CN113517164B - Manufacturing method of carbon nanotube cathode, carbon nanotube cathode and electronic equipment - Google Patents
Manufacturing method of carbon nanotube cathode, carbon nanotube cathode and electronic equipment Download PDFInfo
- Publication number
- CN113517164B CN113517164B CN202110251702.7A CN202110251702A CN113517164B CN 113517164 B CN113517164 B CN 113517164B CN 202110251702 A CN202110251702 A CN 202110251702A CN 113517164 B CN113517164 B CN 113517164B
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- conductive substrate
- cathode
- substrate
- nanotube cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 150
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 149
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 117
- 239000002002 slurry Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000004381 surface treatment Methods 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007650 screen-printing Methods 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000010586 diagram Methods 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 7
- 230000005684 electric field Effects 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/30—Cold cathodes, e.g. field-emissive cathode
- H01J1/304—Field-emissive cathodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/30—Cold cathodes
- H01J2201/304—Field emission cathodes
- H01J2201/30446—Field emission cathodes characterised by the emitter material
- H01J2201/30453—Carbon types
- H01J2201/30469—Carbon nanotubes (CNTs)
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2209/00—Apparatus and processes for manufacture of discharge tubes
- H01J2209/02—Manufacture of cathodes
- H01J2209/022—Cold cathodes
- H01J2209/0223—Field emission cathodes
Abstract
The application discloses a manufacturing method of a carbon nanotube cathode, the carbon nanotube cathode and electronic equipment. The method comprises the following steps: providing a conductive substrate; carrying out surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate; and forming a carbon nanotube layer on the surface of the conductive substrate by using the carbon nanotube slurry to form the carbon nanotube cathode. Through the mode, the bonding strength of the substrate and the carbon nano tube can be improved, and then the field emission current density and the stability of the carbon nano tube are improved, and the preparation process is simple and easy to realize.
Description
Technical Field
The present disclosure relates to field of field emission technology, and in particular, to a method for manufacturing a carbon nanotube cathode, and an electronic device.
Background
Carbon Nanotubes (CNTs) have excellent electrochemical properties, extremely high aspect ratios, and excellent mechanical strength, and thus have been used as electron sources in Field Emission (FE) devices. As a field emission cold cathode material, it has low operating voltage, higher field emission current density and unique operating stability, and thus becomes an important point of research in the field of field emission.
In many applications of vacuum microwave apparatus, not only a higher current density is required to be emitted, but also a low degradation rate of performance during long-term use is required. Cold cathode field emission devices based on carbon nanotubes generally include a substrate and carbon nanotubes coated or printed or grown on the substrate, but carbon nanotubes grown ex-situ on the substrate may be unstable in contact with the substrate due to being wrapped with a paste, and thus current stability and uniformity of an emitter are difficult to control.
In view of this, it is necessary to provide a carbon nanotube field emission cathode and a method for manufacturing the same, so that the manufactured carbon nanotube field emission cathode has a large current area density and uniform stability.
Disclosure of Invention
The application mainly provides a manufacturing method of a carbon nanotube cathode, the carbon nanotube cathode and electronic equipment, and can solve the problem of uneven emission current density caused by unstable contact between a carbon nanotube and a substrate in the prior art.
In order to solve the above technical problems, a first aspect of the present application provides a method for manufacturing a carbon nanotube cathode, the method comprising: providing a conductive substrate; carrying out surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate; and forming a carbon nanotube layer on the surface of the conductive substrate by using the carbon nanotube slurry to form the carbon nanotube cathode.
Wherein, the surface treatment is performed on the conductive substrate to form a concave structure on the surface of the conductive substrate, including: performing a cleaning operation on the conductive substrate; the conductive substrate after the cleaning operation is placed in an alkali solution to form a concave structure on the surface of the conductive substrate.
Wherein the cleaning operation of the conductive substrate includes: performing ultrasonic operation on the conductive substrate; ethanol is adopted to carry out cleaning operation on the conductive substrate after ultrasonic operation; and drying the conductive substrate after the cleaning operation.
Wherein the method further comprises: adding carbon nano tubes, ball milling beads, a binder and metal powder into a ball milling solvent to perform ball milling operation on the carbon nano tubes to form the carbon nano tube slurry.
Wherein, adding carbon nanotube, ball-milling beads, binder and metal powder into a ball-milling solvent to perform ball-milling operation on the carbon nanotube to form the carbon nanotube slurry, comprising: adding the carbon nano tube and ball-milling beads into the ball-milling solvent, and performing ball-milling operation to obtain primary slurry; adding the binder into the primary slurry, and performing ball milling operation to obtain intermediate slurry; and adding the metal powder into the intermediate slurry, and performing ball milling operation to obtain the carbon nano tube slurry.
Wherein the metal powder is one of titanium powder or aluminum powder.
Wherein the forming a carbon nanotube layer on the surface of the conductive substrate using the carbon nanotube paste to form the carbon nanotube cathode includes: printing the carbon nanotube slurry on the surface of the conductive substrate by using a screen printing technology to form the carbon nanotube cathode.
Wherein after the forming a carbon nanotube layer on the surface of the conductive substrate using the carbon nanotube paste to form the carbon nanotube cathode, the method further comprises: heating the carbon nanotube cathode in a vacuum environment with a first preset temperature, and maintaining the first preset time; and raising the temperature of the vacuum environment to a second preset temperature and maintaining the second preset time to obtain the heated carbon nanotube cathode.
Wherein the method further comprises: and removing carbide on the surface of the heated carbon nanotube cathode.
In order to solve the above technical problems, a second aspect of the present application provides a carbon nanotube cathode, which is manufactured by the manufacturing method of the carbon nanotube cathode provided in the first aspect.
To solve the above technical problem, a third aspect of the present application provides an electronic device, which includes the carbon nanotube cathode provided in the first aspect.
The beneficial effects of this application are: in order to solve the problems, the method is characterized in that the surface of the conductive substrate is subjected to surface treatment to form a concave structure on the surface of the conductive substrate, then a carbon nanotube layer is formed on the surface of the conductive substrate by utilizing carbon nanotube slurry to form a carbon nanotube cathode, the conductive substrate after surface treatment can be combined with the carbon nanotube better, the bonding strength of the substrate and the carbon nanotube is improved, the field emission current density and the stability of the carbon nanotube are effectively improved, and the preparation process is simple, easy to operate and easy to realize.
Drawings
FIG. 1 is a schematic block diagram illustrating a method of fabricating a carbon nanotube cathode according to an embodiment of the present disclosure;
FIG. 2 is a schematic block diagram of a flow chart of an embodiment of step S20 of the present application;
FIG. 3 is a schematic block diagram of a process for drying and sintering a carbon nanotube cathode according to one embodiment of the present application;
FIG. 4 is a schematic block diagram of another embodiment of a method for fabricating a carbon nanotube cathode of the present application;
FIG. 5 is a schematic block diagram illustrating the flow of one embodiment of step S60 of the present application;
FIG. 6 is a schematic diagram illustrating a field emission test of an embodiment of a cold cathode of a carbon nanotube;
FIG. 7 is a graph showing the results of the field emission performance of the cold cathode carbon nanotubes of the present application under DC voltage;
FIG. 8 is a graph showing the results of field emission performance of the cold cathode carbon nanotubes of the present application under alternating voltage;
fig. 9 is a graph showing the field emission stability of the cold cathode carbon nanotubes of the present application under alternating voltage.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
The terms "first," "second," and the like in this application are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of features shown. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. Furthermore, the terms "comprise" and "have," as well as any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed steps or elements but may include other steps or elements not listed or inherent to such process, method, article, or apparatus.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the present application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly understand that the embodiments described herein may be combined with other embodiments.
Referring to fig. 1, fig. 1 is a schematic flow chart diagram of an embodiment of a method for manufacturing a carbon nanotube cathode according to the present application. The method for manufacturing the carbon nanotube cathode in the embodiment may include the following steps:
s10, providing a conductive substrate.
The conductive substrate can be a metal substrate or an alloy substrate. The conductive substrate is used for preparing and forming a carbon nano tube layer on the surface so as to obtain the carbon nano tube cathode.
S20, performing surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate.
The surface treatment operation of the conductive substrate is to form a concave structure on the surface of the substrate, and the surface treatment is performed on the surface of the substrate for forming the carbon nanotube layer to form a hollowed-out nano-network structure on the surface of the substrate, so that the surface contact area of the conductive substrate is increased, and the bonding strength of the conductive substrate and the carbon nanotube layer is further enhanced.
The surface treatment operation in this step may be an alkali treatment operation for the conductive substrate. Referring specifically to fig. 2, fig. 2 is a schematic block diagram illustrating a flow of an embodiment of step S20 of the present application. The method specifically comprises the following steps:
s201, performing a cleaning operation on the conductive substrate.
The step cleans the provided conductive substrate, specifically, firstly, ultrasonic operation is performed on the conductive substrate to clean the conductive substrate by utilizing ultrasonic waves, the ultrasonic cleaning time can be 4 to 8 hours, after the ultrasonic cleaning is finished, ethanol is used for cleaning the conductive substrate after the ultrasonic operation, and then drying operation is performed on the conductive substrate after the cleaning operation.
And S202, placing the conductive substrate after the cleaning operation in an alkali solution to form a concave structure on the surface of the conductive substrate.
In the step, alkali treatment can be performed on the conductive substrate after the cleaning operation by using alkali solution, so that the concave of the nano-network structure is formed on the surface of the substrate, the specific surface of the conductive substrate is increased, and the bonding strength of the conductive substrate and the carbon nano tube can be effectively improved.
Specifically, the step can be to put the conductive substrate in an alkali solution, and take out the conductive substrate after standing for a preset period of time under a preset temperature condition, so as to finish the alkali treatment of the substrate.
For example, the alkaline solution is 3M sodium hydroxide solution, the conductive substrate is placed in the 3M sodium hydroxide solution, and after the conductive substrate is kept stand for a preset period of time under a preset temperature condition, the conductive substrate is taken out, and the conductive substrate after the alkaline treatment can be obtained.
Wherein the preset temperature may be 25-35 ℃, for example 28 ℃, 30 ℃, 32 ℃; the preset duration may be 22-26 hours, for example 23 hours, 24 hours, 25 hours.
S30, forming a carbon nano tube layer on the surface of the conductive substrate by utilizing the carbon nano tube slurry to form a carbon nano tube cathode.
The carbon nanotube slurry can be coated or printed on the surface of the conductive substrate to form a carbon nanotube layer, so as to obtain a carbon nanotube cathode.
In a specific embodiment, the carbon nanotube paste is printed on the surface of the conductive substrate by using a screen printing technology to prepare the carbon nanotube cathode. Screen printing is to use a screen as a substrate and make a screen printing plate with graphics and texts by a photosensitive plate making method.
Referring to fig. 3, after step S30, operations such as drying and sintering the carbon nanotube cathode may be performed in a vacuum environment, including the following steps:
and S31, placing the carbon nanotube cathode in a vacuum environment with a first preset temperature for heating, and maintaining the first preset time.
The step is to dry the carbon nanotube cathode. Wherein the first preset temperature may be 150 ℃ to 250 ℃, for example 180 ℃, 200 ℃, 220 ℃; the first preset time may be 1 to 3 hours, for example, 1.5 hours, 2 hours, 2.5 hours.
And S32, raising the temperature of the vacuum environment to a second preset temperature and maintaining the second preset time to obtain the heated carbon nanotube cathode.
And step S31, after the drying of the carbon nanotube cathode is finished, raising the temperature of the vacuum environment to a second preset temperature and continuing heating so as to calcine the carbon nanotube cathode to remove the glue. Wherein the heating rate is 2 ℃/min to 5 ℃/min, such as 2 ℃/min, 3 ℃/min and 4 ℃/min.
Wherein the second preset temperature may be 600 ℃ to 800 ℃, for example 650 ℃, 700 ℃, 750 ℃; the second preset time may be 1 to 3 hours, for example, 1.5 hours, 2 hours, 2.5 hours.
S33, removing carbide on the surface of the heated carbon nanotube cathode.
In the step, the carbide on the surface of the carbon nanotube cathode can be subjected to adhesion and removal treatment, for example, 3M adhesive tape can be used for adhesion and removal of the carbide on the surface of the carbon nanotube cathode.
Thus, the preparation of the carbon nanotube cathode is completed.
According to the embodiment, the substrate is subjected to surface treatment, the hollow nano-reticular structure is formed on the surface of the substrate, the specific surface of the substrate is enlarged, the bonding strength of the carbon nano-tube and the alloy substrate is well improved, and the field emission current density and stability of the carbon nano-tube are further improved.
Referring to fig. 4, fig. 4 is a schematic block flow diagram of another embodiment of a method for manufacturing a carbon nanotube cathode according to the present application. It should be noted that, if there are substantially the same results, the embodiment is not limited to the flow sequence shown in fig. 4. The manufacturing method of the carbon nanotube cathode in the embodiment comprises the following steps:
s40, providing a conductive substrate.
The conductive substrate can be a substrate made of metal or alloy, or an insulating substrate coated with a conductive metal layer or alloy layer, for example, a Ti6Al4V alloy substrate (Ti-6 Al-4V is a nominal chemical composition representation method of a titanium alloy brand TC4, and the composition of the titanium alloy TC4 material is Ti-6Al-4V, belongs to (alpha+beta) titanium alloy, and has good comprehensive mechanical properties. The conductive substrate is used for preparing and forming a carbon nano tube layer on the surface so as to obtain the carbon nano tube cathode.
And S50, performing surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate.
The surface treatment operation of the conductive substrate is to form a concave structure on the surface of the substrate, and the surface treatment is performed on the surface of the substrate for forming the carbon nanotube layer to form a hollowed-out nano-network structure on the surface of the substrate, so that the surface contact area of the conductive substrate is increased, and the bonding strength of the conductive substrate and the carbon nanotube layer is further enhanced.
The surface treatment operation in this step may be an alkali treatment operation for the conductive substrate. The specific reference may be made to step S201 in the previous embodiment, and the description thereof will not be repeated here.
And S60, adding the carbon nano tube, ball milling beads, a binder and metal powder into a ball milling solvent to perform ball milling operation on the carbon nano tube, so as to form carbon nano tube slurry.
Wherein the particle size of the metal powder is 20 nm-50 mu m. In the process of ball milling to prepare the slurry, the metal powder can cause mechanical damage to the carbon nano tube, and the surface defect of the carbon nano tube is increased, so that the emission position of electrons is increased, the work function of a cathode system of the carbon nano tube is further reduced, and the overall emission efficiency is improved.
Wherein, the binder can be sodium carboxymethyl cellulose, and the ball milling solvent can be terpineol; alternatively, the binder may also be polyvinylidene fluoride and the ball milling solvent may also be N-methylpyrrolidone.
The metal powder is a metal powder with a low work function, and can be aluminum powder or titanium powder, for example.
Referring to fig. 5, fig. 5 is a schematic block flow chart of an embodiment of step S60 of the present application. It should be noted that, if there are substantially the same results, the embodiment is not limited to the flow sequence shown in fig. 5. The preparation of the carbon nanotube slurry in this embodiment specifically includes the following steps:
and S61, adding the carbon nano tube and ball-milling beads into a ball-milling solvent, and performing ball-milling operation to obtain primary slurry.
The step adds the carbon nano tube and ball-milling beads into the ball-milling solvent, and carries out ball-milling operation for 2-4 hours to obtain primary slurry.
And S62, adding a binder into the primary slurry, and performing ball milling operation to obtain an intermediate slurry.
In the step, a binder is added into the primary slurry obtained in the step S61, and ball milling operation is carried out for 3-5 hours, so as to obtain intermediate slurry.
And S63, adding metal powder into the intermediate slurry, and performing ball milling operation to obtain the carbon nano tube slurry.
In the step, metal powder is added into the intermediate slurry obtained in the step S62, and the ball milling operation is carried out for 1-3 hours, so as to obtain the carbon nanotube slurry. In the mechanical ball milling process, the metal powder causes mechanical damage to the surface of the carbon nano tube, so that the surface defects of the carbon nano tube are increased, further the electron emission sites are increased, and the work function is effectively reduced.
And S70, forming a carbon nano tube layer on the surface of the conductive substrate by utilizing the carbon nano tube slurry to form a carbon nano tube cathode.
The carbon nanotube slurry can be coated or printed on the surface of the conductive substrate to form a carbon nanotube layer, so as to obtain a carbon nanotube cathode.
In a specific embodiment, the carbon nanotube paste is printed on the surface of the conductive substrate by using a screen printing technology to prepare the carbon nanotube cathode.
After this step, the carbon nanotube cathode may be dried and sintered in a vacuum environment, and details of this step are omitted herein with reference to steps S31 to S33.
In the embodiment, on one hand, alkali treatment is carried out on the conductive substrate, a concave structure is formed on the surface of the conductive substrate, so that a substrate with a large specific surface is obtained, and the bonding strength of the conductive substrate and the carbon nano tube is effectively improved; on the other hand, in the process of preparing the slurry, metal powder and the carbon nanotubes are added for ball milling together, so that mechanical damage is caused to the surfaces of the carbon nanotubes, surface defects of the carbon nanotubes are increased, further electron emission sites are increased, and work functions are effectively reduced. Therefore, the embodiment can effectively improve the field emission current density and stability of the carbon nano tube, and the preparation process is simple and easy to operate.
Steps (1) to (7) are steps of a method for preparing a specific embodiment of the carbon nanotube cathode in this example, including:
(1) Providing a Ti6Al4V alloy substrate;
(2) Performing ultrasonic operation on the Ti6Al4V alloy substrate for 6 hours, cleaning with ethanol, and drying;
(3) Placing the dried Ti6Al4V alloy substrate in 10M NaOH solution, and standing for 24 hours at the temperature of 30 ℃ to finish the surface treatment of the Ti6Al4V alloy substrate;
(4) Preparing carbon nano tube slurry;
the method comprises the steps of a-c:
a. ball milling 0.1 g-0.5 g of carbon nano tube, zrC ball milling beads and 2-6 mL of terpineol for 3 hours to obtain primary slurry;
b. adding 0.05-0.2 g of sodium carboxymethyl cellulose into the primary slurry, and ball milling for 4 hours to obtain intermediate slurry;
c. adding 0.05-0.2 g of titanium powder into the intermediate slurry, and ball milling for 2 hours to obtain the carbon nano tube slurry.
(5) Printing the carbon nanotube slurry on a Ti6Al4V alloy substrate by a screen printing method to obtain a carbon nanotube cathode;
(6) Drying the carbon nanotube cathode in vacuum at 200 ℃ for 2 hours, then heating to 700 ℃ at a heating rate of 3 ℃/min and preserving heat for 2 hours;
(7) And (3) adhering and removing carbide on the surface of the carbon nanotube cathode by using a 3M adhesive tape to finish the preparation of the carbon nanotube cathode.
Referring to fig. 6 to fig. 9 in combination, fig. 6 is a schematic diagram of a field emission test of the cold cathode of the carbon nanotube of the present embodiment, fig. 7 is a schematic diagram of a result of a field emission performance of the cold cathode of the carbon nanotube of the present embodiment tested under a dc voltage, fig. 8 is a schematic diagram of a result of a field emission performance of the cold cathode of the carbon nanotube of the present embodiment tested under an ac voltage, and fig. 9 is a result of a field emission stability of the cold cathode of the carbon nanotube of the present embodiment tested under an ac voltage, wherein D1 and D2 in fig. 7 and fig. 8 are experimental results of a control group.
From the experimental results, it can be seen that: the carbon nanotube cold cathode prepared by the embodiment can obtain an opening electric field of 0.79V/mu m under the drive of direct current, and can obtain a current density of 85.13mA/cm < 2 > under the electric field strength of 2.38V/mu m; can show a current density of 1.226A/cm2 under the drive of alternating current at an electric field strength of 6.1V/μm; and the current density can still reach 0.4A/cm2 after being driven for 15 hours under the electric field intensity of 4.0V/mu m. Therefore, the carbon nanotube cold cathode field emission current prepared by the method of the embodiment is larger and more stable.
The application also provides a carbon nanotube cathode, which is prepared by the method for preparing the carbon nanotube cathode, and the preparation method is not repeated here, and the carbon nanotube cathode prepared by the method has larger and more stable field emission current density due to the enhanced bonding strength of the substrate and the carbon nanotube.
The present application also provides an electronic device, for example, a field emission flat display device or a vacuum electron source, which includes the carbon nanotube cathode provided in the above embodiment, and the preparation process of the electronic device is improved in the above embodiments, so that the electronic device also has the characteristics of larger and more stable field emission current density.
The foregoing description is only exemplary embodiments of the present application and is not intended to limit the scope of the present application, and all equivalent structures or equivalent processes using the descriptions and the drawings of the present application, or direct or indirect application in other related technical fields are included in the scope of the present application.
Claims (7)
1. A method for manufacturing a carbon nanotube cathode, the method comprising:
providing a conductive substrate;
carrying out surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate;
adding carbon nano tubes and ball-milling beads into a ball-milling solvent, and performing ball-milling operation to obtain primary slurry;
adding a binder into the primary slurry, and performing ball milling operation to obtain an intermediate slurry;
adding metal powder into the intermediate slurry, and performing ball milling operation to obtain carbon nanotube slurry, wherein the metal powder is metal powder with a low work function;
printing the carbon nanotube slurry on the surface of the conductive substrate by utilizing a screen printing technology to form the carbon nanotube cathode;
heating the carbon nanotube cathode in a vacuum environment with a first preset temperature, and maintaining the first preset time;
and raising the temperature of the vacuum environment to a second preset temperature and maintaining the second preset time to obtain the heated carbon nanotube cathode.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the surface treatment of the conductive substrate to form a concave structure on the surface of the conductive substrate includes:
performing a cleaning operation on the conductive substrate;
the conductive substrate after the cleaning operation is placed in an alkali solution to form a concave structure on the surface of the conductive substrate.
3. The method of claim 2, wherein the step of determining the position of the substrate comprises,
the cleaning operation of the conductive substrate includes:
performing ultrasonic operation on the conductive substrate;
ethanol is adopted to carry out cleaning operation on the conductive substrate after ultrasonic operation;
and drying the conductive substrate after the cleaning operation.
4. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the metal powder is one of titanium powder or aluminum powder.
5. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the method further comprises the steps of:
and removing carbide on the surface of the heated carbon nanotube cathode.
6. A carbon nanotube cathode produced by the production method according to any one of claims 1 to 5.
7. An electronic device comprising the carbon nanotube cathode of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110251702.7A CN113517164B (en) | 2021-03-08 | 2021-03-08 | Manufacturing method of carbon nanotube cathode, carbon nanotube cathode and electronic equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110251702.7A CN113517164B (en) | 2021-03-08 | 2021-03-08 | Manufacturing method of carbon nanotube cathode, carbon nanotube cathode and electronic equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113517164A CN113517164A (en) | 2021-10-19 |
| CN113517164B true CN113517164B (en) | 2024-03-29 |
Family
ID=78061155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110251702.7A Active CN113517164B (en) | 2021-03-08 | 2021-03-08 | Manufacturing method of carbon nanotube cathode, carbon nanotube cathode and electronic equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113517164B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1512536A (en) * | 2002-12-26 | 2004-07-14 | ����Sdi��ʽ���� | Field emitting display of electronic emitting source including forming multilayer structure |
| CN1841587A (en) * | 2005-04-02 | 2006-10-04 | 鸿富锦精密工业（深圳）有限公司 | Electrode structure and its preparing method |
| CN1897204A (en) * | 2005-07-15 | 2007-01-17 | 清华大学 | Field-transmitting cathode, its production and planar light source |
| CN1988101A (en) * | 2005-12-23 | 2007-06-27 | 鸿富锦精密工业（深圳）有限公司 | Method for preparing field emitting cathode |
| CN101593649A (en) * | 2009-05-22 | 2009-12-02 | 彩虹集团公司 | A kind of carbon nanotube electron emitter and preparation method thereof |
| CN102208317A (en) * | 2010-03-31 | 2011-10-05 | 清华大学 | Carbon nanotube slurry and field emitter prepared from same |
| CN102262988A (en) * | 2010-05-31 | 2011-11-30 | 海洋王照明科技股份有限公司 | Method for manufacturing carbon nanotube cold cathode and application of method |
| CN104465268A (en) * | 2014-12-11 | 2015-03-25 | 谢曌东 | Carbon nanotube fiber array cold cathode preparation method |
| CN105448624A (en) * | 2014-07-10 | 2016-03-30 | 清华大学 | Field emission cathode preparation method |
| CN112242280A (en) * | 2019-07-16 | 2021-01-19 | 清华大学 | Carbon nanotube field emitter and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3740295B2 (en) * | 1997-10-30 | 2006-02-01 | キヤノン株式会社 | Carbon nanotube device, manufacturing method thereof, and electron-emitting device |
-
2021
- 2021-03-08 CN CN202110251702.7A patent/CN113517164B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1512536A (en) * | 2002-12-26 | 2004-07-14 | ����Sdi��ʽ���� | Field emitting display of electronic emitting source including forming multilayer structure |
| CN1841587A (en) * | 2005-04-02 | 2006-10-04 | 鸿富锦精密工业（深圳）有限公司 | Electrode structure and its preparing method |
| CN1897204A (en) * | 2005-07-15 | 2007-01-17 | 清华大学 | Field-transmitting cathode, its production and planar light source |
| CN1988101A (en) * | 2005-12-23 | 2007-06-27 | 鸿富锦精密工业（深圳）有限公司 | Method for preparing field emitting cathode |
| CN101593649A (en) * | 2009-05-22 | 2009-12-02 | 彩虹集团公司 | A kind of carbon nanotube electron emitter and preparation method thereof |
| CN102208317A (en) * | 2010-03-31 | 2011-10-05 | 清华大学 | Carbon nanotube slurry and field emitter prepared from same |
| CN102262988A (en) * | 2010-05-31 | 2011-11-30 | 海洋王照明科技股份有限公司 | Method for manufacturing carbon nanotube cold cathode and application of method |
| CN105448624A (en) * | 2014-07-10 | 2016-03-30 | 清华大学 | Field emission cathode preparation method |
| CN104465268A (en) * | 2014-12-11 | 2015-03-25 | 谢曌东 | Carbon nanotube fiber array cold cathode preparation method |
| CN112242280A (en) * | 2019-07-16 | 2021-01-19 | 清华大学 | Carbon nanotube field emitter and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113517164A (en) | 2021-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100944828B1 (en) | Process for producing cold field-emission cathodes | |
| Kim et al. | Great improvement in adhesion and uniformity of carbon nanotube field emitters through reactive nanometer-scale SiC fillers | |
| Fairchild et al. | Carbon nanotube fiber field emission array cathodes | |
| JP5090917B2 (en) | Enhancement of field emission by non-activated carbon nanotubes | |
| JP2007258172A (en) | Electron emitting element using carbon nanotube and its manufacturing method | |
| JP4903664B2 (en) | Method for manufacturing electron-emitting device | |
| KR20140118017A (en) | Electron emission element and method for manufacturing the same | |
| CN113517164B (en) | Manufacturing method of carbon nanotube cathode, carbon nanotube cathode and electronic equipment | |
| JP4355928B2 (en) | Manufacturing method of field emission cold cathode | |
| WO2022188003A1 (en) | Manufacturing method for carbon nanotube cathode, and carbon nanotube cathode and electronic device | |
| CN116598895A (en) | Modified discharge electrode of ion wind generating device, modification method and application thereof | |
| JP2001291465A (en) | Cold cathode and manufacturing method thereof | |
| JP2016126993A (en) | Carbon nanotube paste for high-output field-emission emitter, and manufacturing method thereof | |
| KR102397196B1 (en) | Carbon nanotube (cnt) paste emitter, method for manufacturing the same and x-ray tube using the same | |
| TWI309055B (en) | Method for making emission source having carbon nanotube | |
| TWI309428B (en) | Emission source having carbon nanotube | |
| TW480537B (en) | Method for enhancing emission efficiency of carbon nanotube emission source field | |
| TW423013B (en) | Wire-coated ion bombarded graphite electron emitters | |
| JP5069486B2 (en) | Thin film type electron emission material, method for manufacturing the same, field emission type device, and field emission type display | |
| US20220399177A1 (en) | Carbon nanotube (cnt) paste emitter, method of manufacturing the same, and x-ray tube apparatus using the same | |
| CN103021762A (en) | Method for processing field emission cathode | |
| TW201001484A (en) | Field emitter and method for making the same | |
| TWI401209B (en) | Field emission componet and method for making same | |
| Lee | Performance of Point-Typed Carbon Nanotube Field Emitters | |
| TWI464777B (en) | Method for manufacturing electron emission source and method for manufacturing cathode plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |