CN103253661A - Method for preparing graphene powder at large scale - Google Patents
Method for preparing graphene powder at large scale Download PDFInfo
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- CN103253661A CN103253661A CN2013102004695A CN201310200469A CN103253661A CN 103253661 A CN103253661 A CN 103253661A CN 2013102004695 A CN2013102004695 A CN 2013102004695A CN 201310200469 A CN201310200469 A CN 201310200469A CN 103253661 A CN103253661 A CN 103253661A
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Abstract
The invention relates to a method for preparing high-quality graphene powder at low cost and large scale. The method comprises the following steps of: adding graphite to mixed solution containing an oxidizing agent and an intercalator, stirring evenly and then performing ultrasonic treatment, and simultaneously, continuously introducing He to form a graphite intercalation compound intercalated with the intercalator and He gas molecules; next, filtering, washing and drying, and performing thermal treatment in air to realize the first time of stripping of the graphite intercalation compound; later, dispersing the graphite intercalation compound in an organic solvent and performing ultrasonic treatment again under the condition of continuously introducing He; and then centrifuging and removing precipitate, and filtering, washing and drying the solution of the upper layer, thereby obtaining the graphene powder. The method provided by the invention is safe and environment-friendly, simple to operate and suitable for large-scale production; the prepared graphene has few defects and good electrical conductivity.
Description
Technical field
The present invention relates to a kind of method of mass preparation Graphene powder, belong to inorganic new material technology field.
Background technology
2004, the Andre K.Geim of Britain graceful Chester university etc. prepared grapheme material.Hereafter, Graphene causes extensive attention with its particular structure and photoelectric property.Graphene is that a kind of carbon atom is with sp
2Hybridized orbital Cheng Jian, the carbon material of the individual layer bi-dimensional cellular shape crystalline network that forms with six-membered ring structure.The structures shape of material its performance, this particular structure of Graphene has been brought particular performances to it, such as having high electronic mobility, being the present known the highest material of physical strength, and also have high thermal conductivity and big specific surface area, these good performances have determined the application of Graphene in various fields, as can be used for lithium ion battery, ultracapacitor, hydrogen storage and biologic material products etc.
At present the known method for preparing Graphene comprises that micromechanics peels off method, ultravacuum Graphene epitaxial growth method, oxidation reduction process, chemical Vapor deposition process, solvent and peel off method, electrolytic process, solvent-thermal method.Wherein the micromechanics method can only produce limited graphene film, generally as fundamental research.Ultravacuum epitaxial method and higher, the complex process of chemical Vapor deposition process cost.Though oxidation reduction process can be accomplished mass preparation, owing in the redox processes, destroyed sp
2The hybridization network structure causes the Graphene defective for preparing more.And the solvent-thermal method reaction times is very long and productive rate is low, has also limited its industrial applications.
Chinese invention patent CN 102066245A has announced " preparation method of graphene ", and this method is in the presence of alkali, will reduce with hydrazine hydrate through purifying, the graphite oxide that peels off.Hydrazine hydrate contains toxic, easily remains in the Graphene, and removes the step that impurity again need be extra.
Chinese invention patent CN 101139090A has announced " a kind of preparation method of two-dimension single layer plumbago alkene ", though this method can obtain high-quality Graphene, obviously, is difficult to accomplish scale preparation.
Summary of the invention
The objective of the invention is at the problems of the prior art, the method for a kind of low cost and energy mass preparation high quality Graphene powder is provided.
The present invention is achieved by the following technical solutions:
A kind of method of mass preparation Graphene powder, its feature comprises the steps:
(1) graphite is joined in the mixing solutions that contains oxygenant and intercalator, stir;
(2) supersound process feeds gas He simultaneously continuously, forms the graphite intercalation compound of intercalator and He molecule intercalation;
(3) filter, wash to neutrality dry then, obtain graphite intercalation compound;
(4) heat-treat in the air atmosphere, the realization graphite intercalation compound is peeled off first;
(5) graphite after will peeling off first is dispersed in the organic solvent, continues to feed gas He in the time of supersound process;
(6) the centrifugal precipitation of removing is got and is namely obtained the Graphene powder after upper solution is filtered, washs, dried.
Wherein,
In the step (1), described oxygenant is selected from concentrated nitric acid, hydrogen peroxide and the vitriol oil; Described intercalator is selected from concentrated nitric acid, hydrogen peroxide, acetic acid, diacetyl oxide, phosphoric acid and phosphoric anhydride; Oxygenant and intercalator are not with a kind of material simultaneously.
In the step (1), the ratio of the quality of described graphite, oxygenant and intercalator is 0.5～1:3～8:0.1～0.8.
In the step (1), the churning time of described graphite in oxygenant and intercalator mixing solutions is 3～9h.
In the step (2), the power of described supersound process is 600～1200w, and the supersound process time is 30～60 minutes; The Ventilation Rate of gas He is 0.1～1L/min in every liter of oxygenant and intercalator mixing solutions.
In the step (3), the temperature of described drying is 60～80 ℃; Time is 5～8h.
In the step (4), described heat treated temperature is 400～800 ℃, and the time is 10～100 seconds; The quick decomposition of intercalator and He molecule are overflowed from graphite layers in the heat treatment process, realize peeling off of graphite intercalation compound.
In the step (5), described organic solvent is selected from N-Methyl pyrrolidone, N, dinethylformamide, methyl-sulphoxide, toluene, Virahol and ethanol; The consumption of organic solvent is 100～1000g/g graphite.
In the step (5), the power of described supersound process is 600～1200w, and the supersound process time is 30～60 minutes; The Ventilation Rate of gas He is 0.1～1L/min in every liter of organic solvent.
In the step (6), the washing composition of described washing is the mixing solutions of ethanol and deionized water.
In the step (6), the temperature of described oven dry is 80～100 ℃, and drying time is 15～24h.
Technique effect of the present invention and advantage are:
1, introduce He gas molecule intercalation first, safer environmental protection, and simple to operate;
2, equipment is simple, production stage is few, productive rate is high, is fit to scale operation;
3, few, the good conductivity of Graphene powder defective that makes.
Description of drawings
The Raman spectrogram of the intercalated graphite that 1 different intercalation times of Fig. 1 embodiment, the auxiliary intercalation of same amount He atom obtain
The Tyndall phenomenon of the few layer graphene dispersion liquid after Fig. 2 embodiment 1 dilution
The Raman spectrogram of Fig. 3 embodiment 1 prepared Graphene dispersion liquid
The SEM figure of Fig. 4 embodiment 1 prepared Graphene
The TEM figure of Fig. 5 embodiment 1 prepared Graphene
The AFM figure of Fig. 6 embodiment 1 prepared Graphene
Embodiment
Below by specific specific examples technical scheme of the present invention is described.Should be understood that one or more method stepss that the present invention mentions do not repel before and after described combination step also exists the additive method step or can also insert the additive method step between these step of clearly mentioning; Should also be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not ordering or the enforceable scope of restriction the present invention for limiting various method steps, the change of its relativeness or adjustment, under the situation of no essence change technology contents, when also being considered as the enforceable category of the present invention.
(1) takes by weighing 3g graphite, add 20g concentrated nitric acid (67wt%) and 1.6g hydrogen peroxide (concentration 30wt%), stir 9h and obtain uniform suspension liquid;
(2) this suspension liquid is placed the ultrasonic 60min of ultrasonic cell pulverizer (800W), and continue to feed He gas with the speed of 0.1L/min;
(3) after ultrasonic and ventilation finishes, vacuum filtration, and with deionized water wash filter residue 3 times, be neutral, then with filter residue 60 ℃ of dry 8h in baking oven, obtain the graphite intercalation compound of drying;
(4) place microwave Muffle furnace, calcined 60 seconds for 400 ℃;
(5) join in the 610g N-Methyl pyrrolidone and obtain dispersion liquid, ultrasonic 60mim in ultrasonic cell pulverizer (1200w), in the time of ultrasonic in every liter of N-Methyl pyrrolidone the speed with 0.1L/min continue to feed He gas;
(6) in whizzer with 600 revolutions per seconds of centrifugal 30min of above-mentioned dispersion liquid, remove precipitation, get upper solution and namely obtain few layer graphene dispersion liquid, this dispersion liquid is adopted filtering with microporous membrane, mixed solution with ethanol and deionized water cleans filter cake, 80 ℃ of dryings are 24 hours then, can obtain few layer graphene.
Fig. 1 has shown the Raman spectrogram of intercalation 9h graphite raw material among the embodiment 1, and as can be seen, the graphite D peak intensity behind the intercalation obviously strengthens, and this phenomenon has proved the formation of graphite intercalation compound.
The Graphene dispersion liquid that obtains for embodiment 1 that Fig. 2 shows dilutes this dispersion liquid with N-Methyl pyrrolidone, use laser beam irradiation, the Tyndall phenomenon of generation.This dispersion liquid left standstill 3 months, did not have precipitation and produced stably dispersing.
The Raman spectrogram of the Graphene dispersion liquid that obtains for embodiment 1 that Fig. 3 shows, as can be seen, the corresponding D of 1350 wave numbers peak wherein, the corresponding G of 1580 wave numbers peak, 2700 wave numbers correspondence 2D peak.The ratio of peak at D peak and G peak is 0.43, and the peak type symmetry at 2D peak, and the distinctive acromion of no graphite proves that prepared Graphene defective is less, excellent performance.
The SEM figure of the Graphene that obtains for embodiment 1 that Fig. 4 shows, as can be seen, the degree that the Graphene that obtains is peeled off is very high.
Fig. 5 is shown as the TEM figure of the Graphene that embodiment 1 obtains, and as can be seen, the lamella of few layer graphene of preparation has 8 atomic layer level thickness.
Fig. 6 shows obtain for embodiment 1 the AFM of Graphene scheme, as can be seen, the lamellar spacing of few layer graphene of preparation is between 2.5～3nm.May residually there be solvent on the Graphene surface that obtains, and the number of plies of Graphene is about 3～8 layers.Through substantive test show the graphene film layer thickness that obtains between 1～10 layer.
The present embodiment operation is identical with embodiment 1, difference is: the churning time of graphite in concentrated nitric acid and hydrogen peroxide is 3h in the step (1), disperse the solvent of ultrasonic usefulness to change N in the step (5), dinethylformamide, prepared Graphene performance is similar to Example 1, has few layer, few, the specific conductivity advantages of higher of defective.
Embodiment 3
The present embodiment operation is identical with embodiment 1, and difference is: step (2) supersound process power is made as 1200W, ultrasonic 30min; The solvent of the ultrasonic usefulness of step (5) dispersion changes the mixture of Virahol and ethanol, Virahol consumption 150g, ethanol consumption 150g into; Prepared Graphene performance is similar to Example 1, has few layer, few, the specific conductivity advantages of higher of defective.
Embodiment 4
The present embodiment operation is identical with embodiment 1, and difference is: oxygenant selects for use the 80g vitriol oil (concentration 98wt%) and intercalator to select the 8g phosphoric anhydride for use in the step (1), and the graphite consumption is 10g; Heat treatment period is 800 ℃, thermal treatment 30 seconds; Step (5) disperses the solvent of ultrasonic usefulness to change methyl-sulphoxide into, supersound process power 600W, ultrasonic 30 seconds; Prepared Graphene performance is similar to Example 1, has few layer, few, the specific conductivity advantages of higher of defective.
The present embodiment operation is identical with embodiment 1, and difference is: oxygenant and intercalator change hydrogen peroxide (concentration 30wt%) and diacetyl oxide in the step (1), and graphite takes by weighing 3g, and hydrogen peroxide is got 160g, and diacetyl oxide is got 4.8g; Speed with 1L/min in the mixing solutions of the middle every liter of oxygenant of supersound process process of step (2) and intercalator continues to feed He; Step (5) disperses the organic solvent of ultrasonic usefulness to change toluene into, and He feeding speed is 1L/min in every liter of organic solvent of ultrasonic procedure; Prepared Graphene performance is similar to Example 1, has few layer, few, the specific conductivity advantages of higher of defective.
Embodiment 6
The present embodiment operation is identical with embodiment 1, and difference is: oxygenant and intercalator change concentrated nitric acid (concentration 67wt%) and the vitriol oil (concentration 98wt%) in the step (1); Step (5) disperses the solvent of ultrasonic usefulness to change the mixture of acetic acid and phosphoric anhydride into, and the acetic acid consumption is 300g, and the consumption of phosphoric anhydride is 310g, and He feeding speed is 0.8L/min in every liter of mixed organic solvents of ultrasonic procedure; (6) 100 ℃ of following dry 15h of step; Prepared Graphene performance is similar to Example 1, has few layer, few, the specific conductivity advantages of higher of defective.
Embodiment 7
The present embodiment operation is identical with embodiment 1, difference is: step (1) oxygenant changes concentrated nitric acid (concentration 67wt%) into, intercalator changes the mixture of diacetyl oxide and phosphoric acid into, and the consumption of each material is graphite 20g, concentrated nitric acid 100g, diacetyl oxide 4g, phosphoric acid 6g; Prepared Graphene performance is similar to Example 1, has few layer, few, the specific conductivity advantages of higher of defective.
Claims (10)
1. the method for a mass preparation Graphene powder may further comprise the steps:
(1) graphite is joined in the mixing solutions that contains oxygenant and intercalator, stir;
(2) supersound process feeds gas He simultaneously continuously, forms the graphite intercalation compound of intercalator and He molecule intercalation;
(3) filter, wash to neutrality dry then, obtain graphite intercalation compound;
(4) heat-treat in the air atmosphere, the realization graphite intercalation compound is peeled off first;
(5) graphite after will peeling off first is dispersed in the organic solvent, continues to feed gas He in the time of supersound process;
(6) the centrifugal precipitation of removing is got and is namely obtained the Graphene powder after upper solution is filtered, washs, dried.
2. the method for a kind of mass preparation Graphene powder as claimed in claim 1 is characterized in that, in the step (1), described oxygenant is selected from concentrated nitric acid, hydrogen peroxide and the vitriol oil; Described intercalator is selected from concentrated nitric acid, hydrogen peroxide, acetic acid, diacetyl oxide, phosphoric acid and phosphoric anhydride; Oxygenant and intercalator are not with a kind of material simultaneously.
3. the method for a kind of mass preparation Graphene powder as claimed in claim 1 is characterized in that, in the step (1), the ratio of the quality of described graphite, oxygenant and intercalator is 0.5～1:3～8:0.1～0.8.
4. the method for a kind of mass preparation Graphene powder as claimed in claim 1 is characterized in that, in the step (1), the churning time of graphite in oxygenant and intercalator mixing solutions is 3～9h.
5. the method for a kind of mass preparation Graphene powder as claimed in claim 1 is characterized in that, in the step (2), the power of described supersound process is 600～1200w, and the supersound process time is 30～60 minutes; The Ventilation Rate of gas He is 0.1～1L/min in every liter of oxygenant and intercalator mixing solutions.
6. the method for a kind of mass preparation Graphene powder as claimed in claim 1 is characterized in that, in the step (3), the temperature of described drying is 60～80 ℃; Time is 5～8h.
7. the method for a kind of mass preparation Graphene powder as claimed in claim 1 is characterized in that, in the step (4), described heat treated temperature is 400～800 ℃, and the time is 10～100 seconds.
8. the method for a kind of mass preparation Graphene powder as claimed in claim 1 is characterized in that, in the step (5), described organic solvent is selected from and is N-Methyl pyrrolidone, N, dinethylformamide, methyl-sulphoxide, toluene, Virahol and ethanol; The consumption of organic solvent is 100～1000g/g graphite.
9. the method for a kind of mass preparation Graphene powder as claimed in claim 1 is characterized in that, in the step (5), the power of described supersound process is 600～1200w, and the supersound process time is 30～60 minutes; The Ventilation Rate of gas He is 0.1～1L/min in every liter of organic solvent.
10. the method for a kind of mass preparation Graphene powder as claimed in claim 1 is characterized in that, in the step (6), the temperature of described oven dry is 80～100 ℃, and drying time is 15～24h.
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Cited By (9)
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| CN104891481A (en) * | 2015-05-30 | 2015-09-09 | 同济大学 | Large-scale preparation method of high-quality graphene |
| CN105060283A (en) * | 2015-08-05 | 2015-11-18 | 深圳市三顺中科新材料有限公司 | Preparation method and application of graphene slurry |
| CN105366668A (en) * | 2015-11-04 | 2016-03-02 | 福建翔丰华新能源材料有限公司 | Method for preparing graphene through supercritical fluid |
| WO2017084606A1 (en) * | 2015-11-18 | 2017-05-26 | 复旦大学 | Method for directly preparing expanded graphite or graphene under normal temperature and normal pressure |
| CN108069417A (en) * | 2016-11-16 | 2018-05-25 | 财团法人纺织产业综合研究所 | Airflow generation device, graphene dispersion liquid and preparation method thereof |
| CN110615430A (en) * | 2019-10-17 | 2019-12-27 | 桂林理工大学 | Novel preparation method of primary few-layer graphene |
| CN113896186A (en) * | 2021-09-10 | 2022-01-07 | 山东建筑大学 | Preparation method of defective graphene |
| CN114408907A (en) * | 2021-12-27 | 2022-04-29 | 无锡菲勒高性能材料有限公司 | Carbon black-based graphene and preparation method and application thereof |
| CN114735687A (en) * | 2022-05-11 | 2022-07-12 | 深圳材启新材料有限公司 | Synthetic method of graphene |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104891481A (en) * | 2015-05-30 | 2015-09-09 | 同济大学 | Large-scale preparation method of high-quality graphene |
| CN104891481B (en) * | 2015-05-30 | 2018-02-09 | 同济大学 | A kind of large-scale preparation method of high-quality graphene |
| CN105060283A (en) * | 2015-08-05 | 2015-11-18 | 深圳市三顺中科新材料有限公司 | Preparation method and application of graphene slurry |
| CN105366668A (en) * | 2015-11-04 | 2016-03-02 | 福建翔丰华新能源材料有限公司 | Method for preparing graphene through supercritical fluid |
| WO2017084606A1 (en) * | 2015-11-18 | 2017-05-26 | 复旦大学 | Method for directly preparing expanded graphite or graphene under normal temperature and normal pressure |
| US10927009B2 (en) | 2015-11-18 | 2021-02-23 | Fudan University | Method for directly preparing expanded graphite or graphene under normal temperature and normal pressure |
| CN108069417A (en) * | 2016-11-16 | 2018-05-25 | 财团法人纺织产业综合研究所 | Airflow generation device, graphene dispersion liquid and preparation method thereof |
| CN110615430A (en) * | 2019-10-17 | 2019-12-27 | 桂林理工大学 | Novel preparation method of primary few-layer graphene |
| CN113896186A (en) * | 2021-09-10 | 2022-01-07 | 山东建筑大学 | Preparation method of defective graphene |
| CN114408907A (en) * | 2021-12-27 | 2022-04-29 | 无锡菲勒高性能材料有限公司 | Carbon black-based graphene and preparation method and application thereof |
| CN114735687A (en) * | 2022-05-11 | 2022-07-12 | 深圳材启新材料有限公司 | Synthetic method of graphene |
| CN114735687B (en) * | 2022-05-11 | 2023-09-26 | 深圳材启新材料有限公司 | Synthesis method of graphene |
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