CN114974921A - Carbon nanotube film supercapacitor electrode material, and preparation method and application thereof - Google Patents
Carbon nanotube film supercapacitor electrode material, and preparation method and application thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention discloses a carbon nanotube film supercapacitor electrode material, and a preparation method and application thereof. The preparation method comprises the following steps: 1) contacting the carbon nanotube film with an oxidizing acid, and simultaneously applying current to the carbon nanotube film to perform joule heating oxidation reaction to obtain an oxidized carbon nanotube film; 2) and loading a strong alkaline substance on the carbon oxide nanotube film, applying current to the carbon oxide nanotube film loaded with the strong alkaline substance in a vacuum state, and performing joule heat activation reaction to obtain the carbon nanotube film supercapacitor electrode material. The preparation method of the carbon nanotube film supercapacitor electrode material provided by the invention has the characteristics of simple process, low equipment requirement, high efficiency and low energy consumption. The prepared electrode material has higher electrochemical activity and better cycle performance when being used for manufacturing a super capacitor.
Description
Technical Field
The invention relates to the technical field of nano carbon materials and energy storage, in particular to a carbon nano tube film supercapacitor electrode material, a preparation method and application thereof.
Background
Since the 21 st century, with the development of science and technology, traditional fossil fuels have been gradually exhausted. Supercapacitors (SCs), also known as electrochemical capacitors, are novel energy storage devices with performance superior to that of conventional capacitors and can replace secondary batteries. Supercapacitors are of particular interest to the scientific and industrial community because of their long useful life, high power density, high coulombic efficiency, and good cycle stability. In addition, due to the abundance of selection of the electrode substrate of the supercapacitor, the electrode substrate of the supercapacitor has great potential in the fields of flexibility and knittability of energy storage devices.
From the existing reports, in order to realize the flexibility and wearability of SCs, researchers generally select a two-dimensional film (for example, a metal film and a CNT (carbon nanotube, the same applies hereinafter) film) as an electrode substrate and load an electrochemically active substance on the surface thereof or activate the electrochemically active substance to prepare an electrode of a supercapacitor.
There are reports in the literature that metal foils are used as electrode substrates and capacitive active materials are loaded thereon as SCs electrodes. For example, Shinde et al, three-dimensional flower-like nano-copper oxide (CuO) was deposited onto smooth copper foil by chemical deposition to yield CuO/Cu composite flexible supercapacitor electrodes (Hierarchical 3D-flow-like CuO nano-structure on copper foil for supercapacitors, rsc advances, 2015, 5, 4443). Although the electrode prepared by the scheme contains CuO with high electrochemical activity, the electrode has higher specific capacitance, and the loaded active substance is easy to fall off in the circulation process due to the fact that the base material is copper foil with a smooth surface, so that the electrode is poor in circulation performance. In addition, the copper foil loaded with CuO by chemical deposition in the scheme needs a long time, and is not suitable for efficient mass preparation.
The document also reports that the carbon nanotube film is taken as a matrix to activate the carbon nanotube film and other electrochemical active substances are loaded to be taken as a super capacitor electrode. For example, Xiang et al activated a CNT film by laser etching to obtain a porous carbon nanotube (pCNT) film, and then modified the pCNT film with Polyaniline (PANI) to prepare a PANI/pCNT film SC electrode (Smart and flexible super-capacitor based on a pore carbon nanotube film and a polyaniline hydroxide, rsc advances, 2016, 6, 24946). Although this solution allows to obtain a high specific capacitance of the electrode, the whole process is excessively complex, time consuming and uses a laser light source, a costly and energy consuming device, which is not advantageous for a low cost and efficient production of the electrode.
In summary, the preparation method of the supercapacitor electrode, especially the flexible electrode in the prior art has the problems of complex process, long time consumption, high energy consumption, high equipment requirement and poor electrode cycle performance, so a simple, short-time and low-cost method is urgently needed to prepare the supercapacitor electrode with high capacitance activity, high cycle performance and flexibility.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a carbon nanotube film supercapacitor electrode material, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a method for preparing a CNT thin film supercapacitor electrode by joule heating rapid activation, comprising:
1) contacting the carbon nanotube film with an oxidizing acid, and simultaneously applying current to the carbon nanotube film to perform Joule thermal oxidation reaction to obtain an oxidized carbon nanotube film;
2) and loading a strong alkaline substance on the carbon oxide nanotube film, and applying current to the carbon oxide nanotube film loaded with the strong alkaline substance in a vacuum state to perform joule heat activation reaction to obtain the carbon nanotube film supercapacitor electrode material.
In a second aspect, the invention also provides the carbon nanotube film supercapacitor electrode material prepared by the method.
In a third aspect, the invention further provides a supercapacitor, and an electrode of the supercapacitor comprises the carbon nanotube film supercapacitor electrode material.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that at least:
the preparation method of the carbon nanotube film supercapacitor electrode material provided by the invention has the characteristics of simple process, low requirement on equipment, high efficiency and low energy consumption. The prepared CNT film super capacitor electrode has higher electrochemical activity and better cycle performance when being used for manufacturing a super capacitor.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical solutions of the present invention and to implement them according to the content of the description, the following description is given of preferred embodiments of the present invention with reference to the detailed drawings.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing CNT thin film supercapacitor electrodes by Joule thermal rapid activation according to an exemplary embodiment of the present invention;
FIG. 2 is an XPS test chart of a CNT film supercapacitor electrode according to an exemplary embodiment of the present invention;
FIG. 3 is a graph showing cyclic voltammetry curves for electrodes of a CNT thin film supercapacitor according to an exemplary embodiment of the present invention;
FIG. 4 is a graph illustrating a charge/discharge curve of a CNT film supercapacitor according to an exemplary embodiment of the present invention;
FIG. 5 is a graph showing electrochemical impedance measurements of CNT thin film supercapacitor electrodes according to an exemplary embodiment of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and thus the scope of the present invention is not limited by the specific embodiments disclosed below.
Moreover, relational terms such as "first" and "second," and the like, may be used solely to distinguish one element or method step from another element or method step having the same name, without necessarily requiring or implying any actual such relationship or order between such elements or method steps.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a CNT thin film supercapacitor electrode by joule heating rapid activation, including the following steps:
1) contacting the carbon nanotube film with an oxidizing acid, and simultaneously applying current to the carbon nanotube film to perform joule heating oxidation reaction to obtain an oxidized carbon nanotube film;
2) loading a strong alkaline substance on the carbon oxide nanotube film, applying current to the carbon oxide nanotube film loaded with the strong alkaline substance in a vacuum state, and performing joule heating activation reaction, wherein the specific reaction equation is 2C +6MOH → 2M + M 2 CO 3 +3H 2 Wherein M represents a metal element, especially an alkali metal element such as sodium and potassium, to obtain the carbon nanotube film supercapacitor electrode material.
In the above technical solution, the carbon nanotube film can be commercially available or can be prepared by itself, for example, the carbon nanotube film can be prepared by a floating vapor deposition method or a liquid phase film formation method, and the preparation methods of the carbon nanotube film are described in the documents in the prior art; the electrical heating means applying a voltage to the carbon nanotube film to cause a current to flow through the carbon nanotube film to generate joule heat.
Based on the technical scheme, the traditional long-time electrochemical oxidation and muffle furnace heating processes are replaced by the rapid oxidation and activation processes based on joule heat generated by electrifying the CNT film. The oxidation and activation process has the characteristics of high efficiency and low energy consumption. In addition, compared with the traditional oxidation method, the joule heating process in the strong acid environment can easily cause the carbon atoms to form bonds with oxygen-containing functional groups, so that the better oxidation effect is achieved on the surface of the CNT film, and the CNT film with higher electrochemical activity can be obtained to be used as a supercapacitor electrode. Finally, the method provided by the invention takes the oxidized carbon nanotube film with good hydrophilicity after oxidation as a substrate, so that the strong alkaline substance can better soak each position in the CNT film, and the activation of the CNT film is more uniform.
The supercapacitor electrode material prepared by the method is only a carbon nanotube film and does not load other active materials, so that the step of compounding the active materials is omitted on one hand, the cost of the active materials is saved, the preparation method is simpler and more economical, on the other hand, the phenomena of separation and peeling of the active materials and a substrate are directly avoided, and the cycle performance of the electrode is greatly improved. The method comprises the steps of rapidly oxidizing CNT in a strong acid solution by Joule heat spontaneously generated by electrifying the CNT, then covering the surface of the CNT with a strong alkaline substance, and activating by using the Joule heat of the CNT in vacuum, thereby preparing the high-electrochemical-activity CNT film supercapacitor electrode based on the rapid Joule heat activation process.
In some embodiments, the carbon nanotube film may include carbon nanotubes and amorphous carbon, and the method may further include the steps of: applying an electric current to the carbon nanotube film prior to contacting the carbon nanotube film with the oxidizing acid to remove amorphous carbon by at least the generated joule heating. It is to be understood that the above-mentioned removal of amorphous carbon is preferably performed in an oxygen-containing atmosphere, preferably in air, but of course, a mixed gas containing oxygen or pure oxygen may be used, for example, a mixed gas of oxygen and argon.
And (3) carrying out third electric heating on the carbon nanotube film, so that on one hand, amorphous carbon in the carbon nanotube film is removed, and meanwhile, iron-based catalyst particles are oxidized and are easier to remove in the subsequent acid soaking process, the purity of the carbon nanotube film is improved, the film resistance is further reduced, the energy consumption in the subsequent joule heating process is reduced, and the internal electron transfer rate in the charging and discharging process is improved. On the other hand, holes or gaps can be formed at the positions occupied by the amorphous carbon, which is beneficial to the permeation and reaction of oxidizing acid and strong alkaline substances, and the CNT film is exposed to more capacitance active sites, so that the performance of the prepared electrode is further improved.
In some embodiments, the carbon nanotube film may further include catalyst particles, and the method may further include: and (3) immersing the carbon nanotube film with the acid solution to remove the amorphous carbon so as to dissolve and remove the catalyst particles in the carbon nanotube film.
In some embodiments, the temperature of the third electric heating may be preferably 200-.
In some embodiments, the acidic solution may include any one or a combination of two or more of hydrochloric acid, nitric acid, and sulfuric acid, and the immersion treatment time may preferably be 6 to 24 hours.
In some embodiments, in step 1), the oxidizing acid may include one or a combination of two or more of oxygen acids such as concentrated sulfuric acid, concentrated nitric acid, chloric acid, hypochlorous acid, and the like, and preferably may be a mixed solution of concentrated sulfuric acid and concentrated nitric acid.
In some embodiments, the step 1) may specifically include: coating the oxidizing acid on the surface of the carbon nanotube film, covering and clamping two surfaces of the carbon nanotube film coated with the oxidizing acid by using the carrier plate, and exposing two ends of the carbon nanotube film to switch on a power supply.
In some embodiments, the carrier plate may comprise any one of a glass plate, a teflon plate.
In some embodiments, the temperature of the joule heating oxidation reaction may preferably be 100-.
In some embodiments, in step 2), the strong alkaline substance may include any one or a combination of two or more of potassium hydroxide and sodium hydroxide.
In some embodiments, step 2) may specifically comprise: and coating the solution of the strong alkaline substance on the surface of the carbon oxide nanotube film and drying the solution to load the strong alkaline substance on the surface of the carbon oxide nanotube film, and then placing the carbon oxide nanotube film loaded with the strong alkaline substance in a vacuum chamber for vacuumizing and carrying out Joule heat activation reaction. The solution is preferably an aqueous solution of a strongly basic substance.
In some embodiments, the concentration of the solution of the strongly basic substance may preferably be 0.1 to 2mol/L, and the degree of vacuum within the vacuum chamber may preferably be 10 -5 -10 -1 Pa。
In some embodiments, the temperature of the Joule heat activation reaction may be preferably 400 ℃ to 800 ℃ and the time may be preferably 10s to 10 min.
In some embodiments, step 1) may further include a step of cleaning the oxidized carbon nanotube film.
In some embodiments, the oxidized carbon nanotube film is washed twice or more with alcohol and water alternately.
In some embodiments, in step 1), conductive silver paste is coated on two ends of the carbon nanotube film to electrically connect the carbon nanotube film with the electrode for the first energization heating.
As a specific application example, the preparation method of the carbon nanotube film supercapacitor electrode material provided by the invention can be implemented by adopting the following technical scheme:
(1) cleaning the carbon nanotube film: the two ends of the commercially available CNT film are connected with the metal foil by using a conductive adhesive and connected with a power supply. After electrifying, keeping the CNT film at a certain temperature for a certain time, removing amorphous carbon of the CNT film by using Joule heat, then soaking the CNT film in hydrochloric acid to remove catalyst particles remained in the preparation process of the film, finally cleaning the film for a plurality of times by using deionized water and alcohol, and drying.
(2) Activation of the carbon nanotube film: and (2) respectively coating the two surfaces of the cleaned CNT obtained in the step (1) with a mixed solution of sulfuric acid and nitric acid, clamping the CNT by using a glass sheet, connecting the two ends of the CNT film with a metal foil by using a conductive adhesive, switching on a power supply, electrifying for a certain time under a certain voltage, and oxidizing the CNT film by using Joule heat. Cleaning the oxidized CNT film for a plurality of times by using alcohol and deionized water, drying, uniformly coating KOH solution on two sides of the dried oxidized CNT film, drying, and adhering the dried CNT film on a copper sample table of a vacuum chamber of a joule heating device through conductive silver colloid (the sample table is connected to a wiring terminal on the wall of the chamber through a lead, and an external power supply is connected with the wiring terminal on the wall of the chamber to realize the electrification of a sample). And then pumping the cavity to a vacuum state, connecting a direct-current power supply to a wiring terminal on the wall of the cavity, and performing joule heat activation for a certain time at a certain temperature after electrifying to prepare the high-electrochemical-activity CNT film supercapacitor electrode based on the rapid joule heat activation process.
More specifically, as a preferred technical solution, the specific steps of step (2) may be: and respectively coating 15 microliters of mixed solution of concentrated sulfuric acid and concentrated nitric acid on two sides of the cleaned CNT, clamping the CNT by using a glass sheet, connecting two ends of a CNT film on a copper foil with the thickness of 0.05mm by using conductive silver adhesive, connecting the two ends of the CNT film with a power supply, and electrifying for 15min under the voltage of 3V. Cleaning an oxidized CNT film for a plurality of times by using alcohol and deionized water, drying, respectively and uniformly coating 10 microliters of the dried two surfaces of the oxidized CNT film, drying after 1M KOH solution, adhering the dried CNT film on a copper sample table of a vacuum chamber of a Joule heating device through conductive silver colloid, pumping the chamber to a vacuum state, connecting a direct-current power supply to a wiring terminal on the wall of the chamber, and performing Joule thermal activation at 800 ℃ for 30 seconds after electrification to prepare the high-electrochemical-activity CNT film supercapacitor electrode based on the rapid Joule thermal activation process.
As another preferred technical solution, the specific steps of step (2) may also be: and respectively coating 20 microliters of mixed solution of concentrated sulfuric acid and concentrated nitric acid on two surfaces of the cleaned CNT, clamping the CNT by using a glass sheet, connecting two ends of a CNT film on a copper foil with the thickness of 0.05mm by using conductive silver paste, connecting the two ends of the CNT film to a power supply, and electrifying for 1min under the voltage of 5V. Cleaning the oxidized CNT film for a plurality of times by using alcohol and deionized water, drying, respectively and uniformly coating 50 microliters of the dried two surfaces of the oxidized CNT film, drying after 0.1M KOH solution, adhering the dried CNT film on a copper sample table of a vacuum chamber of a Joule heating device through conductive silver adhesive, pumping the chamber to a vacuum state, connecting a direct-current power supply to a binding post on the wall of the chamber, and performing Joule thermal activation for 10min at 500 ℃ after electrifying to prepare the high-electrochemical-activity CNT film supercapacitor electrode based on the rapid Joule thermal activation process.
As another preferred technical solution, the specific steps of step (2) may further include: coating 5 microliters of mixed solution of concentrated sulfuric acid and concentrated nitric acid on two sides of the cleaned CNT respectively, clamping the CNT by a glass sheet, connecting two ends of a CNT film on a copper foil with the thickness of 0.05mm by conductive silver paste, connecting a power supply, and electrifying for 30min under the voltage of 1.5V. Cleaning the oxidized CNT film for a plurality of times by using alcohol and deionized water, drying, respectively and uniformly coating 20 microliters of the dried two surfaces of the oxidized CNT film, drying after 0.5M KOH solution, adhering the dried CNT film on a copper sample table of a vacuum chamber of a Joule heating device through conductive silver colloid, pumping the chamber to a vacuum state, connecting a direct-current power supply to a wiring terminal on the wall of the chamber, and carrying out Joule thermal activation at 700 ℃ for 2min after electrification to prepare the high-electrochemical-activity CNT film supercapacitor electrode based on the rapid Joule thermal activation process.
The embodiment of the invention also provides the carbon nanotube film supercapacitor electrode material prepared by the method in any one of the above embodiments.
In some embodiments, the supercapacitor may comprise a plate-like supercapacitor or a thin film supercapacitor.
In some embodiments, the supercapacitor may comprise a plate-like supercapacitor or a thin-film supercapacitor.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustration and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a method for preparing a CNT film supercapacitor electrode material based on joule heat rapid activation, wherein the supercapacitor electrode material is only a carbon nanotube film and is not loaded with other active materials. The method comprises the steps of rapidly oxidizing CNT in a strong acid solution by Joule heat generated by electrifying the CNT in the strong acid solution, then covering the surface of the CNT with a KOH solution, and activating by using the Joule heat in vacuum, thereby preparing the high-electrochemical-activity CNT film supercapacitor electrode based on the rapid Joule heat activation process.
The method for preparing the CNT film supercapacitor electrode based on the joule heat quick activation specifically comprises the following steps:
both ends of a commercial CNT film are connected with a copper foil with the thickness of 0.05mm by conductive silver adhesive and connected with a power supply. And (3) after electrifying, keeping the CNT film at 400 ℃ for 5min to remove amorphous carbon of the CNT film, then soaking the CNT film in hydrochloric acid for 24h to remove residual catalyst particles in the preparation process of the film, finally cleaning the film for 3 times by using deionized water and alcohol, and drying.
Coating 15 microliters of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3: 1 on two surfaces of the cleaned CNT respectively, clamping the CNT by using a glass sheet, connecting two ends of a CNT film on a copper foil with the thickness of 0.05mm by using conductive silver adhesive, connecting the two ends of the CNT film to a power supply, and electrifying for 15min at the voltage of 3V and the temperature of 150 ℃.
Washing the oxidized CNT film with alcohol and deionized water for several times, drying, respectively and uniformly coating 10 microliters on two sides of the dried oxidized CNT film, drying after 1M KOH solution, sticking the dried CNT film on a copper sample table of a vacuum chamber of a Joule heating device through conductive silver colloid, pumping the chamber to a vacuum state, connecting a direct-current power supply to a wiring column on the wall of the chamber, and performing Joule thermal activation at 800 ℃ for 30 seconds after electrification to prepare the high-electrochemical-activity CNT film supercapacitor electrode based on the rapid Joule thermal activation process.
For the CNT film super capacitor prepared in this exampleThe XPS test was performed, and the test result is shown in fig. 2, as can be clearly seen from fig. 2, a large amount of oxygen-containing functional groups are formed on the surface of the CNT thin film supercapacitor electrode prepared in this example during the activation process; FIG. 3 shows the CNT thin film supercapacitor electrodes described above at 10-50mV s -1 A cyclic voltammetry curve at sweep rate, which reflects that the electrode exhibits excellent pseudocapacitance performance; FIG. 4 shows the CNT thin film supercapacitor electrodes described above at 0.5-5A g -1 Charge and discharge curve at current density of 0.5A g -1 The specific time capacitance can reach 227.8F g -1 High specific capacitance of (2); FIG. 5 shows the AC impedance spectrum of the CNT thin film supercapacitor electrode at 0.01-100000HZ, and the curve shows a larger slope in a low frequency region, which shows that the electrode has smaller ion diffusion impedance, and ions can rapidly diffuse to the interface of the electrode and the electrolyte.
Example 2
The embodiment provides a method for preparing a CNT film supercapacitor electrode material based on joule heat quick activation, which specifically comprises the following steps:
both ends of a commercial CNT film are connected with a copper foil with the thickness of 0.05mm by conductive silver adhesive and connected with a power supply. And (3) after electrifying, keeping the CNT film at 300 ℃ for 15min to remove amorphous carbon of the CNT film, then soaking the CNT film in hydrochloric acid for 24h to remove residual catalyst particles in the preparation process of the film, finally cleaning the film for 3 times by using deionized water and alcohol, and drying.
Respectively coating 20 microliters of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 2: 1 on two sides of the cleaned CNT, clamping the CNT by a glass sheet, connecting two ends of a CNT film on a copper foil with the thickness of 0.05mm by conductive silver paste, connecting the two ends of the CNT film to a power supply, and electrifying for 1min at the voltage of 5V and the temperature of 240 ℃.
Cleaning the oxidized CNT film for a plurality of times by using alcohol and deionized water, drying, respectively and uniformly coating 50 microliters on two surfaces of the dried oxidized CNT film, drying after using 0.1M KOH solution, adhering the dried CNT film on a copper sample table of a vacuum cavity of a Joule heating device through conductive silver adhesive, pumping the cavity to be in a vacuum state, connecting a direct-current power supply to a wiring column on the wall of the cavity, and carrying out Joule thermal activation for 10min at 500 ℃ after electrifying to prepare the high electrochemical activity CNT film supercapacitor electrode based on the rapid Joule thermal activation process.
A highly electrochemically active CNT thin film supercapacitor electrode with similar performance to that of example 1 can be prepared.
Example 3
The embodiment provides a method for preparing a CNT film supercapacitor electrode material based on joule heating rapid activation, which specifically comprises the following steps:
both ends of a commercial CNT film are connected with a copper foil with the thickness of 0.05mm by conductive silver adhesive and connected with a power supply. And (3) after electrifying, keeping the CNT film at 500 ℃ for 1min to remove amorphous carbon of the CNT film, then soaking the CNT film in hydrochloric acid for 24h to remove residual catalyst particles in the preparation process of the film, finally cleaning the film for 3 times by using deionized water and alcohol, and drying.
And respectively coating 5 microliters of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3: 1 on two surfaces of the cleaned CNT, clamping the CNT by using a glass sheet, connecting two ends of a CNT film on a copper foil with the thickness of 0.05mm by using conductive silver adhesive, connecting the two ends of the CNT film to a power supply, and electrifying for 15min at the voltage of 2V and the temperature of 100 ℃.
Washing the oxidized CNT film for a plurality of times by using alcohol and deionized water, drying, respectively and uniformly coating 20 microliters of the two surfaces of the dried oxidized CNT film, drying after 0.5M KOH solution, sticking the dried CNT film on a copper sample table of a vacuum chamber of a Joule heating device through conductive silver colloid, pumping the chamber to a vacuum state, connecting a direct-current power supply to a wiring column on the wall of the chamber, and carrying out Joule thermal activation at 700 ℃ for 2min after electrification to prepare the high-electrochemical-activity CNT film supercapacitor electrode based on the rapid Joule thermal activation process.
A highly electrochemically active CNT thin film supercapacitor electrode with similar performance to that of example 1 can be prepared.
Example 4
This example provides a method for preparing an electrode material of a CNT thin film supercapacitor based on joule heating rapid activation, which is substantially the same as example 1 except that:
after electrification, the CNT film is kept at 200 ℃ for 60min to remove amorphous carbon.
High electrochemically active CNT thin film supercapacitor electrodes with similar properties as in example 1 can also be prepared.
Example 5
This example provides a method for preparing an electrode material of a CNT thin film supercapacitor based on joule heating rapid activation, which is substantially the same as example 1 except that:
the mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3: 1 is changed into the mixed solution of hypochlorous acid and concentrated nitric acid with the volume ratio of 3: 1.
High electrochemically active CNT thin film supercapacitor electrodes with similar properties as in example 1 can also be prepared.
Example 6
This example provides a method for preparing an electrode material of a CNT thin film supercapacitor based on joule heating rapid activation, which is substantially the same as example 1 except that:
the 0.1M KOH solution was changed to 0.1M NaOH solution.
High electrochemically active CNT thin film supercapacitor electrodes with similar properties as in example 1 can also be prepared.
Example 7
The present example provides a method for preparing an electrode material of a CNT thin film supercapacitor based on joule heating rapid activation, which is substantially the same as example 3 except that:
the 0.5M KOH solution was changed to 0.5M NaOH solution.
The mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3: 1 is changed into the mixed solution of chloric acid and concentrated nitric acid with the volume ratio of 3: 1.
High electrochemically active CNT thin film supercapacitor electrodes with similar properties as in example 1 can also be prepared.
Comparative example 1
This comparative example provides a method of preparing a CNT thin film supercapacitor electrode material, substantially the same as example 1, except that:
the method omits the steps of coating concentrated sulfuric acid and concentrated nitric acid on the surface of the CNT film and electrifying, directly coats the CNT film without amorphous carbon and catalyst particles with 1M KOH solution, then dries, and then carries out vacuum electrifying heating to obtain the CNT film supercapacitor electrode.
The CNT film supercapacitor electrode prepared by the method is tested to be 0.5A g -1 Lower specific capacitance of only 45F g -1 。
Comparative example 2
This comparative example provides a method of preparing a CNT thin film supercapacitor electrode material, substantially the same as example 1, except that:
the method comprises the steps of omitting the step of electrifying a commercial CNT film to remove surface amorphous carbon, directly coating concentrated sulfuric acid and concentrated nitric acid on the surface of the CNT film, electrifying, coating a 1M KOH solution on the electrified CNT film, drying, and then carrying out vacuum electrifying and heating to obtain the CNT film supercapacitor electrode.
The CNT film super capacitor electrode prepared by the method is tested and is 0.5A g -1 The lower specific capacitance is only 120F g -1 。
Based on the above embodiments and comparative examples, it can be clearly seen that, compared with the preparation process of other supercapacitor electrode materials, the electrode shown in the present invention replaces the conventional long-time electrochemical oxidation and muffle furnace heating process with the rapid oxidation and activation process based on joule heat generated by the CNT thin film energization itself in the preparation process. Therefore, the whole activation process has the characteristics of high efficiency and low energy consumption. In addition, compared with the traditional oxidation method, the Joule heating process in the strong acid environment can easily cause the carbon atoms to form bonds with oxygen-containing functional groups, so that the method has better oxidation effect on the surface of the CNT film, and further can obtain the CNT film with higher electrochemical activity as a supercapacitor electrode. Finally, the method takes the CNT film with good hydrophilicity after oxidation as a substrate, so that the solution of the strong alkaline substance can better soak each position in the CNT film, and the activation of the CNT film is more uniform.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a carbon nanotube film supercapacitor electrode material is characterized by comprising the following steps:
1) contacting the carbon nanotube film with an oxidizing acid, and simultaneously applying current to the carbon nanotube film to perform joule heating oxidation reaction to obtain an oxidized carbon nanotube film;
2) and loading a strong alkaline substance on the carbon oxide nanotube film, applying current to the carbon oxide nanotube film loaded with the strong alkaline substance in a vacuum state, and performing joule heat activation reaction to obtain the carbon nanotube film supercapacitor electrode material.
2. The method of claim 1, wherein the carbon nanotube film comprises carbon nanotubes and amorphous carbon, and further comprising:
before the carbon nanotube film is contacted with the oxidizing acid, applying current to the carbon nanotube film to remove the amorphous carbon by at least the generated Joule heat, wherein the Joule heat temperature is 200-500 ℃, and the time is 1min-1 h;
preferably, the carbon nanotube film further includes catalyst particles, and the method further includes: and (3) immersing the carbon nanotube film subjected to the removal of the amorphous carbon by using an acidic solution, so that the catalyst particles in the carbon nanotube film are dissolved and removed.
3. The method according to claim 2, wherein the acidic solution comprises any one or a combination of two or more of hydrochloric acid, nitric acid and sulfuric acid, and the immersion treatment time is 6 to 24 hours.
4. The method according to claim 1, wherein in step 1), the oxidizing acid comprises one or a combination of two or more of concentrated sulfuric acid, concentrated nitric acid, chloric acid, and hypochlorous acid, preferably a mixed solution of concentrated sulfuric acid and concentrated nitric acid;
preferably, the step 1) specifically comprises: coating the oxidizing acid on the surface of the carbon nanotube film, then covering and clamping two surfaces of the carbon nanotube film coated with the oxidizing acid by using a carrier plate, and exposing two ends of the carbon nanotube film to switch on a power supply;
preferably, the carrier plate includes any one of a glass plate and a teflon plate.
5. The method as claimed in claim 4, wherein the temperature of the Joule thermal oxidation reaction is 100-300 ℃ and the time is 30s-15 min.
6. The preparation method according to claim 1, wherein in step 2), the strongly basic substance comprises any one or two of potassium hydroxide and sodium hydroxide;
preferably, step 2) specifically comprises: coating the solution of the strong alkaline substance on the surface of the carbon oxide nanotube film and drying the solution to load the strong alkaline substance on the surface of the carbon oxide nanotube film, and then placing the carbon oxide nanotube film loaded with the strong alkaline substance in a vacuum chamber for vacuumizing and carrying out Joule heat activation reaction;
preferably, the concentration of the solution of the strong alkaline substance is 0.1-2mol/L, and the vacuum degree in the vacuum chamber is 10 -5 -10 -1 Pa。
7. The method as claimed in claim 6, wherein the temperature of the Joule heat activation reaction is 400-800 ℃ and the time is 10s-10 min.
8. The method according to claim 1, wherein the step 1) further comprises a step of cleaning the oxidized carbon nanotube film;
preferably, the carbon oxide nanotube film is alternately cleaned by alcohol and water for more than two times;
preferably, in the step 1), conductive silver paste is coated at two ends of the carbon nanotube film so as to electrically connect the carbon nanotube film with the electrode for the first energization heating.
9. The carbon nanotube thin film supercapacitor electrode material prepared by the method of any one of claims 1 to 8.
10. A supercapacitor, wherein an electrode of the supercapacitor comprises the carbon nanotube thin film supercapacitor electrode material of claim 9;
preferably, the supercapacitor comprises a plate-shaped supercapacitor or a thin-film supercapacitor.
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