CN102659096A - Preparation methods of graphene dispersion solution and thin film of graphene - Google Patents
Preparation methods of graphene dispersion solution and thin film of graphene Download PDFInfo
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- CN102659096A CN102659096A CN2012101289306A CN201210128930A CN102659096A CN 102659096 A CN102659096 A CN 102659096A CN 2012101289306 A CN2012101289306 A CN 2012101289306A CN 201210128930 A CN201210128930 A CN 201210128930A CN 102659096 A CN102659096 A CN 102659096A
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Abstract
The invention relates to the technical field of graphene preparation and applications, and particularly relates to a method for preparing a high-quality graphene dispersion solution and a method for preparing a graphene thin film on a plurality of substrates by means of the prepared graphene dispersion solution. The preparation method of the graphene dispersion solution includes subjecting graphene to preprocessing to increase spacing of layers of graphite so that ultrasonic exfoliation in a short time is facilitated. The prepared graphene dispersion solution can be subjected to precipitation, spin coating or spraying coating to prepare the graphene thin film with controllable thicknesses. According to the preparation methods of the graphene dispersion solution and thin film of the graphene, ultrasonic time is short in graphene exfoliation, the device is simple, conditions are temperate, costs are low, the prepared graphene dispersion solution is stable, and the quality of the graphene thin film is high. The preparation methods solve problems that the ultrasonic exfoliation is long in time, graphene is easy to agglomerate and precipitate, industrial productions can not be achieved in existing preparation methods of liquid phase exfoliation grapheme, and the like.
Description
Affiliated technical field
The invention belongs to Graphene preparation and Application Areas, relate to high quality, stablize the preparation method of Graphene dispersion liquid and film thereof.
Background technology
Graphene has excellent electricity, mechanics and thermal property, as: Young's modulus is up to 1100Gpa; Elongation at break 125%; Specific surface area 2630m
2/ g (calculated value); Thermal conductivity 5000w/ (mK); Electronic mobility 200000m
2/ (Vs).Because Graphene has the character of such excellence and in the potential using value in various fields, realize that extensive, low-cost, the controlledly synthesis of Graphene and preparation are significant.At present, preparation method of graphene mainly contains micromechanics and peels off method, chemical Vapor deposition process, epitaxial orientation growth method, graphite oxide reduction method, liquid phase and peel off method etc.
Graphite oxide reduction method, liquid phase are peeled off method ability scale preparation; And the graphite oxide reduction method is because oxygenizement, and the graphene oxide structure that obtains has been destroyed, just removes oxygen-containing functional group with the reductive agent reduction; Its phenyl ring conjugated structure can't be repaired; Cause its performance (particularly electroconductibility) to descend, therefore, redox graphene receives very big restriction on it is used.And peel off the Graphene dispersion liquid that method obtains with liquid phase, and the structural integrity of its Graphene, quality is high; And can transfer to and be used to prepare graphene device in other substrate, also can be in dispersion liquid and other substance reactions or blend, and be used to prepare graphene composite material.Therefore, peel off method scale preparation Graphene with liquid phase and be considered to most possible industrialized method, and the graphene-structured of gained complete, do not have a defective.
Prepare the existing report of Graphene dispersion liquid with the liquid phase stripping means, and the Graphene of gained has no defective.(Li X, Zhang G, the Bai X such as Dai Hongjie of U.S. stanford university; Et al.Highly conducting graphene sheets and Langmuir-Blodgett films.Nature Nanotechnology; 2008,3 (9): 538-542) the earliest the report prepare the Graphene dispersion liquid with the liquid phase stripping means, they with the tetrabutyl phosphonium bromide quaternary ammonium salt as intercalator; In liquid phase, peel off, obtain the Graphene of high conductivity.(Hernandez Y, Nicolosi V, Lotya M such as Coleman then; Et al.High-yield production of graphene by liquid-phase exfoliation of graphite.Nature Nanotechnology, 2008,3 (9): 563-568.) reported directly at multiple solvent (N-Methyl pyrrolidone NMP; N, N-DEF DMA, gamma-butyrolactone GBL; 1; 3-dimethyl--2-imidazolidone DMEU) directly peel off graphite in, obtain the Graphene dispersion liquid, but the concentration of Graphene has only 6 μ g/mL in the nmp solvent.(Lotya M such as Coleman subsequently; Hernandez Y; King P J; S ℃ of iety of et al.Liquid phase production of graphene by exfoliaion of graphite in surfactant/water solutions.Journal of American Chemistry; 2009,131 (10): 3611-3620), prepare 0.1mg/mL Graphene dispersion liquid in the method that aqueous phase is peeled off through liquid phase through in water, adding tensio-active agent (sodium laurylsulfonate DDS).The explorations in these early stages are that liquid phase is peeled off preparation Graphene dispersion liquid certain methods and theoretical basis are provided.
Though, (Khan U, O ' Neill A such as Coleman; Lotya M, et al.High-concentration solvent exfoliation of graphene.Small, 2010; 6 (7): 864-871.Lotya M, King P J, Khan U; Et al.High-concentraion, surfactant-stabilized graphene dispersions.ACS Nano, 2010; 4 (6): 3155-3162) make solvent with water and DMF respectively; Prepare the Graphene dispersion liquid of higher concentration (0.3mg/mL, 1mg/mL), but need special tensio-active agent (NaC) with the Graphene dispersion liquid of water as solvent, the ultra-sonic dispersion time (460h) of its overlength can't be realized industriallization simultaneously.(Tour J M such as Tour and Pasquali; Pasquali M.Spontaneous high-concentration dispersions and liquid crystals of graphene.Nature Nanotechnology; 2010; 5 (6): 406-411) directly in chlorsulfonic acid, prepare the Graphene dispersion liquid of concentration, but the strongly-acid of chlorsulfonic acid has a strong impact on its application up to 2mg/mL with graphite.(Liang Y such as Mark C.Hersam; Hersam M C.Highly concentrated graphene solutions via polymer enhanced solvent exfoliation and iterative solvent exchange.Journal of American Chemistry Society; 2010,132 (50): 17661-17663) in ethanol, obtained the Graphene dispersion liquid of 1mg/mL, when ultra-sonic dispersion, will add 1% Natvosol; To regulate the coupling of Graphene and ethanol surface energy; But the Natvosol of its adding is too many, can only be used to prepare graphene composite material, can't be applied in other field.And these the report gained the used solvent of Graphene dispersion liquid be confined to N-Methyl pyrrolidone (NMP) and N; Dinethylformamide (DMF); (Khan U, Porwal H, O ' Neill A such as nearest Coleman; Et al.Solvent-exfoliated graphene at extremely high concentration.Langmuir; 2011,27 (17):, obtain the Graphene dispersion liquid that concentration is 2-60mg/mL at N-Methyl pyrrolidone 9077-9082) with the ultrasonic method of directly peeling off graphite.But the solvent that these dispersion liquids adopt all is some high boiling solvents, in industry, uses and receives certain limitation.
Summary of the invention
The purpose of this invention is to provide a kind of stable Graphene dispersion liquid and the preparation method of film thereof, to solve the problem that prior art exists.
Graphene dispersion liquid preparation process is:
1, graphite is handled under comparatively high temps with organic solvent, made graphite layers apart from enlarging to some extent;
2, with after the organic solvent processing, graphite through pyroprocessing, is removed possibility residual organic solvent or its degradation production under nitrogen protection;
3, peel off dispersion (, can add suitable dispersion agent) with the graphite of above-mentioned pyroprocessing is ultrasonic in The suitable solvent to improve charge stripping efficiency according to the needs of dispersion process;
4,, obtain high density, stable Graphene dispersion liquid with the spinning of above-mentioned graphite treatment liquid;
The graphene film preparation process:
1, above-mentioned Graphene dispersion liquid is diluted to finite concentration, the Graphene dispersant liquid drop with dilution is added on the different substrate materials then;
2, the solvent in the evaporation Graphene dispersion liquid, Graphene will deposit in substrate, forms the Graphene wet film layer;
3,, graphene film is dried together with base material.
Compared with prior art, the present invention has the following advantages:
1, it is short that present method is peeled off the required ultrasonic time of Graphene, and technology is simple, and equipment is simple, mild condition, and cost is low;
2, the Graphene dispersion liquid that is obtained by this forwarding method is highly stable, do not have obviously in 1 year reunite, demixing phenomenon;
3, the Graphene dispersion liquid of the present invention's preparation, 70% Graphene is a single-layer graphene, the product application performance is good;
4, the inventive method can be regulated and control the thickness of graphene film through Graphene dispersion liquid concentration and volume, even can obtain individual layer, successive graphene film.
Description of drawings:
Fig. 1 places Graphene dispersion liquid photo after a year;
Fig. 2 is the AFM figure of Graphene;
Fig. 3 is the Raman spectrogram of Graphene;
Fig. 4 is individual layer, the successive graphene film by the preparation of Graphene dispersion liquid; Wherein b figure is the amplification of circle part among a figure
Fig. 5 is the multi-layer graphene film by the preparation of Graphene dispersion liquid; B figure is the amplification of circle part among a figure.
Embodiment
The embodiment 1 of preparation Graphene dispersion liquid: 1g natural graphite and 20mL gamma-butyrolactone solvent are joined in the autoclave elevated temperature to 210 ℃, heated and stirred 4h, control reaction temperature.Mixture is taken out in cooling back, filter, with Graphite Cake at N
2Protection is handled 2h for 400 ℃ down.Get 0.5g graphite and join in the 100mL methyl alcohol, the ultrasonic 10h that peels off, 2500 rev/mins of spinning 30min.Obtain the Graphene dispersion liquid.
The embodiment 2 of preparation Graphene dispersion liquid: with 2g micro crystal graphite and 30mLN, N-NMF solvent joins in the autoclave, elevated temperature to 180 ℃, heated and stirred 2h, control reaction temperature.Mixture is taken out in cooling back, filter, with Graphite Cake at N
2Protection is handled 4h for 500 ℃ down.Get 0.5g graphite and join in the 100mL Virahol, the ultrasonic 12h that peels off, 2500 rev/mins of spinning 30mm.Obtain the Graphene dispersion liquid.
The embodiment 3 of preparation Graphene dispersion liquid: 1g expanded graphite and 20mL dimethyl sulfoxide solvent are joined in the autoclave elevated temperature to 120 ℃, heated and stirred 5h, control reaction temperature.Mixture is taken out in the cooling back, filters, and Graphite Cake in air, is handled 5h for 300 ℃.Get 0.5g graphite and join 100mLN, in the dinethylformamide solvent, the ultrasonic 12h that peels off, 2500 rev/mins of spinning 30min.Obtain the Graphene dispersion liquid.
The embodiment 4 of preparation Graphene dispersion liquid: 0.1g highly oriented pyrolytic graphite and 5mL N-NMF solvent are joined in the autoclave elevated temperature to 180 ℃, heated and stirred 6h, control reaction temperature.Mixture is taken out in cooling back, filter, with Graphite Cake at N
2Protection is handled 2h for 400 ℃ down.Get 0.5g graphite and join in the 100mL ethanol, the ultrasonic 12h that peels off, 2500 rev/mins of spinning 30min.Obtain the Graphene dispersion liquid.
The embodiment 5 of preparation Graphene dispersion liquid: 10g graphite and 200mL DMSO 99.8MIN. and .N-NMF mixed solvent are joined in the autoclave; Pour nitrogen in the autoclave to pressure be 5 standard atmospheric pressures; Elevated temperature to 200 ℃; Heated and stirred 2h, control reaction temperature.Mixture is taken out in the cooling back, filters, and Graphite Cake under argon shield, is handled 2h for 400 ℃.Get 0.5g graphite and join in the 100mL butanone, the ultrasonic 12h that peels off, 2500 rev/mins of spinning 30min.Obtain the Graphene dispersion liquid.
The embodiment 6 of preparation Graphene dispersion liquid: with 5g graphite and 100mL gamma-butyrolactone and N; N-NMF solvent joins in the autoclave; Pour nitrogen in the autoclave to pressure be 2 standard atmospheric pressures, at elevated temperature to 240 ℃, keep air pressure in 10 normal atmosphere; Heated and stirred 2h, control reaction temperature.Mixture is taken out in cooling back, filter, with Graphite Cake at N
2Protection is handled 2h for 700 ℃ down.Get 0.5g graphite and join in the 100mL water, the ultrasonic 12h that peels off, 2500 rev/mins of spinning 30min.Obtain the Graphene dispersion liquid.
The embodiment 7 of preparation Graphene dispersion liquid: with 1g natural graphite and 20mL N, the dinethylformamide solvent joins in the autoclave, elevated temperature to 120 ℃, heated and stirred 4h, control reaction temperature.Mixture is taken out in cooling back, filter, with Graphite Cake at H
2Protection is handled 2h for 700 ℃ down.Get 0.5g graphite and join in the 100mL Virahol alcohol, the ultrasonic 10h that peels off, 2500 rev/mins of spinning 30min.Obtain the Graphene dispersion liquid.
The embodiment 8 of preparation graphene film: get Graphene dispersion liquid 0.5mL among the embodiment 1; The Graphene dispersion liquid concentration is diluted to 0.02mg/mL; Graphene dispersant liquid drop after the dilution is added on the simple glass sheet that diameter is 20mm; Evaporating solvent, dry back dry 24h under 120 ℃ obtains at the sedimentary graphene film of simple glass sheet.
The embodiment 9 of preparation graphene film: get Graphene dispersion liquid 1mL among the embodiment 4; The Graphene dispersion liquid concentration is diluted to 0.05mg/mL; Graphene dispersion liquid after the dilution is spun on the quartz glass plate; Dry back dry 24h under 150 ℃ obtains being coated in the graphene film on the quartz glass plate.
The embodiment 10 of preparation graphene film: get Graphene dispersion liquid 1mL among the embodiment 6; The Graphene dispersion liquid concentration is diluted to 0.01mg/mL; Graphene dispersion liquid after the dilution is sprayed on the single-chip; Dry back dry 24h under 120 ℃ ℃ obtains being coated in the graphene film on the monocrystalline silicon piece.
The embodiment 11 of preparation graphene film: get Graphene dispersion liquid 1mL among the embodiment 3; The Graphene dispersion liquid concentration is diluted to 0.05mg/mL; Graphene dispersion liquid after the dilution is sprayed on the polysilicon chip; Dry back dry 24h under 180 ℃ obtains being coated in the graphene film on the polysilicon chip.
Claims (10)
1. the preparation method of a Graphene dispersion liquid, its characteristic has following steps: 1) under comparatively high temps, normal pressure or high pressure are down with organic solvent pre-treatment graphite; 2) under protection of inert gas, high temperature sintering is pre-treatment graphite; 3) the ultrasonic graphite of peeling off in solvent; 4) spinning obtains the Graphene dispersion liquid; 5) this Graphene dispersion liquid subsequent applications is to process graphene film.
2. the described Graphene dispersion liquid of claim 1 preparation method, use therein graphite raw material comprises natural graphite, expanded graphite, micro crystal graphite or highly oriented pyrolytic graphite.
3. used solvent comprises among the described Graphene dispersion liquid of claim 1 preparation method: DMSO 99.8MIN. (DMSO), N; Dinethylformamide (DMF) and N-NMF (NMP), gamma-butyrolactone (GBL), N, N-DEF (DMA) or its mixed solution.
4. Graphene dispersion liquid preparation method according to claim 1 is characterized in that: rare gas element is nitrogen, argon gas, hydrogen or their mixed gas.
5. Graphene dispersion liquid preparation method according to claim 1 is characterized in that: the temperature of pre-treatment graphite is 120 ℃～250 ℃.
6. Graphene dispersion liquid preparation method according to claim 1 is characterized in that: can make blanketing with inert gas during the pretreated graphite of 300～500 ℃ of calcinations or without nitrogen protection; 500～800 ℃ of calcinations blanketing with inert gas during pre-treatment graphite.
7. Graphene dispersion liquid preparation method according to claim 1; It is characterized in that: the ultrasonic solvent of peeling off graphite is water, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, butanone, DMSO 99.8MIN. (DMSO), N, dinethylformamide (DMF) and N-NMF (NMP), gamma-butyrolactone (GBL) or its their mixing solutions.
8. the preparation method of graphene film is characterised in that and has following steps: 1) get above-mentioned dispersion liquid or be diluted to finite concentration; That 2) will dilute transfers in the substrate 3) evaporating solvent, obtain graphene film.
9. method for preparing graphene membrane according to claim 2 is characterized in that: the base material of graphene film can be simple glass, silica glass, monocrystalline silicon piece or polysilicon chip.
10. method for preparing graphene membrane according to claim 2 is characterized in that: the mode that obtains graphene film is natural deposition, spin coating or spraying in substrate.
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