CN106986333B - A kind of method of magnanimity controllable preparation graphene nano sieve material - Google Patents
A kind of method of magnanimity controllable preparation graphene nano sieve material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of graphene nano sieve material, pass through the redox reaction using metallic substrates and graphene oxide, obtain the graphene assembly containing metal oxide, then graphene nano is obtained by high-temperature calcination and sieves material or its functional material, realize that graphene nano sieves the regulation in material aperture by adjusting calcination temperature, and the volume size of graphene assembly can be by the volume of adjusting initial oxidation graphene solution, the areas of concentration and metallic substrates regulates and controls, therefore the preparation method of graphene nano sieve material of the invention be it is a kind of can macroscopic preparation of graphene nanometer sieve the new method of material, and the controllable of graphene nano sieve material aperture can be achieved at the same time in this method.
Description
Technical field
The invention belongs to grapheme material fields, sieve material more particularly, to a kind of magnanimity controllable preparation graphene nano
The method of material.
Background technique
Graphene, it is a kind of to arrange the bi-dimensional cellular shape crystal structure materials formed by single layer of carbon atom, since it is with excellent
Different electricity, mechanics and thermal property and be widely used in the fields such as energy storage, catalysis, sensing and flexible electronic device.
The grapheme material prepared by chemical oxidation-reduction method, since the oxygen-containing functional group in graphene oxide layer gradually removes,
Electrostatic repulsion between negative electrical charge weakens, and the π-π sucking action enhancing between the big pi bond of lamella, graphene film interlayer is easily sent out
It is raw to stack phenomenon, cause the specific surface area of graphene sheet layer to reduce, limits the practical application of material.
Graphene nano sieve, a kind of novel graphene nano structure can be regarded as band in graphene nano on piece
Gap is opened and a kind of film of flat porous of formation.It is compared with conventional graphene nanometer sheet, graphene nano sifter device has out
The band gap put, widened specific surface area and more active sites and edge, are being catalyzed it, the energy, sensor and partly lead
There is good application prospect in the fields such as body device.
Currently, the preparation method of graphene nano sieve material mainly has: photoetching, plasma etching, catalysis oxidation and change
Learn vapor deposition etc..However the defects of generally existing cost of these methods is high, low yield, and preparation step is complicated cumbersome, it is unfavorable for
The large-scale production of material.Freeze grinding is carried out under the conditions of liquid nitrogen using cheap graphene oxide composite material although having been reported
Graphene nano sieve material is directly prepared, but the material presence obtained prepares uncontrollable defect, as material hole density is low
It is uneven etc. with pore-size distribution.Therefore, the new method for developing a kind of magnanimity controllable preparation graphene nano sieve functional material is one
A urgent problem to be solved.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of magnanimity controllable preparation graphenes to receive
The method of rice huller screen material and its functional material is contained by the redox reaction using metallic substrates and graphene oxide
There is the graphene assembly of metal oxide, graphene nano then obtained by high-temperature calcination and sieves material or its functional material,
Realize that graphene nano sieves the regulation in material aperture by adjusting calcination temperature, and the volume size of graphene assembly can lead to
The area of the volume of initial oxidation graphene solution, concentration and metallic substrates is overregulated to regulate and control, therefore graphite of the invention
Alkene nanometer sieve material preparation method be it is a kind of can macroscopic preparation of graphene nanometer sieve the new method of material, and this method can be same
Shi Shixian graphene nano sieves the controllable of material aperture.Thus the preparation method of prior art graphene nano sieve material is solved not
The technical problem that prepared by magnanimity and aperture is controllable can be realized simultaneously.
To achieve the above object, according to one aspect of the present invention, a kind of preparation of graphene nano sieve material is provided
Method includes the following steps:
(1) metallic substrates are immersed in the graphene oxide water solution that concentration is 2~20mg/mL, at 60~80 DEG C
Reaction 6~60 hours takes out metallic substrates, obtains three-dimensional grapheme assembly；
(2) the graphene assembly that step (1) obtains is freeze-dried, obtains dry three-dimensional grapheme material；
(3) the three-dimensional grapheme material after the drying of step (2) acquisition is forged at 400~1100 DEG C in an inert atmosphere
It burns 0.5~3 hour, pickling after cooling, graphene nano sieve material can be obtained.
Preferably, step (1) metallic substrates are sheet metal or metal foam, and the metal includes nickel, cobalt or iron.
Preferably, step (1) described metallic substrates are the metallic substrates after cleaning, the cleaning method particularly includes: according to
It is secondary to be cleaned with ethyl alcohol, hydrochloric acid and deionized water, it cleans 10~30 minutes altogether.
Preferably, step (1) graphene oxide water solution is prepared using oxidation stripping method.
Preferably, step (2) further includes following steps: by the graphene assembly of the drying in 200~400rad/
Ball milling 10~30 minutes under min.
Preferably, step (3) the pickling specific steps are as follows: impregnated 5~8 hours in the hydrochloric acid solution of 4~6mol/L.
Preferably, step (3) inert atmosphere is argon atmosphere.
Preferably, the graphene nano sieve material that step (3) obtain is mixed with the organic matter containing nitrogen, sulphur or phosphorus, so
It is placed in argon atmosphere and is calcined 1~2 hour at 800~1000 DEG C of temperature, can be obtained the graphene of nitrogen, sulphur or phosphorus doping
Nanometer sieve functional material.
Preferably, the organic matter containing nitrogen, sulphur or phosphorus is melamine, benzyl disulfide or triphenylphosphine.
Other side according to the invention provides a kind of graphene nano sieve material, makes as described above
Preparation Method is prepared.
Other side according to the invention provides the application of the sieve material of graphene nano described in one kind, is applied to
The electrode material or composite material of energy stores and switching device.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect.
(1) the preparation method simple process of graphene nano of the present invention sieve material, low in cost, is suitable for extensive, macro
Amount prepares graphene nano sieve material, and preparation method yield is high, the amount for the graphene nano sieve material being prepared and
Aperture can be regulated and controled as needed simultaneously；
(2) raw material that the preparation method of graphene nano sieve material of the present invention uses synthesize skill for graphene oxide
Art is mature, at low cost, can produce in enormous quantities；
(3) the graphene nano sieve material that the method for the invention obtains has intensive uniform plane pore structure, so that
Material has very big specific surface area and ion transmission channel abundant；
(4) graphene nano sieve material of the invention is assembled into button cell, and survey can be carried out to its supercapacitive
Examination, the material show good electrochemistry storage performance.The graphene nano sieve and its functional material that the present invention is prepared
It can be used for the electrode material of the energy stores such as supercapacitor, lithium ion battery and fuel cell and switching device, it is also possible to
In the electrochemical properties of load nanometer electroactive material (such as metal oxide or conducting polymer) Lai Tisheng material, such as electrode
The storage performance of material and high rate performance etc..
Detailed description of the invention
Nickel foam induced oxidation graphene solution restores and organizes the picture in kind before and after reaction cartridge in Fig. 1 embodiment 1；
The picture in kind of the graphene assembly of nickel foam is embedded in Fig. 2 embodiment 1；
The scanning electron microscope diagram piece of graphene assembly in Fig. 3 embodiment 1；
The transmission electron microscope picture of graphene assembly in Fig. 4 embodiment 1；
The transmission electron microscope picture that graphene nano sieves in Fig. 5 embodiment 1；
The transmission electron microscope picture that graphene nano sieves in Fig. 6 embodiment 2；
The transmission electron microscope picture that graphene nano sieves in Fig. 7 embodiment 3；
Fig. 8 is that the graphene nano that embodiment 10 is prepared sieves the cyclic voltammetry curve figure that material is used as electrode material.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The preparation method of graphene nano sieve material and its functional material provided by the invention, includes the following steps:
(1) metallic substrates are immersed in the graphene oxide water solution that concentration is 2~20mg/mL, at 60~80 DEG C
Reaction 6~60 hours takes out metallic substrates, obtains three-dimensional grapheme assembly；Metallic substrates are sheet metal or metal foam, gold
Belong to such as nickel, cobalt or iron；Metallic substrates can be cleaned 10~30 minutes altogether by successively being cleaned with ethyl alcohol, hydrochloric acid and deionized water,
So that metallic substrates reactivity is higher.Graphene oxide water solution is prepared using oxidation stripping method (Hummer method).It is living
Property metallic substrates and graphene oxide redox reaction occurs, graphene oxide is reduced, and metallic substrates are oxidized to aoxidize
Object.
(2) the graphene assembly that step (1) obtains is freeze-dried, freeze-drying is generally carried out at -50 DEG C, is obtained
To dry three-dimensional grapheme assembly；Then by the graphene assembly of the drying at 200~400rad/min ball milling
10~30 minutes, obtain graphene powder material；
(3) graphene powder material for obtaining step (2) is in inert atmosphere, preferably in 400~1100 in argon atmosphere
DEG C, it is calcined at preferably 450~900 DEG C 0.5~3 hour, preferably calcination time is 2 hours, in the hydrochloric acid of 4~6mol/L after cooling
It is impregnated 5~8 hours in solution, graphene nano sieve material can be obtained.
Graphene nano sieve material is mixed with the organic matter containing nitrogen, sulphur or phosphorus, for example, with melamine, dibenzyl
Two sulphur or triphenylphosphine mixing, are subsequently placed in argon atmosphere and calcine 1~2 hour at 800~1000 DEG C of temperature, can be obtained
The graphene nano of nitrogen, sulphur or phosphorus doping sieves functional material.
Above-mentioned graphene nano sieve material and its functional material can be applied to the electrode material of energy stores and switching device,
Electrode material including supercapacitor, lithium ion battery and fuel cell etc., it can also be used to load nanometer electroactive material (such as
Metal oxide or conducting polymer etc.) Lai Tisheng material electrochemical properties.
The present invention is by being inserted directly into the container for filling graphene oxide solution for active metal substrate (nickel, cobalt or iron)
In, by the redox reaction between graphene oxide and active metal, the spontaneous reduction of metallic substrates and the entire appearance of assembling
Graphene oxide in device obtains three-dimensional grapheme functional assembly, and the formation of assembly can be by adjusting container size, instead
It is controlled between seasonable with temperature.It is worth noting that, the metal oxide that redox reaction generates can uniformly disperse to adhere to
In graphene assembly.Based on this, we carry out calcination processing to this graphene assembly under inert gas conditions,
Etching reaction can occur with carbon for metal oxide to generate nanoscale hole on the surface of graphene under hot conditions.This
Invention it has been found that calcination temperature is higher, reactivity is bigger, after etching reaction metallic particles occur reunion situation it is tighter
Weight, and the aperture of graphene nano sieve material is bigger, and therefore, the size of the hole of graphene nano sieve material of the present invention can lead to
Calcination temperature is overregulated to realize, is handled finally by sour bubble, is washed off the metal simple-substance and unreacted oxygen in grapheme material
Compound, i.e. acquisition graphene nano sieve material.Further, obtained graphene nano sieve material is passed through into nitridation, vulcanization or phosphorus
Change processing can obtain the graphene nano sieve functional material of Heteroatom doping.
The volume size of graphene assembly of the present invention can be by adjusting the volume of initial oxidation graphene solution and dense
The sizes of degree and corresponding metallic substrates regulates and controls, and graphene oxide solution volume and concentration and metallic substrates are bigger,
Under the reduction of active metal substrate, the graphene assembly of large volume is generated, it, can be with after being further processed, calcining
The graphene nano sieve material of magnanimity is obtained, and at the same time, by regulating and controlling calcination temperature, can be obtained within the scope of 10~200nm
The graphene nano of different pore size size sieves powder body material, and therefore, the preparation method of graphene nano sieve material of the present invention can be with
The magnanimity and controllable preparation of graphene nano sieve material are realized simultaneously.
The following are embodiments:
Embodiment 1
Metal nickel foam (8x10cm) is successively cleaned 30 minutes with ethyl alcohol, hydrochloric acid and deionized water first.Then, it uses
Stripping method (Hummers method) is aoxidized to prepare the graphene oxide water solution that mass concentration is 2~20mg/mL, detailed process
It is as follows: 5g natural flake graphite powder is taken, it is stirred under condition of ice bath with the sodium nitrate of the 115mL concentrated sulfuric acid and 2.5g,
Then 15.0g potassium permanganate is slowly added into solution, temperature is risen to 35 degree after stirring 2 hours, after continuing stirring 2 hours,
It is slowly added to the deionized water of 200mL, temperature is then further increased to 95 degree, and is maintained 30 minutes, is then added into solution
Entering the deionized water of about 500mL, temperature is adjusted to room temperature, and the hydrogenperoxide steam generator of 10mL is added, solution is filtered to obtain solid,
Dilute hydrochloric acid and deionized water centrifuge washing are successively used, graphene oxide solution can be obtained.
Cleaned nickel foam is directly dipped into the graphene oxide water solution for filling 500mL 3.0mg/mL
Reaction is stood in beaker, the reaction temperature of integral system is controlled in 80 DEG C, and the reaction time is 42 hours, specific pictorial diagram
Piece is as shown in Fig. 1.As can be seen that can be reduced directly and assemble when impregnating as the nickel foam of substrate in the process and is entire
Graphene oxide in beaker forms three-dimensional porous graphene assembly, and its specific picture in kind and scanning electron are aobvious
The material that micro mirror picture (attached drawing 2 and Fig. 3 shown in) also shows acquisition is three-dimensional porous structure.The oxygen that redox reaction generates
Changing nickel nano particle can be uniformly adhered on graphene sheet layer, and specific transmission electron microscope picture is as shown in Fig. 4.
Then, the graphene assembly being freeze-dried is placed in tube furnace, calcines 2 hours for 500 DEG C, rises in the case where argon gas protects atmosphere
Warm rate control is in 5 DEG C/min.Taking-up sample is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours and can be obtained after reaction
Graphene nano sieves material, and specific transmission electron microscope picture can be found in attached drawing 5, it can be seen that point in material nano hole
Cloth is about 10-20nm.
Embodiment 2
Metal foam nickel (6x9cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers method) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
It fills and stands reaction in the beaker of the graphene oxide water solution of 250mL 4.0mg/mL, the reaction temperature of integral system is controlled
At 75 DEG C, the reaction time is 30 hours.It can be reduced directly and assemble when impregnating as the nickel foam of substrate in the process and is whole
Graphene oxide in a beaker forms three-dimensional porous graphene assembly.Then, the graphene being freeze-dried is assembled
Body is placed in tube furnace, is calcined 2 hours for 700 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.Reaction terminates
Taking-up sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, afterwards can be obtained graphene nano sieve material, specific saturating
The sub- microscope photograph of radio can be found in attached drawing 6, it can be seen that the distribution in material nano hole is about 40-60nm.
Embodiment 3
Metal nickel sheet (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers method) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have and stand reaction in the beaker of the graphene oxide water solution of 100mL 5.0mg/mL, the reaction temperature of integral system is controlled in
80 DEG C, the reaction time is 35 hours.It can be reduced directly and assemble when impregnating as the nickel foam of substrate in the process and is entire
Graphene oxide in beaker forms three-dimensional porous graphene assembly.Then, the graphene assembly that will be freeze-dried
It is placed in tube furnace, is calcined 2 hours for 900 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.After reaction
Taking-up sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, can be obtained graphene nano sieve material, specific to transmit
Electron microscope picture can be found in attached drawing 7, it can be seen that the distribution in material nano hole is about 100-200nm.
Embodiment 4
Metal iron plate (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers method) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have and stand reaction in the beaker of the graphene oxide water solution of 100mL 2.0mg/mL, the reaction temperature of integral system is controlled in
70 DEG C, the reaction time is 12 hours.In the process entire burning can be reduced directly and assembled when impregnating as the iron plate of substrate
Graphene oxide in cup, forms three-dimensional porous graphene assembly.Then, the graphene assembly being freeze-dried is set
In tube furnace, calcined 2 hours for 800 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.It takes after reaction
Sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, out can be obtained graphene nano sieve material.
Embodiment 5
Metallic cobalt piece (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers method) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have and stand reaction in the beaker of the graphene oxide water solution of 100mL 3.0mg/mL, the reaction temperature of integral system is controlled in
80 DEG C, the reaction time is 16 hours.In the process entire burning can be reduced directly and assembled when impregnating as the cobalt piece of substrate
Graphene oxide in cup, forms three-dimensional porous graphene assembly.Then, the graphene assembly being freeze-dried is set
In tube furnace, calcined 2 hours for 500 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.It takes after reaction
Sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, out can be obtained graphene nano sieve material.
Embodiment 6
Metal foam nickel (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers method) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
It fills and stands reaction in the beaker of the graphene oxide water solution of 100mL 3.0mg/mL, the reaction temperature of integral system is controlled
At 80 DEG C, the reaction time is 35 hours.It can be reduced directly and assemble when impregnating as the nickel foam of substrate in the process and is whole
Graphene oxide in a beaker forms three-dimensional porous graphene assembly.Then, the graphene being freeze-dried is assembled
Body is placed in tube furnace, is calcined 2 hours for 500 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.Reaction terminates
Taking-up sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, afterwards can be obtained graphene nano sieve material.Then by graphite
Alkene nanometer sieve material and melamine powder are mixed, and are calcined 1 hour for 900 DEG C in the case where argon gas protects atmosphere, be can be obtained nitrogen
The graphene nano of doping sieves functional material.
Embodiment 7
Metallic cobalt piece (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers method) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have and stand reaction in the beaker of the graphene oxide water solution of 100mL 3.5mg/mL, the reaction temperature of integral system is controlled in
75 DEG C, the reaction time is 15 hours.In the process entire burning can be reduced directly and assembled when impregnating as the cobalt piece of substrate
Graphene oxide in cup, forms three-dimensional porous graphene assembly.Then, the graphene assembly being freeze-dried is set
In tube furnace, calcined 2 hours for 450 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.It takes after reaction
Sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, out can be obtained graphene nano sieve material.Then graphene is received
Rice huller screen material and benzyl disulfide powder are mixed, and are calcined 1 hour for 900 DEG C in the case where argon gas protects atmosphere, be can be obtained sulphur and mix
Miscellaneous graphene nano sieves functional material.
Embodiment 8
Metal iron plate (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers method) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have and stand reaction in the beaker of the graphene oxide water solution of 100mL 2.5mg/mL, the reaction temperature of integral system is controlled in
65 DEG C, the reaction time is 12 hours.In the process entire burning can be reduced directly and assembled when impregnating as the iron plate of substrate
Graphene oxide in cup, forms three-dimensional porous graphene assembly.Then, the graphene assembly being freeze-dried is set
In tube furnace, calcined 2 hours for 850 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.It takes after reaction
Sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, out can be obtained graphene nano sieve material.Then graphene is received
Rice huller screen material and triphenylphosphine powder are mixed, and are calcined 1 hour for 900 DEG C in the case where argon gas protects atmosphere, be can be obtained phosphorus doping
Graphene nano sieve functional material.
Embodiment 9
Metal foam nickel (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers method) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
It fills and stands reaction in the beaker of the graphene oxide water solution of 100mL 4.0mg/mL, the reaction temperature of integral system is controlled
At 80 DEG C, the reaction time is 32 hours.It can be reduced directly and assemble when impregnating as the nickel foam of substrate in the process and is whole
Graphene oxide in a beaker forms three-dimensional porous graphene assembly.Then, the graphene being freeze-dried is assembled
Body is placed in tube furnace, is calcined 2 hours for 600 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.Reaction terminates
Taking-up sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, afterwards can be obtained graphene nano sieve material.Then by graphite
Alkene nanometer sieve material and melamine, benzyl disulfide powder are mixed, and are calcined 1 hour for 900 DEG C in the case where argon gas protects atmosphere,
It can be obtained nitrogen, the graphene nano of sulphur codope sieves functional material.
Embodiment 10
Metal foam nickel (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers method) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
It fills and stands reaction in the beaker of the graphene oxide water solution of 100mL 3.0mg/mL, the reaction temperature of integral system is controlled
At 80 DEG C, the reaction time is 35 hours.It can be reduced directly and assemble when impregnating as the nickel foam of substrate in the process and is whole
Graphene oxide in a beaker forms three-dimensional porous graphene assembly.Then, the graphene being freeze-dried is assembled
Body is placed in tube furnace, is calcined 2 hours for 500 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.Reaction terminates
Taking-up sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, afterwards can be obtained graphene nano sieve material.Then by graphite
Alkene nanometer sieves material and conductive black and polytetrafluoroethylene (PTFE) and carries out ground and mixed according to the mass ratio of 80:10:10, uniform to coat
On conductive aluminum foil, it is assembled into button cell (ionic liquid that electrolyte uses dilution in acetonitrile), and to its super capacitor performance
It is tested, specific cyclic voltammetry curve can be found in attached drawing 8, it can be seen that potential region can expand compared to aqueous electrolyte
Width arrives 2.8V, and curve is almost in rectangle, and symmetrical and area is big, illustrates the good electrochemistry storage performance of the material.
Embodiment 11
Metallic cobalt piece (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers method) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have and stand reaction in the beaker of the graphene oxide water solution of 100mL 12.0mg/mL, the reaction temperature of integral system is controlled
At 80 DEG C, the reaction time is 16 hours.It can be reduced directly and assemble when impregnating as the cobalt piece of substrate in the process and is entire
Graphene oxide in beaker forms three-dimensional porous graphene assembly.Then, the graphene assembly that will be freeze-dried
It is placed in tube furnace, is calcined 3 hours for 500 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.After reaction
Taking-up sample, which is placed in the hydrochloric acid of 6.0M to impregnate to clean for 8 hours, can be obtained graphene nano sieve material.
Embodiment 12
Metal foam nickel (4x6cm) is successively used into ethyl alcohol, hydrochloric acid first, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers method) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
It fills and stands reaction in the beaker of the graphene oxide water solution of 100mL 20.0mg/mL, the reaction temperature of integral system is controlled
For system at 75 DEG C, the reaction time is 20 hours.It can be reduced directly and assemble when impregnating as the nickel foam of substrate in the process
Graphene oxide in entire beaker, forms three-dimensional porous graphene assembly.Then, the graphene group that will be freeze-dried
Dress body is placed in tube furnace, is calcined 0.5 hour for 1100 DEG C in the case where argon gas protects atmosphere, heating rate is controlled in 5 DEG C/min.Reaction
After take out sample be placed in the hydrochloric acid of 6.0M impregnates 8 hours cleaning can be obtained graphene nano sieve material.Then will
Graphene nano sieve material and melamine, benzyl disulfide powder are mixed, 900 DEG C of calcinings 1 in the case where argon gas protects atmosphere
Hour, it can be obtained nitrogen, the graphene nano of sulphur codope sieves functional material.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of magnanimity and aperture it is controllable graphene nano sieve material preparation method, which comprises the steps of:
(1) metallic substrates are immersed in the graphene oxide water solution that concentration is 2~20mg/mL, are reacted at 60~80 DEG C
15~60 hours, metallic substrates are taken out, three-dimensional grapheme assembly is obtained；The metallic substrates are sheet metal or metal foam；
Using the redox reaction of metallic substrates and graphene oxide, the graphene assembly containing metal oxide is obtained, wherein
The metal oxide that redox reaction generates uniformly disperses to be attached in graphene assembly；
(2) the graphene assembly that step (1) obtains is freeze-dried, obtains dry three-dimensional grapheme material；
(3) the three-dimensional grapheme material after the drying of step (2) acquisition is calcined at 400~1100 DEG C in an inert atmosphere
0.5~3 hour, graphene nano sieve material can be obtained in pickling after cooling；
Regulate and control graphene assembly by the area of the volume of adjusting initial oxidation graphene solution, concentration and metallic substrates
Volume size, after being further processed, calcining, obtain magnanimity graphene nano sieve material；It is real by adjusting calcination temperature
The regulation in existing graphene nano sieve material aperture.
2. preparation method as described in claim 1, which is characterized in that step (1) described metal includes nickel, cobalt or iron.
3. preparation method as described in claim 1, which is characterized in that step (1) described metallic substrates are the metal after cleaning
Substrate, the cleaning method particularly includes: successively cleaned with ethyl alcohol, hydrochloric acid and deionized water, cleaned 10~30 minutes altogether.
4. preparation method as described in claim 1, which is characterized in that step (1) graphene oxide water solution uses oxygen
Change stripping method to be prepared.
5. preparation method as described in claim 1, which is characterized in that step (2) further includes following steps: by the drying
Graphene assembly ball milling 10~30 minutes at 200~400rad/min.
6. preparation method as described in claim 1, which is characterized in that step (3) the pickling specific steps are as follows: 4~
It is impregnated 5~8 hours in the hydrochloric acid solution of 6mol/L.
7. preparation method as described in claim 1, which is characterized in that step (3) inert atmosphere is argon atmosphere.
8. preparation method as described in claim 1, which is characterized in that by step (3) obtain graphene nano sieve material with
Organic matter mixing containing nitrogen, sulphur or phosphorus, is subsequently placed in argon atmosphere and calcines 1~2 hour at 800~1000 DEG C of temperature,
It can be obtained the graphene nano sieve functional material of nitrogen, sulphur or phosphorus doping.
9. a kind of graphene nano sieves material, which is characterized in that it is according to the preparation as described in claim 1~8 any one
Method is prepared.
10. a kind of application of graphene nano sieve material as claimed in claim 9, which is characterized in that be applied to energy stores
With the electrode material or composite material of switching device.
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| CN104649253A (en) * | 2013-11-18 | 2015-05-27 | 国家纳米科学中心 | Preparing methods of porous graphene and porous graphene film |
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| CN104310382A (en) * | 2014-09-29 | 2015-01-28 | 东华大学 | Preparation method for graphene nanometer screen |
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