CN102180458B - Nano-carbon material dispersion liquid and preparation method and equipment thereof - Google Patents

Nano-carbon material dispersion liquid and preparation method and equipment thereof Download PDF

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CN102180458B
CN102180458B CN 201110073495 CN201110073495A CN102180458B CN 102180458 B CN102180458 B CN 102180458B CN 201110073495 CN201110073495 CN 201110073495 CN 201110073495 A CN201110073495 A CN 201110073495A CN 102180458 B CN102180458 B CN 102180458B
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carbon material
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carbon
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CN102180458A (en
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梁奇
梅佳
岳敏
张少波
时浩
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Shenzhen Beiteri New Energy Technology Research Institute Co ltd
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Shenzhen Battery Nanotechnology Co Ltd
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Abstract

The invention discloses a nano-carbon material dispersion liquid, and a preparation method and preparation equipment of the nano-carbon material dispersion liquid, and aims to prepare a nano-carbon material dispersion system which contains uniformly distributed nano-carbon particles and is stable. The dispersion liquid comprises the following components in percentage by mass: 0.5 to 20 percent of the nano-carbon material, and the balance of dispersion solvent. The preparation method comprises the steps of pre-dispersion and high-pressure dissociation dispersion. The preparation equipment consists of pre-dispersion equipment and high-pressure dissociation dispersion equipment. Compared with the prior art, a high-pressure dispersion method is introduced into the preparation method, and more than two paths of 50 to 500MPa high-pressure liquid flows are guided to one place and converged together to ensure that the high-pressure liquid flows generate violent collision to fully dissociate the nano-carbon material in the high-pressure liquid flows, so that the nano-carbon material is uniformly distributed in the dispersion solvent to achieve a more effective dispersion effect of the nano material; besides, the obtained nano-carbon material dispersion liquid is better in dispersion effect, can exist stably for a long time, and is convenient to store and transport.

Description

Nano-carbon material dispersion liquid and preparation method thereof and equipment
Technical field
The present invention relates to a kind of nano material dispersion liquid and preparation method thereof and equipment, particularly a kind of dispersion liquid take nano-carbon material as main component and preparation method thereof and equipment.
Background technology
The particle diameter of nano material is very little, thereby usually all has larger specific surface area and higher free energy, causes to be very easy between the nano-grain reunite.Coacervate generally all exists with several times, decades of times and even 1,100 times of forms to former nano-grain volume.Carry out compound tense in nano material and other material; need to make it in other body material, be in homodisperse distribution; and this reunion existing way of nano-grain can not be scattered in the body material it effectively; the performance that nano material is had is difficult to bring into play fully; and increased the difficulty of processing treatment; also usually can produce negative impact to the performance of matrix material, cause even the deteriorated of composite property.Therefore, the nano material of obtaining uniform and stable dispersion seems most important.Adopt prior art to be difficult to obtain disperse fully and stable nano material dispersion liquid system.
The method for preparing the stable dispersion liquid system that contains nano particle generally includes physical agitation and chemical treatment.Physical agitation comprises and adopts high shear mixing such as high-speed mixer, mixing roll, homogenizer, colloidal mill, and HI high impact is mixed such as ball mill, masher, whetstone grinding machine, ultrasonic oscillator.The preparation method of the disclosed carbon nanotube conductive solution for lithium ionic secondary cell of China Patent Publication No. CN101420035A, its method that adopts ultra-sonic oscillation to disperse has obtained the dispersion liquid of carbon nanotubes.Chemical treatment comprises to be carried out surface modification, adopts tensio-active agent to serve as dispersing auxiliary nano particle.Chinese patent CN101165820A then discloses a kind of carbon black conductive fluid, and tensio-active agent, binding agent, water and carbon black are ground the acquisition dispersion liquid.The nano-carbon material dispersion liquid that aforesaid method obtains can't solve the agglomeration traits of nano-grain fully, can not steady in a long-termly exist, and is unfavorable for storing and transportation, has greatly limited its range of application.
Summary of the invention
The purpose of this invention is to provide a kind of nano-carbon material dispersion liquid and preparation method thereof and equipment, the technical problem that solve is to obtain to contain equally distributed nano-carbon material and can the dispersion liquid that exist steady in a long-term.
The present invention is by the following technical solutions: a kind of nano-carbon material dispersion liquid, and described nano-carbon material dispersion liquid contains the nano-carbon material of 0.5-20% by mass percentage, and all the other are dispersion solvent; Described nano-carbon material is more than one in Graphene, carbon nanotube, carbon nano fiber, soccerballene, carbon black and the acetylene black; The graphite flake number of plies of described Graphene is between 1-100, and the diameter of carbon nanotube and carbon nano fiber is between 0.2-500nm, and the particle diameter of soccerballene, carbon black and acetylene black is between 1-200nm; Described dispersion solvent is water, methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, pimelinketone, methylene dichloride, chloroform, hexanaphthene, benzene, toluene, dimethylbenzene, ethylbenzene, aniline, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, the N-N dimethyl formamide, the N-N N,N-DIMETHYLACETAMIDE, pyridine, the pyrroles, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole dintrile amine salt, 1-butyl-3-Methylimidazole hexafluorophosphate, 1-butyl-3-Methylimidazole fluoroform sulfimide salt, 1-butyl-3-Methylimidazole fluoroform sulphonate or 1-ethyl-3-methylimidazole acetate.
Nano-carbon material dispersion liquid of the present invention contains the dispersing auxiliary greater than 0 to 10% by mass percentage, and described dispersing auxiliary is tensio-active agent, biomacromolecule or hyperbranched polymer; Tensio-active agent is ionogenic surfactant or nonionic surface active agent, ionogenic surfactant is stearic acid, sodium oleate, lauric acid, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lignosulfonate, Dihexadecylphosphate, benzalkonium chloride, Morpan BB or Yelkin TTS, and nonionic agent is glycerin fatty acid ester, poly-sorb fat or polyoxyethylene glycol or Pluronic F68; Biomacromolecule is protein molecule, have chain thymus nucleic acid and Yeast Nucleic Acid, chitosan, starch or the cyclodextrin of spirane structure; Hyperbranched polymer is the hyperbranched polymer of triarylamine and derivative thereof, or the ultrabranching polyamide that contains fluorine-triphenylamine structure is sour, by three (4-bromophenyl) amine and 1, the hyperbranched polymer that the 4-Vinylstyrene obtains through the dehalogenation polycondensation, or by the Grignard reagent compound of three (4-bromophenyl) amine through polycondensation and hyperbranched polymer use.
Nano-carbon material dispersion liquid of the present invention contains the stablizer greater than 0 to 5% by mass percentage, and described stablizer is Xylo-Mucine, xanthan gum, carrageenin, pectin, polyvinylidene difluoride (PVDF) or styrene-butadiene rubber(SBR).
A kind of preparation method of nano-carbon material dispersion liquid, may further comprise the steps: one, pre-dispersed processing, be 0.5-20% by nano-carbon material mass ratio in the final nano-carbon material dispersion liquid, in dispersion solvent, add and carry out behind the nano-carbon material pre-dispersedly, obtain pre-dispersed suspension; Pre-dispersed employing high-speed stirring, grinding, mixing or ultra-sonic oscillation physical method, high-speed stirring speed 2000-8000rmp, time 1-6h; Ball milling speed 30-120rpm, time 2-48h; Closed-smelting machine rotor rotating speed 15-80rpm, time 0.5-5h; Ultra-sonic oscillation frequency 20-40KHz, power density 100-300W/cm 2, time 0.5-8h; Two, the high pressure dispersion treatment of dissociating, pre-dispersed suspension shunting is formed liquid stream more than two strands, liquid stream more than two strands is applied 50-500MPa pressure, then 50-500MPa high pressure liquid stream guiding more than two strands is compiled at a place, make it that sharp impacts occur, obtain nano-carbon material dispersion liquid; Described nano-carbon material is more than one in Graphene, carbon nanotube, carbon nano fiber, soccerballene, carbon black and the acetylene black; The graphite flake number of plies of described Graphene is between 1-100, and the diameter of carbon nanotube and carbon nano fiber is between 0.2-500nm, and the particle diameter of soccerballene, carbon black and acetylene black is between 1-200nm; Described dispersion solvent is water, methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, pimelinketone, methylene dichloride, chloroform, hexanaphthene, benzene, toluene, dimethylbenzene, ethylbenzene, aniline, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, the N-N dimethyl formamide, the N-N N,N-DIMETHYLACETAMIDE, pyridine, the pyrroles, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole dintrile amine salt, 1-butyl-3-Methylimidazole hexafluorophosphate, 1-butyl-3-Methylimidazole fluoroform sulfimide salt, 1-butyl-3-Methylimidazole fluoroform sulphonate or 1-ethyl-3-methylimidazole acetate.
Method of the present invention is compiled liquid after the collision conduit of flowing through and is drawn.
Being dissociated into more than 1 time of method high pressure dispersing chamber of the present invention.
The pre-dispersed processing of method of the present invention, mass ratio by final nano-carbon material dispersion liquid, nano-carbon material 0.5-20%, dispersing auxiliary greater than 0 to 10%, all the other are dispersion solvent, and dispersing auxiliary is dissolved in the dispersion solvent, add carry out behind the nano-carbon material pre-dispersed; Described dispersing auxiliary is tensio-active agent, biomacromolecule or hyperbranched polymer; Tensio-active agent is ionogenic surfactant or nonionic surface active agent, ionogenic surfactant is stearic acid, sodium oleate, lauric acid, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lignosulfonate, Dihexadecylphosphate, benzalkonium chloride, Morpan BB or Yelkin TTS, and nonionic agent is glycerin fatty acid ester, poly-sorb fat or polyoxyethylene glycol or Pluronic F68; Biomacromolecule is protein molecule, have chain thymus nucleic acid and Yeast Nucleic Acid, chitosan, starch or the cyclodextrin of spirane structure; Hyperbranched polymer is the hyperbranched polymer of triarylamine and derivative thereof, or the ultrabranching polyamide that contains fluorine-triphenylamine structure is sour, by three (4-bromophenyl) amine and 1, the hyperbranched polymer that the 4-Vinylstyrene obtains through the dehalogenation polycondensation, or by the Grignard reagent compound of three (4-bromophenyl) amine through polycondensation and hyperbranched polymer use.
The pre-dispersed processing of method of the present invention, mass ratio by final nano-carbon material dispersion liquid, nano-carbon material 0.5-20%, dispersing auxiliary greater than 0 to 10%, stablizer greater than 0 to 5%, all the other are dispersion solvent, dispersing auxiliary, stablizer are dissolved in the dispersion solvent, carry out pre-dispersed behind the adding nano-carbon material; Described stablizer is Xylo-Mucine, xanthan gum, carrageenin, pectin, polyvinylidene difluoride (PVDF) or styrene-butadiene rubber(SBR).
A kind of Preparation equipment of nano-carbon material dispersion liquid, the Preparation equipment of described nano-carbon material dispersion liquid is comprised of pre-dispersed equipment and the high pressure dispersing apparatus that dissociates, the described high pressure dispersing apparatus that dissociates is linked in sequence by the first vacuum breaker, feeder, the second vacuum breaker and high pressure dispersing chamber, is connected to high-pressure pump on the feeder; Described the first vacuum breaker connects the feeder entrance, and the second vacuum breaker connects the feeder outlet.
Equipment high pressure dispersing chamber of the present invention is provided with the chamber body of rigid structure body, center one end of chamber body has a cylindrical flow-guiding channel, the other end has a cylindrical busway, the axis coaxle of flow-guiding channel and busway, the flow-guiding channel internal diameter is greater than the busway internal diameter, the terminal end of flow-guiding channel is connected with circle-shaped equally distributed columniform split channel more than two, split channel extends to the busway along the axis direction of flow-guiding channel and busway, be intersected in the ingress, busway after over-angle turns to, the internal diameter of described split channel is less than the internal diameter of busway.
The present invention compared with prior art, introduce the high pressure dispersing method by the basis at conventional dispersing mode, 50-500MPa high pressure liquid stream guiding more than two strands is compiled at a place, make it that sharp impacts occur, nano-carbon material contained in the high pressure liquid stream is fully dissociated, nano-carbon material is dispersed in the dispersion solvent, realization is to the more effective dispersion effect of nano material, nano-carbon material dispersion liquid obtained by the method for the present invention, not only dispersion effect is better, and can steady in a long-termly exist, be convenient to store and transportation, widen its range of application.
Description of drawings
Fig. 1 is the high pressure of the present invention dispersing apparatus structural representation that dissociates.
Fig. 2 is high pressure dispersing chamber structural representation of the present invention.
Fig. 3 is the SEM figure of the carbon nano tube dispersion liquid of the embodiment of the invention 1.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.Nano-carbon material dispersion liquid of the present invention is comprised of the component of following mass ratio: the nano-carbon material of 0.5-20%, and 0 to 10% dispersing auxiliary, 0 to 5% stablizer, all the other are dispersion solvent.Described nano-carbon material dispersion liquid can stable existence time more than 2 months.
Described nano-carbon material is more than one in Graphene, carbon nanotube, carbon nano fiber, soccerballene, carbon black and the acetylene black.Wherein, the graphite flake number of plies of two-dimensional nano carbon material (Graphene) is between 1-100, the diameter of One-dimensional nanoreticular carbon materials (carbon nanotube and carbon nano fiber) is between 0.2-500nm, and the particle diameter of zero-dimension nano carbon material (soccerballene, carbon black and acetylene black) is between 1-200nm.
Described dispersion solvent is the liquid medium that possesses fluid properties in 0-200 ℃ of temperature range, comprises inorganic medium and organic medium.
Inorganic medium is water.
Organic medium is methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, pimelinketone, methylene dichloride, chloroform, hexanaphthene, benzene, toluene, dimethylbenzene, ethylbenzene, aniline, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, the N-N dimethyl formamide, the N-N N,N-DIMETHYLACETAMIDE, pyridine, the pyrroles, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole dintrile amine salt, 1-butyl-3-Methylimidazole hexafluorophosphate, 1-butyl-3-Methylimidazole fluoroform sulfimide salt, 1-butyl-3-Methylimidazole fluoroform sulphonate or 1-ethyl-3-methylimidazole acetate.
Described dispersing auxiliary is tensio-active agent, biomacromolecule or hyperbranched polymer.
Tensio-active agent is ionogenic surfactant or nonionic surface active agent, can significantly reduce surface tension of liquid or liquid and solid contact interface tension force under few additive, promotes the dispersion of nano-carbon material in liquid medium.Ionogenic surfactant is stearic acid, sodium oleate, lauric acid, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lignosulfonate, Dihexadecylphosphate, benzalkonium chloride, Morpan BB or Yelkin TTS.Nonionic agent is glycerin fatty acid ester, poly-sorb fat (tween) or polyoxyethylene glycol or Pluronic F68.
Biomacromolecule is protein molecule, have chain thymus nucleic acid DNA and RNA (ribonucleic acid), chitosan, starch or the cyclodextrin of spirane structure.
Hyperbranched polymer is the hyperbranched polymer of triarylamine and derivative thereof, or the ultrabranching polyamide that contains fluorine-triphenylamine structure is sour, by three (4-bromophenyl) amine and 1, the hyperbranched polymer that the 4-Vinylstyrene obtains through the dehalogenation polycondensation (being called for short " TAP-1 "), or by the Grignard reagent compound of three (4-bromophenyl) amine through polycondensation and hyperbranched polymer, can play solublization to the dispersion of nano-carbon material in liquid organic medium.
Described stablizer refers to increase the compound of described dispersion solvent viscosity, is Xylo-Mucine CMC, xanthan gum, carrageenin, pectin, polyvinylidene difluoride (PVDF) PVDF or styrene butadiene rubber sbr.Can further strengthen the stability of dispersion liquid.
Described nano-carbon material dispersion liquid can stable existence, refer to nano-carbon material in the dispersion solvent can stably be suspended in obvious sedimentation wherein and not occurs, flocculation causes layering, separation phenomenon occurs between nano-carbon material and the dispersion agent.
The preparation method of nano-carbon material dispersion liquid of the present invention may further comprise the steps:
One, pre-dispersed processing, mass ratio by final nano-carbon material dispersion liquid, nano-carbon material 0.5-20%, dispersing auxiliary 0 to 10%, stablizer 0 to 5%, all the other are dispersion solvent, and dispersing auxiliary, stablizer are dissolved in the dispersion solvent, add carry out behind the nano-carbon material pre-dispersed.Pre-dispersed employing high-speed stirring, grinding, mixing or ultra-sonic oscillation physical method, high-speed stirring speed 2000-8000rmp, time 1-6h; Ball milling speed 30-120rpm, time 2-48h; Closed-smelting machine rotor rotating speed 15-80rpm, time 0.5-5h; Ultra-sonic oscillation frequency 20-40KHz, power density 100-300W/cm 2, time 0.5-8h.Obtain by the way pre-dispersed suspension.Pre-dispersed purpose is nano-carbon material tentatively to be scattered in the dispersion solvent that is dissolved with dispersing auxiliary and stablizer form suspension, is convenient to implement subsequently the high pressure dispersion of dissociating.
Two, the high pressure dispersion treatment of dissociating, pre-dispersed suspension shunting is formed liquid stream more than two strands, liquid stream more than two strands is applied 50-500MPa pressure, then 50-500MPa high pressure liquid stream guiding more than two strands is compiled at a place, make it that sharp impacts occur, nano-carbon material contained in the high pressure liquid stream is fully dissociated, and nano-carbon material is dispersed in the dispersion solvent, obtain favorable dispersity and stable nano-carbon material dispersion liquid, compile liquid after the collision conduit of flowing through and draw.Suspension through pre-dispersed under the effect of high pressure pump assembly, flows to the high pressure dispersing chamber, in the split channel of high pressure dispersing chamber, formed high pressure liquid stream more than two strands by shunting, produce 50-500MPa pressure, high pressure liquid stream is directed at a place to be compiled, and compiles liquid after the collision passage of flowing through and draws.Dissociating of high pressure dispersing chamber can be more than 1 time, with degree of scatter and the stability of further raising nano-carbon material dispersion liquid.
The nano-carbon material dispersion liquid of the inventive method preparation, the electrostatic repulsion of the nanoparticle surface net charge that dependence is fully dissociated is avoided reuniting, form stable colloidal dispersion, can under 25 ℃ of conditions of normal temperature, leave standstill at least 2 months and macroscopic demixing phenomenon does not occur.
The Preparation equipment of nano-carbon material dispersion liquid of the present invention is comprised of pre-dispersed equipment and the high pressure dispersing apparatus that dissociates.
The high-speed stirring that described pre-dispersed equipment is prior art, grinding, mixing or ultrasonic oscillator equipment.
As shown in Figure 1, the high pressure dispersing apparatus that dissociates is linked in sequence by the first vacuum breaker, feeder, the second vacuum breaker and high pressure dispersing chamber, is connected to the 50-500MPa high-pressure pump on the feeder.The first vacuum breaker connects the feeder entrance, and the second vacuum breaker connects the feeder outlet.Pre-dispersed suspension enters from the first vacuum breaker, through feeder, the second vacuum breaker, flows out nano-carbon material dispersion liquid from the high pressure dispersing chamber at last.
The volume that described 50-500MPa high-pressure pump utilizes the to-and-fro movement of piston to form in feeder changes, and realizes sucking from the first vacuum breaker of liquid, extrude from the second vacuum breaker, that is the charging of liquid and discharging.First, second vacuum breaker is in order to prevent liquid stream suck-back.
As shown in Figure 2, the high pressure dispersing chamber is provided with chamber body 1, flow-guiding channel 2, split channel 3 and busway 4.Chamber body 1 is a rigid structure body, center one end of chamber body 1 has a cylindrical flow-guiding channel 2, the body 1 center the other end in chamber has a cylindrical busway 4, the axis coaxle of flow-guiding channel 2 and busway 4, and the internal diameter of flow-guiding channel 2 is greater than the internal diameter of busway 4.Flow-guiding channel 2 terminal ends 21 are connected with columniform split channel 3 more than two, split channel 3 in flow-guiding channel 2 terminal ends 21 with circle-shaped even distribution, split channel 3 is along axis direction to busway 4 extensions of flow-guiding channel 2 with busway 4, after turning to, over-angle is intersected in a place, be 4 ingress 41, busway, the internal diameter of split channel 3 is less than the internal diameter of busway 4.
During work, the volume that forms in feeder when relying on the high-pressure pump piston motion increases, to suck feeder by the first vacuum breaker pipeline through pre-dispersed suspension, relending the volume that forms in feeder when helping the high-pressure pump piston motion reduces and pre-dispersed suspension is extruded in feeder, flow through behind the flow-guiding channel of high pressure dispersing chamber, effect by means of the high-pressure pump piston, for liquid stream provides pressure, be pressed into and form 50-500MPa high pressure liquid stream more than two strands in the narrow split channel, sharp impacts when compiling at a place, the high pressure liquid stream more than two strands occurs, nano-carbon material contained in the fluid is fully dissociated, be dispersed in the dispersion solvent, obtain favorable dispersity and stable nano-carbon material dispersion liquid.Compile liquid after the collision busway of flowing through and draw, can directly obtain favorable dispersity and stable dispersion liquid, also can carry out repeatedly high pressure to dispersion liquid and dissociate with further improving stability.Adopt this high pressure dispersing method can fast and effeciently obtain to contain the dispersion liquid of equally distributed nano-carbon material.Liquid stream this passage of must flowing through could obtain good dispersion effect and maintaining a long-term stability property.
Embodiment 1-12 high-pressure pump adopts the QUANTUM ESP 77S type high-pressure pump of Australian Techni Waterjet company, the first vacuum breaker and the second vacuum breaker all adopt the B-6929 type vacuum breaker of U.S. Harwood Engineering company, the feeder intracavity diameter is identical with the high-pressure pump diameter of piston rod, the flow-guiding channel of high pressure dispersing chamber, split channel, busway are cylindrical, its diameter is respectively 5-20mm, 0.1-0.5mm, 0.5-1mm, and steering angle is 90 °.
Embodiment 1-12 and comparative example's 1 process data and test result see Table 1.
As shown in Figure 3, through the high pressure carbon nano tube dispersion liquid of dispersion treatment that dissociates, carbon nanotube wherein is discrete state, without existing than macro aggregate, the nano material dispersion liquid that employing method of the present invention can obtain to have good dispersion be described.
Nano-carbon material dispersion liquid of the present invention can be applied in different fields.Such as Graphene, carbon nanotube, carbon nano fiber or carbon black, or the conductive additive that the aqueous solution of its mixture or nmp solution can be used as anodal and negative material is applied in the lithium ion battery, to promote its over-all properties.Carbon nanotube or carbon nano fiber, or the dispersion in organic solvent of its mixture can add in the polymer composite, to strengthen its mechanical property.Graphene, carbon nanotube, carbon nano fiber or carbon black, or the dispersion in organic solvent of its mixture can add to as conductive filler material and play antistatic property in the plastics.
Table 1 embodiment 1-12 and comparative example's 1 process data and test result
Figure BDA0000052012740000101
Figure BDA0000052012740000111

Claims (6)

1. the Preparation equipment of a nano-carbon material dispersion liquid, it is characterized in that: the Preparation equipment of described nano-carbon material dispersion liquid is comprised of pre-dispersed equipment and the high pressure dispersing apparatus that dissociates, the described high pressure dispersing apparatus that dissociates is linked in sequence by the first vacuum breaker, feeder, the second vacuum breaker and high pressure dispersing chamber, is connected to high-pressure pump on the feeder; Described the first vacuum breaker connects the feeder entrance, and the second vacuum breaker connects the feeder outlet; Described high pressure dispersing chamber is provided with the chamber body (1) of rigid structure body, center one end of chamber body (1) has a cylindrical flow-guiding channel (2), the other end has a cylindrical busway (4), the axis coaxle of flow-guiding channel (2) and busway (4), flow-guiding channel (2) internal diameter is greater than busway (4) internal diameter, the terminal end of flow-guiding channel (2) (21) is connected with circle-shaped equally distributed columniform split channel (3) more than two, split channel (3) is along flow-guiding channel (2) axis direction (4) extension to the busway with busway (4), be intersected in ingress, busway (4) (41) after over-angle turns to, the internal diameter of described split channel (3) is less than the internal diameter of busway (4).
2. method that adopts the described Preparation equipment of claim 1 to prepare nano-carbon material dispersion liquid, may further comprise the steps: one, pre-dispersed processing, be 0.5-20% by nano-carbon material mass ratio in the final nano-carbon material dispersion liquid, in dispersion solvent, add and carry out behind the nano-carbon material pre-dispersedly, obtain pre-dispersed suspension; Pre-dispersed employing high-speed stirring, ball milling, mixing or ultra-sonic oscillation physical method, high-speed stirring speed 2000-8000rmp, time 1-6h; Ball milling speed 30-120rpm, time 2-48h; Closed-smelting machine rotor rotating speed 15-80rpm, time 0.5-5h; Ultra-sonic oscillation frequency 20-40KHz, power density 100-300W/cm 2, time 0.5-8h; Two, the high pressure dispersion treatment of dissociating, pre-dispersed suspension shunting is formed liquid stream more than two strands, liquid stream more than two strands is applied 50-500MPa pressure, then 50-500MPa high pressure liquid stream guiding more than two strands is compiled at a place, make it that sharp impacts occur, obtain nano-carbon material dispersion liquid; Described nano-carbon material is more than one in Graphene, carbon nanotube, carbon nano fiber, soccerballene and the acetylene black; The graphite flake number of plies of described Graphene is between 1-100, and the diameter of carbon nanotube and carbon nano fiber is between 0.2-500nm, and the particle diameter of soccerballene and acetylene black is between 1-200nm; Described dispersion solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, pimelinketone, methylene dichloride, chloroform, hexanaphthene, benzene, toluene, dimethylbenzene, ethylbenzene, aniline, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, the N-N dimethyl formamide, the N-N N,N-DIMETHYLACETAMIDE, pyridine, the pyrroles, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole dintrile amine salt, 1-butyl-3-Methylimidazole hexafluorophosphate, 1-butyl-3-Methylimidazole fluoroform sulfimide salt, 1-butyl-3-Methylimidazole fluoroform sulphonate or 1-ethyl-3-methylimidazole acetate.
3. the described Preparation equipment of employing claim 1 according to claim 2 prepares the method for nano-carbon material dispersion liquid, it is characterized in that: compile liquid after the collision conduit of flowing through and draw.
4. the described Preparation equipment of employing claim 1 according to claim 3 prepares the method for nano-carbon material dispersion liquid, it is characterized in that: being dissociated into more than 1 time of described high pressure dispersing chamber.
5. the described Preparation equipment of employing claim 1 according to claim 4 prepares the method for nano-carbon material dispersion liquid, it is characterized in that: described pre-dispersed processing, mass ratio by final nano-carbon material dispersion liquid, nano-carbon material 0.5-20%, dispersing auxiliary greater than 0 to 10%, all the other are dispersion solvent, dispersing auxiliary is dissolved in the dispersion solvent, carries out pre-dispersed behind the adding nano-carbon material; Described dispersing auxiliary is tensio-active agent, biomacromolecule or hyperbranched polymer; Tensio-active agent is ionogenic surfactant or nonionic surface active agent, ionogenic surfactant is stearic acid, sodium oleate, lauric acid, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lignosulfonate, Dihexadecylphosphate, benzalkonium chloride, Morpan BB or Yelkin TTS, and nonionic agent is glycerin fatty acid ester, poly-sorb fat or polyoxyethylene glycol or Pluronic F68; Biomacromolecule is protein molecule, have chain thymus nucleic acid and Yeast Nucleic Acid, chitosan, starch or the cyclodextrin of spirane structure; Hyperbranched polymer is the hyperbranched polymer of triarylamine and derivative thereof, or the ultrabranching polyamide that contains fluorine-triphenylamine structure is sour, by three (4-bromophenyl) amine and 1, the hyperbranched polymer that the 4-Vinylstyrene obtains through the dehalogenation polycondensation, or by the Grignard reagent compound of three (4-bromophenyl) amine through polycondensation and hyperbranched polymer.
6. the described Preparation equipment of employing claim 1 according to claim 4 prepares the method for nano-carbon material dispersion liquid, it is characterized in that: described pre-dispersed processing, mass ratio by final nano-carbon material dispersion liquid, nano-carbon material 0.5-20%, dispersing auxiliary greater than 0 to 10%, stablizer greater than 0 to 5%, all the other are dispersion solvent, dispersing auxiliary, stablizer are dissolved in the dispersion solvent, carry out pre-dispersed behind the adding nano-carbon material; Described dispersing auxiliary is tensio-active agent, biomacromolecule or hyperbranched polymer; Tensio-active agent is ionogenic surfactant or nonionic surface active agent, ionogenic surfactant is stearic acid, sodium oleate, lauric acid, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lignosulfonate, Dihexadecylphosphate, benzalkonium chloride, Morpan BB or Yelkin TTS, and nonionic agent is glycerin fatty acid ester, poly-sorb fat or polyoxyethylene glycol or Pluronic F68; Biomacromolecule is protein molecule, have chain thymus nucleic acid and Yeast Nucleic Acid, chitosan, starch or the cyclodextrin of spirane structure; Hyperbranched polymer is the hyperbranched polymer of triarylamine and derivative thereof, or the ultrabranching polyamide that contains fluorine-triphenylamine structure is sour, by three (4-bromophenyl) amine and 1, the hyperbranched polymer that the 4-Vinylstyrene obtains through the dehalogenation polycondensation, or by the Grignard reagent compound of three (4-bromophenyl) amine through polycondensation and hyperbranched polymer; Described stablizer is Xylo-Mucine, xanthan gum, carrageenin, pectin, polyvinylidene difluoride (PVDF) or styrene-butadiene rubber(SBR).
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Publication number Priority date Publication date Assignee Title
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101107330A (en) * 2004-11-25 2008-01-16 东海碳素株式会社 Water dispersion of carbon black and process for producing the same
CN101549866A (en) * 2009-05-14 2009-10-07 上海交通大学 Method for decomposing carbon nano-tube bundle based on high voltage electrostatic spray method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002129065A (en) * 2000-10-20 2002-05-09 Dainippon Ink & Chem Inc Production method for carbon black having water dispersibility
KR101071688B1 (en) * 2008-10-27 2011-10-11 주식회사 펨빅스 Method and Devices for Carbon Nanotube Cutting-Dispersion

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101107330A (en) * 2004-11-25 2008-01-16 东海碳素株式会社 Water dispersion of carbon black and process for producing the same
CN101549866A (en) * 2009-05-14 2009-10-07 上海交通大学 Method for decomposing carbon nano-tube bundle based on high voltage electrostatic spray method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开2002-129065A 2002.05.09

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