CN107902647A - A kind of method that graphene is prepared as electrolyte electrochemical cathodic disbonding graphite using TTAB - Google Patents
A kind of method that graphene is prepared as electrolyte electrochemical cathodic disbonding graphite using TTAB Download PDFInfo
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- CN107902647A CN107902647A CN201711205781.8A CN201711205781A CN107902647A CN 107902647 A CN107902647 A CN 107902647A CN 201711205781 A CN201711205781 A CN 201711205781A CN 107902647 A CN107902647 A CN 107902647A
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Abstract
The invention discloses a kind of method for preparing graphene as electrolyte electrochemical cathodic disbonding graphite using TTAB, it is characterized in that, include the following steps：1）Stock；2）Prepare electric stripper；3）The electric stripping off device of assembling；4）Electricity is peeled off；5）Filtering, washing；6）Ultrasonic disperse；7）The aqueous solution for being freeze-dried obtained graphene is freeze-dried into graphene powder.The advantages of this method be preparing raw material is simple and easy to get, operation easily, cost is low, technical process is simple, step is few, with short production cycle, the small number of plies of graphene degree of imperfection of preparation is few, is extremely suitable for industrial production.
Description
Technical field
The present invention relates to graphene technology, and specifically one kind is using TTAB as electrolyte electrochemical cathodic disbonding graphite
The method for preparing graphene.
Background technology
Graphene is the two-dimensional material of only one carbon atom thickness, be one kind by carbon atom with sp2Hybridized orbit forms
Hexangle type is in the flat film of honeycomb lattice, is a kind of individual layer sheet new material being made of carbon atom.Graphene is both most thin
Material, and most tough material, 200 times more taller than best steel of fracture strength, while it has good elasticity again,
Stretch range can reach the 20% of own dimensions, it is that current nature is most thin, the highest material of intensity.At present, graphene is most
Potential application is the substitute as silicon, manufactures ultra micro transistor npn npn, for producing the supercomputer in future, uses graphite
Alkene substitutes silicon, and the speed of service of computer processor will be hundreds times fast, in addition, graphene is almost fully transparent, only inhales
Receive 2.3% light；On the other hand, it is very fine and close, even minimum gas atom (helium atom) can not also penetrate, these are special
Sign is so that it is highly suitable as the raw material of transparent electron product, such as transparent touch display screen, luminescent screen, energy storage material and too
Positive energy solar panel etc..
A kind of graphene novel nano-material most strong as presently found most thin, maximum intensity, electrical and thermal conductivity performance,
It is referred to as " dark fund ", is " king of new material ", scientist even foretell graphene will " thoroughly change 21 century, it is most likely that
Start the subversiveness have swept the globe a new technology new industrial revolution.
At present, the main method for preparing graphene has；
(1) chemical vapor deposition (CVD) method：The method at high temperature splits carbon source using carbon compounds such as methane as carbon source
Solution generation carbon atom is simultaneously penetrated into metallic matrix, and after reducing temperature, carbon atom can be separated out out of metallic matrix, and then generate stone
Black alkene, however, chemical vapor deposition (CVD) method is of high cost, process is complicated, limit to a certain extent three-dimensional grapheme into
One step develops, and the specific porous metal material of chemical vapor deposition (CVD) method needs, as substrate, this can greatly increase it
Cost；
(2) Hummers methods prepare graphene：The key step of the method is divided into：The synthesis of one, graphene oxides；Two, are reduced
Graphene oxide.Hummers methods are to utilize strong acid (dense H first2SO4) and with strong oxidizing property metal salt (KMnO4) certain
Under conditions of natural flake graphite is prepared into graphene oxide, then graphene oxide quilt under the action of strong reductant (hydrazine)
Reduce and generate graphene.It is this in practical operation although preparing graphene using Hummers methods to be widely used
The step of method, is more, more to the influence factor of building-up process, caused by graphene yield it is relatively low, and synthesize graphene
Degree of imperfection is larger, of low quality；
(3) template：The method, by electrostatic interaction or intermolecular force, forms cladding using graphene oxide as raw material
The graphene oxide of template, graphene oxide is reduced into after graphene and removes template and can prepare graphene, maximum excellent of the method
Gesture is that aperture can regulate and control, you can to prepare the graphene of different pore size by varying template, but the method preparation procedure is more, mistake
Journey is complicated, and time-consuming；
These above-mentioned methods are there are a series of shortcoming, such as：Prepare graphene degree of imperfection is high, preparation process is complicated,
It is of high cost, time-consuming, not easy to operate etc..
So far, the preparation of graphene is also in the elementary step, since graphene has larger specific surface area and leads
Electrically preferably, therefore graphene will be widely used in the electrode material of energy storage device.
The content of the invention
The purpose of the present invention is in view of the deficiencies of the prior art, and provide a kind of electrochemical cathode using TTAB as electrolyte
Peel off the method that graphite prepares graphene.The advantages of this method is that preparing raw material is simple and easy to get, operation is easy, cost
It is low, technical process is simple, step is few, the with short production cycle, structure of product produced and electrochemical performance, is particularly suitable for
In industrial production.
Realizing the object of the invention technical solution is：
A kind of method that graphene is prepared as electrolyte electrochemical cathodic disbonding graphite using TTAB, including following step
Suddenly：
1) stock up：Graphite electrode, NMP, absolute ethyl alcohol, TTAB, D.C. regulated power supply, iron stand and conductive clamp are prepared
It is good spare；
2) electric stripper is prepared：NMP in step 1), absolute ethyl alcohol are weighed, TTAB, be configured to 0.1mol/L TTAB electrifications
Learn and peel off graphene electricity stripper；
3) electric stripping off device is assembled：Using graphite electrode as cathode and anode, by two electrodes are vertical and parallel immersion
Into electric stripper, there is spacing distance between two electrodes, two electrodes are connected with D.C. regulated power supply；
4) electricity is peeled off：The voltage that powers on is arranged to 20V electrochemical strippings 240 minutes；
5) filter, wash：Graphene forerunner's body detergent filtration washing in electric stripper after step 4) is peeled off
Obtain substance A；
6) ultrasonic disperse：Substance A ultrasonic disperse after step 5) is washed, obtains the aqueous solution of graphene, ultrasonic disperse
Effect be by the graphene after washing spread out again and be generation graphene size than more uniform；
7) it is freeze-dried：The aqueous solution freeze-drying for the graphene that step 6) is obtained is freeze-dried into graphene powder
Effect be the deionized water in graphene aqueous solution is dried removing so as to preventing the reunion of graphene to be conducive to graphene
Generation.
NMP described in step 1) is 1-methyl-2-pyrrolidinone.
TTAB described in step 1) is tetradecyltrimethylammonium bromide.
Electric stripper solute is TTAB in step 2), and solvent is that volume ratio is 2:The mixing of 1 NMP and absolute ethyl alcohol are molten
Agent.
Graphite electrode described in step 3) is graphite, and graphite is " crystal " graphite, " crystal " graphite crystallization structure
Make, degree of graphitization is high.
The distance between two graphite electrodes described in step 3) are 3cm.
When the voltage between two graphite electrodes is 20V, TTAB produces C in the electrolytic solution in step 4)17H38N+Ion moves
Move cathode graphite electrode, and C17H38N+Graphite can be inserted between layers, applied voltage underthrust enter to graphite linings it
Between C17H38N+Reduction reaction generation CH occurs for ion4、H2、N2、NH3Deng gas, the gas subsequently generated struts graphite linings,
Then graphene is generated.
Detergent described in step 5) is deionized water and the mixed solution of absolute ethyl alcohol, its effect is to wash away to be blended in stone
Impurity in black alkene, such as：CH3CH2OH、TTAB、NMP、Br-、C17H38N+。
The technical program relative to existing method prepare graphene preparation method have the advantages that it is following a series of：
1. the graphene operation prepared according to the technical program method is easy, raw material is simple and easy to get, cost is low, technical process
Simply, few, with short production cycle, product the structure of step is excellent, is extremely suitable for industrial production.
2. using the graphene that electrochemical stripping graphite is produced can be widely applied to the energy, environment, sensing and
The numerous areas such as biochemical industry, its application prospect with important scientific value and widely.
The advantages of this method be preparing raw material it is simple and easy to get, operation easily, cost is low, technical process is simple, step is few,
With short production cycle, the small number of plies of graphene degree of imperfection of preparation is few, is extremely suitable for industrial production.
Brief description of the drawings
Fig. 1 is the SEM figures of the three-dimensional grapheme obtained in implementation column；
Fig. 2 is the TEM figures of graphene in implementation column；
Fig. 3 is the Raman figures of graphene in implementation column；
Fig. 4 is the XPS figures of graphene in implementation column；
Fig. 5 is the isothermal adsorption desorption curve map of graphene in implementation column.
Embodiment
Present invention is described further with reference to the accompanying drawings and examples, but is not limitation of the invention.
Embodiment：
A kind of method that graphene is prepared as electrolyte electrochemical cathodic disbonding graphite using TTAB, including following step
Suddenly：
1) stock up：Graphite electrode, NMP, absolute ethyl alcohol, TTAB, D.C. regulated power supply, iron stand and conductive clamp are prepared
It is good spare；
2) electric stripper is prepared：NMP in step 1), absolute ethyl alcohol are weighed, TTAB, be configured to 0.1mol/L TTAB electrifications
Learn and peel off graphene electricity stripper；
3) electric stripping off device is assembled：Using graphite electrode as cathode and anode, by two electrodes are vertical and parallel immersion
Into electric stripper, there is spacing distance between two electrodes, two electrodes are connected with D.C. regulated power supply；
4) electricity is peeled off：The voltage that powers on is arranged to 20V electrochemical strippings 240 minutes；
5) filter, wash：Graphene forerunner's body detergent filtration washing in electric stripper after step 4) is peeled off
Obtain substance A；
6) ultrasonic disperse：Substance A ultrasonic disperse after step 5) is washed, obtains the aqueous solution of graphene, ultrasonic disperse
Effect be by the graphene after washing spread out again and be generation graphene size than more uniform；
7) it is freeze-dried：The aqueous solution freeze-drying for the graphene that step 6) is obtained is freeze-dried into graphene powder
Effect be the deionized water in graphene aqueous solution is dried removing so as to preventing the reunion of graphene to be conducive to graphene
Generation.
NMP described in step 1) is 1-methyl-2-pyrrolidinone.
TTAB described in step 1) is tetradecyltrimethylammonium bromide.
Electric stripper solute is TTAB in step 2), and solvent is that volume ratio is 2:The mixing of 1 NMP and absolute ethyl alcohol are molten
Agent.
Graphite electrode described in step 3) is graphite, and graphite is " crystal " graphite, " crystal " graphite crystallization structure
Make, degree of graphitization is high.The distance between two graphite electrodes are 3cm.
When the voltage between two graphite electrodes is 20V, TTAB produces C in the electrolytic solution in step 4)17H38N+Ion moves
Move cathode graphite electrode, and C17H38N+Graphite can be inserted between layers, applied voltage underthrust enter to graphite linings it
Between C17H38N+Reduction reaction generation CH occurs for ion4、H2、N2、NH3Deng gas, the gas subsequently generated struts graphite linings,
Then graphene is generated.
Detergent described in step 5) is deionized water and the mixed solution of absolute ethyl alcohol, its effect is to wash away to be blended in stone
Impurity in black alkene, such as：CH3CH2OH、TTAB、NMP、Br-、C17H38N+。
Specifically：
1) stock up：It is accurate to weigh 10.092gTTAB, 200mlNMP, 100ml absolute ethyl alcohol, graphite, iron stand, directly
Flow regulated power supply：
2) electrolyte quota：10.092gTTAB in step 1) is dissolved into 300ml volume ratios as 2:1 NMP with it is anhydrous
In alcohol mixed solvent, 0.1mol/LTTAB electrochemical stripping liquid is configured to；
3) electric stripping off device assembling：Using graphite electrode as negative and positive the two poles of the earth, they are fixed on iron using the clip with copper wire
On pallet, and by they it is vertical and it is parallel be immersed in electric stripper, spacing is 3cm between two electrodes, by two electrodes with leading
Line is connected on the positive and negative anodes of DC power supply respectively；
4) electricity is peeled off：The voltage that powers on is arranged to 20V electrochemical strippings 240min；
5) filter, wash：Graphene presoma deionized water in electric stripper and anhydrous second after step 4) is peeled off
Alcohol repeatedly washs the foreign ion CH removed on graphene3CH2OH, TTAB, NMP, Br-；
6) ultrasonic disperse：Graphene after step 5) repeatedly washing is added to ultrasonic disperse 60min in deionized water；
7) it is freeze-dried：With liquid nitrogen then the aqueous solution of the graphene after step 6) ultrasonic disperse is frozen into blocks of solid
Into graphene powder after freeze-drying 36H.
Prepared as shown in Figure 1, understanding that electrochemical cathode peels off graphite in organic electrolyte by SEM image in Fig. 1
The graphene gone out has preferable exterior appearance and the number of plies is less；
As shown in Fig. 2, understanding that graphene crystallinity is preferable by TEM in Fig. 2 and selective electron diffraction figure, the number of plies is less, and
Graphene has relatively thin lamellar structure；
As shown in figure 3, understand that the ratio between D peaks and G peaks are 0.51 (I by Fig. 3 Ramans curveD/IG=0.51), Gu graphene
Degree of imperfection is relatively low, and the quality of gained graphene is preferable；
As shown in figure 4, understanding that graphene oxygen content is 1.28wt% by Fig. 4 XPS figures, and-OH is comprised only in graphene and is taken
Dai Ji, admittedly the impurity content of the graphene generated is seldom and purity is very high；
As shown in figure 5, understood by Fig. 5 adsorption desorption isothermal curves and combine BET formula
When V-balance pressure is P, the cumulative volume of adsorbed gas,
The volume of required gas when Vm-catalyst surface covering first layer is full, when P-adsorbate balances under adsorption temp
Pressure, Ps-saturated vapour pressure, C-with by the related constant of absorption) specific surface area that can extrapolate graphene about exists
590-610m2Between/g, Gu the graphene prepared using TTAB as electrolyte electrochemical cathodic disbonding graphite have compared with
Big specific surface area.
Claims (7)
1. a kind of method that graphene is prepared as electrolyte electrochemical cathodic disbonding graphite using TTAB, it is characterized in that, bag
Include following steps：
1) stock up：Graphite electrode, NMP, absolute ethyl alcohol, TTAB, D.C. regulated power supply, iron stand and conductive clamp are ready to standby
With；
2) electric stripper is prepared：NMP in step 1), absolute ethyl alcohol are weighed, TTAB, be configured to the stripping of 0.1mol/L TTAB electrochemistry
From graphene electricity stripper；
3) electric stripping off device is assembled：It is using graphite electrode as cathode and anode, two electrodes are vertical and parallel be immersed in electricity
In stripper, there is spacing distance between two electrodes, two electrodes are connected with D.C. regulated power supply；
4) electricity is peeled off：The voltage that powers on is arranged to 20V electrochemical strippings 240 minutes；
5) filter, wash：Graphene forerunner's body detergent filtration washing in electric stripper after step 4) is peeled off obtains
Substance A；
6) ultrasonic disperse：Substance A ultrasonic disperse after step 5) is washed, obtains the aqueous solution of graphene；
7) it is freeze-dried：The aqueous solution for the graphene that step 6) is obtained is freeze-dried into graphene powder.
2. the side according to claim 1 that graphene is prepared using TTAB as electrolyte electrochemical cathodic disbonding graphite
Method, it is characterised in that：NMP described in step 1) is 1-methyl-2-pyrrolidinone.
3. the side according to claim 1 that graphene is prepared using TTAB as electrolyte electrochemical cathodic disbonding graphite
Method, it is characterised in that：TTAB described in step 1) is tetradecyltrimethylammonium bromide.
4. the side according to claim 1 that graphene is prepared using TTAB as electrolyte electrochemical cathodic disbonding graphite
Method, it is characterised in that：Electric stripper solute is TTAB in step 2), and solvent is that volume ratio is 2:1 NMP and absolute ethyl alcohol it is mixed
Bonding solvent.
5. the side according to claim 1 that graphene is prepared using TTAB as electrolyte electrochemical cathodic disbonding graphite
Method, it is characterised in that：Graphite electrode described in step 3) is graphite, and graphite is " crystal " graphite.
6. the side according to claim 1 that graphene is prepared using TTAB as electrolyte electrochemical cathodic disbonding graphite
Method, it is characterised in that：The distance between two graphite electrodes described in step 3) are 3cm.
7. the side according to claim 1 that graphene is prepared using TTAB as electrolyte electrochemical cathodic disbonding graphite
Method, it is characterised in that：Detergent described in step 5) is deionized water and the mixed solution of absolute ethyl alcohol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111017915A (en) * | 2018-10-10 | 2020-04-17 | 长春工业大学 | Method for preparing graphene from graphite |
| CN111232964A (en) * | 2020-01-19 | 2020-06-05 | 北京石墨烯研究院 | Graphene wafer transfer method, graphene wafer and bubbling system |
| CN114555520A (en) * | 2019-11-15 | 2022-05-27 | 株式会社Lg新能源 | Preparation method of graphene nanosheet |
| CN114604864A (en) * | 2022-04-11 | 2022-06-10 | 东北大学 | Method for preparing graphene by stripping graphite material by virtue of confined electrochemical method |
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| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN102868006A (en) * | 2012-09-21 | 2013-01-09 | 华东理工大学 | Method for preparing graphene through waste lithium batteries |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
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2017
- 2017-11-27 CN CN201711205781.8A patent/CN107902647A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN102868006A (en) * | 2012-09-21 | 2013-01-09 | 华东理工大学 | Method for preparing graphene through waste lithium batteries |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111017915A (en) * | 2018-10-10 | 2020-04-17 | 长春工业大学 | Method for preparing graphene from graphite |
| CN114555520A (en) * | 2019-11-15 | 2022-05-27 | 株式会社Lg新能源 | Preparation method of graphene nanosheet |
| CN114555520B (en) * | 2019-11-15 | 2024-01-02 | 株式会社Lg新能源 | Preparation method of graphene nanosheets |
| CN111232964A (en) * | 2020-01-19 | 2020-06-05 | 北京石墨烯研究院 | Graphene wafer transfer method, graphene wafer and bubbling system |
| CN111232964B (en) * | 2020-01-19 | 2022-05-27 | 北京石墨烯研究院 | Graphene wafer transfer method, graphene wafer and bubbling system |
| CN114604864A (en) * | 2022-04-11 | 2022-06-10 | 东北大学 | Method for preparing graphene by stripping graphite material by virtue of confined electrochemical method |
| CN114604864B (en) * | 2022-04-11 | 2023-08-22 | 东北大学 | Method for preparing graphene by stripping graphite material through limited-area electrochemical method |
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