CN107418511B - The preparation method of FeCo/ redox graphene composite wave-suction material - Google Patents
The preparation method of FeCo/ redox graphene composite wave-suction material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- 229910002546 FeCo Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000011358 absorbing material Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 8
- 238000010792 warming Methods 0.000 abstract description 7
- 238000000137 annealing Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000006249 magnetic particle Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 5
- 230000007717 exclusion Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention discloses a kind of preparation method of FeCo/ redox graphene composite wave-suction material.This method prepares graphite oxide first with Hummers method, prepares graphene oxide solution by ultrasonic treatment.It will be added drop-wise in the graphene oxide solution of 2-5mg/ml dissolved with the solution of ferrous salt and cobalt salt again；Addition alkalinity NaBH in solution system is stated then up4Solution, and 1h is reacted in 60-120 DEG C of oil bath.Then, the product of preparation is warming up to 400-800 DEG C of annealing 1-2h in tube furnace with the heating rate of 5-20 DEG C/min, obtains FeCo/ redox graphene and inhales wave-particle.Environmentally protective, high efficiency and time conservation of the invention and suitable large scale preparation, and the suction wave-particle prepared is high to electro-magnetic wave absorption intensity, effective absorption band is wide；Absorbing property can also be regulated and controled by changing the mass ratio of ferrous salt and cobalt salt and graphene oxide, can satisfy a variety of use demands.
Description
Technical field
The invention belongs to absorbing material technical fields, and in particular to FeCo/ redox graphene composite wave-suction material
Preparation method.
Background technique
With the development of the radar exploration technique, the Stealth Fighter for improving weaponry avoids being identified by radar, to reinforce
Its survival ability and deep strike ability to enemy, the increasingly attention by various countries' military field engineering personnel.Moreover, with
The development of the industries such as communication, electronics and medical treatment, the application of electromagnetic wave it is also more and more extensive.Resulting electromagnetic pollution is serious
Threaten the health and ecological environment of the mankind.It, can be effective by weaponry or electronic equipment surface Coated With Absorbing Material
Decay to the electromagnetic wave of radar emission, reaches stealthy or shielding purpose.Therefore, develop light weight, thickness it is thin, absorb
By force, the absorbing material that effectively absorption band is wide and chemical stability is good has military and industrial circle use demand important
Meaning.
Graphene is concerned because it is with performances such as excellent light, heat, power, electricity.Ratio of the graphene due to its super large
Surface area and good thermal conductivity are highly suitable as absorbing material use.But the graphene conductivity of high-quality is big, to electromagnetism
The reflection of wave is stronger；And redox graphene is reduced because introducing oxygen-containing functional group and residual defect in its preparation process
Conductivity, thus there are preferable matching properties；In addition, oxygen-containing functional group and residual defect can be used as polarization center, reinforce
Absorption to electromagnetic wave.But single redox graphene decays to electro-magnetic wave absorption limited because not having magnetism.Therefore,
How by the graphene oxide of reduction in conjunction with magnetic particle, prepare the redox graphene of carried magnetic particle, coordinate two
The dielectric loss and magnetic loss of person becomes the important method for preparing high-performance wave-absorbing particle.
Preparing magnetic particle/redox graphene composite wave-suction material method now mainly has: (1) in magnetic particle
Selection on, mostly with Fe3O4、α-Fe2O3With γ-Fe2O3、Co3O4、CoFe2O4、NiFe2O4Deng based on.These magnetic particles
Saturation magnetization is lower, and magnetic loss is limited；It (2) is mostly solvent heat, atomic layer deposition method, height in preparation method
The methods of warm calcination method.Used method high temperature, needs reducibility gas (such as H at time-consuming2、NH3) and be not suitable for extensive system
It is standby, if X. H. Li et al. people is in [Journal of Materials Chemistry A (2015), 3:5535-5546] public affairs
Cloth solvent-thermal method prepares CoFe2O4/ graphene oxide, then in H2And NH3High temperature reduction is at FeCo/ graphene under atmosphere
Preparation method.Since FeCo magnetic particle has the characteristics that high saturation and magnetic intensity, high-curie temperature and high conductivity, by
More and more concerns.Therefore, it is necessary to invent a kind of green in conjunction with the advantage of FeCo magnetic particle and redox graphene
Environmental protection, time-saving and efficiency and the technology for being suitble to large scale preparation prepare the magnetic particle/oxygen reduction fossil with excellent absorbing property
Black alkene composite material.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of system of FeCo/ redox graphene absorbing material
Preparation Method, the preparation method is environmentally protective, efficient and suitable large scale preparation；By adjusting FeCo and redox graphene
Mass ratio can regulate and control the electromagnetic parameter of composite material, it is made to meet impedance matching and absorption characteristic requirement, preparative
The excellent absorbing material of energy.
In order to achieve the above object and use demand, technical solution of the present invention are as follows:
FeCo/ redox graphene composite wave-suction material, the FeCo/ redox graphene composite wave-suction material utilize
Ferrous ion and cobalt ions are embedded in surface of graphene oxide by electrostatic adsorption, after carrying out the high temperature anneal after reduction,
Magnetic Fe Co alloy particle is combined with redox graphene；The FeCo/ redox graphene composite wave-absorbing material
For redox graphene in lamellar structure and with apparent fold, FeCo particle is firmly anchored to reduction-oxidation graphite in material
On alkene lamella, and the particle size of FeCo is 50-300nm.
The preparation method of above-mentioned FeCo/ redox graphene composite wave-suction material, comprising the following steps:
Step 1: graphite oxide is prepared using Hummers method, it is sonicated that graphene oxide solution is prepared.
Step 2: ferrous salt and cobalt salt being dissolved in distilled water and are uniformly mixed, under inert gas protection, is added drop-wise to step 1
In obtained graphene oxide solution, mechanical stirring is uniformly mixed and obtains mixed liquor.
Step 3: by NaBH4It is added in the adjusted distilled water to alkalinity, after mixing evenly, is added to step 2 and obtains
Mixed liquor in, react 1h in 60-120 DEG C of oil bath.The product that will be obtained is washed till pH=7 with magnet absorption washing, alcohol, is placed in
Dry 10-24h in 50-80 DEG C of vacuum drying oven.The ferrous salt: cobalt salt: graphene oxide: NaBH4=1.2-6.0g:1.4-
7.2g:100-140ml:5.8-6.7g.
Step 4: the product that step 3 is obtained is ground, and is placed in ceramic Noah's ark, is sent into tube furnace, is warming up to 400-800
DEG C, the high temperature anneal 1-2h is carried out, inert gas is passed through during the high temperature anneal, obtains FeCo/ reduction-oxidation graphite
Alkene composite wave-suction material.
Graphene oxide solution concentration described in step 1 is 2-5mg/ml.
Ferrous salt described in step 2 is frerrous chloride, ferrous sulfate, ferrous nitrate and one of their water and object
Or it is a variety of, the cobalt salt is a kind of or more in cobalt nitrate, cobaltous sulfate, cobalt carbonate, cobalt acetate, cobalt chloride and their hydrate
Kind.The inert gas is nitrogen, argon gas, helium, neon or two or more gaseous mixtures.
Alkaline distilled water pH=9-11, uses NH described in step 33•H2O、NaOH、Na2CO3、NaHCO3One of or it is more
Kind is adjusted.
Heating rate described in step 4 be 5-20 DEG C/min, the inert gas be nitrogen, argon gas, helium, neon or
Two or more gaseous mixtures.
Beneficial effects of the present invention are, preparation process is environmentally protective, high efficiency and time conservation, and is suitble to large scale preparation, pass through
The mass ratio and annealing temperature for changing molysite and cobalt salt and graphene oxide, can regulate and control the electromagnetic parameter and magnetic of composite material
The size of property particle, meets impedance matching and attenuation characteristic；Prepared absorbing material, absorbing property is excellent, effective absorption frequency
Bandwidth.
Detailed description of the invention
Fig. 1 is that FeCo/ redox graphene prepared by embodiment 1 inhales wave-particle surface sweeping electron microscope.
Fig. 2 is that FeCo/ redox graphene prepared by embodiment 1 inhales wave-particle XRD spectra.
Fig. 3 is that FeCo/ redox graphene prepared by embodiment 1 inhales reflection loss song of the wave-particle in 1-18GHz
Line.
Fig. 4 is that FeCo/ redox graphene prepared by embodiment 2 inhales wave-particle surface sweeping electron microscope.
Fig. 5 is that FeCo/ redox graphene prepared by embodiment 2 inhales wave-particle XRD spectra.
Fig. 6 is that FeCo/ redox graphene prepared by embodiment 2 inhales reflection loss song of the wave-particle in 1-18GHz
Line.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, these embodiments are merely to illustrate rather than limit
The scope of the present invention processed.
Embodiment 1:
Step 1: by 2.0g graphite, the dense H of 46ml2SO4It is placed in 500ml three-necked flask, is stirred in 0 DEG C of mixture of ice and water
It mixes uniformly.6.0g potassium permanganate is weighed, is slowly added in batches, control temperature of reaction system reacts 2h between 0-5 DEG C.Then
System is moved into 35 DEG C of water-baths, 2h is reacted.After reaction, 100ml distilled water is slowly added dropwise, reacts 0.5h at 90 DEG C.
Finally, 200ml distilled water and 15mlH is added2O2.HCl and distillation water washing to pH=6-7 by product with 5%.The oxygen that will be obtained
Graphite is ultrasonically treated into graphene oxide solution, and is configured to the concentration of 5mg/ml.
Step 2: measuring 3.6g FeCl2•4H2O and 4.3g CoCl2•6H2O is dissolved in 100ml distilled water, is added drop-wise to and is filled
In the graphene oxide solution prepared in 140ml step 1, and it is passed through argon gas protection, mechanical stirring.
Step 3: weighing 6.3gNaBH4, it is added to and uses NH3•H2O is adjusted into the 100ml distilled water of pH=10, and stirring is equal
It is even, and be slowly added dropwise into step 2 system.After being added dropwise, 1h is reacted at 80 DEG C.The product that will be obtained, is adsorbed with magnet
Washing, alcohol are washed until pH=7.Then sample is placed in 15h in 60 DEG C of vacuum drying ovens.
Step 4: the product that step 3 is obtained is ground, and is placed in ceramic Noah's ark, is sent into tube furnace.It is passed through argon gas exclusion
Oxygen.Then tube furnace is warming up to 500 DEG C with the rate of 10 DEG C/min, keeps the temperature 1h, cooled to room temperature, in the process with argon
Gas is protective gas, obtains FeCo/ redox graphene and inhales wave-particle.
Embodiment 2:
Step 1: with embodiment 1
Step 2: measuring 6.0g FeCl2•4H2O and 7.2g CoCl2•6H2O is dissolved in 100ml distilled water, is added drop-wise to and is filled
In the graphene oxide solution prepared in 140ml step 1, and it is passed through argon gas protection, mechanical stirring.
Step 3: weighing 6.7gNaBH4, it is added to and uses NH3•H2O is adjusted into the 100ml distilled water of pH=9, is stirred evenly,
And it is slowly added dropwise into step 2 system.After being added dropwise, 1h is reacted at 80 DEG C.The product that will be obtained adsorbs water with magnet
It washes, alcohol is washed until pH=7.Then sample is placed in 20h in 70 DEG C of vacuum drying ovens.
Step 4: with embodiment 1
Embodiment 3:
Step 1: by the method for 1 step 1 of embodiment, configuration concentration is the graphene oxide solution of 3mg/ml.
Step 2: measuring 1.2gFeCl2•4H2O and 1.4g CoCl2•6H2O is dissolved in 100ml distilled water, is added drop-wise to and is filled
In the graphene oxide solution prepared in 120ml step 1, and it is passed through nitrogen protection, mechanical stirring.
Step 3: weighing 5.8gNaBH4, it is added to and is adjusted with NaOH into the 100ml distilled water of pH=11, stirred evenly,
And it is slowly added dropwise into step 2 system.After being added dropwise, 1h is reacted at 60 DEG C.The product that will be obtained adsorbs water with magnet
It washes, alcohol is washed until pH=7.Then sample is placed in 10h in 60 DEG C of vacuum drying ovens.
Step 4: the product that step 3 is obtained is ground, and is placed in ceramic Noah's ark, is sent into tube furnace.It is passed through nitrogen exclusion
Oxygen.Then tube furnace is warming up to 400 DEG C with the rate of 5 DEG C/min, keeps the temperature 1.5h, cooled to room temperature, in the process with
Argon gas is protective gas, obtains FeCo/ redox graphene and inhales wave-particle.
Embodiment 4:
Step 1: with embodiment 1
Step 2: measuring 3.6g FeCl2•4H2O and 4.3g CoCl2•6H2O is dissolved in 100ml distilled water, is added drop-wise to and is filled
In the graphene oxide solution prepared in 100ml step 1, and it is passed through argon gas protection, mechanical stirring.
Step 3: weighing 6.3gNaBH4, it is added to and uses NH3•H2O is adjusted into the 100ml distilled water of pH=10.5, and stirring is equal
It is even, and be slowly added dropwise into step 2 system.After being added dropwise, 1h is reacted at 90 DEG C.The product that will be obtained, is adsorbed with magnet
Washing, alcohol are washed until pH=7.Then sample is placed in 10h in 60 DEG C of vacuum drying ovens.
Step 4: the product that step 3 is obtained is ground, and is placed in ceramic Noah's ark, is sent into tube furnace.It is passed through argon gas exclusion
Oxygen.Then tube furnace is warming up to 500 DEG C with the rate of 10 DEG C/min, keeps the temperature 2h, cooled to room temperature, in the process with argon
Gas is protective gas, obtains FeCo/ redox graphene and inhales wave-particle.
Embodiment 5:
Step 1: with embodiment 1
Step 2: measuring 4.5g FeSO4•7H2O and 5.7g Co (CH3COO)2•4H2O is dissolved in 100ml distilled water, is added dropwise
To filling in the graphene oxide solution prepared in 120ml step 1, and it is passed through nitrogen protection, mechanical stirring.
Step 3: weighing 6.0gNaBH4, it is added to and is adjusted with NaOH into the 100ml distilled water of pH=11, stirred evenly,
And it is slowly added dropwise into step 2 system.After being added dropwise, 1h is reacted at 120 DEG C.The product that will be obtained adsorbs water with magnet
It washes, alcohol is washed until pH=7.Then sample is placed in 18h in 70 DEG C of vacuum drying ovens.
Step 4: the product that step 3 is obtained is ground, and is placed in ceramic Noah's ark, is sent into tube furnace.It is passed through argon gas exclusion
Oxygen.Then tube furnace is warming up to 600 DEG C with the rate of 20 DEG C/min, keeps the temperature 2h, cooled to room temperature, in the process with nitrogen
Gas is protective gas, obtains FeCo/ redox graphene and inhales wave-particle.
Embodiment 6:
Step 1: with embodiment 1
Step 2: measuring 2.0g FeSO4•4H2O、2.7g FeCl2With 3.5g Co (CH3COO)2•4H2O、1.5g CoCl2
It is dissolved in 100ml distilled water, is added drop-wise in the graphene oxide solution for filling and being prepared in 130ml step 1, and be passed through argon gas guarantor
Shield, mechanical stirring.
Step 3: weighing 6.0gNaBH4, it is added to NaOH and Na2CO3It adjusts in the 100ml distilled water of pH=11, stirs
It mixes uniformly, and is slowly added dropwise into step 2 system.After being added dropwise, 1h is reacted at 100 DEG C.The product that will be obtained, uses magnet
Absorption washing, alcohol is washed until pH=7.Then sample is placed in 15h in 80 DEG C of vacuum drying ovens.
Step 4: the product that step 3 is obtained is ground, and is placed in ceramic Noah's ark, is sent into tube furnace.It is passed through argon gas exclusion
Oxygen.Then tube furnace is warming up to 800 DEG C with the rate of 10 DEG C/min, keeps the temperature 1h, cooled to room temperature, in the process with nitrogen
Gas is protective gas, obtains FeCo/ redox graphene and inhales wave-particle.
Claims (7)
1. a kind of preparation method of FeCo/ redox graphene composite wave-suction material, it is characterised in that following steps:
Step 1: graphite oxide being prepared using Hummers method, the sonicated graphene oxide that 2-5mg/ml is prepared is molten
Liquid；
Step 2: ferrous salt and cobalt salt being dissolved in distilled water and are uniformly mixed, under inert gas protection, step 1 is added drop-wise to and obtains
Graphene oxide solution in, mechanical stirring be uniformly mixed obtains mixed liquor；
Step 3: by NaBH4It is added in the distilled water for being adjusted to alkalinity, after mixing evenly, adds it to what step 2 obtained
In mixed liquor, 1h is reacted in 60-120 DEG C of oil bath；The product that will be obtained, after being washed till pH=7 with magnet absorption washing, alcohol, vacuum
It is dried to obtain product；The ferrous salt: cobalt salt: graphene oxide: NaBH4=1.2-6.0g:1.4-7.2g:100-140ml:
5.8-6.7g；
Step 4: the product that step 3 is obtained is ground, and is placed in ceramic Noah's ark, is sent into tube furnace, under inert gas shielding, is risen
Temperature carries out the high temperature anneal 1-2h, obtains FeCo/ redox graphene composite wave-suction material, this is compound to 400-800 DEG C
The FeCo particle size of absorbing material is 50-300nm.
2. the preparation method of FeCo/ redox graphene composite wave-suction material according to claim 1, feature exist
In ferrous salt described in step 2 is frerrous chloride, ferrous sulfate, ferrous nitrate and one of their water and object or more
Kind.
3. the preparation method of FeCo/ redox graphene composite wave-suction material according to claim 1, feature exist
In cobalt salt described in step 2 is a kind of in cobalt nitrate, cobaltous sulfate, cobalt carbonate, cobalt acetate, cobalt chloride and their hydrate
Or it is a variety of.
4. the preparation method of FeCo/ redox graphene composite wave-suction material according to claim 1, feature exist
In alkaline distilled water pH=9-11, uses NH described in step 33•H2O、NaOH、Na2CO3、NaHCO3One of or a variety of tune
Section.
5. the preparation method of FeCo/ redox graphene composite wave-suction material according to claim 1, feature exist
In vacuum drying temperature described in step 3 is 50-80 DEG C, vacuum drying time 10-24h.
6. the preparation method of FeCo/ redox graphene composite wave-suction material according to claim 1, feature exist
In heating rate described in step 4 is 5-20 DEG C/min.
7. the preparation method of FeCo/ redox graphene composite wave-suction material according to claim 1, feature exist
In inert gas described in step 2 and step 4 is nitrogen, argon gas, helium, neon or two or more gaseous mixtures.
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| CN109054742B (en) * | 2018-08-10 | 2021-05-11 | 西安工业大学 | Fe-Co-RGO composite wave-absorbing material and preparation method thereof |
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