CN105551814B - A kind of elasticity supercapacitor ring and preparation method thereof - Google Patents
A kind of elasticity supercapacitor ring and preparation method thereof Download PDFInfo
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- CN105551814B CN105551814B CN201610063370.9A CN201610063370A CN105551814B CN 105551814 B CN105551814 B CN 105551814B CN 201610063370 A CN201610063370 A CN 201610063370A CN 105551814 B CN105551814 B CN 105551814B
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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
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- 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 belongs to supercapacitor technologies field, specially a kind of elastic supercapacitor ring and preparation method thereof.Conventional Super capacitor is usually thick and heavy, inflexibility since its material limits, and can not be suitable for wearable demand.For the present invention using flexible highly conductive aligned carbon nanotube strip/conducting polymer as combination electrode, polyvinyl alcohol/phosphoric acid is gel electrolyte, combines continuous winding process that a kind of completely new elastic supercapacitor ring is prepared using painting technique is stained with.The elasticity supercapacitor ring has good deformation nature and good chemical property.It can be worn over finger, and the human bodies such as wrist have broad application prospects in wearable electronic field.
Description
Technical field
The invention belongs to supercapacitor technologies fields, and in particular to a kind of elasticity supercapacitor ring and its preparation side
Method.
Background technique
Wearable electronic is the mainstream development direction of modern electronics industry, and develops light weight, wearable energy flexible
Source storage system becomes the bottleneck problem [1-3] in the field.Supercapacitor is since its charge-discharge velocity is fast, cleanliness without any pollution
The advantages that in wearable field be concerned [4].However, traditional supercapacitor is usually thick and heavy, inflexibility, it is difficult to
Meets the needs of wearable.Therefore, develop a kind of light weight flexibility or even flexible supercapacitor is very necessary.In recent years
Come, it is even ultra-thin although all kinds of supercapacitors flexible [5-7] have been developed by being continually striving to for researchers
Film-form supercapacitor [8], however their configuration is usually or two-dimensional surface shape, be still difficult to meet it is actual can
Wearing demand.
Compared to traditional planar structure, cricoid electronic equipment can not needed due to its unique structure feature
Additional processing can be directly worn on finger, wrist, arm, leg or head, meet wearable demand [9] well.But
It is that up to the present, cricoid supercapacitor is also from having not been reported.Therefore, a kind of ring-type is prepared by a kind of simple method
, the supercapacitor of especially annular resilient becomes the target that area research person constantly pursues.
Summary of the invention
The purpose of the present invention is to provide a kind of elastic supercapacitor rings and preparation method thereof.
Elasticity supercapacitor ring provided by the invention, specific preparation process is as follows:
(1) by being stained with coating, conducting polymer slurry is coated on aligned carbon nanotube strip, compound electric is prepared
Pole；
(2) by continuous winding process, combination electrode is wrapped on pre- distracted elastomeric polymer cyclic group bottom；
(3) by being stained with coating, the wrapped strata second on the elastomeric polymer ring for the combination electrode winding that step (2) obtains
Enol/phosphoric acid gel electrolyte；
(4) by continuous winding process, on the elastomeric polymer ring of the combination electrode winding handled through step (3), into
One step winds one layer of combination electrode；
(5) by being stained with coating, then wrapped layer of polyethylene alcohol/phosphoric acid gel electrolyte, and receive entire device contracting certainly
Right state obtains elastic supercapacitor ring.
In the present invention, the material at elastomeric polymer cyclic group bottom is dimethyl silicone polymer or polyurethane, internal diameter
For 15-150 mm, wall thickness is 0.5-10 mm, and width is 3-20 mm.By the way that the precursor solution of polymer is injected into accordingly
In the mold of size, curing molding obtains annular resilient polymer ring-type substrate.
In the present invention, the pre- multiple that struts at elastomeric polymer cyclic group bottom is 10-300%.
In the present invention, the aligned carbon nanotube strip is to pull straight to obtain from can spin in aligned carbon nanotube array.
Aligned carbon nanotube array can be spun to be prepared by chemical vapour deposition technique, it is specific the preparation method comprises the following steps: being steamed by electron beam
It is Al that hair plated film instrument deposits one layer of structure on silicon wafer2O3The catalyst of/Fe, wherein Al2O3With a thickness of 2-20 nm, the thickness of Fe
Degree is 0.5-1.5 nm.By chemical vapour deposition technique, use argon gas as carrier gas, ethylene as carbon source, hydrogen as reducing agent,
Height-oriented carbon nano pipe array is synthesized on the silicon wafer for being coated with catalyst in advance.Wherein argon gas flow is 350-450
Sccm, ethylene gas flow are 60-120 sccm, and hydrogen gas flow is 30-90 sccm.Reaction temperature is 700-800oC, reaction time are 10-15 min.
In the present invention, aligned carbon nanotube strip with a thickness of 100 nm -100 μm.
In the present invention, the winding speed of continuous winding process is 1-10 cm/s.
In the present invention, conducting polymer slurry is water, poly- (3,4-ethylene dioxythiophene), kayexalate, diformazan
The mixture of base sulfoxide and fluorine carbon nonionic surface active agent.Wherein, conductive polymer poly (3,4-ethylene dioxythiophene), poly-
Sodium styrene sulfonate can be commercial product: Clevios PH1000, Clevios PH500, or with poly- (3,4- enedioxy thiophenes
Pheno): kayexalate mass ratio 1:0-1.5, the aqueous solution that total mass fraction 5-15% is prepared.The volume of dimethyl sulfoxide
Content is 1-10%, and the volume content of fluorine carbon nonionic surface active agent is 0.5-3%.Fluorine carbon nonionic surface active agent is
Du Pont Zonyl FS-300 or FSO-100.
In the present invention, the load quality score 10-90% of conducting polymer.
In the present invention, polyvinyl alcohol/phosphoric acid gel electrolyte is the preparation method comprises the following steps: by the polyethylene of mass fraction 5-15%
Alcohol is added to the water, after being sufficiently swollen 12-24 h, in 90-95oStirring and dissolving under C, and 10-15% phosphoric acid strength is added while hot
Stir 2-24 h.
Elasticity supercapacitor ring prepared by the present invention is sequentially coated with combination electrode using elastomeric polymer ring as substrate
Layer, polyvinyl alcohol/phosphoric acid gel electrolyte liquid layer, composite electrode layers, polyvinyl alcohol/phosphoric acid gel electrolyte liquid layer；Wherein, compound electric
Pole layer is coated on aligned carbon nanotube strip by conducting polymer slurry to be obtained.
Elasticity supercapacitor ring prepared by the present invention, has good chemical property and deformability.Due to orientation
Carbon nanotube has fabulous flexibility and electric conductivity and the good chemical property of conducting polymer, so that the elasticity is super
Capacitor ring can maintain its electrochemistry under the conditions of capable of such as compressing in various strains, distort, stretch, expanding well
Energy.The elasticity supercapacitor ring can directly be worn over the parts such as finger, wrist, arm, ankle, head, neck, in wearable electricity
Subdomains have broad application prospects.
Detailed description of the invention
Fig. 1 is the cross-sectional scans Electronic Speculum microscope figure of elastic supercapacitor ring in embodiment.
Fig. 2 is the constant current charge-discharge curve in embodiment under different current densities.
Fig. 3 is the relation curve of charge and discharge cycles number and capacity ratio in embodiment.
Fig. 4 is the relation curve of degree of extension and capacity ratio in embodiment.
Fig. 5 is the relation curve that number and capacity ratio are compressed in embodiment.
Fig. 6 is the elastic supercapacitor ring structure diagram of the present invention.
Specific embodiment
Below in conjunction with specific implementation case, illustrative explanation and help further understand the present invention, but case study on implementation has
Body details does not represent technical solution whole under present inventive concept merely to illustrate the present invention, therefore should not be construed as pair
The restriction of the total technical solution of the present invention, it is some for the technician, without departing from present inventive concept unsubstantiality increase and
Change, such as simply change or replace with the technical characteristic with same or similar technical effect, belong to present invention protection model
It encloses.
Aligned carbon nanotube array can be spun by chemical vapour deposition technique preparation.It is specific the preparation method is as follows: passing through electricity
It is Al that beamlet evaporation coating instrument deposits one layer of structure on silicon wafer2O3The catalyst of/Fe, wherein Al2O3With a thickness of 3 nm, Fe
With a thickness of 1.2 nm.By chemical vapour deposition technique, use argon gas as carrier gas, ethylene as carbon source, hydrogen as reducing agent,
Height-oriented carbon nano pipe array is synthesized on the silicon wafer for being coated with catalyst in advance.Wherein argon gas flow is 400
Sccm, ethylene gas flow are 90 sccm, and hydrogen gas flow is 60 sccm.Reaction temperature is 740oC, reaction time
For 10 min.Directly from can spin in aligned carbon nanotube array pull out obtain aligned carbon nanotube strip.
Prepare annular resilient polymeric substrates.Dimethyl silicone polymer precursor solution is injected into having a size of internal diameter 15
Mm, 18 mm of outer diameter, depth are in the ring mold of 6 mm 80oC solidifies 2 h, demoulds after cooling.
Prepare conducting polymer slurry.Using business conducting polymer Clevios PH1000 as raw material, addition 5% volume point
The fluorine carbon nonionic surface active agent Zonyl FS-300 of several dimethyl sulfoxides and 1% volume fraction, stirring 2 h mixing are equal
It is even.
Prepare polyvinyl alcohol/phosphoric acid gel electrolyte.1 g polyvinyl alcohol is added in 9 g water, 24 h are sufficiently swollen
Afterwards, in 95 stirring and dissolvings, and 1.5 g phosphoric acid strong stirring, 24 h is added while hot.
Assemble elastic supercapacitor ring.By being stained with coating, the equal refining of conducting polymer slurry is coated to orientation carbon and is received
Combination electrode is prepared on mitron strip, the load capacity of conducting polymer is controlled 65% or so；By continuous winding process,
Combination electrode is wrapped in pre- strut to 130% elastomeric polymer cyclic group bottom with the speed of 1 cm/s；By being stained with coating,
Wrapped layer of polyethylene alcohol/phosphoric acid gel electrolyte；Further one layer of combination electrode of winding；Wrapped layer of polyethylene alcohol/phosphorus again
Acid gel electrolyte, and so that entire device contracting is received nature and obtain elastic supercapacitor ring.Its cross-sectional scans Electronic Speculum is aobvious
Micro mirror figure is as shown in Figure 1, it can be seen that apparent inside and outside combination electrode.
Prepared annular resilient supercapacitor has good chemical property.Fig. 2 is under different current densities
Constant current charge-discharge curve is 0.5,1.0,2.0 and 4.0 A g in current density-1When, the quality specific volume of supercapacitor
Amount is respectively 147.14,134.79,130.53 and 111.3 F g-1.And the supercapacitor has preferable electrochemically stable
Property, with 1 A g-1The continuous cycle charge-discharge of current density 2000 times after, specific capacity fail less than 8%(Fig. 3).The ring-type bullet
Property supercapacitor also has good elasticity.As shown in Figures 4 and 5, after continuous expansion 200 times or compression 1000 times, matter
Measure specific capacity is still initial 92.8% or 102.9%.
Bibliography
[1] Shao Y. L., El-Kady M. F., Wang L. J., et al. Chem. Soc. Rev.,
2015, 44(11): 3639-3665.
[2] Lang X. Y., Hirata A., Fujita T., et al. Nature Nanotechnol.,
2011, 6(4): 232-236.
[3] Kaltenbrunner M., White M. S., Gowacki E. D., et al. Nature
commun., 2012, 3: 770-777.
[4] Yu Z. N., Tetard L., Zhai L., et al. Energy Environ. Sci., 2015,
8(3): 702-730.
[5] Wang L., Feng X., Ren L. T., et al. J. Am. Chem. Soc., 2015, 137
(15): 4920-4923.
[6] Yang X., Zhang F., Zhang L., et al. Adv. Fun. Mater., 2013, 23
(26): 3353-3360.
[7] Wang Gengchao, Chen Mingming, a soup eternal lasting wait Chinese patent, 201410752621.5,2014-12-10.
[8] Tang H. J., Wang J. Y., Yin H. J., et al. Adv. Mater., 2015, 27
(6): 1117-1123.
[9] Jing L, Zhou Y. H., Cheng Z. X., et al. Sensors, 2012, 12(5):
5775-5790。
Claims (8)
1. a kind of preparation method of elasticity supercapacitor ring, it is characterised in that specific step is as follows:
(1) by being stained with coating, conducting polymer slurry is coated on aligned carbon nanotube strip, combination electrode is prepared；
(2) by continuous winding process, combination electrode is wrapped on pre- distracted elastomeric polymer cyclic group bottom；
(3) by being stained with coating, the wrapped layer of polyethylene on the elastomeric polymer ring for the combination electrode winding that step (2) obtains
Alcohol/phosphoric acid gel electrolyte；
(4) by continuous winding process, on the elastomeric polymer ring of the combination electrode winding handled through step (3), further
Wind one layer of combination electrode；
(5) by being stained with coating, then wrapped layer of polyethylene alcohol/phosphoric acid gel electrolyte, and entire device contracting is made to receive nature shape
State obtains elastic supercapacitor ring.
2. preparation method as described in claim 1, it is characterised in that in step (1), the conducting polymer slurry is water, gathers
The mixture of (3,4-ethylene dioxythiophene), kayexalate, dimethyl sulfoxide and fluorine carbon nonionic surface active agent.
3. preparation method as claimed in claim 2, it is characterised in that in the conducting polymer slurry, dimethyl sulfoxide
Volume content is 1-10%, and the volume content of fluorine carbon nonionic surface active agent is 0.5-3%.
4. preparation method as described in claim 1, it is characterised in that in step (1), the thickness of the aligned carbon nanotube strip
Degree is 100 nm-100 μm.
5. preparation method as described in claim 1, it is characterised in that in step (2), the elastomeric polymer cyclic group ground
Material is dimethyl siloxane or polyurethane.
6. preparation method as described in claim 1, it is characterised in that in step (2), the cricoid internal diameter of elastomeric polymer
For 15-150 mm, wall thickness is 0.5-10 mm, and width is 3-20 mm.
7. preparation method as described in claim 1, it is characterised in that in step (2) and step (4), the continuous winding process
Winding speed be 1-10 cm/s.
8. the elastic supercapacitor ring being prepared by one of claim 1-7 the method, which is characterized in that poly- with elasticity
Conjunction object ring is substrate, sequentially forms composite electrode layers, polyvinyl alcohol/phosphoric acid gel electrolyte liquid layer, composite electrode layers, poly- second thereon
Enol/phosphoric acid gel electrolyte liquid layer and form；Wherein, composite electrode layers are coated to aligned carbon nanotube by conducting polymer slurry
It is obtained on strip.
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Citations (4)
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| KR20050075811A (en) * | 2004-01-16 | 2005-07-22 | 한국과학기술연구원 | Carbon-porous media composite electrode and preparation method thereof |
| CN102709069A (en) * | 2012-06-29 | 2012-10-03 | 复旦大学 | Preparation method of linear polymer solar battery |
| CN102876102A (en) * | 2012-04-30 | 2013-01-16 | 长兴化学工业股份有限公司 | Conductive Coating Composition |
| CN103400889A (en) * | 2013-07-02 | 2013-11-20 | 复旦大学 | All-solid-state fibrous coaxial polymer solar cell and super capacitor integrated device and preparation method thereof |
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2016
- 2016-01-31 CN CN201610063370.9A patent/CN105551814B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050075811A (en) * | 2004-01-16 | 2005-07-22 | 한국과학기술연구원 | Carbon-porous media composite electrode and preparation method thereof |
| CN102876102A (en) * | 2012-04-30 | 2013-01-16 | 长兴化学工业股份有限公司 | Conductive Coating Composition |
| CN102709069A (en) * | 2012-06-29 | 2012-10-03 | 复旦大学 | Preparation method of linear polymer solar battery |
| CN103400889A (en) * | 2013-07-02 | 2013-11-20 | 复旦大学 | All-solid-state fibrous coaxial polymer solar cell and super capacitor integrated device and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| A Shape-Memory Supercapacitor Fiber;Jue Deng等;《Angewandte Chemie International Edition》;20151103;第54卷(第51期);第15419–15423页 * |
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