CN108419426A - Coated with silica magnetic graphene tiny balloon and its magnanimity preparation method - Google Patents
Coated with silica magnetic graphene tiny balloon and its magnanimity preparation method Download PDFInfo
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Abstract
A kind of coated with silica magnetic graphene tiny balloon and its magnanimity preparation method, belong to function nano field of material technology.The coated with silica magnetic graphene tiny balloon is nucleocapsid, wherein magnetic graphene tiny balloon is core, and silica is shell.Preparation method is：By raw material ultrasonic disperse, dispersion liquid is spray-dried, isolated powdered loaded has the graphene oxide tiny balloon presoma of metal salt；It carries out roasting reduction and obtains magnetic graphene tiny balloon, ethyl orthosilicate is slowly added dropwise, react 6~10h, obtain reaction product, washed, detach, it is dry, obtain coated with silica magnetic graphene tiny balloon.Large specific surface area, the density of the coated with silica magnetic graphene tiny balloon is small, acid corrosion-resistant；With impedance matching performance and excellent Radar Absorbing Property.
Description
Technical field
The present invention relates to a kind of coated with silica magnetic graphene tiny balloon and its magnanimity preparation methods, belong to function
Technical field of nano material.
Background technology
Graphene is a kind of new material with many excellent properties, for example, the electron mobility of superelevation, low resistivity
And big specific surface area etc..Due to graphene nano scale effect, easily reunite between particle, causes the difficulty of practical application.One
Under fixed external condition, graphene film is assembled into the macroscopic body of more large scale (micron order), can ensure that graphene is excellent
The agglomeration traits of graphene film are solved while performance.Graphene film, grapheme foam, graphene microballoon are most common stone
Black alkene macroscopic view assembling form, shows splendid application prospect in different field respectively.
Graphene microballoon has many advantages, such as that packaging technology is flexible, structure easy-regulating, in recent years by all trades and professions researcher
Concern.Chinese invention patent CN201110355267.9 is using stannic oxide/graphene nano piece in water/fat liquor interface self assembly
At graphene oxide tiny balloon, then graphene hollow microspheres are obtained by electronation.Patent CN201410535693.4
It discloses and is reacted using anti-phase suspension emulsion polymerization, graphene complex microsphere, high temperature carbonization are prepared by constant pressure and dry
Reduction prepares graphene microballoon.Patent CN201310090294.7 disclose a kind of graphene oxide microballoon, graphene microballoon and
Preparation method, this method includes that precursor solution processing is formed microspheroidal drop using electrostatic spray, by microspheroidal drop
Solidification liquid is inputted, graphene oxide microballoon is obtained, by chemical reduction method, it is micro- that graphene oxide microballoon is prepared into graphene
Ball.Patent CN201410260989.X discloses a kind of hollow graphite alkene ball and its preparation method and application, which adopts
With graphene oxide/powder suspension, it is micro- to be prepared for hollow graphite alkene through processes such as atomization drying-reduction treatment-powder dissolutions
Ball, the hollow graphite alkene microballoon are suitable as the positive electrode of lithium-air battery.Patent CN201510773548.4 discloses one
The preparation method of the controllable three-dimensional grapheme microballoon of kind uses graphene oxide/Supporting Media spray drying, high temperature reduction system
Standby, the method for then dissolving out supporter prepares porous three-dimensional grapheme microballoon；The structure graphite alkene microballoon energy storage, absorption,
Wastewater treatment etc. has potential application.CN201710169677.1 also discloses that prepare with scale height rule spherical shape stone
The method of black alkene microballoon and the graphene microballoon are one kind using graphite oxide and graphene as raw material, prepare with scale of spraying
The new method of height rule spherical graphite alkene microballoon.
Nano wave-absorbing material is one of current most effective absorbing material；Wherein magnetic nano-particle plays magnetic loss to electromagnetic wave
Consumption acts on, and nanometer carbon nanobeads have dielectric loss mechanism to electromagnetic wave.Magnetic nano-particle and nanometer carbon nanobeads are mixed will
The absorbing material with composite wave-absorbing mechanism is prepared, thunderstorm activity efficiency is highly efficient.But nano wave-absorption particle is deposited
In easy reunion, difficult the problems such as disperseing, difficulty of construction is caused to increase, microwave absorbing coating and absorbent structure mechanical property are deteriorated.It will be magnetic
Nano-particle and nanometer carbon nanobeads are assembled into the micro-size particles of scale bigger, can give full play to radar wave recombination loss mechanism
Advantage, and provide possibility for its large-scale application.A kind of carried magnetic is disclosed in patent CN201510925343.3
The hollow plumbago alkene method for preparing microsphere of nano-particle；The core of this method is to prepare load using anti-phase suspension emulsion method to have gold
The graphene oxide tiny balloon presoma for belonging to salt, has then been made carried magnetic nano particle using high-temp in-situ reducing process
Hollow plumbago alkene microballoon；Research shows that the hollow plumbago alkene microballoon of carried magnetic nano particle is shown than pure magnetic Nano
Particle and the superior absorbing property of graphene, magnetic nano-particle, graphene and cavity structure play in inhaling wave process
Intrinsic effect and complex effect.But the anti-phase suspension emulsion method that the magnetic graphene tiny balloon preparation process uses, technique
Tediously long, inefficient, microspherulite diameter controllability is poor；In addition, the surface of the hollow plumbago alkene microballoon of this carried magnetic nano particle
It is mainly made of conductive graphene, impedance matching is still poor.
Invention content
The present invention provides a kind of coated with silica magnetic graphene tiny balloon and its magnanimity preparation method, this method with
Graphene oxide, water-soluble polymer and iron, cobalt, nickel metal salt are that raw material prepares dispersion liquid by sonic oscillation, then passes through spray
Load, which is made, in mist seasoning the graphene oxide tiny balloon presoma of metal salt；Roasting reduction under inert gas protection,
Obtain the graphene hollow microspheres of carried magnetic nano particle；Finally using modified Stober methods in magnetic graphene tiny balloon
Surface coats layer of silicon dioxide film.This method solve traditional Water-In-Oil antiphase emulsifiable methods to prepare graphene hollow microspheres work
The problems such as skill complexity is tediously long, and tiny balloon size control is not easy and the uniformity is poor.Coated with silica prepared by the present invention is magnetic
Large specific surface area, the density of graphene hollow microspheres is small, acid corrosion-resistant；Proportioning by regulating and controlling graphene oxide and metal salt can
To cut out the magnetic property and electrical property of magnetic graphene tiny balloon；By regulating and controlling the concentration of ethyl orthosilicate, change titanium dioxide
The thickness of silicon clad, and then reach optimization impedance matching performance；It is excellent that two kinds of measure collective effects so that product of the present invention has
Different Radar Absorbing Property.
In order to achieve the above object, the technical scheme is that：
A kind of coated with silica magnetic graphene tiny balloon of the present invention is nucleocapsid, wherein magnetic graphene
Tiny balloon is core, and silica is shell, the magnetic graphene tiny balloon, and hollow average diameter is 0.1~20 μm,
The cladding thickness of a diameter of 0.4~25 μm of magnetic graphene tiny balloon, the silica is 0.1~5 μm, titanium dioxide
The average grain diameter of silicon coated magnetic graphene hollow microspheres is 0.5~30 μm, and specific surface area is 100~2000m2/ g, density
For 0.4~1.2g/cm3, magnetic saturation intensity (magnetism) reduces degree≤5% after concentrated hydrochloric acid solution corrodes.
A kind of magnanimity preparation method of coated with silica magnetic graphene tiny balloon of the present invention, including following step
Suddenly：
Step 1, dispersion liquid is prepared
Under ul-trasonic irradiation, graphene oxide, deionized water, liquid alcohol, water-soluble polymer are subjected to ultrasonic disperse,
Then metal salt is added, stirs evenly, obtains dispersion liquid；Wherein, by solid-to-liquid ratio, graphene oxide：Deionized water：Liquid alcohol：
Water-soluble polymer：Metal salt=1g：(0.2~2) L：(0.5~1.5) L：(3~10) g：(6~20) g；
Step 2, it is spray-dried
Dispersion liquid is spray-dried, before isolated powdered loaded has the graphene oxide tiny balloon of metal salt
Drive body；Wherein, spray drying temperature is 160~300 DEG C；
Step 3, roasting reduction
(1) the graphene oxide tiny balloon presoma that load is had to metal salt, in inert protective atmosphere, with 5~20
DEG C/min is warming up to 350~400 DEG C, roast 0.5~2h；
(2) 500~900 DEG C are warming up to 5~20 DEG C/min again, roast 3~6h；
(3) room temperature is cooled to 2~10 DEG C/min, obtains magnetic graphene tiny balloon；
Step 4, coated silica
(1) mixed liquor is prepared：It is that 25%~28% ammonium hydroxide mixes by liquid alcohol, deionized water and mass percent concentration
It closes, obtains mixed liquor；Wherein, by volume, liquid alcohol：Deionized water：Mass percent concentration be 25%~28% ammonium hydroxide=
(20~200)：(10~50)：(1~3)；
(2) magnetic graphene tiny balloon is scattered under the stirring of 500~1500rpm/min in mixed liquor, is disperseed
After uniformly, ethyl orthosilicate is slowly added dropwise, reacts 6~10h, obtains reaction product；Wherein, by solid-to-liquid ratio, magnetic graphene is empty
Heart microballoon：Ethyl orthosilicate=1g：The drop rate of (5~20) mL, ethyl orthosilicate are 0.5~2mL/min；
(3) reaction product is removed into supernatant, is washed, detached, obtained solid product is dried, obtains two
Silica coated magnetic graphene hollow microspheres.
In the step 1, the liquid alcohol is the mixing of one or more of methanol, ethyl alcohol, propyl alcohol, ethylene glycol
Object, when for mixture, mixed proportion is arbitrary ratio；
In the step 1, the water-soluble polymer be polyvinyl alcohol or polypyrrole alkanone, or both mixing
Object, when for mixture, mixed proportion is arbitrary ratio.
In the step 1, the metal salt be ferric acetyl acetonade, nickel acetylacetonate, acetylacetone cobalt, ferric nitrate,
One or more of nickel nitrate, cobalt nitrate, ferric acetate, nickel acetate, cobalt acetate, iron chloride, nickel chloride, cobalt chloride mix, when
For mixture when, mixed proportion be arbitrary ratio.
In the step 1, the power of the ultrasonic disperse, ultrasonic wave is 600~1200W, the time of ultrasonic disperse
For 30~60min.
In the step 2, the equipment that the spray drying uses is spray dryer.
In the step 2, the equipment that the separation uses is cyclone separator.
In the step 3 (1), the inert protective atmosphere, it is specially nitrogen, argon gas, neon, helium that inertia, which protects gas,
One or more of gas mixes, and when for mixture, mixed proportion is arbitrary ratio, and inertia protects 50~120mL/ of flow of gas
min。
In the step 4 (1), the liquid alcohol is that one or more of methanol, ethyl alcohol, propyl alcohol, ethylene glycol are mixed
Object is closed, when for mixture, mixed proportion is arbitrary ratio.
In the step 4 (3), the detergent that the washing uses is preferably ethyl alcohol.
In the step 4 (3), the separation is preferably detached with the method for magnet adsorption.
In the step 4 (3), the drying is vacuum drying, and drying temperature is 60~100 DEG C.
Coated with silica magnetic graphene tiny balloon prepared by the present invention has excellent electromagnetic performance and impedance
Matching performance can be used as material obsorbing radar waves.
A kind of coated with silica magnetic graphene tiny balloon and its magnanimity preparation method of the present invention, advantage
For：
1. it is hollow micro- to prepare grain size adjustable coated with silica magnetic graphene in 0.5-30 μ ms with magnanimity
Ball, preparation method is environmentally protective, is simple and efficient and can produce in batches；
2. coated with silica magnetic graphene tiny balloon has small large specific surface area, density, acid corrosion-resistant, electromagnetically
Can adjustable, characteristic that impedance matching performance is excellent, and solve traditional magnetic nano-particle and graphene and easily reunite, difficult disperse
Technical barrier；
3. there is radar wave absorbing frequency band using absorbing material prepared by coated with silica magnetic graphene tiny balloon
Wide, the advantages that absorption intensity is big, performance is stable, the corrosion of light, high-low temperature resistant, salt fog resistance, in defence and military radar wave camouflage and
Domestic electromagnetic, which shields field, has wide application prospect.
4. this method solve traditional Water-In-Oil antiphase emulsifiable method, to prepare graphene hollow microspheres complex process tediously long, hollow
The problems such as microballoon size control is not easy and the uniformity is poor.
Description of the drawings
Fig. 1 is that load has Fe in the embodiment of the present invention 13O4Magnetic graphene tiny balloon SEM scheme (enlargement ratio
It is 1000 ×)；
Fig. 2 is that load has Fe in the embodiment of the present invention 13O4Magnetic graphene tiny balloon section SEM figure (amplification
Multiplying power is 2000 ×)；
Fig. 3 is the SEM figures of coated with silica magnetic graphene tiny balloon in the embodiment of the present invention 1；
Fig. 4 is the electro-magnetic wave absorption of coated with silica magnetic graphene tiny balloon prepared by 1-4 of the embodiment of the present invention
Test result.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail.
Following embodiment removes specified otherwise, and used raw material and equipment are purchased in market.
In following embodiment, the test condition of the electro-magnetic wave absorption test of coated with silica magnetic graphene tiny balloon
For：It is tested according to arch method as defined in GJB2038A, test sample thickness 2.5mm, the content 20wt% of wave absorbing agent.
Embodiment 1
A kind of coated with silica magnetic graphene tiny balloon is nucleocapsid, wherein magnetic graphene tiny balloon
For core, silica is shell, the magnetic graphene tiny balloon, and hollow average diameter is 3 μm, and magnetic graphene is hollow
The cladding thickness of a diameter of 5 μm of microballoon, the silica is 0.5 μm, and coated with silica magnetic graphene is hollow micro-
The average grain diameter of ball is 6 μm, specific surface area 1500m2/ g, density 1.2g/cm3, magnetic is full after concentrated hydrochloric acid solution corrodes
It is 5% to reduce degree with intensity (magnetism).
A kind of magnanimity preparation method of coated with silica magnetic graphene tiny balloon, includes the following steps：
Step 1, dispersion liquid is prepared
Under 1200W ul-trasonic irradiations, graphene oxide, deionized water, ethyl alcohol, polyvinyl alcohol are subjected to ultrasonic disperse
30min, then ferric acetyl acetonade, stirs evenly, and obtains dispersion liquid；Wherein, by solid-to-liquid ratio, graphene oxide：Deionized water：Second
Alcohol：Polyvinyl alcohol：Ferric acetyl acetonade=1g：200mL：1500mL：10g：20g；
Step 2, it is spray-dried
Dispersion liquid is spray-dried by spray dryer, has second through the isolated powdered loaded of cyclone separator
The graphene oxide tiny balloon presoma of sour acetone iron；Wherein, spray drying temperature is 200 DEG C；
Step 3, roasting reduction
(1) the graphene oxide tiny balloon presoma that load is had to acetic acid acetone iron, in the argon that flow is 50mL/min
In gas atmosphere, 400 DEG C are warming up to 10 DEG C/min, roasts 1h；
(2) 600 DEG C are warming up to 10 DEG C/min again, roast 5h；
(3) room temperature is cooled to 5 DEG C/min, obtaining load has Fe3O4Magnetic graphene tiny balloon；
There is Fe to the load of preparation3O4Magnetic graphene tiny balloon characterized, SEM figures are shown in Fig. 1 (enlargement ratios
It is 1000 ×) and Fig. 2 (enlargement ratio be 2000 ×), it can see that microsphere surface is coarse, and grain size is more uniform from Fig. 1 and Fig. 2,
Inside is in hollow-core construction.
Step 4, coated silica
(1) mixed liquor is prepared：It is that 25% ammonium hydroxide mixes by ethyl alcohol, deionized water and mass percent concentration, obtains
Mixed liquor；Wherein, by volume, ethyl alcohol：Deionized water：Mass percent concentration is 25% ammonium hydroxide=500mL：200mL：
10mL；
(2) load there is into Fe3O4Magnetic graphene tiny balloon under 1500rpm/min stir speed (S.S.)s, be stirred,
It is scattered in mixed liquor, after being uniformly dispersed, ethyl orthosilicate is slowly added dropwise, reacts 10h, obtains reaction product；Wherein, by solid-liquid
Than magnetic graphene tiny balloon：Ethyl orthosilicate=1g：The drop rate of 5mL, ethyl orthosilicate are 0.5mL/min；
(3) reaction product is adsorbed in reaction container bottom, topples over removal supernatant, be stirred and washed with 200mL ethyl alcohol
It washs 3 times, is detached solid product and cleaning solution with the method for magnet adsorption, the remaining solid of obtained reaction container bottom is produced
Product are dried in vacuo at a temperature of 60 DEG C, obtain coated with silica magnetic graphene tiny balloon.
Analysis test is carried out to coated with silica magnetic graphene tiny balloon manufactured in the present embodiment, SEM figures are shown in
It is relatively smooth closely knit can to obtain microsphere surface from Fig. 3 by Fig. 3.To coated with silica magnetic graphite manufactured in the present embodiment
The electromagnetic wave absorption performance of alkene tiny balloon is tested according to arch method as defined in GJB2038A, and test result is shown in Fig. 4.
Embodiment 2
A kind of coated with silica magnetic graphene tiny balloon is nucleocapsid, wherein magnetic graphene tiny balloon
For core, silica is shell, the magnetic graphene tiny balloon, and hollow average diameter is 8 μm, and magnetic graphene is hollow
The cladding thickness of a diameter of 10 μm of microballoon, the silica is 3 μm, coated with silica magnetic graphene tiny balloon
Average grain diameter be 15 μm, specific surface area 800m2/ g, density 0.9g/cm3, the magnetic saturation after concentrated hydrochloric acid solution corrodes
It is 3% that intensity (magnetism), which reduces degree,.
A kind of magnanimity preparation method of coated with silica magnetic graphene tiny balloon, includes the following steps：
Step 1, dispersion liquid is prepared
Under 800W ul-trasonic irradiations, graphene oxide, deionized water, ethyl alcohol, polyvinylpyrrolidone are subjected to ultrasound
Disperse 30min, then iron chloride, stirs evenly, and obtains dispersion liquid；Wherein, by solid-to-liquid ratio, graphene oxide：Deionized water：Second
Alcohol：Polyvinylpyrrolidone：Iron chloride=1g：2L：500mL：3g：10g；
Step 2, it is spray-dried
Dispersion liquid is spray-dried by spray dryer, has chlorine through the isolated powdered loaded of cyclone separator
Change the graphene oxide tiny balloon presoma of iron；Wherein, spray drying temperature is 300 DEG C；
Step 3, roasting reduction
(1) the graphene oxide tiny balloon presoma that load is had to iron chloride, in the nitrogen gas that flow is 120mL/min
In atmosphere, 350 DEG C are warming up to 20 DEG C/min, roasts 2h；
(2) 800 DEG C are warming up to 20 DEG C/min again, roast 4h；
(3) room temperature is cooled to 5 DEG C/min, obtaining load has Fe3O4Magnetic graphene tiny balloon；
Step 4, coated silica
(1) mixed liquor is prepared：It is that 25% ammonium hydroxide mixes by ethyl alcohol, deionized water and mass percent concentration, obtains
Mixed liquor；Wherein, by volume, ethyl alcohol：Deionized water：Mass percent concentration is 25% ammonium hydroxide=500mL：200mL：
10mL；
(2) load there is into Fe3O4Magnetic graphene tiny balloon under 1000rpm/min stir speed (S.S.)s, be stirred,
It is scattered in mixed liquor, after being uniformly dispersed, ethyl orthosilicate is slowly added dropwise, reacts 6h, obtains reaction product；Wherein, by solid-liquid
Than magnetic graphene tiny balloon：Ethyl orthosilicate=1g：The drop rate of 20mL, ethyl orthosilicate are 2mL/min；
(3) reaction product is adsorbed in reaction container bottom, topples over removal supernatant, be stirred and washed with 500mL ethyl alcohol
It washs 5 times, is detached solid product and cleaning solution with the method for magnet adsorption, the remaining solid of obtained reaction container bottom is produced
Product are dried in vacuo at a temperature of 60 DEG C, obtain coated with silica magnetic graphene tiny balloon.
To the electromagnetic wave absorption performance of coated with silica magnetic graphene tiny balloon manufactured in the present embodiment according to
Arch method as defined in GJB2038A is tested, and test result is shown in Fig. 4.
Embodiment 3
A kind of coated with silica magnetic graphene tiny balloon is nucleocapsid, wherein magnetic graphene tiny balloon
For core, silica is shell, the magnetic graphene tiny balloon, and hollow average diameter is 5 μm, and magnetic graphene is hollow
The cladding thickness of a diameter of 10 μm of microballoon, the silica is 2 μm, coated with silica magnetic graphene tiny balloon
Average grain diameter be 13 μm, specific surface area 1100m2/ g, density 0.7g/cm3, magnetic is full after concentrated hydrochloric acid solution corrodes
It is 3% to reduce degree with intensity (magnetism).
A kind of magnanimity preparation method of coated with silica magnetic graphene tiny balloon, includes the following steps：
Step 1, dispersion liquid is prepared
Under 1000W ul-trasonic irradiations, graphene oxide, deionized water, ethyl alcohol, polyvinylpyrrolidone are subjected to ultrasound
Disperse 40min, then cobalt acetate, stirs evenly, and obtains dispersion liquid；Wherein, by solid-to-liquid ratio, graphene oxide：Deionized water：Second
Alcohol：Polyvinylpyrrolidone：Cobalt acetate=1g：1L：1L：10g：6g；
Step 2, it is spray-dried
Dispersion liquid is spray-dried by spray dryer, has second through the isolated powdered loaded of cyclone separator
The graphene oxide tiny balloon presoma of sour cobalt；Wherein, spray drying temperature is 250 DEG C；
Step 3, roasting reduction
(1) the graphene oxide tiny balloon presoma that load is had to cobalt acetate, in the nitrogen gas that flow is 80mL/min
In atmosphere, 350 DEG C are warming up to 10 DEG C/min, roasts 2h；
(2) 900 DEG C are warming up to 10 DEG C/min again, roast 3h；
(3) room temperature is cooled to 10 DEG C/min, obtains magnetic graphene tiny balloon；
Step 4, coated silica
(1) mixed liquor is prepared：It is that 25% ammonium hydroxide mixes by propyl alcohol, deionized water and mass percent concentration, obtains
Mixed liquor；Wherein, by volume, propyl alcohol：Deionized water：Mass percent concentration is 25% ammonium hydroxide=300mL：100mL：
10mL；
(2) magnetic graphene tiny balloon is stirred under 500rpm/min stir speed (S.S.)s, is scattered in mixed liquor
In, after being uniformly dispersed, ethyl orthosilicate is slowly added dropwise, reacts 8h, obtains reaction product；Wherein, by solid-to-liquid ratio, magnetic graphene
Tiny balloon：Ethyl orthosilicate=1g：The drop rate of 15mL, ethyl orthosilicate are 2mL/min；
(3) reaction product is adsorbed in reaction container bottom, topples over removal supernatant, be stirred and washed with 400mL ethyl alcohol
It washs 4 times, is detached solid product and cleaning solution with the method for magnet adsorption, the remaining solid of obtained reaction container bottom is produced
Product are dried in vacuo at a temperature of 60 DEG C, obtain coated with silica magnetic graphene tiny balloon.
To the electromagnetic wave absorption performance of coated with silica magnetic graphene tiny balloon manufactured in the present embodiment according to
Arch method as defined in GJB2038A is tested, and test result is shown in Fig. 4.
Embodiment 4
A kind of coated with silica magnetic graphene tiny balloon is nucleocapsid, wherein magnetic graphene tiny balloon
For core, silica is shell, the magnetic graphene tiny balloon, and hollow average diameter is 5 μm, and magnetic graphene is hollow
The cladding thickness of a diameter of 10 μm of microballoon, the silica is 2 μm, coated with silica magnetic graphene tiny balloon
Average grain diameter be 14 μm, specific surface area 900m2/ g, density 1.1g/cm3, the magnetic saturation after concentrated hydrochloric acid solution corrodes
It is 5% that intensity (magnetism), which reduces degree,.
A kind of magnanimity preparation method of coated with silica magnetic graphene tiny balloon, includes the following steps：
Step 1, dispersion liquid is prepared
Under 800W ul-trasonic irradiations, graphene oxide, deionized water, ethyl alcohol, polyvinyl alcohol are subjected to ultrasonic disperse
50min, then nickel nitrate, stirs evenly, and obtains dispersion liquid；Wherein, by solid-to-liquid ratio, graphene oxide：Deionized water：Ethyl alcohol：
Polyvinyl alcohol：Nickel nitrate=1g：1L：0.5L：10g：15g；
Step 2, it is spray-dried
Dispersion liquid is spray-dried by spray dryer, has nitre through the isolated powdered loaded of cyclone separator
The graphene oxide tiny balloon presoma of sour nickel；Wherein, spray drying temperature is 250 DEG C；
Step 3, roasting reduction
(1) the graphene oxide tiny balloon presoma that load is had to nickel nitrate, in the nitrogen gas that flow is 80mL/min
In atmosphere, 400 DEG C are warming up to 20 DEG C/min, roasts 0.5h；
(2) 900 DEG C are warming up to 20 DEG C/min again, roast 3h；
(3) room temperature is cooled to 2 DEG C/min, obtains magnetic graphene tiny balloon；
Step 4, coated silica
(1) mixed liquor is prepared：It is that 25% ammonium hydroxide mixes by propyl alcohol, deionized water and mass percent concentration, obtains
Mixed liquor；Wherein, by volume, propyl alcohol：Deionized water：Mass percent concentration is 25% ammonium hydroxide=200mL：100mL：
10mL；
(2) magnetic graphene tiny balloon is stirred under 1000rpm/min stir speed (S.S.)s, is scattered in mixed liquor
In, after being uniformly dispersed, ethyl orthosilicate is slowly added dropwise, reacts 6h, obtains reaction product；Wherein, by solid-to-liquid ratio, magnetic graphene
Tiny balloon：Ethyl orthosilicate=1g：The drop rate of 10mL, ethyl orthosilicate are 1mL/min；
(3) reaction product is adsorbed in reaction container bottom, topples over removal supernatant, be stirred and washed with 300mL ethyl alcohol
It washs 3 times, is detached solid product and cleaning solution with the method for magnet adsorption, the remaining solid of obtained reaction container bottom is produced
Product are dried in vacuo at a temperature of 60 DEG C, obtain coated with silica magnetic graphene tiny balloon.
To the electromagnetic wave absorption performance of coated with silica magnetic graphene tiny balloon manufactured in the present embodiment according to
Arch method as defined in GJB2038A is tested, and test result is shown in Fig. 4.
Embodiment 5
A kind of coated with silica magnetic graphene tiny balloon is nucleocapsid, wherein magnetic graphene tiny balloon
For core, silica is shell, the magnetic graphene tiny balloon, and hollow average diameter is 8 μm, and magnetic graphene is hollow
The cladding thickness of a diameter of 11 μm of microballoon, the silica is 1 μm, coated with silica magnetic graphene tiny balloon
Average grain diameter be 13 μm, specific surface area 300m2/ g, density 0.8g/cm3, the magnetic saturation after concentrated hydrochloric acid solution corrodes
It is 5% that intensity (magnetism), which reduces degree,.
A kind of magnanimity preparation method of coated with silica magnetic graphene tiny balloon, includes the following steps：
Step 1, dispersion liquid is prepared
Under 600W ul-trasonic irradiations, by graphene oxide, deionized water, ethyl alcohol, ethylene glycol, polyvinyl alcohol and polyethylene
Pyrrolidones carries out ultrasonic disperse 60min, and then ferric nitrate, stirs evenly, and obtains dispersion liquid；Wherein, by solid-to-liquid ratio, stone is aoxidized
Black alkene：Deionized water：Ethyl alcohol：Ethylene glycol：Polyvinyl alcohol：Polyvinylpyrrolidone：Ferric nitrate=1g：1L：0.5L：0.5L：6g：
4g：10g；
Step 2, it is spray-dried
Dispersion liquid is spray-dried by spray dryer, has nitre through the isolated powdered loaded of cyclone separator
The graphene oxide tiny balloon presoma of sour iron；Wherein, spray drying temperature is 160 DEG C；
Step 3, roasting reduction
(1) load is had into the graphene oxide tiny balloon presoma of ferric nitrate, in the nitrogen that flow is 120mL/min and
Argon gas gaseous mixture (mixed volume ratio 1:1) in atmosphere, 400 DEG C is warming up to 5 DEG C/min, roasts 1h；
(2) 500 DEG C are warming up to 5 DEG C/min again, roast 6h；
(3) room temperature is cooled to 2 DEG C/min, obtains magnetic graphene tiny balloon；
Step 4, coated silica
(1) mixed liquor is prepared：It is that 28% ammonium hydroxide mixes by propyl alcohol, ethyl alcohol, deionized water and mass percent concentration,
Obtain mixed liquor；Wherein, by volume, propyl alcohol：Ethyl alcohol：Deionized water：Mass percent concentration is 28% ammonium hydroxide=1L:1L：
500mL：30mL；
(2) magnetic graphene tiny balloon is stirred under 500rpm/min stir speed (S.S.)s, is scattered in mixed liquor
In, after being uniformly dispersed, ethyl orthosilicate is slowly added dropwise, reacts 6h, obtains reaction product；Wherein, by solid-to-liquid ratio, magnetic graphene
Tiny balloon：Ethyl orthosilicate=1g：The drop rate of 10mL, ethyl orthosilicate are 1mL/min；
(3) reaction product is adsorbed in reaction container bottom, topples over removal supernatant, 3 are followed by stirring and washing with 1L ethyl alcohol
It is secondary, solid product and cleaning solution are detached with the method for magnet adsorption, by the remaining solid product of obtained reaction container bottom,
It is dried in vacuo at a temperature of 100 DEG C, obtains coated with silica magnetic graphene tiny balloon.
Embodiment 6
A kind of coated with silica magnetic graphene tiny balloon is nucleocapsid, wherein magnetic graphene tiny balloon
For core, silica is shell, the magnetic graphene tiny balloon, and hollow average diameter is 10 μm, and magnetic graphene is empty
The cladding thickness of a diameter of 18 μm of heart microballoon, the silica is 2 μm, and coated with silica magnetic graphene is hollow micro-
The average grain diameter of ball is 23 μm, specific surface area 800m2/ g, density 0.4g/cm3, magnetic is full after concentrated hydrochloric acid solution corrodes
It is 5% to reduce degree with intensity (magnetism).
A kind of magnanimity preparation method of coated with silica magnetic graphene tiny balloon, includes the following steps：
Step 1, dispersion liquid is prepared
Under 900W ul-trasonic irradiations, graphene oxide, deionized water, methanol, polyvinylpyrrolidone are subjected to ultrasound
Disperse 30min, then iron chloride and acetylacetone cobalt, stir evenly, and obtain dispersion liquid；Wherein, by solid-to-liquid ratio, graphite oxide
Alkene：Deionized water：Methanol：Polyvinylpyrrolidone：Iron chloride：Acetylacetone cobalt=1g：2L：500mL：3g：5g:5g；
Step 2, it is spray-dried
Dispersion liquid is spray-dried by spray dryer, has chlorine through the isolated powdered loaded of cyclone separator
Change the graphene oxide tiny balloon presoma of iron；Wherein, spray drying temperature is 200 DEG C；
Step 3, roasting reduction
(1) the graphene oxide tiny balloon presoma that load is had to iron chloride, in the nitrogen gas that flow is 100mL/min
In atmosphere, 350 DEG C are warming up to 15 DEG C/min, roasts 2h；
(2) 600 DEG C are warming up to 15 DEG C/min again, roast 4h；
(3) room temperature is cooled to 5 DEG C/min, obtains magnetic graphene tiny balloon；
Step 4, coated silica
(1) mixed liquor is prepared：It is that 28% ammonium hydroxide mixes by ethylene glycol, deionized water and mass percent concentration, obtains
To mixed liquor；Wherein, by volume, ethylene glycol：Deionized water：Mass percent concentration is 28% ammonium hydroxide=500mL：200mL：
10mL；
(2) magnetic graphene tiny balloon is stirred under 1000rpm/min stir speed (S.S.)s, is scattered in mixed liquor
In, after being uniformly dispersed, ethyl orthosilicate is slowly added dropwise, reacts 8h, obtains reaction product；Wherein, by solid-to-liquid ratio, magnetic graphene
Tiny balloon：Ethyl orthosilicate=1g：The drop rate of 20mL, ethyl orthosilicate are 2mL/min；
(3) reaction product is adsorbed in reaction container bottom, topples over removal supernatant, be stirred and washed with 500mL ethyl alcohol
It washs 5 times, is detached solid product and cleaning solution with the method for magnet adsorption, the remaining solid of obtained reaction container bottom is produced
Product are dried in vacuo at a temperature of 60 DEG C, obtain coated with silica magnetic graphene tiny balloon.
Claims (10)
1. a kind of coated with silica magnetic graphene tiny balloon, which is characterized in that the coated with silica magnetic graphene
Tiny balloon is nucleocapsid, wherein magnetic graphene tiny balloon is core, and silica is shell.
2. coated with silica magnetic graphene tiny balloon as described in claim 1, which is characterized in that the magnetic stone
Black alkene tiny balloon, hollow average diameter be 0.1~20 μm, a diameter of 0.4~25 μm of magnetic graphene tiny balloon, institute
The cladding thickness for the silica stated is 0.1~5 μm, and the average grain diameter of coated with silica magnetic graphene tiny balloon is
0.5~30 μm, specific surface area is 100~2000m2/ g, density are 0.4~1.2g/cm3, magnetic is full after concentrated hydrochloric acid solution corrodes
Degree≤5% is reduced with intensity (magnetism).
3. the magnanimity preparation method of coated with silica magnetic graphene tiny balloon as claimed in claim 1 or 2, feature exist
In including the following steps：
Step 1, dispersion liquid is prepared
Under ul-trasonic irradiation, graphene oxide, deionized water, liquid alcohol, water-soluble polymer are subjected to ultrasonic disperse, then
Metal salt is added, stirs evenly, obtains dispersion liquid；Wherein, by solid-to-liquid ratio, graphene oxide：Deionized water：Liquid alcohol：It is water-soluble
Property polymer：Metal salt=1g：(0.2~2) L：(0.5~1.5) L：(3~10) g：(6~20) g；
Step 2, it is spray-dried
Dispersion liquid is spray-dried, isolated powdered loaded has the graphene oxide tiny balloon forerunner of metal salt
Body；Wherein, spray drying temperature is 160~300 DEG C；
Step 3, roasting reduction
(1) load is had into the graphene oxide tiny balloon presoma of metal salt, in inert protective atmosphere, with 5~20 DEG C/
Min is warming up to 350~400 DEG C, roasts 0.5~2h；
(2) 500~900 DEG C are warming up to 5~20 DEG C/min again, roast 3~6h；
(3) room temperature is cooled to 2~10 DEG C/min, obtains magnetic graphene tiny balloon；
Step 4, coated silica
(1) mixed liquor is prepared：It is that 25%~28% ammonium hydroxide mixes by liquid alcohol, deionized water and mass percent concentration,
Obtain mixed liquor；Wherein, by volume, liquid alcohol：Deionized water：Mass percent concentration is 25%~28% ammonium hydroxide=(20
~200)：(10~50)：(1~3)；
(2) magnetic graphene tiny balloon is scattered under the stirring of 500~1500rpm/min in mixed liquor, is uniformly dispersed
Afterwards, ethyl orthosilicate is slowly added dropwise, reacts 6~10h, obtains reaction product；Wherein, by solid-to-liquid ratio, magnetic graphene is hollow micro-
Ball：Ethyl orthosilicate=1g：The drop rate of (5~20) mL, ethyl orthosilicate are 0.5~2mL/min；
(3) reaction product is removed into supernatant, is washed, detached, obtained solid product is dried, titanium dioxide is obtained
Silicon coated magnetic graphene hollow microspheres.
4. the magnanimity preparation method of coated with silica magnetic graphene tiny balloon as claimed in claim 3, feature exist
In, in the step 1, the liquid alcohol is the mixture of one or more of methanol, ethyl alcohol, propyl alcohol, ethylene glycol, when
For mixture when, mixed proportion be arbitrary ratio.
5. the magnanimity preparation method of coated with silica magnetic graphene tiny balloon as claimed in claim 3, feature exist
In, in the step 1, the water-soluble polymer be polyvinyl alcohol or polypyrrole alkanone, or both mixture, when for
When mixture, mixed proportion is arbitrary ratio.
6. the magnanimity preparation method of coated with silica magnetic graphene tiny balloon as claimed in claim 3, feature exist
In in the step 1, the metal salt is ferric acetyl acetonade, nickel acetylacetonate, acetylacetone cobalt, ferric nitrate, nitric acid
One or more of nickel, cobalt nitrate, ferric acetate, nickel acetate, cobalt acetate, iron chloride, nickel chloride, cobalt chloride mix, when being mixed
When closing object, mixed proportion is arbitrary ratio.
7. the magnanimity preparation method of coated with silica magnetic graphene tiny balloon as claimed in claim 3, feature exist
In, in the step 1, the ultrasonic disperse, the power of ultrasonic wave is 600~1200W, time of ultrasonic disperse is 30~
60min。
8. the magnanimity preparation method of coated with silica magnetic graphene tiny balloon as claimed in claim 3, feature exist
In in the step 3 (1), the inert protective atmosphere, it is specially in nitrogen, argon gas, neon, helium that inertia, which protects gas,
One or more of mixing, when for mixture, mixed proportion is arbitrary ratio, and inertia protects 50~120mL/min of flow of gas.
9. the magnanimity preparation method of coated with silica magnetic graphene tiny balloon as claimed in claim 3, feature exist
In, in the step 4 (1), the liquid alcohol is one or more of methanol, ethyl alcohol, propyl alcohol, ethylene glycol mixture,
When for mixture, mixed proportion is arbitrary ratio.
10. the magnanimity preparation method of coated with silica magnetic graphene tiny balloon as claimed in claim 3, feature exist
In in the step 4 (3), the drying, for vacuum drying, drying temperature is 60~100 DEG C.
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