CN106847525A - A kind of asymmetric MnO of water system2/FeWO4Ultracapacitor and preparation method thereof - Google Patents
A kind of asymmetric MnO of water system2/FeWO4Ultracapacitor and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910005507 FeWO4 Inorganic materials 0.000 claims abstract description 47
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 239000006258 conductive agent Substances 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 239000011258 core-shell material Substances 0.000 claims abstract description 11
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 10
- 239000007773 negative electrode material Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000000758 substrate Substances 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 239000002070 nanowire Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002057 nanoflower Substances 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 13
- 239000007772 electrode material Substances 0.000 abstract description 10
- 230000004087 circulation Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 description 14
- 238000004146 energy storage Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of asymmetric type supercapacitor, and in particular to a kind of asymmetric MnO of water system2/FeWO4Ultracapacitor, belongs to supercapacitor technologies field.It includes positive pole, negative pole, aqueous electrolyte and barrier film, and the positive electrode material is MnO2, negative electrode material is FeWO4.And open its preparation method：By positive electrode active materials MnO2Or negative active core-shell material FeWO4Anode electrode and negative electrode are respectively prepared with binding agent and conductive agent；The assembling mode of both positive and negative polarity electrode, barrier film press-button type battery is assembled, aqueous electrolyte is added, the ultracapacitor of button is fabricated to.The ultracapacitor is with different materials MnO2With FeWO4Respectively as both positive and negative polarity electrode material, the effect between different materials is made full use of, and using environment-friendly aqueous solvent as electrolyte, expand potential window, there is preferable stable circulation performance while high-quality energy density is ensured.
Description
Technical field
The present invention relates to a kind of asymmetric type supercapacitor, and in particular to a kind of asymmetric MnO of water system2/FeWO4It is super
Capacitor and preparation method thereof, belongs to supercapacitor technologies field.
Background technology
Ultracapacitor has the double dominant of battery and traditional capacitor concurrently, with appearance as a kind of new type of energy storage device
Amount is big (being more than 10000 times of ordinary capacitor), and long lifespan is non-maintaining, and temperature range is (- 20 DEG C~55 DEG C) wide, can short circuit
The features such as super high power discharge and recharge；Have extremely wide in fields such as energy storage type trolleybus, intelligent grid, renewable energy power generations
General application.Using positive and negative pole material energy storage mechnism as differentiation, ultracapacitor can be divided into symmetric form and asymmetric two kinds, its
Middle positive and negative pole material energy storage mechnism it is same or like be symmetric form, otherwise positive and negative pole material energy storage mechnism it is different then for non-right
Title type.Carbon/carbon the double layer capacitor of large-scale application is exactly the representative of symmetric form ultracapacitor, its both positive and negative polarity electricity at present
Pole material is carbon material, belongs to electric double layer capacitance energy storage mechanism.Because both positive and negative polarity electrode material is consistent, so actually should
All it is greatly limited with aspect either energy density or potential window.And in asymmetric type supercapacitor,
There is a pole or two in general positive and negative electrode extremely with the fake capacitance electrode material compared with high-energy-density, because both positive and negative polarity oxidation is gone back
, to difference, so the device potential window of composition is wider, relative energy density is also higher for former electricity.Therefore design has asymmetric
The ultracapacitor of structure is the trend of current development.
Mainly there are carbon material, transition metal oxide, conducting polymer etc. currently used for the electrode material of ultracapacitor.
First, carbon material is often used as electric double layer capacitance electrode material because specific surface area is big, good chemical stability, but
Energy density is low, its range of application is limited by high degree.Conducting polymer has high-energy-density, high-specific-power and right
The features such as environmental nonpollution, but the heat endurance of the conducting polymer materials developed at present is poor, and cycle performance is also to be improved,
Therefore it moves towards practical and also needs to further further investigation.And transition metal oxide is conducted electricity very well due to it, and energy storage
Density is more than 10-100 times of double layer capacitor, the focus as Recent study.RuO2It is the specific capacitance of current report
Highest metal oxide electrode material, can reach 768F g-1, but RuO2Because cost is too high, environmental pollution is easily caused, so
Extensively using difficult.Therefore NiO, Co3O4、MnO2Become RuO etc. cheap transition metal oxide system2Replacer.Wherein
NiO and Co3O4Because its potential window relative narrower (in water system electrolyte, NiO/Co3O4:0.4-0.5V, MnO2：0.9-
1.0V), so its energy density is relatively low, practical application meaning is not high.And MnO2Due to with RuO2Similar properties,
Potential window is wide, and aboundresources, cheap, advantages of environment protection and turn into ideal super capacitor electrode material
Material.
One Chinese patent (publication number is obtained by retrieval：CN103366970B), its one kind is based on MnO2With Fe2O3Receive
Flexible asymmetric super-capacitor of rice structure and its preparation method and application.Preparation method is comprised the following steps：Prepare MnO2
Nanowire positive electrode and Fe2O3Nanotube negative pole, is then assembled into asymmetric super electricity by positive pole, negative pole and electrolyte and barrier film
Container.The complexity for making Asymmetric Supercapacitor is this method reduce, resulting ultracapacitor, energy density reaches
0.47mWh/cm3.The method is simple and easy to apply, can scale growth MnO2Nano wire and Fe2O3Simultaneously processability is excellent for nanotube
Asymmetric Supercapacitor.But this MnO2With Fe2O3The flexible asymmetric super-capacitor of nanostructured uses solid
State electrolyte, so power density ratio is relatively low, cyclical stability is poor；Especially its volume energy density is not high, and expensive,
Therefore Miniature Power Unit and self actuating system are only applicable to.
The content of the invention
The purpose of the present invention is directed to the above-mentioned problems in the prior art, there is provided one kind has high-quality energy density
With the ultracapacitor of good circulation stability.
In order to reach foregoing invention purpose, the present invention uses following technical scheme：A kind of asymmetric MnO of water system2/FeWO4It is super
Level capacitor, the ultracapacitor includes positive pole, negative pole, aqueous electrolyte and barrier film, and the positive electrode material is MnO2, bear
Pole electrode material is FeWO4。
Compared to other symmetric forms or asymmetric manganese dioxide based super capacitor, water system of the present invention is asymmetric
MnO2/FeWO4Ultracapacitor uses aqueous electrolyte, positive pole using rich reserves, it is cheap, environmentally friendly, have various
The MnO of the advantages of oxidation state and structure-rich2, negative pole is using the FeWO with the specific energy higher than carbon material4, FeWO4Though
Right specific capacity is relatively low, but potential window is relatively wide (0-0.8V), especially microstructure stabilization, therefore during the course of the reaction, its structure
Zero deformation, so its cycle performance is excellent.The present invention is exactly with the MnO of both different materials2With FeWO4Respectively as positive and negative
Pole electrode material is assembled into asymmetric type supercapacitor, makes full use of the effect between different materials, and using environment-friendly
Aqueous solvent expands potential window as electrolyte, improves specific capacity, and then improve power density, the quality of ultracapacitor
Energy density, cyclical stability, environmental protection and cheap, practicality is higher, can be widely applied to large-scale energy-storage system, uses
Drive or stand-by power supply.
Preferably, described MnO2It is spinelle shape.Its specific capacitance of the MnO2 of different crystal structure is of different sizes, increases
Rule is substantially：Pyrolusite (28F g-1)<Nickeliferous todorokite<Ramsdellite<Cryptomelane<Sodium manganese ore<Spinelle (241F
g-1).So from the MnO of spinelle shape2Specific capacity is of a relatively high, by the MnO of spinelle shape2With FeWO4It is assembled into asymmetric
Ultracapacitor, the high potential window with 0-1.4V in aqueous electrolyte, according to super capacitor energy formula E=1/
2CU2, improves voltage, and energy is also multiplied；And device cycle excellent performance.
Preferably, described aqueous electrolyte is aqueous solvent LiNO3、K2SO4、KCl、LiCl、Li2SO4、Na2SO4、
NaNO3、KNO3In one or more.The asymmetric MnO of the present invention2/FeWO4Electrolytic solution for super capacitor is aqueous solvent, not only
It is cheap and environment-friendly, make it have preferable application value.
Preferably, the barrier film is PP or PE.
Another object of the present invention is to provide a kind of above-mentioned asymmetric MnO of water system2/FeWO4The preparation side of ultracapacitor
Method, described preparation method comprises the following steps：
S1, by positive electrode active materials MnO2, binding agent, conductive agent be mixed and added into ethanol, second is made under the conditions of 50-70 DEG C
Alcohol is air-dried, and is first made thin rounded flakes, and be pressed in for this thin slice anode electrode is made in the substrate of Stainless steel mesh by repressurization；
S2, by negative active core-shell material FeWO4, binding agent, conductive agent be mixed and added into ethanol, make under the conditions of 50-70 DEG C
Ethanol is air-dried, and is first made thin rounded flakes, and repressurization is made negative electrode；
S3, the assembling mode assembling by both positive and negative polarity electrode, barrier film press-button type battery, add aqueous electrolyte, are fabricated to button
The ultracapacitor of formula.
In the asymmetric MnO of above-mentioned water system2/FeWO4In the preparation method of ultracapacitor, positive electrode active materials in step S1
MnO2Nano flower, binding agent, the mass ratio of conductive agent are 75-85:3-8:7-22, it is understood that be the mass percent of three
Respectively 75-85%, 3-8%, 7-22%.
In the asymmetric MnO of above-mentioned water system2/FeWO4In the preparation method of ultracapacitor, negative active core-shell material in step S2
MnO2Nano wire, binding agent, the mass ratio of conductive agent are 75-85:3-8:7-22, it is understood that be the mass percent of three
Respectively 75-85%, 3-8%, 7-22%.
In the asymmetric MnO of above-mentioned water system2/FeWO4In the preparation method of ultracapacitor, thin rounded flakes in step S1, S2
Thickness is 20-80 μm, and a diameter of 11.0-11.5mm, weight is 2.0-3.0g.If thin rounded flakes are too thin or weight too
It is small, easily cause disk surfaces and crack occur when button cell shell is assembled, in fact it could happen that the problems such as short-circuit；If fruit is circular thin
Piece is too thick or weight is too big, easily causes active material accumulation, and electrolyte can not preferably infiltrate pole piece, influence electrochemistry
The performance of performance.In addition, size is too small, it is easily mobile；It is too big, beyond shell sizes.
In the asymmetric MnO of above-mentioned water system2/FeWO4In the preparation method of ultracapacitor, the pressure in being pressurizeed in step S1, S2
Power is 700-1200MPa.Further preferably, described pressure is 800-1000MPa.Can be preferable in above-mentioned pressure limit
Disk is fixed on a current collector, if pressure is too small on ground, it is impossible to stabilization, scaling easily occurs；If pressure is too big, it may appear that collection
The phenomenon of fluid fracturing, meanwhile, disk is easily sticked on pressurizer acting surface, is difficult to remove.
Compared with prior art, ultracapacitor of the present invention is with different materials MnO2With FeWO4Respectively as both positive and negative polarity electrode
Material is assembled into asymmetric type supercapacitor, makes full use of the effect between different materials, and using environment-friendly aqueous molten
Agent expands potential window as electrolyte, has preferable stable circulation performance, water while high-quality energy density is ensured
It is asymmetric MnO2/FeWO4Ultracapacitor steady operation under the potential window of 0-1.4V, capacity declines after being circulated through 40000 times
Lapse rate is not higher than 1-5%, and when power density is 10kW/kg, corresponding mass energy density is 23.4Wh/kg, when power is close
Spend during for 500W/kg, corresponding mass energy density is 52.1Wh/kg, is applied to large-scale energy-storage system, as driving or standby
Power supply.
Brief description of the drawings
Fig. 1 is positive electrode active materials MnO in ultracapacitor of the present invention2Electron-microscope scanning figure.
Fig. 2 is negative active core-shell material FeWO in ultracapacitor of the present invention4Electron-microscope scanning figure.
Specific embodiment
It is described with reference to the drawings the following is specific embodiment of the invention, technical scheme is made further to retouch
State, but the present invention is not limited to these embodiments.
Embodiment 1
A kind of asymmetric MnO of water system2/FeWO4Ultracapacitor, described ultracapacitor includes positive pole, negative pole, aqueous
Electrolyte and barrier film, the positive electrode material are the MnO of spinelle shape2, MnO2Electron-microscope scanning figure it is as shown in Figure 1；Negative electricity
Pole material is FeWO4, FeWO4Electron-microscope scanning figure it is as shown in Figure 2；Aqueous electrolyte is aqueous solvent LiNO3, barrier film is PP.
And prepared by following method：
By positive electrode active materials MnO2, binding agent, conductive agent by mass percentage 80%:5%:15% is mixed and added into second
Alcohol, air-dries ethanol under the conditions of 60 DEG C, is first made thin rounded flakes, then this thin slice is pressed in into stainless steel under conditions of 900MPa
Anode electrode is made in the substrate of grid；
By negative active core-shell material FeWO4, binding agent, conductive agent by mass percentage 80%:5%:15% is mixed and added into
Ethanol, air-dries ethanol under the conditions of 60 DEG C, is first made thin rounded flakes, then is pressed in this thin slice under conditions of 900MPa stainless
Negative electrode is made in the substrate of steel lattice；
The assembling mode of both positive and negative polarity electrode, barrier film press-button type battery is assembled, aqueous electrolyte LiNO is added3, it is fabricated to
The ultracapacitor of button.The ultracapacitor carries out electro-chemical test under the potential window of 0-1.4V, through 40000 circulations
Capacity attenuation rate is 3.49% afterwards, and mass energy density reaches 52.1Wh/kg.
Embodiment 2
A kind of asymmetric MnO of water system2/FeWO4Ultracapacitor, described ultracapacitor includes positive pole, negative pole, aqueous
Electrolyte and barrier film, the positive electrode material are the MnO of spinelle shape2, negative electrode material is FeWO4, aqueous electrolyte is
Aqueous solvent K2SO4, barrier film is PE.
And prepared by following method：
By positive electrode active materials MnO2, binding agent, conductive agent by mass percentage 84%:6%:10% is mixed and added into second
Alcohol, air-dries ethanol under the conditions of 55 DEG C, is first made thin rounded flakes, then this thin slice is pressed in into stainless steel under conditions of 800MPa
Anode electrode is made in the substrate of grid；
By negative active core-shell material FeWO4, binding agent, conductive agent by mass percentage 84%:6%:10% is mixed and added into
Ethanol, air-dries ethanol under the conditions of 55 DEG C, is first made thin rounded flakes, then is pressed in this thin slice under conditions of 800MPa stainless
Negative electrode is made in the substrate of steel lattice；
The assembling mode of both positive and negative polarity electrode, barrier film press-button type battery is assembled, aqueous electrolyte K is added2SO4, it is fabricated to button
The ultracapacitor of formula.The ultracapacitor carries out electro-chemical test under the potential window of 0-1.4V, after being circulated through 40000 times
Capacity attenuation rate is 4.17%, and mass energy density reaches 45.1Wh/kg.
Embodiment 3
A kind of asymmetric MnO of water system2/FeWO4Ultracapacitor, described ultracapacitor includes positive pole, negative pole, aqueous
Electrolyte and barrier film, the positive electrode material are the MnO of spinelle shape2, negative electrode material is FeWO4, aqueous electrolyte is
Aqueous solvent KCl, barrier film is PP.
And prepared by following method：
By positive electrode active materials MnO2, binding agent, conductive agent by mass percentage 78%:4%:18% is mixed and added into second
Alcohol, air-dries ethanol under the conditions of 65 DEG C, is first made thin rounded flakes, then is pressed in this thin slice under conditions of 1000MPa stainless
Anode electrode is made in the substrate of steel lattice；
By negative active core-shell material FeWO4, binding agent, conductive agent by mass percentage 78%:4%:18% is mixed and added into
Ethanol, air-dries ethanol under the conditions of 65 DEG C, is first made thin rounded flakes, then be pressed in not this thin slice under conditions of 1000MPa
Negative electrode is made in the substrate of steel lattice of becoming rusty；
The assembling mode of both positive and negative polarity electrode, barrier film press-button type battery is assembled, aqueous electrolyte KCl is added, button is fabricated to
The ultracapacitor of formula.The ultracapacitor carries out electro-chemical test under the potential window of 0-1.4V, after being circulated through 40000 times
Capacity attenuation rate is 4.89%, and mass energy density reaches 50.3Wh/kg.
Embodiment 4
A kind of asymmetric MnO of water system2/FeWO4Ultracapacitor, described ultracapacitor includes positive pole, negative pole, electrolysis
Liquid and barrier film, positive electrode material are MnO2, negative electrode material is FeWO4, aqueous electrolyte is aqueous solvent LiNO3, it is described
Barrier film is PP.
And prepared by following method：
By positive electrode active materials MnO2, binding agent, conductive agent by mass percentage 85%:3%:12% is mixed and added into second
Alcohol, air-dries ethanol under the conditions of 50 DEG C, is first made thin rounded flakes, then is pressed in this thin slice under conditions of 1200MPa stainless
Anode electrode is made in the substrate of steel lattice；
By negative active core-shell material FeWO4, binding agent, conductive agent by mass percentage 85%:3%:12% is mixed and added into
Ethanol, air-dries ethanol under the conditions of 50 DEG C, is first made thin rounded flakes, then be pressed in not this thin slice under conditions of 1200MPa
Negative electrode is made in the substrate of steel lattice of becoming rusty；
The assembling mode of both positive and negative polarity electrode, barrier film press-button type battery is assembled, aqueous electrolyte LiNO is added3, it is fabricated to
The ultracapacitor of button.The ultracapacitor carries out electro-chemical test under the potential window of 0-1.4V, through 40000 circulations
Capacity attenuation rate is 3.95% afterwards, and mass energy density reaches 49.6Wh/kg.
Embodiment 5
A kind of asymmetric MnO of water system2/FeWO4Ultracapacitor, described ultracapacitor includes positive pole, negative pole, electrolysis
Liquid and barrier film, positive electrode material are the MnO of spinelle shape2, negative electrode material is FeWO4, aqueous electrolyte is aqueous solvent
LiCl, barrier film is PE.
And prepared by following method：
By positive electrode active materials MnO2, binding agent, conductive agent by mass percentage 75%:8%:7% is mixed and added into second
Alcohol, air-dries ethanol under the conditions of 70 DEG C, is first made thin rounded flakes, then this thin slice is pressed in into stainless steel under conditions of 700MPa
Anode electrode is made in the substrate of grid；
By negative active core-shell material FeWO4, binding agent, conductive agent by mass percentage 75%:8%:7% is mixed and added into second
Alcohol, air-dries ethanol under the conditions of 70 DEG C, is first made thin rounded flakes, then this thin slice is pressed in into stainless steel under conditions of 700MPa
Negative electrode is made in the substrate of grid；
The assembling mode of both positive and negative polarity electrode, barrier film press-button type battery is assembled, aqueous electrolyte LiCl is added, button is fabricated to
The ultracapacitor of formula.The ultracapacitor carries out electro-chemical test under the potential window of 0-1.4V, after being circulated through 40000 times
Capacity attenuation rate is 4.52%, and mass energy density reaches 46.7Wh/kg.
In the above-described embodiments, described binding agent is binding agent common in capacitor, such as PVDF, PTFE, PVA, CMC
Deng described conductive agent is conductive agent common in capacitor, such as ECP, ECP-600JD, CNT, VGCF, SP-Li, is being prepared
The thickness of thin rounded flakes is 20-80 μm in positive pole negative electrode, and a diameter of 11.0-11.5mm, weight is 2.0-3.0g.
In addition, claimed technical scope midrange non-limit part and in embodiment technical scheme it is right
The new technical scheme that the equal replacement of single or multiple technical characteristics is formed, equally all in claimed model
In enclosing；Simultaneously the present invention program it is all enumerate or unrequited embodiment in, parameters in the same embodiment are only
Represent an example (i.e. a kind of feasible scheme) of its technical scheme.
Specific embodiment described herein is only to the spiritual explanation for example of the present invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications or supplement to described specific embodiment or be substituted using similar mode, but simultaneously
Do not deviate by spirit of the invention or surmount scope defined in appended claims.
It is skilled to this area although having made a detailed description and being cited some specific embodiments to the present invention
For technical staff, as long as it is obvious that can be made various changes without departing from the spirit and scope of the present invention or corrected.
Claims (9)
1. the asymmetric MnO of a kind of water system2/FeWO4Ultracapacitor, it is characterised in that described ultracapacitor include positive pole,
Negative pole, aqueous electrolyte and barrier film, the positive electrode material are MnO2, negative electrode material is FeWO4。
2. the asymmetric MnO of water system according to claim 12/FeWO4Ultracapacitor, it is characterised in that described MnO2
It is spinelle shape.
3. the asymmetric MnO of water system according to claim 12/FeWO4Ultracapacitor, it is characterised in that the aqueous electricity
Solution liquid is aqueous solvent LiNO3、K2SO4、KCl、LiCl、Li2SO4、Na2SO4、NaNO3、KNO3In one or more.
4. the asymmetric MnO of a kind of water system2/FeWO4The preparation method of ultracapacitor, it is characterised in that described preparation method bag
Include following steps：
S1, by positive electrode active materials MnO2, binding agent, conductive agent be mixed and added into ethanol, eth oxy is made under the conditions of 50-70 DEG C
It is dry, thin rounded flakes are first made, be pressed in for this thin slice anode electrode be made in the substrate of Stainless steel mesh by repressurization；
S2, by negative active core-shell material FeWO4, binding agent, conductive agent be mixed and added into ethanol, eth oxy is made under the conditions of 50-70 DEG C
It is dry, thin rounded flakes are first made, repressurization is made negative electrode；
S3, the assembling mode assembling by both positive and negative polarity electrode, barrier film press-button type battery, add aqueous electrolyte, are fabricated to button
Ultracapacitor.
5. the asymmetric MnO of water system according to claim 42/FeWO4The preparation method of ultracapacitor, it is characterised in that
Positive electrode active materials MnO in step S12Nano flower, binding agent, the mass ratio of conductive agent are 75-85:3-8:7-22.
6. the asymmetric MnO of water system according to claim 42/FeWO4The preparation method of ultracapacitor, it is characterised in that
Negative active core-shell material MnO in step S22Nano wire, binding agent, the mass ratio of conductive agent are 75-85:3-8:7-22.
7. the asymmetric MnO of water system according to claim 42/FeWO4The preparation method of ultracapacitor, it is characterised in that
The thickness of thin rounded flakes is 20-80 μm in step S1, S2, and a diameter of 11.0-11.5mm, weight is 2.0-3.0g.
8. the asymmetric MnO of water system according to claim 42/FeWO4The preparation method of ultracapacitor, it is characterised in that
Pressure in being pressurizeed in step S1, S2 is 700-1200MPa.
9. the asymmetric MnO of water system according to claim 82/FeWO4The preparation method of ultracapacitor, it is characterised in that
Described pressure is 800-1000MPa.
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