CN103253661B - Method for preparing graphene powder at large scale - Google Patents
Method for preparing graphene powder at large scale Download PDFInfo
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- CN103253661B CN103253661B CN201310200469.5A CN201310200469A CN103253661B CN 103253661 B CN103253661 B CN 103253661B CN 201310200469 A CN201310200469 A CN 201310200469A CN 103253661 B CN103253661 B CN 103253661B
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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 preparing on a large scale graphene powder, belong to New Inorganic Materials technical field.
Background technology
2004, the Andre K.Geim of Britain graceful Chester university etc. prepared grapheme material.Hereafter, Graphene causes extensive attention with its unique 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 forming with six-membered ring structure.The structures shape of material its performance, the structure of this uniqueness of Graphene has been brought unique performance to it, such as thering is high electronic mobility, being the current known the highest material of physical strength, and also there is high thermal conductivity and large 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.
The known method of preparing Graphene comprises micromechanics stripping method, ultravacuum Graphene epitaxial growth method, oxidation reduction process, chemical Vapor deposition process, solvent stripping method, electrolytic process, solvent-thermal method at present.Wherein micromechanics method can only produce limited graphene film, generally as fundamental research.Ultravacuum epitaxial method and chemical Vapor deposition process cost are higher, complex process.Although oxidation reduction process can be accomplished extensive preparation, in redox processes, destroyed sp
2hybridization network structure, causes the Graphene defect preparing more.And the solvent-thermal method reaction times is very long and productive rate is low, also limited its industrial applications.
Chinese invention patent CN 102066245A has announced the preparation method > > of < < Graphene, this method is under alkali exists, and the graphite oxide that passes through purifying, peel off is reduced with hydrazine hydrate.Hydrazine hydrate containing toxic, easily remains in Graphene, and removes impurity and need again extra step.
Chinese invention patent CN 101139090A has announced the preparation method > > of a < < two-dimension single layer plumbago alkene; although the method can obtain high-quality Graphene; but obviously, be difficult to accomplish mass-producing preparation.
Summary of the invention
The object of the invention is to for the problems of the prior art, a kind of low cost is provided and can prepares on a large scale the method for high-quality graphene powder.
The present invention is achieved by the following technical solutions:
A method of preparing on a large scale graphene powder, its feature comprises the steps:
(1) graphite is joined in the mixing solutions that contains oxygenant and intercalator, stir;
(2) supersound process, passes into gas He simultaneously continuously, forms the graphite intercalation compound of intercalator and He molecule intercalation;
(3) filter, wash to neutrality then dry, obtain graphite intercalation compound;
(4) in air atmosphere, heat-treat, realize graphite intercalation compound and peel off first;
(5) graphite after peeling off is first dispersed in organic solvent, in the time of supersound process, continues to pass into gas He;
(6) the centrifugal precipitation of removing, gets after upper solution is filtered, washs, dried and obtains graphene powder.
Wherein,
In 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; It when oxygenant is different with intercalator, is same material.
In step (1), the mass ratio of described graphite, oxygenant and intercalator is 0.5～1:3～8:0.1～0.8.
In step (1), the churning time of described graphite in oxygenant and intercalator mixing solutions is 3～9h.
In step (2), the power of described supersound process is 600～1200w, and the supersound process time is 30～60 minutes; In every liter of oxygenant and intercalator mixing solutions, the Ventilation Rate of gas He is 0.1～1L/min.
In step (3), described dry temperature is 60～80 ℃; Time is 5～8h.
In step (4), described heat treated temperature is 400～800 ℃, and the time is 10～100 seconds; In heat treatment process, intercalator fast decoupled and He molecule are overflowed from graphite layers, realize peeling off of graphite intercalation compound.
In step (5), described organic solvent is selected from N-Methyl pyrrolidone, DMF, methyl-sulphoxide, toluene, Virahol and ethanol; The consumption of organic solvent is 100～1000g/g graphite.
In step (5), the power of described supersound process is 600～1200w, and the supersound process time is 30～60 minutes; In every liter of organic solvent, the Ventilation Rate of gas He is 0.1～1L/min.
In step (6), the washing composition of described washing is the mixing solutions of ethanol and deionized water.
In 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 first He gas molecule intercalation, safer environmental protection, and simple to operate;
2, equipment is simple, production stage is few, productive rate is high, is applicable to scale operation;
3, the graphene powder defect that makes is few, good conductivity.
Accompanying drawing explanation
The Raman spectrogram of the intercalated graphite that different intercalation time of Fig. 1 embodiment 1, 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 dispersing solution
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
By specific specific examples, technical scheme of the present invention is described below.Should be understood that one or more method stepss that the present invention mentions do not repel between the step that also has additive method step or clearly mention at these before and after described combination step can also insert additive method step; Should also be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, without essence change technology contents in the situation that, when being also considered as the enforceable category of the present invention.
Embodiment 1
(1) take 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 in to the ultrasonic 60min of ultrasonic cell disrupte device (800W), and continues to pass into 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 neutrality, then, by filter residue 60 ℃ of dry 8h in baking oven, obtain dry graphite intercalation compound;
(4) be placed in microwave Muffle furnace, calcine 60 seconds for 400 ℃;
(5) join in 610g N-Methyl pyrrolidone and obtain dispersion liquid, ultrasonic 60mim in ultrasonic cell disrupte device (1200w), in the time of ultrasonic, in every liter of N-Methyl pyrrolidone, the speed with 0.1L/min continues to pass into He gas;
(6) in whizzer by 600 revolutions per seconds of centrifugal 30min of above-mentioned dispersion liquid, remove precipitation, get upper solution and obtain few layer graphene dispersion liquid, this dispersion liquid is adopted to filtering with microporous membrane, with the mixed solution of ethanol and deionized water, clean filter cake, then 80 ℃ are dried 24 hours, can obtain few layer graphene.
Fig. 1 has shown the Raman spectrogram of intercalation 9h graphite raw material in embodiment 1, can find out, the graphite D peak intensity after intercalation obviously strengthens, and this phenomenon has proved the formation of graphite intercalation compound.
The graphene dispersing solution obtaining for embodiment 1 that Fig. 2 shows, dilutes this dispersion liquid with N-Methyl pyrrolidone, with laser beam irradiation, and the Tyndall phenomenon of generation.Standing 3 months of this dispersion liquid, produces stably dispersing without precipitation.
The Raman spectrogram of the graphene dispersing solution obtaining for embodiment 1 that Fig. 3 shows, can find out, the corresponding D of 1350 wave numbers peaks wherein, the corresponding G of 1580 wave numbers peaks, 2700 wave numbers correspondence 2D peaks.The ratio of peak at D peak and G peak is 0.43, and the peak type at 2D peak is symmetrical, without the distinctive acromion of graphite, proves that prepared Graphene defect is less, excellent performance.
The SEM figure of the Graphene obtaining for embodiment 1 that Fig. 4 shows, can find out, the degree that the Graphene obtaining is peeled off is very high.
Fig. 5 is shown as the TEM figure of the Graphene that embodiment 1 obtains, and can find out, the lamella of few layer graphene of preparation has 8 atomic layer level thickness.
Fig. 6 shows for embodiment 1, obtain the AFM of Graphene scheme, can find out, the lamellar spacing of few layer graphene of preparation is between 2.5～3nm.The Graphene surface obtaining may remain solvent, and the number of plies of Graphene is about 3～8 layers.Through a large amount of tests, show that obtained graphene film layer thickness is between 1～10 layer.
Embodiment 2
The present embodiment operation is identical with embodiment 1, difference is: in step (1), the churning time of graphite in concentrated nitric acid and hydrogen peroxide is 3h, in step (5), disperse the solvent of ultrasonic use to change N into, dinethylformamide, prepared Graphene performance is similar to Example 1, has that few layer, defect are few, specific conductivity advantages of higher.
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; Step (5) disperses the solvent of ultrasonic use to change the mixture of Virahol and ethanol, Virahol consumption 150g, ethanol consumption 150g into; Prepared Graphene performance is similar to Example 1, has that few layer, defect are few, specific conductivity advantages of higher.
Embodiment 4
The present embodiment operation is identical with embodiment 1, and difference is: in step (1), oxygenant selects the 80g vitriol oil (concentration 98wt%) and intercalator to select 8g phosphoric anhydride, and graphite consumption is 10g; The heat treated time is 800 ℃, thermal treatment 30 seconds; Step (5) disperses the solvent of ultrasonic use to change methyl-sulphoxide into, supersound process power 600W, ultrasonic 30 seconds; Prepared Graphene performance is similar to Example 1, has that few layer, defect are few, specific conductivity advantages of higher.
Embodiment 5
The present embodiment operation is identical with embodiment 1, and difference is: in step (1), oxygenant and intercalator change hydrogen peroxide (concentration 30wt%) and diacetyl oxide into, and graphite takes 3g, and hydrogen peroxide is got 160g, and diacetyl oxide is got 4.8g; In step (2), in the mixing solutions of every liter of oxygenant of supersound process process and intercalator, the speed with 1L/min continues to pass into He; Step (5) disperses the organic solvent of ultrasonic use to change toluene into, and in every liter of organic solvent of ultrasonic procedure, to pass into speed be 1L/min to He; Prepared Graphene performance is similar to Example 1, has that few layer, defect are few, specific conductivity advantages of higher.
Embodiment 6
The present embodiment operation is identical with embodiment 1, and difference is: in step (1), oxygenant and intercalator change concentrated nitric acid (concentration 67wt%) and the vitriol oil (concentration 98wt%) into; Step (5) disperses the solvent of ultrasonic use to change the mixture of acetic acid and phosphoric anhydride into, and acetic acid consumption is 300g, and the consumption of phosphoric anhydride is 310g, and in every liter of mixed organic solvents of ultrasonic procedure, to pass into speed be 0.8L/min to He; Dry 15h at (6) 100 ℃ of steps; Prepared Graphene performance is similar to Example 1, has that few layer, defect are few, specific conductivity advantages of higher.
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 that few layer, defect are few, specific conductivity advantages of higher.
Claims (10)
1. prepare on a large scale a method for graphene powder, comprise the following steps:
(1) graphite is joined in the mixing solutions that contains oxygenant and intercalator, stir;
(2) supersound process, passes into gas He simultaneously continuously, forms the graphite intercalation compound of intercalator and He molecule intercalation;
(3) filter, wash to neutrality then dry, obtain graphite intercalation compound;
(4) in air atmosphere, heat-treat, realize graphite intercalation compound and peel off first;
(5) graphite after peeling off is first dispersed in organic solvent, in the time of supersound process, continues to pass into gas He;
(6) the centrifugal precipitation of removing, gets after upper solution is filtered, washs, dried and obtains graphene powder.
2. a kind of method of preparing on a large scale graphene powder as claimed in claim 1, is characterized in that, in 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; It when oxygenant is different with intercalator, is same material.
3. a kind of method of preparing on a large scale graphene powder as claimed in claim 1, is characterized in that, in step (1), the mass ratio of described graphite, oxygenant and intercalator is 0.5～1:3～8:0.1～0.8.
4. a kind of method of preparing on a large scale graphene powder as claimed in claim 1, is characterized in that, in step (1), the churning time of graphite in oxygenant and intercalator mixing solutions is 3～9h.
5. a kind of method of preparing on a large scale graphene powder as claimed in claim 1, is characterized in that, in step (2), the power of described supersound process is 600～1200w, and the supersound process time is 30～60 minutes; In every liter of oxygenant and intercalator mixing solutions, the Ventilation Rate of gas He is 0.1～1L/min.
6. a kind of method of preparing on a large scale graphene powder as claimed in claim 1, is characterized in that, in step (3), described dry temperature is 60～80 ℃; Time is 5～8h.
7. a kind of method of preparing on a large scale graphene powder as claimed in claim 1, is characterized in that, in step (4), described heat treated temperature is 400～800 ℃, and the time is 10～100 seconds.
8. a kind of method of preparing on a large scale graphene powder as claimed in claim 1, is characterized in that, in step (5), described organic solvent is selected from as N-Methyl pyrrolidone, DMF, methyl-sulphoxide, toluene, Virahol and ethanol; The consumption of organic solvent is 100～1000g/g graphite.
9. a kind of method of preparing on a large scale graphene powder as claimed in claim 1, is characterized in that, in step (5), the power of described supersound process is 600～1200w, and the supersound process time is 30～60 minutes; In every liter of organic solvent, the Ventilation Rate of gas He is 0.1～1L/min.
10. a kind of method of preparing on a large scale graphene powder as claimed in claim 1, is characterized in that, in step (6), the temperature of described oven dry is 80～100 ℃, and drying time is 15～24h.
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| 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 |
| CN105253878B (en) | 2015-11-18 | 2018-06-26 | 复旦大学 | A kind of method that expanded graphite or graphene are directly prepared under normal temperature and pressure |
| CN108069417B (en) * | 2016-11-16 | 2020-06-09 | 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 |
| 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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| US7658901B2 (en) * | 2005-10-14 | 2010-02-09 | The Trustees Of Princeton University | Thermally exfoliated graphite oxide |
| CN102452649B (en) * | 2010-10-18 | 2014-04-02 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene |
| CN101993065B (en) * | 2010-12-17 | 2012-09-05 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene powder |
| CN102491318B (en) * | 2011-12-13 | 2013-08-14 | 河北工业大学 | Method for preparing graphene oxide |
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