CN104556018B - A kind of preparation method of high-quality graphene conductive film - Google Patents
A kind of preparation method of high-quality graphene conductive film Download PDFInfo
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Abstract
The invention belongs to grapheme material preparation technical fields, it is related to a kind of preparation method of high-quality graphene conductive film, natural flake graphite is uniformly mixed in the reactor with nitration mixture first, is then added under intercalator after being stirred to react by filtering, washes and be dried to obtain exfoliated graphite；Progress ultrasound removing will be dispersed in water after exfoliated graphite progress microwave treatment again and forms graphene aqueous solution, is distributed in solvent after graphene aqueous solution is centrifuged and obtains graphene dispersing solution；It filters using drop coating or cellulose filter membrane to after graphene dispersing solution ultrasonic treatment again and to form graphene film, and graphene film surface is processed by shot blasting, while the substrate of graphene film is shifted and heated, grapheme conductive film is prepared；Preparation method is simple, easy to operate, and technological parameter controllability is high, and production cost is low, avoids using strong oxidizer and toxic reducing agent, environmental-friendly.
Description
Technical field:
The invention belongs to grapheme material preparation technical fields, are related to a kind of preparation side of high-quality graphene conductive film
Method.
Background technique:
Graphene (Graphene) be one kind by carbon atom with sp2Hybridized orbit forms the plane that hexangle type is in honeycomb lattice
Film, the two-dimensional material of only one carbon atom thickness.The scientist of Univ Manchester UK in 2004 separates stone for the first time
Black alkene, and confirm that it can be stabilized.It is received significant attention from this new material of this graphene, graphene has very excellent
Performance, specific surface area is up to 2630m2.g-1, sign mobility is up to 200000cm2.v-1.s-1, Young's modulus up to arrives
1.0TPa, thermal conduction constant 5000W.m-1.K-1, optical transmittance is up to 97.7%, and its electric conductivity is also very excellent,
The electric conductivity of metal simple-substance is nearly reached.These characteristics that graphene is shown make its high-performance nanometer electronic device,
The fields such as photoelectric device, gas sensor, composite material, field emmision material and energy stores are widely applied.
Currently, the preparation method of graphene mainly include mechanical stripping method, it is chemical vapour deposition technique, epitaxial growth method, molten
Agent stripping method and chemistry redox method, these methods have its advantage and disadvantage: mechanical stripping method due to stripping means limitation,
It is not suitable for heavy industrialization and prepares graphene；Chemical vapour deposition technique and epitaxial growth method method are due to multiple with technique
It is miscellaneous, condition is harsh, low yield, it is at high cost the disadvantages of, limit its large-scale industrial production and application in graphene；Extension
Growth method is used for electronic device etc. by heating SiC extending and growing graphene, but during heating due to SiC crystal surface
It is easy to happen reconstruct, it is difficult to obtain the uniform graphene of large area, and heating temperature is high, energy consumption is high；The stripping of solvent stripping method
It is lower from efficiency and yield, and applicable solvent is less；Chemistry redox method is current low cost, large scale preparation graphene
More universal method, but strong oxidizer used in chemical stripping method stripping process can destroy the plane of graphene carbon atom
Structure generates defect, the electric conductivity of graphene is caused to reduce, and in poisonous chemicals such as the usually used hydrazine hydrates of reduction process
Matter is easy to pollute the environment.On the other hand, grapheme conductive film is due to its outstanding mechanical property, high conductivity, Gao Wen
The features such as qualitative, in the side such as touch screen, solar battery, supercapacitor, lithium ion cell electrode and some flexible electrodes
Mask has a wide range of applications.However the conductivity of the graphene film of oxidation-reduction method preparation at present is lower, defect is more, mechanics
Performance is poor；And the solvent-dispersible and film forming of graphite bulk material are poor；Using the graphitic carbon slurry of compounded technology preparation
Although having preferable stability and film forming, electric conductivity is poor, and resistance is higher.Therefore there is an urgent need to develop a kind of simple
Efficiently, the low cost preparation method of high-quality graphene conductive film.
Summary of the invention:
It is an object of the invention to overcome that problem and shortage exists in the prior art, seeks design and a kind of high quality stone is provided
The preparation method of black alkene conductive film, the grapheme conductive film conductivity using this method preparation is high, and resistance is low, and stability is good, fits
It is wide with substrate, it is with a wide range of applications.
To achieve the goals above, the present invention prepare high-quality graphene conductive film specifically includes the following steps:
(1), natural flake graphite is uniformly mixed in the reactor with nitration mixture, intercalator is then added, at 35 degrees Celsius
Under be stirred to react 4-12h after filter, be washed to pH=7, dry at 60 c, obtain exfoliated graphite；Wherein natural scale
Graphite: nitration mixture: the amount ratio of intercalator is 1g:3-6ml:1-4g；
(2), the microwave device for being 800-1100w with power processing exfoliated graphite 1-5min obtains the graphite of microwave treatment；
(3), by the graphite dispersion Yu Shuizhong of microwave treatment, ultrasound removing forms the graphene water that concentration is 0.5-2mg/ml
Solution, ultrasonic power are 300-500w, ultrasonic time 30-60min；
(4), graphene aqueous solution is centrifuged to the solid redisperse obtained after 10-20min under 5000-6000rpm speed
The graphene dispersing solution that concentration is 5-20mg/ml is obtained into solvent；
(5), to graphene dispersing solution under 150-300w power condition after ultrasound 10-20min, using existing drop coating or
Cellulose filter membrane filters to form graphene film, is then processed by shot blasting using the prior art to graphene film surface, together
When the substrate of graphene film is shifted and heat treatment, that is, grapheme conductive film is prepared.
Reactor of the present invention is three-necked flask or four-hole boiling flask.
The piece diameter size of natural flake graphite of the present invention is 50-150 μm.
Intercalator of the present invention is the inorganic salts that gas can be generated under external influence, including ferric trichloride, nitric acid
Ammonium, potassium chlorate, lithium chlorate, potassium oxalate, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium bicarbonate, saleratus and carbonic acid
One or more of iron.
Nitration mixture of the present invention is weight percentage concentrated nitric acid that concentration is 65% and weight percent concentration is 98%
The mixed acid of concentrated sulfuric acid composition, wherein the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1:1-3.
Solvent described in step (4) of the present invention includes one of water, ethyl alcohol and isopropanol.
Compared with prior art, the present invention preparing graphene conductive using graphite intercalation-removing-dispersion-film forming method
Film, obtained graphene film are made of graphene film, and the number of plies is 1-5 layers, and extent of exfoliation is high, and defect is few；Using film forming and
The graphene film consistency of polishing treatment means preparation is high, and stability is high, and thickness is uniformly (with a thickness of less than 20 μm)；Through later
After processing, obtained graphene conductive membrane conductivity is high (20000-50000S/m), is far longer than the graphite that conventional method obtains
The conductivity of alkene film；Preparation method is simple, easy to operate, and technological parameter controllability is high, and production cost is low, avoids using strong
Oxidant and toxic reducing agent, environmental-friendly, obtained graphene conductive film quality is high, excellent performance, in lithium ion battery, super
Capacitor, solar battery, FPD, touch screen and flexible electrode field are with a wide range of applications.
Detailed description of the invention:
Fig. 1 is the XRD diagram of the grapheme conductive film of the natural graphite used of the embodiment of the present invention 1 and preparation.
Fig. 2 is the SEM figure of grapheme conductive film prepared by the embodiment of the present invention 1.
Fig. 3 is the TEM figure of grapheme conductive film prepared by the embodiment of the present invention 1, wherein a) is schemed for low power TEM；B) it is
High power TEM figure.
Fig. 4 is the AFM figure of grapheme conductive film prepared by the embodiment of the present invention 1.
Specific embodiment:
The invention will be further described by way of example and in conjunction with the accompanying drawings.
Embodiment 1:
The present embodiment prepares the specific steps of high-quality graphene conductive film are as follows:
(1), the natural graphite that 10g piece diameter is 100 μm is added to 10ml concentrated nitric acid (65%) and the 30ml concentrated sulfuric acid
(98%) nitration mixture formed is uniformly mixed, and 20g iron chloride is then added, 12h is stirred to react under 35 degree, is filtered, is washed to pH
=7,8h is dried at 60 c, obtains exfoliated graphite；
(2), exfoliated graphite is handled under 1000w microwave to 3min and obtains the graphite after microwave treatment, stone in treatment process
Ink can expand, and with spark；
(3), by the graphite dispersion after microwave treatment into water, the ultrasound removing 60min at 500w, obtaining concentration is 0.5-
The graphene aqueous solution of 2mg/ml；
(4), the graphene aqueous solution that 100ml concentration is 2mg/ml is centrifuged at 6000rpm 10min, removes upper water
Solution obtains graphene solid, and obtained graphene solid is dispersed in again in 50ml ethyl alcohol, the ultrasound 15min at 300w,
Form finely dispersed graphene alcohol dispersion liquid；
(5) dispersant liquid drop is coated in clean PET plastic piece surface, film forming is spontaneously dried at room temperature, is thrown with polishing cloth
Light forms fine and close, uniform, flexible grapheme conductive film, by the test of four probes, the film with a thickness of 5 μm, conductivity is
30000S/m。
The XRD diagram of the grapheme conductive film of natural graphite and preparation that the present embodiment uses is as shown in Figure 1, natural graphite exists
26.5 degree there is strong sharp (002) characteristic peak；And grapheme conductive film is only in 26 degree of appearance, one small steamed bun shape
Graphene (002) characteristic peak.
Grapheme conductive film SEM manufactured in the present embodiment figure is as shown in Fig. 2, as can be seen from Figure, grapheme conductive film
Whole even compact, and there are the characters and appearances of apparent graphene fold.
The TEM for the grapheme conductive film that the present embodiment obtains schemes as shown in figure 3, as can be seen that graphene from Fig. 3 (a)
Graphene film of the conductive film by size at 5 μm or so forms；From discovery in Fig. 3 (b), the number of plies of graphene film is for single layer or less
Layer, the crystallinity for the graphene film that electronic diffraction spectrogram is shown is fine, and the conjugated structure of carbon atom is maintained, defect
It is few.
The AFM of the grapheme conductive film that the present embodiment obtains schemes as shown in figure 4, as can be seen from Figure, the graphite of preparation
For alkene chip size at 5 μm or so, sample is uniform, and thickness is about 0.8nm, illustrates that the graphene of preparation is few layer graphene, 1-2
Layer.
Embodiment 2:
The other steps of the present embodiment are same as Example 1, only when intercalator is added, the intercalator of addition be ammonium nitrate,
Potassium chlorate, lithium chlorate, potassium oxalate, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium bicarbonate, saleratus and ferric carbonate
One or more, the amount of addition is identical as iron chloride, the graphene that the grapheme conductive film finally obtained and embodiment 1 obtain
Conductive film similar performance.
Embodiment 3:
The other steps of the present embodiment are same as Example 1, only in film forming procedure, the concentration of the alcohol dispersion liquid of graphene
For 20mg/ml, obtained grapheme conductive film is with a thickness of 20 μm, conductivity 20000S/m.
Embodiment 4:
The present embodiment prepares the specific steps of high-quality graphene conductive film are as follows:
(1), the natural flake graphite that 5g piece diameter is 150 μm is added to 5ml concentrated nitric acid (65%) and the 10ml concentrated sulfuric acid
(98%) nitration mixture formed is uniformly mixed, and 10g ammonium hydrogen carbonate is then added, 8h is stirred to react under 35 degree, is filtered, is washed to pH
=7,60 degree of lower dry 8h, obtain exfoliated graphite；
(2), exfoliated graphite is handled under 800w microwave to 4min and obtains the graphite after microwave treatment, graphite in treatment process
It can expand, and with spark；
(3), by the graphite dispersion after microwave treatment into water, the ultrasound removing 40min at 500w, obtaining concentration is 0.5-
The graphene aqueous solution of 2mg/ml；
(4), the graphene aqueous solution that concentration is 2mg/ml is filtered with the cellulose filter membrane that aperture is 0.22 μm, is obtained
Graphene film is dried in vacuo 4h under 60 degree, forms graphene film flexible；Cellulose filter membrane is dissolved away with acetone again, and will
Graphene film is transferred in quartz substrate, 800 degree of heat treatment 1h under the protection of inert gas, with polishing cloth polishing, is obtained
Grapheme conductive film fine and close, flexible；Tested by four probes, the film with a thickness of 5 μm, conductivity 50000S/m.
Embodiment 5:
The other steps of the present embodiment are same as Example 4, in the last handling process of graphene film, not through overheat at
Reason, the conductivity of obtained grapheme conductive film are 30000S/m.
Embodiment 6:
The other steps of the present embodiment are same as Example 4, and thickness only is obtained by filtration in graphene aqueous solution filter process
For 20 μm of graphene film, the conductivity of the grapheme conductive film finally obtained is 40000S/m.
Claims (1)
1. a kind of preparation method of high-quality graphene conductive film, it is characterised in that specific steps are as follows:
(1), by the natural flake graphite that 5g piece diameter is 150 μm be added to concentrated nitric acid that 5ml mass percent concentration is 65% and
The nitration mixture that the concentrated sulfuric acid that 10ml mass percent concentration is 98% forms is uniformly mixed, and 10g ammonium hydrogen carbonate is then added, at 35 degree
Under be stirred to react 8h, filter, be washed to pH=7,60 degree lower to dry 8h, obtains exfoliated graphite；
(2), exfoliated graphite is handled under 800w microwave 4min and obtains the graphite after microwave treatment, graphite can be swollen in treatment process
It is swollen, and with spark；
(3), by the graphite dispersion after microwave treatment into water, the ultrasound removing 40min at 500w, obtaining concentration is 0.5-2mg/
The graphene aqueous solution of ml；
(4), the graphene aqueous solution that concentration is 2mg/ml is filtered with the cellulose filter membrane that aperture is 0.22 μm, obtained graphite
Alkene film is dried in vacuo 4h under 60 degree, forms graphene film flexible；Cellulose filter membrane is dissolved away with acetone again, and by graphite
Alkene film is transferred in quartz substrate, 800 degree of heat treatment 1h under the protection of inert gas, with polishing cloth polishing, obtain it is fine and close,
Grapheme conductive film flexible；Tested by four probes, the film with a thickness of 5 μm, conductivity 50000S/m.
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| CN104953001A (en) * | 2015-05-29 | 2015-09-30 | 华灿光电(苏州）有限公司 | Transparent electroconductive film preparation method |
| CN104961123B (en) * | 2015-06-18 | 2017-11-17 | 湖南大学 | A kind of native graphite ore deposit peels off method of purification |
| 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 |
| CN105084353B (en) * | 2015-08-19 | 2018-11-13 | 杭州万杵材料科技有限公司 | A kind of production method of grapheme material |
| CN106554010A (en) * | 2015-09-25 | 2017-04-05 | 苏州烯时代石墨烯科技有限公司 | The method of preparation of industrialization big size graphene |
| CN105948026A (en) * | 2016-05-05 | 2016-09-21 | 中国科学院长春应用化学研究所 | Method for preparing graphene through liquid phase chemical technology intercalation and graphite peeling |
| CN106245104B (en) * | 2016-07-20 | 2018-07-17 | 西安交通大学 | A method of preparing graphene based on electrochemical process stripping dual graphite electrodes |
| 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 |
| CN107857260B (en) * | 2017-12-13 | 2020-02-07 | 西北有色金属研究院 | Method for preparing graphene oxide through weak oxidation intercalation stripping |
| CN108584929A (en) * | 2018-07-01 | 2018-09-28 | 张阳 | A kind of production equipment of graphene |
| CN108570726A (en) * | 2018-07-20 | 2018-09-25 | 山东理工大学 | A kind of SnO2/ CuO composite graphite alkene coats the preparation method of cotton carbon fibre material |
| CN108946714A (en) * | 2018-09-05 | 2018-12-07 | 七台河宝泰隆石墨烯新材料有限公司 | The method that green, quick magnanimity prepares graphene oxide |
| CN108928815B (en) * | 2018-09-10 | 2020-04-03 | 明德润和新材料(珠海)有限公司 | Method for preparing high-performance graphene by multi-step weak oxidation-reduction method |
| CN110358141B (en) * | 2019-07-09 | 2022-04-15 | 兰州大学 | Preparation method of flame-retardant high polymer material |
| CN111017916A (en) * | 2020-01-07 | 2020-04-17 | 南开大学 | Preparation method of graphene with controllable layer number |
| CN112723743B (en) * | 2021-03-30 | 2021-06-25 | 广东欧文莱陶瓷有限公司 | Dry grain rock plate and preparation method thereof |
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| CN103523773B (en) * | 2013-09-23 | 2015-09-30 | 武汉大学 | A kind of high connductivity Graphene and grapheme conductive film and preparation method thereof |
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