CN1076313A - Ni-MH battery and manufacturing technology thereof - Google Patents

Ni-MH battery and manufacturing technology thereof Download PDF

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Publication number
CN1076313A
CN1076313A CN92101326A CN92101326A CN1076313A CN 1076313 A CN1076313 A CN 1076313A CN 92101326 A CN92101326 A CN 92101326A CN 92101326 A CN92101326 A CN 92101326A CN 1076313 A CN1076313 A CN 1076313A
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Prior art keywords
battery
active material
powder
component
electrode
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Inventor
李萌初
陆荫文
区学香
连武奎
谢洪超
林祖达
杨福如
谭伯均
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SANJIE BATTERY CO Ltd JIANGMEN
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SANJIE BATTERY CO Ltd JIANGMEN
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Priority to CN92101326A priority Critical patent/CN1076313A/en
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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
    • 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 rechargeable electrochemical cell, particularly relating to by nickel electrode is positive pole and the rechargeable battery that is made of negative pole polynary heterogeneous electrochemical hydrogen storage alloy, the electrode of this battery also comprises the foamed nickel substrate of high capacity density and specific active material, additive and additive agent mixture, makes the chemical property of Ni-MH battery such as discharge capacity, high-multiplying power discharge, self discharge etc. obtain good improvement.

Description

Ni-MH battery and manufacturing technology thereof
The present invention relates to rechargeable electrochemical cell, particularly, the present invention relates to by nickel electrode is positive pole and the rechargeable battery that is made of negative pole polynary heterogeneous electrochemical hydrogen storage alloy.This battery is a feature with excellent electrochemical properties and nonhazardous.
One, operation logic
Ni-MH battery is a kind of environmental sound, the electrochemical energy of high-energy-density.It is nickel oxide electrode NiOOH/Ni(OOH just very) 2, negative pole is hydrogen bearing alloy ML(NiCoMnTi) 5The electrochemical hydrogen storage electrode of making.Separate with vinylon between positive pole and the negative pole, be wound into cylindric electric core and pack in the box hat, and add alkaline aqueous solution as electrolyte solution, adopt the mechanical means sealing making column sealed Ni-MH battery then, it discharges and recharges reaction can be simply schematically as follows:
And the battery overall reaction is:
This shows, Ni-MH battery discharge and recharge the reaction be by proton (H +) transfer between positive pole and negative pole realizes.Compare with traditional secondary cell, for example lead-acid battery and nickel-cadmium cell, Ni-MH battery has significant advantage, and at first Ni-MH battery does not contain cadmium, plumbous such noxious substance, can not bring the harm of environmental pollution to the user; Secondly, because hydrogen-storage electrode has higher specific capacity than cadmium or lead electrode, so Ni-MH battery has higher energy density compared with the conventional batteries system, and range of application is more extensive.
Two, Fa Ming background
1, old battery system
Lead-acid battery and nickel-cadmium cell are two kinds of storage batterys of extensive employing, through years of researches and improvement, performance and mounting technology all have increased significantly, and the development in recent years of particularly column sealed nickel-cadmium cell is particularly swift and violent, however, owing to limit by its electrochemical system, its specific energy can't satisfy the electronics and the more and more higher requirement of communication apparatus of day new life, and simultaneously, plumbous and cadmium all is noxious substances, can cause very big harm to environment, also cause the attention of world all circles day by day.A kind of new chargeable system of electrochemistry that Ni-MH battery grows up on the nickel-cadmium cell technical foundation just.
The nickel-cadmium cell of the invention beginning of this century at first is in the pole plate boxlike stage is arranged, electrode coats active material and additive and pressurization by Punching steel strip and forms, have the manufacturing of pole plate boxlike nickel-cadmium cell simple, but active material utilization is low, specific capacity and heavy-current discharge performance are all relatively poor.The sintered nickel cadmium cell is to the improvement of pole plate boxlike nickel-cadmium cell is arranged, its manufacturing process is comparatively complicated, at first the nickel slurry evenly to be coated in the two sides of punching nickel plated steel strip or micropore Nie Be, and in reducing atmosphere, make sintered base plate with certain porosity and mechanical strength in 900-1000 ℃ of following sintering, adopt chemical method that active material is filled in then and make electrode in the substrate, this is a comparatively complicated chemical process, often wants repeated multiple times can obtain enough active matter qualities.Because the sintered nickel cadmium cell can make very thin and have bigger specific area, has improved the heavy-current discharge performance of battery greatly, can high magnification even ultra-high magnifications discharge.
The column sealed nickel-cadmium cell that the sixties succeed in developing makes that its application is more extensive, has particularly occupied irreplaceable status in Communication Equipment, corresponding further developing of promoting nickel-cadmium cell.
At positive pole-NiOOH/Ni(OH) 2On, various Study on Additive successfully make the specific capacity of sintered type nickel electrode improve constantly, several limit 400MAh/cm that reach 3, and, developed the clean nickel oxide electrode of multiple non-burning for breaking through the restriction of burning clean ni substrate, and mainly contain plastic bonding formula, fiber formula and foam type nickel oxide electrode, especially the latter two make the nickel oxide electrode specific capacity bring up to 500MAh/cm 3, greatly improved the specific capacity of nickel-cadmium cell;
At negative pole-Cd(OH) 2On/the Cd, the research of various active matter formulas and the improvement on the electrode structure have improved electrode activity, and make battery have the ability of quick charge.
In a word, column sealed in recent years nickel-cadmium cell performance greatly improves.With the AA type is that the example weight ratio capacity has been brought up to 38Wh/kg, and can be full of electricity soon in 1-1.5Hrs, however, still is difficult to satisfy the development in science and technology requirement higher to the renewal of battery, simultaneously the inherent defect that exists of nickel-cadmium cell such as:
(1) toxicity of cadmium
(2) memory effect
(3) not anti-overdischarge
The certain applications of column sealed nickel-cadmium cell have also been limited.
2, the present technology status of technical field of nickel
The research of Ni-MH battery starts from the seventies, says that simply Ni-MH battery is that the alloy material storing hydrogen as nickel-hydrogen battery negative pole material that is formed by storage hydrogen negative pole replacement cadmium cathode must possess following character:
1), want chemistry to inhale good reversibility and the capacity height of putting hydrogen;
2), hydrogen sucting platform pressure is suitable;
3), stable in aqueous slkali;
4), has oxidative resistance preferably.
Initial LaNi 5It is alloy, although higher hydrogen absorption capacity is arranged, but because its stability (cycle life) and self-discharge performance are all very poor, be difficult to practical application, in order to address the above problem, field of batteries has been researched and developed the multicomponent alloy hydrogen storage material, such as mishmetal (rich lanthanum and rich cerium) class, and the Ti-Ni class etc., satisfied the requirement of battery substantially.
The research of Ni-MH battery and production aspect, the U.S. and Japan's development are very fast, have reached actual application level.
However, the chemical property parameter of the Ni-MH battery that prior art can reach remains unsafty, according to " JEC Battery Newsletter " (1989, No.1) report, the AA type Ni-MH battery that Japan Panasonic company makes, its 0.2C discharge capacity is 1070MAh, maximum discharge current is 3A, obviously, the discharge appearance of this Ni-MH battery and high-multiplying power discharge are dissatisfactory.According to " PERFORMANCE CHARACTERISTICS OF OVONIC NI/METAL HYDRIDE BATTERIES " (Presenled at The Second International Rechargeable Battery Seminar, March 8,1988 in Deerfield Beach, FL) data that provide show, the Ni-MH battery that U.S. Ovonic company makes, its self discharge is greater than 50%, obviously, the self discharge of this Ni-MH battery is unfavorable.
Present stage, the outstanding shortcoming that exists of Ni-MH battery just was:
1, internal resistance is big, high-rate discharge ability is poor;
2, self discharge is bigger.
Three, Fa Ming purpose, execution mode and corresponding techniques means thereof.
The present invention is to increase the Ni-MH battery capacity, reduce self-discharge of battery and to increase the battery high-multiplying power discharge as purpose.As Ni-MH battery, its self discharge is even more serious than nickel-cadmium cell, this is to be diffused into negative pole because the principal element-positive pole of the existing nickel-cadmium cell self discharge of Ni-MH battery is analysed oxygen, exist the hydrogen bearing alloy precipitated oxygen to be diffused into positive pole again, slowly reduce the factor of NiOOH, put in the hydrogen circulation in the suction of hydrogen-bearing alloy electrode simultaneously, there is the trend of efflorescence in hydrogen bearing alloy, coming off of fine powder causes micro-short circuit, thereby increases the weight of self discharge, can cause battery failure when serious.The present invention adopts the polynary hydrogen bearing alloy of rich group of the lanthanides, such as ML(NiCoMnTi for improving the Ni-MH battery self-discharge performance) 5Or ML(NiCoMnAl) 5Deng, its hydrogen sucting platform pressure is lower, has lowered the effusion tendency of hydrogen between the hydrogen bearing alloy lattice; Meanwhile, when electrode is made, add an amount of adhesive and make it fibrillatable, hydrogen-bearing alloy powder and foamed nickel substrate are coupled together securely, prevented to make Ni-MH battery of the present invention deposit month its discharge rate less than 30% at 30 ℃ owing to powder breaks away from the self discharge that causes.In addition, for overcoming the big inadequately and poor shortcoming of high-rate discharge ability of prior art Ni-MH battery discharge capacity, the present invention has taked some technological means improving these performances, referring to following formula:
This is the positive electrical chemical reaction that the present invention adopts, and its reaction speed is by proton H +The solid-state diffusion step determined, according to the present invention, under the condition that guarantees electrode base board of the present invention (foamed nickel substrate) intensity, the related parameter that has to foamed nickel substrate has carried out preferably, for example preferred porosity is 90-95%, makes foamed nickel substrate have space as much as possible with the filling active material; Simultaneously preferred positive active material Ni(OH) 2Particle diameter and be distributed as: 80～100 μ m particle diameters account for 10% weight; 60～80 μ m particle diameters account for 20% weight; 40～60 μ m particle diameters account for 40% weight; 20～40 μ m particle diameters account for 20% weight; Account for 10% weight less than 20 μ m particle diameters; Therefore improve the active material packing density, promptly just had higher capacity density.But meanwhile, the high-rate discharge ability of battery has been brought adverse effect, its electrochemical process is:
Course of reaction is by proton H +The solid-state diffusion step determine.Since foam nickel electrode aperture big (pore diameter range that the present invention adopts is 200-400 μ m), and sintrered nickel substrate aperture is generally 6-12 μ m, this means proton H +Be diffused into collector (foamed fibre) and will experience longer distance.Owing to improved the active material loading density, limited proton H on the contrary simultaneously +Diffusion velocity, thereby influence its high-rate discharge ability.For this reason, the present invention adds special additive in positive active material, this additive can be in alkaline solution stable existence and have goodish electric conductivity, and be dispersed in Ni(OH) 2Between particle and the nickel foam fiber, play good electric action, thereby shortened proton H in fact greatly +Diffusion length, give electroplax good high-rate discharge ability.
Adopt the said method effect same remarkable for negative pole.
The Ni-MH battery that is made by the present invention not only has higher capacity but also good high-rate discharge ability is arranged, and can reach more than 1100 as AA type capacity, and maximum continuous discharge electric current can reach more than the 5A.
In general, the key measure that strengthens the chemical property of Ni-MH battery is to select a kind of suitable hydrogen bearing alloy as the negative electrode electrochemical material, also is vital and develop the nickel oxide positive electrode of high capacity density and select suitable active material and additive for electrode and additive agent mixture.
Nickel-hydrogen battery electrode can utilize various active material additives and additive agent mixture to remove the chemical property of intensifier electrode, for certain given application, a certain or several specific performance properties of strengthening electrode be possible also be useful, prior art does not but have clearly elaboration at the electrode performance macroscopic view variation aspect that relates to aspect the concrete active material that adapts with concrete electrode and additive for electrode and the additive agent mixture and cause therefrom.According to the present invention, electrode base board, active material, additive, additive agent mixture are so that the trickle change of additive and additive agent mixture all is utilized to influence the variation on the macroscopic view of these chemical properties.To Ni-MH battery of the present invention, particularly the Ni-MH battery of strengthening capacity parameter, high-multiplying power discharge parameter and self discharge parameter is described in detail below.
Fig. 1 is a nickel-hydrogen battery structure schematic diagram of the present invention;
Fig. 2 is discharge curve (b) comparison diagram of high-multiplying power discharge curve of the present invention (a) and prior art;
Fig. 3 is 25 ℃ of self discharge curves (b) comparison diagram of 30 ℃ of self discharge curves of the present invention (a) and prior art;
According to the present invention, a kind of Ni-MH battery comprises the negative plate 2 that comes down to reel, and negative plate 2 comprises electrode base board 3, and electrode base board and shell 4 keep electrically contacting, and shell 4 can be made by suitable electric conducting material such as Fe; Ni-MH battery also comprises a positive plate 5, and electrode base board in the positive plate 58 keeps electrically contacting with battery cap 7, and is that positive plate comes down to reel and aim at the location with negative pole 2, and with the getting in touch of negative pole formation work; Partition 6 is that come down to reel and be arranged between positive plate and the negative plate; Ni-MH battery is sealed with suitable material, and as the iron-clad container etc., and battery 1 can be discharged gas when gas surpasses predetermined limits when using; The potassium hydroxide aqueous solution that contains specific component is as electrolyte;
Below division is carried out in the component and the manufacturing of battery manufacturing, particularly electrode of the present invention.
One, anodal component.The positive plate that the positive pole of Ni-MH battery of the present invention comes down to reel, comprise that preferred porosity is 90-95%'s, pore diameter range is 200-400 μ m's, promptly has big as far as possible space with the filling active material, thereby make the foamed nickel substrate (electrode base board) and active material and the adhesive that just have high capacity density, active material be a kind of be main body based on the following hickelous nydroxide powder of hickelous nydroxide powder, particularly particle size distribution: 80-100 μ m particle diameter account for 10% weight; 60-80 μ m particle diameter account for 20% weight; 40-60 μ m particle diameter account for 40% weight; 20-40 μ m particle diameter account for 20% weight; The following particle diameter of 20 μ m account for 10% weight so that improve the active material packing density promptly anodal have higher capacity density with increase battery capacity and contain divalence cobalt solid solution to improve the component of active material utilization; In addition, the component of active material also contains at least a additive in the following A group material, thereby improves electric conductivity, with increase battery high-multiplying power discharge,
A: nickel powder (preferably 255 #), copper powder, graphite powder, cobalt powder, cobalt hydroxide, cobalt oxide, second piece be black,
And preferably consisting of of active material,
Nickel hydroxide: 75～85% weight, more preferably 80～85% weight;
A:15～25% weight, more preferably 15～20% weight;
The component of adhesive with the mutual cohesive force of each component in the increase electrode, thereby reduces the micro-short circuit that the electrode metal powder comes off and causes by at least a formation in the following B group adhesive (its preferred content is 3～5% weight), promptly reduces self-discharge of battery,
B: polyvinyl alcohol, sodium carboxymethylcellulose, polytetrafluoroethylene, methylcellulose.
Two, negative pole component.The negative plate that nickel-hydrogen battery negative pole of the present invention comes down to reel, comprise preferred porosity be 90-95%, pore diameter range is 200-400 μ m's, promptly has big as far as possible space with the filling active material, thereby make negative pole have foamed nickel substrate and the active material and the adhesive of high capacity density, the component of active material is a kind of with ML(NiCoMnTi) 5Perhaps ML(NiCoMnAL) 5Deng the rich group of the lanthanides mishmetal multicomponent alloy hydrogen storag powder powder material as rational formula is main component, and in addition, the component of active material also contains nickel powder additive (preferably 225 #), thereby be that negative pole has higher capacity to increase battery capacity and improves electric conductivity with the packing density that improves active material, improving high-multiplying power discharge, the consisting of of active material,
ML(NiCoMnTi) 5Or ML(NiCoMnAL) 5: 75～95% weight
Nickel powder: 5～25% weight;
The component of adhesive is by the mutual cohesive force of at least a formation in the above-mentioned B group adhesive (its preferred content is 3～5%) with each component in the increase electrode, the micro-short circuit that causes promptly reduces self-discharge of battery thereby minimizing electrode metal powder, particularly hydrogen-bearing alloy powder come off.
Three, the anodal manufacturing.It is stand-by at first to transfer foregoing anodal foamed nickel substrate, active material and/or the additive of transferring aforementioned positive pole then are stand-by, above-mentioned active material and/or additive are mixed, add again in the viscous aqueous solution by at least a preparation in the aforementioned anodal B group adhesive, make mixed liquor, mechanically it is charged in the above-mentioned stand-by foamed nickel substrate then as vibration, slip etc., and drying and punching out shaping, make high performancely, particularly reduce self-discharge of battery and increase the battery high-multiplying power discharge and increase the nickel oxide positive electrode of capacity.
Four, negative pole manufacturing.The foamed nickel substrate of at first transferring aforementioned negative pole is stand-by, active material and/or the additive of transferring aforementioned negative pole then are stand-by, above-mentioned active material and/or additive are mixed, the B that adds aforementioned negative pole again organizes in the viscous aqueous solution of at least a preparation in the adhesive, make mixed liquor, mechanically it is charged in the above-mentioned stand-by foamed nickel substrate then as vibration, slip etc., and drying and punching out shaping, make high performancely, particularly reduce self-discharge of battery and increase the battery high-multiplying power discharge and increase the storage hydrogen negative electrode of capacity.
Five, battery assembling: between above-mentioned positive plate that makes and negative plate, insert partition such as vinylon diaphragm paper etc., make compounded plate, again compounded plate is wound into electric core pack into suitable containers such as work durm etc., in container, add and contain 15～30 grams per liter LiOHH 2The O component, proportion is the potassium hydroxide aqueous solution of 1.26-1.29, then seal of vessel made Ni-MH battery of the present invention.
＜example 1 〉:
Ni(OH) 2With Ni powder, Co(OH) 2Powder is even by 100: 10: 10 mixed, the polyvinyl alcohol (PVA) and the polytetrafluoroethylene (PTFE) aqueous solution of adding 2% constantly stir and make anodal cream, adopt sliding scale that it is charged in the foamed nickel substrate of 80mm * 40mm, dried 2 hours down at 125 ℃, with 800kg/cm 2Pressure forming, make positive plate.
In addition be the hydrogen-bearing alloy powder of 80 μ m and Ni powder by 100: 10 mixed with average grain diameter, add the 3% polytetrafluoroethylene (PTFE) aqueous solution, paste is made in stirring, with vibration method it is charged in the foamed nickel substrate of 110mm * 40mm then, oven dry is 2 hours in 100 ℃, with 1200kg/cm 2Pressure forming makes negative plate.
Above-mentioned positive plate and negative plate are separated with diaphragm paper, reel and to pack in the AA shaped steel shell, adding proportion is 1.28, contains LiOHH 2The electric liquid of O25 grams per liter, machinery seal and promptly make the AA type Ni-MH battery of capacity up to 1100MAh.
＜example 2 〉:
With Ni(OH) 2Even with Ni powder, CoO powder by 100: 5: 12 mixed, add 3% the PTFE aqueous solution, be modulated into paste, make the anodal cream of AA by preceding method.
With ML(NiCoMnTi) 5Even with the Ni powder by 100: 15 mixed, and make negative pole by preceding method, and be assembled into the AA battery.

Claims (2)

1, a kind of is the Ni-MH battery 1 of purpose to increase battery capacity, to reduce self-discharge of battery and increase the battery high-multiplying power discharge, comprise according to the negative plate that comes down to reel 2 of the present invention, negative plate 2 comprises electrode base board 3, electrode base board and shell 4 keep electrically contacting, and shell can be made by suitable electric conducting material such as Fe; Ni-MH battery 1 also comprises a positive plate 5, and electrode base board in the positive plate 58 keeps electrically contacting with battery cap 7, and is that it comes down to reel and aims at the location with negative pole 2, and with negative pole formation working relation; Partition 6 is that come down to reel and be arranged between positive plate and the negative plate; Ni-MH battery is sealed with suitable material, and as the iron-clad container, and battery 1 can be discharged gas when gas surpasses predetermined limits when using; The potassium hydroxide aqueous solution that contains specific component is as electrolyte; The invention is characterized in, thereby the positive plate of said Ni-MH battery comprise preferred porosity be 90-95%, pore diameter range 200-400 μ m, promptly have foamed nickel substrate and active material and an adhesive that big as far as possible space just has high capacity density with making of filling active material, the component of active material be a kind of based on hickelous nydroxide powder, particularly particle size distribution following-
Particle diameter: 80-100 μ m percent by weight: 10
60-80μm 20
40-60μm 40
20-40μm 20
20 μ m following 10
The hickelous nydroxide powder be main body so that improve that the active material packing density promptly improves positive electrode capacity density and contain divalence cobalt solid solution to improve the component of active material utilization; In addition, the component of active material also contains at least a additive in the following A group material, thereby improves electric conductivity, shortens proton H in fact greatly +Diffusion velocity, increase the battery high-multiplying power discharge,
A: nickel powder (preferably 255 #), copper powder, graphite powder, cobalt powder, cobalt hydroxide, cobalt oxide, second piece be black
And preferably consisting of of active material,
Hickelous nydroxide: 75-85% weight, more preferably 80-85% weight;
A:15-25% weight, more preferably 15-20% weight;
The component of adhesive is by at least a formation in the following B group adhesive (its preferred content is 3～5% weight), thereby the mutual cohesive force of each component reduces the micro-short circuit that the electrode metal powder comes off and causes in the electrode to increase, and promptly reduces self-discharge of battery,
B: polyvinyl alcohol, sodium carboxymethylcellulose, polytetrafluoroethylene, methylcellulose;
Of the present invention another is characterised in that, the component of the negative plate of said Ni-MH battery comprise preferred porosity be 90-98%, pore diameter range is 200-400 μ m's, promptly has big as far as possible space with the filling active material, thereby make negative pole have foamed nickel substrate and the active material and the adhesive of high capacity density, the component of active material is a kind of with ML (NiCoMnTi) 5Perhaps ML (NiCoMnAL) 5Deng mixing the polynary hydrogen storing alloy powder powder material of alkene soil as the rich group of the lanthanides of rational formula is main component, and in addition, the component of active material also contains nickel powder additive (preferably 255 #), thereby be that negative pole has higher capacity density to increase battery capacity and improves electric conductivity with the packing density that improves active material, shorten proton H in fact greatly +Diffusion velocity improving high-multiplying power discharge, the consisting of of active material,
ML (NiCoMnTi) 5Or ML (NiCoMnAL) 5: 75-95%
Nickel powder: 5-25%, its preferred content is 5-15%;
The component of adhesive is by at least a formation in the aforementioned B group adhesive (its preferred content is 3-5%), to increase the mutual cohesive force of each component in the electrode, thereby reduce the micro-short circuit that electrode metal powder, particularly hydrogen-bearing alloy powder come off and cause, promptly reduce self-discharge of battery.
2, a kind of manufacture method of Ni-MH battery, comprise anodal manufacture method, the manufacture method of negative pole and the assembly method of battery, the invention is characterized in-(a) anodal manufacture method: the foamed nickel substrate of at first transferring aforementioned positive pole is stand-by, it is stand-by to transfer aforementioned positive electrode active materials and additive and/or additive agent mixture then, above-mentioned active material and/or additive are mixed, add again in the viscous aqueous solution by at least a preparation in the aforementioned anodal B group adhesive, make mixed liquor, then mechanically as vibration, slide to wait it is charged in the aforementioned stand-by foamed nickel substrate, and drying and punching out shaping, make high performance, particularly reduce self-discharge of battery and increase the battery high-multiplying power discharge and the nickel oxide electrode of increase capacity; (b) manufacture method of negative pole: the foamed nickel substrate of at first transferring aforementioned negative pole is stand-by, it is stand-by to transfer the active material of aforementioned negative pole and additive and/or additive agent mixture then, above-mentioned active material and additive and/or additive agent mixture are mixed, the B that adds aforementioned negative pole again organizes in the viscous aqueous solution of at least a preparation in the adhesive, make mixed liquor, then mechanically as vibration, slide to wait it is charged in the aforementioned stand-by foamed nickel substrate, and drying and punching out shaping, make high performancely, particularly reduce self-discharge of battery and increase the battery high-multiplying power discharge and increase the storage hydrogen negative pole of capacity; (c) assembly method of battery: insert partition such as vinylon diaphragm paper etc. between the negative plate that at positive plate that above-mentioned (a) method makes and (b) method makes, make compounded plate, again compounded plate is wound into electric core pack into suitable containers such as steel cylinder etc., in container, adds and contain 15～30 grams per liter LiOHH 2The O component, proportion is the potassium hydroxide aqueous solution of 1.26-1.29, then seal of vessel made Ni-MH battery of the present invention.
CN92101326A 1992-03-09 1992-03-09 Ni-MH battery and manufacturing technology thereof Pending CN1076313A (en)

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CN92101326A CN1076313A (en) 1992-03-09 1992-03-09 Ni-MH battery and manufacturing technology thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1052578C (en) * 1994-06-15 2000-05-17 国营第七五五厂 Preparation method of slurry-pulling type metal hydride electrode
CN1076882C (en) * 1994-07-29 2001-12-26 瓦尔达电池股份公司 Gasdicht verschlossener alkalischer akkumulator in form einer knopfzelle
US6653023B1 (en) 1999-03-25 2003-11-25 Sanyo Electric Co., Ltd. Rectangular battery
WO2005022677A1 (en) * 2003-09-01 2005-03-10 Byd Company Limited Cylindrical lithium ion secondary battery
US7022434B2 (en) 2000-07-17 2006-04-04 Matsushita Electric Industrial Co., Ltd. Nickel-metal hydride storage battery and production method thereof
CN101636862B (en) * 2007-03-26 2012-03-21 丰田自动车株式会社 Treated active material, method for treating thereof, and paste containing the treated active material
JP2016162755A (en) * 2015-03-03 2016-09-05 三星エスディアイ株式会社Samsung SDI Co., Ltd. Rechargeable battery having cover

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1052578C (en) * 1994-06-15 2000-05-17 国营第七五五厂 Preparation method of slurry-pulling type metal hydride electrode
CN1076882C (en) * 1994-07-29 2001-12-26 瓦尔达电池股份公司 Gasdicht verschlossener alkalischer akkumulator in form einer knopfzelle
US6653023B1 (en) 1999-03-25 2003-11-25 Sanyo Electric Co., Ltd. Rectangular battery
US7022434B2 (en) 2000-07-17 2006-04-04 Matsushita Electric Industrial Co., Ltd. Nickel-metal hydride storage battery and production method thereof
WO2005022677A1 (en) * 2003-09-01 2005-03-10 Byd Company Limited Cylindrical lithium ion secondary battery
KR100749980B1 (en) 2003-09-01 2007-08-16 비와이디 컴퍼니 리미티드 Cylindrical Lithium Ion Secondary Battery
CN101636862B (en) * 2007-03-26 2012-03-21 丰田自动车株式会社 Treated active material, method for treating thereof, and paste containing the treated active material
JP2016162755A (en) * 2015-03-03 2016-09-05 三星エスディアイ株式会社Samsung SDI Co., Ltd. Rechargeable battery having cover

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