CN110938856A - Novel anodic oxidation process of nickel-based thin film energy storage material - Google Patents
Novel anodic oxidation process of nickel-based thin film energy storage material Download PDFInfo
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- CN110938856A CN110938856A CN201911294313.1A CN201911294313A CN110938856A CN 110938856 A CN110938856 A CN 110938856A CN 201911294313 A CN201911294313 A CN 201911294313A CN 110938856 A CN110938856 A CN 110938856A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
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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
- H01G11/46—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
- H01G11/84—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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- 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 belongs to the technical field of new material preparation, and relates to a novel anodic oxidation process of a nickel-based thin film energy storage material. Aiming at preparing NiO/Ni (OH) with excellent performance by a method of preparing a nickel-based metal film and then electrochemically oxidizing the nickel-based metal film2The existing defects of the electrochemical oxidation process in the electrode material method of the super capacitor are that a mode of adding an auxiliary oxidant into electrolyte is provided, the influence of the concentration of the auxiliary oxidant and other electrochemical parameters on the capacitive performance of the prepared nickel oxide/nickel hydroxide electrode material is researched, a novel electrochemical oxidation process of the nickel-based metal film energy storage material which is simple and easy to implement and good in controllability is obtained, and the electric performance of the prepared nickel oxide/nickel hydroxide electrode material is improvedCapacity and electrochemical stability.
Description
Technical Field
The invention belongs to the technical field of new material preparation, and relates to a novel anodic oxidation process of a nickel-based thin film energy storage material.
Background
NiO/Ni(OH)2The electrode material is considered to be a potential super capacitor electrode material due to the excellent characteristics of high electrode potential, large electrochemical capacity, good electrochemical cycling stability and the like. In order to improve the capacitance performance of the electrode, researchers have used methods such as precipitation transformation, sol-gel, magnetron sputtering, electrochemical cathode/anode deposition, hydrothermal method, etc. to prepare nickel oxide/nickel hydroxide electrode materials. The performance of the electrode material is closely related to the specific surface area and the surface structure thereof, and the electrode material with higher specific surface area and a nano-porous network structure can show excellent capacitance characteristics. In the preparation method of the nickel oxide/nickel hydroxide electrode with the nano porous structure, as the film preparation technology such as an electrochemical method, magnetron sputtering and the like is matured day by day, the method of firstly preparing the nickel-based metal film and then oxidizing the nickel-based metal film shows the advantages of simple preparation process, good controllability and the like, can form an active substance film on a conductive substrate in situ, can conveniently regulate and control the appearance and microstructure of the film, and is considered as a better method for preparing the nickel oxide/nickel hydroxide electrode material. In the method for preparing the nickel-based metal film before oxidation, researchers mainly focus on the research of the preparation technology and the process of the film, the research on the next electrochemical oxidation process is few, and at present, two electrochemical oxidation methods are mainly used, wherein one method is an acidic system, and the other method is alkaline system electrolyte anodic oxidation. The former has the advantages of simple and easy operation and high film forming speed, but has the disadvantages of very poor controllability, insufficient cycling stability of electrode materials and need of post-treatment; in the latter, the oxidation is insufficient due to simple electrolyte composition, so that the capacitance performance of the electrode material cannot be fully utilized, and the cycling stability is not good. The patent provides a mode of adding an auxiliary oxidant into an alkaline system electrolyte aiming at the existing electrochemical oxidation process, researches the influence of the concentration of the auxiliary oxidant and other electrochemical parameters on the capacitive performance of the prepared nickel oxide/nickel hydroxide electrode material, obtains a novel electrochemical oxidation process of the nickel-based metal film energy storage material which is simple, feasible and good in controllability, and improves the capacitive performance and the capacitive performance of the prepared nickel oxide/nickel hydroxide electrode materialElectrochemical stability.
Disclosure of Invention
The invention aims at preparing NiO/Ni (OH) with excellent performance by a method of firstly preparing a nickel-based metal film and then electrochemically oxidizing2The existing defects of the electrochemical oxidation process in the electrode material method of the super capacitor are that a mode of adding an auxiliary oxidant into electrolyte is provided, the influence of the concentration of the auxiliary oxidant and other electrochemical parameters on the capacitive performance of the prepared nickel oxide/nickel hydroxide electrode material is researched, a novel electrochemical oxidation process of the nickel-based metal film energy storage material which is simple and easy to implement and good in controllability is obtained, and the capacitive performance and the electrochemical stability of the prepared nickel oxide/nickel hydroxide electrode material are improved.
The purpose of the invention can be realized by the following technical scheme:
a novel anodic oxidation process of a nickel-based thin film energy storage material comprises dissociating an oxidizing anion auxiliary oxidant A in electrolyte, performing electrochemical anodic oxidation by adopting constant potential of two electrodes, taking the nickel-based thin film energy storage material as an anode, and taking a stainless steel or platinum inert electrode as a counter electrode; the technical scheme is as follows:
(1) forming a basic alkaline electrochemical oxidation system;
(2) adding an auxiliary oxidant A into the system to form an oxidation process electrolyte;
(3) and filling the electrolyte of the electrochemical oxidation process into an electrolytic cell, adopting a two-electrode system, taking a stainless steel or platinum inert electrode as a cathode, and taking a nickel-based thin film energy storage material to be oxidized as an anode.
Further, the novel anodic oxidation process of the nickel-based thin film energy storage material comprises the following steps:
(1) preparing 1MKOH solution as a basic alkaline electrochemical oxidation system;
(2) adding an auxiliary oxidant A to fully dissolve the auxiliary oxidant A to form an oxidation process electrolyte;
(3) filling the electrolyte of the electrochemical oxidation process into an electrolytic cell, adopting a two-electrode system, taking a stainless steel or platinum inert electrode as a cathode, taking a nickel-based thin film energy storage material to be oxidized as an anode, and keeping the distance between the cathode and the anode to be 1-2 cm;
(4) controlling the temperature of an electrolytic cell in a constant-temperature water bath to be 30 ℃, carrying out constant-temperature treatment for 20-30min, connecting the electrolytic cell to a constant-potential power supply, and carrying out anodic oxidation for 45min at the pressure of an electrolytic cell of 1.0-1.5V;
(5) taking out the nickel-based film energy storage material after the anodic oxidation is finished, and washing the nickel-based film energy storage material for 2-3 times by using deionized water;
(6) and a three-electrode system is adopted to research the capacitance performance and the electrochemical stability of the oxidized nickel-based thin-film energy storage electrode material.
Preferably, two electrodes are adopted for constant potential electrochemical oxidation, the anode is a nickel-based thin film energy storage material, the cathode is a stainless steel or platinum inert electrode, the electrolyte consists of an auxiliary oxidant A of 1MKOH +10g/L, the bath pressure is 1.1V, the temperature is 30 ℃, and the oxidation time is 45 min.
A three-electrode system is adopted to research the capacitance performance and the electrochemical stability of the oxidized nickel-based thin film energy storage electrode material, cyclic voltammetry and constant current charge and discharge are mainly tested in a typical super capacitor electrolyte (2MKOH solution) to evaluate the capacitance performance and the electrochemical stability of the electrode material, and the electrode material without an oxidant A is used as a comparison sample during electrochemical oxidation. The result shows that the capacitance of the electrode material after oxidation in the presence of the pro-oxidant A is respectively improved by 50-60% compared with that of the electrode material without the pro-oxidant, and the capacitance performance is not reduced after 8000 times of constant current charge-discharge cycles under the sweep rate of 50mV/s and the current density of 33.33A/g, which shows that the sample after oxidation by the oxidation process of the invention has good electrochemical stability. The experiment is repeated for more than 3 times, the data reproducibility is good, and the process is simple and easy to implement and good in controllability.
The invention has the beneficial effects that:
compared with the prior electrochemical anodic oxidation process, the invention has the following advantages:
(1) the method is simple and easy to implement and good in controllability;
(2) the oxidation time is short, and no post-treatment step is needed after oxidation;
(3) the nickel-based thin film energy storage material is fully oxidized by adding the auxiliary oxidant into the alkaline electrolyte, so that the capacitance performance and the electrochemical stability of the electrode material are improved;
(4) the oxidized electrode material does not contain any impurity, so that the electrolyte can not be polluted when the super capacitor works.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a CV curve of a nickel-based thin film energy storage material oxidized with a pro-oxidant A and without A in an electrochemical oxidation electrolyte according to the present invention;
FIG. 2 is a comparison of the initial specific capacitance of the nickel-based thin film energy storage material after the electrochemical oxidation process with the addition of the pro-oxidant A and without the addition of A;
FIG. 3 is the cycle performance of the nickel-based thin film energy storage material after the electrochemical oxidation process with the pro-oxidant A added;
FIG. 4 shows the cycle performance of the nickel-based thin film energy storage material after the electrochemical oxidation process with the pro-oxidant A added.
Detailed Description
Example 1
In the embodiment, a thin copper sheet with the thickness of 0.5mm is used as a substrate, pure Ni and NiB plating layers with the thickness of 3 microns are respectively deposited on the surface of the thin copper sheet by a chemical plating method, then two NiO/NiOH super capacitor electrode materials are prepared by oxidation under the optimal electrochemical oxidation process condition of the invention, a sample subjected to electrochemical oxidation without adding an auxiliary oxidant A is used as a comparison test, a three-electrode system is used for researching the capacitance performance and the electrochemical stability of the oxidized nickel-based thin film energy storage electrode material, cyclic voltammetry and constant current charge and discharge are tested in a typical super capacitor electrolyte (2MKOH solution) to evaluate the capacitance performance and the electrochemical stability of the electrode material, the three-electrode system is used for researching the capacitance performance and the electrochemical stability of the oxidized nickel-based thin film energy storage electrode material, and cyclic voltammetry and constant current charge and discharge are mainly tested in the typical super capacitor electrolyte (2MKOH solution) to evaluate the capacitance performance and the electrochemical stability of the electrode material Chemical stability;
the result shows that the initial capacitance of the electrode material after oxidation in the presence of the pro-oxidant A is respectively improved by 50-60% (56% of the pure nickel film energy storage material and 61% of the NiB film energy storage material, see the figure 1 and the figure 2) compared with that without the pro-oxidant, and the capacitance performance of the two nickel-based energy storage materials is not reduced after 8000 times of cyclic voltammetry charge-discharge cycles with sweep rate of 50mV/s (see the figure 3 and the figure 4), which shows that the sample after oxidation by the oxidation process of the invention has good electrochemical stability. The experiment is repeated for more than 3 times, the data reproducibility is good, and the process is simple and easy to implement and good in controllability.
Comparative example 1
The electrochemical oxidation process for the nickel-based thin film material is divided into an acidic system according to the components of the electrolyte; the acid system is that in the mixed solution of 75% phosphoric acid and 0.5M ammonium fluoride, two-electrode anodic oxidation method is adopted to successfully prepare nickel-base composite membrane electrode material on the surface of metal nickel, and NiF prepared by the method2-Ni(OH)2The sponge porous film (PNC for short) has high specific capacitance, but the cycle life and charge-discharge rate of the sponge porous film need to be improved to eliminate NiF2The PNC is subjected to a series of annealing treatments and an annealing experiment is optimized, when a sample is annealed for 4min at a high temperature of 600 ℃, the PNC is converted into NiO (NNO for short) with a porous structure, the specific capacitance of the NiO is equivalent to that of the PNC, and the NNO shows a slow increase trend and changes stably after 2000 times of constant current charge and discharge tests at a current density of 33.33A/g. Although NNO performs well, its charge-discharge rate is not much improved over PNC.
Comparative example 2
Co doping is carried out on NNO by adopting water bath treatment to improve the conductivity of the nickel-based anodic oxide film so as to achieve the purpose of improving the charge and discharge rate. However, the charge and discharge rate of NNO/Co is slightly improved only in the initial stage of charge and discharge, and the charge and discharge rate is not improved as the charge and discharge progress. The result of the electrode material prepared by the comparative example method shows that the nickel-based composite membrane shows obvious capacitance characteristic through electrochemical test, and the first discharge specific capacitance reaches 505m F/cm2However, the cycle life is not stable, so that the method is improved by two different post-treatment methodsIt is good for its cycle stability. After the oxidized nickel-based thin film electrode is subjected to constant-current charge and discharge post-treatment, the fact that the surface appearance is changed from a compact state to a nanometer petal shape is found, and the stability of the corresponding cycle life is effectively improved; after the nickel-based thin film electrode after oxidation is subjected to hydrothermal post-treatment, the fact that the surface appearance is changed from a compact state to a nano porous state is found, and the stability of the cycle life is effectively improved. The comparative example proposes that a layer containing a plurality of internal pore oxidation layers is obtained on the surface of the metal nickel by adopting a two-electrode anode voltage oscillation method in a sulfuric acid oxidation solution system, and a plurality of nickel hydroxide nano-particles are attached to the oxidation layers, so that the electrical test shows excellent electrochemical characteristics. The anodic oxidation process of the acid system is complex, sometimes the oxidation power supply requirement is higher, the initial capacitance of the prepared electrode material is improved but the stability is not high due to the doping of fluorine in the electrolyte, the pollution of the electrolyte of the super capacitor is easily caused, and the subsequent treatment is needed.
Comparative example 3
The constant potential oxidation process parameters optimized through experiments in the alkaline system are that the concentration of an electrochemical oxidation medium KOH is 4M, the oxidation temperature is 60 ℃, the oxidation voltage is 1.1V, and the oxidation time is 2 h. The oxidation temperature has the greatest influence on the electrochemical performance, and the concentration of the oxidation medium is the second factor, the oxidation process has the advantages that the oxidation temperature is high due to simple oxidation medium composition, the capacitance is small at low temperature, and the circulation stability of the electrode material cannot be given. The anodic oxidation is directly carried out in the alkaline super capacitor electrolyte by adopting the cyclic voltammetry, the power supply requirement of the oxidation process is high, the capacity retention rate is reduced to 94 percent after 1000 cycles, the stability is not good, and the initial capacity utilization rate of the electrode material is not high.
The electrochemical process adopts a constant potential method, is simple and easy to implement and has good controllability, and the initial capacitance is improved by 50-60% through electrochemical tests, and 8000 times of cyclic charge-discharge capacitance is almost not attenuated, so that the capacitance performance and the cyclic stability performance after electrochemical oxidation are improved.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (3)
1. A novel anodic oxidation process of a nickel-based thin film energy storage material is characterized in that an oxidizing anion oxidizing agent A is dissociated in electrolyte, electrochemical anodic oxidation is carried out by adopting constant potential of two electrodes, the nickel-based thin film energy storage material is used as an anode, and a counter electrode is a stainless steel or platinum inert electrode; the technical scheme is as follows: (1) forming a basic alkaline electrochemical oxidation system;
(2) adding an auxiliary oxidant A into the system to form an oxidation process electrolyte;
(3) and filling the electrolyte of the electrochemical oxidation process into an electrolytic cell, adopting a two-electrode system, taking a stainless steel or platinum inert electrode as a cathode, and taking a nickel-based thin film energy storage material to be oxidized as an anode.
2. The novel anodic oxidation process of the nickel-based thin-film energy storage material as claimed in claim 1, characterized by comprising the following steps:
(1) preparing 1MKOH solution as a basic alkaline electrochemical oxidation system;
(2) adding an auxiliary oxidant A to fully dissolve the auxiliary oxidant A to form an oxidation process electrolyte;
(3) filling the electrolyte of the electrochemical oxidation process into an electrolytic cell, adopting a two-electrode system, taking a stainless steel or platinum inert electrode as a cathode, taking a nickel-based thin film energy storage material to be oxidized as an anode, and keeping the distance between the cathode and the anode to be 1-2 cm;
(4) controlling the temperature of an electrolytic cell in a constant-temperature water bath to be 30 ℃, carrying out constant-temperature treatment for 20-30min, connecting the electrolytic cell to a constant-potential power supply, and carrying out anodic oxidation for 45min at the pressure of an electrolytic cell of 1.0-1.5V;
(5) taking out the nickel-based film energy storage material after the anodic oxidation is finished, and washing the nickel-based film energy storage material for 2-3 times by using deionized water;
(6) and a three-electrode system is adopted to research the capacitance performance and the electrochemical stability of the oxidized nickel-based thin-film energy storage electrode material.
3. The novel anodic oxidation process of the nickel-based thin film energy storage material as claimed in claim 2, wherein two electrodes are used for constant potential electrochemical oxidation, the anode is the nickel-based thin film energy storage material, the cathode is a stainless steel or platinum inert electrode, the electrolyte comprises 1MKOH +10g/L of pro-oxidant A, the bath pressure is 1.1V, the temperature is 30 ℃, and the oxidation time is 45 min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058275A (en) * | 2020-08-19 | 2020-12-11 | 天津大学 | Alkaline photoelectrolysis water catalyst for thin film electrode and preparation method and application thereof |
| CN113611546A (en) * | 2021-07-16 | 2021-11-05 | 龙岩学院 | Preparation method and application of nano porous nickel-based oxide film electrode |
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| CN101276692A (en) * | 2008-05-19 | 2008-10-01 | 清华大学 | Nickelous hydroxide composite super capacitor and manufacture process thereof |
| KR20090092413A (en) * | 2008-02-27 | 2009-09-01 | 한양대학교 산학협력단 | Methods of coloring magnesium material and the magnesium material colored by the same |
| CN102005571A (en) * | 2010-09-19 | 2011-04-06 | 昆明理工大学 | Nickel hydroxide membrane electrode and preparation method thereof |
| CN104332324A (en) * | 2014-10-31 | 2015-02-04 | 深圳大学 | Preparation method of porous metal nickel and nickel-based porous film super-capacitor electrode material on surface of porous metal nickel |
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2019
- 2019-12-16 CN CN201911294313.1A patent/CN110938856A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090092413A (en) * | 2008-02-27 | 2009-09-01 | 한양대학교 산학협력단 | Methods of coloring magnesium material and the magnesium material colored by the same |
| CN101276692A (en) * | 2008-05-19 | 2008-10-01 | 清华大学 | Nickelous hydroxide composite super capacitor and manufacture process thereof |
| CN102005571A (en) * | 2010-09-19 | 2011-04-06 | 昆明理工大学 | Nickel hydroxide membrane electrode and preparation method thereof |
| CN104332324A (en) * | 2014-10-31 | 2015-02-04 | 深圳大学 | Preparation method of porous metal nickel and nickel-based porous film super-capacitor electrode material on surface of porous metal nickel |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058275A (en) * | 2020-08-19 | 2020-12-11 | 天津大学 | Alkaline photoelectrolysis water catalyst for thin film electrode and preparation method and application thereof |
| CN112058275B (en) * | 2020-08-19 | 2022-11-01 | 天津大学 | Alkaline photoelectrolysis water catalyst for thin film electrode and preparation method and application thereof |
| CN113611546A (en) * | 2021-07-16 | 2021-11-05 | 龙岩学院 | Preparation method and application of nano porous nickel-based oxide film electrode |
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Application publication date: 20200331 |