CN103943369A - Flexible supercapacitor and manufacturing method thereof - Google Patents
Flexible supercapacitor and manufacturing method thereof Download PDFInfo
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- CN103943369A CN103943369A CN201410134088.6A CN201410134088A CN103943369A CN 103943369 A CN103943369 A CN 103943369A CN 201410134088 A CN201410134088 A CN 201410134088A CN 103943369 A CN103943369 A CN 103943369A
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- electrode material
- membrane
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- ion permeable
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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 flexible supercapacitor and a manufacturing method thereof, and belongs to the field of capacitors. The flexible supercapacitor comprises two layers of electrode material thin films spaced by an ion permeable membrane, and comprises electrolytes arranged between the two layers of the electrode material thin films and electric contacts arranged on the outer surfaces of the two layers of the electrode material thin films, wherein the two layers of the electrode material thin films are deposited on the surfaces of the ion permeable membrane by adopting a chemical depositing or blade coating or steeping method. The flexible supercapacitor is simple in manufacturing technology, low in cost and suitable for conducting polymer electrode materials and inorganic electrode materials.
Description
Technical field
The invention belongs to capacitor area, be specifically related to a kind of flexible super capacitor and preparation method thereof.
Background technology
Ultracapacitor (supercapacitor), be between battery and traditional capacitor, can fast charging and discharging, energy-storage travelling wave tube based on Cathode/Solution Interface electrochemical process.Owing to having the advantages such as high energy density, longer service life cycle, environmental friendliness and fail safe height, ultracapacitor has been widely used in the fields such as traffic, mobile communication, information technology, Aero-Space and science and techniques of defence.The Storage mechanism of ultracapacitor comprises electrochemical double-layer ultracapacitor and redox ultracapacitor (fake capacitance), electrochemical capacitor in double electrode layer is mainly to utilize electrode material to realize energy storage for the adsorptivity of negative ions, and redox ultracapacitor and electrochemical double layer capacitor difference are it is mainly to utilize at electrode surface or the quick and reversible redox reaction of near surface generation to realize energy storage.
Along with the generation of the more and more wearable or novel electron devices that can reel, for example Electronic Paper, collapsible display and other multimedia device, demand for flexible energy storage device is also more and more urgent, is more and more subject to researcher's attention for the research of flexible super capacitor.Compared with traditional ultracapacitor, flexible super capacitor not only needs electrode material to have good chemical property, the more important thing is the performance that needs application and the electrode material of flexible super capacitor to keep under the state such as bending or folding.
Application number is to disclose a kind of flexible super capacitor as shown in Figure 1 and preparation method thereof in 201180043834.5 Chinese patent " compliant conductive polymer energy storing device ", wherein 18 is non-conductive film layer, 14 is conducting polymer thin film, 12 is ion permeable membrane, 16 is conducting polymer thin film, and 20 is non-conductive film layer.This ultracapacitor comprises the two-layer conducting polymer thin film being separated by ion permeable membrane, this conducting polymer thin film is to adopt electrochemical deposition method to be deposited in conductive substrates, and then remove and obtain from conductive substrates, then this conducting polymer thin film is placed on to ion permeable membrane both sides and forms stackingly, finally encapsulate.That the method has prepared is flexible, can reel, folding ultracapacitor.This type of ultracapacitor is in preparation process, there is following defect: the one, preparation method's complexity of the conducting polymer thin film layer in this ultracapacitor, need first in conductive substrates, to deposit, after dry, remove and obtain from substrate again, method of operation complexity, and may destroy film removing in process; The 2nd, removing conducting polymer from substrate has certain requirement to film itself and preparation condition, needs conducting polymer self can form fexible film, and this just makes the method, in actual application, electrode material be had to certain requirement and restriction; The 3rd, inorganic electrode material self can not form the good fexible film of toughness, in the process removing, may damage, and this has also limited the extensive use of the method.
Summary of the invention
The present invention is directed to the defect that background technology exists, a kind of novel flexible super capacitor and preparation method thereof has been proposed, with realize simplify ultracapacitor preparation method, reduce ultracapacitor preparation cost and make ultracapacitor be applicable to the object of conductive polymer electrodes material and inorganic electrode material.
Technical scheme of the present invention is as follows:
A kind of flexible super capacitor, comprise the two-layer electrode material membrane being separated by ion permeable membrane, and comprise the electrolyte being arranged between two-layer electrode material membrane and be arranged in the electric contact on two-layer electrode material membrane outer surface, wherein, two-layer electrode material membrane adopts the method for chemical deposition, blade coating or immersion to be deposited on ion permeable membrane surface.
Further, flexible super capacitor also has the non-conducting material in order to encapsulation around electrode material membrane, ion permeable membrane and electrolyte, electric contact around.
Wherein, electrode material is the inorganic material such as the conducting polymer such as polyaniline, polypyrrole, poly-3,4-rthylene dioxythiophene or nickel oxide, manganese oxide, nickel hydroxide.Ion permeable membrane is organic filter membrane or pvdf membrane.The thickness of ion permeable membrane is 50-200 μ m; The thickness of electrode material membrane is 20-80 μ m.Electrolyte is KOH, NaOH, H
2sO
4or organic bath.
A preparation method for flexible super capacitor, comprises the following steps:
(1), adopt the method for chemical deposition, blade coating or immersion at ion permeable membrane both sides deposition of electrode material film;
(2) ion permeable membrane that, the both sides that obtain in step (1) is deposited to electrode material membrane soaks 10 minutes to 5 hours in electrolyte;
(3), adopt stacked mode, at the outer surface of electrode material membrane, electric contact is set;
(4), the stepped construction obtaining in step (3) is placed between two-layer non-conducting material layer, encapsulation obtains flexible super capacitor.
Wherein, the ion permeable membrane in step (1) is organic filter membrane or pvdf membrane; The thickness of ion permeable membrane is 50-200 μ m; The thickness of electrode material membrane is 20-80 μ m.
Wherein, electrode material is the inorganic material such as the conducting polymer such as polyaniline, polypyrrole, poly-3,4-rthylene dioxythiophene or nickel oxide, manganese oxide, nickel hydroxide.Ion permeable membrane is organic filter membrane or pvdf membrane.The thickness of ion permeable membrane is 50-200 μ m; The thickness of electrode material membrane is 20-80 μ m.Electrolyte is KOH, NaOH, H
2sO
4or organic bath.
Non-conducting material in step (4) is PE(polyethylene) or PET(PETG).In step 4, adopt plastic package method to encapsulate
In flexible super capacitor provided by the invention, adopt the method for chemical deposition, blade coating or immersion at ion permeable membrane both side surface deposition of electrode material film, method of operation is simple, and preparation cost is low, is applicable to conducting polymer materials and inorganic electrode material; The method for packing of ultracapacitor is simple and easy, for the preparation of flexible super capacitor provides important basis.
Brief description of the drawings
The basic structure schematic diagram of the ultracapacitor that Fig. 1 provides for background technology.Wherein 18 is non-conductive film layer, and 14 is conducting polymer thin film, and 12 is ion permeable membrane, and 16 is conducting polymer thin film, and 20 is non-conductive film layer.10 representatives are by above-mentioned five layers of ultracapacitor forming.
Fig. 2 is the basic structure schematic diagram of flexible super capacitor provided by the invention.Wherein 1 is ion permeable membrane, and 2 is electrode material membrane, and 3 is electric contact, and 4 is conducting strip, and 5 is non-conductive film encapsulating material.
Embodiment
Embodiment 1
Taking polyaniline as electrode material, organic filter membrane as ion permeable membrane, Copper Foil as electric contact, the preparation method of the flexible super capacitor that obtains as encapsulating material, KOH as electrolyte of PET:
Step 1: organic filter membrane is cut into the size of 6cm × 8cm, uses successively degreaser, deionized water and absolute ethyl alcohol clean surface;
Step 2: in 500mL beaker, add 340mL deionized water, the aniline monomer of the 8mL concentrated sulfuric acid and 3mL, stirs 30min, and it is mixed;
Step 3: the organic filter membrane after cleaning in step 1 is put into the mixed solution that above-mentioned steps 2 obtains, at the uniform velocity stir 2h;
Step 4: 2g ammonium persulfate is dissolved in 60mL deionized water, utilizes dropping funel ammonium persulfate solution to be dropwise added in the mixed solution that is soaked with organic filter membrane in step 3, at the uniform velocity stir 12h;
Step 5: reacted the organic filter membrane of rear taking-up, used deionized water clean surface, then naturally dried in air, must arrive both sides and deposit organic filter membrane of polyaniline electrode material.
Step 6: organic filter membrane that the both sides that obtain in step 5 are deposited to polyaniline electrode material is cut into the size of 3cm × 4cm, then soaks 30min in the KOH of 5mol/L solution;
Step 7: the Copper Foil of two 2.9cm × 3.9cm sizes of cutting, as electric contact, is placed in the outer surface of organic filter membrane both sides polyaniline film, forms stepped construction;
Step 8: above-mentioned stepped construction is placed between two-layer PET film, and connects strip copper sheet as conducting strip, adopt plastic packaging machine to encapsulate, obtain carbon/polyaniline super capacitor.
Wherein the effect of conducting strip is for two electrodes of ultracapacitor are connected with external circuitry or load.The effect of the existing isolated electrode material of organic filter membrane, has again the effect of support base and the adsorbing electrolyte of electrode material.
Embodiment 2
Taking nickel hydroxide as electrode material, organic filter membrane as ion permeable membrane, Copper Foil as electric contact, the preparation method of the flexible super capacitor that obtains as encapsulating material, KOH as electrolyte of PET:
Step 1: organic filter membrane is cut into the size of 6cm × 8cm, uses successively degreaser, deionized water and absolute ethyl alcohol clean surface;
Step 2: add 10.5g nickelous sulfate in 40mL deionized water, obtain uniform nickel sulfate solution; In 30mL deionized water, add 2.03g potassium peroxydisulfate, obtain potassium persulfate solution;
Step 3: nickel sulfate solution and potassium persulfate solution are mixed, add 20mL25%(mass fraction) ammoniacal liquor form mixed solution, the organic filter membrane after cleaning in step 1 is put into this mixed solution and is at the uniform velocity stirred 30min;
Step 4: after reaction finishes, take out organic filter membrane use deionized water clean surface, then naturally dry in air, must arrive both sides and deposit organic filter membrane of nickel hydroxide electrode material;
Step 5: organic filter membrane that the both sides that obtain in step 4 are deposited to nickel hydroxide electrode material is cut into the size of 3cm × 4cm, then soaks 30min in the KOH of 5mol/L solution;
Step 7: the Copper Foil of two 2.9cm × 3.9cm sizes of cutting, as electric contact, is placed in the outer surface of organic filter membrane both sides polyaniline film, forms stepped construction;
Step 8: above-mentioned stepped construction is placed between two-layer PET film, and connects strip copper sheet as conducting strip, adopt plastic packaging machine to encapsulate, obtain nickel hydroxide ultracapacitor.
Wherein the effect of conducting strip is for two electrodes of ultracapacitor are connected with external circuitry or load.The effect of the existing isolated electrode material of organic filter membrane, has again the effect of support base and the adsorbing electrolyte of electrode material.
Claims (10)
1. a flexible super capacitor, comprise the two-layer electrode material membrane being separated by ion permeable membrane, and comprise the electrolyte being arranged between two-layer described electrode material membrane and be arranged in the electric contact on two-layer described electrode material membrane outer surface, it is characterized in that, two-layer described electrode material membrane adopts the method for chemical deposition, blade coating or immersion to be deposited on described ion permeable membrane surface.
2. flexible super capacitor according to claim 1, is characterized in that, described flexible super capacitor also comprises the non-conducting material in order to encapsulation around described electrode material membrane, ion permeable membrane and electrolyte, electric contact.
3. flexible super capacitor according to claim 1, is characterized in that, described ion permeable membrane is organic filter membrane or pvdf membrane.
4. flexible super capacitor according to claim 1, is characterized in that, described electrode material is conducting polymer or inorganic material.
5. flexible super capacitor according to claim 4, is characterized in that, described conducting polymer is polyaniline, polypyrrole or poly-3,4-rthylene dioxythiophene.
6. flexible super capacitor according to claim 4, is characterized in that, described inorganic material is nickel oxide, manganese oxide, nickel hydroxide.
7. flexible super capacitor according to claim 1, is characterized in that, the thickness of described ion permeable membrane is 50-200 μ m.
8. flexible super capacitor according to claim 1, is characterized in that, the thickness of described electrode material membrane is 20-80 μ m.
9. a preparation method for flexible super capacitor, comprises the following steps:
Step 1: adopt the method for chemical deposition, blade coating or immersion at ion permeable membrane both sides deposition of electrode material film;
Step 2: the ion permeable membrane that the both sides that obtain in step 1 is deposited to electrode material membrane soaks 10 minutes to 5 hours in electrolyte;
Step 3: adopt stacked mode, at the outer surface of electrode material membrane, electric contact is set;
Step 4: the stepped construction obtaining in step 3 is placed between two-layer non-conducting material layer, and encapsulation obtains flexible super capacitor.
10. the preparation method of flexible super capacitor according to claim 9, is characterized in that, in described step 4, adopts plastic package method to encapsulate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410134088.6A CN103943369A (en) | 2014-04-03 | 2014-04-03 | Flexible supercapacitor and manufacturing method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161316A (en) * | 2015-09-16 | 2015-12-16 | 中国科学院电工研究所 | Flexible super capacitor and preparation method thereof |
| CN106229159A (en) * | 2016-09-05 | 2016-12-14 | 南方科技大学 | Flexible super capacitor and the preparation method of flexible super capacitor |
| CN109087815A (en) * | 2018-08-08 | 2018-12-25 | 安徽师范大学 | One-dimensional cobalt molybdate@nickel hydroxide core-shell nano hollow pipe composite material and preparation method and application |
| CN110189925A (en) * | 2019-06-24 | 2019-08-30 | 安徽师范大学 | The preparation method and application of one-dimensional manganese dioxide@carbon@nickel hydroxide core-shell structure copolymer nanowire composite |
| CN110242855A (en) * | 2019-06-06 | 2019-09-17 | 吕大明 | Flexible high pressure hydrogen container |
| CN113571343A (en) * | 2021-06-17 | 2021-10-29 | 南京邮电大学 | Integrated super capacitor and preparation method thereof |
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| CN102385991A (en) * | 2010-08-31 | 2012-03-21 | 三星电机株式会社 | Method of manufacturing lithium ion capacitor and lithium ion capacitor manufactured using the same |
| CN103545119A (en) * | 2013-10-09 | 2014-01-29 | 兰州大学 | Low-cost high-integrated flexible ultrathin ultralight supercapacitor |
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| CN102385991A (en) * | 2010-08-31 | 2012-03-21 | 三星电机株式会社 | Method of manufacturing lithium ion capacitor and lithium ion capacitor manufactured using the same |
| CN103545119A (en) * | 2013-10-09 | 2014-01-29 | 兰州大学 | Low-cost high-integrated flexible ultrathin ultralight supercapacitor |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161316A (en) * | 2015-09-16 | 2015-12-16 | 中国科学院电工研究所 | Flexible super capacitor and preparation method thereof |
| CN105161316B (en) * | 2015-09-16 | 2018-07-27 | 中国科学院电工研究所 | A kind of flexible super capacitor and preparation method thereof |
| CN106229159A (en) * | 2016-09-05 | 2016-12-14 | 南方科技大学 | Flexible super capacitor and the preparation method of flexible super capacitor |
| CN109087815A (en) * | 2018-08-08 | 2018-12-25 | 安徽师范大学 | One-dimensional cobalt molybdate@nickel hydroxide core-shell nano hollow pipe composite material and preparation method and application |
| CN110242855A (en) * | 2019-06-06 | 2019-09-17 | 吕大明 | Flexible high pressure hydrogen container |
| CN110242855B (en) * | 2019-06-06 | 2023-09-19 | 吕大明 | Flexible high-pressure hydrogen storage tank |
| CN110189925A (en) * | 2019-06-24 | 2019-08-30 | 安徽师范大学 | The preparation method and application of one-dimensional manganese dioxide@carbon@nickel hydroxide core-shell structure copolymer nanowire composite |
| CN110189925B (en) * | 2019-06-24 | 2021-09-28 | 安徽师范大学 | Preparation method and application of one-dimensional manganese dioxide @ carbon @ nickel hydroxide core-shell nanowire composite material |
| CN113571343A (en) * | 2021-06-17 | 2021-10-29 | 南京邮电大学 | Integrated super capacitor and preparation method thereof |
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Application publication date: 20140723 |