CN107768605B - Preparation method of electrode material of nickel-metal hydride battery with ultra-long service life - Google Patents

Preparation method of electrode material of nickel-metal hydride battery with ultra-long service life Download PDF

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CN107768605B
CN107768605B CN201610668086.4A CN201610668086A CN107768605B CN 107768605 B CN107768605 B CN 107768605B CN 201610668086 A CN201610668086 A CN 201610668086A CN 107768605 B CN107768605 B CN 107768605B
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nickel
metal hydride
protective layer
hydride battery
nitrogen
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CN107768605A (en
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许志
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Fujian Xinfeng Two Dimensional Material Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/32—Nickel oxide or hydroxide 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
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method of an electrode material of a nickel-metal hydride battery with an ultra-long service life, which comprises the following steps: firstly, removing nickel oxide on the surface of the pore wall of the foamed nickel; growing a carbon-containing or/and nitrogen-containing protective layer on the surface of the pore wall of the foamed nickel; then forming a uniform electrode active material layer on the surface of the carbon-containing or/and nitrogen-containing protective layer; finally, the interior of the nickel foam is filled with an electrode active material. According to the invention, nickel oxide on the surface of the foamed nickel is removed, and a carbon-containing or nitrogen-containing protective layer is formed on the surface of the foamed nickel, the protective layer is highly conductive, and the surface of the protective layer contains a plurality of dangling bonds and active hydroxyl groups, so that the bonding capability of the foamed nickel and an electrode active substance can be effectively increased, and the contact resistance is reduced; the generation of dendrites can be effectively inhibited, and the short circuit of the positive electrode and the negative electrode caused by the penetration of the diaphragm is avoided; the nickel foam can be effectively coated, the nickel foam is prevented from being corroded and consumed in the battery circulation process, the structural integrity of the electrode is maintained, the utilization rate of active substances is improved, and the cycle life of the nickel-metal hydride battery is prolonged.

Description

Preparation method of electrode material of nickel-metal hydride battery with ultra-long service life
Technical Field
The invention relates to the field of nickel-metal hydride batteries and preparation of electrode materials thereof, in particular to a preparation method of an ultra-long-life nickel-metal hydride battery electrode material.
Background
With the increasing severity of urban air pollution, the research and development of batteries for electric vehicles are receiving more and more attention. The nickel-metal hydride battery has the advantages of high capacity, high power, no pollution and the like, compared with the nickel-cadmium battery, the capacity of the nickel-metal hydride battery is improved by more than 50 percent, the pollution of metal to the environment is eliminated, the quick charge can be realized, and the nickel-metal hydride battery is a very important development direction of the current secondary battery. Meanwhile, the nickel-metal hydride battery has excellent performances of low cost and high power, is the only battery system which is actually verified, commercialized and scaled in the battery systems used by the existing hybrid electric vehicles, and all the hybrid electric vehicles which are produced in batches worldwide adopt the nickel-metal hydride battery system.
The nickel-metal hydride battery is an alkaline secondary battery using a hydrogen storage alloy as a negative electrode. The nickel-hydrogen battery is made up by using foamed nickel (or steel mesh) and metal hydride (LaNi)5H6) The cathode is a foamed nickel (nickel oxide) and nickel hydroxide electrode, the anode is a foamed nickel (nickel oxide) and nickel hydroxide electrode, the electrolyte is potassium hydroxide, lithium hydroxide and the like, and the diaphragm is vinylon (or polypropylene or nylon). The foamed nickel has high capacity density, high electrode active matter utilization rate up to 90%, simple production process, less investment in apparatus and high fast charge and discharge performance, so that the conducting skeleton of positive and negative electrodes of nickel-hydrogen battery is foamed nickel. However, since a small amount of copper is generally present in the nickel foam, nickel or copper dendrites are easily formedThe dendrite can pierce through the diaphragm to cause short circuit of the positive electrode and the negative electrode; in addition, the contact between the foamed nickel and the active material is not good enough, so that the foamed nickel substrate can be continuously corroded and consumed in the charge-discharge cycle process of the battery, and meanwhile, the foamed nickel is corroded and dissolved into the electrolyte, so that the components of the electrolyte are changed. Therefore, the short circuit of the anode and the cathode and the damage of the electrode structure are caused, the capacity of the battery is rapidly reduced, the battery cannot be used continuously, and the service life of the battery is short. Because the service life of the nickel-metal hydride battery is short, the problem of battery replacement must be considered when the nickel-metal hydride battery is applied to a hybrid electric vehicle, at least 3000 dollars are needed for replacing the primary battery of the conventional hybrid electric vehicle, the cost is high, and the market advantage of the hybrid electric vehicle is greatly reduced. Therefore, the nickel-metal hydride battery with the ultra-long service life is significant.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of an electrode material of a nickel-metal hydride battery with an ultra-long service life, which solves the problems that the traditional nickel-metal hydride battery has short cycle life due to the reasons that a diaphragm is penetrated by dendritic crystals to cause short circuit of a positive electrode and a negative electrode, and an electrode structure is damaged due to the corrosion and consumption of foam nickel; the invention also aims to provide a nickel-metal hydride battery with an ultra-long service life, and solves the problems that the traditional nickel-metal hydride battery has short cycle life, so that the battery replacement cost of a hybrid power automobile is high, the market advantage is reduced, the market demand of the future power automobile cannot be completely met, and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of an electrode material of a nickel-metal hydride battery with ultra-long service life comprises the following steps:
removing nickel oxide on the surface of the pore wall of the foamed nickel;
growing a carbon-containing or/and nitrogen-containing protective layer on the surface of the pore wall of the foamed nickel;
forming a uniform electrode active material layer on the surface of the carbon-containing or/and nitrogen-containing protective layer;
the interior of the nickel foam is filled with an electrode active material.
Furthermore, the nickel foam is a conductive framework of a positive electrode material or/and a negative electrode material, the surface density of the nickel foam is 200-400g/m2, the porosity is more than or equal to 95%, and the thickness is 1-3 mm.
Further, the method for removing nickel oxide on the surface of the foamed nickel adopts at least one of hydrogen reduction or acid treatment method.
Further, the carbon-containing or/and nitrogen-containing protective layer on the surface of the foamed nickel pore wall is prepared by at least one of Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), Atomic Layer Deposition (ALD) and hydrothermal chemical reaction method.
Further, the thickness of the carbon-containing or/and nitrogen-containing protective layer on the surface of the pore wall of the foamed nickel is about 1nm-5000 nm.
Furthermore, the carbon-containing or/and nitrogen-containing protective layer on the surface of the pore wall of the foamed nickel is highly conductive, and the surface of the protective layer contains a plurality of dangling bonds and active hydroxyl groups, so that the bonding capability of the foamed nickel and an electrode active substance is effectively improved, and the contact resistance is reduced.
Further, the uniform electrode active material layer formed on the surface of the carbon-containing or/and nitrogen-containing protective layer is soaked in the active material solution by an electrochemical soaking method, so that the uniform active material layer is formed on the surface of the carbon-containing/nitrogen-containing protective layer of the foamed nickel.
From the above description of the structure of the present invention, compared with the prior art, the present invention has the following advantages:
according to the invention, nickel oxide on the surface of the electrode conductive framework foam nickel is removed, and a carbon-containing or nitrogen-containing protective layer is formed on the surface of the electrode conductive framework foam nickel, wherein the protective layer is highly conductive and contains a plurality of dangling bonds and active hydroxyl groups on the surface, so that the bonding capability of the foam nickel and an electrode active substance is effectively increased, and the contact resistance is reduced; the protective layer can effectively inhibit the generation of dendrites and avoid the short circuit of the positive electrode and the negative electrode caused by the penetration of the diaphragm; the protective layer can effectively coat the foam nickel, avoid the foam nickel from being corroded and consumed in the battery cycle process, keep the integrity of the electrode structure, and improve the utilization rate of active substances, thereby greatly prolonging the cycle life of the nickel-metal hydride battery. Compared with the nickel-metal hydride battery on the market at present, the nickel-metal hydride battery prepared by the electrode material has the capacity equivalent to that of the nickel-metal hydride battery on the market at present, and the cycle life of the nickel-metal hydride battery is at least 2-3 times longer than that of the nickel-metal hydride battery on the market at present.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of a method for preparing an electrode material for an ultra-long life nickel-hydrogen battery according to the present invention;
FIG. 2 is a schematic structural diagram of an electrode material for an ultra-long-life nickel-metal hydride battery of the present invention;
FIG. 3 is a graph comparing the discharge capacity of the nickel-metal hydride batteries of examples 1, 2 and 3 of the present invention and comparative example with the cycle number.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of an electrode material of a nickel-metal hydride battery with an ultra-long service life, which comprises the following steps:
s01, removing nickel oxide on the surface of the pore wall of the foamed nickel, and adopting at least one of hydrogen reduction or acid treatment methods, wherein the foamed nickel is a conductive framework of the anode material or/and the cathode material, the surface density of the foamed nickel is 200-400g/m2, the porosity is not less than 95%, and the thickness is 1-3 mm;
s02, growing a carbon-containing or/and nitrogen-containing protective layer on the surface of the hole wall of the foamed nickel, wherein the carbon-containing or/and nitrogen-containing protective layer is prepared by at least one of Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), atomic layer deposition technology (ALD) and hydrothermal chemical reaction methods, is highly conductive, and has a plurality of dangling bonds and active hydroxyl groups on the surface, so that the bonding capability of the foamed nickel and an electrode active substance is effectively improved, the contact resistance is reduced, meanwhile, the protective layer can effectively inhibit the generation of dendrites, and the short circuit of the positive electrode and the negative electrode caused by the penetration of the diaphragm is avoided; the nickel foam can be effectively coated, so that the nickel foam is prevented from being corroded and consumed in the battery circulation process, the structural integrity of an electrode is maintained, the utilization rate of active substances is improved, and the cycle life of the nickel-metal hydride battery is greatly prolonged;
s03, forming a uniform electrode active material layer on the surface of the carbon-containing or/and nitrogen-containing protective layer, and soaking the active material layer in an active material solution (such as Ni (OH)) by electrochemical soaking method2) So as to form a uniform active material layer on the surface of the carbon/nitrogen-containing protective layer of the foamed nickel;
s04, filling the foam nickel with an electrode active material.
The electrode structure of the nickel-metal hydride battery prepared by the method is shown in figure 2, the surface of a foamed nickel pore wall 11 is covered by a carbon-containing or/and nitrogen-containing protective layer 12, the outer surface of the foamed nickel pore wall is uniformly distributed with electrode active substances 13-1, and the electrode active substances 13-2 are filled in the pores of the foamed nickel, namely the outermost layer of the foamed nickel pore wall and distributed more randomly.
Example 1
Firstly removing nickel oxide layer on the wall surface of the foamed nickel pore by using a hydrogen reduction method, then forming a carbon/nitrogen-containing protective layer with the thickness of about 500nm on the surface of the foamed nickel by using an Atomic Layer Deposition (ALD) technology, and then immersing a positive active material Ni (OH) by using an electrochemical deposition method2In the solution, a uniform layer of Ni (OH) is formed on the surface2A layer of active material Ni (OH)2Filling the foamed nickel pores in the medium nickel alloy and rolling to form the positive electrode of the nickel-hydrogen battery. The cathode of the nickel-metal hydride battery adopts a conventional steel mesh or a conventional copper mesh plus metal hydride (LaNi)5H6) And finally assembling the nickel-metal hydride battery.
The nickel-metal hydride battery is charged and discharged under 1C, the discharge capacity is about 1500mAh, the capacity of about 950mAh is still kept after 400 cycles, and the capacity is still kept about 63.3%.
Example 2
Removing nickel oxide layer on the wall surface of the foam nickel hole by acid treatment, forming a carbon/nitrogen-containing protective layer with a thickness of about 100nm on the surface of the foam nickel by Chemical Vapor Deposition (CVD), and immersing into a positive active material Ni (OH) by electrochemical deposition2In solution, in the form of its surfaceForm a uniform layer of Ni (OH)2A layer of active material Ni (OH)2Filling the foamed nickel pores in the medium nickel alloy and rolling to form the positive electrode of the nickel-hydrogen battery. The cathode of the nickel-metal hydride battery adopts a conventional steel mesh or a conventional copper mesh plus metal hydride (LaNi)5H6) And finally assembling the nickel-metal hydride battery.
The nickel-metal hydride battery is charged and discharged under 1C, the discharge capacity is about 1500mAh, the capacity of about 950mAh is still kept after 400 cycles, and the capacity is still kept about 63.3%.
Example 3
Removing nickel oxide layer on the wall surface of the foamed nickel hole by hydrogen reduction, forming a carbon/nitrogen-containing protective layer with the thickness of about 1000nm on the surface of the foamed nickel by Atomic Layer Deposition (ALD), and immersing into a positive active material Ni (OH) by electrochemical deposition2In the solution, a uniform layer of Ni (OH) is formed on the surface2A layer of active material Ni (OH)2Filling the foamed nickel pores in the medium nickel alloy and rolling to form the positive electrode of the nickel-hydrogen battery.
Removing nickel oxide on the surface of the nickel foam of the negative conductive framework by the same process as the positive electrode, forming a carbon/nitrogen-containing protective layer with the thickness of about 200nm on the surface of the nickel foam by the Atomic Layer Deposition (ALD), and mixing the nickel foam with metal hydride (LaNi)5H6) And preparing the cathode of the nickel-metal hydride battery, and finally assembling the nickel-metal hydride battery.
The nickel-metal hydride battery is charged and discharged under 1C, the discharge capacity is about 1500mAh, the capacity of 1150mAh is still maintained after 400 cycles, and the capacity is still maintained at about 76.6%.
Comparative example:
comparative example the nickel-metal hydride battery is a commercially available better nickel-metal hydride battery. The nickel-metal hydride battery is charged and discharged under 1C, the discharge capacity of the nickel-metal hydride battery is about 1500mAh, the discharge capacity of the nickel-metal hydride battery begins to rapidly decay after 150 cycles, the 285 th cycle discharge capacity is only about 500mAh, the 325 th cycle discharge capacity is only about 45mAh, and only about 3% of the highest discharge capacity is obtained.
As shown in fig. 3, it can be seen from the comparison graph of the discharge capacity of the nickel-metal hydride batteries of examples 1, 2 and 3 and the comparative example varying with the cycle number that the discharge capacity of the nickel-metal hydride battery prepared by using the electrode material of the nickel-metal hydride battery provided by the invention is equivalent to that of the nickel-metal hydride battery on the market at present, but the cycle life of the nickel-metal hydride battery provided by the invention is 2-3 times of that of the nickel-metal hydride battery on the market at present.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (7)

1. A preparation method of an electrode material of a nickel-metal hydride battery with ultra-long service life is characterized by comprising the following steps: the method comprises the following steps:
removing nickel oxide on the surface of the pore wall of the foamed nickel;
growing a carbon-containing or/and nitrogen-containing protective layer on the surface of the pore wall of the foamed nickel;
forming a uniform electrode active material layer on the surface of the carbon-containing or/and nitrogen-containing protective layer;
the interior of the nickel foam is filled with an electrode active material.
2. The method for preparing the electrode material of the ultra-long-life nickel-metal hydride battery according to claim 1, wherein the method comprises the following steps: the foamed nickel is a conductive framework of a positive electrode material or/and a negative electrode material, and the surface density of the foamed nickel is 200-400g/m2The porosity is more than or equal to 95 percent and the thickness is 1-3 mm.
3. The method for preparing the electrode material of the ultra-long-life nickel-metal hydride battery according to claim 1, wherein the method comprises the following steps: the method for removing the nickel oxide on the surface of the foamed nickel adopts at least one of hydrogen reduction or acid treatment methods.
4. The method for preparing the electrode material of the ultra-long-life nickel-metal hydride battery according to claim 1, wherein the method comprises the following steps: the carbon-containing or/and nitrogen-containing protective layer on the surface of the foamed nickel pore wall is prepared by at least one of Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), Atomic Layer Deposition (ALD) and hydrothermal chemical reaction.
5. The method for preparing the electrode material of the ultra-long-life nickel-metal hydride battery according to claim 1, wherein the method comprises the following steps: the thickness of the carbon-containing or/and nitrogen-containing protective layer on the surface of the foamed nickel pore wall is about 1nm-5000 nm.
6. The method for preparing the electrode material of the ultra-long-life nickel-metal hydride battery according to claim 1, wherein the method comprises the following steps: the carbon-containing or/and nitrogen-containing protective layer on the surface of the pore wall of the foamed nickel is highly conductive, and the surface of the protective layer contains a plurality of dangling bonds and active hydroxyl groups.
7. The method for preparing the electrode material of the ultra-long-life nickel-metal hydride battery according to claim 1, wherein the method comprises the following steps: and forming a uniform electrode active material layer on the surface of the carbon-containing or/and nitrogen-containing protective layer, and impregnating an active material solution by adopting an electrochemical impregnation method, so that a uniform active material layer is formed on the surface of the foamed nickel carbon-containing/nitrogen-containing protective layer.
CN201610668086.4A 2016-08-15 2016-08-15 Preparation method of electrode material of nickel-metal hydride battery with ultra-long service life Active CN107768605B (en)

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PCT/CN2017/095760 WO2018032972A1 (en) 2016-08-15 2017-08-03 Manufacturing method of electrode material of nickel-hydrogen battery having long service-life

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CN108777234B (en) * 2018-05-25 2021-02-05 深圳探影生物科技有限公司 Graphite fiber electrode coated with activated carbon and supercapacitor prepared from graphite fiber electrode
CN110752373B (en) * 2019-10-28 2021-06-15 北京科技大学 High-performance liquid metal battery negative current collector and preparation method thereof

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JPH0487154A (en) * 1990-07-26 1992-03-19 Shin Kobe Electric Mach Co Ltd Hydrogen storage electrode and manufacture thereof
JPH0547379A (en) * 1991-08-07 1993-02-26 Furukawa Battery Co Ltd:The Nickel hydroxide electrode for alkaline secondary battery
CN1492080A (en) * 2003-09-28 2004-04-28 北京航空航天大学 Process for preparing nickel hydroxide material using electric deposition method
CN2696139Y (en) * 2003-11-04 2005-04-27 邝达辉 Large content high power nickle-cadmium charging cell
CN101276692A (en) * 2008-05-19 2008-10-01 清华大学 Nickelous hydroxide composite super capacitor and manufacture process thereof
CN102354609A (en) * 2011-08-23 2012-02-15 吉林大学 Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor

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Publication number Priority date Publication date Assignee Title
JPH0487154A (en) * 1990-07-26 1992-03-19 Shin Kobe Electric Mach Co Ltd Hydrogen storage electrode and manufacture thereof
JPH0547379A (en) * 1991-08-07 1993-02-26 Furukawa Battery Co Ltd:The Nickel hydroxide electrode for alkaline secondary battery
CN1492080A (en) * 2003-09-28 2004-04-28 北京航空航天大学 Process for preparing nickel hydroxide material using electric deposition method
CN2696139Y (en) * 2003-11-04 2005-04-27 邝达辉 Large content high power nickle-cadmium charging cell
CN101276692A (en) * 2008-05-19 2008-10-01 清华大学 Nickelous hydroxide composite super capacitor and manufacture process thereof
CN102354609A (en) * 2011-08-23 2012-02-15 吉林大学 Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor

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