CN109852344A - A kind of composite wave-suction material and preparation method thereof - Google Patents
A kind of composite wave-suction material and preparation method thereof Download PDFInfo
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- CN109852344A CN109852344A CN201910142679.0A CN201910142679A CN109852344A CN 109852344 A CN109852344 A CN 109852344A CN 201910142679 A CN201910142679 A CN 201910142679A CN 109852344 A CN109852344 A CN 109852344A
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 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 claims abstract description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 239000011358 absorbing material Substances 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- -1 graphite alkenyl compound Chemical class 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 239000004575 stone Substances 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 230000007812 deficiency Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000446313 Lamella Species 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 150000004291 polyenes Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003044 adaptive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention belongs to the technical fields of absorbing material more particularly to a kind of composite wave-suction material and preparation method thereof.The present invention provides the preparation methods of composite wave-suction material, comprising: cobalt source, urea and ammonium fluoride are dissolved in water by step 1, carry out hydro-thermal reaction, and cooling and high annealing obtains Co3O4；Step 2, by Co3O4It is dissolved in water with vulcanized sodium, carries out hydro-thermal reaction, then high annealing, obtains three-dimensional cobalt sulfide；Three-dimensional cobalt sulfide is mixed with modifier aqueous solution and is modified by step 3, obtains modified 3 D cobalt sulfide；It is step 4, modified 3 D cobalt sulfide and graphene oxide water solution is compound, obtain primary cobalt sulfide/graphene oxide composite material；Step 5 restores primary cobalt sulfide/graphene oxide composite material heating, is dried to obtain composite wave-suction material.Preparation method of the invention solve conventional graphite alkenyl compound inhale material there is also frequency band is narrow, low efficiency, the technological deficiency of preparation process complexity.
Description
Technical field
The invention belongs to the technical fields of absorbing material more particularly to a kind of composite wave-suction material and preparation method thereof.
Background technique
In recent years, with the high speed development of science and technology, electronic equipment and communications facility are seen everywhere, close with our life
It is connected, but its serious electromagnetic radiation also becomes the pollution sources that we can not ignore, and not only causes harm to the human body,
Huge obstruction also is formd to industrial production and manufacturing.Electromagnetic radiation has become another after water pollution and air pollution
Big pollution problem.Radio-radar absorber (wave absorbing agent) is that one kind can effectively solve the problem that electromagnetic pollution, and electromagnetic wave absorption reduces electromagnetism
The functional material of wave reflection and transmission.Ideal electromagnetic wave absorbent material, it must have, and light weight, thickness be small, absorption band
The features such as wide and chemical property is stablized.In a variety of different electromagnetic wave absorbent materials, it was reported that carbon and its compound are as suction
Wave material has the characteristics that light weight, absorption band are wide, possesses broad application prospect in electromagnetic wave shielding field.Typical example
Son is exactly graphene (RGO) and its compound.
It is well known that the electromagnetic wave absorption performance of an absorbing material and its structure are closely related.For conventional graphite alkenyl
Compound wave absorbing agent, graphene are typically used as substrate and carry out load nano particle, however, conventional graphite alkenyl compound inhales material mesh
The disadvantages of preceding there is also frequency bands narrow, low efficiency, complicated preparation process, its application range is caused to be subject to certain restrictions.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of bandwidths, high-efficient, the simple absorbing material of preparation process.
The present invention provides a kind of preparation methods of composite wave-suction material, which comprises the following steps:
Cobalt source, urea and ammonium fluoride are dissolved in water by step 1, carry out hydro-thermal reaction, and cooling and high annealing obtains
Co3O4；
Step 2, by the Co3O4It is dissolved in water with vulcanized sodium, carries out hydro-thermal reaction, then high annealing, obtains three-dimensional
Cobalt sulfide；
The three-dimensional cobalt sulfide is mixed with modifier aqueous solution and is modified by step 3, obtains modified 3 D cobalt sulfide；
It is step 4, the modified 3 D cobalt sulfide and graphene oxide water solution is compound, obtain primary cobalt sulfide/oxidation
Graphene composite material；
Step 5 restores the primary cobalt sulfide/graphene oxide composite material heating, is dried to obtain composite wave-absorbing material
Material.
Specifically, cobalt source be selected from six hydration cobaltous dichlorides, cabaltous nitrate hexahydrate it is one or more.
Specifically, six hydration cobaltous dichlorides, urea and ammonium fluoride press quality 3.842g, 3.964g, 0.977g dissolution respectively
In water.
More preferably, cobalt source, urea and ammonium fluoride are dissolved in water molten by ultrasonic agitation formation dispersion in step 1
Liquid is carrying out hydro-thermal reaction.The ultrasonic agitation time is 0.5-1h.
Preferably, the molar ratio of the cobalt source, the urea and the ammonium fluoride is 8:3:13 in step 1；
In step 1, the temperature of the hydro-thermal reaction is 120 DEG C -160 DEG C, and the time of the hydro-thermal reaction is 5h-10h；
In step 1, the temperature of the high annealing is 350 DEG C -500 DEG C, and the time of the high annealing is 2h-6h.
Wherein, in step 1, the high annealing carries out in an inert atmosphere, and inert atmosphere can be argon atmosphere.
More preferably, the temperature of the hydro-thermal reaction is 120 DEG C in step 1, the time of the hydro-thermal reaction is 5h；Step
In rapid 1, the temperature of the high annealing is 350 DEG C, and the time of the high annealing is 2h.
Preferably, in step 2, the Co3O4With the mass ratio 1:(3-5 of the vulcanized sodium).
More preferably, in step 2, Co3O4Pass through ultrasonic agitation in water with vulcanized sodium and forms dispersion solution in progress hydro-thermal
Reaction.The ultrasonic agitation time is 0.5-1h.
Preferably, in step 2, the temperature of the hydro-thermal reaction is 120 DEG C -180 DEG C, and the time of the hydro-thermal reaction is
12h-24h；
In step 2, the temperature of the high annealing is 500 DEG C -700 DEG C, and the time of the high annealing is 2h-6h.
More preferably, the temperature of the hydro-thermal reaction is 120 DEG C in step 2, the time of the hydro-thermal reaction is for 24 hours；Step
In rapid 2, the temperature of the high annealing is 500 DEG C, and the time of the high annealing is 2h.
Specifically, passing through Co in step 23O4After vulcanized sodium hydro-thermal reaction, the high temperature anneal is then carried out, can be obtained
To the cobalt sulfide of three-dimensional structure, pattern of the present invention by the cobalt sulfide of the temperature and time control of control high annealing, three-dimensional
The specific surface area of the cobalt sulfide of structure is bigger.
Preferably, in step 3, the modifier aqueous solution be selected from polyallylamine hydrochlorides solution, butene dioic acid solution,
One of polypropylene silicate is a variety of.
Preferably, the mass ratio of the three-dimensional cobalt sulfide and the polyallylamine hydrochlorides solution is 50 in step 3:
1。
Wherein, in step 3, the three-dimensional cobalt sulfide of 50-100mg mixes in the polyallylamine hydrochlorides solution to be changed
Property, incorporation time 0.5-1h, the concentration of polyallylamine hydrochlorides solution is 1mg/mL.
Specifically, three-dimensional cobalt sulfide is modified with modifier aqueous solution in step 3, modified effect can introduce function
Group, enables graphene oxide layer and the microballoon of three-dimensional cobalt sulfide to link together, and modification does not produce three-dimensional cobalt sulfide
It is raw to influence.
Preferably, the concentration of the graphene oxide water solution is 0.2mg/mL in step 4.The graphene oxide
The preparation method of aqueous solution is that the graphene oxide of (0.2-1mg) is dissolved in the deionized water of 100ml, and stirring 0.5h-1h is obtained.
Wherein, by the modified 3 D cobalt sulfide with it is compound in graphene oxide water solution so that graphene oxide wrap up
Modified 3 D cobalt sulfide, recombination time 1-1.5h obtain primary cobalt sulfide/graphene oxide composite material.
Preferably, the heating temperature of the heating reduction is 90-110 DEG C in step 5.
More preferably, the time of the heating reduction is 0.5h in step 5.
Preferably, further including reducing agent in step 5, by the primary cobalt sulfide/graphene oxide composite material and also
Former agent Hybrid Heating reduction, is dried to obtain composite wave-suction material.
Specifically, in step 5, also with reducing agent Hybrid Heating by the primary cobalt sulfide/graphene oxide composite material
Original is separated by solid-liquid separation, solid is dried in vacuo, and drying condition is 60 DEG C of dry 6h, obtains composite wave-suction material.
Preferably, the reducing agent is hydrazine hydrate.
More preferably, the mass fraction of the hydrazine hydrate is 80%.
Specifically, further include reducing agent in step 5, by the primary cobalt sulfide/graphene oxide composite material with
Hydrazine hydrate (mass fraction 80%) Hybrid Heating of 0.5mL-1.5mL restores, and is dried to obtain composite wave-suction material.
Specifically, the effect of step 4 and step 5 is to guarantee that the lamella of modified 3 D cobalt sulfide and graphene oxide can be close
Contact, graphene oxide layer can be coated on the surface of the three-dimensional cobalt sulfide after restoring by reducing agent, be carried out in two steps multiple
Conjunction is in order to guarantee that graphene oxide layer can be in close contact with three-dimensional cobalt sulfide, by the graphene sheet layer after heating reduction
The surface of three-dimensional cobalt sulfide can be coated on.
The present invention also provides a kind of composite wave-suction material, the preparation method including the composite wave-suction material is prepared
Composite wave-suction material.
The modification for three-dimensional cobalt sulfide that the present invention uses, is soaked in graphene oxide solution, be slowly stirred so that
Graphene oxide is attached to three-dimensional cobalt sulfide surface, then using heat treatment redox graphene, covered effect is very good.Stone
Black alkene is formed, and its lattice structure as a kind of two novel ultra-thin carbon-based materials by the carbon atom of single layer is tightly packed
It is sufficiently stable.Wherein carbon atom is with sp2Hybridized orbit arranges, specific surface area with higher, aspect ratio, thermal conductivity, electricity
The advantages that conductance and high mechanical strength.Graphene has excellent mechanical property, under external force, due to atomic plane
Adaptive distortion, C-C key are not easy to disconnect, and graphene lattice structure is able to maintain relatively stable, therefore are macroscopically showing as
Intensity is high, is not likely to produce the phenomenon that fractureing, puncture, tearing.Cobalt sulfide belongs to transient metal sulfide, and cobalt sulfide belongs to semiconductor
Functional material, bandwidth are distributed within the scope of 1.0~2.0eV, and CoS nano material has outstanding photoelectron and optics
Performance.Present invention discover that the composite wave-suction material that the surface that graphene oxide is wrapped in three-dimensional cobalt sulfide is formed is relative to graphene
Base support materials have more excellent absorbing property.Graphene is introduced in composite wave-suction material of the invention can not only reduce again
Close the density of object, moreover it is possible to make full use of the huge specific surface area of graphene, the interfacial polarization effect of reinforcing material makes it have more
Wide absorption band, lighter quality and stronger absorption intensity.
In conclusion the present invention forms binary cladding based on three-dimensional cobalt sulfide, using redox graphene coated
Structure, preparation method mainly uses hydro-thermal reaction, simple to operation, wherein the special three-dimensional sheet that the cobalt sulfide prepared has
Structure is highly beneficial to wave-absorbing effect.It is not only realized in the diadactic structure that the body structure surface coated graphite alkene of three-dimensional cobalt sulfide is formed
Effective absorption band wide purpose, while the usage amount of composite wave-suction material of the invention is low, filling 20% can play suction
Wave energy, this achieve to the light-weighted requirement of product.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 shows the scanning electron microscope (SEM) photograph for the three-dimensional cobalt sulfide that the embodiment of the present invention 1 provides, and amplification factor is 10000 times；
The scanning electron microscope (SEM) photograph of the amplification of the three-dimensional cobalt sulfide of Fig. 2 diagram 1, amplification factor are 80000 times.
Specific embodiment
The present invention provides a kind of composite wave-suction materials and preparation method thereof, inhale for solving conventional graphite alkenyl compound
Material there is also frequency band is narrow, low efficiency, the technological deficiency of preparation process complexity.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Wherein, it is commercially available or self-control that following embodiment is raw materials used, six hydration cobaltous dichlorides, urea, ammonium fluoride, Na2S
It is the pure rank of analysis.
Embodiment 1
The embodiment of the present invention provides the first composite wave-suction material, and preparation method is as follows:
(1) weigh chemicals six used be hydrated cobaltous dichloride, urea and ammonium fluoride quality be respectively 3.842g,
3.964g, 0.977g are added in 330mL distilled water, and 0.5h-1h is stirred by ultrasonic, forms uniform dispersion solution, is transferred to hydro-thermal
Reaction kettle, 120 DEG C of hydro-thermal reaction 5h, cooled to room temperature keep the temperature 2h, so by obtained product at 350 DEG C in argon atmosphere
Cooled to room temperature afterwards obtains the Co of 1.446g3O4；
(2) by Co3O4With the Na of 8.640g2S is added in 180mL aqueous solution, ultrasonic 0.5h-1h, and it is molten to form uniform dispersion
Liquid, 120 DEG C of hydro-thermal reactions for 24 hours, then carry out annealing 2h at 500 DEG C, obtain three-dimensional cobalt sulfide；
(3) powder of the three-dimensional cobalt sulfide of the 100mg of step (2) is transferred to the PAH solution (polyene that concentration is 1mg/mL
Propylamin hydrochloride solution) in, it is slowly stirred 0.5h, then by being centrifugally separating to obtain modified 3 D cobalt sulfide.
(4) first 50mg graphene oxide is dispersed in the deionized water of 100ml, stirs 0.5h, obtains graphene oxide water
Modified 3 D cobalt sulfide 100mg is added in graphene oxide water solution obtained, is slowly stirred 1h, obtains primary by solution
Cobalt sulfide/graphene oxide composite material.
(5) the primary cobalt sulfide/graphene oxide 10ml hydrazine hydrate that mass fraction is 80% being added in step (4) is multiple
In condensation material, heating stirring 0.5h is cooled to room temperature, and centrifuge separation, 60 DEG C of dry 6h, obtain composite wave-absorbing material in a vacuum
Material.For composite wave-suction material manufactured in the present embodiment in 2-18GHz frequency range, reflection loss value is lower than effective frequency of -10dB
Bandwidth is -11.2GHz, and maximum absorption band is in -52.6GHz.
Carrying out electron-microscope scanning analysis to the three-dimensional cobalt sulfide of step (2) as a result as depicted in figs. 1 and 2 can from Fig. 1 and Fig. 2
Know, from scanning electron microscope (SEM) photograph it can be seen that the three-dimensional appearance of the three-dimensional cobalt sulfide of step (2), the vulcanization lamella of microsphere surface intensively divide
Cloth, lamella has ultra-thin thickness as can be seen from Figure 2.Three-dimensional super-thin sheet-shaped cobalt sulfide is successfully prepared known to Fig. 1, Fig. 2
Out.
Embodiment 2
The embodiment of the present invention provides second of composite wave-suction material, and preparation method is as follows:
(1) weigh chemicals six used be hydrated cobaltous dichloride, urea and ammonium fluoride quality be respectively 3.842g,
3.964g, 0.977g are added in 330mL distilled water, and 0.5h-1h is stirred by ultrasonic, forms uniform dispersion solution, is transferred to hydro-thermal
Reaction kettle, 120 DEG C of hydro-thermal reaction 5h, cooled to room temperature keep the temperature 2h, so by obtained product at 350 DEG C in argon atmosphere
Cooled to room temperature afterwards obtains the Co of 1.446g3O4；
(2) by Co3O4With the Na of 8.640g2S is added in 180mL aqueous solution, ultrasonic 0.5h-1h, and it is molten to form uniform dispersion
Liquid, 150 DEG C of hydro-thermal reactions for 24 hours, then carry out annealing 2h at 500 DEG C, obtain three-dimensional cobalt sulfide；
(3) powder of the three-dimensional cobalt sulfide of the 100mg of step (2) is transferred to the PAH solution (polyene that concentration is 1mg/mL
Propylamin hydrochloride solution) in, it is slowly stirred 0.5h, then by being centrifugally separating to obtain modified 3 D cobalt sulfide.
(4) first 80mg graphene oxide is dispersed in the deionized water of 100ml, stirs 0.5h, obtains graphene oxide water
Modified 3 D cobalt sulfide 100mg is added in graphene oxide water solution obtained, is slowly stirred 1h, obtains primary by solution
Cobalt sulfide/graphene oxide composite material.
(5) the primary cobalt sulfide/graphene oxide 10ml hydrazine hydrate that mass fraction is 80% being added in step (4) is multiple
In condensation material, heating stirring 0.5h is cooled to room temperature, and centrifuge separation, 60 DEG C of dry 6h, obtain composite wave-absorbing material in a vacuum
Material.For composite wave-suction material manufactured in the present embodiment in 2-18GHz frequency range, reflection loss value is lower than effective frequency of -10dB
Bandwidth is -13.2GHz, and maximum absorption band is in -45.3GHz.
Embodiment 3
The embodiment of the present invention provides the third composite wave-suction material, and preparation method is as follows:
(1) weigh chemicals six used be hydrated cobaltous dichloride, urea and ammonium fluoride quality be respectively 3.842g,
3.964g, 0.977g are added in 330mL distilled water, and 0.5h-1h is stirred by ultrasonic, forms uniform dispersion solution, is transferred to hydro-thermal
Reaction kettle, 120 DEG C of hydro-thermal reaction 5h, cooled to room temperature keep the temperature 2h, so by obtained product at 350 DEG C in argon atmosphere
Cooled to room temperature afterwards obtains the Co of 1.446g3O4；
(2) by Co3O4With the Na of 8.640g2S is added in 180mL aqueous solution, ultrasonic 0.5h-1h, and it is molten to form uniform dispersion
Liquid, 180 DEG C of hydro-thermal reactions for 24 hours, then carry out annealing 2h at 500 DEG C, obtain three-dimensional cobalt sulfide；
(3) powder of the three-dimensional cobalt sulfide of the 100mg of step (2) is transferred to the PAH solution (polyene that concentration is 1mg/mL
Propylamin hydrochloride solution) in, it is slowly stirred 0.5h, then by being centrifugally separating to obtain modified 3 D cobalt sulfide.
(4) first 100mg graphene oxide is dispersed in the deionized water of 100ml, stirs 0.5h, obtains graphene oxide water
Modified 3 D cobalt sulfide 100mg is added in graphene oxide water solution obtained, is slowly stirred 1h, obtains primary by solution
Cobalt sulfide/graphene oxide composite material.
(5) the primary cobalt sulfide/graphene oxide 10ml hydrazine hydrate that mass fraction is 80% being added in step (4) is multiple
In condensation material, heating stirring 0.5h is cooled to room temperature, and centrifuge separation, 60 DEG C of dry 6h, obtain composite wave-absorbing material in a vacuum
Material.For composite wave-suction material manufactured in the present embodiment in 2-18GHz frequency range, reflection loss value is lower than effective frequency of -10dB
Bandwidth is -10.2GHz, and maximum absorption band is in -50.3GHz.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of composite wave-suction material, which comprises the following steps:
Cobalt source, urea and ammonium fluoride are dissolved in water by step 1, carry out hydro-thermal reaction, and cooling and high annealing obtains Co3O4；
Step 2, by the Co3O4It is dissolved in water with vulcanized sodium, carries out hydro-thermal reaction, then high annealing, obtains three-dimensional vulcanization
Cobalt；
The three-dimensional cobalt sulfide is mixed with modifier aqueous solution and is modified by step 3, obtains modified 3 D cobalt sulfide；
Step 4, will be compound in the modified 3 D cobalt sulfide and graphene oxide water solution, obtain primary cobalt sulfide/oxidation stone
Black alkene composite material；
Step 5 restores the primary cobalt sulfide/graphene oxide composite material heating, is dried to obtain composite wave-suction material.
2. the preparation method of composite wave-suction material according to claim 1, which is characterized in that in step 1, the cobalt source,
The molar ratio of the urea and the ammonium fluoride is 8:3:13；
In step 1, the temperature of the hydro-thermal reaction is 120 DEG C -160 DEG C, and the time of the hydro-thermal reaction is 5h-10h；
In step 1, the temperature of the high annealing is 350 DEG C -500 DEG C, and the time of the high annealing is 2h-6h.
3. the preparation method of composite wave-suction material according to claim 1, which is characterized in that in step 2, the Co3O4With
The mass ratio of the vulcanized sodium is 1:(3-5)；
In step 2, the temperature of the hydro-thermal reaction is 120 DEG C -180 DEG C, and the time of the hydro-thermal reaction is 12h-24h；
In step 2, the temperature of the high annealing is 500 DEG C -700 DEG C, and the time of the high annealing is 2h-6h.
4. the preparation method of composite wave-suction material according to claim 1, which is characterized in that in step 3, the modifying agent
Aqueous solution is selected from one of polyallylamine hydrochlorides solution, butene dioic acid solution, polypropylene silicate or a variety of.
5. the preparation method of composite wave-suction material according to claim 4, which is characterized in that in step 3, the three-dimensional sulphur
The mass ratio for changing cobalt and the polyallylamine hydrochlorides solution is 50:1.
6. the preparation method of composite wave-suction material according to claim 1, which is characterized in that in step 4, the oxidation stone
The concentration of black aqueous solution is 0.2mg/mL.
7. the preparation method of composite wave-suction material according to claim 1, which is characterized in that in step 5, the heating is also
Former heating temperature is 90-110 DEG C.
8. the preparation method of composite wave-suction material according to claim 1, which is characterized in that further include reduction in step 5
Primary cobalt sulfide/the graphene oxide composite material and reducing agent Hybrid Heating are restored, are dried to obtain composite wave-absorbing material by agent
Material.
9. the preparation method of composite wave-suction material according to claim 8, which is characterized in that the reducing agent is hydration
Hydrazine.
10. a kind of composite wave-suction material, which is characterized in that including composite wave-absorbing material as described in any one of claims 1-9
The composite wave-suction material that the preparation method of material is prepared.
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| CN116947111B (en) * | 2023-07-25 | 2024-01-02 | 哈尔滨工业大学（威海） | Method for preparing wave-absorbing material by in-situ vulcanization reaction of graphite nano-sheet composite cobalt particles |
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