WO1993018557A1 - Batterie rechargeable a haute capacite ayant une electrode en bioxyde de manganese - Google Patents

Batterie rechargeable a haute capacite ayant une electrode en bioxyde de manganese Download PDF

Info

Publication number
WO1993018557A1
WO1993018557A1 PCT/CA1992/000101 CA9200101W WO9318557A1 WO 1993018557 A1 WO1993018557 A1 WO 1993018557A1 CA 9200101 W CA9200101 W CA 9200101W WO 9318557 A1 WO9318557 A1 WO 9318557A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
cell
electrochemical cell
rechargeable electrochemical
cells
Prior art date
Application number
PCT/CA1992/000101
Other languages
English (en)
Inventor
Klaus Tomantschger
R. James Book
Robert D. Findlay
Erkut Oran
Original Assignee
Battery Technologies Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Battery Technologies Inc. filed Critical Battery Technologies Inc.
Priority to PCT/CA1992/000101 priority Critical patent/WO1993018557A1/fr
Priority to AU13337/92A priority patent/AU1333792A/en
Publication of WO1993018557A1 publication Critical patent/WO1993018557A1/fr

Links

Classifications

    • 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
    • H01M10/24—Alkaline accumulators
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
    • 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
    • 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
    • H01M50/394—Gas-pervious parts or elements
    • 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
    • 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

Definitions

  • This invention relates to rechargeable cells having manganese dioxide electrodes, and particularly cells which are substantively anode limited in respect of their discharge capacity.
  • the theoretical discharge capacity of the anode is in the range of from 60% to 120% of the theoretical one electron discharge capacity of the M ⁇ 2 electrode.
  • the usual embodiment may be the typical "bobbin" type cylindrical cell, however spirally wound cells, button or coin cells, and flat plate cells may be provided in keeping with the present invention.
  • Manganese dioxide electrodes when used as rechargeable cathodes in ' electrochemical cells, are known to be reversible only if the manganese dioxide is charged and discharged between its nominal status of Mn ⁇ 2 and its fully discharged one electron status of Mn2 ⁇ 3 .
  • the discharge capacity of the Mn ⁇ 2 electrode between the Mn ⁇ 2 status and the M ⁇ O status is termed or designated as the theoretical one electron discharge capacity of the Mn ⁇ 2 electrode. If the discharge process of the Mn ⁇ 2 cathode continues beyond the Mn2 ⁇ ⁇ level, an irreversible phase change has been reported to occur, so that the manganese dioxide electrode is no longer fully rechargeable.
  • the following equation is descriptive of the discharge reaction which takes place as the Mn ⁇ 2 discharges towards its Mn2 ⁇ one electron discharge level in the presence of an aqueous electrolyte.
  • the second step described above occurs at a voltage which is too low to contribute significantly if at all to the service life of the cell, since it occurs below 0.9 volts.
  • the second discharge step described above is irreversible, thereby rendering the Mn0 2 electrode to be non- rechargeable.
  • Mn ⁇ 2/Zn cells there have been a number of steps taken to ensure rechargeability; and specifically, steps have been taken to severely limit the discharge capacity of the anode, or to provide electronic means to preclude overdischarge of the Mn ⁇ 2 cathode, so as to provide rechargeable n ⁇ 2/Zn cells. This has been particularly of concern when it was intended to provide n02/Zn cells in sufficient quantities as to make them commercially viable, meaning especially that ordinary commercially available battery grade manganese dioxide had to be relied upon.
  • Mn0 2 electrode that provides the difficulty as to rechargeability; it being generally considered that it is the material of the anode that is reversible or rechargeable over most if not all of the cycle life of the cell.
  • rechargeable alkaline Mn0 2 /Zn cells that have been brought to the market in the late 1960's and early 1970's were not successful because of the constraints placed upon them.
  • Such cells were also quite low in respect of their energy densities: For example, a D cell may have been rated at only 2 Ah as a rechargeable cell, but could deliver only 6 Ah before the cell was completely exhausted and not further rechargeable.
  • the theoretical capacity of the zinc anode was generally set higher than that of the theoretical one electron discharge capacity of the Mn0 2 , at about 130% to 135% of the theoretical one electron discharge capacity.
  • Amano et al U.S. Patent 3,530,496, issued September 22, 1970.
  • Amano et al make a very strong statement of their intent to limit the depth of discharge of the Mn ⁇ 2 electrode by providing an anode that has its capacity limited to between 20% to 30% of the Mn ⁇ 2 electrode capacity.
  • the available capacity of the Mn0 depends on various parameters such as the drain rate, cutoff voltage, and whether the cell will be subjected to continuous or intermittent use.
  • the available capacity of the Mn ⁇ 2 electrode is neither clearly indicative nor clearly a measure of or a consequence of the balance of the cell, as discussed below.
  • limiting the available anode capacity to less than 30% of the available cathode capacity is equivalent to a theoretical anode capacity limitation of less than 30% of the theoretical one electron Mn0 2 discharge capacity.
  • Amano et al achieve their zinc anode limitations is that they provide cathodes having dimensions that are essentially equal to those of primary alkaline cells, and then reduce the zinc capacity of the anodes by placing an annular or hollow cylindrical gelled zinc anode adjacent to the Mn0 2 cathode and separated from it by a suitable two component separator. Then, the center of the anode is filled with gelled electrolyte that does not have any active anode material added to it. Amano et al also prefer that amalgamated copper particles be included in the anode so as to enhance its conductivity.
  • Amano et al also provide a zinc oxide reserve mass, they employ PTFE as a binder, and they must use a perforated coated screen current collector rather than a single nail which would otherwise be used in a primary Mn0 2 /Zn alkaline cell.
  • Ogawa et al in U.S. Patent 3,716,411, issued February 13, 1973, teach a rechargeable alkaline manganese cell, the discharge capacity of the anode of which is controlled within such a range that the cathode can be recharged; and wherein the anode and cathode face each other through a gas permeable and dendrite impermeable separator.
  • the Ogawa et al cell is strictly anode limited in that the capacity of the anode is held to be not more than about 40% of the theoretical one electron discharge capacity of the manganese dioxide.
  • Ogawa et al discuss the fact that if a zinc-manganese dioxide cell is discharged so that its terminal voltage reaches a voltage below 0.9 volts and down to about 0.75 volts, and where the capacity of the zinc negative electrode is about the same or slightly smaller than that of the manganese dioxide positive electrode, then the effect of the discharge on the manganese dioxide is such that it is non-reversible at least in part.
  • Ogawa et al provide that under no conditions should the depth of discharge of the anode be permitted to exceed 60% of the theoretical one electron discharge capacity of the manganese dioxide cathode.
  • Ogawa et al provide an alternative structure which comprises two positive electrodes, one on either side of the anode, and wherein the inner positive electrode is contained within a perforated nickel plate steel pocket or canister.
  • Kordesch in U.S. Patent 4,091,178, issued May 23, 1978, also provides a rechargeable Mn0 /Zn cell where the theoretical discharge capacity of the anode is specifically limited to about 33% of the one electron discharge capacity of the cathode.
  • Kordesch also provides a charge reserve mass in which a quantity of zinc oxide is placed that is equal to at least 50% of the discharge capacity of the anode. Because there is an excessive capacity of Mn0 2 , as well as additional ZnO, the energy density of the Kordesch cell is quite low.
  • the drain rate of the active material of a cell, and particularly the cathode or positive electrode thereof, may be expressed in terms of milliamperes per gram (mA/g) of the active material of the electrode.
  • mA/g milliamperes per gram
  • that drain rate may change for any given electrode composition; and moreover, the nature of the utilization for which the cell is intended may also affect the design of the electrode and its composition.
  • the utilization of conductive additives, and the quantity thereof, the particle size of the active material, the electrolyte concentration within the cell, and so on may have an effect on the manner in which the cell may be efficiently utilized.
  • a cell may be optimized for high drain rate or low drain rates, and that makes it necessary to perform tests over all of the drain rates that will be encountered in practical applications, using weighing factors for each drain rate as may be determined by the cell designer, so as to determine the best overall performance. It follows that, depending on the cell balance, the drain rate for the cell that is based on the active material content of the cell, will be different for different designs. A full discussion of a number of those factors is to be found in the commonly owned co-pending application of Tomantschger et al, U .S . Patent Application No. 07/667,476, noted above.
  • That application shows the capacity in mAh/ g of active material for Mn ⁇ 2 electrodes in an alkaline electrolyte, as determined in half -cell experiments for various drain rates expressed in mAh/g.
  • the capacity in mAh/ g of active material for Mn ⁇ 2 electrodes in an alkaline electrolyte as determined in half -cell experiments for various drain rates expressed in mAh/g.
  • primary alkaline cells contain a further additional amount of Mn ⁇ 2- This is to preclude the cell from leaking if it is left in an operating device and is utilized as an energy source for extended periods of time. A description of that circumstance is found in Leger, U.S. Patent 2,993,947, issued July 25, 1961.
  • a negative electrode or anode is, of course, provided, with a separator between the negative electrode and the Mn0 2 electrode, and appropriate terminal means contacting the negative electrode and Mn ⁇ 2 electrode so as to provide respective negative and positive terminals for the cell.
  • the manganese dioxide of the Mn ⁇ 2 electrode is capable of being reversibly charged and discharged between the nominal status of Mn ⁇ 2 and the fully discharged one electron status of M ⁇ O ," the discharge capacity of the Mn ⁇ 2 electrode between the Mn ⁇ 2 status and the Mn 2 03 status being the theoretical one electron discharge capacity of that electrode.
  • the present invention contemplates negative electrodes where the principal active component may be chosen from the group consisting of zinc, iron, lead, cadmium, hydrogen, and metal hydrides.
  • the principal active component of the aqueous electrolyte is chosen to accommodate the specific couple between the negative electrode and the positive Mn ⁇ 2 electrode, and particularly may be chosen from the group consisting of alkali metal hydroxides — e.g., KOH — , or an acid such as H2SO4, H3BO3, or H3PO4, or a solution of salt which may be ZnCl, NH4CI, NaCl, or KCl.
  • the negative electrode is, of course, rechargeable.
  • the theoretical discharge capacity of the negative electrode is in the range of from 60% to 120% of the theoretical one electron discharge capacity of the n02 electrode.
  • the active material of the negative electrode is zinc
  • the electrolyte is 4N to 12N potassium hydroxide.
  • the Mn0 2 electrode may include at least one additive which is chosen from the group consisting of 5% to 15% by weight of graphite, 0.1% to 15% by weight of carbon black, an inorganic binder, graphite fibres that are used as a fibrous reinforcing agent, and a hydrophobic organic binder chosen from the group consisting of PTFE, polypropylene, and polyethylene.
  • the hydrophobic material may be present in the range of from 0.1% to 10% by weight of the Mn0 2 electrode.
  • the carbon black may be present as a porous additive in the Mn0 electrode in the range of from 0.1% to 15% by weight thereof.
  • the cathode composition may include hydrogen recombination catalysts such as those taught in commonly owned U.S. Patent application Serial No. 07/520,820, filed July 9, 1990. Still further, so as to provide for overcharge capability, an oxygen evolution catalyst as taught in commonly owned U.S. Patent 4,957,827, issued September 18, 1990, to Kordesch et al, may be utilized. Whatever catalyst is selected, it is chosen so as to be stable over a wide voltage range — typically from 0.9 volts versus Zn to 2.0 volts versus Zn — and also over a wide temperature range — typically from -40 * C to +70 * C — without any significant deterioration in performance of the cell.
  • Such catalysts may be oxides, spinels, or perovskites of nickel, cobalt, iron, manganese, chromium, vanadium, titanium, and silver.
  • the oxygen evolution catalyst may be placed on the outer surface of the cathode, or they may be dispersed throughout the Mn ⁇ 2 electrode.
  • the catho.de composition preferably contains both carbon black as well as the hydrophobic binder. Still further, for purposes of hydrogen gas porosity and accessibility, the cathode composition may further comprise from about 0.1% to 5.0% of a hydrophobic material such as PTFE, polyethylene, or polypropylene, together with an additional porous additive such as from about 0.1% to 5.0% of carbon black. Such additives improve the gas transport characteristics of the cathode, and thereby enhance the hydrogen recombination rate of the cathode.
  • a hydrophobic material such as PTFE, polyethylene, or polypropylene
  • the Mn0 2 electrode may comprise from 0.1% to 5% of a hydrogen evolution catalyst such as one chosen from the group consisting of silver, oxides of silver, silver salts, platinum, and compounds of silver and platinum.
  • a hydrogen evolution catalyst such as one chosen from the group consisting of silver, oxides of silver, silver salts, platinum, and compounds of silver and platinum.
  • the cathode may be molded into pellets and inserted into the can, followed optionally by recompaction. Otherwise, the cathode may be extruded directly into the can, or it may be rolled or cast as a flat cathode for use in flat plate cells or even in respect of button or coin cells.
  • Figure 1 is a typical cylindrical cell in which the present invention may be embodied
  • Figure 2 shows curves comparing the capacity of active material of manganese dioxide cathodes and zinc electrodes intended for use in cells according to the present invention, where the data were determined in half cell . tests;
  • Figures 3 to 8 are graphical representations of the capacity of test cells against the capacity of a control cell, where the test cells all have different balances of the active materials of the positive and negative electrodes, and wherein the test cells are charged and discharged according to a particular test regimen and the control cell is charged and discharged according to standard test procedures;
  • Figure 9 shows the results of cycling tests using deep discharge cycles, for two different cell configurations having differing ratios of anode capacity to cathode capacity.
  • a typical cylindrical cell is shown at 10.
  • the cell comprises a container 12, within which is ' a cathode 14 and an anode 16. Between the cathode and the anode there is located a separator 18.
  • the cell is closed by the closure member 20, through which a current collector 22 extends into the anode 16.
  • the current collector or nail 22 contacts a metal negative cap 24 which is placed or welded across the head of the nail, and across the closure member 20, thereby providing a negative terminal for the cell 10.
  • a pip 26 At the other end of the cell there is formed a pip 26, and it provides the positive terminal for the cell. It is evident that the can 12 contacts the cathode 14 whereas only the cap 24 through nail 22 contacts the anode 16. To preclude short circuit within the cell, the pip 26 is insulated from the anode 16 by an insulating washer or bottom cup 28.
  • an aqueous electrolyte is provided so as to flood the cell and contact and provide ionic paths so that the cell may be charged and discharged.
  • the separator 18 may be permeable to the passage of gases such as hydrogen or oxygen that are produced within the cell on overcharge, standby, or overdischarge conditions.
  • the cell may comprise an absorber made from rayon or polyvinylalcohol fibres, and a barrier which may consist of cellulose, CELLOPHANE (TM), polya ide or polyethylene, or the like.
  • TM CELLOPHANE
  • the separator is such that the cell will not be shorted because of zinc dendrite growth through the separator.
  • Other appropriate separator materials such as those sold in association with the trademark CELGARD (TM) and PERMION (TM) may be used, as well as multi-component designs, the use of several laminates, and so on.
  • the electrolyte is alkaline metal hydroxide such as 4N to 12N potassium hydroxide. It may, as appropriate, contain various additives including dissolved zinc oxide. Other aqueous electrolytes may be utilized, as noted above.
  • the choice of the material of the negative electrode is usually zinc, but it may also be iron, lead, cadmium, hydrogen, or a metal hydride. Accordingly, the choice of the aqueous electrolyte may expand, depending on the couple between the negative electrode and the Mn0 2 cathode, to include other alkaline metal hydroxides, acids such as H2SO4, H3BO3 and H3PO4, or aqueous solutions of salts such as ZnCl, NH 4 C1, NaCl, and KCl. It is desirable that energy densities of different cells might be compared in actual discharge experiments. However, in practice, difficulties in making such comparisons are encountered.
  • the drain rate of a cell may affect the utilization of the theoretical one electron energy capacity for a given Mn ⁇ 2 electrode composition.
  • the practical capacity of an electrode approaches the theoretical capacity of the electrode only in circumstances where a very low drain rate can be maintained.
  • Such circumstances may be, for example, electrical clocks where the clock runs continuously for a long period of time on a single AA cell; but most battery powered devices such as radios, tape players, electric toys, and the like, require considerably higher drain rates.
  • the degree of utilization of the electrode also depends on the composition of the electrode; for example, whether the electrode includes conductive additives, as well as the particle size of the active material of the electrode, the electrolyte concentration, and so on.
  • specific cells can be designed and optimized for high drain rate circumstances, or for low drain rate circumstances.
  • the degree of utilization, and the specific cell design may be predicated upon the configuration of the cell — which may be a coin or button cell, or a flat plate cell, rather than a more typical cylindrical or bobbin type cell.
  • compositions were used to construct half-cells, both as to the Mn ⁇ 2 electrode composition and the anode composition. Each cell is expressed in parts by weight:
  • curve 44 shows the theoretical capacity of manganese dioxide for the one electron (le ⁇ ) discharge
  • curve 46 shows the measured capacity at various drain rates to a cutoff voltage of -435 rnV versus a Hg/HgO reference electrode voltage.
  • Table 3 below, is the composition of the cathode and anode used in the cell of the present invention as specified in Table 2 above.
  • a principal feature of the present invention is that the theoretical discharge capacity of the negative electrode is in the range of from 60% to 120% of the theoretical one electron discharge capacity of the Mn0 2 electrode. However, in order to determine that range, a number of experiments were undertaken, as described below and as illustrated in Figures 3 to 8. In each of Figures 3 to 8, the discharge capacity is on the vertical axis, and is measured in mAh. The horizontal axis shows the number of cycles to which the control and test cells have been subjected, and in each case only six cycles of data are shown. The first bar is indicated at 31C, or 41C, 51C . . .
  • the balance of the test cells and the control cells in Figure 3 is that the theoretical capacity of the zinc electrode is 80% of the theoretical one electron discharge capacity of the Mn0 electrode.
  • the balance in Figure 4 is 90%; the balance in Figure 5 is 100%, the balance in Figure 6 is 110%, the balance in Figure 7 is 120%, and the balance in Figure 8 is 130% . All of the tests are in respect of cylindrical AA alkaline Mn0 /Zn cells, and are indicative of the general nature of the effect of cell balance of the theoretical discharge capacity of the negative electrode with respect to the theoretical one electron discharge capacity of the Mn0 electrode in all cases.
  • a plurality of cylindrical AA alkaline Mn0 2 /Zn cells were manufactured and tested.
  • the cells were balanced, as noted above, by limiting the theoretical discharge capacity of the zinc electrode to 80%, 90%, 100%, 110%, 120%, or 130% of the theoretical one electron capacity of the Mn0 2 electrode of the respective cells.
  • one set of cells from each of the balance sets was tested by continuously discharging the cell on a 10 ohm load resistor to a cutoff voltage of 0.9 volts.
  • a second set of cells was assembled into a four cell battery pack, in series.
  • the battery pack was connected to a 39 ohm load resistor for one week . It should be noted that this test is considered to be abusive, and that in general the useful cell capacity of the cells is considered to have been exhausted within the first 15 hours of discharge. At that time, the voltage of the battery pack will drop significantly, and at the end of the test following one week of discharge, the voltage of the battery pack is about 0 volts.
  • each battery pack is dis-assembled, and each of the cells is recharged and then cycled on a ten ohm load to 0.9 volts cutoff, to determine the degree of recovery of the cells.
  • Each of the bars showing the results of the test cells in Figures 3 through 8, and in each case in cycles 2 through 6, represents an average of four cells per test.
  • cells according to the present invention will provide useful capacity, and are rechargeable.
  • the present invention was applied to AAA, AA, C, and D cells having conventional cylindrical cell configurations.
  • the capacity in ampere-hours of cells in each size was determined, as noted below in Table 4, and the cells were constructed having the respective ratios of the zinc anode to the Mn ⁇ 2 cathode as noted in Table 4.
  • the cumulative capacity of cells in keeping with the present invention and having an anode to one electron Mn0 2 discharge capacity ratio of 100% as compared with cells having an anode to one electron Mn0 2 discharge capacity ratio of 41% was exceeded by more than 70%.
  • the cells with an anode to one electron Mn0 2 discharge capacity ratio of 41% are emulative of prior art cells, particularly such as those taught by Amano et al and Kordesch, as discussed above.
  • the present invention is applicable not only to conventional bobbin type cells, but it may also be applied to button or coin cells, and to flat plate cells.
  • the container or can 12 is a nickel plated deep drawn steel can, although other suitable metal cans may be used. So as to improve the contact and conductivity between the cathode 14 and the can 12, and thereby so as to reduce the internal resistance of the cell, the internal surface of the container 12 may be coated with a conductive coating such as LONZA (TM). Moreover, by using the conductive coating on the interior surface of the container 12, the risk of iron leaching from the can into the cell, which could -result in increased hydrogen gassing, is reduced.
  • TM conductive coating
  • the cathode 14 may be placed into the container 12 by such ordinary cell manufacturing techniques as by being molded into discrete pellets, by being molded into discrete pellets and then recompacted after placement in the container 12, or by being extruded into the container.
  • the closure member 20 is normally formed of a thermoplastic material, and contains a safety vent (not shown) which may be simply a rupturable membrane, or a resealable vent.
  • the plastic closure member is molded from a thermoplastic material having enhanced hydrogen permeation rates, such as polypropylene, talc filled polypropylene, and nylon.

Landscapes

  • Chemical & Material Sciences (AREA)
  • 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

L'invention se rapporte à une batterie rechargeable ayant une électrode positive en bioxyde de manganèse, la batterie ayant une capacité élevée et une densité d'énergie élevée par unité de volume et de poids. La batterie comporte un électrolyte aqueux, habituellement de l'hydroxyde de potassium, mais l'électrolyte peut également être une solution acide ou saline. La capacité de décharge de la batterie est déterminée par la capacité théorique de décharge d'un électron par le bioxyde de manganèse -- car on considère que le bioxyde de manganèse est chargé et déchargé d'une manière réversible uniquement entre l'état nominal MnO2 et celui correspondant à la décharge d'un électron, Mn2O3. L'électrode négative est également rechargeable; bien qu'il s'agisse généralement de zinc, on peut également faire appel au fer, plomb, cadmium, hydrogène ou à un hydrure métallique. La capacité de décharge de la batterie est limitée par la capacité de décharge théorique de l'électrode négative ou anode, qui se situe entre 60 % et 120 % de la capacité de décharge théorique d'un électron par l'électrode de MnO2.
PCT/CA1992/000101 1992-03-09 1992-03-09 Batterie rechargeable a haute capacite ayant une electrode en bioxyde de manganese WO1993018557A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CA1992/000101 WO1993018557A1 (fr) 1992-03-09 1992-03-09 Batterie rechargeable a haute capacite ayant une electrode en bioxyde de manganese
AU13337/92A AU1333792A (en) 1992-03-09 1992-03-09 High capacity rechargeable cell having manganese dioxide electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CA1992/000101 WO1993018557A1 (fr) 1992-03-09 1992-03-09 Batterie rechargeable a haute capacite ayant une electrode en bioxyde de manganese

Publications (1)

Publication Number Publication Date
WO1993018557A1 true WO1993018557A1 (fr) 1993-09-16

Family

ID=4172918

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA1992/000101 WO1993018557A1 (fr) 1992-03-09 1992-03-09 Batterie rechargeable a haute capacite ayant une electrode en bioxyde de manganese

Country Status (2)

Country Link
AU (1) AU1333792A (fr)
WO (1) WO1993018557A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994024718A1 (fr) * 1993-04-20 1994-10-27 Battery Technologies Inc. Electrode positive au dioxyde de manganese pour piles rechargeables et piles contenant ces electrodes
US5424145A (en) * 1992-03-18 1995-06-13 Battery Technologies Inc. High capacity rechargeable cell having manganese dioxide electrode
EP0789410A1 (fr) * 1996-02-02 1997-08-13 Matsushita Electric Industrial Co., Ltd. Batteries et procédé de fabrication d'une matière active positive
US6258132B1 (en) 1999-04-27 2001-07-10 Eveready Battery Company, Inc. Process for producing in an alkaline cell an in situ silver layer on a cathode container

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3530496A (en) * 1967-06-26 1970-09-22 Matsushita Electric Ind Co Ltd Rechargeable alkaline manganese cell
US4957827A (en) * 1988-07-08 1990-09-18 Battery Technologies Inc. Rechargeable alkaline manganese cells with zinc anodes
WO1991017581A1 (fr) * 1990-05-09 1991-11-14 Battery Technologies Inc. Recombinaison catalytique d'hydrogene dans des piles alcalines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3530496A (en) * 1967-06-26 1970-09-22 Matsushita Electric Ind Co Ltd Rechargeable alkaline manganese cell
US4957827A (en) * 1988-07-08 1990-09-18 Battery Technologies Inc. Rechargeable alkaline manganese cells with zinc anodes
WO1991017581A1 (fr) * 1990-05-09 1991-11-14 Battery Technologies Inc. Recombinaison catalytique d'hydrogene dans des piles alcalines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
K.V. Kordesch "Batteries", vol. 1, MARCEL DEKKER INC. "Manga- nese Dioxide", published 1974, New York, pages 281-291, *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5424145A (en) * 1992-03-18 1995-06-13 Battery Technologies Inc. High capacity rechargeable cell having manganese dioxide electrode
WO1994024718A1 (fr) * 1993-04-20 1994-10-27 Battery Technologies Inc. Electrode positive au dioxyde de manganese pour piles rechargeables et piles contenant ces electrodes
WO1995024742A1 (fr) * 1994-03-09 1995-09-14 Battery Technologies Inc. Pile rechargeable de grande capacite a electrode en dioxyde de manganese
EP0789410A1 (fr) * 1996-02-02 1997-08-13 Matsushita Electric Industrial Co., Ltd. Batteries et procédé de fabrication d'une matière active positive
US5744266A (en) * 1996-02-02 1998-04-28 Matsushita Electric Industrial Co., Ltd. Batteries and a method of manufacturing positive active material for the batteries
US5928714A (en) * 1996-02-02 1999-07-27 Matsushita Electric Industrial Co., Ltd. Method of manufacturing positive active material for batteries
US6258132B1 (en) 1999-04-27 2001-07-10 Eveready Battery Company, Inc. Process for producing in an alkaline cell an in situ silver layer on a cathode container

Also Published As

Publication number Publication date
AU1333792A (en) 1993-10-05

Similar Documents

Publication Publication Date Title
US5340666A (en) Rechargeable alkaline manganese cell having improved capacity and improved energy density
US5424145A (en) High capacity rechargeable cell having manganese dioxide electrode
AU676276B2 (en) Manganese dioxide positive electrode for rechargeable cells,and cells containing the same
US5952124A (en) Rechargeable electrochemical cell with modified manganese oxide positive electrode
US5569553A (en) Battery design for achieving end-of-life indication during electrical discharge
US7754386B2 (en) Rechargeable alkaline manganese cell having reduced capacity fade and improved cycle life
US5011752A (en) Rechargeable alkaline manganese dioxide-zinc cell having improved cumulative capacity
US6361899B1 (en) Additives for rechargeable alkaline manganese dioxide cells
WO2006026232A1 (fr) PILE ALCALINE A SUBSTANCE ACTIVE A BASE DE MnO2/NiOOH
CA2281371A1 (fr) Cellule au nickel-zinc rechargeable
AU3154593A (en) Cathodes for zinc manganese dioxide cells having barium additives
US3288642A (en) Rechargeable dry cell having gelled electrolyte
JPH08250108A (ja) リチウム二次電池用負極の製造方法およびリチウム二次電池
Sarakonsri et al. Primary batteries
WO1993018557A1 (fr) Batterie rechargeable a haute capacite ayant une electrode en bioxyde de manganese
US20030077512A1 (en) Electrolyte for alkaline rechargeable batteries
JPH05258773A (ja) 非水電解液二次電池
CA2037744A1 (fr) Element manganese alcalin rechargeable a capacite et densite d'energie ameliorees
Kiehne et al. Batteries, an overview and Outlook
Helen Chapter–7 BATTERIES-FUNDAMENTALS
JPH04363862A (ja) リチウム二次電池
JPS63175349A (ja) リチウム−二酸化マンガン電池

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR CA CS FI HU JP KP KR LK MG MN MW NO PL RO RU SD

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE BF BJ CF CG CI CM GA GN ML MR SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA