CN103833008A - Method for preparing graphene at normal temperature - Google Patents
Method for preparing graphene at normal temperature Download PDFInfo
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- CN103833008A CN103833008A CN201210471513.1A CN201210471513A CN103833008A CN 103833008 A CN103833008 A CN 103833008A CN 201210471513 A CN201210471513 A CN 201210471513A CN 103833008 A CN103833008 A CN 103833008A
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Abstract
The invention discloses a method for preparing graphene at normal temperature. The method adopts natural flake graphite with different meshes as a raw material, graphite is intercalated at room temperature by utilizing concentrated sulfuric acid, persulfate and hydrogen peroxide, expansion peeling is carried out in the static intercalation process of the graphite, and the intercalation process does not need heating or stirring. High-quality graphene can be obtained by peeling graphene aggregates through an ultrasonic process and carrying out in-situ freeze drying. The method has the advantages of simplicity, easy control, mild and safe reaction, no need of any special protection, and realization of the low-cost large-scale preparation of a high-quality graphene material.
Description
Technical field
The present invention relates to the technology of preparing of Graphene, be specially the gentle method of preparing Graphene under normal temperature.
Background technology
" Graphene " this term is just suggested before very early, is used for defining in intercalated graphite compounds independently one deck Two-dimensional Carbon atomic shell.In the structure of single order intercalation, Two-dimensional Carbon atomic shell is adjacent with intercalation thing, and the monolayer carbon atom in this structure is called Graphene.In theory, Graphene was once considered to, because thermal vibration under non-zero absolute temperature causes the difference of fluctuation, cause fluctuation displacement and the interatomic distance of carbon atom suitable, caused its thermodynamic instability, cannot under non-zero absolute temperature, exist.Until 2004, A. K. professor Geim of University of Manchester adopts tape stripping method to prepare self-existent Graphene, and test its unique physical properties, this two-dimensional nano Carbon Materials has just caused whole world scientist's extensive concern and very big interest (Science 2004,306:666.).
The special construction of Graphene has given Graphene a lot of excellent performances, as: peculiar quantum hall effect, high Young's modulus (～1,100 GPa), high elastic coefficient (130 GPa), good (～5,000 Wm of thermal conductivity
-1k
-1), high (200,000 cm of electronic mobility
2v
-1s
-1), high-specific surface area (calculated value, 2,630 m
2g
-1), light transmission is good, be easy to functionalization etc.These excellent performances also make Graphene have broad application prospects in a lot of fields such as nanometer electronic device, nesa coating, electrode materials, matrix material (
nat. Mater. 2007,
6, 183;
science 2009,
324, 1530.).But at present Graphene can't preparation in macroscopic quantity, and expensive price has seriously hindered the application process of Graphene.Therefore, how preparation in macroscopic quantity high quality, the controlled and cheap Graphene of structure have become the Main Bottleneck of current Graphene application and development aspect, are also urgent problems.
The method of preparing at present Graphene mainly contains mechanically peel method, SiC substrate surface epitaxial growth method, chemical Vapor deposition process and liquid chemical method.This several method respectively has relative merits, and comparatively speaking, liquid chemical method requires simple relatively to production unit, can prepare the sample of relative magnanimity, is the relatively more conventional method of preparing Graphene in current laboratory.Chemical method is prepared Graphene and is mainly adopted modification Hummers method, first obtain graphite oxide, obtain graphene oxide by ultrasonic dispersion, and then obtain Graphene by the method for reduction, this method preparation technology is loaded down with trivial details, and easily produce a large amount of chemical waste fluids, be unfavorable for saving production cost and environmental protection.In addition, in chemical oxidation of gold, can produce a lot of defects, thereby have a strong impact on the quality of Graphene product.Graft process, because technique is simple, can not produce strong oxidation in the process of preparation, is one of most potential method of preparation in macroscopic quantity high-quality graphene.Over the past two years, there is gradually the report of preparing Graphene about graft process, but also had some problems in current reported intercalation method, be unfavorable for that mass-producing prepared Graphene.Wherein undertaken in the method for intercalation by halogen or metal halide, before preparation, the mixing of material need to be carried out in glove box, and the bad removal of halogen in the Graphene sample of preparation; Another kind is prepared Graphene by chlorsulfonic acid, because chlorsulfonic acid is that severe corrosive acid-respons is violent, and can discharge a large amount of heat in reaction process, is unfavorable for the preparation in macroscopic quantity of Graphene.Therefore, at present the preparation in macroscopic quantity of Graphene remains a key issue that affect Graphene mass-producing application, if can invent a kind of simple, Graphene that quick, efficient method is prepared magnanimity, has very important significance for the application of Graphene.
Summary of the invention
The object of the present invention is to provide the gentle novel method of preparing Graphene under a kind of room temperature condition.
The invention provides a kind of gentle method of preparing Graphene under room temperature, it is raw material that the method adopts the natural flake graphite of different meshes, utilize the vitriol oil, persulphate and hydrogen peroxide at ambient temperature graphite to be carried out to intercalation, graphite can expand and peel off simultaneously in the process that leaves standstill intercalation, and this process is without heating, without stirring.Then adopt ultrasonic method to peel off Graphene aggregate in conjunction with the dry high-quality graphene that obtains of In-situ condensation.
A gentle method of preparing Graphene under normal temperature, is characterized in that concrete steps are:
The intercalation of A graphite expands: adopting different size natural flake graphite is raw material, and the vitriol oil, persulphate and hydrogen peroxide are once added wherein at ambient temperature, graphite is oxidized to intercalation and expands simultaneously and peel off generation Graphene aggregate;
The cleaning of B Graphene aggregate: the Graphene aggregate of expansion is cleaned repeatedly with clear water, until the pH=7 of water; Carry out again In-situ condensation dry;
Dispersion and the collection of C Graphene aggregate: dry Graphene aggregate is put into organic solvent and adopt the mode of ultrasonic dispersion further to peel off; After centrifugation, carry out again the dry Graphene that obtains of In-situ condensation.
In A step, the whole process that graphite is oxidized intercalation does not need heating or stirs, and under standing condition, can complete.Graphite expands and peels off simultaneously in intercalation process, generates Graphene aggregate.This process is spontaneous to be completed, reaction temperature and, without very exothermic, without dangerous.
In B step, carry out In-situ condensation and be dried, be to reunite again for fear of Graphene aggregate.
In C step, the Graphene after peeling off is reunited, and carries out In-situ condensation again and be dried after centrifugation.
The raw material adopting in the present invention is natural flake graphite, and graphite raw material is of a size of 40-500 μ m.
In the present invention, adopt the vitriol oil, persulphate and hydrogen peroxide to be oxidized intercalation to graphite raw material, the concentration of persulphate in sulfuric acid is 10 mg/mL～2 g/mL, and the volume ratio of sulfuric acid and hydrogen peroxide is 20:1～1:1.
In the present invention, adopt the vitriol oil, persulphate and hydrogen peroxide to be oxidized intercalation to graphite raw material, persulphate preferred concentration in sulfuric acid is 50 mg/mL～1 g/mL, and the preferred volume ratio of sulfuric acid and hydrogen peroxide is 10:1～5:1.
In the present invention, graphite expands in the process of intercalation simultaneously, and leaving standstill the expansion time is that 10 min～40 h(are preferably 20 min～8 h), and expansion temperature is room temperature.
In the present invention, by the Graphene aggregate of expansion is put into clear water, repeatedly washing, until the pH value of water is 7, then carries out lyophilize.Be that 8 h～40 h(are preferably 10 h～20 h) time of drying of Graphene aggregate.
Graphene aggregate is put into organic solvent, and to be that N-Methyl pyrrolidone, DMF, ethanol or acetone carry out ultrasonic, and the ultrasonic time is that 1 h～24 h(is preferably 2 h～6 h).It is dry that Graphene after peeling off carries out In-situ condensation again, and sublimation drying is that 8 h～40 h(are preferably 10 h～16 h).
Feature of the present invention and beneficial effect are:
1, the present invention adopts the natural flake graphite of different size as raw material, adopt the method for at room temperature naturally leniently carrying out intercalation and expansion to prepare Graphene aggregate, realize peeling off of Graphene aggregate by the method for ultrasonic dispersion again, and utilize In-situ condensation dry technology to obtain the Graphene product of magnanimity.
2, reaction process gentleness of the present invention, without very exothermic, without special protection, technical process is simple, and preparation cost is low and Graphene quality is high, can be expected to realize the large-scale production of Graphene.
The present invention has cost low (agents useful for same kind and consumption are few, cheapness), flow process simple (without or stir), the advantages such as safety controlled (process gentleness, without special protection), therefore can be used as a kind of Perfected process that is suitable for macroscopic preparation of graphene.
Accompanying drawing explanation
Contrast photo before and after Fig. 1, graphite expand through gentle intercalation under room temperature.Can find out that this method has good intercalation expansion effect to graphite.
The stereoscan photograph of Fig. 2, intercalation expansion and dry rear Graphene aggregate.Can find out that Graphene aggregate is by forming compared with laminated layer.
Fig. 3, prepare the transmission electron microscope photo of Graphene product.Can find out that Graphene aggregate is by obtaining thinner graphene sheet layer after ultrasonic.
Fig. 4, prepare the XPS spectrum figure of Graphene sample.Can find out and in Graphene sample, mainly contain C and O element.
The C1s peak of Fig. 5, Graphene sample.Can find out that Graphene sample is not substantially containing aerobic functional group.
S2p peak in Fig. 6, Graphene sample.Can find out in the Graphene sample of preparation and substantially not contain S element.
Embodiment
Embodiment 1
Adopt the method for the vitriol oil, Potassium Persulphate, hydrogen peroxide oxidation intercalation that graphite is peeled off: the natural flake graphite that first 0.3 g is of a size of in the present embodiment to 500 μ m once joins 20 mL H
2sO
4, 1 g K
2s
2o
8with 4 mL H
2o
2mixed solution in, room temperature leaves standstill 8 h, crystalline flake graphite carries out the gentle intercalation of nature and expands, expanding volume is 95 mL.Graphene aggregate after expanding is cleaned repeatedly with clear water, until after the pH value of washing lotion becomes 7, utilize In-situ condensation drying machine that Graphene aggregate is dried.
Graphene aggregate powder is disperseed in N-Methyl pyrrolidone (NMP), utilize and ultrasonicly peel off Graphene aggregate, and then obtain the dispersion liquid of Graphene in NMP.Wherein, ultrasonic power is 800 W, and ultrasonic time is 4 h.Product after filtering is carried out to lyophilize, finally obtain Graphene product.
Electron microscopic observation result shows: the Graphene within 5 layers accounts for 35% left and right of product.
Embodiment 2
Adopt the method for sulfuric acid, Potassium Persulphate, hydrogen peroxide oxidation intercalation that graphite is peeled off: the natural flake graphite that first 0.3 g is of a size of in the present embodiment to 300 μ m joins 20 mL H
2sO
4, 1 g K
2s
2o
8with 4 mL H
2o
2mixed solution in, room temperature is placed 8 h, crystalline flake graphite carries out gentle intercalation expansion, expanding volume is 120 mL.Graphene aggregate after expanding is cleaned repeatedly with clear water, until after the pH value of washing lotion becomes 7, Graphene aggregate is carried out to lyophilize.
Ultrasonic dispersion process is with Application Example 1.
Electron microscopic observation result shows, the Graphene within 5 layers accounts for 46% left and right of product.
Embodiment 3
Adopt the method for sulfuric acid, Potassium Persulphate, hydrogen peroxide oxidation intercalation that graphite is peeled off: the natural flake graphite that first 0.3 g is of a size of in the present embodiment to 180 μ m joins 20 mL H
2sO
4, 1 g K
2s
2o
8with 4 mLH
2o
2mixed solution in, room temperature is placed 8 h, crystalline flake graphite carries out gentle intercalation expansion, expanding volume is 100 mL.Graphene aggregate after expanding is cleaned repeatedly with clear water, until after the pH value of washing lotion becomes 7, Graphene aggregate is carried out to lyophilize.
Ultrasonic dispersion process is with Application Example 1.
Electron microscopic observation result shows, the Graphene within 5 layers accounts for 50% left and right of product.
Embodiment 4
Adopt the method for sulfuric acid, Potassium Persulphate, hydrogen peroxide oxidation intercalation that graphite is peeled off: the natural flake graphite that first 0.3 g is of a size of in the present embodiment to 150 μ m joins 20 mL H
2sO
4, 1 g K
2s
2o
8with 4 mL H
2o
2mixed solution in, room temperature is placed 8 h, crystalline flake graphite carries out intercalation expansion, expanding volume is 80 mL.Graphene aggregate after expanding is cleaned repeatedly with clear water, until after the pH value of washing lotion becomes 7, Graphene aggregate is carried out to lyophilize.
Ultrasonic dispersion process is with Application Example 1.
Electron microscopic observation result shows, the Graphene within 5 layers accounts for 54% left and right of product.
Embodiment 5
Adopt the method for sulfuric acid, Potassium Persulphate, hydrogen peroxide oxidation intercalation that graphite is peeled off: the natural flake graphite that first 0.3 g is of a size of in the present embodiment to 70 μ m joins 20 mL H
2sO
4, 1 g K
2s
2o
8with 4 mL H
2o
2mixed solution in, room temperature is placed 8 h, crystalline flake graphite carries out intercalation expansion, expanding volume is 60 mL.Graphene aggregate after expanding is cleaned repeatedly with clear water, until after the pH value of washing lotion becomes 7, Graphene aggregate is carried out to lyophilize.Ultrasonic dispersion process is with Application Example 1.
Electron microscopic observation result shows, the Graphene within 5 layers accounts for 56% left and right of product.
Embodiment 6
Adopt the method for sulfuric acid, Potassium Persulphate, hydrogen peroxide oxidation intercalation that graphite is peeled off: the natural flake graphite that first 0.3 g is of a size of in the present embodiment to 40 μ m joins 20 mL H
2sO
4, 1 g K
2s
2o
8with 4 mL H
2o
2mixed solution in, room temperature is placed 8 h, crystalline flake graphite carries out intercalation expansion, expanding volume is 50 mL.Graphene aggregate after expanding is cleaned repeatedly with clear water, until after the pH value of washing lotion becomes 7, Graphene aggregate is carried out to lyophilize.
Ultrasonic dispersion process is with Application Example 1.
Electron microscopic observation result shows, the Graphene within 10 layers accounts for 60% left and right of product.
Embodiment 7
Adopt the method for sulfuric acid, Potassium Persulphate, hydrogen peroxide oxidation intercalation that graphite is peeled off: the natural flake graphite that first 0.3 g is of a size of in the present embodiment to 300 μ m joins 20 mL H
2sO
4, 1.5 g K
2s
2o
8with 4 mL H
2o
2mixed solution in, room temperature is placed 6 h, crystalline flake graphite carries out fully intercalation and expands, expanding volume is 120 mL.Graphene aggregate after expanding is cleaned repeatedly with clear water, until after the pH value of washing lotion becomes 7, Graphene aggregate is carried out to lyophilize.
Ultrasonic dispersion process is with Application Example 1.
Electron microscopic observation result shows, the Graphene within 5 layers accounts for 46% left and right of product.
Embodiment 8
Adopt the method for sulfuric acid, Potassium Persulphate, hydrogen peroxide oxidation intercalation that graphite is peeled off: the natural flake graphite that first 0.3 g is of a size of in the present embodiment to 300 μ m joins 20 mL H
2sO
4, 2 g K
2s
2o
8with 4 mL H
2o
2mixed solution in, room temperature is placed 5 h, crystalline flake graphite carries out fully intercalation and expands, expanding volume is 120 mL.Graphene aggregate after expanding is cleaned repeatedly with clear water, until after the pH value of washing lotion becomes 7, Graphene aggregate is carried out to lyophilize.
Ultrasonic dispersion process is with Application Example 1.
Electron microscopic observation result shows, the Graphene within 5 layers accounts for 46% left and right of product.
Embodiment 9
Adopt the method for sulfuric acid, ammonium persulphate, hydrogen peroxide oxidation intercalation that graphite is peeled off: the natural flake graphite that first 0.3 g is of a size of in the present embodiment to 300 μ m joins 20 mL H
2sO
4, 1 g (NH
4)
2s
2o
8with 4 mL H
2o
2mixed solution in, room temperature is placed 8 h, crystalline flake graphite carries out intercalation expansion, expanding volume is 120 mL.Graphene aggregate after expanding is cleaned repeatedly with clear water, until after the pH value of washing lotion becomes 7, Graphene aggregate is carried out to lyophilize.
Ultrasonic dispersion process is with Application Example 1.
Electron microscopic observation result shows, the Graphene within 5 layers accounts for 48% left and right of product.
As shown in Figure 1, (50 orders, m), the volume comparative illustration this method before and after expanding has good intercalation for graphite and peels off effect 300 μ 0.3 g natural flake graphite.
As shown in Figure 2, can find out from the scanned photograph of Graphene aggregate expanding, Graphene aggregate is made up of thinner graphene film, illustrates by this method graphite flake layer and has carried out good intercalation and expansion.
As shown in Figure 3, can find out by the transmission electron microscope photo of the Graphene aggregate after ultrasonic in NMP, Graphene aggregate can obtain good graphene sheet layer through ultrasonic dispersion in organic solvent.
As shown in Figure 4, for preparing the full spectrogram of Graphene sample, can find out by curve, in the Graphene sample of preparation, mainly contain C and O element, and contain minute quantity N element.In the Graphene of measuring by XPS, element different is respectively: carbon content 98.24%, oxygen level 1.48%, nitrogen content 0.28%.
As shown in Figure 5, be the C1s peak of Graphene sample, can find out that by curve Graphene sample is not substantially containing aerobic functional group.
As shown in Figure 6, be the S2p peak in Graphene sample, can find out by curve in the Graphene sample of preparation and substantially not contain S element.
Claims (10)
1. a gentle method of preparing Graphene under normal temperature, is characterized in that concrete steps are:
The intercalation of A graphite expands: adopting different size natural flake graphite is raw material, and the vitriol oil, persulphate and hydrogen peroxide are once added wherein at ambient temperature, graphite is oxidized to intercalation and expands simultaneously and peel off generation Graphene aggregate;
The cleaning of B Graphene aggregate: the Graphene aggregate of expansion is cleaned repeatedly with clear water, until the pH=7 of water; Carry out again In-situ condensation dry;
Dispersion and the collection of C Graphene aggregate: dry Graphene aggregate is put into organic solvent and adopt the mode of ultrasonic dispersion further to peel off; After centrifugation, carry out again the dry Graphene that obtains of In-situ condensation.
2. the method for claim 1, is characterized in that natural flake graphite is of a size of 40-500 μ m.
3. the method for claim 1, is characterized in that the concentration of persulphate in sulfuric acid is 10 mg/mL～2 g/mL, and the volume ratio of sulfuric acid and hydrogen peroxide is 20:1～1:1.
4. method as claimed in claim 3, is characterized in that the concentration of persulphate in sulfuric acid is 50 mg/mL～1 g/mL, and the volume ratio of sulfuric acid and hydrogen peroxide is 10:1～5:1.
5. the method for claim 1, is characterized in that graphite expands in the process of intercalation simultaneously, and leaving standstill the expansion time is 10 min～40 h, and expansion temperature is room temperature.
6. method as claimed in claim 5, is characterized in that graphite expands in the process of intercalation simultaneously, and leaving standstill the expansion time is 20 min～8 h.
7. the method for claim 1, is characterized in that the Graphene aggregate of expansion to put into clear water, and repeatedly washing, until the pH value of water is 7, then carries out lyophilize, and be 8 h～40 h the time of drying of Graphene aggregate.
8. method as claimed in claim 7, is characterized in that the Graphene aggregate of expansion to put into clear water, and repeatedly washing, until the pH value of water is 7, then carries out lyophilize, and be 10 h～20 h the time of drying of Graphene aggregate.
9. the method for claim 1, it is characterized in that putting into organic solvent by Graphene aggregate, to be that N-Methyl pyrrolidone, DMF, ethanol or acetone carry out ultrasonic, and the ultrasonic time is 1 h～24 h; It is dry that Graphene after peeling off carries out In-situ condensation again, and sublimation drying is 8 h～40 h.
10. method as claimed in claim 9, it is characterized in that putting into organic solvent by Graphene aggregate, to carry out ultrasonic, the ultrasonic time be 2 h～6 h; It is dry that Graphene after peeling off carries out In-situ condensation again, and sublimation drying is 10 h～16 h.
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| CN106345413A (en) * | 2016-10-20 | 2017-01-25 | 碳为（北京）新材料科技有限公司 | Preparation method of porous spongy graphene |
| CN108083260A (en) * | 2016-11-23 | 2018-05-29 | 比亚迪股份有限公司 | A kind of highly expanded volume graphene aggregation and its preparation method and application |
| CN109107528A (en) * | 2018-08-23 | 2019-01-01 | 中国船舶重工集团公司第七二五研究所 | A kind of preparation method of graphene-supported nickel magnetic composite |
| CN110350201A (en) * | 2019-06-29 | 2019-10-18 | 华南理工大学 | A kind of highly conductive graphene collector of water system battery lightweight and preparation method thereof |
| CN110510603A (en) * | 2019-10-15 | 2019-11-29 | 燕山大学 | A kind of environment-friendly type preparation method of graphene |
| CN112194125A (en) * | 2020-10-21 | 2021-01-08 | 哈尔滨理工大学 | Normal pressure low temperature expansion method for natural flake graphite |
| CN112678811A (en) * | 2020-12-31 | 2021-04-20 | 国网江苏省电力有限公司电力科学研究院 | Two-dimensional material interlayer spacing regulating agent and method for regulating two-dimensional material interlayer spacing |
| CN114314574A (en) * | 2022-01-04 | 2022-04-12 | 复旦大学 | Riboflavin sodium phosphate-assisted large-size graphene water-phase preparation method |
| CN114314574B (en) * | 2022-01-04 | 2023-08-22 | 复旦大学 | Riboflavin sodium phosphate-assisted large-size graphene water-phase preparation method |
| CN114835109A (en) * | 2022-05-19 | 2022-08-02 | 清华大学 | Green recycling method for waste lithium battery graphite negative electrode and graphene |
| CN114835109B (en) * | 2022-05-19 | 2024-04-23 | 清华大学 | Environment-friendly recycling method of waste lithium battery graphite negative electrode and graphene |
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