CN104241062B - Carbon nanotube emission cathode preparation method and carbon nanotube emission negative electrode - Google Patents
Carbon nanotube emission cathode preparation method and carbon nanotube emission negative electrode Download PDFInfo
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- CN104241062B CN104241062B CN201410466558.9A CN201410466558A CN104241062B CN 104241062 B CN104241062 B CN 104241062B CN 201410466558 A CN201410466558 A CN 201410466558A CN 104241062 B CN104241062 B CN 104241062B
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Abstract
This application discloses a kind of carbon nanotube emission cathode preparation method and carbon nanotube emission negative electrode, add in organic solvent including the metal soluble inorganic salt using Graphene, as catalyst according to predetermined ratio, prepare 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, prepare the Graphene layer structure being deposited on described electrically-conductive backing plate；The described Graphene layer structure being deposited on described electrically-conductive backing plate is put into gaseous phase deposition stove growth CNT.In the application owing to using electrophoretic deposition to prepare the Graphene layer structure being deposited on electrically-conductive backing plate, form a lot of paddy shape structure, when CNT is distributed in these paddy shape landform, improve the reliability of negative electrode；Graphene, as good conduction connector, inserts in carbon nanotube network, improves electronics conductive performance in carbon nano tube network.
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
CNT is a kind of Novel Carbon Nanomaterials, compared with other materials existing, there is the conductive and heat-conductive characteristic of excellence, the features such as the outstanding electron emissivity produced by nano level tip and stable mechanochemistry performance, it it is a kind of preferably field emmision material, show as can instant on switch, threshold electric field low and emission big, be expected to be used widely in fields such as vacuum microwave device, Field Emission Display and novel x-ray sources.
In order to realize the CNT application at feds, need to assemble or deposition of carbon nanotubes on substrate, it is thus achieved that there is in unit are the carbon nanotube cathod of high emission electric current and high stability.This assemble method is included in direct growth CNT on substrate and is peeled off by the CNT of growth and be assembled on another substrate.On substrate, direct growth CNT commonly uses chemical gaseous phase deposition.It is carbonaceous gas (such as methane, ethene and acetylene etc.) and reducibility gas (such as hydrogen) to be passed through in high temperature furnace, and carbonaceous gas is pyrolyzed, and the carbon atom of generation forms CNT under catalyst action.Chemical gaseous phase deposition can realize the high-volume of CNT, controllable growth.On the other hand, when the CNT of growth is stripped and is assembled on another substrate, in order to improve the adhesion with substrate, generally binding agent and CNT are mixed and made into slurry, it is then coated with in substrate surface, and through being dried, sinter and obtaining carbon nano-tube film.Due to the insulating properties of these binding agents itself, compared with direct growth method, the electric conductivity between CNT and between CNT and substrate significantly reduces.
Utilizing chemical gaseous phase deposition directly at grown on substrates CNT, owing to CNT is minimum with the contact area of substrate, cause adhesion the most weak, contact resistance is big, 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, including:
Metal soluble inorganic salt using Graphene, as catalyst adds in organic solvent according to predetermined ratio, prepares 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, prepare the Graphene layer structure being deposited on described electrically-conductive backing plate；
The described Graphene layer structure being deposited on described electrically-conductive backing plate is put into gaseous phase deposition stove growth CNT.
In said method, described metal soluble inorganic salt includes the mixture of one or more in the soluble inorganic salt of iron, nickel and cobalt.
In said method, described metal soluble inorganic salt includes nitrate and the villaumite of iron, nickel and cobalt 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 includes 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 gaseous phase deposition stove of the described Graphene layer structure being deposited on described electrically-conductive backing plate being put into grows CNT, specifically includes:
Described cvd furnace is vacuumized, heats up after being passed through the inert gas of certain pressure intensity, after reaching growth temperature, towards hydrogen, be incubated a period of time, then pass to hydrocarbon gas, grow CNT.
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 includes that methane, ethene and/or acetylene, 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 making and preparing in aforementioned manners.
Owing to have employed above technical scheme, make what the application possessed to have the beneficial effects that:
In the detailed description of the invention of the application; owing to using electrophoretic deposition to prepare the Graphene layer structure being deposited on electrically-conductive backing plate; Graphene becomes 1 °～90 ° of angle arrangements with substrate; form a lot of paddy shape structure; when CNT is distributed in these paddy shape landform; obtain stablizing mechanically due to the protection of Graphene, improve the reliability of negative electrode；Graphene, as good conduction connector, inserts in carbon nanotube network, improves electronics conductive performance in carbon nano tube network, the beneficially Flied emission of CNT；The heat that the fabulous heat dispersion of Graphene produces during discharging carbon nano tube field-emission rapidly, prevents carbon nano tube structure from destroying rapidly, improves the service 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.
Detailed description of the invention
Combine accompanying drawing below by detailed description of the invention the application is described in further detail.
As it is shown in figure 1, the carbon nanotube emission cathode preparation method of the application, its a kind of embodiment, comprise the following steps:
Step 102: the metal soluble inorganic salt using Graphene, as catalyst adds in organic solvent according to predetermined ratio, prepares positively charged Graphene electrophoresis solution.
Use 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 (such as 2～10 layers) Graphene and/or their mixture.Graphene can be graphene oxide or redox graphene.Graphene can be prepared by chemical vapour deposition technique and chemical method (Hummer method).
In one embodiment, the one during organic solvent can be methyl alcohol, ethanol, isopropanol, acetone or their mixed solution.
The mixture of one or more in the soluble inorganic salt of iron, nickel and cobalt is included as the metal soluble inorganic salt of catalyst.Metal soluble inorganic salt includes nitrate and the villaumite of iron, nickel and cobalt of iron, nickel and cobalt.Such as Fe (NO3)3、Ni(NO3)2、Co(NO3)2、FeCl3、NiCl2、CoCl2Deng.
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, prepare the Graphene layer structure being deposited on described electrically-conductive backing plate.
Thering is provided electrically-conductive backing plate as the negative electrode of electrophoretic deposition, another electrically-conductive backing plate, as anode, puts into Graphene electrophoresis liquid, under the effect of DC voltage, the Graphene of adsorption catalyst metal cation moves to cathode direction, is deposited in order on electrically-conductive backing plate, prepares uniform Graphene layer structure.This Graphene layer structure has the pattern of random orientation, and Graphene arranges with the different angles of 1 °～90 °, thus the structure of the upper surface formation paddy shape in Graphene layer structure.
Electrically-conductive backing plate for deposited graphite alkene can be the metal substrates such as copper, titanium, chromium, tungsten, molybdenum, or is plated with the insulated substrate (silicon chip, glass etc.) of the metal coatings such as copper, titanium, chromium, tungsten, molybdenum.Metal coating can use at least one in magnetron sputtering, electron beam evaporation, vapour deposition process or electroless plating method to carry 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 vacuum drying, remove the organic solvent of remaining in Graphene layer structure.Drying time is 0.5～2h.
Step 106: the described Graphene layer structure being deposited on described electrically-conductive backing plate is put into gaseous phase deposition stove growth CNT.
Use chemical gaseous phase depositing process growth CNT.The electrically-conductive backing plate of deposited graphite alkene layer structure is put into CVD stove, after vacuumizing, it is passed through the inert gas of certain pressure intensity, such as argon gas or other gas, then starts to warm up, after reaching growth temperature, it is passed through hydrogen, is incubated a period of time, makes catalyst metal ion be reduced into catalyst granules, then pass to hydrocarbon gas, grow CNT.After growth terminates, cooling naturally 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 10～100nm, has bigger draw ratio at 1～20 μm, diameter, has high emission effciency as field emission source.CNT is at least one in the CNT of single wall, double-walled or many walls.
The application also provides for a kind of carbon nanotube emission negative electrode making and preparing in aforementioned manners.Under high electric-field intensity, the carbon nanometer field emission cathode structure of the application, through long Flied emission, carbon nanotube emission current stabilization, is still firmly combined with cathode base, does not has 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, at anaerobic copper sheet surface electrophoretic deposition Graphene layer structure, electrophoretic voltage 80V, electrophoresis time 1min；
After being vacuum dried by the electrically-conductive backing plate 100 DEG C of deposited graphite alkene layer structure, put into CVD reacting furnace.Argon gas it is passed through after vacuumizing; pressure 30kPa, intensification 25min, reach the growth temperature of 700 DEG C; then pass to the hydrogen of 50sccm; insulation 30min, iron ion is reduced into ferrous metal particle, then passes to the acetylene of 20sccm; growth CNT 5min; finally, under 100sccm argon shield, cooling naturally, obtains carbon nanometer field emission cathode structure.
Embodiment two:
By multi-layer graphene and Ni (NO3)2Ultrasonic disperse, in isopropanol, 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, at anaerobic copper sheet surface electrophoretic deposition Graphene layer structure, electrophoretic voltage 140V, electrophoresis time 2.5min；
After being vacuum dried by the electrically-conductive backing plate 100 DEG C of deposited graphite alkene layer structure, put into CVD reacting furnace.Argon gas it is passed through after vacuumizing; pressure 15kPa, intensification 20min, reach the growth temperature of 600 DEG C; then pass to the hydrogen of 50sccm; insulation 30min, nickel ion is reduced into nickel metallic particles, then passes to the acetylene of 10sccm; growth CNT 15min; finally, under 100sccm argon shield, cooling naturally, obtains carbon nanometer field emission cathode structure.
Embodiment three:
By single-layer graphene and Co (NO3)2Ultrasonic disperse, in absolute ethyl alcohol, obtains graphene solution.Graphene and Co (NO3)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, at anaerobic copper sheet surface electrophoretic deposition Graphene layer structure, electrophoretic voltage 200V, electrophoresis time 5min；
After being vacuum dried by the electrically-conductive backing plate 100 DEG C of deposited graphite alkene layer structure, put into CVD reacting furnace.Argon gas it is passed through after vacuumizing; pressure 5kPa, intensification 30min, reach the growth temperature of 800 DEG C; then pass to the hydrogen of 50sccm; insulation 30min, cobalt ions is reduced into cobalt metallic particles, then passes to the acetylene of 5sccm; growth CNT 30min; finally, under 100sccm argon shield, cooling naturally, obtains carbon nanometer field emission cathode structure.
Above content is to combine the further description that the application is made by specific embodiment, it is impossible to assert the application be embodied as be confined to these explanations.For the application person of an ordinary skill in the technical field, on the premise of conceiving without departing from the application, it is also possible to make some simple deduction or replace.
Claims (10)
1. a carbon nanotube emission cathode preparation method, it is characterised in that including:
Metal soluble inorganic salt using Graphene, as catalyst adds in organic solvent according to predetermined ratio, prepares positively charged
The Graphene electrophoresis solution of lotus；
Use electrically-conductive backing plate as negative electrode, respectively anode and described negative electrode are placed in described Graphene electrophoresis solution, power up outward
, prepare the Graphene layer structure being deposited on described electrically-conductive backing plate；Graphene arranges with the different angles of 1 °～90 °,
Upper surface in Graphene layer structure forms the structure of paddy shape；
The described Graphene layer structure being deposited on described electrically-conductive backing plate is put into gaseous phase deposition stove growth CNT.
2. carbon nanotube emission cathode preparation method as claimed in claim 1, it is characterised in that described metal solubility without
Machine salt includes the mixture of one or more in the soluble inorganic salt of iron, nickel and cobalt.
3. carbon nanotube emission cathode preparation method as claimed in claim 2, it is characterised in that described metal solubility without
Machine salt includes nitrate and the villaumite of iron, nickel and cobalt of iron, nickel and cobalt.
4. carbon nanotube emission cathode preparation method as claimed in claim 1, it is characterised in that described metal solubility without
The weight ratio of machine salt and described Graphene is 2～10.
5. carbon nanotube emission cathode preparation method as claimed in claim 1, it is characterised in that described Graphene includes list
Layer graphene and/or multi-layer graphene.
6. carbon nanotube emission cathode preparation method as claimed in claim 1, it is characterised in that described Graphene electrophoresis is molten
The concentration of liquid is 0.02～0.1mg/ml.
7. carbon nanotube emission cathode preparation method as claimed in claim 1, it is characterised in that described will be deposited on described in
Described Graphene layer structure on electrically-conductive backing plate puts into gaseous phase deposition stove growth CNT, specifically includes:
Described cvd furnace is vacuumized, heats up after being passed through the inert gas of certain pressure intensity, after reaching growth temperature, towards hydrogen,
Insulation a period of time, then pass to hydrocarbon gas, grow CNT.
8. carbon nanotube emission cathode preparation method as claimed in claim 7, it is characterised in that the pressure of described inert gas
Strong for being 5～30KPa, described growth temperature is 600～800 DEG C.
9. carbon nanotube emission cathode preparation method as claimed in claim 7, it is characterised in that described hydrocarbon gas includes
Methane, ethene and/or acetylene, described hydrogen and described hydrocarbon gas flow ratio are 2.5～10.
10. carbon nanometer prepared by the carbon nanotube emission cathode preparation method that a kind uses according to any one of claim 1 to 9
Pipe emitting cathode.
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