CN1046824C - Technique for continuously producing hydrogen-storage alloy electrode plate - Google Patents
Technique for continuously producing hydrogen-storage alloy electrode plate Download PDFInfo
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- CN1046824C CN1046824C CN93105890A CN93105890A CN1046824C CN 1046824 C CN1046824 C CN 1046824C CN 93105890 A CN93105890 A CN 93105890A CN 93105890 A CN93105890 A CN 93105890A CN 1046824 C CN1046824 C CN 1046824C
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- hydrogen
- storage alloy
- electrode plate
- nickel
- diaphragm
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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
- H01M4/242—Hydrogen storage electrodes
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention belongs to a hydrogen storage alloy electrode manufacturing method which can be used for the mass continuous production of hydrogen storage alloy electrode pieces used for the preparation of Ni/MH batteries of various model numbers through the plastic bonding process. The main technological flow comprises powder mixture, rolling film forming, film cutting, piece combination and piece division. The yearly output of each production line in the production of a single shift reaches more than 1, 000, 000 pieces, and both the size and the appearance of products are in conformity with standard requirements. The present invention can also be popularized so as to be applied to the batch continuous production of bonding formed films of various metals or non-metal powders.
Description
The invention belongs to the compacting manufacture method of alkaline battery electrode.
NiIn the charge and discharge process of/MH battery, following reversible hydrogen adsorption and desorption reaction takes place on the electrode:
In order to make
Ni/ MH battery has electric power storage ability preferably, and the hydrogen that is adsorbed on the electrode metal surface during charging must be diffused into alloy inside at an easy rate, is absorbed by alloy and forms the metal hydride MH of less stable
n Ab(reaction A); These hydrogen are diffused into alloy surface again again during discharge, oxidized and ejected electron, and only at large current charge or charging is fast when finishing, the hydrogen that just has ADSORPTION STATE is combined into hydrogen molecule and separates out (reacting B).In said process, in order to reduce polarization, shorten the diffusion distance of hydrogen in alloy, must increase the specific surface of alloy, that is to say and will adopt powdery alloy material fork-like farm tool used in ancient China to make hydrogen-bearing alloy electrode.
The existing method that the powdery alloy material is made the cellular hydrogen-storage alloy electrode plate has two classes, i.e. sintering process and plastic bonding method.Sintering process is mainly used in titanium base hydrogen storage alloy electrode and makes (Osumi Yasuaki, ソ-ダ と salt element, 1988,4,1-32; CN1071279A), the plastic bonding rule is mainly used in the making (EP284063 of lanthanon hydrogen storage alloy electrode; CN1071787A).But, the report of unprecedented relevant plastic bonding method complete process process in existing document so far, just list some technological parameters, as the mixed proportion of raw meal, cold pressing or the pressure of hot pressing (J.J.G.Willems such as the percentage by weight of binding agent, Philips J.of Research, Vol.39, Supplement No.1,1984; Tetsuo Sakai, et al, J.Electrochem.Soc., 137 (3), 1990; H.Ogawa, et al, 16th International Power Sources Symp.1988,9), more do not meet relevant with the method introduction of producing hydrogen-storage alloy electrode plate continuously in enormous quantities of plastic bonding method.
The quantity-produced technology in enormous quantities that the purpose of this invention is to provide a kind of hydrogen-storage alloy electrode plate based on the plastic bonding method.
The object of the present invention is achieved like this: (A) mix powder, the hydrogen-bearing alloy powder of 100 parts (weight) is mixed stirring 10～20 minutes with 2～10 parts of plastic adhesives and 4～5 parts of deionized waters with flour mixer, add 12～16 parts of alcohol then, and continue to be stirred to fully and mix, (B) roll extrusion film forming, it is to divide group's weighing on 30～40 ℃ the temperature automatically controlled heating table top that the alloy powder ball that is mixed with binding agent is transplanted on temperature, every Weight control is between 180～260 grams, again the alloy powder ball of minute group is placed on the plastics processing mill of 50～60 ℃ of cylinder surface temperature and laminates repeatedly 8～16 times, each alloy powder ball is pressed into is about 100cm, wide about 15cm, thickness is the diaphragm of 0.40～0.80mm, it is 50～60 ℃ that this diaphragm is sent into temperature, and vacuum degree is 0.1 * 10
-1～5.0 * 10
-1Drying is 2～4 hours in the vacuum drying chamber of torr, (C) cut film, dried plastic bonding alloy diaphragm is delivered to 20 rev/mins film cutting machine, be cut into rectangular according to the required width of battery size along length direction, the corner diaphragm recycling of downcutting, (D) close sheet, with cut in (C) step plastic bonding alloy diaphragm be stacked together with the conducting base that same widths arranged and be contained on the combinating machine, be 0.6～1.5T/cm by pressure
2Two the rolling of combinating machine, pressing forms electrode strip, send again and be rolled onto upward (E) cut-parts of dish that take up, plate rail take up to what volume had an electrode strip on slitter, the sheet cylinder gap is sent in adjustment, start the slitter power supply, determine according to battery size defined length, width and thickness, and the hydrogen-storage alloy electrode plate of predetermined weight.
Above-mentioned (A) mixes in powder step used hydrogen-bearing alloy powder granularity and is advisable with 30～104 μ m, because granularity is too big, discharges and recharges that speed is slow, chemical property is poor, granularity too detailed rules and regulations to discharge and recharge working life short.
Above-mentioned (D) closes in the sheet step can simultaneously press a plastic bonding alloy diaphragm at conducting base, or respectively presses a conducting base on plastic bonding alloy diaphragm two sides, or respectively presses a plastic bonding alloy diaphragm on the conducting base two sides.
The used plastic binder of the present invention is the mixture of polytetrafluoroethylene, tetrafluoroethene and hexafluoropropylene copolymer, silicon rubber, polyvinyl alcohol, polyvinyl formal, carboxymethyl cellulose, polyethylene, polyacrylic acid, poly-epoxy ether formal or butadiene and cinnamic copolymer or above-mentioned substance.
The used conducting base of the present invention is the perforated steel ribbon of nickel wire braid over braid, nickel stretching nets, perforation nickel strap foam nickel strap, sintrered nickel fabric strip or the braid over braid of making after nickel plating on the iron-based body or tension belt or surface process roughening treatment.The silk footpath of braid over braid is 0.14～0.25mm, and the eyelet size is 0.42～1.65mm.The eyelet of stretching nets is the prismatic of the length of side 0.1～1.0mm, and porosity is greater than 50%, and thickness is 0.14～0.20mm.The thickness of foam nickel strap, sintrered nickel fabric strip is 0.8～2.0mm, and porosity is greater than 85%.The porosity of perforation nickel strap, nickel plated steel strip, perforated steel ribbon is 35～40%, and thickness is 0.14～0.20mm.
The inventive method is suitable for producing continuously with the in enormous quantities of plastic bonding legal system hydrogen-storage alloy electrode plate, the annual production of every production line split run production is more than 1,000,000, the length of product electrode slice, width, thickness all reach the requirement critical field, and the corner is neat, no metallic bur power.Randomly draw 2 for per 1000,0.2～0.4C leads one pole and changes into 4～5 times, and every plate electrode capacity just can reach requirement.The present invention also can promote the batch that is used for various metals or non-metal powder bonding film forming and produce continuously.
Embodiment 1
The surface-treated of learning from else's experience, granularity is the hydrogen bearing alloy MmNi of 52 μ m
3.8Co
0.5Mn
0.4Al
0.2Li
0.1Powder 5Kg, PTFE emulsion 340ml, deionized water 200ml are that 20 rev/mins flour mixer mix to stir 15 minutes with rotating speed, add 900ml alcohol then, continue mixing and stirring to fibrillatable.Fibrotic alloy powder ball is transplanted on the little group that is divided into 180 grammes per square metres on the heating table top that temperature is controlled at 30～40 ℃, again these alloy powder balls are delivered to grind on the cylinder (temperature is 50～60 ℃) of roller press and become to be about 100cm, wide about 15cm, thickness are the diaphragm of 0.40mm.Subsequently, it is 50～60 ℃ that this diaphragm is put into temperature, and vacuum degree is 0.1 * 10
-1In the vacuum drying chamber of torr dry 2 hours, take out then and deliver to 20 rev/mins film cutting machine, be cut into wide rectangular of 40mm along length direction.Again with the rectangular combinating machine of sending to of plastic bonding alloy film sheet that cuts out, stacking width is 40mm, the eyelet size is 0.83mm, on the annealing nickel-clad iron braid over braid conducting base of silk footpath 0.14mm, between both move to together that combinating machine is two and roll, pressure with 0.6T/cm2 is pressed into the electrode strip that thickness is 0.40mm, send afterwards to be rolled onto on the dish that takes up.Having volume the plate rail that takes up of electrode strip to be cut into length to the slitter is 95mm, and width is 40mm, and thickness is 0.4mm, and weight is the hydrogen-storage alloy electrode plate of 8.0～8.5 gram/sheets.The electrode slice of this specification is as the cathode pole piece of AA type garden post Ni/MH battery.
Embodiment 2
The hydrogen-bearing alloy powder LaNi of granularity 74 μ m
4.5Mn
0.5With La
0.8Nd
0.2Ni
2.5Co
2.4Al
0.11: 1 hybrid alloys powder 5Kg, it is 0.8 liter of 2% polyvinyl alcohol that plastic binder adopts concentration, it is 1.5mm that conducting base adopts thickness, voidage is 85% foam nickel strap, other parameters and technological process are with embodiment 1, and being cut into length at last is 150mm, width 40mm, thickness is the hydrogen-storage alloy electrode plate of 0.40mm, as the cathode pole piece of A type garden post Ni/MH battery.
Embodiment 3
Conducting base adopts one side (specific practice is that thermal spraying nickel powder or single face nickel powder slurry sintering form) nickel plating perforated steel ribbon through roughened, other are all with embodiment 1, being cut into length is 260mm, width is 32mm, thickness is the hydrogen-storage alloy electrode plate of 0.40mm, as the cathode pole piece of Cs type Ni/MH battery.
Embodiment 4
Used alloyed powder, plastic binder and mixed powder craft and parameter are with embodiment 1.Just to be divided into the little groups that weight is 260 grams to the alloy powder ball, deliver to temperature again and be on 50～60 ℃ the cylinder of roller press and roll growth 100cm, wide 10cm, the diaphragm of thick 0.6mm.This diaphragm being put into temperature again is 50～60 ℃, and vacuum degree is 0.1 * 10
-1In the drying box of torr dry 2 hours, take out then on the film cutting machine of delivering to 20 rev/mins, be cut into wide rectangular of 80mm along the length direction of film.Subsequently this plastic bonding alloy diaphragm being delivered to combinating machine, to overlay steadily the width that moves be 80mm, the eyelet size is 0.83mm, on the annealing nickel-clad iron braid over braid conducting base of silk footpath 0.14mm, on this diaphragm, stack simultaneously the same conducting base of one deck again, the three moves between two the rolling of combinating machine together, uses 1.5T/cm
2Pressure they are pressed together to form thickness be the electrode strip of 0.7～1.0mm, and and then be wound onto on the dish that takes up.Plate rail take up to what this volume had an electrode strip on slitter at last, be cut into long 110mm, wide 80mm, the electrode slice of thick 0.7～1.0mm is as square
NiThe cathode pole piece of/NH battery.
Claims (6)
1. the production technology of a hydrogen-storage alloy electrode plate, adopt the plastic bonding method, it is characterized in that: it is each step in the following order, (A) mix powder, hydrogen-bearing alloy powder and 2～10 parts of plastic binders and 4～5 parts of deionized waters with 100 parts (weight), mix stirring 10～20 minutes with flour mixer, add 12～16 parts of alcohol then, and continue to be stirred to fully and mix, (B) roll extrusion film forming, it is on 30～40 ℃ the temperature automatically controlled heating table top that the alloy powder ball that is mixed with binding agent is transplanted on temperature, divide group's weighing, every Weight control is between 180～260 grams, again the alloy powder ball of minute group is placed on the plastics processing mill of 50～60 ℃ of cylinder surface temperature and laminates repeatedly 8～16 times, each alloy powder ball is pressed into is about 100cm, wide about 15cm, thickness is the diaphragm of 0.40～0.80mm, and it is 50～60 ℃ that this diaphragm is sent into temperature, vacuum degree is 0.1 * 10
-1～5 * 10
-1Drying is 2～4 hours in the vacuum drying chamber of torr, (C) cut film, dried plastic bonding alloy diaphragm is delivered to film cutting machine, be cut into rectangular according to the required width of battery size along length direction, (D) close sheet, with cut in (C) step plastic bonding alloy diaphragm be stacked together with the conducting base that same widths arranged and be contained on the combinating machine, be 0.6～1.5T/cm by pressure
2Two the rolling of combinating machine, pressing forms electrode strip, send being rolled onto on the dish that takes up again, (E) cut-parts have volume the plate rail that takes up of electrode strip to determine length, width and thickness according to the battery size defined and the hydrogen-storage alloy electrode plate of predetermined weight on slitter.
2. the production technology of hydrogen-storage alloy electrode plate according to claim 1, it is characterized in that: the granularity of used hydrogen-bearing alloy powder is 30～104 μ m.
3. the production technology of hydrogen-storage alloy electrode plate according to claim 1, it is characterized in that: above-mentioned (D) closes in the sheet step is simultaneously to press a plastic bonding alloy diaphragm at conducting base, or respectively press a conducting base, or respectively press a plastic bonding alloy diaphragm on the conducting base two sides on plastic bonding alloy diaphragm two sides.
4. the production technology of hydrogen-storage alloy electrode plate according to claim 1 is characterized in that: used plastic binder is the mixture of polytetrafluoroethylene, tetrafluoroethene and hexafluoropropylene copolymer, silicon rubber, polyvinyl alcohol, polyvinyl formal, carboxymethyl cellulose, polyethylene, polyacrylic acid, poly-epoxy ether formal or butadiene and cinnamic copolymer or above-mentioned substance.
5. the production technology of hydrogen-storage alloy electrode plate according to claim 1 is characterized in that: the perforated steel ribbon that used conducting base is nickel wire braid over braid, nickel stretching nets, bore a hole nickel strap, foam nickel strap, sintrered nickel fabric strip or the braid over braid of making after nickel plating on the iron-based body or tension belt or surface pass through roughening treatment.
6. the production technology of hydrogen-storage alloy electrode plate according to claim 4, it is characterized in that: the silk footpath of braid over braid is that 0.14～0.25mm, eyelet size are 0.42～1.65mm, the eyelet of stretching nets be the prismatic, porosity of the length of side 0.1～1.0mm greater than 50%, thickness is 0.14～0.20mm, the thickness of foam nickel strap, sintrered nickel fabric strip is 0.8～2.0mm, porosity is greater than 85%, the thickness of perforation nickel strap, nickel plated steel strip, nickel plating perforated steel ribbon is 0.14～0.20mm, and porosity is 35～40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93105890A CN1046824C (en) | 1993-05-31 | 1993-05-31 | Technique for continuously producing hydrogen-storage alloy electrode plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93105890A CN1046824C (en) | 1993-05-31 | 1993-05-31 | Technique for continuously producing hydrogen-storage alloy electrode plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1083270A CN1083270A (en) | 1994-03-02 |
| CN1046824C true CN1046824C (en) | 1999-11-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93105890A Expired - Fee Related CN1046824C (en) | 1993-05-31 | 1993-05-31 | Technique for continuously producing hydrogen-storage alloy electrode plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE525367C2 (en) * | 2002-11-08 | 2005-02-08 | Nilar Int Ab | An electrode and a method for manufacturing an electrode |
| CN100449824C (en) * | 2005-10-24 | 2009-01-07 | 比亚迪股份有限公司 | Battery pole piece and manufacturing method of lithium ion secordary battery containing the pole piece |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4511400A (en) * | 1984-03-12 | 1985-04-16 | Union Carbide Corporation | Production of tool steels using chemically prepared V2 O3 as a vanadium additive |
| US4728586A (en) * | 1986-12-29 | 1988-03-01 | Energy Conversion Devices, Inc. | Enhanced charge retention electrochemical hydrogen storage alloys and an enhanced charge retention electrochemical cell |
-
1993
- 1993-05-31 CN CN93105890A patent/CN1046824C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4511400A (en) * | 1984-03-12 | 1985-04-16 | Union Carbide Corporation | Production of tool steels using chemically prepared V2 O3 as a vanadium additive |
| US4728586A (en) * | 1986-12-29 | 1988-03-01 | Energy Conversion Devices, Inc. | Enhanced charge retention electrochemical hydrogen storage alloys and an enhanced charge retention electrochemical cell |
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| Publication number | Publication date |
|---|---|
| CN1083270A (en) | 1994-03-02 |
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