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WO1999052169A1 - Pile electrochimique incorporant un agent exterieur de suppression d'hydrogene - Google Patents

Pile electrochimique incorporant un agent exterieur de suppression d'hydrogene Download PDF

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Publication number
WO1999052169A1
WO1999052169A1 PCT/US1999/007405 US9907405W WO9952169A1 WO 1999052169 A1 WO1999052169 A1 WO 1999052169A1 US 9907405 W US9907405 W US 9907405W WO 9952169 A1 WO9952169 A1 WO 9952169A1
Authority
WO
WIPO (PCT)
Prior art keywords
container
hydrogen
removing agent
disposed
battery
Prior art date
Application number
PCT/US1999/007405
Other languages
English (en)
Inventor
Jean W. Bailey
Original Assignee
Eveready Battery Company, 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 Eveready Battery Company, Inc. filed Critical Eveready Battery Company, Inc.
Priority to AU34697/99A priority Critical patent/AU3469799A/en
Priority to CA002327860A priority patent/CA2327860A1/fr
Publication of WO1999052169A1 publication Critical patent/WO1999052169A1/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
    • H01M10/42—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
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • 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
    • H01M10/523—Removing gases inside the secondary cell, e.g. by absorption by recombination on a catalytic material
    • 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
    • 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 generally relates to batteries and, more particularly, to removing hydrogen released from batteries, and is particularly useful for batteries used in sealed compartments such as in a packaged camera, a sealed flashlight, or other sealed device.
  • Conventional alkaline electrochemical cells generally include a steel cylindrical can having a positive electrode, referred to as the cathode, which comprises manganese dioxide as the active material, and is generally formed against the interior surface of the steel can.
  • the electrochemical cell also includes a negative electrode, referred to as the anode, which comprises zinc powder, and is generally centrally disposed in the can.
  • a separator is located between the anode and the cathode, and an alkaline electrolyte solution simultaneously contacts the anode, the cathode, and separator.
  • a conductive current collector is commonly inserted into the anode active material and a seal assembly, which includes a seal member, provides closure to the open end of the cell's steel can to seal the active electrochemical materials in a sealed volume.
  • Standard alkaline cells are commercially available for providing an open circuit voltage of about 1.5 volts.
  • a higher voltage is required, it is common practice to combine multiple cells to form a battery having the required voltage.
  • a plurality of cells are commonly housed in a container and are electrically connected in series. Additionally, external terminals are attached to the outside of the container for making an electrical connection with the cells.
  • small amounts of hydrogen are produced inside an alkaline cell due to corrosion of the zinc anode.
  • a portion of the hydrogen accumulates inside the sealed volume of the battery, while some of the hydrogen permeates through and around the seal, and therefore escapes from the cell's closed volume. Additionally, ventable seals are often used which open and release hydrogen when excessive pressure builds up in the closed volume.
  • hydrogen can present potentially unacceptable conditions, particularly in sealed compartments.
  • hydrogen may become concentrated in the sealed battery compartment of a flashlight or other electrically-operated device, and can potentially lead to problems in operating the device.
  • concentration of hydrogen in a disposable camera that is commercially made available in a sealed airtight package may adversely reduce silver in the photographic film and fog the film, thereby degrading the camera's photographic film.
  • Hydrogen getters and recombination catalysts have been available to remove hydrogen.
  • hydrogen absorbing materials such as hydrogen getters, and recombination catalysts
  • a device such as a flashlight.
  • only certain selected electrically-operated devices are made available with a hydrogen removing material.
  • the present invention provides for the removal of hydrogen generated by a battery by providing the battery with a hydrogen removing agent.
  • a battery is provided having walls defining a volume and including an active cell volume for housing active cell materials. Electrochemically active materials are contained in the active cell volume of the container.
  • the battery further includes a hydrogen removing agent disposed on the battery external from the active cell volume of the container for removing hydrogen produced by the electrochemically active materials.
  • the hydrogen removing agent is disposed on the surface of a seal member that is disposed within an open top end of the container.
  • the hydrogen removing agent is disposed on an inner surface of an outer cover of the battery.
  • the hydrogen removing agent is disposed on a label on the outside walls of the container.
  • the hydrogen removing agent is disposed on the interior walls of a multi-cell battery.
  • FIG. 1 is a longitudinal cross-sectional view of an electrochemical cell having a hydrogen removing agent disposed on the top surface of an annular seal member according to a first embodiment of the present invention
  • FIG. 2 is an exploded perspective view of the annular seal member containing the hydrogen removing agent as shown in FIG. 1;
  • FIG. 3 is a partial longitudinal cross-sectional view of an electrochemical cell having the hydrogen removing agent disposed on a bottom surface of the outer negative cover according to a second embodiment
  • FIG. 4 is a partial longitudinal cross-sectional view of an electrochemical cell having the hydrogen removing agent disposed on an outer can label according to a third embodiment
  • FIG. 5 is a partial cutaway view of a multi-cell battery having a hydrogen removing agent disposed on an inside surface of the battery housing according to a fourth embodiment.
  • FIG. 6 is a comparative graph illustrating the hydrogen volume that is collected from the electrochemical cell shown in FIG. 3 stored in a sealed container as compared to the hydrogen volume from an electrochemical cell absent the hydrogen removing agent.
  • Alkaline cell 10 includes a cylindrical steel can 12 having a closed bottom end 14 and an open top end 16.
  • the closed bottom end of can 12 further includes a positive cover welded or otherwise attached thereto and formed of plated steel with a protruding nub 18 at its center region which forms the positive contact terminal of cell 10.
  • Assembled to the open end 16 of the steel can 12 is a cover and seal assembly which forms the negative contact terminal of cell 10.
  • a metalized, plastic film label 20 is formed about the exterior surface of steel can 12, except for the ends of steel can 12. Film label 20 is formed over the peripheral edge of the positive cover.
  • a cathode 22, preferably formed of a mixture of manganese dioxide, graphite, forty-five percent potassium hydroxide solution, and additives is formed about the interior surface of steel can 12.
  • the current collector 28 contacts an outer negative cover 30 which forms the negative contact teirninal of cell 10.
  • An annular nylon seal 32 is disposed in the open end 16 of the steel can 12 to prevent leakage of the active cell ingredients contained in steel can 12.
  • Nylon seal 32 contacts a metal washer 34 which forms an inner cell cover, and is preferably formed of steel.
  • the outer negative cover 30 is preferably formed of plated steel, and may be held in contact with current collector 28 via pressure contact or a weld. It should be appreciated that the outer negative cover 30 is electrically insulated from the steel can 12 by way of nylon seal 32.
  • the inner cover 34 includes one or more vent openings 36.
  • the outer negative cover 30 also includes one or more openings 38 to vent pressure build-up from within the cell 10 to the outside atmosphere.
  • the active ingredients are sealed in the can 12 in an active cell volume thereof, it should be understood that hydrogen accumulation may develop in the active seal volume of the container due to corrosion of the zinc anode.
  • the hydrogen gas is in the form of very small molecules which are capable of being released from the active cell volume of the container by permeating the seal 32, particularly between the current collector 28 and seal 32.
  • a pressure release vent (not shown) may be provided in the seal 32 to open at a predetermined internal pressure to vent internal pressure, including hydrogen, from within the sealed volume of the can 12.
  • a hydrogen removing agent 40 is disposed on the electrochemical cell 10 external to the active cell volume of the can 12.
  • the hydrogen removing agent 40 is disposed on a top surface 42 of the annular seal 32. While the hydrogen removing agent 40 is shown in the form of a thin circular disk having an opening through which an axial boss 44 of seal 32 extends, it should be appreciated that the hydrogen removing agent may be provided in various shapes, sizes, and locations.
  • the hydrogen removing agent 40 is applied to the surface 42 of the annular seal 32 external to the cell's electrochemically active components, yet it is within the overall volume of the battery such that it is exposed to hydrogen which leaks from the electrochemically active volume of the cell to the outside environment.
  • the hydrogen removing agent 40 removes at least some, and preferably a substantial amount, of the hydrogen accumulation so that excessive hydrogen accumulation can be prevented. This hydrogen removal is especially advantageous when the electrochemical cell 10 is employed in a sealed enclosure such as a flashlight or a camera, as well as other applications.
  • the hydrogen removing agent 40 may include any of a number of available agents that effectively remove hydrogen.
  • the hydrogen removing agent 40 may include a hydrogen recombination catalyst or a hydrogen getter, both of which are known to remove hydrogen.
  • a hydrogen getter is disclosed in U.S. Patent No. 5,837,158, entitled “POLYMER FORMULATIONS FOR GETTERING HYDROGEN,” the disclosure of which is incorporated herein by reference.
  • Hydrogen getters such as that disclosed in the aforementioned patent,
  • -7- remove hydrogen accumulation by providing a controlled reaction between an organic reactant and hydrogen.
  • a hydrogen recombination catalyst for use as the hydrogen removing agent 40 may include a hydrogen recombination catalyst which causes hydrogen and oxygen to combine and produce water.
  • Another example of a suitable hydrogen recombination catalyst is disclosed in U.S. Patent No. 3,893,870, entitled “HYDROGEN ABSORBING MATERIAL FOR ELECTROCHEMICAL CELLS,” the disclosure of which is also incorporated herein by reference. It should be appreciated that other known hydrogen removing agents may be employed for use in the battery, according to the present invention.
  • the hydrogen removing agent 40 may be applied to the surface of seal 32 by any of a number of known application techniques including, but not limited to, spraying, painting, printing, or other application techniques.
  • the hydrogen removing agent 40 could be applied directly to the surface of the seal 32, or could be applied to a carrier surface, such as a tape material, which in turn can be adhered or otherwise applied to the surface of the seal 32.
  • the hydrogen removing agent 40 can be applied in different shapes, sizes, and locations on the seal 32.
  • the hydrogen removing agent 40 is shown disposed on the inside surface of the outer negative cover 30 according to a second embodiment of the present invention.
  • the hydrogen removing agent 40 may be applied to the bottom surface of outer negative cover 30 in various shapes, sizes, and locations, and in a manner similar to that disposed on the seal 32 according to the first embodiment. It should be appreciated that the hydrogen removing agent 40 of the first and second embodiments, is advantageously located external from the internal volume containing the electrochemically active materials of cell 10, yet within the entire volume of the cell 10, and more particularly in the volume defined between the seal 32 and outer negative cover 30.
  • the hydrogen removing agent 40 may be located in other locations on the cell 10 external from the active cell volume containing the electrochemically active materials, without departing from the teachings of the present invention.
  • the hydrogen removing agent 40 could likewise be disposed on the current collector 28 at a location between seal 32 and outer negative cover 30.
  • the hydrogen removing agent 40 could be disposed on the inner cover 34. Accordingly, the hydrogen removing agent 40 is disposed preferably in a location where it will be exposed to hydrogen released from the active materials of the electrochemical cell 10.
  • an electrochemical cell 10 having the hydrogen removing agent 40 disposed outside of the steel can 12 on the outer surface of label 20.
  • the hydrogen removing agent 40 may be applied in the shape of a ring, and is made available for exposure to hydrogen that is released from the electrochemical cell 10 to the outside atmosphere.
  • the hydrogen removing agent 40 may likewise be disposed at other locations on the outside surface of cell 10.
  • the hydrogen removing agent 40 could be disposed on the outer surface of outer negative cover 30.
  • hydrogen removing agent 40 could be disposed on the inner or outer surface of the positive cover.
  • the hydrogen removing agent 40 could be integrally formed in the label 20.
  • a multi-cell battery 50 is illustrated therein which contains a plurality of electrochemical cells 10.
  • the multi-cell battery 50 may include six electrochemical cells 10 connected in series to form a 9-volt battery as is generally known in the battery art.
  • the multi-cell battery 50 includes a container 52 housing the multiple electrochemical cells 10, and has positive and negative contact te ⁇ ninals 54 and 56 provided on the top end of the container 52.
  • the multi-cell battery 50 has the hydrogen removing agent 40 preferably located on an inside surface, such as the inner side walls of the container 52, to remove hydrogen accumulation emitted from the electrochemical cells 10.
  • the hydrogen removing agent 40 is shown on the inside surface of the side walls of container 52, it should also be appreciated that the hydrogen removing agent 40 may be located on the top or bottom inside walls, or an outer surface of one or more of the electrochemical cells 10, or may be located on an outside surface of the container 52.
  • FIG. 6 a graph is shown which illustrates the performance of electrochemical cells having a hydrogen removing agent in the form of a hydrogen recombination catalyst applied to the inside surface of outer negative cover 30 as shown in FIG. 3, and compared to similar electrochemical cells absent the hydrogen removing agent 40.
  • cylindrical alkaline AA-sized cells were tested over a two week period at temperatures of 50°C and 71°C.
  • Hydrogen volume measurements were taken by placing the cells at the corresponding temperature in a bag for the two week test period. The total volume of air in the bag was measured. The air was analyzed for hydrogen concentration and the volume of air was multiplied by the percentage of hydrogen to arrive at the hydrogen volume measurement.
  • Two cells containing the hydrogen removing agent 40 on the bottom surface of the outer negative cover 30 were tested, and the volume of hydrogen accumulated in each cell
  • the hydrogen volume measurement for one cell tested at 50°C is identified by reference numeral 64, and the hydrogen volume measurement for the other cell tested at 71°C is shown by reference numeral 66.
  • the conventional cells which did not include the hydrogen removing agent, provided much greater hydrogen volume measurements as identified by reference numeral 60 for the 50°C test, and reference numeral 62 for the 71°C test.
  • the hydrogen removing agent 40 significantly reduced the volume of hydrogen accumulation in the cell, when contrasted to the conventional cells not containing the hydrogen removing agent.
  • the graphs shown in FIG. 6 illustrate that the amount of hydrogen accumulation tends to be greater when the temperature is increased.
  • a hydrogen removing agent 40 is disposed on an electrochemical cell or battery external to the closed volume containing the electrochemically active materials of the cell to reduce the amount of hydrogen emitted from the cell into the surrounding atmosphere.
  • the electrochemical cell can be employed in an electrically- operated device such as a flashlight or a camera, which often employ a sealed battery compartment.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)

Abstract

Pile incorporant un agent (40) de suppression d'hydrogène placé sur la pile à l'extérieur du volume actif de son boîtier afin de supprimer l'hydrogène produit par les matériaux électrochimiques. Cet agent (40) est situé sur une surface de l'élément d'étanchéité (32) placé à l'intérieur d'une extrémité supérieure ouverte du boîtier (12) selon un mode de réalisation. Dans d'autres modes de réalisation, cet agent de suppression d'hydrogène est placé sur une surface intérieure d'un couvercle extérieur (30) ou sur une étiquette (20) sur les parois extérieures de ce boîtier (12). L'invention concerne également un accumulateur à piles multiples présentant cet agent de suppression d'hydrogène placé sur ses parois extérieures.
PCT/US1999/007405 1998-04-07 1999-04-05 Pile electrochimique incorporant un agent exterieur de suppression d'hydrogene WO1999052169A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU34697/99A AU3469799A (en) 1998-04-07 1999-04-05 Electrochemical cell incorporating an external hydrogen removing agent
CA002327860A CA2327860A1 (fr) 1998-04-07 1999-04-05 Pile electrochimique incorporant un agent exterieur de suppression d'hydrogene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8095098P 1998-04-07 1998-04-07
US60/080,950 1998-04-07

Publications (1)

Publication Number Publication Date
WO1999052169A1 true WO1999052169A1 (fr) 1999-10-14

Family

ID=22160708

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/007405 WO1999052169A1 (fr) 1998-04-07 1999-04-05 Pile electrochimique incorporant un agent exterieur de suppression d'hydrogene

Country Status (3)

Country Link
AU (1) AU3469799A (fr)
CA (1) CA2327860A1 (fr)
WO (1) WO1999052169A1 (fr)

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3943937A (en) * 1974-07-05 1976-03-16 Medtronic, Inc. Gas absorbing implantable electrical medical device
US3953872A (en) * 1973-09-21 1976-04-27 Polaroid Corporation Novel photographic film assemblies
US4054727A (en) * 1975-08-25 1977-10-18 P.R. Mallory & Co. Inc. Battery with an agent for converting hydrogen to water and a second agent for retaining formed water
GB2091934A (en) * 1980-12-29 1982-08-04 Duracell Int Electrochemical cells having hydrogen gas absorbing agent
JPS57148884A (en) * 1981-03-10 1982-09-14 Matsushita Electric Ind Co Ltd Sealed alkaline cell
JPS57205975A (en) * 1981-06-11 1982-12-17 Yuasa Battery Co Ltd Lead battery
EP0075132A1 (fr) * 1981-09-15 1983-03-30 VARTA Batterie Aktiengesellschaft Elément galvanique à "getter" intégré
JPS60127670A (ja) * 1983-12-13 1985-07-08 Kiyoji Sawa 密閉形電池
JPS6119068A (ja) * 1984-07-04 1986-01-27 Matsushita Electric Ind Co Ltd アルカリ亜鉛電池
JPS63231882A (ja) * 1987-03-19 1988-09-27 Sanyo Electric Co Ltd 密閉型蓄電池
WO1991017581A1 (fr) * 1990-05-09 1991-11-14 Battery Technologies Inc. Recombinaison catalytique d'hydrogene dans des piles alcalines
EP0605734A1 (fr) * 1992-06-30 1994-07-13 Yuasa Corporation Pile
JPH07192775A (ja) * 1993-12-24 1995-07-28 Sony Corp 非水電解液二次電池
GB2286680A (en) * 1994-01-31 1995-08-23 Eveready Battery Inc Gas safety indicating device
JPH07302623A (ja) * 1994-05-06 1995-11-14 Matsushita Electric Ind Co Ltd 積層形空気電池
JPH09115491A (ja) * 1995-10-20 1997-05-02 Matsushita Electric Ind Co Ltd 簡易型ガス吸収式鉛蓄電池およびその製造法

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953872A (en) * 1973-09-21 1976-04-27 Polaroid Corporation Novel photographic film assemblies
US3943937A (en) * 1974-07-05 1976-03-16 Medtronic, Inc. Gas absorbing implantable electrical medical device
US4054727A (en) * 1975-08-25 1977-10-18 P.R. Mallory & Co. Inc. Battery with an agent for converting hydrogen to water and a second agent for retaining formed water
GB2091934A (en) * 1980-12-29 1982-08-04 Duracell Int Electrochemical cells having hydrogen gas absorbing agent
JPS57148884A (en) * 1981-03-10 1982-09-14 Matsushita Electric Ind Co Ltd Sealed alkaline cell
JPS57205975A (en) * 1981-06-11 1982-12-17 Yuasa Battery Co Ltd Lead battery
EP0075132A1 (fr) * 1981-09-15 1983-03-30 VARTA Batterie Aktiengesellschaft Elément galvanique à "getter" intégré
JPS60127670A (ja) * 1983-12-13 1985-07-08 Kiyoji Sawa 密閉形電池
JPS6119068A (ja) * 1984-07-04 1986-01-27 Matsushita Electric Ind Co Ltd アルカリ亜鉛電池
JPS63231882A (ja) * 1987-03-19 1988-09-27 Sanyo Electric Co Ltd 密閉型蓄電池
WO1991017581A1 (fr) * 1990-05-09 1991-11-14 Battery Technologies Inc. Recombinaison catalytique d'hydrogene dans des piles alcalines
EP0605734A1 (fr) * 1992-06-30 1994-07-13 Yuasa Corporation Pile
JPH07192775A (ja) * 1993-12-24 1995-07-28 Sony Corp 非水電解液二次電池
GB2286680A (en) * 1994-01-31 1995-08-23 Eveready Battery Inc Gas safety indicating device
JPH07302623A (ja) * 1994-05-06 1995-11-14 Matsushita Electric Ind Co Ltd 積層形空気電池
JPH09115491A (ja) * 1995-10-20 1997-05-02 Matsushita Electric Ind Co Ltd 簡易型ガス吸収式鉛蓄電池およびその製造法

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* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 006, no. 251 (E - 147) 10 December 1982 (1982-12-10) *
PATENT ABSTRACTS OF JAPAN vol. 007, no. 058 (E - 163) 10 March 1983 (1983-03-10) *
PATENT ABSTRACTS OF JAPAN vol. 009, no. 284 (E - 357) 12 November 1985 (1985-11-12) *
PATENT ABSTRACTS OF JAPAN vol. 010, no. 168 (E - 411) 14 June 1986 (1986-06-14) *
PATENT ABSTRACTS OF JAPAN vol. 013, no. 031 (E - 707) 24 January 1989 (1989-01-24) *
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PATENT ABSTRACTS OF JAPAN vol. 096, no. 003 29 March 1996 (1996-03-29) *
PATENT ABSTRACTS OF JAPAN vol. 097, no. 009 30 September 1997 (1997-09-30) *

Also Published As

Publication number Publication date
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CA2327860A1 (fr) 1999-10-14

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