CN112165848A - Composite wave-absorbing material with magnetic metal or oxide thereof loaded on graphene and preparation method thereof - Google Patents
Composite wave-absorbing material with magnetic metal or oxide thereof loaded on graphene and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 162
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 239000002184 metal Substances 0.000 title claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 66
- 239000011358 absorbing material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000011068 loading method Methods 0.000 claims abstract description 54
- 238000010521 absorption reaction Methods 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 150000002739 metals Chemical class 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 3
- 239000002905 metal composite material Substances 0.000 claims 1
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- 238000005470 impregnation Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000000463 material Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
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- 238000002411 thermogravimetry Methods 0.000 description 3
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
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- 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
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
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Abstract
The invention discloses a composite wave-absorbing material with magnetic metal or oxide loaded on graphene and a preparation method thereof. The method takes graphene oxide as a carbon source, impregnates nitrates of magnetic metals such as Fe, Co, Ni and the like, then calcines the impregnated graphene oxide in a protective atmosphere, and prepares the magnetic metal or the oxide/graphene composite wave-absorbing material thereof through thermal decomposition and carbothermic reduction reaction, and further realizes the regulation and control of the loading capacity of the magnetic metals such as Fe, Co, Ni and the like or the oxide thereof in a wider range. The preparation method adopts an impregnation method and a high-temperature roasting method, has simple flow, easy operation and low synthesis cost, does not need complex synthesis equipment and chemical reagents, and is suitable for industrial production; by controlling the process conditions, the loading capacity of the magnetic metal or the oxide thereof can be regulated and controlled in a wider range; the electromagnetic matching and the electromagnetic loss of the graphene and the magnetic metal or the oxide thereof enable the microwave absorption performance of the composite material to be excellent.
Description
Technical Field
The invention relates to a composite wave-absorbing material with magnetic metal or oxide loaded on graphene and a preparation method thereof, belonging to the technical field of microwave absorbing materials.
Background
In recent years, the application of electromagnetic wave absorbing materials in radar detection, electromagnetic interference, electromagnetic pollution and the like has attracted much attention. Although conventional absorbing materials such as magnetic metals, magnetic metal oxides, ferrites, alloys, etc. exhibit good microwave absorption properties, their wide use is limited by the high density and low conductivity of the materials. Carbon materials can act as dielectric absorbers due to their good chemical and thermal stability, excellent dielectric properties and low density, but their low permeability leads to impedance mismatch. It is well known that dielectric loss, magnetic loss and electromagnetic impedance matching together determine the microwave absorption properties of a material, and that dielectric loss or magnetic loss materials alone have poor impedance matching. Therefore, the traditional single-component microwave absorbent can not simultaneously meet the comprehensive performance requirements of thin thickness, light weight, strong microwave absorption and wide absorption frequency band of the wave-absorbing material. The magnetic material and the carbon material are optimally compounded, so that the defect of high density of the magnetic material can be overcome, the electromagnetic matching and synergistic effect can be improved, and the electromagnetic wave absorption which is more excellent than that of a single wave-absorbing material is realized.
Graphene as a two-dimensional carbon material has unique electrical, optical, catalytic and mechanical properties, and becomes the focus of research of researchers in the fields of supercapacitors, lithium batteries, sensors and the like. Graphene has large specific surface area, low density, good conductivity and good chemical stability, and also shows great potential in the field of microwave absorbing materials, and the preparation of high-performance graphene-based wave absorbing materials is always concerned. In order to expand the absorption bandwidth and the absorption strength of the graphene-based composite absorption material, an effective method is to utilize the two-dimensional structure and the huge specific surface area of graphene to compound the graphene with magnetic nanoparticles to form advantage complementation, and simultaneously exert electromagnetic loss in two forms of electric loss and magnetic loss to obtain better electromagnetic wave absorption performance. The magnetic metal and the oxide thereof play important roles in the fields of electrochemical energy storage, photoelectric devices, catalysis and the like by virtue of unique physical and chemical properties, and become one of important branches in the research field of inorganic functional materials. Among magnetic metals and oxides thereof, magnetic metals and oxides thereof such as Fe, Co, Ni and the like are widely researched, the magnetic metal and oxides thereof are excellent in optical, electrical, magnetic and other applications, electromagnetic parameters of a carbon-based composite material can be adjusted by regulating and controlling the loading amount of nanoparticles, and the characteristic is favorable for improving the impedance matching characteristic of the material and widening the frequency band of a wave absorber and becomes a hotspot of research of people. Recently, some researchers have achieved some achievements in the preparation of magnetic metals such as Fe, Co, Ni and the like and oxide nano-particles/graphene composite materials thereof, but the defects that the process is complex, complex synthesis equipment and chemical reagents are needed, the preparation period is long, the synthesis cost is high, the regulation and control of the loading capacity of the magnetic metals and the oxides thereof are difficult and the like exist generally.
Disclosure of Invention
The invention aims to provide a composite wave-absorbing material of graphene loaded magnetic metal or oxide thereof and a preparation method thereof, the composite wave-absorbing material prepared by the method has simple process, easy operation and low synthesis cost, does not need complex synthesis equipment and chemical reagents, and is suitable for industrial production; by controlling the process conditions, the loading capacity of the magnetic metal or the oxide thereof can be regulated and controlled in a wider range; the electromagnetic matching and the electromagnetic loss of the graphene and the magnetic metal or the oxide thereof enable the microwave absorption performance of the composite material to be excellent.
According to the invention, graphene oxide is taken as a carbon source, nitrates of Fe, Co and Ni magnetic metals are impregnated and then calcined in a protective atmosphere, the calcination temperature is controlled, the magnetic metals such as Fe, Co and Ni or oxides thereof are loaded on the graphene through thermal decomposition and carbon thermal reduction reaction, and the regulation and control of the loading amount of the Fe, Co and Ni magnetic metals or oxides thereof in a wide range are further realized, so that the novel carbon-based composite wave-absorbing material which has a natural two-dimensional structure of the graphene and is artificially endowed with appropriate electromagnetic matching and multiple electromagnetic loss mechanisms is prepared, and a new thought and approach are provided for the research of novel carbon-based microwave absorbing materials.
The carbon source used in the invention is graphene oxide, and the Fe, Co and Ni magnetic metals or oxides thereof are from nitrates of the Fe, Co and Ni magnetic metals.
The invention provides a composite wave-absorbing material of graphene loaded magnetic metal or oxide thereof and a preparation method thereof, and the composite wave-absorbing material comprises the following steps:
step one, loading nitrates of magnetic metals on graphene oxide:
adding graphene oxide powder into high-purity water, carrying out ultrasonic treatment for 5-60 min to obtain a graphene oxide solution with the concentration of 0.2-4 mg/mL, adding nitrate of Fe, Co or Ni magnetic metal into the graphene oxide solution to enable the concentration of the nitrate to be 0.001-0.5 mol/L, and continuing to useUltrasonic treating for 5-60 min, pouring into evaporating dish at 40-70%oAnd drying at the temperature of C to obtain a nitrate sample of the graphene oxide loaded Fe, Co or Ni magnetic metal.
Step two, loading magnetic metal or oxide thereof on graphene:
placing the product obtained in the step one into a tube furnace, and reacting the product in the furnace in N2Calcining in the protective atmosphere of one of Ar and He at the temperature of 300-1000-oC, the heating rate is 1 to 5 oCAnd/min, calcining for 1-4 h, and cooling to normal temperature to obtain the graphene loaded magnetic metal or oxide composite material thereof.
Furthermore, the loading capacity of the magnetic metal or the oxide thereof in the obtained product is increased along with the increase of the concentration of the nitrate solution, and the loading capacity can be regulated and controlled. Controlling the calcination temperature at 300-400-oCalcining under C, and loading the oxide of the magnetic metal Co or Ni on the graphene; at 300- oCCalcining, namely loading an oxide of magnetic metal Fe on the graphene; at 500-oCalcining under C, and loading magnetic metal Co or Ni on the graphene; at 700-oAnd C, calcining, and loading magnetic metal Fe on the graphene.
In the method, according to the difference of the composition and the structure of the magnetic metal or the oxide thereof/graphene composite material, the reflection loss peak value of the composite material is-50.60 dB, and the effective absorption bandwidth can reach 5.8 GHz.
The invention has the beneficial effects that:
compared with the problems of complex preparation process, high equipment requirement, high cost and the like of the existing graphene composite microwave absorbing material, the preparation method disclosed by the invention has the advantages of simple flow, easiness in operation, low synthesis cost and no need of complex synthesis equipment and chemical reagents, and is suitable for industrial large-scale production. Moreover, the composition and the loading capacity of the magnetic metal or the oxide thereof are adjustable, and the microwave absorption performance of the material is excellent based on the composition of the magnetic metal or the oxide thereof/graphene, the electromagnetic matching and the electromagnetic loss.
Drawings
FIG. 1 is a block diagram of a process flow of a graphene-loaded magnetic metal or oxide composite wave-absorbing material thereof;
fig. 2 is an XRD pattern of the Co/graphene composite material prepared in example 1;
fig. 3 is an SEM image of the Co/graphene composite prepared in example 2;
FIG. 4 is a TEM image of the Co/graphene composite prepared in example 2;
FIG. 5 is a graph of the reflection loss of the Co/graphene composite prepared in example 2;
FIG. 6 is an XRD pattern of the CoO/graphene composite material prepared in example 4;
FIG. 7 is a graph of the reflection loss of the CoO/graphene composite prepared in example 5;
fig. 8 is an XRD pattern of the Ni/graphene composite prepared in example 6;
FIG. 9 is a TEM image of a Ni/graphene composite prepared in example 6;
FIG. 10 is a graph of the reflection loss of the Ni/graphene composite prepared in example 6;
FIG. 11 is an XRD pattern of the NiO/graphene composite material prepared in example 7;
FIG. 12 is an XRD pattern of the Fe/graphene composite material prepared in example 8;
FIG. 13 is Fe prepared in example 93O4XRD pattern of/graphene composite material;
FIG. 14 is Fe prepared in example 93O4Reflection loss diagram of the/graphene composite material.
Detailed Description
The technical solutions of the present invention are further described below with reference to the accompanying drawings and specific examples, which should be understood as merely illustrative of the present invention and not limiting the scope of the present invention.
The invention provides a preparation method of a graphene-loaded magnetic metal or oxide composite wave-absorbing material thereof, the process flow is shown in figure 1, graphene oxide is taken as a carbon source, nitrates of magnetic metals such as Fe, Co, Ni and the like are impregnated, and then the mixture is calcined in a protective atmosphere to obtain the magnetic metal or oxide/graphene composite wave-absorbing material thereof, and the regulation and control of the loading amounts of the magnetic metals such as Fe, Co, Ni and the like or the oxides thereof in a wider range are further realized.
Example 1:
a preparation method of a graphene loaded Co composite wave-absorbing material is characterized by comprising the following steps:
step one, loading cobalt nitrate on graphene oxide
Adding 200 mg of graphene oxide powder into 100 mL of high-purity water, carrying out ultrasonic treatment for 50 min to obtain a graphene oxide solution with the concentration of 2 mg/mL, and adding 0.1455 g of Co (NO)3)2·6H2Adding O into the graphene oxide solution, continuing to perform ultrasonic treatment for 10 min, pouring into an evaporation dish, and performing ultrasonic treatment at 60 DEGoAnd C, drying at the temperature, namely loading cobalt nitrate on the graphene oxide.
Step two, loading Co on graphene:
placing the product obtained in the step one into a tube furnace, N2Under the protection of atmosphere at 600oCalcining C for 2 h at a temperature rise rate of 2oAnd C/min, obtaining the graphene loaded Co composite material, wherein thermogravimetric analysis shows that the loading amount of the Co nanoparticles is 32.69 wt%.
FIG. 2 is an XRD pattern of the Co/graphene composite material obtained in example 1, 20-30oThe diffraction peak of (2) is the diffraction peak of graphene, and the phases of the prepared material are graphene and Co as can be seen from the figure.
Example 2:
a preparation method of a graphene loaded Co composite wave-absorbing material is characterized by comprising the following steps:
step one, loading cobalt nitrate on graphene oxide
Adding 200 mg of graphene oxide powder into 100 mL of high-purity water, carrying out ultrasonic treatment for 50 min to obtain a graphene oxide solution with the concentration of 2 mg/mL, and adding 0.291 g of Co (NO)3)2·6H2Adding O into the graphene oxide solution, continuing to perform ultrasonic treatment for 10 min, pouring into an evaporation dish, and performing ultrasonic treatment at 60 DEGoAnd C, drying at the temperature, namely loading cobalt nitrate on the graphene oxide.
Step two, loading Co on graphene:
will be described in detailA product obtained is placed in a tube furnace, N2Under the protection of atmosphere at 600oCalcining C for 2 h at a temperature rise rate of 2oAnd C/min, obtaining the Co/graphene composite material, wherein thermogravimetric analysis shows that the loading amount of the Co nanoparticles is 47.46 wt%.
Fig. 3 is an SEM image of the Co/graphene composite material obtained in example 2, from which it can be seen that Co nanoparticles are very uniformly supported on graphene and Co nanoparticles are tightly bound.
FIG. 4 is a TEM image of the Co/graphene composite material obtained in example 2, from which it can be seen that the Co nanoparticles have a particle size of 15-20 nm.
The powder product of example 2 was mixed with wave-transparent matrix paraffin in a certain ratio to prepare a test sample. The electromagnetic parameters (complex permittivity and complex permeability) of the magnetic material in the frequency range of 2-18 GHz are measured by a vector network analyzer by using a coaxial method. And (4) obtaining a reflection loss graph of the wave-absorbing material by the coaxial line theory calculation, wherein the reflection loss graph comprises effective absorption bandwidth and minimum reflection loss. The effective absorption bandwidth represents the width of the frequency range when the reflection loss is less than-10 dB. A reflection loss equal to-10 dB means that 90% of the microwaves are absorbed, and a reflection loss equal to-20 dB means that 99% of the microwaves are absorbed. FIG. 5 is a reflection loss chart of the Co/graphene composite material obtained in example 2, and it can be seen from the chart that when the thickness is 2.2 mm and the frequency range is 11.65-17.45 GHz, the reflection loss value is less than-10 dB, that is, the effective absorption bandwidth (the width of the frequency range when the reflection loss is less than-10 dB) can reach 5.8 GHz, and when the thickness is 2.4 mm, the reflection loss peak value is-50.60 dB, and the comprehensive wave-absorbing performance is excellent.
Example 3:
a preparation method of a graphene loaded Co composite wave-absorbing material comprises the following steps:
step one, loading cobalt nitrate on graphene oxide
Adding 200 mg of graphene oxide powder into 100 mL of high-purity water, carrying out ultrasonic treatment for 50 min to obtain a graphene oxide solution with the concentration of 2 mg/mL, and adding 0.582 g of Co (NO)3)2·6H2Adding O into the graphene oxide solution, continuing to perform ultrasonic treatment for 10 min, and pouringInto evaporating dishes at 60oAnd C, drying at the temperature, namely loading cobalt nitrate on the graphene oxide.
Step two, loading Co on graphene:
placing the product obtained in the step one into a tube furnace, N2Under the protection of atmosphere at 600oCalcining C for 2 h at a temperature rise rate of 2oAnd C/min, obtaining the Co/graphene composite material, wherein thermogravimetric analysis shows that the loading amount of the Co nanoparticles is 60.49 wt%.
Example 4:
a preparation method of a graphene-loaded CoO composite wave-absorbing material comprises the following steps:
step one, loading cobalt nitrate on graphene oxide
Adding 200 mg of graphene oxide powder into 100 mL of high-purity water, carrying out ultrasonic treatment for 50 min to obtain a graphene oxide solution with the concentration of 2 mg/mL, and adding 0.873 g of Co (NO)3)2·6H2Adding O into the graphene oxide solution, continuing to perform ultrasonic treatment for 10 min, pouring into an evaporation dish, and performing ultrasonic treatment at 60 DEGoAnd C, drying at the temperature, namely loading cobalt nitrate on the graphene oxide.
Step two, loading CoO on graphene:
placing the product obtained in the step one into a tube furnace, N2Under the protection of atmosphere at 350oCalcining C for 2 h at a temperature rise rate of 2oAnd C/min, obtaining the graphene supported CoO composite material.
FIG. 6 is the XRD pattern of the CoO/graphene composite material obtained in example 4, and it can be seen that the phases of the prepared material are graphene and CoO.
Example 5:
a preparation method of a graphene-loaded CoO composite wave-absorbing material comprises the following steps:
step one, loading cobalt nitrate on graphene oxide
Adding 200 mg of graphene oxide powder into 100 mL of high-purity water, carrying out ultrasonic treatment for 50 min to obtain a graphene oxide solution with the concentration of 2 mg/mL, and adding 0.291 g of Co (NO)3)2·6H2Adding O into the graphene oxide solution, continuing to perform ultrasonic treatment for 10 min, pouring into an evaporation pan,at 60oAnd C, drying at the temperature, namely loading cobalt nitrate on the graphene oxide.
Step two, loading CoO on graphene:
placing the product obtained in the step one into a tube furnace, N2Under the protection of atmosphere at 350oCalcining C for 2 h at a temperature rise rate of 2oAnd C/min, obtaining the graphene supported CoO composite material.
FIG. 7 is a reflection loss chart of the CoO/graphene composite material obtained in example 5, from which it can be seen that, when the thickness is 2.1 mm and the frequency range is 12.08-17.68 GHz, the reflection loss value is less than-10 dB, i.e. the effective absorption bandwidth (the width of the frequency range when the reflection loss is less than-10 dB) can reach 5.6 GHz, and when the thickness is 5 mm, the reflection loss peak value is-32.64 dB.
Example 6:
a preparation method of a graphene loaded Ni composite material comprises the following steps:
step one, loading nickel nitrate on graphene oxide
Adding 200 mg of graphene oxide powder into 100 mL of high-purity water, carrying out ultrasonic treatment for 50 min to obtain a graphene oxide solution with the concentration of 2 mg/mL, and adding 0.291 g of Ni (NO)3)2·6H2Adding O into the graphene oxide solution, continuing to perform ultrasonic treatment for 10 min, pouring into an evaporation dish, and performing ultrasonic treatment at 60 DEGoAnd C, drying at the temperature, namely loading nickel nitrate on the graphene oxide.
Step two, loading Ni on graphene:
placing the product obtained in the step one into a tube furnace, N2Under the protection of atmosphere at 600oCalcining C for 2 h at a temperature rise rate of 2oAnd C/min, obtaining the graphene loaded Ni composite material.
Fig. 8 is an XRD pattern of the Ni/graphene composite material obtained in example 6, from which it can be seen that the phases of the prepared material are graphene and Ni.
FIG. 9 is a TEM image of the Ni/graphene composite material obtained in example 6, from which it can be seen that Ni nanoparticles are uniformly distributed on graphene and have a particle size of 5-10 nm.
FIG. 10 is a reflection loss chart of the Ni/graphene composite material obtained in example 6, which shows that when the thickness is 1.8 mm and the frequency range is 12.31-17.36 GHz, the reflection loss value is less than-10 dB, that is, the effective absorption bandwidth (the width of the frequency range when the reflection loss is less than-10 dB) can reach 5.05 GHz, and when the thickness is 2 mm, the reflection loss peak value is-32.21 dB.
Example 7:
a preparation method of a graphene-loaded NiO composite wave-absorbing material comprises the following steps:
step one, loading nickel nitrate on graphene oxide
Adding 200 mg of graphene oxide powder into 100 mL of high-purity water, carrying out ultrasonic treatment for 50 min to obtain a graphene oxide solution with the concentration of 2 mg/mL, and adding 0.291 g of Ni (NO)3)2·6H2Adding O into the graphene oxide solution, continuing to perform ultrasonic treatment for 10 min, pouring into an evaporation dish, and performing ultrasonic treatment at 60 DEGoAnd C, drying at the temperature, namely loading nickel nitrate on the graphene oxide.
Step two, loading NiO on graphene:
placing the product obtained in the step one into a tube furnace, N2Under the protection of atmosphere at 300oCalcining C for 2 h at a temperature rise rate of 2oAnd C/min, obtaining the graphene supported NiO composite material.
Fig. 11 is an XRD pattern of the NiO/graphene composite material obtained in example 7, from which it can be seen that the phases of the prepared material are graphene and NiO.
Example 8:
a preparation method of a graphene-loaded Fe composite material comprises the following steps:
step one, loading ferric nitrate on graphene oxide
Adding 200 mg of graphene oxide powder into 100 mL of high-purity water, carrying out ultrasonic treatment for 50 min to obtain a graphene oxide solution with the concentration of 2 mg/mL, and adding 0.404 g of Fe (NO)3)3·9H2Adding O into the graphene oxide solution, continuing to perform ultrasonic treatment for 10 min, pouring into an evaporation dish, and performing ultrasonic treatment at 60 DEGoAnd C, drying at the temperature, namely loading ferric nitrate on the graphene oxide.
Step two, loading Fe by graphene:
placing the product obtained in the step one into a tube furnace, N2Under the protection of atmosphere at 750oCalcining C for 2 h at a temperature rise rate of 2oAnd C/min, obtaining the graphene-loaded Fe composite material.
Fig. 12 is an XRD pattern of the Fe/graphene composite material obtained in example 8, from which it can be seen that the phases of the prepared material are graphene and Fe.
Example 9:
graphene-loaded Fe3O4The preparation method of the composite material comprises the following steps:
step one, loading ferric nitrate on graphene oxide
Adding 200 mg of graphene oxide powder into 100 mL of high-purity water, carrying out ultrasonic treatment for 50 min to obtain a graphene oxide solution with the concentration of 2 mg/mL, and adding 0.808 g of Fe (NO)3)3·9H2Adding O into the graphene oxide solution, continuing to perform ultrasonic treatment for 10 min, pouring into an evaporation dish, and performing ultrasonic treatment at 60 DEGoAnd C, drying at the temperature, namely loading ferric nitrate on the graphene oxide.
Step two, loading Fe on graphene3O4：
Placing the product obtained in the step one into a tube furnace, N2Under the protection of atmosphere at 500oCalcining C for 2 h at a temperature rise rate of 2oC/min to obtain graphene loaded Fe3O4A composite material.
FIG. 13 shows Fe obtained in example 93O4XRD (X-ray diffraction) pattern of/graphene composite material, and phases of the prepared material are graphene and Fe3O4。
FIG. 14 shows Fe obtained in example 93O4The reflection loss graph of the graphene composite material shows that when the thickness is 1.8 mm and the frequency range is 13.1-18 GHz, the reflection loss value is smaller than-10 dB, namely the effective absorption bandwidth (the width of the frequency range when the reflection loss is smaller than-10 dB) can reach 4.9 GHz, and when the thickness is 2.5 mm, the reflection loss peak value of the material is-39.73 dB.
Claims (7)
1. A composite wave-absorbing material with magnetic metal or oxide loaded on graphene is characterized in that: taking graphene oxide as a carbon source, impregnating nitrate of magnetic metal, calcining in a protective atmosphere, controlling the calcining temperature, loading the magnetic metal or oxide thereof on the graphene through thermal decomposition and carbon thermal reduction reaction, further realizing the regulation and control of the loading capacity of the magnetic metal or oxide thereof in a wide range, and keeping the original two-dimensional structure of the graphene to prepare the composite wave-absorbing material of the graphene-loaded magnetic metal or oxide thereof;
the magnetic metal comprises any one of Fe, Co and Ni.
2. A preparation method of the graphene-loaded magnetic metal or oxide composite wave-absorbing material of claim 1 is characterized by comprising the following steps:
step one, loading nitrates of magnetic metals on graphene oxide:
adding graphene oxide powder into high-purity water, performing ultrasonic treatment for 5-60 min to obtain graphene oxide solution, adding nitrate of Fe, Co or Ni magnetic metal into the graphene oxide solution, performing continuous ultrasonic treatment for 5-60 min, pouring into an evaporation dish, and performing ultrasonic treatment at 40-70 deg.CoDrying under C to obtain a nitrate sample of the graphene oxide loaded Fe, Co or Ni magnetic metal;
step two, loading magnetic metal or oxide thereof on graphene:
putting the product obtained in the step one into a tube furnace, calcining in a protective atmosphere at the calcining temperature of 300-oC, the heating rate is 1 to 5oC/min, calcining for 1-4 h, and cooling to normal temperature to obtain the graphene loaded magnetic metal or oxide composite wave-absorbing material thereof.
3. The preparation method of the composite wave-absorbing material with the magnetic metal or the oxide thereof loaded on the graphene according to claim 2, wherein the composite wave-absorbing material is characterized in that: the concentration of the graphene oxide solution is 0.2-4 mg/mL, and after the nitrate is added, the concentration of the nitrate in the mixed solution is 0.001-0.5 mol/L.
4. The preparation method of the composite wave-absorbing material with the magnetic metal or the oxide thereof loaded on the graphene according to claim 2, wherein the composite wave-absorbing material is characterized in that: in step two, at 300-oCalcining under C, and loading the oxide of the magnetic metal Co or Ni on the graphene; at 300- oCCalcining, namely loading an oxide of magnetic metal Fe on the graphene; and preparing the graphene loaded magnetic metal oxide composite wave-absorbing material.
5. The preparation method of the composite wave-absorbing material with the magnetic metal or the oxide thereof loaded on the graphene according to claim 2, wherein the composite wave-absorbing material is characterized in that: in the second step, at 500-oCalcining under C, and loading magnetic metal Co or Ni on the graphene; at 700-oCalcining at the temperature of C, and loading magnetic metal Fe on the graphene; and preparing the graphene loaded magnetic metal composite wave-absorbing material.
6. The preparation method of the composite wave-absorbing material with the magnetic metal or the oxide thereof loaded on the graphene according to claim 2, wherein the composite wave-absorbing material is characterized in that: the graphene, the magnetic metal and the oxide thereof are tightly combined, according to the difference of the composition and the structure of the magnetic metal and the oxide thereof/the graphene composite wave-absorbing material, the reflection loss peak value of the prepared composite wave-absorbing material is-50.60 dB, and when the frequency range is 11.65-17.45 GHz, the reflection loss value is less than-10 dB, namely the effective absorption bandwidth can reach 5.8 GHz.
7. The preparation method of the composite wave-absorbing material with the magnetic metal or the oxide thereof loaded on the graphene according to claim 2, wherein the composite wave-absorbing material is characterized in that: the protective atmosphere comprises N2Ar or He.
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