CN114974921B - Electrode material of carbon nano tube film super capacitor, preparation method and application thereof - Google Patents
Electrode material of carbon nano tube film super capacitor, preparation method and application thereof Download PDFInfo
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- CN114974921B CN114974921B CN202210308519.0A CN202210308519A CN114974921B CN 114974921 B CN114974921 B CN 114974921B CN 202210308519 A CN202210308519 A CN 202210308519A CN 114974921 B CN114974921 B CN 114974921B
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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
- 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
- H01G11/22—Electrodes
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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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a carbon nano tube film super capacitor electrode material, a preparation method and application thereof. The preparation method comprises the following steps: 1) Contacting the carbon nanotube film with 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, applying current to the carbon oxide nanotube film loaded with the strong alkaline substance in a vacuum state, and performing a 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 super capacitors.
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 super capacitor electrode material, a preparation method and application thereof.
Background
In the 21 st century, traditional fossil fuels have gradually exhausted as science and technology have evolved. Super Capacitors (SCs), also known as electrochemical cells, are a new type of energy storage device that has superior performance to traditional capacitors and can replace secondary batteries. Supercapacitors are particularly interesting in scientific and industrial fields because of their long service life, high power density, high coulombic efficiency, good cycling stability and the like. In addition, due to the richness of choice of the electrode matrix of the supercapacitor, the supercapacitor has great potential in the fields of flexibility, braiding and the like of the energy storage device.
From the prior reports, in order to achieve flexibility and wearability of SCs, researchers generally select two-dimensional films (e.g., metal films and CNT (carbon nanotube, the same applies hereinafter) films) as electrode substrates and load electrochemically active materials on their surfaces or activate themselves to prepare electrodes of supercapacitors.
There are reports of using a metal foil as an electrode substrate and supporting a capacitive active material thereon as an SCs electrode. For example, shinde et al, deposited three-dimensional flower-like nano copper oxide (CuO) onto a smooth copper foil by chemical deposition to give a CuO/Cu composite flexible supercapacitor electrode (Hieraracial 3D-flow-like CuO nanostructure on copper foil for supercapacitors. RSC extensions, 2015,5, 4443). The electrode prepared by the scheme contains CuO with high electrochemical activity, so that the electrode has higher specific capacitance, but 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 smooth surface, and the circulation performance of the electrode is poor. In addition, the solution in which CuO is supported on copper foil by chemical deposition requires a long time and is not suitable for efficient mass production.
There are also reports of using carbon nanotube film as matrix to activate itself and supporting other electrochemical active substances as supercapacitor electrode. For example, the preparation of PANI/pCNT thin film SC electrodes (Smart and flexible supercapacitor based on a porous carbon nanotube film and polyaniline hydro.rsc advance, 2016,6, 24946) is performed by activating CNT thin films by laser etching to obtain porous carbon nanotube (pCNT) thin films, and then modifying the pCNT thin films with Polyaniline (PANI). Although this solution makes the electrode obtain a high specific capacitance, the whole process is too complex and time-consuming, and uses a laser light source, which is a costly and energy-consuming device, thus not being advantageous for 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 that a simple, short-time and low-cost method is 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 nano tube film super capacitor electrode material, a preparation method and application thereof.
In order to achieve the purpose of the invention, 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 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 oxidized carbon nanotube film, applying current to the oxidized carbon nanotube film loaded with the strong alkaline substance in a vacuum state, and performing a Joule heat activation reaction to obtain the electrode material of the carbon nanotube film supercapacitor.
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 also 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:
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 CNT film super capacitor electrode has higher electrochemical activity and better cycle performance when being used for manufacturing super capacitors.
The foregoing description is only an overview of the present invention and is intended to enable those skilled in the art to make more clear the teachings of the present application and to be practiced in accordance with the teachings of the present specification, as hereinafter described in more detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing CNT film supercapacitor electrodes by Joule thermal rapid activation according to an exemplary embodiment of the invention;
FIG. 2 is an XPS test chart of a CNT film supercapacitor electrode according to an exemplary embodiment of the invention;
FIG. 3 is a cyclic voltammogram of a CNT thin film supercapacitor electrode according to an exemplary embodiment of the present invention;
FIG. 4 is a graph showing a charge-discharge curve of a CNT thin film supercapacitor electrode according to an exemplary embodiment of the present invention;
FIG. 5 is a graph showing electrochemical impedance testing of CNT film supercapacitor electrodes according to an exemplary embodiment of the present invention.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are 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 described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
Moreover, relational terms such as "first" and "second", and the like, may be used solely to distinguish one from another component or method step having the same name, without necessarily requiring or implying any actual such relationship or order between such components 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, comprising the steps of:
1) Contacting the carbon nanotube film with 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) Loading a strong alkaline substance on the oxidized carbon nanotube film, and applying current to the oxidized carbon nanotube film loaded with the strong alkaline substance under vacuum to perform a Joule thermal activation reaction, wherein the specific reaction equation is 2C+6MOH- & gt2M+M 2 CO 3 +3H 2 Wherein M represents a metal element, particularly 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 may be either commercially available or self-prepared, for example, prepared by a floating vapor deposition method or a liquid phase film forming method, and the preparation methods of the carbon nanotube film are all described in the records of the existing literature; the electric heating means that voltage is applied to the carbon nano tube film so that current flows through the carbon nano tube film to generate joule heat.
Based on the technical scheme, the rapid oxidation and activation process of generating joule heat based on the energization of the CNT film replaces the traditional processes of long-time electrochemical oxidation, muffle furnace heating and the like. 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 thermal process in the strong acid environment can easily lead carbon atoms to form bonds with oxygen-containing functional groups, has better oxidation effect on the surface of the CNT film, and can further obtain the CNT film with higher electrochemical activity as an electrode of the supercapacitor. Finally, the method provided by the invention takes the oxidized carbon nanotube film with good hydrophilicity after oxidation as a matrix, so that the strong alkaline substance wets each position in the CNT film better, and further the activation of the CNT film is more uniform.
The supercapacitor electrode material prepared by the method is only a carbon nano tube film without loading other active materials, so that the step of compounding the active materials is omitted, the cost of the active materials is saved, the preparation method is simpler and more economical, and on the other hand, the phenomena of detachment and peeling of the active materials and a matrix are directly avoided, and the cycle performance of the electrode is greatly improved. The CNT in the strong acid solution is electrified to spontaneously generate Joule heat to rapidly oxidize the CNT, then the surface of the CNT is covered with a strong alkaline substance, and the CNT is activated by the self-Joule heat in vacuum, so that the high electrochemical activity CNT film supercapacitor electrode based on the rapid Joule heat activation process is prepared.
In some embodiments, the carbon nanotube film may include carbon nanotubes and amorphous carbon, and the method may further include the steps of: before the carbon nanotube film is contacted with the oxidizing acid, an electric current is applied to the carbon nanotube film to remove amorphous carbon at least with generated joule heat. It will be appreciated that the amorphous carbon removal is preferably carried out in an atmosphere containing oxygen, preferably air, although a mixed gas containing oxygen or pure oxygen may be used, for example a mixed gas of oxygen and argon.
And on one hand, amorphous carbon in the carbon nano tube film is removed, and meanwhile, the iron-based catalyst particles are oxidized and are easier to remove in the subsequent acid soaking process, so that the purity of the carbon nano tube film is improved, the film resistance is reduced, the energy consumption in the subsequent Joule heating process is reduced, and the internal electron transfer rate is improved during charging and discharging. On the other hand, holes or gaps can be formed at the positions occupied by amorphous carbon, so that the permeation and reaction of oxidizing acid and strong alkaline substances are facilitated, more capacitance active sites are exposed on the CNT film, and 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 immersing the carbon nano tube film with an acidic solution to remove the amorphous carbon so as to dissolve and remove the catalyst particles in the carbon nano tube film.
In some embodiments, the temperature of the third electrical heating may preferably be 200-500 ℃, and the time may preferably be 1min-1h.
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 may preferably be for a period of 6 to 24 hours.
In some embodiments, in step 1), the oxidizing acid may include one or a combination of two or more of 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: and coating the oxidizing acid on the surface of the carbon nano tube film, covering and clamping the two sides of the carbon nano tube film coated with the oxidizing acid by using a carrier plate, and exposing the two ends of the carbon nano tube film to be connected with a power supply.
In some embodiments, the carrier plate may comprise any one of a glass plate, a polytetrafluoroethylene plate.
In some embodiments, the temperature of the Joule thermal oxidation reaction may preferably be 100-300℃and the time may preferably be 30s-15min.
In some embodiments, in step 2), the strongly alkaline substance may include any one or a combination of two or more of potassium hydroxide, 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 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 performing a Joule heat activation reaction. The above solution is preferably an aqueous solution of a strongly alkaline substance.
In some embodiments, the concentration of the solution of the strongly basic substance may be preferably 0.1 to 2mol/L, and the vacuum degree in the vacuum chamber may be preferably 10 -5 -10 -1 Pa。
In some embodiments, the temperature of the joule heat activated reaction may preferably be 400-800 ℃ and the time may preferably be 10s-10min.
In some embodiments, step 1) may further include a step of cleaning the carbon nanotube oxide film.
In some embodiments, the carbon oxide nanotube film is alternately washed two or more times with alcohol and water.
In some embodiments, in step 1), conductive silver paste is coated on both ends of the carbon nanotube film to electrically connect the carbon nanotube film with an electrode for the first electric 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 nano tube film: both ends of a commercially available CNT film were connected to a metal foil using a conductive paste and connected to a power source. After being electrified, the amorphous carbon of the CNT film is removed by utilizing the Joule heat for a certain time at a certain temperature, then the CNT film is soaked in hydrochloric acid to remove the catalyst particles remained in the film preparation process, and finally the film is washed for a plurality of times by deionized water and alcohol and dried.
(2) Activation of the carbon nanotube film: and (3) respectively coating the mixed solution of sulfuric acid and nitric acid on the two sides of the cleaned CNT obtained in the step (1), clamping the mixed solution by using a glass sheet, connecting the two ends of the CNT film with a metal foil by using conductive adhesive, and switching on a power supply, electrifying for a certain time under a certain voltage, and oxidizing the CNT film by using Joule heat. Washing the oxidized CNT film with alcohol and deionized water for several times, 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 stage of a vacuum cavity of a Joule heating device through conductive silver glue (the sample stage is connected to a binding post at the wall of the cavity through a wire, and an external power supply is connected with the binding post on the wall of the cavity to realize the electrifying of a sample). And then the cavity is pumped to a vacuum state, a direct current power supply is connected to a binding post on the wall of the cavity, and after the direct current power supply is electrified, the high electrochemical activity CNT film super capacitor electrode based on the rapid Joule heat activation process is prepared after Joule heat activation for a certain time.
More specifically, as a preferred technical solution, the specific steps of step (2) may be: the two sides of the cleaned CNT are respectively coated with 15 microliters of mixed solution of concentrated sulfuric acid and concentrated nitric acid and clamped by a glass sheet, then the two ends of the CNT film are connected on a copper foil with the thickness of 0.05mm by using conductive silver paste, and the copper foil is connected with a power supply, and the power is electrified for 15min under the voltage of 3V. Washing an oxidized CNT film with alcohol and deionized water for several times, drying, uniformly coating 10 microliters on two sides of the dried oxidized CNT film respectively, drying after 1M KOH solution, gluing the dried CNT film on a copper sample table of a vacuum cavity of a Joule heating device through conductive silver, vacuumizing the cavity, connecting a direct current power supply to a binding post on the wall of the cavity, and activating the Joule heating at 800 ℃ for 30 seconds after electrifying to prepare the high electrochemical activity CNT film supercapacitor electrode based on the rapid Joule heating activation process.
As another preferable technical scheme, the specific steps of the step (2) may also be: the two sides of the cleaned CNT are respectively coated with 20 microliter of mixed solution of concentrated sulfuric acid and concentrated nitric acid and clamped by a glass sheet, then the two ends of the CNT film are connected onto a copper foil with the thickness of 0.05mm by using conductive silver paste and connected to a power supply, and the CNT film is electrified for 1min under the voltage of 5V. Washing the oxidized CNT film with alcohol and deionized water for several times, drying, respectively and uniformly coating 50 microlitres on two sides of the dried oxidized CNT film, drying after 0.1M KOH solution, gluing the dried CNT film on a copper sample stage of a vacuum cavity of a Joule heating device through conductive silver, vacuumizing the cavity, connecting a direct current power supply to a binding post on the wall of the cavity, and activating the high electrochemical activity CNT film supercapacitor electrode based on a rapid Joule heat activation process at 500 ℃ for 10min after electrifying.
As a further preferred technical solution, the specific step of step (2) may be: the two sides of the cleaned CNT are respectively coated with 5 microliter of mixed solution of concentrated sulfuric acid and concentrated nitric acid and clamped by a glass sheet, then the two sides of the CNT film are connected on a copper foil with the thickness of 0.05mm by using conductive silver paste and connected with a power supply, and the CNT film is electrified for 30min under the voltage of 1.5V. Washing the oxidized CNT film with alcohol and deionized water for several times, drying, uniformly coating 20 microlitres on two sides of the dried oxidized CNT film respectively, drying after 0.5M KOH solution, gluing the dried CNT film on a copper sample table of a vacuum cavity of a Joule heating device through conductive silver, vacuumizing the cavity, connecting a direct current power supply to a binding post on the wall of the cavity, and activating the Joule heating at 700 ℃ for 2min after electrifying to prepare the high electrochemical activity CNT film supercapacitor electrode based on the rapid Joule heating activation process.
The embodiment of the invention also provides the carbon nano tube film supercapacitor electrode material prepared by the method in any embodiment.
In some embodiments, the supercapacitor may comprise a flat plate supercapacitor or a thin film supercapacitor.
In some embodiments, the supercapacitor may comprise a flat plate supercapacitor or a thin film supercapacitor.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the selected embodiments are only for illustrating the present invention, and do not limit the scope of the present invention.
Example 1
The present embodiment provides a method for preparing CNT thin film supercapacitor electrode materials based on joule heat rapid activation, wherein the supercapacitor electrode material is only a carbon nanotube thin film without loading other active materials. The CNT in the strong acid solution is electrified to generate self-generated Joule heat to rapidly oxidize the CNT, then the surface of the CNT is covered with KOH solution, and the CNT is activated by the self-generated Joule heat in vacuum, so that the high electrochemical activity CNT film super capacitor electrode based on the rapid Joule heat activation process is prepared.
The method for preparing the CNT film supercapacitor electrode based on the quick activation of Joule heat specifically comprises the following steps:
both ends of the commercial CNT film were connected to a copper foil having a thickness of 0.05mm using conductive silver paste and connected to a power source. After being electrified, the amorphous carbon of the CNT film is removed by maintaining the temperature at 400 ℃ for 5min, then the CNT film is soaked in hydrochloric acid for 24h to remove the catalyst particles remained in the film in the preparation process, and finally the film is washed 3 times by deionized water and alcohol and dried.
The two sides of the cleaned CNT are respectively coated with 15 microlitres of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, and clamped by glass sheets, then the two ends of the CNT film are connected on copper foil with the thickness of 0.05mm by using conductive silver adhesive and connected with a power supply, and the CNT film is electrified for 15min at the temperature of 150 ℃ under the voltage of 3V.
Washing the oxidized CNT film with alcohol and deionized water for several times, drying, respectively and uniformly coating 10 microlitres on two sides of the dried oxidized CNT film, drying after 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, vacuumizing the cavity, connecting a direct current power supply into a wiring column on the wall of the cavity, and activating the high electrochemical activity CNT film supercapacitor electrode based on a rapid Joule heat activation process at 800 ℃ after power on for 30 seconds.
XPS test is carried out on the CNT film supercapacitor electrode prepared in the embodiment, the test result is shown in figure 2, and it is clear from figure 2 that a large number of oxygen-containing functional groups are formed on the surface of the CNT film supercapacitor electrode prepared in the embodiment in the activation process; FIG. 3 shows that the CNT film supercapacitor electrode described above is at 10-50mV s -1 Circulation at a sweeping speedA voltammetric curve reflecting that the electrode exhibits excellent pseudocapacitive properties; FIG. 4 shows that the CNT film supercapacitor electrode is in the range of 0.5-5A g -1 A charge-discharge curve at a current density of 0.5. 0.5A g -1 The time specific capacitance can reach 227.8F g -1 High specific capacitance of (2); FIG. 5 shows the AC impedance spectrum of the CNT film supercapacitor electrode at 0.01-100000HZ, and the curve shows a larger slope in the low frequency region, which shows that the electrode has smaller ion diffusion impedance, and ions can be rapidly diffused to the interface between the electrode and the electrolyte.
Example 2
The embodiment provides a method for preparing an electrode material of a CNT film supercapacitor based on quick activation of Joule heat, which comprises the following steps:
both ends of the commercial CNT film were connected to a copper foil having a thickness of 0.05mm using conductive silver paste and connected to a power source. After being electrified, the amorphous carbon of the CNT film is removed at 300 ℃ for 15min, then the CNT film is soaked in hydrochloric acid for 24h to remove the catalyst particles remained in the film in the preparation process, and finally the film is washed 3 times by deionized water and alcohol and dried.
The two sides of the cleaned CNT are respectively coated with 20 microliters of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 2:1, and clamped by a glass sheet, then the two ends of the CNT film are connected on a copper foil with the thickness of 0.05mm by using conductive silver adhesive and connected with a power supply, and the CNT film is electrified for 1min at the temperature of 240 ℃ under the voltage of 5V.
Washing the oxidized CNT film with alcohol and deionized water for several times, drying, respectively and uniformly coating 50 microlitres on two sides of the dried oxidized CNT film, drying after 0.1M KOH solution, gluing the dried CNT film on a copper sample table of a vacuum cavity of a Joule heating device through conductive silver, vacuumizing the cavity, connecting a direct current power supply to a wire connecting column on the wall of the cavity, and activating the high electrochemical activity CNT film supercapacitor electrode based on a rapid Joule heat activation process at 500 ℃ for 10min after electrifying.
A CNT thin film supercapacitor electrode with high electrochemical activity similar to the performance of example 1 can be prepared.
Example 3
The embodiment provides a method for preparing an electrode material of a CNT film supercapacitor based on quick activation of Joule heat, which comprises the following steps:
both ends of the commercial CNT film were connected to a copper foil having a thickness of 0.05mm using conductive silver paste and connected to a power source. After being electrified, the amorphous carbon of the CNT film is removed by keeping the temperature at 500 ℃ for 1min, then the CNT film is soaked in hydrochloric acid for 24h to remove the catalyst particles remained in the film in the preparation process, and finally the film is washed 3 times by deionized water and alcohol and dried.
The two sides of the cleaned CNT are respectively coated with 5 microliter of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, and clamped by glass sheets, then the two ends of the CNT film are connected on copper foil with the thickness of 0.05mm by using conductive silver adhesive and connected with a power supply, and the CNT film is electrified for 15min at the temperature of 100 ℃ under the voltage of 2V.
Washing the oxidized CNT film with alcohol and deionized water for several times, drying, respectively and uniformly coating 20 microlitres on two sides of the dried oxidized CNT film, drying after 0.5M KOH solution, gluing the dried CNT film on a copper sample table of a vacuum cavity of a Joule heating device through conductive silver adhesive, vacuumizing the cavity, connecting a direct current power supply into a wiring column on the wall of the cavity, and activating the high electrochemical activity CNT film supercapacitor electrode based on a rapid Joule heat activation process at 700 ℃ after electrifying.
A CNT thin film supercapacitor electrode with high electrochemical activity similar to the performance of example 1 can be prepared.
Example 4
This example provides a method for preparing CNT thin film supercapacitor electrode materials based on rapid activation by joule heat, substantially identical to example 1, except that:
amorphous carbon of the CNT film was removed after being energized at 200 c for 60 min.
CNT thin film supercapacitor electrodes of high electrochemical activity can also be prepared with similar properties from example 1.
Example 5
This example provides a method for preparing CNT thin film supercapacitor electrode materials based on rapid activation by joule heat, substantially identical to example 1, except that:
the mixed solution of the concentrated sulfuric acid and the concentrated nitric acid with the volume ratio of 3:1 is replaced by the mixed solution of the hypochlorous acid and the concentrated nitric acid with the volume ratio of 3:1.
CNT thin film supercapacitor electrodes of high electrochemical activity can also be prepared with similar properties from example 1.
Example 6
This example provides a method for preparing CNT thin film supercapacitor electrode materials based on rapid activation by joule heat, substantially identical to example 1, except that:
the 0.1M KOH solution was changed to 0.1M NaOH solution.
CNT thin film supercapacitor electrodes of high electrochemical activity can also be prepared with similar properties from example 1.
Example 7
This example provides a method for preparing CNT thin film supercapacitor electrode materials based on rapid activation by joule heat, substantially identical to example 3, except that:
the 0.5M KOH solution was changed to 0.5M NaOH solution.
The mixed solution of the concentrated sulfuric acid and the concentrated nitric acid with the volume ratio of 3:1 is replaced by the mixed solution of the chloric acid and the concentrated nitric acid with the volume ratio of 3:1.
CNT thin film supercapacitor electrodes of high electrochemical activity can also be prepared with similar properties from example 1.
Comparative example 1
This comparative example provides a method for preparing CNT thin film supercapacitor electrode material, substantially identical to example 1, except that:
and (3) the step of coating concentrated sulfuric acid and concentrated nitric acid on the surface of the CNT film and electrifying is omitted, and the CNT film with amorphous carbon and catalyst particles removed is directly coated with 1M KOH solution, dried and then electrified and heated in vacuum to obtain the CNT film supercapacitor electrode.
Is applied toThe CNT film super capacitor electrode prepared by the method is tested to be 0.5A g -1 The specific capacitance is only 45F g -1 。
Comparative example 2
This comparative example provides a method for preparing CNT thin film supercapacitor electrode material, substantially identical to example 1, except that:
and (3) omitting the step of electrifying the commercial CNT film to remove the surface amorphous carbon, directly coating concentrated sulfuric acid and concentrated nitric acid on the surface of the CNT film, electrifying, coating the electrified CNT film with 1M KOH solution, 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 to be 0.5A g -1 The specific capacitance is only 120F g -1 。
Based on the above examples and comparative examples, it is clear 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 the joule heat generated by energizing the CNT film 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 thermal process in the strong acid environment can easily lead carbon atoms to form bonds with oxygen-containing functional groups, has better oxidation effect on the surface of the CNT film, and can further obtain the CNT film with higher electrochemical activity as an electrode of the supercapacitor. Finally, the method takes the CNT film with good hydrophilicity after oxidation as a matrix, so that the solution of the strong alkaline substance can better infiltrate each position in the CNT film, and further the activation of the CNT film is more uniform.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. Equivalent changes or modifications of the essential characteristics of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the carbon nanotube film supercapacitor electrode material is characterized by comprising the following steps of:
1) Contacting a carbon nanotube film with an oxidizing acid, and simultaneously applying current to the carbon nanotube film to perform a Joule thermal oxidation reaction to obtain the oxidized carbon nanotube film, wherein the oxidizing acid comprises one or more of concentrated sulfuric acid, concentrated nitric acid, chloric acid and hypochlorous acid, the temperature of the Joule thermal oxidation reaction is 100-300 ℃, and the time is 30s-15min;
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 a Joule heat activation reaction to obtain the carbon nanotube film supercapacitor electrode material, wherein the strong alkaline substance comprises any one or two of potassium hydroxide and sodium hydroxide, the temperature of the Joule heat activation reaction is 400-800 ℃, and the time is 10s-10min.
2. The method of manufacturing according to claim 1, wherein the carbon nanotube film comprises carbon nanotubes and amorphous carbon, the method further comprising:
and before the carbon nano tube film is contacted with the oxidizing acid, applying current to the carbon nano tube film, and removing amorphous carbon at least by using generated Joule heat, wherein the Joule heat temperature is 200-500 ℃ and the time is 1min-1h.
3. The method of preparing as claimed in claim 2, wherein the carbon nanotube film further comprises catalyst particles, the method further comprising: and immersing the carbon nano tube film with an acidic solution to remove amorphous carbon, so that catalyst particles in the carbon nano tube film are dissolved and removed.
4. A method of manufacture according to claim 3, 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 is for a period of time of 6 to 24h.
5. The method according to claim 1, wherein in step 1), the oxidizing acid is a mixture of concentrated sulfuric acid and concentrated nitric acid.
6. The method according to claim 5, wherein the step 1) specifically comprises: coating the surface of the carbon nano tube film with the oxidizing acid, covering and clamping the two sides of the carbon nano tube film coated with the oxidizing acid by using a carrier plate, and exposing the two ends of the carbon nano tube film to be connected with a power supply;
the carrier plate comprises any one of a glass plate and a polytetrafluoroethylene plate.
7. The preparation method according to claim 1, wherein 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 performing a Joule heat activation reaction;
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。
8. The method according to claim 1, wherein step 1) further comprises a step of washing the carbon oxide nanotube film, the carbon oxide nanotube film being washed with alcohol and water alternately two or more times;
in 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 an electrode for first electric heating.
9. A carbon nanotube film supercapacitor electrode material prepared by the method of any one of claims 1-8.
10. A supercapacitor, characterized in that the electrode of the supercapacitor comprises the carbon nanotube film supercapacitor electrode material of claim 9;
the super capacitor comprises a flat super capacitor or a thin film super capacitor.
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