CN102709058B - Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors - Google Patents
Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors Download PDFInfo
- Publication number
- CN102709058B CN102709058B CN201210223152.9A CN201210223152A CN102709058B CN 102709058 B CN102709058 B CN 102709058B CN 201210223152 A CN201210223152 A CN 201210223152A CN 102709058 B CN102709058 B CN 102709058B
- Authority
- CN
- China
- Prior art keywords
- nickel
- manganese dioxide
- electrode material
- nickel hydroxide
- composite electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
-
- 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
-
- 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 relates to a preparation method of composite electrode materials of electrochemical super capacitors, in particular to a method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors. The method includes that foam nickel, a nickel piece or a titanium piece serves as an electrode plate, the electrode plate is subjected to cathode electrochemical deposition in potassium permanganate and nickel nitrate mixed aqueous solution electrolyte, the surface of the deposited electrode plate is cleaned by deionized water and dried, and composite electrode materials with the foam nickel, the nickel piece or the titanium piece serving as the electrode plate and with a manganese dioxide-nickel hydroxide composite film on the surface layer are obtained. The manganese dioxide-nickel hydroxide composite electrode materials prepared through the method have superior cycling stability and high specific capacity. The electrode preparation process is simple and convenient and is prone to industrialization.
Description
Technical field
The present invention relates to the preparation method of electric chemical super capacitor combination electrode material, particularly a kind of method preparing ultracapacitor manganese dioxide-nickel hydroxide composite electrode material.
Background technology
Ultracapacitor possesses that power density is large, the response time is fast, the life-span is long, safeguard the advantages such as simple, the fields such as information, electronics, the energy, environment, traffic and military project can be widely used in, and develop that a kind of production cost is low, larger capacity, have excellent instantaneous charge-discharge performance, cyclicity good electrochemical capacitor electrode material extremely urgent.
According to used electrode material, ultracapacitor can be divided into following two large classes: the double electric layers supercapacitor being electrode with material with carbon elements such as active carbons and with metal oxide or conducting polymer be electrode material fake capacitance ultracapacitor or title " Faradic pseudo-capacitor ".Using material with carbon element as electrode, conductance is high, and specific power is high, but limited with electric double layer form charge storage ability, and capacitance and specific energy are all lower.And be attended by H in fake capacitance ultracapacitor charge and discharge process
+or OH
-the electric capacity that the adsorption capacitance embedded and deviate from or generation electrochemical redox reaction cause, can realize the body phase accumulate of two dimension or accurate two dimension, considerably increase charge storage ability.Wherein high, the good conductivity of ruthenium-oxide specific capacity, highly stable in the electrolytic solution; it is the electrode material for super capacitor that current performance is the most excellent; but because ruthenium belongs to rare precious metals; resource-constrained; selling at exorbitant prices; have pollution to environment, cannot carry out large-scale production in a short time, the substitution material finding low-cost and high-performance is current study hotspot.Research finds that the transition metal oxides such as cobalt, manganese, nickel have and RuO
2similar character, is expected to replace RuO
2become and be more suitable for commercial electrode material for super capacitor.Manganese dioxide, because resource is extensive, cheap, environmentally friendly, have the advantages such as multiple oxidation state and structure-rich, is widely used as battery electrode material and catalyst material.The research that manganese dioxide is used as the electrode material of ultracapacitor just grows up in recent years, and it shows good capacitance characteristic in neutral electrolyte, and potential window is wider, is considered to extremely potential a kind of electrode material.But the body phase manganese dioxide conductivity prepared due to conventional method is not good and structure is piled up closely, be unfavorable for transporting of electrolyte ion diffusion and electronics, prepared electrode ratio capacitance numerical value is well below its theoretical specific volume (1370F/g).Recently, exploitation preparation has the manganese dioxide nano particle of nanostructure or film receives publicity for electrode of super capacitor.Based on the feature of nanostructure, manganese dioxide can have high specific area, is conducive to infiltrating electrolyte to greatest extent, shortens ion diffuse path, promotes in electrode surface generation redox reaction, thus improves charge/discharge rate property and ratio capacitance.But nanostructure exists a fatal problem, in cyclic process, be namely easy to recurring structure cave in, the recycle ratio electric capacity of significant attenuation electrode.Nickel hydroxide has good electrochemical redox activity, low cost and high theoretical ratio capacitance characteristic, is the attractive fake capacitance material of a class.But owing to there is the reasons such as grain growth in conjunction with in weak, phase in version and oxidation-reduction process between electrode material and collector, the nickel hydroxide cyclical stability often with high specific capacitance is poor.At present, people have prepared the compound of manganese dioxide and nickel hydroxide by chemical method, and when the mass percent of manganese dioxide is 35.5%, in alkaline electrolyte, ratio capacitance reaches 487.4F/g.
Summary of the invention
The object of the invention is to, the defect of product specific capacity low, poor stability, bad dispersibility and poorly conductive that manganese dioxide doped combination electrode material exists, complicated process of preparation is prepared for overcoming current chemical method, a kind of method preparing ultracapacitor manganese dioxide-nickel hydroxide composite electrode material of improvement is proposed, manganese dioxide prepared by the method and nickel hydroxide composite electrode material have superior cyclical stability, high specific capacity.Electrode production process is simple and convenient, easy industrialization.
The present invention prepares the method for ultracapacitor manganese dioxide-nickel hydroxide composite electrode material, for pole plate carries out cathodic electrochemical deposition in potassium permanganate and nickel nitrate mixed aqueous solution electrolyte with nickel foam, nickel sheet or titanium sheet, post-depositional polar board surface washed with de-ionized water, to dry, namely obtain with nickel foam, nickel sheet or titanium sheet be substrate, top layer has the combination electrode material of manganese dioxide-nickel hydroxide laminated film.
Described potassium permanganate and nickel nitrate mixed aqueous solution electrolyte, wherein, the concentration of potassium permanganate is 0.005mol/L ~ 0.05mol/L, and the concentration of nickel nitrate is 0.004mol/L ~ 0.12mol/L.Be preferably: the concentration of potassium permanganate is 0.01mol/L ~ 0.04mol/L, and the concentration of nickel nitrate is 0.014mol/L ~ 0.12mol/L.
The working temperature of described electrolyte is 20 DEG C ~ 30 DEG C.
Negative electrode constant potential electrochemical deposition current potential is-0.7V ~-0.95V.Preferred deposition current potential is-0.8V.
The present invention adopts electrochemical deposition method simple and easy to operate to adulterate or compound to manganese dioxide, prepared manganese dioxide-nickel hydroxide composite electrode material has higher specific capacity, in the KOH electrolyte of 1mol/L, when current density is 5A/g, specific volume reaches as high as 2334F/g; Instantaneous charge-discharge performance is excellent, can carry out discharge and recharge rapidly under high current density 20A/g condition; Good cycling stability, still can keep more than 82.8% through 500 charge and discharge cycles specific volumes under current density 20A/g condition.The compound of the manganese dioxide-nickel hydroxide prepared by chemical method, when the mass percent of manganese dioxide is 35.5%, in the KOH electrolyte of 1mol/L, ratio capacitance only reaches 487.4F/g.The inventive method is simple to operation, low cost of manufacture, easy industrialization.And while this electrode has high ratio capacitance, the ratio capacitance numerical value of more than 80% can be kept under the high current density discharge and recharge condition of hundreds of times, the fields such as the hybrid power energy can be widely used in.
Accompanying drawing explanation
Fig. 1 (a, b, c, d) is the scanning electron microscope diagram (SEM) of electrochemical deposition layer of manganese dioxide-nickel hydroxide composite electrode material prepared by embodiment 1 to 4;
Fig. 2 (a, b, c) is the x-ray photoelectron spectroscopy figure (XPS) of manganese dioxide-nickel hydroxide composite electrode material prepared by embodiment 1 to 3.
Fig. 3 is the X-ray energy spectrum figure (EDS) of manganese dioxide-nickel hydroxide composite electrode material prepared by enforcement 3;
Fig. 4 is the transmission electron microscope figure (TEM) of manganese dioxide-nickel hydroxide composite electrode material prepared by embodiment 3, and illustration is the selected area electron diffraction figure (SAED) of sample;
Fig. 5 is the discharge curve of manganese dioxide-nickel hydroxide composite electrode material under the current density of 5A/g prepared by embodiment 5 to 8;
Fig. 6 is the electrochemical property test figure of manganese dioxide-nickel hydroxide composite electrode material prepared by embodiment 3; A () is followed successively by the cyclic voltammogram under different scanning speed, b the charge and discharge electrograph of () current density 5A/g, through 500 circulation specific volume variation diagrams when discharge curve (d) current density under (c) different current density condition is 20A/g.
Embodiment
By following examples, the inventive method is described in further detail.
For pole plate carries out cathodic electrochemical deposition in potassium permanganate and nickel nitrate mixed aqueous solution electrolyte with nickel foam, nickel sheet or titanium sheet, post-depositional polar board surface washed with de-ionized water, to dry, namely obtain with nickel foam, nickel sheet or titanium sheet be substrate, top layer has the combination electrode material of manganese dioxide-nickel hydroxide laminated film.
Understood by following examples, the product performance obtained under adopting different process conditions:
Embodiment 1
The electrolysis tank that potassium permanganate and nickel nitrate mixed aqueous solution electrolyte are housed is heated by constant temperature water bath, makes the working temperature of electrolyte be 20 DEG C ~ 30 DEG C;
In electrolyte, potassium permanganate concentration is 0.02mol/L, nickel nitrate concentration is 0.004mol/L
Sedimentation potential is adjusted to-0.8V; Deposition 6min, the about 150nm of gained deposit thickness.
Gained composite film electrode adopts three-electrode system, and (Pt is to electrode, saturated calomel electrode SCE is reference electrode, prepared electrode is work electrode) carry out electrochemical property test, comprise cyclic voltammetry and constant current charge-discharge test, electrolyte is adopted to be the KOH of 1mol/L, charging/discharging voltage :-0.1V ~ 0.5V, current density is: 5A/g, and recording combination electrode material specific volume is 515F/g.
The outward appearance of composite film electrode material deposits is shown in accompanying drawing 1 (a) scanning electron microscope diagram (SEM).As can be seen from Figure in the spherical particle piled up, and particle surface covers nanofiber, in three-dimensional netted interconnect structure.
Embodiment 2
In electrolyte, potassium permanganate concentration is 0.02mol/L, nickel nitrate concentration is 0.014mol/L;
Other conditions, the practice are with embodiment 1.
The about 180nm of gained deposit thickness.
Record combination electrode material specific volume and can reach 1125F/g.
The outward appearance of composite film electrode material deposits is shown in accompanying drawing 1 (b) scanning electron microscope diagram (SEM).The nanofiber of the spherical particle surface coverage of piling up as can be seen from Figure becomes thick and fine and close.
Embodiment 3
In electrolyte, potassium permanganate concentration is 0.02mol/L, nickel nitrate concentration is 0.05mol/L;
Other conditions, the practice are with embodiment 1.The about 200nm of gained deposit thickness.
The outward appearance of composite film electrode material deposits is shown in accompanying drawing 1 (c) scanning electron microscope diagram (SEM).From figure, do not see the pattern that there is spherical particle, be interwoven by the nanofiber loosened completely, and pore size distribution$ is even and obvious.
The x-ray photoelectron spectroscopy figure (XPS) of composite film electrode material is see Fig. 2.
The X-ray energy spectrum figure (EDS) of combination electrode material is see Fig. 3.
The transmission electron microscope figure (TEM) of combination electrode material is see Fig. 4.By XPS analysis, and can determine to there is manganese dioxide and nickel hydroxide in compound in conjunction with EDS and TEM, namely prepare the compound of manganese dioxide-nickel hydroxide.
The chemical property of combination electrode material is see Fig. 6.Electrode material specific volume is higher, and (specific volume can reach 2334F/g (under 5A/g condition), 2120F/g (under 10A/g condition), 1933F/g (under 20A/g condition), 1567F/g (under 40A/g condition), 1292F/g (under 50A/g condition), cyclical stability high (500 specific volumes that circulate under 20A/g current density still keep more than 82.8%).
Embodiment 4
In electrolyte, potassium permanganate concentration is 0.02mol/L, nickel nitrate concentration is 0.12mol/L;
Other conditions, the practice are with embodiment 1.
The about 300nm of gained deposit thickness.
Record gained combination electrode material specific volume and can reach 1368F/g.
The outward appearance of composite film electrode material deposits is shown in accompanying drawing 1 (d) scanning electron microscope diagram (SEM).Nanofiber finer and close as can be seen from Figure presents near-spherical Assembled distribution.
Embodiment 5
The working temperature of electrolyte is 20 DEG C ~ 30 DEG C;
In electrolyte, potassium permanganate concentration is 0.02mol/L, nickel nitrate concentration is 0.05mol/L;
Sedimentation potential is adjusted to-0.7V; The accumulation electricity of deposition is 0.11mAh, the about 200nm of thickness.
Other conditions, the practice are with embodiment 1.
Gained composite film electrode adopts three-electrode system, and (Pt is to electrode, saturated calomel electrode SCE is reference electrode, prepared electrode is work electrode) carry out electrochemical property test, comprise cyclic voltammetry and constant current charge-discharge test, electrolyte is adopted to be the KOH of 1mol/L, charging/discharging voltage :-0.1V ~ 0.45V, current density is: 5A/g.
The flash-over characteristic of gained combination electrode material under the current density of 5A/g is see Fig. 5.Recording combination electrode material specific volume is 745.5F/g.
Embodiment 6
Sedimentation potential is adjusted to-0.75V; Other conditions, the practice are with embodiment 5.The about 200nm of deposit thickness.
The flash-over characteristic of gained combination electrode material under the current density of 5A/g is see Fig. 5.Record composite film electrode specific volume and can reach 766F/g.
Embodiment 7
Sedimentation potential is adjusted to-0.8V; Other conditions, the practice are with embodiment 5.The about 200nm of deposit thickness.
The flash-over characteristic of gained combination electrode material under the current density of 5A/g is see Fig. 5.Record composite film electrode specific volume and can reach 845F/g.
Embodiment 8
Sedimentation potential is adjusted to-0.95V; Other conditions, the practice are with embodiment 5.The about 200nm of deposit thickness.
The flash-over characteristic of gained combination electrode material under the current density of 5A/g is see Fig. 5.Record composite film electrode specific volume and can reach 737F/g.
Embodiment 9
The working temperature of electrolyte is 20 DEG C ~ 30 DEG C;
In electrolyte, potassium permanganate concentration is 0.005mol/L, nickel nitrate concentration is 0.05mol/L;
Sedimentation potential is adjusted to-0.8V; The accumulation electricity of deposition is 0.11mAh, the about 150nm of deposit thickness.
Other conditions, the practice are with embodiment 1.
Gained composite film electrode adopts three-electrode system, and (Pt is to electrode, saturated calomel electrode SCE is reference electrode, prepared electrode is work electrode) carry out electrochemical property test, comprise cyclic voltammetry and constant current charge-discharge test, electrolyte is adopted to be the KOH of 1mol/L, charging/discharging voltage :-0.1V ~ 0.45V, current density is: 10mA/cm
2, recording combination electrode material specific volume is 1196F/g.
Embodiment 10
In electrolyte, potassium permanganate concentration is 0.01mol/L, nickel nitrate concentration is 0.05mol/L;
Other conditions, the practice are with embodiment 9.The about 180nm of deposit thickness.
Record gained composite film electrode specific volume and can reach 1784F/g.
Embodiment 11
In electrolyte, potassium permanganate concentration is 0.02mol/L, nickel nitrate concentration is 0.05mol/L;
Other conditions, the practice are with embodiment 9.The about 200nm of deposit thickness.
Record gained composite film electrode specific volume and can reach 1920F/g.
Embodiment 12
In electrolyte, potassium permanganate concentration is 0.04mol/L, nickel nitrate concentration is 0.05mol/L;
Other conditions, the practice are with embodiment 9.The about 250nm of deposit thickness.
Record gained composite film electrode specific volume and can reach 1580F/g.
Embodiment 13
In electrolyte, potassium permanganate concentration is 0.05mol/L, nickel nitrate concentration is 0.05mol/L;
Other conditions, the practice are with embodiment 9.The about 300nm of deposit thickness.
Record gained composite film electrode specific volume and can reach 920F/g.
Can be found out by above-described embodiment:
1) scanning electron microscopic observation is carried out to by the electrode material prepared by said method, can see that the electrode material obtained along with the increase adding nickel nitrate concentration in electrolyte presents different patterns, wherein, example 3 presents evenly, loose pore structure, be conducive to obtaining large specific area thus the turnover being convenient to electrolyte, ensure that the chemical property of electrode material excellence.
2) XPS analysis is carried out to the sample of above-mentioned preparation, and can determine to there is manganese dioxide and nickel hydroxide in compound in conjunction with EDS and SADE, namely prepared the composite electrode material of manganese dioxide-nickel hydroxide by this method.
3) example 5 to 8 is optimized example 1 to 4 sedimentation potential condition, and show that the ratio capacitance of the electrode material that example 7 is prepared is the highest, namely-0.8V is optimal deposition current potential.
4) example 9 to 13 is the concentration ranges of probing into potassium permanganate, the ratio capacitance of the electrode material that example 9 and example 13 are prepared is not high, and the ratio capacitance of example 10 to example 12 the electrode obtained material is all at more than 1500F/g, namely show that 0.01mol/L ~ 0.04mol/L is optimum concentration range.
5) the electrode material specific volume obtained under example 3 condition higher (specific volume can reach 2334F/g under the charging and discharging currents density of 5A/g), power characteristic is good, cyclical stability high (500 specific volumes that circulate under 20A/g current density still keep more than 82.8%).Thus be that the fields such as the hybrid power energy provide favourable technical support.
Claims (6)
1. prepare the method for ultracapacitor manganese dioxide-nickel hydroxide composite electrode material for one kind, it is characterized in that, for pole plate carries out cathodic electrochemical deposition in potassium permanganate and nickel nitrate mixed aqueous solution electrolyte with nickel foam, nickel sheet or titanium sheet, post-depositional polar board surface washed with de-ionized water, to dry, namely obtain with nickel foam, nickel sheet or titanium sheet be substrate, top layer has the combination electrode material of manganese dioxide-nickel hydroxide laminated film.
2. the method preparing ultracapacitor manganese dioxide-nickel hydroxide composite electrode material according to claim 1, it is characterized in that, described potassium permanganate and nickel nitrate mixed aqueous solution electrolyte, wherein, the concentration of potassium permanganate is 0.005mol/L ~ 0.05mol/L, and the concentration of nickel nitrate is 0.004mol/L ~ 0.12mol/L.
3. the method preparing ultracapacitor manganese dioxide-nickel hydroxide composite electrode material according to claim 1, it is characterized in that, described potassium permanganate and nickel nitrate mixed aqueous solution electrolyte, wherein, the concentration of potassium permanganate is 0.01mol/L ~ 0.04mol/L, and the concentration of nickel nitrate is 0.014mol/L ~ 0.12mol/L.
4. the method preparing ultracapacitor manganese dioxide-nickel hydroxide composite electrode material according to claim 1, is characterized in that, the working temperature of described electrolyte is 20 DEG C ~ 30 DEG C.
5. the method preparing ultracapacitor manganese dioxide-nickel hydroxide composite electrode material according to claim 1, is characterized in that, electrochemical deposition current potential is-0.7 ~-0.95V.
6. the method preparing ultracapacitor manganese dioxide-nickel hydroxide composite electrode material according to claim 1, is characterized in that, electrochemical deposition current potential is-0.8V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210223152.9A CN102709058B (en) | 2012-07-01 | 2012-07-01 | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210223152.9A CN102709058B (en) | 2012-07-01 | 2012-07-01 | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102709058A CN102709058A (en) | 2012-10-03 |
| CN102709058B true CN102709058B (en) | 2015-05-13 |
Family
ID=46901741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210223152.9A Expired - Fee Related CN102709058B (en) | 2012-07-01 | 2012-07-01 | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102709058B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT202100010658A1 (en) * | 2021-04-27 | 2021-07-27 | Novac S R L | Method for electrodeposition in two phases of capacitive material to be applied in the construction of electrodes for energy storage devices and material obtained with the application of this method |
| IT202100010661A1 (en) * | 2021-04-27 | 2021-07-27 | Novac S R L | Nanostructured material for positive electrodes of supercapacitors and related construction method |
| WO2022229994A1 (en) * | 2021-04-27 | 2022-11-03 | Novac S.R.L. | Nanostructured material for positive electrodes of super capacitors and related construction method |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938331A (en) * | 2012-10-11 | 2013-02-20 | 吉林大学 | Foam nickel-base MnO2/C composite electrode material and preparation method thereof |
| CN103996547B (en) * | 2014-06-12 | 2017-01-25 | 中南大学 | Manganese-contained transition metal composite oxide electrode and preparing method and application thereof |
| CN105304352B (en) * | 2015-10-12 | 2018-07-13 | 哈尔滨工业大学深圳研究生院 | Nickel foam autoreaction prepares the method and its supercapacitor applications of manganese dioxide/nickel hydroxide composite nano plate |
| CN107326392B (en) * | 2017-05-24 | 2019-06-25 | 广西大学 | A kind of preparation method of liberation of hydrogen oxygen-separating catalyst |
| CN108896769B (en) * | 2018-08-08 | 2020-05-22 | 福建医科大学 | Human β 2-microglobulin detection method based on gold nanoclusters and kit thereof |
| CN108802139A (en) * | 2018-08-08 | 2018-11-13 | 福建医科大学 | A kind of electrogenerated chemiluminescence method of detection glutathione |
| CN108872209A (en) * | 2018-08-08 | 2018-11-23 | 福建医科大学 | Alkaline phosphatase assay method based on nanogold cluster electrogenerated chemiluminescence probe |
| CN108693172A (en) * | 2018-08-08 | 2018-10-23 | 福建医科大学 | Ascorbic acid electrogenerated chemiluminescence assay method |
| CN108827948A (en) * | 2018-08-08 | 2018-11-16 | 福建医科大学 | Acid phosphatase electrogenerated chemiluminescence measuring method based on gold nano cluster probe |
| CN110379641B (en) * | 2019-07-02 | 2021-07-23 | 武汉理工大学 | Carbon dot/chitosan/manganese dioxide energy storage material and preparation method thereof |
| CN112279313A (en) * | 2020-10-22 | 2021-01-29 | 哈尔滨工业大学 | Preparation method and application of manganese-doped nickel hydroxide composite material |
| CN115418637A (en) * | 2022-08-22 | 2022-12-02 | 河南师范大学 | Method for preparing manganese dioxide coating on surface of nickel-titanium alloy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4092950B2 (en) * | 2001-05-17 | 2008-05-28 | 三菱化学株式会社 | Method for producing lithium nickel manganese composite oxide |
| CN101503805A (en) * | 2009-01-24 | 2009-08-12 | 燕山大学 | Super capacitor and preparation of composite anode material of battery |
| CN101546651A (en) * | 2009-05-07 | 2009-09-30 | 哈尔滨工程大学 | Nano graphite sheet/manganese dioxide doped composite material and preparation method thereof |
| CN101944396A (en) * | 2010-07-29 | 2011-01-12 | 兰州理工大学 | Method for preparing porous mold charcoal/metal oxide composite material for super capacitor electrode |
-
2012
- 2012-07-01 CN CN201210223152.9A patent/CN102709058B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4092950B2 (en) * | 2001-05-17 | 2008-05-28 | 三菱化学株式会社 | Method for producing lithium nickel manganese composite oxide |
| CN101503805A (en) * | 2009-01-24 | 2009-08-12 | 燕山大学 | Super capacitor and preparation of composite anode material of battery |
| CN101546651A (en) * | 2009-05-07 | 2009-09-30 | 哈尔滨工程大学 | Nano graphite sheet/manganese dioxide doped composite material and preparation method thereof |
| CN101944396A (en) * | 2010-07-29 | 2011-01-12 | 兰州理工大学 | Method for preparing porous mold charcoal/metal oxide composite material for super capacitor electrode |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT202100010658A1 (en) * | 2021-04-27 | 2021-07-27 | Novac S R L | Method for electrodeposition in two phases of capacitive material to be applied in the construction of electrodes for energy storage devices and material obtained with the application of this method |
| IT202100010661A1 (en) * | 2021-04-27 | 2021-07-27 | Novac S R L | Nanostructured material for positive electrodes of supercapacitors and related construction method |
| WO2022229994A1 (en) * | 2021-04-27 | 2022-11-03 | Novac S.R.L. | Nanostructured material for positive electrodes of super capacitors and related construction method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102709058A (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102709058B (en) | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors | |
| Pourfarzad et al. | Synthesis of Ni–Co-Fe layered double hydroxide and Fe2O3/Graphene nanocomposites as actively materials for high electrochemical performance supercapacitors | |
| Zhao et al. | Tuning electronic push/pull of Ni-based hydroxides to enhance hydrogen and oxygen evolution reactions for water splitting | |
| Shang et al. | Synthesis of hollow ZnCo2O4 microspheres with enhanced electrochemical performance for asymmetric supercapacitor | |
| CN108054019B (en) | NiCo of laminated structure2S4@NixCo(1-x)(OH)2Preparation method and application of composite material | |
| Wang et al. | Combination of Zn–NiCo2S4 and Zn–air batteries at the cell level: a hybrid battery makes the best of both worlds | |
| CN102938331A (en) | Foam nickel-base MnO2/C composite electrode material and preparation method thereof | |
| Jiang et al. | Design and fabrication of metal-organic frameworks nanosheet arrays constructed by interconnected nanohoneycomb-like nickel-cobalt oxide for high energy density asymmetric supercapacitors | |
| Hu et al. | Hierarchical heterostructures of NiCo 2 O 4@ XMoO 4 (X= Ni, co) as an electrode material for high-performance supercapacitors | |
| Tian et al. | MOF-derived hierarchical core–shell hollow Co 3 S 4@ NiCo 2 O 4 nanosheet arrays for asymmetric supercapacitors | |
| CN105869916A (en) | Method for preparing hydroxyl cobaltous oxide nanotube electrode | |
| CN106057480A (en) | Three-dimensional porous selenide nanocomposite used for super capacitor and preparation method thereof | |
| Moradlou et al. | Interconnected NiCo2S4-coated NiO nanosheet arrays as electrode materials for high-performance supercapacitors | |
| Zhou et al. | High areal capacitance three-dimensional Ni@ Ni (OH) 2 foams via in situ oxidizing Ni foams in mild aqueous solution | |
| CN108878909A (en) | A kind of three-dimensional porous composite material and preparation method and application based on biomass | |
| Xuan et al. | Rational design of hierarchical core-shell structured CoMoO4@ CoS composites on reduced graphene oxide for supercapacitors with enhanced electrochemical performance | |
| Jia et al. | An in situ growth strategy of NiCo-MOF nanosheets with more activity sites for asymmetric supercapacitors | |
| CN109786135A (en) | A kind of copper oxide@nickel molybdate/foam copper combination electrode material and preparation method thereof | |
| Cho et al. | Optimizing nanosheet nickel cobalt oxide as an anode material for bifunctional electrochemical energy storage and oxygen electrocatalysis | |
| Rohit et al. | Facile synthesis of Ce-doped α-cobalt hydroxide nanoflakes battery type electrode with an enhanced capacitive contribution for asymmetric supercapacitors | |
| CN106024414A (en) | Manganese dioxide/polypyrrole composite electrode free of binder, preparation method and application of manganese dioxide/polypyrrole composite electrode | |
| CN108172408A (en) | A kind of NH2-rGO/MnO2Composite material, preparation method and application | |
| CN104282445A (en) | Cobaltosic oxide N-doped carbon nano tube composite electrode material for super capacitor and manufacturing method thereof | |
| Yang et al. | Fabrication of WO3· 2H2O/BC hybrids by the radiation method for enhanced performance supercapacitors | |
| CN111524719A (en) | ED-Mn @ ZIF-67 composite material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150513 Termination date: 20170701 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |