WO2022188003A1 - Manufacturing method for carbon nanotube cathode, and carbon nanotube cathode and electronic device - Google Patents
Manufacturing method for carbon nanotube cathode, and carbon nanotube cathode and electronic device Download PDFInfo
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- WO2022188003A1 WO2022188003A1 PCT/CN2021/079566 CN2021079566W WO2022188003A1 WO 2022188003 A1 WO2022188003 A1 WO 2022188003A1 CN 2021079566 W CN2021079566 W CN 2021079566W WO 2022188003 A1 WO2022188003 A1 WO 2022188003A1
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- carbon nanotube
- conductive substrate
- cathode
- slurry
- ball milling
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 163
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 162
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 111
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000004381 surface treatment Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims description 49
- 238000000498 ball milling Methods 0.000 claims description 42
- 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 14
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000011324 bead Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007650 screen-printing Methods 0.000 claims description 7
- 150000001247 metal acetylides Chemical class 0.000 claims description 6
- 239000012670 alkaline solution Substances 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
- 238000010981 drying operation Methods 0.000 claims description 2
- 238000010586 diagram Methods 0.000 description 14
- 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
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005245 sintering Methods 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
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 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
- 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- 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
Definitions
- the present application relates to the field of field emission technologies, and in particular, to a method for manufacturing a carbon nanotube cathode, a carbon nanotube cathode and an electronic device.
- Carbon nanotubes have excellent electrochemical properties, extremely high aspect ratio and excellent mechanical strength, and thus have been used as electron sources in field emission (FE) devices.
- FE field emission
- Carbon nanotube-based cold cathode field emission devices generally include a substrate and carbon nanotubes coated or printed or grown on the substrate.
- the carbon nanotubes grown ex situ on the substrate will not be in contact with the substrate due to being wrapped in slurry. Therefore, the current stability and uniformity of the emitter are difficult to control.
- the present application mainly provides a method for manufacturing a carbon nanotube cathode, a carbon nanotube cathode and an electronic device, which can solve the problem of uneven emission current density caused by unstable contact between carbon nanotubes and a substrate in the prior art.
- a first aspect of the present application provides a method for manufacturing a carbon nanotube cathode, the method comprising: providing a conductive substrate; forming a concave structure; using the carbon nanotube slurry to form a carbon nanotube layer on the surface of the conductive substrate to form the carbon nanotube cathode.
- performing the surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate includes: performing a cleaning operation on the conductive substrate; placing the conductive substrate after the cleaning operation in an alkaline solution , so as to form a concave structure on the surface of the conductive substrate.
- performing the cleaning operation on the conductive substrate includes: performing an ultrasonic operation on the conductive substrate; using ethanol to perform a cleaning operation on the conductive substrate after the ultrasonic operation; drying the conductive substrate after the cleaning operation operate.
- the method further includes: adding carbon nanotubes, ball milling beads, binder and metal powder into a ball milling solvent, so as to perform a ball milling operation on the carbon nanometers to form the carbon nanotube slurry.
- adding carbon nanotubes, ball milling beads, binder and metal powder into a ball milling solvent to perform ball milling operation on the carbon nanotubes to form the carbon nanotube slurry includes: mixing the carbon nanotubes Pipes and ball milling beads are added to the ball milling solvent, and a ball milling operation is performed to obtain a primary slurry; the binder is added to the primary slurry, and a ball milling operation is performed to obtain an intermediate slurry; the Metal powder is added to the intermediate slurry, and a ball milling operation is performed to obtain the carbon nanotube slurry.
- the metal powder is one of titanium powder or aluminum powder.
- using the carbon nanotube slurry to form a carbon nanotube layer on the surface of the conductive substrate to form the carbon nanotube cathode includes: using a screen printing technology to form a carbon nanotube layer on the surface of the conductive substrate The carbon nanotube paste is printed on the surface to form the carbon nanotube cathode.
- the method further includes: forming the carbon nanotube cathode Heating is performed in a vacuum environment with a first preset temperature and maintained for a first preset time; the temperature of the vacuum environment is raised to a second preset temperature and maintained for a second preset time to obtain a heated of the carbon nanotube cathode.
- the method further includes: removing carbides on the surface of the heated carbon nanotube cathode.
- a second aspect of the present application provides a carbon nanotube cathode, which is prepared by the method for manufacturing a carbon nanotube cathode provided in the first aspect.
- a third aspect of the present application provides an electronic device, the electronic device includes the carbon nanotube cathode provided in the above-mentioned first aspect.
- the beneficial effects of the present application are: different from the situation in the prior art, the present application performs surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate, and then utilizes carbon nanotube slurry to form carbon nanotubes on the surface of the conductive substrate layer to form a carbon nanotube cathode, the conductivity after surface treatment can basically be better combined with carbon nanotubes, improve the bonding strength between the substrate and carbon nanotubes, and then effectively improve the field emission current density and stability of carbon nanotubes,
- the preparation process is simple, easy to operate and easy to realize.
- FIG. 1 is a schematic flow diagram of an embodiment of a method for manufacturing a carbon nanotube cathode of the present application
- FIG. 2 is a schematic block diagram of the flow of an embodiment of step S20 of the present application.
- FIG. 3 is a schematic block diagram of the process of drying and sintering a carbon nanotube cathode in an embodiment of the present application
- FIG. 4 is a schematic flow diagram of another embodiment of a method for manufacturing a carbon nanotube cathode of the present application.
- FIG. 5 is a schematic block diagram of the flow of an embodiment of step S60 of the present application.
- FIG. 6 is a schematic diagram of a field emission test of an embodiment of applying for a carbon nanotube cold cathode
- FIG. 7 is a schematic diagram of the field emission performance results of the carbon nanotube cold cathode of the present application tested under a DC voltage
- FIG. 8 is a schematic diagram of the field emission performance results of the carbon nanotube cold cathode of the present application tested under an alternating voltage
- FIG. 9 is the field emission stability result of the carbon nanotube cold cathode of the present application tested under alternating voltage.
- first and second in this application are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features shown. Thus, a feature delimited with “first”, “second” may expressly or implicitly include at least one of that feature.
- the terms “comprising” and “having”, and any conjugations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device comprising a series of steps or units is not limited to the listed steps or units, but optionally also includes unlisted steps or units, or optionally also includes For other steps or units inherent to these processes, methods, products or devices.
- FIG. 1 is a schematic flow diagram of an embodiment of a method for fabricating a carbon nanotube cathode of the present application.
- the manufacturing method of the carbon nanotube cathode of the present embodiment may include the following steps:
- the conductive substrate can be a metal or alloy substrate. Wherein, the conductive substrate is used to prepare and form a carbon nanotube layer on the surface, so as to obtain a carbon nanotube cathode.
- the surface treatment operation of the conductive substrate in this step is to form a concave structure on the surface of the substrate.
- the surface of the substrate used for forming the carbon nanotube layer is surface treated to form a hollow nano network structure on the surface of the substrate.
- the surface contact area of the conductive substrate further enhances the bonding strength between the conductive substrate and the carbon nanotube layer.
- the surface treatment operation in this step may be an alkali treatment operation on the conductive substrate.
- FIG. 2 is a schematic block diagram of a process flow of an embodiment of step S20 of the present application. This step may specifically include the following steps:
- the provided conductive substrate is cleaned. Specifically, firstly, ultrasonic operation is performed on the conductive substrate to clean the conductive substrate with ultrasonic waves.
- the ultrasonic cleaning time can be 4 to 8 hours.
- ethanol is used to clean the conductive substrate after the ultrasonic operation.
- a cleaning operation is performed on the conductive substrate, and then a drying operation is performed on the conductive substrate after the cleaning operation.
- alkali solution can be used to perform alkali treatment on the conductive substrate after the cleaning operation, so as to form depressions of nano-network structure on the surface of the substrate, increase the specific surface of the conductive substrate, and effectively improve the bonding strength between the conductive substrate and the carbon nanotubes .
- the conductive substrate can be placed in an alkaline solution, and the conductive substrate can be taken out after standing at a preset temperature for a preset period of time to complete the alkali treatment of the substrate.
- the alkaline solution is a 3M sodium hydroxide solution.
- the conductive substrate is placed in a 3M sodium hydroxide solution, and after standing for a predetermined period of time at a preset temperature, the conductive substrate is taken out to obtain an alkaline treated substrate. conductive substrate.
- the preset temperature may be 25°C to 35°C, for example, the preset temperatures are 28°C, 30°C, and 32°C; the preset time period may be 22 to 26 hours, such as 23 hours, 24 hours, and 25 hours. .
- a carbon nanotube layer is formed on the surface of the conductive substrate by using the carbon nanotube slurry, so as to form a carbon nanotube cathode.
- the carbon nanotube slurry can be coated or printed on the surface of the conductive substrate to form a carbon nanotube layer to obtain a carbon nanotube cathode.
- the carbon nanotube slurry is printed on the surface of the conductive substrate by using the screen printing technology to prepare the carbon nanotube cathode.
- Screen printing refers to the use of silk screen as a plate base, and a screen printing plate with graphics and text is made by a photosensitive plate-making method.
- step S30 operations such as drying and sintering the carbon nanotube cathode can be performed in a vacuum environment, including the following steps:
- the carbon nanotube cathode is dried.
- the first preset temperature may be 150°C to 250°C, such as 180°C, 200°C, and 220°C; the first preset time may be 1 to 3 hours, such as 1.5 hours, 2 hours, and 2.5 hours.
- step S31 after the carbon nanotube cathode is dried, the temperature of the vacuum environment is raised to a second preset temperature, and heating is continued, so as to calcine and remove the adhesive from the carbon nanotube cathode.
- the heating rate is 2°C/min to 5°C/min, for example, 2°C/min, 3°C/min, and 4°C/min.
- the second preset temperature may be 600°C to 800°C, such as 650°C, 700°C, and 750°C; the second preset time may be 1 to 3 hours, such as 1.5 hours, 2 hours, and 2.5 hours.
- the carbides on the surface of the carbon nanotube cathode can be removed, for example, 3M adhesive tape can be used to remove the carbides on the surface of the carbon nanotube cathode.
- a hollowed-out nano-net-like structure is formed on the surface of the substrate, and the specific surface of the substrate is increased, which greatly improves the bonding strength of the carbon nanotubes and the alloy substrate, thereby improving the carbon nanotubes.
- Field emission current density and stability are greatly improves the bonding strength of the carbon nanotubes and the alloy substrate, thereby improving the carbon nanotubes.
- FIG. 4 is a schematic flowchart of another embodiment of the method for fabricating a carbon nanotube cathode of the present application. It should be noted that, if there is substantially the same result, the present embodiment is not limited to the sequence of the processes shown in FIG. 4 .
- the manufacturing method of the carbon nanotube cathode of this embodiment includes the following steps:
- the conductive substrate can be a metal or alloy substrate, or an insulating substrate with a conductive metal layer or an alloy layer plated on the surface, such as a Ti6Al4V alloy substrate (Ti-6Al-4V is the nominal chemical composition of the titanium alloy grade TC4. Method, the composition of titanium alloy TC4 material is Ti-6Al-4V, which belongs to ( ⁇ + ⁇ ) type titanium alloy, has good comprehensive mechanical and mechanical properties, and has high specific strength.). Wherein, the conductive substrate is used to prepare and form a carbon nanotube layer on the surface, so as to obtain a carbon nanotube cathode.
- the surface treatment operation of the conductive substrate in this step is to form a concave structure on the surface of the substrate.
- the surface of the substrate used for forming the carbon nanotube layer is surface treated to form a hollow nano network structure on the surface of the substrate.
- the surface contact area of the conductive substrate further enhances the bonding strength between the conductive substrate and the carbon nanotube layer.
- the surface treatment operation in this step may be an alkali treatment operation on the conductive substrate.
- steps S201 to S201 in the previous embodiment which will not be repeated here.
- the particle size of the metal powder is 20 nm to 50 ⁇ m.
- the metal powder will cause mechanical damage to the carbon nanotubes and increase the surface defects of the carbon nanotubes, thereby increasing the emission position of electrons, thereby reducing the work function of the carbon nanotube cathode system and improving the overall emission efficiency.
- the binder can be sodium carboxymethyl cellulose, and the ball milling solvent can be terpineol; or, the binder can also be polyvinylidene fluoride, and the ball milling solvent can also be N-methylpyrrolidone.
- the metal powder is a metal powder with a low work function, such as aluminum powder or titanium powder.
- FIG. 5 is a schematic block diagram of the flow of an embodiment of step S60 of the present application. It should be noted that, if there is substantially the same result, the present embodiment is not limited to the sequence of the processes shown in FIG. 5 .
- the preparation of carbon nanotube slurry in this embodiment specifically includes the following steps:
- carbon nanotubes and ball-milling beads are added to the ball-milling solvent, and the ball-milling operation is performed for 2-4 hours to obtain primary slurry.
- step S61 the binder is added to the primary slurry obtained in step S61, and the ball milling operation is performed for 3-5 hours to obtain the intermediate slurry.
- the metal powder is added to the intermediate slurry obtained in step S62, and the ball-milling operation is performed for 1-3 hours to obtain a carbon nanotube slurry.
- the metal powder causes mechanical damage to the surface of the carbon nanotube, thereby increasing the surface defects of the carbon nanotube, thereby increasing electron emission sites and effectively reducing the work function.
- a carbon nanotube layer is formed on the surface of the conductive substrate by using the carbon nanotube slurry, so as to form a carbon nanotube cathode.
- the carbon nanotube slurry can be coated or printed on the surface of the conductive substrate to form a carbon nanotube layer to obtain a carbon nanotube cathode.
- the carbon nanotube slurry is printed on the surface of the conductive substrate by using the screen printing technology to prepare the carbon nanotube cathode.
- this embodiment performs alkali treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate to obtain a substrate with a larger specific surface, which effectively improves the bonding strength between the conductive substrate and the carbon nanotubes;
- adding metal powder and carbon nanotubes for ball milling operation to cause mechanical damage to the surface of carbon nanotubes, so as to increase the surface defects of carbon nanotubes, thereby increasing the emission sites of electrons and effectively reducing the power. function. Therefore, the present embodiment can effectively improve the field emission current density and stability of the carbon nanotube, and the preparation process is simple and easy to operate.
- Steps (1) to (7) are the method steps of a specific embodiment of preparing a carbon nanotube cathode in this embodiment, including:
- FIG. 6 is a schematic diagram of the field emission test of the carbon nanotube cold cathode of the present embodiment
- FIG. 7 is a schematic diagram of the field emission performance result of the carbon nanotube cold cathode of the present embodiment tested under a DC voltage
- FIG. 8 is a schematic diagram of the field emission performance results of the carbon nanotube cold cathode of the present embodiment tested under an alternating voltage
- FIG. 9 is a field emission stability result of the carbon nanotube cold cathode of the present embodiment tested under an alternating voltage
- D1 and D2 in Figure 7 and Figure 8 are the experimental results of the control group.
- the carbon nanotube cold cathode prepared in this example can obtain an open electric field of 0.79V/ ⁇ m under the driving of direct current, and can obtain an electric field of 85.13mA/cm2 under the electric field strength of 2.38V/ ⁇ m Current density; under the driving of alternating current, it can show a current density of 1.226A/cm2 at an electric field strength of 6.1V/ ⁇ m; and after continuous driving at an electric field strength of 4.0V/ ⁇ m for 15 hours, the current density can still reach 0.4 A/cm2. Therefore, the carbon nanotube cold cathode prepared by the method of this embodiment has a higher field emission current density and is more stable.
- the present application also provides a carbon nanotube cathode, which is prepared by the above-mentioned manufacturing method of a carbon nanotube cathode.
- the preparation method will not be repeated here.
- the carbon nanotube cathode prepared by this method is enhanced by the Therefore, the field emission current density is larger and more stable.
- the present application also provides an electronic device, such as a field emission flat display device or a vacuum electron source, etc.
- the electronic device includes the carbon nanotube cathode provided in the previous embodiment, since its preparation process exists in the above embodiments It also has the characteristics of larger and more stable field emission current density.
Abstract
The present application discloses a manufacturing method for a carbon nanotube cathode, and a carbon nanotube cathode and an electronic device. The method comprises: providing a conductive substrate; performing a surface treatment on the conductive substrate, such that a recessed structure is formed in a surface of the conductive substrate; and utilizing a carbon nanotube paste to form a carbon nanotube layer on the surface of the conductive substrate, so as to form a carbon nanotube cathode. By means of the method, the present application can improve the bonding strength of a substrate and a carbon nanotube, and can thus also improve the field emission current density and stability of the carbon nanotube, and the preparation process is simple and easy to realize.
Description
本申请涉及场发射技术领域，特别是涉及碳纳米管阴极的制作方法、碳纳米管阴极及电子设备。The present application relates to the field of field emission technologies, and in particular, to a method for manufacturing a carbon nanotube cathode, a carbon nanotube cathode and an electronic device.
碳纳米管(CNTs)具有优异的电化学性能，极高的长径比和优异的机械强度，因此已被用于场发射(FE)器件中的电子源。作为一种场发射冷阴极材料，它具有低工作电压，较高的场发射电流密度和独特的工作稳定性，因而成为场发射领域研究的重点。Carbon nanotubes (CNTs) have excellent electrochemical properties, extremely high aspect ratio 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, high field emission current density and unique working stability, so it has become the focus of field emission research.
在许多真空微波设备的应用中，不仅要求能发射较高的电流密度，而且也要求在长期使用过程中性能的劣化率要求低。基于碳纳米管的冷阴极场发射装置一般包括基板以及涂覆或印刷又或生长在基板的碳纳米管，但是非原位生长在基板的碳纳米管会因被浆料包裹而与基板接触不稳定，因而发射体的电流稳定及均匀性都难以控制。In many applications of vacuum microwave equipment, it is not only required to be able to emit a high current density, but also to require a low rate of deterioration in performance during long-term use. Carbon nanotube-based cold cathode field emission devices generally include a substrate and carbon nanotubes coated or printed or grown on the substrate. However, the carbon nanotubes grown ex situ on the substrate will not be in contact with the substrate due to being wrapped in slurry. Therefore, the current stability and uniformity of the emitter are difficult to control.
鉴于此，有必要提供一种碳纳米管场发射阴极及其制备方法，使制得的碳纳米管场发射阴极具有较大的电流面密度和均匀的稳定性。In view of this, it is necessary to provide a carbon nanotube field emission cathode and a preparation method thereof, so that the prepared carbon nanotube field emission cathode has a large current surface density and uniform stability.
【发明内容】[Content of the invention]
本申请主要提供一种碳纳米管阴极的制作方法、碳纳米管阴极及电子设备，能够解决现有技术中的碳纳米管与基底接触不稳定造成的发射电流密度不均匀问题。The present application mainly provides a method for manufacturing a carbon nanotube cathode, a carbon nanotube cathode and an electronic device, which can solve the problem of uneven emission current density caused by unstable contact between carbon nanotubes and a substrate in the prior art.
为解决上述技术问题，本申请第一方面提供了一种碳纳米管阴极的制作方法，所述方法包括：提供一导电基板；对所述导电基板进行表面处理，以在所述导电基板的表面形成凹陷结构；利用所述碳纳米管浆料在所述导电基板的所述表面形成碳纳米管层，以形成所述碳纳米管阴极。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; forming a concave structure; using the carbon nanotube slurry to form a carbon nanotube layer on the surface of the conductive substrate to form the carbon nanotube cathode.
其中，所述对所述导电基板进行表面处理，以在所述导电基板的表面形成凹陷结构，包括：对所述导电基板进行清洁操作；将清洁操作之 后的所述导电基板置于碱溶液中，以在所述导电基板的表面形成凹陷结构。Wherein, performing the surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate includes: performing a cleaning operation on the conductive substrate; placing the conductive substrate after the cleaning operation in an alkaline solution , so as to form a concave structure on the surface of the conductive substrate.
其中，所述对所述导电基板进行清洁操作，包括：对所述导电基板进行超声操作；采用乙醇对超声操作之后的所述导电基板进行清洗操作；对清洗操作之后的所述导电基板进行干燥操作。Wherein, performing the cleaning operation on the conductive substrate includes: performing an ultrasonic operation on the conductive substrate; using ethanol to perform a cleaning operation on the conductive substrate after the ultrasonic operation; drying the conductive substrate after the cleaning operation operate.
其中，所述方法还包括：将碳纳米管、球磨珠、粘结剂和金属粉加入到球磨溶剂中，以对所述碳纳米进行球磨操作，形成所述碳纳米管浆料。Wherein, the method further includes: adding carbon nanotubes, ball milling beads, binder and metal powder into a ball milling solvent, so as to perform a ball milling operation on the carbon nanometers to form the carbon nanotube slurry.
其中，所述将碳纳米管、球磨珠、粘结剂和金属粉加入到球磨溶剂中，以对所述碳纳米进行球磨操作，形成所述碳纳米管浆料，包括：将所述碳纳米管、球磨珠加入到所述球磨溶剂中，进行球磨操作，以得到初级浆料；将所述粘结剂加入到所述初级浆料中，进行球磨操作，以得到中间浆料；将所述金属粉加入到所述中间浆料中，进行球磨操作，以得到所述碳纳米管浆料。Wherein, adding carbon nanotubes, ball milling beads, binder and metal powder into a ball milling solvent to perform ball milling operation on the carbon nanotubes to form the carbon nanotube slurry includes: mixing the carbon nanotubes Pipes and ball milling beads are added to the ball milling solvent, and a ball milling operation is performed to obtain a primary slurry; the binder is added to the primary slurry, and a ball milling operation is performed to obtain an intermediate slurry; the Metal powder is added to the intermediate slurry, and a ball milling operation is performed to obtain the carbon nanotube slurry.
其中，所述金属粉为钛粉或铝粉中的一种。Wherein, the metal powder is one of titanium powder or aluminum powder.
其中，所述利用所述碳纳米管浆料在所述导电基板的所述表面形成碳纳米管层，以形成所述碳纳米管阴极，包括：利用丝网印刷技术在所述导电基板的所述表面印刷所述碳纳米管浆料，以形成所述碳纳米管阴极。Wherein, using the carbon nanotube slurry to form a carbon nanotube layer on the surface of the conductive substrate to form the carbon nanotube cathode includes: using a screen printing technology to form a carbon nanotube layer on the surface of the conductive substrate The carbon nanotube paste is printed on the surface to form the carbon nanotube cathode.
其中，所述利用所述碳纳米管浆料在所述导电基板的所述表面形成碳纳米管层，以形成所述碳纳米管阴极之后，所述方法还包括：将所述碳纳米管阴极置于第一预设温度的真空环境中进行加热，并维持第一预设时间；将所述真空环境的温度升高至第二预设温度，并维持第二预设时间，以得到加热后的所述碳纳米管阴极。Wherein, after using the carbon nanotube slurry to form a carbon nanotube layer on the surface of the conductive substrate to form the carbon nanotube cathode, the method further includes: forming the carbon nanotube cathode Heating is performed in a vacuum environment with a first preset temperature and maintained for a first preset time; the temperature of the vacuum environment is raised to a second preset temperature and maintained for a second preset time to obtain a heated of the carbon nanotube cathode.
其中，所述方法还包括：去除所述加热后的所述碳纳米管阴极表面的碳化物。Wherein, the method further includes: removing carbides on the surface of the heated carbon nanotube cathode.
为解决上述技术问题，本申请第二方面提供了一种碳纳米管阴极，该碳纳米管阴极通过上述第一方面提供的碳纳米管阴极的制作方法制备而成。In order to solve the above technical problems, a second aspect of the present application provides a carbon nanotube cathode, which is prepared by the method for manufacturing a carbon nanotube cathode provided in the first aspect.
为解决上述技术问题，本申请第三方面提供了一种电子设备，所述电子设备包括如上述第一方面提供的碳纳米管阴极。In order to solve the above technical problem, a third aspect of the present application provides an electronic device, the electronic device includes the carbon nanotube cathode provided in the above-mentioned first aspect.
本申请的有益效果是：区别于现有技术的情况，本申请对导电基板进行表面处理，以在导电基板的表面形成凹陷结构，然后利用碳纳米管浆料在导电基板的表面形成碳纳米管层，以形成碳纳米管阴极，表面处理后的导电基本能够更好地与碳纳米管结合，提高基板和碳纳米管的结合强度，进而有效提高碳纳米管的场发射电流密度和稳定性，制备工艺简单，易于操作，易于实现。The beneficial effects of the present application are: different from the situation in the prior art, the present application performs surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate, and then utilizes carbon nanotube slurry to form carbon nanotubes on the surface of the conductive substrate layer to form a carbon nanotube cathode, the conductivity after surface treatment can basically be better combined with carbon nanotubes, improve the bonding strength between the substrate and carbon nanotubes, and then effectively improve the field emission current density and stability of carbon nanotubes, The preparation process is simple, easy to operate and easy to realize.
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。其中：In order to illustrate the technical solutions in the embodiments of the present application more clearly, the following briefly introduces the drawings that are used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative effort. in:
图1是本申请碳纳米管阴极的制作方法一实施例的流程示意框图；1 is a schematic flow diagram of an embodiment of a method for manufacturing a carbon nanotube cathode of the present application;
图2是本申请步骤S20一实施例的流程示意框图；FIG. 2 is a schematic block diagram of the flow of an embodiment of step S20 of the present application;
图3是本申请对碳纳米管阴极进行干燥、烧结一实施例的流程示意框图；3 is a schematic block diagram of the process of drying and sintering a carbon nanotube cathode in an embodiment of the present application;
图4是本申请碳纳米管阴极的制作方法另一实施例的流程示意框图；4 is a schematic flow diagram of another embodiment of a method for manufacturing a carbon nanotube cathode of the present application;
图5是本申请步骤S60一实施例的流程示意框图；FIG. 5 is a schematic block diagram of the flow of an embodiment of step S60 of the present application;
图6是申请碳纳米管冷阴极一实施例的场发射测试示意图；6 is a schematic diagram of a field emission test of an embodiment of applying for a carbon nanotube cold cathode;
图7是本申请碳纳米管冷阴极在直流电压下测试的场发射性能结果示意图；7 is a schematic diagram of the field emission performance results of the carbon nanotube cold cathode of the present application tested under a DC voltage;
图8是本申请碳纳米管冷阴极在交流电压下测试的场发射性能结果示意图；8 is a schematic diagram of the field emission performance results of the carbon nanotube cold cathode of the present application tested under an alternating voltage;
图9是本申请碳纳米管冷阴极在交流电压下测试的场发射稳定性结果。FIG. 9 is the field emission stability result of the carbon nanotube cold cathode of the present application tested under alternating voltage.
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本申请的一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.
本申请中的术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。此外，术语“包括”和“具有”以及他们任何形变，意图在于覆盖不排他的包含。例如包含了一系列步骤或单元的过程、方法、***、产品或设备没有限定于已列出的步骤或单元，而是可选地还包括没有列出的步骤或单元，或可选地还包括对于这些过程、方法、产品或设备固有的其它步骤或单元。The terms "first" and "second" in this application are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features shown. Thus, a feature delimited with "first", "second" may expressly or implicitly include at least one of that feature. Furthermore, the terms "comprising" and "having", and any conjugations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device comprising a series of steps or units is not limited to the listed steps or units, but optionally also includes unlisted steps or units, or optionally also includes For other steps or units inherent to these processes, methods, products or devices.
在本文中提及“实施例”意味着，结合实施例描述的特定特征、结构或特性可以包含在本申请的至少一个实施例中。在说明书中的各个位置出现该短语不一定均是指相同的实施例，也不是与其它实施例互斥的独立的或备选的实施例。本领域技术人员显式地和隐式地理解是，本文所描述的实施例可以与其他实施例结合。Reference herein to an "embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the present application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor a separate or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.
请参阅图1，图1为本申请碳纳米管阴极的制作方法一实施例的流程示意框图。本实施例碳纳米管阴极的制作方法可以包括以下步骤：Please refer to FIG. 1 . FIG. 1 is a schematic flow diagram of an embodiment of a method for fabricating a carbon nanotube cathode of the present application. The manufacturing method of the carbon nanotube cathode of the present embodiment may include the following steps:
S10，提供一导电基板。S10, providing a conductive substrate.
该导电基板可为金属材质或合金材质的基板。其中，导电基板用于在表面制备形成碳纳米管层，以得到碳纳米管阴极。The conductive substrate can be a metal or alloy substrate. Wherein, the conductive substrate is used to prepare and form a carbon nanotube layer on the surface, so as to obtain a carbon nanotube cathode.
S20，对导电基板进行表面处理，以在导电基板的表面形成凹陷结构。S20, performing surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate.
本步骤对导电基板的表面处理操作是为了在基板的表面形成凹陷结构，本步骤对用于对形成碳纳米管层的基板表面进行表面处理，以在基板表面形成镂空纳米网状结构，增大导电基板的表面接触面积，进而增强导电基板与碳纳米管层的结合强度。The surface treatment operation of the conductive substrate in this step is to form a concave structure on the surface of the substrate. In this step, the surface of the substrate used for forming the carbon nanotube layer is surface treated to form a hollow nano network structure on the surface of the substrate. The surface contact area of the conductive substrate further enhances the bonding strength between the conductive substrate and the carbon nanotube layer.
其中，本步骤的表面处理操作可以是对导电基板进行碱处理操作。具体请参照图2，图2为本申请步骤S20一实施例的流程示意框图。本步骤具体可包括以下步骤：Wherein, the surface treatment operation in this step may be an alkali treatment operation on the conductive substrate. For details, please refer to FIG. 2 , which is a schematic block diagram of a process flow of an embodiment of step S20 of the present application. This step may specifically include the following steps:
S201，对导电基板进行清洁操作。S201, a cleaning operation is performed on the conductive substrate.
本步骤对提供的导电基板进行清洁，具体地，首先对导电基板进行超声操作，以利用超声波清洗导电基板，超声清洗时长可为4至8小时，超声波清洗结束后，采用乙醇对超声操作之后的导电基板进行清洗操作，之后对清洗操作之后的导电基板进行干燥操作。In this step, the provided conductive substrate is cleaned. Specifically, firstly, ultrasonic operation is performed on the conductive substrate to clean the conductive substrate with ultrasonic waves. The ultrasonic cleaning time can be 4 to 8 hours. After the ultrasonic cleaning, ethanol is used to clean the conductive substrate after the ultrasonic operation. A cleaning operation is performed on the conductive substrate, and then a drying operation is performed on the conductive substrate after the cleaning operation.
S202，将清洁操作之后的导电基板置于碱溶液中，以在导电基板的表面形成凹陷结构。S202, placing the conductive substrate after the cleaning operation in an alkaline solution to form a concave structure on the surface of the conductive substrate.
本步骤可使用碱溶液对清洁操作之后的导电基板进行碱处理，以在基板的表面形成纳米网状结构的凹陷，增大导电基板的比表面，能够有效提高导电基板与碳纳米管的结合力度。In this step, alkali solution can be used to perform alkali treatment on the conductive substrate after the cleaning operation, so as to form depressions of nano-network structure on the surface of the substrate, increase the specific surface of the conductive substrate, and effectively improve the bonding strength between the conductive substrate and the carbon nanotubes .
具体而言，本步骤可将导电基板置于碱溶液中，并在预设温度条件下静置预设时长后将导电基板取出，完成对基板的碱处理。Specifically, in this step, the conductive substrate can be placed in an alkaline solution, and the conductive substrate can be taken out after standing at a preset temperature for a preset period of time to complete the alkali treatment of the substrate.
例如，碱溶液是3M的氢氧化钠溶液，本步骤将导电基板置于3M的氢氧化钠溶液，在预设温度条件下静置预设时长后，取出导电基板，即可得到碱处理后的导电基板。For example, the alkaline solution is a 3M sodium hydroxide solution. In this step, the conductive substrate is placed in a 3M sodium hydroxide solution, and after standing for a predetermined period of time at a preset temperature, the conductive substrate is taken out to obtain an alkaline treated substrate. conductive substrate.
其中，预设温度可以是25℃～35℃，例如预设温度为28℃、30℃、32℃；预设时长可以是22～26小时，例如预设时长为23小时、24小时、25小时。The preset temperature may be 25°C to 35°C, for example, the preset temperatures are 28°C, 30°C, and 32°C; the preset time period may be 22 to 26 hours, such as 23 hours, 24 hours, and 25 hours. .
S30，利用碳纳米管浆料在导电基板的表面形成碳纳米管层，以形成碳纳米管阴极。S30, a carbon nanotube layer is formed on the surface of the conductive substrate by using the carbon nanotube slurry, so as to form a carbon nanotube cathode.
其中，可将碳纳米管浆料涂覆或印刷在导电基板的表面，以形成碳纳米管层，得到碳纳米管阴极。Wherein, the carbon nanotube slurry can be coated or printed on the surface of the conductive substrate to form a carbon nanotube layer to obtain a carbon nanotube cathode.
在一具体的实施例中，利用丝网印刷技术在导电基板的表面印刷碳纳米管浆料，以制备得到碳纳米管阴极。丝网印刷是指用丝网作为版基，并通过感光制版方法，制成带有图文的丝网印版。In a specific embodiment, the carbon nanotube slurry is printed on the surface of the conductive substrate by using the screen printing technology to prepare the carbon nanotube cathode. Screen printing refers to the use of silk screen as a plate base, and a screen printing plate with graphics and text is made by a photosensitive plate-making method.
请参阅图3，步骤S30之后，可在真空环境对碳纳米管阴极进行干 燥、烧结等操作，包括以下步骤：Referring to Fig. 3, after step S30, operations such as drying and sintering the carbon nanotube cathode can be performed in a vacuum environment, including the following steps:
S31，将碳纳米管阴极置于第一预设温度的真空环境中进行加热，并维持第一预设时间。S31 , heating the carbon nanotube cathode in a vacuum environment with a first preset temperature, and maintaining it for a first preset time.
本步骤对碳纳米管阴极进行干燥操作。其中，第一预设温度可以为150℃～250℃，例如为180℃、200℃、220℃；第一预设时间可以为1～3小时，例如为1.5小时、2小时、2.5小时。In this step, the carbon nanotube cathode is dried. The first preset temperature may be 150°C to 250°C, such as 180°C, 200°C, and 220°C; the first preset time may be 1 to 3 hours, such as 1.5 hours, 2 hours, and 2.5 hours.
S32，将真空环境的温度升高至第二预设温度，并维持第二预设时间，以得到加热后的碳纳米管阴极。S32, raising the temperature of the vacuum environment to a second preset temperature and maintaining the temperature for a second preset time to obtain a heated carbon nanotube cathode.
步骤S31将碳纳米管阴极干燥完毕后，将真空环境的温度升高至第二预设温度继续加热，以对碳纳米管阴极进行煅烧除胶。其中，升温速率为2℃/min～5℃/min，例如为2℃/min、3℃/min、4℃/min。In step S31, after the carbon nanotube cathode is dried, the temperature of the vacuum environment is raised to a second preset temperature, and heating is continued, so as to calcine and remove the adhesive from the carbon nanotube cathode. The heating rate is 2°C/min to 5°C/min, for example, 2°C/min, 3°C/min, and 4°C/min.
其中，第二预设温度可以为600℃～800℃，例如为650℃、700℃、750℃；第二预设时间可以为1～3小时，例如为1.5小时、2小时、2.5小时。The second preset temperature may be 600°C to 800°C, such as 650°C, 700°C, and 750°C; the second preset time may be 1 to 3 hours, such as 1.5 hours, 2 hours, and 2.5 hours.
S33，去除加热后的碳纳米管阴极表面的碳化物。S33, removing carbides on the surface of the heated carbon nanotube cathode.
本步骤可对碳纳米管阴极表面的碳化物进行粘除处理，例如可利用3M的胶带粘除碳纳米管阴极表面的碳化物。In this step, the carbides on the surface of the carbon nanotube cathode can be removed, for example, 3M adhesive tape can be used to remove the carbides on the surface of the carbon nanotube cathode.
至此，完成碳纳米管阴极的制备。So far, the preparation of the carbon nanotube cathode is completed.
本实施例通过对基板进行表面处理，在基板表面形成镂空纳米网状结构的凹陷，加大基板的比表面，很好地提高了碳纳米管与合金基板的结合强度，进而提高碳纳米管的场发射电流密度和稳定性。In this embodiment, by performing surface treatment on the substrate, a hollowed-out nano-net-like structure is formed on the surface of the substrate, and the specific surface of the substrate is increased, which greatly improves the bonding strength of the carbon nanotubes and the alloy substrate, thereby improving the carbon nanotubes. Field emission current density and stability.
请参阅图4，图4是本申请碳纳米管阴极的制作方法另一实施例的流程示意框图。需注意的是，若有实质上相同的结果，本实施例并不以图4所示的流程顺序为限。本实施例的碳纳米管阴极的制作方法包括以下步骤：Please refer to FIG. 4 . FIG. 4 is a schematic flowchart of another embodiment of the method for fabricating a carbon nanotube cathode of the present application. It should be noted that, if there is substantially the same result, the present embodiment is not limited to the sequence of the processes shown in FIG. 4 . The manufacturing method of the carbon nanotube cathode of this embodiment includes the following steps:
S40，提供一导电基板。S40, providing a conductive substrate.
该导电基板可为金属材质或合金材质的基板，或者为表面镀有导电金属层或合金层的绝缘基板，例如可以为Ti6Al4V合金基板(Ti-6Al-4V是钛合金牌号TC4的名义化学成分表示方法，钛合金TC4材料的组成 为Ti-6Al-4V，属于(α+β)型钛合金，具有良好的综合力学机械性能。比强度大。)。其中，导电基板用于在表面制备形成碳纳米管层，以得到碳纳米管阴极。The conductive substrate can be a metal or alloy substrate, or an insulating substrate with a conductive metal layer or an alloy layer plated on the surface, such as a Ti6Al4V alloy substrate (Ti-6Al-4V is the nominal chemical composition of the titanium alloy grade TC4. Method, the composition of titanium alloy TC4 material is Ti-6Al-4V, which belongs to (α+β) type titanium alloy, has good comprehensive mechanical and mechanical properties, and has high specific strength.). Wherein, the conductive substrate is used to prepare and form a carbon nanotube layer on the surface, so as to obtain a carbon nanotube cathode.
S50，对导电基板进行表面处理，以在导电基板的表面形成凹陷结构。S50, performing surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate.
本步骤对导电基板的表面处理操作是为了在基板的表面形成凹陷结构，本步骤对用于对形成碳纳米管层的基板表面进行表面处理，以在基板表面形成镂空纳米网状结构，增大导电基板的表面接触面积，进而增强导电基板与碳纳米管层的结合强度。The surface treatment operation of the conductive substrate in this step is to form a concave structure on the surface of the substrate. In this step, the surface of the substrate used for forming the carbon nanotube layer is surface treated to form a hollow nano network structure on the surface of the substrate. The surface contact area of the conductive substrate further enhances the bonding strength between the conductive substrate and the carbon nanotube layer.
其中，本步骤的表面处理操作可以是对导电基板进行碱处理操作。具体可参照上一实施例中的步骤S201～步骤S201，此处不再进行赘述。Wherein, the surface treatment operation in this step may be an alkali treatment operation on the conductive substrate. For details, reference may be made to steps S201 to S201 in the previous embodiment, which will not be repeated here.
S60，将碳纳米管、球磨珠、粘结剂和金属粉加入到球磨溶剂中，以对碳纳米进行球磨操作，形成碳纳米管浆料。S60, adding carbon nanotubes, ball milling beads, a binder and metal powder into a ball milling solvent, so as to perform a ball milling operation on the carbon nanometers to form a carbon nanotube slurry.
其中，金属粉的粒径为20nm～50μm。本步骤在球磨制备浆料的过程中，金属粉会对碳纳米管造成机械损伤，增加碳纳米管的表面缺陷，从而增多电子的发射位，进而降低碳纳米管阴极***的功函数，提高整体发射效率。The particle size of the metal powder is 20 nm to 50 μm. In this step, in the process of preparing slurry by ball milling, the metal powder will cause mechanical damage to the carbon nanotubes and increase the surface defects of the carbon nanotubes, thereby increasing the emission position of electrons, thereby reducing the work function of the carbon nanotube cathode system and improving the overall emission efficiency.
其中，粘结剂可以是羧甲基纤维素钠，球磨溶剂可以是松油醇；或者，粘结剂还可以是聚偏氟乙烯，球磨溶剂还可以是N-甲基吡咯烷酮。Wherein, the binder can be sodium carboxymethyl cellulose, and the ball milling solvent can be terpineol; or, the binder can also be polyvinylidene fluoride, and the ball milling solvent can also be N-methylpyrrolidone.
其中，金属粉为具有低功函数的金属粉，例如可以是铝粉或钛粉。Wherein, the metal powder is a metal powder with a low work function, such as aluminum powder or titanium powder.
请参阅图5，图5为本申请步骤S60一实施例的流程示意框图。需注意的是，若有实质上相同的结果，本实施例并不以图5所示的流程顺序为限。本实施例制备碳纳米管浆料具体包括以下步骤：Please refer to FIG. 5. FIG. 5 is a schematic block diagram of the flow of an embodiment of step S60 of the present application. It should be noted that, if there is substantially the same result, the present embodiment is not limited to the sequence of the processes shown in FIG. 5 . The preparation of carbon nanotube slurry in this embodiment specifically includes the following steps:
S61，将碳纳米管、球磨珠加入到球磨溶剂中，进行球磨操作，以得到初级浆料。S61, adding carbon nanotubes and ball-milling beads into a ball-milling solvent, and performing a ball-milling operation to obtain a primary slurry.
本步骤将碳纳米管、球磨珠加入到球磨溶剂，并进行球磨操作2～4小时，以得到初级浆料。In this step, carbon nanotubes and ball-milling beads are added to the ball-milling solvent, and the ball-milling operation is performed for 2-4 hours to obtain primary slurry.
S62，将粘结剂加入到初级浆料中，进行球磨操作，以得到中间浆料。S62, adding a binder to the primary slurry, and performing a ball milling operation to obtain an intermediate slurry.
本步骤将粘结剂加入到步骤S61得到的初级浆料中，并进行球磨操作3～5小时，得到中间浆料。In this step, the binder is added to the primary slurry obtained in step S61, and the ball milling operation is performed for 3-5 hours to obtain the intermediate slurry.
S63，将金属粉加入到中间浆料中，进行球磨操作，以得到碳纳米管浆料。S63, adding the metal powder into the intermediate slurry, and performing a ball milling operation to obtain a carbon nanotube slurry.
本步骤将金属粉加入到步骤S62得到的中间浆料中，球磨操作1～3小时，得到碳纳米管浆料。本步骤在进行机械球磨的过程中，金属粉对碳纳米管的表面造成机械损伤，从而使得碳纳米管的表面缺陷增多，进而增多电子的发射位点，有效降低功函数。In this step, the metal powder is added to the intermediate slurry obtained in step S62, and the ball-milling operation is performed for 1-3 hours to obtain a carbon nanotube slurry. In the process of mechanical ball milling in this step, the metal powder causes mechanical damage to the surface of the carbon nanotube, thereby increasing the surface defects of the carbon nanotube, thereby increasing electron emission sites and effectively reducing the work function.
S70，利用碳纳米管浆料在导电基板的表面形成碳纳米管层，以形成碳纳米管阴极。S70, a carbon nanotube layer is formed on the surface of the conductive substrate by using the carbon nanotube slurry, so as to form a carbon nanotube cathode.
其中，可将碳纳米管浆料涂覆或印刷在导电基板的表面，以形成碳纳米管层，得到碳纳米管阴极。Wherein, the carbon nanotube slurry can be coated or printed on the surface of the conductive substrate to form a carbon nanotube layer to obtain a carbon nanotube cathode.
在一具体的实施例中，利用丝网印刷技术在导电基板的表面印刷碳纳米管浆料，以制备得到碳纳米管阴极。In a specific embodiment, the carbon nanotube slurry is printed on the surface of the conductive substrate by using the screen printing technology to prepare the carbon nanotube cathode.
本步骤之后，可在真空环境对碳纳米管阴极进行干燥、烧结等操作，具体请参照步骤S31～步骤S33，此处不再进行赘述。After this step, operations such as drying and sintering the carbon nanotube cathode can be performed in a vacuum environment. For details, please refer to steps S31 to S33, which will not be repeated here.
本实施例一方面对导电基板进行碱处理，在导电基板的表面形成凹陷结构，得到比表面大的基板，有效提高地提高导电基板与碳纳米管的结合力度；另一方面，本实施例在制备浆料的过程中，加入金属粉末与碳纳米管一起进行球磨操作，以对碳纳米管表面造成机械损伤，从而使得碳纳米管的表面缺陷增多，进而增多电子的发射位点，有效降低功函数。因此，本实施例能够有效提高碳纳米管的场发射电流密度和稳定性，且制备工艺简单，易于操作。On the one hand, this embodiment performs alkali treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate to obtain a substrate with a larger specific surface, which effectively improves the bonding strength between the conductive substrate and the carbon nanotubes; In the process of preparing the slurry, adding metal powder and carbon nanotubes for ball milling operation to cause mechanical damage to the surface of carbon nanotubes, so as to increase the surface defects of carbon nanotubes, thereby increasing the emission sites of electrons and effectively reducing the power. function. Therefore, the present embodiment can effectively improve the field emission current density and stability of the carbon nanotube, and the preparation process is simple and easy to operate.
步骤(1)～(7)为本实施例制备碳纳米管阴极一具体实施方式的方法步骤，包括：Steps (1) to (7) are the method steps of a specific embodiment of preparing a carbon nanotube cathode in this embodiment, including:
(1)提供一Ti6Al4V合金基板；(1) Provide a Ti6Al4V alloy substrate;
(2)对Ti6Al4V合金基板进行超声操作6小时后，利用乙醇清洗后干燥；(2) After ultrasonic operation is performed on the Ti6Al4V alloy substrate for 6 hours, it is cleaned with ethanol and then dried;
(3)将干燥后的Ti6Al4V合金基板置于10M的NaOH的溶液中，并 在30℃的温度条件下静置24h，以完成对Ti6Al4V合金基板的表面处理；(3) Place the dried Ti6Al4V alloy substrate in a 10M NaOH solution, and stand for 24h at a temperature of 30°C to complete the surface treatment of the Ti6Al4V alloy substrate;
(4)制备碳纳米管浆料；(4) preparing carbon nanotube slurry;
包括步骤a～c：Including steps a～c:
a.将0.1g～0.5g碳纳米管、ZrC球磨珠以及2～6mL的松油醇球磨3小时，得到初级浆料；a. Ball milling 0.1g～0.5g of carbon nanotubes, ZrC balls and 2～6mL of terpineol for 3 hours to obtain primary slurry;
b.在初级浆料中添加0.05～0.2g羧甲基纤维素钠，球磨4小时，得到中间浆料；b. Add 0.05-0.2g sodium carboxymethyl cellulose to the primary slurry, and ball mill for 4 hours to obtain an intermediate slurry;
c.在中间浆料中添加0.05～0.2g钛粉，球磨2小时，得到碳纳米管浆料。c. Add 0.05-0.2 g of titanium powder to the intermediate slurry, and perform ball milling for 2 hours to obtain carbon nanotube slurry.
(5)通过丝网印刷方法将碳纳米管浆料印刷在Ti6Al4V合金基板上，得到碳纳米管阴极；(5) printing the carbon nanotube slurry on the Ti6Al4V alloy substrate by a screen printing method to obtain a carbon nanotube cathode;
(6)将碳纳米管阴极置于在200℃的真空中干燥2小时，然后以3℃/min的升温速率加热至700℃并保温2小时；(6) placing the carbon nanotube cathode in a vacuum at 200°C to dry for 2 hours, then heating to 700°C at a heating rate of 3°C/min and maintaining the temperature for 2 hours;
(7)使用3M的胶带粘除碳纳米管阴极表面的碳化物，完成碳纳米管阴极的制备。(7) Using 3M tape to stick and remove the carbides on the surface of the carbon nanotube cathode to complete the preparation of the carbon nanotube cathode.
请结合参阅图6～图9，图6为本实施例的碳纳米管冷阴极的场发射测试示意图，图7是本实施例的碳纳米管冷阴极在直流电压下测试的场发射性能结果示意图，图8是本实施例的碳纳米管冷阴极在交流电压下测试的场发射性能结果示意图，图9是本实施例的碳纳米管冷阴极在交流电压下测试的场发射稳定性结果，其中，图7和图8中的D1、D2均为对照组实验结果。Please refer to FIGS. 6 to 9 in conjunction. FIG. 6 is a schematic diagram of the field emission test of the carbon nanotube cold cathode of the present embodiment, and FIG. 7 is a schematic diagram of the field emission performance result of the carbon nanotube cold cathode of the present embodiment tested under a DC voltage. , FIG. 8 is a schematic diagram of the field emission performance results of the carbon nanotube cold cathode of the present embodiment tested under an alternating voltage, FIG. 9 is a field emission stability result of the carbon nanotube cold cathode of the present embodiment tested under an alternating voltage, wherein , D1 and D2 in Figure 7 and Figure 8 are the experimental results of the control group.
通过实验结果可以看出：本实施例制备得到的碳纳米管冷阴极在直流电的驱动下能够获得0.79V/μm的开启电场，且在2.38V/μm的电场强度下能获得85.13mA/cm2的电流密度；在交流电的驱动下能够在6.1V/μm的电场强度下表现出1.226A/cm2的电流密度；并且在4.0V/μm的电场强度下持续驱动15小时后，电流密度依旧能达到0.4A/cm2。因此，本实施例的方法制备的碳纳米管冷阴极场发射电流密度更大，更稳定。It can be seen from the experimental results that the carbon nanotube cold cathode prepared in this example can obtain an open electric field of 0.79V/μm under the driving of direct current, and can obtain an electric field of 85.13mA/cm2 under the electric field strength of 2.38V/μm Current density; under the driving of alternating current, it can show a current density of 1.226A/cm2 at an electric field strength of 6.1V/μm; and after continuous driving at an electric field strength of 4.0V/μm for 15 hours, the current density can still reach 0.4 A/cm2. Therefore, the carbon nanotube cold cathode prepared by the method of this embodiment has a higher field emission current density and is more stable.
本申请还提供一种碳纳米管阴极，该碳纳米管阴极是通过上述碳纳 米管阴极的制作方法制备得到，关于制备方式此处不再进行赘述，该方法制备得到的碳纳米管阴极由于增强了基板与碳纳米管的结合强度，因此，其场发射电流密度更大，更稳定。The present application also provides a carbon nanotube cathode, which is prepared by the above-mentioned manufacturing method of a carbon nanotube cathode. The preparation method will not be repeated here. The carbon nanotube cathode prepared by this method is enhanced by the Therefore, the field emission current density is larger and more stable.
本申请还提供一种电子设备，该电子设备例如场发射平面显示器件或者真空电子源等器件，该电子设备包括如上一实施例提供的碳纳米管阴极，由于其制备工艺存在上述各实施例中的改进，其也具备场发射电流密度更大、更稳定的特点。The present application also provides an electronic device, such as a field emission flat display device or a vacuum electron source, etc., the electronic device includes the carbon nanotube cathode provided in the previous embodiment, since its preparation process exists in the above embodiments It also has the characteristics of larger and more stable field emission current density.
以上所述仅为本申请的实施例，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。The above are only the embodiments of the present application, and are not intended to limit the scope of the patent of the present application. Any equivalent structure or equivalent process transformation made by using the contents of the description and drawings of the present application, or directly or indirectly applied to other related technologies Fields are similarly included within the scope of patent protection of this application.
Claims (11)
- 一种碳纳米管阴极的制作方法，其特征在于，所述方法包括：A method for making a carbon nanotube cathode, wherein the method comprises:提供一导电基板；providing a conductive substrate;对所述导电基板进行表面处理，以在所述导电基板的表面形成凹陷结构；performing surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate;利用所述碳纳米管浆料在所述导电基板的所述表面形成碳纳米管层，以形成所述碳纳米管阴极。A carbon nanotube layer is formed on the surface of the conductive substrate by using the carbon nanotube slurry to form the carbon nanotube cathode.
- 根据权利要求1所述的方法，其特征在于，The method of claim 1, wherein:所述对所述导电基板进行表面处理，以在所述导电基板的表面形成凹陷结构，包括：The performing surface treatment on the conductive substrate to form a concave structure on the surface of the conductive substrate includes:对所述导电基板进行清洁操作；performing a cleaning operation on the conductive substrate;将清洁操作之后的所述导电基板置于碱溶液中，以在所述导电基板的表面形成凹陷结构。The conductive substrate after the cleaning operation is placed in an alkaline solution to form a recessed structure on the surface of the conductive substrate.
- 根据权利要求2所述的方法，其特征在于，The method of claim 2, wherein:所述对所述导电基板进行清洁操作，包括：The cleaning operation on the conductive substrate includes:对所述导电基板进行超声操作；ultrasonically operating the conductive substrate;采用乙醇对超声操作之后的所述导电基板进行清洗操作；Use ethanol to clean the conductive substrate after the ultrasonic operation;对清洗操作之后的所述导电基板进行干燥操作。A drying operation is performed on the conductive substrate after the cleaning operation.
- 根据权利要求1所述的方法，其特征在于，The method of claim 1, wherein:所述方法还包括：The method also includes:将碳纳米管、球磨珠、粘结剂和金属粉加入到球磨溶剂中，以对所述碳纳米进行球磨操作，形成所述碳纳米管浆料。The carbon nanotubes, the ball milling beads, the binder and the metal powder are added to the ball milling solvent to perform a ball milling operation on the carbon nanotubes to form the carbon nanotube slurry.
- 根据权利要求4所述的方法，其特征在于，The method of claim 4, wherein:所述将碳纳米管、球磨珠、粘结剂和金属粉加入到球磨溶剂中，以对所述碳纳米进行球磨操作，形成所述碳纳米管浆料，包括：The carbon nanotubes, ball milling beads, binder and metal powder are added to the ball milling solvent to perform ball milling operation on the carbon nanotubes to form the carbon nanotube slurry, including:将所述碳纳米管、球磨珠加入到所述球磨溶剂中，进行球磨操作，以得到初级浆料；adding the carbon nanotubes and ball-milling beads into the ball-milling solvent, and performing a ball-milling operation to obtain a primary slurry;将所述粘结剂加入到所述初级浆料中，进行球磨操作，以得到中间浆料；adding the binder into the primary slurry, and performing a ball milling operation to obtain an intermediate slurry;将所述金属粉加入到所述中间浆料中，进行球磨操作，以得到所述碳纳米管浆料。The metal powder is added to the intermediate slurry, and a ball milling operation is performed to obtain the carbon nanotube slurry.
- 根据权利要求4所述的方法，其特征在于，The method of claim 4, wherein:所述金属粉为钛粉或铝粉中的一种。The metal powder is one of titanium powder or aluminum powder.
- 根据权利要求1所述的方法，其特征在于，The method of claim 1, wherein:所述利用所述碳纳米管浆料在所述导电基板的所述表面形成碳纳米管层，以形成所述碳纳米管阴极，包括：The forming a carbon nanotube layer on the surface of the conductive substrate by using the carbon nanotube slurry to form the carbon nanotube cathode includes:利用丝网印刷技术在所述导电基板的所述表面印刷所述碳纳米管浆料，以形成所述碳纳米管阴极。The carbon nanotube paste is printed on the surface of the conductive substrate using a screen printing technique to form the carbon nanotube cathode.
- 根据权利要求1所述的方法，其特征在于，The method of claim 1, wherein:所述利用所述碳纳米管浆料在所述导电基板的所述表面形成碳纳米管层，以形成所述碳纳米管阴极之后，所述方法还包括：After the carbon nanotube layer is formed on the surface of the conductive substrate by using the carbon nanotube slurry to form the carbon nanotube cathode, the method further includes:将所述碳纳米管阴极置于第一预设温度的真空环境中进行加热，并维持第一预设时间；heating the carbon nanotube cathode in a vacuum environment with a first preset temperature, and maintaining it for a first preset time;将所述真空环境的温度升高至第二预设温度，并维持第二预设时间，以得到加热后的所述碳纳米管阴极。The temperature of the vacuum environment is increased to a second preset temperature and maintained for a second preset time to obtain the heated carbon nanotube cathode.
- 根据权利要求8所述的方法，其特征在于，The method of claim 8, wherein:所述方法还包括：The method also includes:去除所述加热后的所述碳纳米管阴极表面的碳化物。The carbides on the surface of the heated carbon nanotube cathode are removed.
- 一种碳纳米管阴极，其特征在于，所述碳纳米管冷阴极通过权利要求1～9的制备方法制成。A carbon nanotube cathode, characterized in that the carbon nanotube cold cathode is made by the preparation method of claims 1-9.
- 一种电子设备，其特征在于，所述电子设备包括权利要求10所述的碳纳米管阴极。An electronic device, characterized in that, the electronic device comprises the carbon nanotube cathode of claim 10 .
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