CN103864059B - Graphene high-efficiency preparation method based on extraction purification technology - Google Patents
Graphene high-efficiency preparation method based on extraction purification technology Download PDFInfo
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Abstract
The invention discloses a graphene high-efficiency preparation method based on an extraction purification technology. According to the graphene high-efficiency preparation method, graphite oxide is prepared by an oxidation method, and the graphene oxide is purified mainly by an extraction, so that the purification time of a graphene oxide solution is shortened, and the purification of the graphene oxide can be completed within 6-10 h; finally, the graphene oxide is reduced into graphene by a microwave reduction technology. The graphene high-efficiency preparation method has the advantages that high-purity graphene can be prepared by simple operation and short preparation period without need to purchase expensive and complex equipment and high cost of raw materials, and the graphene high-efficiency preparation method is applicable to large-amount preparation of the graphene, and is expected to be widely used in capacitors, fuel cells, sealing materials, catalyst carriers and other fields.
Description
Technical field
The present invention relates to a kind of method preparing Graphene.Be specially the method preparing Graphene based on purification by liquid extraction technique to high-efficiency, be applicable to the preparation in macroscopic quantity of Graphene.
Background technology
Since the study group that the A.K. Geim of University of Manchester in 2004 leads proposes the concept of Graphene (Graphene), Graphene is as an other bright star of carbon family, obtain the great attention of physics, chemistry and material scholar, therefore, Graphene becomes another " universal material " (Science 2004,306:666.) yielded unusually brilliant results after carbon nanotube.Compared with carbon nanotube, there is perfect hybrid structure in Graphene, have superelevation specific conductivity, the electric transmission speed be exceedingly fast, high rigidity, high-specific surface area and room-temperature quantum Hall effect etc. get most of the attention always (
nat. Mater. 2007,
6, 183;
science 2009,
324, 1530.).Up to the present, scientific research personnel conducts extensive research the preparation of Graphene, about the preparation method of Graphene, has more literature review both at home and abroad, mainly comprises physical method and the large class of chemical process two.Physical method normally with the graphite of cheapness or expanded graphite for raw material; single or multiple lift Graphene is prepared by the direct stripping method of micromechanics stripping method, liquid phase or gas phase; this method raw material is easy to get; operate relatively simple; but due to reasons such as equipment requirements is high, low yield; constrain the large-scale production of Graphene, do not possess the value of practical application.Chemical method is the earliest prepared Graphene and is realized by organic synthesis, concrete operations are with phenyl ring or other aroma system for core, through multistep linked reaction substituted benzene ring or large aromatic nucleus, move in circles, make aroma system become large, finally obtain the Graphene of the two dimensional structure of certain size.Until Stankovich in 2006 etc. have prepared graphene oxide by graphite being carried out oxidation, and adopt hydrazine to reduce the oxy radical removed on graphene oxide, finally obtain Graphene, this method is because cheaper starting materials, equipment requirements are low, simple to operate thus to become the method preparing Graphene of most potentiality and development prospect be also the main method that Graphene is prepared in current laboratory.But also there are some defects in this method.Graphene oxide is with hydrophilic functional groups such as hydroxyl, carboxyl and epoxy group(ing), show strong wetting ability, therefore along with going deep into of purifying, graphene oxide and water form water-setting (molten) glue, no matter adopt suction filtration or centrifugal technology, all be difficult to separation of oxygenated Graphene and the aqueous solution, finally cause product impurity too much.In order to obtain highly purified graphene oxide, present laboratory many employings dialysis is purified to graphene oxide.The method allows impurity small molecules be diffused in water by dialysis membrane, thus by graphene oxide and magazins' layout purifying.Dialysis process, by the restriction of molecular dynamics factor, generally need the time of 2 ~ 4 weeks just can obtain highly purified graphene oxide, and dialysis membrane is expensive, is unfavorable for suitability for industrialized production.Therefore, in order to realize the preparation in macroscopic quantity of Graphene, the purifying velocity of graphene oxide solution must be accelerated.Although also there are some to report in recent years in purification, but still there are some problems in current reported method of purification, such as, the method of electrophoretic deposition purification graphene oxide, because aqueous phase decomposition voltage is low, thus make purification voltage can not be too high, cause danger in order to avoid cause the violent decomposition of aqueous phase to cause the reunion of graphene oxide and a large amount of hydrogen to generate, too low voltage then cannot realize separating-purifying rapidly and efficiently.Therefore; preparation in macroscopic quantity in view of current Graphene remains the key issue affecting Graphene mass-producing application; if low cost, the purification of efficient quick and redox graphene can be realized, the progress of making a breakthrough property in macroscopic preparation of graphene just can be expected to.
Summary of the invention
The object of the present invention is to provide a kind of method preparing Graphene based on purification by liquid extraction technique to high-efficiency.
Technical scheme of the present invention is:
The present invention prepares graphite oxide by oxidation style, purifies, thus shortens the purification time of graphene oxide solution, can complete the purification to graphene oxide in 6 ~ 10 h mainly through extraction to graphene oxide; Finally utilize microwave reduction technology, graphene oxide is reduced to Graphene.Result can by being confirmed the microtexture of Graphene and composition test.
Prepare a method for Graphene based on purification by liquid extraction technique to high-efficiency, it is characterized in that the method comprises the following steps:
A. different size natural flake graphite is adopted to be raw material, the vitriol oil, potassium permanganate and SODIUMNITRATE is added successively as oxygenant under the condition of low temperature, whole process is carried out under the condition stirred, after oxidation 1 ~ 6h, add the distilled water diluting vitriol oil, control temperature is at 50 ~ 100 DEG C, and whole process is carried out under the condition stirred, and prepares graphite oxide;
B. remove excessive potassium permanganate and by product thereof in graphite oxide with hydrogen peroxide and dilute hydrochloric acid, ultrasonic 30min ~ 4h prepares graphene oxide dispersion afterwards;
C. extraction process purification graphene oxide dispersion is adopted, add ethyl acetate, toluene or benzene as extraction agent, violent stirring, after stratification, remove aqueous phase, add distilled water again, repeated multiple times carries out extracting and separating, repeats 2 ~ 3 times, treating can not layering again, recycling suction filtration or centrifugation technique, remove extraction solvent, thus obtain graphene oxide;
D. utilize microwave reduction technology, the graphene oxide of purification by liquid extraction is dispersed in distilled water, add hydrazine hydrate as reductive agent, redox graphene dispersion liquid, then adopt suction filtration or centrifugation technique repeatedly to clean to prepare Graphene.
The raw material adopted in the present invention is natural flake graphite, and graphite raw material is of a size of 45 ~ 500 μm.
The vitriol oil, potassium permanganate and SODIUMNITRATE is adopted to be oxidized graphite raw material in the present invention, the concentration of the vitriol oil is 98%, the mass ratio adding potassium permanganate and graphite is 1:6, and the mass ratio of SODIUMNITRATE and graphite is 1:2, and whole oxidizing temperature controls at 35 ± 5 DEG C.
Adopt the hydrogen peroxide cleaning cleaning of 3% to remove excessive potassium permanganate and by product in the present invention, with the metal oxide in the dilute hydrochloric acid cleaning graphite oxide of 5%, ultrasonic 30min ~ 4h prepares graphene oxide dispersion 1-10 mg/mL afterwards.
In the present invention, the extraction agent of purification by liquid extraction graphene oxide dispersion is ethyl acetate, toluene or benzene, be 1:2 ~ 6:1 with the amount ratio of graphene oxide dispersion volume, repeatedly carry out extracting and separating, then in conjunction with suction filtration or centrifugation technique, remove extraction solvent, thus obtain graphene oxide.
The microwave reduction technology that the graphene oxide that in the present invention, reduction extraction is purified adopts, adding the hydrazine hydrate of 85%, is 1:1 ~ 6:1 with the mass ratio of graphite, power application 60 ~ 120W, and heating 3 ~ 10min, prepares Graphene.
The present invention solves three technical problems in graphene oxide solution purification process.
1. reduce and preparing the impurity introduced in graphene oxide process, select relatively low proportioning raw materials to reduce production cost, shorten preparation time.
2. provide a kind of simple and fast, easily operation, equipment requirements low and the gordian technique of batch-automated purification graphene oxide can be realized, can be used as a kind of desirable method of purification being suitable for macroscopic preparation of graphene.
3. utilize the simplest reduction technique, efficiently prepare graphene product.
The Graphene purity that the present invention obtains, specific conductivity, specific surface area are as shown in table 1:
Table 1
| Purity | Specific conductivity | Specific surface area | |
| Graphene | ≥98.5% | ≥10 3 S/m | 330~450 m 2/g |
A little of the present invention:
Compared with the methods such as the identical character that 1.NTS phonoresponse is prepared is peeled off with chemical vapour deposition, micromechanics with the material of function preparation method of the present invention, liquid phase or gas phase is directly peeled off, epitaxy and traditional oxidation-stripping-reduction, equipment and process process is simple, experiment controllability is good, preparation cost is low, product is easy to get, preparation speed is fast, can accomplish scale production.
2. extraction purification method of the present invention, do not increase by the increase of Graphene preparation amount in the purification phase cycle, equipment requirements is low, and extraction organic solvent reusable edible, economizes on resources, reduce costs, be applicable to the preparation in macroscopic quantity of Graphene.
The present invention is easy and simple to handle, preparation cycle is short, without the need to purchasing equipment and the high cost raw material of complex and expensive, can prepare highly purified Graphene, be applicable to the preparation in macroscopic quantity of Graphene, be expected to be widely used in fields such as electrical condenser, fuel cell, sealing material, support of the catalyst.
Accompanying drawing explanation
Fig. 1. Graphene stereoscan photograph prepared by microwave reduction.Can find out that graphene sheet layer is thinner, obtain high-quality graphene sheet layer.
Fig. 2. Graphene transmission electron microscope photo.Can find out that graphene sheet layer is thinner, obtain high-quality graphene sheet layer.
Fig. 3. prepare the XPS spectrum figure of Graphene sample.Can find out in Graphene sample main containing C and O element.
Embodiment
Embodiment 1:
Measure the vitriol oil of 50 mL 98 %, be placed in the beaker of 500 mL, high purity graphite powder and the 1 g SODIUMNITRATE of 2 g 45 μm is added under ice-water bath protection magnetic agitation, after stirring, slowly add 6 g potassium permanganate powder and the stirring of accompanied by intense, joining day controls, at 30 min, to maintain the temperature at less than 20 DEG C; Increase the temperature to 35 ± 5 DEG C of reaction 1 h; Drip 100mL distilled water diluting mixed solution, control temperature within 80 DEG C, after adding.The hydrogen peroxide measuring 4mL 3% is placed in separating funnel, slowly drips, and mixed solution becomes glassy yellow and produces with bubble, and dilute hydrochloric acid 150 mL of configuration 5% joins in mixed solution, stirs 10 min.Then ultrasonic 30 min ~ 4h obtain graphene oxide, add 300 mL water again to stir, transfer in separating funnel, add the ethyl acetate of 150 mL as extraction agent, strong concussion, mixing aqueous phase and organic phase material, stratification, remove lower floor's waste liquid after 5 min and add 200 mL aqueous phases again, strong concussion, be divided into except lower floor's waste liquid, repeat 2 ~ 3 times, until can not layering again, collect the graphene oxide in organic phase, the aqueous phase of suction filtration or centrifugal segregation organic phase and remnants, graphene oxide after purification is transferred in distilled water and is diluted to 1mg/mL ~ 10mg/mL, add 2 g hydrazine hydrates, put into after stirring in microwave oven, 80 W reduce 5 min, yellow dispersion liquid becomes the turbid liquid of black, after suction filtration is washed to neutrality, mixed dry in 60 DEG C of baking ovens, thus prepare Graphene.
Embodiment 2:
The preparation method of graphene oxide is substantially identical with example 1, and difference is that graphite used is
500μm, the consumption of extraction agent is 200 mL.The hydrazine hydrate added during redox graphene is 4 g, and microwave application 100 W reduces 4 min.
Embodiment 3:
The preparation method of graphene oxide is substantially identical with example 1, and difference is that graphite used is
500μm, the consumption of extraction agent is 300 mL.The hydrazine hydrate added during redox graphene is 8 g, and microwave application 100 W reduces 3 min.
Embodiment 4:
The preparation method of graphene oxide is substantially identical with example 1, and difference is that extraction agent used is benzene, and consumption is 300 mL.The hydrazine hydrate added during redox graphene is 2 g, and microwave application 100 W reduces 3 min.
Embodiment 5:
The preparation method of graphene oxide is substantially identical with example 1, and difference is that extraction agent used is toluene, and consumption is 300 mL.The hydrazine hydrate added during redox graphene is 8 g, and microwave application 100 W reduces 3 min.
Electron microscopic observation result shows, the Graphene within 5 layers accounts for about 70 ~ 80% of product.
As shown in Figure 1, the Graphene prepared as can be seen from microwave reduction retouch photo, can find out that graphene sheet layer is thinner, illustrate and can obtain high-quality graphene sheet layer by this method.
As shown in Figure 2, characterizing transmission electron microscope by the Graphene of ultrasonic-microwave reduction in ethanol can find out, can obtain good graphene sheet layer through ultrasonic disperse.
As shown in Figure 3, for preparing the full spectrogram of Graphene sample, can be found out by curve, in the Graphene sample of preparation, mainly containing C and O element.
Claims (6)
1. prepare a method for Graphene based on purification by liquid extraction technique to high-efficiency, it is characterized in that the method comprises the following steps:
A. different size natural flake graphite is adopted to be raw material, the vitriol oil, potassium permanganate and SODIUMNITRATE is added successively as oxygenant under the condition of low temperature, whole process is carried out under the condition stirred, after oxidation 1 ~ 6h, add the distilled water diluting vitriol oil, control temperature is at 50 ~ 100 DEG C, and whole process is carried out under the condition stirred, and prepares graphite oxide;
B. remove excessive potassium permanganate and by product thereof in graphite oxide with hydrogen peroxide and dilute hydrochloric acid, ultrasonic 30min ~ 4h prepares graphene oxide dispersion afterwards;
C. extraction process purification graphene oxide dispersion is adopted, add ethyl acetate, toluene or benzene as extraction agent, violent stirring, after stratification, remove aqueous phase, add distilled water again, repeated multiple times carries out extracting and separating, repeats 2 ~ 3 times, treating can not layering again, recycling suction filtration or centrifugation technique, remove extraction solvent, thus obtain graphene oxide;
D. utilize microwave reduction technology, the graphene oxide of purification by liquid extraction is dispersed in distilled water, add hydrazine hydrate as reductive agent, redox graphene dispersion liquid, then adopt suction filtration or centrifugation technique repeatedly to clean to prepare Graphene.
2. the method for claim 1, is characterized in that natural flake graphite is of a size of 45 ~ 500 μm.
3. the method for claim 1, it is characterized in that adopting the vitriol oil, potassium permanganate and SODIUMNITRATE to be oxidized graphite raw material, the concentration of the vitriol oil is 98%, the mass ratio adding potassium permanganate and graphite is 1:6, the mass ratio of SODIUMNITRATE and graphite is 1:2, and whole oxidizing temperature controls at 35 ± 5 DEG C.
4. the method for claim 1, it is characterized in that excessive potassium permanganate and by product are removed in the hydrogen peroxide cleaning of employing 3%, with the metal oxide in the dilute hydrochloric acid cleaning graphite oxide of 5%, ultrasonic 30min ~ 4h prepares graphene oxide dispersion 1-10 mg/mL afterwards.
5. the method for claim 1, it is characterized in that the extraction agent of purification by liquid extraction graphene oxide dispersion is ethyl acetate, toluene or benzene, be 1:2 ~ 6:1 with the amount ratio of graphene oxide dispersion volume, repeatedly carry out extracting and separating, again in conjunction with suction filtration or centrifugation technique, remove extraction solvent, thus obtain graphene oxide.
6. the method for claim 1, it is characterized in that the microwave reduction technology that the graphene oxide that reduction extraction is purified adopts, adding the hydrazine hydrate of 85%, is 1:1 ~ 6:1 with the mass ratio of graphite, power application 60 ~ 120W, and heating 3 ~ 10min, prepares Graphene.
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| CN104118866A (en) * | 2014-06-25 | 2014-10-29 | 苏州世优佳电子科技有限公司 | Method for preparing graphene on basis of biological reduction process |
| KR20160088097A (en) * | 2015-01-15 | 2016-07-25 | 주식회사 그래핀올 | Method for Purifying Graphene Oxide |
| CN106450331B (en) * | 2016-10-27 | 2019-02-05 | 萝北奥星新材料有限公司 | The method for preparing graphene conductive agent slurry with graphite tailing |
| CN107632464A (en) | 2017-09-26 | 2018-01-26 | 京东方科技集团股份有限公司 | A kind of display panel, display device and preparation method thereof |
| CN107791614A (en) * | 2017-10-13 | 2018-03-13 | 南京旭羽睿材料科技有限公司 | The preparation of graphene composite film and its processing technology |
| CN108423662B (en) * | 2018-04-09 | 2021-10-01 | 合肥国轩高科动力能源有限公司 | Method for preparing high-concentration graphene based on extraction technology |
| CN109231196B (en) * | 2018-11-21 | 2021-04-27 | 中国科学院兰州化学物理研究所 | Method for preparing graphene oxide based on nonpolar organic solvent transfer purification technology |
| CN111681702B (en) * | 2020-06-09 | 2022-09-13 | 青岛科技大学 | Molecular dynamics-based biofuel purification method |
| CN116553533A (en) * | 2023-05-09 | 2023-08-08 | 浙江道明超导科技有限公司 | Preparation method of graphene sealing material |
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