CN106009787B - A kind of classification dispersion method prepares the method and device of graphene aqueous liquid dispersion - Google Patents
A kind of classification dispersion method prepares the method and device of graphene aqueous liquid dispersion Download PDFInfo
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Abstract
The invention discloses a kind of methods that classification dispersion method prepares graphene aqueous liquid dispersion, step of the present invention includes grapheme material pre-invasion, it is primarily broken, vacuum ultrasonic twice dispersing, finally in the stabilisation electric field arrangement that this law is related to, graphene aqueous liquid dispersion is obtained by electric field stabilization processes.Graphene dispersion fluid solid content prepared by the method is 0.1 wt%, 10 wt%；With without adding dispersing aid, process can serialization, the slurry of preparation can preserve six months or more the advantages without obviously settling in normal temperature and pressure environment.The present invention has without introducing external non-graphite olefinic impurity, and dispersion liquid use scope is wide；High, simple for process, green, stability the is good advantage of degree of scatter.
Description
Technical field
The invention belongs to grapheme material dispersion technology fields, and in particular to it is aqueous that a kind of classification dispersion method prepares graphene
The method and device of dispersion liquid.
Background technology
Graphene is that one kind passing through sp by carbon atom2Hydridization is mutually bonded and the green wood of two-dimentional monolithic layer structure that constitutes
Material, basic structural unit are stable benzene hexatomic ring, and theoretical monolayer thickness is only 0.35nm, be found at present it is most thin
Two-dimensional material.Graphene is the basic structural unit for constituting other graphite materials, can form zero dimension fullerene, curl shape with warpage
Three-dimensional graphite or diamond are formed at one-dimensional carbon nanotube, stacking.This special structure assigns its unique and magical physics
Chemical characteristic, as grapheme material has up to >=2630m2The superelevation theoretical specific surface area of/g；Its electron mobility under room temperature
More than 15000cm2/ Vs is 2 times of the indium antimonide materials with highest mobility being currently known；The thermal conductivity of graphene
Up to 5000Wm-1·K-1, it is 3 times of diamond；Resistivity only has about 10-6Ω·cm；In addition also there is room-temperature quantum Hall
The special natures such as effect and room temperature ferromagnetic effect, therefore be expected to can be used to develop thinner, conductive speed a new generation's electricity faster
Subcomponent or transistor are considered as the critical material for leading Industrial Revolution by industry, in mobile device, space flight and aviation, new energy electricity
The fields such as pond, which are gathered around, to have broad application prospects, currently, domestic graphene prepare with scale technology reaches its maturity, but industrialization process
It develops slowly.It is since the volume density of graphene powder is extremely low from the point of view of macroscopic appearance, work in-process easily floats, secondary workability
It can be poor；With basis material poor compatibility, it is unfavorable for its dispersion, seriously hinders the performance of its nano-meter characteristic.Come from application angle
It sees, stable homogeneous, the graphene dispersing solution of wide concentration range is that it is answered extensively in fields such as catalysis, energy storage, coating, composite materials
Precondition and key technology.For this purpose, correlative study and engineers and technicians successively develop graphene slurry or dispersion
Liquid, however, from the point of view of current effect, dispersibility of the graphene in liquid (aqueous solvent or oil-based solvent) is very undesirable, easily
The defects of reunion, fast sedimentation, low concentration, highlights.It is due to the distinctive nanometer of graphene from the point of view of graphene immanent structure characteristic
The characteristics such as effect, high-specific surface area, height absorption determine that it easily occurs to stack to reunite and have become and restrict its fast development
Bottleneck, therefore be dispersed into and improve product (material) quality and performance, improve the indispensable technological means of process efficiency.
The bottleneck that in order to break through technology, used graphene surface be modified dispersion, graphene liquid phase stripping etc. technologies
To obtain graphene dispersing solution.The dispersing method of graphene includes mainly physical dispersion and chemical dispersion two major classes.Physical is such as
Ball milling, sand milling, grinding, mechanical agitation, sonic oscillation etc.；Chemical method includes surfactant-modified, solvent PH value adjusts, graphite
The methods of alkene graft modification, graphene doping.Dai Hongjie team of Stanford universities of the U.S. is most early in DMF, with tetrabutyl bromine
Change quaternary ammonium salt as intercalator, graphene dispersing solution (Li X, Zhang G, Bai X, et are obtained using liquid phase stripping means
al.Highly conducting graphenesheets and Langmuir-Blodgett films.Nature
Nanotechnology, 2008,3 (9)：538-542).Lotya M etc. by being added the surface of dodecyl sodium sulfate in water
Activating agent, by liquid phase remove method obtain a concentration of 0.1mg/mL graphene dispersing solution (LotyaM,
HernandezY,King P J,etal.Liquid phase production of grapheme by exfoliation
of graphite in surfactant/water solutions.JournalofAmericanChemistrySociety,
2009,131(10):3611–3620.).M.C.Hersam etc. has obtained the graphene dispersing solution (Liang of 1mg/mL in ethanol
Y,Hersam M C.Highly concentrated graphene solutions via polymerenhanced
solvent exfoliation and iterative solvent exchange.Journal ofAmerican
Chemistry Society,2010,132(50):17661-17663.) 1% ethoxy fibre, to be added in ultrasonic disperse
Dimension element, to adjust the matching of graphene and ethyl alcohol surface energy, but its hydroxyethyl cellulose being added is too many, is only used for preparing stone
Black alkene composite material can not be applied in other fields.The above method is required to use dispersing aid, and dispersing aid is deposited
The performance of graphene is being reduced to a certain extent；In addition, the concentration for the graphene slurry that these methods obtain is relatively low, make
Its application is restricted.In order to obtain the dispersion liquid of no dispersing aid, Tour and Pasquali etc. are with graphite directly in acid body
It is the graphene dispersing solution prepared in chlorosulfonic acid at concentrations up to 2mg/mL, but the highly acid of chlorosulfonic acid seriously affects it and storing up
Application (Tour J M, the PasqualiM.Spontaneous high-concentration in the fields such as energy, catalysis
dispersions and liquidcrystals of graphene.Nature Nanotechnology,2010,5(6):
406–411.).In addition to the report of scientific paper, China also discloses more graphene dispersion liquid and preparation method thereof.Chinese patent
CN103935995 is improved the water solubility of graphene, is prepared for stable graphene using the hydrophilic carboxyl, the hydroxyl that introduce substitution
Colloidal dispersion, it is -41~-33mV, the average grain diameter of graphene which, which has Tyndall effect, zeta current potentials,
For 250~400nm.Chinese patent CN104071778A discloses a kind of side of graphene dispersing solution and grapheme material powder
Method, this method be added in watersoluble plumbago alkene slurry specific solvent form azeotropic system will be therein finally by displacement
Moisture is removed by heating evaporation, to obtain graphene organic system slurry, and can be by the way that removal organic solvent is further dried
Obtain graphene powder material.Chinese patent CN104538086A discloses a kind of water-based conducting polymer-graphene dispersing solution
And preparation method thereof, it is interacted using the π-π for generating strong between water-based conducting polymer and graphene, passes through liquid phase ultrasound
Graphite is removed, obtains high concentration, water-based conducting polymer-graphene dispersing solution that the concentration range of high stable is 1-10mg/ml.
The above method has been all made of purely mechanic dispersing technology that is single or being simply classified, which, which has, needs to add dispersion
The shortcomings of auxiliary agent, dispersion stability are poor, dispersion liquid concentration is relatively low.External non-graphite olefinic impurity is introduced in dispersion, no
The performance of graphene nano characteristic is only hindered, and causes to cause unfavorable side reaction or side effect in the application, to graphite
The application characteristic of alkene powder has an adverse effect, and constrains the industrialized development of graphene.
Invention content
The purpose of the present invention is to provide a kind of high-quality, green, without aqueous point good of graphene of dispersing aid, stability
The preparation method and device of dispersion liquid.
General principles are by being classified dispersion technology to obtain stable graphene aqueous liquid dispersion.Its principle
For graphene material, water are placed in stirring container first, stirring at low speed makes graphene surface fully be soaked by water.Then it shifts
Into primarily broken equipment, material high speed rotation power or under the action of extruding force in the equipment confined space can get higher
Kinetic energy, can guarantee there is higher collision probability to make between graphene sheet layer, between graphene and wall；It provides simultaneously
There is extremely strong shearing force, to make the graphene sheet layer of multiple-level stack slide and be divided into the graphene sheet layer knot of fewer layers
Structure.Then it is then transferred in vacuum ultrasonic device and carries out secondary breakup, can make in the form of physical absorption during vacuumizing
It is adsorbed in the gas abjection of graphene, while utilizing cavitation and acoustic streaming effect under ultrasound condition, keeps graphene further newborn
Change shearing, stack effect further weakens.DC electric field device is finally used, the spy of the micro- charge of graphene dispersion particle band is utilized
Property, apply certain electric field in shorter time period, the charge of graphene film layer surface further enhances shape under electric field action
At stable electrification lamella, between lamella due to electrostatic repulsion forces mutual principle to form stable dispersion liquid.
The present invention provides a kind of methods that classification dispersion method prepares graphene aqueous liquid dispersion, in order to realize above-mentioned mesh
, the invention is realized by the following technical scheme：
(1) pre-invasion：By graphene powder：Water quality ratio is 1：9-999；Stirring container is added in graphene powder and water
In, it is stirred using blender, and the range of speeds for adjusting blender is 10-500rpm, mixing time 10-30min makes
Water fully soaks on the surface of graphene, obtains graphene and pre-wets liquid；
(2) primarily broken：Graphene obtained by step (1) is pre-wetted liquid to be transferred in primarily broken equipment, controls rotating speed
Ranging from 1000-10000rpm carries out dispersion 0.5-3h, obtains initial dispersion；
(3) vacuum ultrasonic：Initial dispersion obtained by step (2) is transferred in vacuum ultrasonic device, vacuum degree model is set
It encloses for -0.01~-0.1MPa, ultrasonic power ranging from 500-2000W, working time ranging from 1-30min, acquisition secondary breakup
Liquid；
(4) it stabilizes：Secondary breakup liquid obtained by step (3) is placed in and is stabilized in electric field arrangement, applying voltage range is
50-1000V carries out stabilization processes 10-300s, to obtain graphene aqueous liquid dispersion.
Preferably, above-mentioned graphene is the graphene that surface carries certain charge；It is prepared by the graphene dispersing solution of the present invention
In method, graphene described in step (1) is single-layer graphene, bilayer graphene, few layer graphene (3-4 layers), Multi-layer graphite
Alkene (5-10 layers), graphene oxide, redox graphene, graphene microchip, graphene quantum dot, graphene nanobelt (piece)
And it is formed by functionalization graphene after chemically or physically method introduces atom or functional group in graphene.
Preferably, above-mentioned graphene powder：Water quality ratio is 1:19-99；
Preferably, the primarily broken equipment optimum speed of above-mentioned steps (2) is 6000-10000rpm, mixing time 1-
1.5h；
Preferably, the vacuum degree of above-mentioned steps (3) vacuum ultrasonic device is -0.07~-0.1MPa, and ultrasonic power is
1500-2000W, ultrasonic time 15min；
Preferably, above-mentioned steps (4) DC electric field device, application voltage range are 200-600V, stabilization processes time
For 10-60s,；
The present invention graphene dispersion liquid and preparation method thereof in, the solvent described in step (1) is water, including but not limited to
The water of Types Below, atmospheric water, underground water, surface water, the crystallization water, Biological water, magnetized water, nanometer water, frequency spectrum water, deionized water,
Distilled water, reverse osmosis water, ultra-pure water etc..
In the graphene dispersion liquid and preparation method thereof of the present invention, the stirring container described in step (1) can be that drum etc. can
To hold the utensil of liquid.
In the graphene dispersion liquid and preparation method thereof of the present invention, the primarily broken equipment described in step (2) includes that stirring is strong
Power dispersion machine (such as NX-500 types of Nanhai District Foshan City Nuo Xing mechanical equipments Co., Ltd；The bright hat chemical industry machine in Laizhou City Shahe town
200 types etc. of tool factory production), disc type dispersion machine (such as FS100 types of Qidong Hui Long mixing apparatus factory；The long-range science and technology in Beijing Chinese and Western
The CN61M/FX20-1000 types of Co., Ltd, Germany's NK2000 graphene dispersion machines etc.), (such as Weifang City is prosperous for disc-type heat dispersing machine
The ZPS22-315 of Yu Feihao Environmental Protection Technology Co., Ltd；The CXP types etc. of Shandong magnificent Genie et Environnement of innovation), it is high
Press homogenizer (such as Germany APV high pressure homogenizer APV-2000 types, Langfang City Sheng Tong Machinery Co., Ltd.s JJ10/60, JJ15/40
Ultra-large type high pressure homogenizer, AH2010 type high pressure homogenizers of ATS Engineering Inc etc.), homogenizer (such as Shanghai
The IKA RW20 homogenizers of Na Nuo Industrial Co., Ltd.s production, the Z+ series blenders etc. of the new east HEIDON of Japan), emulsify
(the WIGGENS D-500 laboratory high shear homogenous disperse mulsers of such as Beijing Sang Yi laboratory apparatus research institute like mountain instrument to machine
The German Wiggens D500 high-shearing dispersion emulsifying machines of 's supply, upper lake phase experimental facilities Co., Ltd
Britain's Silverson L5T digital display mulsers of supply etc.), high speed dispersor (such as high speed of Shanghai Han Nuo Instrument Ltd.
SFS-S400 type dispersion machines, the German IKA T18 high speed dispersors etc. of Shanghai Chu Bai laboratory equipments Co., Ltd agency), it is high
Fast dispersion emulsifying machine (the WIGGENS D--500 types laboratory high shears homogenous disperse breast of such as Beijing Sang Yi laboratory apparatus research institute
Change machine, FJ-200 high speed dispersion mulsers of Shanghai Ben Ang scientific instrument Co., Ltd etc.), (such as Shanghai is according to agreeing for the equal pulp grinder of dispersion
The equal pulp grinder of I10-8G types of Mechanical Equipment Company, JJ-2 type refiners of Changzhou Guohua Electric Appliance Co., Ltd. etc.)
In the graphene dispersion liquid and preparation method thereof of the present invention, the vacuum ultrasonic device described in step (3) includes that vacuum is de-
Gas supersonic wave cleaning machine (such as vacuum outgas supersonic wave cleaning machine of Wuxi Tai Ming ultrasonic waves Environmental Protection Technology Co., Ltd) has
Ultrasonic cell disruptor (the VOSHIN98-III type supersonic cell powder of such as Wuxi Wo Xin Instrument Ltd. of vacuum function
Space Proview experimental facilities Co., Ltd Scientz-IID type ultrasonic cell disruptors, Tianjin Ao Tesaiensi are won in broken machine, Beijing
UH-500B liquid crystal Ultrasonic cell smashs of Instrument Ltd. etc.), energy-collecting ultrasonic equipment with vacuum function is (such as south
The XO-1000F types of capital fair current Instrument Ltd. SL type energy-collecting ultrasonic decentralized systems, Nanjing Xian Ou instrument manufacturings Co., Ltd are poly-
Can formula ultrasonoscope etc.) and equipment (vacuum tank etc.) and ultrasonic device with vacuumizing function combined system (such as Suzhou
The vacuum outgas ultrasonic cleaning device etc. of ten thousand ultrasonic equipment Co., Ltd of Aunar).
Purpose to realize the present invention, inventor devise the stabilisation electric field arrangement in step (4), it includes insulation annular
Wall, annular electrode (connecing direct current cathode), central electrode (connects direct-flow positive pole), insulating base, and insulation annular wall connects insulating base,
Vertical connection central electrode at the center of insulating base is equipped with central electrode external connection in insulating base, is filled in the annular wall that insulate
There is annular electrode.
The features of the present invention and advantageous effect are：
(1) it uses and pre-wets, dispersion, vacuum ultrasonic, the three-level dispersion preparation process of last electric field stabilization processes, needle
Process modification is carried out to graphene self-characteristic, develops the dispersing technology suitable for graphene.
(2) present invention cleverly changes the resonance energy of graphene cluster molecule by extra electric field, promotes graphite
Alkene nanostructure is unfolded, and the dispersion of grapheme material difficulty, the easily problems such as floating are efficiently solved.
(3) dispersion liquid concentration in catalysis, is stored up up to 0.1wt%-10wt%, and without adding any dispersing aid
Side reaction is not will produce in the application processes in fields such as energy or negative effect system stability is excellent.
Description of the drawings：
Fig. 1 is the stereoscan photograph of graphene raw material；
(a) figure is the photo that embodiment 1 initially prepares dispersion liquid in Fig. 2, and (b) figure is that embodiment 1 passes through six
Photo after moon sedimentation is settled from known to photo without apparent.
Fig. 3 is the light micrograph of dispersion liquid in embodiment 1；
Fig. 4 is the stereoscan photograph of dispersion liquid in embodiment 1；
It is real that (a) figure, which is light micrograph, (b) figure after 2 graphene dispersing solution of embodiment is stood 6 months, in Fig. 5
Apply the light micrograph after 3 graphene dispersing solution of example is stood 6 months, (c) figure is that 4 graphene dispersing solution of embodiment is stood
Light micrograph, (d) figure after 6 months are the light micrograph after 5 graphene dispersing solution of embodiment is stood 6 months.
It is 3 stone of embodiment that (a) figure, which is photo, (b) figure after 2 graphene dispersing solution of embodiment is stood 6 months, in Fig. 6
Photo, (c) figure of black alkene dispersion liquid standing after 6 months are photo, (d) after 4 graphene dispersing solution of embodiment is stood 6 months
Figure is the photo after 5 graphene dispersing solution of embodiment is stood 6 months.
Fig. 7 is stabilisation electric field arrangement front view of the present invention and its half-sectional view.
Fig. 8 is stabilisation electric field arrangement vertical view of the present invention and its A-A half-sectional views.
Fig. 9 is stabilisation electric field arrangement side view of the present invention and its half-sectional view.
Figure 10 is stabilisation electric field arrangement 3 D stereo sectional view of the present invention.
Cathode, annular anode and the stabilisation electric field arrangement with insulation protection, are powered centered on stabilisation electric field arrangement
Afterwards, stable DC field can be formed between center cathode and annular anode.
As shown, 1 is central electrode external terminal, 2 be insulation annular wall, and 3 be annular electrode, connects direct-flow positive pole, and 4 are
Central electrode connects direct current cathode, and 5 be insulating base.
Specific implementation mode
For the technology contents and effect that the present invention will be described in detail, below with reference to specific implementation example (but be not limited to
Lower embodiment) and attached drawing is coordinated to be explained.
Embodiment 1
A kind of stabilisation electric field arrangement, it includes insulation annular wall 2, annular electrode 3 (connecing direct current cathode), central electrode 4
(connecing direct-flow positive pole), insulating base 5, insulation annular wall 2 connect insulating base 5, and at the center of insulating base 5 vertical connection center
Electrode 4 is equipped with 4 external connection 1 of central electrode in insulating base 5, and annular electrode 3 is housed in the annular wall 2 that insulate.
(1) according to graphene powder：Water quality ratio is 1：9 ratio weighs graphene powder 5g, deionized water respectively
45g is added in beaker, is at the uniform velocity stirred using the general DLH overhead type stirrers of Italian Weir, and adjust agitator speed
For 100rpm, 30min is stirred, water is made fully to soak on the surface of graphene, acquisition pre-wets liquid；
(2) graphene obtained by step (1) is pre-wetted into liquid and is transferred to progress primary in the T18 high speed dispersors of German IKA
Dispersion, it is 1000rpm, working time 0.5h to adjust dispersion machine dispersion disk rotating speed, obtains initial dispersion；
(3) initial dispersion obtained by step (2) is transferred in vacuum ultrasonic cup, and using the inscription ultrasonic wave environmental protection of Wuxi platform
The vacuum outgas supersonic wave cleaning machine of Science and Technology Ltd., setting vacuum degree is -0.1MPa, ultrasonic power 1500W, when work
Between be 15min；Obtain secondary breakup liquid；
(4) secondary breakup liquid obtained by step (3) is placed in stabilisation electric field arrangement central electrode 4 shown in fig. 6 and insulation
In processing chamber between annular wall 2, direct current cathode is connect to annular electrode 3, is connect to central electrode 4 by 4 external connection 1 of central electrode
Direct-flow positive pole, application voltage are 50V, carry out stabilization processes 50s, obtain stable graphene aqueous liquid dispersion.
1 embodiment of table, 1 fundamental technology performance index determining parameter list
| Serial number | Project | Index |
| 1 | Appearance | Black even liquid, without apparent particle or impurity |
| 2 | Viscosity | 2600cps |
| 3 | Concentration | 10wt% |
| 4 | Sedimentation time | 6 months without apparent sedimentation |
| 5 | Liquid phase conductivity | 66000μS/cm |
Embodiment 2
(1) according to graphene powder：Solvent quality ratio is 1：80 ratio weighs graphene powder 5g, deionization respectively
Water 400g is added in beaker, is at the uniform velocity stirred using the general DLH overhead type stirrers of Italian Weir, and adjust blender
Rotating speed is 10rpm, stirs 25min, water is made fully to soak on the surface of graphene, and acquisition pre-wets liquid；
(2) graphene obtained by step (1) is pre-wetted into liquid and is transferred to progress primary in the T18 high speed dispersors of German IKA
Dispersion, it is 1000rpm, working time 60min to adjust dispersion machine dispersion disk rotating speed, obtains initial dispersion；
(3) initial dispersion obtained by step (2) is transferred in vacuum ultrasonic cup, and using the inscription ultrasonic wave environmental protection of Wuxi platform
The vacuum outgas supersonic wave cleaning machine of Science and Technology Ltd., setting vacuum degree is -0.1MPa, ultrasonic power 2000W, when work
Between be 15min；Obtain secondary breakup liquid；
(4) secondary breakup liquid obtained by step (3) is placed in stabilisation electric field arrangement shown in fig. 6, applying voltage is
50V carries out stabilization processes 50s, obtains stable graphene aqueous liquid dispersion.Remaining is the same as embodiment 1.
2 embodiment of table, 2 fundamental technology performance index determining parameter list
| Serial number | Project | Index |
| 1 | Appearance | Black even liquid, without apparent particle or impurity |
| 2 | Viscosity | 1800cps |
| 3 | Concentration | 1.24wt% |
| 4 | Sedimentation time | 6 months without apparent sedimentation |
| 5 | Liquid phase conductivity | 29000μS/cm |
Embodiment 3
(1) according to graphene powder：Solvent quality ratio is 1：99 ratio weighs graphene powder 10g, deionization respectively
Water 990g is added in beaker, is stirred using the WIGGENS WB3000-D high speed large torques of Beijing Sang Yi laboratory apparatus research institute
Device is at the uniform velocity stirred, and it is 500rpm to adjust agitator speed, stirs 10min, so that water is fully soaked on the surface of graphene, obtain
Liquid must be pre-wetted；
(2) graphene obtained by step (1) is pre-wetted into liquid and is transferred to German Wiggens D500 high-shearing dispersion emulsifying machines
Middle progress is primarily broken, and it is 10000rpm, working time 30min to adjust dispersion emulsifying machine dispersion disk rotating speed, obtains first fraction
Dispersion liquid；
(3) that initial dispersion obtained by step (2) is transferred to Shanghai is closeer than the constant temperature that bright instrument manufacturing Co., Ltd produces
It closes in ultrasound reactor kettle, and it is -0.06MPa, ultrasonic power 1000W, working time 15min that vacuum degree, which is arranged,；It obtains
Obtain secondary breakup liquid；
(4) secondary breakup liquid obtained by step (3) is placed in stabilisation electric field arrangement shown in fig. 6, applying voltage is
800V carries out stabilization processes 100s, obtains stable graphene aqueous liquid dispersion.Remaining is the same as embodiment 1.
3 embodiment of table, 3 fundamental technology performance index determining parameter list
Embodiment 4
(1) according to graphene powder：Solvent quality ratio is 1：800 ratio weighs graphene powder 1g, deionization respectively
Water 800g is added in beaker, is stirred using the WIGGENS WB3000-D high speed large torques of Beijing Sang Yi laboratory apparatus research institute
Device is at the uniform velocity stirred, and it is 300rpm to adjust agitator speed, stirs 20min, so that water is fully soaked on the surface of graphene, obtain
Liquid must be pre-wetted；
(2) it graphene obtained by step (1) is pre-wetted into liquid is transferred to the PRIMA imports that innovation is thought to act on behalf of at Co., Ltd and cut
It cuts and carries out primarily broken in emulsion dispersion machine PD500-TP, it is 10000rpm to adjust dispersion machine dispersion disk rotating speed, and the working time is
50min obtains initial dispersion；
(3) initial dispersion obtained by step (2) is transferred in vacuum ultrasonic tank, and uses the limited public affairs of Nanjing fair current instrument
The SL types of department-energy-collecting ultrasonic wave emulsification dispersion system, setting vacuum degree are -0.1MPa, ultrasonic power 500W, and the working time is
10min；Vacuum ultrasonic system is opened, can get secondary breakup liquid after 10min；
(4) secondary breakup liquid obtained by step (3) is placed in stabilisation electric field arrangement shown in fig. 6, applying voltage is
1000V carries out stabilization processes 300s, obtains stable graphene aqueous liquid dispersion.Remaining is the same as embodiment 1.
4 embodiment of table, 4 fundamental technology performance index determining parameter list
| Serial number | Project | Index |
| 1 | Appearance | Black even liquid, without apparent particle or impurity |
| 2 | Viscosity | 197.64cps |
| 3 | Concentration | 0.25wt% |
| 4 | Sedimentation time | 6 months without apparent sedimentation |
| 5 | Liquid phase conductivity | 1405μS/cm |
Embodiment 5
(1) according to graphene powder：Weight of solvent ratio is 1：999 ratio weighs graphene powder 1g, deionization respectively
Water 999g is added in beaker, and the Bidirectional magnetic agitator that prosperous science and trade Co., Ltd is come using Beijing is at the uniform velocity stirred, and is adjusted
Agitator speed is 100rpm, stirs 20min, water is made fully to soak on the surface of graphene, and acquisition pre-wets liquid；
(2) graphene obtained by step (1) is pre-wetted into the AH2010 type height that liquid is transferred to upper ATS Engineering Inc
Carry out primarily broken in pressure homogenizer, it is 6000rpm, working time 35min to adjust dispersion machine dispersion disk rotating speed, is obtained primary
Dispersion liquid；
(3) initial dispersion obtained by step (2) is transferred to the JULABO- that excellent Lay wins the production of technology (Beijing) Co., Ltd
In ACE sonochemistry reaction kettles, and the VACUUBRAND chemical vacuum systems that Pulan moral (Shanghai) trade Co., Ltd is produced
MZ 2C NT+AK+EK are connected to two interfaces of reaction kettle by vacuum tube, and to be built into vacuum ultrasonic device, vacuum is arranged
Degree is -0.08MPa, ultrasonic power 1600W, working time 25min；Obtain secondary breakup liquid；
(4) secondary breakup liquid obtained by step (3) is placed in stabilisation electric field arrangement shown in fig. 6, applying voltage is
680V carries out stabilization processes 180s, obtains stable graphene aqueous liquid dispersion.Remaining is the same as embodiment 1.
5 embodiment of table, 5 fundamental technology performance index determining parameter list
| Serial number | Project | Index |
| 1 | Appearance | Black even liquid, without apparent particle or impurity |
| 2 | Viscosity | 79.14cps |
| 3 | Concentration | 0.1wt% |
| 4 | Sedimentation time | 4 months without apparent sedimentation |
| 5 | Liquid phase conductivity | 1230μS/cm |
Claims (10)
1. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion, it is characterised in that include the following steps：
（1）Pre-invasion：By graphene powder：Water quality ratio is 1：19-99；Graphene powder and water are added in stirring container,
It is stirred using blender, and the range of speeds for adjusting blender is 10-500rpm, mixing time 10-30min makes water
Fully wetting on the surface of graphene obtains graphene and pre-wets liquid；
（2）It is primarily broken：By step（1）Gained graphene pre-wets liquid and is transferred in primarily broken equipment, controls the range of speeds
For 1000-10000rpm, dispersion 0.5-3h is carried out, obtains initial dispersion；
（3）Vacuum ultrasonic：By step（2）Gained initial dispersion is transferred in vacuum ultrasonic device, setting vacuum ranges be-
0.01~-0.1MPa, ultrasonic power ranging from 500-2000W, working time ranging from 1-30min obtain secondary breakup liquid；
（4）It stabilizes：By step（3）Gained secondary breakup liquid, which is placed in, to be stabilized in electric field arrangement, and application voltage range is 200-
600V carries out stabilization processes 10-300s, to obtain graphene aqueous liquid dispersion；
Step（4）Stabilisation electric field arrangement, it include insulation annular wall（2）, annular electrode（3）, central electrode（4）, insulation
Bottom plate（5）, insulate annular wall（2）Connect insulating base（5）, insulating base（5）Center at vertical connection central electrode（4）,
Insulating base（5）In be equipped with central electrode（4）External connection（1）, insulate annular wall（2）In be equipped with annular electrode（3）.
2. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion as described in claim 1, it is characterised in that step
Suddenly（1）Described in graphene be single-layer graphene, bilayer graphene, 3-4 layer graphenes, one kind in 5-10 layer graphenes.
3. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion as described in claim 1, it is characterised in that institute
The water stated is atmospheric water, underground water, surface water, the crystallization water, Biological water, magnetized water, nanometer water, frequency spectrum water, deionized water, distillation
Water, reverse osmosis water or ultra-pure water.
4. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion as described in claim 1, it is characterised in that step
Suddenly（2）Primarily broken equipment rotating speed is 6000-10000rpm, mixing time 1-1.5h.
5. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion as described in claim 1, it is characterised in that step
Suddenly（2）Described in primarily broken equipment include stirring high force dispersion machine, it is disc type dispersion machine, disc-type heat dispersing machine, high-pressure homogeneous
Machine, homogenizer, mulser, high speed dispersor, high speed dispersion mulser, the equal pulp grinder of dispersion.
6. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion as claimed in claim 5, it is characterised in that institute
The stirring high force dispersion machine stated is the NX-500 types of Nanhai District Foshan City Nuo Xing mechanical equipments Co., Ltd；Laizhou City Shahe town is bright
It is preced with 200 types of chemical's production；Disc type dispersion machine is the FS100 types of Qidong Hui Long mixing apparatus factory；Beijing Chinese and Western is long-range
CN61M/FX20-1000 types, the Germany's NK2000 graphene dispersion machines of Science and Technology Ltd.；Disc-type heat dispersing machine is that Weifang City is prosperous
The ZPS22-315 of Yu Feihao Environmental Protection Technology Co., Ltd, the CXP types of the magnificent Genie et Environnement of Shandong innovation；High pressure is equal
Matter machine is Germany APV high pressure homogenizer APV-2000 types, Langfang City Sheng Tong Machinery Co., Ltd.s JJ10/60, JJ15/40 super large
Type high pressure homogenizer, the AH2010 type high pressure homogenizers of ATS Engineering Inc；Homogenizer be Shanghai receive nobelium reality
The IKA RW20 homogenizers of industry Co., Ltd production, the Z+ series blenders of the new east HEIDON of Japan；Mulser is Beijing
The WIGGENS D-500 laboratory high shear homogenous disperse mulsers of Sang Yi laboratory apparatus research institute like mountain instrument（Shanghai）Have
The German Wiggens D500 high-shearing dispersion emulsifying machines of limit company supply, the English of upper lake phase experimental facilities Co., Ltd supply
State's Silverson L5T digital display mulsers；High speed dispersor is the high speed SFS-S400 types point of Shanghai Han Nuo Instrument Ltd.
Dissipate machine, the German IKA T18 high speed dispersors of Shanghai Chu Bai laboratory equipments Co., Ltd agency；High speed dispersion mulser is north
The WIGGENS D-500 types laboratory high shear homogenous disperse mulsers of Jing Sangyi laboratory apparatus research institute, Shanghai sheet hold high science
The FJ-200 high speed dispersion mulsers of Instrument Ltd.；Disperse the I10-8G types that equal pulp grinder is Shanghai Yi Ken Mechanical Equipment Company
Equal pulp grinder, the JJ-2 type refiners of Changzhou Guohua Electric Appliance Co., Ltd..
7. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion as described in claim 1, it is characterised in that step
Suddenly（3）The vacuum degree of vacuum ultrasonic device is -0.07~-0.1MPa, ultrasonic power 1500-2000W, and ultrasonic time is
15min。
8. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion as described in claim 1, it is characterised in that step
Suddenly（3）Described in vacuum ultrasonic device include vacuum outgas supersonic wave cleaning machine, the supersonic cell powder with vacuum function
The assembly of broken machine, the energy-collecting ultrasonic equipment with vacuum function or the vacuum tank with vacuumizing function and ultrasonic device.
9. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion as claimed in claim 8, it is characterised in that institute
The vacuum outgas supersonic wave cleaning machine stated is the vacuum outgas ultrasonic cleaning of Wuxi Tai Ming ultrasonic waves Environmental Protection Technology Co., Ltd
Machine；Ultrasonic cell disruptor with vacuum function is the VOSHIN98-III type ultrasonic waves of Wuxi Wo Xin Instrument Ltd.
Space Proview experimental facilities Co., Ltd Scientz-IID type ultrasonic cell disruptors are won in cell disruptor, Beijing, and Tianjin is difficult to understand special
The UH-500B liquid crystal Ultrasonic cell smashs of Sai Ensi Instrument Ltd.；Energy-collecting ultrasonic equipment with vacuum function is
Nanjing fair current Instrument Ltd. SL type energy-collecting ultrasonic decentralized systems, the XO-1000F types of Nanjing Xian Ou instrument manufacturings Co., Ltd
Energy-gathered ultrasonic instrument；The assembly of vacuum tank and ultrasonic device with vacuumizing function is ten thousand ultrasonic equipment of Suzhou Aunar
The vacuum outgas ultrasonic cleaning device of Co., Ltd.
10. a kind of method that classification dispersion method prepares graphene aqueous liquid dispersion as described in claim 1, it is characterised in that step
Suddenly（4）The stabilization processes time is 10-60s.
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| CN109355726A (en) * | 2018-09-20 | 2019-02-19 | 江苏恒辉安防股份有限公司 | Polymer fiber and preparation method thereof |
| CN109879276A (en) * | 2019-03-15 | 2019-06-14 | 山东华冠智能卡有限公司 | A kind of dispersing method of graphene |
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