CN107098341B - The preparation method of the agent of graphene oxide Hydrothermal Template and its nanocomposite - Google Patents
The preparation method of the agent of graphene oxide Hydrothermal Template and its nanocomposite 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 synthesis, and it discloses and synthesizes ferriferrous oxide nano line using the inducing action of 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 only can be completed in aqueous solution, it is easy to operate, it is at low cost, Material cladding is uniform, gained redox graphene/ferriferrous oxide composite material large specific surface area, its magnetic saturation intensity is up to 35~45emu/g, electronic conductivity is high, substantially increase the electric conductivity of material, electromagnetic shielding performance, accelerate ferriferrous oxide nano line in lithium battery anode, super capacitor Device, the further industrial applications in electromagnetic shielding material field.
Description
Technical field
The present invention relates to field of material preparation, the in particular to agent of graphene oxide new type water thermal stencil and its nano combined material
The preparation method of material.
Background technique
Ferrite has the advantages that wave absorbing efficiency height, bandwidth, at low cost, is earliest practical and most common electromagnetic wave
Absorbent, while Fe3O4There is the theoretical capacity of 926mAh/g, about graphite cathode material as lithium ion battery negative material
2.5 times of material have the advantages such as low in cost, the abundant, safety and environmental protection of raw material sources, are that the lithium ion battery of great prospect is negative
Pole material.But transition metal oxide is due to being also easy to produce dusting there are biggish volume change during removal lithium embedded, then plus
Above their electric conductivity is poor, so that amount of activated substance be made to lose effective electrical contact in cyclic process, therefore substantially reduces
Its cyclical stability.It mainly by material nano and prepares composite material at present etc. transition metal oxide is changed
Property.Particle can be greatly lowered because of dusting and reunion caused by embedding de- lithium process in material nanoization, can greatly improve material
Utilization rate.By compound with carbon material with good conductivity etc., it can be improved the electronic conductivity of metal oxide, enhance
The electrical contact of material entirety, in addition the introducing of carbon material can also limit the dusting of particle significantly.
Nano ferriferrous oxide is a kind of excellent Ferrite Material, since nano material has quantum size effect, small
Dimensional effect, skin effect, macro quanta tunnel effect, make Fe3O4Its specific surface area greatly increases, be greatly lowered particle because
Dusting and reunion caused by embedding de- lithium process, can greatly improve the utilization rate of material, while having special Electromagnetism Characteristics.
Nano ferriferrous oxide has in medical medicine carrier transmission, lithium battery anode, supercapacitor, the fields such as electromagnetic shielding material
It is widely applied.Existing hydro-thermal method synthesizes ferriferrous oxide nano line, can be induced in the synthesis 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 high temperature and pressure, needs
Magnetic field strength is accurately controlled, operation difficulty is increased.Four oxidations three can be also induced by polyethylene glycol (PEG400) template
Iron oriented growth.But organic polymer is introduced in reaction process, is introduced impurity, need to be increased washing step, it is complicated for operation, make simultaneously
Product is impure.The preparation process of nano ferriferrous oxide complexity significantly limits nano ferriferrous oxide in medical medicine carrier
Transmission, lithium battery anode, supercapacitor, the application prospect in the fields such as electromagnetic shielding material.
Graphene (GN) is that one kind by carbon atom passes through sp with hexagonal structure2Monoatomic layer two-dimensional material made of hydridization.
In recent years, due to its unique structure and its excellent electric property, superelevation ground specific surface area is being electromagnetically shielded, is storing up
Can, the fields such as pharmaceutical carrier cause extensive research interest and achieve significant progress.Perfectly graphene conductivity is
10,000 times of fine copper are excellent electrode materials；Meanwhile the specific surface area of superelevation provides sufficient space 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 as tradition electricity
Magnetic shielding material, the absorption for being conducive to electromagnetic wave with single layer two-dimensional sheet structure of the tightly packed formation of carbon atom, with graphite
Alkene is that matrix loads ferrite, the composite wave-suction material that can be obtained light weight, inhale wave frequency bandwidth.By to the anti-of electromagnetic wave
It penetrates, absorption, in military industry field, civil field has wide application.But the technology of preparing of graphene, it is extensive
Using being restricted.As the derivative of graphene, graphene oxide can be realized extensive by improved Hummers method
Mass preparation.A large amount of oxygen-containing functional group, such as hydroxyl, carboxyl and epoxy group are contained in its surface, in water and some organic solvents
In dispersibility preferably, can by a series of liquid-phase Forming Process obtain graphene oxide, by being freeze-dried, doing by spraying
The technologies such as dry can get graphene oxide powder.The method for synthesizing composite material is simple, in supercapacitor, lithium ion battery,
Electromagnetic shielding field has certain potential application.
Xue Weidong et al. has invented the preparation method of a kind of graphene and ferriferrous oxide nano sphere composite material.It is by oxygen
Graphite alkene is placed in the ethylene glycol solution of uniformly mixed ferric chloride hexahydrate, sodium acetate, polyethylene glycol, and ultrasonic agitation is equal
It is even, alkali formula ferrous hydroxide and graphene oxide mother's slurries are obtained, female slurries are placed in reaction kettle, reacts 15 in 200 DEG C
~24 hours.Black reaction product is separated by magnet, is repeatedly washed using deionized water and ethyl alcohol, in 80 DEG C of vacuum ovens
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 material, but ferroso-ferric oxide is packed together in the form of nanosphere, reduces its specific surface area,
Reaction carries out in ethylene glycol organic system, increases deimpurity operating procedure；Graphene oxide only conduct in the reaction
Reaction carriers do not play its effect as template；Graphene oxide bad dispersibility in organic solvent ethylene glycol, preparation
Composite material uniformity it is poor, composite material magnetic saturation intensity is low, poor performance smaller to electro-magnetic wave absorption.
In conclusion induction pattern plate agent present in the preparation process for ferriferrous oxide nano line point in the prior art
Dissipate that property is poor, organic free from admixture that introduces other increases that the impurity removal process of complexity, resulting materials specific surface area be small, magnetic saturation intensity
The problems such as low, smaller to electro-magnetic wave absorption, poor performance, still shortage effective solution scheme.
Summary of the invention
In order to overcome above-mentioned deficiency, it is an object of the present invention to provide a kind of graphene oxides (GO) to make Hydrothermal Template agent
Application in oxide nano thread preparation makes oxide during hydrothermal synthesis by the inducing action of graphene oxide
Oriented growth, synthesis oxide nano wire.Nano wire has anisotropy, generally passes through chemical vapor deposition, low pressure chemical gas
Mutually the methods of deposition, plasma activated chemical vapour deposition, thermal evaporation, electron beam evaporation (EBE), solwution method and hydro-thermal method preparation,
It generally requires substrate or nucleus induces its oriented growth.The present invention is uniformly dispersed in reaction solution using graphene oxide, reaction
Process is completed in aqueous solution, is not introduced into the impurity such as organic polymer, and without increasing washing step, while ion can not penetrate
Lamella reduces the rate that reactive ion combines, while complete using the inducing action that the hydroxyl of graphene oxide synthesizes nano wire
At the synthesis of nano wire.
A second object of the present invention is to provide a kind of novel redox graphene/ferriferrous oxide nano line is compound
The preparation method of material induces ferroso-ferric oxide linear growth, simultaneous oxidation graphene quilt by graphene oxide as template
Reduction synthesizes ferriferrous oxide nano line/redox graphene composite material.Gained composite material has special structure,
Cage structure is formed by redox graphene (rGO), is wrapped in ferriferrous oxide nano line (Fe3O4Nanowire around), greatly
Electronic conductivity, specific surface area and the magnetic saturation intensity for increasing ferriferrous oxide material greatly, limit ferriferrous oxide particles
Dusting, obtain electric conductivity with higher, larger capacitance capacity, electromagnetic shielding performance redox graphene/tetra- oxygen
Change three-iron nanowire composite.And reaction only can be completed in aqueous solution, easy to operate, Material cladding is uniform.
Third purpose of the present invention is to provide a kind of redox graphene/ferroso-ferric oxide of preparation containing aforementioned present invention
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 of preparation containing aforementioned present invention
Nanowire composite.
5th purpose of the invention is to provide a kind of redox graphene/ferroso-ferric oxide of preparation containing aforementioned present invention
The preparation method of the supercapacitor 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 a kind of graphene oxide/ferroferric oxide compound prepared by the present invention super
The energy storage fields such as grade capacitor, battery and the application for being electromagnetically shielded field.
To achieve the goals above, the present invention adopts the following technical scheme:
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 are hydrothermal synthesis reaction.Pass through graphene oxide
Inducing action makes oxide oriented growth during hydrothermal synthesis, synthesis oxide nano wire.
The characteristics of present invention is uniformly dispersed in reaction solution using graphene oxide, reaction process are complete in aqueous solution
At the impurity such as organic polymer being not introduced into, without increasing washing step.Ion can not penetrate lamella simultaneously, reduce reactive ion
In conjunction with rate, nano wire is completed to the inducing action that nano wire synthesizes using the hydroxyl of graphene oxide and its lamellar structure
Synthesis, induce its oriented growth without substrate or nucleus.
A kind of redox graphene/ferriferrous oxide nano line composite material and preparation method thereof, comprising the following steps:
Step 1: in deionized water by the dissolution of a certain amount of graphene oxide, stirring to get finely dispersed graphite oxide
Alkene solution A.
Step 2: a certain amount of sodium hydroxide (NaOH) is dissolved into solution A, stir to get NaOH be completely dissolved it is molten
Liquid B.
Step 3: weighing a certain amount of hypo (Na2S2O3·5H2) and green vitriol O
(FeSO4·7H2O) mixing is added in inner liner of reaction kettle, then appropriate solution B is taken to be added in reaction kettle.
Step 4: reactant issues raw hydrothermal synthesis reaction in sealing reaction kettle certain temperature, is air-cooled to room after the reaction was completed
Temperature.
Step 5: being washed, settle collection, be dried in vacuo and to obtain redox graphene/ferroso-ferric oxide to reaction product
Nanowire composite.
This preparation process using graphene oxide be used as template, induce ferroso-ferric oxide linear growth, be not necessarily to 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 only can be completed in aqueous solution, be not introduced into the impurity such as organic polymer, without increasing washing step,
Easy to operate, at low cost, Material cladding is uniform.In addition, the present invention induces nanometer as Hydrothermal Template agent using graphene oxide
The graphene of line synthesis, substitution preparation process complexity participates in reaction, and economical and efficient is, it can be achieved that large-scale industrial production.
Preferably, graphene oxide used in step 1 is prepared by improved Hummers method, is washed with deionized water
After washing to neutral pH=4~6 obtained by vacuum freeze drying, graphene oxide concentration is 1~5mg/ in graphene oxide solution A
ml。
Preferably, the graphite oxide whipping process of step 1 is that 1~6h of magnetic agitation after 1~2h is stirred by ultrasonic at room temperature.
Preferably, the whipping process of the sodium hydroxide of step 2 is magnetic agitation 1h.
Preferably, NaOH in step 3, FeSO4·7H2O, Na2S2O3·5H2The molar ratio of O is 10:2:1, the body of solution B
Product is 40ml, and reaction kettle is the polytetrafluoro reaction kettle of volume 50ml.
Preferably, 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 for 24 hours.
Preferably, the washing of reaction product, sedimentation collection process in step 5 are as follows: by product redox graphene/tetra- oxygen
Change three-iron nanowire composite deionized water and ethanol washing, attract method to carry out sedimentation collection using magnet in washing process,
Accelerate sinking speed.
It is furthermore preferred that in step 5 reaction product washing, sedimentation the concrete operations of collection process are as follows: by product reduction-oxidation
Graphene/ferriferrous oxide nano line compound pours into the beaker of 250ml, fills it up with deionized water, magnet is placed on beaker bottom
Sedimentation collection is carried out, supernatant is outwelled, 3~5 times repeatedly, removes unreacted ion.Alcohol is filled it up in beaker, equally
Beaker bottom is placed on magnet to collect, outwells supernatant, 2~3 times repeatedly, removes the organic matter in solution.
Preferably, in step 5 reaction product process of vacuum drying are as follows: by redox graphene/tetra- of washes clean
Fe 3 O nanowire composite is put into vacuum oven drying under 60 DEG C of vacuum conditions, by dried reduction-oxidation graphite
Alkene/ferriferrous oxide nano line compound is ground into fine powder.
Preferably, oxygen reduction fossil in the resulting redox graphene of step 5/ferriferrous oxide nano line composite material
The mass fraction of black alkene is 5~20%.
A kind of redox graphene/ferriferrous oxide nano line composite material, redox graphene form cage knot
Structure is wrapped in around ferriferrous oxide nano line.
Gained composite material 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 dusting of ferriferrous oxide particles, obtain electric conductivity with higher, larger electricity
Hold redox graphene/ferriferrous oxide nano line composite material of capacity, electromagnetic shielding performance.
Preferably, the mass fraction of redox graphene is 5~20%.
Preferably, the diameter of ferriferrous oxide nano line is 100~200nm.
Preferably, the length of ferriferrous oxide nano line is 3~7um.
It is a kind of to be applied containing redox graphene prepared by the present invention/ferriferrous oxide nano line composite material electromagnetic shielding
The preparation method of material, the specific steps are as follows:
Step 1: weighing appropriate epoxy resin and mixed with alcohol, magnetic agitation to epoxy resin is uniformly dispersed, and obtains certain
The epoxy resin mixed liquor A of mass fraction.
Step 2: weighing appropriate epoxy curing agent and mixed with alcohol, magnetic agitation to curing agent is uniformly dispersed, and obtains
The epoxy curing agent mixed liquid B of certain mass score.
Step 3: the epoxy in step 1 is added in a certain amount of redox graphene/ferriferrous oxide nano line compound
It stirs evenly in resin mixture liquor A, is uniformly mixed with the epoxy curing agent mixed liquid B in step 2, obtain electromagnetic shielding and apply
Material.
Preferably, coating in step 3 is coated in timber, the surfaces such as plastics, after solvent evaporation, directly as electromagnetic screen
Cover materials'use.
Preferably, coating in step 3 is coated on carbon fiber film, after dry vaporized alcohol is complete in an oven, is obtained
To load-type composite material carbon fiber film；
It is a kind of containing redox graphene prepared by the present invention/ferriferrous oxide nano line composite material supercapacitor
Preparation method, the specific steps are as follows:
Step 1: weighing a certain amount of redox graphene/ferriferrous oxide nano line compound, active carbon, polytetrafluoro
Ethylene (PTFE) crosslinker mixture, a certain amount of alcohol, which is added, makes mixture at paste, is uniformly mixing to obtain supercapacitor
Slurry.
Step 2: the slurry in step 1 being uniformly coated in dry foam nickel surface, is dried to obtain in vacuum environment
Containing redox graphene/ferriferrous oxide nano line composite material electrode slice.
Step 3: the sodium sulfite and aqueous sodium persulfate solution of 2mol/L are prepared respectively, as measurement electrolyte.
Step 4: test C-V curve, regulatory complex operating voltage section are tested it and are such as measured and cycle-index.
Preferably, redox graphene/ferriferrous oxide nano line compound, activity in the crosslinker mixture
Charcoal, polytetrafluoroethylene (PTFE) (PTFE) mass ratio are 8:1:1, and mixing vessel is in the small beaker of 10ml.
A kind of lithium ion battery, the positive electrode of the lithium ion battery is using above-mentioned redox graphene/tetra- oxidations
Three iron composite materials, specific step is as follows for preparation method of lithium ion battery:
Step 1: weighing a certain amount of redox graphene/ferriferrous oxide nano line compound, active carbon, gather inclined fluorine
Ethylene (PVDF) crosslinker mixture, a certain amount of alcohol, which is added, makes mixture at paste, is uniformly mixing to obtain lithium ion battery
Anode sizing agent.
Step 2: the slurry in step 1 being uniformly coated in the foam nickel surface of clean copper foil, is done in vacuum environment
It is dry to obtain containing redox graphene/ferriferrous oxide nano line composite material electrode slice.
Step 3: using LiFePO4 as electrolyte, passing through the positive plate for cutting and obtaining with electrode slice above is anode,
Diaphragm is added, button cell is dressed up in tabletting.
Step 4: test C-V curve, its cycle-index and is tested at specific capacity in regulatory complex operating voltage section.
Preferably, redox graphene/ferriferrous oxide nano line compound, activity in the crosslinker mixture
Charcoal, polytetrafluoroethylene (PTFE) (PTFE) mass ratio are 8:1:1, and mixing vessel is in the small beaker of 10ml.
A kind of redox graphene prepared by the present invention/ferriferrous oxide nano line composite material supercapacitor,
The energy storage fields such as battery and the application for being electromagnetically shielded field.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention synthesizes ferriferrous oxide nano line using the inducing action of graphene oxide, as long as by graphite oxide
Alkene is dispersed in reaction solution, is then added ferroso-ferric oxide presoma, can be synthesized ferriferrous oxide nano line, is reacted
It only can be completed in aqueous solution, easy to operate, at low cost, Material cladding is uniform, is that other nano wires and nano wire are multiple
Condensation material, such as cobaltosic oxide, vanadium oxide, the synthesis of the oxide nano threads such as zinc oxide provide new method.
(2) the ferriferrous oxide nano linear diameter that the present invention synthesizes is in 100~200nm, and length is in 3~7um, reduction-oxidation
Graphene and nanoscale ferroso-ferric oxide large specific surface area, magnetic saturation intensity are up to 35~45emu/g, electronic conductivity
Height substantially increases electric conductivity, the electromagnetic shielding performance of material, accelerates ferriferrous oxide nano line in lithium battery anode, surpasses
Grade capacitor, the further industrial applications in electromagnetic shielding material field.
(3) graphene oxide that the present invention uses is prepared by improved Hummers method, and method is simple, economical and efficient,
Large-scale industrial production can be achieved.
(4) preparation method of the present invention is simple, practical, only can be completed in aqueous solution, is not introduced into organic poly-
The impurity such as object are closed, without increasing washing step, while ion can not penetrate lamella, reduce the rate that reactive ion combines, simultaneously
The synthesis of nano wire is completed to the inducing action that nano wire synthesizes using the hydroxyl of graphene oxide, it is easy to spread.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is redox graphene/ferriferrous oxide nano line composite material scanning electricity that the present invention is prepared
Mirror figure
Fig. 2 is that non-oxidation graphene adds ferroso-ferric oxide obtained and contrast scans electron microscope of the invention
Fig. 3 is redox graphene/ferriferrous oxide nano line composite material TGA curve
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
Present invention will be further explained below with reference to the attached drawings and examples, in order to the understanding of technical staff of the same trade:
Embodiment 1
Redox graphene/ferriferrous oxide nano line composite material preparation process, the specific steps are as follows:
Step 1: using the graphene oxide water solution of improved Hummers method preparation, graphene oxide being washed to pH
=4~6, the powder of graphene oxide is then made using vacuum freeze-drying method.At room temperature, by the graphite oxide of 200mg
Alkene is dissolved in 40ml water, ultrasonic 2h, magnetic agitation 6h, obtains finely dispersed graphene oxide solution A.
Step 2: 8g sodium hydroxide (NaOH) is dissolved into solution A, magnetic agitation 1h, obtain NaOH be completely dissolved it is molten
Liquid B.
Step 3: weighing the hypo (Na of 1.984g2S2O3·5H2) and seven hydrated sulfuric acids of 4.448g O
Ferrous iron (FeSO4·7H2O) mixing is poured into the polytetrafluoro inner liner of reaction kettle of 50ml, and 40ml solution B is poured into reaction kettle.This
When, NaOH, FeSO4·7H2O, Na2S2O3·5H2The molar ratio of O is 10:2:1.
Step 4: sealing reaction kettle keeps the temperature for 24 hours under the conditions of 160 DEG C, is air-cooled to room temperature after the reaction was completed.
Step 5: reaction product is washed.By product redox graphene/ferriferrous oxide nano line compound
It pours into the beaker of 250ml, fills it up with deionized water, magnet is placed on beaker bottom and carries out sedimentation collection, outwells supernatant, so anti-
It is 3~5 times multiple, remove unreacted ion.Alcohol is filled it up in beaker, is equally placed on beaker bottom with magnet and is collected, outwells
Clear liquid 2~3 times repeatedly, 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 dry under 60 DEG C of vacuum conditions, removes residual solvent.By dried redox graphene/ferroso-ferric oxide
Nanowire composite is ground into fine powder.
Embodiment 2
Redox graphene/cobaltosic oxide nano line composite material preparation process, the specific steps are as follows:
Step 1: using the graphene oxide water solution of improved Hummers method preparation, graphene oxide being washed to pH
=4~6, the powder of graphene oxide is then made using spray drying process.At room temperature, the graphene oxide of 200mg is molten
Solution is in 40ml polyethylene glycol PEG200, PEG400, PEG600 or PEG aqueous solution as reaction solution, ultrasonic 2h, magnetic agitation
6h obtains finely dispersed graphene oxide solution A.
Step 2: 8g sodium hydroxide (NaOH) is dissolved into solution A, magnetic agitation 1h, obtain NaOH be completely dissolved it is molten
Liquid B.
Step 3: weighing the hypo (Na of 1.984g2S2O3·5H2) and seven hydrated sulfuric acids of 4.496g O
Cobalt (CoSO4·7H2O) mixing is poured into the polytetrafluoro inner liner of reaction kettle of 50ml, and 40ml solution B is poured into reaction kettle.At this point,
NaOH, CoSO4·7H2O, Na2S2O3·5H2The molar ratio of O is 10:2:1.
Step 4: sealing reaction kettle keeps the temperature for 24 hours under the conditions of 160 DEG C, is air-cooled to room temperature after the reaction was completed.
Step 5: reaction product is washed.By product redox graphene/ferriferrous oxide nano line compound
It pours into the beaker of 250ml, fills it up with deionized water, carry out sedimentation collection from sedimentation using reaction product, outwell supernatant, such as
This 3~5 times repeatedly, remove unreacted ion.Alcohol is filled it up in beaker, is sunk also with reaction product from sedimentation
Drop is collected, and supernatant is outwelled, and 2~3 times repeatedly, 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 dry under 60 DEG C of vacuum conditions, residual solvent is removed, by dried redox graphene/ferroso-ferric oxide
Nanowire composite is ground into fine powder.
Embodiment 3
Containing redox graphene/ferriferrous oxide nano line composite electromagnetic screen coating preparation process, specific steps
It is as follows:
Step 1: weigh 6g epoxy resin, be added in 50ml beaker, be added 4g alcohol, magnetic agitation for 24 hours, until epoxy resin
It is uniformly dispersed, obtains the mixed liquor A that epoxy resin mass fraction is 60%.
Step 2: weigh 6g epoxy curing agent, 50ml beaker be added and exists, be added 4g alcohol, magnetic agitation for 24 hours, until solid
Agent is uniformly dispersed, and obtains the mixed liquid B that epoxy curing agent mass fraction is 60%.
Step 3: mixing in step 1 is added in the graphene oxide/ferriferrous oxide nano line compound for weighing 1.3g reduction
It closes in liquid A, is stirred evenly with glass bar, be uniformly mixed with the mixed liquid B in step 2, obtain the electromagnetism that mass fraction is 10%
Shielding coating.
Step 4: coating in step 3 is coated on carbon fiber film, it can be completely dry to vaporized alcohol in 60 DEG C of baking ovens
After dry, the film for forming load-type composite material is used；It can also be coated in timber, the surfaces such as plastics are directly made after solvent evaporation
For electromagnetic shielding material use.
Embodiment 4
The preparation process of graphene oxide containing reduction/ferriferrous oxide nano line compound supercapacitor, specifically
Steps are as follows:
Step 1: weigh 80mg reduction graphene oxide/ferriferrous oxide nano line compound, the active carbon of 10mg,
10mg polytetrafluoroethylene (PTFE) (PTFE) crosslinking agent, i.e. its mass ratio are 10:1:1；It pours into the small beaker of 10ml, adds a certain amount of wine
Essence makes mixture at paste, and stirs 3h with glass, is allowed to uniformly mixed, obtains super capacitor slurry.
Step 2: the slurry in step 1 uniformly being coated to foam nickel surface dried in step 1, coated area is
10*10mm, the dry 12h in 60 DEG C of vacuum environment.
Step 3: the sodium sulfite and aqueous sodium persulfate solution of 2mol/L are prepared respectively, as measurement electrolyte.
Step 4: test C-V curve, its cycle-index is tested in regulatory complex operating voltage section.
Comparative example 1
The preparation process of ferroso-ferric oxide crystal, the specific steps are as follows:
Step 1: 8g sodium hydroxide (NaOH) is dissolved into solution A, magnetic agitation 1h, obtain NaOH be completely dissolved it is molten
Liquid A.
Step 2: weighing the hypo (Na of 1.984g2S2O3·5H2) and seven hydrated sulfuric acids of 4.448g O
Ferrous iron (FeSO4·7H2O) mixing is poured into the polytetrafluoro inner liner of reaction kettle of 50ml, and 40ml solution A is poured into reaction kettle.This
When, NaOH, FeSO4·7H2O, Na2S2O3·5H2The molar ratio of O is 10:2:1.
Step 3: sealing reaction kettle keeps the temperature for 24 hours under the conditions of 160 DEG C, is air-cooled to room temperature after the reaction was completed.
Step 4: reaction product is washed.Product ferroso-ferric oxide is poured into the beaker of 250ml, deionization is filled it up with
Water, magnet are placed on beaker bottom and carry out sedimentation collection, outwell supernatant, 3~5 times repeatedly, remove unreacted ion.?
Alcohol is filled it up in beaker, equally beaker bottom is placed on magnet and collects, outwell supernatant, 2~3 times repeatedly, removes solution
Interior organic matter.
Step 5: the ferroso-ferric oxide crystal of washes clean in step 4 is put into vacuum oven under 60 DEG C of vacuum conditions
It is dry, residual solvent is removed, dried ferroso-ferric oxide is ground into fine powder.
Surface topography is carried out with 1 resulting materials of comparative example to embodiment 1 using scanning electron microscope instrument to characterize
Obtain Fig. 1 and Fig. 2.
Thermogravimetric analysis is carried out to 1 resulting materials of embodiment using thermogravimetric analyzer and obtains Fig. 3.
Fig. 1 is redox graphene/ferriferrous oxide nano line composite material scanning electron microscope that embodiment 1 is prepared
Figure, structure and morphology are as shown in Figure 1.It is 100~200 nanometers by the diameter that Fig. 1 can obtain ferriferrous oxide nano line, is attached to also
In former graphene oxide layer, graphene oxide layer is by its " latching ", 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 restored obtains
To redox graphene/ferriferrous oxide nano line compound.
Fig. 2 is the octahedra ferroso-ferric oxide crystal scanning electron microscope (SEM) photograph for not adding graphene oxide preparation in comparative example 1, knot
It is as shown in Figure 1 to be configured looks.It may be seen that graphene oxide is not added from Fig. 2, ferroso-ferric oxide isotropic growth is obtained
To blocky ferroso-ferric oxide crystal, a diameter of 400~600 nanometers.
Fig. 3 is the redox graphene/ferriferrous oxide nano line composite material TGA curve prepared in embodiment 1, from
In we can to calculate graphene oxide concentration be 2.5mg/ml and when 5mg/ml, redox graphene with four oxidations three
Iron ratio respectively may be about 8:92 and 17:83.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (8)
1. a kind of redox graphene/ferriferrous oxide nano line composite material and preparation method thereof, which is characterized in that including following
Step:
Step 1: in deionized water by graphene oxide dissolution, stirring to get finely dispersed graphene oxide solution A；
Step 2: sodium hydroxide being dissolved into solution A, the solution B that sodium hydroxide is completely dissolved is stirred to get；
Step 3: weighing hypo and green vitriol mixing is added in inner liner of reaction kettle, then take appropriate molten
Liquid B is added in reaction kettle；
Step 4: reactant issues raw hydrothermal synthesis reaction in sealing reaction kettle certain temperature, is air-cooled to room temperature after the reaction was completed；
Step 5: being washed, settle collection, be dried in vacuo and to obtain redox graphene/ferriferrous oxide nano to reaction product
Line composite material；
Graphene oxide used in the step 1 is prepared by improved Hummers method, is washed with deionized to neutrality
Behind pH=4~6 obtained by vacuum freeze drying, graphene oxide concentration is 1~5mg/ml in graphene oxide solution A, aoxidizes stone
The whipping process of black alkene is that 1~6h of magnetic agitation after 1~2h is stirred by ultrasonic at room temperature；
The molar ratio of reaction raw materials sodium hydroxide in the step 3, hypo, green vitriol is 10:
2:1, the volume of solution B are 40ml, and reaction kettle is the polytetrafluoro reaction kettle of volume 50ml, hydrothermal temperature in the step 4
It is 150~180 DEG C, soaking time is 20~30h.
2. redox graphene as described in claim 1/ferriferrous oxide nano line composite material and preparation method thereof, feature
It is, hydrothermal temperature is 160 DEG C, and soaking time is for 24 hours.
3. redox graphene as described in claim 1/ferriferrous oxide nano line composite material and preparation method thereof, feature
It is, the washing of reaction product, sedimentation collection process in the step 5 are as follows: by product redox graphene/ferroso-ferric oxide
Nanowire composite deionized water and ethanol washing attract method to carry out sedimentation collection in washing process using magnet, and it is heavy to accelerate
Reduction of speed degree, process of vacuum drying are as follows: be put into the redox graphene of washes clean/ferriferrous oxide nano line compound very
Empty drying box is dry under 60 DEG C of vacuum conditions, by dried redox graphene/ferriferrous oxide nano line compound
It is ground into fine powder, reduction-oxidation in the resulting redox graphene of step 5/ferriferrous oxide nano line composite material
The mass fraction of graphene is 5~20%.
4. a kind of redox graphene/ferriferrous oxide nano being prepared by any one of claims 1 to 3 the method
Line composite material, which is characterized in that redox graphene forms cage encapsulated by structures around ferriferrous oxide nano line.
5. a kind of redox graphene/ferriferrous oxide nano that the method containing any one of claims 1 to 33 is prepared
The preparation method of the electromagnetic screen coating of line composite material, which is characterized in that specific step is as follows:
Step 1: weighing appropriate epoxy resin and mixed with alcohol, magnetic agitation to epoxy resin is uniformly dispersed, and obtains certain mass
The epoxy resin mixed liquor A of score；
Step 2: weighing appropriate epoxy curing agent and mixed with alcohol, magnetic agitation to curing agent is uniformly dispersed, and obtains certain
The epoxy curing agent mixed liquid B of mass fraction；
Step 3: the asphalt mixtures modified by epoxy resin in step 1 is added in a certain amount of redox graphene/ferriferrous oxide nano line composite material
It stirs evenly in rouge mixed liquor A, is uniformly mixed with the epoxy curing agent mixed liquid B in step 2, obtain electromagnetic shielding and apply
Material.
6. a kind of redox graphene/ferroso-ferric oxide that the method containing any one of claims 1 to 33 is prepared is compound
The preparation method of the supercapacitor of material, which is characterized in that specific step is as follows:
Step 1: weighing a certain amount of redox graphene/ferriferrous oxide nano line composite material, active carbon, polytetrafluoroethyl-ne
Alkene (PTFE) crosslinker mixture, a certain amount of alcohol, which is added, makes mixture at paste, is uniformly mixing to obtain supercapacitor slurry
Material；
Step 2: the slurry in step 1 being uniformly coated in dry foam nickel surface, is dried to obtain in vacuum environment 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, as measurement electrolyte；
Step 4: test C-V curve, its cycle-index is tested in regulatory complex operating voltage section.
7. a kind of positive electrode is redox graphene/tetra- oxidations that any one of claims 1 to 3 the method is prepared
The lithium ion battery of three iron composite materials, which is characterized in that specific step is as follows for the preparation method of the lithium ion battery:
Step 1: weighing a certain amount of redox graphene/ferriferrous oxide nano line compound, active carbon, Kynoar
(PVDF) crosslinker mixture, a certain amount of alcohol, which is added, makes mixture at paste, is uniformly mixing to obtain lithium ion cell positive
Slurry；
Step 2: the slurry in step 1 is uniformly coated in the foam nickel surface of clean copper foil, it is dry in vacuum environment
To containing redox graphene/ferriferrous oxide nano line composite material electrode slice；
Step 3: using LiFePO4 as electrolyte, with electrode slice above by cutting obtained positive plate as anode, being added
Button cell is dressed up in diaphragm, tabletting；
Step 4: test C-V curve, its cycle-index and is tested at specific capacity in regulatory complex operating voltage section.
8. the redox graphene that any one of claims 1 to 3 the method is prepared/ferriferrous oxide nano line is multiple
Condensation material is in supercapacitor, the energy storage field of battery and the application for being electromagnetically shielded field.
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| CN108365182B (en) * | 2017-12-28 | 2020-11-13 | 杭州电子科技大学 | Iron ion doped nano manganous manganic oxide/multilayer graphene composite material, preparation method thereof and lithium battery applying iron ion doped nano manganous manganic oxide/multilayer graphene composite material |
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