CN104627999A - Production method of anti-overlapping thin-layer graphene - Google Patents
Production method of anti-overlapping thin-layer graphene Download PDFInfo
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Abstract
The invention belongs to the field of graphene preparation of material chemistry, and particularly relates to a production method of anti-overlapping thin-layer graphene. The production method provided by the invention is characterized in that graphite is used as a raw material for ball milling, and the thin-layer graphene is obtained by combining the release force of ball milling, the release force of super acid and the anti-overlapping effect of an inorganic nano material. The method has the advantages of short process, simple equipment and low production cost; and the prepared thin-layer graphene has high quality and relatively good industrial potential. The anti-overlapping thin-layer graphene can be applied to conductive plastics, conductive coatings and ink and also can be applied to the electrodes of lithium batteries and super capacitors as well as the composite materials needing high electrical conductivity and heat conductivity.
Description
Technical field
The invention belongs to technical field of material chemistry, more specifically for a kind of ball-milling technology that adopts produces the method for preventing back folded thin graphene.
Background technology
Since 2004 are found by scientists such as the Geim of Univ Manchester UK, the investigation and application of Graphene is operated in extensively is carried out (Novoselov K.S. all over the world, Geim A.K., Morozov S.V., et al.Electric field effect in atomically thin carbon films [J] .Science, 2004,306 (5696): 666-669).Graphene is a kind of by SP
2the planar nano-carbon material that hydbridized carbon atoms is formed, heat-conduction coefficient is up to 5000W/m.K, and theoretical specific surface area is up to 2630m
2/ g, individual layer specific absorbance only has 2.3%.Be the material that known intensity is the highest, there is the good transparency, electroconductibility and thermal conductivity simultaneously, be expected to there is broad prospect of application in matrix material, energy storage material, electronic material, optics etc.The industrial application exploitation of Graphene, in the urgent need to the technology of a kind of energy large-tonnage, low cost production Graphene.
At present, the technology of producing Graphene comprises mechanically peel method, liquid phase stripping method, oxidation reduction process, chemical Vapor deposition process, thermolysis SiC method, electrochemical process etc.Existing technology all also also exists certain weak point in scale operation Graphene.
Oxidation reduction process, liquid phase stripping method, realize large-tonnage, high-quality graphene manufacturing feasibility.Wherein, oxidation reduction process is based on Hummer method, utilize strong acid to carry out oxide treatment to graphite, obtains graphite oxide, then adopts various technique to its Depth Peeling, obtains graphene oxide, finally carries out reduction treatment and obtains Graphene.Whole process is loaded down with trivial details and complicated, and the process of reducing after initial oxidation can destroy the laminated structure of Graphene, the graphene product poorly conductive finally obtained, and in industrial application is subject to severely restricts compared with peeling off the high-quality graphene that obtains with physics.
Liquid phase stripping method, can obtain high-quality thin graphene.But most of known method, needs tens hours even splitting time of hundreds of hour.Need the method for Centrifugical extraction to obtain the Graphene of lower concentration in last handling process, usually known liquid phase stripping method Graphene productive rate is less.In addition, liquid phase in order to obtain graphene powder, needs to carry out drying treatment after peeling off.The thin graphene specific surface peeled away is large, there is huge Van der Waals force in sheet interlayer, sheet interlayer easily returns folded coinciding with one another, and causes the reduction of specific surface and the reduction of Graphene performance, causes the physicals of Graphene to be returned to original graphite performance to a great extent.
(the Natnael Behabtu such as the James M.Tour of the U.S., Jay R.Lomeda, Micah J.Green, et al.Spontaneous high-concentration dispersions and liquid crystals of grapnene [J] .Nature Nanotechnology 5,406-411 (2010)) utilize super acids-chlorsulfonic acid to carry out liquid phase stripping to graphite, based on the strong protonation of super acids, super acids easily enters the laminated structure of graphite, overcome the Van der Waals force between graphite flake layer, peel away Graphene.After stirring 2-3 days, obtain the Graphene-super acids dispersion liquid of lower concentration, directly wherein there is a large amount of single-layer graphenes in observation dispersion liquid.But add water decomposition chlorsulfonic acid, carry out filtration washing drying, the provide protection of graphene film quench strong acid is returned folded each other in the process, lost the performance of Graphene to a great extent.
Graphite is a kind of typical intercalation compound, when being subject to shearing force, easily sliding and being stripped out between layer and layer.When ball milling, powerful shearing force can be provided to promote the stripping each other of graphite flake layer.The Huanghai Sea waits and adopts the stirring ball-milling equipment (Huanghai Sea, be coated with river equality. the preparation of sheet nano graphite and the friction and wear behavior [J] as lubricating oil additive thereof. friction journal, 25th volume the 4th phase), take natural graphite as the nano graphite flakes preparing more than thickness 10nm after raw material ball milling.Ball milled equipment and process is simple, is easy to realize large-tonnage and produces, but directly uses above-mentioned ball milled not easily to obtain thin graphene sheet in a large number.
Summary of the invention
The object of the present invention is to provide a kind of method of low cost production thin graphene, adopt simple equipment and process just can low cost, a large amount of production thin graphene, thus promote the development of Graphene industry.
Technical scheme of the present invention is:
Prevent back a production method for folded thin graphene, be that raw material obtains through ball milling with graphite, it is characterized in that: take super acids as ball-milling additive, and added inorganic nano material by ball milling thing.
Ball milled is a kind of common industrial method of producing superfine powder, but adopts general milling technology usually not easily to obtain thin graphene sheet in a large number.When being subject to enough Strong shear reactive forces, graphite flake layer easily slides and is stripped out, but based on Van der Waals force strong between graphite flake layer, is easy to secondary agglomeration.Super acids, also known as super acid, is the acid that a kind of acidity is stronger than 100% sulfuric acid.Common super acids has, oleum, chlorsulfonic acid, fluosulfonic acid, fluorine metaantimmonic acid etc.Super acids has strong protonation to graphite flake, can offset Van der Waals force strong between graphite flake layer.Combinationally use the shearing force of ball milling and the strong protonation peeling force of super acids, the limitation that the two is used alone can be overcome, significantly strengthen the Depth Peeling effect to graphite flake, obtain thin graphene sheet.Inorganic nano material is added, the inorganic nano material that can realize particulate state or wire and the Homogeneous phase mixing of thin graphene sheet peeled away in mechanical milling process.After ball milling terminates, carry out filtration drying washing, obtain dry graphene powder.In the process, super acids contact water, will lose to graphene film protonated provide protection.After the provide protection losing super acids, be dispersed in the inorganic nano-particle in graphene film, just play separation graphene film, stop graphene film to return folded effect each other.In the process preparing nano graphite flakes or Graphene, disclosed in the technology such as single employing ball milling is peeled off, super acids is peeled off, mixing inorganic nano material are, but each single technique means has its limitation.In the process of production thin graphene, adopt above-mentioned three kinds of means while combination, there is synergistic effect, low cost, high efficiency production can prevent back folded thin graphene.In the production technique of Graphene, adopt above-mentioned three kinds of technique means to work in coordination with production thin graphene while combination and have no report.
In the present invention, take super acids as ball-milling additive.Graphite can in several specific solvents directly very the dissolving of lower concentration or stripping become Graphene, this process is similar to the lower concentration of polymkeric substance in special solvent and dissolves.Different solvents or medium different from the reactive force of graphite flake layer, graphite solubleness is wherein also different.The spontaneous concentration of ordinary dissolution of Graphite Powder 99 in chlorsulfonic acid is up to 2mg/ml, higher than solubleness in ordinary organic solvents, medium.Common organic solvent, medium or auxiliary agent, the reactive force of such as N-Methyl pyrrolidone, dimethyl formamide, Methylimidazole, glycine, amino dodecane, ionic liquid etc. and graphene film, does not have the strong of super acids and graphene film.In like manner, super acids assists ball milling stripping Graphene stronger than common organic solvent, medium up-stripping Graphene reactive force.Super acids of the present invention, is selected from oleum, chlorsulfonic acid, fluosulfonic acid, fluorine metaantimmonic acid a kind of.Especially, chlorsulfonic acid is a kind of common industrial super acids, and be widely used in organic synthesis and dyestuffs industries, world's annual production is more than 300,000 tons.In addition, the domestic price of chlorsulfonic acid is per ton in 1000-2000 unit, and price is cheap more than N-Methyl pyrrolidone, dimethyl formamide, Methylimidazole, glycine, amino dodecane, ionic liquid, and use cost has competitive power.With regard to up-stripping intensity and cost are comprehensive, the most suitable auxiliary agent peeled off as graphene film ball milling of chlorsulfonic acid.Chlorsulfonic acid is the acid of a kind of severe corrosive, and production process is suitable for carrying out under the condition of automatization or mechanize.
In the present invention, in mechanical milling process, add inorganic nano material.Take super acids as ball-milling medium, ball milling is carried out to graphite, inorganic nano material and the graphene film Homogeneous phase mixing obtained of particulate state or wire.In filtration, washing and drying process, if do not add inorganic nano material, the Graphene sector-meeting losing super acids provide protection is returned folded each other, loses the good physical of graphene film.Add after inorganic nano material, in the filtration in later stage, washing and drying process, inorganic nano material can stop returning of graphene film folded.In the present invention, described inorganic nano material is selected from carbon black, carbon nanotube, white carbon black a kind of, even several combinations.Described carbon black can be a kind of in tire carbon black, graphitized carbon black, colour carbon black.Described carbon nanotube, diameter, between 0.5-100nm, can be the one in single-layer carbon nano-tube, Double-walled Carbon Nanotube, thin wall carbon nano-tube, multilayer carbon nanotube.Described inorganic nano material and the mass ratio of graphite raw material are between 0.05-5.In the thin layer graphite ene product finally obtained, little to its performance impact containing inorganic nano material, without the need to inorganic nano material is therefrom separated again.But also can disturb the performance of thin graphene performance containing too much inorganic nano material, so the mass ratio of preferred inorganic nano material and graphite raw material is between 0.1-0.5.In a lot of industrial application, dispersed graphene film is one of critical process of its application performance of restriction performance in parent, can reduce graphene film and return folded impact, promote and strengthen its dispersibility containing inorganic nano material.Especially, add a small amount of carbon nanotube or graphitized carbon black in mechanical milling process, little to the thin graphene sheet Conductivity obtained, because carbon nanotube or graphitized carbon black inherently have better electroconductibility.
In the present invention, ball-grinding machine is selected from one in agitating ball mill, sand mill, planetary ball mill, tumbling ball mill.Ball-grinding machine is equipment common in industrial production, and structure is simple.Adopt ball-milling technology, be easy to realize large-tonnage and produce.In the process of ball milling, abrading-ball is high speed rotating each other, forms intensive shear power between abrading-ball.The time of ball milling, optional 1-48 hour.
In the present invention, described graphite raw material is the one in crystalline graphite powder, expansible black lead powder, expanded graphite powder, thermo-cracking Graphite Powder 99, even several combinations.Wherein, expanded graphite powder loose and porous inner surface, is formed by connecting by a lot of nanometer grade thickness thin slice, is more easily stripped out.Wherein, crystalline graphite powder is cheap, more easily realizes the suitability for industrialized production of thin graphene.In the present invention, preferably with expanded graphite powder or natural flake graphite powder for raw material.
In the present invention, ball-milling technology will carry out under the condition avoiding water.In mechanical milling process, need the auxiliary strong protonated stripping effect of super acids, super acids contact water will decompose, and loses this reactive force.First carry out except water treatment to graphite raw material, abrading-ball and ball grinder before ball milling; After ball milling terminates, first carry out the squeezing press filtration of power with pressure, reclaim unnecessary super acids as far as possible, with cost-saving; The pressure of press filtration, between 0.3Mpa-3Mpa.Filtering equipment can select the material of carbon steel material or Surface coating four still ethene.After press filtration terminates, filter cake with deionized water wash repeatedly, the thin graphene filter cake obtained is put into drying plant, at 50-150 DEG C of dry 4-48 hour, obtains thin graphene powder.
In the thin graphene powder produced, the number of plies of thin graphene sheet is below 20 layers, and crystal property is good, thickness 0.3-10nm.Antistatic and conductive plastics, coating, ink, rubber can be widely used in, can be used for the electrode materials of lithium cell or ultracapacitor, also can be used for the matrix material that other needs high connductivity, heat conduction.
Advantage of the present invention:
1, use ball-milling technology, easily amplify, there is stronger industrialization potential.
2, production process is simple, and chemical reagent consumption is few, and production cost is low, has good commercial viability.
3, the destruction of Graphene stripping process to graphene-structured is little, can retain the structure of Graphene, electricity and mechanical property preferably.
4, production process metal salt concentration is little, and the thin graphene purity finally obtained is high.
5, the chemical reagent component of whole process use is single, and little on the impact of environment, waste water easily processes.
Accompanying drawing explanation
Accompanying drawing illustrates the thin graphene transmission electron microscope photo that the embodiment of the present invention 1 is produced.
Specific embodiment mode
Further illustrate the present invention below in conjunction with drawings and the specific embodiments mode, accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.Some nonessential improvement that those skilled in the art make according to foregoing of the present invention and adjustment all belong to the scope of protection of the invention.Examples below concrete time, charging capacity etc. is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
Get 400 grams of dried expanded graphite powder, add agitated ball mill, start the chlorsulfonic acid that charge pump injects 12000ml.Add 40 grams of superconductive carbon blacks again, load the abrading-ball of 5 kilograms, Ball-milling Time 10 hours, after ball milling terminates, with the nitrogen pressure squeeze and filter of 1.0Mpa, reclaim unnecessary super acids, recycle.In gained filter cake, carefully slowly inject deionized water, decompose residue super acids, repeatedly press filtration and washing, 80 DEG C of dried in vacuo overnight, obtain dry powder.Accompanying drawing is the thin graphene transmission electron microscope photo that embodiment 1 is produced.In the powder produced, thickness accounts for total graphite flake ratio at below 10nm graphene film and is greater than 50%, and significantly comprise a large amount of thin graphene, the number of plies is between individual layer is to 20 layers.
Get 100 grams of gained thin graphene (wherein containing 9.1% superconductive carbon black), 845 grams of LDPE plastics, 50 grams of polyethylene waxs, 5 grams of stearic acid mixing, extrude with twin screw extruder, obtain thin graphene conductive plastic base particle.Further the conductive plastic base particle containing thin graphene is diluted, obtain the LDPE plastics containing 3% thin graphene, testing its volume specific resistance is 5.43x10
3Ω .cm.Process under the same conditions, reach the high price import graphitized carbon black that identical volume specific resistance needs to add 8-10% content in LDPE, use domestic graphitized carbon black to need interpolation more than 25% content, display gained thin graphene has good industrialization prospect in conductive plastics field.
Embodiment 2
Get 20 grams of dried 800 order natural flake graphites, add horizontal sand mill, then add 100 grams of colour carbon blacks.Start charge pump and inject 3000ml fluosulfonic acid, 8 hours sand milling time.After grinding terminates, with the nitrogen pressure squeeze and filter of 0.8Mpa, reclaim unnecessary super acids, recycle.In gained filter cake, the careful slowly injection NaOH aqueous solution, decomposes residue super acids, repeatedly press filtration and washing, 100 DEG C of dried in vacuo overnight, obtains dry powder.In the powder produced, thickness accounts for total graphite flake ratio at below 10nm graphene film and is greater than 50%, and significantly comprise a large amount of thin graphene, the number of plies is between individual layer is to 20 layers.
Embodiment 3
Get 10 grams of dried 300 order expansible black lead powder, add high-energy planetary formula ball mill, add 5 grams of gas-phase silicas simultaneously, then inject 50ml oleum, inflated with nitrogen ball sealer grinding jar.In order to prevent producing heat in mechanical milling process, temperature in ball grinder being raised, often grinding half an hour and shutting down cooling, guaranteeing that grinding interior temperature is no more than 60 DEG C, Ball-milling Time 24 hours.After ball milling terminates, gained mixture moves in quartz boat, and quartz boat pushes in quartz tube type vacuum oven, and vacuum oven connects water ring vacuum pump, and the interior alkaline solution of water ring vacuum pump does source of recycled water.Open water ring vacuum pump, progressively temperature programming is to 900 DEG C simultaneously, and quartz boat is taken out in cooling, obtains dry powder.In the powder produced, thickness accounts for total graphite flake ratio at below 10nm graphene film and is greater than 50%, and significantly comprise a large amount of thin graphene, the number of plies is between individual layer is to 20 layers.
Embodiment 4
Get 500 grams of dried 600 order cracking Graphite Powder 99s, add tumbling ball mill, start the fluorine metaantimmonic acid that charge pump injects 25000ml.Add 75 grams of single-layer carbon nano-tubes again.Load the abrading-ball of 6 kilograms, Ball-milling Time 16 hours.After ball milling terminates, with the nitrogen pressure squeeze and filter of 1.0Mpa, reclaim unnecessary super acids, recycle.In gained filter cake, carefully slowly inject deionized water, decompose residue super acids, repeatedly press filtration and washing, 60 DEG C of dried in vacuo overnight, obtain dry powder.In the powder produced, thickness accounts for total graphite flake ratio at below 10nm graphene film and is greater than 50%, and significantly comprise a large amount of thin graphene, the number of plies is between individual layer is to 20 layers.
Embodiment 5
Get 10 grams of dried 300 order expansible black lead powder, add high-energy planetary formula ball mill, add 0.5 gram of colour carbon black simultaneously, then inject 50ml chlorsulfonic acid, inflated with nitrogen ball sealer grinding jar.In order to prevent producing heat in mechanical milling process, temperature in ball grinder being raised, often grinding half an hour and shutting down cooling, guaranteeing that grinding interior temperature is no more than 60 DEG C, Ball-milling Time 24 hours.After ball milling terminates, gained mixture moves in quartz boat, and quartz boat pushes in quartz tube type vacuum oven, and vacuum oven connects water ring vacuum pump, and the interior alkaline solution of water ring vacuum pump does source of recycled water.Open water ring vacuum pump, progressively temperature programming, to 900 DEG C, obtains dry powder simultaneously.In the powder produced, thickness accounts for total graphite flake ratio at below 10nm graphene film and is greater than 50%, and significantly comprise a large amount of thin graphene, the number of plies is between individual layer is to 20 layers.
Embodiment 6
Get 400 grams of dried expanded graphite powder, add agitated ball mill, start charge pump and inject the chlorsulfonic acid of 10000ml and the fluorine metaantimmonic acid of 5000ml.Add the carbon nanotube of 40 grams of superconductive carbon blacks and 80 grams of mean diameter 10nm again, load the abrading-ball of 5 kilograms, Ball-milling Time 10 hours, after ball milling terminates, with the nitrogen pressure squeeze and filter of 1.0Mpa, reclaim unnecessary super acids, recycle.In gained filter cake, carefully slowly inject deionized water, decompose residue super acids, repeatedly press filtration and washing, 80 DEG C of dried in vacuo overnight, obtain dry powder.In the powder produced, thickness accounts for total graphite flake ratio at below 10nm graphene film and is greater than 50%, and significantly comprise a large amount of thin graphene, the number of plies is between individual layer is to 20 layers.
Embodiment 7
Get 200 grams of dried expanded graphite powder and 200 grams of dried 300 order natural flake graphite powder, add agitated ball mill, start charge pump and inject the fluosulfonic acid of 10000ml and the oleum of 2000ml.Add 40 grams of gas-phase silicas and 40 grams of single-layer carbon nano-tubes again, load the abrading-ball of 8 kilograms, Ball-milling Time 10 hours, after ball milling terminates, with the nitrogen pressure squeeze and filter of 1.0Mpa, reclaim unnecessary super acids, recycle.In gained filter cake, carefully slowly inject deionized water, decompose residue super acids, repeatedly press filtration and washing, 80 DEG C of dried in vacuo overnight, obtain dry powder.In the powder produced, thickness accounts for total graphite flake ratio at below 10nm graphene film and is greater than 50%, and significantly comprise a large amount of thin graphene, the number of plies is between individual layer is to 20 layers.
Comparative example 1 (use ordinary organic solvents N-Methyl pyrrolidone, do not use the comparative example of super acids)
Get 400 grams of dried expanded graphite powder, add agitated ball mill.Start the N-Methyl pyrrolidone that charge pump injects 12000ml simultaneously.Add 40 grams of superconductive carbon blacks again, load the abrading-ball of 5 kilograms, Ball-milling Time 10 hours.After ball milling terminates, with the nitrogen pressure squeeze and filter of 1.0Mpa, reclaim unnecessary N-Methyl pyrrolidone.Gained filter cake, 120 DEG C of dried in vacuo overnight, obtain dry powder.Graphite flake thickness major part in product is more than 10 nanometers, and thin graphene is little, as seen in the process of wet-milling, adds super acids and compares ordinary organic solvents, medium or auxiliary agent, the stripping of promotion graphite flake of the degree of depth can obtain thin graphene.
Comparative example 2 (not adding the comparative example of inorganic nano material)
Get 400 grams of dried expanded graphite powder, add agitated ball mill.Start the chlorsulfonic acid that charge pump injects 12000ml simultaneously.Load the abrading-ball of 5 kilograms, Ball-milling Time 10 hours.After ball milling terminates, with the nitrogen pressure squeeze and filter of 1.0Mpa, reclaim unnecessary super acids, recycle.In gained filter cake, carefully slowly inject deionized water, decompose residue super acids, repeatedly press filtration and washing repeatedly, 80 DEG C of dried in vacuo overnight, obtain dry powder.Graphite flake thickness major part in product is more than 10 nanometers, and thin graphene is little, and the technique of not adding inorganic nano-particle as seen causes the graphene film peeled away easily to return folded.
Comparative example 3 (do not add inorganic nano material, also do not use the conventional ball milling techniques comparative example of super acids)
Get 400 grams of dried expanded graphite powder, add agitated ball mill, add 20 grams of sodium laurylsulfonate dispersion agents simultaneously.Start the water that charge pump injects 12000ml simultaneously.Load the abrading-ball of 5 kilograms, Ball-milling Time 10 hours.After ball milling terminates, with the nitrogen pressure squeeze and filter of 1.0Mpa, obtain filter cake, 80 DEG C of dried in vacuo overnight, obtain dry powder.Graphite flake thickness major part in product is more than 10 nanometers, and thin graphene is little, and ball-milling technology traditional is as seen difficult to obtain thin graphene sheet.
Claims (7)
1. prevent back a production method for folded thin graphene, be that raw material obtains through ball milling with graphite, it is characterized in that: take super acids as ball-milling additive, and added inorganic nano material by ball milling thing.
2. production method of preventing back folded thin graphene according to claim 1, is characterized in that, described super acids is selected from oleum, chlorsulfonic acid, fluosulfonic acid, fluorine metaantimmonic acid a kind of.
3. production method of preventing back folded thin graphene according to claim 1, is characterized in that, described inorganic nano material is selected from carbon black, carbon nanotube, white carbon black a kind of.
4. production method of preventing back folded thin graphene according to claim 1, is characterized in that, described inorganic nano material and the mass ratio of graphite raw material between 0.05-5, between preferred 0.1-0.5.
5. production method of preventing back folded thin graphene according to claim 1, is characterized in that, described ball-grinding machine is selected from the one in agitating ball mill, sand mill, planetary ball mill, tumbling ball mill.
6. production method of preventing back folded thin graphene according to claim 1, is characterized in that, described graphite raw material is the one in crystalline graphite powder, expansible black lead powder, expanded graphite powder, cracking Graphite Powder 99.
7. production method of preventing back folded thin graphene according to claim 1, is characterized in that, carries out in accordance with the following steps:
(1) getting dried Graphite Powder 99 joins in ball mill, injects ball mill super acids, adds inorganic nano material in ball mill;
(2) ball mill is started, ball milling 1-48 hour;
(3) what obtain step (2) obtains filter cake, filter cake washing, drying after filtration containing thin graphene mixture, obtained finished product.
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| CN105329887A (en) * | 2015-12-08 | 2016-02-17 | 成都新柯力化工科技有限公司 | Method for preparing graphene in screw extruder through crystal form inducing |
| CN105609323A (en) * | 2016-03-17 | 2016-05-25 | 北京理工大学 | Porous nanocarbon slice |
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| CN105609323A (en) * | 2016-03-17 | 2016-05-25 | 北京理工大学 | Porous nanocarbon slice |
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