EP0126143A1 - Pile scellee au nickel-zinc - Google Patents

Pile scellee au nickel-zinc

Info

Publication number
EP0126143A1
EP0126143A1 EP83903885A EP83903885A EP0126143A1 EP 0126143 A1 EP0126143 A1 EP 0126143A1 EP 83903885 A EP83903885 A EP 83903885A EP 83903885 A EP83903885 A EP 83903885A EP 0126143 A1 EP0126143 A1 EP 0126143A1
Authority
EP
European Patent Office
Prior art keywords
cell
zinc
nickel
electrode
cells
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.)
Ceased
Application number
EP83903885A
Other languages
German (de)
English (en)
Other versions
EP0126143A4 (fr
Inventor
Henry Frank Gibbard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Duracell Inc USA
Original Assignee
Gould Inc
Duracell International 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 Gould Inc, Duracell International Inc filed Critical Gould Inc
Publication of EP0126143A1 publication Critical patent/EP0126143A1/fr
Publication of EP0126143A4 publication Critical patent/EP0126143A4/fr
Ceased legal-status Critical Current

Links

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
    • 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
    • H01M10/526—Removing gases inside the secondary cell, e.g. by absorption by gas recombination on the electrode surface or by structuring the electrode surface to improve gas recombination
    • 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
    • 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

Definitions

  • This invention relates to electrochemical cells and, more particularly, to sealed nickel-zinc cells.
  • portable equipment such as, for example, tape and video recorders, power tools, calcul ⁇ ators, radios, electric razors, television sets, tele ⁇ phone pagers, microcomputers, and the like.
  • a primary battery or cell has been utilized as the power source.
  • primary cells offer the advan ⁇ tage of relatively high energy densities, these are relatively expensive because of the continual need 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 energy densities and cycle life capabilities, as well as requiring relatively long times for charging.
  • nickel-cadmium cells Despite the advantages provided by nickel-cadmium cells, there is a continuing demand for many applica ⁇ tions for a power source capable of achieving even higher energy densities and operating at higher working voltages. This situation has led to the investigation of nickel-zinc rechargeable cells for these applica ⁇ tions.
  • the nickel-zinc system is well known and, at least potentially, offers substantial advantages.
  • nickel-zinc cells In comparison to nickel-cadmium cells, nickel-zinc cells have higher working or operating voltages (viz. about 1.65 volts) and potentially can provide significantly higher energy densities •
  • U.S. Patents 3,951,687 and 4,037,033 disclose configurations for nickel-zinc cells. Despite this promise, the commercial use of nickel- zinc cells for the portable applications described here ⁇ in has been extremely limited.
  • a sealed nickel-zinc cell must therefore possess the ability to compensate for the hydrogen gas evolved so that the cell under con- ditions of use should not vent. If the cell vents. decreased performance can result if enough electrolyte is lost. Moreover, discharge of alkaline electrolyte into the environment 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 materials typically used require that such cells vent at significantly lower internal pres- sures, viz. - about 25 p.s.i.g. or so.
  • Japanese Publication Nos. 135433/78 and 138021/78 make reference to hydrogen gas having been absorbed in nickel-zinc batteries by various methods, including (1) producing water by the chemical reaction of hydrogen and oxygen using a gas-phase catalyst such as platinum, pal ⁇ ladium or silver, (2) chemically absorbing hydrogen selectively, using manganese dioxide and a silver or palladium catalyst, (3) producing a metal hydride such as titanium, and (4) producing water electrochemically using a supplementary electrode. It is noted that, how ⁇ ever, since the absorption of hydrogen gas is insuffi ⁇ cient, sealing of the battery has been, difficult because of the build-up of inner pressure, expansion of the cell casing and leakage of the electrolyte solution.
  • a gas-phase catalyst such as platinum, pal ⁇ ladium or silver
  • a metal hydride such as titanium
  • alkaline silver oxide- zinc cells were in the past assembled with the addition of small amounts of manganese dioxide to the silver oxide cathode for the purpose of extending the discharge capacity. It was observed that such cells had some hydrogen absorption properties ascribed to the silver oxide, since it was well known that manganese dioxide was incapable of reacting with hydrogen at room temper ⁇ ature. It was believed, applicants stated, that silver oxide with a small amount of manganese dioxide as a hydrogen absorber would be undesirably expensive and would not absorb hydrogen in sufficient amounts at a sufficiently rapid rate.
  • the Kozawa et al. patent discloses forming a silver catalyzed-manganese dioxide mixture into a shaped article of a desired configuration.
  • the shaped article can then be used in electrochemical cells to absorb hydrogen gas as described in U.S. 3,893,870.
  • the hydrogen gas absorber is stated to be not only relatively inexpensive, but, in addition, to absorb hydrogen gas at a relatively fast rate and to have a relatively high total capacity for absorbing hydrogen gas.
  • Such absorbers can be regenerated, by, for exam ⁇ ple, after having been saturated with hydrogen, exposing the absorber to air at room temperature for 1 to 4 days. It is not explained how such regeneration could be effected in a cell, and it would seem that this would have to be carried out outside of the cell. This approach may accordingly lack the ease of use required in a practical commercial application.
  • Ary WI nickel-zinc system disclosed therein includes various aspects, one of which is a fuel cell cathode unconnected to the remainder of the system. Utilization of this approach 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 will vent.
  • a still further object is to provide a cell of the foregoing type that is simple in construction and which is capable of being economically manufactured.
  • Another object of this invention lies in the provision of a cell of the foregoing type having the capability of being both charged and discharged at relatively high rates without undue internal pressure buildup.
  • Yet another object of this invention is to provide a cell of the foregoing type capable of remaining on open-circuit stand for extended periods of time without undue pressure buildup.
  • 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 2-2 of FIGURE 1 and further illustrating the internal configuration of a cell according to the present invention
  • FIG. 3 is a graph of internal pressure versus time and showing the improved performance of a cell in accordance with the present invention.
  • the present invention is predicated on the discovery that the incorporation of a suitable catalyst for the oxidation of hydrogen gas, for example, Ag,0, into the positive electrodes of a nickel-zinc cell will provide a cell capable of operation without undue hydrogen pressure being built up under virtually all conditions likely to be encountered in use. Even when employed in applications which involve relatively high rate discharges, the internal hydrogen pressure buildup is moderate.
  • a suitable catalyst for the oxidation of hydrogen gas for example, Ag,0
  • the balance of the cell chemis ⁇ try is maintained so that the cell may be readily re ⁇ charged without loss of capacity, even at relatively rapid rates without undue pressure buildup.
  • the cells may also be allowed to stand on open circuit for pro ⁇ longed periods with no difficulty due to pressure build ⁇ up, since the internal pressure tends to decrease on stand.
  • the present invention provides a power source for portable equipment which satisfies the var ⁇ ious requirements in a fashion that will allow the cells to be expeditiously made in commercial production.
  • 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 insula ⁇ tor 20.
  • a perforator disc 22 is secured to the open end 16 of the outer housing 12 by an annular retainer 24 and is provided with a piercing tab 26 adapted to pierce closure 18 in the event the closure is urged outwardly, as by internal pressure buildup within the sealed battery.
  • a resealable vent could be employed; and many such vent constructions are known.
  • 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.
  • a wicking layer 36 for absorbing electrolyte is provided on the side of the separator 34 adjacent the positive electrode layer 32. While the use of such a wicking layer is optional, this has been found to be advantageous.
  • a wicking layer could be likewise pro ⁇ vided adjacent the negative electrode layer 30, if desired; but this has been found not to offer any advan ⁇ tages.
  • 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.
  • a second connecting tab means 40 is electrically connected with positive electrode layer 32 and housing 12.
  • the positive and nega ⁇ tive 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 electrode layers of adequate flexibility are well known.
  • the negative zinc electrodes may thus be made by conventional techniques.
  • 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 the mixture can com ⁇ prise both zinc oxide and zinc, it is preferred to utilize a mixture incorporating little or no zinc metal. It has thus been found that, if the cell is allowed to stand in a completely discharged condition for an extended period, the presence of zinc metal would tend to result in undesired pressure buildup, perhaps causing the cell to vent.
  • binder materials for fabricating zinc electrodes are known and may be employed.
  • the binder material used should desirably be inert in the cell environment and is preferably utilized in an amount just sufficient to hold the mixture together, providing a positive bond as well to the current collector.
  • An elastomeric, self-cured carboxylated styrene-butadiene latex is an example of a suitable binder material.
  • AMSCO RES 4150 and 4816 manufactured by the AMSCO Division of Union Oil Company. It has been found satisfactory to utilize this binder in an amount, for example, of about 4%, based upon the total weight of the negative electrode mixture.
  • the negative electrode may contain other ingredients, as is known. For example, it has been found useful to include a minor amount of cadmium metal which increases the electronic conductivity of the negative electrode. This apparently acts to stabil ⁇ ize the negative electrode against shape change as well as reducing the rate of evolution of hydrogen. Cadmium oxide may likewise be employed to serve as the source of the cadmium metal; however, it has been found that -li ⁇ the use of cadmium oxide may result in a small loss in capacity in comparison to what occurs whencadmium metal is employed. Similarly, bismuth oxide, Bi 2 0 3 , may be . included. This is believed to increase the hydrogen over-voltage of the negative electrode, resulting in the di unition of hydrogen evolution.
  • cadmium or cadmium oxide in an amount of about 5 to 6% by weight, and bismuth oxide in an amount of about 7 to 8% by weight.
  • the positive electrode layer may be made by any of the conventionally known techniques.
  • the use of both sintered and non-sintered elec- trodes is known and either may be utilized. Indeed, it is satisfactory, for example, to employ the techniques used in making nickel electrodes for nickel-cadmium cells.
  • the posi ⁇ tive electrode is modified to incorporate a catalyst for the oxidation of hydrogen in an amount sufficient to catalyze the oxidation of enough of the hydrogen gas evolved during use to prevent undue pressure buildup. It has thus been found that the hydrogen evolved in the cell is oxidized at the positive electrode to effectively provide an internal pressure in the cell that is well below the level at which venting would occur with con ⁇ ventional container materials and closure means. More ⁇ over, this oxidation reaction results in conversion of the NiOOH active material in the nickel-zinc system to the discharged species, Ni(0H) 2 , so that the cell chem ⁇ istry remains at least essentially in balance. This allows the cell to be readily recharged without loss in capacity.
  • SUBSTITUTE SHEET of the nickel, oxygen-containing electrode may be utilized. It is preferred to utilize silver. More particularly, it is believed that elemental silver will be at least principally converted in the cell environ- ment to g 2 0, which serves as the active catalytic spe ⁇ cies for the oxidation of hydrogen in service. This conversion would likewise take place if Ag 2 0 or other silver-containing compounds, serving as percursors, were to be initially incorporated into the positive electrode. It may well be that, to some extent, ele ⁇ mental silver or other catalytically active silver specie are also present.
  • the term silver is intended to refer to elemental silver as well as to g 2 0 and any other silver-containing co - pound present in the cell environment which catalyzes the oxidation of hydrogen. It may perhaps be adequate to employ platinum or palladium. However, these mater ⁇ ials have relatively low hydrogen over-voltages; and, if used, steps should be taken to insure that migration to the negative electrode and depositing thereon, which could well cause massive hydrogen evolution and venting of the cell, is avoided.
  • the catalyst may be incorporated into (i.e. - physically associated with) the nickel electrode by any means desired which results in the catalyst being located in position to oxidize adequately the evolved hydrogen.
  • this may be satisfactorily incorporated into the nickel electrode by the following procedure.
  • the nickel electrodes are soaked in an aqueous solution of silver nitrate at ambient temperatures for a time suf ⁇ ficient to impregnate the electrode (e.g. - 20 minutes has been found satisf ctory), removed and then blotted dry.
  • the electrodes are then placed in a KOH solution (a 10% by weight aqueous solution being suitable) to precipitate silver as Ag 2 0, then removed, drained, and repeatedly washed with water (preferably deionized) until free of KOH (as determined by a negative response in a phenolphthalein test). Following vacuum drying at an elevated temperature for several hours (16 hours has been satisfactory), the electodes are ready for use.
  • a KOH solution a 10% by weight aqueous solution being suitable
  • the amount of catalyst present should, in a func ⁇ tional sense, be sufficient to maintain the internal pressure at the level desired.
  • the amount necessary to effect this result may vary somewhat, depending upon the size of the cell.
  • con ⁇ ventional aqueous solutions, such as potassium hydrox ⁇ ide as an electrolyte
  • the zinc specie(s) formed during discharge is soluble in the electrolyte to a significant extent.
  • the active zinc material thus tends to enter the electrolyte while the system is being dis ⁇ charged, as well as while the system stands in a dis ⁇ charged condition.
  • the zinc specie(s) in the electrolyte 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 phenomenon has been often termed "shape change". Because of this phenomenon, the cell element util ⁇ ized in the present invention should be positioned in the cell in a fashion which will at least minimize, and hopefully eliminate, shape change. It has been found satisfactory, when a cylindrical cell is involved, sim- ply to wind the element such that the element is under compression while in position within the cell. This assists in minimizing shape change as a problem.
  • the replating or redep- osition of zinc often occurs in the form of treed or branched crystals having sharp points (dendrites) which can readily bridge the gap between the plates or elec ⁇ trodes of opposite polarity, thereby causing short circuits and the destruction of the cell.
  • the material used for the separator should be a membrane having a relatively fine, uniformly sized pore structure which allows electrolyte permeation therethrough while preventing dendrite penetration.
  • the material employed should possess chemical stability in the cell environment.
  • suitable materials should possess sufficient flexibility and strength characteristics to adequately endure 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.
  • the separator may comprise a commercially available "Celgard” polypropyl ⁇ ene film (Celanese Fiber Company). It has been found particularly desirable to utilize two layers of such material (each layer about one mil thick being adequate) to form the separator layer 34, the individual layers being shown generally at 42 and 44 (FIG. 2). The use of two layers allows the large pores or holes, due to imperfections produced during manufacture or subse- quently, 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 like ⁇ wise be employed if desired.
  • any conventional alkaline electrolyte used with a nickel-zinc system may be employed.
  • the amount of elec ⁇ trolyte used should be restricted sufficiently so that an effective oxygen recombination reaction will be pro ⁇ vided.
  • 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.
  • a wicking layer 36 is provided on the side of the separator layer adjacent the positive electrode. Any alkali-resistant material capable of absorbing electrolyte can be util ⁇ ized.
  • a non-woven fabric of a synthetic resin, such as polypropylene may be employed.
  • a suitable polypropylene wicking sheet is "Webril 1488" non-woven fabric (Kendall Com ⁇ pany) having a thickness of about 3 mils.
  • first connecting tab 38 this should be made of a conductive material having a hydro ⁇ gen overvoltage characteristic 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, cov ⁇ ered with copper plating, and then covered with silver plating.
  • the second connecting tab 40 may comprise, for example, a nickel element which is electrically con ⁇ nected to the nickel plating 46 of outer housing 12.
  • a wide variety of materials are known for the connecting tabs and the housing for nickel-zinc systems, and such materials may be utilized in the nickel-zinc cell of the present invention.
  • the particular materials of construction may accordingly vary rather widely.
  • a water sealant coating may be applied to the metal or other surfaces in the cell.
  • a suitable sealant is the styrene-buta- diene material described herein as the binder for the negative electrode mixture.
  • 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 example, of about 1 mil.
  • insulators 50, 50' may be included, if desired. While shown as spatially removed from the cell element 28 for simplicity of illustration, insulator 50 may suitably rest upon separator layers 42, 44, which desirably terminate somewhat above the upper end of the elec ⁇ trodes•
  • 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 par- ticular end use application. As one example, a cylin ⁇ drical sub-C size cell for use in cordless or portable power tools may suitably have a capacity of, for exam ⁇ ple, 1.2 Ampere-Hours.
  • the sealed nickel-zinc cells of the present invention 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 without building up pressures that would cause venting.
  • the cells of this invention should be capable of providing a life of . 100 to 200 cycles, even when discharged at rates up to 7C. More moderate discharge rates, viz. - C/2 or lower, should allow the cells to provide a cycle life of up to 500 or more.
  • the cells of this invention may be charged at rates up to 1C or so at ambient temperatures (provided that the cell voltage does not exceed 2.05 volts) without undue pressure buildup. 0 Such cells are thus suitable for use in high rate, intermittent discharge applications (e.g. - discharge for 6 seconds at 8 amperes, followed by 12 seconds of rest — repeated until the cell is discharged) such as is involved in, for example, portable power tool appli- 5 cations. Indeed, applications of this sort are consid ⁇ ered to be relatively demanding; and the characteristics of the cells of this invention should accordingly amply satisfy the commercial requirements for a wide variety of portable equipment applications.
  • a sub-C size cylindrical cell described herein may utilize conventional nickel electrodes employed for nickel-cadmium cells (typical thickness about 22-25 mils) and negative electrodes having the following percentages by weight: 82.42 zinc 5 oxide; 7.88 Bi 2 0,, 5.36 cadmium and 4.34 binder (self- cured carboxylated styrene butadiene binder previously described).
  • the negative electrode may have a thickness about half that of the positive electrode.
  • the ratio of negative active material to positive active mater- 0 ial is suitably about 4:1 (this ratio may be varied as desired although it is preferred to utilize a substan ⁇ tial excess of negative active material).
  • the elec ⁇ trolyte may be a 25% by weight aqueous KOH solution saturated with Zn(OH) 2 and present in the cell in an 5 amount of about 3 cubic centimeters.
  • the cells may be desirably assembled with the electrodes in a discharged condition.
  • Example is illustrative of the present invention, and not in 1.Imitation thereof.
  • Cells according to the present invention were assembled and compared to control cells in a charge- discharge regime, as well as upon open circuit stand.
  • Two cylindrical sub-C size cells in accordance with the present invention were asembled utilizing the parameters for the specific example set forth above.
  • the separator utilized was two layers of "Celgard” polypropylene film (each about 1 mil in thickness), and a “Webril” polypropylene wicking layer (about 3 mils in thickness) was employed.
  • the cell configuration was as is shown in FIGS. 1 and 2.
  • the positive electrodes were impregnated with silver by the following procedure.
  • the nickel elec ⁇ trodes were immersed in a 1 molar solution of silver nitrate in deionized water at ambient temperature under vacuum for 20 minutes.
  • the electrodes were then removed, blotted dry and placed in a 12% by weight KOH aqueous solution for 20 minutes.
  • the electrodes were then removed, drained and repeatedly washed in deionized water until free of KOH (as determined by a negative response in the phenolphthalain test).
  • the electrodes were then vacuum dried at 50°C for 16 hours.
  • the assembled cells were then tested in a charge/ discharge regime as follows.
  • the cells of this invention were subjected to a 4 hour charge at 300 milliamps, followed by a discharge at 600 milliamps until the cell voltage declined to 1.1 volts.
  • the control cells were subjected in the first three cycles to what is considered to be a more moderate charge, 300 milliamps for three hours.
  • the control cells were then discharged using the same regime as for the cells of the present invention.
  • the cells were given a 16 hour charge (1.2 Ampere-Hours received over that time period), and then were discharged using the same regime as for the first three cycles.
  • the cells were charged for 4 hours at about 350 milliamps, discharged using the regime previously described, and this cycling continued until the total time elapsed in the cycling was about 140 hours.
  • the cells were then discharged for about 30 min ⁇ utes, resulting in a removal of about 25% of the capac ⁇ ity, and were allowed to stand on open circuit for about 20 hours.
  • the cells were then exposed to what was bas ⁇ ically an overcharge regime, involving charge at about a C/14 rate for about 50 hours and were then allowed to stand on open circuit.
  • the internal pressure of each cell as a function of time was measured, and the average of the two cells of this invention and that of the control cells is shown in FIG. 3.
  • the average internal pressure for the control cells is represented by curve A, while the average internal pressure for the cells of this inven ⁇ tion is represented by curve B.
  • the period designated by C is essentially the time at which the cells were on open circuit.
  • the internal pressure in the cells of this invention did not develop any general increasing tendency over the cycling regime, but, rather, developed a relatively level internal pressure of about 40 p.s.i.g. or so.
  • the internal pressure in the control cells tended to rise during the cycling regime. It is believed that this tendency would even ⁇ tually result in the control cells venting.
  • the internal pressure in the cells of this invention tended to decline, the contrary was true in the control cells.
  • FIG. 3 has been some- what simplified. More particularly, all of the cells exhibited transient pressure excursions (increases) near the end of charge in each cycle. This is believed due to oxygen evolution at the positive electrode. For simplicity, such excursions are not shown in FIG. 3, which graph is believed to reflect the pressure due to hydrogen evolution.
  • the present invention provides a sealed nickel-zinc cell which copes with the inherent hydrogen evolution occuring in the system in an effective and straightforward manner. More particularly, the hydrogen evolved is oxidized in a fashion which maintains the balance of the cell chemistry.
  • the cells of this invention may accordingly be effectively and rapidly fully recharged.
  • the effectiveness of the hydrogen oxidation reaction allows the cells to be used under even relatively high rate charge/discharge condi ⁇ tions.
  • the cells may be allowed to stand on open circuit for extended periods of time with no tendency for internal pressure buildup whatever.
  • the attributes of the cells of this invention make such cells highly desirable for use in a wide variety of applications.

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  • 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)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Hybrid Cells (AREA)

Abstract

Une pile alcaline rechargeable scellée (10) dans laquelle a lieu un dégagement d'hydrogène en cours de fonctionnement, tel qu'une pile au nickel-zinc, comprend dans l'électrode positive (32) un catalyseur pour l'oxydation de l'hydrogène, par exemple de l'argent, en une quantité suffisante pour oxyder le dégagement d'hydrogène de sorte qu'il est possible de maintenir à l'intérieur de la pile en service une pression interne relativement modérée, et par conséquent la pile peut être utilisée même dans des conditions à taux élevé de charge/décharge, sans mise à l'évent.
EP19830903885 1982-11-19 1983-11-10 Pile scellee au nickel-zinc. Ceased EP0126143A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US44308182A 1982-11-19 1982-11-19
US443081 1982-11-19

Publications (2)

Publication Number Publication Date
EP0126143A1 true EP0126143A1 (fr) 1984-11-28
EP0126143A4 EP0126143A4 (fr) 1985-06-10

Family

ID=23759347

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Application Number Title Priority Date Filing Date
EP19830903885 Ceased EP0126143A4 (fr) 1982-11-19 1983-11-10 Pile scellee au nickel-zinc.

Country Status (7)

Country Link
EP (1) EP0126143A4 (fr)
JP (1) JPH0752656B2 (fr)
DE (1) DE3390339T1 (fr)
GB (1) GB2140967B (fr)
IN (1) IN161624B (fr)
SE (1) SE8403749L (fr)
WO (1) WO1984002232A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS618852A (ja) * 1984-06-22 1986-01-16 Sanyo Electric Co Ltd 非水電解液電池
ES2001034A6 (es) * 1985-07-26 1988-04-16 Saft Sa Procedimiento para la fabricacion de un electrodo de cadmio consolidado por polimero para acumulador alcalino y electrodo obtenido por este procedimiento
HU207612B (en) * 1987-10-27 1993-04-28 Battery Technologies Inc Primary or rechargeable closed electrochemical cell
NL1001168C2 (nl) * 1995-09-11 1997-03-13 Stichting Tech Wetenschapp Werkwijze voor het vervaardigen van een lithiumbatterij.
NL1002318C1 (nl) 1995-09-11 1997-03-13 Stichting Tech Wetenschapp Werkwijze voor het vervaardigen van een lithiumbatterij.
NL2018056B1 (en) * 2016-12-23 2018-07-02 Univ Delft Tech Hybrid battery and electrolyser
US11611115B2 (en) 2017-12-29 2023-03-21 Form Energy, Inc. Long life sealed alkaline secondary batteries
US11552290B2 (en) 2018-07-27 2023-01-10 Form Energy, Inc. Negative electrodes for electrochemical cells
JP7441092B2 (ja) * 2020-03-25 2024-02-29 日本碍子株式会社 ニッケル亜鉛二次電池

Citations (1)

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Publication number Priority date Publication date Assignee Title
FR1058535A (fr) * 1951-07-26 1954-03-17 Accumulatoren Fabrik Ag électrode absorbant l'hydrogène

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BE755337A (fr) * 1969-08-27 1971-02-26 Union Carbide Corp Matiere absorbant l'hydrogene pour les cellules electrochimiques
US3877985A (en) * 1971-06-18 1975-04-15 Gen Electric Cell having anode containing silver additive for enhanced oxygen recombination
JPS5461B2 (fr) * 1973-11-21 1979-01-05
JPS5215282B2 (fr) * 1974-05-29 1977-04-28
JPS5626108B2 (fr) * 1975-01-20 1981-06-16
US4224384A (en) * 1975-09-30 1980-09-23 Union Carbide Corporation Silver catalyzed manganese dioxide hydrogen gas absorber
JPS5313802A (en) * 1976-07-24 1978-02-07 Nippon Telegr & Teleph Corp <Ntt> Call control system for mobile radio
JPS53135433A (en) * 1977-04-28 1978-11-27 Tokyo Shibaura Electric Co Method of charging for enclosed type nickel zinc alkaline storage battery
JPS5579583A (en) * 1978-12-12 1980-06-16 Sony Corp Pulse signal sampling circuit
US4296446A (en) * 1979-11-15 1981-10-20 Rca Corporation Motor speed control circuit
JPS5740625U (fr) * 1980-08-18 1982-03-04
JPS57148485A (en) * 1981-03-10 1982-09-13 Matsushita Electric Ind Co Ltd Equipment for receiving character broadcasting

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
FR1058535A (fr) * 1951-07-26 1954-03-17 Accumulatoren Fabrik Ag électrode absorbant l'hydrogène

Non-Patent Citations (1)

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Title
See also references of WO8402232A1 *

Also Published As

Publication number Publication date
IN161624B (fr) 1988-01-02
JPS59502082A (ja) 1984-12-13
GB2140967A (en) 1984-12-05
GB2140967B (en) 1986-03-05
EP0126143A4 (fr) 1985-06-10
JPH0752656B2 (ja) 1995-06-05
DE3390339T1 (de) 1985-01-10
SE8403749D0 (sv) 1984-07-17
GB8416541D0 (en) 1984-08-01
SE8403749L (sv) 1984-07-17
WO1984002232A1 (fr) 1984-06-07

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