CN102583335B - Preparation method of graphene uniform dispersion - Google Patents
Preparation method of graphene uniform dispersion Download PDFInfo
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- CN102583335B CN102583335B CN201210018109.9A CN201210018109A CN102583335B CN 102583335 B CN102583335 B CN 102583335B CN 201210018109 A CN201210018109 A CN 201210018109A CN 102583335 B CN102583335 B CN 102583335B
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Abstract
The invention relates to a preparation method of graphene uniform dispersion, belonging to the technical field of new nano materials. The preparation method comprises the following steps of: (1) preparing aqueous surfactant solution with the concentration of 0.2-20g/L; (2) mixing raw graphite powder with the aqueous surfactant solution according to the concentration of 1-100g/L, forming suspension and adding the suspension into a high-pressure reactor with strirring; (3) adjusting the rotating speed of the high-pressure reactor to be 50-300rpm and the temperature in the reactor to be 100-300 DEG C, carrying out heat preservation treatment on the raw graphite powder for 5-24 hours and then taking out paste; (4) carrying out 1000-2000rpm centrifugation on the paste for 15-45 minutes, and obtaining supernatant solution which is the dispersion with one-layer and multilayer graphene. The preparation method has the advantages that the aqueous surfactant solution used in the preparation process can be recycled without exhaust emission; the used materials are non-corrosive, non-toxic, non-flammable and non-explosive products; the process can not cause large damage to the protogenic conjugated structure of the graphene; and the low cost can be realized, and the graphene dispersion with excellent dispersity and stability can be prepared.
Description
Technical field
What the present invention relates to is nanometer new material technology field, specifically a kind of preparation method of graphene uniform dispersion.
Background technology
Since being found from Graphene in 2004, just enjoyed the generally favor from physics and Material Field investigator always.Graphene is a kind of by the tightly packed bi-dimensional cellular shape crystalline network carbonaceous material forming of monolayer carbon atom.Although Graphene only has a carbon atomic layer thickness, and be the thinnest a kind of in known materials, however very firmly hard.Graphene is also the outstanding material of current known conductive simultaneously.In addition, Graphene also has the performance of many excellences, as high heat conductance, huge specific surface area etc.Due to the property of Graphene, it has wide practical use at aspects such as electronics, optics, magnetics, biomedicine, sensor, energy storage.For Graphene being applied in to above-mentioned field, the problem that first will solve is can prepare high-quality Graphene and realize scale operation.
The preparation method of grapheme material mainly contains micromechanics stripping method (adhesive tape method), oxidation-reduction method, chemical Vapor deposition process (CVD) etc., wherein adhesive tape method is owing to obtaining the Graphene of purity and structural integrity the best, in the fundamental researchs such as microstructure and conduction, heat conductivility, be used widely, but this method productive rate is extremely low.Oxidation-reduction method can be produced grapheme material in batches, although this grapheme material surface oxy radical (as hydroxyl, epoxy group(ing), carboxyl and carbonyl etc.) cannot thoroughly be eliminated, affect its conductivity, but be suitable for preparing lightweight, high-intensity polymer composites.Due to oxidation stage, use the strong oxidizers such as oleum, nitric acid, potassium permanganate, reduction phase has been used poisonous, the inflammable and explosive strong reductants such as hydrazine hydrate, sodium Metal 99.5 and potassium, Resorcinol, sodium borohydride, this method will run into serious wastewater treatment, the problem such as fire-proof and explosion-proof in scale production process, and complex procedures and cost of material height also will make production cost face the challenge simultaneously.CVD method can larger area (centimeter scale) prepare individual layer or low number of plies grapheme material, at device manufacturing method mask, there is very large application potential, but graphene film size is still limited by transition metal substrate (Cu, Ni, Ru etc.) size, and film shifting process is complicated, how to keep the stability of product performance to be the key that devices in batches is manufactured.From industrial feasibility, consider, the production method of grapheme material need to possess low cost, pollution-free, technique simple, can continuous batch production etc. feature.
Summary of the invention
The object of the invention is to overcome problems of the prior art, a kind of simple to operate, with low cost, method of being easy to prepare in a large number Graphene is provided.
The present invention with graphite raw material powder under high temperature and high pressure environment in water phase surfactant mixture hot soarfing from preparing Graphene.
Step of the present invention is:
(1) according to the concentration preparation water phase surfactant mixture of 0.2～20g/L;
(2) graphite raw material powder is mixed by 1～100g/L concentration with water phase surfactant mixture, form suspension, and add the autoclave with whipping appts;
(3) regulating reactor mixing speed is 50～300rpm, regulates 100～300 ℃ of temperature in the kettle, and pounds per square inch absolute (psia) corresponding in reactor is 0.1～8.6MPa, and under high temperature and high pressure environment, to graphite raw material powder, insulation is processed after 5～24 hours and taken out slurry;
(4) slurry is carried out to high speed centrifugation separation; centrifugal rotational speed is 1000～2000rpm; centrifugal 15～45min makes unstripped graphite granule or the many Graphenes of the number of plies precipitate by centrifugal action, and upper solution is the mixed dispersion liquid of individual layer and number layer graphene.
Graphite raw material powder of the present invention is artificial synthetic graphite powder, natural graphite powder, high temperature pyrolysis Graphite Powder 99 or expansible black lead powder.
Tensio-active agent of the present invention is polyethers P-123, Tween-80, Triton X-100 X-100.Polyvinylpyrrolidone, Tween-85, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, the nonionics such as Sodium desoxycholate and anion surfactant.
The autoclave that the described preparation facilities of wood invention stirs for band.
Advantage of the present invention is: 1, the prices of raw and semifnished materials are cheap; Tensio-active agent reusable edible, can realize low cost, scale production continuous, in enormous quantities; 2, in production process without waste water, exhaust gas emission, starting material non-corrosiveness, murder by poisoning or the inflammable explosive article of use; 3, do not use strong oxidizer, graphene conductive conjugated structure is not produced to considerable damage, can be used for preparing the functional materials of high conduction performance; 4, the graphene dispersing solution of preparation is peeled off well, dispersiveness and excellent in stability.
Accompanying drawing explanation
Fig. 1 is Graphite Powder 99 XRD figure;
Fig. 2 is the XRD figure of the Graphene of preparation in example 1;
Fig. 3 is the TEM photo of the Graphene of preparation in example 1;
Fig. 4 is the TEM photo of the Graphite Powder 99 do not peeled away completely in comparative example 1.
Fig. 5 is the schema that this patent is implemented
Embodiment
Get 1g expansible black lead powder, add in the Tween-80 aqueous solution of 1000mL 0.2g/L, autoclave is warming up to 200 ℃, keep mixing speed 200rpm to carry out hydro-thermal insulation and process 6 hours, then slurries 1000rpm centrifugation 20min, obtains upper solution and is graphene dispersing solution.Under this dispersion liquid room temperature standing 2 hours without sedimentation phenomenon, show to have good stability.In Fig. 1,2,002 and 004 peak is greying characteristic peak, and 002 of Graphene reduces and much illustrates that graphite is effectively peeled off the number of plies and reduced with the relative graphite of 004 peak intensity; In the XRD figure of Graphene, 10.6 ° of positions do not occur that the little surperficial conjugated structure of 001 characteristic peak explanation degree of oxidation of graphite oxide destroys few.
Embodiment 2
Get 10g high temperature pyrolysis Graphite Powder 99, add in the sodium dodecyl benzene sulfonate aqueous solution of 1000mL 2g/L, autoclave is warming up to 160 ℃, keeping mixing speed 180rpm to carry out hydro-thermal insulation processes 10 hours, then slurries 1500rpm centrifugation 40min, obtain upper solution and be graphene dispersing solution, under this dispersion liquid room temperature standing 2 hours without sedimentation phenomenon, show to have good stability.Products obtained therefrom XRD figure is similar to embodiment 1, and 002 and 004 peak intensity of Graphene compares graphite reduction a lot, and 001 characteristic peak of graphite oxide does not appear in 10.6 ° of positions.
Embodiment 3
Get 100g expansible black lead powder, add in the polyethers P-123 aqueous solution of 1000mL 20g/L, autoclave is warming up to 180 ℃, keep mixing speed 160rpm to carry out hydrothermal treatment consists 16 hours, then slurries 2000rpm centrifugation 30min, obtain upper solution and be graphene dispersing solution, under room temperature standing 2 hours without sedimentation phenomenon, show that dispersion stability is good.Products obtained therefrom XRD figure is similar to embodiment 1, and 002 and 004 peak intensity of Graphene compares graphite reduction a lot, and 001 characteristic peak of graphite oxide does not appear in 10.6 ° of positions.
Comparative example 1
Get 10g high temperature pyrolysis Graphite Powder 99, add in 1000mL water, closed reactor is warming up to 160 ℃, keep mixing speed 180rpm to carry out hydrothermal treatment consists 10 hours, then slurries 1500rpm centrifugation 40min.Under this dispersion liquid room temperature, sedimentation in standing 2 hours is obvious.
Comparative example 2
Get 1g expansible black lead powder, add in the Tween-80 aqueous solution of 1000mL 0.2g/L, at room temperature keep mixing speed 200rpm to process 6 hours, then slurries 1000rpm centrifugation 20min.Under this dispersion liquid room temperature, sedimentation in standing 2 hours is obvious.
Comparative example 3
Get 10g high temperature pyrolysis Graphite Powder 99, add in the tetrabutyl ammonium fluoride aqueous solution of 1000mL 2g/L, autoclave is warming up to 160 ℃, keeping mixing speed 180rpm to carry out hydro-thermal insulation processes 10 hours, then slurries 1500rpm centrifugation 40min, under this dispersion liquid room temperature, sedimentation in standing 2 hours is obvious.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, relevant staff can, within not departing from the scope of this invention technological thought, carry out various change and modification completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to claim scope.
Claims (4)
1. a preparation method for graphene uniform dispersion, the steps include:
(1) preparation water phase surfactant mixture, concentration is 0.2～20g/L;
(2) graphite raw material powder is mixed by 1～100g/L concentration with water phase surfactant mixture, form suspension, and add the autoclave with whipping appts;
(3) regulating reactor rotating speed is 50～300rpm, and regulating temperature in the kettle is 100～300 ℃, and pounds per square inch absolute (psia) corresponding in reactor is 0.1～8.6MPa, and under high temperature and high pressure environment, to graphite raw material powder, insulation is processed after 5～24 hours and taken out slurry;
(4) slurry is carried out to high speed centrifugation separation; centrifugal rotational speed is 1000～2000rpm; centrifugation time 15～45min makes unstripped graphite granule or the many Graphenes of the number of plies precipitate by centrifugal action, and upper solution is the dispersion liquid of individual layer and number layer graphene.
2. the preparation method of a kind of graphene uniform dispersion according to claim 1, is characterized in that described graphite raw material powder is artificial synthetic graphite powder, natural graphite powder, high temperature pyrolysis Graphite Powder 99 or expansible black lead powder.
3. the preparation method of uniform dispersion according to claim 1, is characterized in that tensio-active agent is nonionic and anion surfactant.
4. the preparation method of uniform dispersion according to claim 1, is characterized in that tensio-active agent is polyethers P-123, Tween-80, Triton X-100 X-100, polyvinylpyrrolidone, Tween-85, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Sodium desoxycholate.
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