CN106252090B - 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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Abstract
The present invention relates to a kind of high fold grapheme materials 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, includes the following steps：By Fe3O4/ graphene composite material carries out pickling, is drying to obtain.The oxide of the preparation method selection iron of the high fold grapheme material of the present invention constructs the graphene of high fold as template, the redox reaction between the oxide and carbon material of iron can be utilized, cavity is etched on the surface of graphene, not only increase the specific surface area of graphene, good super capacitor energy-storage performance is realized in the channel for more importantly, increasing Ion transfer.
Description
Technical field
The present invention relates to a kind of high fold grapheme materials and preparation method thereof, belong to energy storage device electrode material technology neck
Domain.
Background technology
Ultracapacitor has the advantages that energy density is big, power density is high, it is low with self-discharge rate etc. to have extended cycle life, in crowd
It is multi-field to be all widely used.But with the expansion of supercapacitor applications range, performance of the market to ultracapacitor
It is required that it is higher and higher, and the key factor for influencing performance of the supercapacitor is electrode material, therefore, develops high performance electrode material
Material, improve the energy density of ultracapacitor, reduce its manufacturing cost be supercapacitor technologies research emphasis.
Graphene becomes one of research hotspot of electrode material for super capacitor because of its unique physicochemical property.So
And graphene is easy to happen irreversible reunion even rearrangement and forms graphite, falling sharply for graphene specific surface area is caused, to make
The advantages of obtaining graphene is difficult to effectively play；It is larger additionally, due to graphene film, and electrolyte ion is difficult to across graphene film
Free diffusing；These disadvantages hinder application of the graphene in electrode material for super capacitor field.
High fold graphene has unique pore structure, can provide higher specific surface area and mesoporous, in conjunction with graphene oneself
Body advantage makes the material be expected to become the electrode material of high-performance super capacitor, has in energy storage field, Industrial Catalysis field
There is preferable application prospect.But the most complex process of preparation method, the high energy consumption of high fold graphene in the prior art,
To the more demanding of synthesis device, and then cause its production cost higher, it is difficult to realize industrialization, and graphene knot obtained
Structure is inhomogenous, its chemical property is caused to decline.
Invention content
The purpose of the present invention is to provide a kind of excellent electrochemical performance and simple, the at low cost high fold stones of preparation process
The preparation method of black alkene material.
The present invention also aims to provide high fold grapheme material made from the above method.
The present invention solves the technical solution of the preparation method of high fold grapheme material used by above-mentioned technical problem such as
Under：
A kind of preparation method of high fold grapheme material, includes the following steps：By Fe3O4/ graphene composite material carries out
Pickling is drying to obtain.
The acid that the pickling uses is one kind in hydrochloric acid, sulfuric acid, nitric acid.The mass percent concentration of the acid is 5-
10%。
Above-mentioned Fe3O4The preparation method of/graphene composite material, includes the following steps：
1）By graphene oxide lotion and Fe (OH)3Colloidal sol mixes, and is separated by solid-liquid separation, and Fe (OH) is made3/ graphene oxide is multiple
Condensation material；
2）By Fe obtained (OH)3/ graphene oxide composite material heats under inert gas protection, at 200-500 DEG C
1-5h to get.
The mass ratio of the iron hydroxide in graphene oxide and ferric hydroxide sol in graphene oxide lotion is 1:10-
30。
Step 1）Middle graphene oxide lotion and Fe (OH)3Mechanical agitation is carried out after colloidal sol mixing.When the mechanical agitation
Between be 5-12h.
Step 1）Middle Fe (OH)3The preparation method of colloidal sol includes：By precipitating reagent and FeCl3It mixes, stands, so in a solvent
Afterwards at 50-90 DEG C react 0.5-10h to get.
The precipitating reagent is one or two kinds of in urea, ammonium hydroxide.
The solvent is the one or several kinds in water, ethyl alcohol, acetone.
Step 1）Middle Fe (OH)3The preparation method of colloidal sol is preferably：By urea and FeCl3It mixes, stands, then in water
At 70-90 DEG C react 0.5-10h to get.The urea and FeCl3Mixing is that FeCl is added in urea liquid in water3Solution
In.
A concentration of 0.001-1mol/L of the urea liquid, the FeCl3A concentration of 0.0005-0.5mol/ of solution
L.The time of the standing is 0.5-10h.Urea liquid and FeCl3The volume ratio of solution is 1：5-10.
Step 1）Middle Fe (OH)3Colloidal sol can also use the method included the following steps to be made：
The ethanol solution of ammonia is added into the ethanol solution of ferric trichloride or is added into the acetone soln of ferric trichloride
The acetone soln of ammonia, the pH for adjusting solution is 6, at 50 DEG C, reacts 0.5-3h, is separated by solid-liquid separation, obtains hydrocolloid powder；By colloid
Powder is added to the water mixing to get ferric hydroxide colloid solution.
A concentration of 0.1mol/L of the ethanol solution of ferric trichloride.A concentration of 0.1mol/ of the acetone soln of ferric trichloride
L.A concentration of 0.6mol/L of the ethanol solution of ammonia.A concentration of 0.6mol/L of the acetone soln of ammonia.
The ethanol solution of ammonia is added into the ethanol solution of ferric trichloride or is added into the acetone soln of ferric trichloride
When the acetone soln of ammonia by the way of being slowly added dropwise.
It is described to be separated by solid-liquid separation as filtering.It is washed with absolute ethyl alcohol or acetone after filtering.Washing times are 3-5 times.
It is separated by solid-liquid separation obtained solid and dries 3h in 90 DEG C of baking oven, obtain hydrocolloid powder.
The mass ratio that hydrocolloid powder is added to the water to the hydrocolloid powder and water used in mixing is 1-10：1000.
Step 1）Middle graphene oxide lotion can in water be disperseed to be made by graphene oxide.
Preferably, step 1）The preparation method of middle graphene oxide lotion includes：
It by graphite, sodium nitrate, the concentrated sulfuric acid under the conditions of 0 DEG C, is uniformly mixed, potassium permanganate is then added, react 2h, be added
Water and hydrogen peroxide are stood, and filtering is washed up to graphite oxide；By graphite oxide, graphene oxide is made in ultrasound stripping in water
Lotion.The mass percent concentration of the hydrogen peroxide is 30%.The mass percent concentration of the concentrated sulfuric acid is 98%.
In the above method, corresponded to using 2g graphite, 2g sodium nitrate, 12g potassium permanganate per the 100mL concentrated sulfuric acids.
The water that is added is that the water that 184ml temperature is 25 DEG C and the water that 560mL temperature is 50 DEG C is added.The 184mL temperature
The water that degree is 25 DEG C is used and is slowly added dropwise, time for adding 15min.
It refers to stirring 15min to be uniformly mixed.
After potassium permanganate is added, 30min is stood at 0 DEG C, is stirred to react 2h.
Washing is washed successively using dilute hydrochloric acid and deionized water.A concentration of 1-10% of the dilute hydrochloric acid.
The technical solution of the high fold grapheme material of the present invention is as follows：
The high fold grapheme material of the present invention is made using the above method.
Advantageous effect：
The preparation method of the high fold grapheme material of the present invention selects Fe3O4The graphene of high fold is constructed as template,
Fe can be utilized3O4Redox reaction between carbon material, etches cavity on the surface of graphene, not only increases graphite
The specific surface area of alkene, it is often more important that good super capacitor energy-storage performance is realized in the channel for increasing Ion transfer.
Graphene produced by the present invention has the pattern of high fold, has a classifying porous pore structure, macropore and mesoporous has
Conducive to the free migration of electrolyte ion, the micropore that high fold is formed can improve the specific surface area of material, convenient for forming double electricity
Layer storage charge, to obtain having both the super capacitor anode material of high power density and high-energy density.Its good electricity
Chemical property along with the material iron derive from a wealth of sources with it is at low cost, so that it is also had in fields such as lithium ion battery, Industrial Catalysis
Good application prospect.
Further, the present invention uses Fe (OH)3Sol particles are that template prepares high fold grapheme material, at normal temperatures
Reaction can be completed, compared to the solvent that existing template need not use excess contamination environment, with environmental-friendly, technique is simple
Single, at low cost and low power consumption and other advantages, it is easy to accomplish commercial application.
Further, Fe of the 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 lamellas only can be achieved with Fe (OH) by simply mixing3
Effective cladding of the nano-particle to graphene.In the complex sol system being formed by, the positively charged Fe in surface (OH)3Colloid
The electronegative GO pieces of particle and surface carry out self assembly by electrostatic interaction, have obtained the stratiform with similar sandwich structure
Fe(OH)3/GO/ Fe(OH)3Nanocomposite.Then by being heat-treated to the nanocomposite, in heat treatment
Graphene oxide is reduced to graphene, Fe (OH) in the process3It is converted into Fe3O4, while the pattern of sandwich structure is protected
It stays, good skeleton structure is provided for high fold grapheme material.
Description of the drawings
Fig. 1 is the SEM image of the high fold grapheme material of the embodiment of the present invention 1；
Fig. 2 is the SEM image of the high fold grapheme material of the embodiment of the present invention 2；
Fig. 3 is the Fe of the embodiment of the present invention 13O4The SEM image of/graphene composite material；
Fig. 4 is the Fe of the embodiment of the present invention 23O4The SEM image of/graphene composite material；
Fig. 5 is the XRD spectrum of the high fold grapheme material of the embodiment of the present invention 1；
Fig. 6 is the Fe of the embodiment of the present invention 13O4The XRD spectrum of/graphene composite material；
Fig. 7 is the low temperature nitrogen adsorption desorption curve of the high fold grapheme material of the embodiment of the present invention 1；
Fig. 8 is the high fold grapheme material of the embodiment of the present invention 1 as the forthright again of super capacitor anode material
It can curve；
Fig. 9 is that the high fold grapheme material of the embodiment of the present invention 1 is bent as the cycle of super capacitor anode material
Line.
Specific implementation mode
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention be easier to understand, with reference to attached
The present invention is described in detail for figure and specific implementation mode.
Embodiment 1
The preparation method of the high fold grapheme material of the present embodiment, includes the following steps：
1）Compound concentration is the ferric chloride aqueous solutions of 0.01mol/L, and compound concentration is that the urea of 0.02mol/L is water-soluble
The aqueous solution of urea of 20mL is slowly dropped in the liquor ferri trichloridi of 100mL by liquid, and magnetic agitation is carried out during being added dropwise,
1h is stood after being added dropwise to complete at room temperature, then reacts 5h under 80 DEG C of condition of water bath heating, the Fe of azarin brown is made
(OH)3Colloidal sol, wherein ferric hydroxide colloid particle surface are positively charged；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；184mL25 DEG C of water is slowly added in above-mentioned suspension,
15min is added, and is then sequentially added the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C thereto, is stood
30min discards supernatant liquid, filtering, and the hydrochloric acid and deionized water that filter residue is 10% with mass concentration wash successively, are drying to obtain oxygen
Graphite；Obtained graphene oxide is dispersed in water, ultrasound stripping 1h removes the graphene oxide of stratiform at monolithic
The graphene oxide lotion of a concentration of 0.1g/L is made in graphene oxide；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:20, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heats 3h at 200 DEG C, and Fe is made3O4/ graphene composite material.
3）By step 2）The Fe of middle gained3O4/ graphene composite material, the hydrochloric acid solution for being 10% with mass concentration is in magnetic force
It is embathed under stirring condition for 24 hours, dissolves Fe therein3O4Nano-particle, filtering, gained filter cake is washed with deionized to neutrality, cold
It is lyophilized dry to get high fold grapheme material.
The high fold grapheme material of the present embodiment is made using the above method.
Embodiment 2
The preparation method of the high fold grapheme material of the present embodiment, includes the following 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,
The aqueous solution of urea of 10mL is slowly dropped in the liquor ferri trichloridi of 100mL, magnetic agitation is carried out during being added dropwise, is added dropwise
It is being stored at room temperature 5h after the completion, is then reacting 10h under 70 DEG C of condition of water bath heating, the Fe (OH) of azarin brown is made3It is molten
Glue, wherein ferric hydroxide colloid particle surface are positively charged；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；The water that 184mL temperature is 25 DEG C is slowly added to above-mentioned suspension
In, 15min is added, and then sequentially adds the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C thereto, quiet
30min is set, liquid is discarded supernatant, is filtered, the hydrochloric acid and deionized water that filter residue is 5% with mass concentration wash successively, are drying to obtain oxygen
Graphite；Obtained graphene oxide is dispersed in water, ultrasound stripping 1h removes the graphene oxide of stratiform at monolithic
The graphene oxide lotion of a concentration of 0.1g/L is made in graphene oxide；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:30, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heats 2h at 300 DEG C, and Fe is made3O4/ graphene composite material.
3）By step 2）The Fe of middle gained3O4/ graphene composite material, the hydrochloric acid solution for being 5% with mass concentration is in magnetic force
It is embathed under stirring condition for 24 hours, dissolves Fe therein3O4Nano-particle, filtering, gained filter cake is washed with deionized to neutrality, cold
It is lyophilized dry to get high fold grapheme material.
Embodiment 3
The preparation method of the high fold grapheme material of the present embodiment, includes the following 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, is carried out magnetic agitation during being added dropwise, is added dropwise
It stands 10h at room temperature after the completion, then reacts 0.5h under 90 DEG C of condition of water bath heating, the Fe of azarin brown is made
(OH)3Colloidal sol, wherein ferric hydroxide colloid particle surface are positively charged；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；It is that 25 DEG C of water are slowly added to above-mentioned suspension by 184mL temperature
In, 15min is added, and then sequentially adds the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C thereto, quiet
30min is set, liquid is discarded supernatant, is filtered, the hydrochloric acid and deionized water that filter residue is 3% with mass concentration wash successively, are drying to obtain oxygen
Graphite；Obtained graphene oxide is dispersed in water, ultrasound stripping 1h removes the graphene oxide of stratiform at monolithic
The graphene oxide lotion of a concentration of 0.1g/L is made in graphene oxide；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:24, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heats 2h at 500 DEG C, and Fe is made3O4/ graphene composite material.
3）By step 2）The Fe of middle gained3O4/ graphene composite material, the hydrochloric acid solution for being 8% with mass concentration is in magnetic force
It is embathed under stirring condition for 24 hours, dissolves Fe therein3O4Nano-particle, filtering, gained filter cake is washed with deionized to neutrality, cold
It is lyophilized dry to get high fold grapheme material.
Embodiment 4
The preparation method of the high fold grapheme material of the present embodiment, includes the following steps：
1）Under magnetic stirring, 0.6mol/L is slowly added dropwise into the ethanol solution of the ferric trichloride of a concentration of 0.1mol/L
Ammonia ethanol solution, controlled at 50 DEG C, the pH for adjusting solution is 6, reacts 3h, filtering, filter residue washs 3 with absolute ethyl alcohol
It is secondary, obtained solid is dried into 3h in 90 DEG C of baking oven, obtains hydrocolloid powder；1000g distilled water is added in 10g hydrocolloid powders
Middle stirring is to get ferric hydroxide colloid solution；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；The water that 184mL temperature is 25 DEG C is slowly added to above-mentioned suspension
In, 15min is added, and then sequentially adds the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C thereto, quiet
30min is set, liquid is discarded supernatant, is filtered, the hydrochloric acid and deionized water that filter residue is 5% with mass concentration wash successively, are drying to obtain oxygen
Graphite；Obtained graphene oxide is scattered in 1000mL water, ultrasound stripping 1h, the stripping of the graphene oxide of stratiform at
The graphene oxide lotion of a concentration of 0.1g/L is made in the graphene oxide of monolithic；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:20, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heats 2h at 300 DEG C, and Fe is made3O4/ graphene composite material.
3）By step 2）The Fe of middle gained3O4/ graphene composite material, the hydrochloric acid solution for being 10% with mass concentration is in magnetic force
It is embathed under stirring condition for 24 hours, dissolves Fe therein3O4Nano-particle, filtering, gained filter cake is washed with deionized to neutrality, cold
It is lyophilized dry to get high fold grapheme material.
Embodiment 5
The preparation method of the high fold grapheme material of the present embodiment, includes the following steps：
1）Under magnetic stirring, 0.6mol/L is slowly added dropwise into the acetone soln of the ferric trichloride of a concentration of 0.1mol/L
Ammonia acetone soln, controlled at 50 DEG C, the pH for adjusting solution is 6, reacts 5h, filtering, filter residue washs * * 5 with acetone
It is secondary, obtained solid is dried into 4h in 90 DEG C of baking oven, obtains hydrocolloid powder；1000g distilled water is added in 3g hydrocolloid powders
Middle stirring is to get ferric hydroxide colloid solution；
2g graphite powders, 2g sodium nitrate are weighed, and is added in the concentrated sulfuric acid of 100mL a concentration of 98%, in 0 DEG C of condition of ice bath
Under, stirring 15min makes it be uniformly mixed, and 12g potassium permanganate is then added, and cooling 30min is stood under 0 DEG C of condition of ice bath,
Then it is stirred to react 2h under condition of ice bath, obtains suspension；The water that 184mL temperature is 25 DEG C is slowly added to above-mentioned suspension
In, 15min is added, and then sequentially adds the hydrogen peroxide of water and 40mL a concentration of 30% that 560mL temperature is 50 DEG C thereto, quiet
30min is set, liquid is discarded supernatant, is filtered, the hydrochloric acid and deionized water that filter residue is 5% with mass concentration wash successively, are drying to obtain oxygen
Graphite；Obtained graphene oxide is scattered in 1000mL water, ultrasound stripping 1h, the stripping of the graphene oxide of stratiform at
The graphene oxide lotion of a concentration of 0.1g/L is made in the graphene oxide of monolithic；
2）Take step 1）In graphene oxide lotion obtained and ferric hydroxide sol will aoxidize stone under agitation
Black alkene lotion is added to Fe (OH)3In colloidal sol, the Fe in graphene oxide and ferric hydroxide sol in graphene oxide lotion
(OH)3Mass ratio be 1:20, then ultrasonic disperse 1h, stirring 50min make graphene oxide and Fe (OH)3It is anti-that self assembly occurs
It answers, filters, obtain Fe (OH)3/ graphene oxide composite material；In the tube furnace for being passed through nitrogen, by Fe obtained (OH)3/ oxygen
Graphite alkene composite material heats 2h at 500 DEG C, and Fe is made3O4/ graphene composite material.
3）By step 2）The Fe of middle gained3O4/ graphene composite material, the hydrochloric acid solution for being 10% with mass concentration is in magnetic force
It is embathed under stirring condition for 24 hours, dissolves Fe therein3O4Nano-particle, filtering, gained filter cake is washed with deionized to neutrality, cold
It is lyophilized dry to get high fold grapheme material.
Test example
1）Pattern test
High fold grapheme material obtained in embodiment 1 and embodiment 2 is subjected to SEM detections respectively, as a result respectively such as
Shown in Fig. 1 and Fig. 2.
By Fe obtained in embodiment 1 and embodiment 23O4/ graphene composite material carries out SEM detections respectively, as a result distinguishes
As shown in Figure 3 and Figure 4.
By Fig. 1 and Fig. 2 it is found that grapheme material prepared by the present invention has very abundant pleated structure, in fold knot
Also there is abundant pore structure on structure.
As can be seen from figs. 3 and 4 in Fe3O4In/graphene composite material, Fe3O4Nano particle uniform adsorption is in graphene
Both side surface, and form the Fe of similar sandwich structure3O4/ graphene/Fe3O4Nanocomposite.
2）Object is mutually tested
High fold grapheme material obtained in embodiment 1 is subjected to XRD detections, the results are shown in Figure 5.
By Fe obtained in embodiment 13O4/ graphene composite material carries out XRD detections, and the results are shown in Figure 6.
As shown in Figure 5, sample made from embodiment 1 has more sharp diffraction maximum, peak position and each diffraction maximum of graphene
It is corresponding.
It will be appreciated from fig. 6 that sample made from embodiment 1 has sharp diffraction maximum, peak position and standard card（PDF NO.
88-0866）Each diffraction maximum corresponds to, and belongs to Fe3O4Diffraction maximum.
3）Low temperature nitrogen adsorption desorption is tested
High fold grapheme material obtained in embodiment 1 is subjected to low temperature nitrogen desorption experiment, low temperature nitrogen adsorption desorption
Curve is as shown in Figure 7.
As shown in Figure 7, wherein the presence of absorption hysteresis loop shows mesoporous presence, the specific surface for being computed material is 382
m2/g。
4）Electrochemical property test
By Fe obtained in embodiment 13O4/ graphene composite material is as super capacitor anode material, with commercialization
Activated carbon is positive electrode, ultracapacitor is made, respectively under the current density of 1A/g, 2A/g, 5A/g, 10A/g, 20A/g
Charge and discharge are carried out, and carry out loop test, test results are shown in figure 8.Wherein, charge and discharge cycles under the current density of 2A/g
1000 times, cyclic curve is as shown in Figure 9.
By Fig. 8 and Fig. 9 it is found that the high fold grapheme material of present invention specific capacitance under the discharge current density of 1A/g is high
Up to 239 F/g, and there is good multiplying power discharging property and charge and discharge cycles stability.
It is above disclosed to be merely a preferred embodiment of the present invention, the right of the present invention cannot be limited with this certainly
Range, therefore, the equivalent variations done in the scope of the invention still fall within the range that the present invention is covered.
Claims (4)
1. a kind of preparation method of high fold grapheme material, which is characterized in that include the following steps：Fe3O4/ graphenes are answered
Condensation material carries out pickling, is drying to obtain；
The acid that the pickling uses is one kind in hydrochloric acid, sulfuric acid, nitric acid；
The preparation method of the Fe3O4/ graphene composite materials includes the following steps：
1）Graphene oxide lotion is uniformly mixed with 3 colloidal sols of Fe (OH), is separated by solid-liquid separation, and it is compound that Fe (OH) 3/ graphene oxide is made
Material；
2）Under inert gas protection by 3/ graphene oxide composite materials of Fe obtained (OH), 1-5h is heated at 200-500 DEG C,
To obtain the final product；
The mass ratio of the iron hydroxide in graphene oxide and ferric hydroxide sol in graphene oxide lotion is 1:10-30；
Step 1）Middle Fe (OH)3The preparation method of colloidal sol is：By urea and FeCl3It mixes, stands, then at 70-90 DEG C in water
Lower reaction 0.5-10h to get；A concentration of 0.001-1mol/L of the urea liquid, the FeCl3Solution it is a concentration of
0.0005-0.5mol/L；The time of the standing is 0.5-10h；Urea liquid and FeCl3The volume ratio of solution is 1：5-10.
2. the preparation method of high fold grapheme material as described in claim 1, which is characterized in that step 1）Middle graphite oxide
The preparation method of alkene lotion includes：
By graphite, sodium nitrate, the concentrated sulfuric acid under the conditions of 0 DEG C, be uniformly mixed, be then added potassium permanganate, react 2h, be added water and
Hydrogen peroxide is stood, and graphite oxide is washed to obtain in filtering；By graphite oxide, graphene oxide lotion is made in ultrasound stripping in water；Often
The 100mL concentrated sulfuric acids are corresponded to using 2g graphite, 2g sodium nitrate, 12g potassium permanganate.
3. the preparation method of high fold grapheme material as claimed in claim 2, which is characterized in that the addition water is to be added
The water that the water and 560mL temperature that 184mL temperature is 25 DEG C are 50 DEG C.
4. a kind of using high fold grapheme material made from preparation method as described in claim 1.
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| 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 |
| CN112007667A (en) * | 2020-07-31 | 2020-12-01 | 金陵科技学院 | Selenium-modified reduced graphene oxide-loaded CoSe2Preparation method and application thereof |
| CN115246638B (en) * | 2022-08-22 | 2023-11-17 | 东北大学秦皇岛分校 | Preparation method and application of hollow mesoporous carbon sphere with inner surface being wrinkled |
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