CN103560019B - A kind of zinc ion hybrid super capacitor - Google Patents
A kind of zinc ion hybrid super capacitor Download PDFInfo
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- CN103560019B CN103560019B CN201310520779.5A CN201310520779A CN103560019B CN 103560019 B CN103560019 B CN 103560019B CN 201310520779 A CN201310520779 A CN 201310520779A CN 103560019 B CN103560019 B CN 103560019B
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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 present invention relates to a kind of zinc ion hybrid super capacitor, comprise positive pole, negative pole, barrier film, electrolyte and housing, it is characterized in that: positive active material is composite metal oxide ZnMxOy(M=Fe, Co, Mn, 0 < x < 3, x and y ratio are 1:1～1:4), negative electrode active material is the Carbon Materials that carries out ion reversible adsorption, electrolyte is made up of zinc salt and deionized water. Composite metal oxide preparation technology used is simple, and material synthesizes wide material sources.
Description
Technical field
The present invention relates to a kind of zinc ion hybrid super capacitor, belong to battery and ultracapacitor.
Background technology
Ultracapacitor is a kind of energy storage device between battery and common electric capacity, there is specific power high, have extended cycle life, high current charge-discharge, environmental friendliness, safe and non-maintaining advantage, has broad application prospects in fields such as electronic information, instrument and meter, Aero-Space, communications and transportation. Ultracapacitor can be divided into double layer capacitor and electrochemical capacitor according to energy storage mechanism, double layer capacitor relies on the material with carbon element reversible adsorption ion of both positive and negative polarity to carry out energy storage, electrochemical capacitor is except having electric double layer energy storage, also there is redox reaction, generating portion fake capacitance, specific energy significantly improves.
In recent years, power characteristic, the obvious ultracapacitor of energy response are mated to composite power source use with the electrokinetic cell of other type, in meeting the instructions for use of energy-conservation and new-energy automobile, can greatly improve the efficiency of battery, increase the service life. For example, by lithium ion battery and ultracapacitor composition composite power source, ultracapacitor can be in the high-power output operating mode work such as startup, acceleration, climbing, lithium ion battery provides the continual mileage required drive of automobile, the combination of the two, improve the power performance of automobile, extended the service life of battery.
Dissimilar electrokinetic cell and the combination of ultracapacitor inspire people to carry out the inside binding of electrokinetic cell, by the characteristic element of the characteristic element of a certain electrokinetic cell and another electrokinetic cell, by the optimal design of system, in same monomer, merge, can make it have the feature of two kinds of electrical source of power concurrently, the combination of existing Ni-MH battery and ultracapacitor, for example, within 1997, Muscovite ESMA company is by water system AC/Ni (OH)2Ultracapacitor is successfully for automobile dynamic system, for the fast development of battery and super capacitor mixed energy storage device is laid a good foundation. The Introduction To Cn Patent of application number 200810111891.2 a kind of hickelous nydroxide positive pole that mixes CNT and carbonyl nickel, the ultracapacitor of the carbon fiber of processing with electronickelling composition, maximum energy storage density reaches 20Wh/kg. The Introduction To Cn Patent of application number 201010265362.5 a kind of nano nickel oxide composite electrode for ultracapacitor and preparation method thereof, in Powdered nano oxidized nickel material, mix a certain amount of metallic element and make composite, electrode specific capacity is high, and cost is low.
Also there is the fusion of lithium ion battery and ultracapacitor, for example, the JMEnergy of Japan, Asahi Chemical Industry, NEC-TOKIN, ACT, Supreme Being visitor, FDK, TAIYO YUDAN, the research and development lithium-ion capacitors such as Hitachi changes into, part has realized commercialization, (the publication number US2009/0197171A1 of Japanese fuji heavy industry Co., Ltd., US2010/0142121A1, US2010/0128415A1, US7, 733, 629B2, application number 200580004509.2, application number 200580001498.2, application number 200680032109.7, application number 200680038604.9, application number 200680042376.2, application number 200680046167.5, application number 200680049541.7, application number 200710145884.X) planned lithium-ion capacitor is applied to Subaru automobile. application number is that 200410093962.2 Chinese patent has been reported a kind of high tension super capacitor, the Chinese patent of application number 200810046091.7 has reported that one contains C, the high potential super capacitor electrode material of Fe and P element, the Chinese patent of application number 201010280801.X has reported that a kind of LiFePO4 loads on active carbon as positive active material, the Chinese patent of application number 200710035051.8 has reported that a kind of mixture of anode material for lithium-ion batteries and electrode material for super capacitor that adopts is as positive active material, the Chinese patent of application number 200710035205.3 has been reported a kind of super capacitance cell, anodal active electrode material adopts lithium ion to embed the mixture of compound and porous carbon material, negative electrode active electrode material adopts the mixture of porous carbon material and graphite type material, application number is that 200810031490.6 Chinese patent has been reported a kind of novel energy-storing device and manufacture method thereof that has ultracapacitor and lithium ion battery characteristics concurrently, the Chinese patent of application number 201010592947.8 has been reported a kind of novel water system organic system mixed type lithium ion battery. for liquid fluid system, also there is a lot of research. publication number is the ultracapacitor that the Chinese patent of CN1866427A has been reported a kind of electroactive substance based in liquid phase.
Except the structure of energy storage device is studied, people have carried out developmental research to crucial energy storage material. Electrode material, as the core of ultracapacitor, directly has influence on the performance of ultracapacitor. Conventional electrode material General Requirements is: superior cycle life; Higher stability; Little to occurring in the electrochemical reaction resistance of electrode surface; High-specific surface area; Suitable aperture and pore-size distribution; Ensure the circulation of electrolyte in duct; Good wetability; Be conducive to form solution electrode interface; Minimum ohmic internal resistance; Be easy to processing. Material with carbon element is most widely used at present, most effective ultracapacitor energy storage material, but due to its adsorpting aggregation ion energy storage that relies on porous material, energy density is lower. In recent years, metal oxide, lithium-containing compound, conducting polymer etc. are used as super capacitor material in succession, in order to improve the energy density of device.
Composite metal oxide is two kinds and the above metal-doped energy storage material being compounded to form, as ZnCo2O4、ZnMn2O4、ZnFe2O4Deng reacting with lithium, be applied to lithium ion battery. After electric discharge first, there is Zn in composite metal oxide0、Mn0Deng conversion. The metal and the Li that generate2There is reversible reaction (NanoResearch, 2011,4,505 – 510) in O. Zinc-manganese oxygen composite metal oxide, as a kind of energy storage material, has been applied to lithium ion battery negative research (application number 200810047721.2, application number 20100545470.8).
Zinc ion battery is as a kind of novel rechargeable secondary cell (application number 200910106650.3, application number 200910036704.3, application number 200910179722.7, application number 200910205640.5, application number 200910188791.4, application number 200910188792.9, application number 200910238912.1), there is " whirlwind chair " formula energy storage feature of class lithium ion battery. When charging, zinc ion is deviate from from positive pole, through electrolyte, deposits at negative pole; When electric discharge, negative pole zinc is dissolved as zinc ion, through electrolyte, is embedded into (Angew.Chem.Int.Ed.2012,51,933 – 935) in manganese oxide positive electrode, and its reaction mechanism is as follows:
The metal oxides such as manganese dioxide, cobalt oxide and nickel oxide have obtained broad research as electrode of super capacitor active material, and the ultracapacitor of research carry out to(for) compound metal oxide is a useful exploration.
Summary of the invention
The object of the present invention is to provide a kind of zinc ion hybrid super capacitor, composite metal oxide preparation technology used is simple, and material synthesizes wide material sources.
Technical scheme technical scheme of the present invention is achieved in that a kind of zinc ion hybrid super capacitor, comprises positive pole, negative pole, barrier film, electrolyte and housing; It is characterized in that: positive active material is composite metal oxide ZnMxOy, negative electrode active material is the Carbon Materials that carries out ion reversible adsorption, electrolyte is made up of zinc salt and deionized water.
The Carbon Materials of described ion reversible adsorption is a kind of in active carbon, activated carbon fiber, expanded graphite, graphite, Graphene, CNT, charcoal-aero gel, nanometer door carbon, Carbon foam, carbonaceous mesophase spherules and skeleton carbon and the combination that comprises at least one above-mentioned material. Zinc salt in described electrolyte is the one in zinc sulfate, zinc nitrate, zinc chloride. Positive active material is composite metal oxide, can be chemical formula ZnMxOy, M=Fe here, Co, Mn, 0 < x < 3, x and y ratio are 1:1～1:4, preferably ZnMn2O4，ZnFe2O4，ZnCo2O4As the active material of anodal zinc ion deintercalation of the present invention.
In the present invention, barrier film is the porous polymer membrane with ion diffusion, can be polyethylene barrier film, polypropylene diaphragm, polyethylene and polypropylene composite materials barrier film, cellulose barrier film. In addition,, in the present invention, both positive and negative polarity is respectively to be sticked on collector and made by active material and conductive agent. Can use the method for generally preparing battery pole piece that active material and conductive agent and binding agent are uniformly dispersed and make slurry in solvent, be coated on collector and make. Conductive agent can be carbon nano-fiber, Graphene, conductive carbon black, CNT, binding agent can be Kynoar, polytetrafluoroethylene (PTFE), cellulose, butadiene-styrene rubber, and collector can make titanium foil, steel foil, titanizing fiber cloth, titanium metal net, steel wire netting; Described binding agent is a kind of in polytetrafluoroethylene (PTFE), butadiene-styrene rubber, CMC or their combination; Described barrier film is the one in polyethylene, polypropylene, fibreglass diaphragm.
Good effect of the present invention: positive active material is composite metal oxide, negative electrode active material is the Carbon Materials that can carry out ion reversible adsorption; Electrolyte is made up of zinc salt and deionized water; Composite metal oxide preparation technology used is simple, and material source is extensive.
Brief description of the drawings:
Fig. 1 is the zinc-manganese oxygen compound XRD diffraction pattern of the embodiment of the present invention 1.
Fig. 2 is the zinc-manganese oxygen compound SEM photo of the embodiment of the present invention 1.
Fig. 3 is the hybrid super capacitor charging and discharging curve of the embodiment of the present invention 1.
Fig. 4 is the cyclic voltammetry curve of the hybrid super capacitor of the embodiment of the present invention 1.
Detailed description of the invention
Below by the drawings and specific embodiments, the present invention is specifically described, described embodiment is the specific descriptions to claim of the present invention just, and claim includes but not limited to described embodiment content.
Embodiment 1
Take manganese carbonate, citric acid and zinc carbonate (amount of substance is than being 1:6:6). Manganese carbonate and citric acid mix by magnetic agitation in water, are warming up to 60 DEG C, and isothermal reaction 30min, adds zinc carbonate, continue to stir 2h, are cooled to room temperature, and by the product sedimentation and filtration of gained, deionized water is cleaned, and 60 DEG C of vacuum drying are to constant weight; By 700 DEG C of calcining 2h of the product obtaining, obtain zinc-manganese oxygen composite metal oxide ZnMn2O4。
According to mass ratio, 70:20:10 takes ZnMn2O4, VGCF, PTFE make electrode film, being pressed in diameter is the stainless (steel) wire disk of 16mm, dry after as positive plate; According to mass ratio 80:10:10 take negative electrode active material (active carbon), VGCF, PTFE make electrode film, are pressed in the stainless (steel) wire disk that diameter is 16mm, dry after as negative plate, positive/negative plate mass ratio is 1:1.6.
Positive plate, barrier film, negative plate are superposeed successively, be put in button shell, add 1M zinc sulfate solution, make hybrid super capacitor.
Embodiment 2
Take di-iron trioxide and zinc oxide is put into ball grinder according to amount of substance 1:1, material is 1:20 with ball mass ratio, and ball milling 3h obtains presoma. Presoma, at 700 DEG C of calcining 2h, obtains zinc-iron composite metal oxide ZnFe2O4。
According to mass ratio, 70:20:10 takes ZnFe2O4, VGCF, PTFE make slurry, is coated in the upper without titanium coating one side of activated carbon fiber cloth, cuts the disk that diameter is 16mm, dry, roll-in is as positive plate; According to mass ratio 73:17:10 take negative electrode active material (active carbon and MCMB quality are 60:40), VGCF, PTFE make slurry, be coated in activated carbon fiber cloth without in titanium coating one side, cut the disk that diameter is 16mm, dry, roll-in is as negative plate, and positive/negative plate mass ratio is 1:1.2.
Positive plate, barrier film, negative plate are superposeed successively, be put in button shell, add 1M solder(ing)acid, make hybrid super capacitor.
Embodiment 3
According to mass ratio 1:2 take zinc nitrate, cobalt nitrate is made the aqueous solution, nitrogen atmosphere stirs after 1h, adds NaOH, controls reaction time 3min. Product washing, dry, obtain 600 DEG C of calcining 1h of composite material precursor, obtain zinc cobalt composite metal oxide ZnCo2O4。
According to mass ratio, 70:20:10 takes ZnCo2O4, VGCF, PTFE make electrode film, being pressed in diameter is the stainless (steel) wire disk of 16mm, dry after as positive plate; According to mass ratio 79:11:10 take negative electrode active material (mass ratio of Graphene and expanded graphite is 70:30), VGCF, PTFE make electrode film, being pressed in diameter is the stainless (steel) wire disk of 16mm, after dry, as negative plate, positive/negative plate mass ratio is 1:1.6.
Positive plate, barrier film, negative plate are superposeed successively, be put in button shell, add 1M zinc nitrate aqueous solution, make hybrid super capacitor.
Claims (3)
1. a zinc ion hybrid super capacitor, comprises positive pole, negative pole, barrier film, electrolyte and housing, it is characterized in that: positive active material is composite metal oxide ZnMxOyWherein M=Fe, Co, Mn, 0 < x < 3, x and y ratio are 1:1～1:4, and negative electrode active material is the Carbon Materials that carries out ion reversible adsorption, and electrolyte is made up of zinc salt and deionized water.
2. a kind of zinc ion hybrid super capacitor according to claim 1, is characterized in that the described Carbon Materials that carries out ion reversible adsorption is a kind of in active carbon, graphite, Graphene, CNT, charcoal-aero gel, nanometer door charcoal, Carbon foam, carbonaceous mesophase spherules and skeleton carbon and their combination.
3. a kind of zinc ion hybrid super capacitor according to claim 1, is characterized in that the zinc salt in described electrolyte is the one in zinc sulfate, zinc nitrate, zinc chloride.
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| CN201310520779.5A CN103560019B (en) | 2013-10-30 | 2013-10-30 | A kind of zinc ion hybrid super capacitor |
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| CN103560019B true CN103560019B (en) | 2016-05-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107204243A (en) * | 2017-05-03 | 2017-09-26 | 中国第汽车股份有限公司 | A kind of zinc ion electrolytic solution for super capacitor |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104882638A (en) * | 2015-04-27 | 2015-09-02 | 云南蓝光矩阵科技有限公司 | Graphite carbon fiber battery |
| CN106981371A (en) * | 2016-01-15 | 2017-07-25 | 黄潮 | A kind of water system electrolyte super capacitance cell |
| CN110010373B (en) * | 2019-03-27 | 2021-02-19 | 中国科学院福建物质结构研究所 | Electrode zinc embedding treatment method and application thereof in preparation of battery type super capacitor |
| CN109994322B (en) * | 2019-03-27 | 2020-12-29 | 中国科学院福建物质结构研究所 | Battery type super capacitor and application thereof |
| CN110993358A (en) * | 2019-12-24 | 2020-04-10 | 合肥国轩高科动力能源有限公司 | Flexible zinc ion capacitor |
| CN114974910B (en) * | 2022-06-06 | 2024-03-22 | 安徽信息工程学院 | Electrode material and preparation method thereof |
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| CN101162651A (en) * | 2007-09-27 | 2008-04-16 | 南京航空航天大学 | High energy denseness water system ru-based composite metal oxide super capacitor |
| CN101217073A (en) * | 2007-12-28 | 2008-07-09 | 上海奥威科技开发有限公司 | A mixed type polymer super capacitor |
| CN102651484A (en) * | 2012-05-10 | 2012-08-29 | 中国第一汽车股份有限公司 | Energy storage device combining with characteristics of lithium ion battery and super-capacitor |
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Patent Citations (3)
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|---|---|---|---|---|
| CN101162651A (en) * | 2007-09-27 | 2008-04-16 | 南京航空航天大学 | High energy denseness water system ru-based composite metal oxide super capacitor |
| CN101217073A (en) * | 2007-12-28 | 2008-07-09 | 上海奥威科技开发有限公司 | A mixed type polymer super capacitor |
| CN102651484A (en) * | 2012-05-10 | 2012-08-29 | 中国第一汽车股份有限公司 | Energy storage device combining with characteristics of lithium ion battery and super-capacitor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107204243A (en) * | 2017-05-03 | 2017-09-26 | 中国第汽车股份有限公司 | A kind of zinc ion electrolytic solution for super capacitor |
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Inventor after: Rong Changru Inventor after: Han Jinlei Inventor after: Zhang Kejin Inventor after: Lin Weiqing Inventor after: Li Liying Inventor after: Chen Shuli Inventor after: Wei Xiaochuan Inventor before: Rong Changru Inventor before: Han Jinlei Inventor before: Zhang Kejin Inventor before: Chen Shuli Inventor before: Wei Xiaochuan |
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