CN109686595B - Activation method of conductive carbon cloth and application of supercapacitor of conductive carbon cloth - Google Patents
Activation method of conductive carbon cloth and application of supercapacitor of conductive carbon cloth Download PDFInfo
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- CN109686595B CN109686595B CN201910084424.3A CN201910084424A CN109686595B CN 109686595 B CN109686595 B CN 109686595B CN 201910084424 A CN201910084424 A CN 201910084424A CN 109686595 B CN109686595 B CN 109686595B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000004744 fabric Substances 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000004913 activation Effects 0.000 title claims abstract description 9
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 abstract description 14
- 238000011156 evaluation Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- 150000001721 carbon Chemical class 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses an activation method of conductive carbon cloth and application of a super capacitor of the conductive carbon cloth. And (3) taking a 1M KOH solution as an electrolyte, adopting a two-electrode system, and carrying out cyclic voltammetry treatment under certain conditions to obtain the activated conductive carbon cloth. Performing electrochemical performance evaluation on the conductive carbon cloth in a 1M KOH electrolyte within a potential window range of-1-0V, and comparing the performance with that of the original carbon cloth which is not subjected to activation treatment, wherein the capacity of the original carbon cloth is 1.40F/cm2The maximum capacity of the activated carbon cloth can reach 1.84F/cm2The activation treatment method can obviously improve the specific capacitance of the carbon cloth.
Description
Technical Field
The invention belongs to the field of super capacitors, and particularly relates to an activation method of conductive carbon cloth and application of a super capacitor.
Background
Due to the crisis of fossil fuels and the increasing demand for renewable energy, the development of clean energy and the development of high-performance electrochemical energy storage devices have become important issues concerning human survival and development. Meanwhile, with the rapid development of electronics and information industries, people have higher and higher requirements on energy storage equipment, and compared with a lithium ion battery, a super capacitor has strong advantages in the aspects of power density and high stability, so that the super capacitor is widely applied to portable electronics, hybrid electric vehicles and standby energy systems. However, the super capacitor has the problems of high price, low energy density and the like, so that on the premise of keeping high power density, the trend and the hot spot for developing a new generation of super capacitor are to improve the energy density of the super capacitor.
According to the calculation formula of energy density E-0.5 CV2The energy density of a supercapacitor can be improved in terms of both specific capacitance and operating voltage. From the perspective of specific capacitance, an electrode material with high specific capacitance, such as a pseudocapacitive electrode material, can be selected. From the view point of working voltage, the working voltage of the whole capacitor can be widened by combining different potential windows of the anode and the cathode to construct the water system asymmetric super capacitor. Among various electrode materials, carbon-based materials, such as carbon spheres, carbon nanotubes, and graphene, are widely used as a supercapacitor negative electrode due to their high specific surface area, low cost, excellent conductivity, and excellent electrochemical properties. However, these carbon-based materials have a low specific capacitance due to their inherent electric double layer mechanism, limiting the total capacity C (1/C-1/C)Is just+1/CNegative pole) The improvement of (2) becomes a main obstacle of the energy density of the super capacitor.
The conductive carbon cloth is made of a plurality of uniform carbon fibers, is a conductive textile with low price, has excellent mechanical elasticity and strength, has great application prospect in the aspect of manufacturing flexible electrodes, and not only can be used as a flexible current collector of other electrode materials, but also can be directly used as a flexible electrode. However, compared to other carbon materials, the original conductive carbon cloth commercialized has been rarely used directly as an energy storage material because of its low electrochemical activity on the one hand and its small specific surface area on the other hand, which results in its low energy storage capacity. Therefore, how to improve the electrochemical performance of the commercial conductive carbon cloth becomes a hot spot for researching flexible electrodes.
Disclosure of Invention
Based on the current situation, the conductive carbon cloth is activated in a KOH solution by a cyclic voltammetry method, functional groups are introduced to the surface of the conductive carbon cloth to generate pseudo capacitance, the surface area of the conductive carbon cloth is increased, and the electrochemical performance of the conductive carbon cloth is improved. Specifically, KOH solution is used as electrolyte, a two-electrode system is adopted, cyclic voltammetry treatment is carried out under certain conditions, activated conductive carbon cloth can be obtained, and the specific capacitance of the activated carbon cloth can reach 1.8 within a potential window range of-1-0V4F/cm2The material can be directly used as a negative electrode material of a flexible super capacitor; meanwhile, due to the three-dimensional network structure of the conductive carbon cloth, other cathode materials can be borne, and the cathode material of the super capacitor with higher specific capacitance is further obtained.
The technical method comprises the following steps:
(1) cleaning the conductive carbon cloth: placing the carbon cloth in a 3M hydrochloric acid, deionized water, acetone and absolute ethyl alcohol solution in sequence, ultrasonically cleaning for 20min, and drying for later use;
(2) activating the conductive carbon cloth: preparing a KOH solution with a certain concentration as an electrolyte, adopting an electrochemical workstation two-electrode system, taking conductive carbon cloth as a working electrode, taking a platinum sheet as a counter electrode, and adopting a cyclic voltammetry method in the electrochemical workstation two-electrode system to activate the conductive carbon cloth under the conditions of a certain potential range and a certain scanning rate to obtain the activated conductive carbon cloth. The concentration range of the electrolyte KOH solution is 1-6M. The voltage range is-0.8 to-1.2V; the scanning speed is 5-20 mV/s; the activation time is 5-20 s.
The technical scheme of the invention applies the prepared activated carbon cloth electrode to the super capacitor.
Compared with the conductive carbon cloth before activation, the specific capacitance of the activated conductive carbon cloth is obviously improved. The reason is that: the surface of the activated carbon cloth becomes rough, so that the electric double layer capacitance of the material is improved; a large number of oxidation groups are introduced in the activation process, so that the pseudo-capacitance of the carbon cloth is increased.
Drawings
FIG. 1 is a graph comparing an activated carbon cloth with an unactivated carbon cloth of example 1; wherein (a) is a cyclic voltammogram of the activated carbon cloth and the non-activated carbon cloth in example 1, the figure (b) is a charge-discharge diagram of the activated carbon cloth and the non-activated carbon cloth in example 1, and the figure (c) is a multiplying power performance diagram of the activated carbon cloth and the non-activated carbon cloth in example 1.
FIG. 2 is a graph comparing an activated carbon cloth with an unactivated carbon cloth of example 2; wherein, (a) is a cyclic voltammogram of the activated carbon cloth and the unactivated carbon cloth of the example 2, and (b) is a charge-discharge diagram of the activated carbon cloth and the unactivated carbon cloth of the example 2; figure (c) is a graph of rate performance for activated and unactivated carbon cloths of example 2.
FIG. 3 is a graph comparing an activated carbon cloth with an unactivated carbon cloth of example 3; wherein (a) is a cyclic voltammogram of the activated carbon cloth and the non-activated carbon cloth in example 3, the figure (b) is a charge-discharge diagram of the activated carbon cloth and the non-activated carbon cloth in example 3, and the figure (c) is a multiplying power performance diagram of the activated carbon cloth and the non-activated carbon cloth in example 3.
Detailed Description
In order to further understand the summary and features of the present invention, several examples of the present invention are given below, and it should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
The experimental procedures in the following examples are conventional unless otherwise specified.
Example 1
(1) Cleaning the conductive carbon cloth: placing the carbon cloth in a 3M hydrochloric acid, deionized water, acetone and absolute ethyl alcohol solution in sequence, ultrasonically cleaning for 20min, and drying for later use;
(2) activating the conductive carbon cloth: preparing 1M KOH solution as electrolyte, using conductive carbon cloth as a working electrode, using a platinum sheet as a counter electrode, and adopting a cyclic voltammetry method in a two-electrode system of an electrochemical workstation to treat the conductive carbon cloth for 10s under the conditions that the potential range is-1 to-0.9V and the scanning rate is 10 mV/s. The unactivated conductive carbon cloth is labeled 1 and the activated carbon cloth is labeled 2.
(3) The electrode is used as a negative electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a three-electrode testing system is formed, 1M KOH is used as electrolyte, a CHI660D electrochemical testing system is adopted, cyclic voltammetry and charge-discharge testing are carried out at constant current density, and the charge-discharge voltage range is-1-0V.
The electrochemical test result shows that the charging and discharging time of the activated carbon cloth electrode is higher than that of the blank carbon cloth (figure 1b), and the specific capacitance calculation formula is used
Specific capacitance of the activated carbon cloth electrode under different current densities is obtained (figure 1c), and the figure shows thatThe maximum area specific capacitance of the activated conductive carbon cloth can reach 1.72F/cm2Is obviously superior to the blank carbon cloth.
Example 2
(1) Cleaning the conductive carbon cloth: placing the carbon cloth in a 3M hydrochloric acid, deionized water, acetone and absolute ethyl alcohol solution in sequence, ultrasonically cleaning for 20min, and drying for later use;
(2) activating the conductive carbon cloth: preparing 1M KOH solution as electrolyte, using conductive carbon cloth as a working electrode, using a platinum sheet as a counter electrode, and adopting a cyclic voltammetry method in a two-electrode system of an electrochemical workstation to process the conductive carbon cloth for 10s under the conditions that the potential range is-0.9 to-0.8V and the scanning rate is 10 mV/s. The unactivated conductive carbon cloth is labeled 1 and the activated carbon cloth is labeled 3.
(3) The electrode is used as a negative electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a three-electrode testing system is formed, 1MKOH is used as electrolyte, a CHI660D electrochemical testing system is adopted, cyclic voltammetry and charge-discharge testing are carried out at constant current density, and the charge-discharge voltage range is-1-0V.
The electrochemical test result shows that the charging and discharging time of the activated carbon cloth electrode is higher than that of the blank carbon cloth (figure 2b), and the specific capacitance calculation formula is used
The specific capacitance of the activated carbon cloth electrode under different current densities is obtained (figure 2c), and the figure shows that the maximum area specific capacitance of the activated conductive carbon cloth can reach 1.61F/cm2Is obviously superior to the blank carbon cloth.
Example 3
(1) Cleaning the conductive carbon cloth: placing the carbon cloth in a 3M hydrochloric acid, deionized water, acetone and absolute ethyl alcohol solution in sequence, ultrasonically cleaning for 20min, and drying for later use;
(2) activating the conductive carbon cloth: preparing a 1M KOH solution as an electrolyte, using conductive carbon cloth as a working electrode, using a platinum sheet as a counter electrode, and treating the conductive carbon cloth for 20s under the conditions of a potential range of-1 to-0.9V and a scanning rate of 5mV/s by adopting a cyclic voltammetry method in a two-electrode system of an electrochemical workstation. The unactivated conductive carbon cloth is labeled 1 and the activated carbon cloth is labeled 4.
(3) The electrode is used as a negative electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a three-electrode testing system is formed, 1MKOH is used as electrolyte, a CHI660D electrochemical testing system is adopted, cyclic voltammetry and charge-discharge testing are carried out at constant current density, and the charge-discharge voltage range is-1-0V.
The electrochemical test result shows that the charging and discharging time of the activated carbon cloth electrode is higher than that of the blank carbon cloth (figure 1b), and the specific capacitance calculation formula is used
The specific capacitance of the activated carbon cloth electrode under different current densities is obtained (figure 1c), and the maximum area specific capacitance after the conductive carbon cloth is activated can reach 1.84F/cm2Is obviously superior to the blank carbon cloth.
Claims (2)
1. The method for activating the conductive carbon cloth is characterized by comprising the following steps of:
(1) cleaning the conductive carbon cloth: sequentially placing the carbon cloth in 2-3M hydrochloric acid, deionized water, acetone and absolute ethyl alcohol solution, ultrasonically cleaning, and drying for later use;
(2) activating the conductive carbon cloth: using a KOH solution as an electrolyte, wherein the concentration range of the KOH solution is 1-6M, using conductive carbon cloth as a working electrode, using a platinum sheet as a counter electrode, and adopting a cyclic voltammetry method in a two-electrode system of an electrochemical workstation, wherein the voltage range is-0.8 to-1.2V; the scanning speed is 5-20 mV/s; the activation time is 5-20s, and the activated conductive carbon cloth is obtained.
2. Use of the activated carbon cloth electrode prepared according to claim 1 in a supercapacitor.
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| CN109686595B true CN109686595B (en) | 2020-11-10 |
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| CN110690057B (en) * | 2019-09-27 | 2021-02-02 | 同济大学 | Nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material and preparation method and application thereof |
| CN113077990A (en) * | 2021-03-17 | 2021-07-06 | 三峡大学 | Double-potential interval activation for improving Co (OH)2Method for performance of super capacitor |
Citations (5)
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|---|---|---|---|---|
| JP2008066681A (en) * | 2006-09-11 | 2008-03-21 | Osaka Prefecture Univ | Electrochemical capacitor and method of manufacturing zinc electrode used in the electrochemical capacitor |
| CN105780364A (en) * | 2016-02-26 | 2016-07-20 | 浙江大学 | Method for preparing super-microporous flexible carbon cloth and product thereof and application |
| CN107221454A (en) * | 2017-06-08 | 2017-09-29 | 陕西师范大学 | A kind of all-solid-state flexible ultracapacitor based on porous carbon fiber cloth and preparation method thereof |
| CN107768150A (en) * | 2017-10-26 | 2018-03-06 | 吉林大学 | Copper ion doped polyaniline electrode with carbon cloth as substrate and preparation method thereof |
| CN107934955A (en) * | 2017-11-17 | 2018-04-20 | 浙江大学 | A kind of method of activation process commercialization carbon cloth |
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2019
- 2019-01-18 CN CN201910084424.3A patent/CN109686595B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008066681A (en) * | 2006-09-11 | 2008-03-21 | Osaka Prefecture Univ | Electrochemical capacitor and method of manufacturing zinc electrode used in the electrochemical capacitor |
| CN105780364A (en) * | 2016-02-26 | 2016-07-20 | 浙江大学 | Method for preparing super-microporous flexible carbon cloth and product thereof and application |
| CN107221454A (en) * | 2017-06-08 | 2017-09-29 | 陕西师范大学 | A kind of all-solid-state flexible ultracapacitor based on porous carbon fiber cloth and preparation method thereof |
| CN107768150A (en) * | 2017-10-26 | 2018-03-06 | 吉林大学 | Copper ion doped polyaniline electrode with carbon cloth as substrate and preparation method thereof |
| CN107934955A (en) * | 2017-11-17 | 2018-04-20 | 浙江大学 | A kind of method of activation process commercialization carbon cloth |
Non-Patent Citations (1)
| Title |
|---|
| Cobalt-based composite films on electrochemically activated carbon cloth as high performance overall water splitting electrodes;Karolina Kordek;《International Journal of Hydrogen Energy》;20180308;第44卷(第1期);正文第24页右栏第3段，附图1 * |
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