CN103400702B - A kind of flexible coaxial linear supercapacitor and preparation method thereof - Google Patents
A kind of flexible coaxial linear supercapacitor and preparation method thereof Download PDFInfo
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- CN103400702B CN103400702B CN201310280290.5A CN201310280290A CN103400702B CN 103400702 B CN103400702 B CN 103400702B CN 201310280290 A CN201310280290 A CN 201310280290A CN 103400702 B CN103400702 B CN 103400702B
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Abstract
The invention belongs to supercapacitor technologies field, be specifically related to flexible coaxial linear supercapacitor and preparation method thereof.Traditional linear supercapacitor, due to the restriction of electrode material, does not have stretchable characteristic.Ultracapacitor of the present invention being enclosed with the elastomer of aligned carbon nanotube for electrode in ultracapacitor, surface-coated H
3pO
4-? PVA gel electrolyte, vacuumize; Be wrapped with one deck aligned carbon nanotube at interior electrode, as external electrode, surface is coated with H equally
3pO
4-PVA gel electrolyte, vacuumize.The specific volume of this ultracapacitor can reach 18F/g, and after stretching 100 times (amount of tension is 75%), the performance of capacitor remains unchanged substantially.
Description
Technical field
The invention belongs to supercapacitor technologies field, be specifically related to flexible coaxial linear supercapacitor and preparation method thereof.
Background technology
Flexible portable's equipment be current electronic device mainstream development direction, and elasticity is one of their requisite characteristics
[1-2].Therefore resilient electronic device, as electric chemical super capacitor
[3-6], lithium ion battery
[7], organic solar batteries
[8], Organic Light Emitting Diode
[9-10], field-effect transistor
[11], and artificial skin transducer
[12]deng being studied widely.But these devices are all realize in traditional plane substrate, and this hinders their development to a great extent.Because for portable use, it is light that these equipment must meet quality, and volume is little, and efficiency is high, must have certain elasticity simultaneously, and this is considered to have challenge, or even impossible, so this has breakthrough research with regard to exigence in relevant field.
Recently, the trial of many preparation wire microdevices has been had, the preparation of such as linear supercapacitor.The electrodes enwind that two are enclosed with electrolyte normally forms by they
[13-14], also having some successfully to study is about coaxial configuration linear supercapacitor
[15-16].Compared to plane structure, the advantage that linear structure has light weight and can work out.Usually, the ultracapacitor of coaxial configuration and winding arrangement still has excellent performance under bending condition, but they but do not have elasticity, and elasticity is most important in numerous applications.The electronic textile device of such as practical application, if not there is elasticity, often easy fracture and breakage.Up to now, not about the research of the high-performance linear ultracapacitor that can stretch, this is mainly subject to the restriction of electrode material.Here, we use the method for elastomer wrapping up aligned carbon nanotube, prepare and have flexible linear supercapacitor, for the design of related electronic devices and multiple device thereof provides new thinking.
Summary of the invention
The object of the present invention is to provide a kind of flexible coaxial linear supercapacitor and preparation method thereof.
The preparation method of flexible coaxial linear supercapacitor provided by the invention, concrete steps are:
To be enclosed with the elastomer of aligned carbon nanotube for electrode in ultracapacitor, surface-coated H
3pO
4-PVA gel electrolyte, vacuumize;
Then at interior electrode outer wrapping one deck aligned carbon nanotube, as external electrode, surface applies H equally
3pO
4-PVA gel electrolyte, vacuumize, is namely prepared into flexible coaxial linear supercapacitor.The concrete structure of this capacitor as shown in Figure 2.
In the present invention, described in be enclosed with the preparation method of the elastomer of aligned carbon nanotube as follows:
Use two motors and a translation stage, the two ends of an elastomer are fixed on two motors, can spin carbon nano pipe array one is fixed on translation stage, then carbon nano-tube film is pulled out from array, and rides on elastomer with the angle of setting; Synchronous unlatching two motors, the elastomer that two ends are fixed on two motors rotates thereupon, continuous print carbon nano-tube film is constantly wrapped on elastomer with the angle (i.e. helical angle) of setting, by setting the translational speed of translation stage, the helical angle on elastomer can be made to remain unchanged; Continuously carry out said process, namely can prepare the elastomer being enclosed with aligned carbon nanotube.
In the present invention, helical angle is that 30-85 degree are better, and preferred helical angle is 60-75 degree.
In the present invention, the thickness being wrapped in the carbon nano-tube film on elastomer is 20nm-5mm, and preferred thickness is 1 μm--5 μm of microns.
This elastic conductive fiber prepared by the present invention, its extensibility can reach 100%, and can bend arbitrarily and weave, and has extraordinary flexibility.
This ultracapacitor has tensility due to its elastic substrates, and according to above-mentioned steps parcel aligned carbon nanotube with after electrolyte is prepared into ultracapacitor, specific volume can reach 18F/g, stretching 100 times (amount of tension is 75%) afterwards specific volume substantially remain unchanged.
The present invention have studied the impact of different-thickness carbon nano-tube on ultracapacitor performance.Result shows, and when carbon nano-tube thickness is increased to 330 μm from 110 μm, the current value of cyclic voltammetry curve increases along with the increase of thickness, and when thickness continues to increase, because electrolyte is difficult to infiltrate in blocked up carbon nano-tube, electric current no longer increases.Consider the increase of carbon nanotube mass, when thickness is 330 μm, there is the highest specific volume.The long-term stability of further this ultracapacitor of test, after charge and discharge cycles 1000 times, specific volume remains unchanged substantially.
Meanwhile, we have detected ultracapacitor before the stretching after the change of performance.Test different stretch amount is on the impact of this ultracapacitor, and result shows, and when amount of tension is 0-75%, performance remains unchanged substantially.After amount of tension reaches 100%, the performance of ultracapacitor just creates obvious decline, and this ultracapacitor all has stable performance in larger range of stretch as seen.Further test is under the amount of tension of 75%, and after stretching for 100 times, the property retention of ultracapacitor is about 95%.After stretching 75%, after 1000 discharge and recharges, the property retention of ultracapacitor, more than 90%, has embodied good stability.
Accompanying drawing explanation
Fig. 1 is supercapacitor structures figure of the present invention.
Fig. 2 is ultracapacitor preparation flow figure of the present invention.
Fig. 3 is ultracapacitor picture of the present invention.Wherein, a is interior electrode scanning electron microscope diagram sheet, and b is elastomer scanning electron microscope diagram sheet, and c-e is ultracapacitor cross section different multiples scanning electron microscope diagram sheet.
Fig. 4 is the cyclic voltammogram of different-thickness electrode.
Fig. 5 is different-thickness electrode constant current charge-discharge curve.
Fig. 6 is different-thickness electrode specific volume comparison diagram.
Fig. 7 is cycle-index and Capacity Ratio relation curve.
Fig. 8 is different curvature radius cyclic voltammogram.
Fig. 9 is different stretch amount cyclic voltammogram.
Figure 10 is drawing numbers and Capacity Ratio relation curve.
Figure 11 is after stretching 75%, and Capacity Ratio is about the curve of cycle-index.
Embodiment
The first, the synthesis of aligned carbon nanotube array can be spun.
Orthotropic carbon nano pipe array is with Fe (1nm)/Al
2o
3(10nm)/SiO
2/ Si is synthesized by typical chemical vapour deposition technique in tube furnace quartz ampoule as catalyst.Wherein ethene (75sccm) is as carbon source, and argon gas (400sccm) and hydrogen (25sccm) are as carrier gas.The thickness of the carbon nano-tube permutation of synthesis is 250 microns.
The second, the preparation of flexible coaxial linear supercapacitor
The two ends of an elastomer are fixed on two motors, carbon nano pipe array can be spun one and be placed on translation stage, then carbon nano-tube film be pulled out from array, and ride on elastomer with certain angle.When two motors and translation stage are opened simultaneously time, continuous print carbon nano-tube film can constantly be rolled on elastomer, by the coupling speed of translation stage and the rotating speed of motor, the helical angle of carbon nano-tube on fiber can be made to remain unchanged.Thus obtain the electrically conductive elastic fiber of stable electrical properties.
Uniform painting one deck H on this electrically conductive elastic fiber
3pO
4-PVA gel electrolyte, vacuumize 30 minutes.On the electrically conductive elastic fiber scribbling electrolyte, wrap up one deck continuous print orientation carbon nanotube film with said method again, and be coated with one deck H again
3pO
4-PVA gel electrolyte, vacuumize 30 minutes.
3rd, the assembling of ultracapacitor
On the above-mentioned ultracapacitor prepared, draw interior electrode and external electrode respectively with wire, complete the preparation of linear supercapacitor.
Fig. 4-Fig. 7 shows the impact of different-thickness carbon nano-tube on ultracapacitor performance.Result shows, when carbon nano-tube thickness is increased to 330 μm from 110 μm, the current value of cyclic voltammetry curve increases along with the increase of thickness, and when thickness continues to increase, because electrolyte is difficult to infiltrate in blocked up carbon nano-tube, electric current no longer increases.Consider the increase of carbon nanotube mass, when thickness is 330 μm, there is the highest specific volume.The long-term stability result of this ultracapacitor is after charge and discharge cycles 1000 times, and specific volume remains unchanged substantially.
Fig. 9-Figure 11 show ultracapacitor before the stretching after the change of performance.Test different stretch amount is on the impact of this ultracapacitor, and result shows, when amount of tension is 0-75%, performance remains unchanged substantially.After amount of tension reaches 100%, the performance of ultracapacitor just creates obvious decline, and this ultracapacitor all has stable performance in larger range of stretch as seen.Under the amount of tension of 75%, after stretching for 100 times, the property retention of ultracapacitor is about 95%.After stretching 75%, after 1000 discharge and recharges, the property retention of ultracapacitor, more than 90%, has embodied good stability.
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Claims (6)
1. a preparation method for flexible coaxial linear supercapacitor, is characterized in that concrete steps are:
To be enclosed with the elastomer of aligned carbon nanotube for electrode in ultracapacitor, surface-coated H
3pO
4-PVA gel electrolyte, vacuumize;
Then at interior electrode outer wrapping one deck aligned carbon nanotube, as external electrode, surface applies H equally
3pO
4-PVA gel electrolyte, vacuumize, is namely prepared into flexible coaxial linear supercapacitor;
The described preparation process being enclosed with the elastomer of aligned carbon nanotube is as follows:
Use two motors and a translation stage, the two ends of an elastomer are fixed on two motors, can spin carbon nano pipe array one is fixed on translation stage, then carbon nano-tube film is pulled out from array, and rides on elastomer with the angle of setting; Synchronous unlatching two motors, the elastomer that two ends are fixed on two motors rotates thereupon, continuous print carbon nano-tube film is constantly wrapped on elastomer with the angle of setting and helical angle, by setting the translational speed of translation stage, the helical angle on elastomer can be made to remain unchanged; Continuously carry out said process, namely can prepare the elastomer being enclosed with aligned carbon nanotube.
2. preparation method according to claim 1, is characterized in that described helical angle is 30 ~ 85 degree.
3. preparation method according to claim 2, is characterized in that described helical angle is 60 ~ 75 degree.
4. preparation method according to claim 1, is characterized in that the thickness of described carbon nano-tube film is 20nm ~ 5mm.
5. preparation method according to claim 4, is characterized in that the thickness of the carbon nano-tube film be wrapped on elastomer is 1 μm ~ 5 μm.
6. the flexible coaxial linear supercapacitor that preparation method prepares as described in one of claim 1-5.
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| CN103904366B (en) * | 2014-03-09 | 2016-08-17 | 宁国市龙晟柔性储能材料科技有限公司 | A kind of flexible wire lithium ion battery and preparation method thereof |
| CN104252973B (en) * | 2014-09-04 | 2017-01-11 | 复旦大学 | Color-changing fibriform supercapacitor and preparation method thereof |
| CN104282444A (en) * | 2014-09-07 | 2015-01-14 | 复旦大学 | Stretchable line-shaped super capacitor with carbon nano tube/polyaniline composite materials as counter electrodes and manufacturing method of stretchable line-shaped super capacitor |
| CN104392845B (en) * | 2014-10-17 | 2017-03-29 | 复旦大学 | A kind of stretchable linear supercapacitor and preparation method of lithium ion battery |
| CN104538201A (en) * | 2014-12-26 | 2015-04-22 | 浙江理工大学 | Method for preparing textile fiber and PPy nanowire composite super capacitor |
| CN104916453A (en) * | 2015-04-17 | 2015-09-16 | 浙江大学 | Coaxial graphene fiber supercapacitor and manufacturing method thereof |
| CN105355454A (en) * | 2015-11-09 | 2016-02-24 | 复旦大学 | Coaxial line super capacitor with shape memory and preparation method thereof |
| US9972451B2 (en) | 2015-11-30 | 2018-05-15 | City University Of Hong Kong | Polyelectrolyte and a method for manufacturing an energy storage device |
| CN105428090B (en) * | 2015-12-13 | 2017-12-29 | 复旦大学 | Fibrous ultracapacitor with high output voltage and preparation method thereof |
| CN105671654B (en) * | 2016-01-21 | 2018-06-26 | 合肥工业大学 | A kind of ion induction type artificial skin array structure and preparation method thereof |
| CN112885611A (en) | 2019-11-29 | 2021-06-01 | 清华大学 | Super capacitor |
| CN111785527B (en) * | 2020-07-17 | 2022-04-22 | 广德天运新技术股份有限公司 | Pseudo-capacitive fibrous supercapacitor without blank volume in electrode and preparation method thereof |
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Denomination of invention: Elastic coaxial linear supercapacitor and production method thereof Effective date of registration: 20190726 Granted publication date: 20151118 Pledgee: Anhui Jingdu Investment Development Co., Ltd. Pledgor: NINGGUO LONGSHENG FLEXIBLE ENERGY STORAGE MATERIALS TECHNOLOGY CO., LTD. Registration number: 2019340000419 |