CN104058392A - Method for preparing graphene colloid dispersion liquid - Google Patents
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Abstract
The invention relates to a method for preparing a graphene colloid dispersion liquid. The method comprises the following steps: (1) adding graphite oxide into water, performing ultrasonic dispersion to obtain graphene oxide colloid with uniformly dispersed monolithic layer; (2) adding a surfactant into the graphene oxide colloid, uniformly mixing and performing ultrasonic dispersion; (3) adding a reducing agent into the solution obtained in the step (2), reacting until the pH rises to 10.5-11.5, leading the mixed liquid at 70-90 DEG C to react to obtain the graphene colloid dispersion liquid with stable dispersion. Compared with the prior art, the graphene dispersion liquid prepared by the method can be applied to the fields of large-scale preparation, storage and transportation of graphene, preparation of the graphene composite material, and the like. The graphene dispersion liquid has the advantages of high concentration, good dispersion and long-time stability, wherein the graphene sheet is uniform in grain diameter distribution and good in peeling degree; the cost is low, the preparation process is simple, the environment is not polluted, and large-scale industrial production can be easily realized.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene colloidal dispersion, belong to the preparation field of nano material.
Background technology
Graphene is a kind of by the tightly packed bi-dimensional cellular shape carbon material forming of monolayer carbon atom.2004, the people such as British scientist Geim successfully prepared the Graphene of stable existence under room temperature, caused widely and to pay close attention to (Novoselov K, Geim A, et al.Science, 2004, v306:666-669).Graphene has excellent electric property (specific conductivity is up to 106S/cm), thermal property (thermal conductivity is 3000-5000J/mKs), mechanical property (intensity is that 110-130GPa, Young's modulus are 1.0TPa) and optical property (transmittance can reach 97.7%), therefore in electronics, high-strength material, Energy conversion and storage, catalysis, sensor field, all has broad application prospects.
The method of preparing Graphene is mainly divided into two classes: method and from top to bottom method from bottom to top; The former comprises micromechanics stripping method and chemical reduction graphene oxide method etc., and the latter comprises epitaxial growth method and chemical Vapor deposition process etc.In preparing numerous methods of Graphene, chemical reduction graphene oxide method is considered to most possibly realize the method for suitability for industrialized production Graphene; It has, and cost is low, output is high, control the advantages such as easy.But because graphene oxide surface hydrophilicity oxy radical in reduction process reduces gradually, the electrostatic repulsion of sheet interlayer weakens, Graphene can produce reunion, and dispersiveness progressively declines, and even produces precipitation (Stankovich S, et al.Carbon, 2007, v45:1558-1565).
Because pi-pi bond strong between graphene layer interacts, the Graphene of structural integrity is easily assembled and precipitates in the dispersion medium such as water and organic solvent, is unfavorable for extensive preparation and the application of Graphene.In order to address this problem, people process graphene functionalized, have not only improved its solvability, and utilize number of chemical key can regulate and control the structure of Graphene, give the performance that Graphene is new.According to whether introducing new covalent linkage, graphene functionalized treatment process is divided into covalent linkage functionalization and non covalent bond functionalization.The former is generally used for and prepares graphene composite material, and wherein Graphene generally has good solubility; But due to the introducing of other functional groups, destroyed the large π key of Graphene conjugated structure, its electroconductibility and other performances are significantly reduced.Non covalent bond functionalization is surface-functionalized by utilizing the non covalent bonds such as π-π interaction, ionic linkage and hydrogen bond that decorating molecule is carried out Graphene, not only can keep the character of Graphene self, and can keep the solvability of Graphene.The people such as Li have studied Graphene dispersion state and electrical charge rejection effect thereof.Result shows, why graphene oxide can water-solublely be mainly because its surface negative charge repels mutually, has formed stable colloidal solution, and having more than is the wetting ability of oxy radical.They utilize this discovery by controlling its reducing degree, when removing the oxygen-containing functional groups such as the hydroxyl of graphene oxide, epoxy group(ing), retain carboxyl negative ion wherein, make its can be in the aqueous solution stable dispersion (Li D, et al.Nanotechnology, 2008, v3:101-105).
At present, many important achievements in the Study on dispersity of Graphene, have been obtained.Pay the grand firm people of grade by being dissolved in alcohol after Graphene and cyclodextrin mixing, make the graphene dispersing solution (preparation method of high-stability graphene dispersing solution with good stability; Publication No.: CN102515149A; Date of publication: 2012.06.27).The people such as Zhang Wen are dispersed in graphene oxide in the organic solvents such as methyl alcohol, then dispersion liquid is sprayed into and in liquid nitrogen vessel, carry out fast frozen, its product returns to and reduces processing after room temperature, obtains Graphene slurry (a kind of preparation method of graphene dispersing solution of black; Publication No.: CN103496691A; Date of publication: 2014.01.08).The people such as Chen Guohua adopt and will for example, after redox graphene and mixed solvent (METHYLPYRROLIDONE and water mix according to the volume ratio of 9: 1) blend, carry out the method for ball-milling processing, prepare the graphene dispersing solution (preparation method of a kind of high density small pieces footpath graphene dispersing solution of 2.5～10mg/ml; Publication No.: CN103407998A; Date of publication: 2013.11.27).The people such as Xu Yan have prepared few layer graphene suspension, and adopt ultra-high voltage or overcritical equipment to carry out nanometer refinement dispersion treatment (a kind of graphene dispersing solution preparation method to graphene solution; Publication No.: CN103253656A; Date of publication: 2013.08.21).Grandson waits people quietly and adopts solution exchange method that graphene oxide is scattered in DMF, makes graphene dispersing solution (a kind of preparation method of Graphene colloidal dispersion that concentration is about 0.5mg/ml after reduction; Publication No.: CN102633256A; Date of publication: 2012.08.15).But in the existing research about Graphene dispersiveness, ubiquity and is adopted poisonous organic solvent, complicated process of preparation, the graphene aqueous solution concentration of stable dispersion is low, and lamella size is little, the problems such as specific conductivity reduction of Graphene after surface modification treatment.Therefore, exploring the method tool that a kind ofly can prepare high density, have the graphene aqueous solution of good dispersiveness and stability concurrently is of great significance.
Summary of the invention
Object of the present invention is exactly that a kind of preparation method of high-quality Graphene colloidal dispersion is provided in order to overcome the defect of above-mentioned prior art existence.Be characterized in take that water is as dispersion system, it is higher that synergy by ultrasonic, tensio-active agent and high temperature makes Graphene reach the stable dispersion concentration of higher quality and Graphene, is dried as again dissolving and still can reach same concentration and stability after graphene powder.
Object of the present invention can be achieved through the following technical solutions:
(1) according to the mass ratio of water and graphite oxide, be (400～1000): 1 ratio is added to the water graphite oxide, ultrasonic dispersion 2～3 hours, the homodisperse graphene oxide colloid of monolithic layer that formation concentration is 1～2.5mg/ml;
(2) by tensio-active agent, according to the mass ratio with graphene oxide colloid, be 1: the ratio of (50～100) adds in graphene oxide colloid, adopt magnetic stirrer to mix (rotating speed 100rmp～500rmp, 10～30 minutes) rear ultrasonic dispersion 1 hour (operating frequency >=40kHz), temperature is 40～50 ℃;
Wherein, tensio-active agent is at least one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate.
(3) adding with the volume ratio of step (2) gained liquid is 1: the reductive agent of (10～1000), room temperature (20～25 ℃) reaction 1-3 hour, until pH rises to approximately 11, mixed solution is placed in to 80 ℃ of reactions 12 hours, can obtain having the black redox graphene colloid of Investigation of stabilized dispersion of nano, wherein Graphene almost all (> 90%) with the state of individual layer, exist.This Graphene colloidal dispersion still can keep its dispersiveness constant after standing 1 month.
Wherein, reductive agent is at least one in hydrazine, hydrazine hydrate, dimethylhydrazine, sodium borohydride, xitix, gallic acid.
The hydrophobic grouping of surfactant molecule one end and Graphene combination; the other end hydrophilic radical and water mutual effect; like this when Graphene particle during in mutual collision because the entropy-elasticity of surfactant molecule layer and the protection of hydration layer have stoped their gathering; produce sterically hindered effect, thereby improved stability.In addition, decreasing by surfactant the surface tension of solvent, can promote peeling off of Graphene, thereby can have higher dispersion concentration.
Ultrasonic stripping method is a kind of conventional limellar stripping, pulverizing means.Ultrasonic wave is density interphase eradiation in graphite oxide suspension, make liquid-flow produce thousands of micro-bubble, the negative pressuren zone that these bubbles form in ultrasonic wave longitudinal propagation forms, growth, and at zone of positive pressure rapid closing, this closure 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 ", and each lamella is peeled off rapidly.The size of graphene oxide can be by regulating the size of ultrasonic power and the length of ultrasonic time to control.
Effect ultrasonic in the present invention is not only to peel off graphene oxide, but also play, tensio-active agent is well dispersed in to the effect in graphene oxide colloid.Because the consumption of tensio-active agent is higher than micelle-forming concentration, so in solution, surfactant molecule will inevitably form micelle, and then has reduced on the whole the efficiency of its dispersed graphite alkene.Ultrasonic wave is by the effect of micelle core water and then significantly suppressed the formation of micelle.While adding hydrazine hydrate to carry out reduction reaction, carry out the pre-reaction of middle thermophase, be conducive to the dispersion of redox graphene.Because directly carry out pyroreaction, along with temperature rising pedesis increases, cause graphene film flocculation rate to increase.In addition, temperature raises and can reduce the activity of tensio-active agent, is also unfavorable for the dispersion of Graphene.
(4) Graphene colloidal dispersion is placed in 80～100 ℃ of degree dry after, obtain graphene powder; According to the mass ratio of water and Graphene, be (400～1000): 1 ratio is added to the water dry graphene powder, ultrasonic dispersion is after 10～30 seconds, the homodisperse Graphene colloid of monolithic layer that formation concentration is 1～2.5mg/ml, it is dispersed with the graphene dispersing solution before dry;
The graphene dispersing solution that adopts the method to prepare can be used for extensive preparation, storage and the transportation of Graphene and prepares the fields such as graphene composite material.
Compared with prior art, tool of the present invention has the following advantages:
1, the graphene dispersing solution that prepared by the present invention has advantages of that concentration is high, good dispersity, can maintaining a long-term stability property, graphene sheet layer particle size distribution wherein evenly, degree of peeling off good (being all almost individual layer);
2, cost is low, and preparation technology is simple, and non-environmental-pollution is easy to realize large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the principle schematic that Graphene disperses in water;
Fig. 2 is the AFM figure of single-layer graphene in embodiment 1;
Fig. 3 is the grain size distribution plan of Graphene in embodiment 1;
Fig. 4 is the XPS figure of graphene oxide in embodiment 1 (1) and Graphene (2);
Fig. 5 is the Raman figure of Graphene in embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The graphite oxide dispersion liquid of configuration 2.0mg/ml, makes graphene oxide colloid in ultrasonic 3 hours, and the principle schematic that Graphene disperses in water as shown in Figure 1.The Sodium dodecylbenzene sulfonate that adds 1.0wt%, stirs and makes it to dissolve completely after 10 minutes, and 50 ℃ ultrasonic 1 hour; The hydrazine hydrate that adds 0.2vol%, after 25 ℃ of standing 1h, pH rises to 10.7.80 ℃ are heated 12h, can make the graphene dispersing solution of black.Get 200ml graphene dispersing solution vacuum filtration film forming, the dry rear four point probe that adopts is tested its square resistance.
As shown in Figure 2, Graphene atomic force microscope (AFM) phenogram, can find out that the degree of peeling off of redox graphene is better, and lamella diameter is generally between 200-500nm; From the lateral dimension figure of measurement surfaceness, can find out, after reduction, Graphene is not almost reunited, and thickness is generally between 0.3-0.7nm, is mainly single-layer graphene.Redox processes is little to the structure deteriorate of Graphene, and only surface forms minority hole.
Be illustrated in figure 3 the dynamic light scattering-size distribution figure of gained graphene dispersing solution, as can be seen from the figure, the size distribution of Graphene is even, be mainly 150-450nm, match with the analytical data of AFM, median size is 288.5nm, and polydispersity coefficient is 0.265, illustrates that this particle size 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 that is illustrated in figure 4 graphene oxide and the rear Graphene of reduction thereof, can find out and in graphene oxide, contain many oxygen-containing functional groups (OH, 286.5eV;-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, have also explained that the Graphene making has the reason of excellent electrical conductivity.
Be illustrated in figure 5 Raman spectrum (Raman) analysis chart of Graphene, at 1576cm
-1near the G peak due to E2g generation of vibration, at 1340cm
-1the D peak that place is caused by defect; Wherein, G peak illustrates that apparently higher than D peak (D/G=0.72) structure deteriorate of Graphene is little, has reflected restorative good to graphene sheet layer structure of reduction process in the method, and defect is few.
Embodiment 2
The graphite oxide dispersion liquid of configuration 1.0mg/ml, makes graphene oxide colloid for ultrasonic 3 hours.The Sodium dodecylbenzene sulfonate that adds 1.0wt%, stirs and makes it to dissolve completely after 10 minutes, and 40 ℃ ultrasonic 1 hour; The hydrazine hydrate that adds 0.2vol%, after 25 ℃ of standing 2h, pH rises to 11.80 ℃ are heated 12h, can make the graphene dispersing solution of black.Get 200ml graphene dispersing solution vacuum filtration film forming, the dry rear four point probe that adopts is tested its square resistance.
Embodiment 3
The graphite oxide dispersion liquid of configuration 2.0mg/ml, makes graphene oxide colloid for ultrasonic 3 hours.The sodium lauryl sulphate that adds 2.0wt%, stirs and makes it to dissolve completely after 30 minutes, and 50 ℃ ultrasonic 1 hour; The hydrazine hydrate that adds 0.1vol%, after 25 ℃ of standing 2h, pH rises to 11.80 ℃ are heated 12h, can make the graphene dispersing solution of black.Get 200ml graphene dispersing solution vacuum filtration film forming, the dry rear four point probe that adopts is tested its square resistance.
Embodiment 4
The graphite oxide dispersion liquid of configuration 2.0mg/ml, makes graphene oxide colloid for ultrasonic 3 hours.The sodium lauryl sulphate that adds 0.5wt%, stirs and makes it to dissolve completely after 30 minutes, and 50 ℃ ultrasonic 1 hour; The hydrazine hydrate that adds 0.2vol%, after 25 ℃ of standing 1h, pH rises to 11.80 ℃ are heated 12h, can make the graphene dispersing solution of black.Get 200ml graphene dispersing solution vacuum filtration film forming, the dry rear four point probe that adopts is tested its square resistance.
The graphene dispersing solution electroconductibility that embodiment 1～embodiment 4 prepares is as shown in table 1.
The electroconductibility of table 1 embodiment 1～4
Embodiment 5
The graphite oxide dispersion liquid of configuration 2.5mg/ml, makes graphene oxide colloid for ultrasonic 2 hours.The sodium lauryl sulphate that adds 1.5wt%, stirs and makes it to dissolve completely after 30 minutes, and 50 ℃ ultrasonic 1 hour; The hydrazine hydrate that adds 0.2vol%, after 25 ℃ of standing 1h, pH rises to 11.80 ℃ are heated 12h, can make the graphene dispersing solution of black.
The above-mentioned description to embodiment is can understand and use invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (9)
1. a preparation method for Graphene colloidal dispersion, is characterized in that, comprises the following steps:
(1) graphite oxide is added to the water, ultrasonic dispersion, obtains the homodisperse graphene oxide colloid of monolithic layer;
(2) tensio-active agent is joined in graphene oxide colloid, mix rear ultrasonic dispersion;
(3) in step (2) gained solution, add reductive agent, react to pH and rise to 10.5～11.5, then mixed solution is placed in to 70～90 ℃ of reactions, obtain having the Graphene colloidal dispersion of Investigation of stabilized dispersion of nano.
2. the preparation method of a kind of Graphene colloidal dispersion according to claim 1, is characterized in that, in step (1), the mass ratio of water and graphite oxide is 400: 1～1000: 1.
3. the preparation method of a kind of Graphene colloidal dispersion according to claim 1, is characterized in that, the tensio-active agent adding in step (2) and the mass ratio of graphene oxide colloid are 1: 50～1: 100.
4. according to the preparation method of a kind of Graphene colloidal dispersion described in claim 1 or 3, it is characterized in that, described tensio-active agent is Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
5. the preparation method of a kind of Graphene colloidal dispersion according to claim 1, is characterized in that, the solution temperature in step (2) after ultrasonic dispersion is 40～50 ℃.
6. the preparation method of a kind of Graphene colloidal dispersion according to claim 1, is characterized in that, the volume ratio of the reductive agent adding in step (3) and step (2) gained liquid is 1: 10～1: 1000.
7. according to the preparation method of a kind of Graphene colloidal dispersion described in claim 1 or 6, it is characterized in that, described reductive agent is at least one in hydrazine, hydrazine hydrate, dimethylhydrazine, sodium borohydride, xitix or gallic acid.
8. the preparation method of a kind of Graphene colloidal dispersion according to claim 1, it is characterized in that, in step (2) gained solution, add reductive agent, 20～25 ℃ are reacted 1～3 hour, rise to 10.5～11.5 to pH, then mixed solution is placed in to 70～90 ℃ of reactions 10～14 hours, obtains having the Graphene colloidal dispersion of Investigation of stabilized dispersion of nano.
9. the preparation method of a kind of Graphene colloidal dispersion according to claim 1, is characterized in that, by Graphene colloidal dispersion be placed in 80～100 ℃ of degree dry after, obtain graphene powder; The ratio that according to the mass ratio of water and Graphene is 400: 1～1000: 1 is added to the water dry graphene powder, and ultrasonic dispersion is after 10～30 seconds, the homodisperse Graphene colloid of monolithic layer that to form concentration be 1～2.5mg/ml.
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| CN105731444A (en) * | 2016-04-22 | 2016-07-06 | 武汉理工大学 | Preparation method of graphene easy to disperse |
| CN106590078A (en) * | 2016-12-16 | 2017-04-26 | 深圳大学 | Graphene-modified nano thermal insulating slurry and preparation method thereof |
| WO2018108016A1 (en) * | 2016-12-16 | 2018-06-21 | 深圳大学 | Graphene modified nano heat-insulating slurry and preparation method therefor |
| CN107032342A (en) * | 2017-04-28 | 2017-08-11 | 青岛德通纳米技术有限公司 | A kind of preparation method of the stable aqueous dispersion of graphene |
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| CN108467027A (en) * | 2018-03-13 | 2018-08-31 | 镇江致达新材料科技有限公司 | A kind of method of the microwave radiation technology preparation with wearability CGN/HA composite materials |
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| CN113336221A (en) * | 2021-07-22 | 2021-09-03 | 山东科技大学 | Preparation method of porous graphene dispersion liquid attached with oxygen-containing groups |
| CN113336221B (en) * | 2021-07-22 | 2022-07-29 | 山东科技大学 | Preparation method of porous graphene dispersion liquid attached with oxygen-containing group |
| CN115536010A (en) * | 2021-12-17 | 2022-12-30 | 曲靖华金雨林科技有限责任公司 | Preparation method of graphene |
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