CN102897756A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN102897756A CN102897756A CN2012103475770A CN201210347577A CN102897756A CN 102897756 A CN102897756 A CN 102897756A CN 2012103475770 A CN2012103475770 A CN 2012103475770A CN 201210347577 A CN201210347577 A CN 201210347577A CN 102897756 A CN102897756 A CN 102897756A
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Abstract
The invention discloses a preparation method of graphene. Specifically, graphite oxide prepared by existing technology is dispersed in a green reducing agent, and oxygen on the graphite oxide is removed through an unbalance reaction in hot water, so that the graphite oxide is reduced into graphene. The graphene prepared by the method provided by the invention has low oxygen content and high conductivity; the method has advantages of simple operation, low cost and high efficiency, and really realizes graphene preparation in kilogram level; no reducing agent severely harmful to the environment or strongly toxic is used; therefore, the method causes no environmental pollution, greatly simplifies the growth process, suits industrial production, and has potential application value in the fields based on graphene.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to a kind of preparation method of Graphene, particularly prepare the preparation method of feather weight graphene powder.
Background technology
2004, the Graphene (Graphene) that professor Geim of Univ Manchester UK finds was a kind of carbonaceous novel material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape structure.Theoretical investigation is found: Graphene has 200,000cm
2The carrier mobility of/Vs.The movement velocity of electronics in Graphene reaches 1/300 of the light velocity, and electroconductibility can be compared with metallic copper.In addition, Graphene has larger catalysis characteristics with its larger specific surface area, is widely used in the energy, catalytic field, such as lithium ion battery, ultracapacitor etc.
The preparation method of the Graphene of having studied at present mainly contains micromechanics stripping method, liquid chemical method, pyrolysis SiC method, CVD method etc.For micromechanics stripping method, pyrolysis SiC method and the prepared Graphene of CVD method, to present the film morphology productive rate lower because of its prepared Graphene, is difficult to be applied to the larger energy field of demand.Adopt the Graphene of liquid chemical method preparation, large with its specific surface area, productive rate is large, and is with low cost and be expected to be applied to energy field.So far existing many pieces of documents have openly been reported, adopt the Graphene of liquid chemical method preparation as the huge applications prospect of active substance in fields such as lithium ion battery, ultracapacitors.
Yet liquid chemical method prepares the process of Graphene and is divided into two parts, at first with the hot graphite in sky at strong oxidizer, as in the vitriol oil, potassium permanganate and the hydrogen peroxide fully oxidation make simultaneously graphite expansion, obtain graphite oxide.Next is in reducing atmosphere above-mentioned graphite oxide to be reduced, thereby obtains Graphene, also claims graphene oxide.
Existing reduction means mainly contain following several: be heated to reduction more than 200 degree in rare gas element, but the prepared Graphene of this kind method does not usually show relatively poor electric conductivity and catalysis characteristics because reduction is thorough 1.; 2. in microwave oven, carry out microwave reduction, but because microwave oven is difficult in rare gas element, therefore prepared Graphene also presents the halfway situation of reduction; 3. in reductive agent, such as sodium borohydride etc., in industry, during preparation feather weight Graphene, these residues often produce huge harm to environment, perhaps need to spend more human and material resources and remove to process residue.
CN102320598A discloses a kind of preparation method of Graphene, specifically graphite oxide is expanded in High Temperature Furnaces Heating Apparatus, and then reduction obtains Graphene in being dissolved with the liquid ammonia solution of metal.Used liquefied ammonia is a kind of pungency article in the method, and is harmful, unfriendly to environment, and secondly liquefied ammonia need to could be preserved under the certain temperature in certain pressure intensity, otherwise can volatilize; In addition, the Graphene for preparing by the method contains nitrogen atom doping, causes prepared relatively poor, the loaded down with trivial details preparation technology of Graphene purity, has limited the application of the method in the Graphene industry member.
Summary of the invention
The objective of the invention is to have proposed a kind of preparation method of Graphene in order to solve existing liquid chemical method in the problems referred to above that preparation exists during Graphene.
Technical scheme of the present invention is: a kind of preparation method of Graphene is specially: the graphite oxide dissolving is scattered in the green reducing agent, carries out hydro-thermal reaction in hydrothermal reaction kettle, then filter and can obtain graphene powder.
It is resulting that described graphite oxide specifically carries out oxide treatment by strong oxidizer to natural graphite.
Described green reducing agent can be a kind of or any two kinds of mixing in acid, alkali, alcohol, the water.The green reducing agent here need to be liquid, so that graphite oxide can be uniformly dispersed, if green reducing agent is solid-state, can be with in the solvent that it is dissolved in its character conforms to, if green reducing agent is liquid then can directly uses.
In the described step graphite oxide dissolving is dispersed in the green reducing agent, the concentration of graphite oxide is at 0.1 ~ 1000mg/ml.
Described acid can be mineral acid, example hydrochloric acid; Can be organic acid also, such as acetic acid.
Described alkali can be a kind of in aqueous sodium hydroxide solution, calcium hydroxide aqueous solution, the ammoniacal liquor.
Described alcohol can be a kind of in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, the Virahol.
Described water is the pure water through purifying treatment.
Described hydrothermal reaction kettle is for reaction provides an airtight environment, can bear corresponding temperature and pressure, is a kind of existing instrument; The volume of graphite oxide and green reducing agent accounts for 30 ~ 80% of water heating kettle volume.
The described hydro-thermal reaction time more than 3 hours, the temperature of hydro-thermal reaction more than 100 degree, concrete reaction times and temperature are regulated according to different green reducing agents.
Beneficial effect of the present invention: the preparation method of Graphene of the present invention is dispersed in the green reducing agent by the graphite oxide with the preparation of prior art means, in thermal and hydric environment, by unbalance response, the oxygen on the graphite oxide is removed, so that it is reduced, thereby obtain Graphene.The Graphene oxygen level of method method preparation of the present invention is low, electricity is led height, simple to operate, and with low cost, and efficient is high, can be really in the preparation that realizes the feather weight Graphene, do not adopt or toxicity stronger reductive agent large to environmental hazard, environmentally safe is simplified the growth flow process greatly, be fit to carry out suitability for industrialized production, have potential actual application value in the field based on Graphene.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment one, employing water are as green reducing agent reduction-oxidation preparing graphite alkene, and its concrete steps are as follows:
The 0.5g graphite oxide is placed in the 40ml water ultra-sonic dispersion; The mixture of above-mentioned graphite oxide and water is placed the hydrothermal reaction kettle of 50ml, under 180 degree, kept 12 hours; Behind the naturally cooling water after the hydro-thermal reaction and the filtration of Graphene mixture are obtained Graphene.
By the Graphene that this embodiment obtains, the ratio of its Sauerstoffatom and carbon atom is 10%, and Raman D peak intensity is 0.8 with the ratio of G peak intensity, demonstrates graphite oxide and has obtained good reduction.
Embodiment two, employing ethanol are as green reducing agent reduction-oxidation preparing graphite alkene, and its concrete steps are as follows:
The 1g graphite oxide is placed in the 40ml ethanol ultra-sonic dispersion; The mixture of above-mentioned graphite oxide and ethanol is placed the hydrothermal reaction kettle of 100ml, under 100 degree, kept 12 hours; Behind the naturally cooling ethanol after the hydro-thermal reaction and the filtration of Graphene mixture are obtained Graphene.
By the Graphene that this embodiment obtains, the ratio of its Sauerstoffatom and carbon atom is 8%, and Raman D peak intensity is 0.7 with the ratio of G peak intensity, demonstrates graphite oxide and has obtained good reduction.
Embodiment three, employing acetic acid are as green reducing agent reduction-oxidation preparing graphite alkene, and its concrete steps are as follows:
The 0.3g graphite oxide is placed in the 40ml acetic acid ultra-sonic dispersion; The mixture of above-mentioned graphite oxide and acetic acid is placed the hydrothermal reaction kettle of 80ml, under 130 degree, kept 12 hours; Behind the naturally cooling acetic acid after the hydro-thermal reaction and the filtration of Graphene mixture are obtained Graphene.
By the Graphene that this embodiment obtains, the ratio of its Sauerstoffatom and carbon atom is 14%, and Raman D peak intensity is 0.9 with the ratio of G peak intensity, demonstrates graphite oxide and has obtained good reduction.
Embodiment four, employing ammoniacal liquor are as green reducing agent reduction-oxidation preparing graphite alkene, and its concrete steps are as follows:
The 2g graphite oxide is placed in the 80ml ammoniacal liquor ultra-sonic dispersion; The mixture of above-mentioned graphite oxide and ammoniacal liquor is placed the hydrothermal reaction kettle of 150ml, under 120 degree, kept 4 hours; Behind the naturally cooling ammoniacal liquor after the hydro-thermal reaction and the filtration of Graphene mixture are obtained Graphene.
By the Graphene that this embodiment obtains, the ratio of its Sauerstoffatom and carbon atom is 7%, and Raman D peak intensity is 0.9 with the ratio of G peak intensity, demonstrates graphite oxide and has obtained good reduction.
Those of ordinary skill in the art will appreciate that embodiment described here is in order to help reader understanding's principle of the present invention, should to be understood to that protection scope of the present invention is not limited to such special statement and embodiment.Those of ordinary skill in the art can make various other various concrete distortion and combinations that do not break away from essence of the present invention according to these technology enlightenments disclosed by the invention, and these distortion and combination are still in protection scope of the present invention.
Claims (10)
1. the preparation method of a Graphene is specially: the graphite oxide dissolving is scattered in the green reducing agent, reacts in hydrothermal reaction kettle, then filter and can obtain graphene powder.
2. the preparation method of Graphene according to claim 1 is characterized in that, described graphite oxide specifically carries out oxide treatment by strong oxidizer to natural graphite and obtains.
3. the preparation method of Graphene according to claim 1 is characterized in that, described green reducing agent is specially a kind of or any two kinds of mixing in acid, alkali, alcohol, the water.
4. the preparation method of Graphene according to claim 1 is characterized in that, described graphite oxide is dissolved is dispersed in the green reducing agent, and the concentration of graphite oxide is 0.1 ~ 1000mg/ml.
5. the preparation method of Graphene according to claim 3 is characterized in that, described acid-specific is mineral acid or organic acid.
6. the preparation method of Graphene according to claim 3 is characterized in that, described alkali is specially a kind of in aqueous sodium hydroxide solution, calcium hydroxide aqueous solution, the ammoniacal liquor.
7. the preparation method of Graphene according to claim 3 is characterized in that, described alcohol is specially a kind of in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, the Virahol.
8. the preparation method of Graphene according to claim 3 is characterized in that, described water is the pure water through purifying treatment.
9. the preparation method of Graphene according to claim 1 is characterized in that, the volume of graphite oxide and green reducing agent accounts for 30 ~ 80% of water heating kettle volume.
10. the preparation method of Graphene according to claim 1 is characterized in that, the described hydro-thermal reaction time more than 3 hours, temperature 100 the degree more than.
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Cited By (7)
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| CN103332678A (en) * | 2013-05-24 | 2013-10-02 | 东莞上海大学纳米技术研究院 | Preparation methods of graphene and graphene-oxide compound |
| CN103950926A (en) * | 2014-05-14 | 2014-07-30 | 石家庄铁道大学 | Method for quickly preparing single-layer graphene |
| CN104108709A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Porous graphene and preparation method thereof |
| CN106145097A (en) * | 2016-06-13 | 2016-11-23 | 南京工业大学 | The preparation method of the redox graphene that a kind of hydrophilic and hydrophobic is controlled |
| CN106185902A (en) * | 2016-07-18 | 2016-12-07 | 中国科学院兰州化学物理研究所 | A kind of method that clean oxidation technology prepares the controlled graphene oxide of size |
| CN106800290A (en) * | 2015-11-25 | 2017-06-06 | 衡阳市骏杰化工有限公司 | A kind of preparation method of Graphene |
| CN108083264A (en) * | 2018-02-26 | 2018-05-29 | 盐城科迈特新材料有限公司 | A kind of preparation method of three-dimensional grapheme |
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| CN101912777A (en) * | 2010-07-30 | 2010-12-15 | 清华大学 | Three-dimensional self-assembly of graphene oxide and preparation method and application thereof |
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| CN103332678A (en) * | 2013-05-24 | 2013-10-02 | 东莞上海大学纳米技术研究院 | Preparation methods of graphene and graphene-oxide compound |
| CN103332678B (en) * | 2013-05-24 | 2016-03-23 | 东莞上海大学纳米技术研究院 | The preparation method of Graphene and Graphene-complex oxide |
| CN103950926A (en) * | 2014-05-14 | 2014-07-30 | 石家庄铁道大学 | Method for quickly preparing single-layer graphene |
| CN103950926B (en) * | 2014-05-14 | 2016-02-10 | 石家庄铁道大学 | A kind of method preparing single-layer graphene fast |
| CN104108709A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Porous graphene and preparation method thereof |
| CN106800290A (en) * | 2015-11-25 | 2017-06-06 | 衡阳市骏杰化工有限公司 | A kind of preparation method of Graphene |
| CN106145097A (en) * | 2016-06-13 | 2016-11-23 | 南京工业大学 | The preparation method of the redox graphene that a kind of hydrophilic and hydrophobic is controlled |
| CN106145097B (en) * | 2016-06-13 | 2018-07-27 | 南京工业大学 | A kind of preparation method for the redox graphene that hydrophilic and hydrophobic is controllable |
| CN106185902A (en) * | 2016-07-18 | 2016-12-07 | 中国科学院兰州化学物理研究所 | A kind of method that clean oxidation technology prepares the controlled graphene oxide of size |
| CN106185902B (en) * | 2016-07-18 | 2017-12-22 | 中国科学院兰州化学物理研究所 | A kind of method that clean oxidation technology prepares the controllable graphene oxide of size |
| CN108083264A (en) * | 2018-02-26 | 2018-05-29 | 盐城科迈特新材料有限公司 | A kind of preparation method of three-dimensional grapheme |
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Application publication date: 20130130 |