CN109686595A - A kind of activation method and its supercapacitor applications of conduction carbon cloth - Google Patents

A kind of activation method and its supercapacitor applications of conduction carbon cloth Download PDF

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Publication number
CN109686595A
CN109686595A CN201910084424.3A CN201910084424A CN109686595A CN 109686595 A CN109686595 A CN 109686595A CN 201910084424 A CN201910084424 A CN 201910084424A CN 109686595 A CN109686595 A CN 109686595A
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carbon cloth
electrode
conductive carbon
activation
electrolyte
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CN109686595B (en
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肖婷
王书琳
车鹏程
谭新玉
向鹏
姜礼华
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Anhui Hongyuntong Electronic Technology Co ltd
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China Three Gorges University CTGU
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/26Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/34Carbon-based characterised by carbonisation or activation of carbon
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses the activation methods and its supercapacitor applications of a kind of conductive carbon cloth.Using 1M KOH solution as electrolyte, using two electrode systems, cyclic voltammetry processing is carried out under certain condition, the conductive carbon cloth of activation can be obtained.In 1 M KOH electrolyte, chemical property evaluation is carried out to conductive carbon cloth within the scope of -1 ~ 0V potential window, and compared with the original carbon cloth not being activated carries out performance, original carbon cloth capacity is 1.40 F/cm2, carbon cloth maximum capacity is up to 1.84 F/cm after activation processing2, illustrate that this activating treatment method can be obviously improved the specific capacitance of carbon cloth.

Description

A kind of activation method and its supercapacitor applications of conduction carbon cloth
Technical field
The invention belongs to supercapacitor fields, and in particular to a kind of activation method and its supercapacitor of conduction carbon cloth Using.
Background technique
Due to being continuously increased for fossil fuel crisis and renewable energy demand, clean energy resource is developed, develops high-performance electric Chemical energy storage device becomes the key subjects of relationship human survival and development.Meanwhile with the hair at full speed of electronics and information industry Exhibition, requirement of the people to energy storage device is higher and higher, and compared with lithium ion battery, supercapacitor is in power density and high stable Property aspect there is the strong advantage of teaching, this obtains it in portable electronic, hybrid vehicle and spare energy system It is widely applied.However, supercapacitor there is also prices it is higher, energy density is low the problems such as, therefore keep compared with Gao Gong Under the premise of rate density, the energy density for improving supercapacitor is to develop the trend and hot spot of supercapacitor of new generation.
According to the calculation formula E=0.5CV of energy density2, the energy density of supercapacitor can by specific capacitance and Improve in terms of operating voltage two.From the point of view of specific capacitance, the electrode material with high specific capacitance can be selected, such as counterfeit electricity Appearance type electrode material.From the point of view of operating voltage, it is non-can to construct water system by the potential window for combining anode different with cathode Symmetrical supercapacitor widens the operating voltage of entire capacitor.In various electrode materials, carbon-based material, such as carbon ball, carbon Nanotube and graphene are extensive due to its high-specific surface area, low cost, excellent electric conductivity and excellent chemical property As super capacitor anode.However, these carbon-based materials have lower specific capacitance due to its intrinsic layer mechanism, Limit total capacity C (1/C=1/CJust+1/CIt is negative) promotion, become the major obstacle of super capacitor energy density.
Conductive carbon cloth is made of many uniform carbon fibers, is a kind of cheap conductive spinning product, has excellent Mechanical elasticity and intensity therefore have great application prospect in terms of manufacturing flexible electrode, can be used as other electrodes The flexible current-collecting body of material, but also can be directly as flexible electrode.But, other carbon materials are compared, it is commercialized original Conductive carbon cloth is seldom used directly to energy storage material, this is because on the one hand the electro-chemical activity of conductive carbon cloth is lower, another party Its specific surface area of face is smaller, these reasons cause its energy storage capability low.Therefore, the electricity of the conductive carbon cloth of business how is improved Chemical property becomes a big hot spot of research flexible electrode.
Summary of the invention
Based on the above status, conductive carbon cloth is activated in KOH solution by the present invention by cyclic voltammetry, by function Group introduces its surface to generate fake capacitance, and increases its surface area simultaneously, and then promotes the chemical property of conductive carbon cloth. Specifically using KOH solution as electrolyte, using two electrode systems, cyclic voltammetry processing is carried out under certain condition, can be obtained To the conductive carbon cloth of activation, carbon cloth after activation processing within the scope of -1~0V potential window specific capacitance up to 1.84F/cm2, can Directly as flexible super capacitor negative electrode material;Simultaneously because the three-dimensional net structure of conductive carbon cloth, can carry other cathode Material further obtains the super capacitor anode material with more high specific capacitance.
Technical method of the invention the following steps are included:
(1) clean conductive carbon cloth: by carbon cloth be placed sequentially in the hydrochloric acid of 3M, deionized water, acetone, in ethanol solution It is cleaned by ultrasonic 20min, then dries stand-by;
(2) activate conductive carbon cloth: configuration a certain concentration KOH solution is as electrolyte, using two electrode of electrochemical workstation System, using conductive carbon cloth as working electrode, platinized platinum is used as to electrode, using the circulation in two electrode system of electrochemical workstation Voltammetric method activates conductive carbon cloth under the conditions of certain potentials range and sweep speed, the conductive carbon after being activated Cloth.The electrolyte KOH solution concentration range is 1~6M.Voltage range is -0.8~-1.2V;Sweep speed be 5~ 20mV/s;Activation time is 5-20s.
Technical solution of the present invention is by preparation-obtained activation carbon cloth application of electrode in supercapacitor.
The present invention activation after conductive carbon cloth compared to activation before, specific capacitance is obviously improved.The reason is that: after activation Carbon cloth surfaces become the coarse electric double layer capacitance for making material and are promoted;A large amount of oxide groups are introduced in activation process increases carbon The fake capacitance of cloth.
Detailed description of the invention
Fig. 1 is the comparison diagram that carbon cloth and unactivated carbon cloth are activated in embodiment 1;Wherein, (a) is that embodiment 1 activates carbon cloth With the cyclic voltammogram of unactivated carbon cloth, scheming (b) is the charge and discharge electrograph that embodiment 1 activates carbon cloth and unactivated carbon cloth, and figure (c) is The high rate performance figure of embodiment 1 activation carbon cloth and unactivated carbon cloth.
Fig. 2 is the comparison diagram that carbon cloth and unactivated carbon cloth are activated in embodiment 2;Wherein, (a) is that embodiment 2 activates carbon cloth With the cyclic voltammogram of unactivated carbon cloth, scheming (b) is the charge and discharge electrograph that embodiment 2 activates carbon cloth and unactivated carbon cloth;Scheming (c) is The high rate performance figure of embodiment 2 activation carbon cloth and unactivated carbon cloth.
Fig. 3 is the comparison diagram that carbon cloth and unactivated carbon cloth are activated in embodiment 3;Wherein, (a) is that embodiment 3 activates carbon cloth With the cyclic voltammogram of unactivated carbon cloth, scheming (b) is the charge and discharge electrograph that embodiment 3 activates carbon cloth and unactivated carbon cloth, and figure (c) is The high rate performance figure of embodiment 3 activation carbon cloth and unactivated carbon cloth.
Specific embodiment
To further appreciate that summary of the invention and feature of the invention, several embodiments of the present invention are given below, it should be appreciated that These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Experimental method in following embodiments is unless otherwise instructed conventional method.
Embodiment 1
(1) clean conductive carbon cloth: by carbon cloth be placed sequentially in the hydrochloric acid of 3M, deionized water, acetone, in ethanol solution It is cleaned by ultrasonic 20min, then dries stand-by;
(2) activate conductive carbon cloth: configuration 1M KOH solution is as electrolyte, using conductive carbon cloth as working electrode, platinized platinum As to electrode, using the cyclic voltammetric method in two electrode system of electrochemical workstation, potential range be -1~-0.9V and Sweep speed is handled conductive carbon cloth under conditions of being 10mV/s, time 10s.It is unactivated conduction carbon cloth label be, Carbon cloth after activation is labeled as 2.
It (3) is to pole with platinum electrode using this electrode as negative electrode, saturated calomel electrode is reference electrode, three electricity of composition Pole test system, using CHI660D electrochemical test system, is followed using 1M KOH as electrolyte with constant current density Ring volt-ampere and charge-discharge test, charging/discharging voltage range is in -1~0V.
Electrochemical results show, the charge and discharge time for activating carbon cloth electrode is higher than blank carbon cloth (attached drawing 1b), by than Capacitor calculation formulaObtain specific capacitance (attached drawing 1c) of the activation carbon cloth electrode under different current densities, You Tuke Know, maximum area specific capacitance can achieve 1.72F/cm after conductive carbon cloth activation2, hence it is evident that it is better than blank carbon cloth.
Embodiment 2
(1) clean conductive carbon cloth: by carbon cloth be placed sequentially in the hydrochloric acid of 3M, deionized water, acetone, in ethanol solution It is cleaned by ultrasonic 20min, then dries stand-by;
(2) activate conductive carbon cloth: configuration 1M KOH solution is as electrolyte, using conductive carbon cloth as working electrode, platinized platinum It is -0.9~-0.8V in potential range using the cyclic voltammetric method in two electrode system of electrochemical workstation as to electrode Conductive carbon cloth is handled under conditions of being 10mV/s with sweep speed, time 10s.It is unactivated conduction carbon cloth label be 1, the carbon cloth after activation is labeled as 3.
It (3) is to pole with platinum electrode using this electrode as negative electrode, saturated calomel electrode is reference electrode, three electricity of composition Pole test system, using CHI660D electrochemical test system, is recycled using 1MKOH as electrolyte with constant current density Volt-ampere and charge-discharge test, charging/discharging voltage range is in -1~0V.
Electrochemical results show, the charge and discharge time for activating carbon cloth electrode is higher than blank carbon cloth (attached drawing 2b), by than Capacitor calculation formulaObtain specific capacitance (attached drawing 2c) of the activation carbon cloth electrode under different current densities, You Tuke Know, maximum area specific capacitance can achieve 1.61F/cm after conductive carbon cloth activation2, hence it is evident that it is better than blank carbon cloth.
Embodiment 3
(1) clean conductive carbon cloth: by carbon cloth be placed sequentially in the hydrochloric acid of 3M, deionized water, acetone, in ethanol solution It is cleaned by ultrasonic 20min, then dries stand-by;
(2) activate conductive carbon cloth: configuration 1M KOH solution is as electrolyte, using conductive carbon cloth as working electrode, platinized platinum As to electrode, using the cyclic voltammetric method in two electrode system of electrochemical workstation, potential range be -1~-0.9V and Sweep speed is handled conductive carbon cloth under conditions of being 5mV/s, time 20s.It is unactivated conduction carbon cloth label be, Carbon cloth after activation is labeled as 4.
It (3) is to pole with platinum electrode using this electrode as negative electrode, saturated calomel electrode is reference electrode, three electricity of composition Pole test system, using CHI660D electrochemical test system, is recycled using 1MKOH as electrolyte with constant current density Volt-ampere and charge-discharge test, charging/discharging voltage range is in -1~0V.
Electrochemical results show, the charge and discharge time for activating carbon cloth electrode is higher than blank carbon cloth (attached drawing 1b), by than Capacitor calculation formulaObtain specific capacitance (attached drawing 1c) of the activation carbon cloth electrode under different current densities, You Tuke Know, maximum area specific capacitance can achieve 1.84F/cm after conductive carbon cloth activation2, hence it is evident that it is better than blank carbon cloth.

Claims (4)

1.一种导电碳布的活化方法,其特征在于,导电碳布的活化包括以下步骤:1. an activation method of conductive carbon cloth, is characterized in that, the activation of conductive carbon cloth comprises the following steps: (1)清洗导电碳布:将碳布依次放置在2-3M盐酸、去离子水、丙酮、无水乙醇溶液中超声清洗后,烘干待用;(1) Cleaning the conductive carbon cloth: Place the carbon cloth in 2-3M hydrochloric acid, deionized water, acetone, and anhydrous ethanol solution for ultrasonic cleaning, and then dry it for later use; (2)活化导电碳布:以KOH溶液作为电解液,以导电碳布作为工作电极,铂片作为对电极,采用电化学工作站两电极体系中的循环伏安方法,在一定电位范围和扫描速率条件下对导电碳布进行活化,得到活化后的导电碳布。(2) Activated conductive carbon cloth: KOH solution is used as the electrolyte, conductive carbon cloth is used as the working electrode, and platinum sheet is used as the counter electrode. The cyclic voltammetry method in the two-electrode system of the electrochemical workstation is used. In a certain potential range and scanning rate The conductive carbon cloth is activated under the conditions to obtain the activated conductive carbon cloth. 2.根据权利要求1所述的电极碳布的活化方法,其特征在于,步骤(2)中电解液KOH溶液浓度范围为1~6M。2 . The method for activating electrode carbon cloth according to claim 1 , wherein in step (2), the concentration range of the electrolyte KOH solution is 1-6M. 3 . 3.根据权利要求1所述的电极碳布的活化方法,其特征在于,步骤(2)中电压范围为-0.8~-1.2V;扫描速率为5~20 mV/s;活化时间为5-20s。3. The activation method of electrode carbon cloth according to claim 1, wherein the voltage range in step (2) is -0.8~-1.2V; the scanning rate is 5~20 mV/s; the activation time is 5- 20s. 4.根据权利要求1-3任一项所制备得到的活化碳布电极在超级电容器上的应用。4. Application of the activated carbon cloth electrode prepared according to any one of claims 1-3 on a supercapacitor.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110690057A (en) * 2019-09-27 2020-01-14 同济大学 Nickel-intercalated manganese dioxide-based flexible quasi-solid-state supercapacitor material and its preparation method and application
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

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JP2008066681A (en) * 2006-09-11 2008-03-21 Osaka Prefecture Univ Electrochemical capacitor and method for producing electrochemical capacitor zinc electrode
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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
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110690057A (en) * 2019-09-27 2020-01-14 同济大学 Nickel-intercalated manganese dioxide-based flexible quasi-solid-state supercapacitor material and its preparation method and application
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

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