CN104241062A - Carbon nano tube emitting cathode preparation method and carbon nano tube emitting cathode - Google Patents
Carbon nano tube emitting cathode preparation method and carbon nano tube emitting cathode Download PDFInfo
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- CN104241062A CN104241062A CN201410466558.9A CN201410466558A CN104241062A CN 104241062 A CN104241062 A CN 104241062A CN 201410466558 A CN201410466558 A CN 201410466558A CN 104241062 A CN104241062 A CN 104241062A
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Abstract
The invention discloses a carbon nano tube emitting cathode preparation method and a carbon nano tube emitting cathode. The method includes the steps that graphene and metal solubility inorganic salt serving as a catalyst are added into organic solvent according to the predetermined proportion, and accordingly a graphene electrophoresis solution with a positive charge is obtained; a conducting substrate is used as a cathode, an anode and the cathode are arranged in the graphene electrophoresis solution, an electric field is additionally arranged, and a graphene layer structure which is deposited on the conducting substrate is obtained; the graphene layer structure which is deposited on the conducting substrate is placed into a vapor deposition furnace for growing carbon nano tubes. Due to the fact that an electrophoretic deposition method is used for manufacturing the graphene layer structure which is deposited on the conducting substrate, a plurality of valley structures are formed, when the carbon nano tubes are distributed in the valley terrains, and the reliability of the cathode is improved; the graphene is used as a good conductive connecting body and is inserted into a carbon nano tube network structure, and therefore the conduction performance of electrons in a carbon nano tube network is improved.
Description
Technical field
The application relates to Flied emission technology, particularly relates to a kind of carbon nanotube emission cathode preparation method and carbon nanotube emission negative electrode.
Background technology
Carbon nano-tube is a kind of Novel Carbon Nanomaterials, compared with other materials existing, there is excellent conductive and heat-conductive characteristic, the features such as the outstanding electron emissivity produced by nano level tip and stable mechanochemistry performance, it is a kind of desirable field emmision material, show as can instant on switch, threshold electric field low and emission large, be expected to be used widely in fields such as vacuum microwave device, Field Emission Display and New X radiographic sources.
In order to realize the application of carbon nano-tube at feds, needing assembling or deposition of carbon nanotubes on substrate, obtaining carbon nanotube cathod unit are with high emission electric current and high stability.This assemble method to be included on substrate direct growth carbon nano-tube and the carbon nano-tube of growth to be peeled off and be assembled on another substrate.On substrate, direct growth carbon nano-tube commonly uses chemical vapour deposition (CVD).It passes in high temperature furnace by carbonaceous gas (as methane, ethene and acetylene etc.) and reducibility gas (as hydrogen), and carbonaceous gas generation pyrolysis, the carbon atom of generation forms carbon nano-tube under catalyst action.Chemical vapour deposition (CVD) can realize in enormous quantities, the controllable growth of carbon nano-tube.On the other hand, when the carbon nano-tube grown is stripped and is assembled on another substrate, in order to improve the adhesion with substrate, usually binding agent and carbon nano-tube are mixed and made into slurry, then substrate surface is coated on, and through super-dry, sintering and obtain carbon nano-tube film.Due to the insulating properties of these binding agents itself, compared with direct growth method, the conductivity between carbon nano-tube and between carbon nano-tube and substrate significantly reduces.
Utilize chemical vapour deposition (CVD) directly in grown on substrates carbon nano-tube, because the contact area of carbon nano-tube and substrate is minimum, cause adhesion very weak, contact resistance is large, reduces emission current and the reliability of carbon nanotube cathod.
Summary of the invention
The application provides a kind of carbon nanotube emission cathode preparation method and carbon nanotube emission negative electrode.
According to the first aspect of the application, the application provides a kind of carbon nanotube emission cathode preparation method, comprising:
Using Graphene, add in organic solvent as the metal soluble inorganic salt of catalyst according to predetermined ratio, obtained positively charged Graphene electrophoresis solution;
Use electrically-conductive backing plate as negative electrode, respectively anode and described negative electrode are placed in described Graphene electrophoresis solution, extra electric field, the obtained Graphene layer structure be deposited on described electrically-conductive backing plate;
The described Graphene layer structure be deposited on described electrically-conductive backing plate is put into gaseous phase deposition stove carbon nano-tube.
In said method, described metal soluble inorganic salt comprises one or more the mixture in the soluble inorganic salt of iron, nickel and cobalt.
In said method, described metal soluble inorganic salt comprises the nitrate of iron, nickel and cobalt and the villaumite of iron, nickel and cobalt.
In said method, the weight ratio of described metal soluble inorganic salt and described Graphene is 2 ~ 10.
In said method, described Graphene comprises single-layer graphene and/or multi-layer graphene.
In said method, the concentration of described Graphene electrophoresis solution is 0.02 ~ 0.1mg/ml.
In said method, described the described Graphene layer structure be deposited on described electrically-conductive backing plate is put into gaseous phase deposition stove carbon nano-tube, specifically comprises:
Described cvd furnace is vacuumized, heats up after passing into the inert gas of certain pressure intensity, after reaching growth temperature, towards hydrogen, insulation a period of time, then pass into hydrocarbon gas, carbon nano-tube.
In said method, the pressure of described inert gas is for being 5 ~ 30KPa, and described growth temperature is 600 ~ 800 DEG C.
In said method, described hydrocarbon gas comprises methane, ethene and/or acetylene, and described hydrogen and described hydrocarbon gas flow ratio are 2.5 ~ 10.
According to the second aspect of the application, the application provides a kind of carbon nanotube emission negative electrode using said method to prepare.
Owing to have employed above technical scheme, the beneficial effect that the application is possessed is:
In the embodiment of the application, the Graphene layer structure be deposited on electrically-conductive backing plate is obtained owing to using electrophoretic deposition, Graphene becomes 1 ° ~ 90 ° angular array with substrate, form a lot of paddy shape structure, when carbon nano-tube is distributed in these paddy shape landform, what obtain mechanically due to the protection of Graphene is stable, improves the reliability of negative electrode; Graphene, as good conduction connector, inserts in carbon nanotube network, improves the conductive performance of electronics in carbon nano tube network, be conducive to the Flied emission of carbon nano-tube; The fabulous heat dispersion of Graphene discharges the heat produced in carbon nano tube field-emission process rapidly, prevents carbon nano tube structure from destroying rapidly, improves the useful life of negative electrode.
Accompanying drawing explanation
Fig. 1 is the carbon nanotube emission cathode preparation method flow chart in one embodiment of the application.
Embodiment
By reference to the accompanying drawings the application is described in further detail below by embodiment.
As shown in Figure 1, the carbon nanotube emission cathode preparation method of the application, its a kind of execution mode, comprises the following steps:
Step 102: using Graphene, add in organic solvent as the metal soluble inorganic salt of catalyst according to predetermined ratio, obtained positively charged Graphene electrophoresis solution.
Adopt ultrasonic or additive method, Graphene and soluble catalyst metal inorganic salt are scattered in organic solvent, obtain uniform and stable graphene solution.Graphene can be single-layer graphene, multilayer (as 2 ~ 10 layers) Graphene and/or their mixture.Graphene can be graphene oxide or redox graphene.Graphene can by chemical vapour deposition technique and chemical method (Hummer method) preparation.
In one embodiment, organic solvent can be the one in methyl alcohol, ethanol, isopropyl alcohol, acetone or their mixed solution.
Metal soluble inorganic salt as catalyst comprises one or more the mixture in the soluble inorganic salt of iron, nickel and cobalt.Metal soluble inorganic salt comprises the nitrate of iron, nickel and cobalt and the villaumite of iron, nickel and cobalt.As Fe (NO
3)
3, Ni (NO
3)
2, Co (NO
3)
2, FeCl
3, NiCl
2, CoCl
2deng.
In order to obtain homodisperse graphene solution, solution concentration is preferably 0.02-0.1mg/ml, and Graphene and the metal soluble inorganic salt weight ratio in the solution as catalyst can be 2 ~ 10.
Step 104: use electrically-conductive backing plate as negative electrode, respectively anode and described negative electrode are placed in described Graphene electrophoresis solution, extra electric field, the obtained Graphene layer structure be deposited on described electrically-conductive backing plate.
There is provided electrically-conductive backing plate as the negative electrode of electrophoretic deposition, another electrically-conductive backing plate is as anode, put into Graphene electrophoresis liquid, under the effect of direct voltage, the Graphene of adsorption catalyst metal cation moves to cathode direction, be deposited in order on electrically-conductive backing plate, prepare uniform Graphene layer structure.This Graphene layer structure has the pattern of random orientation, and Graphene, with the different angles of 1 ° ~ 90 ° arrangement, thus forms the structure of paddy shape at the upper surface of Graphene layer structure.
Electrically-conductive backing plate for deposited graphite alkene can be the metal substrates such as copper, titanium, chromium, tungsten, molybdenum, or plating has the insulated substrate (silicon chip, glass etc.) of the metal coatings such as copper, titanium, chromium, tungsten, molybdenum.Metal coating can adopt magnetron sputtering, electron beam evaporation, and at least one in vapour deposition process or electroless plating method carries out plating.
Electrophoretic deposition applied voltage can be 80 ~ 200V, and electrophoresis time can be 1 ~ 5min, and the spacing of negative electrode and anode is 0.1 ~ 1cm.
By the electrically-conductive backing plate of deposited graphite alkene layer structure 100 DEG C of vacuumizes, organic solvent remaining in removing Graphene layer structure.Drying time is 0.5 ~ 2h.
Step 106: the described Graphene layer structure be deposited on described electrically-conductive backing plate is put into gaseous phase deposition stove carbon nano-tube.
Adopt chemical gaseous phase depositing process carbon nano-tube.The electrically-conductive backing plate of deposited graphite alkene layer structure is put into CVD stove, after vacuumizing, pass into the inert gas of certain pressure intensity, as argon gas or other gas, then start to heat up, after reaching growth temperature, pass into hydrogen, insulation a period of time, make catalyst metal ion be reduced into catalyst granules, then hydrocarbon gas is passed into, carbon nano-tube.After growth terminates, naturally cool under argon atmosphere.
Ar pressure can be 5 ~ 30KPa, and growth temperature can be 600 ~ 800 DEG C.Hydrocarbon gas can be the gas of the carbon elements such as methane, ethene, acetylene, and hydrogen and hydrocarbon gas flow ratio can be 2.5 ~ 10, and growth time is 5 ~ 30min.
The length of carbon nanotube that growth obtains is at 1 ~ 20 μm, and diameter, at 10 ~ 100nm, has larger draw ratio, has high emission effciency as field emission source.Carbon nano-tube is at least one in the carbon nano-tube of single wall, double-walled or many walls.
The application also provides a kind of carbon nanotube emission negative electrode using said method to prepare.Under high electric field strength, the carbon nanometer field emission cathode structure of the application is through long Flied emission, and carbon nanotube emission current stabilization, is still combined firmly with cathode base, does not have peeling phenomenon.
Embodiment one:
By single-layer graphene and Fe (NO3)
3ultrasonic disperse, in absolute ethyl alcohol, obtains graphene solution.Graphene and Fe (NO3)
3weight ratio is 10, and Graphene concentration is 0.1mg/ml; Using anaerobic copper sheet as negative electrode, ITO electro-conductive glass, as anode, inserts in graphene solution, in anaerobic copper sheet surface electrical swimming deposited graphite alkene layer structure, and electrophoretic voltage 80V, electrophoresis time 1min;
After electrically-conductive backing plate 100 DEG C of vacuumizes of deposited graphite alkene layer structure, put into CVD reacting furnace.Argon gas is passed into after vacuumizing; pressure 30kPa, intensification 25min, reach the growth temperature of 700 DEG C; then the hydrogen of 50sccm is passed into; insulation 30min, iron ion is reduced into ferrous metal particle, then passes into the acetylene of 20sccm; carbon nano-tube 5min; finally, naturally cool under 100sccm argon shield, obtain carbon nanometer field emission cathode structure.
Embodiment two:
By multi-layer graphene and Ni (NO
3)
2ultrasonic disperse, in isopropyl alcohol, obtains graphene solution.Graphene and Ni (NO3)
2weight ratio is 5, and Graphene concentration is 0.06mg/ml; Using anaerobic copper sheet as negative electrode, ITO electro-conductive glass, as anode, inserts in graphene solution, in anaerobic copper sheet surface electrical swimming deposited graphite alkene layer structure, and electrophoretic voltage 140V, electrophoresis time 2.5min;
After electrically-conductive backing plate 100 DEG C of vacuumizes of deposited graphite alkene layer structure, put into CVD reacting furnace.Argon gas is passed into after vacuumizing; pressure 15kPa, intensification 20min, reach the growth temperature of 600 DEG C; then the hydrogen of 50sccm is passed into; insulation 30min, nickel ion is reduced into nickel metallic particles, then passes into the acetylene of 10sccm; carbon nano-tube 15min; finally, naturally cool under 100sccm argon shield, obtain carbon nanometer field emission cathode structure.
Embodiment three:
By single-layer graphene and Co (NO
3)
2ultrasonic disperse, in absolute ethyl alcohol, obtains graphene solution.Graphene and Co (NO
3)
3weight ratio is 2, and Graphene concentration is 0.02mg/ml; Using anaerobic copper sheet as negative electrode, ITO electro-conductive glass, as anode, inserts in graphene solution, in anaerobic copper sheet surface electrical swimming deposited graphite alkene layer structure, and electrophoretic voltage 200V, electrophoresis time 5min;
After electrically-conductive backing plate 100 DEG C of vacuumizes of deposited graphite alkene layer structure, put into CVD reacting furnace.Argon gas is passed into after vacuumizing; pressure 5kPa, intensification 30min, reach the growth temperature of 800 DEG C; then the hydrogen of 50sccm is passed into; insulation 30min, cobalt ions is reduced into cobalt metallic particles, then passes into the acetylene of 5sccm; carbon nano-tube 30min; finally, naturally cool under 100sccm argon shield, obtain carbon nanometer field emission cathode structure.
Above content is the further description done the application in conjunction with concrete execution mode, can not assert that the concrete enforcement of the application is confined to these explanations.For the application person of an ordinary skill in the technical field, under the prerequisite not departing from the application's design, some simple deduction or replace can also be made.
Claims (10)
1. a carbon nanotube emission cathode preparation method, is characterized in that, comprising:
Using Graphene, add in organic solvent as the metal soluble inorganic salt of catalyst according to predetermined ratio, obtained positively charged Graphene electrophoresis solution;
Use electrically-conductive backing plate as negative electrode, respectively anode and described negative electrode are placed in described Graphene electrophoresis solution, extra electric field, the obtained Graphene layer structure be deposited on described electrically-conductive backing plate;
The described Graphene layer structure be deposited on described electrically-conductive backing plate is put into gaseous phase deposition stove carbon nano-tube.
2. carbon nanotube emission cathode preparation method as claimed in claim 1, it is characterized in that, described metal soluble inorganic salt comprises one or more the mixture in the soluble inorganic salt of iron, nickel and cobalt.
3. carbon nanotube emission cathode preparation method as claimed in claim 2, it is characterized in that, described metal soluble inorganic salt comprises the nitrate of iron, nickel and cobalt and the villaumite of iron, nickel and cobalt.
4. carbon nanotube emission cathode preparation method as claimed in claim 1, it is characterized in that, the weight ratio of described metal soluble inorganic salt and described Graphene is 2 ~ 10.
5. carbon nanotube emission cathode preparation method as claimed in claim 1, it is characterized in that, described Graphene comprises single-layer graphene and/or multi-layer graphene.
6. carbon nanotube emission cathode preparation method as claimed in claim 1, it is characterized in that, the concentration of described Graphene electrophoresis solution is 0.02 ~ 0.1mg/ml.
7. carbon nanotube emission cathode preparation method as claimed in claim 1, is characterized in that, described the described Graphene layer structure be deposited on described electrically-conductive backing plate is put into gaseous phase deposition stove carbon nano-tube, specifically comprises:
Described cvd furnace is vacuumized, heats up after passing into the inert gas of certain pressure intensity, after reaching growth temperature, towards hydrogen, insulation a period of time, then pass into hydrocarbon gas, carbon nano-tube.
8. carbon nanotube emission cathode preparation method as claimed in claim 7, it is characterized in that, the pressure of described inert gas is for being 5 ~ 30KPa, and described growth temperature is 600 ~ 800 DEG C.
9. carbon nanotube emission cathode preparation method as claimed in claim 7, it is characterized in that, described hydrocarbon gas comprises methane, ethene and/or acetylene, and described hydrogen and described hydrocarbon gas flow ratio are 2.5 ~ 10.
10. the carbon nanotube emission negative electrode using the carbon nanotube emission cathode preparation method according to any one of claim 1 to 9 to prepare.
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