CN103030132B - A kind of method that carbon nano-tube macroscopic body is prepared in self assembly - Google Patents
A kind of method that carbon nano-tube macroscopic body is prepared in self assembly Download PDFInfo
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- CN103030132B CN103030132B CN201210560855.0A CN201210560855A CN103030132B CN 103030132 B CN103030132 B CN 103030132B CN 201210560855 A CN201210560855 A CN 201210560855A CN 103030132 B CN103030132 B CN 103030132B
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Abstract
The present invention announces a kind of method that silk ribbon shape carbon nano-tube macroscopic body is prepared in self assembly, is related to technical field of nanometer material preparation science.First long CNT is carried out aoxidize truncate using wet chemistry method, obtained the short carbon nanometer tube neutral aqueous solution of polymolecularity, remove solution water by carrying out to short carbon nanometer tube neutral aqueous solution drying, self assembly prepares the carbon nano-tube macroscopic body of silk ribbon shape.The carbon nano-tube macroscopic body of present invention preparation, its length is about several centimetres, and sectional dimension is in micron order.After annealing, this carbon nanometer tube ribbon has good electric conductivity, and electrical conductivity reaches 140 S/cm.
Description
Technical field
The present invention relates to technical field of nanometer material preparation science, the short carbon nanometer tube neutrality of particularly a kind of polymolecularity
The method that silk ribbon shape macroscopic body is prepared in aqueous solution self assembly.
Background technology
CNT (carbon nanotubes, CNTs) is a kind of carbon nanomaterial with one-dimensional tubular structure.Carbon
Nanotube has excellent Wuli-Shili-Renli system approach, has broad application prospects in fields such as mechanics, electricity and electronics.
The performance of CNT emerges from often by the macroscopic body of its some ad hoc structure forms, and carbon obtained at present
Nanotube is all generally to exist in the form of a powder.The carbon nano-tube macroscopic body of this powder morphology is usually unable to give full play to
Some excellent properties of CNT itself but also the direct application of CNT can be limited.Accordingly, it would be desirable to by CNT
Re-assembly and be built into the macroscopic body with ad hoc structure form, particularly there is the CNT assembly of one-dimensional macroscopic structure
(as carbon nano-tube fibre), it shows very superior electric conductivity etc..At present, the carbon of assembling preparation one-dimensional macroscopic structure is received
The conventional method of mitron assembly has dry spinning method and wet spinning process, and both approaches generally require custom-designed setting
For device, operation is more complicated and deals with also than relatively time-consuming.Particularly wet spinning process, due to needing to prepare high dispersive
Property carbon nano tube dispersion liquid and introduce some other materials, such as surfactant, polymer etc., after this often gives CNT
Continuous process and the difficulty brought of application.Recently, CNT is processed using the chlorosulfonic acid of high concentration and to obtain high concentration
Carbon nano-tube solution, is then assembled into the carbon nano-tube fibre of one-dimensional macroscopic structure, and it shows superior performance.But it is this
Using the chlorosulfonic acid of high concentration, there are strong corrosivity in method, the requirement to instrument and equipment is very high and operates and also relatively endangers
Danger.Therefore, a kind of pure nano-carbon tube solution with neutrality of invention assembles and prepares the carbon nano-tube macroscopic body of one-dimentional structure and have
Important realistic meaning.
Content of the invention
The purpose of the present invention is aiming at some shortcomings of prior art, there is provided a kind of short carbon nanometer tube of polymolecularity
The method that silk ribbon shape macroscopic body is prepared in neutral aqueous solution self assembly.
The present invention is achieved by the following technical solutions, and the present invention is first with lacking that long carbon nano tube surface distorts
Fall into, it is carried out aoxidize truncate using wet chemistry method, obtained short carbon nanometer tube neutral aqueous solution, this aqueous solution has high dispersive
Property, homogeneous, stable feature；Recycle the oxygen on this these feature of short carbon nanometer tube neutral aqueous solution and short carbon nanometer tube surface
Change the interaction between functional group, completely remove its solution water by drying, be self-assembled into the carbon nano-tube macroscopic of silk ribbon shape
Body.The carbon nanometer tube ribbon with satisfactory electrical conductivity can be obtained through high annealing.
The process for assembly preparing of the present invention comprises the steps：
1. the preparation of the short carbon nanometer tube neutral aqueous solution of polymolecularity：
Original long carbon nanotube powder and potassium permanganate solid are added separately to excessive dense sulfur with certain proportioning
In acid solution, the reaction mixture obtaining is placed in continuously stirred reaction 3h in 50 DEG C of water-bath, and the mixed liquor having reacted is spent
Ionized water dilutes, and adds the reduction of excessive hydrogen peroxide solution and removes the manganese dioxide solid generating, through filtering with microporous membrane with
And after the washing of dilute hydrochloric acid solution, deionized water is washed to the supernatant by high speed centrifugation again is neutrality for the solid that obtains
(PH=6-7), then take off after a layer solid add deionized water ultrasonic disperse 1h, remove sub-cloud through low-speed centrifugal further a small amount of
Not sufficiently reactive CNT, takes the dark solution that upper strata is homogeneous, stable, that is, the short carbon nanometer tube obtaining polymolecularity is neutral
Aqueous solution.
2. the self assembly preparation of the carbon nano-tube macroscopic body of silk ribbon shape：
The short carbon nanometer tube neutral aqueous solution of polymolecularity prepared by step (1) is poured in beaker and is placed directly within
In air dry oven under uniform temperature, dry the carbon nano-tube macroscopic body obtaining silk ribbon shape after completely removing moisture.
3. high annealing：
The silk ribbon shape carbon nano-tube macroscopic body that step (2) is obtained is placed directly within quartz tube furnace and carries out high annealing.
The feature that silk ribbon shape carbon nano-tube macroscopic body method is prepared in the self assembly that the present invention provides mainly has two aspects：The
One, adopt improved Hummer method (a kind of be commonly used to the traditional method preparing graphene oxide) to realize carbon nanometer first
The truncate of pipe, the length major part of the CNT obtaining is in below 200nm, and obtains with polymolecularity, high concentration
Short carbon nanometer tube neutral aqueous solution, this CNT neutral aqueous solution is in the preparation of composite, lithium ion battery battery
The fields such as pole material, biomedicine will have broad application prospects；Second, using the short carbon nanometer tube neutral aqueous solution of gained
Homogeneous, stable feature and short carbon nanometer tube surface functional group interphase interaction, by simple cold drying, realize carbon
The self assembly of nanotube, has obtained the carbon nano-tube macroscopic body with silk ribbon shape.This assemble method is safe, simple, easy, is carbon
A kind of new route of nanotube assembling, is that CNT provides new approach in the application of field of microelectronic devices.
Brief description
Fig. 1 is the transmission electron microscope photo of the original carbon nanotubes bought.
Fig. 2 is the uv-visible absorption spectra of the CNT neutral aqueous solution of variable concentrations.
Fig. 3 is the transmission electron microscope photo of short carbon nanometer tube in CNT neutral aqueous solution.
Fig. 4 (a) (b) is respectively the front of carbon nanometer tube ribbon and the stereoscan photograph of side.
Specific embodiment
Example 1：
By the CNT bought (purity about 95%, source：Chengdu organic chemistry company limited, Fig. 1) 0.5 gram and
1.5 grams of potassium permanganate solid is added sequentially in the beaker of concentrated sulphuric acid (98%) fill 15ml, after stirring, puts
Stir process 3 hours in 50 DEG C of thermostat water bath, after being cooled to room temperature, are diluted with the deionized water of about 100ml, not
Disconnected stirring, adds 30% hydrogen peroxide solution of about 10ml, stirring reaction, after 15 minutes, uses filtering with microporous membrane.Obtain is black
Agitator treating in the dilute hydrochloric acid of the 4% of 100ml directly poured into by color solid, then with filtering with microporous membrane, and deionized water filters
Washing, the black solid obtaining is poured into after being sufficiently stirred in the deionized water of 200ml again, averagely pours in 4 centrifuge tubes and uses
Centrifuge is centrifuged 30 minutes under 14000 turns, after layering, outwells the supernatant, and continues to add appropriate going toward in centrifuge tube
Ionized water is sufficiently stirred for washing and then recentrifuge, layering, outwells the supernatant, is so centrifuged repeatedly washing 5 times, clear to upper strata
Liquid is in neutral (PH=6～7), finally collects the centrifugal deposition obtaining and adds the deionized water of about 200ml, in ultrasound wave
Ultrasonic disperse 1 hour in cleaning machine, the dispersion liquid obtaining averagely is poured into and is used centrifuge in 4 centrifuge tubes in 3000 turns of lower centrifugations 30
After minute, careful extraction collects upper strata dispersion soln, collects the short carbon nanometer tube aqueous solution that dispersion soln is high dispersive,
Its solution is in neutrality, and its concentration is about 2.5mg/ml, the suction of the uv-visible absorption spectra of the solution of this different diluted concentration
Receipts value and solution concentration are in good linear relationship (Fig. 2).The length of its CNT is about at below 200nm (Fig. 3).
The above-mentioned short carbon nanometer tube neutral aqueous solution taking 10ml is poured in the beaker of 25ml, and is placed on 80 DEG C of perseverance
In warm air dry oven be dried 24 hours, the silk ribbon shape carbon nano-tube macroscopic body that self assembly obtains be deposited on the wall of beaker and
Bottom, this carbon nanometer tube ribbon about several centimeters, sectional dimension is micron level.(Fig. 4)
Carbon nanometer tube ribbon obtained above is lain in and is placed in quartz boat in the quartz ampoule of tube furnace, with 20 DEG C/
The heating rate of min is warming up to 700 DEG C, after keeping 3 hours at this temperature, naturally cools to room temperature, simultaneously in this whole mistake
Journey is passed through flowing argon protection.Carbon nanometer tube ribbon after the annealing obtaining remains in that original mode of appearance, through electric conductivity
Test shows, this carbon nanometer tube ribbon has good electric conductivity, and electrical conductivity is up to 140S/cm.
The comprising the following steps that of conductivity measurement：The two ends of a piece carbon nanometer tube ribbon being about 3cm are conductive with Copper Foil
Glue is separately fixed on the copper electrode of two interval 1.5cm, is then recorded by 2 points of volt-ampere methods of testing with electrochemical workstation
Its electric conductivity.
Embodiment 2：
The preparation flow of the neutral aqueous solution of short carbon nanometer tube is with embodiment 1.
The short carbon nanometer tube neutral aqueous solution taking 10ml is poured in the beaker of 25ml, and is placed on 30 DEG C of constant temperature drum
It is dried 24 hours in wind drying baker, is similarly obtained self assembly and obtains being about several centimeters, sectional dimension is micron level CNT
Silk ribbon macroscopic body.
Carbon nanometer tube ribbon obtained above is lain in and is placed in quartz boat in the quartz ampoule of tube furnace, with 20 DEG C/
The heating rate of min is warming up to 700 DEG C, after keeping 3 hours at this temperature, naturally cools to room temperature, simultaneously in this whole mistake
Journey is passed through flowing nitrogen protection.Carbon nanometer tube ribbon after the annealing obtaining remains in that original mode of appearance, through electric conductivity
Test shows, this carbon nanometer tube ribbon has good electric conductivity, and electrical conductivity is up to 120S/cm.
Embodiment 3：
By the CNT bought (purity about 95%, source：Chengdu organic chemistry company limited, Fig. 1) 0.5 gram and
0.5 gram of potassium permanganate solid is added sequentially in the beaker of concentrated sulphuric acid (98%) fill 15ml, after stirring, puts
Stir process 3 hours in 50 DEG C of thermostat water bath, after being cooled to room temperature, are diluted with the deionized water of about 100ml, not
Disconnected stirring, adds 30% hydrogen peroxide solution of about 10ml, stirring reaction, after 15 minutes, uses filtering with microporous membrane.Obtain is black
Agitator treating in the dilute hydrochloric acid of the 4% of 100ml directly poured into by color solid, then with filtering with microporous membrane, and deionized water filters
Washing, the black solid obtaining is poured into after being sufficiently stirred in the deionized water of 200ml again, averagely pours in 4 centrifuge tubes and uses
Centrifuge is centrifuged 30 minutes under 14000 turns, after layering, outwells the supernatant, and continues to add appropriate going toward in centrifuge tube
Ionized water is sufficiently stirred for washing and then recentrifuge, layering, outwells the supernatant, is so centrifuged repeatedly washing 5 times, clear to upper strata
Liquid is in neutral (PH=6～7), finally collects the centrifugal deposition obtaining and adds the deionized water of about 200ml, in ultrasound wave
Ultrasonic disperse 1 hour in cleaning machine, the dispersion liquid obtaining averagely is poured into and is used centrifuge in 4 centrifuge tubes in 3000 turns of lower centrifugations 30
After minute, careful extraction collects upper strata dispersion soln, collects the short carbon nanometer tube aqueous solution that dispersion soln is high dispersive, its
Solution is in neutrality, and its concentration is about 1.5mg/ml, and the length of its CNT is in 200nm.
The above-mentioned short carbon nanometer tube neutral aqueous solution taking 15ml is poured in the beaker of 25ml, and is placed on 80 DEG C of perseverance
In warm air dry oven be dried 24 hours, the silk ribbon shape carbon nano-tube macroscopic body that self assembly obtains be deposited on the wall of beaker and
Bottom, this carbon nanometer tube ribbon is about several centimeters, and sectional dimension is micron level.
Carbon nanometer tube ribbon obtained above is lain in and is placed in quartz boat in the quartz ampoule of tube furnace, with 20 DEG C/
The heating rate of min is warming up to 1000 DEG C, after keeping 3 hours at this temperature, naturally cools to room temperature, simultaneously in this whole mistake
Journey is passed through flowing argon protection.Carbon nanometer tube ribbon after the annealing obtaining remains in that original mode of appearance.
Claims (7)
1. the method that silk ribbon shape macroscopic body is prepared in a kind of short carbon nanometer tube neutral aqueous solution self assembly of polymolecularity, its feature exists
In first jointly carrying out to long CNT aoxidizing truncate using concentrated sulphuric acid and potassium permanganate, the short carbon having obtained polymolecularity is received
Mitron neutral aqueous solution, removes solution water by carrying out to short carbon nanometer tube neutral aqueous solution drying, self assembly prepares silk
The carbon nano-tube macroscopic body of banding.
2. method according to claim 1, comprises the following steps：
(1) preparation of the short carbon nanometer tube neutral aqueous solution of polymolecularity：
By original long carbon nanotube powder and potassium permanganate solid with 1：1～1：It is molten that 3 proportioning is added to excessive concentrated sulphuric acid
In liquid, after reacting 3 hours at 50 DEG C, successively through water dilution, hydrogen peroxide reduction except the manganese dioxide solid of dereaction generation, then
The solid that filtration, centrifuge washing obtain further centrifuging and taking upper strata dispersion soln after ultrasonic disperse obtains the short of polymolecularity
CNT neutral aqueous solution；
(2) the self assembly preparation of the carbon nano-tube macroscopic body of silk ribbon shape：
The short carbon nanometer tube neutral aqueous solution of polymolecularity prepared by step (1) is poured in beaker and is placed directly within air blast
Dry in drying baker, dry the carbon nano-tube macroscopic body obtaining silk ribbon shape after completely removing moisture；
(3) the silk ribbon shape carbon nano-tube macroscopic body that step (2) obtains is placed directly within quartz tube furnace under inertia shielding gas
Carry out high annealing.
3. method according to claim 2 it is characterised in that：In step (1), the short carbon nanometer tube of described polymolecularity
Neutral aqueous solution, has the characteristics that polymolecularity, homogeneous, stable, and concentration is 1.5-2.5mg/ml, short carbon nanometer tube therein
Length is less than 200nm.
4. method according to claim 2 it is characterised in that：In step (2), dry in described air dry oven, dry
Dry temperature, is the temperature of 30～80 DEG C of constant temperature.
5. method according to claim 2 it is characterised in that：In step (2), described silk ribbon shape carbon nano-tube macroscopic
Body, its length is about several centimetres, and sectional dimension is micron order.
6. method according to claim 2 it is characterised in that：In step (3), described inertia shielding gas refer to argon or
Nitrogen.
7. method according to claim 2 it is characterised in that：In step (3), described silk ribbon shape carbon nano-tube macroscopic body
It is placed directly within quartz tube furnace and carries out high annealing, specially:Silk ribbon shape carbon nano-tube macroscopic body is placed directly within quartz ampoule
In formula stove, being passed through noble gases is shielding gas, is heated to 700 DEG C -1000 DEG C, and keeps 3h at such a temperature, then in protection
Room temperature is naturally cooled under gas.
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| CN101092739A (en) * | 2007-04-13 | 2007-12-26 | 北京化工大学 | Method for preparing high water soluble Nano carbon tube grafted by super branched polymer |
| CN101148255A (en) * | 2006-09-19 | 2008-03-26 | 北京大学 | Surface assembling method for single-wall carbon nanotube |
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| CN101148255A (en) * | 2006-09-19 | 2008-03-26 | 北京大学 | Surface assembling method for single-wall carbon nanotube |
| CN101092739A (en) * | 2007-04-13 | 2007-12-26 | 北京化工大学 | Method for preparing high water soluble Nano carbon tube grafted by super branched polymer |
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