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WO1997017737A1 - Piles alcalines rechargeables contenant des anodes en zinc non additionnees de mercure - Google Patents

Piles alcalines rechargeables contenant des anodes en zinc non additionnees de mercure Download PDF

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Publication number
WO1997017737A1
WO1997017737A1 PCT/CA1995/000634 CA9500634W WO9717737A1 WO 1997017737 A1 WO1997017737 A1 WO 1997017737A1 CA 9500634 W CA9500634 W CA 9500634W WO 9717737 A1 WO9717737 A1 WO 9717737A1
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WIPO (PCT)
Prior art keywords
zinc
powder
cell
anode
surfactant
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
PCT/CA1995/000634
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English (en)
Inventor
Josef Daniel-Ivad
James Book
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Battery Technologies Inc
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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/CA1995/000634 priority Critical patent/WO1997017737A1/fr
Priority to AU37690/95A priority patent/AU3769095A/en
Publication of WO1997017737A1 publication Critical patent/WO1997017737A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/24—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
    • 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
    • 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
    • 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 a sealed rechargeable cell containing mercury-free zinc anodes, and to a method of manufacture which includes treating a zinc active powder to coat the powder with indium acetate. It more particularly is concerned with a rechargeable cell, in which zinc active powder has been treated to coat the powder with both an organic surfactant and with indium.
  • Rechargeable galvanic cells with which this invention is concerned comprise a cathode, a zinc anode, a separator having at least one layer of a semipermeable membrane and an aqueous alkaline electrolyte, such as an aqueous solution of potassium hydroxide.
  • the cathode may comprise manganese dioxide, bismuth modified manganese oxides, silver oxide, nickel oxyhydroxides or an air electrode.
  • Graphite or carbon black is admixed to the cathode active materials to impart electronic conductivity, while potassium hydroxide is admixed to provide the necessary ionic conductivity to the cathode.
  • the zinc anode mixture will include zinc as one of the main constituents, and will also include electrolyte and other constituents in known manner. These cells display superior electrical performance, in particular at high discharge rates or at low temperatures, and are widely used in many applications.
  • Kiel in DE 1,086,309 (1961) is one of the oldest proposals and introduces art relating to zinc-indium alloys, as well as indium ions in the electrolyte.
  • Kiel describes a primary or secondary galvanic cell with a zinc electrode in an acidic, neutral or alkaline electrolyte, characterized by the addition of indium compounds to the electrolyte or alloying indium with high purity zinc. It describes in great detail the self discharge of zinc active material in acidic, neutral and alkaline electrolytes resulting in the liberation of hydrogen gas, cell leakage and the resulting limited shelf life of the respective cells.
  • the claims define indium additions to a galvanic cell containing a zinc negative electrode, either in the form of a zinc-indium alloy or, alternatively addition of In compounds to the electrolyte, in which the zinc has a purity of 99.99%, and the use of an alkaline, acidic or neutral electrolyte.
  • A. Kawakami in U.S. patent 3,642,539 (1972) adds an indium compound to the cell bottom, the separator or the electrolyte, to prevent dendrite or spongy zinc in rechargeable zinc air cells.
  • H. Ikeda in Japanese published application J6032363 (1976) treats zinc powder in an acidic indium chloride solution and then filters, washes and dries the zinc powder.
  • Winger states that the use of mercury cannot be completely eliminated, as if the amount of mercury is below 0.04% by weight, storage stability is adversely affected even with the addition of both a compound having polyethylene oxide linkages and indium.
  • United States patent No. 5,198,315 apparently discloses a primary zinc alkaline cell which uses non-amalgamated zinc alloy powder as an anode active substance.
  • the zinc alloy powder is surface coated with indium and has a bulk specific gravity adjusted to range from 2.90 to 3.50 grams per cubic centimetre.
  • Two methods of coating the zinc alloy with indium particles are described. The first method involves charging a heated mixer with a predetermined amount of zinc alloy powder and a predetermined amount of indium particles and nitrogen gas, and mixing at 180° C for one hour.
  • the second method involves mixing a predetermined amount of zinc alloy powder with a predetermined amount of an indium salt, such as indium sulphate in water and stirring for 30 minutes.
  • the resulting zinc alloy powder was filtered, washed with purified water, had the water adhering on the zinc alloy powder replaced by acetone and then dried at 45° C for one day.
  • United States patent No. 5,168,018 to Yoshizawa discloses a method of manufacturing a mercury free zinc alkaline battery in which the anode comprises zinc alloy powder as an active material and contains an indium hydroxide powder dispersed therein and an organic corrosion inhibitor, such as perfluoroalkyl polyethylene oxide surfactant.
  • the indium hydroxide powder used is preferably synthesized by neutralizing an aqueous solution of indium chloride or indium sulphate. It is indicated that indium chloride is preferred, as indium hydroxide powder based on indium chloride has a better corrosion resistance than when indium sulphate is used.
  • a negative zinc electrode for use with an electrolyte, such as aqueous potassium hydroxide, in rechargeable galvanic cells, which negative electrode exhibits superior performance characteristics, as compared to known cells of this type.
  • a mercury-free rechargeable cell that performs at least twenty charge and discharge cycles comprising: a cathode; an electrolyte; an anode; and a separator between the anode and the cathode, wherein the anode comprises a zinc active powder that has been coated with a film of one of a surfactant and a solution of a surfactant and a film of an aqueous solution of indium acetate, to retard dendrite growth and hydrogen evolution during at least twenty charge and discharge cycles, wherein each of the surfactant and the indium acetate solutions have been uniformly distributed as a film on the coated zinc active powder prior to assembly into the rechargeable cell, and wherein the coated zinc active powder is subsequently assembled into the electrochemical cell, without removing zinc acetate, and the surfactant, any solvent for the surfactant and the solution of the indium acetate comprise a minor part of the zinc active powder.
  • the electrolyte comprises an aqueous solution
  • the cathode active materials include a hydrogen recombination catalyst.
  • the catalyst can be provided as a coating on the cathode exterior.
  • the surfactant is preferably selected from the group comprising polypropylene glycols and polyethyleneglycols.
  • a mercury-free rechargeable cell comprising: an anode; a cathode having an active powder including oxides of manganese; a separator including at least one semipermeable membrane layer; an electrolyte solution in the separator, the cathode and the anode, and filling pores thereof, wherein the anode mixture comprises a zinc active powder, the electrolyte, an indium acetate additive and a nonionic surfactant of a molecular weight in the range of 300 to 1500 selected from the group consisting of polypropylene glycols and polyethoxyglycols.
  • Yet another aspect of the present invention provides a method of manufacturing a mercury-free zinc anode for use in electrochemical cell, a method comprising the steps of:
  • the electrolyte can comprise an aqueous solution of potassium hydroxide having a concentration in the range of about 25% to 45%. It may also include potassium zincate having a concentration in the range 0 to 12%. The electrolyte may also, or alternatively, comprise a mixture of potassium hydroxide having a concentration in the range of 4 to 6 molar, and potassium fluoride having a concentration in the range of 1.0 to 2.5 molar.
  • the materials of the cell can include a finely divided hydrogen recombination catalyst comprising at least one of a hydrogen storage alloy, silver, and a silver oxide which are electronically and ionically connected to the manganese oxide of the cathode.
  • the hydrogen recombination catalyst comprises 0.1-5% by weight of the electrochemically active material of the cathode.
  • FIG. 1 shows a cross sectional elevation view of an alkaline zinc-manganese dioxide rechargeable cell 10.
  • the cell comprises the following main units: a steel can 12 defining a cylindrical inner space, a cathode 14 formed by a plurality of hollow cylindrical pellets 16 pressed in the can, a zinc anode 18 made of an anode gel and arranged in the hollow interior of the cathode 14, and a cylindrical separator 20 separating the anode
  • the ionic conductivity between and in the anode and the cathode is provided by the presence of potassium hydroxide electrolyte added into the cell in a predetermined quantity.
  • the can 12 is closed at the bottom end, that is the positive terminal, a circular pip 12.
  • the upper end of the can 12 is hermetically sealed by a cell closure assembly which comprises a negative cap 24 formed by a thin metal sheet, a current collector nail 26 attached to the negative cap 24 and penetrating deeply into the anode gel to provide electrical contact with the anode, and a plastic top 28 electrically insulating the negative cap 24 from the can 12.
  • the separator 20 consists of two laminated layers i.e.: a first or inner layer 30 made of a fibrous sheet material wettable by the electrolyte, and a second or outer layer 32 being impermeable for small particles but retaining ionic permeability.
  • An expedient material for the first layer 30 is Dexter paper (grade 7490 or 7498-2) or nonwoven polyamide. The difference between these two types of paper lies in their thickness. Both types of these materials can be used in primary and secondary cells to separate mechanically the anode and the cathode electrodes and to serve as an electrolyte reservoir.
  • the macroporous structure of the inner layer 30 cannot prevent solid contamination particles from moving between the two separated spaces.
  • the second layer 32 which has a microporous structure and preferably is an appropriate thin cellophane layer.
  • the two layer separator is wound to form the separator 20.
  • the bottom of the separator is sealed with hot melt adhesive.
  • the zinc active material may comprise at least one of a metallic zinc powder, zinc alloy powder and zinc oxide powder.
  • the metallic zinc powder preferably has purity of 99.98%, while the zinc alloy powder preferably comprises 99% zinc.
  • Such powders are commercially available, and generally have a particle size of between 20 and 400 Tyler mesh.
  • the metal powders may also contain lead or indium or bismuth as minor alloying agents, typically from about 0.02% to about 0.08% by weight of lead and /or up to 0.2% by weight of indium or bismuth. Up to about 20% by weight of solid zinc oxide may be incorporated into the active material of the anode.
  • cells of the present invention also gave good cycle life when no solid zinc oxide was initially added to the cell.
  • the zinc anode used is "mercury-free", that is it contains no mercury within the limitations of conventional processing methods and the extremely small natural content of this material. It may contain minor, residual amounts of mercury which do not affect its properties.
  • the zinc active materials are first treated with a small amount of an organic surfactant or wetting agent.
  • the surfactant should be stable and effective in the presence of the concentrated potassium hydroxide electrolyte.
  • the preferred surfactants for rechargeable alkaline cells are selected from the group of nonionic and anionic surfactants having a molecular weight of from about 300 to about 1500, and more particularly are compounds containing polyethylene oxide or polypropylene oxide chains, their copolymers or mixtures thereof.
  • any indium salt or compound used in the film treatment process must be soluble in water and must not adversely affect rechargeable cells during at least 20 discharge cycles. It has now surprisingly been found, that in addition to indium sulphate, only indium acetate satisfies these criteria. While indium chlorides and indium nitrates are soluble enough to be used in the film treatment process of the zinc active powders, they negatively affect a rechargeable cell during multiple discharge-charge cycles, in that cells leak and/or bulge and/or prematurely fail during the discharge- charge cycling. These surprising findings were recorded for cells that all had the zinc active powder treated with the same organic surfactant, and the compositions of the zinc active powder and of the anode mixture were the same.
  • the most effective surfactants be those with polyoxyethylene or polyoxypropylene chains and a molecular weight between about 300 to 1,500. Compounds below a molecular weight of 300 were ineffective. Compounds with molecular weights more than 1,500 were difficult to process and showed an insufficient effect on hydrogen evolution and /or zinc dendrite formation.
  • the zinc active materials are then coated with a film of an aqueous solution of indium acetate.
  • concentration of indium acetate is selected to ensure that the coated zinc anode active materials will demonstrate the required level of dendrite prevention and hydrogen evolution.
  • the weight of each of the surfactant and the indium acetate i.e. discounting weight of water in the aqueous solutions, is preferably less than about 0.5%, and most preferably from about 0.01% to 0.25%, based on the total weight of the zinc active powder.
  • the effective amounts of surfactant and indium acetate solution required are unexpectedly low.
  • the amounts are chosen such that no free solution remains and the zinc is free flowing after both treatments and without washing and drying.
  • Liquid to solid blenders are used to treat the zinc active material with the surfactant or its solution.
  • the surfactant or its solution and the zinc active material are mixed for a sufficient time to ensure that the surfactant is uniformly distributed as a film on the zinc particles.
  • a small amount of an aqueous solution of indium acetate is added to the treated zinc active material, and blending is continued to ensure uniform distribution on the powder particles.
  • the pH of the aqueous solution of indium acetate is about pH 4.5.
  • the resultant blend In contrast to the prior art, there is no need for the resultant blend to be filtered, washed and dried prior to incorporation into a cell and such lengthy steps can be eliminated, so that both labour and capital are saved. If the anode is to be of the gelled type, suitable gelling agents and other additives can then be incorporated into the blend followed by adding the alkaline electrolyte. The gelled anode can then be used in known manner.
  • a gelled zinc anode manufactured by the method described above can be used in rechargeable alkaline manganese dioxide/zinc galvanic cells. These cells can be assembled in cylindrical, button, coin, or rectangular containers. For a gelled zinc electrode as used in rechargeable alkaline manganese dioxide /zinc cells up to 20% zinc oxide powder could be included.
  • Zinc anodes manufactured by the method of the present invention typically contain 1.43 to 2.4 grams of treated zinc powder per cm3 of gel and may contain up to 0.8 grams of solid zinc oxide powder per cm 3 gel. The pores or spaces around the powdered materials are filled by gelled electrolyte, an aqueous solution of potassium hydroxide, which can include potassium zincate.
  • the zinc to zinc oxide powder ratio can vary from 10/90 (discharged state) to 100/0 (fully charged state).
  • the aqueous electrolyte is usually 25% to 40% potassium hydroxide solution, optionally with zinc oxide dissolved in it up to saturation.
  • the zinc oxide reacts with potassium hydroxide and water to form potassium zincate K 2 Zn(OH) 4 .
  • the negative electrode is processed by kneading the zinc /zinc oxide powder mixture with 4% to 10% PTFE colloidal suspension, by weight of the zinc powder, and the paste is subsequently applied to at least one side of the current collector by e.g. a rolling process followed by an optional pressing step.
  • the separator 20 is at least partially wetted by the electrolyte and preferably contains at least one barrier layer of a semi-permeable or ion- exchange membrane. It has been known that in rechargeable cells, in particular those employing zinc with little or no mercury, shorts can develop during charge /discharge cycling. The chosen membrane should provide the function of a barrier preventing dendritic zinc shorts from occurring. Dendritic growth of zinc has been found by the inventors to be synergistically retarded by the combination of the films of indium and surfactant covering the zinc active materials and the semipermeable barrier layers.
  • the separator 20 may contain at least two layers, an absorbent layer with wicking properties serving as an electrolyte reservoir and a barrier layer which is resistant to zinc dendrite growth.
  • the absorbent layer may contain non-woven rayon, or polyvinyl alcohol or polyamide fibers.
  • Suitable materials for the barrier layer include cellophane, sausage casing and acrylic acid grafted polyethylene or polypropylene.
  • the separator 20 comprises a laminate of the absorbent layer and the barrier layer.
  • the separator 20 may contain one or more barrier layers and one or more absorbent layers. Microporous polypropylene barrier layers such as "CELGARD" have been shown to be resistant to dendrite growth.
  • cathode active materials can be used with the anode 18 of the present invention.
  • the cathode active materials comprise at least one of manganese dioxide, manganese oxyhydroxide, bismuth modified manganese oxide, silver oxide, nickel oxyhydroxide or oxygen in an air electrode.
  • the electrolyte is generally an aqueous solution of potassium hydroxide and can include zinc oxide to form potassium zincate.
  • a suitable manganese oxide positive electrode for use in a rechargeable cell is described in US patent 5,300,371, the contents of which are hereby incorporated by reference.
  • Suitable active materials utilizing manganese oxides comprise e.g. electrolytically or chemically synthesized manganese dioxide containing typically over 90% of four valent manganese dioxide and minor amounts of lower valence oxides.
  • manganese oxides are used as active material in the positive electrode typically 5% to 15%, by weight of the cathode, of graphite and carbon black are added to the electrode mixture.
  • a suitable finely divided hydrogen recombination catalyst can be added to the positive electrode 14.
  • Effective catalysts include silver, its oxides, and compounds as well as metal alloys capable of absorbing hydrogen.
  • Hydrogen absorbing alloys are intermetallic alloys, such as LaNi x or NiTi y , which when in electronic and ionic contact with the cathode active material may serve as an intermediary for the reaction of hydrogen with the metal oxide.
  • the hydrogen recombination catalyst can be as described in US 5,162,169 (1992), the contents of which are also hereby incorporated by reference.
  • 0.01% to 5%, by weight of the cathode, of Ag.O catalyst powder is added to the positive electrode.
  • Weight is that of surfactant or indium salt and does not include weight of water forming aqueous carrier solution.
  • the indium acetate was provided as an aqueous solution with a concentration of 16.9% indium acetate and a pH of about 4.5. It was prepared by dissolving the indium acetate in deionized water. A 10% aqueous dispersion of polyethylene glycol was used in preparing the negative electrode mixture, as follows:
  • the cells in the test group and the cells in the comparative group with the indium sulphate treatment passed the following three tests without leakage or bulging and with no signs of shorting by zinc dendrite development: -
  • test cells Five further groups of test cells were built using the film treatment processes with solutions of indium acetate and polyethylene glycol, all as described in example 1 except the composition of the zinc powder was varied as follows:
  • Comparative cell groups 6,7,8,9 and 10 had compositions of the zinc powders identical to the compositions in groups 1,2,3,4 and 5, but the zinc powders were not treated with a film of the aqueous solution of indium acetate. Cells of groups 6 -10 all leaked, bulged or shorted at various stages of tests (1), (2) or (3).
  • the groups with molecular weight of 300, 500, 1,000, and 1,500, for both surfactants passed tests (1), (2) and (3) described in example 1 without leakage, bulging or dendrite shorting.
  • Groups with polyethylene glycol or polypropylene glycol of molecular weight 200 showed a high percentage of cells leaking or bulging in tests (1), (2) or (3).
  • Groups with polyethylene glycol or polypropylene glycol of about 1,600 molecular weight showed poor electrical performance as well as leakage and bulging. This demonstrates that the molecular weight range of 300-1500 gives the best performance.
  • Example 1 Five additional groups of cells were built as described in Example 1. All electrode processing and cell assembly operations were as described in Example 1. The compositions of the negative electrode and the positive electrode were as in Table la of Example 1, except for using different indium salts as in Table 4. The indium salts constitute a selection of indium salts soluble in water.
  • Each of the cell groups 13 to 17 was divided into 3 subgroups and tested on one of the following three tests: (1) Twenty (20) repeated discharge /charge cycles using a 3.9ohm load resistor to an end of discharge voltage of 0.9 volts.

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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)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

On enrobe la poudre active de zinc destinée à une cellule électrochimique rechargeable sans mercure, d'une part d'un tensioactif et d'autre part, d'une solution aqueuse d'acétate d'indium. Sans procéder à une étape ultérieure de filtrage, lavage ou séchage, on assemble cette poudre de façon à constituer la cellule électrochimique. Ladite cellule peut comporter un catalyseur de recombinaison de l'hydrogène en contact avec la matière électrochimiquement active de la cathode.
PCT/CA1995/000634 1995-11-06 1995-11-06 Piles alcalines rechargeables contenant des anodes en zinc non additionnees de mercure Ceased WO1997017737A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CA1995/000634 WO1997017737A1 (fr) 1995-11-06 1995-11-06 Piles alcalines rechargeables contenant des anodes en zinc non additionnees de mercure
AU37690/95A AU3769095A (en) 1995-11-06 1995-11-06 Rechargeable alkaline cells containing zinc anodes without added mercury

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CA1995/000634 WO1997017737A1 (fr) 1995-11-06 1995-11-06 Piles alcalines rechargeables contenant des anodes en zinc non additionnees de mercure

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0822607A1 (fr) * 1996-07-31 1998-02-04 Rayovac Corporation Pile électrochimique rechargeable à électrolyte alcalin
EP1021844A1 (fr) * 1997-08-01 2000-07-26 Duracell Inc. Forme de particule d'electrode a base de zinc
US6558493B1 (en) * 1994-12-07 2003-05-06 Carglass Luxembourg Sarl-Zug Branch Releasing of bonded screens
EP1693912A4 (fr) * 2003-12-10 2006-08-23 Hitachi Maxell Pile type bouton alcaline et son procede de production
WO2006111835A1 (fr) * 2005-04-20 2006-10-26 Revolt Technology Ltd Electrode de zinc comprenant un agent gelifiant organique et un liant organique
JP2013502026A (ja) * 2009-08-07 2013-01-17 パワージェニックス・システムズ・インコーポレーテッド 炭素繊維亜鉛電極
EP2996182A1 (fr) * 2014-08-21 2016-03-16 Johnson & Johnson Vision Care Inc. Formulations d'électrolyte pour utilisation dans des éléments énergétiques biocompatibles
US9383593B2 (en) 2014-08-21 2016-07-05 Johnson & Johnson Vision Care, Inc. Methods to form biocompatible energization elements for biomedical devices comprising laminates and placed separators
US9577259B2 (en) 2014-08-21 2017-02-21 Johnson & Johnson Vision Care, Inc. Cathode mixture for use in a biocompatible battery
US9599842B2 (en) 2014-08-21 2017-03-21 Johnson & Johnson Vision Care, Inc. Device and methods for sealing and encapsulation for biocompatible energization elements
US9715130B2 (en) 2014-08-21 2017-07-25 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form separators for biocompatible energization elements for biomedical devices
US9793536B2 (en) 2014-08-21 2017-10-17 Johnson & Johnson Vision Care, Inc. Pellet form cathode for use in a biocompatible battery
US9899700B2 (en) 2014-08-21 2018-02-20 Johnson & Johnson Vision Care, Inc. Methods to form biocompatible energization elements for biomedical devices comprising laminates and deposited separators
US9923177B2 (en) 2014-08-21 2018-03-20 Johnson & Johnson Vision Care, Inc. Biocompatibility of biomedical energization elements
US9941547B2 (en) 2014-08-21 2018-04-10 Johnson & Johnson Vision Care, Inc. Biomedical energization elements with polymer electrolytes and cavity structures
US10345620B2 (en) 2016-02-18 2019-07-09 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form biocompatible energization elements incorporating fuel cells for biomedical devices
US10361404B2 (en) 2014-08-21 2019-07-23 Johnson & Johnson Vision Care, Inc. Anodes for use in biocompatible energization elements
US10361405B2 (en) 2014-08-21 2019-07-23 Johnson & Johnson Vision Care, Inc. Biomedical energization elements with polymer electrolytes
US10381687B2 (en) 2014-08-21 2019-08-13 Johnson & Johnson Vision Care, Inc. Methods of forming biocompatible rechargable energization elements for biomedical devices
US10451897B2 (en) 2011-03-18 2019-10-22 Johnson & Johnson Vision Care, Inc. Components with multiple energization elements for biomedical devices
US10627651B2 (en) 2014-08-21 2020-04-21 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form biocompatible energization primary elements for biomedical devices with electroless sealing layers
US10775644B2 (en) 2012-01-26 2020-09-15 Johnson & Johnson Vision Care, Inc. Ophthalmic lens assembly having an integrated antenna structure
US12126014B2 (en) 2019-01-23 2024-10-22 Energizer Brands, Llc Alkaline electrochemical cells comprising increased zinc oxide levels

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US4118551A (en) * 1977-10-31 1978-10-03 Yardney Electric Corporation Mercury-free zinc electrode

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
US4118551A (en) * 1977-10-31 1978-10-03 Yardney Electric Corporation Mercury-free zinc electrode

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6558493B1 (en) * 1994-12-07 2003-05-06 Carglass Luxembourg Sarl-Zug Branch Releasing of bonded screens
EP0822607A1 (fr) * 1996-07-31 1998-02-04 Rayovac Corporation Pile électrochimique rechargeable à électrolyte alcalin
EP1021844A1 (fr) * 1997-08-01 2000-07-26 Duracell Inc. Forme de particule d'electrode a base de zinc
EP1693912A4 (fr) * 2003-12-10 2006-08-23 Hitachi Maxell Pile type bouton alcaline et son procede de production
US8003247B2 (en) 2003-12-10 2011-08-23 Hitachi Maxell Energy, Ltd. Button-type alkaline battery and method of manufacturing the same
JP2008537302A (ja) * 2005-04-20 2008-09-11 レボルト テクノロジー リミティド 電極
EP1715536A3 (fr) * 2005-04-20 2007-10-10 ReVolt Technology AS Electrode de zinc comprenant un gélifiant organique et un liant organique.
WO2006111835A1 (fr) * 2005-04-20 2006-10-26 Revolt Technology Ltd Electrode de zinc comprenant un agent gelifiant organique et un liant organique
US8039150B2 (en) 2005-04-20 2011-10-18 Revoit Technology Ltd. Agglomerated zinc powder anode
JP2013502026A (ja) * 2009-08-07 2013-01-17 パワージェニックス・システムズ・インコーポレーテッド 炭素繊維亜鉛電極
US10763495B2 (en) 2009-08-07 2020-09-01 Zincfive Power, Inc. Carbon fiber zinc negative electrode
US9947919B2 (en) 2009-08-07 2018-04-17 Zincfive Power, Inc. Carbon fiber zinc negative electrode
US10451897B2 (en) 2011-03-18 2019-10-22 Johnson & Johnson Vision Care, Inc. Components with multiple energization elements for biomedical devices
US10775644B2 (en) 2012-01-26 2020-09-15 Johnson & Johnson Vision Care, Inc. Ophthalmic lens assembly having an integrated antenna structure
US9899700B2 (en) 2014-08-21 2018-02-20 Johnson & Johnson Vision Care, Inc. Methods to form biocompatible energization elements for biomedical devices comprising laminates and deposited separators
US10361405B2 (en) 2014-08-21 2019-07-23 Johnson & Johnson Vision Care, Inc. Biomedical energization elements with polymer electrolytes
US9793536B2 (en) 2014-08-21 2017-10-17 Johnson & Johnson Vision Care, Inc. Pellet form cathode for use in a biocompatible battery
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