CN104058392B - A kind of preparation method of graphene colloid dispersion solution - Google Patents
A kind of preparation method of graphene colloid dispersion solution Download PDFInfo
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- CN104058392B CN104058392B CN201410261400.8A CN201410261400A CN104058392B CN 104058392 B CN104058392 B CN 104058392B CN 201410261400 A CN201410261400 A CN 201410261400A CN 104058392 B CN104058392 B CN 104058392B
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Abstract
The preparation method that the present invention relates to a kind of graphene colloid dispersion solution, comprises the following steps: graphite oxide is added to the water by (1), ultrasonic disperse, obtains the homodisperse graphene oxide colloid of monolithic layer;(2) surfactant is joined in graphene oxide colloid, ultrasonic disperse after mix homogeneously;(3) adding reducing agent in step (2) gained solution, reaction rises to 10.5~11.5 to pH, then mixed liquor is placed in 70~90 DEG C of reactions, obtains the graphene colloid dispersion solution with Investigation of stabilized dispersion of nano.Compared with prior art, the graphene dispersing solution that prepared by the present invention can be used for the extensive preparation of Graphene, stores and transport and prepare the fields such as graphene composite material;Graphene dispersing solution prepared by the present invention have concentration height, good dispersion, can the advantage of maintaining a long-term stability property, graphene sheet layer particle size distribution therein is uniform, splitting good;Cost is low, and preparation technology is simple, non-environmental-pollution, it is easy to accomplish large-scale industrial production.
Description
Technical field
The preparation method that the present invention relates to a kind of graphene colloid dispersion solution, belongs to the preparation field of nano material.
Background technology
Graphene is a kind of bi-dimensional cellular shape material with carbon element tightly packed by monolayer carbon atom.2004, British scientist Geim et al. was successfully prepared the Graphene that room-temperature stable exists, and caused concern (NovoselovK, GeimA, etal.Science, 2004, v306:666-669) widely.Graphene has the electric property (electrical conductivity is up to 106S/cm) of excellence, thermal property (thermal conductivity is 3000-5000J/m K s), mechanical property (intensity is 110-130GPa, elastic modelling quantity is 1.0TPa) and optical property (light transmittance can reach 97.7%), therefore all has broad application prospects in fields such as electronics, high-strength material, energy conversion and storage, catalysis, sensors.
The method preparing Graphene is broadly divided into two classes: method and from top to bottom method from bottom to top;The former includes micromechanics stripping method and electronation graphene oxide method etc., and the latter includes epitaxial growth method and chemical vapour deposition technique etc..In the numerous methods preparing Graphene, electronation graphene oxide method is considered as the method most possibly realizing industrialized production Graphene;It has the advantages such as cost is low, yield is high, control is easy.But, owing in reduction process, surface of graphene oxide hydrophilic oxy radical gradually decreases, the electrostatic repulsion of sheet interlayer weakens, Graphene can produce to reunite, and dispersibility progressively declines, and even produces precipitation (StankovichS, etal.Carbon, 2007, v45:1558-1565).
Owing to pi-pi bond strong between graphene layer interacts, the Graphene of structural integrity is easily assembled in the disperse medium such as water and organic solvent and precipitates, and is unfavorable for extensive preparation and the application of Graphene.In order to solve this problem, graphene functionalized is processed by people, not only improves its dissolubility, and utilizes multiple chemical bond can regulate and control the structure of Graphene, gives the performance that Graphene is new.According to whether introducing new covalent bond, graphene functionalized processing method is divided into covalent bond functionalization and non-covalent bond functionalization.The former is generally used for and prepares graphene composite material, and wherein Graphene generally has good dissolubility;But due to the introducing of other functional groups, destroy the big π key conjugated structure of Graphene so that it is electric conductivity and other performances significantly reduce.Non-covalent bond functionalization, by utilizing the non-covalent bonds such as π-π interaction, ionic bond and hydrogen bond to make decorating molecule carry out surface-functionalized to Graphene, can not only keep the character of Graphene self, and can keep the dissolubility of Graphene.Li et al. have studied graphene dispersion state and electrical charge rejection effect thereof.It is shown that graphene oxide why can be dissolved in water mutually exclusive mainly due to its surface negative charge, define stable colloid solution, be not only the hydrophilic of oxy radical.They utilize this discovery by controlling its reducing degree, carboxyl anion therein is retained so that it is can stable dispersion (LiD, etal.Nanotechnology in aqueous when removing the oxygen-containing functional group such as the hydroxyl of graphene oxide, epoxy radicals, 2008, v3:101-105).
At present, the Study on dispersity of Graphene has been achieved for many important achievements.Fu Honggang et al. is dissolved in alcohol after Graphene and cyclodextrin being mixed, and prepares the graphene dispersing solution (preparation method of high-stability graphene dispersing solution with good stability;Publication No.: CN102515149A;Date of publication: 2012.06.27).Zhang Wen et al. is dispersed in graphene oxide in the organic solvents such as methanol, then dispersion liquid is sprayed in liquid nitrogen container and carry out fast frozen, its product recovers to carry out reduction treatment to room temperature, obtains the Graphene slurry (preparation method of a kind of graphene dispersing solution of black;Publication No.: CN103496691A;Date of publication: 2014.01.08).Chen Guohua et al. adopts the method that will carry out ball-milling treatment according to the volume ratio of 9: 1 after blended to redox graphene and mixed solvent (such as METHYLPYRROLIDONE and water mix), prepares the graphene dispersing solution (preparation method of a kind of high concentration small flake diameter graphene dispersion of 2.5~10mg/ml;Publication No.: CN103407998A;Date of publication: 2013.11.27).Xu Yan et al. is prepared for form the few-layer graphene alkene suspension, and adopts supertension or supercritical equipment that graphene solution carries out a nanometer refinement dispersion process (a kind of graphene dispersion liquid and preparation method thereof;Publication No.: CN103253656A;Date of publication: 2013.08.21).Sun Jing et al. adopts solution exchange method to be scattered in DMF by graphene oxide, prepares the graphene dispersing solution (preparation method of a kind of graphene colloid dispersion solution that concentration is about 0.5mg/ml after reduction;Publication No.: CN102633256A;Date of publication: 2012.08.15).But existing about in the research of graphene dispersion, it is common to also existing and adopt poisonous organic solvent, complicated process of preparation, the graphene aqueous solution concentration of stable dispersion is low, and lamella size is little, the problem such as the electrical conductivity reduction of Graphene after surface modification treatment.Therefore, explore a kind of can prepare high concentration, have concurrently good dispersibility and stability graphene aqueous solution method tool be of great significance.
Summary of the invention
The purpose of the present invention is contemplated to overcome the defect that above-mentioned prior art exists and the preparation method providing a kind of high-quality graphene colloid dispersion solution.It is characterized in water for dispersion, make Graphene reach the stable dispersion concentration of higher quality and Graphene by the synergism of ultrasonic, surfactant and high temperature higher, dry and still can reach same concentration and stability for again dissolving after graphene powder.
The purpose of the present invention can be achieved through the following technical solutions:
(1) it is (400~1000) according to the mass ratio of water Yu graphite oxide: graphite oxide is added to the water by the ratio of 1, ultrasonic disperse 2~3 hours, forms the homodisperse graphene oxide colloid of monolithic layer that concentration is 1~2.5mg/ml;
(2) it is 1 by surfactant according to the mass ratio with graphene oxide colloid: the ratio of (50~100) adds in graphene oxide colloid, adopt magnetic stirrer mix homogeneously (rotating speed 100rmp~500rmp, 10~30 minutes) ultrasonic disperse 1 hour (operating frequency >=40kHz) afterwards, temperature is 40~50 DEG C;
Wherein, surfactant is at least one in dodecylbenzene sodium sulfonate, sodium lauryl sulphate.
(3) volume ratio added with step (2) gained liquid is 1: the reducing agent of (10~1000), room temperature (20~25 DEG C) is reacted 1-3 hour, until pH rises to about 11, mixed liquor is placed in 80 DEG C react 12 hours, can obtaining the black redox graphene colloid with Investigation of stabilized dispersion of nano, wherein Graphene is almost whole (> 90%) exists with the state of monolayer.This graphene colloid dispersion solution still can keep its dispersibility constant after standing 1 month.
Wherein, reducing agent is at least one in hydrazine, hydrazine hydrate, Dimethylhydrazine, sodium borohydride, ascorbic acid, gallic acid.
The hydrophobic group of surfactant molecule one end and Graphene combine; other end hydrophilic group and aqueous phase mutual effect; so when Graphene granule when mutually collision owing to the entropic elasticity of surfactant molecule layer and the protection of hydrated sheath prevent their gathering; produce sterically hindered effect, thus improve stability.It addition, surfactant reduces the surface tension of solvent, it is possible to promote the stripping of Graphene, thus can have higher dispersion concentration.
Ultrasonic stripping method is a kind of conventional limellar stripping, pulverizing means.Ultrasound wave is density interphase eradiation in graphite oxide suspension, liquid flowing is made to produce thousands of micro-bubble, the negative pressuren zone that these bubbles are formed in ultrasound wave longitudinal propagation is formed, growth, and at zone of positive pressure rapid closing, this Guan Bi can form instantaneous pressure and high temperature.The high pressure and the high temperature that successively produce constantly impact graphite oxide just as a succession of little " blast ", make each lamella rapid deterioration.The size of graphene oxide can be controlled by the length of the size of adjustment ultrasonic power and ultrasonic time.
Effect ultrasonic in the present invention is not only in that stripping graphene oxide, but also plays the effect being well dispersed in by surfactant in graphene oxide colloid.Owing to the consumption of surfactant is higher than critical micelle concentration, therefore in solution, surfactant molecule will necessarily form micelle, and then reduces the efficiency of its dispersed graphite alkene on the whole.Ultrasound wave is by the effect of micelle core water and then the formation that significantly suppress micelle.When addition hydrazine hydrate carries out reduction reaction, carry out the pre-reaction of middle thermophase, be conducive to the dispersion of redox graphene.Because being made directly pyroreaction, increasing along with temperature raises Brownian movement, causing that graphene film flocculation rate increases.Additionally, temperature rising can reduce the activity of surfactant, also it is unfavorable for the dispersion of Graphene.
(4) graphene colloid dispersion solution is placed in 80~100 DEG C of degree dried, obtains graphene powder;It is (400~1000) according to the mass ratio of water Yu Graphene: dry graphene powder is added to the water by the ratio of 1, after ultrasonic disperse 10~30 seconds, forming the homodisperse Graphene colloid of monolithic layer that concentration is 1~2.5mg/ml, its dispersibility is with the graphene dispersing solution before drying;
Graphene dispersing solution prepared by the method is adopted to can be used for the extensive preparation of Graphene, store and transport and prepare the fields such as graphene composite material.
Compared with prior art, present invention have the advantage that
1, graphene dispersing solution prepared by the present invention have concentration height, good dispersion, can the advantage of maintaining a long-term stability property, graphene sheet layer particle size distribution therein is uniform, splitting good (being all almost monolayer);
2, cost is low, and preparation technology is simple, non-environmental-pollution, it is easy to accomplish large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is Graphene scattered principle schematic in water;
Fig. 2 is the AFM figure of single-layer graphene in embodiment 1;
Fig. 3 is the grain size scattergram of Graphene in embodiment 1;
Fig. 4 is the XPS figure of graphene oxide (1) and Graphene (2) in embodiment 1;
Fig. 5 is the Raman figure of Graphene in embodiment 1.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The graphite oxide dispersion of configuration 2.0mg/ml, ultrasonic 3 hours prepared graphene oxide colloids, scattered principle schematic is as shown in Figure 1 in water for Graphene.Adding the dodecylbenzene sodium sulfonate of 1.0wt%, so as to be completely dissolved after stirring 10 minutes, 50 DEG C ultrasonic 1 hour;Adding the hydrazine hydrate of 0.2vol%, after 25 DEG C of standing 1h, pH rises to 10.7.80 DEG C of heating 12h, can prepare the graphene dispersing solution of black.Take 200ml graphene dispersing solution vacuum filtration film forming, dried employing its square resistance of four probe tests.
As in figure 2 it is shown, Graphene atomic force microscope (AFM) phenogram, it can be seen that the splitting of redox graphene is better, and lamella diameter is generally between 200-500nm;It can be seen that Graphene is almost without reunion after reduction from the lateral dimension figure weighing surface roughness, thickness is generally between 0.3-0.7nm, is mainly single-layer graphene.Oxidation-reduction process is little to the structural deterioration of Graphene, and only surface forms minority hole.
It is illustrated in figure 3 the dynamic light scattering-grain size distribution of gained graphene dispersing solution, as can be seen from the figure, the even particle size distribution of Graphene, it is mainly 150-450nm, match with the analytical data of AFM, mean diameter is 288.5nm, and polydispersity coefficient is 0.265, illustrates that this granularmetric analysis data reliability is high.Testing its Zeta potential is-38~-41.8mV, and the good stability of this dispersion liquid is described.
X-ray photoelectron power spectrum (XPS) figure of Graphene after being illustrated in figure 4 graphene oxide and reducing, it can be seen that containing many oxygen-containing functional group (-OH, 286.5eV in graphene oxide;-C=O, 287.5eV;-COOH, 289eV), but after reduction, these oxygen-containing functional groups disappear, and illustrate that Graphene reducing degree prepared by the method is good, also explains prepared Graphene and have the reason of excellent electrical conductivity.
It is illustrated in figure 5 Raman spectrum (Raman) analysis chart of Graphene, at 1576cm-1Neighbouring due to the G peak of E2g vibration generation, at 1340cm-1The D peak that place is caused by defect;Wherein, apparently higher than D peak (D/G=0.72), G peak illustrates that the structural deterioration of Graphene is little, reflects restorative good to graphene film Rotating fields of reduction process in the method, and defect is few.
Embodiment 2
The graphite oxide dispersion of configuration 1.0mg/ml, ultrasonic 3 hours prepared graphene oxide colloids.Adding the dodecylbenzene sodium sulfonate of 1.0wt%, so as to be completely dissolved after stirring 10 minutes, 40 DEG C ultrasonic 1 hour;Adding the hydrazine hydrate of 0.2vol%, after 25 DEG C of standing 2h, pH rises to 11.80 DEG C of heating 12h, can prepare the graphene dispersing solution of black.Take 200ml graphene dispersing solution vacuum filtration film forming, dried employing its square resistance of four probe tests.
Embodiment 3
The graphite oxide dispersion of configuration 2.0mg/ml, ultrasonic 3 hours prepared graphene oxide colloids.Adding the sodium lauryl sulphate of 2.0wt%, so as to be completely dissolved after stirring 30 minutes, 50 DEG C ultrasonic 1 hour;Adding the hydrazine hydrate of 0.1vol%, after 25 DEG C of standing 2h, pH rises to 11.80 DEG C of heating 12h, can prepare the graphene dispersing solution of black.Take 200ml graphene dispersing solution vacuum filtration film forming, dried employing its square resistance of four probe tests.
Embodiment 4
The graphite oxide dispersion of configuration 2.0mg/ml, ultrasonic 3 hours prepared graphene oxide colloids.Adding the sodium lauryl sulphate of 0.5wt%, so as to be completely dissolved after stirring 30 minutes, 50 DEG C ultrasonic 1 hour;Adding the hydrazine hydrate of 0.2vol%, after 25 DEG C of standing 1h, pH rises to 11.80 DEG C of heating 12h, can prepare the graphene dispersing solution of black.Take 200ml graphene dispersing solution vacuum filtration film forming, dried employing its square resistance of four probe tests.
The graphene dispersing solution electric conductivity that embodiment 1~embodiment 4 prepares is as shown in table 1.
The electric conductivity of table 1 embodiment 1~4
Embodiment 5
The graphite oxide dispersion of configuration 2.5mg/ml, ultrasonic 2 hours prepared graphene oxide colloids.Adding the sodium lauryl sulphate of 1.5wt%, so as to be completely dissolved after stirring 30 minutes, 50 DEG C ultrasonic 1 hour;Adding the hydrazine hydrate of 0.2vol%, after 25 DEG C of standing 1h, pH rises to 11.80 DEG C of heating 12h, can prepare the graphene dispersing solution of black.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and use invention.These embodiments obviously easily can be made various amendment by person skilled in the art, and General Principle described herein is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art's announcement according to the present invention, the improvement made without departing from scope and amendment all should within protection scope of the present invention.
Claims (5)
1. the preparation method of a graphene colloid dispersion solution, it is characterised in that comprise the following steps:
(1) graphite oxide is added to the water, ultrasonic disperse, obtains the homodisperse graphene oxide colloid of monolithic layer;
(2) surfactant is joined in graphene oxide colloid, ultrasonic disperse after mix homogeneously;
(3) in step (2) gained solution, reducing agent is added, 20~25 DEG C are reacted 1~3 hour, rise to 10.5~11.5 to pH, then mixed liquor is placed in 70~90 DEG C and reacts 10~14 hours, obtain the graphene colloid dispersion solution with Investigation of stabilized dispersion of nano;
The surfactant added in step (2) and the mass ratio of graphene oxide colloid are 1:50~1:100, described surfactant is dodecylbenzene sodium sulfonate or sodium lauryl sulphate, and in step (2), the solution temperature after ultrasonic disperse is 40~50 DEG C.
2. the mass ratio of the preparation method of a kind of graphene colloid dispersion solution according to claim 1, it is characterised in that in step (1), water and graphite oxide is 400:1~1000:1.
3. the preparation method of a kind of graphene colloid dispersion solution according to claim 1, it is characterised in that the reducing agent added in step (3) and the volume ratio of step (2) gained liquid are 1:10~1:1000.
4. the preparation method of a kind of graphene colloid dispersion solution according to claim 1 or 3, it is characterised in that described reducing agent is at least one in hydrazine, hydrazine hydrate, Dimethylhydrazine, sodium borohydride, ascorbic acid or gallic acid.
5. the preparation method of a kind of graphene colloid dispersion solution according to claim 1, it is characterised in that graphene colloid dispersion solution is placed in 80~100 DEG C of degree dried, obtains graphene powder;Being added to the water by dry graphene powder according to the ratio that mass ratio is 400:1~1000:1 of water Yu Graphene, ultrasonic disperse, after 10~30 seconds, forms the homodisperse Graphene colloid of monolithic layer that concentration is 1~2.5mg/mL.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101613098A (en) * | 2009-06-12 | 2009-12-30 | 中国科学院宁波材料技术与工程研究所 | A kind of solution phase preparation method of Graphene |
CN102502612A (en) * | 2011-11-21 | 2012-06-20 | 南京工业大学 | Method for preparing grapheme through oxidation reduction |
CN103011135A (en) * | 2011-09-20 | 2013-04-03 | 安炬科技股份有限公司 | Graphene preparation method |
-
2014
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101613098A (en) * | 2009-06-12 | 2009-12-30 | 中国科学院宁波材料技术与工程研究所 | A kind of solution phase preparation method of Graphene |
CN103011135A (en) * | 2011-09-20 | 2013-04-03 | 安炬科技股份有限公司 | Graphene preparation method |
CN102502612A (en) * | 2011-11-21 | 2012-06-20 | 南京工业大学 | Method for preparing grapheme through oxidation reduction |
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