CN109994322A - A kind of cell type supercapacitor and application thereof - Google Patents
A kind of cell type supercapacitor and application thereof Download PDFInfo
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- CN109994322A CN109994322A CN201910239334.7A CN201910239334A CN109994322A CN 109994322 A CN109994322 A CN 109994322A CN 201910239334 A CN201910239334 A CN 201910239334A CN 109994322 A CN109994322 A CN 109994322A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of cell type supercapacitors and application thereof, it includes anode, cathode, the diaphragm being set between anode and cathode and electrolyte or electrolyte, wherein, positive active material is Mn oxide, negative electrode active material is carbon material, includes zinc ion in electrolyte or gel electrolyte；Contain zinc ion at least one electrode in the anode and cathode.The problems such as positive and negative electrode current potential mismatches, internal resistance is big, coulombic efficiency is low and cycle life is poor can be efficiently solved, to obtain the cell type supercapacitor that at low cost, operating voltage is high, capacity is high, can be quickly charged and discharged and has extended cycle life.
Description
Technical field
The invention belongs to electrochemical energy storing device fields, are related to a kind of cell type supercapacitor, and in particular to Yi Zhong electricity
Pond type supercapacitor and application thereof.
Background technique
In field of batteries, the importance of cost and security performance is increasingly prominent, and then aqueous electrolyte replacement mainstream is organic
Electrolyte becomes the focus of people's research.Currently, the solution containing zinc ion is used for rechargeable battery although having been reported, it is existing
Some Zinc ion battery cycle life is equal less than 500 times.Meanwhile in cyclic process, the shape of zinc metal sheet cathode dendrite easy to form
At negative electrode volume expansion can be caused, while being had and being punctured the risk that diaphragm causes battery short circuit.
Supercapacitor is a kind of new type of energy storage device between battery and conventional electrostatic capacitor.With battery phase
There is bigger specific power (10 times or more) than, supercapacitor, and have that abrupt release ultrahigh current, the charging time is short, fills
The characteristic that discharging efficiency is high, has extended cycle life, but its energy density is far below battery.Patent document CN 103560019B is adopted
With metal composite oxide (two kinds or more the metal-doped energy storage materials being compounded to form, such as ZnCo2O4、ZnMn2O4、
ZnFe2O4) it is positive electrode active materials, zinc and carbon material form negative electrode active material, prepare a kind of zinc ion hybrid capacitor
Device.However, the hybrid super capacitor pressure drop is very big (> 0.4 V), and high-temperature calcination is needed to prepare ZnCo2O4、ZnMn2O4、
ZnFe2O4Equal metal composite oxides are as a positive electrode active material, and complex process, at high cost.Simultaneously as metallic zinc exists
Zinc dendrite problem in cathode, high-power charge and discharge process still has.107910195 A of patent document CN uses carbon materials
Material is positive active material, and zinc metal sheet or zinc foil are negative electrode material, prepares a kind of Zinc ion battery type supercapacitor, but zinc metal sheet
Dendrite problems caused by cathode and its security risk still remain.
Summary of the invention
To improve above-mentioned technical problem, the present invention provides a kind of cell type supercapacitor comprising anode, is set cathode
It is disposed between the positive electrode and the negative electrode diaphragm and electrolyte or gel electrolyte, the positive active material is Mn oxide, is born
Pole active material is carbon material, contains zinc ion in electrolyte or gel electrolyte；At least one of the anode and cathode
Contain zinc ion in electrode.
According to the present invention, the mass fraction of zinc ion can be active matter in counter electrode in the positive and/or cathode
0.01~30wt% of matter, such as can be 1~25wt%, 10~20wt%；For example, the quality of zinc ion is divided in the anode
Number can be positive active material 1~20wt%, preferably 10~20wt%, as an example, it is described anode in zinc ion matter
Measure 1wt%, 5wt%, 10wt%, 15wt%, 20wt% that score can be positive active material；Zinc ion in the cathode
Mass fraction can be negative electrode active material 5~20wt%, preferably 10~20wt%, as an example, in the cathode zinc from
The mass fraction of son can be 5wt%, 10wt%, 20wt% of negative electrode active material.Wherein, make to contain in anode and/or cathode
The purpose of zinc ion is that the current potential between positive electrode and negative electrode is made to match, and makes the operating voltage range of cell type supercapacitor
It is big as far as possible with capacitor.
Such as make to contain in anode and/or cathode by carrying out electrochemical treatments in zinc salt to anode and/or cathode
Zinc ion.As example, using the positive or negative pole of cell type supercapacitor as working electrode, zinc is to electrode, by work electricity
Pole and electrode is placed in solution of zinc sulfate, in working electrode and to constant voltage is applied between electrode, makes the super electricity of cell type
Contain zinc ion in the positive or negative pole of container.
According to the present invention, contain zinc ion in the anode and/or cathode of the cell type supercapacitor.Preferably, institute
It states and is embedded in zinc ion in the lattice of positive active material；Preferably, the cathode (preferably negative electrode active material) adsorbs zinc ion.
According to the present invention, the Mn oxide can be selected from MnO2、Mn3O4、Mn2O3At least one of with MnO；The manganese
The crystal form of oxide is not particularly limited, and can be α, β, γ, δ and any one of unformed；Wherein, the Mn oxide
Source is not particularly limited.Illustratively, the Mn oxide can be selected from α-MnO2、α-Mn2O3、Mn3O4, MnO or unformed
MnO2。
According to the present invention, the carbon material can be selected from active carbon, activated carbon fibre, carbon aerogels, carbon nanotube, mesoporous
At least one of carbon, graphene, carbide derived carbon and nanometer door charcoal；Preferably active carbon, carbon aerogels, carbon nanotube and
At least one of graphene.
According to the present invention, the zinc ion in the electrolyte or in gel electrolyte is selected from zinc nitrate, zinc sulfate, chlorination
Zinc, trifluoracetic acid zinc, zine methqne-sulfonate, trifluoromethane sulfonic acid zinc, ethylsulfonic acid zinc, propyl sulfonic acid zinc, tetrafluoro boric acid zinc, benzene sulphur
At least one of sour zinc, zinc perchlorate；It is preferably selected from zinc sulfate and/or trifluoromethane sulfonic acid zinc.
Solvent in the electrolyte is selected from least one of water, organic solvent and ionic liquid；The organic solvent
Selected from least one of esters, sulfone class, ethers, nitrile, alkane and olefines organic solvent；The ionic liquid is selected from imidazoles
At least one of class, piperidines, pyroles, quaternary amines and amides ionic liquid.Preferably, the solvent is selected from water or second
Nitrile.
Preferably, in the electrolyte zinc ion concentration be 0.1~4mol/L, more preferably 1~2mol/L, such as
1mol/L,1.5mol/L,2mol/L,3mol/L,4mol/L.Preferably, also contain manganese in the electrolyte or gel electrolyte
Ion, the manganese ion come from least one of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride；The concentration of the manganese ion is
0.01~2mol/L, preferably 0.1~1mol/L, for example, 0.1mol/L, 0.2mol/L, 0.5mol/L.As an example, described
Electrolyte or gel electrolyte can be selected from zinc sulfate solution, trifluoromethane sulfonic acid zinc aqueous solution, trifluoromethane sulfonic acid zinc
At least one of acetonitrile solution and manganese sulfate solution.According to the present invention, the gel electrolyte is the gel containing zinc ion
State polymer, gel polymer can be selected from polyvinyl alcohol, polyethylene glycol oxide, agar, gelatin, one of sodium polyacrylate and xanthan
At least one of glue, preferably xanthan gum, polyvinyl alcohol or polyethylene glycol oxide.Wherein, the source of the zinc ion and concentration
With meaning as described above.Illustratively, the gel electrolyte can be selected from xanthan gum, polyvinyl alcohol and polyoxyethylene
The mixture of at least one of alkene and zinc sulfate.
According to the present invention, positive active material Mn oxide is different from the capacity density of carbon element, is
Keep the positive active material suitable with the capacity of negative electrode active material, the capacity of cell type supercapacitor is big as far as possible, described negative
The mass ratio of pole active material and positive active material can be (2~10): 1, it is therefore preferable to (4.5~6): 1, as an example,
Mass ratio can be 2:1,3:1,4:1,4.5:1,5:1,6:1,7:1,8:1,9:1,10:1.
According to the present invention, the diaphragm is not particularly limited, diaphragm known in the art can be used.For example, it is described every
Film can be selected from least one of porous polymer film, inorganic porous film, organic compound film and inorganic composite film；
Preferably at least one of filter paper, fibreglass diaphragm and polypropylene diaphragm.
According to the present invention, the anode further includes conductive agent, binder and plus plate current-collecting body；Specifically, it is described anode by
Positive active material, conductive agent and binder are adhered on plus plate current-collecting body and are made.Similarly, the cathode further includes conduction
Agent, binder and negative current collector；Specifically, the cathode is adhered to cathode by negative electrode active material, conductive agent and binder
It is made on collector.
Wherein, the conductive agent, binder, plus plate current-collecting body and negative current collector are not particularly limited, using ability
Domain known product.For example, the conductive agent can be conductive black (such as Super P), carbon nanotube, graphene and section
Qin is at least one of black；The binder can in Kynoar, polytetrafluoroethylene (PTFE), cellulose and butadiene-styrene rubber extremely
Few one kind；The plus plate current-collecting body and negative current collector can be in titanium foil, stainless steel foil, titanium net, stainless (steel) wire and graphite papers
At least one.
According to the present invention, specific capacity >=30mAh/g of the cell type supercapacitor, illustratively, the cell type
The specific capacity of supercapacitor be 30mAh/g, 36mAh/g, 40mAh/g, 41mAh/g, 45mAh/g, 48mAh/g, 50mAh/g,
53mAh/g,56mAh/g,60mAh/g.Preparation method according to the present invention, the cycle charge-discharge of the cell type supercapacitor
Number >=100 time, such as >=1000 times, >=2000 times, >=2500 times.
The present invention also provides the purposes of the cell type supercapacitor, are used for storage energy, such as store electric flux.
Beneficial effects of the present invention:
Cell type supercapacitor provided by the invention has both secondary cell high-energy density and capacitor high power density.
Contain zinc ion in the anode and/or cathode of the cell type supercapacitor, positive electrode and negative electrode current potential can be efficiently solved
Mismatch the problems such as mismatching with capacity.Also, the cell type super capacitor utensil is at low cost, operating voltage is high, capacity is high,
It is simple and at low cost good characteristics, the preparation process such as to can be quickly charged and discharged and have extended cycle life.
Detailed description of the invention
Fig. 1 is the cell type supercapacitor charging and discharging curve figure of the embodiment of the present invention 1.
Fig. 2 is the cyclic voltammetry curve figure of the cell type supercapacitor of the embodiment of the present invention 1.
Fig. 3 is the cycle performance test curve figure of the cell type supercapacitor of the embodiment of the present invention 1.
Fig. 4 be loop test before and 2000 times circulation after, 1 zinc metal sheet electrode (left side) of comparative example and 1 activated carbon electrodes of embodiment
(right side) surface picture.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1
The preparation of conventional cathode and cathode: by α-manganese dioxide, acetylene black, butadiene-styrene rubber (SBR) according to mass ratio 80:
Electrode slurry is made in 10:10, is coated on titanium foil, is used as anode after dry；Active carbon, second are weighed according to mass ratio 80:10:10
Electrode slurry is made in acetylene black, SBR, is coated on titanium foil, is used as cathode after dry.
The processing of positive electrode and negative electrode: using manganese dioxide positive pole as working electrode, zinc is to electrode, by working electrode and to electricity
Pole is placed in 2mol/L solution of zinc sulfate, in working electrode and to 1 V constant voltage is applied between electrode, is kept for 2 hours；With work
Property charcoal cathode be working electrode, zinc be to electrode, working electrode and to the time between electrode in 1 V constant potential, keep 2 small
When.
The assembling of cell type supercapacitor: will treated anode, diaphragm, treated, and cathode is successively stacked to shell
In, add the aqueous solution of 2mol/L zinc sulfate and 0.1mol/L manganese sulfate, assembled battery type supercapacitor.
Embodiment 2~10: preparation method is same as Example 1, only the positive zinc ion in cell type supercapacitor
Mass fraction (the referred to as zinc ion content of anode), the cathode zinc ion for accounting for electrode active material account for the quality of electrode active material
Score (zinc ion content of abbreviation cathode), the quality of positive electrode active materials, negative electrode active material, cathode and positive active material
It is more different than (abbreviation cathode/anode), electrolyte composition, it is specific as shown in table 1.
Table 1.
Embodiment 13: unlike the first embodiment, xanthan gum, zinc sulfate are dissolved in the water, prepare xanthan gum-sulphur
Sour gel of zinc electrolyte, positive plate, gel electrolyte, negative electrode tab are sequentially overlapped, and are put into button shell, and all solid state electricity is made
Pond type supercapacitor.
Embodiment 14~15: the positive zinc ion in the only cell type supercapacitor different from embodiment 13 accounts for electrode
Mass fraction (the referred to as zinc ion content of anode), the cathode zinc ion of active material account for the mass fraction of electrode active material
(zinc ion content of abbreviation cathode), positive electrode active materials, negative electrode active material, cathode and positive active material mass ratio
(abbreviation cathode/anode), gel electrolyte ingredient are different, specific as shown in table 2.
Table 2.
Comparative example 1
The preparation of conventional cathode and cathode: electricity is made according to mass ratio 80:10:10 in α-manganese dioxide, acetylene black, SBR
Pole slurry is coated on titanium foil, is used as anode after dry；Using metal zinc metal sheet as cathode.
The assembling of Zinc ion battery: anode, diaphragm, negative electrode tab are successively stacked in shell, add 2mol/L zinc sulfate
And the aqueous solution of 0.1mol/L manganese sulfate, Zinc ion battery is made.
Comparative example 2
The preparation of conventional cathode and cathode: electricity is made according to mass ratio 80:10:10 in α-manganese dioxide, acetylene black, SBR
Pole slurry is coated on titanium foil, is used as anode after dry；Active carbon, acetylene black, SBR are made according to mass ratio 80:10:10
Electrode slurry is coated on titanium foil, and cathode is used as after dry, and cathode and positive mass ratio are 1:1.
The assembling of supercapacitor: positive plate, diaphragm, negative electrode tab are sequentially overlapped, and are put into button shell, are added
The aqueous solution of 2mol/L zinc sulfate and 0.1mol/L manganese sulfate, is made typical ultracapacitor.
Product prepared by embodiment 1~15 and comparative example 1~2 uses the Land battery of Wuhan Lan electricity company at room temperature
Tester test, is tested with constant current charge-discharge method and cyclic voltammetry, and voltage range is 0~1.6V.Specifically, in 0.5 A/
G current density, 0~1.6 V voltage range is interior to carry out constant current charge-discharge curve test: in 2mV/s sweep speed, 0~1.6 V electricity
It presses and carries out cyclic voltammetry curve test in range；Cycle performance is carried out in 0.5 A/g current density, 0~1.6 V voltage range
Test.
The cell type supercapacitor and the battery of comparative example 1~2 or the results of property of supercapacitor of embodiment 1~15
It is shown in Table 3.
The specific capacity of the device of 3 embodiment 1~15 of table and comparative example 1~2
It is calculated from the curve of Fig. 1,2, the specific discharge capacity of cell type supercapacitor prepared by the present embodiment 1 is up to
40mAh/g as can be seen from Figure 3 has stable charge and discharge curve and superior cyclical stability, recycles 2500 times, capacity hardly damages
It loses, the cell type supercapacitor for illustrating prepared by the present embodiment 1 has excellent chemical property.As shown in figure 4, comparative example 1 is made
For standby Zinc ion battery after 2000 charge and discharge cycles, zinc metal sheet surface generates the dendrite (left figure) of sharp protrusion, there is peace
Full hidden danger；The present embodiment 1 prepares cell type supercapacitor after 2000 charge and discharge cycles, and activated carbon negative electrode is in charge and discharge
Front and back improves the safety issue of dendrite without (right figure) is substantially change well.
As seen from Table 3, the specific capacity for the cell type supercapacitor that prepared by embodiment 1~15 is that specific discharge capacity is up to 30
~53mAh/g, the typical ultracapacitor of remote super comparative example 2, especially implements 4~6, when the zinc ion of anode and cathode accounts for electricity
The mass fraction of pole active material is 10~20%, when the ratio of cathode and positive active material is (4.5~6): when 1, preparation
Cell type supercapacitor specific capacity highest.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of cell type supercapacitor, which is characterized in that it includes anode, cathode, is set between anode and cathode
The active material of diaphragm and electrolyte or gel electrolyte, the anode is Mn oxide, and the active material of the cathode is
Carbon material includes zinc ion in the electrolyte or gel electrolyte；Contain at least one electrode in the anode and cathode
There is zinc ion.
2. cell type supercapacitor according to claim 1, which is characterized in that it is described anode and/or cathode in zinc from
The mass fraction that son accounts for counter electrode active material is 0.01~30wt%；Preferably 10~20wt%.
3. cell type supercapacitor according to claim 1, which is characterized in that the negative electrode active material and anode are living
Property substance mass ratio be (2~10): 1；Preferably (4.5~6): 1.
4. described in any item cell type supercapacitors according to claim 1~3, which is characterized in that the Mn oxide choosing
From MnO2、Mn3O4、Mn2O3At least one of with MnO；
For example, the crystal form of the Mn oxide is α, β, γ, δ and at least one of unformed.
5. cell type supercapacitor according to any one of claims 1 to 4, which is characterized in that the carbon material is selected from
In active carbon, activated carbon fibre, carbon aerogels, carbon nanotube, mesoporous carbon, graphene, carbide derived carbon and nanometer door charcoal
It is at least one.
6. described in any item cell type supercapacitors according to claim 1~5, which is characterized in that the electrolyte is solidifying
Zinc ion in glue electrolyte comes from zinc nitrate, zinc sulfate, zinc chloride, trifluoracetic acid zinc, zine methqne-sulfonate, trifluoromethane sulfonic acid
At least one of zinc, ethylsulfonic acid zinc, propyl sulfonic acid zinc, tetrafluoro boric acid zinc, ZINC P-PHENOLSULFONATE, zinc perchlorate；
The molar concentration of the zinc ion is 0.1mol/L~4mol/L, and preferably molar concentration is 1mol/L~2mol/L.
7. described in any item cell type supercapacitors according to claim 1~6, which is characterized in that in the electrolyte
Solvent is selected from least one of water, organic solvent and ionic liquid；
The organic solvent is selected from least one of esters, sulfone class, ethers, nitrile, alkane and olefines organic solvent；
The ionic liquid is selected from least one of imidazoles, piperidines, pyroles, quaternary amines and amides ionic liquid.
8. described in any item cell type supercapacitors according to claim 1~7, which is characterized in that the gel electrolyte
For the gel polymer containing zinc ion.The polymer is selected from polyvinyl alcohol, polyethylene glycol oxide, agar, gelatin, polyacrylic acid
At least one of ester sodium and xanthan gum.
9. described in any item cell type supercapacitors according to claim 1~8, which is characterized in that the electrolyte is solidifying
Also contain manganese ion in glue electrolyte, the manganese ion comes from least one of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride；
Preferably, the molar concentration of the manganese ion is 0.01mol/L~2mol/L.
10. the purposes of described in any item cell type supercapacitors according to claim 1~9, is used for storage energy, such as deposits
Storage energy.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110993358A (en) * | 2019-12-24 | 2020-04-10 | 合肥国轩高科动力能源有限公司 | Flexible zinc ion capacitor |
| CN111508728A (en) * | 2020-04-29 | 2020-08-07 | 绍兴博捷智能科技有限公司 | Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof |
| CN112216523A (en) * | 2020-09-02 | 2021-01-12 | 青岛大学 | Preparation method of flame-retardant polymer gel electrolyte with ultrahigh specific capacitance |
| CN112713010A (en) * | 2020-12-21 | 2021-04-27 | 浙江理工大学 | Method for preparing flexible planar micro energy storage device by laser printing sacrificial pattern and flexible planar micro energy storage device |
| CN112786961A (en) * | 2021-03-23 | 2021-05-11 | 上海电气集团股份有限公司 | Biomass-based gel electrolyte, lithium ion battery, preparation method and application |
| CN113097574A (en) * | 2021-02-22 | 2021-07-09 | 江苏师范大学 | Preparation method of solid-liquid mixed electrolyte of zinc ion battery |
| CN113097575A (en) * | 2021-02-22 | 2021-07-09 | 江苏师范大学 | Preparation method of zinc ion battery gel electrolyte |
| CN113851331A (en) * | 2021-10-30 | 2021-12-28 | 海南大学 | Preparation method of zinc ion gel electrolyte |
| CN114242465A (en) * | 2021-12-28 | 2022-03-25 | 华中科技大学 | Water-system zinc ion hybrid capacitor and preparation method thereof |
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| CN110993358A (en) * | 2019-12-24 | 2020-04-10 | 合肥国轩高科动力能源有限公司 | Flexible zinc ion capacitor |
| CN111508728A (en) * | 2020-04-29 | 2020-08-07 | 绍兴博捷智能科技有限公司 | Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof |
| CN111508728B (en) * | 2020-04-29 | 2021-09-28 | 绍兴容辛能源技术有限公司 | Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof |
| CN112216523A (en) * | 2020-09-02 | 2021-01-12 | 青岛大学 | Preparation method of flame-retardant polymer gel electrolyte with ultrahigh specific capacitance |
| CN112713010A (en) * | 2020-12-21 | 2021-04-27 | 浙江理工大学 | Method for preparing flexible planar micro energy storage device by laser printing sacrificial pattern and flexible planar micro energy storage device |
| CN113097574A (en) * | 2021-02-22 | 2021-07-09 | 江苏师范大学 | Preparation method of solid-liquid mixed electrolyte of zinc ion battery |
| CN113097575A (en) * | 2021-02-22 | 2021-07-09 | 江苏师范大学 | Preparation method of zinc ion battery gel electrolyte |
| CN112786961A (en) * | 2021-03-23 | 2021-05-11 | 上海电气集团股份有限公司 | Biomass-based gel electrolyte, lithium ion battery, preparation method and application |
| CN113851331A (en) * | 2021-10-30 | 2021-12-28 | 海南大学 | Preparation method of zinc ion gel electrolyte |
| CN113851331B (en) * | 2021-10-30 | 2023-02-03 | 海南大学 | Preparation method of zinc ion gel electrolyte |
| CN114242465A (en) * | 2021-12-28 | 2022-03-25 | 华中科技大学 | Water-system zinc ion hybrid capacitor and preparation method thereof |
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