CN102515152A - Method for preparing spheroidal graphene - Google Patents
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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 body 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 integral framework of the Graphene of soccerballene from zero dimension, unidimensional carbon nanotube CNTs, two dimension to three-dimensional diamond and graphite.Single-layer graphene is with sp by carbon atom
2The monoatomic layer that hydridization connects constitutes, and its basic structural unit is a benzene six-ring the most stable in the organic materials, and its theoretic throat is merely 0.335nm, is the thinnest two-dimensional material of being found at present.Graphene is the elementary cell that constitutes other graphite material, can warpage becomes the soccerballene of zero dimension, curls into unidimensional CNTs 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, still about the chemical research of Graphene shorter mention also around the research boom of Graphene.Going up with " Calling all chemists (accusing chemical letter from home) " at Nature Nanotechnology (Nature Journal nanotechnology divide periodical) as Ruoff serve as to inscribe 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, the high-quality grapheme material of mass preparation is the basis of all application, and the chemical prepn process of development simple controllable is the most convenient, feasible approach, and this needs long-term and unremitting exploration of chemists and effort.The preparation method of 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 usual way prepared graphene major part of document introduction exists with Graphene sheet or belt-like form, and for can self-assembly through certain processing graphene film be three-dimensional material-graphene nano ball or SG alkene flower research also seldom.Disclose a kind of preparation method of graphene nano ball among the Chinese patent publication number CN102120573A, it adopts the method for reacting under the microwave radiation to obtain the graphite that the graphene nano ball adheres to, then through disperseing the centrifugal graphene nano ball for preparing.The method that a kind of CVD legal system is equipped with SG alkene flower is disclosed among the foreign patent publication number WO2010/128650A2.All adopt the self-assembly mode to form the three-dimensional material of Graphene through chemical reaction in the aforesaid method; In practical application; Even can be good at disperseing also is to disperse with spherical mode; Graphene ball or Graphene are spent and are difficult for being separated into the monomer Graphene, and the advantageous property of the graphene film that so just weakened has limited its range of application.And the Graphene density small volume of preparation is big, in transportation and storage process, can take very large space, causes the waste of resource.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing SG 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 adopts following technical scheme: a kind of method for preparing SG 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, time 5-24h carries out granulating and drying then, obtains SG alkene; Or with the 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, handles 2-5 time, carries out granulating and drying then, obtains SG 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 through high temperature granulation or freezing granulation processing, makes SG alkene, the Graphene spherical structure homogeneous of formation; Volume is little, and density is big, conducts electricity very well, convenient transportation; Can be used as carbosphere and be applied to support of the catalyst, medicament transport, lithium ion battery and ultracapacitor can make this SG alkene be separated into the Graphene monomer below 10 layers through supersound process; Fabulous reservation the advantageous property of original monomer Graphene, be convenient to be applied to various fields, safety performance is high; Can prepare production continuously, treatment capacity is controllable, suitable for mass production.
Description of drawings
Fig. 1 is the SEM figure of the SG alkene of the embodiment of the invention 1 preparation.
Fig. 2 is the TEM figure () of the SG alkene of the embodiment of the invention 1 preparation.
Fig. 3 is the TEM figure (two) of the SG alkene of the embodiment of the invention 1 preparation.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed explanation.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 earlier and contain carboxyl, hydroxyl, and interlayer contains the graphite oxide (graphite oxide) of 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 through 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 the Graphene lamella through 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 the SiO with photo-resist
2In/Si the substrate; After the roasting; Separate unnecessary graphite flake repeatedly 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 the lamella of thickness less than 10nm behind the sheet layer, these thin lamellas mainly rely on Van der Waals force or capillary force and SiO
2Combine closely, under AFM, pick out the Graphene lamella that thickness only has several monatomic bed thickness at last.
Two, preparation SG 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, time 5-24h carries out granulating and drying then, obtains SG alkene.
Method two; With the Graphene powder; Dispersed with stirring is in water, and concentration is 3-10mg/mL, carries out dispersion treatment with the Microfluidizer M-110L high pressure microjet nano-dispersed appearance that adopts U.S. MICROFLUIDICS then; Pressure is 10000-40000 sterling/square inch (PSI); Handle 2-5 time, carry out granulating and drying then, obtain SG alkene.
The equipment that granulating and drying adopts is pyrolysis granulating and drying equipment, freezing granulating and drying equipment; Also can use fluidisation mist projection 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, the Graphene lamella distributes between 1-10.
The SG alkene of method of the present invention preparation, use U.S. Kang Ta company model as the tap density of the automatic tap density instrumentation amount SG alkene of autotap more than 0.2g/mL.
Embodiment 1,
The first step, Graphene prepares the Graphene powder according to disclosed oxide-reduction method embodiment one among the Chinese patent publication number CN101997120A.The tap density of Graphene is 0.09g/mL.
Second step was dispersed in the Graphene powder in the water, and concentration is 3mg/mL, frequency 28kHz, power 1800W/cm
2, supersound process 10min carries out granulating and drying, and obtaining microscopic appearance is globular 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 SG alkene is 0.25g/mL.Shown in Fig. 2 and 3, the Graphene lamella distributes between 1-10, and the thin layer graphene film 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.Earlier the SiC single-crystal surface is cleaned, process is following: 1, pure tetrafluoro-methane, acetone, ethanol, the deionized water ultrasonic multiple of operational analysis cleaned, with the organic matter removal of surface adsorption; 2, with using deionized water rinsing behind the vitriol oil and ydrogen peroxide 50 mixed solution (volume ratio 1: 1) the immersion 5min, remove oxide compound, metal and the organic impurity on surface; 3,, remove the zone of oxidation on surface with 5% hydrofluoric acid solution etching surface 3min; 4, for several times at last, dry up, put into Vakuumkammer rapidly with high pure nitrogen with deionized water rinsing.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 through reflection high energy electron diffraction (RHEED) confirmatory sample in deposition process, the sample reheat carries out anneal to 1250-1450 ℃ and constant temperature 10-20min then.The tap density of Graphene is 0.08g/mL.
Second step: the 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 globular Graphene powder.The tap density of SG 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.The concrete operations step is following: 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, in tube furnace, carry out The high temperature anneal, planar substrates is heated to 1000 ℃ with 5 ℃/min of temperature rise rate, feed the decomposable presoma ethene of high temperature atmosphere then, carbon atom will be in nickel dam surface growth deposition, and the time is 30min.In air, be cooled to room temperature; 3, having the substrate of Graphene to put into concentration on the surface is that the ferric chloride Solution(38 of 1mol/L carries out chemical corrosion, and soak time is 24h.Graphene will swim in solution surface.4, filter, use deionized water wash, the utilization prior art is carried out drying.Obtain the Graphene powder.The tap density of Graphene is 0.09g/mL.
Second step: the 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 globular Graphene powder.The tap density of SG alkene is 0.23g/mL.
Embodiment 4,
The first step, the Graphene of electrochemical process preparation.The Graphene of electrochemical process preparation 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 through 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 radical in cathodic reduction, combines with πDian Zi in the graphene film, forms the graphene film of ion liquid functionalization; Use the black precipitate in the absolute ethanol washing electrolyzer at last, 60 ℃ of following dry 2h can obtain Graphene.The tap density of Graphene is 0.05g/mL.
Second step: the Graphene powder is dispersed in the water, and concentration is 10mg/mL, adopts high pressure microjet nano-dispersed appearance to carry out dispersion treatment then; Pressure is 40000 pounds of/square inch PSI; Handle 5 times, carry out granulating and drying then, obtaining microscopic appearance is globular Graphene powder.The tap density of SG alkene is 0.26g/mL.
Embodiment 5,
The first step, Graphene prepares the Graphene powder according to disclosed oxide-reduction method embodiment one among the Chinese patent publication number CN101997120A.The tap density of Graphene is 0.09g/mL.
Second step: the Graphene powder is dispersed in the water; Concentration is 3mg/mL; Carry out dispersion treatment with the Microfluidizer M-110L high pressure microjet nano-dispersed appearance that adopts U.S. MICROFLUIDICS then, pressure is 10000 pounds of/square inch PSI, handles 2 times; Carry out granulating and drying then, obtaining microcosmic type looks is globular Graphene powder.The tap density of SG 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 for use, 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, and concentration is 3mg/mL, adopts the Microfluidizer M-110L high pressure microjet nano-dispersed appearance of U.S. MICROFLUIDICS to carry out dispersion treatment then; Pressure is 30000 pounds of/square inch PSI; Handle 3 times, carry out granulating and drying then, obtaining microscopic appearance is globular Graphene powder.The tap density of SG alkene is 0.23g/mL.
Method characteristics of the present invention are:
One, utilizes simple process flow to prepare SG alkene, use more extensive.Prepared graphene all is to be formed through physical agglomeration by the Graphene below 10 layers; Have the big 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, fields such as medicament transport; Can be separated into monomer Graphene through supersound process again, make its application more extensive with excellent physicochemical property.
Two, realized scale operation.Whole process flow can prepare production continuously, and treatment capacity also can be regulated according to the controlled amount of equipment.
Three, realized the production of the SG alkene of orderly reunion.In the high temperature granulation process, utilize the quick vaporization of solvent effectively to control the orderly reunion of Graphene.In the freezing granulation process; Quick freezing makes the drop that contains Graphene in very short time, become solid powder, compares with direct lyophilize, through solution is separated into small-particle; Aggravated the possibility of orderly reunion greatly; And the solvent rate of sublimation is fast, Graphene is reunited in order be just can be separated into the monomer Graphene through simple ultrasonic by loose Graphene ball.In granulation process, also shorten greatly time of drying, shortened the PT, uses manpower and material resources sparingly.
Claims (7)
1. method for preparing SG 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, time 5-24h carries out granulating and drying then, obtains SG alkene; Or with the 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), handles 2-5 time, carries out granulating and drying then, obtains SG alkene.
2. the method for preparing SG alkene according to claim 1 is characterized in that said Graphene prepares by art methods.
3. the method for preparing SG alkene according to claim 2 is characterized in that, said 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 SG alkene according to claim 1 is characterized in that, said Graphene is scattered in water or the alcohol, and concentration is 8mg/mL.
5. the method for preparing SG alkene according to claim 1 is characterized in that, said supersound process, time 8h.
6. the method for preparing SG alkene according to claim 1 is characterized in that, said dispersion treatment, and pressure is 30000 pounds/square inch (PSI).
7. the method for preparing SG alkene according to claim 1 is characterized in that, said dispersion treatment 3 times.
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