CN106986333A - A kind of method that magnanimity controllable preparation graphene nano sieves material - Google Patents
A kind of method that magnanimity controllable preparation graphene nano sieves material Download PDFInfo
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Abstract
The invention discloses the preparation method that a kind of graphene nano sieves material, by using metallic substrates and the redox reaction of 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 and control in material aperture by adjusting calcining heat, and the volume size of graphene assembly can be by adjusting the volume of initial oxidation graphene solution, the areas of concentration and metallic substrates regulates and controls, therefore the present invention graphene nano sieve material preparation method for it is a kind of can macroscopic preparation of graphene nanometer sieve material new method, and this method can realize the controllable of graphene nano sieve material aperture simultaneously.
Description
Technical field
The invention belongs to grapheme material field, material is sieved more particularly, to a kind of magnanimity controllable preparation graphene nano
The method of material.
Background technology
Graphene, a kind of bi-dimensional cellular shape crystal structure materials by single layer of carbon atom arrangement form, due to its have it is 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, because the oxygen-containing functional group in graphene oxide layer is gradually removed,
Electrostatic repulsion between negative electrical charge weakens, the π-π sucking actions enhancing between the big pi bond of lamella, is easily sent out between graphene sheet layer
Raw to stack phenomenon, causing the specific surface area of graphene sheet layer reduces, and limits the practical application of material.
Graphene nano is sieved, and a kind of new graphene nano structure can be regarded as band on graphene nanometer sheet
A kind of film of flat porous formed by gap opening.Compared with conventional graphene nanometer sheet, graphene nano sifter device has out
The band gap put, the specific surface area of expansion and more avtive spots and edge, make it in catalysis, the energy and is partly led at sensor
There is good application prospect in the fields such as body device.
At present, the preparation method of graphene nano sieve material mainly has：Photoetching, plasma etching, catalysis oxidation and change
Learn vapour deposition etc..But these method generally existing costs are high, low yield, the complicated defect such as cumbersome of preparation process 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
Directly to prepare graphene nano sieve material, but the material obtained is in the presence of uncontrollable defect is prepared, such as material hole density is low
It is uneven etc. with pore-size distribution.Therefore, it is one to develop a kind of new method of magnanimity controllable preparation graphene nano sieve functional material
Individual urgent problem to be solved.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, received the invention provides a kind of magnanimity controllable preparation graphene
The method of rice huller screen material and its functional material, by using metallic substrates and the redox reaction of graphene oxide, is contained
There is the graphene assembly of metal oxide, then obtaining graphene nano by high-temperature calcination sieves material or its functional material,
Realize that graphene nano sieves the regulation and control in material aperture by adjusting calcining heat, and the volume size of graphene assembly can lead to
The area for overregulating the volume, concentration and metallic substrates of initial oxidation graphene solution regulates and controls, therefore the graphite of the present invention
The preparation method of alkene nanometer sieve material for it is a kind of can macroscopic preparation of graphene nanometer sieve material new method, and this method can be same
Shi Shixian graphene nanos sieve the controllable of material aperture.Thus the preparation method of prior art graphene nano sieve material is solved not
It can realize that magnanimity is prepared and the controllable technical problem in aperture simultaneously.
To achieve the above object, according to one aspect of the present invention, there is provided the preparation that a kind of graphene nano sieves material
Method, comprises 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 for obtaining step (1) is freeze-dried, and obtains dry three-dimensional grapheme material；
(3) the dried three-dimensional grapheme material for obtaining step (2) is forged at 400~1100 DEG C in an inert atmosphere
Burn 0.5~3 hour, pickling after cooling, you can obtain graphene nano sieve material.
Preferably, step (1) described 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, and the specific method of the cleaning is：According to
It is secondary to be cleaned with ethanol, hydrochloric acid and deionized water, clean 10~30 minutes altogether.
Preferably, step (1) graphene oxide water solution is prepared using oxidation stripping method.
Preferably, step (2) also comprises the following steps：By the graphene assembly of the drying in 200~400rad/
Ball milling 10~30 minutes under min.
Preferably, step (3) described pickling is concretely comprised the following steps：Soaked 5~8 hours in 4~6mol/L hydrochloric acid solution.
Preferably, step (3) described inert atmosphere is argon gas atmosphere.
Preferably, graphene nano sieve material step (3) obtained is mixed with the organic matter containing nitrogen, sulphur or phosphorus, so
After be placed in argon gas atmosphere and calcined 1~2 hour at 800~1000 DEG C of temperature, you can obtain 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.
Material is sieved there is provided a kind of graphene nano according to another aspect of the present invention, it makes as described above
Preparation Method is prepared.
According to another aspect of the present invention there is provided the application that a kind of described graphene nano sieves material, it is applied to
The electrode material or composite of energy stores and switching device.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect.
(1) the preparation method technique of graphene nano sieve material of the present invention is simple, with low cost, it is adaptable to extensive, grand
Amount prepares graphene nano sieve material, and the preparation method yield is high, the amount of the graphene nano sieve material 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 is used is graphene oxides, and it synthesizes skill
Art is ripe, and cost is low, can produce in enormous quantities；
(3) the graphene nano sieve material that the method for the invention is obtained has intensive uniform plane pore structure so that
Material has very big specific surface area and abundant ion transmission channel；
(4) the graphene nano sieve material of the present invention is assembled into button cell, and its super capacitor performance is surveyed
Examination, the material shows good electrochemistry storing up electricity performance.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 ultracapacitor, lithium ion battery and fuel cell and switching device, it is also possible to
The electrochemical properties of material, such as electrode are lifted in load nanometer electroactive material (such as metal oxide or conducting polymer)
Storing up electricity performance and high rate performance of material etc..
Brief description of the drawings
Picture in kind before and after the reduction of nickel foam induced oxidation graphene solution and assembling are reacted in Fig. 1 embodiments 1；
The picture in kind of the graphene assembly of nickel foam is embedded with Fig. 2 embodiments 1；
The scanning electron microscope diagram piece of graphene assembly in Fig. 3 embodiments 1；
The transmission electron micrograph of graphene assembly in Fig. 4 embodiments 1；
The transmission electron micrograph that graphene nano is sieved in Fig. 5 embodiments 1；
The transmission electron micrograph that graphene nano is sieved in Fig. 6 embodiments 2；
The transmission electron micrograph that graphene nano is sieved in Fig. 7 embodiments 3；
Fig. 8 is the cyclic voltammetry curve figure that the graphene nano sieve material that embodiment 10 is prepared is used as electrode material.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
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 each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
Graphene nano sieve material and its preparation method of functional material that the present invention is provided, comprise 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 by successively with ethanol, hydrochloric acid and deionized water, be cleaned 10~30 minutes altogether,
So that metallic substrates reactivity is higher.Graphene oxide water solution is prepared using oxidation stripping method (Hummer methods).It is living
Property metallic substrates and graphene oxide occur redox reaction, graphene oxide is reduced, and metallic substrates are oxidized to oxidation
Thing.
(2) the graphene assembly for obtaining step (1) is freeze-dried, and freeze-drying is general in -50 DEG C of progress, obtains
To dry three-dimensional grapheme assembly；Then by the graphene assembly of the drying under 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 gas atmosphere
DEG C, calcined at preferably 450~900 DEG C 0.5~3 hour, preferably calcination time is 2 hours, in 4~6mol/L hydrochloric acid after cooling
Soaked 5~8 hours in solution, you can obtain graphene nano sieve material.
Graphene nano sieve material is mixed with the organic matter containing nitrogen, sulphur or phosphorus, such as with melamine, dibenzyl
Two sulphur or triphenylphosphine mixing, are subsequently placed in argon gas atmosphere and are calcined 1~2 hour at 800~1000 DEG C of temperature, you can obtained
The graphene nano sieve functional material of nitrogen, sulphur or phosphorus doping.
Above-mentioned graphene nano sieve material and its functional material can be applied to the electrode material of energy stores and switching device,
Include the electrode material of ultracapacitor, 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.) lift the electrochemical properties of material.
The present invention by active metal substrate (nickel, cobalt or iron) by being inserted directly into the container for filling graphene oxide solution
In, by the redox reaction between graphene oxide and active metal, the spontaneous reduction of metallic substrates and the whole appearance of assembling
Graphene oxide in device, obtains three-dimensional grapheme functional assembly body, the formation of assembly can be by adjusting container size, instead
Controlled between seasonable with temperature.It is worth noting that, the metal oxide of redox reaction generation can uniformly disperse attachment
In graphene assembly.Based on this, we carry out calcination processing under inert gas conditions to this graphene assembly,
Etching reaction can occur with carbon for metal oxide produce nano level hole on the surface of graphene under hot conditions.This
Invention it has been found that calcining heat 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 big I of the hole of graphene nano sieve material of the present invention is led to
Overregulate calcining heat to realize, handled finally by sour bubble, wash the metal simple-substance and unreacted oxygen in grapheme material off
Compound, that is, obtain graphene nano sieve material.Further, obtained graphene nano is sieved into material and passes through 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, can be with after further handling, calcining
The graphene nano sieve material of magnanimity is obtained, and at the same time, by regulating and controlling calcining heat, be can obtain in the range of 10~200nm
The graphene nano sieve powder body material of different pore size size, therefore, the preparation method of graphene nano of the present invention sieve material can be with
Magnanimity and the controllable preparation of graphene nano sieve material are realized simultaneously.
It is embodiment below：
Embodiment 1
Metal nickel foam (8x10cm) is cleaned 30 minutes with ethanol, hydrochloric acid and deionized water successively first.Then, use
Stripping method (Hummers methods) is aoxidized to prepare the graphene oxide water solution that mass concentration is 2~20mg/mL, its detailed process
It is as follows：5g natural flake graphite powder is taken, it is stirred with the 115mL concentrated sulfuric acids and 2.5g sodium nitrate under condition of ice bath and mixed,
Then it is slow that 15.0g potassium permanganate is added into solution, after stirring 2 hours, temperature is risen to 35 degree, continued after stirring 2 hours,
200mL deionized water is slowly added to, temperature is then further increased to 95 degree, and is maintained 30 minutes, is then added into solution
Enter about 500mL deionized water, temperature adjustment to normal temperature adds 10mL hydrogenperoxide steam generator, solution suction filtration is obtained into solid,
Watery hydrochloric acid and deionized water centrifuge washing are used successively, you can obtain graphene oxide solution.
Cleaned nickel foam is directly dipped into the graphene oxide water solution that fills 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, its specific pictorial diagram
Piece is as shown in Figure 1.As can be seen that can be reduced directly and assemble in immersion as the nickel foam of substrate in the process and be whole
Graphene oxide in beaker, forms three-dimensional porous graphene assembly, and its specific picture and scanning electron in kind are aobvious
The material that micro mirror picture (accompanying drawing 2 and Fig. 3 shown in) also show acquisition is three-dimensional porous structure.The oxygen of redox reaction generation
Changing nickel nano particle can be uniformly adhered on graphene sheet layer, and its specific transmission electron micrograph is as shown in Figure 4.
Then, the graphene assembly being freeze-dried is placed in tube furnace, calcines 2 hours for 500 DEG C, rise under argon gas protection atmosphere
Warm speed control is in 5 DEG C/min.Taking-up sample is placed in soaking in 6.0M hydrochloric acid after reaction terminates cleans and can obtain for 8 hours
Graphene nano sieves material, and its specific transmission electron micrograph can be found in accompanying drawing 5, it can be seen that point in material nano hole
Cloth is about 10-20nm.
Embodiment 2
Metal foam nickel (6x9cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers methods) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
Reaction is stood in the beaker for the graphene oxide water solution for filling 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 in immersion as the nickel foam of substrate in the process and be whole
Graphene oxide in individual 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 under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.Reaction terminates
Taking-up sample, which is placed in soaking in 6.0M hydrochloric acid cleaning for 8 hours, afterwards can obtain graphene nano sieve material, and it is specific saturating
The sub- microscope photograph of radio can be found in accompanying drawing 6, it can be seen that the distribution in material nano hole is about 40-60nm.
Embodiment 3
Metal nickel sheet (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers methods) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have 100mL 5.0mg/mL graphene oxide water solution beaker in stand reaction, 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 in immersion as the nickel foam of substrate in the process and be whole
Graphene oxide in beaker, forms three-dimensional porous graphene assembly.Then, by the graphene assembly being freeze-dried
It is placed in tube furnace, is calcined 2 hours for 900 DEG C under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.After reaction terminates
Taking-up sample, which is placed in soaking in 6.0M hydrochloric acid cleaning for 8 hours, can obtain graphene nano sieve material, its specific transmission
Electron microscope picture can be found in accompanying drawing 7, it can be seen that the distribution in material nano hole is about 100-200nm.
Embodiment 4
Metal iron plate (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers methods) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have 100mL 2.0mg/mL graphene oxide water solution beaker in stand reaction, the reaction temperature of integral system is controlled in
70 DEG C, the reaction time is 12 hours.In the process whole burning can be reduced directly and assemble as the iron plate of substrate in immersion
Graphene oxide in cup, forms three-dimensional porous graphene assembly.Then, the graphene assembly being freeze-dried is put
In tube furnace, calcined 2 hours for 800 DEG C under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.Reaction takes after terminating
Go out sample be placed in 6.0M hydrochloric acid soak 8 hours cleaning can obtain graphene nano sieve material.
Embodiment 5
Metallic cobalt piece (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers methods) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have 100mL 3.0mg/mL graphene oxide water solution beaker in stand reaction, the reaction temperature of integral system is controlled in
80 DEG C, the reaction time is 16 hours.In the process whole burning can be reduced directly and assemble as the cobalt piece of substrate in immersion
Graphene oxide in cup, forms three-dimensional porous graphene assembly.Then, the graphene assembly being freeze-dried is put
In tube furnace, calcined 2 hours for 500 DEG C under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.Reaction takes after terminating
Go out sample be placed in 6.0M hydrochloric acid soak 8 hours cleaning can obtain graphene nano sieve material.
Embodiment 6
Metal foam nickel (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers methods) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
Reaction is stood in the beaker for the graphene oxide water solution for filling 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 in immersion as the nickel foam of substrate in the process and be whole
Graphene oxide in individual 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 under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.Reaction terminates
Taking-up sample, which is placed in soaking in 6.0M hydrochloric acid cleaning for 8 hours, afterwards can obtain 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 under argon gas protection atmosphere, you can obtain nitrogen
The graphene nano sieve functional material of doping.
Embodiment 7
Metallic cobalt piece (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers methods) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have 100mL 3.5mg/mL graphene oxide water solution beaker in stand reaction, the reaction temperature of integral system is controlled in
75 DEG C, the reaction time is 15 hours.In the process whole burning can be reduced directly and assemble as the cobalt piece of substrate in immersion
Graphene oxide in cup, forms three-dimensional porous graphene assembly.Then, the graphene assembly being freeze-dried is put
In tube furnace, calcined 2 hours for 450 DEG C under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.Reaction takes after terminating
Go out sample be placed in 6.0M hydrochloric acid soak 8 hours cleaning can obtain 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 under argon gas protection atmosphere, you can obtain sulphur and mix
Miscellaneous graphene nano sieve functional material.
Embodiment 8
Metal iron plate (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers methods) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have 100mL 2.5mg/mL graphene oxide water solution beaker in stand reaction, the reaction temperature of integral system is controlled in
65 DEG C, the reaction time is 12 hours.In the process whole burning can be reduced directly and assemble as the iron plate of substrate in immersion
Graphene oxide in cup, forms three-dimensional porous graphene assembly.Then, the graphene assembly being freeze-dried is put
In tube furnace, calcined 2 hours for 850 DEG C under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.Reaction takes after terminating
Go out sample be placed in 6.0M hydrochloric acid soak 8 hours cleaning can obtain 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 under argon gas protection atmosphere, you can obtain phosphorus doping
Graphene nano sieve functional material.
Embodiment 9
Metal foam nickel (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers methods) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
Reaction is stood in the beaker for the graphene oxide water solution for filling 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 in immersion as the nickel foam of substrate in the process and be whole
Graphene oxide in individual 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 under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.Reaction terminates
Taking-up sample, which is placed in soaking in 6.0M hydrochloric acid cleaning for 8 hours, afterwards can obtain 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 under argon gas protection atmosphere,
Nitrogen, the graphene nano sieve functional material of sulphur codope can be obtained.
Embodiment 10
Metal foam nickel (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers methods) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
Reaction is stood in the beaker for the graphene oxide water solution for filling 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 in immersion as the nickel foam of substrate in the process and be whole
Graphene oxide in individual 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 under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.Reaction terminates
Taking-up sample, which is placed in soaking in 6.0M hydrochloric acid cleaning for 8 hours, afterwards can obtain graphene nano sieve material.Then by graphite
Alkene nanometer sieve material is with conductive black and polytetrafluoroethylene (PTFE) according to 80:10:10 mass ratio is ground mixing, uniform coating
On conductive aluminum foil, button cell (electrolyte uses the ionic liquid of dilution in acetonitrile) is assembled into, and to its super capacitor performance
Tested, its specific cyclic voltammetry curve can be found in accompanying drawing 8, it can be seen that potential region can expand compared to aqueous electrolyte
Width arrives 2.8V, and curve is almost rectangular, and symmetrical and area is big, illustrates the good electrochemistry storing up electricity performance of the material.
Embodiment 11
Metallic cobalt piece (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Stripping method (Hummers methods) is aoxidized to prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into Sheng
Have 100mL 12.0mg/mL graphene oxide water solution beaker in stand reaction, the reaction temperature of integral system controlled
At 80 DEG C, the reaction time is 16 hours.It can be reduced directly and assemble in immersion as the cobalt piece of substrate in the process and be whole
Graphene oxide in beaker, forms three-dimensional porous graphene assembly.Then, by the graphene assembly being freeze-dried
It is placed in tube furnace, is calcined 3 hours for 500 DEG C under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.After reaction terminates
Taking-up sample, which is placed in soaking in 6.0M hydrochloric acid cleaning for 8 hours, can obtain graphene nano sieve material.
Embodiment 12
Metal foam nickel (4x6cm) is used into ethanol successively first, hydrochloric acid, deionized water is cleaned 30 minutes.Using embodiment 1
Oxidation stripping method (Hummers methods) prepare graphene oxide water solution.Cleaned nickel foam is directly dipped into
Reaction is stood in the beaker for the graphene oxide water solution for filling 100mL 20.0mg/mL, the reaction temperature of integral system is controlled
System is at 75 DEG C, and the reaction time is 20 hours.It can be reduced directly and assemble in immersion as the nickel foam of substrate in the process
Graphene oxide in whole beaker, forms three-dimensional porous graphene assembly.Then, by the graphene group being freeze-dried
Dress body is placed in tube furnace, is calcined 0.5 hour for 1100 DEG C under argon gas protection atmosphere, heating rate is controlled in 5 DEG C/min.Reaction
Taking-up sample, which is placed in soaking in 6.0M hydrochloric acid cleaning for 8 hours, after end can obtain graphene nano sieve material.Then will
Graphene nano sieves material and melamine, and benzyl disulfide powder is mixed, 900 DEG C of calcinings 1 under argon gas protection atmosphere
Hour, you can obtain nitrogen, the graphene nano sieve functional material of sulphur codope.
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, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (10)
1. a kind of graphene nano sieves the preparation method of material, it is characterised in that comprise the following steps：
(1) metallic substrates are immersed in the graphene oxide water solution that concentration is 2~20mg/mL, 6 is reacted at 60~80 DEG C
~60 hours, metallic substrates are taken out, three-dimensional grapheme assembly is obtained；
(2) the graphene assembly for obtaining step (1) is freeze-dried, and obtains dry three-dimensional grapheme material；
(3) the dried three-dimensional grapheme material for obtaining step (2) is in an inert atmosphere in calcining at 400~1100 DEG C
0.5~3 hour, pickling after cooling, you can obtain graphene nano sieve material.
2. preparation method as claimed in claim 1, it is characterised in that step (1) described metallic substrates are sheet metal or metal
Foam, the metal includes nickel, cobalt or iron.
3. preparation method as claimed in claim 1, it is characterised in that step (1) described metallic substrates are the metal after cleaning
Substrate, the specific method of the cleaning is：Cleaned, cleaned 10~30 minutes altogether with ethanol, hydrochloric acid and deionized water successively.
4. preparation method as claimed in claim 1, it is characterised in that step (1) described graphene oxide water solution uses oxygen
Change stripping method to prepare.
5. preparation method as claimed in claim 1, it is characterised in that step (2) also comprises the following steps：By the drying
Graphene assembly ball milling 10~30 minutes under 200~400rad/min.
6. preparation method as claimed in claim 1, it is characterised in that step (3) described pickling is concretely comprised the following steps：4~
Soaked 5~8 hours in 6mol/L hydrochloric acid solution.
7. preparation method as claimed in claim 1, it is characterised in that step (3) described inert atmosphere is argon gas atmosphere.
8. preparation method as claimed in claim 1, it is characterised in that the graphene nano for obtaining step (3) sieve material with
Organic matter mixing containing nitrogen, sulphur or phosphorus, is subsequently placed in argon gas atmosphere and is calcined 1~2 hour at 800~1000 DEG C of temperature,
The graphene nano sieve functional material of nitrogen, sulphur or phosphorus doping can be obtained, the organic matter containing nitrogen, sulphur or phosphorus is preferably three
Poly cyanamid, benzyl disulfide or triphenylphosphine.
9. a kind of graphene nano sieves material, it is characterised in that it is according to the preparation as described in claim 1~8 any one
Method is prepared.
10. a kind of graphene nano as claimed in claim 9 sieves the application of material, it is characterised in that applied to energy stores
With the electrode material or composite of switching device.
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| WO2019033752A1 (en) * | 2017-08-18 | 2019-02-21 | 京东方科技集团股份有限公司 | Method for preparing graphene circuit pattern, substrate, and electronic product |
| CN112939478A (en) * | 2021-01-14 | 2021-06-11 | 南昌大学 | Preparation method of porous film material for shielding terahertz waves |
| CN115417404A (en) * | 2022-09-26 | 2022-12-02 | 科泽新材料股份有限公司 | Method for preparing graphene oxide by using waste graphene film leftover materials |
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| CN104600238A (en) * | 2014-12-22 | 2015-05-06 | 华中科技大学 | Method for preparing directly soaking reaction type foamed nickel-graphene three-dimensional porous electrode |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019033752A1 (en) * | 2017-08-18 | 2019-02-21 | 京东方科技集团股份有限公司 | Method for preparing graphene circuit pattern, substrate, and electronic product |
| CN109411149A (en) * | 2017-08-18 | 2019-03-01 | 京东方科技集团股份有限公司 | Graphene circuit pattern and preparation method thereof, electronic product |
| CN109411149B (en) * | 2017-08-18 | 2021-01-22 | 京东方科技集团股份有限公司 | Graphene circuit pattern, preparation method thereof and electronic product |
| US11372300B2 (en) | 2017-08-18 | 2022-06-28 | Boe Technology Group Co., Ltd. | Method of preparing graphene circuit pattern |
| CN112939478A (en) * | 2021-01-14 | 2021-06-11 | 南昌大学 | Preparation method of porous film material for shielding terahertz waves |
| CN115417404A (en) * | 2022-09-26 | 2022-12-02 | 科泽新材料股份有限公司 | Method for preparing graphene oxide by using waste graphene film leftover materials |
| CN115417404B (en) * | 2022-09-26 | 2024-01-12 | 科泽新材料股份有限公司 | Method for preparing graphene oxide from waste graphene film scraps |
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