CN103456581B - Carbon nanotube field emission cathode and preparation method thereof - Google Patents
Carbon nanotube field emission cathode and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of carbon nanotube field emission cathode and preparation method thereof.This carbon nanotube field emission cathode includes electrically-conductive backing plate and the graphene layer stacked gradually on described electrically-conductive backing plate and carbon nanotube layer.The theoretical specific surface area of Graphene is up to 2600m2/ g, the two-dimensional structure of its uniqueness can carry out effective electric heating transmission, there is the calorifics more excellent than CNT and electric property, graphene layer is set between electrically-conductive backing plate and carbon nanotube layer, give full play to the characteristic that Graphene specific surface area is huge and conductive radiator is excellent, the adhesive force of carbon nanotube layer can be improved, improve emission current and stability.
Description
Technical field
The present invention relates to Flied emission technical field, particularly relate to a kind of carbon nanotube field emission cathode and system thereof
Preparation Method.
Background technology
CNT is a kind of Novel Carbon Nanomaterials, and it has the conductivity of excellence, by nano level tip
And the feature such as the outstanding electron emissivity produced and stable mechanochemistry characteristic, it is a kind of preferable
Field emmision material, show as can instant on switch, threshold electric field is low, and emission is big, is expected on the scene
It is used widely in the field of penetrating.
It is critical only that of CNT application in Flied emission is prepared and can be launched electronics, transmitting by continuous-stable
The carbon nanotube cathod that electric current is bigger.At present, conventional method include chemical vapor deposition (CVD) method,
Silk screen print method and electrophoresis method.Wherein, electrophoresis method technique is simple and easy to control, and manufacturing cycle is short, Ke Yi
On the substrate of arbitrary shape and size, large area prepares carbon nanotube field emission cathode, and actual application prospect is wide.
It is to be dispersed in water or organic solvent, CNT, dispersant, charge additive etc. at direct current
Or under AC field effect, CNT is to anode or movable cathode, and deposits on electrically-conductive backing plate.Electricity
Swimming method has problems in that, carbon nanotube layer is more weak with the adhesion of electrically-conductive backing plate, and contact resistance is big, leads
Causing Flied emission electric current less, transmitting is not sufficiently stable.
Summary of the invention
Based on this, it is necessary to for providing, a kind of emission current is relatively big, launch more stable carbon nano tube field sends out
Penetrate negative electrode.
A kind of carbon nanotube field emission cathode, including electrically-conductive backing plate with stack gradually on described electrically-conductive backing plate
Graphene layer and carbon nanotube layer.
Wherein in an embodiment, the material of described graphene layer includes Graphene and the first charge additive.
Wherein in an embodiment, the quality of described first charge additive is the quality of described Graphene
0.13～64%.
Wherein in an embodiment, described first charge additive be magnesium ion, aluminium ion, nickel ion,
Iron ion or silver ion.
Wherein in an embodiment, the material of described carbon nanotube layer includes that CNT and the second electric charge add
Add agent.
Wherein in an embodiment, the quality of described second charge additive is the quality of described CNT
0.13～64%.
Wherein in an embodiment, described second charge additive be magnesium ion, aluminium ion, nickel ion,
Iron ion or silver ion.
Wherein in an embodiment, the thickness of described graphene layer is 0.1 micron～1 micron.
Wherein in an embodiment, the thickness of described carbon nanotube layer is 1 micron～10 microns.
The preparation method of a kind of carbon nanotube field emission cathode, comprises the steps:
Electrically-conductive backing plate is provided；
The preparation electrophoresis liquid containing Graphene and the electrophoresis liquid containing CNT respectively；
Being put into by described electrically-conductive backing plate in the described electrophoresis liquid containing Graphene, electrophoretic deposition Graphene is in institute
State on electrically-conductive backing plate, obtain being laminated with the electrically-conductive backing plate of graphene layer；And
The described electrically-conductive backing plate being laminated with graphene layer is put in the described electrophoresis liquid containing CNT, electricity
On swimming deposition of carbon nanotubes extremely described graphene layer, cambium layer is laminated on the carbon nanotube layer on described graphene layer,
Obtain described carbon nanotube field emission cathode.
Wherein in an embodiment, also include the step dried by described carbon nanotube layer.
Wherein in an embodiment, described described electrically-conductive backing plate is put into the described electrophoresis liquid containing Graphene
In, electrophoretic deposition Graphene on described electrically-conductive backing plate, obtains being laminated with the electrically-conductive backing plate of graphene layer
In step, the voltage of described electrophoresis is 100 volts～200 volts, and the time of electrophoresis is 10 seconds～60 seconds.
Wherein in an embodiment, described described electrically-conductive backing plate is put into the described electrophoresis liquid containing Graphene
In, electrophoretic deposition Graphene on described electrically-conductive backing plate, obtains being laminated with the electrically-conductive backing plate of graphene layer
In step, with described electrically-conductive backing plate as negative electrode, conductive substrate is as anode, described negative electrode and the distance of anode
It it is 0.1 centimetre～5 centimetres.
Wherein in an embodiment, described the described electrically-conductive backing plate being laminated with graphene layer is put into described in contain
Having in the electrophoresis liquid of CNT, on electrophoretic deposition CNT to described graphene layer, cambium layer is laminated on institute
Stating in the step of the carbon nanotube layer on graphene layer, the voltage of described electrophoresis is 100 volts～200 volts, electricity
The time of swimming is 1 minute～5 minutes.
Wherein in an embodiment, described the described electrically-conductive backing plate being laminated with graphene layer is put into described in contain
Having in the electrophoresis liquid of CNT, on electrophoretic deposition CNT to described graphene layer, cambium layer is laminated on institute
State in the step of the carbon nanotube layer on graphene layer, using the described electrically-conductive backing plate of Graphene that is laminated with as the moon
Pole, conductive substrate is as anode, and the distance of described negative electrode and anode is 0.1 centimetre～5 centimetres.
Above-mentioned carbon nanotube field emission cathode includes electrically-conductive backing plate and the Graphene stacking gradually on electrically-conductive backing plate
Layer and carbon nanotube layer, the theoretical specific surface area of Graphene is up to 2600m2/ g, the two-dimensional structure energy of its uniqueness
Enough carry out effective electric heating transmission, there is the calorifics more excellent than CNT and electric property, in conduction
Graphene layer is set between substrate and carbon nanotube layer, give full play to Graphene specific surface area huge and conduction
The characteristic that heat radiation is excellent, it is possible to increase the adhesive force of carbon nanotube layer, improves emission current and stability.
Accompanying drawing explanation
Fig. 1 is the structural representation of the carbon nanotube field emission cathode of an embodiment；
Fig. 2 is the flow chart of the preparation method of the carbon nanotube field emission cathode of an embodiment；
Fig. 3 is that the emission current I of the carbon nanotube field emission cathode of embodiment 1 and comparative example 1 is with electric field E
Change curve；
Fig. 4 be the Flied emission electric current I of the carbon nanotube field emission cathode of embodiment 1 and comparative example 1 in time
Change curve.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, the most right
The detailed description of the invention of the present invention is described in detail.Elaborate in the following description a lot of detail with
It is easy to fully understand the present invention.But the present invention can come real to be a lot different from alternate manner described here
Executing, those skilled in the art can do similar improvement in the case of intension of the present invention, therefore this
Bright do not limited by following public being embodied as.
Referring to Fig. 1, the carbon nanotube field emission cathode 100 of an embodiment, including electrically-conductive backing plate 10 He
Stack gradually the graphene layer 20 on conductive laminate 10 and carbon nanotube layer 30.
In the present embodiment, electrically-conductive backing plate 10 be stainless steel substrate, titanium-base, copper base, aluminium base,
The metal basal board such as chrome substrate or ni substrate.
In another embodiment, electrically-conductive backing plate 10 for be plated with tungsten, molybdenum, titanium, nickel, chromium, gold, silver or
The insulated substrate of the metal coatings such as platinum, wherein, insulated substrate is glass, pottery or silicon chip.
In other embodiments, electrically-conductive backing plate 10 is indium tin oxide electro-conductive glass (ito glass).
The material of graphene layer 20 includes Graphene and the first charge additive.
Graphene is a kind of New Two Dimensional carbon nanomaterial, and its theoretical specific surface area is up to 2600m2/ g so that
Carbon nanometer layer 30 can relatively reliable be attached on graphene layer 20, is conducive to improving carbon nano tube field-emission
The launch stability of negative electrode 100.
Graphene can be the mixing of single-layer graphene, multi-layer graphene or single-layer graphene and multi-layer graphene
Thing.Can be graphene oxide or reduced graphene.
Preferably, the thickness of reduced graphene is 1.1 nanometers～3.7 nanometers, and the thickness of graphene oxide is 5.0
Nanometer～8.6 nanometers.
The two-dimensional structure of Graphene uniqueness can carry out effective electric heating transmission, has more excellent than CNT
Different thermal property and electric property, its thermal conductivity reaches 3000W/ (m K), and room temperature electron mobility reaches
15000cm2/(V·s).Therefore, graphene layer 20 has preferable thermal property and electric property.
First charge additive is soluble metal ion, preferably magnesium ion (Mg2+), aluminium ion (Al3+),
Nickel ion (Ni2+), iron ion (Fe3+) or silver ion (Ag+).
Preferably, the quality of the first charge additive be Graphene quality 0.13～64%.
Preferably, the thickness of graphene layer 20 is 0.1 micron～1 micron.0.1 micron～1 micron this thickness
In the range of degree, graphene layer 20 can form the thin film of more uniformly continuous, follow-up CNT
Uniform deposition and conductive and heat-conductive.
The material of carbon nanotube layer 30 includes CNT and the second charge additive.
CNT can be SWCN, multi-walled carbon nano-tubes, modified SWCN and
At least one in modified multi-walled carbon nano-tubes.
A diameter of 2 nanometers of CNT～20 nanometers, a length of 1 micron～100 microns, length is preferably
1～20 micron.
Second charge additive is soluble metal ion, preferably magnesium ion (Mg2+), aluminium ion (Al3+),
Nickel ion (Ni2+), iron ion (Fe3+) or silver ion (Ag+).
Preferably, the quality of the second charge additive be CNT quality 0.13～64%.
Preferably, the thickness of carbon nanotube layer 30 is 1 micron～10 microns.1 micron～the thickness of 10 microns
In the range of degree, the uniformity of carbon nanotube layer 30 is preferable, obtains relatively reasonable carbon nanotube density simultaneously,
Be conducive to reducing the screen effect in emission process on the scene, thus improve field emission performance.
Above-mentioned carbon nanotube field emission cathode 100 arranges stone between electrically-conductive backing plate 10 and carbon nanotube layer 30
Ink alkene layer 20, Graphene and CNT are all carbon nanomaterials so that graphene layer 20 and carbon nanotube layer
Having the strongest Van der Waals force between 30, therefore carbon nanotube layer 30 can closely be combined with graphene layer 20,
Overcome ask more weak with electrically-conductive backing plate adhesion of carbon nanotube layer in the carbon nanotube field emission cathode of routine
Topic, improves the stability of emission current during Flied emission.
Further, Graphene has huge two-dimensional areas, and carbon nanotube layer 30 is by graphene layer 20 and conduction
Substrate 10 contacts, and owing to contact area increases, contact resistance is obviously reduced, thus improves emission current.
Owing to Graphene has the heat dispersion of excellence, make graphene layer 20 can discharge this carbon nanometer rapidly
The heat that pipe field-transmitting cathode 100 produces in emission process, prevents carbon nanotube layer 30 from damaging rapidly, enters
One step is conducive to improving launch stability, and improves service life.
Refer to Fig. 2, the preparation method of the carbon nanotube field emission cathode of an embodiment, comprise the steps:
Step S110: electrically-conductive backing plate is provided.
Electrically-conductive backing plate can be stainless steel substrate, titanium-base, copper base, aluminium base, chrome substrate or ni substrate
Deng metal basal board；Or for be plated with the exhausted of the metal coatings such as tungsten, molybdenum, titanium, nickel, chromium, gold, silver or platinum
Edge substrate, wherein insulated substrate is glass, pottery or silicon chip.
In other embodiment, electrically-conductive backing plate is ito glass.
Electrically-conductive backing plate is cleaned 10 minutes with acetone, EtOH Sonicate successively, then dries up with nitrogen, standby.
Step S120: the preparation electrophoresis liquid containing Graphene and the electrophoresis liquid containing CNT respectively.
By Graphene and the first electric charge additive ultrasonic disperse in the first organic solvent, preparation obtains containing stone
The electrophoresis liquid of ink alkene.
Graphene can be the mixing of single-layer graphene, multi-layer graphene or single-layer graphene and multi-layer graphene
Thing.Can be graphene oxide or reduced graphene.
Chemical vapour deposition technique and chemical method (Hummer method) can be used to prepare Graphene, it would however also be possible to employ
Commercially available Graphene.
First electric charge additive is soluble metal inorganic salt, preferably magnesium nitrate (Mg (NO3)2), magnesium chloride
(MgCl2), magnesium sulfate (MgSO4), aluminum nitrate (Al (NO3)3), aluminum chloride (AlCl3), Nickel dichloride. (NiCl2),
Iron chloride (FeCl3) or silver nitrate (AgNO3).
Graphene and the first electric charge additive are scattered in the first organic solvent simultaneously so that the first electric charge adds
Add the adsorption of metal ions in agent that is first electric charge additive on Graphene, make Graphene charged, to realize
Electrophoresis.
Preferably, the concentration of Graphene is 0.05mg/mL～0.5mg/mL.Select this concentration, make follow-up electrophoresis
The uniformity of deposition is preferable, prepares the more uniform graphene layer of thickness.Meanwhile, under this concentration,
Obtain an appropriate sedimentation rate.When the concentration of Graphene is more than 0.5mg/mL, should be containing Graphene
The bad dispersibility of electrophoresis liquid, deposition effect is bad；When the concentration of Graphene is less than 0.05mg/mL, heavy
Long-pending speed is too slow, and preparation efficiency is low.
Preferably, the quality of the first electric charge additive is the 1～100% of the quality of Graphene, in the range of this
Electrophoretic deposition process can be realized with comparalive ease.When the consumption of the first electric charge additive is less than Graphene quality
1% time, very little, electrophoresis is difficult to the electrically charged amount of Graphene；When the consumption of the first electric charge additive is big
When the 100% of Graphene quality, electrophoresis liquid does not have the ion of absorption move to electrode, it is suppressed that Graphene
To movable cathode, also it is unfavorable for electrophoresis.
It is highly preferred that the quality of the first electric charge additive accounts for the 25～50% of the quality of Graphene.
Preferably, the first organic solvent is at least one in methanol, ethanol, propanol and acetone, is preferably
Ethanol.
By CNT and the second electric charge additive ultrasonic disperse in the second organic solvent, preparation is contained
The electrophoresis liquid of CNT.
CNT can be SWCN, multi-walled carbon nano-tubes, modified SWCN and
At least one in modified multi-walled carbon nano-tubes.
A diameter of 2 nanometers of CNT～20 nanometers, a length of 1 micron～100 microns.Length is preferably
1～20 micron.
CNT can use universal method such as arc discharge method, chemical vapour deposition technique or laser ablation method
Deng preparation, it would however also be possible to employ commercially available CNT.
Second electric charge additive is soluble metal inorganic salt, preferably magnesium nitrate (Mg (NO3)2), magnesium chloride
(MgCl2), magnesium sulfate (MgSO4), aluminum nitrate (Al (NO3)3), aluminum chloride (AlCl3), Nickel dichloride. (NiCl2),
Iron chloride (FeCl3) or silver nitrate (AgNO3).
CNT and the second electric charge additive are scattered in the second organic solvent simultaneously so that the second electric charge
Adsorption of metal ions in additive that is second electric charge additive, on CNT, makes CNT charged,
To realize electrophoresis.
Preferably, the concentration of CNT is 0.01mg/mL～0.1mg/mL.Select this concentration, make follow-up electricity
The uniformity of swimming deposition is preferable, prepares the more uniform carbon nanotube layer of thickness.Meanwhile, in this concentration
Under, it is thus achieved that an appropriate sedimentation rate.When the concentration of CNT is more than 0.1mg/mL, this contains
The bad dispersibility of the electrophoresis liquid of CNT, deposition effect is bad；When the concentration of CNT is less than
During 0.01mg/mL, sedimentation rate is too slow, and preparation efficiency is low.
Preferably, the quality of the second electric charge additive is the 1～100% of the quality of CNT, in this scope
In can realize electrophoretic deposition process with comparalive ease.When the consumption of the second electric charge additive is less than CNT
Quality 1% time, very little, electrophoresis is difficult to the electrically charged amount of CNT；When the second electric charge additive
When consumption is more than the 100% of carbon nanotube mass, electrophoresis liquid does not have the ion of absorption move to electrode, suppression
CNT, to movable cathode, is also unfavorable for electrophoresis.
It is highly preferred that the quality of the second electric charge additive accounts for the 25～50% of the quality of CNT.
Preferably, the second organic solvent is at least one in methanol, ethanol, propanol and acetone, is preferably
Ethanol.
The preparation electrophoresis liquid containing Graphene and the ultrasonic disperse equipment used by electrophoresis liquid containing CNT are
Supersonic cleaning machine or biomixer.The time of ultrasonic disperse is preferably 1 hour～3 hours.
Step S130: put into by electrically-conductive backing plate in the electrophoresis liquid containing Graphene, electrophoretic deposition Graphene is to leading
On electric substrate, obtain being laminated with the electrically-conductive backing plate of graphene layer.
The electrically-conductive backing plate of step S110 is put in the electrophoresis liquid containing Graphene as negative electrode, simultaneously will conduction
Substrate is put in this electrophoresis liquid containing Graphene as anode and is carried out electrophoresis.At direct current or the work of AC field
Under with, with the Graphene of electric charge to movable cathode, make to be deposited on the Graphene of electric charge on electrically-conductive backing plate,
Cambium layer is laminated on the graphene layer on electrically-conductive backing plate, obtains being laminated with the electrically-conductive backing plate of graphene layer.
Conductive substrate as anode is metal substrate, preferably anaerobic copper sheet or stainless steel substrates.
The thickness of graphene layer was controlled by voltage and the time of electrophoresis.Preferably, the voltage of electrophoresis is 100
Lie prostrate～200 volts.The time of electrophoresis is 10 seconds～60 seconds.
The spacing of the electrically-conductive backing plate preferably as negative electrode and the conductive substrate as anode is 0.1 centimetre～5
Centimetre.Select this spacing, be conducive to reducing the edge effect existed between negative electrode and anode.It is highly preferred that
This spacing is 0.1 centimetre～1 centimetre.
Preferably, when shape and the shape of electrically-conductive backing plate of required graphene layer and follow-up carbon nanotube layer
Time different, in order to prepare the graphene layer and carbon nanotube layer with regular shape and accurate dimension,
Being pre-formed certain photoetching agent pattern on electrically-conductive backing plate, then redeposited Graphene, forms graphene layer.
Step S140: the electrically-conductive backing plate being laminated with graphene layer is put in the electrophoresis liquid containing CNT,
Electrophoretic deposition CNT is on graphene layer, and cambium layer is laminated on the carbon nanotube layer on graphene layer, obtains
Carbon nanotube field emission cathode.
The electrically-conductive backing plate being laminated with graphene layer step S130 prepared is put into as negative electrode and is received containing carbon
In the electrophoresis liquid of mitron, put in this electrophoresis liquid containing CNT as anode using conductive substrate simultaneously
Row electrophoresis.Under the effect of direct current or AC field, with the CNT of electric charge to movable cathode, make band
The CNT having electric charge is deposited on graphene layer, and cambium layer is laminated on carbon nanotube layer on graphene layer,
To carbon nanotube field emission cathode.
Conductive substrate as anode is metal substrate, preferably anaerobic copper sheet or stainless steel substrates.
The thickness of carbon nanotube layer was controlled by voltage and the time of electrophoresis.Preferably, the voltage of electrophoresis is
100 volts～200 volts.The time of electrophoresis is 1 minute～5 minutes.
The electrically-conductive backing plate being laminated with graphene layer preferably as negative electrode and the conductive substrate as anode
Spacing is 0.1 centimetre～5 centimetres.Select this spacing, be conducive to reducing the edge existed between negative electrode and anode
Effect.It is highly preferred that this spacing is 0.1 centimetre～1 centimetre.
On electrically-conductive backing plate, certain photoresist it was pre-formed before electrophoretic deposition Graphene prepares graphene layer
During pattern, after the carbon nanotube layer that electrophoresis cambium layer is laminated on graphene layer, then with dissolving photoresist
Solution photoetching agent pattern is removed, thus obtain that there is regular shape and the graphene layer of accurate dimension and carbon
Nanotube layer.
Preferably, after forming CNT, also include the step being dried, residual to remove in carbon nanotube layer
The organic solvent deposited, improves the adhesion of carbon nanotube layer and electrically-conductive backing plate, to improve launch stability.
Preferably, the step being dried is to be dried 1 hour～5 hours at 50 DEG C～100 DEG C.
The preparation method technique of above-mentioned carbon nanotube field emission cathode is simple, and without High Temperature High Pressure, energy consumption is low,
Preparation cost is low, beneficially promotion and application, it is possible to preparation cost is low, emission current is relatively big and launch stability
Higher carbon nanotube field emission cathode.
It is expanded on further below by way of specific embodiment.
Embodiment 1
Prepare carbon nanotube field emission cathode
(1) reduced graphene of thickness 1.1～3.7nm is added in dehydrated alcohol, and add 50%MgCl2
(in terms of Graphene quality), as the first electric charge additive, Graphene concentration is 0.05mg/ml, ultrasonic disperse
1h, obtains the electrophoresis liquid of graphene-containing；
(2) diameter is added in dehydrated alcohol less than 8nm, the multi-walled carbon nano-tubes of length 5～15 μm, and
Add 25%MgCl2(in terms of carbon nanotube mass) as the second electric charge additive, carbon nanotube concentration is
0.01mg/ml, ultrasonic disperse 1h, obtain the electrophoresis liquid of carbon nanotubes；
(3) using ito glass as electrically-conductive backing plate, using this electrically-conductive backing plate as negative electrode, using anaerobic copper sheet as
Anode, before using, priority acetone, EtOH Sonicate clean 10min, and nitrogen dries up.Then, by cleaning, do
Dry electrically-conductive backing plate and anaerobic copper sheet insert in the electrophoresis liquid of graphene-containing, negative electrode and anode spacing 0.1cm, directly
Flow electrophoresis voltage 120V, electrophoresis time 1min, deposited graphite alkene on electrically-conductive backing plate, cambium layer is laminated on conduction
Graphene layer on substrate；Wherein, the thickness of this graphene layer is 1 micron, the first electric charge in graphene layer
Additive Mg2+The quality that quality is Graphene 12%；
(4) using the above-mentioned electrically-conductive backing plate of graphene layer that is laminated with as negative electrode, using anaerobic copper sheet as anode,
The electrically-conductive backing plate and anaerobic copper sheet that are laminated with graphene layer are inserted in the electrophoresis liquid containing CNT, negative electrode
With anode spacing 0.1cm, direct current electrophoretic voltage 100V, electrophoresis time 5min, graphene layer deposits carbon
Nanotube, cambium layer is laminated on the carbon nanotube layer on graphene layer；Wherein, the thickness of carbon nanotube layer is 10
Micron, the second charge additive Mg in carbon nanotube layer2+The quality that quality is CNT 6%；
(5) sample that above-mentioned steps (4) prepares is vacuum dried 1 hour at 60 DEG C, obtains carbon
Nanotube field emitting cathode.
Embodiment 2
Prepare carbon nanotube field emission cathode
(1) graphene oxide of thickness 5.0～8.6nm is added in dehydrated alcohol, and add 1%Mg (NO3)2
(in terms of Graphene quality), as the first electric charge additive, Graphene concentration is 0.5mg/ml, ultrasonic disperse
1h, obtains the electrophoresis liquid of graphene-containing；
(2) by diameter less than 10～20nm, the SWCN of length 10～20 μm adds dehydrated alcohol
In, and add 1%Mg (NO3)2(in terms of carbon nanotube mass) is as the second electric charge additive, carbon nanometer
Pipe concentration is 0.1mg/ml, and ultrasonic disperse 3h obtains the electrophoresis liquid of carbon nanotubes；
(3) there is the glass substrate of layer of titanium metal as electrically-conductive backing plate using deposition, using this electrically-conductive backing plate as negative electrode,
Using stainless steel substrates as anode, before using, priority acetone, EtOH Sonicate clean 10min, and nitrogen dries up.So
After, electrically-conductive backing plate clean, that be dried and stainless steel substrates are inserted in the electrophoresis liquid of graphene-containing, negative electrode and sun
Die opening 5cm, direct current electrophoretic voltage 200V, electrophoresis time 10s, deposited graphite alkene on electrically-conductive backing plate,
Cambium layer is laminated on the graphene layer on electrically-conductive backing plate；Wherein, the thickness of this graphene layer is 0.1 micron, graphite
First charge additive Mg in alkene layer2+The quality that quality is Graphene 0.2%；
(4) using the above-mentioned electrically-conductive backing plate of graphene layer that is laminated with as negative electrode, using stainless steel substrates as anode,
The electrically-conductive backing plate and stainless steel substrates that are laminated with graphene layer are inserted in the electrophoresis liquid containing CNT, negative electrode
With anode spacing 5cm, direct current electrophoretic voltage 100V, electrophoresis time 1min, graphene layer deposits carbon and receives
Mitron, cambium layer is laminated on the carbon nanotube layer on graphene layer；Wherein, the thickness of carbon nanotube layer is 1 micro-
Rice, the second charge additive Mg in carbon nanotube layer2+The quality that quality is CNT 0.2%；
(5) sample that above-mentioned steps (4) prepares is vacuum dried 5 hours at 100 DEG C, obtains carbon
Nanotube field emitting cathode.
Embodiment 3
Prepare carbon nanotube field emission cathode
(1) reduced graphene of thickness 1.1～3.7nm is added in acetone, and add 100%Al (NO3)3
(in terms of Graphene quality), as the first electric charge additive, Graphene concentration is 0.1mg/ml, ultrasonic disperse
1h, obtains the electrophoresis liquid of graphene-containing；
(2) by diameter less than 10～20nm, the multi-walled carbon nano-tubes of length 50 μm adds in acetone, and adds
Add 100%Al (NO3)3(in terms of carbon nanotube mass) as the second electric charge additive, carbon nanotube concentration is
0.04mg/ml, ultrasonic disperse 3h, obtain the electrophoresis liquid of carbon nanotubes；
(3) there is the glass substrate of metallic silver layer as electrically-conductive backing plate using deposition, using this electrically-conductive backing plate as negative electrode,
Using stainless steel substrates as anode, before using, priority acetone, EtOH Sonicate clean 10min, and nitrogen dries up.So
After, electrically-conductive backing plate clean, that be dried coats SU-82025 photoresist, through whirl coating, front baking, exposure
And development, electrically-conductive backing plate is formed the circular photoetching agent pattern of a diameter of 3mm.Further, will be formed with
The electrically-conductive backing plate of circular photoetching agent pattern and stainless steel substrates insert in the electrophoresis liquid of graphene-containing, negative electrode and anode
Spacing 1cm, direct current electrophoretic voltage 100V, electrophoresis time 30s, deposited graphite alkene on electrically-conductive backing plate, shape
Become the graphene layer being laminated on electrically-conductive backing plate；Wherein, the thickness of this graphene layer is 0.6 micron, Graphene
First charge additive Al in Ceng3+The quality that quality is Graphene 12%；
(4) using the above-mentioned electrically-conductive backing plate of graphene layer that is laminated with as negative electrode, using stainless steel substrates as anode,
The electrically-conductive backing plate and stainless steel substrates that are laminated with graphene layer are inserted in the electrophoresis liquid containing CNT, negative electrode
With anode spacing 1cm, direct current electrophoretic voltage 200V, electrophoresis time 1min, graphene layer deposits carbon and receives
Mitron, cambium layer is laminated on carbon nanotube layer on graphene layer；Wherein, the thickness of carbon nanotube layer is 7 microns,
Second charge additive Al in carbon nanotube layer3+The quality that quality is CNT 12%；
(5) (SU-8Remover purchases the sample that above-mentioned steps (4) prepares to be put into SU-8 removing glue
Buy from MicroChem company of the U.S.) in solution, 80 DEG C of heating 1min, remove remaining photoresist, and use
Acetone and alcohol flushing are clean, obtain having regular shape and the graphene layer of accurate dimension and carbon nanotube layer；
(6) sample that above-mentioned steps (5) prepares is vacuum dried 5 hours at 60 DEG C, obtains carbon
Nanotube field emitting cathode.
Comparative example 1
Prepare carbon nanotube field emission cathode
(1) diameter is added in dehydrated alcohol less than 8nm, the multi-walled carbon nano-tubes of length 5～15 μm, and
Add 25%MgCl2(in terms of carbon nanotube mass) as the second electric charge additive, carbon nanotube concentration is
0.01mg/ml, ultrasonic disperse 1h, obtain the electrophoresis liquid of carbon nanotubes；
(2) using ito glass as electrically-conductive backing plate, using this electrically-conductive backing plate as negative electrode, using anaerobic copper sheet as
Anode, before using, priority acetone, EtOH Sonicate clean 10min, and nitrogen dries up.Then, by cleaning, do
Dry electrically-conductive backing plate and anaerobic copper sheet insert in the electrophoresis liquid of carbon nanotubes, negative electrode and anode spacing 0.1cm,
Direct current electrophoretic voltage 100V, electrophoresis time 5min, deposition of carbon nanotubes on electrically-conductive backing plate, cambium layer is laminated on
Carbon nanotube layer on electrically-conductive backing plate；Wherein, the thickness of this carbon nanotube layer is 10 microns, carbon nanotube layer
In the first charge additive Mg2+The quality that quality is CNT 6%；
(3) sample that above-mentioned steps (2) prepares is vacuum dried 1 hour at 60 DEG C, obtains carbon
Nanotube field emitting cathode.
Diode structure is used respectively the carbon nanotube field emission cathode of preparing of embodiment 1 and comparative example 1 to be entered
Row electron field emission property is tested.Test result is as it is shown on figure 3, the carbon nano tube field of embodiment 1 preparation is sent out
The threshold electric field penetrating negative electrode (curve A) is 1.8V/ μm, cloudy with the carbon nano tube field-emission of comparative example 1 preparation
The threshold electric field of pole (curve B) is that 2.9V/ μm is compared, and have dropped 38%.When electric field intensity is 6V/ μm
Time, the cathode current emission increases to 2.3mA from 1mA, adds 130%.
The carbon nanotube field emission cathode prepared embodiment 1 and comparative example 1 respectively carries out field emission stability
Test, as shown in Figure 4.Result shows, the carbon nanotube field emission cathode of embodiment 1 preparation has well
Launch stability, emission current kept stable in the DC test time of 8h, illustrate that embodiment 1 is made
Carbon nanotube layer and the electrically-conductive backing plate of standby carbon nanotube field emission cathode are firmly combined with.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed,
But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for this area
Those of ordinary skill for, without departing from the inventive concept of the premise, it is also possible to make some deformation and
Improving, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended
Claim is as the criterion.
Claims (6)
1. a preparation method for carbon nanotube field emission cathode, comprises the steps:
Electrically-conductive backing plate is provided；
The preparation electrophoresis liquid containing Graphene and the electrophoresis liquid containing CNT respectively；
Being put into by described electrically-conductive backing plate in the described electrophoresis liquid containing Graphene, electrophoretic deposition Graphene is in institute
State on electrically-conductive backing plate, obtain being laminated with the electrically-conductive backing plate of graphene layer；And
The described electrically-conductive backing plate being laminated with graphene layer is put in the described electrophoresis liquid containing CNT, electricity
On swimming deposition of carbon nanotubes extremely described graphene layer, cambium layer is laminated on the carbon nanotube layer on described graphene layer,
Obtain described carbon nanotube field emission cathode；
Wherein, by CNT and the second electric charge additive ultrasonic disperse in the second organic solvent, prepare
To the electrophoresis liquid containing CNT, the quality of the second electric charge additive is the quality of CNT
1～100%, a diameter of 10 nanometers of CNT～20 nanometers, a length of 10 microns～20 microns；In shape
After becoming carbon nanotube layer, also include the step being dried, to remove the organic solvent of residual in carbon nanotube layer,
The step being dried is to be dried 1 hour～5 hours at 50 DEG C～100 DEG C.
The preparation method of carbon nanotube field emission cathode the most according to claim 1, it is characterised in that
Described being put into by described electrically-conductive backing plate in the described electrophoresis liquid containing Graphene, electrophoretic deposition Graphene is in institute
Stating on electrically-conductive backing plate, obtain being laminated with in the step of the electrically-conductive backing plate of graphene layer, the voltage of described electrophoresis is
100 volts～200 volts, the time of electrophoresis is 10 seconds～60 seconds.
The preparation method of carbon nanotube field emission cathode the most according to claim 1, it is characterised in that
Described being put into by described electrically-conductive backing plate in the described electrophoresis liquid containing Graphene, electrophoretic deposition Graphene is in institute
State on electrically-conductive backing plate, obtain being laminated with in the step of the electrically-conductive backing plate of graphene layer, with described electrically-conductive backing plate be
Negative electrode, conductive substrate is as anode, and the distance of described negative electrode and anode is 0.1 centimetre～5 centimetres.
The preparation method of carbon nanotube field emission cathode the most according to claim 1, it is characterised in that
Described the described electrically-conductive backing plate being laminated with graphene layer is put in the described electrophoresis liquid containing CNT, electricity
On swimming deposition of carbon nanotubes extremely described graphene layer, cambium layer is laminated on the carbon nanotube layer on described graphene layer
Step in, the voltage of described electrophoresis is 100 volts～200 volts, and the time of electrophoresis is 1 minute～5 minutes.
The preparation method of carbon nanotube field emission cathode the most according to claim 1, it is characterised in that
Described the described electrically-conductive backing plate being laminated with graphene layer is put in the described electrophoresis liquid containing CNT, electricity
On swimming deposition of carbon nanotubes extremely described graphene layer, cambium layer is laminated on the carbon nanotube layer on described graphene layer
Step in, using the described electrically-conductive backing plate of Graphene that is laminated with as negative electrode, conductive substrate is as anode, institute
The distance stating negative electrode and anode is 0.1 centimetre～5 centimetres.
6. prepared by the preparation method of carbon nanotube field emission cathode as described in Claims 1 to 5 any one
Carbon nanotube field emission cathode.
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| CN104241062B (en) * | 2014-09-12 | 2016-08-24 | 中国科学院深圳先进技术研究院 | Carbon nanotube emission cathode preparation method and carbon nanotube emission negative electrode |
| CN104409303A (en) * | 2014-10-31 | 2015-03-11 | 深圳先进技术研究院 | X ray source based on carbon nanotube/graphite alkene composite cathode structure |
| CN105514344B (en) * | 2015-11-28 | 2018-09-07 | 哈尔滨工业大学 | The method that lithium ion battery cathode surface is modified is realized by electrophoretic deposition graphene |
| CN105513921B (en) * | 2015-12-25 | 2017-11-10 | 深圳先进技术研究院 | Carbon nanometer field-transmitting cathode and its preparation method and application |
| CN105470078A (en) * | 2015-12-29 | 2016-04-06 | 无锡吉仓纳米材料科技有限公司 | Focused tripolar structured fully-packaged X-ray bulb tube based on carbon nanotube cold cathode |
| CN107314353B (en) * | 2017-07-03 | 2020-06-02 | 鄂尔多斯市紫荆创新研究院 | Graphene metal composite multilayer radiator with high heat conductivity and preparation method thereof |
| CN108172488B (en) * | 2017-12-26 | 2020-10-23 | 深圳先进技术研究院 | Carbon nano field emission cathode and manufacturing method and application thereof |
| CN110277292B (en) * | 2019-05-08 | 2020-11-27 | 中山大学 | Medium-low temperature vacuum thermoelectric conversion device and preparation method thereof |
| CN115445888B (en) * | 2022-08-09 | 2023-04-28 | 哈尔滨工业大学 | Magnesium alloy-based layered composite material and preparation method thereof |
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