CN102786045B - Method for preparing oxidized graphene - Google Patents
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- CN102786045B CN102786045B CN201210265540.3A CN201210265540A CN102786045B CN 102786045 B CN102786045 B CN 102786045B CN 201210265540 A CN201210265540 A CN 201210265540A CN 102786045 B CN102786045 B CN 102786045B
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Abstract
The invention belongs to a graphene preparation technology and relates to an improvement on an oxidized graphene preparation method. Preparation steps are as follows: preparing oxidized graphite; preparing an oxidized graphite aqueous solution; freezing; unfreezing; and drying. The invention provides a method for preparing the oxidized graphene through cold expansion stripping, which avoids environment pollution, is beneficial to environmental protection, has a simple process, is complete in oxidized graphite stripping, cause less damage on graphite sheets and is convenient for mass production.
Description
Technical field
The invention belongs to Graphene technology of preparing, relate to the improvement to graphene oxide preparation method.
Background technology
Graphene is SP
2hydridization carbon atom arrangement becomes cellular hexaplanar crystal, and thickness is only individual layer atom, is a kind of Novel Carbon Nanomaterials, is the elementary cell that forms graphite, carbon nanotube and soccerballene etc., has novel physics-chem characteristic.Research shows, the specific surface area of Graphene can be up to 2600m
2/ g, Young's modulus is about 1100GPa, and breaking tenacity is 125GPa, and physical strength is 1060GPa, thermal conductivity 5000W/mK.Graphene also has excellent electron transport ability, and under room temperature, its electronic mobility is up to 15000cm
2/ VS.Graphene is (Novoselov since within 2004, being found first, K.S.et al Science, 2004,306,606), cause immediately the very big interest of scientific circles, become in recent years one of active material of chemistry, Materials science and physics research, in fields such as aerospace, novel material, electric power, electronics, have a good application prospect.
Prior art discloses the preparation method of graphite alkene, comprise graphite oxide reduction method, micromechanics stripping method, chemical Vapor deposition process, SiC epitaxial growth method and electrochemical process etc., wherein, micromechanics stripping method, chemical Vapor deposition process, SiC epitaxial growth method and electrochemical process all have complex process, high in cost of production shortcoming.And the graphite oxide reduction rule with the advantage such as with low cost, can quantifying standby, method is simple becomes study hotspot.Graphite oxide reduction method is conventionally first by graphite oxidation and peel off into graphene oxide, restore and obtain Graphene, wherein, by graphite oxidation and peel off that to obtain graphene oxide be committed step, simultaneously, due to good water-soluble of graphene oxide, in the practical application of preparing matrix material, there is larger advantage.
At present, supersound process is the method for peeling off graphite oxide generally adopting, as the method > > of a CN201110065030.7 < < preparing graphene oxide by chemical peeling mentioned graphite oxide in organic solvent with the ultrasonic 0.5-1 hour of frequency of 40-50kHz, also need under the rotating speed of 3000-5000 rev/min, obtain graphene oxide lamella by centrifugal treating 20-90 minute later; And for example the method > > of a CN200910062869.8 < < realizing large-scale preparation of monolayer oxidized graphene points out that the time that ultrasonic dispersion is peeled off is 0.5-10 hour, also needs to filter the precipitation of not disperseing; For another example the preparation method > > of CN200910070735.0 < < single-layer graphene mentions graphite oxide aqueous solution ultrasonic water bath under 150w power and processes 3h, afterwards through the centrifugal graphene oxide that obtains.
In general, the ultrasonic method using at present all needs the treatment time of growing; And to cause peeling off the graphene oxide size obtaining inhomogeneous due to hyperacoustic ununiformity; During supersound process, easily cause graphite oxide solution temperature to raise rapidly; The laminated structure of high-power ultrasonic also easy disruptive oxidation Graphene; The use of organic solvent easily causes the pollution of environment.Therefore develop a kind of environmental protection, graphene oxide preparation technology is particularly important.
Summary of the invention
The object of the invention is: provide a kind of cold expansion to peel off the method for preparing graphene oxide, with reach be beneficial to environmental protection, technique simple, peel off completely, graphite flake layer destroyed to less, to be convenient to scale operation object.
Technical scheme of the present invention is: a kind of preparation method of graphene oxide, it is characterized in that, and the step of preparation is:
1, prepare graphite oxide: adopt Hummers method or Staudenmaier method to be oxidized intercalation to crystalline flake graphite or highly oriented pyrolytic graphite and obtain graphite oxide; The interlamellar spacing of oxidized graphite flake layer is 0.6nm～1.0nm;
2, the preparation graphite oxide aqueous solution: dry graphite oxide powder is dissolved in deionized water, stirs 20min～60min and be made into the graphite oxide aqueous solution, concentration is 0.1mg/mL～10mg/mL;
3, freezing: the graphite oxide aqueous solution that is no less than 10ml to be placed in not to the freezer higher than 0 ℃, to place and be no less than 60min, make it completely icing, while utilizing water freezing, form hydrogen bond and cause volume to become large cold expansion principle peeling off graphite oxide;
4, thaw: after the freezing graphite oxide aqueous solution is taken out, at room temperature thaw, obtain graphite oxide aqueous solution;
5, dry: by graphite oxide aqueous solution dry 8h～12h in the vacuum drying oven of 60 ℃～80 ℃, to obtain graphene oxide.
Advantage of the present invention is: provide a kind of cold expansion to peel off the method for preparing graphene oxide, avoided environmental pollution, be conducive to environmental protection, technique is simple, and graphite oxide is peeled off completely, less to the destruction of graphite flake layer, is convenient to scale operation.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of the graphite oxide of preparation in embodiment 1.
Fig. 2 is transmission electron microscope (TEM) photo of the graphene oxide of preparation in embodiment 1.
Embodiment
Below the present invention is described in further details.A preparation method for graphene oxide, is characterized in that, the step of preparation is:
1, prepare graphite oxide: adopt Hummers method or Staudenmaier method to be oxidized intercalation to crystalline flake graphite or highly oriented pyrolytic graphite and obtain graphite oxide; The interlamellar spacing of oxidized graphite flake layer is 0.6nm～1.0nm;
2, the preparation graphite oxide aqueous solution: dry graphite oxide powder is dissolved in deionized water, stirs 20min～60min and be made into the graphite oxide aqueous solution, concentration is 0.1mg/mL～10mg/mL;
3, freezing: the graphite oxide aqueous solution that is no less than 10ml to be placed in not to the freezer higher than 0 ℃, to place and be no less than 60min, make it completely icing, while utilizing water freezing, form hydrogen bond and cause volume to become large cold expansion principle peeling off graphite oxide;
4, thaw: after the freezing graphite oxide aqueous solution is taken out, at room temperature thaw, obtain graphite oxide aqueous solution;
5, dry: by graphite oxide aqueous solution dry 8h～12h in the vacuum drying oven of 60 ℃～80 ℃, to obtain graphene oxide.
More complete for graphite oxide is peeled off, after the freezing graphite oxide aqueous solution is thawed, can again carry out the freezing and operation of thawing, the number of times of repetitive operation is 1～5 time, and then carries out drying treatment.
Principle of work of the present invention is: utilize good water-soluble of graphite oxide, be mixed with the aqueous solution that homogeneous disperses, when freezing, rely on water freezing to form hydrogen bond, and Hyarogen-bonding is greater than the model ylid bloom action power of oxidized graphite flake interlayer, while utilizing water freezing, volume becomes large feature oxidized graphite flake layer is strutted, and obtains graphene oxide.Preparation process is simple, has avoided the use of organic solvent, environmentally safe simultaneously.The formation of hydrogen bond is more even, can not cause the destruction of graphite flake layer.
Embodiment 1
Adopt Hummers method, in dry single port flask, add 98% vitriol oil 100mL, with low-temperature cooling fluid circulating pump, be cooled to 0 ℃, in stirring, add successively 4g natural flake graphite, 2g NaNO
3with 12g KMnO
4, control reacting liquid temperature at 10～15 ℃, stirring reaction 2h; Then beaker is placed in to the water bath with thermostatic control of 35 ℃ of left and right, when question response liquid temp rises to 35 ℃ of left and right, continues to stir 30min; Finally in stirring, add 200mL deionized water, control reacting liquid temperature in 100 ℃, continue to stir 2h.With deionized water, reaction solution is diluted to the H2O2 that adds again 100mL5% after 800～1000mL, filtered while hot, HCI with 5% and deionized water fully wash until sulfate radical-free ion in filtrate (detecting with BaC1 solution), by filter cake dry 12h in 80 ℃ of vacuum drying ovens, obtain dry oxidized graphite flake, the interlamellar spacing of graphite oxide is 0.6nm, and its transmission electron microscope photo as shown in Figure 1.It is standby that grinding obtains graphite oxide powder.
Get 0.1g graphite oxide and be dissolved in (graphite oxide concentration is 2mg/mL) in 50mL deionized water, magnetic agitation 30min, obtains the finely dispersed graphite oxide aqueous solution.Then be placed in the freezer 2h of-10 ℃, make it completely icing, then take out under room temperature it is dissolved, in 60 ℃ of vacuum drying ovens, dry 12h obtains graphene oxide, adopts transmission electron microscope to analyze, and sees accompanying drawing 2.
Embodiment 2
Adopt Staudenmaier method to add natural flake graphite in the concentrated nitric acid mixed solution of 98% the vitriol oil and 65%, wherein the vitriol oil and concentrated nitric acid volume ratio are 3:1, under magnetic agitation, add SODIUMNITRATE, under normal temperature, react 24h, obtain graphite oxide, by reactant dilution, the dilute hydrochloric acid with 5% and deionized water wash in filtrate without SO
4 2-and be neutral, obtain graphite oxide powder after drying and grinding, graphite oxide interlamellar spacing is 1.0nm.
Get 0.2g graphite oxide and be dissolved in (graphite oxide concentration is 4mg/mL) in 50mL deionized water, magnetic agitation 40min, obtains the finely dispersed graphite oxide aqueous solution.Then be placed in-5 ℃ of freezer 3h, make it completely icing, make afterwards it dissolve under normal temperature, in 80 ℃ of vacuum drying ovens, dry 8h obtains graphene oxide, and the graphene oxide of preparing in its transmission electron microscope photo and embodiment is similar.
Embodiment 3
Graphite oxide preparation method is with embodiment 1.
Get 0.3g graphite oxide and be dissolved in (graphite oxide concentration is 6mg/mL) in 50mL deionized water, magnetic agitation 60min, obtains the finely dispersed graphite oxide aqueous solution.Then be placed in-10 refrigerator-freezer 1h, make it completely icing, make afterwards it dissolve under normal temperature, in 70 ℃ of vacuum drying ovens, dry 10h obtains graphene oxide, and the graphene oxide of preparing in its transmission electron microscope photo and embodiment is similar.
Embodiment 4
Graphite oxide preparation method is with embodiment 1.
Get 0.1g graphite oxide and be dissolved in (graphite oxide concentration is 4mg/mL) in 50mL deionized water, magnetic agitation 40min, is mixed with the finely dispersed graphite oxide aqueous solution.Then be placed in-5 ℃ of refrigerator-freezer 3h, make it completely icing, under normal temperature, make afterwards it dissolve, repeat freezing-process of melting 5 times, finally in 80 ℃ of vacuum drying ovens, dry 12h obtains graphene oxide, and the graphene oxide of preparing in its transmission electron microscope photo and embodiment is similar.
Claims (2)
1. a preparation method for graphene oxide, is characterized in that, the step of preparation is:
1.1, prepare graphite oxide: adopt Hummers method or Staudenmaier method to be oxidized intercalation to crystalline flake graphite or highly oriented pyrolytic graphite and obtain graphite oxide; The interlamellar spacing of oxidized graphite flake layer is 0.6nm～1.0nm;
1.2, the preparation graphite oxide aqueous solution: dry graphite oxide powder is dissolved in deionized water, stirs 20min～60min and be made into the graphite oxide aqueous solution, concentration is 0.1mg/mL～10mg/mL;
1.3, freezing: the graphite oxide aqueous solution that is no less than 10mL to be placed in not to the freezer higher than 0 ℃, to place and be no less than 60min, make it completely icing, while utilizing water freezing, form hydrogen bond and cause volume to become large cold expansion principle peeling off graphite oxide;
1.4, thaw: after the freezing graphite oxide aqueous solution is taken out, at room temperature thaw, obtain graphite oxide aqueous solution;
1.5, dry: by graphite oxide aqueous solution dry 8h～12h in the vacuum drying oven of 60 ℃～80 ℃, to obtain graphene oxide.
2. the preparation method of graphene oxide according to claim 1, is characterized in that, after the freezing graphite oxide aqueous solution is thawed, again carries out the freezing and operation of thawing, and the number of times of repetitive operation is 1～5 time, and then carries out drying treatment.
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| CN103833023B (en) * | 2012-11-27 | 2015-10-28 | 海洋王照明科技股份有限公司 | Graphene nanobelt and preparation method thereof |
| CN103058179B (en) * | 2013-01-21 | 2014-12-10 | 张家港市东大工业技术研究院 | Method for preparing spongy graphene oxide by using freeze-drying method |
| CN103224229B (en) * | 2013-04-15 | 2015-07-15 | 中国科学院宁波材料技术与工程研究所 | Method for rapid preparation of graphene powder by freezing filtration |
| CN103204499B (en) * | 2013-04-24 | 2015-07-08 | 张家港市东大工业技术研究院 | Method for preparing spongy graphene |
| CN103483516B (en) * | 2013-09-27 | 2015-06-03 | 厦门大学 | Preparation method of graphene oxide-boron-modified phenolic resin |
| CN104003376A (en) * | 2014-05-21 | 2014-08-27 | 张家港市东大工业技术研究院 | Method for rapidly preparing high specific surface area graphene oxide |
| PL229934B1 (en) * | 2014-05-30 | 2018-09-28 | Instytut Tech Materialow Elektronicznych | Method for producing flaky graphene by way of direct exfoliation of graphite |
| CN104925787B (en) * | 2015-03-19 | 2018-05-15 | 青岛科技大学 | A kind of method that constant pressure and dry prepares graphene aerogel |
| CN105731440B (en) * | 2016-02-01 | 2017-09-05 | 成都新柯力化工科技有限公司 | A kind of utilization phase change materials peel off the method for preparing graphene microchip |
| CN105523553B (en) * | 2016-02-04 | 2017-07-04 | 成都新柯力化工科技有限公司 | It is a kind of suddenly to freeze the method that unimolecule water expansion prepares Graphene by single cold end |
| CN106564893A (en) * | 2016-11-10 | 2017-04-19 | 电子科技大学 | Hundred micron-order graphene oxide and preparation method thereof |
| CN110327927A (en) * | 2019-07-10 | 2019-10-15 | 大英聚能科技发展有限公司 | A kind of modified graphene material of high catalytic activity and preparation method thereof |
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Address after: 100095 box 81, Haidian District, Beijing Patentee after: AECC BEIJING INSTITUTE OF AERONAUTICAL MATERIALS Address before: 100095 Beijing 81 mailbox in Haidian District, Beijing Patentee before: AVIC BEIJING INSTITUTE OF AERONAUTICAL MATERIALS |
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Effective date of registration: 20211208 Address after: No. 108, 1f, building 1, yard 3, Fengzhi East Road, Haidian District, Beijing 100094 Patentee after: BEIJING GRAPHENE TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Address before: 100095 box 81, Haidian District, Beijing Patentee before: AECC BEIJING INSTITUTE OF AERONAUTICAL MATERIALS |
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