WO1993000716A1 - Anode de zinc alcaline immobilisee destinee a des elements rechargeables a conductivite et a capacite d'accumulation ameliorees - Google Patents

Anode de zinc alcaline immobilisee destinee a des elements rechargeables a conductivite et a capacite d'accumulation ameliorees Download PDF

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Publication number
WO1993000716A1
WO1993000716A1 PCT/CA1992/000270 CA9200270W WO9300716A1 WO 1993000716 A1 WO1993000716 A1 WO 1993000716A1 CA 9200270 W CA9200270 W CA 9200270W WO 9300716 A1 WO9300716 A1 WO 9300716A1
Authority
WO
WIPO (PCT)
Prior art keywords
anode
zinc
alkaline
fibers
zinc anode
Prior art date
Application number
PCT/CA1992/000270
Other languages
English (en)
Inventor
Karl Kordesch
Leo Binder
Waltraud Taucher
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 JP5501279A priority Critical patent/JPH06508716A/ja
Priority to EP92913716A priority patent/EP0591358A1/fr
Publication of WO1993000716A1 publication Critical patent/WO1993000716A1/fr

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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
    • H01M4/624—Electric conductive fillers
    • 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
    • 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

  • the present invention relates to immobilized alkaline zinc anodes for rechargeable cells with improved conductivity and cumulative capacity.
  • the original anode gel contains about 60% by eight zinc
  • only one half of the zinc is consumed as an active electrode material.
  • the remaining half of the zinc powder is disposed of, or collected for recycling, with the used battery.
  • Zinc powder is not expensive and the rejected fraction has done its work as an electronically -conductive component of the anode mass.
  • the rechargeable version of the zinc/ manganese dioxide system requires a capacity limiting zinc anode, therefore the amount of zinc usable in the anode is determined by the active cathode mass i.e. the over dosage of zinc is not a possible way of providing the required mass after a number of charge-discharge cycles.
  • the oxidation and reduction of zinc particles in the anode belong to the normal electrode process.
  • a particular zinc particle can only then be regarded as taking an active part in the anode process if it continues to stay in electric contact with the other adjacent zinc particles and with the current collector.
  • the oxidation and reduction process has the side effect of insulating the zinc particles from one another, and the insulated zinc isles cannot participate in the electrochemical process anymore, therefore the ⁇ discharge capacity decreases after each cycle.
  • the reduction of the amount of mercury decreases the quality of the contacts among the anode particles i.e. the conductivity of the anode decreases as well.
  • the primary object of the present invention lies in providing an immobilized alkaline zinc anode structure for rechargeable cells, in which there is a slower decrease in the utilization of the zinc mass during the cycle life of the cell using the anode.
  • This primary object indirectly includes the need for increasing the conductivity of the anode.
  • a further objective lies in aint ⁇ iining the conductivity of the anode even if the amount of mercury is decreased or fully eliminated.
  • a still further objective lies in providing an anode structure, in which the utilization of available space is increased compared to those ones using a perforated metal carrier.
  • the conductivity of the zinc gell anode is increased, and the capacity fade from cycle to cycle is slowed down if a conductive fiber structure is admixed to the anode mass in an amount of at least 0.15% weight.
  • the performance will not be improved if the fiber structure is added in an amount exceeding about 2 to 5%, and in case of higher amounts of fiber the effective loss in zinc volume will be remarkable and form an economic upper limit.
  • the conductive fiber structure prevents the formation is isolated zinc particles without contact to the current collector w hich is particularly important in mercury -free cells.
  • the fiber structure serves as a three- dimensional substrate for the zinc deposition.
  • the fibers themselves do not have to be made of electrically conductive materials, they can be made of non-conductive materials such as glass, polymers, etc., and can be coated by the conductive material either by electroless plating or by vacuum deposition such as cathode sputtering.
  • the optimum range for the length to diameter ratio was found to be between 100:1 and 1000:1, the fiber diameter lies in the micron range, typically between about 5 and 20 microns.
  • Preferable fiber materials are polyimide, polyester and polyvinyl alcohol.
  • the coating material can be copper, silver, gold, nickel and similar metals or alloys of these metals. In case of mercury-free cells the use of copper should be avoided, since it tends to corrode the non-amalgamated zinc.
  • Figure 1 shows the test set up for conductivity measurements
  • Figure 2 shows individual discharge capacity and cumulative cycle capacity versus cycle number curves, filler: 0.3% silver plated polyimide fibers;
  • Figure 3 shows curves similar to Figure 2, filler: 0.3% copper plated polyimide fibers;
  • Figure 4 shows curves similar to Figure 2, filler: 0.3% silver plated polyimide fibers, no copper cage;
  • Figure 5 shows curves similar to Figure 2, filler: 0.6% copper plated polyimide fibers, no copper cage;
  • Figure 6 shows curves similar to Figure 2, filler: 0.6% silver plated polyimide fibers, no copper cage;
  • the coated fiber structure was made by electroless plating.
  • the non-conducting substrate fiber material was degreased with potassium hydroxide solution, rinsed with water and activated with a solution of tin(II) chloride in a water/hydrochloric acid mixture.
  • a complex solution of silver ions was used to catalyze the substrates.
  • the materials were immersed in a solution consisting of a salt of the covering metal, a complexing agent, formaldehyde and water. All these operations were performed in a beaker-cell equipped with a paddle starrer.
  • the first inspection of the plated materials was done by checking the uniformity and brilliance of the deposition under a "stereo" microscope (magnification up to 63:1). The adherence of the metal coating to the substrate was also examined.
  • the coated fibers were added to the commonly used anode mixture in amounts ranging from 0.1% to 2%.
  • the conductivity of the paste obtained was measured using the test set up shown in Figure 1.
  • anode mix 1 w as pressed in a glass tube 2 of predetermined length and cross-section, and a pair of piston type contact electrodes 3, 4 were attached to both ends of the mix in the glass tube 2.
  • a resistance brid ge 5 using an LRC meter was connected to the electrodes 3, 4.
  • the conductivities of pastes containing a conductive filler were compared with the conductivity of the standard mixture.
  • One series of tests was carried out using anode mixtures before discharge and another series after discharge. The tests were carried out in the less favourable case, i.e., when the addition of the fiber is about its minimum to demonstrate thereby the significant improvement offered by the presence of the coated fibers.
  • ELS el ectrol ess sil ver coating on polyimide fibers
  • ELC el ectrol ess copper coating on polyimide fibers
  • the increase in conductivity has two main reasons.
  • the first one is the direct contact between the fibers and the zinc particles while the second one is the capillary effect of the fibrous structure, whereby the electrolyte is more evenly distributed in the anode mix.
  • Cylindrical LR-14 (C-size) alkaline manganese dioxide cells were taken which were designed as disclosed in the paper of Y. Sharma, A. Haynes, L. Binder and K. Kordesch: J. Power Sources 27 (1989) 145.
  • the cycling tests were limited to a period of 40 days. The whole test program was done by a computer controlled device which was capable of operating 48 batteries simultaneously. In the cycling tests the constant resistor discharge method was used, each cell was loaded by a 3.9 ohm resistor until a cut-off voltage of 0.9 V was reached. The charging occurred by a trickle charger which provided 1.72 V constant voltage through 20 hours.
  • Figures 2 to 6 comprise the results of these tests in the form of curves showing the individual and cumulative discharge capacities as a function of cycle number.
  • the curves of the corresponding standard cell i.e., which does not have any conductive filler having also been illustrated.
  • Tables 2 and 3 show the percentual increase of cycle capacities and the cumulative capacity data, respectively which demonstrate more clearly the improved behaviour of the fiber containing anodes compared to that of the standard cells.
  • the first positive results were obtained by adding about 0.16% silver or copper plated polyimide fibers.
  • the nature of the metal used for metallization of the polymer seemed to be without visible influence.
  • Figure 4 shows the behaviour of a cell without copper cage and having 0.3% silver plated polyimide fibers in the anode. Although such a cell is much better than the standard one used for the comparison, the 0.3% conductive fibers could not fully compensate the lack of the anode cage.
  • FIGS. 5 and 6 show the discharge curves of such cells i.e., with anodes comprising 0.6% copper resp. silver coated fibers and no copper screen (cage). It should be noted that the standard cells used for comparison were identical with the tested ones, the only difference being in that the anode gel of the standard cells did not comprise the conductive finings.
  • the cell performance showed no significant improvements in case of using higher concentration of the conductive fibers.
  • the initial loss of capacity, actually a "changing of the slope" of the cycle curve is an additional desired feature, because it takes less capacity out at the initial manganese dioxide discharges and thereby improves the cycle life. In other words this is a depth of discharge shift which is especially helpful with manganese dioxide.

Abstract

Anode de zinc alcaline immobilisée pour des éléments rechargeables, et qui comprent des particules de zinc, de l'oxyde de zinc, un électrolyte alcalin, et un agent gélifiant. Ces constituants sont mélangés afin de former une masse anodique d'une forme prédéterminée. Une structure à fibres conductrices est mélangée à la masse anodique de façon à présenter une teneur d'au moins 0,15 % en poids, la structure se composant de fibres dans la plage micrométrique et présentant un rapport longueur/diamètre compris entre 1:100 et 1:1000, et un diamètre compris entre 5 micromètres et 20 micromètres environ. Les fibres se composent de préférence d'un matériau non conducteur tel qu'un polyimide, sur laquelle est placée une couche conductrice de cuivre, argent, or ou nickel. Les fibres relient réciproquement les particules de zinc, et leur capillarité leur permet d'agir comme un réservoir d'électrolyte additionnel. La conductivité améliorée réduit la baisse en capacité de décharge à des nombres de cycles plus élevés. L'anode de zinc alcaline peut être utilisée essentiellement dans des éléments rechargeables alcalins de bioxyde de manganèse/zinc.
PCT/CA1992/000270 1991-06-24 1992-06-18 Anode de zinc alcaline immobilisee destinee a des elements rechargeables a conductivite et a capacite d'accumulation ameliorees WO1993000716A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP5501279A JPH06508716A (ja) 1991-06-24 1992-06-18 改良型電気電導度及び蓄積容量を有する蓄電池用固定アルカリ亜鉛陽極
EP92913716A EP0591358A1 (fr) 1991-06-24 1992-06-18 Anode de zinc alcaline immobilisee destinee a des elements rechargeables a conductivite et a capacite d'accumulation ameliorees

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU2104/91 1991-06-24
HU912104A HUT63513A (en) 1991-06-24 1991-06-24 Immobilized alkali-zinc anode of improved conductivity and cumulative capacity for rechargeable cells

Publications (1)

Publication Number Publication Date
WO1993000716A1 true WO1993000716A1 (fr) 1993-01-07

Family

ID=10957779

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA1992/000270 WO1993000716A1 (fr) 1991-06-24 1992-06-18 Anode de zinc alcaline immobilisee destinee a des elements rechargeables a conductivite et a capacite d'accumulation ameliorees

Country Status (6)

Country Link
EP (1) EP0591358A1 (fr)
JP (1) JPH06508716A (fr)
AU (1) AU2181692A (fr)
CA (1) CA2112384A1 (fr)
HU (1) HUT63513A (fr)
WO (1) WO1993000716A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999010943A1 (fr) * 1997-08-22 1999-03-04 Eveready Battery Company, Inc. Piles alcalines resistantes aux chutes de tension
US6602629B1 (en) 2000-05-24 2003-08-05 Eveready Battery Company, Inc. Zero mercury air cell
US6919142B2 (en) 2001-12-13 2005-07-19 Rovcal, Inc. Conducting polymer additives for alkaline electrochemical cell having zinc anode
US7481851B2 (en) * 2003-07-03 2009-01-27 The Gillette Company Alkaline cell with improved anode
US9136563B2 (en) 2010-02-09 2015-09-15 Bae Systems Plc Rechargeable batteries
CN111600025A (zh) * 2020-04-23 2020-08-28 同济大学 一种具有弹性保护层的锌负极材料及其制备和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102484246A (zh) * 2009-08-07 2012-05-30 鲍尔热尼系统公司 碳纤维锌负电极
JP6347971B2 (ja) * 2014-03-20 2018-06-27 株式会社日本触媒 亜鉛負極合剤、亜鉛負極及び電池
JP6456138B2 (ja) * 2014-12-26 2019-01-23 株式会社日本触媒 電極及びそれを用いて構成される電池

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF APPLIED ELECTROCHEMISTRY vol. 22, no. 2, 1992, LONDON GB pages 95 - 98 W. TAUCHER ET AL 'Conductive Fillers for Immobilized Alkaline Zinc Anodes' *
JOURNAL OF POWER SOURCES. vol. 13, no. 1, September 1984, LAUSANNE CH pages 9 - 21 L.BINDER ET AL 'Experimental Study of Rechargeable Alkaline Zinc Electrodes' *
JOURNAL OF POWER SOURCES. vol. 13, no. 1, September 1984, LAUSANNE CH pages 9 - 21 L.BINDER ET AL 'Experimental Study of Rechargeable Alkaline Zinc Electrodes' see page 16; table 2 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999010943A1 (fr) * 1997-08-22 1999-03-04 Eveready Battery Company, Inc. Piles alcalines resistantes aux chutes de tension
US6602629B1 (en) 2000-05-24 2003-08-05 Eveready Battery Company, Inc. Zero mercury air cell
US6919142B2 (en) 2001-12-13 2005-07-19 Rovcal, Inc. Conducting polymer additives for alkaline electrochemical cell having zinc anode
US7481851B2 (en) * 2003-07-03 2009-01-27 The Gillette Company Alkaline cell with improved anode
US9136563B2 (en) 2010-02-09 2015-09-15 Bae Systems Plc Rechargeable batteries
CN111600025A (zh) * 2020-04-23 2020-08-28 同济大学 一种具有弹性保护层的锌负极材料及其制备和应用

Also Published As

Publication number Publication date
HU912104D0 (en) 1991-12-30
JPH06508716A (ja) 1994-09-29
EP0591358A1 (fr) 1994-04-13
AU2181692A (en) 1993-01-25
CA2112384A1 (fr) 1993-01-07
HUT63513A (en) 1993-08-30

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