CN106252091A - A kind of Fe3o4/ graphene composite material and preparation method thereof - Google Patents

A kind of Fe3o4/ graphene composite material and preparation method thereof Download PDF

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CN106252091A
CN106252091A CN201610785271.1A CN201610785271A CN106252091A CN 106252091 A CN106252091 A CN 106252091A CN 201610785271 A CN201610785271 A CN 201610785271A CN 106252091 A CN106252091 A CN 106252091A
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composite material
preparation
graphene
graphene oxide
water
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CN106252091B (en
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方华
王力臻
吴仕德
李晓峰
张爱琴
王丽霞
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Zhengzhou University of Light Industry
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of Fe3O4/ graphene composite material and preparation method thereof, belongs to energy storage device electrode field of material technology.The Fe of the present invention3O4The preparation method of/graphene composite material comprises the steps: graphene oxide emulsion and Fe (OH)3Colloidal sol mix homogeneously, solid-liquid separation, prepare Fe (OH)3/ graphene oxide composite material；By prepared Fe (OH)3/ graphene oxide composite material, under inert gas shielding, heats 1 5h at 200 500 DEG C, to obtain final product.The preparation method of the present invention realizes Fe (OH) by the electrostatic force between colloidal particle3Combining closely between colloidal particle and GO lamella, only can be achieved with Fe (OH) by simple mixing3The nanoparticle effective cladding to Graphene.Then by this nano composite material being carried out heat treatment, Fe (OH)3It is converted into Fe3O4, the pattern of sandwich structure is retained simultaneously.

Description

A kind of Fe3O4/ graphene composite material and preparation method thereof
Technical field
The present invention relates to a kind of Fe3O4/ graphene composite material and preparation method thereof, belongs to energy storage device electrode material skill Art field.
Background technology
In recent years, along with the fast development of green energy resource industry, electrochemical energy storage technology is sent out in human society and life Waving the most important effect, various electrochemical energy storing device are in fields such as electric motor car, energy storage, communication power supply and electronic products Apply more and more extensive.Wherein, lithium ion battery and ultracapacitor have that energy density is big, power density is high, the circulation longevity Life is long, self-discharge rate is low and the many merits such as " green " environmental protection, becomes the focus of application.
Along with the application of lithium ion battery and ultracapacitor is more and more extensive, each application is to lithium ion battery And the performance requirement of ultracapacitor is more and more higher, but, due to lithium ion battery and the restriction of ultracapacitor self, its Performance improve encounter bigger bottleneck, the bottleneck of electrode material performance be restriction lithium ion battery and ultracapacitor performance carry High key factor.Therefore, high performance new electrode materials is developed to solving lithium ion battery and ultracapacitor performance bottle Seem for neck significant.
Fe3O4Have that theoretical specific capacity is high, raw material resources abundant, relative low price and environmentally safe etc. many excellent Point, is respectively provided with wide application prospect as lithium ion battery and super capacitor anode material.But its initial coulomb efficiency Low, cyclical stability is poor, and high rate performance is poor.The Fe of preparation nanostructured3O4With construct Fe3O4/ C composite can be one Determine to solve in degree the problems referred to above.
Graphene, because having high theoretical specific surface and good electric conductivity, has become as and Fe3O4Composite wood optimal carbon material Material.Research shows, significantly increases Fe with Graphene recombination energy3O4Chemical property.But, owing to Graphene is prone to reunite, It is difficult to prepare Fe3O4At the scattered composite of graphenic surface uniform, stable, and it has been reported that preparation method technique multiple Miscellaneous, energy consumption is high, and the requirement to synthesis device is higher, thus improves production cost, it is difficult to realize industrialization.
Summary of the invention
It is an object of the invention to provide one and can make Fe3O4At the scattered Fe of graphenic surface uniform, stable3O4/ The preparation method of graphene composite material.
The present invention also aims to the Fe providing said method to prepare3O4/ graphene composite material.
The present invention solves the Fe that above-mentioned technical problem is used3O4The technical scheme of the preparation method of/graphene composite material As follows:
A kind of Fe3O4The preparation method of/graphene composite material, comprises the steps:
1) by graphene oxide emulsion and Fe (OH)3Colloidal sol mixes, solid-liquid separation, prepares Fe (OH)3/ graphene oxide composite wood Material；
2) by prepared Fe (OH)3/ graphene oxide composite material, under inert gas shielding, heats 1-5h at 200-500 DEG C, Obtain.
Graphene oxide in graphene oxide emulsion is 1:10-with the mass ratio of the hydrated ferric oxide. in ferric hydroxide sol 30。
Graphene oxide emulsion and Fe (OH) in step 1)3Mechanical agitation is carried out after colloidal sol mixing.During described mechanical agitation Between be 5-12h.
Fe (OH) in step 1)3The preparation method of colloidal sol includes: by precipitant and FeCl3Mix in a solvent, stand, so After at 50-90 DEG C react 0.5-10h, to obtain final product.
Described precipitant is the one or two kinds of in carbamide, ammonia.
Described solvent is one or several in water, ethanol, acetone.
Fe (OH) in step 1)3The preparation method of colloidal sol is preferably: by carbamide and FeCl3Water mixes, stands, then At 70-90 DEG C, react 0.5-10h, to obtain final product.Described carbamide and FeCl3In water, mixing is that urea liquid is added FeCl3Solution In.
The concentration of described urea liquid is 0.001-1mol/L, described FeCl3The concentration of solution is 0.0005-0.5mol/ L.The time of described standing is 0.5-10h.Urea liquid and FeCl3The volume ratio of solution is 1:5-10.
Fe (OH) in step 1)3Colloidal sol can also use the method comprised the steps to prepare:
In the ethanol solution of ferric chloride, add the ethanol solution of ammonia or in the acetone soln of ferric chloride, add ammonia Acetone soln, the pH of regulation solution is 6, at 50 DEG C, reacts 0.5-3h, solid-liquid separation, obtains hydrocolloid powder；By hydrocolloid powder It is added to the water mixing, obtains ferric hydroxide colloid solution.
The concentration of the ethanol solution of ferric chloride is 0.1mol/L.The concentration of the acetone soln of ferric chloride is 0.1mol/ L.The concentration of the ethanol solution of ammonia is 0.6mol/L.The concentration of the acetone soln of ammonia is 0.6mol/L.
In the ethanol solution of ferric chloride, add the ethanol solution of ammonia or add in the acetone soln of ferric chloride The mode of dropping is used during the acetone soln of ammonia.
Described solid-liquid separation is for filtering.With dehydrated alcohol or washing with acetone after filtration.Washing times is 3-5 time.
The solid that solid-liquid separation obtains dries 3h in the baking oven of 90 DEG C, obtains hydrocolloid powder.
The mass ratio that hydrocolloid powder is added to the water the hydrocolloid powder used by mixing and water is 1-10:1000.
In step 1), graphene oxide emulsion can be disperseed to prepare by graphene oxide in water.
Preferably, in step 1), the preparation method of graphene oxide emulsion includes:
By graphite, sodium nitrate, concentrated sulphuric acid under the conditions of 0 DEG C, mix homogeneously, be subsequently adding potassium permanganate, react 2h, add water and Hydrogen peroxide, stands, and filters, washs and i.e. obtain graphite oxide；Graphite oxide ultrasonic stripping in water is prepared graphene oxide emulsion. The mass percent concentration of described hydrogen peroxide is 30%.The mass percent concentration of concentrated sulphuric acid is 98%.
In said method, every 100mL concentrated sulphuric acid correspondence uses 2g graphite, 2g sodium nitrate, 12g potassium permanganate.
Described addition water is to add the water that 184mL temperature is 25 DEG C and the water that 560mL temperature is 50 DEG C.Described 184mL temperature Degree be the hydromining of 25 DEG C with being slowly added dropwise, time for adding is 15min.
Mix homogeneously refers to stir 15min.
After adding potassium permanganate, at 0 DEG C, stand 30min, stir 2h.
Washing uses dilute hydrochloric acid and deionized water to wash successively.The concentration of described dilute hydrochloric acid is 1-10%.
The Fe of the present invention3O4The technical scheme of/graphene composite material is as follows:
The Fe of the present invention3O4/ graphene composite material uses said method to prepare.
The Fe of the present invention3O4The preparation method of/graphene composite material realizes Fe by the electrostatic force between colloidal particle (OH)3Combining closely between colloidal particle and GO lamella, only can be achieved with Fe (OH) by simple mixing3Nanoparticle pair Effective cladding of Graphene.Formed complex sol system in, the Fe (OH) of surface positively charged3Colloidal particle and surface Electronegative GO sheet carries out self assembly by electrostatic interaction, has obtained the Fe (OH) of the stratiform with similar sandwich structure3/ GO/ Fe(OH)3Nano composite material.Then by this nano composite material is carried out heat treatment, oxygen during heat treatment Functionalized graphene is reduced to Graphene, Fe (OH)3It is converted into Fe3O4, the pattern of sandwich structure is retained simultaneously.The present invention Method to have preparation method simple, process costs is low, the feature that energy consumption is low, is very suitable for commercial application.
The Fe of the present invention3O4The Fe that the preparation method of/graphene composite material prepares3O4/ graphene composite material can conduct Lithium ion battery and the negative material of ultracapacitor, wherein Fe3O4Nanoparticle stores electric charge, graphite by electrochemical reaction Alkene provides passage and the Stability Analysis of Structures skeleton of electric transmission, and three-dimensional porous structure is conducive to the free migration of electrolyte ion, Thus give full play to Fe3O4Cooperative effect between nanoparticle and Graphene, obtains having high power density and high-energy-density concurrently Lithium ion battery and super capacitor anode material.
Accompanying drawing explanation
Fig. 1 is the Fe of embodiments of the invention 13O4The XRD figure spectrum of/graphene composite material；
Fig. 2 is the Fe of embodiments of the invention 13O4The SEM image of/graphene composite material；
Fig. 3 is the Fe of embodiments of the invention 23O4The SEM image of/graphene composite material；
Fig. 4 is the Fe of embodiments of the invention 13O4/ graphene composite material follows as the multiplying power of lithium ion battery negative material Ring curve；
Fig. 5 is the Fe of embodiments of the invention 13O4/ graphene composite material is bent as the circulation of super capacitor anode material Line.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect be easier to understand, below in conjunction with attached The present invention is described in detail for figure and detailed description of the invention.
Embodiment 1
The Fe of the present embodiment3O4The preparation method of/graphene composite material, comprises the steps:
1) compound concentration is the ferric chloride aqueous solutions of 0.01mol/L, and compound concentration is the aqueous solution of urea of 0.02mol/L, will The aqueous solution of urea of 20mL is added drop-wise in the liquor ferri trichloridi of 100mL, carries out magnetic agitation, after being added dropwise to complete during dropping At room temperature stand 1h, under the condition of water bath heating of 80 DEG C, then react 5h, prepare the Fe (OH) of azarin brown3Colloidal sol, its Middle ferric hydroxide colloid particle surface is positively charged；
Weigh 2g graphite powder, 2g sodium nitrate, and add in the concentrated sulphuric acid that 100mL concentration is 98%, under the condition of ice bath of 0 DEG C, stir Mix 15min and make its mix homogeneously, be subsequently adding 12g potassium permanganate, under the condition of ice bath of 0 DEG C, stand cooling 30min, then exist Under condition of ice bath, stirring reaction 2h, obtains suspension；Being added in above-mentioned suspension by the water of 184mL25 DEG C, 15min adds, so After be sequentially added into water that 560mL temperature is 50 DEG C wherein and 40mL concentration is the hydrogen peroxide of 30%, stand 30min, supernatant discarded Liquid, filter, filtering residue mass concentration be 10% hydrochloric acid and deionized water wash successively, be drying to obtain graphite oxide；Obtain Graphene oxide is dispersed in water, ultrasonic stripping 1h, the graphene oxide of stratiform is peeled off into the graphene oxide of monolithic, prepares Concentration is the graphene oxide emulsion of 0.1g/L；
2) the graphene oxide emulsion and ferric hydroxide sol prepared in step 1) is taken, under agitation, by graphene oxide Emulsion joins Fe (OH)3In colloidal sol, the graphene oxide in graphene oxide emulsion and the Fe (OH) in ferric hydroxide sol3 Mass ratio be 1:20, then ultrasonic disperse 1h, stirring 50min makes graphene oxide and Fe (OH)3There is self-assembling reaction, mistake Filter, obtains Fe (OH)3/ graphene oxide composite material；In the tube furnace being passed through nitrogen, by prepared Fe (OH)3/ oxidation stone Ink alkene composite heats 3h at 200 DEG C, to obtain final product.
Embodiment 2
The Fe of the present embodiment3O4The preparation method of/graphene composite material, comprises the steps:
1) compound concentration is the ferric chloride aqueous solutions of 0.2mol/L, and compound concentration is the aqueous solution of urea of 0.5mol/L, will The aqueous solution of urea of 10mL is added drop-wise in the liquor ferri trichloridi of 100mL, carries out magnetic agitation, after being added dropwise to complete during dropping Stand 5h in room temperature, under the condition of water bath heating of 70 DEG C, then react 10h, prepare the Fe (OH) of azarin brown3Colloidal sol, wherein Ferric hydroxide colloid particle surface is positively charged；
Weigh 2g graphite powder, 2g sodium nitrate, and add in the concentrated sulphuric acid that 100mL concentration is 98%, under the condition of ice bath of 0 DEG C, stir Mix 15min and make its mix homogeneously, be subsequently adding 12g potassium permanganate, under the condition of ice bath of 0 DEG C, stand cooling 30min, then exist Under condition of ice bath, stirring reaction 2h, obtains suspension；Being added in above-mentioned suspension by the water that 184mL temperature is 25 DEG C, 15min adds Complete, it is sequentially added into water that 560mL temperature is 50 DEG C the most wherein and 40mL concentration is the hydrogen peroxide of 30%, stand 30min, abandon Remove supernatant, filter, filtering residue mass concentration be 5% hydrochloric acid and deionized water wash successively, be drying to obtain graphite oxide；? The graphene oxide obtained is dispersed in water, ultrasonic stripping 1h, the graphene oxide of stratiform is peeled off into the graphite oxide of monolithic Alkene, prepared concentration is the graphene oxide emulsion of 0.1g/L；
2) the graphene oxide emulsion and ferric hydroxide sol prepared in step 1) is taken, under agitation, by graphene oxide Emulsion joins Fe (OH)3In colloidal sol, the graphene oxide in graphene oxide emulsion and the Fe (OH) in ferric hydroxide sol3 Mass ratio be 1:30, then ultrasonic disperse 1h, stirring 50min makes graphene oxide and Fe (OH)3There is self-assembling reaction, mistake Filter, obtains Fe (OH)3/ graphene oxide composite material；In the tube furnace being passed through nitrogen, by prepared Fe (OH)3/ oxidation stone Ink alkene composite heats 2h at 300 DEG C, to obtain final product.
Embodiment 3
The Fe of the present embodiment3O4The preparation method of/graphene composite material, comprises the steps:
1) compound concentration is the ferric chloride aqueous solutions of 0.5mol/L, and compound concentration is the aqueous solution of urea of 1mol/L, will The aqueous solution of urea of 12.5mL is added drop-wise in the liquor ferri trichloridi of 100mL, carries out magnetic agitation, be added dropwise to complete during dropping After at room temperature stand 10h, under the condition of water bath heating of 90 DEG C, then react 0.5h, prepare the Fe (OH) of azarin brown3Molten Glue, wherein ferric hydroxide colloid particle surface is positively charged；
Weigh 2g graphite powder, 2g sodium nitrate, and add in the concentrated sulphuric acid that 100mL concentration is 98%, under the condition of ice bath of 0 DEG C, stir Mix 15min and make its mix homogeneously, be subsequently adding 12g potassium permanganate, under the condition of ice bath of 0 DEG C, stand cooling 30min, then exist Under condition of ice bath, stirring reaction 2h, obtains suspension；Being that 25 DEG C of water add in above-mentioned suspension by 184mL temperature, 15min adds Complete, it is sequentially added into water that 560mL temperature is 50 DEG C the most wherein and 40mL concentration is the hydrogen peroxide of 30%, stand 30min, abandon Remove supernatant, filter, filtering residue mass concentration be 3% hydrochloric acid and deionized water wash successively, be drying to obtain graphite oxide；? The graphene oxide obtained is dispersed in water, ultrasonic stripping 1h, the graphene oxide of stratiform is peeled off into the graphite oxide of monolithic Alkene, prepared concentration is the graphene oxide emulsion of 0.1g/L；
2) the graphene oxide emulsion and ferric hydroxide sol prepared in step 1) is taken, under agitation, by graphene oxide Emulsion joins Fe (OH)3In colloidal sol, the graphene oxide in graphene oxide emulsion and the Fe (OH) in ferric hydroxide sol3 Mass ratio be 1:24, then ultrasonic disperse 1h, stirring 50min makes graphene oxide and Fe (OH)3There is self-assembling reaction, mistake Filter, obtains Fe (OH)3/ graphene oxide composite material；In the tube furnace being passed through nitrogen, by prepared Fe (OH)3/ oxidation stone Ink alkene composite heats 2h at 500 DEG C, to obtain final product.
Embodiment 4
The Fe of the present embodiment3O4The preparation method of/graphene composite material, comprises the steps:
1) in the ethanol solution of the ferric chloride that concentration is 0.1mol/L, under magnetic stirring, drip the second of the ammonia of 0.6mol/L Alcoholic solution, controlling temperature is 50 DEG C, and the pH of regulation solution is 6, reacts 3h, filters, filtering residue absolute ethanol washing 3 times, will To solid in the baking oven of 90 DEG C, dry 3h, obtain hydrocolloid powder；10g hydrocolloid powder is added in 1000g distilled water and stirs, Obtain ferric hydroxide colloid solution；
Weigh 2g graphite powder, 2g sodium nitrate, and add in the concentrated sulphuric acid that 100mL concentration is 98%, under the condition of ice bath of 0 DEG C, stir Mix 15min and make its mix homogeneously, be subsequently adding 12g potassium permanganate, under the condition of ice bath of 0 DEG C, stand cooling 30min, then exist Under condition of ice bath, stirring reaction 2h, obtains suspension；Being added in above-mentioned suspension by the water that 184mL temperature is 25 DEG C, 15min adds Complete, it is sequentially added into water that 560mL temperature is 50 DEG C the most wherein and 40mL concentration is the hydrogen peroxide of 30%, stand 30min, abandon Remove supernatant, filter, filtering residue mass concentration be 5% hydrochloric acid and deionized water wash successively, be drying to obtain graphite oxide；? The graphene oxide obtained is dispersed in water, ultrasonic stripping 1h, the graphene oxide of stratiform is peeled off into the graphite oxide of monolithic Alkene, prepared concentration is the graphene oxide emulsion of 0.1g/L；
2) the graphene oxide emulsion and ferric hydroxide sol prepared in step 1) is taken, under agitation, by graphene oxide Emulsion joins Fe (OH)3In colloidal sol, the graphene oxide in graphene oxide emulsion and the Fe (OH) in ferric hydroxide sol3 Mass ratio be 1:20, then ultrasonic disperse 1h, stirring 50min makes graphene oxide and Fe (OH)3There is self-assembling reaction, mistake Filter, obtains Fe (OH)3/ graphene oxide composite material；In the tube furnace being passed through nitrogen, by prepared Fe (OH)3/ oxidation stone Ink alkene composite heats 2h at 300 DEG C, to obtain final product.
Embodiment 5
The Fe of the present embodiment3O4The preparation method of/graphene composite material, comprises the steps:
1) under magnetic stirring, drip in the acetone soln of the ferric chloride that concentration is 0.1mol/L 0.6mol/L ammonia third Ketone solution, controlling temperature is 50 DEG C, and the pH of regulation solution is 6, reacts 5h, filters, and filtering residue washing with acetone 5 times, by obtain Solid dries 4h in the baking oven of 90 DEG C, obtains hydrocolloid powder；3g hydrocolloid powder is added in 1000g distilled water and stirs, to obtain final product Ferric hydroxide colloid solution；
Weigh 2g graphite powder, 2g sodium nitrate, and add in the concentrated sulphuric acid that 100mL concentration is 98%, under the condition of ice bath of 0 DEG C, stir Mix 15min and make its mix homogeneously, be subsequently adding 12g potassium permanganate, under the condition of ice bath of 0 DEG C, stand cooling 30min, then exist Under condition of ice bath, stirring reaction 2h, obtains suspension；Being added in above-mentioned suspension by the water that 184mL temperature is 25 DEG C, 15min adds Complete, it is sequentially added into water that 560mL temperature is 50 DEG C the most wherein and 40mL concentration is the hydrogen peroxide of 30%, stand 30min, abandon Remove supernatant, filter, filtering residue mass concentration be 5% hydrochloric acid and deionized water wash successively, be drying to obtain graphite oxide；? The graphene oxide obtained is dispersed in water, ultrasonic stripping 1h, the graphene oxide of stratiform is peeled off into the graphite oxide of monolithic Alkene, prepared concentration is the graphene oxide emulsion of 0.1g/L；
2) the graphene oxide emulsion and ferric hydroxide sol prepared in step 1) is taken, under agitation, by graphene oxide Emulsion joins Fe (OH)3In colloidal sol, the graphene oxide in graphene oxide emulsion and the Fe (OH) in ferric hydroxide sol3 Mass ratio be 1:20, then ultrasonic disperse 1h, stirring 50min makes graphene oxide and Fe (OH)3There is self-assembling reaction, mistake Filter, obtains Fe (OH)3/ graphene oxide composite material；In the tube furnace being passed through nitrogen, by prepared Fe (OH)3/ oxidation stone Ink alkene composite heats 2h at 500 DEG C, to obtain final product.
Test example
1) thing is tested mutually
The Fe that will prepare in embodiment 13O4/ graphene composite material carries out XRD detection, and result is as shown in Figure 1.
As shown in Figure 1, the sample that embodiment 1 prepares has sharp-pointed diffraction maximum, peak position and standard card (PDF NO. 88-0866) each diffraction maximum is corresponding, belongs to Fe3O4Diffraction maximum.
2) pattern test
The Fe that will prepare in embodiment 1 and embodiment 23O4/ graphene composite material carries out SEM detection respectively, and result is the most such as Shown in Fig. 2 and Fig. 3.
From Fig. 2 and Fig. 3, at Fe3O4In/graphene composite material, Fe3O4Nano-particle uniform adsorption is at Graphene Both side surface, and define the Fe of similar sandwich structure3O4/ Graphene/Fe3O4Nano composite material.
3) electrochemical property test
The Fe that will prepare in embodiment 13O4/ graphene composite material is as lithium ion battery negative material, with lithium sheet for auxiliary Electrode and reference electrode, prepare simulation lithium ion battery, carry out discharge and recharge respectively under 0.2C, 0.5C, 1C, 2C, 10C multiplying power, And carrying out loop test, test result is as shown in Figure 4.
The Fe that will prepare in embodiment 13O4/ graphene composite material is as super capacitor anode material, with commercialization Activated carbon is positive electrode, prepares ultracapacitor, respectively under the electric current density of 1A/g, 2A/g, 5A/g, 10A/g, 20A/g Carrying out discharge and recharge, and carry out loop test, test result is as shown in Figure 5.
As shown in Figure 4, the composite prepared by embodiment 1 is as lithium ion battery negative material, in the charge and discharge of 0.2C Under electricity multiplying power, discharge capacity reaches 1100 mAh/g first.
As shown in Figure 5, the composite prepared by embodiment 1 is electric in the electric discharge of 1A/g as super capacitor anode material It is up to 624 F/g than electric capacity under current density, and there is good multiplying power discharging property.
The above disclosed the preferred embodiments of the present invention that are only, can not limit the right of the present invention with this certainly Scope, therefore, with the equivalent variations done in the scope of the invention, still falls within the scope that the present invention is contained.

Claims (9)

1. a Fe3O4The preparation method of/graphene composite material, it is characterised in that comprise the steps:
1) by graphene oxide emulsion and Fe (OH)3Colloidal sol mix homogeneously, solid-liquid separation, prepare Fe (OH)3/ graphene oxide is multiple Condensation material；
2) by prepared Fe (OH)3/ graphene oxide composite material, under inert gas shielding, heats 1-5h at 200-500 DEG C, Obtain.
2. Fe as claimed in claim 13O4The preparation method of/graphene composite material, it is characterised in that graphene oxide breast Graphene oxide in liquid is 1:10-30 with the mass ratio of the hydrated ferric oxide. in ferric hydroxide sol.
3. Fe as claimed in claim 13O4The preparation method of/graphene composite material, it is characterised in that described in step 1) Fe(OH)3The preparation method of colloidal sol includes:
By precipitant and FeCl3Mix in a solvent, stand, at 50-90 DEG C, then react 0.5-10h, to obtain final product.
4. Fe as claimed in claim 33O4The preparation method of/graphene composite material, it is characterised in that described precipitant is One or two kinds of in carbamide, ammonia.
5. Fe as claimed in claim 33O4The preparation method of/graphene composite material, it is characterised in that described solvent be water, One or several in ethanol, acetone.
6. Fe as claimed in claim 13O4The preparation method of/graphene composite material, it is characterised in that aoxidize in step 1) The preparation method of graphene emulsion includes:
By graphite, sodium nitrate, concentrated sulphuric acid under the conditions of 0 DEG C, mix homogeneously, be subsequently adding potassium permanganate, react 2h, add water and Hydrogen peroxide, stands, and filters, washs to obtain graphite oxide；Graphite oxide ultrasonic stripping in water is prepared graphene oxide emulsion.
7. Fe as claimed in claim 63O4The preparation method of/graphene composite material, it is characterised in that every dense sulfur of 100mL Acid is corresponding uses 2g graphite, 2g sodium nitrate, 12g potassium permanganate.
8. Fe as claimed in claim 63O4The preparation method of/graphene composite material, it is characterised in that described addition water is Add the water that 184mL temperature is 25 DEG C and the water that 560mL temperature is 50 DEG C.
9. one kind uses the Fe that preparation method as claimed in claim 1 prepares3O4/ graphene composite material.
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CN108493003A (en) * 2018-03-28 2018-09-04 江苏大学 A kind of preparation method and application of ferroferric oxide nano granules
CN109317124A (en) * 2018-11-13 2019-02-12 湖北文理学院 A kind of three-dimensional grapheme magnetic stirring bar and its analysis application
CN109585185A (en) * 2018-11-16 2019-04-05 郑州轻工业学院 The confinement the preparation method and its stored energy application of a kind of nitrogen, sulphur codope graphene film
CN109627488A (en) * 2018-12-07 2019-04-16 深圳市克得磁材技术有限公司 Graphene composite Nano Fe3O4Material obsorbing radar waves and preparation method thereof
CN109626518A (en) * 2018-12-28 2019-04-16 广东省工程技术研究所 Magnetic graphite alkenyl Fen+The method of the heterogeneous Fenton processing dyeing waste water of three-diemsnional electrode
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CN114873986A (en) * 2022-06-23 2022-08-09 重庆永固新型建材有限公司 Cement-based crack repair slurry and preparation method thereof

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