CN107098341A - Graphene oxide new type water thermal stencil agent and its preparation method of nano composite material - Google Patents
Graphene oxide new type water thermal stencil agent and its preparation method of nano composite material Download PDFInfo
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Abstract
The invention discloses a kind of application of graphene oxide in the preparation of hydro-thermal reaction oxide nano thread, pass through the inducing action of graphene oxide, make oxide oriented growth during Hydrothermal Synthesiss, and disclose the inducing action synthesis ferriferrous oxide nano line for utilizing graphene oxide, as long as graphene oxide is dispersed in reaction solution, then ferroso-ferric oxide presoma is added, ferriferrous oxide nano line can be synthesized, reaction can only be completed in aqueous solution, it is simple to operate, cost is low, Material cladding is uniform, gained redox graphene/ferriferrous oxide composite material specific surface area is big, its magnetic saturation intensity is up to 35~45emu/g, electronic conductivity is high, substantially increase the electric conductivity of material, capability of electromagnetic shielding, accelerate ferriferrous oxide nano line in lithium battery anode, ultracapacitor, the further industrial applications in electromagnetic shielding material field.
Description
Technical field
The present invention relates to field of material preparation, the more particularly to agent of graphene oxide new type water thermal stencil and its nano combined material
The preparation method of material.
Background technology
Ferrite has the advantages that wave absorbing efficiency height, bandwidth, cost are low, is electromagnetic wave practical and the most frequently used earliest
Absorbent, while Fe3O4There is 926mAh/g theoretical capacity, about graphite cathode material as lithium ion battery negative material
2.5 times of material, are that the lithium ion battery of great prospect is born with advantages such as the abundant, safety and environmental protections of with low cost, raw material sources
Pole material.But transition metal oxide is also easy to produce efflorescence due to there are larger Volume Changes during removal lithium embedded, then add
Above their electric conductivity is poor, so that amount of activated material loses effective electrical contact in cyclic process, therefore substantially reduces
Its cyclical stability.It is main at present by material nano and to prepare composite etc. transition metal oxide is changed
Property.Particle efflorescence and reunion caused by embedding de- lithium process can be greatly lowered in material nanoization, can greatly improve material
Utilization rate.By compound with carbon material with good conductivity etc., it is possible to increase the electronic conductivity of metal oxide, enhance
The overall electrical contact of material, the in addition introducing of carbon material can also limit the efflorescence of particle significantly.
Nano ferriferrous oxide is a kind of excellent Ferrite Material, has quantum size effect due to nano material, small
Dimensional effect, skin effect, macro quanta tunnel effect, make Fe3O4Its specific surface area is greatly increased, be greatly lowered particle because
Efflorescence and reunion caused by embedding de- lithium process, can greatly improve the utilization rate of material, while having special Electromagnetism Characteristics.
Nano ferriferrous oxide is in medical medicine carrier transmission, lithium battery anode, ultracapacitor, and the field such as electromagnetic shielding material has
Extensive use.Existing hydro-thermal method synthesizes ferriferrous oxide nano line, can be induced in building-up process by magnetic field, by four
Fe 3 O crystal oriented growth in the solution and formed.But magnetic field is added in the hydrothermal reaction process of HTHP, is needed
Magnetic field intensity is accurately controlled, operation difficulty is added.The oxidation three of polyethylene glycol (PEG400) template induction four can also be passed through
Iron oriented growth.But organic polymer is introduced in course of reaction, impurity is introduced, washing step need to be increased, complex operation makes simultaneously
Product is impure.The complicated preparation technology of nano ferriferrous oxide significantly limit nano ferriferrous oxide in medical medicine carrier
Transmit, lithium battery anode, ultracapacitor, the application prospect in the field such as electromagnetic shielding material.
Graphene (GN) is that one kind passes through sp by carbon atom with hexagonal structure2The monoatomic layer two-dimensional material of hydridization.
In recent years, due to its unique structure, and its excellent electric property, superelevation ground specific surface area, it is in electromagnetic shielding, storage
Can, the field such as pharmaceutical carrier causes extensive research interest and achieves significant progress.Perfectly graphene electrical conductivity is
10,000 times of fine copper, are excellent electrode materials；Meanwhile, the specific surface area of superelevation provides the space of abundance for electrode reaction.By
In the good biocompatibility of carbon material, the graphene of superhigh specific surface area can be used as pharmaceutical carrier.Carbon material is used as traditional electricity
Magnetic shielding material, the absorption for being conducive to electromagnetic wave with individual layer two-dimensional sheet structure of the tightly packed formation of carbon atom, with graphite
Alkene is that matrix loads ferrite, can obtain light weight, inhale the composite wave-suction material of wave frequency bandwidth.By to the anti-of electromagnetic wave
Penetrate, absorption, in military industry field, civil area has wide application.But the technology of preparing of graphene, its is extensive
Using being restricted.As the derivative of graphene, graphene oxide can be realized extensive by improved Hummers methods
It is prepared by mass.Substantial amounts of oxygen-containing functional group, such as hydroxyl, carboxyl and epoxy radicals are contained in its surface, in water and some organic solvents
In dispersiveness preferably, graphene oxide can be obtained by a series of liquid-phase Forming Process, it is dry by freeze-drying, spraying
The technology such as dry can obtain graphene oxide powder.The method for synthesizing composite material is simple, in ultracapacitor, lithium ion battery,
Electromagnetic shielding field has certain potential application.
The preparation method of a kind of graphene and ferriferrous oxide nano sphere composite is invented in Xue Wei east et al..It is by oxygen
Graphite alkene is placed in the ethylene glycol solution of well mixed ferric chloride hexahydrate, sodium acetate, polyethylene glycol, and ultrasonic agitation is equal
It is even, alkali formula ferrous hydroxide and the female slurries of graphene oxide are obtained, female slurries are placed in reactor, 15 are reacted in 200 DEG C
~24 hours.Black reaction product is separated by magnet, repeatedly washed using deionized water and ethanol, in 80 DEG C of vacuum drying chambers
Middle drying 12 hours, obtains graphene and ferriferrous oxide nano sphere composite nano materials.The graphene obtained by this method
Ferriferrous oxide nano sphere composite, but ferroso-ferric oxide is packed together in nanosphere form, reduces its specific surface area,
Reaction is carried out in ethylene glycol organic system, adds deimpurity operating procedure；Graphene oxide only conduct in the reaction
Reaction carriers, do not play it as the effect of template；Graphene oxide bad dispersibility in organic solvent ethylene glycol, is prepared
Composite lack of homogeneity, composite magnetic saturation intensity is low, smaller to electro-magnetic wave absorption, poor performance.
In summary, induction pattern plate agent present in preparation technology in the prior art for ferriferrous oxide nano line point
Dissipate that property is poor, organic free from admixture that introduces other adds that complicated impurity removal process, resulting materials specific surface area be small, magnetic saturation intensity
The problems such as low, smaller to electro-magnetic wave absorption, poor performance, still lack effective solution.
The content of the invention
In order to overcome above-mentioned deficiency, Hydrothermal Template agent is made it is an object of the present invention to provide a kind of graphene oxide (GO)
Application in oxide nano thread preparation, by the inducing action of graphene oxide, makes oxide during Hydrothermal Synthesiss
Oriented growth, synthesis oxide nano wire.Nano wire has anisotropy, typically passes through chemical vapor deposition, low pressure chemical gas
Mutually prepared by the method such as deposition, plasma activated chemical vapour deposition, thermal evaporation, electron beam evaporation (EBE), solwution method and hydro-thermal method,
Generally require substrate or nucleus induces its oriented growth.The present invention is uniformly dispersed using graphene oxide in reaction solution, is reacted
Process is completed in aqueous solution, is not introduced into the impurity such as organic polymer, without increasing washing step, while ion can not be passed through
Lamella, the speed that reduction reactive ion is combined, while the inducing action synthesized using the hydroxyl of graphene oxide to nano wire is complete
Into the synthesis of nano wire.
Second object of the present invention is to provide a kind of new redox graphene/ferriferrous oxide nano line and is combined
The preparation method of material, by graphene oxide as template, induces ferroso-ferric oxide linear growth, simultaneous oxidation graphene quilt
Reduction, synthesis ferriferrous oxide nano line/redox graphene composite.Gained composite has special structure,
Cage structure is formed by redox graphene (rGO), ferriferrous oxide nano line (Fe is wrapped in3O4Nanowire around), greatly
Big electronic conductivity, specific surface area and the magnetic saturation intensity for adding ferriferrous oxide material, limits ferriferrous oxide particles
Efflorescence, obtain with higher electric conductivity, larger capacitance capacity, capability of electromagnetic shielding the oxygen of redox graphene/tetra-
Change three-iron nanowire composite.And reaction can only be completed in aqueous solution, simple to operate, Material cladding is uniform.
3rd purpose of the invention is to provide a kind of redox graphene/ferroso-ferric oxide prepared containing the invention described above
The preparation method of the electromagnetic screen coating of nanowire composite.
4th purpose of the invention is to provide a kind of redox graphene/ferroso-ferric oxide prepared containing the invention described above
Nanowire composite.
5th purpose of the invention is to provide a kind of redox graphene/ferroso-ferric oxide prepared containing the invention described above
The preparation method of the ultracapacitor of nanowire composite.
6th purpose of the invention is to provide a kind of lithium ion battery, and the positive electrode of the lithium ion battery is using above-mentioned
Redox graphene/ferriferrous oxide composite material.
7th purpose of the invention is to provide graphene oxide/ferroferric oxide compound prepared by a kind of present invention super
The energy storage fields such as level capacitor, battery and the application for being electromagnetically shielded field.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of graphene oxide makees application of the template in oxide nano thread preparation, and the oxide is four oxidations three
Iron, cobaltosic oxide, vanadium oxide, the oxide nano thread preparation method is hydrothermal synthesis reaction.Pass through graphene oxide
Inducing action, makes oxide oriented growth during Hydrothermal Synthesiss, synthesis oxide nano wire.
The characteristics of present invention is uniformly dispersed using graphene oxide in reaction solution, course of reaction is complete in aqueous solution
Into the impurity such as organic polymer being not introduced into, without increasing washing step.Ion can not pass through lamella simultaneously, reduce reactive ion
With reference to speed, the inducing action synthesized to nano wire using the hydroxyl of graphene oxide and its lamellar structure completes nano wire
Synthesis, induce its oriented growth without substrate or nucleus.
A kind of redox graphene/ferriferrous oxide nano line composite material and preparation method thereof, comprises the following steps：
Step 1：By the dissolving of a certain amount of graphene oxide in deionized water, stirring obtains finely dispersed graphite oxide
Alkene solution A.
Step 2：A certain amount of sodium hydroxide (NaOH) is dissolved into solution A, it is molten that stirring obtains that NaOH is completely dissolved
Liquid B.
Step 3：Weigh a certain amount of hypo (Na2S2O3·5H2) and green vitriol O
(FeSO4·7H2O) mixing is added in inner liner of reaction kettle, then takes appropriate solution B to add in reactor.
Step 4：Reactant is air-cooled to room after the completion of sealing reactor certain temperature issues raw hydrothermal synthesis reaction, reaction
Temperature.
Step 5：Reaction product is washed, collection is settled, is dried in vacuo to obtain redox graphene/ferroso-ferric oxide
Nanowire composite.
This preparation technology as template, induces ferroso-ferric oxide linear growth using graphene oxide, without substrate or
Nucleus induces its oriented growth.Simultaneous oxidation graphene is reduced, and synthesis ferriferrous oxide nano line/redox graphene is multiple
Condensation material.Reaction can only be completed in aqueous solution, be not introduced into the impurity such as organic polymer, without increasing washing step,
Simple to operate, cost is low, and Material cladding is uniform.In addition, the present invention induces nanometer using graphene oxide as Hydrothermal Template agent
Line is synthesized, and is substituted the complicated graphene of preparation technology and is participated in reaction, large-scale industrial production can be achieved in economical and efficient.
It is preferred that, graphene oxide used is prepared by improved Hummers methods in step 1, is washed with deionized water
Wash to neutral pH=4~6 obtained by vacuum freeze drying, graphene oxide concentration is 1~5mg/ in graphene oxide solution A
ml。
It is preferred that, the graphite oxide whipping process of step 1 is 1~6h of magnetic agitation after 1~2h of ultrasonic agitation at room temperature.
It is preferred that, the whipping process of the sodium hydroxide of step 2 is magnetic agitation 1h.
It is preferred that, NaOH, FeSO in step 34·7H2O, Na2S2O3·5H2O mol ratio is 10：2：1, the body of solution B
Product is 40ml, and reactor is volume 50ml polytetrafluoro reactor.
It is preferred that, hydrothermal temperature is 150~180 DEG C in step 4, and soaking time is 20~30h.
It is furthermore preferred that hydrothermal temperature is 160 DEG C in step 4, soaking time is 24h.
It is preferred that, the washing of reaction product, sedimentation collection process are in step 5：By the oxygen of product redox graphene/tetra-
Change three-iron nanowire composite to be washed with deionized water and ethanol, sedimentation collection carried out using attraction method in washing process,
Accelerate sinking speed.
It is furthermore preferred that washing, the sedimentation collection process concrete operations of reaction product are in step 5：By product reduction-oxidation
Graphene/ferriferrous oxide nano line compound is poured into 250ml beaker, fills it up with deionized water, magnet is placed on beaker bottom
Sedimentation collection is carried out, supernatant is outwelled, so repeatedly 3~5 times, unreacted ion is removed.Alcohol is filled it up with beaker, equally
Beaker bottom collection is placed on magnet, supernatant is outwelled, so repeatedly 2~3 times, the organic matter in solution is removed.
It is preferred that, the process of vacuum drying of reaction product is in step 5：By redox graphene/tetra- of washes clean
Fe 3 O nanowire composite is put into vacuum drying chamber and dried under 60 DEG C of vacuum conditions, by dried reduction-oxidation graphite
Alkene/ferriferrous oxide nano line compound grinds to form fine powder.
It is preferred that, oxygen reduction fossil in redox graphene/ferriferrous oxide nano line composite obtained by step 5
The mass fraction of black alkene is 5~20%.
A kind of redox graphene/ferriferrous oxide nano line composite, redox graphene formation cage knot
Structure, is wrapped in around ferriferrous oxide nano line.
Gained composite of the invention has special structure, forms cage structure by redox graphene (rGO), wraps
It is rolled in ferriferrous oxide nano line (Fe3O4Nanowire) around, considerably increase ferriferrous oxide material electronic conductivity,
Specific surface area and magnetic saturation intensity, limit the efflorescence of ferriferrous oxide particles, obtain having higher electric conductivity, larger electricity
Hold capacity, redox graphene/ferriferrous oxide nano line composite of capability of electromagnetic shielding.
It is preferred that, the mass fraction of redox graphene is 5~20%.
It is preferred that, the diameter of ferriferrous oxide nano line is 100~200nm.
It is preferred that, the length of ferriferrous oxide nano line is 3~7um.
A kind of electromagnetic shielding of the redox graphene/ferriferrous oxide nano line composite prepared containing the present invention is applied
The preparation method of material, is comprised the following steps that：
Step 1：Weigh appropriate epoxy resin to mix with alcohol, magnetic agitation to epoxy resin is uniformly dispersed, obtain certain
The epoxy resin mixed liquor A of mass fraction.
Step 2：Weigh appropriate epoxy curing agent to mix with alcohol, magnetic agitation to curing agent is uniformly dispersed, and obtains
The epoxy curing agent mixed liquid B of certain mass fraction.
Step 3：The epoxy that a certain amount of redox graphene/ferriferrous oxide nano line compound is added in step 1
Stir, be well mixed with the epoxy curing agent mixed liquid B in step 2 in resin mixture liquor A, obtain electromagnetic shielding and apply
Material.
It is preferred that, coating in step 3 is coated in timber, the surface such as plastics, after after solvent evaporation, directly as electromagnetic screen
Cover materials'use.
It is preferred that, coating in step 3 is coated on carbon fiber film, after dry vaporized alcohol is complete in an oven, obtained
To load-type composite material carbon fiber film；
A kind of ultracapacitor of the redox graphene/ferriferrous oxide nano line composite prepared containing the present invention
Preparation method, comprise the following steps that：
Step 1：Weigh a certain amount of redox graphene/ferriferrous oxide nano line compound, activated carbon, polytetrafluoro
Ethene (PTFE) crosslinker mixture, adding a certain amount of alcohol makes mixture into pasty state, is uniformly mixing to obtain ultracapacitor
Slurry.
Step 2：Slurry in step 1 is uniformly coated in dry foam nickel surface, vacuum environment and be dried to obtain
Electrode slice containing redox graphene/ferriferrous oxide nano line composite.
Step 3：2mol/L sodium sulfite and aqueous sodium persulfate solution is prepared respectively, is used as measurement electrolyte.
Step 4：C-V curve is tested, regulatory complex operating voltage is interval, tests it and such as measures and cycle-index.
It is preferred that, redox graphene/ferriferrous oxide nano line compound, activity in the crosslinker mixture
Charcoal, polytetrafluoroethylene (PTFE) (PTFE) mass ratio are 8:1:1, stainless steel is in 10ml small beaker.
A kind of lithium ion battery, the positive electrode of the lithium ion battery is aoxidized using above-mentioned redox graphene/tetra-
Three iron composite materials, preparation method of lithium ion battery is comprised the following steps that：
Step 1：Weigh a certain amount of redox graphene/ferriferrous oxide nano line compound, activated carbon, gather inclined fluorine
Ethene (PVDF) crosslinker mixture, adding a certain amount of alcohol makes mixture into pasty state, is uniformly mixing to obtain lithium ion battery
Anode sizing agent.
Step 2：Slurry in step 1 is uniformly coated in the foam nickel surface of the copper foil of cleaning, vacuum environment and done
It is dry to obtain the electrode slice containing redox graphene/ferriferrous oxide nano line composite.
Step 3：Using LiFePO4 as electrolyte, using electrode slice above by cutting obtained positive plate as positive pole,
Barrier film is added, button cell is dressed up in tabletting.
Step 4：C-V curve is tested, regulatory complex operating voltage is interval, specific capacity and test its cycle-index.
It is preferred that, redox graphene/ferriferrous oxide nano line compound, activity in the crosslinker mixture
Charcoal, polytetrafluoroethylene (PTFE) (PTFE) mass ratio are 8:1:1, stainless steel is in 10ml small beaker.
A kind of redox graphene prepared by present invention/ferriferrous oxide nano line composite ultracapacitor,
The energy storage such as battery field and the application for being electromagnetically shielded field.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) present invention using graphene oxide inducing action synthesis ferriferrous oxide nano line, as long as by graphite oxide
Alkene is dispersed in reaction solution, then adds ferroso-ferric oxide presoma, you can synthesis ferriferrous oxide nano line, reaction
It can only be completed in aqueous solution, simple to operate, cost is low, Material cladding is uniform, be that other nano wires and nano wire are multiple
Condensation material, such as cobaltosic oxide, vanadium oxide, the oxide nano thread such as zinc oxide synthesis provide new method.
(2) the ferriferrous oxide nano linear diameter that the present invention is synthesized is in 100~200nm, and length is in 3~7um, reduction-oxidation
Graphene and nanoscale ferroso-ferric oxide specific surface area are big, and its magnetic saturation intensity is up to 35~45emu/g, electronic conductivity
Height, substantially increases electric conductivity, the capability of electromagnetic shielding of material, accelerates ferriferrous oxide nano line in lithium battery anode, surpasses
Level capacitor, the further industrial applications in electromagnetic shielding material field.
(3) graphene oxide that the present invention is used is prepared by improved Hummers methods, and method is simple, economical and efficient,
Large-scale industrial production can be achieved.
(4) preparation method of the present invention is simple, practical, can only be completed in aqueous solution, is not introduced into organic poly-
The impurity such as compound, without increasing washing step, while ion can not pass through lamella, reduce the speed that reactive ion is combined, simultaneously
The inducing action synthesized using the hydroxyl of graphene oxide to nano wire completes the synthesis of nano wire, it is easy to promote.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not constitute the improper restriction to the application.
The scanning electricity for redox graphene/ferriferrous oxide nano line composite that Fig. 1 prepares for the present invention
Mirror figure
Fig. 2 is that non-oxidation graphene adds obtained ferroso-ferric oxide and the contrast scans electron microscope of the present invention
Fig. 3 is redox graphene/ferriferrous oxide nano line composite TGA curves
Embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
The present invention is further described with reference to the accompanying drawings and examples, in order to the understanding of technical staff of the same trade：
Embodiment 1
The preparation process of redox graphene/ferriferrous oxide nano line composite, is comprised the following steps that：
Step 1：The graphene oxide water solution prepared using improved Hummers methods, graphene oxide is washed to pH
=4~6, the powder of graphene oxide is then made using vacuum freeze-drying method.At room temperature, by 200mg graphite oxide
Alkene is dissolved in 40ml water, ultrasonic 2h, magnetic agitation 6h, obtains finely dispersed graphene oxide solution A.
Step 2：8g sodium hydroxides (NaOH) are dissolved into solution A, magnetic agitation 1h, obtain that NaOH is completely dissolved is molten
Liquid B.
Step 3：Weigh 1.984g hypo (Na2S2O3·5H2O) and 4.448g seven hydrated sulfuric acids
Ferrous iron (FeSO4·7H2O) mixing is poured into 50ml polytetrafluoro inner liner of reaction kettle, and 40ml solution Bs are poured into reactor.This
When, NaOH, FeSO4·7H2O, Na2S2O3·5H2O mol ratio is 10：2：1.
Step 4：Reactor is sealed, is incubated under the conditions of 160 DEG C after the completion of 24h, reaction and is air-cooled to room temperature.
Step 5：Reaction product is washed.By product redox graphene/ferriferrous oxide nano line compound
In the beaker for pouring into 250ml, deionized water is filled it up with, magnet is placed on beaker bottom and carries out sedimentation collection, outwells supernatant, so anti-
It is multiple 3~5 times, remove unreacted ion.Alcohol is filled it up with beaker, beaker bottom collection is equally placed on magnet, is outwelled
Clear liquid, so repeatedly 2~3 times, removes the organic matter in solution.
Step 6：The redox graphene of washes clean in step 5/ferriferrous oxide nano line compound is put into very
Empty drying box is dried under 60 DEG C of vacuum conditions, removes residual solvent.By dried redox graphene/ferroso-ferric oxide
Nanowire composite grinds to form fine powder.
Embodiment 2
The preparation process of redox graphene/cobaltosic oxide nano line composite, is comprised the following steps that：
Step 1：The graphene oxide water solution prepared using improved Hummers methods, graphene oxide is washed to pH
=4~6, the powder of graphene oxide is then made using spray drying process.At room temperature, it is 200mg graphene oxide is molten
Solution in 40ml polyethylene glycol PEG200, PEG400, PEG600 or the PEG aqueous solution as reaction solution, ultrasonic 2h, magnetic agitation
6h, obtains finely dispersed graphene oxide solution A.
Step 2：8g sodium hydroxides (NaOH) are dissolved into solution A, magnetic agitation 1h, obtain that NaOH is completely dissolved is molten
Liquid B.
Step 3：Weigh 1.984g hypo (Na2S2O3·5H2O) and 4.496g seven hydrated sulfuric acids
Cobalt (CoSO4·7H2O) mixing is poured into 50ml polytetrafluoro inner liner of reaction kettle, and 40ml solution Bs are poured into reactor.Now,
NaOH, CoSO4·7H2O, Na2S2O3·5H2O mol ratio is 10：2：1.
Step 4：Reactor is sealed, is incubated under the conditions of 160 DEG C after the completion of 24h, reaction and is air-cooled to room temperature.
Step 5：Reaction product is washed.By product redox graphene/ferriferrous oxide nano line compound
In the beaker for pouring into 250ml, deionized water is filled it up with, sedimentation collection is carried out from sedimentation using reaction product, outwells supernatant, such as
This 3~5 times repeatedly, remove unreacted ion.Alcohol is filled it up with beaker, is sunk also with reaction product from sedimentation
Drop is collected, and outwells supernatant, so repeatedly 2~3 times, removes the organic matter in solution.
Step 6：The redox graphene of washes clean in step 5/ferriferrous oxide nano line compound is put into very
Empty drying box is dried under 60 DEG C of vacuum conditions, residual solvent is removed, by dried redox graphene/ferroso-ferric oxide
Nanowire composite grinds to form fine powder.
Embodiment 3
Preparation process containing redox graphene/ferriferrous oxide nano line composite electromagnetic screen coating, specific steps
It is as follows：
Step 1：6g epoxy resin is weighed, is added in 50ml beakers, 4g alcohol, magnetic agitation 24h, to epoxy resin is added
It is uniformly dispersed, obtains the mixed liquor A that epoxy resin mass fraction is 60%.
Step 2：6g epoxy curing agents are weighed, 50ml beakers is added and exists, 4g alcohol, magnetic agitation 24h, to admittedly is added
Agent is uniformly dispersed, and obtains the mixed liquid B that epoxy curing agent mass fraction is 60%.
Step 3：Graphene oxide/ferriferrous oxide nano line the compound for weighing 1.3g reduction adds mixing in step 1
Close in liquid A, stirred, be well mixed with the mixed liquid B in step 2 with glass bar, obtain the electromagnetism that mass fraction is 10%
Shielding coating.
Step 4：Coating in step 3 is coated on carbon fiber film, can treat that vaporized alcohol is completely dry in 60 DEG C of baking ovens
After dry, the film for forming load-type composite material is used；Also timber can be coated in, the surface such as plastics, after after solvent evaporation, direct work
Used for electromagnetic shielding material.
Embodiment 4
The preparation process of the ultracapacitor of graphene oxide containing reduction/ferriferrous oxide nano line compound, specifically
Step is as follows：
Step 1：Weigh 80mg reduction graphene oxide/ferriferrous oxide nano line compound, 10mg activated carbon,
10mg polytetrafluoroethylene (PTFE) (PTFE) crosslinking agent, i.e. its mass ratio are 10:1:1；In the small beaker for pouring into 10ml, plus a certain amount of wine
Essence, makes mixture into pasty state, and stirs 3h with glass, is allowed to well mixed, obtains super capacitor slurry.
Step 2：Slurry in step 1 is uniformly coated into foam nickel surface dried in step 1, coated area is
10*10mm, dries 12h in 60 DEG C of vacuum environment.
Step 3：2mol/L sodium sulfite and aqueous sodium persulfate solution is prepared respectively, is used as measurement electrolyte.
Step 4：C-V curve is tested, regulatory complex operating voltage is interval, tests its cycle-index.
Comparative example 1
The preparation process of ferroso-ferric oxide crystal, is comprised the following steps that：
Step 1：8g sodium hydroxides (NaOH) are dissolved into solution A, magnetic agitation 1h, obtain that NaOH is completely dissolved is molten
Liquid A.
Step 2：Weigh 1.984g hypo (Na2S2O3·5H2O) and 4.448g seven hydrated sulfuric acids
Ferrous iron (FeSO4·7H2O) mixing is poured into 50ml polytetrafluoro inner liner of reaction kettle, and 40ml solution As are poured into reactor.This
When, NaOH, FeSO4·7H2O, Na2S2O3·5H2O mol ratio is 10：2：1.
Step 3：Reactor is sealed, is incubated under the conditions of 160 DEG C after the completion of 24h, reaction and is air-cooled to room temperature.
Step 4：Reaction product is washed.In the beaker that product ferroso-ferric oxide is poured into 250ml, deionization is filled it up with
Water, magnet is placed on beaker bottom and carries out sedimentation collection, outwells supernatant, so repeatedly 3~5 times, removes unreacted ion.
Alcohol is filled it up with beaker, beaker bottom collection is equally placed on magnet, supernatant is outwelled, so repeatedly 2~3 times, solution is removed
Interior organic matter.
Step 5：The ferroso-ferric oxide crystal of washes clean in step 4 is put into vacuum drying chamber under 60 DEG C of vacuum conditions
Dry, remove residual solvent, dried ferroso-ferric oxide is ground to form to fine powder.
Surface topography is carried out using SEM instrument to embodiment 1 and the resulting materials of comparative example 1 to characterize
Obtain Fig. 1 and Fig. 2.
Thermogravimetric analysis is carried out to the resulting materials of embodiment 1 using thermogravimetric analyzer and obtains Fig. 3.
Fig. 1 is redox graphene/ferriferrous oxide nano line composite ESEM that embodiment 1 is prepared
Figure, its structure and morphology is as shown in Figure 1.It is 100~200 nanometers by Fig. 1 diameters that can obtain ferriferrous oxide nano line, is attached to also
In former graphene oxide layer, graphene oxide layer is by its " pinning ", and in hydrothermal reaction process, graphene oxide is as mould
Plate agent, promotes the oriented growth of ferroso-ferric oxide, and simultaneous oxidation graphene is reduced, and the graphene oxide reduced is obtained
To redox graphene/ferriferrous oxide nano line compound.
Fig. 2 be in comparative example 1 plus the octahedra ferroso-ferric oxide crystal scanning electron microscope (SEM) photograph for preparing of graphene oxide, it is tied
Configuration looks are as shown in Figure 1.It may be seen that not adding graphene oxide from Fig. 2, ferroso-ferric oxide isotropic growth is obtained
To block ferroso-ferric oxide crystal, its a diameter of 400~600 nanometers.
Fig. 3 is the redox graphene/ferriferrous oxide nano line composite TGA curves prepared in embodiment 1, from
In we when can calculate graphene oxide concentration for 2.5mg/ml and 5mg/ml, redox graphene with four oxidations three
Iron ratio respectively may be about 8:92 and 17：83.
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of graphene oxide makees application of the template in oxide nano thread preparation, it is characterised in that the oxide
For ferroso-ferric oxide, cobaltosic oxide, vanadium oxide or zinc oxide, the preparation method of the oxide nano thread is that Hydrothermal Synthesiss are anti-
Should.
2. a kind of redox graphene/ferriferrous oxide nano line composite material and preparation method thereof, it is characterised in that including following
Step：
Step 1：By graphene oxide dissolving in deionized water, stirring obtains finely dispersed graphene oxide solution A；
Step 2：Sodium hydroxide is dissolved into solution A, stirring obtains the solution B that sodium hydroxide is completely dissolved；
Step 3：Weigh hypo and green vitriol mixing is added in inner liner of reaction kettle, then take appropriate molten
Liquid B is added in reactor；
Step 4：Reactant is air-cooled to room temperature after the completion of sealing reactor certain temperature issues raw hydrothermal synthesis reaction, reaction；
Step 5：Reaction product is washed, collection is settled, is dried in vacuo to obtain redox graphene/ferriferrous oxide nano
Line composite.
3. redox graphene as claimed in claim 2/ferriferrous oxide nano line composite material and preparation method thereof, its feature
It is, graphene oxide used is prepared by improved Hummers methods in the step 1, is washed with deionized into
Property pH=4~6 after graphene oxide concentration is 1~5mg/ml obtained by vacuum freeze drying, in graphene oxide solution A, oxidation
The whipping process of graphene is 1~6h of magnetic agitation after 1~2h of ultrasonic agitation at room temperature.
4. redox graphene as claimed in claim 2/ferriferrous oxide nano line composite material and preparation method thereof, its feature
It is, reaction raw materials sodium hydroxide in the step 3, hypo, the mol ratio of green vitriol is 10：
2：1, the volume of solution B is 40ml, and reactor is hydrothermal temperature in volume 50ml polytetrafluoro reactor, the step 4
For 150~180 DEG C, soaking time is 20~30h, and hydrothermal temperature preferably is 160 DEG C, and soaking time is 24h.
5. redox graphene as claimed in claim 2/ferriferrous oxide nano line composite material and preparation method thereof, its feature
It is, the washing of reaction product, sedimentation collection process are in the step 5：By product redox graphene/ferroso-ferric oxide
Nanowire composite is washed with deionized water and ethanol, and sedimentation collection is carried out using attraction method in washing process, accelerates heavy
Reduction of speed degree, process of vacuum drying is：The redox graphene of washes clean/ferriferrous oxide nano line compound is put into very
Empty drying box is dried under 60 DEG C of vacuum conditions, by dried redox graphene/ferriferrous oxide nano line compound
Grind to form reduction-oxidation in fine powder, redox graphene/ferriferrous oxide nano line composite obtained by step 5
The mass fraction of graphene is 5~20%.
6. a kind of redox graphene/ferriferrous oxide nano wire rod prepared by claim 2 to 5 methods described
Material, it is characterised in that redox graphene formation cage encapsulated by structures is around ferriferrous oxide nano line.
7. a kind of redox graphene that methods described containing claim 2 to 5 is prepared/ferriferrous oxide nano line is combined
The preparation method of the electromagnetic screen coating of material, it is characterised in that comprise the following steps that：
Step 1：Weigh appropriate epoxy resin to mix with alcohol, magnetic agitation to epoxy resin is uniformly dispersed, and obtains certain mass
The epoxy resin mixed liquor A of fraction；
Step 2：Weigh appropriate epoxy curing agent to mix with alcohol, magnetic agitation to curing agent is uniformly dispersed, obtain certain
The epoxy curing agent mixed liquid B of mass fraction；
Step 3：The asphalt mixtures modified by epoxy resin that a certain amount of redox graphene/ferriferrous oxide nano line composite is added in step 1
Stir, be well mixed with the epoxy curing agent mixed liquid B in step 2 in fat mixed liquor A, obtain electromagnetic shielding and apply
Material.
8. redox graphene/ferriferrous oxide composite material that a kind of methods described containing claim 2 to 5 is prepared
The preparation method of ultracapacitor, it is characterised in that comprise the following steps that：
Step 1：Weigh a certain amount of redox graphene/ferriferrous oxide nano line composite, activated carbon, polytetrafluoroethyl-ne
Alkene (PTFE) crosslinker mixture, adding a certain amount of alcohol makes mixture into pasty state, is uniformly mixing to obtain ultracapacitor slurry
Material；
Step 2：Slurry in step 1 is uniformly coated in dry foam nickel surface, vacuum environment and be dried to obtain containing also
The electrode slice of former graphene oxide/ferriferrous oxide composite material；
Step 3：Sodium sulfite and aqueous sodium persulfate solution are prepared respectively, are used as measurement electrolyte；
Step 4：C-V curve is tested, regulatory complex operating voltage is interval, tests its cycle-index.
9. a kind of positive electrode is that redox graphene/ferroso-ferric oxide that claim 2 to 5 methods described is prepared is multiple
The lithium ion battery of condensation material, it is characterised in that the preparation method of the lithium ion battery is comprised the following steps that：
Step 1：Weigh a certain amount of redox graphene/ferriferrous oxide nano line compound, activated carbon, Kynoar
(PVDF) crosslinker mixture, adding a certain amount of alcohol makes mixture into pasty state, is uniformly mixing to obtain lithium ion cell positive
Slurry；
Step 2：Slurry in step 1 is uniformly coated in the foam nickel surface of the copper foil of cleaning, it is dry in vacuum environment
To the electrode slice containing redox graphene/ferriferrous oxide nano line composite；
Step 3：Using LiFePO4 as electrolyte, using electrode slice above by cutting obtained positive plate as positive pole, add
Button cell is dressed up in barrier film, tabletting；
Step 4：C-V curve is tested, regulatory complex operating voltage is interval, specific capacity and test its cycle-index.
10. the redox graphene that method described in claim 2 to 5 is prepared/ferriferrous oxide nano line composite wood
Expect in the energy storage such as ultracapacitor, battery field and be electromagnetically shielded the application in field.
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