CA1209200A - Sealed nickel-zinc battery - Google Patents
Sealed nickel-zinc batteryInfo
- Publication number
- CA1209200A CA1209200A CA000433359A CA433359A CA1209200A CA 1209200 A CA1209200 A CA 1209200A CA 000433359 A CA000433359 A CA 000433359A CA 433359 A CA433359 A CA 433359A CA 1209200 A CA1209200 A CA 1209200A
- Authority
- CA
- Canada
- Prior art keywords
- cell
- zinc
- electrode
- nickel
- separator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 39
- 239000011701 zinc Substances 0.000 claims abstract description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 6
- 230000001427 coherent effect Effects 0.000 claims abstract description 3
- 239000000853 adhesive Substances 0.000 claims abstract 2
- 230000001070 adhesive effect Effects 0.000 claims abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005215 recombination Methods 0.000 claims description 11
- 230000006798 recombination Effects 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 description 103
- 239000010410 layer Substances 0.000 description 30
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 5
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 235000006491 Acacia senegal Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011536 re-plating Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- 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
- H01M4/244—Zinc 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/72—Grids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/30—Arrangements for facilitating escape of gases
- H01M50/342—Non-re-sealable arrangements
- H01M50/3425—Non-re-sealable arrangements in the form of rupturable membranes or weakened parts, e.g. pierced with the aid of a sharp member
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
SEALED NICKEL-ZINC BATTERY
A sealed, rechargeable nickel-zinc cell includes a zinc electrode active mass essentially free of zinc metal when at full discharge, a carboxylated styrene-butadiene binder retaining the zinc electrode mixture in a coherent structure, a predetermined amount of cadmium being included in the zinc electrode mixture, a separator preferably comprising at least two layers of material free of any adhesive binding the layers together and a wicking layer positioned between the nickel positive electrode and the separator.
SEALED NICKEL-ZINC BATTERY
A sealed, rechargeable nickel-zinc cell includes a zinc electrode active mass essentially free of zinc metal when at full discharge, a carboxylated styrene-butadiene binder retaining the zinc electrode mixture in a coherent structure, a predetermined amount of cadmium being included in the zinc electrode mixture, a separator preferably comprising at least two layers of material free of any adhesive binding the layers together and a wicking layer positioned between the nickel positive electrode and the separator.
Description
~2~32~
SE~LE~ NIC~ZINC E~
-BACKGROUND OF THE INVEIITION
1. Field Of The Invention This invention relates to electroche~ical cells and more particularly, to sealed, rechargeable nickel-zinc cells.
SE~LE~ NIC~ZINC E~
-BACKGROUND OF THE INVEIITION
1. Field Of The Invention This invention relates to electroche~ical cells and more particularly, to sealed, rechargeable nickel-zinc cells.
2. Description Of The Prior Art Many kinds of portable equipment, such as, for example, tape and video recorders, power tools, calcu-lators, radios, electric razors, television sets, tele-phone pagers, microcomputers, and the like, have been developed over the last several years; and their use has become relatively widespread. In so~e situations, a primary battery or cell has been utilized as the power source. However, while primary cells offer the advantage of relatively high enery densities, these are relatively expensive because of the continual n~ed for replacement.
For this reason, it has been useful to employ a rechargeable cell as the power source. Various types of lead-acid cells have been utilized, particularly where cost is the primary consideration. However, such cells have relatively low eneryy densities and cycle life capabilities, as well as requiring relati~ely long times for charging.
- ? - ~L~20~00 . .
The inadequacies of primary and lead-acid cells have led to the use of nickel-cadmium cells in some applications. Such cells, while xela~ively expensive in comparison to lead-acid cellsr offer relatively high energy densities and an extremely long cycle life.
Moreover, this type of cell is capable of being employed at relatively high charge/discharge rates.
Despite the advantages provided by nickel cadmium cells, there is a continuing demand for many applications for a power source capable of achieviny even higher energy densities and operating at higher working voltages.
This situation has led to the investigation of nickel-zinc rechargeable cells for these applications. The nickel-zinc system is well known and, at least potentially, offers substantial advantages. In comparison to nickel-cadmium cells, nickel-zinc cells have higher working or operating voltages (viz. about 1.65 volts) and poten-tially can provide significantly higher energy densities.
U.S. Patents 3,951,687 and 4,037,033 disclos~ configura-2~ tions for nickel-zinc cells.
Despite this promise, the commercial use of nickel-zinc cells for the portable applications described herein has been extremely limited. This is principally due to the inability to deal adequately with the rela-tively high internal pressures inherent in this system.Thus, while the cadmium electrode in a nickel-cadmium ! cell is marginally kher~odynamically stable with respect to reduction of aqueous alkaline battery electrolytes with consequent evolution of hydrogen gas, the zinc electrode in a nickel-zinc system is unstable. The nickel-zinc system accordingly tends to evolve hydrogen yas under all conditions of service, viz., charger discharge, overcharge and open-circuit stand.
To be commercially useful f a sealed nickel-zinc cell must therefore possess the ability to compensate ~21~9;2~
--3~
.
for the hydrogen gas evolved so that the cell under conditions of use should not vent. If the cell vents, decreased performance can result if enough electrolyte is lost. Moreover, discharge of alkaline eletrolyte into the environ~ent could be harmful to electronic or other components in the area where the cell is employed.
The internal pressures which can be tolerated depend upon the strength of the containers utilized. For small cylindrical cells that typically use container materials which will rupture at about 450 to 500 p.s.i.g. (at such pressures the container top typically separates from the container), safety considerations dictate that venting means be employed which will vent at internal pressures of about 250 p.s.i.g. or so~ In prismatic cells, the plastic container ~aterials typi-cally used require that such cells vent at significantly lower internal pressures, viz. - about 25 p.s.i.gO or so .
The internal pressures developed in sealed nickel-zinc cells under conditions of use can readily exceed 250 p.s.i.g. under various conditions. A considerable amount of effort has been expended to develop a nickel-zinc system capable of operation at satisfactorily low internal pressures.
In addition, there ar~ a number of other problems involved in developing commercially practical sealed nickel-zinc cells. Thus, regardless of the means uti lized to compensate for the hydrogen gas evolved, pro-blems of undue pressure build-up have been found to occur upon stand. It has thus been found thatt if nickel-zinc cells are allowed to stand in a completely discharged condition for an extended period of time, the internal pressure build-up can reach a level where venting of the cell occurs.
~4~ ~209~
A further problem resides in the relatively high impedance values of the prior nickel-zinc cells. For whatever reason, prior nickel-zinc cells seem to be characterized by impedance levels which restrict the current levels that can be utilized.
Still further, prior cells of this type appear to have less than an optimum tolerance to overcharge con-ditions. While not fully understood, it is believed that the less than optimum tolerance is due to the separator configurations previously utilized. Also, in this regard, it appears that the cycle life of nickel-zinc cells, particularly at high discharge rates, are less than optimum.
Lastly, prior cells of this type seem to result in service in zinc passivation. This, of course, can adversely affect the capacity.
Accordingly, despite the prior efforts to provide a commercially viable sealed, nickel-zinc cell, such cells still have made little, if any, inroad as re-placements for the various power sources now e~ployedfor portable equipment applications. There certainly exists the need to provide a com~ercially attractive and cost-effective s~aled nickel-zinc cell capable of obviating to a satisfactory degree the various problems discussed herein.
OBJECTS OF T~E INVE~TION
It is accordingly a principal object of the present invention to provide a sealed, nickel-zinc cell providing improved cycle life and electrical performance in service.
Another object is to provide a cell of the foregoing type that is simple in construction and which is capable of being economically manufactured.
, -5- ~2~Z~
A still further object of this invention lies in the provision of a cell of the foregoing type having the capabilit~ of operation at relatively high current levels.
Yet another object of this invention is to provide a cell of the foregoing type capable of being allowed to stand for prolonged periods of time in a discharged condition without undue internal pressure build-up.
Another object of the present invention is to provide a cell of the ~oregoing type which minimizes zinc passivation.
A still further object is to provide a cell of the foregoing type which possesses improved tolerance to overcharge conditions.
Other objects and advantages of the present inven-tion will become apparent from the following detailed description, and from the drawings in which:
FIGURE 1 is a side elevation of a nickel-zinc cell embodying the present invention and partially cut-away to show the internal configuration;
FIG ~ 2 is a cross-sectional view taken generally along lines ~-2 of FIG~RE 1 and further illustrating the internal configuration of a cell according to the present inventicn;
~5 FIG. 3 is a graph illustrating the cycle life performance of a cell of the present invention compared to prior art!cells, and FIG. 4 is a graph illustrating the hydrogen pressure developed within a nickel-zinc cell with and without 30 the hydrogen recombination catalyst utilized according to one aspect of the present invention.
~ hile the invention is susceptible to various modifications and alternative ~orms, there is shown in the drawings and will herein be described in detail, ~ Z092~0 the preferred embodiments. It is to be understood, however, that it is not intended to li~it the invention to the specific forms disclosed. On the contrary, it is intended to cover all modifications and alternative forms falling within the spirit and scope of the inven-tion as expressed in the appended claims.
S~MMARY OF THE INVE~lTION
In general, the present invention is predicated on the discovery that nickel-zinc cells having improved electrical performance characteristics can be provided by selection of the mixture utilized for the negative electrode, the particular binder erilployed for the nega-tive electrode, and the separator system utilized.
Each of ~hese parameters will individually impart im-proved performance to the cell. Optimum performance isprovided by utilizing all of the features which will be described herein.
In addition, for some applications, an auxiliary feature of this invention provides a specific means for dealing with the intexnal pressure build-up due to the evolution of hydrogen.
DETAILED DESCRIPTION OF THE INVENTION
Turning now to the illustrative embodiment, there is shown in the drawings a rechargeable, sealed nick~l-zinc cell incorporating the present in~ention, the cell being generally designated at 10. The particular con-figuration of the cell is only exemplaryJ and may be ~odified as desired. The cell 10 comprises an outer housing 12 defining a cell 14. The cup-shaped housing 12 has an open end 16 which is closed by closure 18 sealingly Mounted upon open end 16 by an annular insu-lator 20. A perforator disc 22 is secured to the open end 16 of the outer housing 12 by an annular retainer 24 an~ is provided with a piercing tab 26 adapted ko pierce closure 18 in the event the closure is urged outwardly, as by internal pressure buildup within the sealed battery. If desired, a resealable vent could be employed, and many such vent constructions are known.
As best seen in FIG. 2, a cell element shown generally at 28 is contained in cell 14 in the form of a wound roll comprising a negative electrode layer 30, a positive electrode layer 32, and a separator shown generally at 34, intermediate the electrode layers.
Pursuant to one aspect of the present inven-tion, a wicking layer for absorbing electrolyte is preferably provided. It has thus been found that the inclusion of a wicking layer on the side of the separator adjacent the positive electrode layer serves - to impart to the cell longer cycle life, particularly when the service regime involves relatively high dis-charge rates (e.g. - about 2C or higher)~
Any alkali-resistant material capable of absorbing electrolyte can be utilized. In general, a non-woven fabric of a synthetic resin, such as poly-propylene, may be employed. One illustrative example 2S of a suitable polypropylene wicking sheet is WE~RIL M
1488 non-woven fabric (Kendall Company) having a thick-ness of about 3 mils.
Accordingly, as best seen in FIG. 2, a wicking layer 36 for absorbing electrolyte is provided on the side of the separator 34 adjacent the positive electrode layer 32. A wicking layer could be likewise provided adjacent the negative electrode layer 30, i~ desired.
However, and while the use of a wicking layer adjacent the negative electrode may offer advantage in relation to the inclusion of no wicking layer ad3acent either lZ0~20~
electrode, it has been found that superior perfo~mance is achieved when a wicking layer is present only on this side of the separator adjacent the positive elec-trode la~er.
As best seen in FIGURE 1, perforator disc 22 cooperates with closure 18 in defining the negative terminal of the housing. More specifically, a first connecting means tab 38 is electrically connected to the negative electrode layer 30, extending outwardly from the roll into electrically connected association with closure 18.
Outer housing 12 suitably comprises a metal can which defines the positive terminal of the battery.
Thus, as is illustrated in FIGURE 1, a second con-necting tab means 40 is electrically connected withpositive electrode layer 32 and housing 12.
When utilized in a cylindrical cell, as is shown in the illustrative embodiment, the positive and negative electrode layers and the separator should be sufficiently flexible so that a wound element can be provided. The manufacturing techniques to provide suitable positive and negative electrode layers of adequate flexibility are well known.
The negative zinc electrodes may thus be made by conventional techniques. As one exarnple, a powdered mixture of the desired materials and a binder can be rolled onto a suitable current collector, such as, for example, a copper screen.
While such mixtures have previously utilized both zinc oxide and zinc, it has been found that the pres-ence of zinc metal tends to result in undesired pressure buildup if the cell is allowed to stand in a completely -9- ~20~
discharged condition for an extended time period. This pressure build-u~ could reach a level causing the cell to vent. For this reason, pursuant to a principal aspect of the present invention, the mixture utilized incorporates little or no zinc metal.
A variety of binder materials for fabricating zinc electrodes is known. Typically, the binder ~a~erial used is inert in the cell environment and is incorporated in an amount just sufficient to hold the mixture together, providing a positive bond as well to the current collector.
Previously utilized binder materials, such as polytetrafluoroethylene, require relatively large amounts to be employed in order to achieve the desired coherent structure for the negative electrode, amounts on the order of 10% by weight based upon the weight of the mixture often being used. Such relatively large amounts of binder result in the cell having relatively high impedance values. This restricts the current level which the cell can utilize in service.
j 20 Accordingly, a further principal aspect of the I present invention comprises utilizing an elastomeric, self-cured carboxylated styrene-butadiene latex as the binder material. It has been found satisfactory to utilize this binder in an amount preferably in the range of about 3.8% to about 5%, based upon the total weight of the negative electrode mixture. Amounts in this level have been found to achie~e an adequate co-herent structure for the negative electrodes. Moreover, and importantly, this results in cel 15 characterized by relatively low impedance in comparison to prior cells and may thus allow significantly higher current levels in service. Amounts in excess of 5% by weight may certainly be utilized, but such amounts offer little advantage and tend to provide increased impedance.
æ~
.
Specific illustrative examples of suitable binders are AMSCOTM R~S 4150 and 4816, manufactured by th~ AMSCO
Division of Union Oil Company.
If desired, the negative electrode may contain other ingredients, some of which are known. Moreover, pursuant to a further aspect of the present invention, it has been found useful to include a minor but signifi-cant amount of cadmium. This is believed to act to stabilize the negative electrode against shape change as well a.s reducing the rate of evolution of hydrogen.
Indeed, the cadmium present is electrochemically inert until the operating cell voltage has decreased to about 1.30 volts or so. Under these conditions,1 the inclu-sion of cadmium appears to serve to minimize zinc passivation that would otherwise occur.
The amount of cadmium utilized should be such as to provide 20% of the ampere-hour capacity of the positive active material. Amounts above this minimum level may certainly be utilized, -the upper limit likely being constrained by economic considerations. Based upon the total weight of the negative electrode mixture, the amount of cadmium in the range of about 5 to 6%
or so should be suitable to provide such minimum.
The cadmium component may be utilized in the mixture as cadmium oxide. However, it is preferred to utilize cadmium metal. The use of cadmium oxide may accordingly result in some loss in capacity.
It has also been found useful to include in the negative electrode mixture bismuth oxide, Bi2O3, in an amount of about 7 to 8% based upon the weight of the negative electrode mixture. This is believed to function as a corrosion inhibitor.
.2~2~
Prior techniques have utilized calcium hydroxide as a further component of the negative electrode mixture.
The negative electrode mixtures described herein provide satisfactory performance; and, accordingly, there is no necessity for incluAing calcium hydroxide~ It is accor-dinyly preferred that the negative electrode mixture be essentially free of calcium.
As is well known, in nickel-zinc systems using conventional aqueous solutions, such as potassiu~ hydro-xide, as an electrolyte, the zinc specie(s) formedduring discharge is soluble in the electrolyte to a siynficant extent. Some of the active zinc material thus tends to enter the electrolyte while the system is being discharged, as well as while the system stands in a discharged condition. Upon recharging of the battery system, the zinc specie(s) in the electrolyte returns to the zinc electrode but can alter the electrode struc-ture. The active zinc material can thus migrate from the edges or periphery of the electrode structure and collect in the central regions of electrode, resulting in an irreversible loss of capacity. This pheno~enon has been often termed "shape change".
Because of this phenomenon, the cell element uti-lized in the present invention should be positioned in the cell in a fashion which will at least minimize shape change. It has been found satisfactory~ when a cylindrical cell is involved, simply to wind the ele~ent such that the element is under compression while in position within the cell. This assists in minimizing shape change as a problem.
As is likewise well known, the replating or re-deposition of zinc often occurs in the form of ~reed or branched crystals having sharp points (dendrites~ which can readily bridge the gap between the plates or elec-trodes of opposite polarity, thereby causing ~hort circuits and the destruction of the cell. Accordingly, the material used for the separator should be a mem-brane having a relatively fine, uniformly sized porestructure which allows electrolyte permeation there-through while preventing dendrite penetration. Still further, the material employed should possess chemical stability in the cell environment. Additionally, suitable materials should possess sufficient flexi-bility and strength characteristics to endure adequately any shape change and/or electrode expansion that might take place during service. A large number of materials have been proposed for use and are well known, as are their methods of manufacture.
As one illustrative e~ample, the separator may comprise a commercially available CELGARDTM poly-propylene film (Celanese Fiber Company). It has been found particularly desirable to utilize two layers of such material (each layer about one mil thick being adequ~te) to form,the separator layer 34, the indiv-idual layers bein~ shown generally at 42 and 44 (FIG.
23. T~e use of two layers allows the large pores or holes, due to imperfections produced during manu-facture or subsequently, in each layer to be non-aligned with respect to each other to minimize problems with dendrites. Of course, a single layer or more than two layers may likewise be employed if de,sired.
Prior techniques have utiliYed either films such as polyvinyl alcohol on the separator or as cements to bond the individual layers together to form a com-posite, integral structure. However, it has been found that such techniques substantially decrease the tolerance of the cell to overcharge conditions. Pursuant to yet s~
-13- ~ æ ~ ~ 2 00 another aspect of the present invention, it is preferred to utilize a separator construction free of any film on the separator layer or layers utilized and with no cement or other bond beiny em~loyed where multiple separator layers are utilized. In this ~ashion, the resulting cell has been found to possess superior tolerance to overcharge conditions~
Any conventional alkaline electrolyte used with a nickel-zinc system ~ay be employed~ As one exar~ple, it is satisfactory to utilize an aqueous potassium hydroxide solution containing about 25% by weight potassium hydro-xide. It is desirable to utilize initially an electrolyte saturated with Zn(OH)2 so as to prevent initïal dissolu-tion of zinc oxide into the electrolyte. As is known in the sealed cell art, the amount of electrolyte used should be restricted sufficiently so that an effective oxygen recombination reaction will be provided. In the illustrative e~bodiment, the necessary electrolyte can be added to the open space in the core of the wound cell element 28 prior to the sealing of the cell.
With respect to the first connecting tab 38, this should be made of a conductive material having an over-voltage for hydrogen evolution at least approximately as high as that of zinc. An illustrative example is a nickel element, plated with copper and then overplated with silver. The closure 18 may suitably coMprise a steel sheet plated with nickel which is, in turn, covered with copper plating, and then covered with silver plating.
The second connecting tab 40 may comprise, for example, a nickel ele~ent which is electrically connected to the nickel plating 46 of outer housing 12.
A wide variety of materials are known *or the connecting tabs and the housing for nickel-zinc systems, and such materials may be utilized in the nickel-zinc -14- ~ 2 ~ ~ 2 ~ ~
cell of the present invention. The particular ~aterials of construction may accordingly vary rather widely.
Further, if desired, a water sealant coating, as is known, may be applied to the r~etal or other surfaces in the ce]l. A suitable sealant is the styrene-butadiene material described herein as the binder for the negative electrode mixture. As shown in FIG~RE 1, a coating 48 has been applied to the exposed surfaces of the closure 18 and the first connecting tab 38. This may be applied by brushing on to a thickness, for examplel of about 1 mil.
In addition, to insure that adequate insulation is provided between the cell element 28 and the ter~inals, insulators 50, 50' may be included, if desired. ~hile shown as spatially re~oved from the cell element 28 for simplicity of illustration, insulator 50 may suitably rest upon separator layers 42 r 44 which desirably terminate somewhat above the upper end of the electrodes.
The nickel-zinc cell of the present invention may be utilized in either a prismatic or cylindrical design, as is desired for the particular application. Likewise, the capacity of the cell may vary within wide limits, the size being dictated by the requirements of the particular end use application. As one example, a cylindrical sub-C size cell for use in cordless or portable power tools may suitably have a capacity of, for example, 1.2 Ampere-~iours.
The cells of the present invention ~ust likewise incorporate a means for oxidizing the hydrogen evolved in service to maintain a satisfactorily low internal pressure within the cell. A variety of catalytic means are known and may be employed.
In this regard, an auxiliary aspect of the present invention provides as the hydrogen oxidation source a 26~0 hydrogen recombination catalyst located in the cell which is free of electrical connection -to the cell elements. Any fuel cell cathode may suitably be employed. As an illustrative example, the recombina-tion catalyst may suitably comprise carbon clothhaving about 1% by weight platinum catalyst on carbon particles bonded to the cloth by a hydrophobic binder, such as polytetrafluoroethylene. Suitable recom-bination catalysts such as the illustrative embodi-ment are commercially available. As is seen in thedrawings, a hydrogen recombination catalyst 52 is positioned in the axial core space of the wound role cell element and is free of electrical connection to the cell electrodes. In this fashion, the assem-bly of the cell is facilitated.
Utilization of the hydrogen recombinationcatalyst has been found to substantially reduce the internal pressure developed under typical cycling conditions. However, the performance upon prolonged stand and high rate charge/discharge conditions can certainly be improved. Under either of these condi-tions, internal pressure can develop to the point where the cells may well ve~t.
For these reasons, it is preferred to utilize, as the means for dealing with the hydrogen evolution a positive electrode which contains a catalyst such as silver for the oxidation of hydro-genO Sealed nickel-zinc cells utilizing this approach are characterized by relatively low internal pressures in use and on stand and are capable of being operated under relatively high rate charge and discharge with-out building up pressures that would cause venting.
-16- ~ 20~
FIG. 3 demonstrates the extended cycle life of cells pursuant to the present invention at high dis-charge rates. Curves A and C of FIG. 3 represent dis-cllarge curves of cells accordiny to the present inven-tion at two hour and one-half hour rates, respectively.
Curves B and D are discharge curves for previous state-of-the-art nickel-zinc cells at 2.5-hour and 1 hour discharge rates, respectively. These latter rates should be substantially less stressful than the cor-responding rates used for the cells of this invention.As ~ay he seen in FIG. 3, the discharge capacity of the cells of this invention is maintained substantially higher than the discharge capacity of a conventional nickel-zinc cell up to two hundred cycles or more.
15 - FIG. 4 illustrates the perfor~ance of a cell which is achieved using the hydrogen reco~bination catalyst 52. Curve ~ illustrates the hydrogen pressure developed in the absence of the recombination catalyst 52, and the Curve F illustrates the hydrogen pressure developed 2~ in the cell where the recombination electrode 52 is provided. The substantial decrease in the developed pressure due to the inclusion of the recombination catalyst is apparent~
One exa~ple of suitable parameters to provide a 1.2 Ampere-Hour, sub-C size, cell pursuant to the pre-sent invention is as follows. The negative electrode ! layer comprises a first ~ixture of zinc, zinc oxide, cadmium oxide, bismuth oxide and a styrene-butadiene binder rolled onto a copper screen. Based upon the weight of the ~ixture, zinc was present in an a~ount of 4~5~, cadmium oxide in an amount of 5.8%, bismuth oxide in an amount of 7.5~ and binder in an amount of about 4%, the balance being ~inc oxide. The hydrogen recom-bination catalyst comprised a 0.1 inch x 1 inch carbon -17~
cloth strip containing 1% by weight platinum. The negative electrode dimensions w~re 0.016 inch x 1.31 inch x 9 inch and the positive lectrode dimensions were 0.028 inch x 1.2 inch x 7 inch.
The negative electrode may initially contain a charyed zinc mass in the amount of about 35% of the total theoretical Ampere-Hour capacity; however, this should be converted to zinc oxide by the reaction of the zinc with the added cadmium oxide and bis~uth oxide.
The resulting cadmiuM should represent about 25% of the 1.2 Ampere-Hour battery capacity. The amount of zinc oxide initially present is roughly 425% of the Ampere-~our capacity of the cell, the actual capacity being limited by the positive electrode.
For this reason, it has been useful to employ a rechargeable cell as the power source. Various types of lead-acid cells have been utilized, particularly where cost is the primary consideration. However, such cells have relatively low eneryy densities and cycle life capabilities, as well as requiring relati~ely long times for charging.
- ? - ~L~20~00 . .
The inadequacies of primary and lead-acid cells have led to the use of nickel-cadmium cells in some applications. Such cells, while xela~ively expensive in comparison to lead-acid cellsr offer relatively high energy densities and an extremely long cycle life.
Moreover, this type of cell is capable of being employed at relatively high charge/discharge rates.
Despite the advantages provided by nickel cadmium cells, there is a continuing demand for many applications for a power source capable of achieviny even higher energy densities and operating at higher working voltages.
This situation has led to the investigation of nickel-zinc rechargeable cells for these applications. The nickel-zinc system is well known and, at least potentially, offers substantial advantages. In comparison to nickel-cadmium cells, nickel-zinc cells have higher working or operating voltages (viz. about 1.65 volts) and poten-tially can provide significantly higher energy densities.
U.S. Patents 3,951,687 and 4,037,033 disclos~ configura-2~ tions for nickel-zinc cells.
Despite this promise, the commercial use of nickel-zinc cells for the portable applications described herein has been extremely limited. This is principally due to the inability to deal adequately with the rela-tively high internal pressures inherent in this system.Thus, while the cadmium electrode in a nickel-cadmium ! cell is marginally kher~odynamically stable with respect to reduction of aqueous alkaline battery electrolytes with consequent evolution of hydrogen gas, the zinc electrode in a nickel-zinc system is unstable. The nickel-zinc system accordingly tends to evolve hydrogen yas under all conditions of service, viz., charger discharge, overcharge and open-circuit stand.
To be commercially useful f a sealed nickel-zinc cell must therefore possess the ability to compensate ~21~9;2~
--3~
.
for the hydrogen gas evolved so that the cell under conditions of use should not vent. If the cell vents, decreased performance can result if enough electrolyte is lost. Moreover, discharge of alkaline eletrolyte into the environ~ent could be harmful to electronic or other components in the area where the cell is employed.
The internal pressures which can be tolerated depend upon the strength of the containers utilized. For small cylindrical cells that typically use container materials which will rupture at about 450 to 500 p.s.i.g. (at such pressures the container top typically separates from the container), safety considerations dictate that venting means be employed which will vent at internal pressures of about 250 p.s.i.g. or so~ In prismatic cells, the plastic container ~aterials typi-cally used require that such cells vent at significantly lower internal pressures, viz. - about 25 p.s.i.gO or so .
The internal pressures developed in sealed nickel-zinc cells under conditions of use can readily exceed 250 p.s.i.g. under various conditions. A considerable amount of effort has been expended to develop a nickel-zinc system capable of operation at satisfactorily low internal pressures.
In addition, there ar~ a number of other problems involved in developing commercially practical sealed nickel-zinc cells. Thus, regardless of the means uti lized to compensate for the hydrogen gas evolved, pro-blems of undue pressure build-up have been found to occur upon stand. It has thus been found thatt if nickel-zinc cells are allowed to stand in a completely discharged condition for an extended period of time, the internal pressure build-up can reach a level where venting of the cell occurs.
~4~ ~209~
A further problem resides in the relatively high impedance values of the prior nickel-zinc cells. For whatever reason, prior nickel-zinc cells seem to be characterized by impedance levels which restrict the current levels that can be utilized.
Still further, prior cells of this type appear to have less than an optimum tolerance to overcharge con-ditions. While not fully understood, it is believed that the less than optimum tolerance is due to the separator configurations previously utilized. Also, in this regard, it appears that the cycle life of nickel-zinc cells, particularly at high discharge rates, are less than optimum.
Lastly, prior cells of this type seem to result in service in zinc passivation. This, of course, can adversely affect the capacity.
Accordingly, despite the prior efforts to provide a commercially viable sealed, nickel-zinc cell, such cells still have made little, if any, inroad as re-placements for the various power sources now e~ployedfor portable equipment applications. There certainly exists the need to provide a com~ercially attractive and cost-effective s~aled nickel-zinc cell capable of obviating to a satisfactory degree the various problems discussed herein.
OBJECTS OF T~E INVE~TION
It is accordingly a principal object of the present invention to provide a sealed, nickel-zinc cell providing improved cycle life and electrical performance in service.
Another object is to provide a cell of the foregoing type that is simple in construction and which is capable of being economically manufactured.
, -5- ~2~Z~
A still further object of this invention lies in the provision of a cell of the foregoing type having the capabilit~ of operation at relatively high current levels.
Yet another object of this invention is to provide a cell of the foregoing type capable of being allowed to stand for prolonged periods of time in a discharged condition without undue internal pressure build-up.
Another object of the present invention is to provide a cell of the ~oregoing type which minimizes zinc passivation.
A still further object is to provide a cell of the foregoing type which possesses improved tolerance to overcharge conditions.
Other objects and advantages of the present inven-tion will become apparent from the following detailed description, and from the drawings in which:
FIGURE 1 is a side elevation of a nickel-zinc cell embodying the present invention and partially cut-away to show the internal configuration;
FIG ~ 2 is a cross-sectional view taken generally along lines ~-2 of FIG~RE 1 and further illustrating the internal configuration of a cell according to the present inventicn;
~5 FIG. 3 is a graph illustrating the cycle life performance of a cell of the present invention compared to prior art!cells, and FIG. 4 is a graph illustrating the hydrogen pressure developed within a nickel-zinc cell with and without 30 the hydrogen recombination catalyst utilized according to one aspect of the present invention.
~ hile the invention is susceptible to various modifications and alternative ~orms, there is shown in the drawings and will herein be described in detail, ~ Z092~0 the preferred embodiments. It is to be understood, however, that it is not intended to li~it the invention to the specific forms disclosed. On the contrary, it is intended to cover all modifications and alternative forms falling within the spirit and scope of the inven-tion as expressed in the appended claims.
S~MMARY OF THE INVE~lTION
In general, the present invention is predicated on the discovery that nickel-zinc cells having improved electrical performance characteristics can be provided by selection of the mixture utilized for the negative electrode, the particular binder erilployed for the nega-tive electrode, and the separator system utilized.
Each of ~hese parameters will individually impart im-proved performance to the cell. Optimum performance isprovided by utilizing all of the features which will be described herein.
In addition, for some applications, an auxiliary feature of this invention provides a specific means for dealing with the intexnal pressure build-up due to the evolution of hydrogen.
DETAILED DESCRIPTION OF THE INVENTION
Turning now to the illustrative embodiment, there is shown in the drawings a rechargeable, sealed nick~l-zinc cell incorporating the present in~ention, the cell being generally designated at 10. The particular con-figuration of the cell is only exemplaryJ and may be ~odified as desired. The cell 10 comprises an outer housing 12 defining a cell 14. The cup-shaped housing 12 has an open end 16 which is closed by closure 18 sealingly Mounted upon open end 16 by an annular insu-lator 20. A perforator disc 22 is secured to the open end 16 of the outer housing 12 by an annular retainer 24 an~ is provided with a piercing tab 26 adapted ko pierce closure 18 in the event the closure is urged outwardly, as by internal pressure buildup within the sealed battery. If desired, a resealable vent could be employed, and many such vent constructions are known.
As best seen in FIG. 2, a cell element shown generally at 28 is contained in cell 14 in the form of a wound roll comprising a negative electrode layer 30, a positive electrode layer 32, and a separator shown generally at 34, intermediate the electrode layers.
Pursuant to one aspect of the present inven-tion, a wicking layer for absorbing electrolyte is preferably provided. It has thus been found that the inclusion of a wicking layer on the side of the separator adjacent the positive electrode layer serves - to impart to the cell longer cycle life, particularly when the service regime involves relatively high dis-charge rates (e.g. - about 2C or higher)~
Any alkali-resistant material capable of absorbing electrolyte can be utilized. In general, a non-woven fabric of a synthetic resin, such as poly-propylene, may be employed. One illustrative example 2S of a suitable polypropylene wicking sheet is WE~RIL M
1488 non-woven fabric (Kendall Company) having a thick-ness of about 3 mils.
Accordingly, as best seen in FIG. 2, a wicking layer 36 for absorbing electrolyte is provided on the side of the separator 34 adjacent the positive electrode layer 32. A wicking layer could be likewise provided adjacent the negative electrode layer 30, i~ desired.
However, and while the use of a wicking layer adjacent the negative electrode may offer advantage in relation to the inclusion of no wicking layer ad3acent either lZ0~20~
electrode, it has been found that superior perfo~mance is achieved when a wicking layer is present only on this side of the separator adjacent the positive elec-trode la~er.
As best seen in FIGURE 1, perforator disc 22 cooperates with closure 18 in defining the negative terminal of the housing. More specifically, a first connecting means tab 38 is electrically connected to the negative electrode layer 30, extending outwardly from the roll into electrically connected association with closure 18.
Outer housing 12 suitably comprises a metal can which defines the positive terminal of the battery.
Thus, as is illustrated in FIGURE 1, a second con-necting tab means 40 is electrically connected withpositive electrode layer 32 and housing 12.
When utilized in a cylindrical cell, as is shown in the illustrative embodiment, the positive and negative electrode layers and the separator should be sufficiently flexible so that a wound element can be provided. The manufacturing techniques to provide suitable positive and negative electrode layers of adequate flexibility are well known.
The negative zinc electrodes may thus be made by conventional techniques. As one exarnple, a powdered mixture of the desired materials and a binder can be rolled onto a suitable current collector, such as, for example, a copper screen.
While such mixtures have previously utilized both zinc oxide and zinc, it has been found that the pres-ence of zinc metal tends to result in undesired pressure buildup if the cell is allowed to stand in a completely -9- ~20~
discharged condition for an extended time period. This pressure build-u~ could reach a level causing the cell to vent. For this reason, pursuant to a principal aspect of the present invention, the mixture utilized incorporates little or no zinc metal.
A variety of binder materials for fabricating zinc electrodes is known. Typically, the binder ~a~erial used is inert in the cell environment and is incorporated in an amount just sufficient to hold the mixture together, providing a positive bond as well to the current collector.
Previously utilized binder materials, such as polytetrafluoroethylene, require relatively large amounts to be employed in order to achieve the desired coherent structure for the negative electrode, amounts on the order of 10% by weight based upon the weight of the mixture often being used. Such relatively large amounts of binder result in the cell having relatively high impedance values. This restricts the current level which the cell can utilize in service.
j 20 Accordingly, a further principal aspect of the I present invention comprises utilizing an elastomeric, self-cured carboxylated styrene-butadiene latex as the binder material. It has been found satisfactory to utilize this binder in an amount preferably in the range of about 3.8% to about 5%, based upon the total weight of the negative electrode mixture. Amounts in this level have been found to achie~e an adequate co-herent structure for the negative electrodes. Moreover, and importantly, this results in cel 15 characterized by relatively low impedance in comparison to prior cells and may thus allow significantly higher current levels in service. Amounts in excess of 5% by weight may certainly be utilized, but such amounts offer little advantage and tend to provide increased impedance.
æ~
.
Specific illustrative examples of suitable binders are AMSCOTM R~S 4150 and 4816, manufactured by th~ AMSCO
Division of Union Oil Company.
If desired, the negative electrode may contain other ingredients, some of which are known. Moreover, pursuant to a further aspect of the present invention, it has been found useful to include a minor but signifi-cant amount of cadmium. This is believed to act to stabilize the negative electrode against shape change as well a.s reducing the rate of evolution of hydrogen.
Indeed, the cadmium present is electrochemically inert until the operating cell voltage has decreased to about 1.30 volts or so. Under these conditions,1 the inclu-sion of cadmium appears to serve to minimize zinc passivation that would otherwise occur.
The amount of cadmium utilized should be such as to provide 20% of the ampere-hour capacity of the positive active material. Amounts above this minimum level may certainly be utilized, -the upper limit likely being constrained by economic considerations. Based upon the total weight of the negative electrode mixture, the amount of cadmium in the range of about 5 to 6%
or so should be suitable to provide such minimum.
The cadmium component may be utilized in the mixture as cadmium oxide. However, it is preferred to utilize cadmium metal. The use of cadmium oxide may accordingly result in some loss in capacity.
It has also been found useful to include in the negative electrode mixture bismuth oxide, Bi2O3, in an amount of about 7 to 8% based upon the weight of the negative electrode mixture. This is believed to function as a corrosion inhibitor.
.2~2~
Prior techniques have utilized calcium hydroxide as a further component of the negative electrode mixture.
The negative electrode mixtures described herein provide satisfactory performance; and, accordingly, there is no necessity for incluAing calcium hydroxide~ It is accor-dinyly preferred that the negative electrode mixture be essentially free of calcium.
As is well known, in nickel-zinc systems using conventional aqueous solutions, such as potassiu~ hydro-xide, as an electrolyte, the zinc specie(s) formedduring discharge is soluble in the electrolyte to a siynficant extent. Some of the active zinc material thus tends to enter the electrolyte while the system is being discharged, as well as while the system stands in a discharged condition. Upon recharging of the battery system, the zinc specie(s) in the electrolyte returns to the zinc electrode but can alter the electrode struc-ture. The active zinc material can thus migrate from the edges or periphery of the electrode structure and collect in the central regions of electrode, resulting in an irreversible loss of capacity. This pheno~enon has been often termed "shape change".
Because of this phenomenon, the cell element uti-lized in the present invention should be positioned in the cell in a fashion which will at least minimize shape change. It has been found satisfactory~ when a cylindrical cell is involved, simply to wind the ele~ent such that the element is under compression while in position within the cell. This assists in minimizing shape change as a problem.
As is likewise well known, the replating or re-deposition of zinc often occurs in the form of ~reed or branched crystals having sharp points (dendrites~ which can readily bridge the gap between the plates or elec-trodes of opposite polarity, thereby causing ~hort circuits and the destruction of the cell. Accordingly, the material used for the separator should be a mem-brane having a relatively fine, uniformly sized porestructure which allows electrolyte permeation there-through while preventing dendrite penetration. Still further, the material employed should possess chemical stability in the cell environment. Additionally, suitable materials should possess sufficient flexi-bility and strength characteristics to endure adequately any shape change and/or electrode expansion that might take place during service. A large number of materials have been proposed for use and are well known, as are their methods of manufacture.
As one illustrative e~ample, the separator may comprise a commercially available CELGARDTM poly-propylene film (Celanese Fiber Company). It has been found particularly desirable to utilize two layers of such material (each layer about one mil thick being adequ~te) to form,the separator layer 34, the indiv-idual layers bein~ shown generally at 42 and 44 (FIG.
23. T~e use of two layers allows the large pores or holes, due to imperfections produced during manu-facture or subsequently, in each layer to be non-aligned with respect to each other to minimize problems with dendrites. Of course, a single layer or more than two layers may likewise be employed if de,sired.
Prior techniques have utiliYed either films such as polyvinyl alcohol on the separator or as cements to bond the individual layers together to form a com-posite, integral structure. However, it has been found that such techniques substantially decrease the tolerance of the cell to overcharge conditions. Pursuant to yet s~
-13- ~ æ ~ ~ 2 00 another aspect of the present invention, it is preferred to utilize a separator construction free of any film on the separator layer or layers utilized and with no cement or other bond beiny em~loyed where multiple separator layers are utilized. In this ~ashion, the resulting cell has been found to possess superior tolerance to overcharge conditions~
Any conventional alkaline electrolyte used with a nickel-zinc system ~ay be employed~ As one exar~ple, it is satisfactory to utilize an aqueous potassium hydroxide solution containing about 25% by weight potassium hydro-xide. It is desirable to utilize initially an electrolyte saturated with Zn(OH)2 so as to prevent initïal dissolu-tion of zinc oxide into the electrolyte. As is known in the sealed cell art, the amount of electrolyte used should be restricted sufficiently so that an effective oxygen recombination reaction will be provided. In the illustrative e~bodiment, the necessary electrolyte can be added to the open space in the core of the wound cell element 28 prior to the sealing of the cell.
With respect to the first connecting tab 38, this should be made of a conductive material having an over-voltage for hydrogen evolution at least approximately as high as that of zinc. An illustrative example is a nickel element, plated with copper and then overplated with silver. The closure 18 may suitably coMprise a steel sheet plated with nickel which is, in turn, covered with copper plating, and then covered with silver plating.
The second connecting tab 40 may comprise, for example, a nickel ele~ent which is electrically connected to the nickel plating 46 of outer housing 12.
A wide variety of materials are known *or the connecting tabs and the housing for nickel-zinc systems, and such materials may be utilized in the nickel-zinc -14- ~ 2 ~ ~ 2 ~ ~
cell of the present invention. The particular ~aterials of construction may accordingly vary rather widely.
Further, if desired, a water sealant coating, as is known, may be applied to the r~etal or other surfaces in the ce]l. A suitable sealant is the styrene-butadiene material described herein as the binder for the negative electrode mixture. As shown in FIG~RE 1, a coating 48 has been applied to the exposed surfaces of the closure 18 and the first connecting tab 38. This may be applied by brushing on to a thickness, for examplel of about 1 mil.
In addition, to insure that adequate insulation is provided between the cell element 28 and the ter~inals, insulators 50, 50' may be included, if desired. ~hile shown as spatially re~oved from the cell element 28 for simplicity of illustration, insulator 50 may suitably rest upon separator layers 42 r 44 which desirably terminate somewhat above the upper end of the electrodes.
The nickel-zinc cell of the present invention may be utilized in either a prismatic or cylindrical design, as is desired for the particular application. Likewise, the capacity of the cell may vary within wide limits, the size being dictated by the requirements of the particular end use application. As one example, a cylindrical sub-C size cell for use in cordless or portable power tools may suitably have a capacity of, for example, 1.2 Ampere-~iours.
The cells of the present invention ~ust likewise incorporate a means for oxidizing the hydrogen evolved in service to maintain a satisfactorily low internal pressure within the cell. A variety of catalytic means are known and may be employed.
In this regard, an auxiliary aspect of the present invention provides as the hydrogen oxidation source a 26~0 hydrogen recombination catalyst located in the cell which is free of electrical connection -to the cell elements. Any fuel cell cathode may suitably be employed. As an illustrative example, the recombina-tion catalyst may suitably comprise carbon clothhaving about 1% by weight platinum catalyst on carbon particles bonded to the cloth by a hydrophobic binder, such as polytetrafluoroethylene. Suitable recom-bination catalysts such as the illustrative embodi-ment are commercially available. As is seen in thedrawings, a hydrogen recombination catalyst 52 is positioned in the axial core space of the wound role cell element and is free of electrical connection to the cell electrodes. In this fashion, the assem-bly of the cell is facilitated.
Utilization of the hydrogen recombinationcatalyst has been found to substantially reduce the internal pressure developed under typical cycling conditions. However, the performance upon prolonged stand and high rate charge/discharge conditions can certainly be improved. Under either of these condi-tions, internal pressure can develop to the point where the cells may well ve~t.
For these reasons, it is preferred to utilize, as the means for dealing with the hydrogen evolution a positive electrode which contains a catalyst such as silver for the oxidation of hydro-genO Sealed nickel-zinc cells utilizing this approach are characterized by relatively low internal pressures in use and on stand and are capable of being operated under relatively high rate charge and discharge with-out building up pressures that would cause venting.
-16- ~ 20~
FIG. 3 demonstrates the extended cycle life of cells pursuant to the present invention at high dis-charge rates. Curves A and C of FIG. 3 represent dis-cllarge curves of cells accordiny to the present inven-tion at two hour and one-half hour rates, respectively.
Curves B and D are discharge curves for previous state-of-the-art nickel-zinc cells at 2.5-hour and 1 hour discharge rates, respectively. These latter rates should be substantially less stressful than the cor-responding rates used for the cells of this invention.As ~ay he seen in FIG. 3, the discharge capacity of the cells of this invention is maintained substantially higher than the discharge capacity of a conventional nickel-zinc cell up to two hundred cycles or more.
15 - FIG. 4 illustrates the perfor~ance of a cell which is achieved using the hydrogen reco~bination catalyst 52. Curve ~ illustrates the hydrogen pressure developed in the absence of the recombination catalyst 52, and the Curve F illustrates the hydrogen pressure developed 2~ in the cell where the recombination electrode 52 is provided. The substantial decrease in the developed pressure due to the inclusion of the recombination catalyst is apparent~
One exa~ple of suitable parameters to provide a 1.2 Ampere-Hour, sub-C size, cell pursuant to the pre-sent invention is as follows. The negative electrode ! layer comprises a first ~ixture of zinc, zinc oxide, cadmium oxide, bismuth oxide and a styrene-butadiene binder rolled onto a copper screen. Based upon the weight of the ~ixture, zinc was present in an a~ount of 4~5~, cadmium oxide in an amount of 5.8%, bismuth oxide in an amount of 7.5~ and binder in an amount of about 4%, the balance being ~inc oxide. The hydrogen recom-bination catalyst comprised a 0.1 inch x 1 inch carbon -17~
cloth strip containing 1% by weight platinum. The negative electrode dimensions w~re 0.016 inch x 1.31 inch x 9 inch and the positive lectrode dimensions were 0.028 inch x 1.2 inch x 7 inch.
The negative electrode may initially contain a charyed zinc mass in the amount of about 35% of the total theoretical Ampere-Hour capacity; however, this should be converted to zinc oxide by the reaction of the zinc with the added cadmium oxide and bis~uth oxide.
The resulting cadmiuM should represent about 25% of the 1.2 Ampere-Hour battery capacity. The amount of zinc oxide initially present is roughly 425% of the Ampere-~our capacity of the cell, the actual capacity being limited by the positive electrode.
Claims (19)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A sealed, rechargeable nickel-zinc cell com-prising a sealed housing defining a cell space, an electrochemical cell element contained in said cell space, said electrochemical cell element including a zinc electrode comprising a current collector and an active mass, a nickel electrode and a separator there-between, a predetermined amount of an alkaline electro-lyte contained in said cell housing, a positive terminal electrically connected to said positive electrode, a negative terminal electrically connected to said zinc electrode and a means for oxidizing the hydrogen evolved in service to maintain a satisfactorily low internal pressure within said cell, said zinc electrode being essentially free of zinc metal as constructed in the discharged state.
2. The cell of claim 1 wherein said zinc elec-trode comprises a mixture of zinc oxide, a source of cadmium in an amount to provide at least about 20% of the Ampere-Hour capacity of the nickel electrode and a carboxylated styrene butadiene binder in an amount sufficient to provide a coherent zinc electrode structure.
3. The cell of claim 2 wherein said binder is present in an amount of from about 3.8 to about 5%, based upon the weight of the zinc electrode active mass.
4. The cell of claim 2 wherein said negative electrode includes bismuth oxide.
5. The cell of claim 1 wherein said cell space is cylindrical and said electrochemical cell element comprises a wound roll having an axial core space.
6. The cell of claim 5 wherein said hydrogen oxidation means comprises a hydrogen recombination catalyst positioned in the core space of said wound roll and being free of electrical connection to said cell element.
7. The cell of claim 6 wherein said hydrogen re-combination catalyst comprises a carbon strip having platinum catalyst carried thereon.
8. The cell of claim 1 wherein said separator comprises at least two layers of a microporous poly-propylene film.
9. The cell of claim 1 wherein said alkaline electrolyte is an aqueous potassium hydroxide solution.
10. The cell of claim 1 wherein said electro-chemical cell element includes an electrolyte absorbing wicking layer positioned between said positive electrode and said separator.
11. The cell of claim 10 wherein said wicking layer comprises a non-woven polypropylene material.
12. A sealed, rechargeable alkaline cell com-prising a sealed housing defining a cell space, an electrochemical cell element contained in said cell space, said electrochemical cell element including a zinc electrode mixture having a carboxylated styrene-butadiene binder, a positive nickel electrode and a separator therebetween, a predetermined amount of an alkaline electrolyte contained in said cell housing, a positive terminal electrically connected to said posi-tive electrode, a negative terminal electrically con-nected to said zinc electrode, and a hydrogen oxidation means to oxidize the hydrogen evolved in service to maintain a satisfactorily low internal pressure within said cell.
13. The cell of claim 12 wherein said binder is present in an amount of from about 3.8 to about 5% by weight of the zinc electrode active mass.
14. The cell of claim 12 wherein said zinc elec-trode active mass is essentially free of zinc metal.
15. The cell of claim 14 wherein said zinc elec-trode active mass contains bismuth oxide.
16. The cell of claim 15 wherein said separator comprises at least two layers of a microporous polypro-pylene film.
17. The cell of claim 16 wherein said two layers are free of adhesive.
18. The cell of claim 17 wherein said electro-chemical cell element includes an electrolyte absorbing wicking layer positioned between said positive elec-trode and said separator.
19. The cell of claim 18 wherein said alkaline electrolyte is an aqueous potassium hydroxide solution.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40238382A | 1982-07-27 | 1982-07-27 | |
| US50968683A | 1983-06-30 | 1983-06-30 | |
| US509,686 | 1983-06-30 | ||
| US402,383 | 1989-09-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1209200A true CA1209200A (en) | 1986-08-05 |
Family
ID=27017846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000433359A Expired CA1209200A (en) | 1982-07-27 | 1983-07-27 | Sealed nickel-zinc battery |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0114884A4 (en) |
| JP (1) | JPS59501521A (en) |
| AU (1) | AU549585B2 (en) |
| CA (1) | CA1209200A (en) |
| IN (1) | IN162152B (en) |
| MX (1) | MX154785A (en) |
| PH (1) | PH18838A (en) |
| WO (1) | WO1984000642A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE50086T1 (en) * | 1985-07-26 | 1990-02-15 | Saft Sa | PROCESS FOR MANUFACTURE OF POLYMER REINFORCED CADMIUM ELECTRODE FOR ALKALINE BATTERY AND ELECTRODE OBTAINED BY THIS PROCESS. |
| US5477936A (en) * | 1991-10-19 | 1995-12-26 | Honda Giken Kogyo Kabushiki Kaisha | Electric motor vehicle and battery unit for electric motor vehicle |
| JPH06278667A (en) * | 1993-01-26 | 1994-10-04 | Honda Motor Co Ltd | Electric vehicle |
| JP3317560B2 (en) * | 1993-10-19 | 2002-08-26 | 本田技研工業株式会社 | Battery cooling structure for electric vehicles |
| JP3412701B2 (en) * | 1993-10-19 | 2003-06-03 | 本田技研工業株式会社 | Cover structure and battery storage case structure for electric vehicles |
| KR100287119B1 (en) * | 1994-07-26 | 2001-05-02 | 윤종용 | Method for forming nickel electrode for alkaline secondary battery |
| CN1336015A (en) * | 1998-12-15 | 2002-02-13 | 杜拉塞尔公司 | electrochemical cell package |
| DE10050018A1 (en) * | 2000-10-06 | 2002-04-11 | Pk Bauelemente & Vertriebs Ag | Rechargeable battery comprises an activated charcoal layer, an electrolytic layer, an electrical connection, and a zinc layer mixed with a catalyst consisting of an antimony alloy as crystalline powder in the gamma phase |
| US20130136991A1 (en) | 2011-11-30 | 2013-05-30 | Lawrence Livermore National Security, Llc | High energy/power density nickel oxide/hydroxide materials and nickel cobalt oxide/hydroxide materials and production thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2738375A (en) * | 1953-02-11 | 1956-03-13 | Electric Storage Battery Co | Storage battery plates and methods of manufacturing the same |
| US3669746A (en) * | 1970-08-03 | 1972-06-13 | Gates Rubber Co | Separators for secondary alkaline batteries having a zinc-containing electrode |
| JPS5461B2 (en) * | 1973-11-21 | 1979-01-05 | ||
| JPS5132365A (en) * | 1974-09-13 | 1976-03-18 | Toshihiro Goto | DENRYOKURYOKINHYOJISOCHI |
| GB1474720A (en) * | 1974-12-24 | 1977-05-25 | Matsushita Electric Industrial Co Ltd | Storage batteries |
| JPS5626108B2 (en) * | 1975-01-20 | 1981-06-16 | ||
| US4022953A (en) * | 1975-08-22 | 1977-05-10 | Energy Research Corporation | Zinc electrodes for secondary batteries |
| JPS5262633A (en) * | 1975-11-19 | 1977-05-24 | Matsushita Electric Industrial Co Ltd | Nickel zinc battery |
| JPS5529548A (en) * | 1978-08-22 | 1980-03-01 | Ngk Spark Plug Co Ltd | Sodium silicate adhesive and its preparation |
| JPH0194534A (en) * | 1987-10-06 | 1989-04-13 | Csk Corp | Optical card reader |
| JPH0262633A (en) * | 1988-08-30 | 1990-03-02 | Fujitsu Ltd | Inter-program communication system |
| EP0408935A3 (en) * | 1989-07-17 | 1991-05-08 | Siemens Aktiengesellschaft | Method and device for separating short circuit zones and conducting paths |
| JP2572854B2 (en) * | 1989-08-14 | 1997-01-16 | 日産自動車株式会社 | Vehicle traction control device |
| JP2921876B2 (en) * | 1989-09-06 | 1999-07-19 | マツダ株式会社 | Energy absorption structure on the side of the vehicle |
-
1983
- 1983-07-21 JP JP58502757A patent/JPS59501521A/en active Granted
- 1983-07-21 WO PCT/US1983/001132 patent/WO1984000642A1/en not_active Ceased
- 1983-07-21 AU AU18878/83A patent/AU549585B2/en not_active Ceased
- 1983-07-21 EP EP19830902660 patent/EP0114884A4/en not_active Withdrawn
- 1983-07-27 PH PH29307A patent/PH18838A/en unknown
- 1983-07-27 CA CA000433359A patent/CA1209200A/en not_active Expired
- 1983-07-27 MX MX198175A patent/MX154785A/en unknown
- 1983-11-21 IN IN1431/CAL/83A patent/IN162152B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PH18838A (en) | 1985-10-10 |
| JPH0438106B2 (en) | 1992-06-23 |
| WO1984000642A1 (en) | 1984-02-16 |
| EP0114884A4 (en) | 1985-02-28 |
| MX154785A (en) | 1987-12-11 |
| AU1887883A (en) | 1984-02-23 |
| EP0114884A1 (en) | 1984-08-08 |
| AU549585B2 (en) | 1986-01-30 |
| IN162152B (en) | 1988-04-09 |
| JPS59501521A (en) | 1984-08-23 |
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