CN104058399A - Direct preparation method of high-purity high-quality graphene - Google Patents
Direct preparation method of high-purity high-quality graphene Download PDFInfo
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Abstract
The invention discloses a direct preparation method of high-purity high-quality graphene, and belongs to the technical field of chemical synthesis. The method comprises the following steps: carrying out a metal coupling reaction on alkali metals or alkaline earth metals and multi-halogenated hydrocarbon which are taken as raw materials in a multi-halogenated hydrocarbon body or an benign solvent under an inert environment so as to directly prepare graphene; reacting the graphene with the rest of active alkali metals or alkaline earth metals by utilizing an alcohol, water or an acid so as to prepare the high-quality graphene; washing the high-quality graphene with an organic solvent and carrying out acid washing, water washing, filtering, drying and the like on the high-quality graphene so as to obtain the high-purity graphene. The method has the advantages of simple equipment, low cost, less byproduct, high yield, high graphene purity and the like, and is easy to prepare. The prepared graphene can serve as chemical reaction materials and conductive materials for preparing catalyst carriers and battery electrode materials, and has wide application prospects in physics, microelectronics and the like.
Description
Technical field
The present invention relates to graphene preparation method, belong to Graphene chemosynthesis technical field.
Background technology
Graphene (Graphene) is a kind of novel material of the individual layer sheet structure being made up of carbon atom.Be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Graphene be at present the thinnest be in the world the hardest nano material also, it is almost completely transparent, only absorbs 2.3% light; Thermal conductivity is up to 5300 W/mK, and higher than carbon nanotube and diamond, under normal temperature, its electronic mobility exceedes 15000 cm2/Vs, again than CNT (carbon nano-tube) or silicon wafer height, and resistivity only approximately 10
-6Ω cm, lower than copper or silver, be the material of world resistivity minimum.Because its resistivity is extremely low, the speed of electronic migration is exceedingly fast, and is therefore expected to can be used to thinner, conduction speed electronic component of new generation or the transistor faster of development.Because Graphene is in fact a kind of transparent, good conductor, be also applicable to for manufacturing transparent touch screen, tabula rasa or even solar cell.Graphene (Graphene) is a kind of new carbon of broad research in recent years.
The range of application of Graphene is wide.Ultra-thin according to Graphene, the characteristic of intensity super large, Graphene can be widely used in each field, such as ultralight flak jackets, ultra-thin and ultra-light type aircraft material etc.According to its excellent electroconductibility, make it also there is huge application potential at microelectronic.Graphene likely can become the substitute of silicon, manufactures superminiature transistor, is used for producing following supercomputer, and the electronic mobility that carbon is higher can make following computer obtain higher speed.Grapheme material or a kind of good properties-correcting agent in addition, at new energy field as aspect ultracapacitor, lithium ion battery, due to its highly conc, high-specific surface area, applicable to as electrode materials auxiliary agent.
Graphene is the material of intensity maximum in the world up to now, if make with Graphene the film (thickness approximately 1,000,000 nanometers) that thickness is equivalent to bread and cheese plastic packaging bag thickness according to measuring and calculating, it can bear the pressure of about two tons of heavy articles so, and be unlikely to fracture; Second: Graphene is electroconductibility best material in the world.
The range of application of Graphene is wide.Ultra-thin according to Graphene, the characteristic of intensity super large, Graphene can be widely used in each field, such as ultralight flak jackets, ultra-thin and ultra-light type aircraft material etc.According to its excellent electroconductibility, make it also there is huge application potential at microelectronic.Graphene likely can become the substitute of silicon, manufactures superminiature transistor, is used for producing following supercomputer, and the electronic mobility that carbon is higher can make following computer obtain higher speed.Grapheme material or a kind of good properties-correcting agent in addition, at new energy field as aspect ultracapacitor, lithium ion battery, due to its highly conc, high-specific surface area, applicable to as electrode materials auxiliary agent.
The research boom of Graphene has also attracted the interest of domestic and international material preparation research, and what the preparation method of grapheme material had reported has: mechanically peel method, chemical oxidization method, crystal epitaxy method, chemical Vapor deposition process, organic synthesis method and carbon nanotube stripping method etc.
Micromechanics stripping method
2004, Geim etc. used micromechanics stripping method first, successfully peeled off and observe single-layer graphene from high directional heat cracking graphite.Geim study group utilizes this method successfully to prepare accurate two-dimentional Graphene and observed its pattern, has disclosed the reason that Graphene two dimensional crystal structure exists.Micromechanics stripping method can be prepared high-quality graphene, but has the low and high deficiency of cost of productive rate, does not meet industrialization and large-scale production requirement, can only serve as laboratory preparation on a small scale.
Chemical Vapor deposition process
Chemical Vapor deposition process (Chemical Vapor Deposition, CVD) is prepared aspect the problem of Graphene and has been had new breakthrough (preparing high-quality graphene with reference to chemical Vapor deposition process) in mass-producing first.CVD method refers to that reactive material issues biochemical reaction in gaseous state condition, generate the solid matrix surface that solid matter is deposited on heating, and then making the Technology of solid material, the Chen of the Hong of the Kong of Massachusetts Institute of Technology etc., Korea S Cheng Jun shop university etc. and Purdue University etc. is utilizing CVD legal system for Graphene.What they used is the simple and easy cvd furnace of a kind of tubulose taking nickel as substrate, passes into carbonaceous gas, as: hydrocarbon polymer, the surface that it at high temperature resolves into carbon atom and be deposited on nickel, form Graphene, by slight chemical etching, make graphene film separate and obtain graphene film with nickel sheet.This film specific conductivity in the time that transmittance is 80% can reach 1.1 × 10
6s/m, becomes the potential substitute of transparent conductive film.Can prepare the large-area Graphene of high quality by CVD method, but the expensive of desirable substrate material monocrystalline nickel, and this may be the important factor that affects Graphene suitability for industrialized production.CVD method can meet the requirement that high-quality graphene is prepared in mass-producing, but cost is higher, complex process.
Oxidation reduction process
Oxidation-reduction method preparation cost is cheap and easily realize, and becomes the best approach of preparing Graphene, and can prepare stable graphene suspension, has solved Graphene and has been difficult for the problem of disperseing.Oxidation-reduction method refers to natural graphite and strong acid and strong oxidizing property substance reaction generation graphite oxide (GO), be prepared into graphene oxide (mono-layer graphite oxide) through ultrasonic dispersion, add reductive agent to remove the oxy radical on graphite oxide surface, as carboxyl, epoxy group(ing) and hydroxyl, obtain Graphene.After oxidation-reduction method is suggested, become with its simple technique the easiest method that Graphene is prepared in laboratory, obtain vast Graphene investigator's favor.The discoveries such as Ruoff are by adding chemical substance for example dimethylhydrazine, Resorcinol, sodium borohydride (NaBH
4) and liquid hydrazine etc. remove the oxy radical of graphene oxide, just can obtain Graphene.Oxidation-reduction method can be prepared stable graphene suspension, has solved Graphene and has been difficult to be dispersed in the problem in solvent.The shortcoming of oxidation-reduction method is that preparation in macroscopic quantity easily brings the Graphene of waste liquor contamination and preparation to have certain defect, for example, the textural defect of the topological defect such as five-ring, seven-membered ring or existence-OH group, these will cause Graphene part electrical property loss of energy, and the application of Graphene is restricted.
Solvent stripping method
It is that a small amount of graphite is scattered in solvent that solvent is peeled off ratio juris, forms the dispersion liquid of lower concentration, utilizes hyperacoustic effect to destroy the Van der Waals force of graphite layers, and now solvent can insert graphite layers, peels off layer by layer, prepares Graphene.This method can not destroyed the structure of Graphene as oxidation-reduction method, can prepare high-quality Graphene.The productive rate of Graphene the highest (being approximately 8%) in nitrogen methyl-2-pyrrolidone, specific conductivity is 6500S/m.Research finds that high directional heat cracking graphite, thermal expansion graphite and crystallite synthetic graphite are suitable for solvent stripping method and prepare Graphene.Solvent stripping method can be prepared high-quality Graphene, and the process that whole liquid phase is peeled off is not introduced any defect on the surface of Graphene, for its application in the field such as microtronics, multifunctional composite provides wide application prospect.Shortcoming is that productive rate is very low.
Solvent-thermal method
Solvent-thermal method refers in special closed reactor (autoclave), adopt organic solvent as reaction medium, by reaction system being heated to critical temperature (or approaching critical temperature), in reaction system, self produce high pressure and carry out a kind of effective ways prepared by material.Solvent-thermal method has solved the problem that Graphene is prepared in mass-producing, has also brought specific conductivity very low negative impact simultaneously.For solving the deficiency brought thus, investigator combines solvent-thermal method and oxidation reduction process to have prepared high-quality Graphene.The graphene film resistance that under the discovery solvent thermal conditions such as Dai prepared by redox graphene is less than under conventional conditions prepares Graphene.Solvent-thermal method is more and more subject to scientist's concern because of the feature that can prepare high-quality graphene under high-temperature and high-pressure enclosing system.
Other method
The preparation method of Graphene also has high temperature reduction, photoreduction, epitaxial crystal growth method, microwave method, arc process, electrochemical process etc.At present, the production method of Graphene mainly contains mechanically peel method and thermal expansion graphite method.Wherein, mechanically peel method is that expensive high orientation pyrolytic graphite adhesive plaster is repeatedly bondd and peeled off, and finally transfers on substrate material surface.This method efficiency is low, output is little, cost is high, can only be limited to Laboratory Production.And thermal expansion graphite method step complexity, and large to the broken ring of graphene-structured.Polyhalohydrocarbon is prepared high-quality graphene in conjunction with oxidation reduction process method through active metal linked reaction, the method abundant raw material, environmental protection, and the novel method that can accomplish scale production are proposed herein on above the whole bag of tricks basis.
Summary of the invention
The object of the invention is to overcome problems of the prior art, provide a kind of method simple, technique environmental protection, with low cost, the method for can mass-producing preparing high-quality graphene.
The direct preparation method who the invention discloses a kind of high purity high-quality graphene, belongs to chemosynthesis technical field.The inventive method is taking basic metal or alkaline-earth metal and polyhalohydrocarbon as raw material, and by carrying out metal linked reaction in the polyhalohydrocarbon body under inert environments or optimum solvent, the mol ratio of metal and polyhalohydrocarbon is preferably between 0.5-30; React 0.1-72 hour under 0-300 ° of C after, make Graphene crude product, then utilize water, alcohol or acid to remove residue basic metal or alkaline-earth metal, prepare high-quality graphene, then make high purity high-quality graphene through organic solvent washing, pickling, washing, filtration, after dry.It is simple that the inventive method has method, and processing ease is with low cost, the advantages such as by product is few, high yield and high purity, Graphene of the present invention is as chemical reaction raw material, electro-conductive material preparation, support of the catalyst, battery electrode material, physics, microtronics aspect has wide application prospect.
of the present inventiona direct preparation method for high purity high-quality graphene, is characterised in that taking active basic metal or alkaline-earth metal and polyhalohydrocarbon as raw material, by the metal linked reaction direct preparation of high-purity degree high-quality graphene of halohydrocarbon, comprises the following steps:
(1) under under protection of inert gas, active basic metal or alkaline-earth metal are dispersed in polyhalohydrocarbon body or its optimum solvent and carry out linked reaction, or polyhalohydrocarbon body or its solution are dripped or added in active basic metal or alkaline-earth metal reaction system, in encloses container under 0-300 ° of C, carry out, after linked reaction 0.1-72 hour, making the suspension of Graphene crude product;
(2) in above-mentioned suspension, add alcohol, water or acid to react and make high-quality graphene with the active basic metal of residue or alkaline-earth metal;
(3) after this mixture is filtered, then it is dry afterwards to carry out repeatedly organic solvent washing, pickling, washing, filtration, removes solvent and the by product of Graphene crude product in aaerosol solution, makes high purity graphite alkene.
Preparation method as claimed in claim 1, it is characterized in that, described polyhalohydrocarbon is many halogenated aliphatic hydrocarbons, many halogenated aromatics, many halos hydrocarbon with condensed rings or its mixture, its feature structure formula is as shown in Figure 1 in structure, X group is F, Cl, Br, I atom, three vinyl halides bases or phenyl-pentahalide base, can be halogen atom of the same race or not of the same race or group, as: tetrabromo (fluorine, chlorine or iodine) ethene, hexabromo (fluorine, chlorine or iodine) generation-1,3-butadiene; Hexabromo (fluorine, chlorine or iodine) benzene, trichlorine tribromo (fluorine or iodine) benzene; Tetrabromo (fluorine, chlorine or iodine) change carbon, perbromo-(fluorine, chlorine or iodine) for alkane, perchloro-(fluorine, bromine, iodine) Dai Juyi (third, fourth or penta) alkene, perchloro-(fluorine, bromine, iodine) for polystyrene, poly-tetrachloro (fluorine, bromine, iodine) ethene, poly-perchloro-(fluorine, bromine, iodine) generation third (fourth, penta or benzene second) alkene; Eight chlorine (fluorine, bromine or iodine) naphthalene, tetrachloro tetrabromo (fluorine or iodine) naphthalene; Ten chlorine (fluorine, bromine or iodine) anthracenes (phenanthrene), hexabromo (iodine) tetrachloroanthracene (phenanthrene), chlordene tetrabromo anthracene (phenanthrene); As ten chlorine (fluorine, bromine, iodine) pyrene, hexabromo tetrachloro pyrene, tetrabromo chlordene pyrene; Perchloro-(fluorine, bromine, iodine) for biphenyl, perchloro-(bromine, iodine) for terphenyl, many chlorine (bromine, iodine) for benzanthrene (pyrene) etc., most preferably be tetrabromo (chlorine) ethene, tetrabromo (chlorine) is changed carbon, hexabromo (chlorine or fluorine) benzene, eight bromines (chlorine or fluorine) naphthalene, ten bromines (chlorine or fluorine) anthracenes (phenanthrene), ten bromines (chlorine or fluorine) pyrene, perchloro-(bromine) for one or more mixtures in biphenyl, poly-tetrachloro (bromine or fluorine) ethene.
Preparation method as claimed in claim 1, it is characterized in that, described basic metal or alkaline-earth metal are selected from one or more the combination in active metal lithium, sodium, potassium, magnesium, calcium, strontium, barium, lanthanum, most preferably are the one or more combination in lithium, sodium, potassium, magnesium.
Preparation method as claimed in claim 1, it is characterized in that, described polyhalohydrocarbon solvent is selected from the solvent not reacting with raw material basic metal or alkaline-earth metal and polyhalohydrocarbon, as C5-C20 alkane, C1-C16 ethers (simple ether or mixed ether), C0-C5 alky-substituted aromatic hydro carbons or acetals solvent etc., specifically, it can be paraffin oil, (methyl, ethyl) tetrahydrofuran (THF), dioxane, second (third, fourth, penta, oneself) ether, first and second (third, fourth, penta, oneself) ether, second the third (fourth, penta, oneself) ether, the third (fourth, penta, oneself) ether, (three contractings, two contractings, one contracting) second (third, fourth) glycol diformazan (second, third, fourth, benzene) ether, benzene first (second, third, fourth) ether, phenyl ether, diformazan (second, third, fourth) phenylate, benzylic ether, glyceryl ether, eicosane, benzene, first (second, third, fourth) benzene, diformazan (second, third, fourth) benzene, front three (second, third, fourth) benzene, biphenyl, the mixture of one or more in dimethyl diphenyl.
Preparation method as claimed in claim 1, is characterized in that, the mol ratio between described basic metal or alkaline-earth metal and polyhalohydrocarbon, in the scope of 0.1-100, most preferably is 0.5-30 scope.
Preparation method as claimed in claim 1, it is characterized in that, described polyhalohydrocarbon body or its solution and the direct hybrid reaction in active metal or drip or add polyhalohydrocarbon body or its solution in the reaction solution of active metal along with what react also can add in polyhalohydrocarbon body or solution or linked reaction is carried out in supplementary active metal.
Preparation method as claimed in claim 1, alcohol, water or the acid that it is characterized in that reduction used or elimination however, residual base metal or alkaline-earth metal is that one or more compositions that are selected from methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, ethylene glycol, propylene glycol, glycerine, water, hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, formic acid, acetic acid react and make high-quality graphene with residue basic metal or alkaline-earth metal.
Preparation method as claimed in claim 1, it is characterized in that refiltering and being dried after organic solvent washing used, pickling, washing, solvent for use can be one or more the reaction solvent of washing composition eccysis remnants in sherwood oil, acetone, ether, ethanol, methyl alcohol, DMAc or DMF, washing acid is one or more combination solutions in hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, formic acid, acetic acid, by the salt of deionized water eccysis remnants, dry and preserve, make high purity graphite alkene.
Preparation method as claimed in claim 1, is characterized in that, at the temperature of described reaction in the scope of 0 ° of C to 300 ° of C, carries out, and most preferably is 30 ° of C-180 ° of C; If but during with sodium Metal 99.5 coupling zellon, Perchlorobenzene, bromobenzene or ethylene tetrabromide, temperature of reaction is defined as 120 ° below C, does not comprise the 120-400 ° of sodium Metal 99.5 linked reaction within the scope of C.
Preparation method as claimed in claim 1, it is characterized in that described reaction pressure scope is 0.1-5Mpa, can under normal pressure or compressive reaction condition, carry out, corresponding with the activity of reaction raw materials metal and polyhalohydrocarbon, but in the time that polyhalohydrocarbon is tetracol phenixin, carbon tetrabromide, Perchlorobenzene, be defined as synthesis under normal pressure.
The preparation method of Graphene of the present invention has the following advantages:
1. this reaction can be carried out under atmospheric low-temperature condition, and equipment is simple, processing ease, and processing step is few, is easy to carry out large-scale industrial production;
2. raw materials cost is cheap, and by product is few, the environmental protection synthetic method of the recycled atom economy type of solvent;
3. reaction yield is higher, even can reach 100%, and quality product is high, and electroconductibility is strong;
Based on above-mentioned advantage, Graphene of the present invention is as chemical reaction raw material, and prepared by conducting film, support of the catalyst, battery electrode material, and physics, microtronics aspect has wide application prospect.
figure of description explanation:
The polyhalohydrocarbon modular construction of Fig. 1 synthesizing graphite alkene;
The electron scanning micrograph of Fig. 2 Graphene;
The EDS gamma-spectrometric data of Fig. 3 Graphene;
The XRD spectrum data of Fig. 4 Graphene;
Fig. 5 Graphene BET specific surface test (ASAP2010).
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.
In following embodiment, method therefor is ordinary method if no special instructions, need pay special attention to detonation and explosion hazard but repeat the present embodiment as needed, and common postgraduate or technical staff please don't test without authorization, needs the careful enforcement test of synthetic veteran researchist.
The concrete grammar that the present embodiment is prepared Graphene comprises the following steps.
Synthesizing of embodiment 1, Graphene
In clean dry reactor, add 100mL toluene, sodium Metal 99.5 3.0g; 6.0 grams of hexabromobenzene; under argon shield condition, back flow reaction, after 8 hours, stops heating, and cool to room temperature obtains black graphene suspension; then add 30 milliliters of dehydrated alcohols; after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then clean 3 times, washing 3 times, 10% salt pickling 2 times with acetone; water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 2, Graphene
In clean dry reactor, add 100mL toluene, potassium metal 2.0g; 4.0 grams of Perchlorobenzenes; under nitrogen protection condition, back flow reaction, after 8 hours, stops heating, and cool to room temperature obtains black graphene suspension; then add 50 milliliters of dehydrated alcohols; after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then with acetone clean 3 times, washing 3 times, 10% phosphoric acid washes 2 times; water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 3, Graphene
In clean dry reactor, add 10mL dimethylbenzene, 50mL tetrahydrofuran (THF), sodium Metal 99.5 3.0g, 6.0 grams of hexabromobenzene, after back flow reaction 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 30 milliliters of anhydrous methanols, after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then with acetone clean 3 times, washing 3 times, 10% sulfuric acid washes 2 times, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 4, Graphene
In clean dry reactor, add 100mL phenyl ether, sodium Metal 99.5 3.0g, 5.0 grams of hexabromobenzene, after 8 hours, stop heating 110 ° of C reactions, cool to room temperature obtains black graphene suspension, then add 30 milliliters of dehydrated alcohols, after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then clean 3 times, washing 3 times, 10% salt pickling 2 times with acetone, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 5, Graphene
In clean dry reactor, add 100mL tetrahydrofuran (THF), potassium metal 3.0g, 4.0 grams of hexabromobenzene, after back flow reaction 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 25 ml methanol, after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then clean 3 times, washing 3 times, 10% salt pickling 2 times with acetone, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 6, Graphene
In clean dry reactor, add 10mL zellon, toluene 50mL, potassium metal 3.0g, back flow reaction is after 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then adds 40 milliliters of anhydrous propyl alcohol, and stirring reaction is after 2 hours, the thick product of Graphene that decompress filter obtains, clean 3 times, washing 3 times, 10% salt pickling 2 times with acetone again, then water repeatedly washs to neutrality, vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 7, Graphene
In clean dry reactor, add 10mL ethylene tetrabromide, toluene 50mL, sodium Metal 99.5 3.0g, back flow reaction is after 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then adds 60 milliliters of ethanol, and stirring reaction is after 2 hours, decompress filter obtains the thick product of Graphene, clean 3 times, washing 3 times, 10% salt pickling 2 times with acetone again, then water repeatedly washs to neutrality, vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 8, Graphene
In clean dry reactor, add 10mL ethylene tetrabromide, potassium metal 3.0g, back flow reaction is after 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then adds 30 milliliters of ethanol, and stirring reaction is after 2 hours, decompress filter obtains the thick product of Graphene, clean 3 times, washing 3 times, 10% salt pickling 2 times with acetone again, then water repeatedly washs to neutrality, vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 9, Graphene
In clean dry reactor, add 100mL tetrahydrofuran (THF), potassium metal 3.0g, ten 4.0 grams of bromine anthracenes, after back flow reaction 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 50 milliliters of ethanol, after stirring reaction 2 hours, decompress filter obtains the thick product of Graphene, then cleans 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 10, Graphene
In clean dry reactor, add 100mL dimethylbenzene, potassium metal 5.0g, 4.0 grams of 2.0g ethylene tetrabromide, 2.0g hexabromobenzene, ten bromine pyrenes, after back flow reaction 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 30 milliliters of anhydrous methanols, after stirring reaction 2 hours, decompress filter obtains the thick product of Graphene, then cleans 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 11, Graphene
In clean dry reactor, add 100mL tirethylene glycol dme, metallic lithium 6.0g, 4.0 grams of 1.0g politefs, 3.0g hexabromobenzene, ten bromine anthracenes, after back flow reaction 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 30 milliliters of dehydrated alcohols, after stirring reaction 2 hours, decompress filter obtains the thick product of Graphene, then cleans 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 12, Graphene
In clean dry reactor, add 100mL trimethylbenzene, sodium Metal 99.5 6.0g, 5.0 grams of hexabromobenzene, 2.0 grams of Perchlorobenzenes, ten 4.0 grams of bromine anthracenes, after back flow reaction 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 30 milliliters of dehydrated alcohols, after stirring reaction 2 hours, decompress filter obtains the thick product of Graphene, then cleans 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 13, Graphene
In clean dry reactor, add 100mL phenyl ether, metallic lithium 3.0g, 5.0 grams of hexabromobenzene, luxuriant and rich with fragrance 4.0 grams of ten bromines, after back flow reaction 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 30 milliliters of dehydrated alcohols, after stirring reaction 2 hours, decompress filter obtains the thick product of Graphene, then cleans 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 14, Graphene
In clean dry reactor, add 100mL tetrahydrofuran (THF), potassium metal 7.0g, 5.0 grams of hexabromobenzene, 4.0 grams of ten bromine pyrenes, after back flow reaction 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 30 milliliters of dehydrated alcohols, after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then clean 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 15, Graphene
In clean dry reactor, add 100mL dioxane, MAGNESIUM METAL 6.0g, 6.0 grams of hexabromobenzene, 4.0 grams of ten bromine anthracenes, ten 2.0 grams of bromine pyrenes, back flow reaction, after 10 hours, stop heating, and cool to room temperature obtains black graphene suspension, then add 30 milliliters of dehydrated alcohols, after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then clean 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 16, Graphene
In clean dry reactor, add 100mL tirethylene glycol dme, ethylene tetrabromide 4.0g, potassium metal 6.0g, 6.0 grams of hexabromobenzene, 4.0 grams of ten bromine anthracenes, ten 2.0 grams of bromine pyrenes, back flow reaction are after 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then adds 30 milliliters of dehydrated alcohols, and stirring reaction is after 2 hours, the thick product of Graphene that decompress filter obtains, clean 3 times, washing 3 times, 10% salt pickling 2 times with ether again, then water repeatedly washs to neutrality, vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 17, Graphene
In clean dry reactor, add 3.0 grams of 100mL triethylene Glycol dme, ethylene tetrabromide, potassium metal 6.0g, 6.0 grams of hexabromobenzene, 4.0 grams of ten bromine pyrenes, ten 2.0 grams of bromine pyrenes, back flow reaction are after 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 30 milliliters of dehydrated alcohols, after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then clean 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 18, Graphene
In clean dry reactor, add 100mL phenyl ether, zellon 2.0g, potassium metal 6.0g, 6.0 grams of hexaiodo benzene, 3.0 grams of ten bromine anthracenes, ten 1.0 grams of bromine pyrenes, back flow reaction are after 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 30 milliliters of dehydrated alcohols, after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then clean 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 19, Graphene
In clean dry reactor, add 100mL phenyl ether, zellon 2.0g, potassium metal 6.0g, 6.0 grams of hexabromobenzene, 3.0 grams of ten bromine anthracenes, 1.0 grams of decabromodiphenyls, back flow reaction are after 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then add 30 milliliters of dehydrated alcohols, after stirring reaction 2 hours, the thick product of Graphene that decompress filter obtains, then clean 3 times, washing 3 times, 10% salt pickling 2 times with ether, water repeatedly washs to neutrality again, and vacuum-drying obtains Graphene sterling.
Synthesizing of embodiment 20, Graphene
In clean dry reactor, add 100mL phenyl ether, potassium metal 8.0g, tetracol phenixin 2.0g, zellon 2.0g, 6.0 grams of hexaiodo benzene, 3.0 grams of ten bromine anthracenes, 1.0 grams of perbromo terphenyls, back flow reaction are after 10 hours, stop heating, cool to room temperature obtains black graphene suspension, then adds 30 milliliters of dehydrated alcohols, and stirring reaction is after 2 hours, the thick product of Graphene that decompress filter obtains, clean 3 times, washing 3 times, 10% salt pickling 2 times with ether again, then water repeatedly washs to neutrality, vacuum-drying obtains Graphene sterling.
The prepared Graphene crystal grain of embodiment 1 is detected by following method.
1. Graphene crystal grain scanning electronic microscope (SEM) and X-ray energy spectrometer characterize and detect
Graphene crystal grain prepared by embodiment 1 carries out scanning electronic microscope (SEM) and characterizes detection, method is: Graphene black powder takes a morsel, ultrasonic dispersion in dehydrated alcohol, then getting 1-2 drips to and in sample table, dries metal spraying, then the prepared Graphene crystalline-granular texture of sem observation, as shown in Figure 2, its EDAX data have been tested simultaneously, as shown in Figure 3: in the electron scanning micrograph of the Graphene crystal grain of Fig. 2, can find out, the Graphene crystalline-granular texture of preparing by the inventive method, size can reach below micron order; Fig. 3 is its gamma-spectrometric data, can find out that this Graphene crystal grain is mainly made up of Elements C and residual halogen, and carbon content is 90.26%, and residual halogen atom content is 3.97%.
2. Graphene crystal grain XRD characterizes and detects
Graphene prepared by embodiment 1 carries out Graphene crystal grain XRD and characterizes detection, as shown in Figure 4, can find out the charateristic avsorption band of the Graphene of 2 θ between 15-35 from the XRD figure spectrum of Graphene crystal grain.
The test of 3.BET specific surface
Bian N
2as adsorbed gas, Graphene crystal grain prepared by embodiment 1 carries out BET specific surface test (ASAP2010).The BET specific surface of the Graphene crystal grain making as shown in Figure 5, is 1.37 m
2/ g, total pore volume is 0.013 mL/g, mean pore size is 32.9 nm.
Claims (10)
1. the direct preparation method of a high purity high-quality graphene, this preparation method characteristic is taking active basic metal or alkaline-earth metal and polyhalohydrocarbon as raw material, by the metal linked reaction direct preparation of high-purity degree high-quality graphene of halohydrocarbon, comprise the following steps:
(1) under under protection of inert gas, active basic metal or alkaline-earth metal are dispersed in polyhalohydrocarbon body or its optimum solvent and carry out linked reaction, or polyhalohydrocarbon body or its solution are dripped or added in active basic metal or alkaline-earth metal reaction system, in encloses container under 0-300 ° of C, carry out, after linked reaction 0.1-72 hour, making the suspension of Graphene crude product;
(2) in above-mentioned suspension, add alcohol, water or acid to react and make high-quality graphene with the active basic metal of residue or alkaline-earth metal;
(3) after this mixture is filtered, then it is dry afterwards to carry out repeatedly organic solvent washing, pickling, washing, filtration, removes solvent and the by product of Graphene crude product in aaerosol solution, makes high purity graphite alkene.
2. preparation method as claimed in claim 1, it is characterized in that, described polyhalohydrocarbon is many halogenated aliphatic hydrocarbons, many halogenated aromatics, many halos hydrocarbon with condensed rings or its mixture, its feature structure formula is as shown in Figure 1 in structure, X group is F, Cl, Br, I atom, three vinyl halides bases or phenyl-pentahalide base, can be halogen atom of the same race or not of the same race or group, as: tetrabromo (fluorine, chlorine or iodine) ethene, hexabromo (fluorine, chlorine or iodine) generation-1,3-butadiene; Hexabromo (fluorine, chlorine or iodine) benzene, trichlorine tribromo (fluorine or iodine) benzene; Tetrabromo (fluorine, chlorine or iodine) change carbon, perbromo-(fluorine, chlorine or iodine) for alkane, perchloro-(fluorine, bromine, iodine) Dai Juyi (third, fourth or penta) alkene, perchloro-(fluorine, bromine, iodine) for polystyrene, poly-tetrachloro (fluorine, bromine, iodine) ethene, poly-perchloro-(fluorine, bromine, iodine) generation third (fourth, penta or benzene second) alkene; Eight chlorine (fluorine, bromine or iodine) naphthalene, tetrachloro tetrabromo (fluorine or iodine) naphthalene; Ten chlorine (fluorine, bromine or iodine) anthracenes (phenanthrene), hexabromo (iodine) tetrachloroanthracene (phenanthrene), chlordene tetrabromo anthracene (phenanthrene); As ten chlorine (fluorine, bromine, iodine) pyrene, hexabromo tetrachloro pyrene, tetrabromo chlordene pyrene; Perchloro-(fluorine, bromine, iodine) for biphenyl, perchloro-(bromine, iodine) for terphenyl, many chlorine (bromine, iodine) for benzanthrene (pyrene) etc., most preferably be tetrabromo (chlorine) ethene, tetrabromo (chlorine) is changed carbon, hexabromo (chlorine or fluorine) benzene, eight bromines (chlorine or fluorine) naphthalene, ten bromines (chlorine or fluorine) anthracenes (phenanthrene), ten bromines (chlorine or fluorine) pyrene, perchloro-(bromine) for one or more mixtures in biphenyl, poly-tetrachloro (bromine or fluorine) ethene.
3. preparation method as claimed in claim 1, it is characterized in that, described basic metal or alkaline-earth metal are selected from one or more the combination in active metal lithium, sodium, potassium, magnesium, calcium, strontium, barium, lanthanum, most preferably are the one or more combination in lithium, sodium, potassium, magnesium.
4. preparation method as claimed in claim 1, it is characterized in that, described polyhalohydrocarbon solvent is selected from the solvent not reacting with raw material basic metal or alkaline-earth metal and polyhalohydrocarbon, as C5-C20 alkane, C1-C16 ethers (simple ether or mixed ether), C0-C5 alky-substituted aromatic hydro carbons or acetals solvent etc., specifically, it can be paraffin oil, (methyl, ethyl) tetrahydrofuran (THF), dioxane, second (third, fourth, penta, oneself) ether, first and second (third, fourth, penta, oneself) ether, second the third (fourth, penta, oneself) ether, the third (fourth, penta, oneself) ether, (three contractings, two contractings, one contracting) second (third, fourth) glycol diformazan (second, third, fourth, benzene) ether, benzene first (second, third, fourth) ether, phenyl ether, diformazan (second, third, fourth) phenylate, benzylic ether, glyceryl ether, eicosane, benzene, first (second, third, fourth) benzene, diformazan (second, third, fourth) benzene, front three (second, third, fourth) benzene, biphenyl, the mixture of one or more in dimethyl diphenyl.
5. preparation method as claimed in claim 1, is characterized in that, the mol ratio between described basic metal or alkaline-earth metal and polyhalohydrocarbon, in the scope of 0.1-100, most preferably is 0.5-30 scope.
6. preparation method as claimed in claim 1, it is characterized in that, described polyhalohydrocarbon body or its solution and the direct hybrid reaction in active metal or drip or add polyhalohydrocarbon body or its solution in the reaction solution of active metal along with what react also can add in polyhalohydrocarbon body or solution or linked reaction is carried out in supplementary active metal.
7. preparation method as claimed in claim 1, alcohol, water or the acid that it is characterized in that reduction used or elimination however, residual base metal or alkaline-earth metal is that one or more compositions that are selected from methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, ethylene glycol, propylene glycol, glycerine, water, hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, formic acid, acetic acid react and make high-quality graphene with residue basic metal or alkaline-earth metal.
8. preparation method as claimed in claim 1, it is characterized in that refiltering and being dried after organic solvent washing used, pickling, washing, solvent for use can be one or more the reaction solvent of washing composition eccysis remnants in sherwood oil, acetone, ether, ethanol, methyl alcohol, DMAc or DMF, washing acid is one or more combination solutions in hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, formic acid, acetic acid, by the salt of deionized water eccysis remnants, dry and preserve, make high purity graphite alkene.
9. preparation method as claimed in claim 1, is characterized in that, at the temperature of described reaction in the scope of 0 ° of C to 300 ° of C, carries out, and most preferably is 30 ° of C-180 ° of C; If but during with sodium Metal 99.5 coupling zellon, Perchlorobenzene, bromobenzene or ethylene tetrabromide, temperature of reaction is defined as 120 ° below C, does not comprise the 120-400 ° of sodium Metal 99.5 linked reaction within the scope of C.
10. preparation method as claimed in claim 1, it is characterized in that described reaction pressure scope is 0.1-5Mpa, can under normal pressure or compressive reaction condition, carry out, corresponding with the activity of reaction raw materials metal and polyhalohydrocarbon, but in the time that polyhalohydrocarbon is tetracol phenixin, carbon tetrabromide, Perchlorobenzene, be defined as synthesis under normal pressure.
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