CN104528711A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN104528711A CN104528711A CN201510050309.6A CN201510050309A CN104528711A CN 104528711 A CN104528711 A CN 104528711A CN 201510050309 A CN201510050309 A CN 201510050309A CN 104528711 A CN104528711 A CN 104528711A
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Abstract
The invention belongs to the technical field of material processing and synthesis, and particularly relates to a preparation method of graphene. The preparation method comprises the steps of preparation of graphene oxide and reduction of graphene oxide. In the graphene oxide preparation process, potassium chlorate is selected as an oxidizer for the advanced oxidation stage. The graphene oxide reduction process comprises the following steps: weighing the graphene oxide powder in a crucible, putting in a muffle furnace, vacuumizing with a vacuum pump until the inside of the muffle furnace is in a vacuum state, introducing circulating nitrogen as protective gas, heating to 800 DEG C, introducing a hydrogen-inert gas mixture for 2-3 seconds, stopping introducing the gas, continuing heating until the temperature of the muffle furnace reaches 1200 DEG C, keeping for 15-25 seconds, cooling to room temperature, and taking out the crucible to obtain the graphene product.
Description
Technical field
The invention belongs to materials processing synthesis technical field, be specifically related to a kind of preparation method of Graphene.
Background technology
Graphene (Graphene) a kind ofly forms with sp2 hybridized orbital the flat film that hexangle type is honeycomb lattice by carbon atom, only has the two-dimensional material of a carbon atom thickness.2004, Univ Manchester UK physicist An Deliehaimu and Constantine Nuo Woxiaoluofu, successfully from graphite, isolate Graphene in an experiment, and confirm that it can Individual existence, two people are also because " testing in the initiative of two-dimensional graphene material " serves as reasons, common acquisition Nobel Prize in physics in 2010, from then on Graphene has just entered into the sight line of people, increases gradually its research.Graphene is the thinnest in the world is also the hardest nano material, and it is almost completely transparent, and only absorb the light of 2.3%, thermal conductivity is up to 5300W/ (mK), and higher than carbon nanotube and diamond, under normal temperature, its electronic mobility is more than 15000cm
2/ (Vs), again than CNT (carbon nano-tube) or silicon wafer height, and resistivity only about 10-6 Ω cm, than copper or silver lower, be the material that world resistivity is minimum.Because its resistivity is extremely low, therefore can be used to develop thinner, conduction speed new electronic component or transistor faster.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 etc.
The preparation method of current Graphene common are micromechanics stripping method, crystal epitaxy method, oxidation-reduction method, chemical Vapor deposition process etc.Master a kind of the simplest method peeled off by micromechanics, namely directly stripped down from larger crystal by graphene platelet.2004, Geim etc. used micromechanics stripping method first, successfully peeled off from high directional heat cracking graphite (highly oriented pyrolytic graphite) and observed single-layer graphene.The method can prepare high-quality graphene; but there is the deficiency that productive rate is low and cost is high, Product size is wayward, cannot prepare the enough Graphenes of length reliably; do not meet industrialization and large-scale production requirement, at present can only as laboratory preparation on a small scale.First sample surfaces is etched by oxidation or H2 by crystal epitaxy method, and then electronics bombardment is heated to 1000 DEG C to remove oxide compound under high vacuum, and the removal situation of oxide on surface is detected with Auger electron spectrum, after oxide compound is completely removed, sample is heated to 1250 ~ 1450 DEG C, can graphene layer be formed.Harsh and the obtained Graphene of this method condition is not easily separated from substrate, can not be used for manufacturing Graphene in a large number.Chemical Vapor deposition process refers to that reactive material issues biochemical reaction at gaseous condition; generate the solid matrix surface that solid matter is deposited on heating, and then the Technology of obtained solid material, the method can meet the requirement that high-quality graphene is prepared in mass-producing; but cost is higher, complex process.Oxidation-reduction method this method is a kind of common method that the most simply can obtain Graphene in a large number, relatively more conventional method of reducing is chemical reduction method, hydrazine hydrate, quadrol, sodium borohydride etc. is adopted to reduce and Rapid Thermal reduction, but after various method reduction, all can there is a process of reuniting in Graphene, cause the specific surface area of Graphene less than normal, be generally less than 700m
2/ g, and in product, oxy radical content is higher, is generally more than 8%, Graphene is second-rate.
Summary of the invention
For solving above-mentioned deficiency of the prior art, the present invention aims to provide a kind of preparation method of Graphene, and the method technique is simple, and reaction time is short, and in product, oxy radical content is low.For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of preparation method of Graphene, comprise the preparation of graphene oxide and reduction two steps of graphene oxide, it is characterized in that, Potcrate is selected to make the oxygenant in deep oxidation stage in the preparation process of described graphene oxide, the reduction of described graphene oxide specifically comprises the following steps: take above-mentioned graphene oxide powder as in crucible, be put in retort furnace, it is vacuum state in vacuum pump evacuation to retort furnace, pass into circulating nitrogen gas as shielding gas, when being heated to 800 DEG C, pass into the mixed gas 2-3s of hydrogen and argon gas, stop ventilation, continuing to be heated to muffle furnace is 1200 DEG C, maintain 15 ~ 25s, cooling down is to room temperature, take out crucible, obtain graphene product.
Concrete, the preparation method of described graphene oxide is as follows: in graphite: sulfuric acid mass ratio be 1: 30 ~ 70 ratio add the vitriol oil in four-hole boiling flask, put in ice-water bath and be cooled to-3-5 DEG C; Ultrasonication, slowly adds required graphite in four-hole boiling flask simultaneously, opens and stirs; By graphite: saltpetre mass ratio is 1: 1 ~ 0.75 slowly add saltpetre in four-hole boiling flask, after reaction 1-3h, by graphite: Potcrate mass ratio is 1: 16-18 add Potcrate in four-hole boiling flask, deep oxidation reaction 3-5h under ultrasonic wave state; Be heated to 30-35 DEG C and continue reaction 2-3h, close ultrasonic; The water adding graphite quality 100 times, in four-hole boiling flask, is warming up to 100 DEG C, adds graphite 30-50 deionized water dilution doubly, with potassium hydroxide aqueous solution washing to neutral, filter, namely obtain graphene oxide after oven dry after stirring reaction 2-3h.
Concrete, described hydrogen is hydrogen with the mixed traffic ratio of argon gas: argon gas is 3: 1, and wherein said rare gas element is argon gas or helium.
The present invention adopts Potcrate to make the oxygenant in deep oxidation stage in graphene oxide preparation process, the problem that the graphene oxide purity avoiding the potassium permanganate in ordinary method not wash clean clearly causing is low, makes guarantee as raw material as the quality purity of the graphene oxide of Graphene raw materials.Prepare in the process of Graphene to adopt in graphene oxide reduction and do with circulating nitrogen gas the shielding gas reacted; in retort furnace heating up process; when temperature is increased to 800 DEG C; pass into rapidly the mixed gas of hydrogen and rare gas element; the oxygen content of further reduction reaction system; reductive action due to hydrogen reduces the content of oxy radical in reactive material further, makes the oxygen level of oxy radical lower than 1%, improves purity and the quality of product.Therefore the present invention has the graphene preparation method that product purity is high, technique simple, be applicable to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention will be further described; it is to be noted that following examples are only the indicative explanations done the present invention in the mode of example sentence; but protection scope of the present invention is not limited in this, all those skilled in the art all fall into protection scope of the present invention with the replacement of spirit of the present invention to the equivalence that the present invention does.
Embodiment 1
A preparation method for Graphene, comprises the preparation of graphene oxide and reduction two steps of graphene oxide.First graphite oxidation is prepared into graphene oxide, in oxidising process, selects Potcrate to make the oxygenant in deep oxidation stage.Concrete operations are: take the 300g vitriol oil in four-hole boiling flask, put in ice-water bath and be cooled to-3-5 DEG C; Slowly add 10g graphite in four-hole boiling flask, open and stir, and ultrasonication; Continual ultrasonic process is constant, slowly adds 7.5g saltpetre in four-hole boiling flask, adds 160g Potcrate after reaction 1-3h, deep oxidation reaction 3-5h under ultrasonic state; Be heated to 30-35 DEG C and continue reaction 2-3h; Close ultrasonic; Add 1000g deionized water afterwards, be warming up to 100 DEG C, stirring reaction 2-3h, again add the dilution of 300g deionized water, with potassium hydroxide aqueous solution washing to neutral, filter, after oven dry, namely obtain graphene oxide.
Get above-mentioned graphene oxide powder as in crucible; be put in retort furnace, be vacuum state in vacuum pump evacuation to retort furnace, pass into circulating nitrogen gas as shielding gas; when being heated to 800 DEG C; pass into the gas 2-3s that hydrogen and helium gas flow ratio are 3: 1 ratios, stop ventilation, continuing to be heated to muffle furnace is 1200 DEG C; maintain 15s; cooling down, to room temperature, is taken out crucible, is obtained graphene product.
Detecting oxygen level in graphene product is 0.96%.
Embodiment 2
A preparation method for Graphene, comprises the preparation of graphene oxide and reduction two steps of graphene oxide.First graphite oxidation is prepared into graphene oxide, in oxidising process, selects Potcrate to make the oxygenant in deep oxidation stage.Concrete operations are: take the 700g vitriol oil in four-hole boiling flask, put in ice-water bath and be cooled to-3-5 DEG C; Slowly add 10g graphite in four-hole boiling flask, open and stir, and ultrasonication; Continual ultrasonic process is constant, slowly adds 10g saltpetre in four-hole boiling flask, adds 180g Potcrate after reaction 1-3h, deep oxidation reaction 3-5h under ultrasonic state; Be heated to 30-35 DEG C and continue reaction 2-3h; Close ultrasonic; Add 1000g deionized water afterwards, be warming up to 100 DEG C, stirring reaction 2-3h, again add the dilution of 500g deionized water, with potassium hydroxide aqueous solution washing to neutral, filter, after oven dry, namely obtain graphene oxide.
Get above-mentioned graphene oxide powder as in crucible; be put in retort furnace, be vacuum state in vacuum pump evacuation to retort furnace, pass into circulating nitrogen gas as shielding gas; when being heated to 800 DEG C; pass into the gas 2-3s that hydrogen and argon flow amount ratio are 3: 1 ratios, stop ventilation, continuing to be heated to muffle furnace is 1200 DEG C; maintain 25s; cooling down, to room temperature, is taken out crucible, is obtained graphene product.
Detecting oxygen level in graphene product is 0.98%.
Claims (4)
1. the preparation method of a Graphene, comprise the preparation of graphene oxide and reduction two steps of graphene oxide, it is characterized in that, Potcrate is selected to make the oxygenant in deep oxidation stage in the preparation process of described graphene oxide, the reduction of described graphene oxide specifically comprises the following steps: take above-mentioned graphene oxide powder as in crucible, be put in retort furnace, it is vacuum state in vacuum pump evacuation to retort furnace, pass into circulating nitrogen gas as shielding gas, when being heated to 800 DEG C, pass into the mixed gas 2-3s of hydrogen and rare gas element, stop ventilation, continuing to be heated to muffle furnace is 1200 DEG C, maintain 15 ~ 25s, cooling down is to room temperature, take out crucible, obtain graphene product.
2. the preparation method of a kind of Graphene as claimed in claim 1, it is characterized in that, the preparation method of described graphene oxide is as follows: in graphite: sulfuric acid mass ratio be 1: 30 ~ 70 ratio add the vitriol oil in four-hole boiling flask, put in ice-water bath and be cooled to-3-5 DEG C; Ultrasonication, slowly adds required graphite in four-hole boiling flask simultaneously, opens and stirs; By graphite: saltpetre mass ratio is 1: 1 ~ 0.75 slowly add saltpetre in four-hole boiling flask, after reaction 1-3h, by graphite: Potcrate mass ratio is 1: 16-18 add Potcrate in four-hole boiling flask, deep oxidation reaction 3-5h under ultrasonic wave state; Be heated to 30-35 DEG C and continue reaction 2-3h, close ultrasonic; The water adding graphite quality 100 times, in four-hole boiling flask, is warming up to 100 DEG C, adds graphite 30-50 deionized water dilution doubly, with potassium hydroxide aqueous solution washing to neutral, filter, namely obtain graphene oxide after oven dry after stirring reaction 2-3h.
3. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, described hydrogen is hydrogen with the mixed traffic ratio of argon gas: rare gas element is 3: 1.
4. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, described rare gas element is argon gas or helium.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI552956B (en) * | 2015-05-29 | 2016-10-11 | 國立臺灣科技大學 | Producing method of graphene and applications thereof |
| CN106674904A (en) * | 2016-12-30 | 2017-05-17 | 中国科学院深圳先进技术研究院 | Heat conducting composite material and preparation method thereof |
| CN109294466A (en) * | 2018-09-21 | 2019-02-01 | 佛山市森昂生物科技有限公司 | A kind of cold preparation method for twining adhesive tape of pipeline corrosion protection |
| CN109768164A (en) * | 2018-12-18 | 2019-05-17 | 杭州电子科技大学 | A kind of preparation method of flexible optical detector |
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| CN102324279A (en) * | 2011-07-21 | 2012-01-18 | 哈尔滨工业大学 | Method for preparing graphene conductive film based on nanometer soft printing technology |
| CN102586507A (en) * | 2012-03-21 | 2012-07-18 | 陕西科技大学 | Method for preparing acrylic resin modified graphene oxide leather tanning agent |
| CN102674334A (en) * | 2012-05-24 | 2012-09-19 | 同济大学 | Preparation method of graphene with nano ferroferric oxide precipitated on surface |
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2015
- 2015-01-28 CN CN201510050309.6A patent/CN104528711A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324279A (en) * | 2011-07-21 | 2012-01-18 | 哈尔滨工业大学 | Method for preparing graphene conductive film based on nanometer soft printing technology |
| CN102586507A (en) * | 2012-03-21 | 2012-07-18 | 陕西科技大学 | Method for preparing acrylic resin modified graphene oxide leather tanning agent |
| CN102674334A (en) * | 2012-05-24 | 2012-09-19 | 同济大学 | Preparation method of graphene with nano ferroferric oxide precipitated on surface |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI552956B (en) * | 2015-05-29 | 2016-10-11 | 國立臺灣科技大學 | Producing method of graphene and applications thereof |
| CN106674904A (en) * | 2016-12-30 | 2017-05-17 | 中国科学院深圳先进技术研究院 | Heat conducting composite material and preparation method thereof |
| CN109294466A (en) * | 2018-09-21 | 2019-02-01 | 佛山市森昂生物科技有限公司 | A kind of cold preparation method for twining adhesive tape of pipeline corrosion protection |
| CN109768164A (en) * | 2018-12-18 | 2019-05-17 | 杭州电子科技大学 | A kind of preparation method of flexible optical detector |
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Application publication date: 20150422 |
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