CN104386678A - Preparation method of graphene - Google Patents
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- CN104386678A CN104386678A CN201410635484.7A CN201410635484A CN104386678A CN 104386678 A CN104386678 A CN 104386678A CN 201410635484 A CN201410635484 A CN 201410635484A CN 104386678 A CN104386678 A CN 104386678A
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Abstract
The invention discloses an efficient preparation method of graphene, belonging to the field of nanotechnology. The method mainly comprises the following steps: at a temperature lower than room temperature, mixing a natural crystalline flake graphite material with sodium nitrate, concentrated sulfuric acid and potassium permanganate, performing ball milling treatment, diluting, adding oxydol to react, neutralizing with sodium hydroxide, and then performing ultrasonic treatment to obtain a graphene oxide suspension; and by using hydrazine hydrate and thiourea dioxide as composite reducer, reducing the graphene oxide solution to prepare graphene having the thickness of a single or several atomic layers. According to the invention, the ball milling process is introduced into the graphite oxidation process, thus improving the graphite oxidation and stripping efficiency and reducing the consumption of the strong oxidizer; the long process of graphene oxide filtration and washing is successfully omitted, and the preparation period is shortened; and the composite reducer is used to improve the reduction efficiency, so that graphene having a higher reduction degree can be obtained. The preparation method disclosed by the invention is simple in process, high in efficiency, low in cost and easy to realize industrial 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 the preparation in macroscopic quantity of grapheme material.
Technical background
Graphene is by the bi-dimensional cellular shape crystal of monolayer carbon atomic building.Because of electricity, the performance such as calorifics and mechanics of its uniqueness, as lightweight, intensity is high, the large (2600m of specific surface area
2/ g), specific conductivity is high, snappiness good, resistance to chemical attack is strong, Graphene has broad application prospects in fields such as nano electron device, lithium ion battery, fuel cell, solar cell, ultracapacitor, molecule sensor and hydrogen storage materials.
2004, the method that people's reported first such as the scientist Novoselov of Univ Manchester UK adopt micromechanics to peel off graphite prepares single crystal graphene film (Novoselov, K.S., et al.Science 306,666 (2004)), and find the at room temperature Absorbable organic halogens existence of this single crystal graphene film, there is metallicity.But this graphene preparation method efficiency is extremely low, can only be applicable to fundamental research.2006, the people such as Novoselov reported again under high temperature and uht conditions, in the method (Novoselov, K.S., et al.Science 312,1191 (2006)) of carbide silicon face extending and growing graphene.But this graphene preparation method cost is high, and prepared Graphene is not easily separated from substrate.At present, except above-mentioned 2 kinds of methods, chemical Vapor deposition process (CVD) and chemical stripping method has been developed again.CVD efficiency is lower, controllability is poor.Chemical stripping method is mainly based on the Hummers method (Hummers of improvement, W., et al.J.Am.Chem.Soc.80,1339 (1958)), the strong oxidizer such as the vitriol oil and potassium permanganate is namely adopted to be oxidized graphite, to graphite oxide supersound process, after filtration, wash, obtain graphene oxide, then graphene oxide is reduced, after reduction more after filtration, washing obtain Graphene.
Chemical stripping method be generally acknowledged can the higher method of the efficiency of macroscopic preparation of graphene.But, also there is shortcoming clearly in chemical stripping method: one is have employed a large amount of strong oxidizers, and cause the structural integrity of the Graphene obtained to be seriously damaged, existing defects is more, the electric property of the Graphene thus obtained significantly worsens, especially specific conductivity; Two is to be separated from oxygenant suspension by graphene oxide, must adopt dilution, filter and washing methods, but the viscosity of graphene oxide greatly, washs, it is very difficult to filter, and whole process is very consuming time; Three is that graphene oxide reduction process is longer, and reduction is not thorough.These shortcoming extreme influence utilization and extention of this method.
Summary of the invention
In order to solve the shortcomings such as oxygenant consumption in chemical stripping method is large, consuming time, reduction is not thorough, the invention provides the graphene preparation method that a kind of process is simple, productive rate is high, the method prepares the Perfected process of Graphene in a large number.
In order to realize above-mentioned technical purpose, the present invention is achieved by the following technical programs:
(1) SODIUMNITRATE, potassium permanganate and the vitriol oil are placed in ball grinder, mix, then add graphite raw 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 vitriol oil is 98%; Described graphite is 500 object natural flake graphites; The usage ratio of described graphite, SODIUMNITRATE, potassium permanganate, the vitriol oil 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, and the ice cube added and the mass ratio of the vitriol oil are 1 ~ 2:1;
(2) the graphite suspension deionized water that step (1) obtains is diluted to 3 ~ 10mg/mL, and add hydrogen peroxide wherein, at 90 ~ 95 DEG C of stirred in water bath reaction 1h, then use sodium hydroxide solution adjust ph to 7 ~ 8, and supersound process 1h;
Described hydrogen peroxide mass percent concentration is 30%; Potassium permanganate mass ratio in this hydrogen peroxide and step (1) is 0.5 ~ 1:1; Described ultrasonic frequency is 40kHz, and power is 240W;
(3) add sodium hydroxide and complex reducing agent in the graphene oxide suspension obtained to step (2), heating, to stir, reaction 3h, obtain graphene suspension, after filtration, washing, drying, finally obtains the Graphene of individual layer and several atomic shell;
Described complex reducing agent is made up of hydrazine hydrate and thiourea peroxide, mass ratio 1:0.5 ~ 1; Graphite raw material mass ratio in this complex reducing agent and step (1) is 1 ~ 2:1; The temperature of described reaction is 93 ~ 98 DEG C; The mass ratio of described sodium hydroxide and thiourea peroxide is 1:1.
Further, before step (1), by graphite raw material, SODIUMNITRATE, potassium permanganate, the vitriol oil and ball grinder and the abundant cooling process of abrading-ball, described abundant cooling refers to puts into refrigerator, is cooled to 0 DEG C.
Further, zirconium dioxide abrading-ball in described step (1) by large (diameter 14mm), in (diameter 10mm), little (diameter 6mm) three kinds of size compositions, the ratio of quantity is about 1:3:7, and abrading-ball is 2 ~ 5:1 with the quality of material ratio of loading.
Compared with prior art, the present invention has following technique effect:
1. by ball milling, method of shelling combines with chemical peeling this preparation method, improve oxidation and the charge stripping efficiency of graphite, thus reduce the consumption of strong oxidizer, simultaneously the oxidising process of graphite control in, in low temperature range, at utmost alleviate the destruction of oxidising process to graphene-structured integrity;
2. this Optimization of preparation preparation process, avoids the washing of graphene oxide, the lengthy procedure of filtration, substantially reduces preparation process;
3. this preparation method replaces single reductive agent with complex reducing agent, improves the reduction efficiency of graphene oxide, and the remnants at utmost reduced on reduced graphene sheet contain oxygen functional group.
Accompanying drawing explanation
Fig. 1 is natural flake graphite (X-ray diffraction (XRD) collection of illustrative plates of the Graphene sample of Fig. 1 a), prepared by the embodiment of the present invention 1 (Fig. 1 b) and embodiment 2 (Fig. 1 c).
Field emission scanning electron microscope (FESEM) photo of the Graphene sample of Fig. 2 prepared by the embodiment of the present invention 1.
Field emission scanning electron microscope (FESEM) photo of the Graphene sample of Fig. 3 prepared by the embodiment of the present invention 2.
Fig. 4 is the embodiment of the present invention 1 (Raman (Raman) spectrum of the Graphene sample of Fig. 4 a) and prepared by embodiment 2 (Fig. 4 b).
Fig. 5 is the embodiment of the present invention 3 (FTIR spectrum of the Graphene sample that Fig. 5 a) is prepared with embodiment 4 (Fig. 5 b).
Embodiment
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, SODIUMNITRATE, potassium permanganate, the vitriol oil, ball grinder (tetrafluoroethylene material) with transpiration hole and abrading-ball (zirconium dioxide material) are cooled to 0 DEG C, by SODIUMNITRATE 0.6g, potassium permanganate 3g, vitriol oil 20mL is placed in ball grinder and mixes, add graphite 2g, dry ice 60g and abrading-ball 350g, ball grinder after charging is placed in jacket, ball milling 2h on planetary ball mill, rotating speed 250rpm, afterwards, 45g ice cube is added in ball grinder, ball milling 1h again, in mechanical milling process, room temperature controls at 15 ~ 25 DEG C,
Second step, adds 200mL deionized water, stirs in ball grinder, graphite oxide suspension is poured out from ball grinder, adds the hydrogen peroxide of 9mL 30%, at 90 DEG C of stirred in water bath reaction 1h, instillation sodium hydroxide solution, adjust ph to 8, supersound process 1h;
3rd step, adds 0.5g sodium hydroxide, after stirring and dissolving in above-mentioned graphene oxide suspension, add hydrazine hydrate and 0.5g thiourea peroxide powder that 3mL mass concentration is 50%, stir, heat, at 95 DEG C of reaction 3h, filter, wash, 80 DEG C of vacuum-dryings, obtain graphite rare.
The productive rate of this embodiment is up to 12.3%.Relative to conventional chemical stripping method, this embodiment has higher productive rate.This may cause slippage, the stripping of graphite layers due to the shear action of ball milling, facilitates the insertion reaction of sulfuric acid molecule, graphite layers apart from increasing, containing the formation of oxygen functional group, thus improves the efficiency of chemical stripping.Compose with the XRD of crystalline flake graphite that (Fig. 1 a) contrasts, and the XRD of the Graphene that this embodiment obtains composes (Fig. 1 b) (002) diffraction peak and moves to left to 24.5 °, and intensity is more weak, broadening is serious.This illustrates that obtained graphene layer spacing is much larger than the interlamellar spacing of natural graphite, also shows that graphene sheet layer is very thin, the crystal degree of order is lower.FESEM picture (Fig. 2) shows, and the chiffon shape of the transparent fold of the graphene film that this embodiment obtains, shows the characteristic feature of monoatomic layer or several atomic layer level thickness Graphene.(Fig. 4 a) presents the characteristic peak of Graphene, and D peak is at 1348cm for the Raman spectrum of the Graphene that this embodiment obtains
-1near, G peak is at 1582cm
-1near, the ratio I of D peak and the integrated intensity at G peak
d/ I
gbe 0.98; Stronger D peak is owing to removing containing oxygen functional group in reduction process, cause carbon bonds on graphene sheet layer and cause structural defect.
Embodiment 2
The first step, by 500 order natural flake graphites, SODIUMNITRATE, potassium permanganate, the vitriol oil, ball grinder (tetrafluoroethylene material) with transpiration hole and abrading-ball (zirconium dioxide material) are chilled to 0 DEG C, by SODIUMNITRATE 1.1g, potassium permanganate 4g, vitriol oil 40mL is placed in ball grinder and mixes, add graphite 2g, dry ice 95g and abrading-ball 350g, ball grinder after charging is placed in jacket, ball milling 3h on planetary ball mill, rotating speed 250rpm, afterwards, 92g ice cube is added in ball grinder, ball milling 2h again, in mechanical milling process, room temperature controls at 20 ~ 25 DEG C,
Second step, adds 250mL deionized water, stirs in ball grinder, graphite oxide suspension is poured out from ball grinder, adds the hydrogen peroxide of 10mL 30%, at 90 DEG C of stirred in water bath reaction 1h, instillation sodium hydroxide solution, adjust ph to 8, supersound process 1h;
Follow-up preparation process is identical with embodiment 1, and this embodiment productive rate is 12.8%.Compose with the XRD of crystalline flake graphite (Fig. 1 a) compared with, the XRD of the Graphene that this embodiment obtains composes (Fig. 1 c) (002) diffraction peak near 25.0 °, and intensity is more weak, broadening is obvious.This illustrates that obtained graphene layer spacing is much larger than the interlamellar spacing of natural graphite, also shows that graphene sheet layer is very thin, the crystal degree of order is lower.FESEM picture (Fig. 3) shows, and the chiffon shape of the transparent fold of the graphene film that this embodiment obtains, shows the characteristic feature of monoatomic layer or several atomic layer level thickness Graphene.The Raman spectrum (Fig. 4 b) of the Graphene that this embodiment obtains presents the characteristic peak of Graphene, and D peak is at 1352cm
-1near, G peak is at 1586cm
-1near, the ratio I of D peak and the integrated intensity at G peak
d/ I
gbe 1.02; Stronger D peak is owing to removing containing oxygen functional group in reduction process, cause carbon bonds on graphene sheet layer and cause structural defect.
Embodiment 3
The first step, by 500 order natural flake graphites, SODIUMNITRATE, potassium permanganate, the vitriol oil, ball grinder (tetrafluoroethylene material) with transpiration hole and abrading-ball (zirconium dioxide material) are chilled to 0 DEG C, by SODIUMNITRATE 0.8g, potassium permanganate 3.5g, vitriol oil 30mL is placed in ball grinder and mixes, add graphite 2g, dry ice 98g and abrading-ball 350g, ball grinder after charging is placed in jacket, ball milling 2h on planetary ball mill, rotating speed 250rpm, afterwards, 84g ice cube is added in ball grinder, ball milling 1h again, in mechanical milling process, room temperature controls at 20 ~ 25 DEG C,
Second step, adds 200mL deionized water, stirs in ball grinder, graphite oxide suspension is poured out from ball grinder, adds the hydrogen peroxide of 10mL 30%, at 90 DEG C of stirred in water bath reaction 1h, instillation sodium hydroxide solution, adjust ph to 8, supersound process 1h;
Follow-up preparation process is identical with embodiment 1, and the productive rate of this embodiment is 12.5%.Fig. 5 a is the infrared spectra of the Graphene that this embodiment obtains.At 3446cm
-1locate the O-H stretching vibration of the corresponding planar water of wider absorption peak, at 1721cm
-1the stretching vibration of the corresponding carboxyl functional group C=O of faint absorption peak at place, and at 1031cm
-1place's absorption peak is the epoxide group between corresponding graphene layer.At 1561cm
-1and 1459cm
-1the absorption peak skeletal vibration of corresponding graphene sheet layer and the stretching vibration of C-OH respectively at place.
Embodiment 4
Other operation stepss are with embodiment 3,3rd step changes to some extent: in above-mentioned graphene oxide suspension, add 2g sodium hydroxide, after stirring and dissolving, add hydrazine hydrate and 2g thiourea peroxide powder that 4mL mass concentration is 50%, stir, heat, at 95 DEG C of reaction 3h, filter, wash, 80 DEG C of vacuum-dryings, obtain 244mg graphite rare.
The Graphene productive rate of this embodiment is 12.2%.The productive rate of this embodiment and embodiment 1,2,3 close.(Fig. 5 is a) substantially identical for infrared spectra (Fig. 5 b) and the embodiment 3 of the Graphene that this embodiment obtains.Obviously, with the Graphene infrared spectra of embodiment 3 (Fig. 5 a) compared with, the Graphene infrared spectra (Fig. 5 b) of this embodiment is 1721,1459 and 1031cm
-1the absorption peak at place disappears or significantly weakens.This shows, carboxyl, hydroxyl and epoxy group(ing) etc. in the Graphene that this embodiment obtains containing oxygen function can roll into a ball removal more thorough.This due to the hydrazine hydrate of suitable proportion and thiourea peroxide complex reducing agent, may create synergistic effect, and the efficiency removed containing oxygen functional group is higher.
Claims (3)
1. a preparation method for Graphene, is characterized in that, comprises the following steps:
(1) SODIUMNITRATE, potassium permanganate and the vitriol oil are placed in ball grinder, mix, then add graphite raw 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 vitriol oil is 98%; Described graphite is 500 object natural flake graphites; The usage ratio of described graphite, SODIUMNITRATE, potassium permanganate, the vitriol oil 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, and the ice cube added and the mass ratio of the vitriol oil are 1 ~ 2:1;
(2) the graphite suspension deionized water that step (1) obtains is diluted to 3 ~ 10mg/mL, and add hydrogen peroxide wherein, at 90 ~ 95 DEG C of stirred in water bath reaction 1h, then use sodium hydroxide solution adjust ph to 7 ~ 8, and supersound process 1h;
Described hydrogen peroxide mass percent concentration is 30%; Potassium permanganate mass ratio in this hydrogen peroxide and step (1) is 0.5 ~ 1:1; Described ultrasonic frequency is 40kHz, and power is 240W;
(3) add sodium hydroxide and complex reducing agent in the graphene oxide suspension obtained to step (2), heating, to stir, reaction 3h, obtain graphene suspension, after filtration, washing, drying, finally obtains the Graphene of individual layer and several atomic shell;
Described complex reducing agent is made up of hydrazine hydrate and thiourea peroxide, mass ratio 1:0.5 ~ 1; Graphite raw material mass ratio in this complex reducing agent and step (1) is 1 ~ 2:1; The temperature of described reaction is 93 ~ 98 DEG C; The mass ratio of described sodium hydroxide and thiourea peroxide is 1:1.
2. the preparation method of Graphene as claimed in claim 1, it is characterized in that, before step (1), by graphite raw material, SODIUMNITRATE, potassium permanganate, the vitriol oil and ball grinder and the abundant cooling process of abrading-ball, described abundant cooling refers to puts into refrigerator, is cooled to 0 DEG C.
3. the preparation method of Graphene as claimed in claim 1, it is characterized in that, zirconium dioxide abrading-ball in described step (1) is by three kinds of size compositions, diameter is 14mm, 10mm and 6mm respectively, the ratio of the quantity of three kinds of size abrading-balls is 1:3:7, and abrading-ball is 2 ~ 5:1 with the quality of material ratio of loading.
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CN105271188A (en) * | 2015-09-23 | 2016-01-27 | 合肥国轩高科动力能源有限公司 | Method for one-step preparation of carboxyl functional graphene |
JP2016175828A (en) * | 2015-03-17 | 2016-10-06 | グラフェネア エス.エー.Graphenea S.A. | Method for obtaining graphene oxide |
CN106082195A (en) * | 2016-06-17 | 2016-11-09 | 青岛大学 | A kind of ball milling formula preparation method of Graphene |
CN106517155A (en) * | 2016-10-10 | 2017-03-22 | 福州博力达机电有限公司 | Environment friendly method of 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 |
CN108910873A (en) * | 2018-10-09 | 2018-11-30 | 柳州蓓蒂芬科技有限公司 | Graphene oxide synthetic method |
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JP2016175828A (en) * | 2015-03-17 | 2016-10-06 | グラフェネア エス.エー.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 one-step preparation of carboxyl functional graphene |
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 |
CN106517155A (en) * | 2016-10-10 | 2017-03-22 | 福州博力达机电有限公司 | Environment friendly method of 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 |
CN110734057A (en) * | 2018-07-19 | 2020-01-31 | 矿物股份有限公司 | Synthesis method of graphene oxide |
CN110734057B (en) * | 2018-07-19 | 2023-01-10 | 矿物股份有限公司 | Synthesis method of graphene oxide |
CN108910873A (en) * | 2018-10-09 | 2018-11-30 | 柳州蓓蒂芬科技有限公司 | Graphene oxide synthetic method |
CN110643272A (en) * | 2019-11-08 | 2020-01-03 | 陕西科技大学 | Graphene oxide modified waterborne polyurethane heat-conducting flame-retardant antistatic coating film-forming agent and preparation method thereof |
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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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 |