CN107572511A - A kind of method of green large-scale production graphene - Google Patents
A kind of method of green large-scale production graphene Download PDFInfo
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Abstract
The present invention relates to a kind of method of green large-scale production graphene, this method comprises the following steps：(1) 0.1 ~ 10M electrolyte is prepared；(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, fixed negative pole material among foam paper；(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper；(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 5 ~ 15 DEG C；(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell respectively；(6) lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is 8 ~ 20V, starts electrochemical intercalation and stripping；(7) graphene dispersing solution is produced after being ultrasonically treated, centrifuging in solvent through filtering and washing, electrolyte ion to be washed away to electrochemical intercalation, the intercalated graphite flakes peeled off, come off；(8) graphene dispersing solution is obtained through vacuum filter, freeze-drying.Cost of the present invention is extremely cheap, technique is simple and environmental protection.
Description
Technical field
The present invention relates to graphene production field, more particularly to a kind of method of green large-scale production graphene.
Background technology
Graphene is a kind of two-dimensional material for novel super-high performance that last decade grows up, and it passes through sp by carbon atom2
The monolayer honeycomb shape lattice structure that hydridization is formed.The thickness of graphene only has 0.334 nm, is known in the world at present
Most thin material, and form graphite elementary cell, it can wrap up the fullerene to form zero dimension certainly, can also from
Packing is rolled into one-dimensional CNT, and layer upon layer forms the graphite of three-dimensional（Allen M J, Tung V C, Kaner
R B. Honeycomb carbon: A review of graphene[J].Chemical Reviews, 2010, 110
(1): 132-145. ).Due to this special structure, graphene has many special excellent properties.Its theory compares surface
Product is up to 2630 m2/ g, possess the Young's modulus (~ 1100GPa) and fracture strength (125GPa) of superelevation, and excellent heat biography
The property led (~ 5000W/ (m × k)) and carrier conductivity (2 × 105cm2/ v), in addition, graphene is electrically and magnetically learning performance etc.
Also there are a lot of other characteristics, such as room-temperature quantum Hall effect, bipolarity field effect, ferromagnetism, superconductivity.These are excellent
Performance cause graphene have in fields such as nano electron device, gas sensor, energy stores and composites it is wide should
With prospect (Geim A K, Novoselov K S. The rise of graphene [J] Nature Materials,
2007, 6(3): 183-191.)。
2004, Manchester Geim groups（Novoselov K S, Geim A K, Morozov S V,
eta.l Electric FieldEffect in Atomically Thin Carbon Films [J]. Science,2004,
306:666-669.）The New Two Dimensional atomic crystal of individual layer or thin layer is obtained with mechanical stripping method first.The discovery of graphene
Supplemented with carbon material family from zero dimension to the integral framework of three-dimensional carbon material.For graphene research field, really challenge is raw
The thin layer of graphite of high quality is produced, thus allows for large-scale application（GEIM A K, NOVOSELOV K S. The rise
of grapheme[J].Nat Mater, 2007, 6(3): 183-91.）.The method for preparing graphene at present mainly has machinery
Stripping method, chemical vapor deposition, carborundum pyrolysismethod, CNT patterning method, chemical oxidation peel off the method that restores, electrochemistry stripping
From method etc..
(1) mechanical stripping method：Highly oriented pyrolytic graphite is pre-processed through row, by graphite adhesion and pressed with adhesive tape repeatedly
Slowly tear after reality, then doubling adhesive tape again, slowly removed after being gently compacted.The process is operated repeatedly until tape surface is sent out
Existing ultrathin transparent spot, as multi-layer graphene, locally might have single-layer graphene, then again be transferred to adhesive tape ultra-thin
SiO2In silicon chip substrate.Due to not by chemical attack, the graphene being prepared has very outstanding intrinsic this stripping means
Performance, but its complex operation, yield are extremely low.The machinery stripping graphene separately having been reported that in recent years is to mix general crystalline flake graphite to glue
Placed after knot agent in three rollers or five roller mills, shearing force when being separated by the extruding between roller bearing and roller bearing realizes graphite flake
Separation.This method is simple to operate, can industrialize, but obtained graphene is influenceed by the impact of grinder roll shaft, is hardly resulted in
Piece footpath is large-sized graphene film, generally at hundreds of nanometers.
(2) chemical vapor deposition：By two kinds（Usually hydrogen and methane）Or two or more gases（Modified or doping）
Raw material mixes according to a certain percentage to be imported in CVD reaction warehouses, is chemically reacted after the temperature of additional setting or other energy,
Form solid-state material and deposit to substrate or catalyst surface, so as to obtain the method for solid-state material.P. W. Sutter et al.
（SUTTER P W,FLEGE J-I,SUTTER E A. Epitaxial graphene on ruthenium [J]. Nat
Mater,2008,7(5): 406-11.）Using metal Ru as substrate, ruthenium is penetrated under 1150 degrees Celsius of high temperature using carbon atom,
Then after being cooled to 850 degrees Celsius, the carbon atom for floating over ruthenium surface forms the single layer of carbon atom of laminated structure, finally grows up to complete
A layer graphene.Graphene platelet prepared by this method has one disadvantage in that, is exactly often in uneven thickness, and can influence piece
The property of layer.Kim etc.（KIM K S,ZHAO Y, JANG H,et al. Large-scale pattern growth of
graphene films forstretchable transparent electrodes [J]. Nature, 2009,457
(7230): 706-10.）(one layer of Si0 is first grown on Si surfaces on Ni surfaces using carbonaceous gas2, then redeposited Ni films)
Catalytic growth has gone out large-area graphene.Ruoff etc. also obtains the graphene film of high quality on Cu paper tinsels surface（LIX,CAI
W,AN J, etal. Large-Area Synthesis of High-Quality and Uniform Graphene
Filmson Copper Foils [J]. Science, 2009,324(5932): 1312-4.）.This metal catalysed processes life
Dilute graphite that length obtains is polycrystalline, and it gives a kind of new thinking for the growth and transfer of graphene.However, this catalysis side
The graphene platelet that method obtains is difficult control uniformly and the number of plies is uneven, and the cost of catalyst metals is also high in addition, to graphene
Large-scale production bring difficulty.
(3) carborundum pyrolysismethod：SiC epitaxial growth methods are considered as one of best practice for producing graphene wafer, mainly
Reason is that carborundum itself provides dielectric substrate.Carborundum under ultra-high vacuum environment is heated to 1150 according to external condition
At ~ 2000 DEG C, carbon, the difference of silicon atom surface vapor pressure, the silicon atom evaporation on top layer are escaped, and remaining carbon atom is reconstructed
Generate graphene（GEIM A K, NOVOSELOV K S. The rise of grapheme[J].Nat Mater, 2007,
6(3): 183-91.）.This preparation method needs highly energy-consuming and longer experimental period and prepares cost, is also given with this
Prepare with scale graphene brings difficulty.
(4) CNT patterning method：2009, D.V. Kosynkin are reported on nature first cut more wall carbon
Nanotube prepares the dilute method of graphite（KOSYNKIN D V,HIGGINBOTHAM A L, SINITSKII A, et al.
Longitudinal unzipping ofcarbon nanotubes to form graphene nanoribbons [J].
Nature, 2009,458(7240): 872-6.）.Oxidation processes are carried out to multi-walled carbon nanotube first, then radially
Cut, being broken into individual layer or few layer has water-soluble graphene nanobelt, recovers conductive capability by being chemically treated.This method
Yield is high, can obtain the intrinsic graphene arrowband with excellent electrical properties, but product has many faults of construction and the number of plies can not
Control.Akiko Natori（ITO J, NAKAMURA J,NATORI A. Semiconducting nature of the
oxygen-adsorbed graphemesheet [J]. J Appl Phys, 2008,103(11): 113712-5.）Report
Metallic atom is inserted between the Guan Yuguan of multi-walled carbon nanotube, the method that multi-walled carbon nanotube is cut along caliber direction, so
After being neutralized again with acid using AMMONIA TREATMENT afterwards, short annealing handles to obtain the dilute lamella of graphite and nanobelt.Cutting carbon nanotubes method
New method is started to prepare High-performance graphene, but scale low cost cutting carbon nanotubes prepare graphene and still have one
Segment distance.
Other reduction-oxidation graphite method can realize the large-scale production of graphene, but the graphene prepared is present largely
Oxidation defect, the heavy damage complete structure of graphene, and then limit its excellent performance, especially electric property, together
When redox graphene when need to use the environmentally harmful chemicals such as hydrazine hydrate, HI, be unfavorable for environmental protection.
In summary, existing preparation method can not realize the graphene of green prepare with scale high quality, serious limitation
The industrial applications process of graphene.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of cost is extremely cheap, technique is simple and environmentally friendly green rule
The method that modelling produces graphene.
To solve the above problems, a kind of method of green large-scale production graphene of the present invention, including following step
Suddenly：
(1) 0.1 ~ 10M electrolyte is prepared；
(2) anode material is put into the electrolytic cell added with the electrolyte, and fixed with foam paper, it is solid among the foam paper
Determine cathode material；
(3) the tubule for connecting inert gas is inserted in the electrolyte, and be fixed on the foam paper；
(4), in electrolyte periphery plus a cooling system, the temperature of the electrolyte is made at 5 ~ 15 DEG C；
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 1 ~ 5 cm；
(6) continuously lead to inert gas shielding at the anode material, open power supply, at the same regulating power source voltage be 8 ~
20V, start electrochemical intercalation and stripping；
(7), to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away is after in solvent
It is ultrasonically treated, centrifugation, produces graphene dispersing solution；
(8) the graphene dispersing solution is obtained through vacuum filter, freeze-drying.
(1) middle electrolyte refers to sodium sulphate, sulfuric acid, ammonium sulfate, potassium sulfate, sodium hydroxide, potassium hydroxide, nitre to the step
One or more of mixed liquors in sour sodium, potassium nitrate, ammonium nitrate.
(2) anode material refers to any one in graphite paper, graphite rod, graphite block, tabletting expanded graphite to the step.
(2) middle cathode material refers to that graphite rod, graphite paper, graphite block, Pt electrodes and other electrochemistry are lazy to the step
Any one in property electrode.
(3) middle inert gas refers to any one in argon gas, nitrogen, carbon dioxide to the step.
(7) middle solvent refers to distilled water, ethanol, n-butanol, dimethylformamide to the step（DMF）, dimethyl sulfoxide (DMSO)
（DMSO）, 1-METHYLPYRROLIDONE（NMP）, benzene,toluene,xylene, 1,2- dichloro-benzenes, ethyl acetate, methyl acetate, acetic acid fourth
One or more in ester, carbon disulfide, carbon tetrachloride, cyclohexanone, N- rings ethyl pyrrolidone, dimethyl acetamide, benzylamine
Mixture.
(7) middle supersound process condition refers to that ultrasonic power is 250W ~ 2000W to the step, and the time is 20 ~ 40min, secondary
Number is 2 times.
The condition of the step (8) middle vacuum filter refers to that vacuum is 5 ~ 50 KPa, the aperture of filter membrane for 0.1 μm ~
0.6μm。
The condition of the step (8) middle freeze-drying refers to that vacuum is 20 ~ 100 Pa, and temperature is -25 DEG C ~ -5 DEG C, when
Between be 20 ~ 30h.
The present invention has advantages below compared with prior art：
1st, the concentrated acid of the invention that need not be prepared used in graphene oxide, strong, weak oxidant and a large amount of water, its separation method are simply easy
OK, first step separation only needs filtering and washing, after second step is separated into ultrasound centrifugation can realize complete recovery.
2nd, the present invention prevents it in stripping process, due to electrochemistry and just to anode material by inert atmosphere protection
The synergy of ecological oxygen and aoxidized by large area, so as to which low degree of oxidation can be obtained by inert gas shielding and height is led
Electric rate（1100 S/cm）Graphene, effectively reduce conventional method intercalation peel off electrochemical reaction process in graphene oxygen
Change, remain the integrality of graphene-structured.
As shown in Fig. 1 Raman spectrums, with the rising of electrolytic cell temperature, graphene degree of oxidation accordingly increases；With
The increase of concentration of electrolyte, graphene degree of oxidation has corresponding reduction.By low temperature control in the invention and argon gas protection
Control obtained graphene that there is good structural intergrity and low degree of oxidation, it was confirmed that the invention it is scientific and practical
Property.
As shown in figure 4, graphene has the also larger piece footpath of preferable size integrity degree.SEAD spectral line explanation,
The characteristics of graphene crystal structure is complete, and crystallinity is high.
As shown in figure 5, the C/O of the graphene is than high, in addition, from the point of view of the fitting result that C is finely composed, only a small amount of C-
Outside O keys, remaining is the C of sp2 hydridization.Illustrate that the graphene that this method obtains has relatively low degree of oxidation.
3rd, charge stripping efficiency of the present invention is exceedingly fast, and 1g graphenes are obtained in laboratory small device at most needs 5 min.Together
When, gained graphene has preferable lamella to be distributed, and is easy to orient the preparation of controllable grapheme.
As shown in Fig. 2 graphene has preferable lamella to be distributed, illustrate that the graphene that this method obtains has good lamella chi
Very little distribution, it is easy to orient the preparation of controllable grapheme.
As shown in figure 3, graphene has fabulous lamellar structure, illustrate that this method there can be fabulous stripping effect to graphite
Fruit, so as to obtain the graphene of the individual layer of large stretch of particle diameter.
4th, the present invention prepared by graphene yield, quality it is high, the number of plies less than 3 layers graphene yield 60% with
On, individual layer rate reaches more than 40%, and the piece footpath yardstick of graphene is between 2 μm ~ 20 μm, and the graphene defect of preparation is few, matter
Amount is high, especially electric property, and the conductance of graphene tabletting film forming can meet electronics industry in 1100 more than S/cm
Requirement to graphene product.
5th, raw material of the present invention is cheap and environmentally friendly, and the cost of 1g high-quality graphenes is not as good as 0.3 yuan, the cost of its dispersion solvent
Divide species according to difference, therefore, greatly reduce the production cost of graphene.
6th, electrolyte solution electrolysis of the present invention only produces oxygen and hydrogen and environment non-hazardous, electrolyte can be weighed by recovery
It is multiple to use, it is green, unstripped bulk graphene can it is compressing again after be continuing with, device therefor is simple, energy consumption
It is low, easily realize industrial mass production.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is graphene product Raman spectrum of the present invention.（A is temperature-degree of oxidation；B is concentration-degree of oxidation）
Fig. 2 is graphene product SEM (electron scanning micrograph) of the present invention.
Fig. 3 is graphene product AFM (atomic force microscopy) of the present invention.
Fig. 4 is graphene product TEM of the present invention (projection electron microscope photo).
Fig. 5 is graphene product XPS of the present invention（X-ray photoelectron power spectrum）.
Embodiment
A kind of method of green large-scale production graphene of embodiment 1, comprises the following steps：
(1) 300ml, 1M ammonium sulfate are prepared as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 5 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 1cm.
(6) continuously lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is 8V,
Start electrochemical intercalation and stripping.
(7) to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away after
First it is ultrasonically treated in nmp solvent under conditions of ultrasonic power is 250W, time 40min, number are 2 times, then
10min is centrifuged with 8000rpm rotating speeds, produces graphene dispersing solution.
(8) by graphene dispersing solution after vacuum filter under the conditions of vacuum is 5 KPa, the aperture of filter membrane is 0.1 μm,
Freeze-dried 30h is obtained under conditions of vacuum is 20 Pa, temperature is -25 DEG C.
Graphene yield of the number of plies less than 3 layers is more than 60%, and individual layer rate reaches more than 40%, the piece footpath yardstick of graphene
Between 2 μm ~ 20 μm.
A kind of method of green large-scale production graphene of embodiment 2, comprises the following steps：
(1) 300ml, 1M ammonium sulfate are prepared as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 10 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 5 cm.
(6) continuously lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is
20V, start electrochemical intercalation and stripping.
(7) to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away after
First it is ultrasonically treated in nmp solvent under conditions of ultrasonic power is 2000W, time 20min, number are 2 times, then
10min is centrifuged with 8000rpm rotating speeds, produces graphene dispersing solution.
(8) by graphene dispersing solution after vacuum filter under the conditions of vacuum is 50 KPa, the aperture of filter membrane is 0.6 μm,
Freeze-dried 20h is obtained under conditions of vacuum is 100 Pa, temperature is -5 DEG C.
Graphene yield of the number of plies less than 3 layers is more than 50%, and individual layer rate reaches more than 30%, the piece footpath yardstick of graphene
Between 2 μm ~ 10 μm.
A kind of method of green large-scale production graphene of embodiment 3, comprises the following steps：
(1) 300ml, 1M sodium hydroxide solution are prepared as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 15 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 2 cm.
(6) lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is 10V, starts electrification
Learn intercalation and stripping.
(7) to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away after
First it is ultrasonically treated in DMSO solvents under conditions of ultrasonic power is 500W, time 35min, number are 2 times, then
10min is centrifuged with 8000rpm rotating speeds, produces graphene dispersing solution.
(8) by graphene dispersing solution after vacuum filter under the conditions of vacuum is 10 KPa, the aperture of filter membrane is 0.2 μm,
Freeze-dried 22h is obtained under conditions of vacuum is 30 Pa, temperature is -20 DEG C.
Graphene yield of the number of plies less than 3 layers is more than 60%, and individual layer rate reaches more than 40%, the piece footpath yardstick of graphene
Between 2 μm ~ 20 μm.
A kind of method of green large-scale production graphene of embodiment 4, comprises the following steps：
(1) 300ml, 2M ammonium sulfate are prepared as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 8 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 3 cm.
(6) continuously lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is
12V, start electrochemical intercalation and stripping.
(7), to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away is after molten
Agent（Ethanol：Distilled water=9ml：1 ml）Middle elder generation is under conditions of ultrasonic power is 750W, time 30min, number are 2 times
It is ultrasonically treated, 10min is then centrifuged with 8000rpm rotating speeds, produces graphene dispersing solution.
(8) by graphene dispersing solution after vacuum filter under the conditions of vacuum is 15 KPa, the aperture of filter membrane is 0.3 μm,
Freeze-dried 24h is obtained under conditions of vacuum is 40 Pa, temperature is -15 DEG C.
Graphene yield of the number of plies less than 3 layers is more than 40%, and individual layer rate reaches more than 20%, the piece footpath yardstick of graphene
Between 2 μm ~ 10 μm.
A kind of method of green large-scale production graphene of embodiment 5, comprises the following steps：
(1) 300ml, 1M ammonium sulfate+sulfuric acid are prepared（1:1）Solution is as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 12 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 4 cm.
(6) continuously lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is
14V, start electrochemical intercalation and stripping.
(7), to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away is after molten
First be ultrasonically treated in agent under conditions of ultrasonic power is 1000W, time 25min, number are 2 times, then with
8000rpm rotating speeds centrifuge 10min, produce graphene dispersing solution.
(8) by graphene dispersing solution after vacuum filter under the conditions of vacuum is 20 KPa, the aperture of filter membrane is 0.4 μm,
Freeze-dried 26h is obtained under conditions of vacuum is 50 Pa, temperature is -10 DEG C.
Graphene yield of the number of plies less than 3 layers is more than 40%, and individual layer rate reaches more than 10%, the piece footpath yardstick of graphene
Between 5 μm ~ 10 μm.
A kind of method of green large-scale production graphene of embodiment 6, comprises the following steps：
(1) 300ml, 10M ammonium sulfate are prepared as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 10 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 2 cm.
(6) continuously lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is
16V, start electrochemical intercalation and stripping.
(7), to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away is after molten
First be ultrasonically treated in agent under conditions of ultrasonic power is 1250W, time 25min, number are 2 times, then with
8000rpm rotating speeds centrifuge 10min, produce graphene dispersing solution.
(8) by graphene dispersing solution after vacuum filter under the conditions of vacuum is 30 KPa, the aperture of filter membrane is 0.5 μm,
Freeze-dried 28h is obtained under conditions of vacuum is 60 Pa, temperature is -5 DEG C.
Graphene yield of the number of plies less than 3 layers is more than 40%, and individual layer rate reaches more than 10%, the piece footpath yardstick of graphene
Between 2 μm ~ 10 μm.
A kind of method of green large-scale production graphene of embodiment 7, comprises the following steps：
(1) 300ml, 0.1M ammonium sulfate are prepared as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 5 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 4cm.
(6) continuously lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is
18V, start electrochemical intercalation and stripping.
(7) to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away after
First it is ultrasonically treated in DMF solvent under conditions of ultrasonic power is 1500W, time 20min, number are 2 times, then
10min is centrifuged with 8000rpm rotating speeds, produces graphene dispersing solution.
By graphene dispersing solution under the conditions of vacuum is 40 KPa, the aperture of filter membrane is 0.15 μm vacuum filter
Afterwards, freeze-dried 25h is obtained under conditions of vacuum is 70 Pa, temperature is -25 DEG C.
Graphene yield of the number of plies less than 3 layers is more than 60%, and individual layer rate reaches more than 30%, the piece footpath yardstick of graphene
Between 2 μm ~ 20 μm.
A kind of method of green large-scale production graphene of embodiment 8, comprises the following steps：
(1) 300ml, 10M sulfuric acid solution are prepared as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 15 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 4 cm.
(6) continuously lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is
10V, start electrochemical intercalation and stripping.
(7) to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away after
First it is ultrasonically treated in DMF solvent under conditions of ultrasonic power is 1750W, time 20min, number are 2 times, then
10min is centrifuged with 8000rpm rotating speeds, produces graphene dispersing solution.
(8) by graphene dispersing solution after vacuum filter under the conditions of vacuum is 45KPa, the aperture of filter membrane is 0.25 μm,
Freeze-dried 23h is obtained under conditions of vacuum is 80 Pa, temperature is -10 DEG C.
Graphene yield of the number of plies less than 5 layers is more than 60%, and individual layer rate reaches more than 20%, the piece footpath yardstick of graphene
Between 1 μm ~ 10 μm.
A kind of method of green large-scale production graphene of embodiment 9, comprises the following steps：
(1) 300ml, 5M ammonium sulfate are prepared as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 10 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 4 cm.
(6) continuously lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is
10V, start electrochemical intercalation and stripping.
(7) to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away after
First it is ultrasonically treated in DMF solvent under conditions of ultrasonic power is 2000W, time 20min, number are 2 times, then
10min is centrifuged with 8000rpm rotating speeds, produces graphene dispersing solution.
By graphene dispersing solution under the conditions of vacuum is 50 KPa, the aperture of filter membrane is 0.35 μm vacuum filter
Afterwards, freeze-dried 27h is obtained under conditions of vacuum is 90 Pa, temperature is -10 DEG C.
Graphene yield of the number of plies less than 3 layers is more than 20%, and individual layer rate reaches more than 5%, the piece footpath yardstick of graphene
Between 5 μm ~ 10 μm.
A kind of method of green large-scale production graphene of embodiment 10, comprises the following steps：
(1) 1L, 2M ammonium sulfate are prepared as electrolyte.
(2) anode material is put into the electrolytic cell added with electrolyte, and fixed with foam paper, it is fixed cloudy among foam paper
Pole material.
(3) the tubule for connecting inert gas is inserted in electrolyte, and be fixed on foam paper.
(4), in electrolyte periphery plus a cooling system, the temperature of electrolyte is made at 10 DEG C.
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 4 cm.
(6) continuously lead to inert gas shielding at anode material, open power supply, while regulating power source voltage is
10V, start electrochemical intercalation and stripping.
(7) to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away after
First it is ultrasonically treated in nmp solvent under conditions of ultrasonic power is 1000W, time 30min, number are 2 times, then
10min is centrifuged with 8000rpm rotating speeds, produces graphene dispersing solution.
By graphene dispersing solution under the conditions of vacuum is 25 KPa, the aperture of filter membrane is 0.45 μm vacuum filter
Afterwards, freeze-dried 26h is obtained under conditions of vacuum is 60 Pa, temperature is -15 DEG C.
Graphene yield of the number of plies less than 3 layers is more than 60%, and individual layer rate reaches more than 40%, the piece footpath yardstick of graphene
Between 2 μm ~ 20 μm.
(1) middle electrolyte refers to sodium sulphate, sulfuric acid, ammonium sulfate, potassium sulfate, sodium hydroxide, potassium hydroxide, sodium nitrate, nitric acid to step
One or more of mixed liquors in potassium, ammonium nitrate.
(2) anode material refers to any one in graphite paper, graphite rod, graphite block, tabletting expanded graphite to step.
Cathode material refers to appointing in graphite rod, graphite paper, graphite block, Pt electrodes and other electrochemicaUy inert electrodes
Meaning is a kind of.
(3) middle inert gas refers to any one in argon gas, nitrogen, carbon dioxide to step.
(7) middle solvent refers to distilled water, ethanol, n-butanol, dimethylformamide to step（DMF）, dimethyl sulfoxide (DMSO)
（DMSO）, 1-METHYLPYRROLIDONE（NMP）, benzene,toluene,xylene, 1,2- dichloro-benzenes, ethyl acetate, methyl acetate, acetic acid fourth
One or more in ester, carbon disulfide, carbon tetrachloride, cyclohexanone, N- rings ethyl pyrrolidone, dimethyl acetamide, benzylamine
Mixture.
Claims (9)
1. a kind of method of green large-scale production graphene, comprises the following steps：
(1) 0.1 ~ 10M electrolyte is prepared；
(2) anode material is put into the electrolytic cell added with the electrolyte, and fixed with foam paper, it is solid among the foam paper
Determine cathode material；
(3) the tubule for connecting inert gas is inserted in the electrolyte, and be fixed on the foam paper；
(4), in electrolyte periphery plus a cooling system, the temperature of the electrolyte is made at 5 ~ 15 DEG C；
(5) the positive pole of dc source and negative pole are connected to the anode material and cathode material in electrolytic cell, and two interpolars respectively
Away from for 1 ~ 5 cm；
(6) continuously lead to inert gas shielding at the anode material, open power supply, at the same regulating power source voltage be 8 ~
20V, start electrochemical intercalation and stripping；
(7), to electrochemical intercalation, the intercalated graphite flakes peeled off, come off through filtering and washing, electrolyte ion to be washed away is after in solvent
It is ultrasonically treated, centrifugation, produces graphene dispersing solution；
(8) the graphene dispersing solution is obtained through vacuum filter, freeze-drying.
A kind of 2. method of green large-scale production graphene as claimed in claim 1, it is characterised in that：The step (1) in
Electrolyte refers in sodium sulphate, sulfuric acid, ammonium sulfate, potassium sulfate, sodium hydroxide, potassium hydroxide, sodium nitrate, potassium nitrate, ammonium nitrate
One or more of mixed liquors.
A kind of 3. method of green large-scale production graphene as claimed in claim 1, it is characterised in that：The step is (2) positive
Pole material refers to any one in graphite paper, graphite rod, graphite block, tabletting expanded graphite.
A kind of 4. method of green large-scale production graphene as claimed in claim 1, it is characterised in that：The step (2) in
Cathode material refers to any one in graphite rod, graphite paper, graphite block, Pt electrodes and other electrochemicaUy inert electrodes.
A kind of 5. method of green large-scale production graphene as claimed in claim 1, it is characterised in that：The step (3) in
Inert gas refers to any one in argon gas, nitrogen, carbon dioxide.
A kind of 6. method of green large-scale production graphene as claimed in claim 1, it is characterised in that：The step (7) in
Solvent refers to distilled water, ethanol, n-butanol, dimethylformamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, benzene, toluene, two
Toluene, 1,2- dichloro-benzenes, ethyl acetate, methyl acetate, butyl acetate, carbon disulfide, carbon tetrachloride, cyclohexanone, N- ring ethyls
One or more of mixtures in pyrrolidones, dimethyl acetamide, benzylamine.
A kind of 7. method of green large-scale production graphene as claimed in claim 1, it is characterised in that：The step (7) in
Supersound process condition refers to that ultrasonic power is 250W ~ 2000W, and the time is 20 ~ 40min, and number is 2 times.
A kind of 8. method of green large-scale production graphene as claimed in claim 1, it is characterised in that：The step (8) in
The condition of vacuum filter refers to that vacuum is 5 ~ 50 KPa, and the aperture of filter membrane is 0.1 μm ~ 0.6 μm.
A kind of 9. method of green large-scale production graphene as claimed in claim 1, it is characterised in that：The step (8) in
The condition of freeze-drying refers to that vacuum is 20 ~ 100 Pa, and temperature is -25 DEG C ~ -5 DEG C, and the time is 20 ~ 30h.
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| CN112135792A (en) * | 2018-05-16 | 2020-12-25 | 安赛乐米塔尔公司 | Method for producing pristine graphene from kish graphite |
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| CN110133069A (en) * | 2019-04-16 | 2019-08-16 | 上海工程技术大学 | Surface graphene graphite base carbon material and its preparation method and application |
| CN110526241A (en) * | 2019-07-31 | 2019-12-03 | 山西大同大学 | A kind of electrolytic oxidation prepares the device and method of graphene oxide |
| CN110357087A (en) * | 2019-08-14 | 2019-10-22 | 中国科学院兰州化学物理研究所 | A method of graphene oxide is prepared based on high concentration inorganic salt solution removing |
| CN112357914A (en) * | 2020-11-03 | 2021-02-12 | 北京工业大学 | Method for preparing high/low disorder degree graphene oxide through electrochemical treatment |
| CN112357914B (en) * | 2020-11-03 | 2024-02-02 | 北京工业大学 | Method for preparing high/low disordered graphene oxide through electrochemical treatment |
| CN112408368A (en) * | 2020-11-27 | 2021-02-26 | 烟台德鹏晟阳碳材料有限公司 | Method for electrochemically preparing graphene with low structural defects |
| WO2022183585A1 (en) * | 2021-03-04 | 2022-09-09 | 广东邦普循环科技有限公司 | Method for preparing graphene by using waste negative electrode graphite of lithium battery and graphene |
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