CN102515152B - Method for preparing spheroidal graphene - Google Patents
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- CN102515152B CN102515152B CN2011104395177A CN201110439517A CN102515152B CN 102515152 B CN102515152 B CN 102515152B CN 2011104395177 A CN2011104395177 A CN 2011104395177A CN 201110439517 A CN201110439517 A CN 201110439517A CN 102515152 B CN102515152 B CN 102515152B
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Abstract
The invention discloses a method for preparing spheroidal graphene, and a technical problem to be solved is to increase the density of graphene and make the transportation and storage convenient. The method comprises the following steps: dispersing graphene in water or alcohol, carrying out ultrasonic processing or ball milling, and carrying out granulation and drying to obtain the spheroidal graphene; or dispersing graphene in water with stirring, carrying out decentralized processing, and carrying out granulation and drying to obtain the spheroidal graphene. Compared with the prior art, by high temperature granulation or low temperature refrigeration granulation processing, the obtained graphene has uniform structure, small volume, large density, good electrical conductivity, and convenience in transportation, and can be applied in catalyst carrier, drug delivery, lithium ion battery and super capacitor as a carbosphere; by ultrasonic processing, the spheroidal graphene is dispersed into graphene monomers with less than 10 layers, and the excellent properties of the graphene are kept, the obtained spheroidal graphene can be convenient for being applied in various fields, the safety performance is high, the continuous preparation production can be realized, the processing capacity can be controllable and adjustable, and the invention is suitable for large scale production.
Description
Technical field
The present invention relates to a kind of method for preparing nano material, particularly a kind of method for preparing the graphene powder material.
Technical background
2004, the Geim group of Manchester Manchester university obtained two-dimentional atomic crystal---the Graphene of individual layer first with the mechanically peel method.Carbon material family has been enriched in the discovery of Graphene, has formed the Graphene of carbon nanotube CNTs, two dimension of soccerballene from zero dimension, one dimension to the integral framework of diamond and the graphite of three-dimensional.Single-layer graphene is with sp by carbon atom
2The monoatomic layer that hydridization connects consists of, and its basic structural unit is benzene six-ring the most stable in the organic materials, and its theoretic throat is 0.335nm only, is the thinnest two-dimensional material of finding at present.Graphene is the elementary cell that consists of other graphite material, can warpage becomes the soccerballene of zero dimension, curls into the CNTs of one dimension or is stacked to three-dimensional graphite.This special construction has contained abundant and peculiar physical phenomenon, makes Graphene show the physicochemical property of many excellences, thereby causes " carbon " research boom of scientific and technological circle's new round.
It is to be noted currently worldwide mainly to concentrate on the physical properties, particularly electronic structure and electrical properties of this bidimensional material around the research boom of Graphene, but about the chemical research of Graphene shorter mention also.As Ruoff Nature Nanotechnology (the Nature Journal nanotechnology is divided periodical) upper take " Calling all chemists (accusing chemical letter from home) " for inscribing described in the commentary of delivering, the research of Graphene more polyvoltine scholar's the participation that waiting in expectation.In the Graphene chemical research, prepare on a large scale the basis that high-quality grapheme material is all application, the simple controlled chemical preparation process of development be make things convenient for the most, feasible approach, this needs the long-term and unremitting exploration of chemists and effort.The preparation method of the Graphene of prior art mainly contains: mechanically peel method, graphite oxide reduction method, epitaxial growth method, chemical Vapor deposition process CVD, electrochemical method, arc process.The prepared Graphene major part of the usual way of Introduction of Literatures exists with Graphene sheet or belt-like form, and for can self-assembly by certain processing graphene film be three-dimensional material-graphene nanospheres or globular graphite alkene flower research also seldom.Disclose a kind of preparation method of graphene nanospheres among the China Patent Publication No. CN102120573A, it adopts the method for reacting under the microwave radiation to obtain the graphite that graphene nanospheres adheres to, then by disperseing the centrifugal graphene nanospheres for preparing.The method of the standby globular graphite alkene flower of a kind of CVD legal system is disclosed among the foreign patent publication number WO2010/128650A2.All adopt the self-assembly mode to form the three-dimensional material of Graphene by chemical reaction in the aforesaid method, in actual applications, even can be good at disperseing also is to disperse in spherical mode, Graphene ball or Graphene are spent and are difficult for being separated into the monomer Graphene, so just the weakened advantageous property of graphene film has limited its range of application.And the Graphene density small volume of preparation is large, can take very large space in transportation and storage process, causes the waste of resource.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing globular graphite alkene, the technical problem that solve is to improve the density of Graphene, convenient transportation and storing, and disperse easily and use.
The present invention is by the following technical solutions: a kind of method for preparing globular graphite alkene may further comprise the steps: Graphene is scattered in water or the alcohol, and concentration is 3-10mg/mL, supersound process, power density 1000-1800W/cm
2, frequency 20-28kHz, time 10min-10h, or rotational speed of ball-mill 10-50rpm, then time 5-24h carries out granulating and drying, obtains globular graphite alkene; Or with graphene powder, dispersed with stirring is in water, and concentration is 3-10mg/mL, carries out dispersion treatment, and pressure is 10000-40000 sterling/square inch PSI, processes 2-5 time, then carries out granulating and drying, obtains globular graphite alkene.
Graphene of the present invention prepares by art methods.
The art methods of employing of the present invention is oxide-reduction method, mechanically peel method, epitaxial growth method, chemical Vapor deposition process, electrochemical method, arc process.
Of the present invention Graphene is scattered in water or the alcohol, concentration is 8mg/mL.
Supersound process of the present invention, time 8h.
Dispersion treatment of the present invention, pressure are 30000 pounds/square inch (PSI).
Dispersion treatment of the present invention 3 times.
The present invention compared with prior art; by high temperature granulation or cryogenic freezing granulation processing; make globular graphite alkene; the Graphene spherical structure homogeneous that forms, volume is little, and density is large; conduct electricity very well; convenient transportation can be used as carbosphere and is applied to support of the catalyst, medicament transport; lithium ion battery and ultracapacitor; can make this globular graphite alkene be separated into Graphene monomer below 10 layers by supersound process, fabulous reservation the advantageous property of original monomer Graphene, be convenient to be applied to various fields; safety performance is high; can continuous production production, treatment capacity is controllable, suitable for mass production.
Description of drawings
Fig. 1 is the SEM figure of the globular graphite alkene of the embodiment of the invention 1 preparation.
Fig. 2 is the TEM figure () of the globular graphite alkene of the embodiment of the invention 1 preparation.
Fig. 3 is the TEM figure (two) of the globular graphite alkene of the embodiment of the invention 1 preparation.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.The method for preparing spherical graphite alkene of the present invention may further comprise the steps:
One, preparation Graphene, the Graphene that Graphene can adopt the method for prior art to obtain comprises the Graphene that oxide-reduction method, mechanically peel method, epitaxial growth method, chemical Vapor deposition process CVD, electrochemical method, arc process prepare.
The Graphene of oxide-reduction method preparation is referring to document: 1.Hummers, W.S.; Offeman, R.E.J.Am.Chem.Soc., 1958,80 (6): 1339; 1987.Graphite must arrive the edge through chemical oxidation first and contain carboxyl, hydroxyl, and interlayer contains the graphite oxide (graphite oxide) of the oxy radicals such as epoxy and carbonyl.This process can make the graphite layers distance expand about 0.78nm to from 0.34nm.2. Yang Yong hilllock, Chen Chengmeng, Wen Yuefang, Yang Quanhong, Wang Maozhang. novel charcoal material, 2008,23 (3): 193; 3.Shin, H.J.; Kim, K.K.; Benayad, A.; Yoon, S.M.; Park, H.K.; Jung, I.S.; Jin, M.H.; Jeong, H.K.; Kim, J.M.; Choi, J.Y.; Lee, Y.H.Adv.Funct.Mater., 2009,19 (12).Above-mentioned graphite oxide is peeled off the graphene oxide (grapheme oxide) that (peeling off as ultrasonic) obtains monoatomic layer thickness by external force.Further reduction prepares Graphene.
The Graphene of mechanically peel method preparation is referring to document: 1.Novoselov K S, Geim A K, Morozov S V, Jiang D, Zhang Y, Dubonos S V, Grigorieva I V, Firsov A A.Science, 2004,306 (5696): 666～669; 2.Novoselov K S, Jiang D, Schedin F, Booth T J, Khotkevich V V, Morozov S V, Geim A K.Proc, Natl.Acad.Sci.USA, 2005,102 (30): 10451～10453.Go out graphene sheet layer by mechanical force from the sur-face peeling of highly oriented pyrolytic graphite.Mainly be the groove face that goes out wide 20 μ m-2mm, dark 5 μ m with oxygen plasma Shu Zaigao orientation pyrolytic graphite (HOPG) surface etch, and it is compressed on SiO with photo-resist
2In/Si the substrate, after the roasting, repeatedly separate unnecessary graphite flake with scotch tape, the graphite flake that remains on the Si wafer is soaked in the acetone, and ultrasonic cleaning in a large amount of water and propyl alcohol, remove mostly than obtaining thickness behind the sheet layer less than the lamella of 10nm, these thin lamellas mainly rely on Van der Waals force or capillary force and SiO
2Combine closely, under atomic force microscope, pick out the graphene sheet layer that thickness only has several monatomic bed thickness at last.
Two, preparation globular graphite alkene,
Method one: Graphene is scattered in water or the alcohol, and concentration is 3-10mg/mL, adopts the high power treatment mode, ultrasonic power density 1000-1800W/cm
2, frequency 20-28kHz, time 10min-10h, or rotational speed of ball-mill 10-50rpm, then time 5-24h carries out granulating and drying, obtains globular graphite alkene.
Method two; With graphene powder, dispersed with stirring is in water, concentration is 3-10mg/mL, then carry out dispersion treatment with the Microfluidizer M-110L high pressure microjet nano-dispersed instrument that adopts U.S. MICROFLUIDICS, pressure is 10000-40000 sterling/square inch (PSI), process 2-5 time, then carry out granulating and drying, obtain globular graphite alkene.
The equipment that granulating and drying adopts is pyrolysis granulating and drying equipment, freezing granulating and drying equipment, also can use the fluidization spray granulating equipment, spray drying device or cohesion granulating equipment, granulating and drying speed can be for per hour 50mL be to 5L, and the employing industrial equipments per hour can reach 500L.
The Graphene of method preparation of the present invention, with the observation of the S-4800 of Hitachi field emission scanning electron microscope, microscopic appearance is spherical, diameter distributes at 5-15 μ m.With JEOL-2100F high resolution field transmission electron microscopy observation, graphene sheet layer distributes between 1-10.
The globular graphite alkene of method of the present invention preparation is that the tap density of automatic tap density instrumentation amount globular graphite alkene of autotap is more than 0.2g/mL with U.S. Kang Ta company model.
Embodiment 1,
The first step, Graphene prepares graphene powder according to disclosed oxide-reduction method embodiment one among the China Patent Publication No. CN101997120A.The tap density of Graphene is 0.09g/mL.
Second step is dispersed in water graphene powder, and concentration is 3mg/mL, frequency 28kHz, power 1800W/cm
2, supersound process 10min carries out granulating and drying, and obtaining microscopic appearance is spherical graphene powder.
As shown in Figure 1, the Graphene microscopic appearance is spherical, and diameter distributes at 5-15 μ m, and the tap density of globular graphite alkene is 0.25g/mL.Shown in Fig. 2 and 3, graphene sheet layer distributes between 1-10, and thin layer graphite alkene sheet is with uniform microspheres form stable existence.
Embodiment 2,
The first step, the Graphene of epitaxial growth method preparation.Referring to document: 1, Berger, C.; Song, Z.; Li, T.; Li, X.; Ogbazghi, A.Y.; Feng, R.; Dai, Z.T.; Marchenkov, A.N.; Conrad, E.H.; First, P.N.; De Heer, W.A.J.Phys.Chem.B, 2004,108 (52): 19912; 2, Berger, C.; Song, Z.; Li, X.; Wu, X.; Brown, N.; Naud, C.; Mayou, D.; Li, T.; Hass, J.; Marchenkov, A.N.; Conrad, E.H.; First, P.N.; De Heer, W.A.Science, 2006,312 (5777): 1191.First the SiC single-crystal surface is cleaned, process is as follows: 1, use analytically pure tetrafluoro-methane, acetone, ethanol, deionized water ultrasonic multiple to clean, with the organic matter removal of surface adsorption; 2, with using deionized water rinsing behind the vitriol oil and hydrogen peroxide mixed solution (volume ratio 1: 1) the immersion 5min, remove oxide compound, metal and the organic impurity on surface; 3, with 5% hydrofluoric acid solution etching surface 3min, remove the zone of oxidation on surface; 4, with deionized water rinsing for several times at last, dry up with high pure nitrogen, put into rapidly vacuum chamber.Under ultrahigh vacuum(HHV) (1.33 * 10
-8Pa) be heated to 700-1000 ℃ and keep substrate evaporation Si, depositing time is about 1-10min.Condition of surface by reflection high energy electron diffraction (RHEED) confirmatory sample in deposition process, then sample reheats to 1250-1450 ℃ and constant temperature 10-20min and carries out anneal.The tap density of Graphene is 0.08g/mL.
Second step: graphene powder is dispersed in the alcohol, and concentration is 10mg/mL, frequency 20kHz, power 1000W/cm
2, supersound process 10h carries out granulating and drying, and obtaining microscopic appearance is spherical graphene powder.The tap density of globular graphite alkene is 0.21g/mL.
Embodiment 3,
The first step, the Graphene of chemical Vapor deposition process preparation, the Graphene of chemical Vapor deposition process preparation is referring to document: Obraztsov, A.N.Nat.Nanotechnol., 2009,4:212.Concrete operation step is as follows: 1, utilize sputtering method to plate uniform nickel dam at thickness for the monocrystalline silicon sheet surface of 0.7mm, thickness is 400nm, with this as planar substrates.2, carry out the high temperature anneal in tube furnace, planar substrates is heated to 1000 ℃ with 5 ℃/min of temperature rise rate, then pass into the decomposable presoma ethene of high temperature atmosphere, carbon atom will be in nickel dam surface growth deposition, and the time is 30min.In air, be cooled to room temperature; 3, the surface being had the substrate of Graphene put into concentration is that the ferric chloride Solution of 1mol/L carries out chemical corrosion, and soak time is 24h.Graphene will swim in solution surface.4, filter, use deionized water wash, use prior art to carry out drying.Obtain graphene powder.The tap density of Graphene is 0.09g/mL.
Second step: graphene powder is dispersed in the alcohol, and concentration is 8mg/mL, frequency 20kHz, power 1800W/cm
2, supersound process 8h carries out granulating and drying, and obtaining microscopic appearance is spherical graphene powder.The tap density of globular graphite alkene is 0.23g/mL.
Embodiment 4,
The first step, the Graphene of electrochemical production.The Graphene of electrochemical production is referring to document: Liu, N.; Luo, F.; Wu, H.X.; Liu, Y.H.; Zhang, C.; Chen, J.Adv.Funct.Mater., 2008,18 (10): 1518.Method by the electrochemical oxidation graphite rod has prepared Graphene.Two diameters high purity graphite rod (purity is 99.99%) that is 1cm inserted abreast contain ionic liquid [C
8Mim]
+[PF
6]
-The aqueous solution in, two interelectrode distances are 6cm, control voltage 15V, graphite anode rod is corroded behind the 30min, positively charged ion in the ionic liquid forms free radical in cathodic reduction, and the π-electron in graphene film is combined, and forms the graphene film of ion liquid functionalization, use at last the black precipitate in the absolute ethanol washing electrolyzer, 60 ℃ of lower dry 2h can obtain Graphene.The tap density of Graphene is 0.05g/mL.
Second step: graphene powder is dispersed in water, and concentration is 10mg/mL, then adopts high pressure microjet nano-dispersed instrument to carry out dispersion treatment, pressure is 40000 pounds of/square inch PSI, process 5 times, then carry out granulating and drying, obtaining microscopic appearance is spherical graphene powder.The tap density of globular graphite alkene is 0.26g/mL.
Embodiment 5,
The first step, Graphene prepares graphene powder according to disclosed oxide-reduction method embodiment one among the China Patent Publication No. CN101997120A.The tap density of Graphene is 0.09g/mL.
Second step: graphene powder is dispersed in water, concentration is 3mg/mL, then carry out dispersion treatment with the Microfluidizer M-110L high pressure microjet nano-dispersed instrument that adopts U.S. MICROFLUIDICS, pressure is 10000 pounds of/square inch PSI, process 2 times, then carry out granulating and drying, obtaining microcosmic type looks is spherical graphene powder.The tap density of globular graphite alkene is 0.25g/mL.
Embodiment 6,
Step 1: the Graphene that adopts the arc process preparation.The Graphene of arc process preparation is referring to document: Subrahmanyam, K.S.; Panchakarla, L.S.; Govindaraj, A.; Rao, C.N.R.J.Phys.Chem.C, 2009,113 (11): 4257.It is the graphite rod of 8cm that anode and cathode is all selected diameter, and initial gas pressure is 5 * 10
4Pa, the arc-over electric current remains on 120A, under argon gas atmosphere, when two Graphite Electrodess produce arc-over near meeting, the anode graphite electrode is evaporated consumption, continuous discharge 12h can collect the carbon species of CNTs and other form, and can obtain Graphene in the reaction chamber wall zone near negative electrode.The tap density of Graphene is 0.06g/mL.
Step 2: with the graphene powder of preparation, dispersed with stirring is in water, concentration is 3mg/mL, then adopt the Microfluidizer M-110L high pressure microjet nano-dispersed instrument of U.S. MICROFLUIDICS to carry out dispersion treatment, pressure is 30000 pounds of/square inch PSI, process 3 times, then carry out granulating and drying, obtaining microscopic appearance is spherical graphene powder.The tap density of globular graphite alkene is 0.23g/mL.
Method characteristic of the present invention is:
One, utilizes simple process flow to prepare globular graphite alkene, use more extensive.Prepared Graphene all is to be formed by physical agglomeration by the Graphene below 10 layers, have the large characteristics of the little density of volume, be convenient to transportation, both can be used as carbosphere and be applied to support of the catalyst, the fields such as medicament transport, can be separated into the monomer Graphene with excellent physicochemical property by supersound process again, make its application more extensive.
Two, realized scale operation.Whole technical process can continuous production production, and treatment capacity also can be according to the big or small controllable adjustment of equipment.
Three, realized the production of the globular graphite alkene of orderly reunion.In the high temperature granulation process, utilize the fast vaporizing of solvent effectively to control the orderly reunion of Graphene.In the cryogenic freezing granulation process, quick freezing makes the drop that contains Graphene become solid powder within very short time, compare with direct lyophilize, by being small-particle with Solution Dispersion, greatly aggravated the possibility of orderly reunion, and the solvent rate of sublimation is fast, Graphene is reunited in order be just can be separated into the monomer Graphene by simple ultrasonic by loose Graphene ball.In granulation process, also greatly shorten time of drying, shortened the production time, uses manpower and material resources sparingly.
Claims (7)
1. method for preparing globular graphite alkene, may further comprise the steps: Graphene is scattered in water or the alcohol, and concentration is 3-10mg/mL, supersound process, power density 1000-1800W/cm
2, frequency 20-28kHz, time 10min-10h, or rotational speed of ball-mill 10-50rpm, then time 5-24h carries out granulating and drying, obtains globular graphite alkene; Or with graphene powder, dispersed with stirring is in water, and concentration is 3-10mg/mL, carries out dispersion treatment, and pressure is 10000-40000 pound/square inch, processes 2-5 time, then carries out granulating and drying, obtains globular graphite alkene.
2. the method for preparing globular graphite alkene according to claim 1 is characterized in that, described Graphene prepares by art methods.
3. the method for preparing globular graphite alkene according to claim 2 is characterized in that, described art methods is oxide-reduction method, mechanically peel method, epitaxial growth method, chemical Vapor deposition process, electrochemical method, arc process.
4. the method for preparing globular graphite alkene according to claim 1 is characterized in that, described Graphene is scattered in water or the alcohol, and concentration is 8mg/mL.
5. the method for preparing globular graphite alkene according to claim 1 is characterized in that, described supersound process, time 8h.
6. the method for preparing globular graphite alkene according to claim 1 is characterized in that, described dispersion treatment, and pressure is 30000 pound/square inches.
7. the method for preparing globular graphite alkene according to claim 1 is characterized in that, described dispersion treatment 3 times.
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