CN103545123A - Hybrid energy storage device with zinc ion battery and supercapacitor - Google Patents

Hybrid energy storage device with zinc ion battery and supercapacitor Download PDF

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CN103545123A
CN103545123A CN201310520835.5A CN201310520835A CN103545123A CN 103545123 A CN103545123 A CN 103545123A CN 201310520835 A CN201310520835 A CN 201310520835A CN 103545123 A CN103545123 A CN 103545123A
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carbon
zinc
active
ion battery
negative electrode
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CN201310520835.5A
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CN103545123B (en
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荣常如
韩金磊
陈书礼
张克金
魏晓川
王丹
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中国第一汽车股份有限公司
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a hybrid energy storage device with a zinc ion battery and a supercapacitor. The hybrid energy storage device with the zinc ion battery and the supercapacitor comprises a core body, an electrolyte and a shell body. The core body is composed of a positive electrode, a negative electrode and a separator between the positive electrode and the negative electrode. The positive electrode and the negative electrode are respectively formed by active substances, a conductive agent and a current collector, wherein the active substances and the conductive agent adhere to the current collector. The two positive electrode active materials are provided. The first positive electrode active material is a composite metal oxide, and the second positive electrode active material is a carbon material capable of conducting reversible adsorption of ions. The two negative electrode active materials are provided. The first negative electrode active material is zinc and the second negative electrode active material is a carbon material capable of conducting reversible adsorption of ions. The electrolyte is composed of zinc salt and deionized water. The composite metal oxide is simple in preparation technology and environmentally friendly.

Description

A kind of hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently
Technical field
The present invention relates to a kind of hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently, belong to battery and ultracapacitor technical 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 cell.Yet electrical source of power energy density at present used is lower, automobile continual mileage is short; Power density is less, and automobile starting, climbing and acceleration performance are poor; Bulking value is large, and inconvenience is installed; Useful life is short, can not be identical with car load; Cost is higher, and car load integrated cost is 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 have hindered the large-scale application of electrical source of power on energy-conservation and new-energy automobile.
In recent years, people develop new system battery on the one hand, promote original battery performance; On the other hand, power characteristic, the obvious electrokinetic cell inside/outside of energy response are mated to the use that combines, meet the instructions for use of energy-conservation and new-energy automobile.For example, lithium ion battery and ultracapacitor are formed to composite power source by external management system, power source as automobile, 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, has improved the power performance of automobile, has extended the useful life of battery; And inner combination, 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, make its feature that has two kinds of electrokinetic cells concurrently, realize the raising of power density, energy density, for example, by thering is the de-graphite material of lithium ion embedding, merge with the active carbon that forms electric double layer, make lithium-ion capacitor, by " whirlwind chair " transmission of lithium ion, carry out energy storage.
Similar with lithium ion battery, recently to occur Zinc ion battery, as a kind of novel rechargeable secondary cell, also has " whirlwind chair " formula energy storage feature.During charging, zinc ion is deviate from from positive pole, through electrolyte, at negative pole, deposits; During 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:
xZn 2+?+?2 xe ?+?MnO 2?1?Zn? x MnO 2
Zn?1?Zn 2+?+?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 has been reported Zinc ion battery and preparation method thereof.The development of Zinc ion battery, for the development of ultracapacitor provides new binding site.
Ultracapacitor is a kind of energy storage device between battery and common electric capacity, according to energy storage mechanism, can be divided into double electric layer capacitor and electrochemical capacitor, double electric 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.By current existing battery material and active 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 successfully for automobile dynamic system, for the fast development of battery and super capacitor mixed energy storage device is laid a good foundation.The JM Energy 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 US2009/0197171 A1 of Japanese fuji heavy industry Co., Ltd., US2010/0142121 A1, US2010/0128415 A1, US7, 733, 629 B2, 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 aspect hybrid electrochemical capacitor, and ultracapacitor electric bus has appearred in urban, relies on website passenger getting on/off gap, completes charging, has realized the minimum pattern of comprehensive operation cost.
Electrode material, as the core of ultracapacitor, directly has influence on the performance of ultracapacitor.Material with carbon element is current most widely used ultracapacitor active material, General Requirements: 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; Guarantee the circulation of electrolyte in duct; Good wetability; Be conducive to form solution electrode interface; Minimum ohmic internal resistance; Be easy to processing.But because material with carbon element mainly relies on the adsorpting aggregation ion energy storage of porous material, energy density is lower.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.Composite metal oxide is two kinds and the above metal-doped energy storage material being compounded to form, as ZnCo 2o 4, ZnMn 2o 4, ZnFe 2o 4deng reacting with lithium, be applied to lithium ion battery.After electric discharge first, there is Zn in composite metal oxide 0, Mn 0deng conversion.The metal and the Li that generate 2there is reversible reaction (Nano Research, 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).And adopt composite metal oxide and Carbon Materials to form positive active material, and zinc and active carbon form negative electrode active material, and the hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently of combination have not been reported.
Summary of the invention
The object of the present invention is to provide a kind of hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently, composite metal oxide preparation technology used is simple, environmental friendliness.
Technical scheme of the present invention is achieved in that a kind of hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently, comprise core body, electrolyte and housing, core body is comprised of positive pole, negative pole, the barrier film that is placed between the two, 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 composite metal oxide ZnM xo y(M=Fe, Co, Mn, 0 < x < 3, x and y ratio are 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 comprised of zinc salt and deionized water; Positive active material (C+ZnM xo y) and conductive agent stick to and on collector, make positive plate, negative electrode active material (C+Zn) and conductive agent stick to and on collector, make negative plate; Positive/negative plate and barrier film are assembled into shell, inject electrolyte, and hybrid energy-storing device is made in encapsulation.
Described composite metal oxide is shaped as irregular graininess, the microspheroidal, hollow spheres of rule, bar-shaped, flower-shaped, needle-like and cellular.Described Carbon Materials is a kind of in active carbon, activated carbon fiber, expanded graphite, graphite, Graphene, carbon nano-tube, 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 a kind of in zinc sulfate, zinc nitrate, zinc chloride.
Good effect of the present invention: a kind of hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently merges the material with electric double layer and redox energy storage feature in same device; Composite metal oxide preparation technology used is simple, environmental friendliness.
Accompanying drawing explanation
Fig. 1 is the zinc-manganese oxygen composite metal oxide XRD diffraction pattern of the embodiment of the present invention 1.
Fig. 2 is the zinc-manganese oxygen composite metal oxide SEM photo 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.
Embodiment
The hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently of the present invention, comprises core body, electrolyte and housing, and core body is comprised of positive pole, negative pole, the barrier film that is placed between the two.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 composite metal oxide ZnM xo y, 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 comprised of zinc salt and deionized water; Positive active material (C+ZnM xo y) and conductive agent stick to and on collector, make positive plate, negative electrode active material (C+Zn) and conductive agent stick to and on collector, make negative plate; 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 de-embedding between both positive and negative polarity, by the redox reaction occurring, carries out energy storage, and energy density is higher, but power density is relatively low.In existing double electric layer capacitor (EDLC), both positive and negative polarity be active carbon as the symmetrical structure of active material, by gathering and the diffusion of electric double layer electric charge, carry out energy storage, there is very high power density, but simultaneously energy density performance is very low.
As previously mentioned, in the present invention, have the hybrid energy-storing device of Zinc ion battery and ultracapacitor concurrently, positive active material is for carrying out the composite metal oxide ZnM of the de-embedding of zinc ion xo ymaterial and Carbon Materials.Negative electrode active material is zinc and Carbon Materials, and in charge and discharge process, collaborative the carrying out of physics aggregation and spreading of electrochemical reaction and electric charge deviate from the embedding of ion, and the large specific area of Carbon Materials or pore structure provide storage and reaction channel for ion.Corresponding with it, electrolyte solution is zinc salt solution.
Below, to forming the staple of hybrid energy-storing device of the present invention, describe.
As mixed structure of the present invention, can be by power and the energy response of the amount appropriate change hybrid super capacitor device of the active material of different energy storage modes in positive pole and negative pole.As the composite metal oxide of positive active material of the present invention, can be chemical formula ZnM xo y, M=Fe here, Co, Mn, 0 < x < 3, x and y ratio are 1:1~1:4, preferably ZnMn 2o 4, ZnFe 2o 4, ZnCo 2o 4active material as the de-embedding of anodal zinc ion of the present invention.As Carbon Materials of the present invention, can be active carbon, activated carbon fiber, expanded graphite, Graphene, carbon nano-tube, charcoal-aero gel, nanometer door carbon, Carbon foam, carbonaceous mesophase spherules and skeleton carbon.
Positive pole can have multiple combination mode, ZnMn 2o 4/ active carbon, ZnMn 2o 4/ activated carbon fiber, ZnMn 2o 4/ expanded graphite, ZnMn 2o 4/ Graphene, ZnMn 2o 4/ carbon nano-tube, ZnMn 2o 4/ charcoal-aero gel, ZnMn 2o 4/ nanometer door carbon, ZnMn 2o 4/ Carbon foam, ZnMn 2o 4/ skeleton carbon, ZnMn 2o 4/ active carbon/activated carbon fiber, ZnMn 2o 4/ active carbon/Graphene, ZnMn 2o 4/ active carbon/carbon nano-tube, ZnMn 2o 4/ active carbon/expanded graphite; ZnFe 2o 4/ active carbon, ZnFe 2o 4/ activated carbon fiber, ZnFe 2o 4/ expanded graphite, ZnFe 2o 4/ Graphene, ZnFe 2o 4/ carbon nano-tube, ZnFe 2o 4/ charcoal-aero gel, ZnFe 2o 4/ nanometer door carbon, ZnFe 2o 4/ Carbon foam, ZnFe 2o 4/ skeleton carbon, ZnFe 2o 4/ active carbon/activated carbon fiber, ZnFe 2o 4/ active carbon/Graphene, ZnFe 2o 4/ active carbon/carbon nano-tube, ZnFe 2o 4/ active carbon/expanded graphite; ZnCo 2o 4/ active carbon, ZnCo 2o 4/ activated carbon fiber, ZnCo 2o 4/ expanded graphite, ZnCo 2o 4/ Graphene, ZnCo 2o 4/ carbon nano-tube, ZnCo 2o 4/ charcoal-aero gel, ZnCo 2o 4/ nanometer door carbon, ZnCo 2o 4/ Carbon foam, ZnCo 2o 4/ skeleton carbon, ZnCo 2o 4/ active carbon/activated carbon fiber, ZnCo 2o 4/ active carbon/Graphene, ZnCo 2o 4/ active carbon/carbon nano-tube, ZnCo 2o 4/ active carbon/expanded graphite.
Corresponding with it, negative pole can have multiple combination mode, Zn/ active carbon, Zn/ activated carbon fiber, Zn/ expanded graphite, Zn/ Graphene, Zn/ carbon nano-tube, Zn/ MCMB, Zn/ charcoal-aero gel, Zn/ nanometer door carbon, Zn/ Carbon foam, Zn/ skeleton carbon, Zn/ active carbon/activated carbon fiber, Zn/ active carbon/Graphene, Zn/ active carbon/carbon nano-tube, Zn/ active 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, 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, carbon nano-tube, binding agent can be Kynoar, polytetrafluoroethylene, 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 polytetrafluoroethylene, butadiene-styrene rubber, CMC or their combination; Described barrier film is a kind of in polyethylene, polypropylene, fibreglass diaphragm.
Below by the drawings and specific embodiments, the present invention is specifically described, accompanying drawing 1~3rd, to illustrating of the preferred embodiment of the present invention.
Embodiment 1
According to amount of substance, than 1:6:6, take manganese carbonate, citric acid and zinc carbonate.Manganese carbonate and citric acid mix by magnetic agitation in water, are warming up to 60 ℃, 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 ℃ of vacuumizes are to constant weight; By 700 ℃ of calcining 2h of the product obtaining, obtain zinc-manganese oxygen composite metal oxide ZnMn 2o 4.
According to mass ratio 70:20:10, take positive active material (ZnMn 2o 4with quality of activated carbon than for 40:60), VGCF, PTFE make electrode film, being pressed in diameter is on the stainless (steel) wire disk of 16mm, dry after as anode pole piece; According to mass ratio 80:10:10, take negative electrode active material (zinc is 40:60 with quality of activated carbon ratio), VGCF, PTFE, in deionization/ethanol water, make slurry, roll film, being pressed in diameter is on the stainless (steel) wire disk of 16mm, after dry, as negative plate, positive/negative plate mass ratio is 1:1.5.
Positive plate, barrier film, negative plate are superposeed successively, be put in button shell, add 1M zinc sulfate solution, make hybrid electrochemical capacitor.
Embodiment 2
The di-iron trioxide and the zinc oxide that the amount of substance such as take are put into ball grinder, and material is 1:20 with ball mass ratio, and ball milling 3h, obtains composite material precursor.Presoma, at 700 ℃ of calcining 2h, obtains zinc-iron oxygen composite metal oxide ZnFe 2o 4.
According to mass ratio 70:20:10, take positive active material (ZnFe 2o 4with quality of activated carbon than for 40:60), in deionized water, to make solid content be 60% slurry for VGCF, PTFE, is coated in simultaneously go up without titanium coating of activated carbon fiber cloth, cuts the disk that diameter is 16mm, is dried, roll-in is as anode pole piece; According to mass ratio 80:10:10, take negative electrode active material (zinc and carbon nano-tube mass ratio are 60:40), VGCF, PTFE, in deionized water, 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 1:1.5.
Positive plate, barrier film, negative plate are superposeed successively, be put in button shell, add 1M zinc sulfate solution, make hybrid electrochemical 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, the 600 ℃ of calcining 1h of presoma that obtain, obtain zinc cobalt composite metal oxide ZnCo 2o 4.
According to quality (g), than 70:20:10, take positive active material (ZnCo 2o 4with quality of activated carbon than for 40:60), VGCF, PTFE, in deionized water, make solid content and be 50% slurry, be coated on stainless (steel) wire, dry, roll-in, cuts diameter and is the disk of 16mm as anode pole piece; According to mass ratio 75:15:10, take negative electrode active material (zinc and Graphene mass ratio are 70:30), VGCF, PTFE, in deionized water, make solid content and be 60% slurry, be coated on stainless (steel) wire, dry, roll-in, cut diameter and be the disk of 16mm as negative plate, 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 electrochemical capacitor.
Embodiment 4
According to mass flow ratio 10:1:1, take polyvinylpyrrolidone, manganese acetate and zinc acetate, in ethanol, be uniformly mixed, electrostatic spinning obtains presoma, by 100 ℃ of constant temperature 5h of the presoma obtaining, 700 ℃ of calcining 5h, obtain fibrous zinc-manganese oxygen composite metal oxide ZnMn 2o 4.
According to mass ratio 70:20:10, take positive active material (ZnMn 2o 4with Graphene mass ratio be 40:60), VGCF, PTFE make electrode film, being pressed in diameter is on the stainless (steel) wire disk of 16mm, dry after as anode pole piece; According to mass ratio 80:10:10, take negative electrode active material (mass ratio of zinc, expanded graphite and activated carbon fiber is 40:10:50), VGCF, PTFE, in deionization/ethanol water, make slurry, roll film, being pressed in diameter is on the stainless (steel) wire disk of 16mm, after dry, as negative plate, positive/negative plate mass ratio is 1:1.5.
Positive plate, barrier film, negative plate are superposeed successively, be put in button shell, add 1M zinc nitrate aqueous solution, make hybrid electrochemical capacitor.
Embodiment 5
According to amount of substance, than 1:2:35:35, take manganese sulfate, zinc nitrate, ammonium sulfate and carbonic hydroammonium is uniformly mixed in water, add 25ml ethanol to stir 2h, 60 ℃ of constant temperature 8h, by the product washing obtaining, 80 ℃ are dried to constant weight, 600 ℃ of calcining 5h, obtain spherical zinc-manganese oxygen composite metal oxide ZnMn 2o 4.
According to mass ratio 70:20:10, take positive active material (ZnMn 2o 4with charcoal-aero gel mass ratio be 40:60), VGCF, PTFE make electrode film, being pressed in diameter is on the stainless (steel) wire disk of 16mm, dry after as anode pole piece; According to mass ratio 80:10:10, take negative electrode active material (mass ratio of zinc, Graphene and activated carbon fiber is 40:10:50), VGCF, PTFE, in deionization/ethanol water, make slurry, roll film, being pressed in diameter is on the stainless (steel) wire disk of 16mm, after dry, as negative plate, positive/negative plate mass ratio is 1:1.5.
Positive plate, barrier film, negative plate are superposeed successively, be put in button shell, add 1M zinc sulfate solution, make hybrid electrochemical capacitor.
Described embodiment is the specific descriptions to claim of the present invention just, and claim includes but not limited to described embodiment content.

Claims (5)

1. a hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently, comprise core body, electrolyte and housing, core body is comprised of anodal, negative pole and the barrier film that is placed between the two, 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 composite metal oxide ZnM xo y(M=Fe, Co, Mn, 0 < x < 3, x and y ratio are 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 comprised of zinc salt and deionized water.
2. a kind of hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently according to claim 1, is characterized in that positive active material (C+ZnM xo y) and conductive agent stick to and on collector, make positive plate, negative electrode active material (C+Zn) and conductive agent stick to and on collector, make negative plate; Positive plate, barrier film and negative plate are stacked or reel and to be assembled into shell, inject electrolyte, and hybrid energy-storing device is made in encapsulation.
3. a kind of hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently according to claim 1, it is characterized in that described composite metal oxide is shaped as irregular graininess, the microspheroidal of rule, hollow spheres, bar-shaped, flower-shaped, needle-like and cellular.
4. a kind of hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently according to claim 1, is characterized in that described material with carbon element is a kind of in active carbon, activated carbon fiber, expanded graphite, graphite, Graphene, carbon nano-tube, charcoal-aero gel, nanometer door carbon, Carbon foam, carbonaceous mesophase spherules and skeleton carbon or their combination.
5. a kind of hybrid energy-storing device that has Zinc ion battery and ultracapacitor concurrently according to claim 1, is characterized in that zinc salt in described electrolyte is a kind of in zinc sulfate, zinc nitrate, zinc chloride.
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CN104272522A (en) * 2014-03-04 2015-01-07 清华大学深圳研究生院 Chargeable zinc ion battery
CN104882638A (en) * 2015-04-27 2015-09-02 云南蓝光矩阵科技有限公司 Graphite carbon fiber battery
CN104979550A (en) * 2015-06-17 2015-10-14 河南力源电池有限公司 Novel 3V lithium ion battery capable of cyclically charging and discharging and manufacturing process of novel 3V lithium ion battery
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CN110942919A (en) * 2019-12-18 2020-03-31 湖北大学 Water system zinc ion hybrid supercapacitor capable of being rapidly charged and discharged and preparation method thereof
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