CN102568865A - 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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- CN102568865A CN102568865A CN2012100409175A CN201210040917A CN102568865A CN 102568865 A CN102568865 A CN 102568865A CN 2012100409175 A CN2012100409175 A CN 2012100409175A CN 201210040917 A CN201210040917 A CN 201210040917A CN 102568865 A CN102568865 A CN 102568865A
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- 239000003990 capacitor Substances 0.000 title abstract description 21
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- 239000007772 electrode material Substances 0.000 claims abstract description 7
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- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
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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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- -1 Kynoar Polymers 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002322 conducting polymer Substances 0.000 claims description 6
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- 238000007639 printing Methods 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 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
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 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
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 15
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
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- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- 235000019257 ammonium acetate Nutrition 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000000935 solvent evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
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- Electric Double-Layer Capacitors Or The Like (AREA)
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 the ultracapacitor technical field, be specifically related to a kind of preparation method and application in driving system certainly thereof of ultracapacitor.
Background technology
Along with the great demand of modern society to the various energy, searching cleaning, the reproducible energy have become the countries in the world questions of common interest.Solar energy and wind energy are good green energy resources, but they in fact all are intermittent energy sources, and be for example perhaps overcast and rainy at night, the obtaining efficient and can reduce greatly of solar energy; And wind energy also can't guarantee energy supply in all weather of the year.Other some collection of energy technology are nano generator etc. for example, can effectively the small kinetic energy in the surrounding environment be converted into electric energy, but its lower power output causes these technology can't 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 storage, 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 is just receiving the many concerns of People more and more owing to have higher power density and longer cycle life.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 in super capacitor with solar energy, wind energy and other various energy storage, and then can be used for driving miniaturized electronic devices.
Portable and wearable electronic sensor will have great application prospect, for example portable display screen, electronics skin and distributed sensor etc. in future.Have the expert to think, transducer will played the part of irreplaceable role in the various aspects of our life and work in this century.If use battery or external power supply to come driving sensor, the annual whole world mass energy of will using up, and produce countless reluctant old and useless batterys, seriously restricted economy and social development.Generally believing at present, is best solution from the driving sensor network, with the development that effectively drives World Economics in decades to come in.Can guarantee that from Driving technique sensor network independently uses, thereby no longer rely on additional power source.Is electric energy through solar cell with conversion of solar energy; Utilize kinetic energy that nano generator or piezoelectric ceramic etc. produce the wind energy in the environment, mankind's activity etc. to be converted into electric energy; And then be stored in the ultracapacitor, and then utilize it to come driving sensor, dispense with outer connecting power or battery.From the abundant energy in the environment of driving system, and pollution-free, really realize clean energy technology, military and civilian aspect all great application prospect can be arranged.
Among the preparation method of present ultracapacitor; Usually adopt strong acid or highly basic as liquid electrolyte, reveal, need encapsulation very closely in order to prevent electrolyte; Caused the volume and weight of capacitor to increase, unsuitable being used on the portable electronic device.Choose low-cost, stable, the flexible all solid state ultracapacitor efficiently of suitable capacitance material and manufacture craft preparation, and then to combine formation with nano generator or solar cell etc. be developing tendency in future from the driving system surely.
Summary of the invention
Problem to present 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 have big unit-area capacitance, and device can both keep electrochemical properties preferably before and after bending.
Realize that the concrete technical scheme that the object of the invention adopted is following:
A kind of preparation method of the flexible super capacitor based on paper is specially: at first, and at flexible and nonconducting polymer such as the surface deposition layer of polyethylene alcohol of paper or vinylidene, polytetrafluoroethylene, polystyrene; Secondly, various metal films such as deposited gold or silver, copper, iron, aluminium on said treated paper form flexible conductive paper substrate; Then, various metal oxides of preparation or conducting polymer on said compliant conductive substrate form electrode material; At last, through solid electrolyte two cube electrode materials are assembled into ultracapacitor.
As improvement of the present invention, said paper is printing, writing paper, drawing paper or electrically-insulating paper.
As improvement of the present invention, said 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, said conducting polymer is polyaniline, polypyrrole, gathers 3,4-ethene dioxythiophene or its derivative.
The invention also discloses the ultracapacitor and the application in driving system certainly thereof that utilize above-mentioned preparation method's preparation.
The flexible all solid state ultracapacitor of method preparation of the present invention has good bendable folding endurance and electrochemical properties, is having a good application prospect aspect energy storage and the energy management.
Technique effect of the present invention is embodied in: the technology of preparation flexible super capacitor is simple, be easy to carry out production control, owing to adopt paper as substrate, cost is cheap relatively, 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 showed the application prospect of ultracapacitor in driving system certainly.
Description of drawings
Shown in Figure 1 is the preparation flow of solid-state super capacitor electrode of the present invention.
Scanning electron microscope diagram sheet for the polyaniline nano network that on paper, deposits shown in Figure 2.
Shown in Figure 3 is the cyclic voltammetric characteristic curve of solid-state super electric capacity under differently curved degree based on polyaniline.
Shown in Figure 4 is the application sketch map of solid-state super electric capacity in driving system certainly.
Shown in Figure 5 is the comparison diagram that direct current and super capacitor drive strain transducer.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
1. printing paper is cut into suitable size, immerse in the certain density polyvinyl alcohol water solution, treat that paper takes out and the oven dry redundant moisture after all drenching.
2. the paper of handling with said method is as substrate; Utilize the certain thickness copper film of electron beam evaporation; The thickness of copper film can specifically confirm according to actual conditions, as long as guarantee the following polyaniline film of can growing on the copper film, and copper film does not come off and gets final product under the bending situation.
3. utilize on the above-mentioned paper that deposits copper film, the grow polyaniline film of one deck suitable thickness of solution polymerization process.The thickness of film can be confirmed according to concrete selection of actual conditions, not come off as long as guarantee the thickness of polyaniline, as being the 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 after a period of time and be bonded together, middlely keep apart with barrier film.
5. after treating the excessive moisture volatilization fully in polyvinyl alcohol and the phosphoric acid solution, can carry out packaging and testing.
1. the Kynoar with certain mass is dissolved in the methyl pyrrolidone, and gets the newsprint immersion of suitable size, treats that paper takes out after soaking into fully, treats that solvent evaporates fully.
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 confirm according to concrete selection of actual conditions, as long as guarantee fund's film conductance is good, and does not come off and gets final product.
3. the paper that will deposit golden film immerses in the mixed solution of certain density manganese acetate and ammonium acetate, and the method through electro-deposition deposits a certain amount of manganese oxide on golden film.
4. get and take out behind the certain hour in the mixed solution that two above-mentioned paper that deposited manganese oxide are dipped into certain density polyvinyl alcohol and sulfuric acid and be bonded together, middlely separate with barrier film.
5. treat in polyvinyl alcohol and the sulfuric acid solution that the redundant moisture complete laggard row encapsulation of volatilizing processes ultracapacitor.
The foregoing description only is exemplary, and wherein each kind of parameter or sample type as for example, are not the qualifications to method of the present invention only.For example, being used 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 or the like all kinds paper.The solution that is used to soak into paper can also be flexible and nonconducting polymer such as polytetrafluoroethylene, polystyrene.The metal that is plated on the paper can also be various metals such as silver, iron, aluminium, tantalum.The metal oxide that deposits on the 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 for polyaniline or polypyrrole, gather 3,4-ethene dioxythiophene and derivative thereof etc.
To utilizing the device of the said preparation of method of the present invention, the pattern of the various nanostructures of confirming with ESEM to grow on the paper, structure of matter etc., and tested the electrology characteristic of solid capacitor of capacitance characteristic and the preparation of sample.Describe below in conjunction with accompanying drawing.
Shown in Figure 1 is the preparation flow of solid-state super capacitor electrode.At first paper is soaked non-conductive polymer, treat that depositing metal films on paper deposits electrochemical active material, at last like metal oxide or conducting polymer etc. after the solvent evaporation fully on metallic film.Can see that this method is simple, various metallic films can be used as electrode material.
Scanning electron microscope diagram sheet for the polyaniline nano network that on paper, deposits shown in Figure 2.As can be seen from the figure the polyaniline nano network mainly is made up of the polyaniline nano-line of diameter about 100 nanometers.They twine weave in each other and have big surface area, form the favorable conductive passage, and the electrolyte that can adsorb in a large number, help improving its chemical property.
Shown in Figure 3 is the cyclic voltammetric characteristic curve of solid-state super electric capacity under differently curved degree based on polyaniline.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 do not receive the crooked influence of device basically.
Shown in Figure 4 is the application sketch map of solid-state super electric capacity in driving system certainly.Constantly push nano generator through oscillator, the nanometer generating chance will produce alternating current.The alternating current of nano generator output is passed through bridge rectifier, can obtain direct current, so just can be stored in the solid-state super capacitor, and then drive various transducers with the electric energy in the ultracapacitor.Like this, just do not need battery in the entire circuit, realized driving certainly.
Shown in Figure 5 is the comparison diagram that direct current and super capacitor drive strain transducer.From figure, can see that the current characteristics of the strain transducer under super capacitor and the dc powered is basic identical, show that super capacitor has the possibility that replaces DC power supply, further illustrates the applicability of ultracapacitor in driving system certainly.
Can reach a conclusion from above-mentioned analysis, the present invention is substrate with paper, and depositing metal films deposits the material with electro-chemical activity then as electrode on metallic film above that, processes an electrode of ultracapacitor.The electrode of two ultracapacitors is bonded together with solid electrolyte, and the centre separates with barrier film, has promptly processed flexible solid-state super capacitor.Find that through test the super capacitor of this method preparation has good electrochemical properties, having a good application prospect aspect the energy storage, and can be suitable for from the driving system.
Claims (8)
1. the preparation method based on the ultracapacitor of paper specifically comprises the steps:
At first, at the nonconducting polymer of paper surface deposition one deck;
Secondly, through above-mentioned sheet processed surface deposition metal film, form flexible conductive paper substrate;
Then, preparation metal oxide or conducting polymer on said conductive substrates form electrode material;
At last, with two described electrode material assemblings, promptly form ultracapacitor through solid electrolyte.
2. preparation method according to claim 1 is characterized in that, said paper is printing, writing paper, drawing paper or electrically-insulating paper.
3. preparation method according to claim 1 and 2 is characterized in that, said nonconducting polymer is polyvinyl alcohol, Kynoar, polytetrafluoroethylene or polystyrene.
4. according to the described preparation method of one of claim 1-3, it is characterized in that described metal film can be the film of gold, silver, copper, iron, aluminium or tantalum.
5. according to the described preparation method of one of claim 1-4, it 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.
6. according to the described preparation method of one of claim 1-5, it is characterized in that said conducting polymer is polyaniline, polypyrrole, gathers 3,4-ethene dioxythiophene or its derivative.
7. the prepared ultracapacitor of the described preparation method of one of claim 1-6.
8. the application of the described ultracapacitor of claim 7 in driving system certainly.
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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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| CN102568865B CN102568865B (en) | 2014-06-18 |
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