CN105948025A - Method for electrochemically preparing graphene - Google Patents
Method for electrochemically preparing graphene Download PDFInfo
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- CN105948025A CN105948025A CN201610291695.2A CN201610291695A CN105948025A CN 105948025 A CN105948025 A CN 105948025A CN 201610291695 A CN201610291695 A CN 201610291695A CN 105948025 A CN105948025 A CN 105948025A
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a method for electrochemically preparing graphene. The method comprises the following steps: 1, intercalating and expanding graphite paper by adopting graphite paper as a positive electrode and an aqueous intercalator solution as an electrolyte to obtain expanded graphite; 2, filtering and washing the expanded graphite, and carrying out ultrasonic peeling treatment on the expanded graphite to obtain a flocculent graphene slurry; and 3, filtering the graphene slurry, and drying the graphene slurry through adopting a microwave vacuum drier to obtain fluffy graphene powder. The electrochemical method solves the problem of use of heavy metal-containing reagents, strong acids, strong oxidants and expensive organic liquids in the graphene preparation process in the prior art, and has the advantages of simple preparation technology, low energy consumption and low cost.
Description
Technical field
The present invention relates to graphene preparation technology, relate in particular to a kind of method that electrochemistry prepares Graphene.
Background technology
Since within 2004, being found, Graphene receives much concern as a kind of new carbon.It is a kind of completely bysp 2 The thickness that the carbon atom of hydridization is constituted is only the quasi-two dimensional crystal material of monoatomic layer or several monoatomic layer, there is the performance that high light transmittance and electric conductivity, high-specific surface area, high intensity and pliability etc. are excellent, it is expected to obtain extensively application in fields such as high-performance nanometer electronic device, photoelectric device, gas sensor, composite, field emmision material and energy storages.But, the low cost of high-quality graphene, a large amount of preparation are still faced adverse conditions, and constrain development and the application of this material.
At present, the method preparing Graphene has a variety of, wherein based on oxidation-reduction method, liquid phase stripping method and mechanical stripping method, and electrochemical process because its preparation technology is simple, energy consumption is low, low cost, easy industrialization, be the most also widely adopted.The unit using electrochemical method to prepare Graphene mainly has Suzhou nanometer institute, this especially big of graceful side, Fudan University and ocean king's illumination etc., and the concrete preparation method of constituent parts is as follows:
Suzhou nanometer prepare Graphene in the electrochemistry proposing Application No. 201210314278.7 on August 30th, 2012 method, its technical scheme is: 1, is mixed with thermoplastic adhesive by natural flake graphite and is under high pressure pressed into thin slice；2, the nitration mixture (concentration is 10M) using concentrated sulphuric acid and acetic acid carries out intercalation prepare expansible graphite as intercalator, connection 2V voltage；3, inflatable heating under 700 DEG C of high temperature is prepared as expanded graphite；4, above-mentioned expanded graphite is pressed into the most under elevated pressure conditions thin slice, and electrolysis obtains reexpansion graphite in mixed acid solution again；5, carry out washing reexpansion graphite then at NMP, DMSO(dimethyl sulfoxide), DMF(N, N '-dimethyl Methanamide) in ultrasonic prepare Graphene.Have employed the nitration mixture of concentrated sulphuric acid and spirit acid in this technology, acidity, oxidisability are relatively strong, and big to environmental hazard, thermoplastic adhesive will be mixed in Graphene by carbonization；The organic reagent that ultrasonic stripping uses is expensive and big to environmental hazard, is not suitable for industrialized production.
The production method of the Graphene that University of Manchester proposes Application No. 201280022677.4 on March 9th, 2012, the method uses graphite to make positive pole and negative pole, use ionic liquid as electrolyte, wherein, cation is NH4+, alkylammonium, and anion is mainly tetrafluoroborate, perchlorate, hexafluorophosphate.But owing to anion is relatively big, the concentration of ionic liquid is little, generally zero point several moles every liter, and intercalation expansion reaction is mainly carried out at negative pole.In NMP, DMSO, DMF equal solvent, carry out ultrasonic stripping again obtain Graphene.Using ionic liquid as electrolyte relatively costly, using high boiling point, poisonous organic solvent is that stripper brings potential safety hazard, and drying cost increase simultaneously is unfavorable for industrialized production.
Fudan University proposes the preparation method of a kind of Graphene of Application No. 201310516701.6 on October 29th, 2013, the method uses acid solution that crystalline flake graphite raw material is carried out immersion treatment, after being disposed, the crystalline flake graphite of acidifying is immersed in active matter solution, obtaining graphene dispersing solution after supersound process, drying obtains graphene powder after processing.But the acid solution that the method uses is containing strong oxidizer, such as the sulphuric acid of potassium permanganate, nitric acid, hydrogen peroxide etc.；The active substance used is generally alkaline matter, such as sodium hydroxide, sodium carbonate etc.；Using the organic solvents such as ethanol, NMP, methanol, isopropanol, DMSO, DMF is stripper.Preparation process use strong acid, highly basic, strong oxidizer the harshest to the requirement of equipment.
Graphene that Haiyangwang Lighting Technology Co., Ltd. proposes Application No. 201310038908.7 on January 31st, 2013 and preparation method thereof, the method is with graphite rod as positive pole, platinum is negative pole, positive pole negative pole inserts after applying 0.8～1.5V voltage holding in electrolyte 1～5 minute, apply the voltage of 10～15V again and keep 4～15 minutes, then by electrolyte filtering and dry；Then the solid product of drying is placed under atmosphere of inert gases, is irradiated with laser, i.e. obtain described Graphene.But the mixture that electrolyte is ionic liquid and water used in the method (water is 1:0.5～2 with the proportioning of ionic liquid), ionic liquid is the most expensive, causes preparation cost higher.Further, use laser lift-off Graphene to there is again slow problem, be also not suitable for industrial mass and prepare.
Beijing University of Chemical Technology proposes a kind of method using electrochemistry auxiliary to prepare monolayer large scale graphene oxide of Application No. 201410361416.6 on July 27th, 2014, the method is under the conditions of electrochemical reaction, take the crystalline flake graphite sheet that anode expands, clean with deionized water, normal temperature drying, pulverizer is pulverized, and makes graphite powder particle diameter at micron order.Under ice bath, by graphite powder and concentrated sulphuric acid, potassium permanganate mixes, stirring, sequentially pass through low temperature, middle temperature, pyroreaction, it is the hydrogen peroxide of 30% that reaction terminates to add mass concentration in backward mixture, the most neutral with dilute hydrochloric acid and deionized water rinsing, prepares the large-sized graphene oxide of monolayer after ultrasonic, centrifugal.In the method, first using sulphuric acid to prepare expanded graphite as electrolyte, the expanded graphite lamella obtained is thicker.Again by concentrated sulphuric acid potassium permanganate mixed solution reoxidation, reduce the Graphene number of plies.This mode makes Graphene excessively oxidated, and the middle part of graphene film can produce substantial amounts of hole, and then causes the electric conductivity of product and barrier property the most drastically to decline.Further, since the over oxidation of Graphene, the viscosity of graphene solution steeply rises, and the separation for Graphene brings difficulty；In preparation process, the heavy metal ion of residual will affect the Graphene use in the field such as battery, coating.
Summary of the invention
It is an object of the invention to solve the above-mentioned problems in the prior art, thering is provided a kind of method that electrochemistry prepares Graphene, the present invention uses the method for electrochemistry to solve prior art and uses during preparing Graphene containing the reagent of heavy metal, strong acid, strong oxidizer and the problem of expensive organic liquid；Meanwhile, preparation technology is simple, energy consumption is low, low cost.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of electrochemistry prepares the method for Graphene, it is characterised in that comprise the steps:
(1) using graphite paper as positive pole, using the aqueous solution of intercalator as electrolyte, graphite paper is carried out intercalation, expansion, obtains expanded graphite；
(2) filter, wash expanded graphite, then expanded graphite is carried out ultrasonic lift-off processing, obtain cotton-shaped Graphene slurry；
(3) filtering graphite alkene slurry, then uses microwave vacuum dryer that Graphene slurry is dried process, obtains fluffy graphene powder after drying.
After described step (1) carries out intercalation to graphite paper, the aqueous solution of newly configured intercalator is as electrolyte, again the graphite paper after intercalation is taken out, again immersing in newly configured electrolyte as positive pole and expand, obtain suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.
In the expansion process of described step (1), the graphite paper after intercalation immerses in electrolyte with the speed of 1 20mm/min and expands.
Described step (1) is 0.1 30mA/g in electric current density or under conditions of voltage is 0.5 10V, graphite paper is carried out intercalation, under conditions of voltage is 2 20V, the graphite paper after intercalation is expanded.
Intercalator in described step (1) includes that main intercalator, described main intercalator are the mixing of one or more in alkene sulphuric acid, ammonium sulfate, sodium sulfate, potassium sulfate, sodium sulfonate dodecylbenzene sodium sulfonate, sodium lauryl sulphate.
The concentration of described main intercalator is 0.1 15M.
Intercalator in described step (1) also includes that auxiliary intercalator, described auxiliary intercalator are the mixing of one or more in nitrate, acetic acid, acetate, phosphoric acid, phosphate, oxalic acid, oxalates, chloride, chlorate.
Described electrolyte is formed by the aqueous solution of main intercalator and the aqueous solution of auxiliary intercalator, and in described electrolyte, main intercalator is 0.5 10:1 with the mol ratio of auxiliary intercalator, and the concentration of described main intercalator is 0.05 5M.
Described step (1) use graphite cake as negative pole.
Graphite paper in described step (1) is that 80 mesh crystalline flake graphites are chemically treated, high-temperature expansion roll-in prepared, and its purity is more than 99.5%.
Expanded graphite in described step (2) carries out ultrasonic lift-off processing in stripper, and expanded graphite is 1:7 20 with the mass ratio of stripper, and described stripper is water or nonionic surfactant solution.
Using the strainer filtering expanded graphite of 400 mesh in described step (2), use pure water expanded graphite, washing times is 15 times.
In described step (3), the time of dried is 2 30min.
Employing it is an advantage of the current invention that:
One, in the present invention, using graphite paper is Graphene prepared by raw material, has the advantage that degree of oxidation is low and conductivity is high, it is possible to reduce the energy consumption in preparation process.Surface also helps Graphene with certain functional group and disperses in water or nonionic surfactant solution simultaneously.The method using electrochemistry carries out intercalation, expansion to graphite paper, and such process advan is when the intercalation stage, and intercalator is quick intercalation and diffusion in graphite paper, during the expansion stage, and the decomposition of hydrone.Avoid prior art during preparing Graphene, use strong acid, strong oxidizer and the problem of expensive organic liquid.Meanwhile, the high energy consumption problem in preparation process is solved.It addition, the present invention uses microwave vacuum dryer mode withering to Graphene slurry, have that power consumption is little, production efficiency is high and the advantage such as good economy performance.
Two, in the present invention, after graphite paper is carried out intercalation, using newly configured electrolyte to expand the graphite paper after intercalation, electrolyte components is relatively easy, cheap and environmental friendliness advantage to use newly configured electrolyte to have, and can reduce the cost that when subsequent step filters, electrolyte solution loss causes.
Three, in the present invention, in expansion process, the graphite paper after intercalation immerses in electrolyte with the speed of 1 20mm/min and expands, and such mode can make the graphite paper even inflation after intercalation, and expansion character is more preferable.
Four, in the present invention, in the present invention, in the intercalation stage, if electric current density is less than 0.5V less than 0.1mA/g or voltage, intercalation or intercalation speed will not be occurred the slowest.If electric current density is higher than 30mA/g, being mainly electrolysed water on graphite paper surface, intercalation is incomplete, causes energy waste, if voltage is more than 10V, will cause again the over oxidation of graphite flake layer.Therefore, it is 0.1 30mA/g or under conditions of voltage is 0.5 10V, graphite paper to be carried out intercalation most widely suited in electric current density.It addition, when expanding, if voltage is not decomposed less than 2V, the water of graphite layers, and then caused expanding unsuccessfully, if voltage is higher than 20V, Graphene over oxidation will be caused again, and expansion process excessively acutely will be unfavorable for obtaining the Graphene of thin layer.Therefore, expanding the graphite paper after intercalation under conditions of voltage is 2 20V, expansion effect is optimal.
Five, in the present invention, step (1) individually use the mixing of one or more in sulphuric acid, ammonium sulfate, sodium sulfate, potassium sulfate, dodecylbenzene sodium sulfonate, sodium lauryl sulphate as main intercalator, realize the intercalation of graphite paper, the raw material of intercalator is easy to get, add kind few, advantageously reduce preparation cost.And using main intercalator and the mode of auxiliary intercalator cooperation, the most beneficially high-order converts to low order and forms lower intercalation Stages graphite, consequently facilitating preparation thin graphene.Additionally, main intercalator is the mixing of one or more in sulphuric acid, ammonium sulfate, sodium sulfate, potassium sulfate, dodecylbenzene sodium sulfonate, sodium lauryl sulphate, and auxiliary intercalator is the mixing of one or more in nitrate, acetic acid, acetate, phosphoric acid, phosphate, oxalic acid, oxalates, chloride, chlorate.The concentration of the most main intercalator and auxiliary intercalator is relatively low, non-highly acid, oxidizing species, little to equipment corrosion, environmental pollution is little, with low cost.Further, use above-mentioned intercalator that chemical reaction will not occur during preparing Graphene, after prepared by Graphene, the repeatable utilization of intercalator, reduce preparation cost.
Six, in the present invention, when being used alone main intercalator, the concentration of main intercalator is 0.1 15M；Main intercalator and auxiliary intercalator with the use of time, both mol ratios are 0.5 10:1, and the concentration of main intercalator is 0.05 5M, use such proportioning and concentration to be conducive to improving the intercalation effect of graphite paper, reduce intercalation and Bulking Time.
Seven, in the present invention; use graphite cake as negative pole; graphite paper is positive pole; not introducing other impurity in preparation process, operation is simply conducive to the quick preparation of Graphene, simultaneously; because graphite cake raw material is easy to get; price is low, also helps reduction preparation cost and preparation difficulty, is suitable for large-scale industrial and produces.
Eight, in the present invention, the purity graphite paper more than 99.5% is used to prepare Graphene, it is possible to ensure that the purity of the Graphene of preparation is higher.
Nine, in the present invention, during ultrasonic lift-off processing, if expanded graphite is higher than 1:20 with the mass ratio of stripper, there is the defect that energy consumption is high and benefit is low, if and the mass ratio of expanded graphite and stripper is less than 1:7, cause again ultrasonic splitting time to extend at double, and it cannot be guaranteed that ultrasonic effect is preferable.Therefore, expanded graphite and stripper use the mass ratio of 1:7 20 to peel off, it is possible to ensure that expanded graphite is fully exfoliated.It addition, stripper uses water or nonionic surfactant solution, there is with low cost, little to operator and environmental hazard advantage.
Ten, in the present invention, step (2) uses the strainer filtering expanded graphite of 400 mesh, use pure water expanded graphite 15 times, the electrolyte remaining in expanded graphite can be rapidly removed, expanded graphite number of dropouts is little, and yield is high, thus ensures the better quality of the Graphene prepared.
11, in the present invention, in step (3), the time of dried is 2 30min, it is ensured that Graphene slurry can be completely dried.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphene product that the present invention prepares；
Fig. 2 is the transmission electron microscope picture of the graphene product that the present invention prepares；
Fig. 3 is the Raman figure of the graphene product that the present invention prepares.
Detailed description of the invention
Embodiment 1
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of electric current density is 0.1mA/g, graphite paper is carried out intercalation；After intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 2V, being immersed in electrolyte with the speed of 1mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes that main intercalator, described main intercalator are sulphuric acid, and its concentration is 0.5 15M.
Graphite paper in this step is that 80 mesh crystalline flake graphites are chemically treated, high-temperature expansion roll-in prepared, and its purity is more than 99.5%.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 1 time after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:7 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is water.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 2min, obtain fluffy graphene powder after drying.
Embodiment 2
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, electric current density is graphite paper to be carried out intercalation under conditions of 30mA/g, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 20V, being immersed in electrolyte with the speed of 5mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes that main intercalator, described main intercalator are ammonium sulfate, and its concentration is 0.5 4M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 5 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:20 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is nonionic surfactant solution.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 30min, obtain fluffy graphene powder after drying.
Embodiment 3
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of voltage is 0.5V, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 3V, being immersed in electrolyte with the speed of 20mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes that main intercalator, described main intercalator are sodium sulfate, and its concentration is 0.5 2M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 2 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:10 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is nonionic surfactant solution.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 10min, obtain fluffy graphene powder after drying.
Embodiment 4
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of voltage is 10V, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 15V, being immersed in electrolyte with the speed of 5mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes that main intercalator, described main intercalator are potassium sulfate, and its concentration is 0.5 2M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 3 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:13 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is nonionic surfactant solution.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 5min, obtain fluffy graphene powder after drying.
Embodiment 5
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of electric current density is 15mA/g, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 12V, being immersed in electrolyte with the speed of 15mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes that main intercalator, described main intercalator are sodium sulfonate dodecylbenzene sodium sulfonate, and its concentration is 0.1 0.5M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 4 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:9 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is water.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 20min, obtain fluffy graphene powder after drying.
Embodiment 6
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of voltage is 5V, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 17V, being immersed in electrolyte with the speed of 5mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes that main intercalator, described main intercalator are sodium lauryl sulphate, and its concentration is 0.1 0.5M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 3 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:17 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is nonionic surfactant solution.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 25min, obtain fluffy graphene powder after drying.
Embodiment 7
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of electric current density is 25mA/g, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 16V, being immersed in electrolyte with the speed of 3mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes that main intercalator, described main intercalator are the mixing of ammonium sulfate, sodium sulfate and potassium sulfate, and its concentration is 0.5 3M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 2 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:20 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is nonionic surfactant solution.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 10min, obtain fluffy graphene powder after drying.
Embodiment 8
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of electric current density is 10mA/g, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 2V, being immersed in electrolyte with the speed of 10mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes main intercalator and auxiliary intercalator, described main intercalator is dilute sulfuric acid, described auxiliary intercalator is nitrate, described electrolyte is formed by the aqueous solution of dilute sulfuric acid and the aqueous solution of nitrate, in electrolyte, dilute sulfuric acid is 0.5:1 with the mol ratio of nitrate, and the concentration of dilute sulfuric acid is 0.2 3M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 2 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:7 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is nonionic surfactant solution.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 8min, obtain fluffy graphene powder after drying.
Embodiment 9
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of electric current density is 3mA/g, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 20V, being immersed in electrolyte with the speed of 4mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes main intercalator and auxiliary intercalator, described main intercalator is ammonium sulfate, described auxiliary intercalator is acetic acid, described electrolyte is formed by the aqueous solution of ammonium sulfate and the aqueous solution of acetic acid, in electrolyte, main intercalator is 10:1 with the mol ratio of auxiliary intercalator, and the concentration of ammonium sulfate is 0.2 5M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 3 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:20 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is water.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 5min, obtain fluffy graphene powder after drying.
Embodiment 10
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of voltage is 5V, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 2V, being immersed in electrolyte with the speed of 5mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes main intercalator and auxiliary intercalator, described main intercalator is sodium sulfate, described auxiliary intercalator is acetate, described electrolyte is formed by the aqueous solution of sodium sulfate and the aqueous solution of acetate, in electrolyte, sodium sulfate is 1:1 with the mol ratio of acetate, and the concentration of sodium sulfate is 0.2 2M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 3 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:12 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is nonionic surfactant solution.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 3min, obtain fluffy graphene powder after drying.
Embodiment 11
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of voltage is 10V, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 18V, being immersed in electrolyte with the speed of 15mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes main intercalator and auxiliary intercalator, described main intercalator is potassium sulfate, described auxiliary intercalator phosphoric acid, described electrolyte is formed by the aqueous solution of potassium sulfate and the aqueous solution of phosphoric acid, in electrolyte, potassium sulfate is 3:1 with the mol ratio of phosphoric acid, and the concentration of potassium sulfate is 0.2 2M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 1 time after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:13 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is water.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 7min, obtain fluffy graphene powder after drying.
Embodiment 12
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of electric current density is 30mA/g, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 5V, being immersed in electrolyte with the speed of 12mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes main intercalator and auxiliary intercalator, described main intercalator is sodium sulfonate dodecylbenzene sodium sulfonate, described auxiliary intercalator is phosphate, described electrolyte is formed by aqueous solution and the phosphatic aqueous solution of sodium sulfonate dodecylbenzene sodium sulfonate, in electrolyte, sodium sulfonate dodecylbenzene sodium sulfonate and phosphatic mol ratio are 5:1, and the concentration of sodium sulfonate dodecylbenzene sodium sulfonate is 0.05 0.3M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 4 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:19 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is water.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 22min, obtain fluffy graphene powder after drying.
Embodiment 13
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of voltage is 4V, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 14V, being immersed in electrolyte with the speed of 18mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes main intercalator and auxiliary intercalator, described main intercalator is sodium lauryl sulphate, described auxiliary intercalator is the mixing of oxalic acid, oxalates, chloride and chlorate, described electrolyte is formed by the aqueous solution of main intercalator and the aqueous solution of auxiliary intercalator, in electrolyte, main intercalator is 6:1 with the mol ratio of auxiliary intercalator, and the concentration of main intercalator is 0.05 0.3M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 1 time after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:7 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is nonionic surfactant solution.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 28min, obtain fluffy graphene powder after drying.
Embodiment 14
A kind of electrochemistry prepares the method for Graphene, comprises the steps:
(1) using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of electric current density is 0.5mA/g, graphite paper is carried out intercalation, after intercalation completes, take out the graphite paper after intercalation, same in this electrolyte, under conditions of voltage is 5V, being immersed in electrolyte with the speed of 5mm/min by graphite paper after intercalation and expand, obtain after having expanded suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.Wherein, intercalation operation and expansion process are carried out in same electrolyte, significantly simplify preparation section.
Intercalator in this step includes main intercalator and auxiliary intercalator, described main intercalator is the mixing of dilute sulfuric acid, ammonium sulfate and sodium sulfate, described auxiliary intercalator is nitrate, described electrolyte is formed by the aqueous solution of main intercalator and the aqueous solution of auxiliary intercalator, in electrolyte, main intercalator is 2:1 with the mol ratio of auxiliary intercalator, and the concentration of described main intercalator is 0.2 2M.
(2) the strainer filtering expanded graphite of 400 mesh is used, use pure water expanded graphite 2 times after filtration, after having washed, in stripper, expanded graphite is carried out ultrasonic lift-off processing, expanded graphite is 1:11 with the mass ratio of stripper, obtains cotton-shaped Graphene slurry after having peeled off.Wherein, stripper is nonionic surfactant solution.
(3) Graphene slurry is carried out filtration treatment, after filtration filter completes, use microwave vacuum dryer that Graphene slurry is dried process 13min, obtain fluffy graphene powder after drying.
Embodiment 15
Any embodiment in this enforcement and above-mentioned 1 14 is essentially identical, differ primarily in that: the intercalation operation in step (1) is not carried out with expansion process in same electrolyte, particularly as follows: using graphite paper as positive pole, use graphite cake as negative pole, using the aqueous solution of intercalator as electrolyte, the method using electrochemistry, under conditions of electric current density is 0.1 30mA/g or under conditions of voltage is 0.5 10V, graphite paper is carried out intercalation, after intercalation completes, the aqueous solution of newly configured intercalator is as electrolyte, again the graphite paper after intercalation is taken out again as positive pole, then immerse in newly configured electrolyte with the speed of 1 20mm/min and expand, obtain suspending surface porosity porous in the electrolytic solution, vermiform expanded graphite particles.Wherein, the preparation of electrolyte for convenience, newly configured electrolyte is preferably identical with the electrolyte that intercalation operation is used but it also may different from the electrolyte that intercalation operation is used.
Through experimental results demonstrate, using specific component and specific parameter in embodiment 1 15, it is possible to high conductivity and the graphene product of the low number of plies are prepared in scale, following table is the performance parameter being respectively adopted the Graphene prepared after the method in embodiment 1 15:
Claims (10)
1. the method that an electrochemistry prepares Graphene, it is characterised in that comprise the steps:
(1) using graphite paper as positive pole, using the aqueous solution of intercalator as electrolyte, graphite paper is carried out intercalation, expansion, obtains expanded graphite；
(2) filter, wash expanded graphite, then expanded graphite is carried out ultrasonic lift-off processing, obtain cotton-shaped Graphene slurry；
(3) filtering graphite alkene slurry, then uses microwave vacuum dryer that Graphene slurry is dried process, obtains fluffy graphene powder after drying.
The method that a kind of electrochemistry the most as claimed in claim 1 prepares Graphene, it is characterized in that: after described step (1) carries out intercalation to graphite paper, the aqueous solution of newly configured intercalator is as electrolyte, again the graphite paper after intercalation is taken out, again immersing in newly configured electrolyte as positive pole and expand, obtain suspending surface porosity porous, vermiform expanded graphite particles in the electrolytic solution.
The method that a kind of electrochemistry the most as claimed in claim 1 or 2 prepares Graphene, it is characterised in that: in the expansion process of described step (1), the graphite paper after intercalation immerses in electrolyte with the speed of 1 20mm/min and expands.
The method that a kind of electrochemistry the most as claimed in claim 1 or 2 prepares Graphene, it is characterized in that: described step (1) is 0.1 30mA/g in electric current density or under conditions of voltage is 0.5 10V, graphite paper is carried out intercalation, under conditions of voltage is 2 20V, the graphite paper after intercalation is expanded.
The method that a kind of electrochemistry the most as claimed in claim 1 or 2 prepares Graphene, it is characterized in that: the intercalator in described step (1) includes that main intercalator, described main intercalator are the mixing of one or more in alkene sulphuric acid, ammonium sulfate, sodium sulfate, potassium sulfate, sodium sulfonate dodecylbenzene sodium sulfonate, sodium lauryl sulphate.
The method that a kind of electrochemistry the most as claimed in claim 5 prepares Graphene, it is characterised in that: the concentration of described main intercalator is 0.1 15M.
The method that a kind of electrochemistry the most as claimed in claim 5 prepares Graphene, it is characterized in that: the intercalator in described step (1) also includes that auxiliary intercalator, described auxiliary intercalator are the mixing of one or more in nitrate, acetic acid, acetate, phosphoric acid, phosphate, oxalic acid, oxalates, chloride, chlorate.
The method that a kind of electrochemistry the most as claimed in claim 7 prepares Graphene, it is characterized in that: described electrolyte is formed by the aqueous solution of main intercalator and the aqueous solution of auxiliary intercalator, in described electrolyte, main intercalator is 0.5 10:1 with the mol ratio of auxiliary intercalator, and the concentration of described main intercalator is 0.05 5M.
The method that a kind of electrochemistry the most as claimed in claim 1 prepares Graphene, it is characterized in that: the expanded graphite in described step (2) carries out ultrasonic lift-off processing in stripper, expanded graphite is 1:7 20 with the mass ratio of stripper, and described stripper is water or nonionic surfactant solution.
The method that a kind of electrochemistry the most as claimed in claim 1 prepares Graphene, it is characterised in that: in described step (3), the time of dried is 2 30min.
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