CN103935995B - A kind of preparation method of stable graphene colloid dispersion solution - Google Patents
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Abstract
The invention discloses a kind of preparation method of stable graphene colloid dispersion solution, relate to technical field of graphene preparation.It is Hummer ' s legal system by improving for graphene oxide, use dispersion agent process after reduction, can obtain stable graphene colloid dispersion solution, its concentration is 0.21 ~ 0.25mg/mL, the single-layer graphene wherein containing 14 ~ 25wt%.This graphene colloid dispersion solution has Tyndall effect, and its zeta current potential is-41 ~-33mV, and the median size of Graphene is 250 ~ 400nm.The method is simple, and reaction process easily controls, and to equipment without particular requirement, cost is lower, is easy to promote, and can be widely used in the fields such as nanoelectronics, sensor, nano-complex, battery, ultracapacitor and hydrogen storage material.
Description
Technical field
The present invention relates to the reduction of the preparing technical field of Graphene, particularly graphene oxide and the preparation method of stable graphene colloid dispersion solution.
Background technology
Graphene, as a kind of novel Two-dimensional Carbon nano material, attracts to come from worldwide paying close attention in recent years.The special nanostructure that Graphene has makes it possess wide application prospect in fields such as such as nanoelectronics, sensor, nano-complex, battery, ultracapacitor and hydrogen storage materials.But lacking the controlled approach preparing Graphene on a large scale but becomes effective exploitation and applies keeping in check of its potential.As carbon nanotube and other nano materials many, in the process of batch production Graphene, the challenge of most critical comes from the reunion of Graphene itself.When fully not disperseing, the high-specific surface area that Graphene has, make it to tend to form irreversible aggregate, even the stacking formation graphite again by van der Waals interaction, but and the excellent performance of Graphene major part exists only in monolithic graphite alkene.This problem by many for the purpose of volume production, mentioned by the document of chemical transfer method and liquid phase stripping method synthesizing graphite alkene and patent.So, how effectively to prevent the industrialization of reuniting for Graphene from having vital meaning.
Univ Texas-Austin USA Ruoff teach problem group (StankovichS, DikinDA, PinerRD, etal.Synthesisofgraphene-basednanosheetsviachemicalreduc tionofexfoliatedgraphiteoxide [J] .Carbon, 2007,457:1558-1565; StankovichS, DikinDA, PinerRD, etal.Synthesisofgraphene-basednanosheetsviachemicalreduc tionofexfoliatedgraphiteoxide [J] .Carbon, 2007,457:1558-1565.) and Univ California-Los Angeles USA Kaner teach problem group (LiD, M ü llerMB, GiljeS, etal.Processableaqueousdispersionsofgraphenenanosheets [J] .Naturenanotechnology, 2008,32:101-105; TungVC, AllenMJ, YangY, etal.High-throughputsolutionprocessingoflarge-scalegraph ene [J] .Naturenanotechnology, 2009,41:25-29.) reported once and utilize oxidation reduction process to prepare Graphene.This approach based on liquid phase comprises graphite is obtained hydrophilic graphite oxide by chemical oxidation, again by ultrasonic fully in water thus peel off and obtain single-layer graphene oxide, the graphene oxide of electrical insulating property can utilize the materials such as hydrazine to become the Graphene of conduction by the method migration of chemical reduction.But still irreversible reunion can be there is due to the hydrophobic property of itself in the Graphene prepared via oxidation reduction process.Graphene after reunion does not have solubility in water, thus limits its further process and application.
(the SimmonsTJ such as Simmons, BultJ, HashimDP, etal.NoncovalentfunctionaliZationasanalternativetooxidat iveacidtreatmentofsinglewallcarbonnanotubeswithapplicati onsforpolymercomposites [J] .ACSnano, 2009,34:865-870.) once utilized 1-pyrene formic acid to make the non-covalent functionalization of nanotube walls thus the stable dispersions of formation Single Walled Carbon Nanotube.Carboxyl (-COOH) in 1-pyrene formic acid by the interaction of the stacking mechanism aromatic ring of a kind of nondestructive π-π, can make tube wall functionalization thus promotes the stability of Single Walled Carbon Nanotube in water.
Based on this idea, the invention provides a kind of simple method and also keep its excellent properties in order to prepare the colloidal dispersion be made up of individual layer, few layer graphene on a large scale simultaneously.In the present invention, introduce that an analogy 1-pyrene formic acid is more cheap but mechanism is similar and the medium that dispersing property is as good as---the substituent of the naphthalene containing different hydrophilic group, as 1-naphthoic acid.This medium can embed in graphene sheet layer as a kind of " molecule wedge ".On the one hand, by the stacking mechanism of non-covalent π-π, the aromatic moieties of naphthalene can penetrate into the interlayer of Graphene and destroy Van der Waals force gradually thus the Graphene of acquisition individual layer and few layer.On the other hand, by introducing the hydrophilic carboxyl, the hydroxyl that replace, improving the water-soluble of Graphene, promoting the formation of stable graphene colloid dispersion solution.
By consulting related data, there is patent report to use dispersion agent stripping graphite or graphene oxide to prepare the method for dispersion liquid, comprising:
1. Chinese patent 201110251178.X document introduces " a kind of preparation method of single-layer graphene oxide solution ".This patent, by Graphite Powder 99 and oxidant reaction, after thermal treatment is tentatively peeled off, mixes ultrasonic with dispersion agent alcohol, benzene, tetrahydrofuran (THF), obtained single-layer graphene oxide solution.
2. Chinese patent 201110388712.1 document introduction " preparation method of Graphene ".Graphite Powder 99 joins in the non-aqueous polar solvents being dissolved with acene condensed ring class arene derivatives and forms mixed system by this patent, prepares graphene solution by liquid phase stripping method.
3. Chinese patent 201210128930.6 document introduction " preparation method of a kind of graphene dispersing solution and film thereof ".The strong polar aprotic solvent pretreating graphite at high temperature under high pressure such as this patent utilization NMP, DMF, DMSO, after thermal treatment in protective atmosphere, ultrasonic stripping in a solvent, prepares graphene dispersing solution.
4. Chinese patent 201310273258.4 document introduction " preparation method of a kind of Graphene/thermotropic liquid crystal full-aromatic polyester matrix material ".Graphene oxide thermal reduction in polycondensation that this patent utilization 6-Hydroxy-2-naphthoic acid is modified generates Graphene, and dispersed in full-aromatic polyester resin, forms the fibre composite with excellent conductive performance.
In sum, the report also preparing stable graphene colloid dispersion solution about the problem being easy to reunite in reduction process with dispersion agent solution graphene oxide is not thus found.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method providing a kind of easy graphene colloid dispersion solution, to prepare stable high concentration graphene colloidal dispersion.
The present invention solves its technical problem and adopts following technical scheme:
The preparation method of stable graphene colloid dispersion solution provided by the invention utilizes redox reaction and colloid-stabilised theory, and regulation and control comprise the various factors of reductive agent consumption, recovery time and dispersant concentration, kind.The preparation process of stable graphene colloid dispersion solution, specific as follows:
1. graphite is mixed with oxygenant, through ultrasonic centrifugal after, generate stable graphene oxide;
2., in the basic conditions, with reductive agent reductase 12 ~ 4 hour, obtain Graphene;
3. by graphene dispersion in be dissolved with different hydrophilic group naphthalene substituent organic solvent in, through ultrasonic eccentric cleaning, obtain stable graphene colloid dispersion solution, its concentration be 0.21 ~ 0.25mg/mL, wherein containing the single-layer graphene of 14 ~ 25wt%.
The graphite raw material used can be the Graphite Powder 99 of 1g, 99.85wt%.
The oxygenant used can be the H of 23mL, 98wt%
2sO
4with the NaNO of 100mg, 99.0wt%
3and the KMnO of 1500mg, 99.5wt%
4, be oxidized the H of rear 10mL, 30wt%
2o
2termination reaction.
Described ultrasonic centrifuging process can be: with the frequency ultrasound 15 ~ 30min of 60 ~ 90kHz, with the centrifugal 4 ~ 6min of the rotating speed of 8000 ~ 12000r/min.
The alkaline condition of described reduction can be pH=10 ~ 11.
The reductive agent used can be the hydrazine hydrate of 0.1 ~ 0.2mL, 50.0wt%.
The quality of the substituent of the naphthalene containing different hydrophilic group used can be 2.5 ~ 5.0mg, this substituent can be any one in the 6-Hydroxy-2-naphthoic acid of the 1-naphthoic acid of 98wt%, the Isosorbide-5-Nitrae-naphthalic acid of 95wt%, the 1-hydroxy-2-naphthoic acid of 98wt%, the 2-hydroxyl-3-naphthoic acid of 97wt%, 98wt%.
Described graphene oxide can be 1:0.1 ~ 0.2 with the mass ratio of the substituent of the naphthalene containing different hydrophilic group, this substituent can be any one in the 6-Hydroxy-2-naphthoic acid of the 1-naphthoic acid of 98wt%, the Isosorbide-5-Nitrae-naphthalic acid of 95wt%, the 1-hydroxy-2-naphthoic acid of 98wt%, the 2-hydroxyl-3-naphthoic acid of 97wt%, 98wt%.
The volume of the organic solvent used can be 50 ~ 100mL, and this organic solvent can be any one in the Virahol of the methyl alcohol of 99.5wt%, the ethanol of 99.7wt%, the propyl alcohol of 99.7wt%, the butanols of 99.5wt%, 99.7wt%, or several combination.
Prepared stable graphene colloid dispersion solution has Tyndall effect, and its zeta current potential can be-41 ~-33mV, and the median size of Graphene can be 250 ~ 400nm.
Compared with prior art, the present invention has the following advantages:
1. preparation is simple for present method.Compare traditional mechanically peel method to the dependence of highly oriented pyrolytic graphite, the raw material of present method only needs lower-cost Graphite Powder 99; Compare chemical Vapor deposition process and hot reducing method to the requirement of equipment, present method reaction process easily controls, and to equipment without particular requirement, and there is energy consumption problem hardly.
2. the graphene colloid dispersion solution stability prepared of present method is better, has Tyndall effect.After tested, its zeta current potential is-41 ~-33mV, exceedes the threshold value-30mV that colloid-stabilised theory defines.
3. the stable graphene colloid dispersion solution particle prepared of present method is tiny.After tested, its median size is 250 ~ 400nm.
4. the large percentage of single-layer graphene in the stable graphene colloid dispersion solution prepared of present method.The quantity observing single-layer graphene under the tem accounts for 25 ~ 40% of individual layer and few layer graphene total quantity, and the mass percent of its correspondence is 14 ~ 25%.
5. the stable graphene colloid dispersion solution that prepared by present method will be prepared into film by coating process future, and be applied in the relative photo Electricity Functional devices such as ultracapacitor, solar cell and thin film transistor.
Accompanying drawing explanation
Fig. 1 is the TEM figure of individual layer in stable graphene colloid dispersion solution, few layer graphene.
Fig. 2 is the Raman collection of illustrative plates of graphite, graphene oxide and Graphene, the D peak of graphite Raman spectrum and the strength ratio at G peak, to compare with graphene oxide with Graphite Powder 99 and present obvious rising, show that in reduction process, hydrazine hydrate changes the structure of graphene oxide consumingly, makes the latter be reduced fully.And 2D peak generation left avertence, then illustrate that the number of plies is within 10 layers, more close to the category of Graphene.
Fig. 3 is the zeta potential ph diagram ph of the graphene dispersing solution of embodiment 2 to embodiment 7 gained, and its value is respectively-22.6mV ,-36.2mV ,-33.4mV ,-40.4mV ,-35.5mV ,-37.6mV.Wherein, the zeta current potential of the stable graphene colloid dispersion solution of embodiment 3 to embodiment 7 gained all exceedes the threshold value-30mV that colloid-stabilised theory defines, and proves that these dispersion liquids have certain colloidal stability.As a comparison, the zeta current potential in embodiment 2 does not exceed threshold value, its less stable.
Fig. 4 is the median size figure of Graphene in the graphene dispersing solution of embodiment 2 to embodiment 7 gained, and its value is respectively 720.5nm, 387.3nm, 397.1nm, 257.5nm, 334.7nm, 305.2nm.Compared with embodiment 2, in the stable graphene colloid dispersion solution of embodiment 3 to embodiment 7 gained, the median size of Graphene significantly reduces, better dispersed.
Embodiment
The preparation method of a kind of stable graphene colloid dispersion solution provided by the invention, is characterized in that: Hummer ' the s legal system first passing through to improve is for graphene oxide; Then, under the alkaline condition of pH=10 ~ 11, with the hydrazine hydrate reduction 2 ~ 4 hours of 0.1 ~ 0.2mL, 50.0wt%, Graphene is obtained; By the Graphene of process be dissolved with different hydrophilic group naphthalene substituent organic solvent for ultrasonic peel off dispersion, centrifuging and taking supernatant liquor, obtain stable graphene colloid dispersion solution, its concentration is 0.21 ~ 0.25mg/mL, the single-layer graphene wherein containing 14 ~ 25wt%.
The method specifically comprises the following steps:
1. by the H of the Graphite Powder 99 of 99.85wt% priority with 23mL, 98wt%
2sO
4with the NaNO of 100mg, 99.0wt%
3and the KMnO of 1500mg, 99.5wt%
4there is oxidizing reaction in mixing, adds the H of 10mL, 30wt%
2o
2termination reaction, after ultrasonic eccentric cleaning, generates stable graphene oxide;
2., under the alkaline condition of pH=10 ~ 11, with the hydrazine hydrate reduction 2 ~ 4 hours of 0.1 ~ 0.2mL, 50.0wt%, obtain the Graphene after reduction;
3. the Graphene of above-mentioned process is joined ultrasonic stripping dispersion in the solvent of preparation, eccentric cleaning, obtains stable graphene colloid dispersion solution, and its concentration is 0.21 ~ 0.25mg/mL, the single-layer graphene wherein containing 14 ~ 25wt%.
Described solvent, it is the organic solvent mixed system of the substituent of the naphthalene being dissolved with different hydrophilic group, the substituent of naphthalene is the 1-naphthoic acid of the 98wt% of 2.5 ~ 5.0mg, 1 of 95wt%, any one in the 6-Hydroxy-2-naphthoic acid of the 1-hydroxy-2-naphthoic acid of 4-naphthalic acid, 98wt%, the 2-hydroxyl-3-naphthoic acid of 97wt%, 98wt%, organic solvent is any one or a few combination in the Virahol of the methyl alcohol of the 99.5wt% of 50 ~ 100mL, the ethanol of 99.7wt%, the propyl alcohol of 99.7wt%, the butanols of 99.5wt%, 99.7wt%.
Described solvent is prepared by following method: at room temperature by the substituent of naphthalene by being that 0.1 ~ 0.2:1 takes with graphene oxide mass ratio, join in the organic solvent of 50 ~ 100mL, by the abundant stirring and dissolving of magnetic stirring apparatus.
Described stable graphene colloid dispersion solution is made up of following method: join in solvent by the Graphene after reduction, with the frequency ultrasound 15 ~ 30min of 60 ~ 90kHz, with the centrifugal 4 ~ 6min of the rotating speed of 12000r/min, wash away remaining organism, throw out is dispersed in 100mL distilled water, the ultrasonic 30min of first 70kHz, after the centrifugal 5min of 10000r/min, gained supernatant liquid is stable graphene colloid dispersion solution, its concentration is 0.21 ~ 0.25mg/mL, the single-layer graphene wherein containing 14 ~ 25wt%.
Prepared stable graphene colloid dispersion solution has Tyndall effect, and its zeta current potential is-41 ~-33mV, and the median size of Graphene is 250 ~ 400nm.
Below in conjunction with specific embodiment and accompanying drawing, the invention will be further described, but be not limited to described content below.
Embodiment 1
A preparation method for graphene dispersing solution, comprises following processing step:
By the Graphite Powder 99 of 1g, 99.85wt% and the H of 23mL, 98wt%
2sO
4mix in 250mL beaker, stirred at ambient temperature 24 hours; In 40 DEG C of water-baths, in beaker, add the NaNO of 100mg, 99.0wt%
3and stir 5min, make it abundant dissolving.The KMnO of 1500mg, 99.5wt% is slowly added in cup
4, about 20min adds, and controls temperature of reaction below 5 DEG C, stirs 30min.In beaker, add 3mL distilled water, wait for 5min, then add 3mL distilled water, after waiting for 5min, add 40mL distilled water, stir 15min.Stop water-bath, in beaker, add the H of 140mL distilled water and 10mL, 30wt%
2o
2at room temperature stir 5min, termination reaction.Use the centrifugal 4min of whizzer 10000r/min, wash with the HCl of 5wt%, repeat twice.Then use the centrifugal 4min of whizzer 8000r/min, arrive for three times neutral with distilled water wash.Throw out is dispersed in 100mL distilled water, the ultrasonic 30min of 90kHz; By the solution of gained with 8000r/min rotating speed, centrifugal 5min, supernatant liquid is graphene oxide solution.Obtained graphene oxide solution after 8 ~ 12 hours, is taken 25mg through 60 DEG C of vacuum-dryings, and being dispersed in 100mL, pH is in the NaOH solution of 10 ~ 11, the ultrasonic 20min of 70kHz, add the hydrazine hydrate of 0.1 ~ 0.2mL, 50.0wt%, reductase 12 ~ 4 hour in 95 DEG C of water-baths, obtain Graphene.
Embodiment 2
A preparation method for stable graphene dispersing solution, comprises following processing step:
Be dissolved in the ethanol of 100mL, 99.7wt% by the Graphene in embodiment 1, the ultrasonic 30min of 70kHz peels off dispersion, through the centrifugal 5min of 12000r/min, with distilled water wash 2 ~ 3 times, washes away remaining ethanol.Be dispersed in by throw out in 100mL distilled water, the ultrasonic 30min of 70kHz, through the centrifugal 5min of 10000r/min, gained supernatant liquid is that concentration is 0.20mg/mL, dispersion liquid containing the single-layer graphene of the 12wt% that has an appointment.Prepared graphene dispersing solution does not have obvious Tyndall effect, and its zeta current potential is-22.6mV, and the median size of Graphene is 720.5nm.
Embodiment 3
A preparation method for stable graphene colloid dispersion solution, comprises following processing step:
Graphene in embodiment 1 is dissolved in the ethanol of 100mL, 99.7wt% of the 1-naphthoic acid of 4mg, 98wt%, the ultrasonic 30min of 70kHz peels off dispersion, through the centrifugal 5min of 12000r/min, with distilled water wash 2 ~ 3 times, wash away remaining 1-naphthoic acid and ethanol.Be dispersed in by throw out in 100mL distilled water, the ultrasonic 30min of 70kHz, through the centrifugal 5min of 10000r/min, gained supernatant liquid is that concentration is 0.25mg/mL, colloidal dispersion containing the single-layer graphene of the 25wt% that has an appointment.Prepared stable graphene colloid dispersion solution has Tyndall effect, and its zeta current potential is-36.2mV, and the median size of Graphene is 387.3nm.
Embodiment 4
A preparation method for stable graphene colloid dispersion solution, comprises following processing step:
Be dissolved in by Graphene in embodiment 1 in the propyl alcohol of 50mL, 99.7wt% of the Isosorbide-5-Nitrae-naphthalic acid of 2.5mg, 95wt%, the ultrasonic 30min of 70kHz peels off dispersion, through the centrifugal 5min of 12000r/min, with distilled water wash 2 ~ 3 times, wash away remaining Isosorbide-5-Nitrae-naphthalic acid and propyl alcohol.Be dispersed in by throw out in 100mL distilled water, the ultrasonic 30min of 70kHz, through the centrifugal 5min of 10000r/min, gained supernatant liquid is that concentration is 0.21mg/mL, colloidal dispersion containing the single-layer graphene of the 15wt% that has an appointment.Prepared stable graphene colloid dispersion solution has Tyndall effect, and its zeta current potential is-33.4mV, and the median size of Graphene is 397.1nm.
Embodiment 5
A preparation method for stable graphene colloid dispersion solution, comprises following processing step:
Graphene in embodiment 1 is dissolved in the butanols of 60mL, 99.5wt% of the 1-hydroxy-2-naphthoic acid of 5mg, 98wt%, the ultrasonic 30min of 70kHz peels off dispersion, through the centrifugal 5min of 12000r/min, with distilled water wash 2 ~ 3 times, wash away remaining 1-hydroxy-2-naphthoic acid and butanols.Be dispersed in by throw out in 100mL distilled water, the ultrasonic 30min of 70kHz, through the centrifugal 5min of 10000r/min, gained supernatant liquid is that concentration is 0.25mg/mL, colloidal dispersion containing the single-layer graphene of the 22wt% that has an appointment.Prepared stable graphene colloid dispersion solution has Tyndall effect, and its zeta current potential is-40.4mV, and the median size of Graphene is 257.5nm.
Embodiment 6
A preparation method for stable graphene colloid dispersion solution, comprises following processing step:
Graphene in embodiment 1 is dissolved in the Virahol of 50mL, 99.7wt% of the 2-hydroxyl-3-naphthoic acid of 3mg, 97wt%, the ultrasonic 30min of 70kHz peels off dispersion, through the centrifugal 5min of 12000r/min, with distilled water wash 2 ~ 3 times, wash away remaining 2-hydroxyl-3-naphthoic acid and Virahol.Be dispersed in by throw out in 100mL distilled water, the ultrasonic 30min of 70kHz, through the centrifugal 5min of 10000r/min, gained supernatant liquid is that concentration is 0.22mg/mL, colloidal dispersion containing the single-layer graphene of the 14wt% that has an appointment.Prepared stable graphene colloid dispersion solution has Tyndall effect, and its zeta current potential is-35.5mV, and the median size of Graphene is 334.7nm.
Embodiment 7
A preparation method for stable graphene colloid dispersion solution, comprises following processing step:
Graphene in embodiment 1 is dissolved in the methyl alcohol of 80mL, 99.5wt% of the 6-Hydroxy-2-naphthoic acid of 3.5mg, 98wt%, the ultrasonic 30min of 70kHz peels off dispersion, through the centrifugal 5min of 12000r/min, with distilled water wash 2 ~ 3 times, wash away remaining 6-Hydroxy-2-naphthoic acid and methyl alcohol.Be dispersed in by throw out in 100mL distilled water, the ultrasonic 30min of 70kHz, through the centrifugal 5min of 10000r/min, gained supernatant liquid is that concentration is 0.22mg/mL, colloidal dispersion containing the single-layer graphene of the 17wt% that has an appointment.Prepared stable graphene colloid dispersion solution has Tyndall effect, and its zeta current potential is-37.6mV, and the median size of Graphene is 305.2nm.
Obviously, those skilled in the art can carry out various change and modification to the preparation method of stable graphene colloid dispersion solution of the present invention and not depart from the spirit and scope of the present invention.Like this, if belong within claim of the present invention and equivalent technical scope thereof to these amendments of the present invention and modification, then the present invention is also intended to comprise these change and modification.
Claims (9)
1. a preparation method for stable graphene colloid dispersion solution, is characterized in that having following steps:
(1) graphite raw material is mixed with oxygenant, through ultrasonic centrifugal after, generate stable graphene oxide;
(2) in the basic conditions, with reductive agent reductase 12 ~ 4 hour, Graphene is obtained;
(3) by graphene dispersion in be dissolved with different hydrophilic group naphthalene substituent organic solvent in, through ultrasonic eccentric cleaning, obtain stable graphene colloid dispersion solution, its concentration is 0.21 ~ 0.25mg/mL, wherein containing the single-layer graphene of 14 ~ 25wt%; The quality of the substituent of the naphthalene containing different hydrophilic group used is 2.5 ~ 5.0mg, this substituent is any one in the 6-Hydroxy-2-naphthoic acid of the 1-naphthoic acid of 98wt%, the Isosorbide-5-Nitrae-naphthalic acid of 95wt%, the 1-hydroxy-2-naphthoic acid of 98wt%, the 2-hydroxyl-3-naphthoic acid of 97wt%, 98wt%.
2. the preparation method of stable graphene colloid dispersion solution according to claim 1, is characterized in that the Graphite Powder 99 that used graphite raw material is 1g, 99.85wt%.
3. the preparation method of stable graphene colloid dispersion solution according to claim 1, is characterized in that the H that used oxygenant is 23mL, 98wt%
2sO
4with the NaNO of 100mg, 99.0wt%
3and the KMnO of 1500mg, 99.5wt%
4, be oxidized the H of rear 10mL, 30wt%
2o
2termination reaction.
4. the preparation method of stable graphene colloid dispersion solution according to claim 1, is characterized in that described ultrasonic centrifuging process is: with the frequency ultrasound 15 ~ 30min of 60 ~ 90kHz, with the centrifugal 4 ~ 6min of the rotating speed of 8000 ~ 12000r/min.
5. the preparation method of stable graphene colloid dispersion solution according to claim 1, is characterized in that the alkaline condition reduced is pH=10 ~ 11.
6. the preparation method of stable graphene colloid dispersion solution according to claim 1, is characterized in that used reductive agent is the hydrazine hydrate of 0.1 ~ 0.2mL, 50.0wt%.
7. the preparation method of stable graphene colloid dispersion solution according to claim 1, it is characterized in that graphene oxide is 1:0.1 ~ 0.2 with the mass ratio of the substituent of the naphthalene containing different hydrophilic group, this substituent is any one in the 6-Hydroxy-2-naphthoic acid of the 1-naphthoic acid of 98wt%, the Isosorbide-5-Nitrae-naphthalic acid of 95wt%, the 1-hydroxy-2-naphthoic acid of 98wt%, the 2-hydroxyl-3-naphthoic acid of 97wt%, 98wt%.
8. the preparation method of stable graphene colloid dispersion solution according to claim 1, it is characterized in that the volume of used organic solvent is 50 ~ 100mL, this organic solvent is any one in the Virahol of the methyl alcohol of 99.5wt%, the ethanol of 99.7wt%, the propyl alcohol of 99.7wt%, the butanols of 99.5wt%, 99.7wt%, or several combination.
9. the preparation method of stable graphene colloid dispersion solution according to claim 1, it is characterized in that prepared stable graphene colloid dispersion solution has Tyndall effect, its zeta current potential is-41 ~-33mV, and the median size of Graphene is 250 ~ 400nm.
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| CN105399087B (en) * | 2015-12-11 | 2017-10-03 | 安军伟 | What a kind of reducing agent consumption suitable for fast filtering was reduced prepares graphene method |
| CN107304047B (en) * | 2016-04-21 | 2020-05-26 | 常州二维碳素科技股份有限公司 | Dispersing method of multilayer graphene |
| CN107857992A (en) * | 2017-11-21 | 2018-03-30 | 四川长虹电器股份有限公司 | Daiamid-6 fiber composite that graphene is modified and preparation method thereof |
| CN108726513A (en) * | 2018-09-05 | 2018-11-02 | 广东墨睿科技有限公司 | A kind of preparation method of graphene dispersing solution |
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| CN102976314A (en) * | 2012-11-29 | 2013-03-20 | 中国科学院宁波材料技术与工程研究所 | Novel titanium dioxide-graphene nano-composite material as well as manufacturing method and application thereof |
| CN103623741A (en) * | 2013-11-27 | 2014-03-12 | 中国科学院长春应用化学研究所 | Graphene dispersing agent, preparation method thereof and preparation method of graphene |
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