CN103579584B - A kind of alkaline battery tubular type nickel electrode and preparation method thereof - Google Patents
A kind of alkaline battery tubular type nickel electrode and preparation method thereof Download PDFInfo
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- CN103579584B CN103579584B CN201310560485.5A CN201310560485A CN103579584B CN 103579584 B CN103579584 B CN 103579584B CN 201310560485 A CN201310560485 A CN 201310560485A CN 103579584 B CN103579584 B CN 103579584B
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- 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
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- 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
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- 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
- H01M4/30—Pressing
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- 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
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- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/76—Containers for holding the active material, e.g. tubes, capsules
- H01M4/765—Tubular type or pencil type electrodes; tubular or multitubular sheaths or covers of insulating material for said tubular-type 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
- Y02E60/10—Energy storage using batteries
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- Cell Electrode Carriers And Collectors (AREA)
Abstract
The present invention relates to a kind of alkaline battery tubular type nickel electrode and preparation method thereof, the conductive base core that tubular type nickel electrode comprises at least one, the collector electrode be connected with conductive base core one end, it also comprises the comb be set in outside conductive base core, one end of comb closes the other end and collector electrode offsets, the number of conductive base core is identical with the number of described comb, is filled with active material between conductive base core and comb.Comb of the present invention adopts the strong textile material Woven and set of alkali resistance to form, to the stress that active material one is inside, offset the negative effect that active material change in volume is brought, guarantee electrode in use active material do not come off, extend the useful life of electrode.
Description
Technical field
the present invention relates to a kind of alkaline battery, be specifically related to a kind of alkaline battery tubular type nickel electrode and preparation method thereof.
Background technology
in alkaline battery, active material hydroxy nickel oxide/nickel hydroxide widely uses in multiple storage battery system, as Ni-H cell, metal-hydrogen nickel battery, Hawkins cell, zinc-nickel cell etc.Nickel hydroxide comprises α, β two kinds of crystal formations, and corresponding to β, γ two kinds of crystal formations of hydroxy nickel oxide, be the reaction mechanism of diffusion of protons, electrochemical reaction process is along with change in volume.
traditionally, the preparation method of nickel electrode has 3 kinds: 1, bag (box) formula electrode, and active material mixes with conductive materials graphite etc. and is filled in bag or is contained in the punching steel box of nickel plating, makes electrode after compacting; 2, sintered electrode, mixes nickel powder by certain ratio with pore creating material, compressing or be coated on skeleton together with nickel plated steel strip skeleton, prepares sintered type matrix by sintering under reducing atmosphere, makes electrode after chemistry or electrochemical impregnation active material; 3, foam type or fiber type nickel electrode, adopts nickel foam or fiber nickel felt as the collector of electrode, makes electrode after the active material that active material, conductive agent, additive and binding agent form is filled in collector hole.Bag (box) formula nickel electrode mechanical strength is good, reliability is high, material is cheap, but specific capacity, specific energy are lower, heavy-current discharge performance is poor, existing bag (box) formula nickel electrode application reduces gradually, now only for not high to volume, quality requirement, the fixing field of employment that electric current is little.Sintered type nickel electrode mechanical strength is high, conduct electricity very well, high rate performance is high, but specific capacity is low, cost is high, energy consumption is high, and particularly nickel consumption is high, is difficult to reduce costs.Because matrix has high porosity and low-density feature, foam type and fiber type nickel electrode have very height ratio capacity, but the mechanical strength of electrode is low, the change in volume because of active material causes that the expansion of electrode causes electrode deformation, active material comes off, and affects electrode cycle life.We have proposed zinc-nickel single flow battery (ZL 200610109424.7), have the advantages that specific energy is high, specific power is large, operating temperature range is broad, and abundant raw materials, cost are low, can not to environment, be with a wide range of applications as accumulation power supply, be applicable to supportingly with the regenerative resource such as wind energy, solar energy carry out regenerative resource energy storage.In zinc-nickel single flow battery, nickel electrode is one of important parts, also faces the difficult problem that nickel electrode specific capacity is low, cost is high.
there is following problem in current finished product nickel electrode: in (1) charge and discharge process, and hydroxy nickel oxide/nickel hydroxide volume has significant change (expand, shrink), and cause active material to come off seriously, electrode life is impaired; (2) nickel electrode face amount is little, becomes the bottleneck of restriction alkaline battery total capacitance, specific energy; (3) complex process, cost are high, especially sintered nickel electrode, and cost accounts for the over half of single battery cost, become alkaline battery cost restraining factors and the alkaline battery specific energy restraining factors for scale energy storage.
in sum, improving of new Type Nickel Electrodes is the key effectively improving and improve alkaline battery.
Summary of the invention
technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of alkaline battery tubular type nickel electrode and preparation method thereof, guarantee that in use procedure, positive active material does not come off, and improves the capacity of nickel electrode, extends battery.
for solving above technical problem, a kind of technical scheme that the present invention takes is:
a kind of alkaline battery tubular type nickel electrode, comprise the conductive base core of at least one, the collector electrode be connected with conductive base core one end, the comb be set in outside conductive base core, one end of comb closes the other end and collector electrode offsets, the number of conductive base core is identical with the pipe number of comb, is filled with active material between conductive base core and comb.
preferably, comb is woven by fiber textile material, is formed through curing agent solidifying and setting, and fiber textile material is the one or more combination in Polyamide Yarns, polypropylene fiber silk, polytetrafluoroethylene, Kynoar.
preferably, the porosity of=50% of comb, the braiding aperture of comb is not more than 50 microns, and the hole of comb is less than the particle diameter of active material.
preferably, the shape of cross section of comb is the one in circle, ellipse, square, rectangle, kidney-shaped.
preferably, the material of conductive base core is the one in nickel foam, nickel, nickel plating stainless steel, nickel-plated steel.
preferably, the shape of cross section of conductive base core be circle, annular, star, square in one.
preferably, one end of comb is closed by detaining underseal.
further preferably, the button end is the seal buckle supporting with comb, and the material of seal buckle is the one or more combination thing in nylon, polyethylene, polyvinyl chloride, polyvinyl alcohol, furane resins.
preferably, active material is the mixed Ni electrode slurry containing nickel hydroxide, nickel powder, cobalt oxide.
active component in active material is the mixed oxide of nickel hydroxide, hydroxy nickel oxide, can be that alkaline battery commonly uses ball nickel, nano-sized nickel hydroxide or their mixture, can be the coated nickel hydroxide of hydroxy cobalt oxide.
preferably, the material of collector electrode is the one in nickel, nickel plating stainless steel, nickel-plated steel, and the offset shape at position of collector electrode and comb is the shape be sealed and matched mutually with pipe in comb.
relate to a preparation method for above-mentioned alkaline battery tubular type nickel electrode, comprise the following steps:
1, with loom, fiber textile material is made into the grey cloth of the single tube with blank pipe, along with the braiding of fiber textile material is joined together to form multitube grey cloth between single tube, multitube grey cloth is cut into required dimensions and immerses curing agent, after drying, core rod is inserted in blank pipe, extract core rod out after solidification, after revising, obtain comb 3;
2, by active material 4 granulation in comminutor with water or ethanol water, wherein, the granular size after granulation is not more than 0.5mm, and the volume ratio of water or ethanol water and active material 4 is not more than 20%;
3, collector electrode 1 and conductive base core 2 are same material integrative-structure, or collector electrode 1 is Split type structure with conductive base core 2 and the two is welded together, comb 3 is set in conductive base core 2 outer and make conductive base core 2 be in comb 3 center, with powder-filling machine fro, the particle of making in step (2) is clamp-oned also compacting in comb 3, with the button end, the other end of described comb is closed, wherein, comb 3 stress caused by interior extrusion expansion be not less than 5 newton/centimetre;
4, the electrode base material chemical activation obtained in step (3) or electrochemical process are activated, obtain alkaline battery tubular type nickel electrode.Wherein, the electrode base material 3-10 hour of chemical activation for obtaining with persulfate, aqueous hypochlorite solution soaking step (3); Electrochemical process activation is for the electrode base material that step (3) obtained is with electric 3-5 time of 0.1-0.5 multiplying power current charge-discharge.
due to the employing of above technical scheme, the present invention compared with prior art tool has the following advantages:
1, active material of the present invention is filled in pipe, conductive base core with combine closely fully, actual face amount is greater than the nickel electrode of other existing type, and battery total capacitance is large.
, comb of the present invention adopts the braiding of alkali resistance strong fiber textile material, curing agent solidifying and setting forms, to the stress that positive active material one is inside, anode volume can be offset and change the negative effect brought, alleviate hydroxy nickel oxide/nickel hydroxide change in volume, guarantee nickel electrode in use positive active material do not come off, the useful life of electrode can be extended.
, nickel electrode manufacture craft of the present invention is easy, efficiency is high, cost is low, steady quality is reliable, contributes to the manufacturing cost reducing nickel electrode and alkaline battery.
Accompanying drawing explanation
fig. 1 is structural representation of the present invention;
in figure: 1, collector electrode; 2, conductive base core; 3, comb; 4, active material.
Embodiment
below in conjunction with drawings and Examples, the invention will be further described:
embodiment 1
as shown in Figure 1, alkaline battery tubular type nickel electrode of the present invention, comprising 19 diameters is 4.5mm, the circular shaped foam nickel bar of the long porous loose structure for 70mm is as conductive base core 2, the collector electrode 1 be connected with conductive base core 2 one end, the material of collector electrode 1 is nickel plating stainless steel, the length being arranged with number identical with conductive base core outside conductive base core 2 is 70 mm, internal diameter is 5 mm, wall thickness is the circular comb 3 of 0.5 mm, comb 3 is woven by Polyamide Yarns, form through curing agent solidifying and setting, the porosity of comb 3 is 50%, braiding aperture is 50 microns, the vinyon button underseal that one end of comb 3 is 5mm by external diameter closes, the other end and collector electrode 1 offset, collector electrode 1 offsets partly for external diameter is that the low round platform of 5mm is to seal comb 3 with comb 3, the nickel electrode slurry mixed is filled with in space between conductive base core 2 with comb 3, in slurry, the percentage by weight of each component is nickel hydroxide 34%, nickel powder 34%, cobalt oxide 5%, water 25%, CMC 0.7% and PTFE 1.3%.
the preparation method of alkaline battery tubular type nickel electrode is as follows: Polyamide Yarns is made into the grey cloth of the single tube with blank pipe by (1) with loom, along with the braiding of Polyamide Yarns is joined together to form multitube grey cloth between single tube, multitube grey cloth being cut into required dimensions immerses in curing agent bisphenol type epoxy vinyl esters resin, after drying, circular core rod is inserted in blank pipe, extract core rod out after solidification, after revising, obtain comb 3; (2) by active material 4(nickel hydroxide 34%, nickel powder 34%, cobalt oxide 5%, water 25%, CMC 0.7% and PTFE 1.3%) water granulation in comminutor with 25%, the granular size after granulation is 0.5mm; (3) by the parts of nickel foam conductive base core 2 with the integrally welded structure of collector electrode 1, comb 3 is set in conductive base core 2 outer and make conductive base core 2 be in the center of comb 3, with powder-filling machine fro, the particle that step (2) is made is clamp-oned compacting in comb 3, with the button end, the other end of comb 3 is closed, wherein, the stress of comb 3 caused by interior extrusion expansion be 5 newton/centimetre; (4) electrode base material obtained in step (3) to be immersed in the 7M KOH aqueous solution 15 hours, then with 0.25 multiplying power current charge-discharge electricity 5 times, to obtain final product.Discharge and recharge auxiliary electrode is excessive sintering cadmium electrode, charging/discharging voltage scope 0.9-1.8V.
embodiment 2
a kind of alkaline battery tubular type nickel electrode, comprising long 10 external diameters for 100mm is 4.5mm, wall thickness is that the nickel plating steel pipe of 0.5mm is as conductive base core 2, the collector electrode 1 integrated with conductive base core 2 one end, collector electrode 1 is long 100mm, the spill nickel plating steel disc of wide 20mm, the length being arranged with number identical with conductive base core outside conductive base core 2 is 105 mm, internal diameter is 5 mm, wall thickness is the circular comb 3 of 0.4 mm, comb 3 is woven by polypropylene fiber silk, form through curing agent solidifying and setting, the porosity of comb 3 is 55%, braiding aperture is 50 microns, the polyvinyl alcohol plastic button underseal that one end of comb 3 is 5mm by external diameter closes, collector electrode 1 offsets partly for external diameter is that the low round platform of 5mm is to seal comb 3 with comb 3, the nickel electrode slurry mixed is filled with in space between conductive base core 2 with comb 3, in slurry, the percentage by weight of each component is nickel hydroxide 85%, nickel powder 7%, cobalt oxide 6%, CMC 0.7% and PTFE 1.3%.
the preparation method of alkaline battery tubular type nickel electrode is as follows: polypropylene fiber silk is made into the grey cloth of the single tube with blank pipe by (1) with loom, along with the braiding of Polyamide Yarns is joined together to form multitube grey cloth between single tube, multitube grey cloth being cut into required dimensions immerses in curing agent bisphenol type epoxy vinyl esters resin, after drying, circular core rod is inserted in blank pipe, extract core rod out after solidification, after revising, obtain comb 3; (2) by active material 4(nickel hydroxide 85%, nickel powder 7%, cobalt oxide 6%, CMC 0.7% and PTFE 1.3%) be the granulation in comminutor of 95% ethanol water with mass fraction, granular size after granulation is 0.4mm, and the volume ratio of ethanol water and active material 4 is 15%; (3) matter of drawing materials is the conductive base core 2 of nickel-plated steel and the parts of collector electrode 1 integrative-structure, comb 3 is set in conductive base core 2 outer and make conductive base core 2 be in the center of comb 3, with powder-filling machine fro, the particle that step (2) is made is clamp-oned compacting in comb 3, with the button end, the other end of comb 3 is closed, wherein, the stress of comb 3 caused by interior extrusion expansion be 5 newton/centimetre; (4) electrode base material obtained in step (3) to be immersed in the 7M KOH aqueous solution 10 hours, then with 0.1 multiplying power current charge-discharge electricity 3 times, to obtain final product.Discharge and recharge auxiliary electrode is excessive sintering cadmium electrode, charging/discharging voltage scope 1-1.7 V.
embodiment 3
a kind of alkaline battery tubular type nickel electrode, comprising long 38 length of sides for 250mm is that the stainless steel column of open squares nickel plating of 5.5cm is as conductive base core 2, the collector electrode 1 welded mutually with conductive base core 2 one end, the material of collector electrode 1 is nickel plating stainless steel, the length being arranged with number identical with conductive base core outside conductive base core 2 is 250 mm, internal diameter is 6 mm, wall thickness is the circular comb 3 of 0.5 mm, comb 3 is woven by Kynoar, form through curing agent solidifying and setting, the porosity of comb 3 is 55%, braiding aperture is 45 microns, the igelite button underseal that one end of comb 3 is 6mm by external diameter closes, collector electrode 1 offsets partly for external diameter is that the low round platform of 6mm is to seal comb 3 with comb 3, the nickel electrode slurry mixed is filled with in space between conductive base core 2 with comb 3, in slurry, the percentage by weight of each component is nickel hydroxide 83%, nickel powder 10%, cobalt oxide 5%, CMC 0.7% and PTFE 1.3%.
the preparation method of alkaline battery tubular type nickel electrode is as follows: Kynoar is made into the grey cloth of the single tube with blank pipe by (1) with loom, along with the braiding of Polyamide Yarns is joined together to form multitube grey cloth between single tube, multitube grey cloth being cut into required dimensions immerses in curing agent bisphenol type epoxy vinyl esters resin, after drying, circular core rod is inserted in blank pipe, extract core rod out after solidification, after revising, obtain comb 3; (2) by active material 4(nickel hydroxide 83%, nickel powder 10%, cobalt oxide 5%, CMC 0.7% and PTFE 1.3%) be the granulation in comminutor of 95% ethanol water with mass fraction, granular size after granulation is 0.4mm, and the volume ratio of ethanol water and active material 4 is 20%; (3) matter of drawing materials is the conductive base core 2 of nickel-plated steel and the parts of collector electrode 1 integrative-structure, comb 3 is set in conductive base core 2 outer and make conductive base core 2 be in the center of comb 3, with powder-filling machine fro, the particle that step (2) is made is clamp-oned compacting in comb 3, with the button end, the other end of comb 3 is closed, wherein, the stress of comb 3 caused by interior extrusion expansion be 7 newton/centimetre; (4) electrode base material obtained in step (3) to be immersed in persulfate, aqueous hypochlorite solution 7 hours, to obtain final product.
comb of the present invention adopts the strong textile material Woven and set of alkali resistance to form, to the stress that positive active material one is inside, offset anode volume change the negative effect brought, guarantee nickel electrode in use positive active material do not come off, extend the useful life of electrode.
above to invention has been detailed description, but the invention is not restricted to the embodiments described.The equivalence change that all Spirit Essences according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (9)
1. the alkaline battery preparation method of tubular type nickel electrode, described alkaline battery tubular type nickel electrode comprises the conductive base core (2) of at least one, the collector electrode (1) be connected with conductive base core one end, the comb (3) be set in outside conductive base core, one end of described comb (3) is closed, the other end and described collector electrode (1) offset, the number of described conductive base core (2) is identical with the pipe number of described comb (3), be filled with active material (4) between described conductive base core (2) and comb (3), described preparation method comprises the following steps:
A fiber textile material is made into the grey cloth of the single tube with blank pipe by () with loom, along with the braiding of fiber textile material is joined together to form multitube grey cloth between single tube, multitube grey cloth is cut into required dimensions and immerses curing agent, after drying, core rod is inserted in blank pipe, extract core rod out after solidification, after revising, obtain comb (3);
B (), by active material (4) granulation in comminutor with water or ethanol water, wherein, the granular size after granulation is not more than 0.5mm, and the volume ratio of water or ethanol water and active material (4) is not more than 20%;
C () collector electrode (1) and conductive base core (2) are same material integrative-structure, or collector electrode (1) and conductive base core (2) are for Split type structure and the two welded together, described comb (3) is set in conductive base core (2) and make described conductive base core (2) be in described comb (3) center outward, with powder-filling machine fro, the particle of making in described step (2) is clamp-oned also compacting in described comb (3), with the button end, the other end of described comb is closed, wherein, described comb (3) stress caused by interior extrusion expansion be not less than 5 newton/centimetre;
D the electrode base material chemical activation obtained in described step (c) or electrochemical process activate by (), obtain alkaline battery tubular type nickel electrode; Wherein, the electrode base material 3-10 hour that obtains for soaking described step (c) by persulfate, aqueous hypochlorite solution of chemical activation; Electrochemical process activation is for the electrode base material that described step (c) obtained is with electric 3-5 time of 0.1-0.5 multiplying power current charge-discharge.
2. preparation method according to claim 1, it is characterized in that: described comb (3) is woven by fiber textile material, formed through curing agent solidifying and setting, and described fiber textile material is the one or more combination in Polyamide Yarns, polypropylene fiber silk, polytetrafluoroethylene, Kynoar.
3. preparation method according to claim 1, it is characterized in that: the porosity of=50% of described comb (3), the braiding aperture of described comb (3) is not more than 50 microns.
4. preparation method according to claim 1, is characterized in that: the shape of cross section of described comb (3) is the one in circle, ellipse, square, rectangle, kidney-shaped.
5. preparation method according to claim 1, is characterized in that: the material of described conductive base core (2) is the one in nickel, nickel-plated steel, the shape of cross section of described conductive base core (2) be circle, annular, star, square in one.
6. preparation method according to claim 1, is characterized in that: one end of described comb (3) is closed by detaining underseal.
7. preparation method according to claim 6, it is characterized in that: be the seal buckle supporting with described comb (3) at the bottom of described button, the material of described seal buckle is the one or more combination thing in nylon, polyethylene, polyvinyl chloride, polyvinyl alcohol, furane resins.
8. preparation method according to claim 1, is characterized in that: described active material (4) is the mixed Ni electrode slurry containing nickel hydroxide, nickel powder, cobalt oxide.
9. preparation method according to claim 1, it is characterized in that: the material of described collector electrode (1) is the one in nickel, nickel-plated steel, the offset shape at position of described collector electrode (1) and described comb (3) is the shape be sealed and matched mutually with the interior pipe of described comb (3).
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| CN1129856A (en) * | 1994-09-20 | 1996-08-28 | 三洋电机株式会社 | Nickel electrode active material, a nickel electrode and a nickel alkali storage cell using such nickel electrode active material, and production methods of such material electrode, and cell |
| JP4710225B2 (en) * | 2001-09-03 | 2011-06-29 | 株式会社Ｇｓユアサ | Method for producing nickel electrode material |
| CN202004088U (en) * | 2011-03-31 | 2011-10-05 | 湖南丰日电源电气股份有限公司 | Battery negative plate for rapid trains |
| CN102800846A (en) * | 2012-08-30 | 2012-11-28 | 上海锦众信息科技有限公司 | Preparation method for positive electrode of power battery |
| CN203553276U (en) * | 2013-11-12 | 2014-04-16 | 张家港智电芳华蓄电研究所有限公司 | Tube type nickel electrode for alkaline batteries |
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- 2013-11-12 CN CN201310560485.5A patent/CN103579584B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1129856A (en) * | 1994-09-20 | 1996-08-28 | 三洋电机株式会社 | Nickel electrode active material, a nickel electrode and a nickel alkali storage cell using such nickel electrode active material, and production methods of such material electrode, and cell |
| JP4710225B2 (en) * | 2001-09-03 | 2011-06-29 | 株式会社Ｇｓユアサ | Method for producing nickel electrode material |
| CN202004088U (en) * | 2011-03-31 | 2011-10-05 | 湖南丰日电源电气股份有限公司 | Battery negative plate for rapid trains |
| CN102800846A (en) * | 2012-08-30 | 2012-11-28 | 上海锦众信息科技有限公司 | Preparation method for positive electrode of power battery |
| CN203553276U (en) * | 2013-11-12 | 2014-04-16 | 张家港智电芳华蓄电研究所有限公司 | Tube type nickel electrode for alkaline batteries |
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