CN102347180B - CNT (carbon nano tube) cathode material and preparation method thereof - Google Patents
CNT (carbon nano tube) cathode material and preparation method thereof Download PDFInfo
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- CN102347180B CN102347180B CN201010240867.6A CN201010240867A CN102347180B CN 102347180 B CN102347180 B CN 102347180B CN 201010240867 A CN201010240867 A CN 201010240867A CN 102347180 B CN102347180 B CN 102347180B
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Abstract
The invention provides a CNT (carbon nano tube) cathode material comprising a conductive substrate, a CNT deposited on the conductive substrate, metal nano particles which are doped in the CNT, wherein the metal nano particles account for 0.3-20wt% of the CNT. According to the CNT (carbon nano tube) cathode material and a preparation method thereof, the metal nano particles and the CNT are deposited in the conductive substrate and subjected to the high-temperature processing, so that metallic oxides with electrical conductivity are formed between the CNT and the conductive substrate, thus the adhesive forces of the CNT and the conductive substrate are strengthened, thereby obviously improving the stability of emission currents in a field emission process. In addition, ohmic contact with low resistance is formed between the CNT and the conductive substrate so as to eliminate potential barriers between the CNT and the conductive substrate, thus a threshold electric field of the field emission is reduced remarkably, and the emission current density is improved effectively.
Description
[technical field]
The present invention relates to carbon nanotube cathode material, particularly relate to a kind of carbon nanotube cathod and preparation method thereof.
[background technology]
Field emission light source, as a kind of environmental protection lighting source, has the plurality of advantages such as fast, the frivolous and environmental suitability of energy savings, environmental protection, startup is strong, has huge development potentiality.Cold-cathode material is the core component of field emission light source, but traditional processing technology is complicated, and rate of finished products is not high, and cost is difficult to reduce.Carbon nano-tube is a kind of desirable one-dimensional material, it has very large draw ratio and minimum tip curvature radius, a very large field enhancement factor can be obtained under certain electric field, there is very excellent electron field emission property, therefore can adopt carbon nano-tube as cathode material to prepare field emission light source.
The preparation of carbon nanotube cathode material, first needs to prepare uniform carbon nano-tube film.The preparation method of traditional carbon nanotube cathod is divided into two classes usually, i.e. direct growth method and grafting.The advantage of direct growth method be carbon nano-tube and substrate good bonding strength, impurity is less and can form carbon nano pipe array according to certain cycle growth, but the growth temperature of direct growth method is higher than 600 DEG C, be difficult to realize large-area homoepitaxial in common substrate of glass.Grafting comprises electrophoresis, liquid phase deposition and silk screen print method etc., particularly, liquid phase deposition manufacturing cycle is long, and the carbon nano-tube thickness formed exists uneven phenomenon, and dispersion effect is bad, thus the emission effciency of carbon nano-tube is made to receive larger restriction.Carbon nanocapsule thin film Surface coating prepared by silk screen print method organic substance, is difficult to eliminate organic substance, affects the current density emission effciency of carbon nano-tube in the process of sintering.
And utilize the method for electrophoresis carbon nano-tube film depositing in conductive substrates in actual application, possessed the advantage that technique is simple, with low cost, manufacturing cycle is short, carbon nanotube cathode material prepared by the large area in enormous quantities that can realize some cycles array in the substrate of arbitrary shape, therefore has very large application prospect.Be uniformly dispersed although traditional electrophoresis prepares the preparation-obtained cathode material of method that carbon nano-tube prepares cathode material, there is carbon nano-tube and hold flaky phenomenon, thus cause the situation of field emission performance instability.
[summary of the invention]
Based on this, be necessary to provide a kind of carbon nanotube cathode material strengthening carbon nano-tube and substrate adhesion.
A kind of carbon nanotube cathode material, comprise electrically-conductive backing plate, the carbon nano-tube be deposited on described electrically-conductive backing plate, also comprise the metal nanoparticle be doped in described carbon nano-tube, the mass percent that described metal nanoparticle accounts for carbon nano-tube is 0.3% ~ 20%.
Preferably, described metal nanoparticle is at least one in silver nano-grain, indium oxide nano particle or copper nano particles.
In addition, there is a need to provide a kind of preparation method strengthening the carbon nanotube cathode material of carbon nano-tube and substrate adhesion.
A preparation method for carbon nanotube cathode material, comprises the steps: to provide conductive substrates and anode electrode; PAGE production liquid, described electrophoresis liquid comprises carbon nano-tube, Mg (NO
3)
2, and metal nanoparticle; With described anode electrode for positive pole, described conductive substrates is negative pole, in described electrophoresis liquid in metal nanoparticle described in electrophoretic deposition and described carbon nano-tube to described conductive substrates; Clean deposition has the conducting base of described metal nanoparticle and described carbon nano-tube, and heat-treats.
Preferably, also comprise before described electrophoresis step and described conductive substrates carried out ultrasonic cleaning respectively with acetone soln, ethanol solution and deionized water successively and dry.
Preferably, the step of described PAGE production liquid is by carbon nano-tube, Mg (NO
3)
2, and metal nanoparticle be dissolved in the solution containing dispersant, the concentration of described carbon nano-tube is 1 ~ 15g/L, described Mg (NO
3)
2concentration be 0.8 ~ 5g/L, the concentration of metal nanoparticle is 0.05 ~ 0.2g/L.
Preferably, the condition of described electrophoresis step is electrophoretic deposition 3 ~ 30 minutes under the voltage conditions of 50 ~ 300V, and the distance of described electrically-conductive backing plate and anode electrode is 3 ~ 15 centimetres.
Preferably, described metal nanoparticle is at least one in silver nano-grain, indium oxide nano particle or copper nano particles.
Preferably, described conductive substrates is ito glass, and described anode electrode is at least one in copper electrode, platinum electrode or stainless steel electrode.
Preferably, described dispersant is isopropyl alcohol or isobutanol.
Preferably, described heat treated step is incubated 0.5 hour ~ 4 hours after sintering under the temperature conditions of 380 DEG C ~ 500 DEG C.
Metal nanoparticle and carbon nano-tube deposit in conductive substrates by electrophoresis by above-mentioned carbon nanotube cathode material and preparation method thereof, and pass through high-temperature heat treatment, thus between carbon nano-tube and conductive substrates, form the metal oxide with conductivity, make the Adhesion enhancement of carbon nano-tube and conductive substrates, significantly improve the stability of emission current in Flied emission process.In addition, owing to defining the ohmic contact of low resistance between carbon nano-tube and conductive substrates, to eliminate the potential barrier between carbon nano-tube and conductive substrates, the threshold field of Flied emission is obviously reduced, effectively improves emission.
[accompanying drawing explanation]
The schematic diagram of the electrophoresis experiment device that the preparation method that Fig. 1 is the carbon nanotube cathode material of an embodiment adopts.
[embodiment]
A kind of carbon nanotube cathode material, the metal nanoparticle comprising electrically-conductive backing plate, be deposited on the carbon nano-tube on described electrically-conductive backing plate and be doped in described carbon nano-tube, the mass percent that metal nanoparticle accounts for carbon nano-tube is 0.3% ~ 20%.
Metal nanoparticle is at least one in silver nano-grain, indium oxide nano particle or copper nano particles.The preparation method of above-mentioned carbon nanotube cathode material, comprises the steps:
(1) conductive substrates and anode electrode are provided.Conductive substrates is the glass containing conductive layer, such as, can be the glass containing indium tin oxide (Indium Tin Oxides, ITO), and anode electrode can be metal electrode, is preferably at least one in copper electrode, platinum electrode or stainless steel electrode.
(2) PAGE production liquid, described electrophoresis liquid comprises carbon nano-tube, Mg (NO
3)
2and metal nanoparticle.The step of PAGE production liquid is specifically: by carbon nano-tube, Mg (NO
3)
2, and metal nanoparticle be dissolved in the solution containing dispersant, by magnetic agitation or ultrasonic disperse even.Wherein, the concentration of carbon nano-tube is 1 ~ 15g/L, Mg (NO
3)
2concentration be 0.8 ~ 5g/L, metal nanoparticle is at least one in silver nano-grain, indium oxide nano particle or copper nano particles, and concentration is 0.05 ~ 0.2g/L, and dispersant is at least one in isopropyl alcohol or isobutanol.Mg (NO
3)
2as the solute in electrophoresis liquid,
(3) conductive substrates is carried out ultrasonic cleaning and drying respectively with acetone soln, ethanol solution and deionized water successively.The ultrasonic cleaning time is 5 ~ 60 minutes.
(4) take anode electrode as positive pole, conductive substrates is negative pole, and in electrophoresis liquid, electrophoretic deposition metal nanoparticle and carbon nano-tube are in conductive substrates.In the process of electrophoretic deposition, conductive substrates is preferably 3 ~ 15 centimetres as the distance of cathode electrode and anode electrode; Electrophoretic voltage is preferably 50 ~ 300V; Electrophoresis time is preferably 3 ~ 30 minutes.Electrophoresis liquid keeps magnetic agitation in electrophoresis process.
(5) use washed with de-ionized water to deposit the conducting base of metal nanoparticle and carbon nano-tube, and heat-treat.Use washed with de-ionized water conducting base, heat treated step be by cleaning after conductive substrates under the temperature conditions of 380 DEG C ~ 500 DEG C, sinter moisturizing afterwards 0.5 hour ~ 4 hours.
As shown in Figure 1, electrophoresis liquid is placed on magnetic stirring apparatus 10, be uniformly dispersed under the effect of magnetic stir bar 20, ito glass 30 is as cathode electrode, under the effect of DC power supply 50, electrophoretic deposition metal nanoparticle and carbon nano-tube are in ito glass 30, and anode electrode 40 is at least one in copper electrode, platinum electrode or stainless steel electrode.
Carbon nanotube cathode material of the present invention and preparation method thereof is elaborated below in conjunction with specific embodiment.
Embodiment 1
Select ito glass, use acetone soln, ethanol solution and deionized water ultrasonic cleaning 20 minutes successively and drying.Using the ito glass after cleaning-drying as negative electrode, platinum electrode is as anode, distance between the two poles of the earth is 10 centimetres, ito glass is placed in electric current liquid, the electrophoresis liquid that magnetic agitation prepares with electrophoretic deposition metal nanoparticle under the voltage conditions of 250V and carbon nano-tube to conductive substrates 10 minutes.Finally by after the conductive substrates washed with de-ionized water drying that deposited, sinter at 500 DEG C, and be incubated 3 hours and be cooled to room temperature, adhesive force can be obtained good, the minus plate that Flied emission current density is high.
Mg (the NO that in embodiment 1, electrophoresis liquid comprises carbon nano-tube that content is 1.5g, 40ml concentration is 1.48g/L
3)
2and content is the metal nanoparticle of 0.05g/L, solvent is the isopropyl alcohol of 100mL, and by magnetic stirrer or ultrasonic disperse even.
Embodiment 2
Select ito glass, use acetone soln, ethanol solution and deionized water ultrasonic cleaning 20 minutes successively and drying.Using the ito glass after cleaning-drying as negative electrode, platinum electrode is as anode, distance between the two poles of the earth is 15 centimetres, ito glass is placed in electric current liquid, the electrophoresis liquid that magnetic agitation prepares with electrophoretic deposition metal nanoparticle under the voltage conditions of 300V and carbon nano-tube to conductive substrates 20 minutes.Finally by after the conductive substrates washed with de-ionized water drying that deposited, sinter at 450 DEG C, and be incubated 4 hours and be cooled to room temperature, adhesive force can be obtained good, the minus plate that Flied emission current density is high.
Mg (the NO that in embodiment 2, electrophoresis liquid comprises carbon nano-tube that content is 4.2g, 80ml concentration is 1.48g/L
3)
2solution and content are the metal nanoparticle of 0.2g/L, and solvent is the isopropyl alcohol of 200mL, and by magnetic stirrer or ultrasonic disperse even.
Embodiment 3
Select ito glass, use acetone soln, ethanol solution and deionized water ultrasonic cleaning 20 minutes successively and drying.Using the ito glass after cleaning-drying as negative electrode, platinum electrode is as anode, distance between the two poles of the earth is 3 centimetres, ito glass is placed in electric current liquid, the electrophoresis liquid that magnetic agitation prepares with electrophoretic deposition metal nanoparticle under the voltage conditions of 150V and carbon nano-tube to conductive substrates 3 minutes.Finally by after the conductive substrates washed with de-ionized water drying that deposited, sinter at 380 DEG C, and be incubated 0.5 hour and be cooled to room temperature, adhesive force can be obtained good, the minus plate that Flied emission current density is high.
Mg (the NO that in embodiment 3, electrophoresis liquid comprises carbon nano-tube that content is 0.15g, 40ml concentration is 1.48g/L
3)
2solution and content are the metal nanoparticle of 0.15g/L, and solvent is the isopropyl alcohol of 110mL, and by magnetic stirrer or ultrasonic disperse even.
Embodiment 4
Select ito glass, use acetone soln, ethanol solution and deionized water ultrasonic cleaning 20 minutes successively and drying.Using the ito glass after cleaning-drying as negative electrode, platinum electrode is as anode, distance between the two poles of the earth is 8 centimetres, ito glass is placed in electric current liquid, the electrophoresis liquid that magnetic agitation prepares with electrophoretic deposition metal nanoparticle under the voltage conditions of 200V and carbon nano-tube to conductive substrates 15 minutes.Finally by after the conductive substrates washed with de-ionized water drying that deposited, sinter at 430 DEG C, and be incubated 2.5 hours and be cooled to room temperature, adhesive force can be obtained good, the minus plate that Flied emission current density is high.
Mg (the NO that in embodiment 4, electrophoresis liquid comprises carbon nano-tube that content is 2.4g, 80ml concentration is 1.48g/L
3)
2solution and content are the copper nano particles of 0.12g/L, and solvent is the isobutanol of 110mL, and by magnetic stirrer or ultrasonic disperse even.
Embodiment 5
Select ito glass, use acetone soln, ethanol solution and deionized water ultrasonic cleaning 20 minutes successively and drying.Using the ito glass after cleaning-drying as negative electrode, platinum electrode is as anode, distance between the two poles of the earth is 5 centimetres, ito glass is placed in electric current liquid, the electrophoresis liquid that magnetic agitation prepares with electrophoretic deposition metal nanoparticle under the voltage conditions of 100V and carbon nano-tube to conductive substrates 30 minutes.Finally by after the conductive substrates washed with de-ionized water drying that deposited, sinter at 400 DEG C, and be incubated 3 hours and be cooled to room temperature, adhesive force can be obtained good, the minus plate that Flied emission current density is high.
Mg (the NO that in embodiment 5, electrophoresis liquid comprises carbon nano-tube that content is 3.5g, 60ml concentration is 1.48g/L
3)
2solution and content are the copper nano particles of 0.1g/L, and solvent is the isobutanol of 200mL, and by magnetic stirrer or ultrasonic disperse even.
Metal nanoparticle and carbon nano-tube deposit in conductive substrates by electrophoresis by the preparation method of above-mentioned carbon nanotube cathode material, before pass through high-temperature heat treatment, thus between carbon nano-tube and conductive substrates, form the metal oxide with conductivity, make the Adhesion enhancement of carbon nano-tube and conductive substrates, the stability of emission current in Flied emission process of having fallen ill significantly, in addition, also between carbon nano-tube and conductive substrates, define the ohmic contact of low resistance, to eliminate the potential barrier between carbon nano-tube and conductive substrates, the threshold field of Flied emission is obviously reduced, effectively improve emission.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively 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 the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (1)
1. a preparation method for carbon nanotube cathode material, comprises the steps:
Select ito glass, use acetone soln successively, ethanol solution and deionized water ultrasonic cleaning also drying in 20 minutes, using the ito glass after cleaning-drying as negative electrode, platinum electrode is as anode, distance between the two poles of the earth is 8 centimetres, ito glass is placed in electric current liquid, the electrophoresis liquid that magnetic agitation prepares with electrophoretic deposition metal nanoparticle under the voltage conditions of 200V and carbon nano-tube to conductive substrates 15 minutes, finally by after the conductive substrates washed with de-ionized water drying that deposited, sinter at 430 DEG C, and be incubated 2.5 hours and be cooled to room temperature, adhesive force can be obtained good, the minus plate that Flied emission current density is high,
Mg (the NO that electrophoresis liquid comprises carbon nano-tube that content is 2.4g, 80ml concentration is 1.48g/L
3)
2solution and content are the copper nano particles of 0.12g/L, and solvent is the isobutanol of 110mL, and by magnetic stirrer or ultrasonic disperse even.
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| CN103515169B (en) * | 2012-06-21 | 2016-08-03 | 上海联影医疗科技有限公司 | A kind of nano field emission electron source and preparation method thereof |
| CN111081504B (en) * | 2019-12-10 | 2022-07-05 | 深圳先进技术研究院 | Field emission cathode and preparation method thereof |
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| CN1378700A (en) * | 1999-10-12 | 2002-11-06 | 松下电器产业株式会社 | Electron-emitting device and electron source comprising the same, field-emission image display, fluorescent lamp, and methods for producing them |
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| CN1209945C (en) * | 2001-11-29 | 2005-07-06 | 京东方科技集团股份有限公司 | Panel fluorescent source based on nano carbon tube and method for manufacturing same |
| CN100490076C (en) * | 2003-03-21 | 2009-05-20 | 北卡罗来纳-查佩尔山大学 | Self-assembly method, method for manufacturing cathode and device for depositing material |
| CN100565755C (en) * | 2005-04-18 | 2009-12-02 | 华东师范大学 | A kind of method with producing large-area field emitting cold cathode with composite nano-carbon film |
| CN101188179B (en) * | 2006-11-15 | 2010-05-26 | 清华大学 | Making method for field emission electron source |
| JP5272349B2 (en) * | 2007-02-26 | 2013-08-28 | 東レ株式会社 | Electron emission source paste and electron-emitting device |
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| CN1378700A (en) * | 1999-10-12 | 2002-11-06 | 松下电器产业株式会社 | Electron-emitting device and electron source comprising the same, field-emission image display, fluorescent lamp, and methods for producing them |
| CN1711620A (en) * | 2002-10-09 | 2005-12-21 | 毫微-专卖股份有限公司 | Enhanced field emission from carbon nanotubes mixed with particles |
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| CN1897204A (en) * | 2005-07-15 | 2007-01-17 | 清华大学 | Field-transmitting cathode, its production and planar light source |
| CN101593568A (en) * | 2008-05-30 | 2009-12-02 | 三星电机株式会社 | The electrocondution slurry and the printed circuit board (PCB) that uses it that contain carbon nano-tube |
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