CN109320286B - Magnetic graphene-based aerogel material with ordered structure and preparation method thereof - Google Patents
Magnetic graphene-based aerogel material with ordered structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnetic graphene-based aerogel material with an ordered structure and a preparation method thereof, and belongs to the technical field of new materials. The preparation method takes the magnetic polymer nanofiber as a regulation factor, and forms a three-dimensional network structure in which the magnetic polymer nanofiber and graphene sheet layers are orderly crosslinked and oriented by an ice template method and a magnetic field orientation technology and a directional freezing technology, so that the structural construction of the magnetic graphene-based aerogel material with ordered microstructure is realized. The graphene aerogel material with the ordered structure is expected to be applied to devices with sensing, driving and other functions in a force field, an electric field, a magnetic field or a complex field.
Description
Technical Field
The invention relates to a graphene aerogel material, belongs to the technical field of new materials, and particularly relates to a magnetic graphene-based aerogel material with an ordered structure and a preparation method thereof.
Background
The graphene is represented by sp2Two-dimensional flakes composed of hybridized carbon atoms having a honeycomb structure and only a single atomic layer thickness. The aerogel material is a three-dimensional porous material with low density and high specific surface area, which is obtained by adopting a special process to replace liquid in wet gel with gas and not changing the structure and volume of a gel network significantly. The existing graphene aerogel is mainly applied to the fields of catalysis, adsorption, heat insulation, energy conversion and the like, and the characteristics of excellent electrical property of graphene and high specific surface area of the aerogel are fully utilized. But because there is surface tension in the preparation process of graphite alkene aerogel because graphite alkene aquogel skeleton internal solvent, can take place the collapse and the structural failure of skeleton under the drying, lead to inside three-dimensional space structure of graphite alkene aerogel can't obtain effective control, the graphite alkene aerogel performance of preparing simultaneously confines electrochemical performance and adsorption efficiency to, makes the application of graphite alkene aerogel obtain the restriction. Therefore, the regulation and control and the functionalization of the structure are simultaneously realized in the preparation process of the graphene-based aerogel, which is a bottleneck restricting the development of the graphene-based aerogel material. For example: chinese invention patent application (application publication No. CN106006615A, application publication No. 2016-10-12) discloses a preparation method of natural drying of graphene aerogel. The invention provides a preparation method for preparing graphene aerogel by mixing a graphene oxide solution and borax by using ethylenediamine as a reducing agent and then naturally drying. The invention utilizes borate crosslinking to improve the rigidity of the aerogel and reduce the capillary force in the drying process. The preparation method is simple and easy to control, and the obtained graphene aerogel is excellent in mechanical property, low in production cost and easy to produce in batches. However, the method is greatly influenced by external natural conditions, needs a relatively stable and appropriate external environment, and is difficult to effectively popularize and apply nationwide or globally. Meanwhile, the aerogel does not show good electrical properties and has limitations in application.
The Chinese invention patent application (application publication No. CN106044752A, application publication No. 2016-10-26) discloses a preparation method of a high-orientation graphene aerogel: placing the graphene or graphene oxide dispersion liquid in a container with an electrode, obtaining the highly oriented graphene or graphene oxide dispersion liquid by an external electric field orientation method, continuously maintaining the action of an electric field, freezing and solidifying in liquid nitrogen, and obtaining the highly oriented graphene aerogel after freeze drying or supercritical drying. The method induces the graphene sheet layers to generate orientation arrangement through the action of an electric field, has higher requirements on the quality of the prepared graphene sheet layers, and cannot be effectively applied to materials with non-conductivity or poor conductivity.
The Chinese invention patent application (application publication No. CN103977748A, application publication No. 2015-10-28) discloses a magnetic graphene-based aerogel material and a preparation method thereof: the preparation method comprises the steps of loading ferroferric oxide magnetic nanoparticles by taking graphene oxide as a carrier, enhancing the form stability of the ferroferric oxide magnetic nanoparticles by taking a carbon nano tube as a framework or by means of calcium ion crosslinking, and obtaining graphene oxide magnetic aerogel through freeze drying to obtain graphene magnetic graphene-based aerogel, wherein the internal structure of the obtained magnetic graphene-based aerogel presents an irregular distribution state, so that various performances of the obtained magnetic graphene-based aerogel are poor.
The Chinese invention patent application (application publication No. CN107140620A, application publication No. 2017-09-08) discloses a preparation method of a magnetic graphene-based aerogel, which comprises the following steps: the preparation method comprises the steps of crosslinking dopamine modified graphene oxide with iron ions, heating and reducing to self-assemble a three-dimensional graphene hydrogel structure, and carrying out freeze drying and heat treatment to reduce to obtain the magnetic graphene-based aerogel material. The method is complex in preparation process and single in type of magnetic factors, effective application effects cannot be achieved aiming at different magnetic factors, and the prepared magnetic graphene-based aerogel material is single in function.
The graphene aerogel has the characteristics of large specific surface area and high porosity, and is effectively applied to the field of adsorption, for example, Chinese invention patent application (application publication number is CN106006616A, application publication date is 2016-10-12) discloses a preparation method of the graphene aerogel with high adsorption performance. The graphene aerogel is prepared by reducing graphene oxide by using ammonia borane and ferrous sulfate in a matching manner. The invention utilizes ammonia borane and ferrous sulfate to accelerate the reduction speed of the constant-temperature hydrothermal reaction, and has the advantages of simple and convenient operation, simple preparation method and high adsorption effect on fuel rhodamine B. Although the invention has better adsorbability for dye (rhodamine B), the invention has no verification on the adsorbability of other kinds of dyes, pigments and other pollutants, and the good adsorbability cannot be ensured.
The Chinese invention patent application (application publication No. CN 106006620A, application publication No. 2016-10-12) discloses a preparation method of graphene oxide and graphene aerogel. The method utilizes an improved Hummer method to synthesize the graphene oxide solution and the graphene aerogel, and can be effectively applied to the environment. The graphene aerogel prepared by the method has good adsorption characteristics on hydrophilic pollutants (rhodamine B) and hydrophobic pollutants. However, the preparation process of the method is complicated, the condition requirements are strict, the requirements on various parameters are high when the sample is processed, the batch production and production cost are limited, and the method is difficult to effectively popularize in the aspect of industrialization.
In addition, the aerogel has good application prospect in the field of heat insulation due to the excellent heat insulation performance and the heat resistance of the graphene, for example, Chinese patent application (application publication number is CN105923641A, application publication date: 2017-05-03) discloses a preparation method of a high-temperature-resistant, antioxidant and heat-conductive alumina/graphene foam composite material. The aluminum oxide/graphene aerogel is prepared by compounding aluminum oxide powder and graphene aerogel in a solvent and then freezing and drying. The prepared composite material is ablated for 5 hours at 800 ℃ in an air environment, the thermal weight loss is lower than 60%, and the thermal conductivity is higher than 9W/m.K. However, the method for preparing the graphene aerogel material is complex, and the prepared graphene aerogel material has a loose structure and is fragile and difficult to realize the value because no cross-linking agent or supporting material is provided and only inorganic ions are provided.
In summary, there is no report in the prior art on a magnetic graphene-based aerogel material with ordered and controllable internal microstructure.
Disclosure of Invention
In order to solve the technical problems, the invention provides a magnetic graphene-based aerogel material with an ordered structure and a preparation method thereof. According to the preparation method, the graphene sheet layers are coated on the surfaces of the magnetic nanofibers and are processed by a magnetic field orientation technology and an oriented freezing technology, the graphene sheet layers coated with the magnetic polymer nanofibers are directionally arranged under the action of magnetic field force, and are continuously directionally arranged along the growth direction of ice crystals in the oriented freezing process to form an obvious ordered three-dimensional frame structure, and finally anisotropy and functionalization of the microstructure of the graphene aerogel are realized.
In order to achieve the purpose, the invention discloses a magnetic graphene-based aerogel material with an ordered structure, wherein the internal structure of the magnetic graphene-based aerogel material is a three-dimensional network structure formed by ordered crosslinking and oriented arrangement of magnetic polymer nanofibers and graphene sheet layers, and the physical properties of the magnetic graphene-based aerogel material have anisotropic characteristics in different macroscopic physical directions.
Specifically, the ordered crosslinking means that the graphene sheet layer and the magnetic polymer nanofiber are regularly interconnected through the action of a crosslinking agent to form a continuous graphene large sheet layer and a magnetic polymer nanofiber bundle, and the graphene sheet layer and the magnetic polymer nanofiber are interconnected to form a complete and continuous structural system.
Specifically, the orientation arrangement refers to inducing the magnetic polymer nanofibers to generate orientation arrangement along the magnetic field direction by an electromagnetic field orientation technology, and the magnetic polymer nanofibers drive the graphene sheet layers to generate orientation arrangement in the internal space to jointly form an orientation arrangement three-dimensional network structure.
Specifically, the orientation arrangement of the magnetic polymer nanofiber and the graphene sheet layer in the internal microstructure of the magnetic graphene-based aerogel material can be directional arrangement, partially ordered arrangement, gradient arrangement or gradient arrangement.
Specifically, the orientation arrangement mode is to control an external condition to induce graphene sheet layers or magnetic polymer nanofibers to be arranged in a certain direction, and the orientation of the graphene sheet layers and the orientation of the magnetic polymer nanofibers do not need to be kept the same.
Specifically, the partially ordered arrangement mode means that the internal structure is a locally ordered structure, and can be that single component materials in a graphene sheet layer and a magnetic polymer nanofiber bundle are ordered or that disordered regions exist in the whole range, and the order degree of the disordered regions is lower than that of the oriented arrangement. Meanwhile, compared with the directional arrangement, the requirement on external induction conditions is lower, and the experimental process is more convenient.
Specifically, the gradient arrangement mode or the gradual change arrangement mode means that the graphene sheet layer and the magnetic polymer nanofiber have the same or different characteristics of change trend and rule characteristic such as size, thickness, content, arrangement direction, arrangement angle, connection mode and the like.
Further, the difference of the electromagnetic field orientation treatment and the difference of the orientation freezing treatment can regulate and control the internal microstructure of the magnetic graphene-based aerogel material to be arranged in a specific rule, so that the magnetic graphene-based aerogel can be endowed with the anisotropic characteristics of the physical properties in different macroscopic physical directions.
Specifically, the physical properties with anisotropic properties mainly include mechanical properties, electrical conductivity, magnetic properties, and the like.
Specifically, the anisotropic property of the mechanical property of the magnetic graphene-based aerogel means that the mechanical properties of the graphene sheet layer and the magnetic polymer nanofiber, such as compressive stress, elastic modulus, compressive recovery rate, compressive cycle stability and the like, are differentiated in different directions, such as radial direction, axial direction and the like, due to the different arrangement modes of the graphene sheet layer and the magnetic polymer nanofiber.
Specifically, the anisotropic property of the conductivity of the magnetic graphene-based aerogel means that electrons are mainly transmitted by virtue of the graphene sheet layer due to the large difference in conductivity between the graphene sheet layer and the magnetic polymer nanofibers, so that the magnetic graphene-based aerogel has the characteristic of differentiating electrical properties such as conductivity, electron transmission speed and the like in different directions such as the radial direction, the axial direction and the like according to the difference in arrangement modes, angles and the like between the graphene sheet layer and the magnetic polymer nanofibers.
Specifically, the anisotropic property of the magnetic graphene-based aerogel means that the magnetic nanofibers are subjected to orientation treatment by an external electromagnetic field and then are oriented and arranged along the direction of the magnetic field, and the internal magnetic nanofibers can present different arrangement modes according to the direction of the external electromagnetic field and different treatment modes and conditions, so that the magnetic graphene-based aerogel presents the characteristic of differentiation of the magnetic property along the direction of the magnetic field and the direction of a non-magnetic field.
Further, the magnetic polymer nanofiber is a nanofiber regulated and controlled by a magnetic factor, and the magnetic factor is one of strontium ferrite, nickel ferrite, cobalt ferrite, ferroferric oxide or iron cobalt nickel metal.
Further, the magnetic graphene-based aerogel material comprises the following components in percentage by mass: 90-50% of graphene, 25-5% of magnetic polymer nano-fiber and 25-5% of PVA.
In order to better realize the technical purpose of the invention, the invention discloses a preparation method of a magnetic graphene-based aerogel material with an ordered structure, which comprises the following steps:
1) mixing the polymer nanofiber master batch with the magnetic polymer nanoparticles subjected to demagnetization treatment, and performing melt extrusion, emulsification and shearing to obtain a magnetic polymer nanofiber dispersion liquid;
2) uniformly mixing the magnetic polymer nanofiber dispersion liquid, the graphene oxide aqueous solution and the PVA (polyvinyl alcohol) aqueous solution to obtain a mixed solution, placing the mixed solution in an electromagnetic field for standing and carrying out directional treatment, carrying out directional freezing treatment on the mixed solution subjected to the directional treatment of the electromagnetic field by using liquid nitrogen, and continuously freezing and drying to obtain the magnetic graphene oxide aerogel with an orderly-arranged internal microstructure;
3) and (3) placing the magnetic graphene oxide aerogel in a hydrazine hydrate atmosphere under a closed condition for gas-phase reduction treatment to obtain the magnetic graphene-based aerogel.
Preferably, the ordered arrangement of the internal microstructure in step 2) includes gradient arrangement, partial ordered arrangement or directional arrangement.
Further, the intensity of the electromagnetic field in the step 2) is 0.01-2T, and the direction of the magnetic field is in the vertical direction or the horizontal direction.
Specifically, the magnetic field orientation technology provides a magnetic field force effect by using an electromagnetic field, drives a magnetic factor to generate directional movement under the magnetic field force effect, and further drives the polymer nanofiber and the graphene sheet layer to generate ordered arrangement. And the arrangement direction and the arrangement form of the polymer nanofibers can be controlled by adjusting the angle of the magnetic field, and the final magnetic size of the magnetic graphene-based aerogel can be controlled by adjusting the magnetic field intensity, the orientation time, the frequency and the like.
Further, the directional freezing treatment in the step 2) is as follows: the freezing angle is 0-90 degrees, and the freezing time is 0.5-2 hours.
Specifically, the directional freezing technology can be used for quickly and effectively fixing and strengthening the ordered arrangement of the oriented structures under the action of an external magnetic field, so that the ordered three-dimensional frame structure in the graphene aerogel is further strengthened. And various ordered structures can be obtained by adjusting the directional freezing angle, so that the anisotropy of the graphene aerogel structure is realized.
Further, the freeze-drying in step 2) is: the freezing temperature is-20 ℃ to-80 ℃, the freezing time is 12-72 hours, and the drying time is 20-90 hours.
Further, the magnetic factor in the magnetic polymer nanoparticles is one of strontium ferrite, nickel ferrite, cobalt ferrite, ferroferric oxide or iron-cobalt-nickel metal.
Further, the graphene oxide aqueous solution is prepared by a modified Hummers method. The specific preparation process is as follows:
adding potassium persulfate and phosphorus pentoxide into concentrated sulfuric acid, stirring and dispersing uniformly, heating to 80 ℃, adding natural graphite powder, carrying out heat preservation reaction to obtain pre-oxidized graphene, continuing to add concentrated sulfuric acid and potassium permanganate into the pre-oxidized graphene, heating to 45 ℃, carrying out heat preservation reaction, slowly adding deionized water after the process is finished until no gas is discharged, heating to 95 ℃, continuing to carry out heat preservation reaction, transferring the reaction solution into deionized water, stirring vigorously, dropwise adding hydrogen peroxide after the reaction solution is cooled until no color change and no gas are generated in the reaction solution, washing the sample to be neutral by sequentially adopting a dilute hydrochloric acid solution with the mass fraction of 10% and deionized water, and preparing into a uniformly dispersed graphene oxide aqueous solution with the concentration of 1-15 mg/mL for later use.
Preferably, the concentration of the graphene oxide aqueous solution is 1-15 mg/mL.
Preferably, the PVA solution is 0.5 to 5 mass percent.
Further, the polymer nanofiber master batch is made of at least one of PVA-co-PE (ethylene vinyl alcohol copolymer), POE (polyolefin elastomer), PA6 (nylon 6), PA66 (nylon 66), PET (polyethylene terephthalate) or PPT (polytrimethylene terephthalate).
Further, the conditions for carrying out the gas phase reduction treatment in the hydrazine hydrate atmosphere are as follows: the reduction temperature is 50-90 ℃, and the reduction time is 1-6 hours.
Specifically, the reduction method has the advantages that after the magnetic graphene oxide aerogel with the ordered structure is obtained through directional treatment, hydrazine hydrate can fully enter the interior of the magnetic graphene oxide aerogel and fully contact the magnetic graphene oxide aerogel under the gas phase condition because the magnetic graphene oxide aerogel has extremely high porosity and specific surface area, the graphene oxide lamella is effectively reduced, and the electrical conductivity is enhanced on the basis of not influencing the structure and the mechanical property of the graphene oxide aerogel.
Further, the magnetic polymer nanofiber is prepared by dissolving polymer nanofiber master batches in an alcohol-water system, heating and dissolving, then adding magnetic polymer nanoparticles subjected to demagnetization treatment, stirring and mixing, precipitating and separating out, shearing and dispersing to obtain composite particles, then mixing the composite particles with cellulose acetate butyrate, and carrying out melt extrusion, emulsification, shearing and other steps to obtain the uniformly dispersed magnetic polymer nanofiber dispersion.
The beneficial effects of the invention are mainly embodied in the following aspects:
1. the polymer nanofiber is endowed with magnetism, the graphene sheet layers coated with the magnetic polymer nanofiber are driven to be directionally arranged by utilizing the induction of a magnetic factor to a magnetic field, the fixing and the strengthening of an oriented structure are realized in the directional freezing process, and the formed graphene aerogel with the directionally arranged internal microstructure has a wide application prospect in the field of aerogel materials;
2. the preparation method provided by the invention can realize independent or coexisting structure systems of multiple ordered structures such as gradient arrangement, partial ordered arrangement, oriented arrangement and the like of the internal microstructure of the graphene aerogel through regulating and controlling processing conditions such as magnetic field intensity, magnetic field direction, oriented freezing angle and the like on the basis of realizing the ordered structures, and lays a foundation for preparing the magnetic controllable graphene aerogel with good mechanical properties.
Drawings
FIG. 1 is an SEM image of magnetic polymer nanofibers prepared according to the present invention;
FIG. 2 is a TEM image of a magnetic polymer nanofiber prepared according to the present invention;
FIG. 3 shows the macro-morphology of the magnetic graphene-based aerogel material with an ordered structure prepared according to the present invention;
fig. 4 is a microscopic ordered structure diagram of the magnetic graphene-based aerogel material prepared by the present invention;
FIG. 5 is a schematic diagram of the alignment structure of the magnetic graphene-based aerogel material prepared according to the present invention;
FIG. 6 is a schematic diagram of a gradient arrangement structure of the magnetic graphene-based aerogel material of the present invention;
fig. 7 is a schematic diagram of a gradient arrangement structure of the magnetic graphene-based aerogel material of the present invention.
Wherein the numbers in the figures are as follows:
the magnetic polymer nanofiber comprises a magnetic polymer nanofiber 1 and a graphene sheet layer 2;
and the symbol H in the figure indicates the magnetic field direction.
Detailed Description
In order to better explain the invention, the following further illustrate the main content of the invention in connection with specific examples, but the content of the invention is not limited to the following examples.
Example 1:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 10mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 10mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 1T, and circulating the magnetizing orientation for 6 times, wherein the direction of the magnetic field is 90 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 0 degree, transferring the mixed solution after being completely frozen to the condition of-60 ℃ for continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
Example 2:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 1mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 1mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 1T, and circulating the magnetizing orientation for 6 times, wherein the direction of the magnetic field is 90 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 0 degree, transferring the mixed solution after being completely frozen to the condition of-60 ℃ for continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
Example 3:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 5mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 5mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 1T, and circulating the magnetizing orientation for 6 times, wherein the direction of the magnetic field is 90 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 0 degree, transferring the mixed solution after being completely frozen to the condition of-60 ℃ for continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
Example 4:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 5mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 5mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 0.01T, and circularly magnetizing for 6 times, wherein the direction of the magnetic field is 90 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 0 degree, transferring the mixed solution after being completely frozen to the condition of-60 ℃ for continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
Example 5:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 5mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 5mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 2T, and circulating the magnetizing orientation for 6 times, wherein the direction of the magnetic field is 90 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 0 degree, transferring the mixed solution after being completely frozen to the condition of-60 ℃ for continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
Example 6:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 5mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 5mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 1T, and circularly magnetizing for 1 time, wherein the direction of the magnetic field is 90 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 0 degree, transferring the mixed solution after being completely frozen to the condition of-60 ℃ for continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
Example 7:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 5mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 5mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 1T, and circulating the magnetizing orientation for 3 times, wherein the direction of the magnetic field is 90 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 0 degree, transferring the mixed solution after being completely frozen to the condition of-60 ℃ for continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
Example 8:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 5mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 5mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 1T, and circulating the magnetizing orientation for 6 times, wherein the direction of the magnetic field is 90 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 45 degrees, transferring the mixed solution after the mixed solution is completely frozen to the condition of-60 ℃, continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
Example 9:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 5mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 5mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 1T, and circulating the magnetizing orientation for 6 times, wherein the direction of the magnetic field is 90 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 90 degrees, transferring the mixed solution after the mixed solution is completely frozen to the condition of-60 ℃, continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
Example 10:
the embodiment provides a preparation method of a magnetic graphene-based aerogel material, which comprises the following specific preparation processes:
1) preparing a graphene oxide solution: the method comprises the steps of taking natural graphite powder, concentrated sulfuric acid, potassium persulfate, phosphorus pentoxide and potassium permanganate as raw materials, preparing graphene oxide by an improved Hummers method, and uniformly dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution with the concentration of 5 mg/mL.
2) Preparation of magnetic polymer nanofiber dispersion: heating and dissolving a PVA-co-PE polymer master batch in an alcohol-water system, adding magnetic polymer nanoparticles (ferroferric oxide nanoparticles) subjected to demagnetization treatment, stirring, mixing, precipitating, and shearing for dispersion to obtain composite particles, mixing the composite particles with cellulose acetate butyrate powder according to a certain mass, and then performing melt extrusion, emulsification, shearing and other steps to prepare a uniformly dispersed magnetic polymer nanofiber dispersion liquid.
3) Preparation of magnetic graphene-based aerogel: and (3) taking 20mL of graphene oxide solution with the concentration of 5mg/mL and 5mL of magnetic polymer nanofiber dispersion liquid with the concentration of 5mg/mL into a beaker, adding 5mL of PVA solution with the concentration of 5mg/mL, and stirring and ultrasonically dispersing to obtain a mixed solution. Placing the beaker filled with the mixed solution at the position of a sample table at the center of an electromagnetic coil, starting a cooling and circulating water device, setting the intensity of the magnetizing magnetic field to be 1T, and circulating the magnetizing orientation for 6 times, wherein the direction of the magnetic field is 30 degrees. And quickly placing the mixed solution subjected to magnetizing and orienting treatment on the top end of an orienting freezing mold, carrying out orienting freezing treatment on the mixed solution by using liquid nitrogen, wherein the orienting freezing angle is 0 degree, transferring the mixed solution after being completely frozen to the condition of-60 ℃ for continuously freezing for 24 hours, and drying for 90 hours under the condition of a vacuum degree of 15Pa to obtain the magnetic graphene-based aerogel with the ordered structure.
4) Gas-phase reduction treatment of the magnetic graphene-based aerogel: adding 2mL of hydrazine hydrate solution into a 25mL beaker, transferring the 25mL beaker filled with hydrazine hydrate and the prepared magnetic graphene oxide aerogel into a 500mL beaker, sealing, heating in a water bath at 80 ℃ for 2h, naturally cooling to room temperature, and taking out.
As can be seen from fig. 1 and 2, in the magnetic polymer nanofiber prepared in embodiment 1 of the present invention, the magnetic polymer nanoparticles are distributed in the middle of the fiber, so that the polymer nanofiber has magnetism.
FIG. 3 is a macroscopic morphology of the aerogel material prepared in example 1; the aerogel material has smooth surface and complete structure.
As can be seen from fig. 4, 5, 6 and 7, the magnetic field orientation technique and the directional freezing technique are controlled to control different ordered three-dimensional framework structures inside the magnetic graphene-based aerogel.
Wherein, fig. 4 shows that the mass ratio of the graphene oxide to the magnetic polymer nanofiber is 2: 1, under the conditions of 1T magnetic field intensity and 45 degrees magnetic field angle orientation 6 times, and further at 45 degrees oriented freezing to obtain the internal micro ordered arrangement of microscope picture. It can be found that the magnetic polymer nanofibers coated with graphene oxide exhibit a certain degree of ordered arrangement, but a certain degree of entanglement occurs when the content of the magnetic polymer nanofibers is too high.
Fig. 5 shows that the mass ratio of graphene oxide to magnetic polymer nanofiber is 4: 1, orienting for 6 times under the conditions that the magnetic field intensity is 1T and the magnetic field angle is 90 degrees, and then further directionally freezing at 90 degrees, so that the occurrence of directional arrangement of the magnetic polymer nanofibers can be obviously observed, and the anisotropy of the magnetic graphene-based aerogel is realized. However, the alignment is not limited to fig. 5, and the graphene sheet layer and the magnetic polymer nanofiber may be aligned in different directions.
As shown in fig. 6, by adjusting the external induction conditions, the graphene sheet layer 2 and the magnetic polymer nanofiber 1 can be arranged in a gradient manner according to the size, thickness, content, arrangement direction, arrangement angle, connection mode, and other characteristics.
As shown in fig. 7, by adjusting the external induction conditions, the graphene sheet layer 2 and the magnetic polymer nanofiber 1 can be gradually arranged according to the size, thickness, content, arrangement direction, arrangement angle, connection mode, and other characteristics.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (9)
1. A magnetic graphene-based aerogel material with an ordered structure is internally of a three-dimensional network structure formed by ordered crosslinking and oriented arrangement of magnetic polymer nanofibers and graphene sheet layers, and has anisotropic characteristics in physical properties in different macroscopic physical directions;
the ordered crosslinking means that the graphene sheet layers and the magnetic polymer nanofibers are regularly connected with each other through the action of a crosslinking agent respectively to form continuous graphene large sheet layers and magnetic polymer nanofiber bundles, and meanwhile, the graphene sheet layers and the magnetic polymer nanofibers are connected with each other to form a complete and continuous structural system; the oriented arrangement is that the magnetic polymer nano-fibers are induced to be oriented and arranged along the direction of a magnetic field by an electromagnetic field orientation technology, and the magnetic polymer nano-fibers drive the graphene sheet layers to be oriented and arranged in the internal space to jointly form an oriented three-dimensional network structure;
specifically, the magnetic polymer nanofibers and the graphene sheet layers are arranged in a gradient, partially ordered or oriented manner in the internal microstructure of the magnetic graphene-based aerogel material.
2. The magnetic graphene-based aerogel material with an ordered structure according to claim 1, wherein: the magnetic polymer nanofiber is a nanofiber regulated and controlled by a magnetic factor, and the magnetic factor is one of strontium ferrite, nickel ferrite, cobalt ferrite, ferroferric oxide or iron, cobalt and nickel metals.
3. A method for preparing the magnetic graphene-based aerogel material with an ordered structure according to claim 1, comprising the following steps:
1) mixing the polymer nanofiber master batch with the magnetic polymer nanoparticles subjected to demagnetization treatment, and performing melt extrusion, emulsification and shearing to obtain a magnetic polymer nanofiber dispersion liquid;
2) uniformly mixing the magnetic polymer nanofiber dispersion liquid, the graphene oxide aqueous solution and the PVA aqueous solution to obtain a mixed solution, placing the mixed solution in an electromagnetic field for standing and directional treatment, performing directional freezing treatment on the mixed solution subjected to the directional treatment of the electromagnetic field by using liquid nitrogen, and continuously freezing and drying to obtain the magnetic graphene oxide aerogel with the orderly arranged internal microstructure;
3) and (3) placing the magnetic graphene oxide aerogel in a hydrazine hydrate atmosphere under a closed condition for gas-phase reduction treatment to obtain the magnetic graphene-based aerogel.
4. The method for preparing the magnetic graphene-based aerogel material with the ordered structure according to claim 3, wherein the method comprises the following steps: the electromagnetic field intensity in the step 2) is 0.01-2T, and the direction of the magnetic field is a vertical direction or a horizontal direction.
5. The method for preparing the magnetic graphene-based aerogel material with the ordered structure according to claim 3, wherein the method comprises the following steps: the directional freezing treatment in the step 2) comprises the following steps: the freezing angle is 0-90 degrees, and the freezing time is 0.5-2 hours.
6. The method for preparing the magnetic graphene-based aerogel material with the ordered structure according to claim 3, wherein the method comprises the following steps: the freeze drying in the step 2) comprises the following steps: the freezing temperature is-20 ℃ to-80 ℃, the freezing time is 12-72 hours, and the drying time is 20-90 hours.
7. The method for preparing the magnetic graphene-based aerogel material with the ordered structure according to claim 3, wherein the method comprises the following steps: the conditions of the gas phase reduction treatment in the step 3) are as follows: the reduction temperature is 50-90 ℃, and the reduction time is 1-6 hours.
8. The method for preparing the magnetic graphene-based aerogel material with the ordered structure according to claim 3, 4, 5, 6, or 7, wherein the method comprises the following steps: the magnetic factor in the magnetic polymer nano-particles is one of strontium ferrite, nickel ferrite, cobalt ferrite, ferroferric oxide or iron-cobalt-nickel metal.
9. The method for preparing the magnetic graphene-based aerogel material with the ordered structure according to claim 3, 4, 5, 6, or 7, wherein the method comprises the following steps: the polymer nanofiber master batch is made of at least one of PVA-co-PE, POE, PA6, PA66, PET or PPT.
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| CN117447226A (en) * | 2023-09-18 | 2024-01-26 | 吉林建筑大学 | Novel shaped ceramic-paraffin composite phase change energy storage material and preparation method thereof |
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