CN103643281B - The preparation method of electrophoretic deposition carbon nanotube field emitter in a kind of aqueous solution - Google Patents
The preparation method of electrophoretic deposition carbon nanotube field emitter in a kind of aqueous solution Download PDFInfo
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- CN103643281B CN103643281B CN201310567298.XA CN201310567298A CN103643281B CN 103643281 B CN103643281 B CN 103643281B CN 201310567298 A CN201310567298 A CN 201310567298A CN 103643281 B CN103643281 B CN 103643281B
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Abstract
The invention discloses the preparation method of electrophoretic deposition carbon nanotube field emitter in a kind of aqueous solution, (1) is ultrasonic by nitric acid or obtains carboxylic carbon nano-tube with heating condition process CNT again；(2) by the carboxylic carbon nano-tube proper amount of surfactant aid dispersion that obtains in step (1) in deionized water, ultrasonic 1 4h makes CNT fully dispersed；(3) carbon nano-tube aqueous solutions obtained in step (2) is centrifuged 10 30min, discards the supernatant, finally give electrical conductivity and control at 5～10 μ S cm‑1CNT water system electrophoresis liquid；(4) pole plate of two nugget genus is placed in parallel in above-mentioned CNT water system electrophoresis liquid, polar plate spacing controls 0.5～3cm, the DC voltage of 30～60V is applied between two-plate, deposition 0.5～10min taking-up metal polar plate air-dries, (5) annealing, makes annealing treatment at a temperature of 380～500 DEG C.
Description
Technical field
The invention belongs to carbon nanotube cold cathode field of material preparation, be specifically related to one electrophoretic deposition carbon in aqueous and receive
Mitron field emission body is with the method improving its field emission stability.
Background technology
CNT has a lot of excellent performance as field emmision material, almost close to the tip surface area of theoretical limit,
High chemical stability, excellent electric conductivity, heat-conductive characteristic and mechanical strength, thus CNT has extremely low field
Launching cut-in voltage, be resistant to great electric current density, and electric current transmission is the most stable, therefore CNT is especially suitable for
As cold-cathode field emissive material, the field emitting electronic source prepared based on carbon nano-tube material is of future generation most promising cold
Negative electrode technology of preparing.
At present, prepare the method for field emission body of Nano carbon tube and mainly have two kinds of fundamental types: growth method and transfer method.Carbon is received
Mitron direct growth technique is the most complex, and growth temperature is high, and substrate material is had considerable restraint, large area
Growth cost is high, the most inadequate with substrate bond strength, thus has a strong impact on launch stability and service life.Transfer
Method mainly includes silk screen printing and electrophoretic deposition.Wherein electrophoretic deposition can obtain the highest sedimentation rate, is that one has very much
The technique of prospects for commercial application, it be a kind of cheap, reproducibility is good, process under room temperature and be widely used in industrial circle
Deposition technique.The speed size of electrophoretic deposition is unrelated with the size of nano-particle, thus convenient acquisition even compact is heavy
Lamination, the current subject matter of electrophoretic deposition is that the adhesive force between sedimentary and substrate is poor.
And for commercial Application, water system reaction has CNT in bigger captivation, and water system and has well
Dispersibility and dispersion stabilization, in current water system, electrophoretic deposition mainly faces the electrolysis aerogenesis of water to sedimentary uniformity with viscous
The harmful effect of attached power.In water solution system, electrophoretic deposition CNT is necessary for solving the electrolysis problem of water, for pole
The gas produced on plate has at present can oxidized sacrifice layer (such as active metal pole plate), electrolyte, semipermeable membrane by introducing
Or use pulse ac power supply to solve.Although in organic solution there is not electrolysis and the product of water in electrophoretic deposition CNT
Gas problem, but the dispersibility of CNT and dispersion stabilization are the best, adhesion is very poor, it is thus achieved that field emission body send out
Penetrate stability and uniformity is undesirable.
Summary of the invention
It is an object of the invention to, propose the preparation method of electrophoretic deposition carbon nanotube field emitter in aqueous solution, at present
Electrophoretic deposition is prepared Carbon Nanotube Cold Cathode Field Emission Research and is embodied with the some shortcomings of technology, utilizes CNT at aqueous liquid
System compares in organic solvent more preferable dispersion stabilization and and comparatively speaking aqueous liquid tie up in commercial Application more
Big advantage, prepares the field emission body of Nano carbon tube with good launch stability and life-span.
The present invention is achieved by the following technical solutions, the system of electrophoretic deposition carbon nanotube field emitter in a kind of aqueous solution
Preparation Method, comprises the steps:
(1) ultrasonic by nitric acid (weight concentration is at 20-35%) or again with under heating condition process CNT obtain
Carboxylic carbon nano-tube, and with supersound process 1-4h, with 0.45 μm mixed cellulose ester water system filter membrane sucking filtration, and spends
Ionized water cyclic washing, is 6～7 to washing liquid pH value, obtains carboxylic carbon nano-tube；
The condition of described heating can be 120 DEG C of condensing refluxes；
(2) by the carboxylic carbon nano-tube proper amount of surfactant aid dispersion that obtains in step (1) in (such as 200ml,
Volume is more than 20 times of nanotube) in deionized water, ultrasonic 1-4h makes CNT fully dispersed；
(3) the carbon nano-tube aqueous solutions centrifugal 10-30min under 3000-6000r/min that will obtain in step (2),
Discarding the supernatant, lower floor separates out the most ultrasonic 10-30min of thing and disperses in deionized water, 3000-6000r/min the most again
Under be centrifuged 10-30min, discard the supernatant, lower floor separate out the most ultrasonic 10-30min of thing disperse in deionized water, as
This repetitive operation 2-10 time, removes free surfactant in aqueous, finally gives electrical conductivity and control 5～10
μS·cm-1CNT water system electrophoresis liquid；Thus effectively suppress the electrolysis of water；
(4) pole plate (such as 0.2 × 10 × 10mm) of two nugget genus is placed in parallel in above-mentioned CNT water system electrophoresis liquid,
Polar plate spacing controls 0.5～3cm, applies the DC voltage of 30～60V between two-plate, slow after deposition 0.5～10min
Slowly taking out metal polar plate, in being placed horizontally at fume hood, more than 10h air-dries, such as 24h natural air drying；
(5) annealing, makes annealing treatment at a temperature of 380～500 DEG C, or logical protective gas nitrogen, carbon dioxide or argon
Annealing；
Further, especially the metal polar plate after natural air drying in (4) is placed in the quartz boat in tube furnace, directly
Rise to a relatively low annealing temperature (450 ± 20 DEG C) with the heating rate of 10 ± 2 DEG C/min, be incubated 0.5～1h；Or
First it is passed through protective gas (N2/ Ar), rise to 450 DEG C with the heating rate of 10 DEG C/min again after 10min and be incubated 0.5～1h.
Surfactant described in step (2) is anionic surfactant dodecyl sodium sulfate (SDS) or 12
Sodium alkyl benzene sulfonate (SDBS) or nonionic surfactant triton x-100, addition is that 50mg(takes nanometer
The 5-40% of pipe quality).It is pretreated that the pole plate of metal is cleaned etc..
Metal polar plate material described in step (4) is rustless steel (316L), Cu, Al or Ti.
Described in step (4), preprocessing process is for first to clean with deionized water with acetone or alcohols solvent ultrasonic cleaning again.
The present invention passes through nitric acid treatment, introduces carboxyl in carbon nano tube surface, thus is substantially improved CNT in Metal Substrate
The adhesion of basal surface, then by the most ultrasonic centrifugal, free surfactant, carbon nano-tube aqueous solutions electrical conductivity control
Make at proper range, thus effectively suppress the electrolysis of water in electrophoresis process, then impose high DC electric field, on the one hand improve
Deposition velocity, improves CNT adhesive force, the final carbon obtaining the field emission performance with excellence the most further
Nanotube field emitter.
By the functionalization of CNT and the selection to metal polar plate material, present invention efficiently solves electrophoretic deposition
The problem that method prepares field emission body of Nano carbon tube poor adhesion；By the most ultrasonic being centrifuged, electrical conductivity of solution is controlled suitably
Scope, efficiently solve the electrolysis of electrophoretic deposition CNT water in aqueous solution and deposit uneven problem, finally
Obtain the field emission body of Nano carbon tube with stationary field emitting performance.
The invention has the beneficial effects as follows: the one of offer is improved electrophoretic deposition carbon nanotube field emitter in aqueous solution and launched steady
Method mainly has two aspect features qualitatively: first, by the functionalization of CNT and to metal polar plate material
Select, present invention efficiently solves the problem that electrophoretic deposition prepares field emission body of Nano carbon tube poor adhesion；Enhance
CNT and the bond strength of metallic substrates, add electron emission stability and the service life of field emission body.Second,
Control, in suitable scope, to efficiently solve electrophoresis in aqueous solution by electrical conductivity of solution by the most ultrasonic being centrifuged
The electrolysis of deposition of carbon nanotubes water and deposit uneven problem, is effectively increased being uniformly dispersed of CNT in emitter
Property, it is thus achieved that there is the field emission body of Nano carbon tube of stationary field emitting performance.
Accompanying drawing explanation
Fig. 1 is electrophoretic deposition set schematic diagram.
Detailed description of the invention
1. the preparation of carboxylic carbon nano-tube:
To be placed in purchased from the original carbon nanotubes of Chengdu organic chemistry company limited in the salpeter solution of suitably dilution, ultrasonic 3h
Or 120 DEG C of condensing reflux 3h, then with 0.45 μm cellulose mixture film sucking filtration, and be washed with deionized water to filtrate PH
Value is 6～7, obtains carboxylic carbon nano-tube.
2. the dispersion of CNT:
Above-mentioned gained carboxylic carbon nano-tube is placed in 200ml or above deionized water, in surfactant aid dispersion
Under ultrasonic 3h obtain CNT aqueous dispersions.
3. the preparation of CNT water system electrophoresis liquid:
Above-mentioned CNT aqueous dispersions is centrifuged 20min with the rotating speed of 4000r/min, discards the supernatant, lower leafing
Going out the most ultrasonic 20min of thing to be scattered in 200ml deionized water, such repeatable operation is for several times until ultrasonic rear gained solution
Electrical conductivity is at 10 μ S cm-1Hereinafter, then with 3000r/min be centrifuged 10min take the supernatant obtain CNT water system electricity
Swimming liquid.
4. electrophoretic deposition:
As it is shown in figure 1, two pieces of 0.2 × 10 × 10mm metal polar plates are used acetone ultrasonic cleaning in advance, then use deionized water
Cleaning, be then placed in parallel in above-mentioned CNT water system electrophoresis liquid, polar plate spacing 0.5～3cm, between two-plate
Apply the DC voltage of 30～60V, be slowly withdrawn metal polar plate after deposition 0.5～10min, be placed horizontally in fume hood
24h natural air drying.DC is DC source, and 1 is electrophoresis tank.
5. annealing:
Pole plate after above-mentioned natural air drying is placed in the quartz boat in tube furnace, directly with the heating rate of 10 DEG C/min
Rise to 450 DEG C, be incubated 0.5～1h；Or first it is passed through protective gas (N2/ Ar), again with the liter of 10 DEG C/min after 10min
Temperature speed rises to 450 DEG C and is incubated 0.5～1h.
Embodiment 1:
By 200mg CNT, (purity about 95%, purchased from many walls carbon of Chengdu organic chemistry company limited CVD growth
Nanotube, caliber 20-30nm, length 10-30 μm) join 50ml nitric acid and 150ml deionized water mixed solution
In, supersound process 3h, then with 0.45 μm cellulose mixture film sucking filtration, and be washed with deionized water to filtrate pH value be 6～7,
Obtain carboxylic carbon nano-tube.
Above-mentioned gained carboxylic carbon nano-tube is placed in 200ml deionized water, adds 50mg dodecyl sodium sulfate,
Ultrasonic disperse 3h obtains CNT aqueous dispersions.
Above-mentioned CNT aqueous dispersions is centrifuged 20min with the rotating speed of 4000r/min, discards the supernatant, lower metafiltration
Go out the most ultrasonic 20min of thing to be scattered in 200ml deionized water, so centrifugal ultrasonic 5 times, then with 3000r/min from
Heart 10min takes the supernatant and obtains CNT water system electrophoresis liquid.
150ml deionization is constant, and the nitric acid mixed solution carboxylation reaction using 40ml nitric acid or 60ml nitric acid to obtain obtains
To identical carboxylic carbon nano-tube.
Two pieces of 0.2 × 10 × 10mm stainless steel polar plates are used in advance acetone ultrasonic cleaning, then cleans with deionized water, then
It is placed in parallel in above-mentioned CNT water system electrophoresis liquid, polar plate spacing 1cm, between two-plate, applies the direct current of 60V
Voltage, is slowly withdrawn after deposition 5min, is placed horizontally at 24h natural air drying in fume hood.As pole plate uses spacing 2cm
Copper coin or titanium plate can obtain identical result the most completely.
Stainless steel polar plate after above-mentioned natural air drying is placed in the quartz boat in tube furnace, is passed through Ar, after 10min again with
The heating rate of 10 DEG C/min rises to 450 DEG C and is incubated 0.5h.Anneal all without significant difference for 380 DEG C, 420 DEG C, 500 DEG C.
Embodiment 2: dodecyl sodium sulfate in embodiment 1 is replaced with dodecylbenzene sodium sulfonate or triton x-100,
Other steps are with embodiment 1.
Embodiment 3: change supersound process 3h in carboxylic carbon nano-tube preparation process in embodiment 1 into 120 DEG C and condense back
Stream 3h, other steps are with embodiment 1.
Embodiment 4: stainless steel polar plate used in embodiment 1 electrophoretic deposition process is replaced with aluminium sheet, copper coin or titanium
Plate.Other steps are with embodiment 1.
Embodiment 5: the electrophoretic deposition time in embodiment 1 is replaced with 0.5min or 2min or 10min, other steps
With embodiment 1.
Embodiment 6: changing polar plate spacing in embodiment 1 electrophoretic deposition process into 0.5cm, voltage replaces with 30V, other
Step is with embodiment 1.
Embodiment 7: changing polar plate spacing in embodiment 1 electrophoretic deposition process into 3cm, other steps are with embodiment 1.
Embodiment 8: change not being passed through annealing process in embodiment 1 into protective gas, be directly warmed up to 450 DEG C, other
Step is with embodiment 1.
The present embodiment only gives the application examples that part is concrete, but for a person skilled in the art, also can according to
The change of equivalent is designed in upper enlightenment, and this is still considered to be covered by among the scope of protection of present invention.
Claims (4)
1. a preparation method for electrophoretic deposition carbon nanotube field emitter in aqueous solution, is characterized in that comprising the steps:
(1) ultrasonic at 20-35% nitric acid by weight concentration or under with heating condition process CNT obtain carboxylated carbon
Nanotube, supersound process 1-4h, with 0.45 μm mixed cellulose ester water system filter membrane sucking filtration, and use deionized water cyclic washing, extremely
Washing liquid pH value is 6 ~ 7, obtains carboxylic carbon nano-tube；
(2) by the carboxylic carbon nano-tube proper amount of surfactant aid dispersion that obtains in step (1) in deionized water, super
Sound 1-4h makes CNT fully dispersed；
(3) the carbon nano-tube aqueous solutions centrifugal 10-30min under 3000-6000r/min that will obtain in step (2), discards upper strata
Clear liquid, lower floor separates out the most ultrasonic 10-30min of thing and disperses in deionized water, more centrifugal 10-under 3000-6000r/min
30min, discards the supernatant, and lower floor separates out the most ultrasonic 10-30min of thing and disperses in deionized water, repeats operation 2-10
Secondary, remove free surfactant in aqueous, finally give electrical conductivity and control at 5 ~ 10 μ S cm-1CNT water
It it is electrophoresis liquid；Thus effectively suppress the electrolysis of water；
(4) two pieces of metal polar plates being placed in parallel in above-mentioned CNT water system electrophoresis liquid, polar plate spacing controls 0.5 ~
3cm, applies the DC voltage of 30 ~ 60V, is slowly withdrawn metal polar plate, is placed horizontally at logical after deposition 0.5 ~ 10min between two plates
Natural air drying in wind cupboard；Metal polar plate after natural air drying is placed in the quartz boat in tube furnace, directly with 10 ± 2 DEG C/min's
Heating rate rises to a relatively low annealing temperature 450 ± 20 DEG C, is incubated 0.5 ~ 1h；Or first it is passed through protective gas N2/ Ar,
Rise to 450 DEG C with the heating rate of 10 DEG C/min again after 10min and be incubated 0.5 ~ 1h.
In aqueous solution the most according to claim 1, the preparation method of electrophoretic deposition carbon nanotube field emitter, is characterized in that
The condition of described heating is 120 DEG C of condensing refluxes.
In aqueous solution the most according to claim 1, the preparation method of electrophoretic deposition carbon nanotube field emitter, is characterized in that
Surfactant described in step (2) be anionic surfactant dodecyl sodium sulfate or dodecylbenzene sodium sulfonate or
Person's nonionic surfactant triton x-100.
In aqueous solution the most according to claim 1, the preparation method of electrophoretic deposition carbon nanotube field emitter, is characterized in that
Described in step (4), metal polar plate material is rustless steel, Cu, Al or Ti.
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| CN1617954A (en) * | 2001-11-30 | 2005-05-18 | 北卡罗来纳-查佩尔山大学 | Deposition method for nanostructure materials |
| CN1691246A (en) * | 2004-04-22 | 2005-11-02 | 清华大学 | Method for preparing carbon nanometer tube field emission cathode |
| CN103030930A (en) * | 2011-09-30 | 2013-04-10 | 徐州师范大学 | Method for manufacturing carbon nano tube field emitter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1617954A (en) * | 2001-11-30 | 2005-05-18 | 北卡罗来纳-查佩尔山大学 | Deposition method for nanostructure materials |
| CN1691246A (en) * | 2004-04-22 | 2005-11-02 | 清华大学 | Method for preparing carbon nanometer tube field emission cathode |
| CN103030930A (en) * | 2011-09-30 | 2013-04-10 | 徐州师范大学 | Method for manufacturing carbon nano tube field emitter |
Non-Patent Citations (2)
| Title |
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| 基于丝网印刷技术的碳纳米管场发射冷阴极制作;李广山等;《光子学报》;20080930;第37卷(第9期);3.2.1、图2 * |
| 碳纳米管的低压化学气相沉积法制备及其应用研究;庞飞燕;《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》;20091215(第12期);第53页第2段、第55页第1段 * |
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