CN102568865B - Preparation method of flexible super capacitor based on paper and application thereof - Google Patents
Preparation method of flexible super capacitor based on paper and application thereof Download PDFInfo
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- CN102568865B CN102568865B CN201210040917.5A CN201210040917A CN102568865B CN 102568865 B CN102568865 B CN 102568865B CN 201210040917 A CN201210040917 A CN 201210040917A CN 102568865 B CN102568865 B CN 102568865B
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- 229920000767 polyaniline Polymers 0.000 claims description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
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- 239000004411 aluminium Substances 0.000 claims description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
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- 239000004332 silver Substances 0.000 claims description 4
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- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
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- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
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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 preparation method of a flexible super capacitor based on paper and application thereof in a self-drive system. The preparation method concretely comprises the following steps: firstly depositing a layer of non-conductive polymer on the surface of the paper; secondly, depositing a metal membrane on the surface of the processed paper to form a flexible conductive paper substrate; thirdly, preparing a metal oxide or a conductive polymer on the conductive substrate to form an electrode material; and finally, assembling two electrode materials by adopting a solid electrolyte to form a super capacitor. The flexible full-solid super capacitor prepared by the method has good bending property and electrochemical properties and has good application prospect in the aspects of energy storage and energy management, especially in the self-drive system.
Description
Technical field
The invention belongs to ultracapacitor technical field, be specifically related to a kind of preparation method of ultracapacitor and the application in self-driven system thereof.
Background technology
Along with the great demand of modern society to the various energy, searching is clean, the reproducible energy has become countries in the world questions of common interest.Solar energy and wind energy are good green energy resources, but they are in fact all intermittent energy sources, for example at night or overcast and rainy, and the obtaining efficiency and can greatly reduce of solar energy; And wind energy also cannot ensure Power supply in all weather of the year.Other such as nano generators of some energy collection technologies etc. can be electric energy by the small kinetic transformation in surrounding environment effectively, but its lower power stage cause these technology cannot accomplish to drive constantly miniaturized electronic devices.These restrictions can utilize energy storage system to solve, because energy storage system can get up various scattered energy storages, and can export according to the stable energy that provides constantly of actual demand.Present stage, various storage batterys, lithium battery and ultracapacitor etc. can be used for storage of electrical energy.
Ultracapacitor, owing to having higher power density and longer cycle life, is just being subject to people and is more and more paying close attention to.It can be used as the electrical storage device of solar energy, wind power generation as the energy storage device of power-type, also can be used as the electrical source of power of electric automobile, also has increasing application at military aerospace and consumer electronic product.Therefore, can be by solar energy, wind energy and other various energy storages in super capacitor, and then can be used for driving miniaturized electronic devices.
Portable and wearable electronic sensor will have in future huge application prospect, such as Portable Displays, electronics skin and distributed sensor etc.Have expert to think, this century, transducer will be played the part of irreplaceable role in the various aspects of our life and work.If carry out driving sensor with battery or external power supply, the annual whole world mass energy of will using up, and produce countless reluctant old and useless batterys, seriously restrict economy and social development.Generally believe at present, self-driven sensor network is best solution, will effectively drive in decades to come in the development of World Economics.Self-driven technology can ensure that sensor network independently uses, thereby no longer relies on additional power source.Convert solar energy into electrical energy by solar cell, utilize nano generator or piezoelectric ceramic etc. that the kinetic energy of the wind energy in environment, mankind's activity generation etc. is converted into electric energy, and then be stored in ultracapacitor, and then use it to driving sensor, without external power supply or battery.Self-driven system is the energy in environment fully, and pollution-free, really realizes clean energy technology, military and civilian aspect all can have huge application prospect.
In the preparation method of current ultracapacitor, conventionally adopt strong acid or highly basic as liquid electrolyte, in order to prevent electrolyte leakage, need encapsulation very closely, cause the volume and weight of capacitor to increase, be not suitable for being used on portable electronic device.Choose suitable capacitance material and manufacture craft and prepare low cost, stable, efficient flexible all-solid-state supercapacitor, so with nano generator or solar cell etc. be the trend of future development surely in conjunction with forming self-driven system.
Summary of the invention
For the problem of current existence, the present invention aims to provide a kind of preparation method of the flexible super capacitor based on paper, utilize the prepared super capacitor device of method of the present invention to there is large unit-area capacitance, and device can keep good electrochemical properties before and after bending.
Realize the concrete technical scheme that object of the present invention adopts as follows:
A preparation method for flexible super capacitor based on paper, is specially: first, and at flexible and nonconducting polymer such as the surface deposition layer of polyethylene alcohol of paper or vinylidene, polytetrafluoroethylene, polystyrene; Secondly, on described treated paper, the various metal films such as deposited gold or silver, copper, iron, aluminium, form flexible conductive paper substrate; Then, on described compliant conductive substrate, prepare various metal oxides or conducting polymer, form electrode material; Finally, by solid electrolyte, two cube electrode materials are assembled into ultracapacitor.
As improvement of the present invention, described paper is printing, writing paper, drawing paper or electrically-insulating paper.
As improvement of the present invention, described nonconducting polymer is polyvinyl alcohol, Kynoar, polytetrafluoroethylene or polystyrene.
As improvement of the present invention, described metal film can be the film of gold, silver, copper, iron, aluminium or tantalum.
As improvement of the present invention, described metal oxide is manganese oxide, iron oxide, vanadium oxide, nickel oxide, cobalt oxide, molybdenum oxide, tin oxide or indium oxide.
As improvement of the present invention, described conducting polymer is polyaniline, polypyrrole, poly-3,4-rthylene dioxythiophene or its derivative.
The invention also discloses and utilize ultracapacitor prepared by above-mentioned preparation method and the application in self-driven system thereof.
Flexible all-solid-state supercapacitor prepared by method of the present invention has good bendable folding endurance and electrochemical properties, aspect stored energy and energy management, is having a good application prospect.
Technique effect of the present invention is embodied in: the technique of preparing flexible super capacitor is simple, be easy to carry out production control, and owing to adopting paper as substrate, cost is relatively cheap, suitable for mass production.The flexible super electric capacity of preparing has good electrochemical properties, can be used for storing the electric energy of solar cell and nano generator generation, drives strain transducer, has shown the application prospect of ultracapacitor in self-driven system.
Brief description of the drawings
Figure 1 shows that the preparation flow of solid-state super capacitor electrode of the present invention.
Figure 2 shows that the scanning electron microscope diagram sheet of the polyaniline nano network depositing on paper.
Figure 3 shows that solid state super capacitor based on the polyaniline cyclic voltammetric characteristic curve under differently curved degree.
Figure 4 shows that the application schematic diagram of solid state super capacitor in self-driven system.
Figure 5 shows that direct current and super capacitor drive the comparison diagram of strain transducer.
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
Embodiment 1
1. printing paper is cut into suitable size, immerse in certain density polyvinyl alcohol water solution, treat that paper takes out and dry unnecessary moisture after all drenching.
2. the paper of processing using said method is as substrate, utilize the certain thickness copper film of electron beam evaporation, the thickness of copper film can specifically be determined according to actual conditions, if the polyaniline film that can grow below on guarantee copper film, and in bending situation, copper film does not come off.
3. utilize the grow polyaniline film of one deck suitable thickness of solution polymerization process on the above-mentioned paper that deposits copper film.The thickness of film can be determined according to concrete selection of actual conditions, as long as ensure that the thickness of polyaniline does not come off, as being 10-100 micron.
4. get two above-mentioned paper of having grown polyaniline film and be dipped in the mixed solution of certain density polyvinyl alcohol and phosphoric acid, take out and be bonded together after a period of time, centre keeps apart with barrier film.
5. after the excessive moisture volatilization completely in polyvinyl alcohol and phosphoric acid solution, can carry out packaging and testing.
1. the Kynoar of certain mass is dissolved in methyl pyrrolidone, and gets the newsprint immersion of suitable size, treat that paper takes out after soaking into completely, treats that solvent evaporates completely.
2. on above-mentioned treated paper, utilize magnetically controlled sputter method to prepare the golden film of one deck suitable thickness.The thickness of film can be determined according to concrete selection of actual conditions, as long as guarantee fund's film conductance is good, and not come off.
3. the paper that has deposited golden film is immersed in the mixed solution of certain density manganese acetate and ammonium acetate, on golden film, deposit a certain amount of manganese oxide by the method for electro-deposition.
4. get in the mixed solution that two above-mentioned paper that deposited manganese oxide are dipped into certain density polyvinyl alcohol and sulfuric acid and take out and be bonded together after certain hour, middlely separate with barrier film.
5. after moisture evaporation unnecessary in polyvinyl alcohol and sulfuric acid solution is complete, encapsulates and make ultracapacitor.
Above-described embodiment is only exemplary, and wherein each kind of parameter or sample type only as an example, are not the restrictions to method of the present invention.For example, for being not limited to printing paper or newsprint as the paper of substrate base, can also be various printings, writing paper, kent, drawing paper, electrically-insulating paper etc. all kinds paper.Can also be the flexibility such as polytetrafluoroethylene, polystyrene and nonconducting polymer for infiltrating the solution of paper.The metal plating on paper can also be the various metals such as silver, iron, aluminium, tantalum.The metal oxide depositing on metal film can also be manganese oxide or iron oxide, vanadium oxide, nickel oxide, cobalt oxide, molybdenum oxide, tin oxide, indium oxide etc., the conducting polymer of deposition can also be polyaniline or polypyrrole, poly-3,4-rthylene dioxythiophene and derivative thereof etc.
To utilizing the device of preparing described in method of the present invention, determine pattern, the structure of matter etc. of the various nanostructures of growing on paper with ESEM, and tested the electrology characteristic of the capacitance characteristic of sample and the solid capacitor of preparation.Describe below in conjunction with accompanying drawing.
Figure 1 shows that the preparation flow of solid-state super capacitor electrode.First paper is soaked to non-conductive polymer, after treating solvent evaporation completely, depositing metal films on paper finally deposits electrochemical active material, as metal oxide or conducting polymer etc. on metallic film.Can see, the method is simple, and various metallic films can be used as electrode material.
Figure 2 shows that the scanning electron microscope diagram sheet of the polyaniline nano network depositing on paper.As can be seen from the figure polyaniline nano network is mainly made up of at the polyaniline nano-line of 100 nanometer left and right diameter.They are mutually wound around weave in and have large surface area, form good conductive channel, and the electrolyte that can adsorb in a large number, are conducive to improve its chemical property.
Figure 3 shows that solid state super capacitor based on the polyaniline cyclic voltammetric characteristic curve under differently curved degree.As can be seen from the figure, the device of preparation is under differently curved degree, and it is good that electrochemical properties keeps, and is not substantially subject to the impact of device bending.
Figure 4 shows that the application schematic diagram of solid state super capacitor in self-driven system.Constantly push nano generator by oscillator, nanometer generating chance will produce alternating current.The alternating current of nano generator output, by bridge rectifier, can be obtained to direct current, so just can be stored in solid-state super capacitor, and then drive various transducers with the electric energy in ultracapacitor.Like this, in whole circuit, just do not need battery, realized self-driven.
Figure 5 shows that direct current and super capacitor drive the comparison diagram of strain transducer.As we can see from the figure, the current characteristics of the strain transducer under super capacitor and DC powered is basic identical, shows that super capacitor has the possibility that replaces DC power supply, further illustrates the applicability of ultracapacitor in self-driven system.
Can reach a conclusion from above-mentioned analysis, the present invention is taking paper as substrate, and depositing metal films, as electrode, then deposits the material with electro-chemical activity on metallic film thereon, makes an electrode of ultracapacitor.The electrode of two ultracapacitors is bonded together with solid electrolyte, and centre separates with barrier film, has made flexible solid-state super capacitor.Find after tested, super capacitor prepared by the method has good electrochemical properties, has a good application prospect, and can be suitable for and self-driven system aspect stored energy.
Claims (7)
1. a preparation method for the ultracapacitor based on paper, specifically comprises the steps:
First, form the nonconducting polymer of one deck by being immersed in paper surface, described nonconducting polymer is polyvinyl alcohol, Kynoar, polytetrafluoroethylene or polystyrene;
Secondly,, through above-mentioned paper surface depositing metallic films after treatment, form flexible conductive paper substrate;
Then, in described conductive substrates, prepare metal oxide or conducting polymer, form electrode material;
Finally, by the electrode material assembling described in two, form ultracapacitor by solid electrolyte.
2. preparation method according to claim 1, is characterized in that, described paper is printing, writing paper, drawing paper or electrically-insulating paper.
3. preparation method according to claim 1 and 2, is characterized in that, described metal film is the film of gold, silver, copper, iron, aluminium or tantalum.
4. preparation method according to claim 1 and 2, is characterized in that, described metal oxide is manganese oxide, iron oxide, vanadium oxide, nickel oxide, cobalt oxide, molybdenum oxide, tin oxide or indium oxide.
5. preparation method according to claim 1 and 2, is characterized in that, described conducting polymer is polyaniline, polypyrrole, poly-3,4-ethene dioxythiophene or its derivative.
6. the described prepared ultracapacitor of preparation method of one of claim 1-5.
7. the application of ultracapacitor claimed in claim 6 in self-driven system.
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| CN201210040917.5A CN102568865B (en) | 2012-02-22 | 2012-02-22 | Preparation method of flexible super capacitor based on paper and application thereof |
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| CN201210040917.5A CN102568865B (en) | 2012-02-22 | 2012-02-22 | Preparation method of flexible super capacitor based on paper and application thereof |
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| CN113066671B (en) * | 2021-03-02 | 2023-07-28 | 浙江工业大学 | Thermoelectric flexible supercapacitor and preparation method thereof |
| CN113080977B (en) * | 2021-03-25 | 2022-12-20 | 山东科技大学 | Preparation method of flexible electrode, flexible electrode and use method of flexible electrode |
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| CN101376715A (en) * | 2008-09-26 | 2009-03-04 | 南京大学 | Preparation of large area flexible self-supporting polyaniline nanostructured film |
| CN102169999A (en) * | 2011-04-02 | 2011-08-31 | 南昌大学 | Paper type battery formed by metallic nano-material |
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| CN101376715A (en) * | 2008-09-26 | 2009-03-04 | 南京大学 | Preparation of large area flexible self-supporting polyaniline nanostructured film |
| CN102169999A (en) * | 2011-04-02 | 2011-08-31 | 南昌大学 | Paper type battery formed by metallic nano-material |
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