CN106252090A - A kind of high fold grapheme material and preparation method thereof - Google Patents
A kind of high fold grapheme material and preparation method thereof Download PDFInfo
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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
- H01G11/84—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
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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
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/30—Electrodes characterised by their material
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of high fold grapheme material and preparation method thereof, belong to energy storage device electrode field of material technology.The preparation method of the high fold grapheme material of the present invention, comprises the steps: Fe3O4/ graphene composite material carries out pickling, is drying to obtain.The preparation method of the high fold grapheme material of the present invention selects the oxide of ferrum to construct the Graphene of high fold as template, the redox reaction between the oxide of ferrum and material with carbon element can be utilized, cavity is etched at graphenic surface, not only increase the specific surface area of Graphene, more importantly, increase the passage of ion migration, it is achieved good super capacitor energy-storage performance.
Description
Technical field
The present invention relates to a kind of high fold grapheme material and preparation method thereof, belong to energy storage device electrode material technology neck
Territory.
Background technology
The advantage such as ultracapacitor has that energy density is big, power density is high, have extended cycle life and self-discharge rate is low, crowd
Multi-field all it is widely used.But, along with the expansion of supercapacitor applications scope, the market performance to ultracapacitor
Require more and more higher, and the key factor affecting ultracapacitor performance is electrode material, therefore, develop high performance electrode material
Material, improves the energy density of ultracapacitor, reduces the emphasis that its manufacturing cost is supercapacitor technologies research.
Graphene is because of the physicochemical property of its uniqueness, one of study hotspot becoming electrode material for super capacitor.So
And, Graphene is susceptible to irreversible reunion and even resets formation graphite, causes falling sharply of Graphene specific surface area, so that
The advantage obtaining Graphene is difficult to effectively play；Relatively big additionally, due to graphene film, and electrolyte ion is difficult to through graphene film
Free diffusing；These shortcomings hinder the Graphene application in electrode material for super capacitor field.
High fold Graphene has the pore structure of uniqueness, is provided that higher specific surface area and mesoporous, in conjunction with Graphene from
Body advantage, makes this material be expected to become the electrode material of high-performance super capacitor, and in energy storage field, Industrial Catalysis field all has
There is preferable application prospect.But, the most complex process of preparation method of high fold Graphene of the prior art, energy consumption are high,
Requirement to synthesis device is higher, and then causes its production cost higher, it is difficult to realize industrialization, and the Graphene knot prepared
Structure heterogeneity, causes its chemical property to decline.
Summary of the invention
It is an object of the invention to provide a kind of excellent electrochemical performance and preparation technology is simple, the high fold stone of low cost
The preparation method of ink alkene material.
The present invention also aims to the high fold grapheme material providing said method to prepare.
The present invention solves the technical scheme of the preparation method of the high fold grapheme material that above-mentioned technical problem is used such as
Under:
The preparation method of a kind of high fold grapheme material, comprises the steps: Fe3O4/ graphene composite material carries out acid
Wash, be drying to obtain.
The acid that described pickling uses is the one in hydrochloric acid, sulphuric acid, nitric acid.The mass percent concentration of described acid is 5-
10%。
Above-mentioned 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 being slowly added dropwise 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, stirring reaction 2h.
Washing uses dilute hydrochloric acid and deionized water to wash successively.The concentration of described dilute hydrochloric acid is 1-10%.
The technical scheme of the high fold grapheme material of the present invention is as follows:
The high fold grapheme material of the present invention uses said method to prepare.
Beneficial effect:
The preparation method of the high fold grapheme material of the present invention selects Fe3O4The Graphene of high fold is constructed as template, can
To utilize Fe3O4And the redox reaction between material with carbon element, etches cavity at graphenic surface, not only increases Graphene
Specific surface area, it is often more important that add the passage of ion migration, it is achieved good super capacitor energy-storage performance.
The Graphene that the present invention prepares has the pattern of high fold, has a classifying porous pore structure, macropore and mesoporous have
Being beneficial to the free migration of electrolyte ion, the micropore that high fold is formed can improve the specific surface area of material, it is simple to forms double electricity
Layer stores electric charge, thus obtains having concurrently the super capacitor anode material of high power density and high-energy-density.Its good electricity
Chemical property adds wide material sources and the low cost of this material ferrum so that it is also have in the field such as lithium ion battery, Industrial Catalysis
Good application prospect.
Further, the present invention uses Fe (OH)3Sol particles is that template prepares high fold grapheme material, at normal temperatures
Reaction can be completed, compare existing template and need not use the solvent of excess contamination environment, there is environmental friendliness, technique letter
List, low cost and low power consumption and other advantages, it is easy to accomplish commercial application.
Further, the Fe of the present invention3O4The preparation method of/graphene composite material is made by the electrostatic between colloidal particle
Firmly realize Fe (OH)3Combining closely between colloidal particle and GO lamella, only can be achieved with Fe (OH) by simple mixing3
The nanoparticle effective cladding to Graphene.Formed complex sol system in, the Fe (OH) of surface positively charged3Colloid
Particle and surface electronegative GO sheet carries out self assembly by electrostatic interaction, has obtained having the stratiform of similar sandwich structure
Fe(OH)3/GO/ Fe(OH)3Nano composite material.Then by this nano composite material is carried out heat treatment, at heat treatment
During graphene oxide be reduced to Graphene, Fe (OH)3It is converted into Fe3O4, the pattern of sandwich structure is protected simultaneously
Stay, provide good framing structure for high fold grapheme material.
Accompanying drawing explanation
Fig. 1 is the SEM image of the high fold grapheme material of embodiments of the invention 1；
Fig. 2 is the SEM image of the high fold grapheme material of embodiments of the invention 2；
Fig. 3 is the Fe of embodiments of the invention 13O4The SEM image of/graphene composite material；
Fig. 4 is the Fe of embodiments of the invention 23O4The SEM image of/graphene composite material；
Fig. 5 is the XRD figure spectrum of the high fold grapheme material of embodiments of the invention 1；
Fig. 6 is the Fe of embodiments of the invention 13O4The XRD figure spectrum of/graphene composite material；
Fig. 7 is the low temperature nitrogen adsorption desorption curve of the high fold grapheme material of embodiments of the invention 1；
Fig. 8 is that the high fold grapheme material of embodiments of the invention 1 is bent as the high rate performance of super capacitor anode material
Line；
Fig. 9 is the high fold grapheme material cyclic curve as super capacitor anode material of embodiments of the invention 1.
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 preparation method of the high fold grapheme material of the present embodiment, 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 slowly dropped in the liquor ferri trichloridi of 100mL, carries out magnetic agitation, drip during dropping
At room temperature stand 1h after one-tenth, under the condition of water bath heating of 80 DEG C, then react 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 slowly added in above-mentioned suspension by the water of 184mL25 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 10% 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 3h at 200 DEG C, prepares Fe3O4/ graphene composite material.
3) by step 2) in the Fe of gained3O4/ graphene composite material, with the hydrochloric acid solution that mass concentration is 10% at magnetic force
Embathe 24h under stirring condition, dissolve Fe therein3O4Nanoparticle, filters, and gained filter cake is washed with deionized to neutrality, cold
Lyophilizing is dry, obtains high fold grapheme material.
The high fold grapheme material of the present embodiment uses said method to prepare.
Embodiment 2
The preparation method of the high fold grapheme material of the present embodiment, 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 slowly dropped in the liquor ferri trichloridi of 100mL, carries out magnetic agitation, drip during dropping
Stand 5h in room temperature after one-tenth, 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；The water that 184mL temperature is 25 DEG C is slowly added in above-mentioned suspension,
15min adds, and 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, abandoning supernatant, filter, filtering residue mass concentration be 5% hydrochloric acid and deionized water wash successively, be drying to obtain oxidation
Graphite；The graphene oxide obtained is dispersed in water, ultrasonic stripping 1h, the graphene oxide of stratiform is peeled off into the oxygen of monolithic
Functionalized graphene, 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, prepares Fe3O4/ graphene composite material.
3) by step 2) in the Fe of gained3O4/ graphene composite material, with the hydrochloric acid solution that mass concentration is 5% at magnetic force
Embathe 24h under stirring condition, dissolve Fe therein3O4Nanoparticle, filters, and gained filter cake is washed with deionized to neutrality, cold
Lyophilizing is dry, obtains high fold grapheme material.
Embodiment 3
The preparation method of the high fold grapheme material of the present embodiment, 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 slowly dropped in the liquor ferri trichloridi of 100mL, carries out magnetic agitation during dropping, dropping
At room temperature stand 10h after completing, under the condition of water bath heating of 90 DEG C, then react 0.5h, prepare the Fe of azarin brown
(OH)3Colloidal 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；It is that 25 DEG C of water are slowly added in above-mentioned suspension by 184mL temperature, 15min
Add, be 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,
Abandoning 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 oxidation stone of monolithic
Ink 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, prepares Fe3O4/ graphene composite material.
3) by step 2) in the Fe of gained3O4/ graphene composite material, with the hydrochloric acid solution that mass concentration is 8% at magnetic force
Embathe 24h under stirring condition, dissolve Fe therein3O4Nanoparticle, filters, and gained filter cake is washed with deionized to neutrality, cold
Lyophilizing is dry, obtains high fold grapheme material.
Embodiment 4
The preparation method of the high fold grapheme material of the present embodiment, comprises the steps:
1) in the ethanol solution of the ferric chloride that concentration is 0.1mol/L, under magnetic stirring, it is slowly added dropwise the ammonia of 0.6mol/L
Ethanol 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,
The solid obtained is dried 3h in the baking oven of 90 DEG C, obtains hydrocolloid powder；10g hydrocolloid powder is added in 1000g distilled water
Stirring, obtains 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；The water that 184mL temperature is 25 DEG C is slowly added in above-mentioned suspension,
15min adds, and 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, abandoning supernatant, filter, filtering residue mass concentration be 5% hydrochloric acid and deionized water wash successively, be drying to obtain oxidation
Graphite；The graphene oxide obtained is scattered in 1000mL water, ultrasonic stripping 1h, the graphene oxide of stratiform is peeled off into single
The graphene oxide of sheet, 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, prepares Fe3O4/ graphene composite material.
3) by step 2) in the Fe of gained3O4/ graphene composite material, with the hydrochloric acid solution that mass concentration is 10% at magnetic force
Embathe 24h under stirring condition, dissolve Fe therein3O4Nanoparticle, filters, and gained filter cake is washed with deionized to neutrality, cold
Lyophilizing is dry, obtains high fold grapheme material.
Embodiment 5
The preparation method of the high fold grapheme material of the present embodiment, comprises the steps:
1) in the acetone soln of the ferric chloride that concentration is 0.1mol/L, under magnetic stirring, it is slowly added dropwise the ammonia of 0.6mol/L
Acetone soln, 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 will
The solid obtained dries 4h in the baking oven of 90 DEG C, obtains hydrocolloid powder；3g hydrocolloid powder is added in 1000g distilled water and stirs
Mix, 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；The water that 184mL temperature is 25 DEG C is slowly added in above-mentioned suspension,
15min adds, and 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, abandoning supernatant, filter, filtering residue mass concentration be 5% hydrochloric acid and deionized water wash successively, be drying to obtain oxidation
Graphite；The graphene oxide obtained is scattered in 1000mL water, ultrasonic stripping 1h, the graphene oxide of stratiform is peeled off into single
The graphene oxide of sheet, 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, prepares Fe3O4/ graphene composite material.
3) by step 2) in the Fe of gained3O4/ graphene composite material, with the hydrochloric acid solution that mass concentration is 10% at magnetic force
Embathe 24h under stirring condition, dissolve Fe therein3O4Nanoparticle, filters, and gained filter cake is washed with deionized to neutrality, cold
Lyophilizing is dry, obtains high fold grapheme material.
Test example
1) pattern test
By in embodiment 1 and embodiment 2 prepare high fold grapheme material carry out SEM detection respectively, result respectively as Fig. 1 with
Shown in Fig. 2.
The Fe that will prepare in embodiment 1 and embodiment 23O4/ graphene composite material carries out SEM detection respectively, and result is respectively
As shown in Figure 3 and Figure 4.
From Fig. 1 and Fig. 2, grapheme material prepared by the present invention has very abundant pleated structure, ties at fold
Also there is on structure abundant pore structure.
From Fig. 3 and Fig. 4, 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.
2) thing is tested mutually
The high fold grapheme material prepared in embodiment 1 is carried out XRD detection, and result is as shown in Figure 5.
The Fe that will prepare in embodiment 13O4/ graphene composite material carries out XRD detection, and result is as shown in Figure 6.
As shown in Figure 5, the sample that embodiment 1 prepares has the most sharp-pointed diffraction maximum, peak position and each diffraction maximum of Graphene
Corresponding.
It will be appreciated from fig. 6 that 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.
3) low temperature nitrogen adsorption desorption test
The high fold grapheme material prepared in embodiment 1 is carried out low temperature nitrogen desorption test, low temperature nitrogen adsorption desorption curve
As shown in Figure 7.
As shown in Figure 7, the existence wherein adsorbing back stagnant ring shows mesoporous existence, and the specific surface being computed material is 382
m2/g。
4) electrochemical property test
The Fe that will prepare in embodiment 13O4/ graphene composite material is as super capacitor anode material, with the work of commercialization
Property carbon be positive electrode, prepare ultracapacitor, enter under the electric current density of 1A/g, 2A/g, 5A/g, 10A/g, 20A/g respectively
Row discharge and recharge, and carry out loop test, test result is as shown in Figure 8.Wherein, charge and discharge cycles 1000 under the electric current density of 2A/g
Secondary, cyclic curve is as shown in Figure 9.
From Fig. 8 and Fig. 9, the high fold grapheme material of the present invention is higher than electric capacity under the discharge current density of 1A/g
Reach 239 F/g, and there is good multiplying power discharging property and charge and discharge cycles stability.
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 (10)
1. the preparation method of one kind high fold grapheme material, it is characterised in that comprise the steps: Fe3O4/ Graphene is multiple
Condensation material carries out pickling, is drying to obtain.
The preparation method of high fold grapheme material the most as claimed in claim 1, it is characterised in that the acid that described pickling uses
For the one in hydrochloric acid, sulphuric acid, nitric acid.
The preparation method of high fold grapheme material the most as claimed in claim 1, it is characterised in that described Fe3O4/ Graphene
The preparation method of composite comprises the steps:
1) graphene oxide emulsion and Fe (OH)3Colloidal sol mix homogeneously, solid-liquid separation, prepare Fe (OH)3/ graphene oxide is combined
Material；
2) by prepared Fe (OH)3/ graphene oxide composite material, under inert gas shielding, heats 1-5h at 200-500 DEG C,
Obtain.
The preparation method of high fold grapheme material the most as claimed in claim 3, it is characterised in that in graphene oxide emulsion
Graphene oxide and ferric hydroxide sol in the mass ratio of hydrated ferric oxide. be 1:10-30.
The preparation method of high fold grapheme material the most as claimed in claim 3, it is characterised in that Fe described in step 1)
(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.
The preparation method of high fold grapheme material the most as claimed in claim 5, it is characterised in that described precipitant is urine
One or two kinds of in element, ammonia.
The preparation method of high fold grapheme material the most as claimed in claim 5, it is characterised in that described solvent is water, second
One or several in alcohol, acetone.
The preparation method of high fold grapheme material the most as claimed in claim 3, it is characterised in that graphite oxide in step 1)
The preparation method of alkene 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；Often
100mL concentrated sulphuric acid correspondence uses 2g graphite, 2g sodium nitrate, 12g potassium permanganate.
The preparation method of high fold grapheme material the most as claimed in claim 8, it is characterised in that described addition water is for adding
184mL temperature is the water of 25 DEG C and water that 560mL temperature is 50 DEG C.
10. one kind uses the high fold grapheme material that preparation method as claimed in claim 1 prepares.
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