CN100382377C - Formation method of sealed nickel metal hydride secondary battery - Google Patents
Formation method of sealed nickel metal hydride secondary battery Download PDFInfo
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- CN100382377C CN100382377C CNB2004100403225A CN200410040322A CN100382377C CN 100382377 C CN100382377 C CN 100382377C CN B2004100403225 A CNB2004100403225 A CN B2004100403225A CN 200410040322 A CN200410040322 A CN 200410040322A CN 100382377 C CN100382377 C CN 100382377C
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The present invention relates to a formation method for a sealed nickel metal hydride secondary battery. The battery is formed by the method that hydrogen storage alloy capable of electrochemically absorbing and releasing hydrogen serves as negative electrode active substance to form the negative electrode, and the active substance, namely nickel hydroxide, serves as a main body in which metal cobalt or cobalt compound serving as a conductive agent is added to form a positive electrode. A diaphragm is clamped between the negative electrode and the positive electrode to be combined into an electrode group, and alkaline electrolyte is injected. The sealed nickel metal hydride secondary battery formed by a sealed seal opening is characterized in that after the alkaline electrolyte is injected within 2 hours, initial charge is carried out with the quantity of 0.25 to 1 C, the initial charge quantity is at least 0.08 C, and the battery is placed for 2 to 8 hours at a room temperature of 45 DEG C after the initial charge. According to the method, the sealed nickel metal hydride secondary battery is unnecessary to enhance the adding quantity of the metal cobalt or the cobalt compound, and the higher discharge capacity can be ensured. Furthermore, the voltage is reduced a little during storage, the storage performance is ensured, and simultaneously, the time required by the formation is shortened.
Description
Technical field
At the chemical synthesizing method that the present invention relates to the hermetic type nickel metal hydride secondary battery.
Background technology
The following formation of hermetic type nickel metal hydride secondary battery: but the hydrogen-storage alloy of electrochemical hydrogenation and dehydrogenation constitutes negative pole as negative electrode active material, the active material nickel hydroxide is that metallic cobalt or the cobalt compound that main body adds as conductive agent constitutes anodal, folder is combined into electrode group with barrier film between negative pole, the positive pole, inject alkaline electrolyte, airtight sealing forms the hermetic type nickel metal hydride secondary battery.
In recent years, along with popularizing of portable small-sized electronic equipment and instrument, the market demand of small-sized secondary batteries is increasing.Wherein, the anodal nickel hydroxide that uses, electrolyte adopt the NI-G of alkaline electrolyte, advantage such as nickel metal hydride secondary battery is big because of its energy density, relative cost is low supply falls short of demand on market especially.But especially adopt the hydrogen-storage alloy of electrochemical hydrogenation and dehydrogenation to compare with the NI-G secondary cell as the nickel metal hydride secondary battery of negative electrode active material, energy density is higher, and does not have the pollution of cadmium, thereby is subjected to people's favor especially.
The positive active material of hermetic type nickel metal hydride secondary battery is a nickel hydroxide, positive plate can be divided into two kinds of sintered type and thickener formulas according to the production method difference, and wherein thickener formula nickel is anodal because simple for production, active material packing density height, thereby be widely adopted.In order to obtain the thickener formula nickel positive pole of higher capacity density, generally adopt spherical nickel hydroxide as active material add binding agent, deionized water is modulated into pastel and is filled in the foamed metal substrate, drying compacting forms again.In order to guarantee to electrically contact fully between spherical nickel hydroxide and the metal substrate and between the nickel hydroxide particle, reduce contact resistance, generally when modulation nickel positive pole thickener, also need add cobalt compounds such as metallic cobalt, cobalt black, cobalt hydroxide, to improve the nickel hydroxide utilance as conductive agent.The metallic cobalt and the cobalt compound that add at first dissolve in alkaline electrolyte, with OH
-React, form water miscible cobalt complex ion HCoO
2 -, and in alkaline electrolyte, spread HCoO during the battery initial charge
2 -At first be oxidized to the hydroxy cobalt oxide (CoOOH) of conductivity, separating out between the spherical nickel hydroxide particle and between nickel hydroxide particle and the foaming metal matrix, form the cobalt conductive network, thereby improved the nickel hydroxide active material utilization.
Generally speaking, the 3～10wt% that is nickel hydroxide active material and conductive agent summation as the metallic cobalt and the cobalt compound addition of conductive agent in the hermetic type nickel metal hydride secondary battery positive pole is for well.If the conductive agent addition less than 3wt%, then can not form the favorable conductive network in nickel hydroxide positive plate, thereby active material utilization is lower, cause discharge capacity of the cell to descend; If the conductive agent addition greater than 10wt%, though then can form the favorable conductive network in nickel hydroxide positive plate, owing to the nickel hydroxide active matter quality reduces relatively, thereby can not improve capacity.
But, place in the battery discharge attitude by the cobalt conductive mesh that hydroxy cobalt oxide is formed, when especially the condition of high temperature is placed, the easily hydrogen reduction that is discharged by the hydrogen-storage alloy negative pole, perhaps with the stripping of cobalt complex ion, cause between the nickel hydroxide active material conductivity to reduce and cause that capacity reduces, and perhaps forms the very inactive Co of chemical property
3O
4, same, cause the nickel hydroxide active material utilization to descend, and because Co
3O
4Be insoluble in the alkali lye, be difficult to be converted into the hydroxy cobalt oxide of conductivity when charging once more behind the battery storage, thereby cause the irreversible loss of capacity behind the battery storage.In order to prevent the appearance of above-mentioned phenomenon, the more cobalt compound of volume must be in the nickel positive pole, added, but the relative minimizing of active material nickel hydroxide amount can be caused like this, can cause the nickel positive electrode capacity to reduce, promptly battery capacity descends.
In addition, nickel metal hydride batteries through seal airtight after, need to place 12～24 hours in room temperature, again through several charge and discharge cycles, the anodal and metal hydride cathode of nickel is activated fully.General little electric current such as the 0.1C of adopting of charge and discharge cycles charges to 150% of specified volume, be discharged to cell voltage 1.0V with 0.2C again, through 3～5 such charge and discharge cycles, battery capacity reaches maximum, become to handle through 30～45 ℃ of heat of placing 12～24 hours again, finally finish battery and change into.Owing to needed to place 12～24 hours before changing into, need several charge and discharge cycles when changing into, and handle through maturation in 12～24 hours, thereby battery change into need the very long cycle, and can take extensive capital equipment in a large number.
Also have, nickel metal hydride batteries seal airtight after, place a period of time earlier before changing into, main purpose is that the cobalt compound that joins in the nickel positive pole can be added in the alkaline electrolyte as far as possible, and diffusion homogeneous, when primary charging subsequently, the cobalt complex ion that dissolves in is oxidized to hydroxy cobalt oxide.But,, can cause a series of problems if the time of placing before the initial charge is longer.Because electrolyte not only is distributed in positive pole, but also is distributed on barrier film and the negative pole, thereby is dissolved in the HCoO of electrolyte
2 -Also can be along with electrolyte is distributed on positive pole, barrier film and the negative pole, and along with the prolongation of standing time before the initial charge, the cobalt compound that originally was present in the positive pole can be further with cobalt complex ion HCoO
2 -Form diffuses to barrier film and negative pole, thereby causes effectively cobalt content minimizing in the positive pole, finally can cause the decline of active material nickel hydroxide utilance and shelf characteric.During next battery seal, be difficult to can enclose air in certain amount, airborne oxygen can be with HCoO with avoiding
2 -Be oxidized to the comparatively Co of inertia
3O
4If, place the long period before the battery initial charge, then can make HCoO
2 -The Co that are converted into more
3O
4, thereby also can cause the effectively minimizing of cobalt content in the positive pole.The 3rd, diffuse to the HCoO of barrier film and negative pole
2 -Even, not oxidized, on barrier film and negative pole, also can be deposited as β-Co (OH)
2, the β-Co that deposits on its septation (OH)
2β-CoOOH can be oxidized to, positive and negative intereelectrode short-circuit can be caused when serious, and the β-Co on the negative pole (OH)
2Can in charging process, be reduced to metallic cobalt, also very likely cause short circuit between positive pole, negative pole if form brill dendrite.The 4th, place the long period before the battery initial charge, the airborne oxygen of enclosing also can be with the hydrogen-storage alloy surface oxidation in the negative pole, cause cathode hydrogen storing alloy, the activation difficulty is owing to above reason, when nickel metal hydride batteries changes into, place the long period, can cause the decline of nickel hydroxide active material utilization and shelf characteric on the contrary.
Summary of the invention
In view of the common chemical synthesizing method of nickel metal hydride batteries not only needs the long cycle, take production equipment in a large number, and can cause above-mentioned a series of problem, the present invention proposes a kind of chemical synthesizing method of hermetic type nickel metal hydride secondary battery, addressing the above problem.
For achieving the above object, but the present invention constitutes negative pole to the hydrogen-storage alloy of electrochemical hydrogenation and dehydrogenation as negative electrode active material, the active material nickel hydroxide is that metallic cobalt or the cobalt compound that main body adds as conductive agent constitutes anodal, folder is combined into electrode group with barrier film between negative pole, the positive pole, inject alkaline electrolyte, when the airtight hermetic type nickel metal hydride secondary battery that seals formation changes into, after injecting alkaline electrolyte, carry out initial charge with 0.25C～1C electric current in 2 hours.
The charge volume of initial charge is at least 0.08C.
Room temperature after the initial charge～45 ℃ placement 2～8 hours.
Adopt the such chemical synthesizing method of the present invention, the addition that need not to improve cobalt in the nickel positive pole or cobalt compound just can guarantee the specific discharge capacity that battery is higher, and voltage reduces fewly when storing, and guarantees shelf characteric, and shortening simultaneously changing into required time.This be because, the hermetic type nickel metal hydride secondary battery of above-mentioned formation carries out initial charge in 2 hours immediately after injecting alkaline electrolyte, after can making on the one hand the cobalt that adds in the positive pole or cobalt compound dissolve in alkali lye, have little time to diffuse to barrier film and negative pole, the cobalt complex ion HCoO that also can reduce on the other hand or avoid dissolving in
2 -Be oxidized to Co
3O
4Can guarantee effectively that like this cobalt or the cobalt compound that add in the positive pole still are retained in positive pole basically, thereby need not in positive pole, to add more cobalts or cobalt compound, just can guarantee positive electrode active material utilization and shelf characteric, also can reduce simultaneously or the cobalt avoiding adding in the positive pole or cobalt compound with cobalt complex ion HCoO
2 -Form diffuses to the possibility of the positive and negative intereelectrode short-circuit that barrier film or negative pole cause.Battery carries out initial charge in 2 hours immediately after injecting alkaline electrolyte, the hydrogen-storage alloy that also can reduce or avoid negative pole is because of the long oxidation that causes standing time, and owing to carried out initial charge and make the hydrogen-storage alloy of negative pole absorb a part of hydrogen, thereby can reduce or avoid the oxidation of hydrogen-storage alloy in put procedure subsequently.Because battery has carried out initial charge in 2 hours immediately after injecting alkaline electrolyte, thereby also can reduce standing time, promptly shortens battery and changes into the required cycle.
Carrying out shelving of a period of time after the initial charge, is for the alkali lye that makes injection further spreads at inside battery, and electrolyte is evenly distributed at inside battery, and what help like this carrying out subsequently discharges and recharges.
Embodiment
As above-mentioned, the hermetic type nickel metal hydride secondary battery is airtight according to the present invention seal after, should after injecting alkaline electrolyte, carry out initial charge in 2 hours immediately for well.It is long more to this section period that initial charge begins to inject alkaline electrolyte, and then the cobalt that adds in the positive pole dissolves in the cobalt complex ion HCoO that electrolyte is got over multiform one-tenth
2 -Be oxidized to Co
3O
4Possibility also big more, cause that cobalt content reduces relatively in the positive pole, also can cause cathode hydrogen storing alloy because of the placement oxidation in addition, so this section period should be short more good more, but consider practical condition, thereby this section period 2 hours with interior for well.
Charge volume during above-mentioned battery initial charge should be 0.08C at least, and 0.08C～0.2C is then better.Because the cobalt that adds in the above-mentioned anode and cobalt compound itself does not have conductivity or conductivity is not good, only after being converted into hydroxy cobalt oxide, just has good electrical conductivity, the not good problem of transformation efficiency when considering the cobalt that added or cobalt compound initial charge, so the initial charge amount should change the required electric weight of hydroxy cobalt oxide into greater than the cobalt that adds in the positive pole.During charge volume 0.08C, the cobalt of adding or cobalt compound can be converted into hydroxy cobalt oxide fully originally.For well, charging current has then prolonged the initial charge time less than 0.25C to charging current as before, can cause changing into time lengthening in 0.25C～1C scope during initial charge; Non-equilibrium state when the initial charge electric current then can aggravate the battery initial charge greater than 1C.
Placement after the initial charge with room temperature～45 ℃, time be 2～8 hours for well.When room temperature is placed with 4～8 hours for well, the laying temperature raising, then can be corresponding shortening standing time, for example 45 ℃ of placements with 2～4 hours for well.
Below be example with the airtight nickel metal hydride secondary battery of cylindrical AA type, the embodiment of the invention is described in detail in detail.
Embodiment 1
Spherical nickel hydroxide (solid solution 1.5wt%Co and 3wt%Zn) 95 weight portions of commercial average grain diameter 15 μ m, cobalt black 5 weight portions that add average grain diameter number micron, and adding deionized water, 2wt%CMC solution and 60wt%PTFE dispersion liquid are an amount of, making pastel through stirring, to be filled to vesicularity be in the 95% foaming nickel porous body, after the drying, prune shaping, make AA type 1800mAh nickel positive plate.
Adopt MmNi
5Negative plate that the class hydrogen-storage alloy powder is made and polypropylene diaphragm and above-mentioned anodal combine volume coiled electrode group insert in the AA shaped steel shell, seal after injecting proportion and be about 1.30 the alkaline electrolyte based on potassium hydroxide, making capacity specifications is the AA type cylindrical enclosure nickel metal hydride secondary battery of 1800mAh.Wherein be approximately 1 hour to sealing from injecting alkaline electrolyte, therefore, if after sealing, just carry out initial charge, then according to the present invention, need to carry out initial charge within an hour after sealing, like this, in fact initial charge is carried out within 1-2 hour after injecting alkaline electrolyte; If carried out initial charge before sealing, then charging is carried out within 0-1 hour after injecting alkaline electrolyte.Because the charging before airtight the sealing belongs to opening and changes into, technology is complicated, so present embodiment is to adopt to seal to change into as preferred version afterwards.
In this example, immediately with the initial charge of 0.5C electric current, the charging interval was respectively 5,6,8,10,12,16,20 minutes behind each battery seal.Placed in 45 ℃ of atmosphere 4 hours after the initial charge, then with 0.2C current charges 6 hours, place maturation in 8 hours in 45 ℃ of atmosphere, again with the 0.2C discharge, voltage ends during for 1.0V.Above-mentioned various battery is called after A respectively
1, A
2, A
3, A
4, A
5, A
6, A
7
The another one battery is by the scheme that changes into of prior art, seals the back room temperature and places 12 hours, and with 0.1C charging 15 hours, 0.2C ended when being discharged to voltage for 1.0V, after three such charge and discharge cycles activation, and battery X as a comparative example.
Battery A
1, A
2, A
3, A
4, A
5, A
6, A
7And X, with 0.2C charging 7.5 hours, 0.5C end when being discharged to voltage for 1.0V, measure the discharge capacity of each battery, and calculate (comprising nickel hydroxide and cobalt black) weight ratio capacity (weight ratio capacity is the whole active material weight of discharge capacity of the cell divided by the anodal filling of nickel) of nickel positive pole according to whole active matter qualities of institute's filling in the nickel positive pole.
In addition, above-mentioned each battery was placed 28 days in 40 ℃ of atmosphere under discharge attitude situation, place after 28 days again with 0.2C charging 7.5 hours, 0.5C end when being discharged to voltage for 1.0v, circulate three times, write down for the third time discharge capacity as storing back answer capacity, the answer capacity obtains the storage capacity response rate divided by discharge capacity before storing.Each corresponding data of battery sees Table 1.
By table 1 data as can be known, increase with the initial charge amount, the voltage drop that the battery discharge attitude was stored after 28 days reduces, the capacity response rate also obviously rises, but the initial charge amount during less than 0.08C the anodal weight ratio capacity of battery nickel be starkly lower than comparative example battery X, be the initial charge amount hour, can have a strong impact on discharge capacity of the cell.Therefore the initial charge amount should be 0.08C at least, so both can guarantee that battery has higher discharge capacity, and voltage reduces little, capacity response rate height behind the battery storage, has promptly improved shelf characteric.Simultaneously, the present invention has also shortened greatly and has changed into required time, enhances productivity.
Table 1
Embodiment 2:
The raw material and the manufacture craft that adopt with embodiment 1 are identical, and making capacity specifications is the AA type cylindrical enclosure nickel metal hydride secondary battery of 1800mAh.Wherein be approximately 1 hour to sealing from injecting alkaline electrolyte.Initial charge immediately behind each battery seal is respectively 0.25C charging 20 minutes, 0.25C charging 32 minutes, 0.4C charging 12.5 minutes, 0.4C charging 15 minutes, 0.8C charging 6 minutes, 0.8C charging 7.5 minutes, 1C charging 5 minutes.Each battery was placed 4 hours in 45 ℃ of atmosphere after the initial charge, and then with 0.2C charging 6 hours, maturation was 8 hours in 45 ℃ of atmosphere, and again with the 0.2C discharge, voltage ends during for 1.0v.Above-mentioned various battery is called after B respectively
1, B
2, B
3, B
4, B
5, B
6, B
7, the same with embodiment 1, also measure discharge capacity and obtain weight ratio capacity, and 28 days discharge attitude storage back measuring voltages, obtain voltage drop and capacity response rate.Each corresponding data sees Table 2.
By table 2 data as can be known, the initial charge electric current is 0.25C～1C, the initial charge amount is during greater than 0.08C, weight ratio capacity and comparative example battery X are basic identical, but store back voltage reduction and be starkly lower than comparative example battery X, the capacity response rate then obviously is better than comparative example battery X, and the time that changes into also shortens greatly than comparative example battery X.Therefore, the initial charge electric current is preferable when 0.25C～1C.
Table 2
Embodiment 3:
The raw material and the manufacture craft that adopt with embodiment 1 are identical, making capacity specifications is the AA type cylindrical enclosure nickel metal hydride secondary battery of 1800mAh, wherein be approximately 1 hour to sealing, behind each battery seal, immediately with 0.5C initial charge 10 minutes from injecting alkaline electrolyte.After the initial charge each battery in room temperature atmosphere, placed 4 hours, 8 hours and 45 ℃ of atmosphere in placed 2 hours, then with 0.2C current charges 6 hours, maturation was 8 hours in 45 ℃ of atmosphere, again with the 0.2C discharge, voltage ends during for 1.0v.Above-mentioned each battery is respectively C
1, C
2, C
3The same with embodiment, also measure discharge capacity, obtain weight ratio capacity, and after the storage of 28 days discharge attitudes, measuring voltage is obtained voltage drop and capacity response rate.Each corresponding data sees Table 3.
Table 3
By table 3 data as can be known, place after the initial charge and adopt 45 ℃ to place 2～4 hours, when perhaps placing 4～8 hours under the room temperature, weight ratio capacity is compared basic identical with the comparative example battery, but storing the back voltage drop obviously reduces, the capacity response rate obviously improves, and the time that changes into equally also shortens a lot than comparative example battery X.Therefore, it is better to adopt room temperature～45 ℃ to place 2～8 hours effects after the initial charge, when wherein laying temperature is higher, can be corresponding shortening standing time.
The present invention is not limited to the foregoing description, and is all applicable for all hermetic type nickel metal hydride secondary batteries, promptly is not only applicable to cylindrical battery, also is suitable for the battery of other shapes.
Claims (10)
1. the chemical synthesizing method of hermetic type nickel metal hydride secondary battery, but described battery is the hydrogen-storage alloy by electrochemical hydrogenation and dehydrogenation constitutes negative pole as negative electrode active material, the active material nickel hydroxide is that metallic cobalt or the cobalt compound that main body adds as conductive agent constitutes anodal, folder is combined into electrode group with barrier film between negative pole, the positive pole, inject alkaline electrolyte, the airtight hermetic type nickel metal hydride secondary battery that seals formation is characterized in that: carried out initial charge with interior with 0.25C～1C electric current in 2 hours after injecting alkaline electrolyte.
2. the chemical synthesizing method of hermetic type nickel metal hydride secondary battery as claimed in claim 1 is characterized in that: described metallic cobalt or the cobalt compound that adds in the positive pole as conductive agent is metallic cobalt, cobalt black or hydroxide cobalt.
3. the chemical synthesizing method of hermetic type nickel metal hydride secondary battery as claimed in claim 1 is characterized in that: the charge volume of the initial charge after injecting alkaline electrolyte in 2 hours is at least 0.08C.
4. the chemical synthesizing method of hermetic type nickel metal hydride secondary battery as claimed in claim 3 is characterized in that: after injecting alkaline electrolyte in 2 hours, carry out shelving after the initial charge that charge volume is at least 0.08C with 0.25C～1C electric current.
5. the chemical synthesizing method of hermetic type nickel metal hydride secondary battery as claimed in claim 4, it is characterized in that: after injecting alkaline electrolyte in 2 hours, carry out shelving after the charging that charge volume is at least 0.08C with 0.25C～1C electric current and be meant that room temperature～45 ℃ placed 2～8 hours.
6. the chemical synthesizing method of hermetic type nickel metal hydride secondary battery as claimed in claim 1 is characterized in that: carry out initial charge within an hour after injecting alkaline electrolyte.
7. the chemical synthesizing method of hermetic type nickel metal hydride secondary battery as claimed in claim 1 is characterized in that: carry out initial charge between 1-2 hour after injecting alkaline electrolyte.
8. the chemical synthesizing method of hermetic type nickel metal hydride secondary battery as claimed in claim 1 is characterized in that: before sealing, inject behind the alkaline electrolyte and to carry out initial charge with interior in 1 hour.
9. as the chemical synthesizing method of claim 4 or 5 described hermetic type nickel metal hydride secondary batteries, it is characterized in that: after shelving, adopt 0.1C～0.5C electric current to continue to charge to 1C～1.5C capacity, in 20～50 ℃ of atmosphere, place maturation in 4～12 hours, again with 0.1C～0.5C current discharge, voltage ends during for 1.0V.
10. as the chemical synthesizing method of claim 4 or 5 described hermetic type nickel metal hydride secondary batteries, it is characterized in that: described in 2 hours, is 0.08C～0.2C with the charge volume that 0.25C～the 1C electric current charges after injecting alkaline electrolyte.
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| CNB2004100403225A CN100382377C (en) | 2004-07-22 | 2004-07-22 | Formation method of sealed nickel metal hydride secondary battery |
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| CNB2004100403225A CN100382377C (en) | 2004-07-22 | 2004-07-22 | Formation method of sealed nickel metal hydride secondary battery |
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| CN100382377C true CN100382377C (en) | 2008-04-16 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405714A (en) * | 1992-07-31 | 1995-04-11 | Sanyo Electric Co., Ltd. | Method for activating an alkaline storage cell employing a non-sintered type nickel positive electrode |
| US5435055A (en) * | 1992-12-10 | 1995-07-25 | Furukawa Denchi Kabushiki Kaisha | Method of manufacturing a sealed alkaline storage battery using positive paste nickel electrodes |
| CN1326236A (en) * | 2000-05-31 | 2001-12-12 | 深圳市比亚迪实业有限公司 | Method for making Ni-base accumulator |
-
2004
- 2004-07-22 CN CNB2004100403225A patent/CN100382377C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405714A (en) * | 1992-07-31 | 1995-04-11 | Sanyo Electric Co., Ltd. | Method for activating an alkaline storage cell employing a non-sintered type nickel positive electrode |
| US5435055A (en) * | 1992-12-10 | 1995-07-25 | Furukawa Denchi Kabushiki Kaisha | Method of manufacturing a sealed alkaline storage battery using positive paste nickel electrodes |
| CN1326236A (en) * | 2000-05-31 | 2001-12-12 | 深圳市比亚迪实业有限公司 | Method for making Ni-base accumulator |
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