CN110010373B - Electrode zinc embedding treatment method and application thereof in preparation of battery type super capacitor - Google Patents
Electrode zinc embedding treatment method and application thereof in preparation of battery type super capacitor Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- H01G11/46—Metal oxides
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- H—ELECTRICITY
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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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
- H01G11/84—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
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- 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 an electrode zinc-embedding treatment method and application thereof in preparation of a zinc ion battery type super capacitor. The electrode is processed by embedding zinc by an electrochemical method, specifically, an electrode to be processed is used as a working electrode, a conductive electrode is used as a counter electrode, the working electrode and the counter electrode are placed in a solution containing zinc ions, and voltage or current is applied between the working electrode and the counter electrode. At least one electrode in the positive electrode and the negative electrode of the battery type super capacitor is subjected to zinc embedding treatment according to the method, so that the problems of potential mismatching of the positive electrode and the negative electrode, low working voltage, low coulombic efficiency, poor cycle life and the like can be effectively solved, and the battery type super capacitor which is low in cost, high in working voltage, high in capacity, capable of being charged and discharged rapidly and long in cycle life is obtained.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage devices, and relates to an electrode zinc embedding treatment method and application thereof in preparation of a battery type super capacitor.
Background
In the field of batteries, the importance of cost and safety performance is increasingly prominent, and the replacement of mainstream organic electrolytes by aqueous electrolytes has become a hot point of research. Currently, although solutions containing zinc ions have been reported for use in rechargeable batteries, the cycle life of existing zinc ion batteries is less than five hundred times. Meanwhile, in the circulation process, the zinc sheet cathode is easy to form dendritic crystals, the volume expansion of the cathode can be caused, and meanwhile, the risk of battery short circuit caused by membrane puncture exists.
A super capacitor is a new type of energy storage device between a battery and a conventional electrostatic capacitor. Compared with a battery, the super capacitor has larger specific power (more than 10 times), has the characteristics of instant release of extra large current, short charging time, high charging and discharging efficiency and long cycle life, but has much lower energy density than the battery. Patent document CN 103560019B uses a composite metal oxide (an energy storage material formed by doping and compounding two or more metals, such as ZnCo)2O4、ZnMn2O4、ZnFe2O4) The zinc-ion mixed super capacitor is prepared by using a cathode active material consisting of zinc and a carbon material as an anode active material. However, the hybrid supercapacitor is very high in voltage drop (>0.4V) and high temperature calcination is required to prepare ZnCo2O4、ZnMn2O4、ZnFe2O4And the composite metal oxide is used as a positive electrode active substance, and has complex process and high cost. Meanwhile, as the metal zinc exists in the negative electrode, the zinc dendrite problem still exists in the high-power charging and discharging process. Patent document CN 107910195 a adopts a carbon material as a positive electrode active material and a zinc sheet or a zinc foil as a negative electrode material to prepare a zinc ion battery type supercapacitor, but the dendrite problem and the potential safety hazard caused by the zinc sheet negative electrode still exist.
Disclosure of Invention
The invention provides an electrode zinc embedding treatment method, which comprises the following steps: the electrode to be processed is used as a working electrode, a conductive electrode is used as a counter electrode, the working electrode and the counter electrode are placed in a zinc embedding solution containing zinc ions, voltage or current is applied between the working electrode and the counter electrode, and the electrode is subjected to zinc embedding processing by an electrochemical method, so that the working potentials of the positive electrode and the negative electrode before assembly are matched. For example, the counter electrode is at least one of zinc, platinum and graphite, and is preferably zinc.
According to the zinc-embedded treatment method of the present invention, the method of applying a voltage or a current between the working electrode and the counter electrode may be at least one selected from a constant voltage method, a constant current charge-discharge method, a linear scanning method, and a cyclic voltammetry method; preferably, the method of applying voltage or current is a constant voltage method or a constant current charge and discharge method.
Further, the current density range of the constant current method is 0.01-50A/g, and the treatment time is 0.1-60 h.
Further, the voltage range of the constant voltage method is 0-2V, and the processing time is 0.1-48 h. For example, the voltage range of the constant voltage method is 0.2-1.8V, 0.5-1.5V; as an example, the voltage may be 0.2V, 0.5V, 0.6V, 1.0V, 1.2V, 1.4V, 1.5V, 1.8V, 2.0V. For example, the treatment time can be 1-24 h and 1.5-8 h; as an example, the processing time is 2h, 4h, 6 h.
Further, the current density of the constant current charge and discharge method is in the range of 0.01-50A/g, such as 0.1-40A/g, 1-30A/g, 5-25A/g; the voltage range is 0-2V, such as 0.2-1.8V and 0.5-1.5V; the treatment time is 0.1 to 60 hours, for example, 0.5 to 50 hours, 1 to 40 hours, 2 to 10 hours, and for example, the treatment time is 2 hours, 4 hours, 6 hours.
Further, the scanning speed range of the linear scanning method is 0.05 mV/s-100 mV/s, such as 0.1-80 mV/s, 0.5-60 mV/s, 1-50 mV/s, 5-30 mV/s, the voltage range is 0-2V, and the processing time is 0.1-60 h. Further, the sweep rate of the cyclic voltammetry is in the range of 0.05mV/s to 100mV/s, such as 0.1 mV/s to 80mV/s, 0.5 mV/s to 60mV/s, 1 mV/s to 50mV/s, 5mV/s to 30mV/s, the voltage range is 0V to 2V, and the cycle number is 1 to 20 times.
According to the zinc insertion treatment method of the present invention, the active material in the positive electrode may be a manganese oxide. For example, the manganeseThe oxide may be selected from MnO2、Mn3O4、Mn2O3And MnO; the crystal form of the manganese oxide is not particularly limited, and may be any one of α, β, γ, δ and amorphous; wherein the source of the manganese oxide is not particularly limited. Illustratively, the manganese oxide may be selected from alpha-MnO2、α-Mn2O3、Mn3O4MnO or amorphous MnO2。
According to the zinc intercalation treatment method of the present invention, the active material in the negative electrode may be a carbon material. For example, the carbon material may be selected from at least one of activated carbon, activated carbon fiber, carbon aerogel, carbon nanotube, mesoporous carbon, graphene, carbide-skeleton carbon, and nanometal carbon; preferably at least one of activated carbon, carbon aerogel, carbon nanotubes and graphene.
According to the zinc intercalation treatment method of the present invention, the zinc ions in the zinc intercalation solution are derived from at least one of aqueous solutions of zinc nitrate, zinc sulfate, zinc chloride, zinc trifluoroacetate, zinc methanesulfonate, zinc trifluoromethanesulfonate, zinc ethylsulfonate, zinc propylsulfonate, zinc tetrafluoroborate, zinc benzenesulfonate and zinc perchlorate; as an example, the zinc ion may be derived from at least one of an aqueous solution of zinc nitrate, zinc sulfate, zinc chloride, zinc trifluoromethanesulfonate. The concentration of the zinc ions can be 0.1-4 mol/L, preferably 1-2 mol/L, such as 1mol/L, 1.5mol/L, 2 mol/L. Further, the zinc intercalation solution can also comprise a gel electrolyte, for example, the gel electrolyte can be selected from at least one of polyvinyl alcohol, polyethylene oxide, agar, gelatin, sodium polyacrylate and xanthan gum, preferably xanthan gum, polyvinyl alcohol or polyethylene oxide. Preferably, the zinc intercalation solution may be selected from aqueous zinc sulphate solution, aqueous zinc trifluoromethanesulfonate solution, a mixture of aqueous zinc sulphate solution and xanthan gum, a mixture of aqueous zinc sulphate solution and polyvinyl alcohol, and a mixture of aqueous zinc sulphate solution and polyethylene oxide.
According to an embodiment of the present invention, the operation of the constant voltage method may include: and taking an electrode to be treated as a working electrode and a zinc sheet as a counter electrode, placing the working electrode and the counter electrode in a zinc embedding solution, and keeping for 1-2 hours under the constant voltage of 0-2.0V.
According to an embodiment of the present invention, the operation of the constant current charge and discharge method includes: the electrode to be treated is used as a working electrode, a zinc sheet is used as a counter electrode, the working electrode and the counter electrode are placed in a zinc embedding solution, and the working electrode and the counter electrode are kept for a certain time under constant current. For example, the current density may be 0.05 to 0.15A/g, such as 0.1A/g.
The invention also provides application of the electrode pre-zinc-embedding treatment method in preparation of a zinc ion battery type super capacitor.
The invention also provides a preparation method of the battery type super capacitor, which comprises the following steps:
(1) preparing a conventional positive electrode and a conventional negative electrode;
(2) performing electrochemical zinc intercalation on a conventional anode, or performing electrochemical zinc intercalation on a conventional cathode, or performing electrochemical zinc intercalation on the conventional anode and the conventional cathode simultaneously;
(3) assembling the positive electrode, the diaphragm and the negative electrode in sequence, adding electrolyte, and packaging to form the battery type super capacitor; or assembling the positive electrode, the gel electrolyte and the negative electrode in sequence, and packaging into a battery type super capacitor;
preferably, the electrochemical zinc intercalation in the step (2) adopts the electrode zinc intercalation treatment method.
According to the method for preparing the battery type supercapacitor of the present invention, the conventional methods for preparing the positive and negative electrodes in step (1) may employ methods known in the art. For example, the positive electrode is made by adhering a positive electrode active material, a conductive agent, and a binder to a positive electrode current collector; the negative electrode is made by adhering a negative electrode active material, a conductive agent, and a binder to a negative electrode current collector.
According to the method for preparing a battery type supercapacitor of the present invention, the active material in the positive electrode has the meaning as described above. The active material in the negative electrode has the meaning as described above. For example, the mass ratio of the negative electrode active material to the positive electrode active material may be (2 to 10):1, for example (4.5 to 6):1, and for example, the mass ratio may be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10: 1.
According to the preparation method of the present invention, the electrolyte may be at least one of an aqueous solution containing zinc ions, an organic electrolyte, and an ionic liquid. For example, the zinc ions may be provided by materials including, but not limited to: at least one of zinc nitrate, zinc sulfate, zinc chloride, zinc trifluoroacetate, zinc methylsulfonate, zinc trifluoromethylsulfonate, zinc ethylsulfonate, zinc propylsulfonate, zinc tetrafluoroborate, zinc benzenesulfonate and zinc perchlorate; preferably zinc sulfate or zinc trifluoromethanesulfonate. The concentration of zinc ions in the electrolyte solution can be 0.1-4 mol/L, preferably 1-2 mol/L; as an example, the concentration is 1mol/L, 1.5mol/L, 2 mol/L. Preferably, the electrolyte solution may further contain manganese sulfate, for example, the concentration of manganese sulfate is 0.01-2 mol/L, preferably 0.1-1 mol/L. Wherein, the organic solvent can be at least one of ester, sulfone, ether, nitrile, alkane and olefin organic solvents; for example, ethers and esters; illustratively, the organic flux may be dimethyl ether, propylene carbonate, ethylene carbonate. Wherein, the ionic liquid can be at least one selected from imidazole, piperidine, pyrrole, quaternary ammonium and amide ionic liquids. Illustratively, the electrolyte solution may be selected from: zinc sulfate aqueous solution, zinc sulfate aqueous solution + manganese sulfate aqueous solution, zinc trifluoromethanesulfonate aqueous solution, and acetonitrile solution of zinc trifluoromethanesulfonate.
According to the preparation method of the present invention, the gel state polymer in the gel electrolyte may be selected from at least one of polyvinyl alcohol, polyethylene oxide, agar, gelatin, sodium polyacrylate, and xanthan gum; preferably xanthan gum.
According to the preparation method of the present invention, the battery type supercapacitor may be an all-solid battery type supercapacitor and/or a semi-solid battery type supercapacitor.
According to the preparation method provided by the invention, the specific capacity of the battery type super capacitor is more than or equal to 30mAh/g, and exemplarily, the specific capacity of the capacitor is 30mAh/g, 36mAh/g, 40mAh/g, 41mAh/g, 45mAh/g, 48mAh/g, 50mAh/g, 53mAh/g, 56mAh/g and 60 mAh/g. According to the preparation method, the number of times of cyclic charge and discharge of the battery type super capacitor is more than or equal to 100 times, such as more than or equal to 1000 times, more than or equal to 2000 times and more than or equal to 2500 times.
The invention also provides a battery type super capacitor obtained by the preparation method.
The invention has the beneficial effects that:
in the zinc embedding treatment method, a manganese compound is used as an anode active substance, a carbon material is used as a cathode active substance, an aqueous solution containing zinc ions, an organic electrolyte or an ionic liquid is used as an electrolyte or a gel electrolyte containing the zinc ions, and the anode or/and the cathode are/is subjected to zinc embedding treatment, so that the problems of mismatching of the potentials of the anode and the cathode before assembly, large internal resistance, low coulombic efficiency, poor cycle life and the like can be effectively solved, and the capacity of the battery type super capacitor is maximized. The prepared super capacitor cathode material does not have the safety problem of zinc dendrite, and the battery type super capacitor also has the advantages of reduced pressure, higher specific capacity and excellent cycle performance.
Drawings
Fig. 1 is a charge-discharge curve diagram of the battery type supercapacitor according to embodiment 1 of the present invention.
Fig. 2 is a cyclic voltammogram of the battery type supercapacitor according to example 1 of the present invention.
Fig. 3 is a graph showing the cycle performance test of the battery type supercapacitor according to example 1 of the present invention.
Fig. 4 is a cyclic voltammogram of the comparative example 1 battery-type supercapacitor of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Constant current charge-discharge, cyclic voltammetry of the products prepared in examples and comparative examples were tested at room temperature using the Land equipment of wuhan blue electricity corporation.
Example 1
Preparation of conventional positive and negative electrodes: preparing electrode slurry from alpha-manganese dioxide, acetylene black and Styrene Butadiene Rubber (SBR) according to a mass ratio of 80:10:10, coating the electrode slurry on a titanium foil, and drying the titanium foil to obtain a positive electrode; and weighing the active carbon, the acetylene black and the SBR according to the mass ratio of 80:10:10 to prepare electrode slurry, coating the electrode slurry on a titanium foil, and drying to obtain the negative electrode.
And (3) zinc embedding treatment of the positive electrode and the negative electrode: taking an alpha-manganese dioxide positive electrode as a working electrode and zinc as a counter electrode, placing the working electrode and the counter electrode in 2mol/L zinc sulfate solution, applying 1V constant voltage between the working electrode and the counter electrode, keeping for 2 hours, and performing zinc embedding treatment on the positive electrode; the active carbon cathode is used as a working electrode, zinc is used as a counter electrode, the constant potential is kept for 2 hours at 1V between the working electrode and the counter electrode by a constant potential method, and the zinc is embedded into the cathode.
Assembling the super capacitor: and stacking the anode subjected to zinc embedding treatment, the diaphragm and the cathode subjected to zinc embedding treatment into the shell in sequence, adding electrolyte (2mol/L zinc sulfate and 0.1mol/L manganese sulfate aqueous solution), and assembling into the battery type super capacitor.
Examples 2 to 15
Different from example 1, the positive electrode zinc intercalation voltage or current density, the negative electrode zinc intercalation voltage or current density, the zinc intercalation time, the zinc intercalation solution, the zinc intercalation energization mode, and the mass ratio of the negative electrode to the positive electrode active material (referred to as negative electrode/positive electrode) are shown in table 1.
Table 1.
Comparative example 1
Preparation of conventional positive and negative electrodes: preparing electrode slurry from alpha-manganese dioxide, acetylene black and SBR according to a mass ratio of 80:10:10, coating the electrode slurry on a titanium foil, and drying the titanium foil to obtain a positive electrode; preparing electrode slurry from active carbon, acetylene black and SBR according to a mass ratio of 80:10:10, coating the electrode slurry on a titanium foil, drying the electrode slurry to serve as a negative electrode, wherein the mass ratio of the negative electrode active carbon to the positive electrode alpha-manganese dioxide is 1: 1.
Assembling the battery type super capacitor: and sequentially overlapping the positive plate, the diaphragm and the negative plate, putting the overlapped positive plate, the diaphragm and the negative plate into a button shell, and adding 2mol/L zinc sulfate and 0.1mol/L manganese sulfate aqueous solution to prepare the conventional battery type super capacitor.
Example 16
The capacitors provided in examples 1 to 15 and comparative example 1 were tested at room temperature by a constant current charging and discharging method and cyclic voltammetry, and the voltage range was 0 to 1.6V. The specific test method comprises the following steps: constant current charge and discharge curve test is carried out within the range of 0.5A/g current density and 0-1.6V voltage: performing cyclic voltammetry curve test at a scanning rate of 2mV/s and within a voltage range of 0-1.6V; and carrying out cycle performance test in the voltage range of 0-1.6V at the current density of 0.5A/g. The results of the performance tests of the capacitors of examples 1-15 and the conventional capacitor of comparative example 1 are shown in Table 2.
Table 2.
As can be seen from fig. 1 to 3, the battery type supercapacitor prepared in example 1 has high specific discharge capacity (42mAh/g), stable charge-discharge curve and excellent cycling stability (2500 cycles with almost no loss of capacity), which indicates that the battery type supercapacitor prepared in example 1 has excellent electrochemical performance.
From fig. 4, which is a cyclic voltammetry graph of the conventional battery type supercapacitor prepared in comparative example 1, it can be seen that the specific discharge capacity of the battery type supercapacitor is much smaller than that of example 1, which shows that the device performance is greatly affected without electrode pretreatment.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (22)
1. An electrode zinc-embedding treatment method for preparing a battery type super capacitor, which comprises the following steps: taking an electrode to be processed as a working electrode, taking the working electrode as a positive electrode and a negative electrode, taking a conductive electrode as a counter electrode, placing the working electrode and the counter electrode in a zinc-embedded solution containing zinc ions, and applying voltage or current between the working electrode and the counter electrode to match working potentials of the positive electrode and the negative electrode before assembly;
the counter electrode is at least one of zinc, platinum and graphite;
the active material of the positive electrode is manganese oxide, and the active material of the negative electrode is a carbon material;
the method for applying voltage or current between the working electrode and the counter electrode is at least one selected from a constant voltage method, a constant current charging and discharging method, a linear scanning method and a cyclic voltammetry method.
2. The method according to claim 1, wherein the counter electrode is zinc.
3. The electrode zinc-embedding treatment method according to claim 1, wherein the method of applying voltage or current between the working electrode and the counter electrode is a constant voltage method or a constant current charge-discharge method.
4. The electrode zinc-embedding treatment method according to claim 1 or 3, wherein the voltage range of the constant voltage method is 0-2V, and the treatment time is 0.1-48 h.
5. The method for treating zinc embedded in an electrode according to claim 1, wherein the constant current method has a current density of 0.01A/g to 50A/g and a treatment time of 0.1 to 60 hours.
6. The electrode zinc-embedding treatment method according to claim 1 or 3, wherein the constant current charge and discharge method has a current density ranging from 0.01A/g to 50A/g, a voltage ranging from 0V to 2V, and a treatment time ranging from 0.1 h to 60 h.
7. The electrode zinc-embedding treatment method according to claim 1, wherein the scanning rate of the linear scanning method is in the range of 0.05mV/s to 100mV/s, the voltage is in the range of 0V to 2V, and the treatment time is in the range of 0.1 h to 60 h.
8. The method for treating zinc embedded in an electrode according to claim 1, wherein the sweep rate of cyclic voltammetry is in the range of 0.05mV/s to 100mV/s, the potential is in the range of 0V to 2V, and the cycle number is in the range of 1V to 20.
9. The method for zinc intercalation treatment of an electrode according to claim 1, wherein the zinc ions in the zinc intercalation solution are derived from at least one of zinc nitrate, zinc sulfate, zinc chloride, zinc trifluoroacetate, zinc methanesulfonate, zinc trifluoromethanesulfonate, zinc ethylsulfonate, zinc propylsulfonate, zinc tetrafluoroborate, zinc benzenesulfonate and zinc perchlorate.
10. The method for treating zinc intercalation into electrode according to claim 9, wherein the molar concentration of zinc ions in the zinc intercalation solution is 0.1-4 mol/L.
11. The electrode zinc intercalation processing method according to claim 9 or 10, wherein the zinc intercalation solution further comprises a gel electrolyte; the gel electrolyte is selected from at least one of polyvinyl alcohol, polyethylene oxide, agar, gelatin, sodium polyacrylate and xanthan gum.
12. The method of claim 1, wherein the manganese oxide is selected from MnO2、Mn3O4、Mn2O3And MnO;
the carbon material is selected from at least one of activated carbon, activated carbon fiber, carbon aerogel, carbon nanotube, mesoporous carbon, graphene, carbide skeleton carbon and nanomesh carbon.
13. Use of the electrode zinc-intercalation treatment method of any one of claims 1 to 12 in the preparation of a battery-type supercapacitor.
14. Use according to claim 13, wherein the battery-type supercapacitor is a zinc-ion battery-type supercapacitor.
15. A method for preparing a battery type super capacitor is characterized by comprising the following steps,
(1) respectively preparing a positive electrode and a negative electrode;
(2) performing zinc embedding treatment on the positive electrode, or performing zinc embedding treatment on the negative electrode, or performing zinc embedding treatment on the positive electrode and the negative electrode simultaneously;
(3) assembling the positive electrode, the diaphragm and the negative electrode in sequence, adding electrolyte, and packaging to form the battery type super capacitor; or assembling and packaging the positive electrode, the gel electrolyte and the negative electrode in sequence to form a battery type super capacitor;
the zinc-embedded treatment method of any one of claims 1 to 12 is adopted for the electrode in the step (2).
16. The method of claim 15, wherein the active material of the positive electrode is manganese oxide and the active material of the negative electrode is carbon material.
17. The method for manufacturing a battery-type supercapacitor according to claim 15, wherein the mass ratio of the active material of the negative electrode to the active material of the positive electrode is (2-10): 1.
18. The method for manufacturing a battery-type supercapacitor according to claim 17, wherein the mass ratio of the active material of the negative electrode to the active material of the positive electrode is (4.5-6): 1.
19. The method of claim 15, wherein the electrolyte is at least one of an aqueous solution containing zinc ions, an organic electrolyte, and an ionic liquid;
the gel electrolyte is selected from at least one of polyvinyl alcohol, polyethylene oxide, agar, gelatin, sodium polyacrylate and xanthan gum.
20. The production method according to any one of claims 15 to 19, wherein the battery-type supercapacitor is an all-solid-battery-type supercapacitor and/or a semi-solid-battery-type supercapacitor.
21. The preparation method of claim 20, wherein the specific capacity of the battery type supercapacitor is greater than or equal to 30 nAh/g.
22. The preparation method of claim 20, wherein the number of times of cyclic charge and discharge of the battery type supercapacitor is not less than 100.
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| CN101783419B (en) * | 2009-01-16 | 2015-05-13 | 清华大学深圳研究生院 | Rechargeable zinc ion battery |
| WO2012043398A1 (en) * | 2010-09-29 | 2012-04-05 | エスペック株式会社 | Method for drying electrode pair, method for manufacturing lithium-ion secondary battery, method for manufacturing electric double-layer capacitor, and method for manufacturing lithium-ion capacitor |
| CN104064370A (en) * | 2013-03-21 | 2014-09-24 | 中国科学院金属研究所 | Method for realizing energy density maximization of supercapacitor |
| CN103401030B (en) * | 2013-07-09 | 2016-05-04 | 哈尔滨工程大学 | A kind of water system can be filled magnesium or zinc ion capacitor batteries |
| CN103545113B (en) * | 2013-10-30 | 2016-05-11 | 中国第一汽车股份有限公司 | A kind of lithium ion hybrid super capacitor |
| CN103560019B (en) * | 2013-10-30 | 2016-05-04 | 中国第一汽车股份有限公司 | A kind of zinc ion hybrid super capacitor |
| CN106298252B (en) * | 2015-05-19 | 2018-12-25 | 中国科学院金属研究所 | A kind of stacked high-energy density super capacitor structure |
| CN105958131B (en) * | 2016-06-20 | 2018-10-26 | 南开大学 | Rechargeable aqueous zinc ion battery with long cycle life and high energy density |
| CN106277231B (en) * | 2016-07-28 | 2019-03-19 | 华中农业大学 | A kind of method that electrochemistry removes heavy metal in liquid |
| CN106381513A (en) * | 2016-08-31 | 2017-02-08 | 昆明理工大学 | Preparation method and application of multi-stage nanosheet zinc oxide |
| CN107910195B (en) * | 2017-10-26 | 2020-07-28 | 刘小林 | Hybrid super capacitor |
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