CN103545123B - A kind of hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently - Google Patents
A kind of hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently Download PDFInfo
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- CN103545123B CN103545123B CN201310520835.5A CN201310520835A CN103545123B CN 103545123 B CN103545123 B CN 103545123B CN 201310520835 A CN201310520835 A CN 201310520835A CN 103545123 B CN103545123 B CN 103545123B
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 31
- 239000007774 positive electrode material Substances 0.000 claims abstract description 23
- 239000002905 metal composite material Substances 0.000 claims abstract description 22
- 239000007773 negative electrode material Substances 0.000 claims abstract description 21
- 230000004888 barrier function Effects 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006258 conductive agent Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000013543 active substance Substances 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 125
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 19
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
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- 239000010439 graphite Substances 0.000 claims description 14
- 239000004964 aerogel Substances 0.000 claims description 8
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
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- 150000002500 ions Chemical class 0.000 abstract description 7
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- 238000010521 absorption reaction Methods 0.000 abstract 2
- 229910007477 ZnMn2O4 Inorganic materials 0.000 description 18
- 239000003990 capacitor Substances 0.000 description 18
- 229910003119 ZnCo2O4 Inorganic materials 0.000 description 16
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 15
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 15
- 238000004146 energy storage Methods 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
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- 229910001416 lithium ion Inorganic materials 0.000 description 11
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
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- QSBNYRIUDYMODP-UHFFFAOYSA-N [Mn]O[Zn] Chemical compound [Mn]O[Zn] QSBNYRIUDYMODP-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
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- 239000004744 fabric Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
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- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229950000845 politef Drugs 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
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- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- AHKUMISTYQVMAP-UHFFFAOYSA-N oxoiron;zinc Chemical compound [Zn].[Fe]=O AHKUMISTYQVMAP-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
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Classifications
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently, including core body, electrolyte and housing, core body by positive pole, negative pole, be placed in barrier film therebetween and form, both positive and negative polarity is adhered to made on a current collector by active substance, conductive agent respectively。Positive active material has two kinds, and the first positive active material is metal composite oxide, and the second positive active material is the Carbon Materials that can carry out ion reversible absorption；Negative electrode active material has two kinds, and the first negative electrode active material is zinc, and the second negative electrode active material is the Carbon Materials that can carry out ion reversible absorption, and electrolyte is made up of zinc salt and deionized water。Metal composite oxide preparation technology used is simple, environmental friendliness。
Description
Technical field
The present invention relates to a kind of hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently, belong to battery and supercapacitor technologies field。
Background technology
The development of energy-conservation and new-energy automobile, has promoted the continuous lifting of the electrical source of power technology such as lithium ion battery, fuel cell, ultracapacitor, metal-air battery。But, presently used electrical source of power energy density is relatively low, and automobile continual mileage is short；Power density is less, and automobile starting, climbing and acceleration are poor；Bulking value is big, installs inconvenience；Service life is short, it is impossible to identical with car load；Relatively costly, car load integrated cost remains high；Operating temperature range is narrow, and it is poor to adapt to；Charging interval is long, and auxiliary facility has high input。These reasons hinder electrical source of power large-scale application on energy-conservation and new-energy automobile。
In recent years, people are exploitation new system battery on the one hand, promotes original battery performance；On the other hand, power characteristic, the obvious electrokinetic cell inside/outside of energy response are mated the use that combines, meets energy-conservation and new-energy automobile instructions for use。Such as, lithium ion battery and ultracapacitor are formed composite power source by external management system, power source as automobile, ultracapacitor can in high-power output operating mode work such as startup, acceleration, climbings, lithium ion battery provides the continual mileage required drive of automobile, combination, improves the power performance of automobile, extends the service life of battery；And internal combustion, it it is the characteristic element of the characteristic element by a certain electrokinetic cell and another electrokinetic cell, designed by the optimization of system, at same monomer endomixis so that it is have the feature of two kinds of electrokinetic cells concurrently, it is achieved power density, energy density raising, such as, merge having the embedding de-graphite material of lithium ion with the activated carbon forming electric double layer, make lithium-ion capacitor, transmitted by " the whirlwind chair " of lithium ion and carry out energy storage。
Zinc ion battery that is similar with lithium ion battery, that recently occur, as a kind of novel rechargeable secondary cell, it may have " whirlwind chair " formula energy storage feature。During charging, zinc ion is deviate from from positive pole, through electrolyte, at cathode deposition；During electric discharge, negative pole zinc is dissolved as zinc ion, through electrolyte, is embedded in manganese oxide positive electrode (Angew.Chem.Int.Ed.2012,51,933 935), and its reaction mechanism is as follows:
xZn2++2xe - +MnO21Zn x MnO2
Zn1Zn2++2e -
Application number 200910106650.3, application number 200910036704.3, application number 200910179722.7, application number 200910205640.5, application number 200910188791.4, application number 200910188792.9, the Chinese patent of application number 200910238912.1 reports Zinc ion battery and preparation method thereof。The development of Zinc ion battery, the development for ultracapacitor provides new binding site。
Ultracapacitor is a kind of energy storage device between battery and conventional capacitive, double layer capacitor and electrochemical capacitor can be divided into according to energy storage mechnism, 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, there is also redox reaction, generating section fake capacitance, specific energy is greatly improved。By current existing battery material and activated carbon combination, exploitation mixed type electrochemical capacitor is an important directions of ultracapacitor development。
Within 1997, Muscovite ESMA company is by water system AC/Ni (OH)2Ultracapacitor is used successfully to automobile dynamic system, and the fast development for battery Yu super capacitor mixed energy storage device is laid a good foundation。The JMEnergy of Japan, Asahi Chemical Industry, NEC-TOKIN, ACT, Supreme Being visitor, FDK, TAIYO YUDAN, the research and development lithium-ion capacitor such as Hitachi's chemical conversion, part has been carried out commercialization, Japanese fuji heavy industry Co., Ltd. (publication number US2009/0197171A1, 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。
China also has made great progress in hybrid electrochemical capacitor, and urban occurs in that ultracapacitor electric bus, relies on website passenger getting on/off gap, completes charging, it is achieved that the pattern that comprehensive operation cost is minimum。
Electrode material, as the core of ultracapacitor, directly influences the performance of ultracapacitor。Material with carbon element is ultracapacitor active material most widely used at present, generally requires: superior cycle life；Higher stability；The electrochemical reaction resistance being likely to occur in electrode surface is little；High-specific surface area；Suitable aperture and pore-size distribution；Ensure electrolyte circulation in duct；Good wettability；Advantageously form solution electrode interface；Minimum ohmic internal resistance；It is prone to processing。But owing to material with carbon element relies primarily on the adsorpting aggregation ion energy storage of porous material, energy density is relatively low。In recent years, metal-oxide is used as super capacitor material, in order to improve the energy density of device, conventional by manganese oxide, nickel oxide and cobalt oxide etc.。Metal composite oxide is two kinds and the above metal-doped energy storage material being compounded to form, such as ZnCo2O4、ZnMn2O4、ZnFe2O4Etc. can reacting with lithium, it is applied to lithium ion battery。After electric discharge first, there is Zn in metal composite oxide0、Mn0Deng conversion。The metal generated and Li2There is reversible reaction (NanoResearch, 2011,4,505 510) in O。Zinc-manganese oxygen metal composite 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)。And adopting metal composite oxide and Carbon Materials composition positive active material, zinc forms negative electrode active material with activated carbon, and the hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently of combination have not been reported。
Summary of the invention
It is an object of the invention to provide a kind of hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently, metal composite oxide preparation technology used is simple, environmental friendliness。
The technical scheme is that and be achieved in that: a kind of hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently, including core body, electrolyte and housing, core body by positive pole, negative pole, be placed in barrier film therebetween and form, it is characterized in that: positive active material has two kinds, the first positive active material is material with carbon element (C), and the second positive active material is metal composite oxide ZnMxOy(M=Fe, Co, Mn, 0 < x < 3, x and y ratio is 1:1～1:4), negative electrode active material has two kinds, and the first negative electrode active material is zinc (Zn), and the second negative electrode active material is material with carbon element (C)；Electrolyte is made up of zinc salt and deionized water；Positive active material (C+ZnMxOy) and conductive agent adhere to and make positive plate on a current collector, negative plate is made in negative electrode active material (C+Zn) and conductive agent adhesion on a current collector；Positive/negative plate and barrier film are assembled into shell, inject electrolyte, and hybrid energy-storing device is made in encapsulation。
Described metal composite oxide is shaped as irregular graininess, the microspheroidal of rule, hollow spheres, bar-shaped, flower-shaped, needle-like and cellular。Described Carbon Materials is a kind of in activated 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 comprising at least one above-mentioned material。The described zinc salt in electrolyte is the one in zinc sulfate, zinc nitrate, zinc chloride。
The positive effect of the present invention: the material with electric double layer and oxidoreduction energy storage characteristic is merged in same device by a kind of hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently；Metal composite oxide preparation technology used is simple, environmental friendliness。
Accompanying drawing explanation
Fig. 1 is the zinc-manganese oxygen metal composite oxide XRD diffraction pattern of the embodiment of the present invention 1。
Fig. 2 is the zinc-manganese oxygen metal composite oxide SEM photograph of the embodiment of the present invention 1。
Fig. 3 is the hybrid energy-storing device charging and discharging curve of the embodiment of the present invention 1。
Detailed description of the invention
The hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently of the present invention, including core body, electrolyte and housing, core body by positive pole, negative pole, be placed in barrier film therebetween and form。Positive active material has two kinds, and the first positive active material is material with carbon element (C), and the second positive active material is metal composite oxide ZnMxOy, negative electrode active material has two kinds, and the first negative electrode active material is zinc (Zn), and the second negative electrode active material is material with carbon element (C)；Electrolyte is made up of zinc salt and deionized water；Positive active material (C+ZnMxOy) and conductive agent adhere to and make positive plate on a current collector, negative plate is made in negative electrode active material (C+Zn) and conductive agent adhesion on a current collector；Positive/negative plate and barrier film are assembled into shell, inject electrolyte, and hybrid energy-storing device is made in encapsulation。
In existing Zinc ion battery, zinc ion is deintercalation between both positive and negative polarity, carries out energy storage by the redox reaction occurred, and energy density is higher, but power density is relatively low。In existing double layer capacitor (EDLC), both positive and negative polarity is the activated carbon symmetrical structure as active substance, carries out energy storage by the gathering of electric double layer electric charge and diffusion, has very high power density, but energy density performance simultaneously is very low。
As it was previously stated, in the present invention, having the hybrid energy-storing device of Zinc ion battery and ultracapacitor concurrently, namely positive active material is the metal composite oxide ZnM that can carry out zinc ion deintercalationxOyMaterial and Carbon Materials。Negative electrode active material is zinc and Carbon Materials, and in charge and discharge process, the embedding of ion deviates from that the physics aggregation and spreading of electrochemical reaction and electric charge is collaborative to carry out, and the big specific surface area of Carbon Materials or pore structure are that ion provides storage and reaction channel。Corresponding with it, electrolyte solution is zinc salt solution。
Below, the staple of the hybrid energy-storing device constituting the present invention is illustrated。
Mixed structure as the present invention, it is possible to suitably changed power and the energy response of hybrid super capacitor device by the amount of the active substance of energy storage modes different in positive pole and negative pole。Metal composite oxide as the positive active material of the present invention, it is possible to be chemical formula ZnMxOy, M=Fe, Co, Mn, 0 < x < 3 here, x and y ratio is 1:1～1:4, it is preferred that ZnMn2O4, ZnFe2O4, ZnCo2O4Active substance as the positive pole zinc ion deintercalation of the present invention。Carbon Materials as the present invention, it is possible to be activated carbon, activated carbon fiber, expanded graphite, Graphene, CNT, charcoal-aero gel, nanometer door carbon, Carbon foam, carbonaceous mesophase spherules and skeleton carbon。
Positive pole can have multiple combination mode, ZnMn2O4/ activated carbon, ZnMn2O4/ activated carbon fiber, ZnMn2O4/ expanded graphite, ZnMn2O4/ Graphene, ZnMn2O4/ CNT, ZnMn2O4/ charcoal-aero gel, ZnMn2O4/ nanometer door carbon, ZnMn2O4/ Carbon foam, ZnMn2O4/ skeleton carbon, ZnMn2O4/ activated carbon/activated carbon fiber, ZnMn2O4/ activated carbon/Graphene, ZnMn2O4/ active carbon/carbon, ZnMn2O4/ activated carbon/expanded graphite；ZnFe2O4/ activated carbon, ZnFe2O4/ activated carbon fiber, ZnFe2O4/ expanded graphite, ZnFe2O4/ Graphene, ZnFe2O4/ CNT, ZnFe2O4/ charcoal-aero gel, ZnFe2O4/ nanometer door carbon, ZnFe2O4/ Carbon foam, ZnFe2O4/ skeleton carbon, ZnFe2O4/ activated carbon/activated carbon fiber, ZnFe2O4/ activated carbon/Graphene, ZnFe2O4/ active carbon/carbon, ZnFe2O4/ activated carbon/expanded graphite；ZnCo2O4/ activated carbon, ZnCo2O4/ activated carbon fiber, ZnCo2O4/ expanded graphite, ZnCo2O4/ Graphene, ZnCo2O4/ CNT, ZnCo2O4/ charcoal-aero gel, ZnCo2O4/ nanometer door carbon, ZnCo2O4/ Carbon foam, ZnCo2O4/ skeleton carbon, ZnCo2O4/ activated carbon/activated carbon fiber, ZnCo2O4/ activated carbon/Graphene, ZnCo2O4/ active carbon/carbon, ZnCo2O4/ activated carbon/expanded graphite。
Corresponding with it, negative pole can have multiple combination mode, Zn/ activated carbon, Zn/ activated carbon fiber, Zn/ expanded graphite, Zn/ Graphene, Zn/ CNT, Zn/ MCMB, Zn/ charcoal-aero gel, Zn/ nanometer of door carbon, Zn/ Carbon foam, Zn/ skeleton carbon, Zn/ activated carbon/activated carbon fiber, Zn/ activated carbon/Graphene, Zn/ active carbon/carbon, Zn/ activated carbon/expanded graphite, Zn/ activated carbon fiber/expanded graphite, Zn/ activated carbon fiber/Graphene。
In the present invention, barrier film is the porous polymer membrane with ion diffusion, it is possible to be polyethylene diagrams, polypropylene diaphragm, polyethylene and polypropylene composite materials barrier film, cellulosic separator。Additionally, in the present invention, both positive and negative polarity is adhered to by active substance and conductive agent respectively and makes on a current collector。The method being typically prepared battery pole piece can be used to be uniformly dispersed in a solvent make slurry with conductive agent and binding agent by active substance, and coating prepares on a current collector。Conductive agent can be carbon nano-fiber, Graphene, conductive carbon black, CNT, and binding agent can be Kynoar, politef, cellulose, butadiene-styrene rubber, and collector can make titanium foil, titanizing fiber cloth, steel foil, titanium metal net, steel wire netting；Described binding agent is a kind of in politef, butadiene-styrene rubber, hydroxymethyl cellulose or their combination；Described barrier film is the one in polyethylene, polypropylene, fibreglass diaphragm。
Below by the drawings and specific embodiments, the present invention being specifically described, accompanying drawing 1～3 is the illustration to the preferred embodiment of the present invention。
Embodiment 1
Manganese carbonate, citric acid and zinc carbonate is weighed than 1:6:6 according to amount of substance。Manganese carbonate and citric acid by magnetic agitation mix homogeneously, are warming up to 60 DEG C in water, isothermal reaction 30min, add zinc carbonate, continue stirring 2h, are cooled to room temperature, are precipitated by the product of gained and filter, and deionized water is cleaned, and 60 DEG C of vacuum dryings are to constant weight；The product 700 DEG C calcining 2h that will obtain, obtains zinc-manganese oxygen metal composite oxide ZnMn2O4。
Positive active material (ZnMn is weighed according to mass ratio 70:20:102O4With quality of activated carbon than for 40:60), VGCF, PTFE make electrode film, be pressed on the stainless (steel) wire disk that diameter is 16mm, after drying as anode pole piece；Negative electrode active material (zinc and quality of activated carbon than for 40:60), VGCF, PTFE is weighed according to mass ratio 80:10:10, deionization/ethanol water makes slurry, rolls film, be pressed on the stainless (steel) wire disk that diameter is 16mm, dried as negative plate, positive/negative plate mass ratio is 1:1.5。
Positive plate, barrier film, negative plate are sequentially overlapped, are put in button shell, add 1M zinc sulfate solution, make hybrid electrochemical capacitor。
Embodiment 2
The iron sesquioxide and the zinc oxide that the amount of substance such as weigh put into ball grinder, and material and ball mass ratio are 1:20, and ball milling 3h obtains composite material precursor。Presoma calcines 2h at 700 DEG C, obtains zinc-iron oxygen metal composite oxide ZnFe2O4。
Positive active material (ZnFe is weighed according to mass ratio 70:20:102O4With quality of activated carbon ratio for 40:60), VGCF, PTFE make the slurry that solid content is 60% in deionized water, 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 anode pole piece；Negative electrode active material (zinc and carbon nanotube mass than for 60:40), VGCF, PTFE is weighed according to mass ratio 80:10:10, make slurry in deionized water, be coated in activated carbon fiber cloth without titanium coating one side on, cut the disk that diameter is 16mm, dry, roll-in is as negative plate, and positive/negative plate mass ratio is 1:1.5。
Positive plate, barrier film, negative plate are sequentially overlapped, are put in button shell, add 1M zinc sulfate solution, make hybrid electrochemical capacitor。
Embodiment 3
Weigh zinc nitrate according to mass ratio 1:2, aqueous solution made by cobalt nitrate, after nitrogen atmosphere stirring 1h, adds sodium hydroxide, controls response time 3min。Product washs, dry, the presoma obtained 600 DEG C calcining 1h, obtains zinc cobalt metal composite oxide ZnCo2O4。
Positive active material (ZnCo is weighed than 70:20:10 according to quality (g)2O4With quality of activated carbon ratio for 40:60), VGCF, PTFE, make the slurry that solid content is 50% in deionized water, be coated on stainless (steel) wire, dry, roll-in, cut disk that diameter is 16mm as anode pole piece；Negative electrode active material (zinc and Graphene mass ratio are 70:30), VGCF, PTFE is weighed according to mass ratio 75:15:10, make the slurry that solid content is 60% in deionized water, it is coated on stainless (steel) wire, dry, roll-in, cutting disk that diameter is 16mm as negative plate, positive/negative plate mass ratio is 1:1.2。
Positive plate, barrier film, negative plate are sequentially overlapped, are put in button shell, add 1M solder(ing)acid, make hybrid electrochemical capacitor。
Embodiment 4
Polyvinylpyrrolidone, manganese acetate and zinc acetate is weighed according to mass flow ratio 10:1:1, being uniformly mixed in ethanol, electrostatic spinning obtains presoma, the 100 DEG C of constant temperature 5h of presoma that will obtain, 700 DEG C of calcining 5h, obtain threadiness zinc-manganese oxygen metal composite oxide ZnMn2O4。
Positive active material (ZnMn is weighed according to mass ratio 70:20:102O4Be 40:60 with Graphene mass ratio), VGCF, PTFE make electrode film, be pressed on the stainless (steel) wire disk that diameter is 16mm, after drying as anode pole piece；Negative electrode active material (mass ratio of zinc, expanded graphite and activated carbon fiber is 40:10:50), VGCF, PTFE is weighed according to mass ratio 80:10:10, deionization/ethanol water makes slurry, roll film, it is pressed on the stainless (steel) wire disk that diameter is 16mm, dried as negative plate, positive/negative plate mass ratio is 1:1.5。
Positive plate, barrier film, negative plate are sequentially overlapped, are put in button shell, add 1M zinc nitrate aqueous solution, make hybrid electrochemical capacitor。
Embodiment 5
Weigh manganese sulfate, zinc nitrate, ammonium sulfate and ammonium hydrogen carbonate according to amount of substance than 1:2:35:35 to be uniformly mixed in water, add 25ml ethanol stirring 2h, 60 DEG C of constant temperature 8h, the product washing that will obtain, 80 DEG C are dried to constant weight, 600 DEG C of calcining 5h, obtain spherical zinc-manganese oxygen metal composite oxide ZnMn2O4。
Positive active material (ZnMn is weighed according to mass ratio 70:20:102O4Be 40:60 with charcoal-aero gel mass ratio), VGCF, PTFE make electrode film, be pressed on the stainless (steel) wire disk that diameter is 16mm, after drying as anode pole piece；Negative electrode active material (mass ratio of zinc, Graphene and activated carbon fiber is 40:10:50), VGCF, PTFE is weighed according to mass ratio 80:10:10, deionization/ethanol water makes slurry, roll film, it is pressed on the stainless (steel) wire disk that diameter is 16mm, dried as negative plate, positive/negative plate mass ratio is 1:1.5。
Positive plate, barrier film, negative plate are sequentially overlapped, are put in button shell, add 1M zinc sulfate solution, make hybrid electrochemical capacitor。
Described embodiment is the specific descriptions of the claim to the present invention, and claim includes but not limited to described embodiment content。
Claims (3)
1. the hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently, including core body, electrolyte and housing, core body is by positive pole, negative pole and is placed in barrier film therebetween and forms, it is characterized in that, positive active material has two kinds, the first positive active material is material with carbon element C, and the second positive active material is metal composite oxide ZnMxOyNamely < ratio of x < 3, x and y is 1:1～1:4, and negative electrode active material has two kinds, and the first negative electrode active material is zinc Zn, and the second active substance is material with carbon element C, and electrolyte is made up of zinc salt and deionized water for M=Fe, Co, Mn, 0。
2. a kind of hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently according to claim 1, is characterized in that positive active material C+ZnMxOyAdhering to conductive agent and make positive plate on a current collector, negative electrode active material C+Zn and conductive agent adhere to makes negative plate on a current collector；Positive plate, barrier film and negative plate stacking or winding are assembled into shell, inject electrolyte, and hybrid energy-storing device is made in encapsulation。
3. a kind of hybrid energy-storing device having Zinc ion battery and ultracapacitor concurrently according to claim 1, is characterized in that described metal composite oxide is shaped as spherical, bar-shaped, flower-shaped, needle-like and cellular；Material with carbon element is a kind of of activated carbon, graphite, Graphene, CNT, charcoal-aero gel, nanometer door carbon, Carbon foam, carbonaceous mesophase spherules and skeleton carbon or their combination。
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