CN104941543A - Method for preparing graphene/ferrite composite nanometer microspheres having high magnetic-electric performances - Google Patents
Method for preparing graphene/ferrite composite nanometer microspheres having high magnetic-electric performances Download PDFInfo
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Abstract
The invention belongs to the field of novel material preparation and provides a method for preparing graphene/ferrite composite nanometer microspheres having high magnetic-electric performances. Ferrites are manganous ferrite and nickel ferrite. According to the method, first graphene oxide is prepared, and then graphene/manganous ferrite or graphene/nickel ferrite composite nanometer microspheres are synthesized in one step through a hydrothermal method (a solvothermal method). The synthesizing method is simple. The obtained graphene/manganous ferrite or graphene/nickel ferrite composite nanometer microspheres are high in specific surface area and have high magnetism; and by controlling the ratio of graphene oxide to manganous ferrite or the ratio of graphene oxide to nickel ferrite, it is guaranteed that the composite nanometer microspheres can achieve very good wave-absorbing properties. Prepared graphene/manganous ferrite and graphene/nickel ferrite nanocomposite materials not only have excellent electromagnetic loss performances, but also can serve as a light and high-strength wave-absorbing material to be applied to the fields of sewage treatment, energy, stealth and electronics.
Description
Technical field
The invention belongs to field of new material preparation, relate to graphene/ferrate composite material and preparation method thereof, be specially a kind of preparation method of strong magnetic electricity performance graphene/ferrate composite nano-microsphere, described ferrite is Manganese Ferrite, nickel ferrite based magnetic loaded.
Background technology
Spinel type ferrite is a kind of two composite dielectric material, and have magnetic absorbing and electric absorption double-absorption function, in addition it also has higher u
rvalue and cheap preparation cost, present ferrite is a kind of microwave absorption being subject to people's extensive concern.Compare with other absorbing materials, Ferrite Material has the advantages such as absorption efficiency is high, coating is thin, bandwidth, can not only be widely used on the military hardware facilities such as aircraft, tank, guided missile and radar, and also have a lot of application at civil area, as microwave dark room material, microwave attenuator element etc.Nowadays along with the high speed development of electronic technology, produce increasing electromagnetic wave, these electromagnetic waves can not only upset the normal operation of some electronic equipments, also can damage our healthy.Ferrite at low frequency in addition, has larger u
rvalue and less ε
rvalue, therefore it has obvious advantage as matching materials, has good application prospect.But as traditional absorbing material, ferrite also has the deficiencies such as density is large, poor stability, and these just limit its extensive use.Preparing the most frequently used method of Manganese Ferrite is at present sol-gel process, but the gel precursor that sol-gal process is prepared is easy to deliquescence, easily forms hard aggregation phenomenon after oven dry, shrinks large time dry.
Since Geim in 2004 etc. utilize adhesive tape repeatedly to peel off obtained Graphene on native graphite, the whole world has started the upsurge of one research Graphene.Chemically become in key mode, form the carbon atom of Graphene two-dimensional structure with sp
2mode hydridization, this hybrid form makes carbon atom and adjacent three carbon atoms form stable C-C key by σ key, and such bonding pattern gives Graphene stable structure, becomes the material that the known intensity of the mankind is the highest.Form large π key in the pi-electron delocalization provided perpendicular to carbon atom a large amount of on graphene planes, electronics can move freely wherein simultaneously, and therefore Graphene all has excellent electric conductivity usually.Such as Graphene is a kind of zero gap semiconductor, and electronics wherein movement velocity can reach 1/300 of the light velocity, and Graphene carrier mobility speed is up to 2 × 0
5cm
2v
-1s
-1deng.In addition, Graphene also has good thermal property and magnetic performance.The fields such as the specific area that Graphene is higher makes it at ultracapacitor, Chu Qing, unimolecule chemical sensor have huge potential application.
Along with the fast development of nanometer technology, the multi-functional nanometer material with excellent optical, mechanics, electricity and magnetic performance becomes a study hotspot.Research some metals the earliest and metal oxide, can not extensive uses due to poor chemical stability, particle diameter disunity, the problem such as serious of reuniting.Recently, people begin one's study various metal, and metal oxide and semi-conductor nano particles combine to solve the various problems such as stability with the two-dimensional structure of Graphene.Because the combination between nano particle and graphene base body does not need molecular link to connect, too much influence be there is no to the electronic structure of graphenic surface electronics, therefore many second-phase components can be deposited on Graphene lamella on thus combination property both realizing, such as in catalysis, energy storage, sensing, the fields such as photoelectron.Inorganic Non-metallic Materials is at present for their synthetic method, and pattern controls and the character workers that study science have done a large amount of work, and the research of graphene composite material based on this is also a focus now.
Summary of the invention
The object of the invention is the preparation method providing a kind of strong magnetic electricity performance Graphene/Manganese Ferrite, Graphene/nickel ferrite based magnetic loaded composite nano-microsphere, comprises the following steps:
Steps A. prepare graphene oxide:
Steps A 1. for raw material, carries out weighing with crystalline graphite powder, the concentrated sulfuric acid, SPA, potassium permanganate, deionized water, hydrogen peroxide, watery hydrochloric acid; Wherein, crystalline graphite powder and concentrated sulfuric acid ratio are 1g:(90 ~ 150mL), the ratio of crystalline graphite powder and SPA is 1g:(10 ~ 18mL), the ratio of graphite powder and potassium permanganate is 1g:(3 ~ 10g), hydrogen peroxide concentration is 18 ~ 35%;
Steps A 2. room-temperature water bath, adds the concentrated sulfuric acid and SPA nitration mixture, after mechanical agitation to nitration mixture temperature is back to room temperature in the three-necked bottle of condenser pipe; Divide within half an hour and add crystalline graphite powder three times, room temperature mechanical stirs 1 ~ 3 hour; Gradation slowly adds potassium permanganate, and now system temperature slowly raises, and control potassium permanganate adds speed makes system temperature not higher than 40 DEG C; Treat that potassium permanganate feeds in raw material complete, obtain blackish green solution, raised temperature to 40 ~ 60 DEG C, stir 8 ~ 24h, obtain crystalline graphite powder oxidation stripper;
Crystalline graphite powder to be oxidized under stripper mechanical agitation slowly impouring by steps A 3. to be had in the deionized water of ice cube, obtains sepia mixing material, continues to stir until system is back to room temperature; Then pipette hydrogen peroxide with pipette, dropping to mixing material color by brown stain is glassy yellow;
Steps A 3 is obtained mixed solution and carries out centrifugation by steps A 4., obtain yellow mercury oxide, with washed with de-ionized water to neutral, namely obtain oxide yellow Graphene, be dry 24 ~ 48h in 40 ~ 60 DEG C of vacuum drying chambers in temperature, obtain final black thin paper shape graphene oxide;
When preparing Graphene/Manganese Ferrite composite nano-microsphere,
Step B. solvent-thermal method one-step synthesis Graphene/Manganese Ferrite composite nano-microsphere:
Step B1. with ethylene glycol, molecular weight be 800 ~ 3000 polyethylene glycol, ferric chloride (FeCl36H2O), four water acetic acid manganese, acetate for initiation material, described acetate is acetic acid sodium salt or acetic acid sylvite; FeCl
3be 1:2 with the mol ratio of manganese acetate; FeCl
3be 1g:(10 ~ 40mL with ethylene glycol ratio); FeCl
3be 1g:(0.1 ~ 1g with polyethylene glycol ratio); FeCl
3be 1g:(1 ~ 10g with acetate ratio); FeCl
3be 1g:(10 ~ 100mg with graphene oxide ratio); Wherein, ethylene glycol is solvent, molecular weight be 800 ~ 3000 polyethylene glycol be reducing agent, ferric chloride (FeCl36H2O), four water acetic acid manganese are raw material, add acetate with thinking that synthesis provides alkaline environment;
Step B2. is under 25 ~ 80 DEG C of water bath sonicator conditions, polyethylene glycol is dissolved in ethylene glycol and obtains clear solution, then steps A being obtained graphene oxide adds in clear solution, under mechanical agitation, Graphene to be oxidized dissolves obtain dark solution completely, add iron chloride again and manganese acetate obtains red tan solution, continue after dissolving to add acetate, obtain the molten slurry of rufous, continue ultrasonic agitation 1 ~ 3 hour;
The stainless steel crystallization still that the molten slurry of the rufous that step B2 obtains by step B3. proceeds to polytetrafluoro lining leaves standstill 15 ~ 24h in 180 DEG C of baking ovens; Then, be separated with magnet and obtain black solid, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dryings, obtain final Graphene/Manganese Ferrite composite nano-microsphere.
In addition, when preparing Graphene/nickel ferrite based magnetic loaded composite nano-microsphere,
Step B. solvent-thermal method one-step synthesis Graphene/nickel ferrite based magnetic loaded composite nano-microsphere:
Step B1. with deionized water, nine water ferric nitrates, six water nickel nitrates, urea for initiation material; FeNO
3be 1:2 with the mol ratio of nickel nitrate; FeNO
3be 1g:(10 ~ 40mL with deionized water ratio); FeNO
3be 1g:(1 ~ 10g with urea ratio); FeNO
3be 1g:(10 ~ 100mg with graphene oxide ratio); Wherein, deionized water is solvent, and urea is reducing agent, simultaneously for synthesis provides alkaline environment, nine water ferric nitrates, six water nickel nitrates are raw material;
Step B2. is under 25 ~ 80 DEG C of water bath sonicator conditions, steps A being obtained graphene oxide adds in deionized water, under mechanical agitation, Graphene to be oxidized dissolves obtain dark solution completely, add ferric nitrate again and nickel nitrate obtains red tan solution, continue after dissolving to add urea, obtain the molten slurry of rufous, continue ultrasonic agitation 1 ~ 3 hour;
The stainless steel crystallization still that the molten slurry of the rufous that step B2 obtains by step B3. proceeds to polytetrafluoro lining leaves standstill 15 ~ 24h in 180 DEG C of baking ovens; Then, be separated with magnet and obtain black solid, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dryings, obtain final Graphene/Manganese Ferrite composite nano-microsphere.
It should be noted that, the maximum feature of the present invention is to adopt solvent-thermal method one-step synthesis Graphene/Manganese Ferrite or Graphene/nickel ferrite based magnetic loaded composite nano-microsphere, Manganese Ferrite and nickel ferrite based magnetic loaded are the ferrite of close character, only because the difference of Manganese Ferrite and nickel ferrite based magnetic loaded in solvent-thermal method one-step synthesis process, select corresponding solvent, reducing agent and raw material, its solvent-thermal method processing step and parameter all identical, thus prepare between Graphene/Manganese Ferrite or Graphene/nickel ferrite based magnetic loaded composite nano-microsphere be have monistic.
Beneficial effect of the present invention is:
The present invention adopts hydro-thermal method (solvent-thermal method) one-step synthesis Graphene/Manganese Ferrite or Graphene/nickel ferrite based magnetic loaded composite nano-microsphere, and this synthetic method is simple; Graphene/the Manganese Ferrite obtained, Graphene/nickel ferrite based magnetic loaded Nano microsphere, has larger specific area; There is ferromagnetism simultaneously; By the ratio of controlled oxidization Graphene and Manganese Ferrite or graphene oxide and nickel ferrite based magnetic loaded, ensure that being prepared into composite nano-microsphere can reach good absorbing property.The present invention is prepared into Graphene/Manganese Ferrite Nano microsphere reflectivity and is less than the frequency range of-10dB at 9-13GHz, and frequency range is 4GHz, reaches maximum reflection loss for-42dB (as shown in Figure 3) at 10.5GHz; Graphene/nickel ferrite based magnetic loaded Nano microsphere reflectivity is less than the frequency range of-10dB at 13-138Hz, and frequency range is 5GHz, reaches maximum reflection loss for-40dB (as shown in Figure 5) at 15.2GHz; And Nano microsphere yardstick makes this kind of composite can be scattered in uniformly in water, ethanol, acetone equal solvent, has good dissolubility.The present invention is prepared into Graphene/Manganese Ferrite, Graphene/nickel ferrite based magnetic loaded nano composite material not only shows excellent magnetic particles, and the absorbing material that also can be used as a kind of high-strength light is applied to the fields such as sewage disposal, the energy, stealthy and electronics.
Accompanying drawing explanation
Fig. 1 is that embodiment 2 is prepared into Graphene/Manganese Ferrite composite nano-microsphere scanning electron microscope (SEM) photograph.
Fig. 2 is that embodiment 2 is prepared into Graphene/Manganese Ferrite composite nano-microsphere transmission electron microscope picture.
Fig. 3 is that embodiment 2 is prepared into Graphene/Manganese Ferrite composite nano-microsphere microwave electromagnetic reflecting properties figure.
Fig. 4 is that embodiment 6 is prepared into Graphene/nickel ferrite based magnetic loaded composite nano-microsphere scanning electron microscope (SEM) photograph.
Fig. 5 is that embodiment 6 is prepared into Graphene/nickel ferrite based magnetic loaded composite nano-microsphere microwave electromagnetic reflecting properties figure.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is further detailed explanation, but embodiment further illustrates of the present invention, instead of limit the scope of the invention.
Embodiment 1
(1) crystalline graphite powder, the concentrated sulfuric acid, SPA, potassium permanganate, deionized water, hydrogen peroxide, watery hydrochloric acid is taken; Wherein crystalline graphite powder and concentrated sulfuric acid ratio are 1g:120mL; The ratio of crystalline graphite powder and SPA is 1g:15mL; The ratio of graphite powder and potassium permanganate is 1g:6g; Hydrogen peroxide concentration is 30%;
(2) room-temperature water bath, the concentrated sulfuric acid and phosphoric acid mixing acid is added in the 500mL three-necked bottle of condenser pipe, mechanical agitation is back to room temperature to nitration mixture temperature, control crystalline graphite powder addition, divide within half an hour and feed in raw material complete three times, room temperature mechanical stirs 2 hours, gradation slowly adds potassium permanganate, now system temperature slowly raises, and controls to add potassium permanganate amount and makes system temperature not higher than 40 DEG C, and it is overheated in water-bath prevention system to add ice cube in right amount; Treat that potassium permanganate feeds in raw material complete, obtain blackish green solution, raised temperature to 60 DEG C, stir the oxidation stripping that 12h carries out crystalline graphite powder;
(3) slow impouring under crystalline graphite powder oxidation stripper mechanical agitation in (2) is had in the deionized water of ice cube, control impouring speed in case system is overheated, obtain sepia mixing material, continue to stir until system is back to room temperature; Then pipette hydrogen peroxide with pipette, dropping to mixing material color by brown stain is glassy yellow;
(4) centrifugation (3) solution obtains yellow mercury oxide, with the alternately washing of deionized water, watery hydrochloric acid, last with Silver detection residual chlorine ion, ensure that cleaning is rear without Chloride residue, deionized water obtains oxide yellow Graphene after being washed till neutrality, being dry 48h in 50 DEG C of vacuum drying chambers in temperature, is finally black thin paper shape material;
(5) be no more than under 80 DEG C of bath temperatures, 1g is gathered second 2 20000 and is dissolved in 100ml ethylene glycol solution by mechanical agitation, is after transparent and homogeneous solution until system, add graphene oxide, ultrasonic agitation is until Graphene dissolves completely, and whole system is homogeneous dark solution, stand-by; By FeCl
3be 1g:14.8mg with graphene oxide ratio, add ferric chloride (FeCl36H2O), according to iron ion and manganese ion mol ratio 2:1, add manganese acetate; Continue to stir after half an hour, add 6g sodium acetate solid, continue ultrasonic agitation after 2 hours mother liquor proceed to stainless steel polytetrafluoro high pressure crystallizing kettle, 180 DEG C of crystallization 24h; Be separated the black solid obtained with magnet, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dried overnight, obtain final Graphene/Manganese Ferrite composite nano-microsphere.
By test, record product reflectivity and be less than the frequency range of-10dB at 12-16GHz, frequency range is 4GHz, reaches maximum reflection loss for-24.5dB at 13.5GHz.
Embodiment 2
The preparation of graphene oxide is with embodiment 1;
Be no more than under 80 DEG C of bath temperatures, 1g is gathered second 2 20000 and is dissolved in 100ml ethylene glycol solution by mechanical agitation, is after transparent and homogeneous solution until system, add graphene oxide, ultrasonic agitation is until Graphene dissolves completely, and whole system is homogeneous dark solution, stand-by; By FeCl
3be 1g:18.5mg with graphene oxide ratio, add ferric chloride (FeCl36H2O), according to iron ion and manganese ion mol ratio 2:1, add manganese acetate; Continue to stir after half an hour, add 6g sodium acetate solid, continue ultrasonic agitation after 2 hours mother liquor proceed to stainless steel polytetrafluoro high pressure crystallizing kettle, 180 DEG C of crystallization 24h.Be separated the black solid obtained with magnet, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dried overnight, obtain final Graphene/Manganese Ferrite composite nano-microsphere.
By test, its scanning electron microscope (SEM) photograph as shown in Figure 1, its transmission electron microscope picture as shown in Figure 2, its microwave electromagnetic reflecting properties figure as shown in Figure 3, as seen from the figure, record product reflectivity and be less than the frequency range of-10dB at 9-13GHz, frequency range is 4GHz, maximum reflection loss is reached for-42dB at 10.5GHz.
Embodiment 3
The preparation of graphene oxide is with embodiment 1;
Be no more than under 80 DEG C of bath temperatures, 1g is gathered second 2 20000 and is dissolved in 100ml ethylene glycol solution by mechanical agitation, is after transparent and homogeneous solution until system, add graphene oxide, ultrasonic agitation is until Graphene dissolves completely, and whole system is homogeneous dark solution, stand-by; By FeCl
3be 1g:22.2mg with graphene oxide ratio, add ferric chloride (FeCl36H2O), according to iron ion and manganese ion mol ratio 2:1, add manganese acetate; Continue to stir after half an hour, add 6g sodium acetate solid, continue ultrasonic agitation after 2 hours mother liquor proceed to stainless steel polytetrafluoro high pressure crystallizing kettle, 180 DEG C of crystallization 24h; Be separated the black solid obtained with magnet, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dried overnight, obtain final Graphene/Manganese Ferrite Nano microsphere.
Record product reflectivity and be less than the frequency range of-10dB at 14-18GHz, frequency range is 4GHz, reaches maximum reflection loss for-27.5dB at 16.2GHz.
Embodiment 4
The preparation of graphene oxide is with embodiment 1;
Be no more than under 80 DEG C of bath temperatures, 1g is gathered second 2 20000 and is dissolved in 100ml ethylene glycol solution by mechanical agitation, is after transparent and homogeneous solution until system, add graphene oxide, ultrasonic agitation is until Graphene dissolves completely, and whole system is homogeneous dark solution, stand-by; By FeCl
3be 1g:37mg with graphene oxide ratio, add ferric chloride (FeCl36H2O), according to iron ion and manganese ion mol ratio 2:1, add manganese acetate.Continue to stir after half an hour, add 6g sodium acetate solid, continue ultrasonic agitation after 2 hours mother liquor proceed to stainless steel polytetrafluoro high pressure crystallizing kettle, 180 DEG C of crystallization 24h; Be separated the black solid obtained with magnet, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dried overnight, obtain final Graphene/Manganese Ferrite Nano microsphere.
Record product reflectivity and be less than the frequency range of-10dB at 11-15GHz, frequency range is 4GHz, reaches maximum reflection loss for-20dB at 12.5GHz.
Embodiment 5
The preparation of graphene oxide is with embodiment 1;
Be no more than under 80 DEG C of bath temperatures, mechanical agitation will add graphene oxide in deionized water, and ultrasonic agitation is until Graphene dissolves completely, and whole system is homogeneous dark solution, stand-by; By FeNO
3be 1g:10mg with graphene oxide ratio, add nine water ferric nitrates, according to iron ion and nickel ion mol ratio 2:1, add nickel nitrate; Continue to stir after half an hour, add 4.8g urea solid, continue ultrasonic agitation after 2 hours mother liquor proceed to stainless steel polytetrafluoro high pressure crystallizing kettle, 180 DEG C of crystallization 24h; Be separated the black solid obtained with magnet, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dried overnight, obtain final Graphene/nickel ferrite based magnetic loaded Nano microsphere.
Record this product reflectivity and be less than the frequency range of-10dB at 13-17Hz, frequency range is 4GHz, reaches maximum reflection loss for-22.4dB at 15GHz.
Embodiment 6
The preparation of graphene oxide is with embodiment 1;
Be no more than under 80 DEG C of bath temperatures, mechanical agitation will add graphene oxide in deionized water, and ultrasonic agitation is until Graphene dissolves completely, and whole system is homogeneous dark solution, stand-by; By FeNO
3be 1g:12.4mg with graphene oxide ratio, add nine water ferric nitrates, according to iron ion and nickel ion mol ratio 2:1, add nickel nitrate; Continue to stir after half an hour, add 4.8g urea solid, continue ultrasonic agitation after 2 hours mother liquor proceed to stainless steel polytetrafluoro high pressure crystallizing kettle, 180 DEG C of crystallization 24h; Be separated the black solid obtained with magnet, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dried overnight, obtain final Graphene/nickel ferrite based magnetic loaded Nano microsphere.
By test, as shown in Figure 4, as shown in Figure 5, record this product reflectivity as seen from the figure and be less than the frequency range of-10dB at 13-18Hz, frequency range is 5GHz to its microwave electromagnetic reflecting properties figure to its scanning electron microscope (SEM) photograph, reaches maximum reflection loss for-40dB at 15.2GHz.
Embodiment 7
The preparation of graphene oxide is with embodiment 1;
Be no more than under 80 DEG C of bath temperatures, mechanical agitation will add graphene oxide in deionized water, and ultrasonic agitation is until Graphene dissolves completely, and whole system is homogeneous dark solution, stand-by; By FeNO
3be 1g:14.9mg with graphene oxide ratio, add nine water ferric nitrates, according to iron ion and nickel ion mol ratio 2:1, add nickel nitrate; Continue to stir after half an hour, add 4.8g urea solid, continue ultrasonic agitation after 2 hours mother liquor proceed to stainless steel polytetrafluoro high pressure crystallizing kettle, 180 DEG C of crystallization 24h; Be separated the black solid obtained with magnet, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dried overnight, obtain final Graphene/nickel ferrite based magnetic loaded Nano microsphere.
Record this product reflectivity and be less than the frequency range of-10dB at 15-18GHz, frequency range is 3GHz, reaches maximum reflection loss for-26.5dB at 16.5GHz.
Claims (2)
1. a preparation method for strong magnetic electricity performance graphene/ferrate composite nano-microsphere, is characterized in that, described ferrite is Manganese Ferrite or nickel ferrite based magnetic loaded, and described preparation method comprises the following steps:
Steps A. be that graphene oxide prepared by raw material with crystalline graphite powder:
Step B. adopts solvent-thermal method one-step synthesis graphene/ferrate composite nano-microsphere;
B1. synthesizing graphite alkene/Manganese Ferrite composite nano-microsphere:
First., with ethylene glycol, molecular weight be 800 ~ 3000 polyethylene glycol, ferric chloride (FeCl36H2O), four water acetic acid manganese, acetate for initiation material, described acetate is acetic acid sodium salt or acetic acid sylvite; The mol ratio of Fe and Mn is 1:2; Ferric chloride (FeCl36H2O) and ethylene glycol ratio are 1g:10 ~ 40mL; Ferric chloride (FeCl36H2O) and polyethylene glycol ratio are 1g:0.1 ~ 1g; Ferric chloride (FeCl36H2O) and acetate ratio are 1g:1 ~ 10g; Ferric chloride (FeCl36H2O) and graphene oxide ratio are 1g:10 ~ 100mg;
Then, under 25 ~ 80 DEG C of water bath sonicator conditions, polyethylene glycol is dissolved in ethylene glycol and obtains clear solution, again graphene oxide is added in clear solution, under mechanical agitation, Graphene to be oxidized dissolves obtain dark solution completely, then adds iron chloride and manganese acetate obtains red tan solution, continues to add acetate after dissolving, obtain the molten slurry of rufous, continue ultrasonic agitation 1 ~ 3 hour;
Finally, the stainless steel crystallization still molten for rufous slurry being proceeded to polytetrafluoro lining leaves standstill 15 ~ 24h in 160 DEG C ~ 200 DEG C baking ovens; Be separated with magnet and obtain black solid, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dryings, obtain final Graphene/Manganese Ferrite composite nano-microsphere;
B2. synthesizing graphite alkene/nickel ferrite based magnetic loaded composite nano-microsphere:
First, with deionized water, nine water ferric nitrates, six water nickel nitrates, urea for initiation material; The mol ratio of Fe and Ni is 1:2; Nine water ferric nitrates and deionized water ratio are 1g:10 ~ 40mL; Nine water ferric nitrates and urea ratio are 1g:1 ~ 10g; Nine water ferric nitrates and graphene oxide ratio are 1g:10 ~ 100mg;
Then, under 25 ~ 80 DEG C of water bath sonicator conditions, graphene oxide is added in deionized water, under mechanical agitation, Graphene to be oxidized dissolves obtain dark solution completely, add ferric nitrate again and nickel nitrate obtains red tan solution, continue after dissolving to add urea, obtain the molten slurry of rufous, continue ultrasonic agitation 1 ~ 3 hour;
Finally, the stainless steel crystallization still molten for rufous slurry being proceeded to polytetrafluoro lining leaves standstill 15 ~ 24h in 160 DEG C ~ 200 DEG C baking ovens; Be separated with magnet and obtain black solid, after deionized water and ethanol are repeatedly washed, in 80 DEG C of vacuum drying chamber dryings, obtain final Graphene/Manganese Ferrite composite nano-microsphere.
2., by the preparation method of magnetic electricity performance graphene/ferrate composite nano-microsphere strong described in claim 1, it is characterized in that, steps A. taking crystalline graphite powder as the concrete steps that graphene oxide prepared by raw material is:
Steps A 1. for raw material, carries out weighing with crystalline graphite powder, the concentrated sulfuric acid, SPA, potassium permanganate, deionized water, hydrogen peroxide, watery hydrochloric acid; Wherein, crystalline graphite powder and concentrated sulfuric acid ratio are 1g:90 ~ 150mL, and the ratio of crystalline graphite powder and SPA is 1g:10 ~ 18mL, and the ratio of graphite powder and potassium permanganate is 1g:3 ~ 10g, and hydrogen peroxide concentration is 18 ~ 35%;
Steps A 2. room-temperature water bath, adds the concentrated sulfuric acid and SPA nitration mixture, after mechanical agitation to nitration mixture temperature is back to room temperature in the three-necked bottle of condenser pipe; Divide within half an hour and add crystalline graphite powder three times, room temperature mechanical stirs 1 ~ 3 hour; Gradation slowly adds potassium permanganate, and control potassium permanganate adds speed makes system temperature not higher than 40 DEG C; Treat that potassium permanganate feeds in raw material complete, obtain blackish green solution, raised temperature to 40 ~ 60 DEG C, stir 8 ~ 24h, obtain crystalline graphite powder oxidation stripper;
Crystalline graphite powder to be oxidized under stripper mechanical agitation slowly impouring by steps A 3. to be had in the deionized water of ice cube, obtains sepia mixing material, continues to stir until system is back to room temperature; Then pipette hydrogen peroxide with pipette, dropping to mixing material color by brown stain is glassy yellow;
Steps A 3 is obtained mixed solution and carries out centrifugation by steps A 4., obtain yellow mercury oxide, with washed with de-ionized water to neutral, namely obtain oxide yellow Graphene, be dry 24 ~ 48h in 40 ~ 60 DEG C of vacuum drying chambers in temperature, obtain final black thin paper shape graphene oxide.
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| CN105348775A (en) * | 2015-12-08 | 2016-02-24 | 电子科技大学 | Crosslinkable polyaryl ether nitrile/ferroferric oxide hybridized magnetic material and manufacturing method thereof |
| CN107057135A (en) * | 2016-12-22 | 2017-08-18 | 中北大学 | A kind of High-performance graphene/FeNixThe preparation of/natural rubber electromagnetic wave absorbent material |
| CN107705998A (en) * | 2017-10-16 | 2018-02-16 | 浙江工业大学 | A kind of ferrite@graphenes hydrogel composite material and its application in electrochemical energy storage field |
| CN107705998B (en) * | 2017-10-16 | 2019-06-14 | 浙江工业大学 | A kind of ferrite@graphene hydrogel composite material and its application in electrochemical energy storage field |
| CN109896520A (en) * | 2019-04-12 | 2019-06-18 | 北京环境特性研究所 | A kind of magnetizing reduction stannic oxide/graphene nano composite material and preparation method and application |
| CN111289589A (en) * | 2020-03-26 | 2020-06-16 | 中南大学 | Manganese dioxide-oxidized multi-walled carbon nanotube modified glassy carbon electrode and application thereof |
| CN112645373A (en) * | 2020-12-17 | 2021-04-13 | 安徽理工大学 | Gamma-AlOOH/RGO composite wave-absorbing material and preparation method thereof |
| CN112645373B (en) * | 2020-12-17 | 2023-05-02 | 安徽理工大学 | Gamma-AlOOH/RGO composite wave-absorbing material and preparation method thereof |
| JP7519144B2 (en) | 2021-05-04 | 2024-07-19 | ティーエムティーピー ラブズ， インコーポレイテッド | Apparatus and method for exfoliating graphite |
| CN114975949A (en) * | 2022-06-13 | 2022-08-30 | 鸡西市唯大新材料科技有限公司 | Preparation method of lithium ion carbon negative electrode material |
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