CN104386678B - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN104386678B CN104386678B CN201410635484.7A CN201410635484A CN104386678B CN 104386678 B CN104386678 B CN 104386678B CN 201410635484 A CN201410635484 A CN 201410635484A CN 104386678 B CN104386678 B CN 104386678B
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Abstract
The high efficiency preparation method that the invention discloses a kind of Graphene, belongs to field of nanometer technology. The method mainly comprises: lower than under room temperature condition, natural flake graphite raw material is mixed with sodium nitrate, the concentrated sulfuric acid and potassium permanganate, after ball-milling treatment, dilution, adds hydrogen peroxide reaction, neutralizes with NaOH, ultrasonic processing subsequently, obtains graphene oxide suspension; Taking hydrazine hydrate and thiourea dioxide as complex reducing agent, graphene oxide solution is reduced, make the Graphene of individual layer or several atomic layer level thickness. The present invention introduces mechanical milling process in graphite oxidation process, has improved oxidation, the charge stripping efficiency of graphite, has reduced the consumption of strong oxidizer; The very long process of successfully having avoided graphene oxide filtration, washing, has shortened manufacturing cycle; Adopt complex reducing agent, improved reduction efficiency, obtain the higher Graphene of reducing degree. Technique of the present invention is simple, and efficiency is high, with low cost, is easy to suitability for industrialized production.
Description
Technical field
The invention belongs to technical field of nano material, relate to the technology of preparing of grapheme material, be applicable to graphiteThe preparation in macroscopic quantity of alkene material.
Technical background
Graphene is the bi-dimensional cellular shape crystal by monolayer carbon atomic building. Because of its unique electricity, calorifics andThe performances such as mechanics, as lightweight, intensity is high, the large (2600m of specific area2/ g), high, the pliability of electrical conductivityGood, resistance to chemical attack is strong etc., and Graphene is at nano electron device, lithium ion battery, fuel cell, the sunThe fields such as energy battery, ultracapacitor, molecule sensor and hydrogen storage material have broad application prospects.
2004, people's reported first such as the scientist Novoselov of Univ Manchester UK employing microcomputerTool is peeled off the method for graphite and is prepared single crystal graphene film (Novoselov, K.S., etal.Science306,666(2004)), and find that this single crystal graphene film at room temperature can stable existence, there is metallicity. But,This graphene preparation method efficiency is extremely low, can only be applicable to basic research. 2006, the people such as NovoselovReport again under high temperature and ultra-high pressure condition, in the method for monocrystalline silicon carbide surface extending and growing graphene(Novoselov, K.S., etal.Science312,1191 (2006)). But this graphene preparation methodCost is high, and prepared Graphene is difficult for separating from substrate. At present, except above-mentioned 2 kinds of methods, send out againChemical vapour deposition technique (CVD method) and chemical stripping method are opened up. CVD method efficiency is lower, controllability is poor.Chemical stripping method is Hummers method (Hummers, W., the etal.J.Am.Chem.Soc. based on improvement mainly80,1339 (1958)), adopt the strong oxidizer such as the concentrated sulfuric acid and potassium permanganate to be oxidized graphite, to oxidationThe ultrasonic processing of graphite, after filtration, washing, obtain graphene oxide, then graphene oxide is reduced,After reduction more after filtration, washing obtain Graphene.
Chemical stripping method be generally acknowledge can macroscopic preparation of graphene the higher method of efficiency. But, chemistry strippingAlso there is shortcoming clearly from method: the one, adopt a large amount of strong oxidizers, cause the Graphene that makesStructural intergrity is seriously damaged, and exists defect more, thereby the electric property of the Graphene obtaining is remarkableWorsen especially electrical conductivity; The 2nd, for graphene oxide is separated from oxidant suspension, mustMust adopt dilution, filtration and washing methods, but the viscosity of graphene oxide is large, washs, filter very tiredDifficulty, whole process is very consuming time; The 3rd, graphene oxide reduction process is longer, and reduction is not thorough. TheseShortcoming has greatly affected the utilization and extention of this method.
Summary of the invention
In order to solve the shortcomings such as in chemical stripping method, oxidant consumption is large, consuming time, reduction is not thorough, the present inventionThe graphene preparation method that a kind of process is simple, productive rate is high is provided, and the method is to prepare in a large number the reason of GrapheneThink method.
In order to realize above-mentioned technical purpose, the present invention is achieved by the following technical programs:
(1) sodium nitrate, potassium permanganate and the concentrated sulfuric acid are placed in to ball grinder, mix, then add graphiteRaw material, dry ice and zirconium dioxide abrading-ball, ball milling 2～3h, rotating speed 250rpm, adds ice cube afterwards again,Ball milling 1～2h, obtains brown graphite suspension;
The mass concentration of the described concentrated sulfuric acid is 98%; Described graphite is 500 object natural flake graphites;The usage ratio of described graphite, sodium nitrate, potassium permanganate, the concentrated sulfuric acid and dry ice is 1g:0.3～0.6g:1.5～2G:10～20mL:30～60g; To be that deionized water is freezing form described ice cube, the ice cube adding and the concentrated sulfuric acidMass ratio be 1～2:1;
(2) graphite suspension deionized water step (1) being obtained is diluted to 3～10mg/mL, and toWherein add hydrogen peroxide, at 90～95 DEG C of stirred in water bath reaction 1h, then regulate pH with sodium hydroxide solutionValue is to 7～8, and ultrasonic processing 1h;
Described hydrogen peroxide mass percent concentration is 30%; Potassium permanganate matter in this hydrogen peroxide and step (1)Amount is than being 0.5～1:1; Described supersonic frequency is 40kHz, and power is 240W;
(3) in the graphene oxide suspension obtaining to step (2), add NaOH and complex reducing agent,Heating, stirring, reaction 3h, obtains graphene suspension, after filtration, and washing, dry, finally obtain listThe Graphene of layer and several atomic layers;
Described complex reducing agent is made up of hydrazine hydrate and thiourea dioxide, mass ratio 1:0.5～1; This composite reductionGraphite raw material mass ratio in agent and step (1) is 1～2:1; The temperature of described reaction is 93～98 DEG C;The mass ratio of described NaOH and thiourea dioxide is 1:1.
Further, in step (1) before, by graphite raw material, sodium nitrate, potassium permanganate, the concentrated sulfuric acid withAnd ball grinder and the abundant cooling processing of abrading-ball, described abundant cooling referring to put into refrigerator, is cooled to 0 DEG C.
Further, the zirconium dioxide abrading-ball in described step (1) by large (diameter 14mm), in (straightFootpath 10mm), little (diameter 6mm) three kinds of size compositions, the ratio of quantity is about 1:3:7, abrading-ball and dressThe quality of material ratio entering is 2～5:1.
Compared with prior art, the present invention has following technique effect:
1. this preparation method combines the ball milling method of shelling with chemical peeling, the oxidation that has improved graphite withCharge stripping efficiency, thus the consumption of strong oxidizer reduced, during the oxidizing process of graphite is controlled at simultaneously, low temperatureIn scope, at utmost alleviate the destruction of oxidizing process to graphene-structured integrality;
This Optimization of preparation preparation process, avoided the washing of graphene oxide, the very long mistake of filtrationJourney, has shortened preparation process greatly;
3. this preparation method replaces single reducing agent with complex reducing agent, has improved the reduction effect of graphene oxideRate, the remnants that at utmost reduce on reduced graphene sheet contain oxygen functional group.
Brief description of the drawings
Fig. 1 is that (Fig. 1 a), (b) (Fig. 1 c) with embodiment 2 for Fig. 1 for the embodiment of the present invention 1 for natural flake graphiteX-ray diffraction (XRD) collection of illustrative plates of prepared Graphene sample.
Fig. 2 is the field emission scanning electron microscope (FESEM) of the prepared Graphene sample of the embodiment of the present invention 1Photo.
Fig. 3 is the field emission scanning electron microscope (FESEM) of the prepared Graphene sample of the embodiment of the present invention 2Photo.
Fig. 4 is that (Fig. 4 a) and embodiment 2 (b) prepared Graphene sample of Fig. 4 for the embodiment of the present invention 1Raman (Raman) spectrum.
Fig. 5 be the embodiment of the present invention 3 (Fig. 5 a) and embodiment 4 (the Graphene sample that Fig. 5 b) is preparedFourier's infrared spectrum.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
The first step, by 500 order natural flake graphites, sodium nitrate, potassium permanganate, the concentrated sulfuric acid, band transpiration holeBall grinder (polytetrafluoroethylene (PTFE) material) and abrading-ball (zirconium dioxide material) be cooled to 0 DEG C, by nitric acidSodium 0.6g, potassium permanganate 3g, concentrated sulfuric acid 20mL are placed in ball grinder and mix, add graphite 2g,Dry ice 60g and abrading-ball 350g, be placed in jacket, ball on planetary ball mill by the ball grinder after chargingMill 2h, rotating speed 250rpm afterwards, adds 45g ice cube in ball grinder, then ball milling 1h, mechanical milling processMiddle room temperature is controlled at 15～25 DEG C;
Second step adds 200mL deionized water in ball grinder, stirs, by graphite oxide suspensionFrom ball grinder, pour out, add the hydrogen peroxide of 9mL30%, at 90 DEG C of stirred in water bath reaction 1h, splash intoSodium hydroxide solution, regulates pH value to 8, ultrasonic processing 1h;
The 3rd step adds 0.5g NaOH in above-mentioned graphene oxide suspension, after stirring and dissolving, addsEnter 3mL mass concentration and be 50% hydrazine hydrate and 0.5g thiourea dioxide powder, stir, heating, 95DEG C reaction 3h, filter, washing, 80 DEG C of vacuum drying, obtain graphite rare.
The productive rate of this embodiment is up to 12.3%. With respect to conventional chemical stripping method, this embodiment has higherProductive rate. This may due to the shearing force effect of ball milling cause graphite layers slippage, peel off, promoted sulphurThe insertion reaction of acid molecule, graphite layers be apart from increasing, containing the formation of oxygen functional group, thereby improved chemical strippingFrom efficiency. (Fig. 1 a) contrasts, the XRD of the Graphene that this embodiment makes with the XRD spectrum of crystalline flake graphite(Fig. 1's spectrum b) (002) diffraction maximum moves to left to 24.5 °, and intensity is weak, broadening is serious. This explanation makesGraphene layer spacing, much larger than the interlamellar spacing of native graphite, also shows that graphene sheet layer is very thin, the crystal degree of orderLower. FESEM picture (Fig. 2) demonstration, the graphene film that this embodiment makes is the chiffon of transparent foldShape, shows the characteristic feature of monoatomic layer or several atomic layer level thickness Graphenes. The stone that this embodiment makes(Fig. 4 a) presents the characteristic peak of Graphene to the Raman spectrum of China ink alkene, and D peak is at 1348cm-1Near, GPeak is at 1582cm-1Near, the ratio I of D peak and the integrated intensity at G peakD/IGBe 0.98; Stronger D peak isOwing to removing containing oxygen functional group in reduction process, cause carbon bond on graphene sheet layer rupture and cause structural lackingFall into.
Embodiment 2
The first step, by 500 order natural flake graphites, sodium nitrate, potassium permanganate, the concentrated sulfuric acid, band transpiration holeBall grinder (polytetrafluoroethylene (PTFE) material) and abrading-ball (zirconium dioxide material) be chilled to 0 DEG C, by nitric acidSodium 1.1g, potassium permanganate 4g, concentrated sulfuric acid 40mL are placed in ball grinder and mix, add graphite 2g,Dry ice 95g and abrading-ball 350g, be placed in jacket, ball on planetary ball mill by the ball grinder after chargingMill 3h, rotating speed 250rpm afterwards, adds 92g ice cube in ball grinder, then ball milling 2h, mechanical milling processMiddle room temperature is controlled at 20～25 DEG C;
Second step adds 250mL deionized water in ball grinder, stirs, by graphite oxide suspensionFrom ball grinder, pour out, add the hydrogen peroxide of 10mL30%, at 90 DEG C of stirred in water bath reaction 1h, dripEnter sodium hydroxide solution, regulate pH value to 8, ultrasonic processing 1h;
Follow-up preparation process is identical with embodiment 1, and this embodiment productive rate is 12.8%. XRD with crystalline flake graphite(Fig. 1 a) compares spectrum, and (Fig. 1 is (002) diffraction peak c) for the XRD spectrum of the Graphene that this embodiment makesNear 25.0 °, intensity is weak, broadening is obvious. The graphene layer spacing that this explanation makes is much larger than natural stoneThe interlamellar spacing of China ink, also shows that graphene sheet layer is very thin, the crystal degree of order is lower. FESEM picture (Fig. 3)Show, the graphene film that this embodiment makes is the chiffon shape of transparent fold, shows monoatomic layer or severalThe characteristic feature of atomic layer level thickness Graphene. (Fig. 4 b) for the Raman spectrum of the Graphene that this embodiment makesPresent the characteristic peak of Graphene, D peak is at 1352cm-1Near, G peak is at 1586cm-1Near, D peak and GThe ratio I of the integrated intensity at peakD/IGBe 1.02; Stronger D peak is owing to removing containing oxygen functional group in reduction process,Cause carbon bond fracture on graphene sheet layer and cause structural defect.
Embodiment 3
The first step, by 500 order natural flake graphites, sodium nitrate, potassium permanganate, the concentrated sulfuric acid, band transpiration holeBall grinder (polytetrafluoroethylene (PTFE) material) and abrading-ball (zirconium dioxide material) be chilled to 0 DEG C, by nitric acidSodium 0.8g, potassium permanganate 3.5g, concentrated sulfuric acid 30mL are placed in ball grinder and mix, add graphite 2g,Dry ice 98g and abrading-ball 350g, be placed in jacket, ball on planetary ball mill by the ball grinder after chargingMill 2h, rotating speed 250rpm afterwards, adds 84g ice cube in ball grinder, then ball milling 1h, mechanical milling processMiddle room temperature is controlled at 20～25 DEG C;
Second step adds 200mL deionized water in ball grinder, stirs, by graphite oxide suspensionFrom ball grinder, pour out, add the hydrogen peroxide of 10mL30%, at 90 DEG C of stirred in water bath reaction 1h, dripEnter sodium hydroxide solution, regulate pH value to 8, ultrasonic processing 1h;
Follow-up preparation process is identical with embodiment 1, and the productive rate of this embodiment is 12.5%. Fig. 5 a is this enforcementThe infrared spectrum of the Graphene that example makes. At 3446cm-1The O-H that locates the corresponding adsorbed water of wider absworption peak stretchesContracting vibration, at 1721cm-1The stretching vibration of the corresponding carboxyl functional group C=O of faint absworption peak at place, andAt 1031cm-1Place's absworption peak is the epoxide group between corresponding graphene layer. At 1561cm-1And 1459cm-1The absworption peak at place is the skeletal vibration of corresponding graphene sheet layer and the stretching vibration of C-OH respectively.
Embodiment 4
Other operating procedures change to some extent with embodiment 3, the three steps: in above-mentioned graphene oxide suspension, addEnter 2g NaOH, after stirring and dissolving, adding 4mL mass concentration is 50% hydrazine hydrate and 2g dioxyChange thiocarbamide powder, stir, heat, at 95 DEG C of reaction 3h, filtration, washing, 80 DEG C of vacuum drying,Obtain 244mg graphite rare.
The Graphene productive rate of this embodiment is 12.2%. The productive rate of this embodiment is close with embodiment 1,2,3.(b) (Fig. 5 is a) basic identical with embodiment 3 for Fig. 5 for the infrared spectrum of the Graphene that this embodiment makes. AobviousSo, with the Graphene infrared spectrum of embodiment 3 (Fig. 5 a) compared with, the Graphene infrared spectrum of this embodiment(Fig. 5 is b) 1721,1459 and 1031cm-1The absworption peak at place disappears or significantly weakens. This shows, is somebody's turn to doCarboxyl, hydroxyl and epoxy radicals etc. in the Graphene that embodiment makes containing oxygen function can roll into a ball removal more thorough. ThisMay, due to the hydrazine hydrate of proper proportion and thiourea dioxide complex reducing agent, produce cooperative effect, removeEfficiency containing oxygen functional group is higher.
Claims (3)
1. a preparation method for Graphene, is characterized in that, comprises the following steps:
(1) sodium nitrate, potassium permanganate and the concentrated sulfuric acid are placed in to ball grinder, mix, then add graphiteRaw material, dry ice and zirconium dioxide abrading-ball, ball milling 2～3h, rotating speed 250rpm, adds ice cube afterwards again,Ball milling 1～2h, obtains brown graphite suspension;
The mass concentration of the described concentrated sulfuric acid is 98%; Described graphite is 500 object natural flake graphites;The usage ratio of described graphite, sodium nitrate, potassium permanganate, the concentrated sulfuric acid and dry ice is 1g:0.3～0.6g:1.5～2G:10～20mL:30～60g; To be that deionized water is freezing form described ice cube, the ice cube adding and the concentrated sulfuric acidMass ratio be 1～2:1;
(2) graphite suspension deionized water step (1) being obtained is diluted to 3～10mg/mL, and toWherein add hydrogen peroxide, at 90～95 DEG C of stirred in water bath reaction 1h, then regulate pH with sodium hydroxide solutionValue is to 7～8, and ultrasonic processing 1h;
Described hydrogen peroxide mass percent concentration is 30%; Potassium permanganate matter in this hydrogen peroxide and step (1)Amount is than being 0.5～1:1; Described supersonic frequency is 40kHz, and power is 240W;
(3) in the graphene oxide suspension obtaining to step (2), add NaOH and complex reducing agent,Heating, stirring, reaction 3h, obtains graphene suspension, after filtration, and washing, dry, finally obtain listThe Graphene of layer and several atomic layers;
Described complex reducing agent is made up of hydrazine hydrate and thiourea dioxide, mass ratio 1:0.5～1; This composite reductionGraphite raw material mass ratio in agent and step (1) is 1～2:1; The temperature of described reaction is 93～98 DEG C;In described step (3), the mass ratio of NaOH and thiourea dioxide is 1:1.
2. the preparation method of Graphene as claimed in claim 1, is characterized in that, step (1) itBefore, by graphite raw material, sodium nitrate, potassium permanganate, the concentrated sulfuric acid and ball grinder and the abundant cooling processing of abrading-ball,Described abundant cooling referring to put into refrigerator, is cooled to 0 DEG C.
3. the preparation method of Graphene as claimed in claim 1, is characterized in that, described step (1)In zirconium dioxide abrading-ball by three kinds of size compositions, diameter is respectively 14mm, 10mm and 6mm, threeThe ratio of planting the quantity of size abrading-ball is 1:3:7, and abrading-ball is 2～5:1 with the quality of material ratio packing into.
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| EP3070053B1 (en) * | 2015-03-17 | 2018-02-28 | Graphenea, S.A. | Method for obtaining graphene oxide |
| CN105271188A (en) * | 2015-09-23 | 2016-01-27 | 合肥国轩高科动力能源有限公司 | Method for preparing carboxyl functionalized graphene by one-step method |
| CN106082195A (en) * | 2016-06-17 | 2016-11-09 | 青岛大学 | A kind of ball milling formula preparation method of Graphene |
| CN106517155B (en) * | 2016-10-10 | 2018-11-06 | 福州博力达机电有限公司 | A kind of environmentally friendly method for preparing graphene |
| CN106824142A (en) * | 2016-12-19 | 2017-06-13 | 华南农业大学 | A kind of thiourea dioxide reduces magnetic oxygenated Graphene and preparation method and application |
| CN108046242A (en) * | 2017-12-20 | 2018-05-18 | 昆明理工大学 | A kind of preparation method of poroid graphene |
| RU2720780C2 (en) * | 2018-07-19 | 2020-05-13 | Общество с ограниченной ответственностью "Минерал" | Graphene oxide synthesis method |
| CN108910873A (en) * | 2018-10-09 | 2018-11-30 | 柳州蓓蒂芬科技有限公司 | Graphene oxide synthetic method |
| CN110643272B (en) * | 2019-11-08 | 2022-03-01 | 陕西科技大学 | Graphene oxide modified waterborne polyurethane heat-conducting flame-retardant antistatic coating film-forming agent and preparation method thereof |
| CN111204753A (en) * | 2020-02-12 | 2020-05-29 | 西安工程大学 | Method for preparing graphene oxide by stripping graphite oxide |
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| CN102320598A (en) * | 2011-07-26 | 2012-01-18 | 河南大学 | Preparation method of graphene |
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Effective date of registration: 20191209 Address after: 168 Building No. 5, Fenghuang West Road, Jiangsu, Taizhou 225300, China Patentee after: Taizhou enmet graphene Technology Co., Ltd Address before: 243002 Anhui city in Ma'anshan Province, Huashan District East Lake Road No. 59 Patentee before: Anhui University of Technology |
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