 10: 100, respectively; the reaction temperature is 70-90 ℃, the rotating speed is less than 100r/min, and the time is 1-2 h; the casting temperature is 70-80 ℃; the drying temperature is 40-50 ℃.
10. Use of the magnetoelectric coupling type electromagnetic shielding film according to claim 2 or 3 in flexible electromagnetic shielding.
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