CN103928239A - Surface modification method of supercapacitor electrode material active carbon fibers - Google Patents
Surface modification method of supercapacitor electrode material active carbon fibers Download PDFInfo
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- CN103928239A CN103928239A CN201410188975.1A CN201410188975A CN103928239A CN 103928239 A CN103928239 A CN 103928239A CN 201410188975 A CN201410188975 A CN 201410188975A CN 103928239 A CN103928239 A CN 103928239A
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- 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
Abstract
The invention discloses a surface modification method of supercapacitor electrode material active carbon fibers and relates to the technical field of supercapacitors. Industrial-waste-level carbon fibers after physical activation are used as original samples, and soaking in 30%-95% nitric acid is carried out for 6-48 hours; and then heat processing under the temperature of 40-200 DEG C is carried out for 6-12 hours, and active carbon fiber supercapacitor electrode materials with the modified surface are obtained. The surface activity of the materials is improved by simple surface modifying, and the supercapacitor electrode materials with high capacity, good rate capability and stable cycle performance are obtained.
Description
Technical field:
The present invention relates to the technical field of ultracapacitor, be specifically related to a kind of surface modifying method of electrode material for super capacitor activated carbon fiber.
Background technology:
Since entering 21 century, continuous approach exhaustion along with non-renewable energy resources such as oil, natural gas and coals, it is increasing that development of world economy is affected by it, China belongs to the relatively deficient country of petroleum resources, along with constantly riseing of International Petroleum Price, economy to national and Oil Safety are brought and had a strong impact on, so the research and development of clean energy resource there is important effect to the sustainable development of national economy.
The most a kind of novel electrochemical energy storage device of ultracapacitor, it possesses, and electrode material is abundant, power density is large, discharge and recharge life-span length and security performance high, is subject to the extensive concern of whole world scientist and government department.Super capacitor itself has the performance of quick charge, can be used in some products that need quick charge, and such as electric motor car, flashlight etc.; The performance of heavy-current discharge can make super capacitor be used on electric tool, such as automobile starter etc.; In addition it also can be used as the back-up source of the Weak current power supplies such as static random memory, data transmission system.Along with widening of its application, market demand is also progressively improving, and it is crucial that the electrode material that obtains high power capacity that therefore how can cheap and simple becomes research.
In the world, fiber-like material with carbon element is considered to the new material with gold equal value, and it is the new material after the metal materials such as stone implement and iron and steel.Be accompanied by the rising of demand, just inevitably produced a large amount of industrial waste grade carbon fibers, and activated carbon fiber is generally acknowledged electrode material for super capacitor, but by physically activated, can only obtain the poor active-carbon fibre material of surface activity as raw material, capacity is lower, doubly forthright very poor, cannot meet the application demand on market at all.
The industrial waste grade carbon fiber that the present invention be take after physically activated is raw material, increases the surface activity of material through simple surface modification, has obtained the electrode material for super capacitor of better performances.
Summary of the invention:
The technical problem that the present invention solves is, utilizes existing active-carbon fibre material, provides that a kind of step is few, the simple surface modifying method of technique, has reached the object of obvious raising material electrochemical performance.
It is raw material that physically activated postindustrial waste material grade carbon fiber is take in the present invention, obtains being rich in the activated carbon fiber of surface oxygen functional group through nitric acid dousing and two steps of heat treatment, increased material surface activity, and then improve material electrochemical performance.
Concrete technical scheme of the present invention is as follows:
A surface modifying method for electrode material for super capacitor activated carbon fiber soaks activated carbon fiber 6～48 hours in the nitric acid of mass concentration 30%～95%; In the activated carbon fiber that the surface of soaking is wrapped in to nitric acid heat treatment 6～12 hours at 40～200 ℃, obtain the activated carbon fiber electrode material for super capacitor of surface modification.
Preferred nitric acid mass concentration is 62%～68%.Preferred soak time is 12～18 hours.The too short effect that affects modification of soak time, but soak time is oversize also inoperative to modification.Best soaking conditions is in the nitric acid of mass concentration 65%, to soak 12 hours.
Preferred heat treatment temperature is 80～160 ℃.Experiment shows, 160 ℃ do not have too large raising with the heat treatment temperature modified effect of 200 ℃, and therefore, too high heat treatment temperature can only waste energy.Experiment shows, best heat-treat condition is heat treatment 12 hours at 80 ℃.
The active carbon fiber electrode material of surface modification prepared by the present invention has higher capacity, better high rate performance and more stable cycle performance.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the present invention and to prepare the performance of material, provide relevant indicators below.
Fig. 1 is activated carbon fiber surface modification schematic flow sheet of the present invention.
Fig. 2 is the XRD comparison diagram before and after activated carbon fiber surface modification.
Fig. 3 is the CV comparison diagram before and after activated carbon fiber surface modification.
Fig. 4 is the capacity comparison figure under the different current densities before and after activated carbon fiber surface modification.
Fig. 5 is at 10mA/cm before and after activated carbon fiber surface modification
2current density under cycle performance comparison diagram.
Embodiment:
Embodiment 1:
Activated carbon fiber (former state) after water is cleaned is put into the beaker that 65% nitric acid is housed and is soaked, leach and obtained the surperficial activated carbon fiber that is wrapped in nitric acid, put into rapidly the vacuum drying oven of 80 ℃ and heat-treat 12 hours, after taking out, cooling has obtained electrode material (nitric acid 65%) naturally.
The active-carbon fibre material of active-carbon fibre material former state and surface modification mixes according to mass ratio 85:10:5 with conductive auxiliary agent (super P), binding agent (PTFE) respectively, roll and be pressed into sheet, adopt the assembling mode of symmetry electrode to be assembled into button capacitor, electrolyte is elected the KOH solution of conventional 6M as.Table 1 provides C, H, N, the O test result before and after activated carbon fiber surface modification.
Table 1
From Fig. 2 and table 1, can find out, through there is no significantly change in the material crystals main structure after modification, but improve the content of the oxygen-containing functional group of material, aspect capacity lifting, play key effect; As can be seen from Figure 3, the oxygen-containing functional group of introducing can increase material surface activity; As can be seen from Figure 4 the peak capacity after modification is increased to 214F/g from 139F/g, and lifting amplitude is 54%, and promotes the capacity under more obviously high magnification, 100mA/cm
2current density under capacity from 41F/g, bring up to 160F/g, lifting amplitude is 290%; In Fig. 5, can find out that the capability retention after 3000 circulations still can reach 100% after modification.
Embodiment 2:
The difference part of embodiment 2 and embodiment 1 is to select 40 ℃ of different temperatures, 160 ℃ and 200 ℃ to heat-treat material, and other conditions are identical, and the peak capacity being assembled into after capacitor testing is respectively 179F/g, 204F/g and 202F/g.
Embodiment 3:
Embodiment 3 has been to select rare nitric acid that concentration is 35% to soak material with the difference part of embodiment 1, and other conditions are identical, and the peak capacity being assembled into after capacitor testing is 163F/g, 100mA/cm
2current density under capacity be 105F/g.
Embodiment 4:
Embodiment 4 has been to select the fuming nitric aicd that concentration is 95% to soak material with the difference part of embodiment 1, and other conditions are identical, and the peak capacity being assembled into after capacitor testing is 165F/g, 100mA/cm
2current density under capacity be 109F/g.
Embodiment 5:
Embodiment 5 is that with the difference part of embodiment 1 heat treatment time becomes 6 hours, and other conditions are identical, and the peak capacity being assembled into after capacitor testing is 192F/g, 100mA/cm
2current density under capacity be 125F/g.
Embodiment 6
Embodiment 6 is not have heat treated step with the difference part of embodiment 1, only has the step of nitric acid dousing, and other condition is identical, and the peak capacity being assembled into after capacitor testing is 159F/g, 100mA/cm
2current density under capacity be 80F/g.
Claims (5)
1. a surface modifying method for electrode material for super capacitor activated carbon fiber soaks activated carbon fiber 6～48 hours in the nitric acid of mass concentration 30%～95%; In the activated carbon fiber that the surface of soaking is wrapped in to nitric acid heat treatment 6～12 hours at 40～200 ℃, obtain the activated carbon fiber electrode material for super capacitor of surface modification.
2. the surface modifying method of electrode material for super capacitor activated carbon fiber according to claim 1, is characterized in that, described nitric acid mass concentration, is 62%～68%; Described soak time is 12～18 hours.
3. the surface modifying method of electrode material for super capacitor activated carbon fiber according to claim 1, is characterized in that, described heat treatment, and temperature is 80～160 ℃.
4. the surface modifying method of electrode material for super capacitor activated carbon fiber according to claim 1 and 2, is characterized in that, activated carbon fiber is soaked 12 hours in the nitric acid of mass concentration 65%.
5. according to the surface modifying method of the electrode material for super capacitor activated carbon fiber described in claim 1 or 3, it is characterized in that described heat treatment is heat treatment 12 hours at 80 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105097302A (en) * | 2015-09-15 | 2015-11-25 | 江苏苏通碳纤维有限公司 | Activated carbon fibers for supercapacitor and preparation method therefor |
| CN109748257A (en) * | 2018-12-18 | 2019-05-14 | 燕山大学 | The method and lithium battery of lithium ion battery negative material are prepared using the waste of reinforcing bar electroslag pressure welding work progress |
| CN110127658A (en) * | 2019-07-01 | 2019-08-16 | 青海民族大学 | A kind of supercapacitor mesoporous carbon nanometer combined electrode material and preparation method thereof |
| CN113782349A (en) * | 2021-09-09 | 2021-12-10 | 合肥学院 | Method for improving electrochemical performance of carbon electrode material |
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| CN101302668A (en) * | 2008-05-28 | 2008-11-12 | 哈尔滨工业大学 | Modifying method of active carbon fiber |
| CN102482466A (en) * | 2009-09-09 | 2012-05-30 | 普瑞曼聚合物株式会社 | Carbon fiber-reinforced resin composition |
| CN103088465A (en) * | 2011-10-28 | 2013-05-08 | 香港理工大学 | Hollow graphite carbon nanometer sphere in-situ modification amorphous carbon nanometer fibers or carbon nano-tubes and preparation method thereof |
| CN103334295A (en) * | 2013-06-07 | 2013-10-02 | 江苏大学 | Activation method for enhancing specific capacitance of polyacrylonitrile-based carbon fibers |
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2014
- 2014-05-06 CN CN201410188975.1A patent/CN103928239A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101302668A (en) * | 2008-05-28 | 2008-11-12 | 哈尔滨工业大学 | Modifying method of active carbon fiber |
| CN102482466A (en) * | 2009-09-09 | 2012-05-30 | 普瑞曼聚合物株式会社 | Carbon fiber-reinforced resin composition |
| CN103088465A (en) * | 2011-10-28 | 2013-05-08 | 香港理工大学 | Hollow graphite carbon nanometer sphere in-situ modification amorphous carbon nanometer fibers or carbon nano-tubes and preparation method thereof |
| CN103334295A (en) * | 2013-06-07 | 2013-10-02 | 江苏大学 | Activation method for enhancing specific capacitance of polyacrylonitrile-based carbon fibers |
Non-Patent Citations (1)
| Title |
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| YAU-REN NIAN等: ""Nitric Acid Modification of Activated Carbon Electrodes for Improvement of Electrochemical Capacitance"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105097302A (en) * | 2015-09-15 | 2015-11-25 | 江苏苏通碳纤维有限公司 | Activated carbon fibers for supercapacitor and preparation method therefor |
| CN109748257A (en) * | 2018-12-18 | 2019-05-14 | 燕山大学 | The method and lithium battery of lithium ion battery negative material are prepared using the waste of reinforcing bar electroslag pressure welding work progress |
| CN109748257B (en) * | 2018-12-18 | 2020-07-31 | 燕山大学 | Method for preparing lithium ion battery cathode material by using wastes generated in steel bar electroslag pressure welding construction process and lithium battery |
| CN110127658A (en) * | 2019-07-01 | 2019-08-16 | 青海民族大学 | A kind of supercapacitor mesoporous carbon nanometer combined electrode material and preparation method thereof |
| CN113782349A (en) * | 2021-09-09 | 2021-12-10 | 合肥学院 | Method for improving electrochemical performance of carbon electrode material |
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Application publication date: 20140716 |