CN110678055A - Graphene/ferroferric oxide composite material, preparation method and application thereof - Google Patents
Graphene/ferroferric oxide composite material, preparation method and application thereof Download PDFInfo
- Publication number
- CN110678055A CN110678055A CN201810710068.7A CN201810710068A CN110678055A CN 110678055 A CN110678055 A CN 110678055A CN 201810710068 A CN201810710068 A CN 201810710068A CN 110678055 A CN110678055 A CN 110678055A
- Authority
- CN
- China
- Prior art keywords
- graphene
- optionally
- ferroferric oxide
- composite material
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application provides a graphene/ferroferric oxide composite material, the composite material comprises reduced graphene oxide and ferroferric oxide nano particles, and the composite material is of a three-dimensional porous structure. The application also provides a preparation method of the graphene/ferroferric oxide composite material, the graphene/ferroferric oxide composite material prepared by the preparation method and application of the graphene/ferroferric oxide composite material. In some embodiments, the graphene/ferroferric oxide composite material of the present application may be used as or for preparing an electromagnetic wave shielding material or an electromagnetic wave absorbing material.
Description
Technical Field
The present application belongs to the field of materials. Specifically, the application relates to a graphene/ferroferric oxide composite material, and a preparation method and application thereof.
Background
In recent years, rapid changes in the scientific and technological field enable various electronic and electrical devices which are convenient to live to be flooded in life, and increasingly complex electromagnetic environments are formed, and accordingly more serious electromagnetic radiation and electromagnetic interference greatly affect the health of people and the normal work of the electronic devices. In which excessive electromagnetic radiation interferes with the human metabolic, immune, and reproductive systems, and the problem of electromagnetic signal interference between devices can cause clutter of communication and detection signals and failure of related components of precision electronic and electrical devices. In addition, the radar detection technology based on the electromagnetic wave is widely applied in the military field, and the detection distance and the detection precision of the target are greatly improved by various high-performance and multifunctional radars such as an ultra-wideband radar, a synthetic aperture radar, a pulse Doppler radar and the like. How to reduce the radar Reflection Cross Section (RCS) of military equipment to weaken the detection capability of enemy radar is also a big problem which deeply affects the development of military equipment at present. Meanwhile, with the integration degree and the integration degree of electronic and electrical equipment on military ships and aircrafts becoming higher and higher, the problems of electromagnetic compatibility and electromagnetic interference among electronic components applying electromagnetic waves of different frequency bands are becoming more and more prominent. In order to solve the above problems, it is necessary to develop an ultra-wideband, high-absorption electromagnetic wave absorbing material capable of covering different frequency bands, so as to minimize adverse electromagnetic wave signals.
At present, the development of the wave-absorbing material is mainly based on the absorption and attenuation of centimeter waves, and along with the increasing of electronic equipment applying electromagnetic waves with higher frequency bands, such as the development of millimeter wave band 77GHz automobile radar and 5G technology, and the popularization of millimeter wave radars in the fields of terminal guidance of missiles, navigation of airports and ships and the like, the demand of people on the millimeter wave-absorbing material is more urgent. In addition, compared with the electromagnetic wave frequency band which has urgent need for the high-performance wave-absorbing material, the terahertz wave-absorbing material is also indispensable in the fields of future communication and detection. Particularly, recently, electronic devices based on a terahertz frequency band (0.1THz-10THz) are rapidly developed, the overall size of the terahertz device can be smaller than that of a microwave device, the terahertz device has great application potential in the fields of high-speed communication, high-precision imaging, nondestructive testing, military terahertz radar and the like, particularly in the space field, a great amount of manpower and financial resources are invested in the terahertz field research in all major countries at present, and terahertz communication, imaging equipment and terahertz radar are developed at present. In the foreseeable future, the electromagnetic environment of our life necessarily intersects with electronic and electrical equipment applying different frequency bands of microwave and terahertz wave, and the military radar technology requiring a long detection distance and high detection precision necessarily moves to a road integrating microwave and terahertz wave band multi-band radars. Therefore, the ultra-wideband wave-absorbing material with strong absorption capacity for both microwave and terahertz wave bands is urgently needed to be researched and developed. However, from microwave to terahertz wave, the wavelength span is very large, from tens of centimeters to tens of micrometers, which puts higher demands on the structural and compositional design of the absorbing material.
The two-dimensional carbon nanomaterial graphene has very unique optical, electrical and mechanical properties, has great application potential in the field of wave-absorbing materials, and is used as a loading platform, and the large two-dimensional planar structure of the graphene is used for loading other wave-absorbing components, so that the interface polarization, multiple scattering and magnetic loss capability of the whole material system on electromagnetic waves can be further improved. However, most wave absorbing components of graphene-based wave absorbing materials exist in a filler form, and the problems of poor dispersion uniformity, high wave absorbing density and the like are easily caused. And the problems of high refractive index, strong surface reflection and poor terahertz absorption performance in the terahertz frequency band are easily generated. Therefore, most of the graphene-based wave-absorbing materials reported at present are mainly concentrated in centimeter wave bands, have narrow absorption frequency bands and low absorption strength, and are difficult to cope with increasingly complex and diverse electromagnetic environments in life and the combined detection of radars applying different wave band electromagnetic wave technologies.
Disclosure of Invention
In one aspect, the present application provides a graphene/ferroferric oxide composite material, the composite material comprises reduced graphene oxide and ferroferric oxide nanoparticles, and the composite material is a three-dimensional porous structure.
In some embodiments, the composite material is a foam-like structure.
In some embodiments, the composite material is a bulk material.
In some embodiments, the ferroferric oxide nanoparticles having an average particle size of 1nm to 50nm, 3nm to 30nm, or 6nm to 20nm are distributed on the graphene redox sheets in the composite.
In some embodiments, the reduced graphene oxide sheets have an average area of 64 μm2-1600μm2Or 100 μm2-900μm2。
In some embodiments, the number of layers of reduced graphene oxide is 1 to 10 layers or 1 to 5 layers.
In some embodiments, the composite has a density of 1mg/cm3-20mg/cm3Or 2mg/cm3-5mg/cm3。
In some embodiments, the pore size of the three-dimensional porous structure is from 30 μm to 100 μm.
In some embodiments, the porosity of the three-dimensional porous structure is 90% or more, 95% or more, 97% or more, or 99% or more.
In some embodiments, the mass ratio of the reduced graphene oxide to the ferroferric oxide nanoparticles in the composite material is 0.35-6:1 or 0.8-3: 1.
The composite material of the present disclosure can absorb or shield electromagnetic waves, such as microwaves or terahertz waves.
In some embodiments, the composite material is capable of absorbing or shielding electromagnetic waves in the 2GHz-10THz frequency range.
In some embodiments, the composite has an average absorption of no less than 90% and an average reflectance of no greater than-10 dB for electromagnetic waves in the 2GHz-110GHz and 2GHz-2.5THz frequency ranges.
In some embodiments, the composite has an average absorption of no less than 96% and an average reflection of no more than-14 dB for electromagnetic waves in the 2GHz-110GHz and 2GHz-2.5THz frequency ranges.
In some embodiments, the composite has an average absorption of no less than 98% and an average reflection of no more than-17 dB for electromagnetic waves in the 2GHz-110GHz and 2GHz-2.5THz frequency ranges.
In some embodiments, the composite has an average absorption of no less than 99% and an average reflectance of no greater than-20 dB for electromagnetic waves in the 2GHz-110GHz and 2GHz-2.5THz frequency ranges.
In some embodiments, the composite has an absorptivity of greater than 90% for electromagnetic waves of each frequency in the 3.4GHz-110GHz and 3.4GHz-2.5THz frequency ranges and a reflectivity of less than-10 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite material has an absorptivity of greater than 90% for electromagnetic waves of each frequency in the 0.1THz-2.5THz frequency range, and a reflectivity of less than-10 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite material has an absorptivity of greater than 96% for electromagnetic waves of each frequency in the 0.1THz-2.5THz frequency range, and a reflectivity of less than-14 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite material has an absorptivity of greater than 98% for electromagnetic waves of each frequency in the 0.1THz-2.5THz frequency range, and a reflectivity of less than-17 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite material has an absorptivity of greater than 99% for electromagnetic waves of each frequency in the 0.1THz-2.5THz frequency range, and a reflectivity of less than-20 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite has an average absorptivity of no less than 99.00% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-20 dB.
In some embodiments, the composite has an average absorptivity of no less than 99.60% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-24 dB.
In some embodiments, the composite has an average absorptivity of no less than 99.90% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-30 dB.
In some embodiments, the composite has an average absorptivity of no less than 99.96% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-34 dB.
In some embodiments, the composite has an average absorptivity of no less than 99.98% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-38 dB.
On the other hand, the application provides a preparation method of a graphene/ferroferric oxide composite material, which comprises the following steps:
mixing graphene oxide and a metal organic compound of iron in an organic solvent to form a mixed solution;
carrying out solvothermal reaction on the mixed solution to form a three-dimensional graphene/ferroferric oxide gel material;
removing the organic solvent in the three-dimensional graphene/ferroferric oxide gel-like material, and reducing the obtained material to obtain a graphene/ferroferric oxide composite material with a three-dimensional porous structure;
the composite material comprises reduced graphene oxide and ferroferric oxide nanoparticles.
In some embodiments of the preparation process, the organometallic compound of iron is selected from iron pentacarbonyl Fe (CO)5Ferric triacetylacetonate, ferrocopper reagent salts Fe (cup)3Any one of or any combination of iron caprylate, iron oxalate and iron oleate.
In some embodiments of the preparation method, the organic solvent is selected from any one or a mixture of two or more of methanol, ethanol, ethylene glycol, isopropanol, tert-butanol or dimethylformamide in any proportion.
In some embodiments of the method of making, the step of removing the organic solvent comprises: and replacing the organic solvent in the graphene/ferroferric oxide gel-like material with water to obtain an intermediate material, and removing the water in the obtained intermediate material.
In some embodiments, the step of replacing the organic solvent in the graphene/ferroferric oxide gel-like material with water is: and standing the graphene/ferroferric oxide gel-like material in a series of mixed liquids of the organic solvent and water sequentially and finally standing in pure water, wherein the proportion of water in the series of mixed liquids is increased sequentially, so that the organic solvent in the graphene/ferroferric oxide gel-like material is replaced by water.
In some embodiments of the method of making, the step of removing water from the resulting intermediate material is: the intermediate material containing water is freeze-dried.
In some embodiments of the preparation method, the graphene oxide sheets used for the solvothermal reaction have an average area of 25 μm2-2500μm2、64μm2-1600μm2Or 100 μm2-900μm2。
In some embodiments of the preparation method, the graphene oxide sheets used for the solvothermal reaction are single-layer graphene oxide or few-layer graphene oxide, preferably 1 to 5-layer graphene oxide.
In some embodiments of the preparation method, the mass ratio of graphene oxide to the metal-organic compound of iron in the mixed solution is 0.1-8:1 or 0.6-3: 1.
In some embodiments of the method of making, the concentration of graphene oxide in the mixed liquor is 0.3mg/mL to 30mg/mL or 0.75mg/mL to 4 mg/mL.
In some embodiments of the preparation method, the solvothermal reaction temperature is from 120 ℃ to 220 ℃ or from 150 ℃ to 200 ℃ and the solvothermal reaction time is from 8h to 36h or from 10h to 20 h.
In some embodiments of the method of making, the reducing is performed in an inert atmosphere.
In some embodiments of the methods of making, the reducing is performed at a reduction temperature of 200 ℃ to 600 ℃ or 200 ℃ to 400 ℃ for 0.5h to 6h or 1h to 3 h.
In some embodiments of the method of making, the organometallic compound of iron is ferric triacetylacetonate.
In some embodiments of the preparation method, the graphene/ferroferric oxide gel-like material is filled with an organic solvent.
In some embodiments of the method of making, the intermediate material is filled with water.
In some embodiments of the method of making, the step of removing water from the intermediate material is: freeze-drying the intermediate material containing water at-196 deg.C to-10 deg.C or-70 deg.C to-30 deg.C; and optionally, the freeze-drying temperature is-20 ℃ to 15 ℃ or-5 ℃ to 5 ℃, and the freeze-drying time is 40h to 180h or 96h to 150 h.
In some embodiments of the methods of making, the rate of heating to the reduction temperature is from 2 ℃/min to 20 ℃/min or from 5 ℃/min to 10 ℃/min.
In another aspect, the present application provides a graphene/ferroferric oxide composite material prepared according to the preparation method disclosed herein.
In another aspect, the present application provides a use of the graphene/ferroferric oxide composite material of the present disclosure as or in the preparation of an electromagnetic wave shielding material or an electromagnetic wave absorbing material.
In some embodiments of the use, the electromagnetic wave is a microwave or terahertz wave.
In some embodiments of the use, the electromagnetic wave has a frequency in the range of 2GHz to 10 THz.
In another aspect, the present application provides an electromagnetic wave shielding material or device and an electromagnetic wave absorbing material or device, including the graphene/ferroferric oxide composite material or the graphene/ferroferric oxide composite material prepared by the preparation method disclosed herein.
Drawings
Fig. 1 is a scanning electron microscope image of the graphene/ferroferric oxide composite material in example 1.
Fig. 2 is a transmission electron microscope image of the inner hole wall of the graphene/ferroferric oxide composite material in example 1.
FIG. 3 is a graph showing a reflectivity test curve of the graphene/ferroferric oxide composite material in example 1 in a frequency range of 2GHz-110 GHz.
Fig. 4 is a reflectivity test curve diagram of the graphene/ferroferric oxide composite material in example 1 in the frequency range of 0.1THz-2.5 THz.
Detailed Description
Definition of
The following definitions and methods are provided to better define the present application and to guide those of ordinary skill in the art in the practice of the present application. Unless otherwise indicated, terms are to be understood in accordance with their ordinary usage by those of ordinary skill in the relevant art. All patent documents, academic papers, and other publications cited herein are incorporated by reference in their entirety.
The term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
The term "few-layer graphene oxide" as used herein refers to more than 1 layer, but not more than 10 layers, of these graphene oxides.
The term "solvothermal reaction" as used herein refers to a reaction carried out in a closed system (e.g., in a stainless steel reactor with a polytetrafluoroethylene lining) with an organic solvent as the reaction medium under high temperature conditions.
The term "bulk material" as used herein refers to a three-dimensional macroscopic solid material.
Where a range of numerical values is recited herein, the range includes the endpoints thereof, and all the individual integers and fractions within the range, and also includes each of the narrower ranges therein formed by all the various possible combinations of those endpoints and internal integers and fractions to form subgroups of the larger group of values within the stated range to the same extent as if each of those narrower ranges were explicitly recited. For example, the ferroferric oxide nanoparticles having an average particle size of "1 nm to 50 nm" mean that the average particle size may be 1nm, 1.5nm, 1.8nm, 2nm, 2.5nm, 3nm, 4nm, 5nm, 6nm, 7nm, 7.4nm, 8nm, 9nm, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 28nm, 30nm, 32nm, 35nm, 38nm, 40nm, 42nm, 45nm, 48nm, 50nm, ranges formed by the above, and the like.
The method for testing the microwave frequency band reflectivity of the graphene/ferroferric oxide composite material comprises the following steps: based on a bow test device, the reflectivity of the material is tested in a microwave frequency band (for example, 2GHz-110 GHz).
The method for testing the terahertz frequency band reflectivity of the graphene/ferroferric oxide composite material comprises the following steps: based on a terahertz time-domain spectroscopy system, a reflectivity test is carried out on the material in a terahertz frequency band (such as 0.1THz-2.5 THz).
Detailed description of the embodiments
In one aspect, the present application provides a graphene/ferroferric oxide composite material, the composite material comprises reduced graphene oxide and ferroferric oxide nanoparticles, and the composite material is a three-dimensional porous structure.
In some embodiments, the composite material is a foam-like structure.
In some embodiments, the composite material is a bulk material.
In some embodiments, the ferroferric oxide nanoparticles having an average particle size of 1nm to 50nm (e.g., 1nm, 1.5nm, 1.8nm, 2nm, 2.5nm, 3nm, 4nm, 5nm, 6nm, 7nm, 7.4nm, 8nm, 9nm, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 28nm, 30nm, 32nm, 35nm, 38nm, 40nm, 42nm, 45nm, 48nm, or 50nm, etc.), 3nm to 30nm, or 6nm to 20nm, in the composite are distributed on the reduced graphene oxide sheet.
In some embodiments, the reduced graphene oxide sheets have an average area of 64 μm2-1600μm2(e.g., 64 μm)2，80μm2，100μm2，120μm2，150μm2，200μm2，300μm2，350μm2，400μm2，450μm2，500μm2，600μm2，700μm2，800μm2，900μm2，1000μm2，1200μm2，1300μm2，1400μm2，1500μm2Or 1600 μm2Etc.), or 100 μm2-900μm2。
In some embodiments, the number of layers of reduced graphene oxide is 1-10 (e.g., 1,2, 3, 4, 5, 6, 7, 8, 9, 10 layers), or 1-5 layers.
In some embodiments, the composite has a density of 1mg/cm3-20mg/cm3(e.g., 1 mg/cm)3，1.6mg/cm3，2mg/cm3，3mg/cm3，4mg/cm3，5mg/cm3，6mg/cm3，7mg/cm3，8mg/cm3，9mg/cm3，10mg/cm3，11mg/cm3，12mg/cm3，13mg/cm3，14mg/cm3，15mg/cm3，16mg/cm3，17mg/cm3，18mg/cm3，19mg/cm3Or 20mg/cm3Etc.), or 2mg/cm3-5mg/cm3。
In some embodiments, the three-dimensional porous structure has a pore size of 30 μm to 100 μm (e.g., 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, or 100 μm, etc.).
In some embodiments, the three-dimensional porous structure has a porosity of 90% or more (e.g., 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, or 99.9%, etc.), 95% or more, 97% or more, or 99% or more.
In some embodiments, the mass ratio of reduced graphene oxide to ferroferric oxide nanoparticles in the composite material is 0.35-6:1 (e.g., 0.35:1, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.5:1, 1.8:1, 2:1, 2.5:1, 2.8:1, 3:1, 3.5:1, 3.8:1, 4:1, 4.3:1, 4.6:1, 5:1, 5.4:1, 5.7:1, or 6:1, etc.), or 0.8-3: 1.
The composite material disclosed by the invention can absorb or shield electromagnetic waves (such as microwaves or terahertz waves), has broadband wave-absorbing characteristics and excellent wave-absorbing performance, and can be used as a wave-absorbing material or a shielding material with ultra-broadband and strong absorption of microwave and terahertz wave bands.
In some embodiments, the composite material is capable of absorbing or shielding electromagnetic waves in the frequency range of 2GHz-10THz, such as 2GHz-110GHz, 2GHz-2.5THz, 3.4GHz-110GHz, 3.4GHz-2.5THz, and 0.1THz-2.5 THz.
In some embodiments, the composite has an average absorption of no less than 90% and an average reflectance of no greater than-10 dB for electromagnetic waves in the 2GHz-110GHz and 2GHz-2.5THz frequency ranges.
In some embodiments, the composite has an average absorption of no less than 96% and an average reflection of no more than-14 dB for electromagnetic waves in the 2GHz-110GHz and 2GHz-2.5THz frequency ranges.
In some embodiments, the composite has an average absorption of no less than 98% and an average reflection of no greater than-17 d B for electromagnetic waves in the 2GHz-110GHz and 2GHz-2.5THz frequency ranges.
In some embodiments, the composite has an average absorption of no less than 99% and an average reflectance of no greater than-20 dB for electromagnetic waves in the 2GHz-110GHz and 2GHz-2.5THz frequency ranges.
In some embodiments, the composite has an absorptivity of greater than 90% for electromagnetic waves of each frequency in the 3.4GHz-110GHz and 3.4GHz-2.5THz frequency ranges and a reflectivity of less than-10 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite material has an absorptivity of greater than 90% for electromagnetic waves of each frequency in the 0.1THz-2.5THz frequency range, and a reflectivity of less than-10 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite material has an absorptivity of greater than 96% for electromagnetic waves of each frequency in the 0.1THz-2.5THz frequency range, and a reflectivity of less than-14 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite material has an absorptivity of greater than 98% for electromagnetic waves of each frequency in the 0.1THz-2.5THz frequency range, and a reflectivity of less than-17 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite material has an absorptivity of greater than 99% for electromagnetic waves of each frequency in the 0.1THz-2.5THz frequency range, and a reflectivity of less than-20 dB for electromagnetic waves of each frequency in the frequency range.
In some embodiments, the composite has an average absorptivity of no less than 99.00% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-20 dB.
In some embodiments, the composite has an average absorptivity of no less than 99.60% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-24 dB.
In some embodiments, the composite has an average absorptivity of no less than 99.90% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-30 dB.
In some embodiments, the composite has an average absorptivity of no less than 99.96% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-34 dB.
In some embodiments, the composite has an average absorptivity of no less than 99.98% over the frequency range 0.1THz to 2.5THz and an average reflectivity of no greater than-38 dB.
In some embodiments, the graphene/ferroferric oxide bulk composite absorption performance may be more excellent in a frequency band greater than 2.5THz compared to a frequency band of 0.1THz to 2.5 THz.
On the other hand, the application provides a preparation method of a graphene/ferroferric oxide composite material, which comprises the following steps:
reacting graphene oxide with a metal-organic compound of iron (e.g., iron triacetylacetonate, iron pentacarbonyl Fe (CO))5Iron octoate, etc.) in an organic solvent (e.g., ethanol, isopropanol, or dimethylformamide) to form a mixed solution;
subjecting the mixed solution to a solvothermal reaction (e.g., in a sealed container such as a teflon-lined reaction vessel) to form a three-dimensional graphene/ferroferric oxide gel-like material;
removing the organic solvent in the three-dimensional graphene/ferroferric oxide gel-like material, and reducing the obtained material to obtain a graphene/ferroferric oxide composite material with a three-dimensional porous structure;
the composite material comprises reduced graphene oxide and ferroferric oxide nanoparticles.
In some embodiments of the method of preparation, the mixing is preferably carried out under ultrasound and/or uniform agitation to form a stable colloidal mixed solution.
Through solvothermal reaction, a precursor of iron (namely, a metal organic compound of the iron) is converted into ferroferric oxide nano particles, and meanwhile, a three-dimensional graphene/ferroferric oxide block gel material is formed, wherein the graphene is reduced to a certain extent.
In some embodiments of the preparation process, the organometallic compound of iron is selected from iron pentacarbonyl Fe (CO)5Ferric triacetylacetonate, ferrocopper reagent salts Fe (cup)3Any one of or any combination of iron caprylate, iron oxalate and iron oleate.
In some embodiments of the preparation method, the organic solvent is selected from any one or a mixture of two or more of methanol, ethanol, ethylene glycol, isopropanol, tert-butanol or dimethylformamide in any proportion.
In some embodiments of the method of making, the step of removing the organic solvent comprises: and replacing the organic solvent in the graphene/ferroferric oxide gel-like material with water to obtain an intermediate material, and removing the water in the obtained intermediate material.
In some embodiments, the step of replacing the organic solvent in the graphene/ferroferric oxide gel-like material with water is: and standing the graphene/ferroferric oxide gel-like material in a series of mixed liquids of the organic solvent and water sequentially and finally standing in pure water, wherein the proportion of water in the series of mixed liquids is increased sequentially, so that the organic solvent in the graphene/ferroferric oxide gel-like material is replaced by water.
In some embodiments, the series of mixed liquids of organic solvent and water has at least two or more concentration gradients. For example, the concentration gradient of a series of mixed liquids of the organic solvent and water used in the replacement process for removing the organic solvent may be: the ratio of organic solvent to water is 10:1, 10:9, 10:8, 10:7, 10:6, 10:5, 10:4, 10:3, 10:2, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10 and the like in this order so that the ratio of water in the series of mixed liquids is increased in this order, and finally the material is left standing in pure water to replace the organic solvent in the gel-like material with water.
In some embodiments of the method of making, the step of removing water from the resulting intermediate material is: the intermediate material containing water is freeze-dried.
In some embodiments of the preparation method, the graphene oxide sheets used for the solvothermal reaction have an average area of 25 μm2-2500μm2(e.g., 25 μm)2，28μm2，30μm2，35μm2，38μm2，40μm2，50μm2，64μm2，80μm2，100μm2，120μm2，150μm2，200μm2，300μm2，350μm2，400μm2，450μm2，500μm2，600μm2，700μm2，800μm2，900μm2，1000μm2，1200μm2，1300μm2，1400μm2，1500μm2，1600μm2，1700μm2，1800μm2，1900μm2，2000μm2，2200μm2，2300μm2，2400μm2Or 2500 μm2Etc.), 64 μm2-1600μm2Or 100 μm2-900μm2。
In some embodiments of the preparation method, the graphene oxide sheets used for the solvothermal reaction are single-layer graphene oxide or few-layer graphene oxide as defined above, preferably 1 to 5-layer graphene oxide.
In some embodiments of the preparation method, the mass ratio of graphene oxide to the metal-organic compound of iron in the mixed solution is 0.1-8:1 (e.g., 0.1:1, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.5:1, 1.8:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, etc.), or 0.6-3: 1.
In some embodiments of the methods of making, the concentration of graphene oxide in the mixed liquor is 0.3mg/mL to 30mg/mL (e.g., 0.3mg/mL, 0.75mg/mL, 0.8mg/mL, 1.0mg/mL, 1.5mg/mL, 1.8mg/mL, 2.0mg/mL, 2.5mg/mL, 2.8mg/mL, 3.0mg/mL, 4.0mg/mL, 5.0mg/mL, 6.0mg/mL, 7.0mg/mL, 8.0mg/mL, 9.0mg/mL, 10.0mg/mL, 12.0mg/mL, 15.0mg/mL, 18.0mg/mL, 20.0mg/mL, 22.0mg/mL, 25.0mg/mL, 28.0mg/mL or 30.0mg/mL, etc.), or 0.75mg/mL to 4 mg/mL.
In some embodiments of the methods of making, the solvothermal reaction temperature is 120 ℃ to 220 ℃ (e.g., 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, or 220 ℃, etc.), or 150 ℃ to 200 ℃, and the solvothermal reaction time is 8h to 36h (e.g., 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, or 36h, etc.), or 10h to 20 h.
In some embodiments of the method of making, the reducing is performed in an inert atmosphere.
In some embodiments of the methods of making, the reducing is performed at a reduction temperature of 200 ℃ to 600 ℃ (e.g., 200 ℃, 210 ℃, 220 ℃, 230 ℃, 250 ℃, 260 ℃, 280 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 350 ℃, 360 ℃, 380 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 450 ℃, 460 ℃, 480 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 550 ℃, 560 ℃, 580 ℃, or 600 ℃, etc.), or 200 ℃ to 400 ℃ for 0.5h to 6h (e.g., 0.5h, 0.8h, 1h, 1.5h, 1.8h, 2h, 2.5h, 2.8h, 3h, 3.5h, 3.8h, 4h, 4.5h, 4.8h, 5h, 5.5h, 5.8h, or 6h, etc.), or 1h to 3 h.
In some embodiments of the preparation method, the metal organic compound of iron is ferric triacetylacetonate, and the mass ratio of graphene oxide to ferric triacetylacetonate in the mixed solution is 0.1-8:1 or 0.6-3: 1.
In some embodiments of the preparation method, the graphene/ferroferric oxide gel-like material is filled with an organic solvent.
In some embodiments of the method of making, the intermediate material is filled with water.
In some embodiments of the method of making, the step of removing water from the intermediate material is: freeze-drying the intermediate material containing water, wherein the freezing temperature is-196 ℃ to-10 ℃ (e.g. -196 ℃, -190 ℃, -180 ℃, -170 ℃, -160 ℃, -150 ℃, -140 ℃, -130 ℃, -120 ℃, -110 ℃, -100 ℃, -90 ℃, -80 ℃, -70 ℃, -60 ℃, -50 ℃, -40 ℃, -30 ℃, -20 ℃ or-10 ℃, etc.), or-70 ℃ to-30 ℃; and optionally a freeze-drying temperature of-20 ℃ to 15 ℃ (e.g., -20 ℃, -19 ℃, -18 ℃, -17 ℃, -16 ℃, -15 ℃, -14 ℃, -13 ℃, -12 ℃, -11 ℃, -10 ℃, -9 ℃, -8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃, 0 ℃, 1 ℃,2 ℃, 5 ℃, 8 ℃, 10 ℃, 12 ℃, or 15 ℃ etc.), or-5 ℃ to 5 ℃, a freeze-drying time of 40h to 180h (e.g., 40h, 50h, 60h, 70h, 80h, 90h, 96h, 100h, 110h, 120h, 130h, 140h, 150h, 160h, 170h, or 180h, etc.), or 96h-150 h.
In some more specific embodiments, the freeze-drying process is to freeze the intermediate material containing water to a solid state at a freezing temperature of-196 ℃ to-10 ℃, and then to remove ice by freeze-drying the resulting solid composite of completely frozen graphene/ferroferric oxide and ice at a freeze-drying temperature of-20 ℃ to 15 ℃ for a period of 40h to 180 h.
In some embodiments of the methods of making, the rate of temperature increase to the reduction temperature during the reduction is from 2 ℃/min to 20 ℃/min (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 ℃/min, etc.), or from 5 ℃/min to 10 ℃/min.
In another aspect, the present application provides a graphene/ferroferric oxide composite material prepared according to the preparation method disclosed herein.
In another aspect, the present application provides a use of the graphene/ferroferric oxide composite material of the present disclosure as an electromagnetic wave shielding material or an electromagnetic wave absorbing material, or a use for preparing an electromagnetic wave shielding material or an electromagnetic wave absorbing material.
In some embodiments of the use, the electromagnetic wave is a microwave or terahertz wave.
In some embodiments of the use, the electromagnetic wave has a frequency in the range of 2GHz to 10 THz.
In another aspect, the present application provides an electromagnetic wave shielding material or device and an electromagnetic wave absorbing material or device, including the graphene/ferroferric oxide composite material or the graphene/ferroferric oxide composite material prepared by the preparation method disclosed herein.
The inventions of the present application provide one or more of the following advantages:
(1) the graphene/ferroferric oxide composite material disclosed by the invention realizes strong absorption and attenuation of electromagnetic waves and has broadband wave-absorbing characteristics by utilizing the synergistic effect between graphene and loaded magnetic ferroferric oxide nanoparticles, and can be used as an ultra-broadband wave-absorbing material or shielding material with microwave and terahertz wave bands. For example, efficient absorption of electromagnetic waves in the frequency band including microwave and terahertz waves (e.g., 2GHz-10THz) can be achieved.
(2) The graphene/ferroferric oxide composite material disclosed by the invention has a three-dimensional porous foam-like structure, and is beneficial to reducing the surface reflection of electromagnetic waves. The material has the advantages of low density, high electromagnetic wave absorption rate and the like.
(3) The density of the graphene/ferroferric oxide composite material prepared by the preparation method disclosed by the invention is controllable and can be 1mg/cm3-20mg/cm3Within the range of (A), the compression resilience and the temperature resistance are good.
(4) The graphene/ferroferric oxide composite material with light weight, high temperature resistance, ultra-wide frequency and high wave absorption performance prepared by the invention has great application value in the fields of civil electromagnetic radiation interference resistance, military stealth and the like (such as military aviation fighters, tanks, missiles, surface naval vessels and the like).
Examples
The following examples are for the purpose of illustration only and are not intended to limit the scope of the present application.
Example 1:
1) respectively weighing graphene oxide and triacetylacetone iron powder in a mass ratio of 1:1 in a container filled with ethanol, and carrying out intense ultrasonic treatment and stirring uniformly to form a stable colloidal solution. The concentration of graphene oxide in the mixed solution was kept at 1.0 mg/ml.
2) And transferring the obtained colloidal solution into a polytetrafluoroethylene lining, putting the lining into a stainless steel reaction kettle, preserving the heat for 18 hours at the temperature of 200 ℃, naturally cooling the reaction kettle to the room temperature, taking out the graphene/ferroferric oxide gel material filled with ethanol, and completely replacing the graphene/ferroferric oxide gel material into a water system.
The method for replacing ethanol in the graphene/ferroferric oxide gel-like material filled with ethanol with water comprises the following steps: standing the colloidal material in a series of mixed liquor of ethanol and water successively and finally in pure water, wherein the proportion of water in the series of mixed liquor is increased in sequence and the proportion of ethanol to water is 10:1, 10:9, 10:8, 10:7, 10:6, 10:5, 10:4, 10:3, 10:2, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 and 1:10 in sequence, and finally standing the material in pure water to replace the water system.
3) The water system is gradually frozen to a solid state at-50 ℃.
4) And (3) freezing and drying the obtained completely frozen solid compound of the graphene/ferroferric oxide and the ice at-5 ℃ for 120 h. And then obtaining the graphene/ferroferric oxide composite material.
5) Carrying out heat treatment on the obtained graphene/ferroferric oxide composite material at 300 ℃ for 1 hour in inert gas argon to finally obtain the graphene/ferroferric oxide composite material with the density of 1.6mg/cm3The thickness of the graphene/ferroferric oxide block composite material is 8 mm. The composite wave-absorbing material has a highly porous three-dimensional structure (figure 1), and ferroferric oxide nano particles with the average particle size of 7.4nm are uniformly distributed on a reduced graphene oxide sheet (figure 2).
6) And carrying out microwave frequency band 2GHz-110GHz reflectivity test and terahertz frequency band 0.1THz-2.5THz reflectivity test on the obtained graphene/ferroferric oxide block composite material.
In a frequency band of 2GHz-110GHz, the graphene/ferroferric oxide block composite material has excellent wave-absorbing performance, wherein the reflectivity is lower than-10 dB, namely the effective bandwidth with the absorptivity exceeding 90% is 106.6GHz (3.4-110GHz) (shown in figure 3), and the average reflectivity of the whole frequency band of 2GHz-110GHz is close to-20 dB.
In the frequency band of 0.1THz-2.5THz, the absorption performance of the graphene/ferroferric oxide block composite material is more excellent, the reflectivity of the graphene/ferroferric oxide block composite material in the whole test frequency band is lower than-10 dB (shown in figure 4), and meanwhile, the average reflectivity of the whole frequency band reaches-38 dB. Meanwhile, as can be seen from the trend of the graph in fig. 4, compared with the frequency band of 0.1THz to 2.5THz, the graphene/ferroferric oxide bulk composite material disclosed by the invention has more excellent wave-absorbing performance in the frequency band greater than 2.5 THz. The result shows that the graphene/ferroferric oxide block composite material is an ultra-wideband and high-performance wave-absorbing material with microwave and terahertz wave absorption performance.
Example 2:
1) respectively weighing graphene oxide and triacetylacetone iron powder in a mass ratio of 1.5:1 in a container filled with ethanol, and carrying out intense ultrasonic treatment and uniform stirring to form a stable colloidal solution. The concentration of graphene oxide in the mixed solution was kept at 2.0 mg/ml.
2) And transferring the obtained colloidal solution into a polytetrafluoroethylene lining, putting the lining into a stainless steel reaction kettle, preserving the heat at 180 ℃ for 12 hours, naturally cooling the reaction kettle to room temperature, taking out the graphene/ferroferric oxide gel material filled with ethanol, and completely replacing the graphene/ferroferric oxide gel material into a water system.
3) The water system is gradually frozen to a solid state at-70 ℃.
4) And (3) freezing and drying the obtained completely frozen solid compound of the graphene/ferroferric oxide and the ice at-20 ℃ for 120 h. And then obtaining the graphene/ferroferric oxide composite material.
5) Carrying out heat treatment on the obtained graphene/ferroferric oxide composite material at 400 ℃ for 1.5 in inert gas argonHour, finally the density is 2.3mg/cm3The thickness of the graphene/ferroferric oxide block composite material is 10 mm.
6) And carrying out microwave frequency band 2GHz-110GHz reflectivity test and terahertz frequency band 0.1THz-2.5THz reflectivity test on the obtained graphene/ferroferric oxide block composite material.
Example 3:
1) respectively weighing graphene oxide and triacetylacetone iron powder in a mass ratio of 2:1 in a container filled with ethanol, and carrying out intense ultrasonic treatment and stirring uniformly to form a stable colloidal solution. The concentration of graphene oxide in the mixed solution was kept at 0.75 mg/ml.
2) And transferring the obtained colloidal solution into a polytetrafluoroethylene lining, putting the lining into a stainless steel reaction kettle, preserving the heat at 160 ℃ for 16 hours, naturally cooling the reaction kettle to room temperature, taking out the graphene/ferroferric oxide gel material filled with ethanol, and completely replacing the graphene/ferroferric oxide gel material into a water system.
3) The water system is gradually frozen to a solid state at-30 ℃.
4) And (3) freezing and drying the obtained completely frozen solid compound of the graphene/ferroferric oxide and the ice at 5 ℃ for 150 hours. And then obtaining the graphene/ferroferric oxide composite material.
5) Carrying out heat treatment on the obtained graphene/ferroferric oxide composite material at 600 ℃ for 2 hours in inert gas argon to finally obtain the graphene/ferroferric oxide composite material with the density of 1.4mg/cm3The thickness of the graphene/ferroferric oxide block composite material is 9 mm.
6) And carrying out microwave frequency band 2GHz-110GHz reflectivity test and terahertz frequency band 0.1THz-2.5THz reflectivity test on the obtained graphene/ferroferric oxide block composite material.
While the invention has been described in detail by way of the general description and the specific embodiments, it will be apparent to those skilled in the art that certain modifications or improvements may be made in the invention and any combination may be made as required. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The graphene/ferroferric oxide composite material comprises reduced graphene oxide and ferroferric oxide nanoparticles, and is of a three-dimensional porous structure.
2. The composite material of claim 1, wherein:
optionally, the composite is a foam-like structure;
optionally, the composite material is a bulk material;
optionally, ferroferric oxide nano particles with the average particle size of 1nm-50nm, 3nm-30nm or 6nm-20nm are distributed on the reduced graphene oxide sheet;
optionally, the reduced graphene oxide sheets have an average area of 64 μm2-1600μm2Or 100 μm2-900μm2；
Optionally, the number of layers of the reduced graphene oxide is 1-10 or 1-5;
optionally, the composite has a density of 1mg/cm3-20mg/cm3Or 2mg/cm3-5mg/cm3；
Optionally, the pore size of the three-dimensional porous structure is 30 μm to 100 μm;
optionally, the porosity of the three-dimensional porous structure is 90% or more, 95% or more, 97% or more, or 99% or more;
optionally, the mass ratio of the reduced graphene oxide to the ferroferric oxide nanoparticles in the composite material is 0.35-6:1 or 0.8-3: 1.
3. The composite material of claim 1 or 2, wherein the composite material is capable of absorbing or shielding electromagnetic waves;
optionally, the composite material is capable of absorbing or shielding microwave or terahertz waves;
optionally, the composite material is capable of absorbing or shielding electromagnetic waves in the 2GHz-10THz frequency range;
optionally, the composite has an average absorption rate of no less than 90%, no less than 96%, no less than 98% or no less than 99% and an average reflectance of no more than-10 dB, no more than-14 dB, no more than-17 dB or no more than-20 dB for electromagnetic waves in the frequency ranges of 2GHz-110GHz and 2GHz-2.5 THz;
optionally, the composite material has an absorptivity of greater than 90% for electromagnetic waves of each frequency in the 3.4GHz-110GHz and 3.4GHz-2.5THz frequency ranges and a reflectivity of less than-10 dB for electromagnetic waves of each frequency in the frequency ranges;
optionally, the composite has an absorptivity of greater than 90%, greater than 96%, greater than 98%, or greater than 99% for electromagnetic waves of each frequency in the 0.1THz-2.5THz frequency range, and a reflectivity of less than-10 dB, less than-14 dB, less than-17 dB, or less than-20 dB for electromagnetic waves of each frequency in the frequency range; and/or the composite has an average absorption of no less than 99.00%, no less than 99.60%, no less than 99.90%, no less than 99.96% or no less than 99.98% over the 0.1THz-2.5THz frequency range and an average reflectance of no more than-20 dB, no more than-24 dB, no more than-30 dB, no more than-34 dB or no more than-38 dB.
4. The preparation method of the graphene/ferroferric oxide composite material comprises the following steps:
mixing graphene oxide and a metal organic compound of iron in an organic solvent to form a mixed solution;
carrying out solvothermal reaction on the mixed solution to form a three-dimensional graphene/ferroferric oxide gel material;
removing the organic solvent in the three-dimensional graphene/ferroferric oxide gel-like material, and reducing the obtained material to obtain a graphene/ferroferric oxide composite material with a three-dimensional porous structure;
the composite material comprises reduced graphene oxide and ferroferric oxide nanoparticles.
5. The production method according to claim 4, wherein:
optionally, the organometallic compound of iron is selected from iron pentacarbonyl Fe (CO)5TriacetylacetonatoIron, copper-iron reagent salts Fe (cup)3Any one or any combination of iron caprylate, iron oxalate and iron oleate;
optionally, the organic solvent is selected from any one or a mixture of two or more of methanol, ethanol, ethylene glycol, isopropanol, tert-butanol or dimethylformamide in any proportion;
optionally, the step of removing the organic solvent comprises: replacing an organic solvent in the graphene/ferroferric oxide gel-like material with water to obtain an intermediate material, and removing the water in the obtained intermediate material; wherein, the step of optionally replacing the organic solvent in the graphene/ferroferric oxide gel-like material with water comprises the following steps: standing the graphene/ferroferric oxide gel-like material in a series of mixed liquids of the organic solvent and water in sequence, and finally standing in pure water, wherein the proportion of water in the series of mixed liquids is increased in sequence, so that the organic solvent in the graphene/ferroferric oxide gel-like material is replaced by water;
optionally, the step of removing water from the resulting intermediate material is: freeze-drying the intermediate material containing water;
optionally, the graphene oxide sheets used for the solvothermal reaction have an average area of 25 μm2-2500μm2、64μm2-1600μm2Or 100 μm2-900μm2；
Optionally, the graphene oxide sheets used for the solvothermal reaction are single-layer graphene oxide or few-layer graphene oxide, preferably 1-5 layers of graphene oxide.
Optionally, the mass ratio of the graphene oxide to the metal organic compound of iron in the mixed solution is 0.1-8:1 or 0.6-3: 1;
optionally, the concentration of graphene oxide in the mixed solution is 0.3mg/mL-30mg/mL or 0.75mg/mL-4 mg/mL;
optionally, the solvothermal reaction temperature is 120-220 ℃ or 150-200 ℃, and the solvothermal reaction time is 8-36 h or 10-20 h;
optionally, the reduction is carried out in an inert atmosphere;
optionally, the reduction is carried out at a reduction temperature of 200 ℃ to 600 ℃ or 200 ℃ to 400 ℃ for 0.5h to 6h or 1h to 3 h.
6. The production method according to claim 5, wherein:
optionally, the organometallic compound of iron is ferric triacetylacetonate;
optionally, the graphene/ferroferric oxide gel-like material is filled with an organic solvent;
optionally, the intermediate material is filled with water;
optionally, the step of removing water from the intermediate material is: freeze-drying the intermediate material containing water at-196 deg.C to-10 deg.C or-70 deg.C to-30 deg.C; and optionally, the freeze-drying temperature is-20 ℃ to 15 ℃ or-5 ℃ to 5 ℃, and the freeze-drying time is 40h to 180h or 96h to 150 h;
optionally, the heating rate of heating to the reduction temperature is 2-20 deg.C/min or 5-10 deg.C/min.
7. The graphene/ferroferric oxide composite material prepared by the preparation method according to any one of claims 4 to 6.
8. Use of the graphene/ferroferric oxide composite material according to any one of claims 1 to 3 and 7 as or in preparation of an electromagnetic wave shielding material or an electromagnetic wave absorbing material.
9. The use of claim 8, wherein:
optionally, the electromagnetic wave is a microwave or terahertz wave;
optionally, the electromagnetic wave frequency range is 2GHz-10 THz.
10. An electromagnetic wave shielding material or device, or an electromagnetic wave absorbing material or device, comprising the graphene/ferroferric oxide composite material according to any one of claims 1 to 3 or 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810710068.7A CN110678055A (en) | 2018-07-02 | 2018-07-02 | Graphene/ferroferric oxide composite material, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810710068.7A CN110678055A (en) | 2018-07-02 | 2018-07-02 | Graphene/ferroferric oxide composite material, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110678055A true CN110678055A (en) | 2020-01-10 |
Family
ID=69065238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810710068.7A Pending CN110678055A (en) | 2018-07-02 | 2018-07-02 | Graphene/ferroferric oxide composite material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110678055A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112003026A (en) * | 2020-08-26 | 2020-11-27 | 中国科学院兰州化学物理研究所 | Reduced graphene oxide/ferroferric oxide/aluminum nitride composite material wave absorbing agent, preparation method thereof and wave absorbing material |
| CN113278400A (en) * | 2021-07-13 | 2021-08-20 | 信维通信（江苏）有限公司 | Graphene foam composite wave-absorbing material and preparation method thereof |
| CN113321530A (en) * | 2021-07-06 | 2021-08-31 | 长安大学 | Airport pavement wave absorbing agent and preparation method thereof, airport wave absorbing pavement panel and preparation method thereof |
| CN114538424A (en) * | 2022-03-22 | 2022-05-27 | 中国科学技术大学 | Preparation method of ordered mesoporous carbon modified graphene material |
| CN115353677A (en) * | 2022-08-12 | 2022-11-18 | 华南理工大学 | Epoxidized natural rubber electromagnetic shielding composite material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977748A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Magnetic aerogel and preparation method thereof |
| CN105633360A (en) * | 2015-12-23 | 2016-06-01 | 四川大学 | Amorphous state ferriferrous oxide/graphene aerogel composite material and preparation method and application thereof |
| CN106422995A (en) * | 2015-08-11 | 2017-02-22 | 中国科学院化学研究所 | Graphene aerogel and hybrid composite material thereof as well as preparation method and application of graphene aerogel |
| CN106753237A (en) * | 2016-11-28 | 2017-05-31 | 深圳大学 | A kind of Graphene/ferroso-ferric oxide composite wave-suction material and preparation method thereof |
| CN107072128A (en) * | 2016-12-07 | 2017-08-18 | 中国航空工业集团公司北京航空材料研究院 | Wide band electromagnetic wave absorbing material based on polyaniline graphene three-dimensional porous structure |
-
2018
- 2018-07-02 CN CN201810710068.7A patent/CN110678055A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977748A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Magnetic aerogel and preparation method thereof |
| CN106422995A (en) * | 2015-08-11 | 2017-02-22 | 中国科学院化学研究所 | Graphene aerogel and hybrid composite material thereof as well as preparation method and application of graphene aerogel |
| CN105633360A (en) * | 2015-12-23 | 2016-06-01 | 四川大学 | Amorphous state ferriferrous oxide/graphene aerogel composite material and preparation method and application thereof |
| CN106753237A (en) * | 2016-11-28 | 2017-05-31 | 深圳大学 | A kind of Graphene/ferroso-ferric oxide composite wave-suction material and preparation method thereof |
| CN107072128A (en) * | 2016-12-07 | 2017-08-18 | 中国航空工业集团公司北京航空材料研究院 | Wide band electromagnetic wave absorbing material based on polyaniline graphene three-dimensional porous structure |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112003026A (en) * | 2020-08-26 | 2020-11-27 | 中国科学院兰州化学物理研究所 | Reduced graphene oxide/ferroferric oxide/aluminum nitride composite material wave absorbing agent, preparation method thereof and wave absorbing material |
| CN113321530A (en) * | 2021-07-06 | 2021-08-31 | 长安大学 | Airport pavement wave absorbing agent and preparation method thereof, airport wave absorbing pavement panel and preparation method thereof |
| CN113321530B (en) * | 2021-07-06 | 2022-11-25 | 长安大学 | Airport pavement wave absorbing agent and preparation method thereof, airport wave absorbing pavement panel and preparation method thereof |
| CN113278400A (en) * | 2021-07-13 | 2021-08-20 | 信维通信（江苏）有限公司 | Graphene foam composite wave-absorbing material and preparation method thereof |
| CN113278400B (en) * | 2021-07-13 | 2021-09-24 | 信维通信（江苏）有限公司 | Graphene foam composite wave-absorbing material and preparation method thereof |
| CN114538424A (en) * | 2022-03-22 | 2022-05-27 | 中国科学技术大学 | Preparation method of ordered mesoporous carbon modified graphene material |
| CN115353677A (en) * | 2022-08-12 | 2022-11-18 | 华南理工大学 | Epoxidized natural rubber electromagnetic shielding composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110678055A (en) | Graphene/ferroferric oxide composite material, preparation method and application thereof | |
| Peymanfar et al. | Microwave absorption performance of ZnAl2O4 | |
| Feng et al. | Preparation, characterization and microwave absorbing properties of FeNi alloy prepared by gas atomization method | |
| Yan et al. | Nanoparticles and 3D sponge-like porous networks of manganese oxides and their microwave absorption properties | |
| Sun et al. | Metal–organic framework-based Fe/C@ Co3O4 core–shell nanocomposites with outstanding microwave absorption properties in low frequencies | |
| Wang et al. | Synthesis, characterization and enhanced electromagnetic properties of NiFe2O4@ SiO2-decorated reduced graphene oxide nanosheets | |
| Granitzer et al. | Magnetic study of Fe3O4 nanoparticles incorporated within mesoporous silicon | |
| Sun et al. | Facile synthesis of lightweight 3D hierarchical NiCo2O4 nanoflowers/reduced graphene oxide composite foams with excellent electromagnetic wave absorption performance | |
| Zhang et al. | High efficiency microwave absorption nanocomposites of multiple-phase core-shell CoNi alloy@ C loaded on rGO conducting network | |
| Cao et al. | The effect of microstructure of graphene foam on microwave absorption properties | |
| Yang et al. | Carbonyl iron/glass fiber cloth composites: Achieving multi-spectrum stealth in a wide temperature range | |
| Li et al. | Ultralight Fe@ C nanocapsules/sponge composite with reversibly tunable microwave absorption performances | |
| Qiao et al. | Hierarchical CoNi alloys toward microwave absorption application: Chain-like versus particle-like | |
| CN112430451A (en) | Nitrogen-doped graphene/cobalt-zinc ferrite composite aerogel wave-absorbing material and preparation method thereof | |
| JP7105435B2 (en) | Magnetic material, manufacturing method thereof, and electromagnetic wave absorbing sheet | |
| KR102273260B1 (en) | Core-Shell Composites for Shielding Electromagnetic Interference and Method for Preparing the Same | |
| CN112375541A (en) | Nitrogen-doped graphene nickel ferrite composite wave-absorbing material and preparation method thereof | |
| CN112897569B (en) | Preparation method of nickel/zinc oxide/carbon/reduced graphene oxide ultrathin wave absorber | |
| CN108610590B (en) | Microwave absorbing material and preparation method thereof | |
| Ting | Synthesis, characterization of Fe3O4/polymer composites with stealth capabilities | |
| Lim et al. | Electromagnetic wave absorption properties of Fe/MgO composites synthesized by a simple ultrasonic spray pyrolysis method | |
| Sun et al. | Metal–organic framework-derived C/Co/Co 3 O 4 nanocomposites with excellent microwave absorption properties in low frequencies | |
| Qu et al. | Ultrafine well-dispersed Co nanocrystals onto crumpled sphere-like rGO for superior low-frequency microwave absorption | |
| CN117594990A (en) | Preparation method of high-performance magnetoelectric cooperative gradient broadband metamaterial electromagnetic wave absorber | |
| Gordani et al. | Microstructure, phase, magnetic properties, and electromagnetic wave absorption of graphene oxide–Ni0. 7Zn0. 3Fe2O4–Al2O3 aerogel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200110 |
|
| RJ01 | Rejection of invention patent application after publication |