WO2000011736A1 - Battery construction having pressure release mechanism - Google Patents

Battery construction having pressure release mechanism Download PDF

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Publication number
WO2000011736A1
WO2000011736A1 PCT/US1999/018667 US9918667W WO0011736A1 WO 2000011736 A1 WO2000011736 A1 WO 2000011736A1 US 9918667 W US9918667 W US 9918667W WO 0011736 A1 WO0011736 A1 WO 0011736A1
Authority
WO
WIPO (PCT)
Prior art keywords
cover
electrochemical cell
pressure relief
battery
relief mechanism
Prior art date
Application number
PCT/US1999/018667
Other languages
French (fr)
Inventor
George R. Sondecker
Gary A. Laisy
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 JP2000566907A priority Critical patent/JP4323722B2/en
Priority to EP99943719A priority patent/EP1108269B1/en
Priority to AU56757/99A priority patent/AU5675799A/en
Priority to AT99943719T priority patent/ATE253258T1/en
Priority to CA002340387A priority patent/CA2340387A1/en
Priority to DE69912454T priority patent/DE69912454T2/en
Publication of WO2000011736A1 publication Critical patent/WO2000011736A1/en

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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
    • 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
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/75—Wires, rods or strips
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/148—Lids or covers characterised by their shape
    • H01M50/154—Lid or cover comprising an axial bore for receiving a central current collector
    • 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
    • H01M50/147—Lids or covers
    • H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
    • H01M50/167—Lids or covers characterised by the methods of assembling casings with lids by crimping
    • 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
    • H01M50/147—Lids or covers
    • H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
    • H01M50/171—Lids or covers characterised by the methods of assembling casings with lids using adhesives or sealing agents
    • 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
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/182—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for cells with a collector centrally disposed in the active mass, e.g. Leclanché cells
    • 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
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • 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
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/342—Non-re-sealable arrangements
    • H01M50/3425—Non-re-sealable arrangements in the form of rupturable membranes or weakened parts, e.g. pierced with the aid of a sharp member
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/552—Terminals characterised by their shape
    • H01M50/559—Terminals adapted for cells having curved cross-section, e.g. round, elliptic or button cells
    • H01M50/56—Cup shaped terminals
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/571—Methods or arrangements for affording protection against corrosion; Selection of materials therefor
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • the present invention generally relates to an electrochemical cell construction.
  • the present invention relates to the containers and collector assemblies used for an electrochemical cell, such as an alkaline cell.
  • Figure 1 shows the construction of a conventional C sized alkaline cell 10.
  • cell 10 includes a cylindrically shaped can 12 having an open end and a closed end.
  • Can 12 is preferably formed of an electrically conductive material, such that an outer cover 11 welded to a bottom surface 14 at the closed end of can 12 serves as an electrical contact terminal for the cell.
  • Cell 10 further typically includes a first electrode material 15, which may serve as the positive electrode (also known as a cathode).
  • the first electrode material 15 may be preformed and inserted into can 12, or may be moulded in place so as to contact the inner surfaces of the can 12.
  • first electrode material 15 will typically include MnO .
  • a separator 17 is inserted into the space defined by first electrode 15. Separator 17 is preferably a non-woven fabric. Separator 17 is provided to maintain a physical separation of the first electrode material 15 and a mixture of electrolyte and a second electrode material 20 while allowing the transport of ions between the electrode materials.
  • an electrolyte is dispensed into the space defined by separator 17, along with the mixture 20 of electrolyte and a second electrode material, which may be the negative electrode (also known as the anode).
  • the electrolyte/second electrode mixture 20 preferably includes a gelling agent.
  • mixture 20 is formed of a mixture of an aqueous KOH electrolyte and zinc, which serves as the second electrode material. Water and additional additives may also be included in mixture 20.
  • a preassembled collector assembly 25 is inserted into the open end of can 12
  • Can 12 is typically slightly tapered at its open end This taper serves to support the collector assembly in a desired o ⁇ entation p ⁇ or to secu ⁇ ng it in place
  • an outer cover 45 is placed over collector assembly 25
  • Collector assembly 25 is secured in place by radially squeezing the can against collector assembly 25
  • the end edge 13 of can 12 is c ⁇ mped over the pe ⁇ pheral lip of collector assembly 25, thereby secu ⁇ ng outer cover 45 and collector assembly 25 within the end of can 12.
  • collector assembly 25 one function served by collector assembly 25 is to provide for a second external elect ⁇ cal contact for the electrochemical cell Additionally, collector assembly 25 must seal the open end of can 12 to prevent the electrochemical mate ⁇ als therein from leaking from this cell. Additionally, collector assembly 25 must exhibit sufficient strength to withstand the physical abuse to which batte ⁇ es are typically exposed.
  • collector assembly 25 may allow ternally generated hydrogen gas to permeate therethrough to escape to the exte ⁇ or of the electrochemical cell Further, collector assembly 25 should include some form of pressure relief mechanism to relieve pressure produced internally within the cell should this pressure become excessive Such conditions may occur when the electrochemical cell internally generates hydrogen gas at a rate that exceeds that at which the internally generated hydrogen gas can permeate through the collector assembly to the exte ⁇ or of the cell
  • the collector assembly 25 shown Figure 1 includes a seal 30, a collector nail 40, an inner cover 44, a washer 50, and a plurality of spurs 52.
  • Seal 30 is shown as including a central hub 32 having a hole through which collector nail 40 is inserted. Seal 30 further includes a V-shaped portion 34 that may contact an upper surface 16 of first electrode 15.
  • Seal 30 also includes a pe ⁇ pheral upstanding wall 36 that extends upward along the pe ⁇ phery of seal 30 in an annular fashion Pe ⁇ pheral upstanding wall 36 not only serves as a seal between the interface of collector assembly 25 and can 12, but also serves as an elect ⁇ cal insulator for preventing an elect ⁇ cal short from occur ⁇ ng between the positive can and negative contact terminal of the cell
  • Inner cover 44 which is formed of a ⁇ gid metal, is provided to increase the ⁇ gidity and support the radial compression of collector assembly 25 thereby improving the sealing effectiveness As shown Figure 1, inner cover 44 is configured to contact cential hub portion 32 and pe ⁇ pheral upstanding wall 36 By configu ⁇ ng collector assembly 25 in this fashion, inner cover 44 serves to enable compression of central hub portion 32 by collector nail 40 while also supporting compression of pe ⁇ pheral upstanding wall 36 by the inner surface of can 12
  • Outer cover 45 is typically made of a nickel-plated steel and is configured to extend from a region defined by the annular pe ⁇ pheral upstanding wall 36 of seal 30 and to be elect ⁇ cal contact with a head portion 42 of collector nail 40 Outer cover 45 may be welded to head portion 42 of collector nail 40 to prevent any loss of contact As shown m Figure 1, when collector assembly 25 is inserted into the open end of can 12, collector nail 40 penetrates deeply within the electrolyte/second electrode mixture 20 to establish sufficient elect ⁇ cal contact therewith.
  • outer cover 45 includes a pe ⁇ pheral lip 47 that extends upwardly along the circumference of outer cover 45
  • pe ⁇ pheral upstanding wall 36 of seal 30 of a length greater than that of pe ⁇ pheial lip 47, a portion of pe ⁇ pheral upstanding wall 36 may be folded over pe ⁇ pheral lip 47 du ⁇ ng the c ⁇ mping process so as to prevent any portion of the upper edge 13 of can 12 from coming into contact with outer cover 45.
  • Seal 30 is preferably formed of nylon.
  • a pressure relief mechanism is provided for enabling the relief of internal pressure when such pressure becomes excessive
  • inner cover 44 and outer cover 45 are typically provided with apertures 43 that allow the hydrogen gas to escape to the exte ⁇ or of cell 10
  • the mechanism shown includes an annular metal washer 50 and a plurality of spurs 52 that are provided between seal 30 and inner cover 44.
  • Each spur 52 includes a pointed end 53 that is pressed against a thin intermediate portion 38 of seal 30.
  • Spurs 52 are biased against the lower inner surface of inner cover 44 such that when the internal pressure of cell 10 increases and seal 30 consequently becomes deformed by pressing upward toward inner cover 44, the pointed ends 53 of spurs 52 penetrate through the thin intermediate portion 38 of seal 30 thereby rupturing seal 30 and allowing the escape of the internally-generated gas through apertures 43.
  • collector assembly 25 performs all the above- noted desirable functions satisfactorily, as apparent from its cross-sectional profile this particular collector assembly occupies a significant amount of space within the interior of the cell 10. It should be noted that the construction shown in Figure 1 is but one example of a cell construction. Other collector assemblies exist that may have lower profiles and hence occupy less space within the cell. However, such collector assemblies typically achieve this reduction in occupied volume at the expense of the sealing characteristics of the collector assembly or the performance and reliability of the pressure relief mechanism.
  • the measured external and internal volumes for several batteries that were commercially available at the priority date of this application are listed in the tables shown in Figures 2A and 2B.
  • the tables list the volumes (cc) for D, C, AA, and AAA sized batteries.
  • the collector assembly volume and the percentage of the total cell volume that constitutes the collector assembly volume is provided in Figure 2B for those commercially available batteries listed in Figure 2A.
  • Also provided in Figure 2A is a percentage of the total cell volume that constitutes the internal volume that is available for containing the electrochemically active materials.
  • the “total cell volume” includes all of the volume, including any internal void spaces, of the battery.
  • the total volume ideally includes all of the cross-hatched area as shown in Figure 3A.
  • the “internal volume” of the battery is represented by the cross-hatched area shown in Figure 3B.
  • the "internal volume”, as used herein, is that volume inside the cell or battery that contains the electrochemically active materials as well as any voids and chemically inert materials (other than the collector nail) that are confined within the sealed volume of the cell.
  • Such chemically inert materials may include separators, conductors, and any inert additives in the electrodes
  • the term “'electrochemically active mate ⁇ als” includes the positive and negative electrodes and the electrolyte
  • the "collector assembly volume” includes the collector nail, seal, inner cover, washer, spurs and any void volume between the bottom surface of the negative cover and the seal (indicated by the cross-hatched area in Figure 3C)
  • the “container volume” includes the volume of the can, label, negative cover, void volume between the label and negative cover, positive cover, and void volume between the positive cover and can (shown by the cross-hatched area m Figure 3D) If the label extends onto and into contact with the negative cover (outer cover 45), the void volume present between the label and negative cover is included in the container volume, and therefore is also considered as part of the total volume Otherwise, that void volume is not included in either of the container volume or the total volume.
  • the sum total of the "internal volume”, “collector assembly volume”, and “container volume” is equal to the “total volume”. Accordingly, the internal volume available for electrochemically active mate ⁇ als can be confirmed by measu ⁇ ng the collector assembly volume and container volume and subtracting the collector assembly volume and the container volume from the measured total volume of the battery.
  • the present invention provides an electrochemical cell comp ⁇ sing a can for containing electrochemically active mate ⁇ als including positive and negative electrodes and an electrolyte, the can having an open end, a closed end with an end wall extending across the closed end, and side walls extending between the open and closed ends; a first cover positioned across the open end; and a pressure relief mechanism formed in a surface of the can
  • the present invention provides a method of prepa ⁇ ng an electrochemical cell comp ⁇ sing the steps of: forming a can having an open end and a closed end; forming a pressure relief mechanism m a surface of the can; dispensing electrochemically active mate ⁇ als in the can; and sealing a first cover across the open end of the can.
  • the pressure relief mechanism is preferably formed m the end wall of the can, and preferably includes an arc-shaped groove formed in a surface of the end wall of the can
  • a second cover is preferably positioned on the end wall of the can to be in elect ⁇ cal contact therewith and to extend over the pressure relief mechanism.
  • the cell is preferably a cy nd ⁇ cal cell.
  • a collector assembly may be employed that has a significantly lower profile and thereby occupies significantly less space within an electrochemical cell. Furthermore, this arrangement may enable cell constructions exhibiting lower water loss over time than p ⁇ or assemblies, thereby increasing the cell's shelf life.
  • An additional advantage of the invention is that a reliable pressure relief mechanism can be provided that does not occupy a significant percentage of the available cell volume Yet another advantage is that the cell constructions may be simpler to manufacture and iequire less mate ⁇ als, thereby possibly having lower manufactu ⁇ ng costs Moreover, cell constructions are enabled that require less radial compressive force to be applied by the can to adequately seal the cell, thereby allowing for the use of a can having thinner side walls, and thus resulting in greater internal cell volume
  • Figure 1 is a cross section of a conventional C sized alkaline electrochemical cell
  • Figure 2A is a table showing the relative total battery volumes and internal cell volumes available for electrochemically active mate ⁇ als, as measured for those batte ⁇ es that were commercially available at the p ⁇ o ⁇ ty date of this application,
  • Figure 2B is a table showing the relative total battery volumes and collector assembly volumes as measured for those batte ⁇ es that were commercially available as provided in Figure 2A,
  • Figures 3A-3D are cross sections of a conventional C sized alkaline electrochemical cell that illustrate the total battery and va ⁇ ous component volumes
  • Figure 4A is a cross section of a C sized alkaline electrochemical cell constructed in accordance with a first preferred embodiment of the present invention having a rollback cover, an annular L-shaped (J-shaped) seal, and a pressure relief mechanism formed in the can bottom surface;
  • Figure 4B is a cross section of the top portion of a C sized alkaline electrochemical cell constructed m accordance with a first preferred embodiment of the present invention having a rollback cover and including an L-shaped annular seal;
  • Figure 4C is an exploded perspective view of the electrochemical cell shown in Figure 4A illustrating assembly of the collector seal and cover assembly;
  • FIG. 5 is a bottom view of a battery can having a pressure relief mechanism formed in the closed end of the can, in accordance with an embodiment of the present invention
  • Figure 6 is a cross-sectional view taken along line X-X of the can vent shown in Figure 5
  • Figure 7 is a cross section of a C sized alkaline electrochemical cell having a beverage can-type construction according to a second preferred embodiment of the present invention
  • Figure 8A is a partially exploded perspective view of the battery shown in Figure 7;
  • Figures 8B and 8C are cross-sectional views of a portion of the battery shown in Figure 7 illustrating the process for forming the beverage can-type construction
  • Figure 8D is an enlarged cross-sectional view of a portion of the battery shown in Figure 7;
  • Figure 9 is a cross section of a C sized alkaline electrochemical cell having a beverage can-type construction according to a second preferred embodiment of the present invention;
  • Figure 10A is a table showing the calculated total and internal cell volume for va ⁇ ous batte ⁇ es constructed in accordance with the present invention
  • Figure 10B is a table showing the calculated total volume and collector assembly volume for va ⁇ ous batte ⁇ es constructed in accordance with the present invention
  • Figure 11 is a cross section of a C sized alkaline electrochemical cell having a collector feed through construction according to a third preferred embodiment of the present invention
  • Figure 12 is an exploded assembly view of the electrochemical cell shown in
  • Figure 13 is a flow diagram illustrating a method of assembly of the electrochemical cell shown in Figures 11 and 12.
  • a p ⁇ mary objective of the present invention is to increase the internal volume available in a battery for containing the electrochemically active mate ⁇ als, without det ⁇ mentally decreasing the reliability of the pressure relief mechanism provided in the battery and without increasing the likelihood that the battery would otherwise leak.
  • a pressure relief mechanism a surface of the can, more preferably m the closed end of the can, for releasing internal pressure from within the can when the internal pressure becomes excessive.
  • the pressure relief mechanism is preferably formed by providing a groove in the surface of can.
  • This groove may be formed, for example, by coining a bottom surface of the can, cutting a groove in the bottom surface, or moulding the groove in the bottom surface of the can at the time the positive electrode is moulded.
  • a suitable thickness of the metal at the bottom of the coined groove is approximately 50 ⁇ m (2 mils).
  • a suitable thickness is approximately 75 ⁇ m (3 mils).
  • the groove may be formed as an arc of approximately 300 degrees. By keeping the shape formed by the groove slightly open, the pressure relief mechanism will have an effective hinge.
  • the pressure relief mechanism is preferably positioned beneath an outer cover so as to prevent the electrochemical materials from dangerously spraying directly outward from the battery upon rupture. Also, if the battery were used in series with another battery such that the end of the positive terminal of the battery is pressed against the negative terminal of another battery, the provision of an outer cover over pressure relief mechanism allows the mechanism to bow outwardly under the positive protrusion and ultimately rupture. If no outer cover is present in such circumstances, the contact between the two batteries may otherwise prevent the pressure relief mechanism from rupturing. Furthermore, if an outer cover is not provided over the pressure relief mechanism, the pressure relief mechanism at the positive end of the battery may be more susceptible to damage.
  • the outer cover also shields the pressure relief mechanism from the corrosive effects of the ambient environment and therefore reduces the possibility of premature venting and/or leaking.
  • the pressure relief mechanism is formed under an outer cover at the closed end of the battery can.
  • the outer cover preferably serves as the positive external battery terminal.
  • a battery in a preferred embodiment, comprises a can for containing electrochemical materials including positive and negative electrodes and an electrolyte, the can having a first end, an open second end, side walls extending between the first and second ends, and an end wall extending across the first end; a pressure relief mechanism formed in the end wall of the can for releasing internal pressure from within the can when the internal pressure becomes excessive; a first outer cover positioned on the end wall of the can to be in electrical contact therewith and to extend over the pressure relief mechanism; a second outer cover positioned across the open second end of the can; and an insulator disposed between the can and the second outer cover for electrically insulating the can from the second outer cover.
  • the size of the area circumscribed by the groove is preferably selected such that upon rupture due to excessive internal pressure, the area within the groove may pivot at the hinge within the positive protrusion of the outer cover without interference from the outer cover.
  • the size of the area defined by the groove, as well as the selected depth of the groove depends upon the diameter of the can and the pressure at which the pressure relief mechanism is to rupture and allow internally-generated gases to escape.
  • an electrochemical cell in a first preferred embodiment, includes a collector assembly which closes and seals the open end of a can.
  • the collector assembly includes a collector, such as a nail, disposed in electrical contact with an electrode, for example the negative electrode.
  • a cover Also included in the collector assembly is a cover.
  • An annular seal having an L-shaped cross section is disposed between the can and the cover for electrically insulating the can from the cover and creating a seal between the cover and the can.
  • the seal may further include an extended vertical member to form a J-shaped cross section.
  • the pressure relief mechanism is present in a surface of the can.
  • the open end of the can is sealed by placing an annular seal, having either a J- shaped or an L-shaped cross section, in the open end of the can.
  • the seal is of nylon, although other suitable materials could be used.
  • a bead is preferably formed around the circumference of the open end of the can
  • the seal is preferably coated with a mate ⁇ al such as asphalt to protect it from the electrochemically active materials and to provide a better seal
  • the annular seal may be configured with a J-shaped cross section which includes an extended vertical wall at the outermost pe ⁇ meter thereof, a shorter vertical wall at the radially inward side of the seal and has a ho ⁇ zontal base member formed between the vertical walls With the presence of the short vertical section, the annular seal is referred to herein as having either a J-shaped or L-shaped cross section It should be appreciated that the J-shaped seal could also be configured absent the short vertical section to form a plain L-shaped cross section.
  • the electrochemical cell may be assembled as follows
  • the can preferably a cylmd ⁇ cal can, is formed with side walls defining the open end and preferably a bead for receiving internally disposed battery mate ⁇ als p ⁇ or to closure of the can Disposed within the can are the active electrochemical cell mate ⁇ als including the positive and negative electrodes and the electrolyte, as well as the separator, and any additives.
  • the outer cover, with a collector fastened to the bottom surface of the cover, and the annular seal, are assembled and inserted into the open end of the can to seal and close the can
  • the collector preferably a nail
  • the collector and cover are engaged with the seal to form a collector assembly, and the collector assembly is inserted in the can such that the preferably rolled back pe ⁇ pheral edge of the outer cover is disposed against the inside wall of the annular seal above the bead, which supports the seal
  • the collector assembly is forcibly disposed within the open end of the can to snugly engage and close the can opening.
  • the outer edge of the can is preferably c ⁇ mped inward to axially force and hold the seal and outer cover in place.
  • the inside surface of the outer cover and at least a top portion ot the collector are coated with an anti-corrosion coating
  • the anti-corrosion coating includes mate ⁇ als that are electrochemically compatible with the anode Examples of such electrochemically compatible mate ⁇ als include epoxy, Teflon ® , polyolefins.
  • the coating may be sprayed or painted on and preferably covers that portion of the inside surface of the outer cover and collector which is exposed to the active mate ⁇ als in the void region above the positive and negative electrodes of the cell It should also be appreciated that the mside surface of the cover could be plated with tin, copper, or other similarly electrochemically compatible mate ⁇ als By providing an anti- corrosion coating, any corrosion of the outer cover and collector may be reduced and/or prevented, which advantageously reduces the amount of gassing which may otherwise occur within the electrochemical cell. Reduction in gassing within the cell results in reduced internal pressure build-up.
  • an electrochemical cell comp ⁇ ses a can for containing electrochemically active mate ⁇ als including at least positive and negative electrodes and an electrolyte, the can having an open end and a closed end, and side walls extending between the open end and closed end; a first outer cover positioned across the open end of the can; a collector elect ⁇ cally coupled to the first outer cover and extending internally within the can to elect ⁇ cally contact one of the positive and negative electrodes; and an annular seal having an L- shaped cross section disposed between the can and the first outer cover for elect ⁇ cally insulating the can from the first outer cover and creating a seal between the first outer cover and the can.
  • the seal may further include an extended vertical member to form a J-shaped cross section.
  • a pressure relief mechanism is formed in a surface of the can for releasing internal pressure from withm the can when the internal pressure becomes excessive.
  • an electrochemical cell in a second preferred embodiment, includes a collector assembly which closes and seals the open end of a can
  • the collector assembly includes a collector, such as a nail, disposed in elect ⁇ cal contact with an electrode, for example the negative electrode
  • a cover An insulating mate ⁇ al is deposited directly on the cover or the can, or both, so as to elect ⁇ cally insulate the can from the cover when the cover is assembled to the can The cover is sealed across the open end of the can to form a double seam closure
  • the pressure relief mechanism is present in a surface of the can
  • the cover of the collector assembly is connected and sealed to the open top end of the can to form a double seam closure in which the can is elect ⁇ cally insulated from the cover
  • a beverage can-type sealing technique is used to form the closure
  • a collector such as a nail is elect ⁇ cally connected, preferably by welding, to the inner surface of the cover
  • a coating of elect ⁇ cally insulating mate ⁇ al such as an epoxy, nylon, Teflon®, or vinyl, is deposited on the cover or the can, or both.
  • the inner surface of the cover, as well as the pe ⁇ pheral portion of the upper surface of the cover is coated with a layer of the elect ⁇ cal insulation mate ⁇ al.
  • the portion of the collector that extends within the void area between the bottom of the cover and the top surface of the electrode/electrolyte mixture, is preferably also coated with the elect ⁇ cal insulation
  • the inner and outer surfaces of the can are also coated m the region of the open end of the can.
  • Such coatings may be applied directly to the can and cover, for example by spraying, dipping, or electrostatic deposition.
  • the coating of elect ⁇ cally insulating mate ⁇ al may be applied either to the cover or to the can, or to both the cover and the can, by any suitable means provided that it forms an elect ⁇ cally insulating seal between the cover and the can By providing such a coating, the cover may be elect ⁇ cally insulated from the can.
  • the insulation coating By applying the insulation coating to the areas of the can, cover and collector nail within the battery that are proximate the void area within the battery's internal volume, those areas may be protected from corrosion While a coating consisting of a single layer of the epoxy, nylon, Teflon®, or vinyl mate ⁇ als noted above will function to prevent such corrosion, it is conceivable that the coating may be applied using layers of two different mate ⁇ als or made of single layers of different mate ⁇ als applied to different regions of the components For example, the penpheral region of the cover may be coated with a single layer of mate ⁇ al that functions both as an elect ⁇ cal insulator and an anti-corrosion layer, while the central portion on the inner surface of the cover may be coated with a single layer of a mate ⁇ al that functions as an anti-corrosion layer but does not also function as an elect ⁇ cal insulator Such mate ⁇ als may include, for example, asphalt or polyamide.
  • either one of the can or cover may be coated with a mate ⁇ al that functions as both an elect ⁇ cal insulator and anti-corrosion layer, while the other of these two components may be coated with a mate ⁇ al that functions only as an anti-corrosion layer.
  • the elect ⁇ cal insulation would be provided where needed (i.e., between the cover/can interface), while the surfaces partially defining the void area in the internal volume of the cell will still be protected from the corrosive effects of the electrochemical mate ⁇ als within the cell
  • mate ⁇ als may be selected that are lower in cost or exhibit optimal characte ⁇ stics for the intended function.
  • a conventional sealant may be applied to the bottom surface of the pe ⁇ pheral edge of the cover.
  • the cover is placed over the open end of the can.
  • the can has an outward extending flange formed at its open end.
  • the cover preferably has a slightly curved pe ⁇ pheral edge that conforms to the shape of the flange.
  • a seaming chuck is placed on the cover, such that an annular downward extending portion of the seaming chuck is received by an annular recess formed in the cover.
  • a first seaming roll is moved in a radial direction toward the pe ⁇ pheral edge of the cover. As the first seaming roll is moved toward the pe ⁇ pheral edge and flange, its curved surface causes the pe ⁇ pheral edge to be folded around the flange.
  • the seaming chuck, can, and cover are rotated about a central axis, such that the pe ⁇ pheral edge is folded around the flange about the entire circumference of the can Furthermore, as the fust seaming roll continues to move radially inward, the flange and pe ⁇ pheral edge are folded downward After the pe ⁇ pheral edge and the flange have been folded into this position, the first seaming roll is moved away from the can, and a second seaming roll is then moved radially inward toward the flange and penpheral edge
  • the second seaming roll has a different profile than the first seaming roll
  • the second seaming roll applies sufficient force against the flange and pe ⁇ pheral edge to press and flatten the folded flange and pe ⁇ pheral edge against the exte ⁇ or surface of the can, which is supported by the seaming chuck As a result of this process, the pe ⁇ pheral edge of the can is folded around and under the flange and is
  • a D sized can constructed m accordance with this embodiment of the present invention was filled with water as was a D sized can constructed with a conventional seal, such as that illustrated in Figure 1.
  • the two cans were maintained at 71°C and weighed over time to determine the amount of water lost from the cans.
  • the conventional construction lost 270 mg per week, and the construction in accordance with the present invention did not lose any weight over the same time pe ⁇ od.
  • the beverage can-type construction utilises minimal space m the battery inte ⁇ or, reduces the number of process steps required to manufacture a battery, and significantly reduces the cost of mate ⁇ als and the cost of the manufactu ⁇ ng process. Furthermore, the thickness of the can walls may be significantly reduced, for example to 150 ⁇ m (6 mils) or less. As a result, the internal volume available for containing the electrochemically active mate ⁇ als may be increased.
  • the percentage of the total battery volume that may be used to contain the electrochemically active mate ⁇ als may be as high as 97 volume percent, while collector assembly volume may be as low as 1 6 volume percent
  • the volumes of batteries of othei sizes are included in the table shown in Figures 10A and 10B
  • the battery can is first formed as a tube with two open ends
  • the tube may for example be extruded, seam elded, soldered or cemented, using conventional techniques
  • the tube may be formed for example of steel, aluminium, or plastic
  • the tube defines the side walls of the can
  • a first open end of the tube is then sealed by secu ⁇ ng a cover thereto using the beverage can sealing technique outlined above, with the exception that no elect ⁇ cal insulation is required between this cover and the side walls
  • a positive contact terminal may be welded or otherwise secured to the outer surface of the cover
  • the battery may then be filled and the cover of a collector assembly may be secured to the second open end of the can in the same manner as desc ⁇ bed above.
  • the cover of the collector assembly may be sealed to the tube before the tube is filled and sealed to the other cover
  • a battery comp ⁇ ses a can for containing electrochemically active mate ⁇ als including at least positive and negative electrodes and an electrolyte, the can having a first end, an open second end, side walls extending between the first and second ends, and an end wall extending across the first end, the can further having a flange that extends outward from the open second end of the can towards the first end, a cover for sealing the open end of the can, the cover having a pe ⁇ pheral edge that extends over and around the flange and is c ⁇ mped between the flange and an exte ⁇ or surface of the side walls of the can; and elect ⁇ cal insulation provided between the flange and the pe ⁇ pheral edge of the cover and between the can and the pe ⁇ pheral edge
  • the elect ⁇ cal insulating mate ⁇ al is preferably provided in the form of a coating deposited directly on at least one of the can and the outer cover.
  • an electrochemical cell includes a collector assembh which closes and seals the open end of a can
  • the collector assembly includes a collector, such as a nail, disposed in elect ⁇ cal contact with an electrode, for example the negative electrode
  • a cover having an aperture preferably formed centrally in the cover. The collector is disposed in and extends through the aperture in the cover.
  • a dielect ⁇ c insulating mate ⁇ al is disposed between the collector and the cover to provide dielect ⁇ c insulation therebetween Accordingly, the collector nail is elect ⁇ cally isolated from the cover.
  • the pressure relief mechanism is present in a surface of the can.
  • the dielect ⁇ c insulating mate ⁇ al may be an organic macromolecular mate ⁇ al, such as an organic polymer. Suitable mate ⁇ als include epoxy, rubber, and nylon. Other dielect ⁇ c mate ⁇ als may be used that are resistant to the electrolyte used. For alkaline cells, preferably the dielect ⁇ c mate ⁇ al is resistant to attack by potassium hydroxide (KOH) and is non-corrosive in the presence of potassium hydroxide.
  • KOH potassium hydroxide
  • the dielect ⁇ c insulating material may be assembled to the collector assembly as explained further below.
  • the cover of the collector assembly is connected and sealed to the open top end of the can, preferably by forming a double seam closure by a beverage can-type sealing technique.
  • the can preferably has an outward extending flange formed at its open end.
  • the cover preferably has a slightly curved pe ⁇ pheral edge that conforms to the shape of the flange.
  • the battery can is first formed as a tube with two open ends.
  • the tube may for example be extruded, seam welded, soldered or cemented, using conventional techniques.
  • the tube may be formed for example of steel, aluminium, or plastic.
  • the tube defines the side walls of the can.
  • a first open end of the tube is then sealed by secu ⁇ ng a cover thereto using the beverage can sealing technique outlined above
  • a positive contact terminal may be welded or otherwise secured to the outer surface of the cover
  • the battery may then be filled and the cover of a collector assembly may be secured to the second open end of the can in the same manner as desc ⁇ bed above Alternatively, the cover of the collector assembly may be sealed to the tube before the tube is filled and sealed to the other cover
  • the electrochemical cell according to the third preferred embodiment allows for a direct connection between the can and the cover, which preferably provides a pressure seal therebetween, but does not require elect ⁇ cal isolation between the cover and the side walls of the can.
  • the collector preferably a nail
  • the collector is dielect ⁇ cally insulated from the cover such that the negative and positive terminals of the electrochemical cell are elect ⁇ cally isolated from one another
  • a sealant be applied at the closure joining the can to the cover to assist in the sealing of the cover to the can.
  • a conventional sealant may be applied to the bottom surface of the pe ⁇ pheral edge of the cover.
  • the electrochemical cell preferably further includes an outer cover in elect ⁇ cal contact with the collector.
  • the outer cover may be welded by spot weld or otherwise elect ⁇ cally connected to the collector
  • a dielect ⁇ c mate ⁇ al such as annular pad is disposed between the outer cover and the inner cover.
  • Suitable dielect ⁇ c mate ⁇ als include nylon, other elastome ⁇ c mate ⁇ als, rubber, and epoxy, which may be applied on the top surface of the inner cover or on the bottom surface of the outer cover Accordingly, an acceptable standard battery terminal may be provided, preferably as the negative terminal, at the collector end of the electrochemical cell
  • the assembly of an electrochemical cell according to the third preferred embodiment is illustrated in the assembly view of Figure 12 and is further illustrated in the flow diagram of Figure 13.
  • the preferred method of assembly includes providing a can formed with a closed bottom end and open top end, and disposing into the can the active electrochemical materials including the negative electrode, the positive electrode, and an electrolyte, as well as the separator and other cell additives. Once the active electrochemical cell materials are disposed within the can, the can is ready for closure and sealing with the collector assembly.
  • the collector assembly Prior to closing the can, the collector assembly is assembled by first disposing the collector, preferably a nail, within an aperture formed in the cover, preferably along with a ring or disc of insulating material, so that the collector is disposed in the opening of the insulating ring.
  • the insulating ring is preferably formed of a material which provides dielectric insulation and can be heated to reform and settle between the cover and the collector, for example epoxy.
  • other organic macromolecular dielectric insulation materials may be used in place of epoxy, such as a rubber grommet, an elastomeric material, or other dielectric materials that may form adequate insulation between the collector and the cover.
  • a recess is formed in the top surface of the cover, centred about the aperture.
  • the ring of insulating material may be disposed in the recess on top of the cover and the top head of a collector nail may be disposed thereabove.
  • the insulating ring may assembled to the collector nail and cover, and the insulating ring heated to a temperature sufficiently high enough to melt the ring such that the ring reforms and flows into the aperture in the cover to provide continuous dielectric insulation between the collector nail and the cover.
  • a temperature of 20°C to 200°C for a time of a few seconds to twenty-four hours may be adequate to reform and cure the insulating material.
  • the insulated material is preferably cooled.
  • the collector nail is centred in the aperture such that the nail does not contact the cover.
  • an electrical dielectric insulating pad such as an annular dielectric pad is disposed on top of the cover so as to extend radially outward from the perimeter of the nail.
  • a conductive negative cover is then preferably disposed on top of the collector nail and pad, and is welded or otherwise formed in electrical contact with the collector nail.
  • Can closure preferably employs a double seam closure, although other suitable can closure techniques may be used.
  • a second cover is connected to the closed end of the can, preferably overlying a pressure relief mechanism.
  • the percentage of the total battery volume that may be used to contain the electrochemically active materials may be as high as 96 volume percent, while collector assembly volume may be as low as 2.6 volume percent.
  • the volumes of batteries of other sizes are included in the table shown in Figures 10A and 10B.
  • an electrochemical cell comprises a can for containing electrochemically active materials including at least positive and negative electrodes and an electrolyte, the can having an open end, a closed end, and side walls extending between the open and closed ends; a cover positioned across the open end of the can and connected to the can, the cover having an aperture extending therethrough; a current collector extending through the aperture in the cover and extending internally within the can to electrically contact one of the positive and negative electrodes; and an insulating material disposed between the collector and the cover for electrically insulating the collector from the cover and creating a seal between the collector and the cover.
  • a pressure relief mechanism is formed in a surface of the can for releasing internal pressure from within the can when the internal pressure becomes excessive.
  • the electrochemical cell preferably includes a first contact terminal electrically coupled to the collector and a dielectric mate ⁇ al disposed between the first contact terminal and the cover for elect ⁇ cally insulating the cover from the first contact terminal
  • the can may be formed to have the protrusion for the positive battery terminal formed directly in the closed end of the can
  • the void space existing between the closed end of the can and the positive outer cover may be used to contain electrochemically active mate ⁇ als or otherw lse provide space for the collection of gases, which otherwise must be provided within the cell
  • the increase in cell volume obtained by forming the protrusion directly in the bottom of the can is not provided in the table in Figure 10A, it will be appreciated by those skilled in the art that the internal volume is typically one percent greater than the volumes listed for the cells listed in the table which are formed with a separate cover
  • a p ⁇ nt layer may be applied directly onto the exte ⁇ or surface of the battery can to provide a label.
  • the label directly onto the exte ⁇ or of the can as a p ⁇ nt layer, rather than with a label substrate, the internal volume of the cell may be further increased since one does not have to account for the thickness of a label substrate to construct a cell that meets the ANSI or other exte ⁇ or size standards
  • directly is meant that no label substrate is present between the p ⁇ nt layer and the external surface of the battery can.
  • Current label substrates have thicknesses on the order of 75 ⁇ m (3 mils).
  • these conventional labels effectively add about 250 ⁇ m (10 mils) to the diameter and of 330 ⁇ m (13 mils) to the c ⁇ mp height of the battery.
  • the battery can must have a diameter that is selected to accommodate the thickness of the label seam m order to meet the ANSI or other size standards.
  • the diameter of the can may be correspondingly increased approximately 250 ⁇ m (10 mils). Such an increase in the diameter of the can significantly increases the internal volume of the battery.
  • the internal volume of the battenes with substrate labels could be further increased, for example by 2 percent (1.02 cc) for a D sized battery, 2.6 percent (0.65 cc) for a C sized battery, 3.9 percent (0 202 cc) for an A A sized cell and 5 5 percent (0 195 cc) for an AAA sized battery, if the labels were p ⁇ nted directly on the exte ⁇ or of the can
  • Labels may also be pnnted on the can using transfer p ⁇ nting techniques in which the label image is first p ⁇ nted on a transfer medium and then transferred directly onto the can exte ⁇ or Distorted lithography may also be used whereby intentionally distorted graphics are p ⁇ nted on flat mate ⁇ al so as to account for subsequent stress distortions of the flat mate ⁇ al as it is shaped into the tube or cylinder of the cell can
  • the exte ⁇ or surface of the can is preferably cleaned
  • a base coat of p ⁇ mer may be applied to the exte ⁇ or surface of the can
  • the p ⁇ nt layer is then applied directly on top of the base coat on the can by known lithographic p ⁇ nting techniques
  • the label may further comp ⁇ se an elect ⁇ cally insulating overcoat
  • a varnish overcoat is preferably applied over the p ⁇ nt layer to cover and protect the p ⁇ nt layer, and also to serve as an elect ⁇ cally insulating layer
  • the p ⁇ nted label may be cured with the use of high temperature heating or ultraviolet radiation techniques.
  • the thickness of the label may be significantly reduced compared with a conventional label on a substrate, to a maximum thickness of approximately 13 ⁇ m (0 5 mils)
  • the p ⁇ nted label has a base coat layer of a thickness in the range of about 2 5 to 5 ⁇ m (0.1 to 0 2 mil), a p ⁇ nt layer of a thickness of approximately 2.5 ⁇ m (0.1 mil), and a varnish overcoat layer of a thickness in the range of about 2.5 to 5 ⁇ m (0.1 to 0.2 mil).
  • the can is able to be increased m diameter, thereby offe ⁇ ng a further increase in available volume for active cell mate ⁇ als while maintaining a predetermined outside diameter of the battery
  • a battery can may be made with thinner walls, on the order of 100-200 ⁇ m (4-8 mils), since the construction techniques outlined below do not require the thicker walls that are required in conventional batte ⁇ es to ensure a sufficient c ⁇ mp and seal
  • a label may be lithographed directly onto the exte ⁇ or surface of the battery can
  • the internal volume of the cell may be further increased since one does not have to account for the thickness of the label substrate to construct a cell that meets the ANSI exte ⁇ or size standards
  • inventive constructions in batte ⁇ es utilising other electrochemical systems
  • inventive constructions may be employed in p ⁇ mary systems such as carbon-zmc and lithium based batte ⁇ es and in rechargeable batte ⁇ es, such as NiCd, metal hyd ⁇ de, and Li based batte ⁇ es.
  • certain constructions of the present invention may be used in raw cells (i.e., cells without a label as used m battery packs or multi-cell batte ⁇ es) Additionally, although the present invention has been desc ⁇ bed above in connection with cylmd ⁇ cal batte ⁇ es, certain constructions of the present invention may be employed m constructing p ⁇ smatic cells.
  • FIG. 4A through 4C An electrochemical battery 300 constructed in accordance with a first preferred embodiment of the present invention is shown in Figures 4A through 4C.
  • a pressure relief mechanism 370 is formed in the closed end 314 of can 312.
  • the pressure relief mechanism 370 is formed by providing a groove 372 m the bottom surface of can 312, as shown in Figures 5 and 6.
  • the groove is formed as an arc of approximately 300 degrees.
  • the shape formed by the groove is slightly open so that the pressure relief mechanism has an effective hinge.
  • the size of the area circumsc ⁇ bed by the groove 372 is selected such that upon rupture due to excessive internal pressure, the area withm the groove 372 may pivot at the hmge withm the positive protrusion of outer cover 311 without interference from outer cover 311
  • the pressure relief mechanism 370 is positioned beneath outer cover 311 so as to prevent the electrochemical mate ⁇ als from dangerously spraying directly outward from the battery upon rupture
  • the open end of can 312 is sealed by placing either a nylon seal 330 having a J- shaped cross section or a nylon seal 330' having an L-shaped cross section in the open end of can 312, inserting a negative outer cover 345 having a rolled back pe ⁇ pheral edge 347 within nylon seal 330 or 330', and subsequently c ⁇ mpmg the outer edge 313 of can 312 to hold seal 330 or 330' and cover 345 in place
  • a bead 316 is formed around the circumference of the open end of can 312
  • Nylon seal 330 or 330' is coated with asphalt to protect it from the electrochemically active mate ⁇ als and to provide a better seal
  • the annular nylon seal 330 is shown configured with a J-shaped cross section which includes an extended vertical wall 332 at the outermost pe ⁇ meter thereof, a shorter vertical wall 336 at the radially inward side of the seal and has a ho ⁇ zontal base member 334 formed between the vertical walls 332 and 336
  • the J-shaped nylon seal 330 is configured absent the short vertical section 336 to form a plain L-shaped cross section
  • the cy nd ⁇ cal can 312 is formed with side walls defining the open end and bead 316 for receiving internally disposed battery mate ⁇ als p ⁇ or to closure of the can Disposed withm can 312 are the active electrochemical cell mate ⁇ als including the positive and negative electrodes and the electrolyte, as well as the separator, and any additives
  • the outer cover 345, with the collector nail 340 welded or otherwise fastened to the bottom surface of cover 345, and annular nylon seal 330 are assembled and inserted into the open end of can 312 to seal and close can 312.
  • the collector nail 340 is preferably welded via spot weld 342 to the bottom side of outer cover 345 Together, collector nail 340 and cover 345 are engaged with seal 330 to form the collector assembly, and the collector assembly is inserted in can 312 such that the rolled back peripheral edge 347 of outer cover 345 is disposed against the inside wall of annular seal 330 above bead 316 which supports seal 330.
  • the collector assembly is forcibly disposed within the open end of can 312 to snugly engage and close the can opening. Thereafter, the outer edge 313 of can 12 is crimped inward to axially force and hold seal 330 and outer cover 345 in place. Referring back to Figure 4B, the inside surface of outer cover 345 and at least a top portion of collector nail 340 are further shown coated with an anti-corrosion coating 344.
  • FIG. 7 An electrochemical battery 400 constructed in accordance with a second preferred embodiment of the present invention is shown in Figures 7 through 9.
  • a negative outer cover 445 is secured to the open end of can 412 using a beverage can- type sealing technique.
  • the method of making a battery having the construction shown in Figure 7 is described below with reference to Figures 8A-8D.
  • a collector nail 440 Prior to attaching negative outer cover 445 to the open end of can 412, a collector nail 440 is welded to the inner surface of cover 445.
  • the inner surface of cover 445, as well as the peripheral portion of the upper surface of cover 445 is coated with a layer 475 of electrical insulation material.
  • the portion of collector nail 440 that extends within the void area between the bottom of cover 445 and the top surface of the negative electrode/electrolyte mixture 120, is also coated with the electrical insulation.
  • negative outer cover 445 is electrically insulated from can 412.
  • sealant 473 is applied to the bottom surface of peripheral edge 470 of cover 445. Once the sealing procedure is complete, sealant 473 migrates to the positions shown in Figure 8D.
  • outer cover 445 is placed over the open end of can 412 as shown in Figure 8B.
  • Can 412 has an outward extending flange 450 formed at its open end.
  • outer cover 445 has a slightly curved peripheral edge 470 that conforms to the shape of flange 450.
  • a first seaming roll 510 is moved in a radial direction toward the pe ⁇ pheral edge 470 of outer cover 445 As first seaming roll 510 is moved toward pe ⁇ pheral edge 470 and flange 450, its curved surface causes pe ⁇ pheral edge 470 to be folded around flange 450.
  • first seaming roll 510 moves radially inward, seaming chuck 500, can 412, and outer cover 445 are rotated about a central axis, such that pe ⁇ pheral edge 470 is folded around flange 450 about the entire circumference of can 412 Further, as first seaming roll 510 continues to move radially inward, flange 450 and pe ⁇ pheral edge 470 are folded downward to the position shown in Figure 8C.
  • first seaming roll 510 is moved away from can 412, and a second seaming roll 520 is then moved radially inward toward flange 450 and pe ⁇ pheral edge 470.
  • Second seaming roll 520 has a different profile than first seaming roll 510. Second seaming roll 520 applies sufficient force against flange 450 and pe ⁇ pheral edge 470 to press and flatten the folded flange and pe ⁇ pheral edge against the exte ⁇ or surface of can 412, which is supported by seaming chuck 500.
  • the battery can is first formed as a tube with two open ends.
  • the tube defines the side walls 614 of can 612.
  • a first open end of the tube is then sealed by secu ⁇ ng an inner cover 616 thereto using the beverage can sealing technique outlined above, with the exception that no elect ⁇ cal insulation is required between inner cover 616 and side walls 614.
  • a positive outer cover 618 is welded to the outer surface of inner cover 616.
  • the battery is then filled and a negative outer cover 645 secured to the second open end of can 612 in the same manner as desc ⁇ bed above.
  • An electrochemical battery 700 constructed with a feed through collector in accordance with a third preferred embodiment of the present invention is shown in Figures 11 through 13.
  • electrochemical cell 700 includes an electrically conductive can 712 having a closed end 314 and an open end in which a low volume collector assembly 725 and outer negative cover 750 are assembled. Electrochemical cell 700 includes a positive electrode 115 in contact with the interior walls of can 712 and in contact with a separator 117 that lies between a positive electrode 115 and a negative electrode 120.
  • Electrochemical cell 700 includes a pressure relief mechanism 370 formed in the closed end 314 of can 712, which allows for employment of low volume collector assembly 725.
  • the pressure relief mechanism 370 is formed as a groove as described herein in connection with Figures 4A, 4B, 5, and 6.
  • a positive outer cover 311 is connected to the closed end of can 712 and overlies the pressure relief mechanism 370. The assembly and location of positive outer cover 311 is provided as shown and described herein in connection with Figure 4A.
  • Electrochemical cell 700 includes a collector assembly 725 which closes and seals the open end of can 712.
  • Collector assembly 725 includes a collector nail 740 disposed in electrical contact with the negative electrode 120.
  • a first or inner cover 745 having a central aperture 751 formed therein.
  • the collector nail 740 is disposed and extends through the aperture 751 in inner cover 745.
  • a dielectric insulating material 744 is disposed between collector nail 740 and first cover 745 to provide dielectric insulation therebetween. Accordingly, the collector nail 740 is electrically isolated from inner cover 745.
  • Inner cover 745 in turn is connected and sealed to the open top end of can 712. Inner cover 745 is sealed to can 712 by forming a double seam closure at the peripheral edges 450 and 470 as explained herein in connection with Figures 7-9.
  • the collector nail 740 is dielectrically insulated from inner cover 745 such that the negative and positive terminals of the electrochemical cell are elect ⁇ cally isolated from one another A sealant is applied at the closure joining the can to the cover to adequately seal the can. as explained in connection with the battery shown and desc ⁇ bed herein in connection with Figures 7-8D
  • Electrochemical cell 700 further includes an outer cover 750 in elect ⁇ cal contact with collector nail 740 Outer cover 750 is welded by spot weld 742 to collector nail 740 A dielect ⁇ c mate ⁇ al as annular pad 748 is disposed between outer negative cover 750 and inner cover 745 Accordingly, an acceptable standard battery terminal is provided at the negative end of electrochemical cell 700
  • the assembly of electrochemical cell 700 is illustrated in the assembly view of Figure 12 and is further illustrated in the flow diagram of Figure 13
  • the method 770 of assembly of electrochemical cell 700 includes providing can 712 formed with a closed bottom end and open top end
  • Step 774 includes disposing into can 712 the active electrochemical mate ⁇ als including the negative electrode, the positive electrode, and an electrolyte, as well as the separator and other cell additives
  • the collector assembly is assembled by first disposing the collector nail 740 within aperture 751 formed m inner cover 745 along with a ⁇ ng of insulating mate ⁇ al according to step 776
  • Collector nail 740 is disposed in the opening 742 of insulating ⁇ ng 744 which may include a ⁇ ng or disk of epoxy which provides dielect ⁇ c insulation and can be heated to reform and settle between the inner cover 745 and collector nail 740
  • Also shown formed in inner cover 745 is a
  • the total battery volume, collector assembly volume, and internal volume available for electrochemically active mate ⁇ al for each battery are determined by viewing a Computer Aided Design (CAD) drawing, a photograph, or an actual cross section of the battery which has been encased in epoxy and longitudinally cross- sectioned.
  • CAD Computer Aided Design
  • the use of a CAD drawing, photograph, or actual longitudinal cross section to view and measure battery dimensions allows for inclusion of all void volumes that might be present in the battery.
  • the cross-sectional view of the battery taken through its central longitudinal axis of symmetry is viewed and the entire volume is measured by geomet ⁇ c computation
  • the cross-sectional view of the battery taken through its central longitudinal axis of symmetry is viewed, and the components making up the internal volume, which includes the electrochemically active mate ⁇ als, void volumes and chemically inert mate ⁇ als (other than the collector nail) that are confined within the sealed volume of the cell, are measured by geomet ⁇ c computation.
  • the cross- sectional view of the battery taken through its central longitudinal axis of symmetry thereof is viewed, and the components making up the collector assembly volume, which include the collector nail, seal, inner cover, and any void volume defined between the bottom surface of the negative cover and the seal, are measured by geomet ⁇ c computation
  • the container volume may likewise be measured by viewing the central longitudinal cross section of the battery and computing the volume consumed by the can, label, negative cover, void volume between the label and negative cover, positive cover, and void volume between the positive cover and the can
  • the volume measurements are made by viewing a cross section of the battery taken through its longitudinal axis of symmetry This provides for an accurate volume measurement, since the battery and its components are usually axial symmet ⁇ c.
  • the battery was first potted in epoxy and, after the epoxy solidified, the potted battery and its components were ground down to the central cross section through the axis of symmetry More particularly, the battery was first potted in epoxy and then ground short of the central cross section.
  • the cross-sectional view of the battery was used to make a drawing.
  • a Mitutoyo optical comparator with QC-4000 software was used to trace the contour of the battery and its individual components to generate a drawing of the central cross section of the battery. In doing so, the battery was securely fixed in place and the contour of the battery parts were saved in a format that could later be used in solid modelling software to calculate the battery volumes of interest.
  • the drawing may be adjusted to compensate for any battery components that are not aligned exactly through the centre of the battery. This may be accomplished by using the measurements that were taken from the battery before cross sectioning the battery and those measurements taken from the disassembled identical battery.
  • the diameter and length of the current collector nail, and overall outside diameter of the battery can be modified to profile the drawing more accurately by adjusting the drawing to include the corresponding known cross-sectional dimensions to make the drawing more accurate for volume measurements.
  • the detail of the seal, cover, and crimp areas were used as they were drawn on the optical comparitor.
  • the drawing was imported into solid modelling software.
  • a solid three-dimensional volume representation was generated by rotating the contour of the cross section on both the left and right sides by one-hundred- eighty degrees (180°) about the longitudinal axis of symmetry. Accordingly, the volume of each region of interest is calculated by the software and, by rotating the left and right sides by one-hundred-eighty degrees (180°) and summing the left and right volumes together an average volume value is determined, which may be advantageous in those situations where the battery has non-symmetrical features.
  • the volumes which include any non-symmetrical features can be adjusted as necessary to obtain more accurate volume measurements.
  • Figures 10A and 10B show volumes of various different types of battery constructions that are more fully disclosed in US 60/102,951 filed 2 October 1998 and US 60/097,445 filed 21 August 1998.
  • a D sized battery constructed using the construction shown in Figure 4A has an internal volume that is 93 5 volume percent when the can walls are 250 ⁇ m (10 mils) thick, and an internal volume that is 94.9 volume percent when the can walls are 200 ⁇ m (8 mils) thick
  • a D sized battery constructed using the construction shown in Figure 4A has a collector assembly volume that is 2 percent of the total volume when the can walls are 250 ⁇ m (10 mils) thick and 200 ⁇ m (8 mils) thick
  • a D sized battery constructed using the construction shown m Figure 11 had an internal volume that was 97.0 volume percent when the can
  • a D sized battery constructed using the construction shown in Figure 11 had an internal volume that was 96 0 volume percent when the can walls were 200 ⁇ m (8 mils) thick
  • a D sized battery constructed using the construction shown in Figure 11 had a collector assembly volume that was 2.6 percent of the total volume when the can walls were 200 ⁇ m (8 mils) thick.
  • the C, AA, and AAA sized batte ⁇ es having similar construction also exhibited significant improvements in internal volume efficiency, as is apparent from the table in Figure 10A.
  • the internal volume of the batte ⁇ es with substrate labels could be further increased 2 percent (1.02 cc) for a D sized battery, 2.6 percent (0.65 cc) for a C sized battery, 3.9 percent (0.202 cc) for an AA sized cell, and 5.5 percent (0.195 cc) for an AAA sized battery, if the labels were p ⁇ nted directly on the exte ⁇ or of the can.

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Abstract

An electrochemical cell, preferably a cylindrical cell, is provided comprising: a can (312) for containing electrochemically active materials including positive and negative electrodes and an electrolyte, the can (312) having an open end, a closed end with an end wall (314) extending across the closed end, and side walls extending between the open and closed ends; a first cover (345) positioned across the open end; and a pressure relief mechanism (370) formed in a surface of the can (312), preferably an arc-shaped groove (372) formed in the end wall (314) of the can (312). A second cover (311) is preferably positioned on the end wall of the can (312) to be in electrical contact therewith and to extend over the pressure relief mechanism (370). Also provided is a method of preparing an electrochemical cell comprising the steps of: forming a can (312) having an open end and a closed end; forming a pressure relief mechanism (370) in a surface of the can (312); dispensing electrochemically active materials in the can (312); and sealing a first cover (345) across the open end of the can (312). The cell construction allows a large internal volume to be available for containing electrochemically active materials.

Description

BATTERY CONSTRUCTION HAVING PRESSURE RELEASE MECHANISM
The present invention generally relates to an electrochemical cell construction.
More particularly, the present invention relates to the containers and collector assemblies used for an electrochemical cell, such as an alkaline cell.
Figure 1 shows the construction of a conventional C sized alkaline cell 10. As shown, cell 10 includes a cylindrically shaped can 12 having an open end and a closed end. Can 12 is preferably formed of an electrically conductive material, such that an outer cover 11 welded to a bottom surface 14 at the closed end of can 12 serves as an electrical contact terminal for the cell.
Cell 10 further typically includes a first electrode material 15, which may serve as the positive electrode (also known as a cathode). The first electrode material 15 may be preformed and inserted into can 12, or may be moulded in place so as to contact the inner surfaces of the can 12. For an alkaline cell, first electrode material 15 will typically include MnO . After the first electrode 15 has been provided in can 12, a separator 17 is inserted into the space defined by first electrode 15. Separator 17 is preferably a non-woven fabric. Separator 17 is provided to maintain a physical separation of the first electrode material 15 and a mixture of electrolyte and a second electrode material 20 while allowing the transport of ions between the electrode materials.
Once separator 17 is in place within the cavity defined by first electrode 15, an electrolyte is dispensed into the space defined by separator 17, along with the mixture 20 of electrolyte and a second electrode material, which may be the negative electrode (also known as the anode). The electrolyte/second electrode mixture 20 preferably includes a gelling agent. For a typical alkaline cell, mixture 20 is formed of a mixture of an aqueous KOH electrolyte and zinc, which serves as the second electrode material. Water and additional additives may also be included in mixture 20. Once the first electrode 15, separator 17, the electrolyte, and mixture 20 have been formed inside can 12, a preassembled collector assembly 25 is inserted into the open end of can 12 Can 12 is typically slightly tapered at its open end This taper serves to support the collector assembly in a desired oπentation pπor to secuπng it in place After collector assembly 25 has been inserted, an outer cover 45 is placed over collector assembly 25 Collector assembly 25 is secured in place by radially squeezing the can against collector assembly 25 The end edge 13 of can 12 is cπmped over the peπpheral lip of collector assembly 25, thereby secuπng outer cover 45 and collector assembly 25 within the end of can 12. As descπbed further below, one function served by collector assembly 25 is to provide for a second external electπcal contact for the electrochemical cell Additionally, collector assembly 25 must seal the open end of can 12 to prevent the electrochemical mateπals therein from leaking from this cell. Additionally, collector assembly 25 must exhibit sufficient strength to withstand the physical abuse to which batteπes are typically exposed. Also, because electrochemical cells may produce hydrogen gas, collector assembly 25 may allow ternally generated hydrogen gas to permeate therethrough to escape to the exteπor of the electrochemical cell Further, collector assembly 25 should include some form of pressure relief mechanism to relieve pressure produced internally within the cell should this pressure become excessive Such conditions may occur when the electrochemical cell internally generates hydrogen gas at a rate that exceeds that at which the internally generated hydrogen gas can permeate through the collector assembly to the exteπor of the cell
The collector assembly 25 shown Figure 1 includes a seal 30, a collector nail 40, an inner cover 44, a washer 50, and a plurality of spurs 52. Seal 30 is shown as including a central hub 32 having a hole through which collector nail 40 is inserted. Seal 30 further includes a V-shaped portion 34 that may contact an upper surface 16 of first electrode 15.
Seal 30 also includes a peπpheral upstanding wall 36 that extends upward along the peπphery of seal 30 in an annular fashion Peπpheral upstanding wall 36 not only serves as a seal between the interface of collector assembly 25 and can 12, but also serves as an electπcal insulator for preventing an electπcal short from occurπng between the positive can and negative contact terminal of the cell
Inner cover 44, which is formed of a πgid metal, is provided to increase the πgidity and support the radial compression of collector assembly 25 thereby improving the sealing effectiveness As shown Figure 1, inner cover 44 is configured to contact cential hub portion 32 and peπpheral upstanding wall 36 By configuπng collector assembly 25 in this fashion, inner cover 44 serves to enable compression of central hub portion 32 by collector nail 40 while also supporting compression of peπpheral upstanding wall 36 by the inner surface of can 12
Outer cover 45 is typically made of a nickel-plated steel and is configured to extend from a region defined by the annular peπpheral upstanding wall 36 of seal 30 and to be electπcal contact with a head portion 42 of collector nail 40 Outer cover 45 may be welded to head portion 42 of collector nail 40 to prevent any loss of contact As shown m Figure 1, when collector assembly 25 is inserted into the open end of can 12, collector nail 40 penetrates deeply within the electrolyte/second electrode mixture 20 to establish sufficient electπcal contact therewith. In the example shown in Figure 1, outer cover 45 includes a peπpheral lip 47 that extends upwardly along the circumference of outer cover 45 By forming peπpheral upstanding wall 36 of seal 30 of a length greater than that of peπpheial lip 47, a portion of peπpheral upstanding wall 36 may be folded over peπpheral lip 47 duπng the cπmping process so as to prevent any portion of the upper edge 13 of can 12 from coming into contact with outer cover 45.
Seal 30 is preferably formed of nylon. In the configuration shown in Figure 1, a pressure relief mechanism is provided for enabling the relief of internal pressure when such pressure becomes excessive Further, inner cover 44 and outer cover 45 are typically provided with apertures 43 that allow the hydrogen gas to escape to the exteπor of cell 10 The mechanism shown includes an annular metal washer 50 and a plurality of spurs 52 that are provided between seal 30 and inner cover 44. Each spur 52 includes a pointed end 53 that is pressed against a thin intermediate portion 38 of seal 30. Spurs 52 are biased against the lower inner surface of inner cover 44 such that when the internal pressure of cell 10 increases and seal 30 consequently becomes deformed by pressing upward toward inner cover 44, the pointed ends 53 of spurs 52 penetrate through the thin intermediate portion 38 of seal 30 thereby rupturing seal 30 and allowing the escape of the internally-generated gas through apertures 43.
Although the above-described collector assembly 25 performs all the above- noted desirable functions satisfactorily, as apparent from its cross-sectional profile this particular collector assembly occupies a significant amount of space within the interior of the cell 10. It should be noted that the construction shown in Figure 1 is but one example of a cell construction. Other collector assemblies exist that may have lower profiles and hence occupy less space within the cell. However, such collector assemblies typically achieve this reduction in occupied volume at the expense of the sealing characteristics of the collector assembly or the performance and reliability of the pressure relief mechanism.
The measured external and internal volumes for several batteries that were commercially available at the priority date of this application are listed in the tables shown in Figures 2A and 2B. The tables list the volumes (cc) for D, C, AA, and AAA sized batteries. The collector assembly volume and the percentage of the total cell volume that constitutes the collector assembly volume is provided in Figure 2B for those commercially available batteries listed in Figure 2A. Also provided in Figure 2A is a percentage of the total cell volume that constitutes the internal volume that is available for containing the electrochemically active materials.
The "total cell volume" includes all of the volume, including any internal void spaces, of the battery. For the battery shown in Figure 1, the total volume ideally includes all of the cross-hatched area as shown in Figure 3A. The "internal volume" of the battery is represented by the cross-hatched area shown in Figure 3B. The "internal volume", as used herein, is that volume inside the cell or battery that contains the electrochemically active materials as well as any voids and chemically inert materials (other than the collector nail) that are confined within the sealed volume of the cell. Such chemically inert materials may include separators, conductors, and any inert additives in the electrodes As descπbed herein, the term "'electrochemically active mateπals" includes the positive and negative electrodes and the electrolyte The "collector assembly volume" includes the collector nail, seal, inner cover, washer, spurs and any void volume between the bottom surface of the negative cover and the seal (indicated by the cross-hatched area in Figure 3C) The "container volume" includes the volume of the can, label, negative cover, void volume between the label and negative cover, positive cover, and void volume between the positive cover and can (shown by the cross-hatched area m Figure 3D) If the label extends onto and into contact with the negative cover (outer cover 45), the void volume present between the label and negative cover is included in the container volume, and therefore is also considered as part of the total volume Otherwise, that void volume is not included in either of the container volume or the total volume.
It should be appreciated that the sum total of the "internal volume", "collector assembly volume", and "container volume" is equal to the "total volume". Accordingly, the internal volume available for electrochemically active mateπals can be confirmed by measuπng the collector assembly volume and container volume and subtracting the collector assembly volume and the container volume from the measured total volume of the battery.
Because the exteπor dimensions of the electrochemical cell are generally fixed by the Ameπcan National Standards Institute (ANSI) or other standards organisations, the greater the space occupied by the collector assembly, the less space that there is available within the cell for the electrochemical mateπals. Consequently, a reduction in the amount of electrochemical mateπals that may be provided withm the cell results in a shorter service life for the cell. It is therefore desirable to maximise the mteπor volume within an electrochemical cell that is available for the electrochemically active components.
We have now found that this may be achieved by constructing an electrochemical cell where the space occupied by the collector assembly and the space occupied by the container volume are minimised while still maintaining adequate sealing characteπstics and a reliable pressure relief mechanism
Accordingly, in a first aspect, the present invention provides an electrochemical cell compπsing a can for containing electrochemically active mateπals including positive and negative electrodes and an electrolyte, the can having an open end, a closed end with an end wall extending across the closed end, and side walls extending between the open and closed ends; a first cover positioned across the open end; and a pressure relief mechanism formed in a surface of the can
In a second aspect, the present invention provides a method of prepaπng an electrochemical cell compπsing the steps of: forming a can having an open end and a closed end; forming a pressure relief mechanism m a surface of the can; dispensing electrochemically active mateπals in the can; and sealing a first cover across the open end of the can.
The pressure relief mechanism is preferably formed m the end wall of the can, and preferably includes an arc-shaped groove formed in a surface of the end wall of the can A second cover is preferably positioned on the end wall of the can to be in electπcal contact therewith and to extend over the pressure relief mechanism. The cell is preferably a cy ndπcal cell.
Advantageously, by providing a pressure relief mechanism in a surface of the can, a collector assembly may be employed that has a significantly lower profile and thereby occupies significantly less space within an electrochemical cell. Furthermore, this arrangement may enable cell constructions exhibiting lower water loss over time than pπor assemblies, thereby increasing the cell's shelf life. An additional advantage of the invention is that a reliable pressure relief mechanism can be provided that does not occupy a significant percentage of the available cell volume Yet another advantage is that the cell constructions may be simpler to manufacture and iequire less mateπals, thereby possibly having lower manufactuπng costs Moreover, cell constructions are enabled that require less radial compressive force to be applied by the can to adequately seal the cell, thereby allowing for the use of a can having thinner side walls, and thus resulting in greater internal cell volume
The present invention will be further understood by reference to the drawings, in which
Figure 1 is a cross section of a conventional C sized alkaline electrochemical cell,
Figure 2A is a table showing the relative total battery volumes and internal cell volumes available for electrochemically active mateπals, as measured for those batteπes that were commercially available at the pπoπty date of this application,
Figure 2B is a table showing the relative total battery volumes and collector assembly volumes as measured for those batteπes that were commercially available as provided in Figure 2A,
Figures 3A-3D are cross sections of a conventional C sized alkaline electrochemical cell that illustrate the total battery and vaπous component volumes,
Figure 4A is a cross section of a C sized alkaline electrochemical cell constructed in accordance with a first preferred embodiment of the present invention having a rollback cover, an annular L-shaped (J-shaped) seal, and a pressure relief mechanism formed in the can bottom surface;
Figure 4B is a cross section of the top portion of a C sized alkaline electrochemical cell constructed m accordance with a first preferred embodiment of the present invention having a rollback cover and including an L-shaped annular seal;
Figure 4C is an exploded perspective view of the electrochemical cell shown in Figure 4A illustrating assembly of the collector seal and cover assembly;
Figure 5 is a bottom view of a battery can having a pressure relief mechanism formed in the closed end of the can, in accordance with an embodiment of the present invention,
Figure 6 is a cross-sectional view taken along line X-X of the can vent shown in Figure 5, Figure 7 is a cross section of a C sized alkaline electrochemical cell having a beverage can-type construction according to a second preferred embodiment of the present invention;
Figure 8A is a partially exploded perspective view of the battery shown in Figure 7;
Figures 8B and 8C are cross-sectional views of a portion of the battery shown in Figure 7 illustrating the process for forming the beverage can-type construction,
Figure 8D is an enlarged cross-sectional view of a portion of the battery shown in Figure 7; Figure 9 is a cross section of a C sized alkaline electrochemical cell having a beverage can-type construction according to a second preferred embodiment of the present invention;
Figure 10A is a table showing the calculated total and internal cell volume for vaπous batteπes constructed in accordance with the present invention; Figure 10B is a table showing the calculated total volume and collector assembly volume for vaπous batteπes constructed in accordance with the present invention;
Figure 11 is a cross section of a C sized alkaline electrochemical cell having a collector feed through construction according to a third preferred embodiment of the present invention; Figure 12 is an exploded assembly view of the electrochemical cell shown in
Figure 11 ; and
Figure 13 is a flow diagram illustrating a method of assembly of the electrochemical cell shown in Figures 11 and 12.
As descπbed above, a pπmary objective of the present invention is to increase the internal volume available in a battery for containing the electrochemically active mateπals, without detπmentally decreasing the reliability of the pressure relief mechanism provided in the battery and without increasing the likelihood that the battery would otherwise leak.
This may be achieved by forming a pressure relief mechanism a surface of the can, more preferably m the closed end of the can, for releasing internal pressure from within the can when the internal pressure becomes excessive. As a result, the known complex collector/seal assemblies may be replaced with a collector assembly that consumes less volume and has fewer parts. Thus, a significant improvement in internal cell volume efficiency may be obtained.
The pressure relief mechanism is preferably formed by providing a groove in the surface of can. This groove may be formed, for example, by coining a bottom surface of the can, cutting a groove in the bottom surface, or moulding the groove in the bottom surface of the can at the time the positive electrode is moulded. For an AA sized battery, a suitable thickness of the metal at the bottom of the coined groove is approximately 50 μm (2 mils). For a D sized battery, a suitable thickness is approximately 75 μm (3 mils). The groove may be formed as an arc of approximately 300 degrees. By keeping the shape formed by the groove slightly open, the pressure relief mechanism will have an effective hinge.
The pressure relief mechanism is preferably positioned beneath an outer cover so as to prevent the electrochemical materials from dangerously spraying directly outward from the battery upon rupture. Also, if the battery were used in series with another battery such that the end of the positive terminal of the battery is pressed against the negative terminal of another battery, the provision of an outer cover over pressure relief mechanism allows the mechanism to bow outwardly under the positive protrusion and ultimately rupture. If no outer cover is present in such circumstances, the contact between the two batteries may otherwise prevent the pressure relief mechanism from rupturing. Furthermore, if an outer cover is not provided over the pressure relief mechanism, the pressure relief mechanism at the positive end of the battery may be more susceptible to damage. The outer cover also shields the pressure relief mechanism from the corrosive effects of the ambient environment and therefore reduces the possibility of premature venting and/or leaking. Thus, preferably the pressure relief mechanism is formed under an outer cover at the closed end of the battery can. The outer cover preferably serves as the positive external battery terminal. Accordingly, in a preferred embodiment, a battery is provided that comprises a can for containing electrochemical materials including positive and negative electrodes and an electrolyte, the can having a first end, an open second end, side walls extending between the first and second ends, and an end wall extending across the first end; a pressure relief mechanism formed in the end wall of the can for releasing internal pressure from within the can when the internal pressure becomes excessive; a first outer cover positioned on the end wall of the can to be in electrical contact therewith and to extend over the pressure relief mechanism; a second outer cover positioned across the open second end of the can; and an insulator disposed between the can and the second outer cover for electrically insulating the can from the second outer cover.
The size of the area circumscribed by the groove is preferably selected such that upon rupture due to excessive internal pressure, the area within the groove may pivot at the hinge within the positive protrusion of the outer cover without interference from the outer cover. In general, the size of the area defined by the groove, as well as the selected depth of the groove, depends upon the diameter of the can and the pressure at which the pressure relief mechanism is to rupture and allow internally-generated gases to escape.
In a first preferred embodiment, an electrochemical cell is provided that includes a collector assembly which closes and seals the open end of a can. The collector assembly includes a collector, such as a nail, disposed in electrical contact with an electrode, for example the negative electrode. Also included in the collector assembly is a cover. An annular seal having an L-shaped cross section is disposed between the can and the cover for electrically insulating the can from the cover and creating a seal between the cover and the can. The seal may further include an extended vertical member to form a J-shaped cross section. The pressure relief mechanism is present in a surface of the can.
The open end of the can is sealed by placing an annular seal, having either a J- shaped or an L-shaped cross section, in the open end of the can. Preferably, the seal is of nylon, although other suitable materials could be used. An outer cover, preferably serving as the negative terminal, which preferably has a rolled back peπpheral edge, is inserted within the seal Subsequently the outer edge of the can may be cπmped to hold the seal and cover in place To help hold the seal in place, a bead is preferably formed around the circumference of the open end of the can The seal is preferably coated with a mateπal such as asphalt to protect it from the electrochemically active materials and to provide a better seal
The annular seal may be configured with a J-shaped cross section which includes an extended vertical wall at the outermost peπmeter thereof, a shorter vertical wall at the radially inward side of the seal and has a hoπzontal base member formed between the vertical walls With the presence of the short vertical section, the annular seal is referred to herein as having either a J-shaped or L-shaped cross section It should be appreciated that the J-shaped seal could also be configured absent the short vertical section to form a plain L-shaped cross section.
The electrochemical cell may be assembled as follows The can, preferably a cylmdπcal can, is formed with side walls defining the open end and preferably a bead for receiving internally disposed battery mateπals pπor to closure of the can Disposed within the can are the active electrochemical cell mateπals including the positive and negative electrodes and the electrolyte, as well as the separator, and any additives.
Together, the outer cover, with a collector fastened to the bottom surface of the cover, and the annular seal, are assembled and inserted into the open end of the can to seal and close the can The collector, preferably a nail, is preferably fastened to the bottom side of the outer cover by welding, such as via a spot weld. Together, the collector and cover are engaged with the seal to form a collector assembly, and the collector assembly is inserted in the can such that the preferably rolled back peπpheral edge of the outer cover is disposed against the inside wall of the annular seal above the bead, which supports the seal The collector assembly is forcibly disposed within the open end of the can to snugly engage and close the can opening. Thereafter, the outer edge of the can is preferably cπmped inward to axially force and hold the seal and outer cover in place. Preferably, the inside surface of the outer cover and at least a top portion ot the collector are coated with an anti-corrosion coating The anti-corrosion coating includes mateπals that are electrochemically compatible with the anode Examples of such electrochemically compatible mateπals include epoxy, Teflon®, polyolefins. nylon, elastomeπc mateπals, or any other inert mateπals, either alone or in combination with other mateπals The coating may be sprayed or painted on and preferably covers that portion of the inside surface of the outer cover and collector which is exposed to the active mateπals in the void region above the positive and negative electrodes of the cell It should also be appreciated that the mside surface of the cover could be plated with tin, copper, or other similarly electrochemically compatible mateπals By providing an anti- corrosion coating, any corrosion of the outer cover and collector may be reduced and/or prevented, which advantageously reduces the amount of gassing which may otherwise occur within the electrochemical cell. Reduction in gassing within the cell results in reduced internal pressure build-up.
Accordingly, m an example of the first embodiment, an electrochemical cell is provided that compπses a can for containing electrochemically active mateπals including at least positive and negative electrodes and an electrolyte, the can having an open end and a closed end, and side walls extending between the open end and closed end; a first outer cover positioned across the open end of the can; a collector electπcally coupled to the first outer cover and extending internally within the can to electπcally contact one of the positive and negative electrodes; and an annular seal having an L- shaped cross section disposed between the can and the first outer cover for electπcally insulating the can from the first outer cover and creating a seal between the first outer cover and the can. The seal may further include an extended vertical member to form a J-shaped cross section. A pressure relief mechanism is formed in a surface of the can for releasing internal pressure from withm the can when the internal pressure becomes excessive.
In a second preferred embodiment, an electrochemical cell is provided that includes a collector assembly which closes and seals the open end of a can The collector assembly includes a collector, such as a nail, disposed in electπcal contact with an electrode, for example the negative electrode Also included in the collector assembly is a cover An insulating mateπal is deposited directly on the cover or the can, or both, so as to electπcally insulate the can from the cover when the cover is assembled to the can The cover is sealed across the open end of the can to form a double seam closure The pressure relief mechanism is present in a surface of the can
The cover of the collector assembly is connected and sealed to the open top end of the can to form a double seam closure in which the can is electπcally insulated from the cover Preferably, a beverage can-type sealing technique is used to form the closure
However, pπor to attaching the cover to the open end of the can, a collector such as a nail is electπcally connected, preferably by welding, to the inner surface of the cover Next, a coating of electπcally insulating mateπal, such as an epoxy, nylon, Teflon®, or vinyl, is deposited on the cover or the can, or both. Preferably the inner surface of the cover, as well as the peπpheral portion of the upper surface of the cover, is coated with a layer of the electπcal insulation mateπal. The portion of the collector that extends within the void area between the bottom of the cover and the top surface of the electrode/electrolyte mixture, is preferably also coated with the electπcal insulation Preferably, the inner and outer surfaces of the can are also coated m the region of the open end of the can. Such coatings may be applied directly to the can and cover, for example by spraying, dipping, or electrostatic deposition. It will be appreciated that the coating of electπcally insulating mateπal may be applied either to the cover or to the can, or to both the cover and the can, by any suitable means provided that it forms an electπcally insulating seal between the cover and the can By providing such a coating, the cover may be electπcally insulated from the can.
By applying the insulation coating to the areas of the can, cover and collector nail within the battery that are proximate the void area within the battery's internal volume, those areas may be protected from corrosion While a coating consisting of a single layer of the epoxy, nylon, Teflon®, or vinyl mateπals noted above will function to prevent such corrosion, it is conceivable that the coating may be applied using layers of two different mateπals or made of single layers of different mateπals applied to different regions of the components For example, the penpheral region of the cover may be coated with a single layer of mateπal that functions both as an electπcal insulator and an anti-corrosion layer, while the central portion on the inner surface of the cover may be coated with a single layer of a mateπal that functions as an anti-corrosion layer but does not also function as an electπcal insulator Such mateπals may include, for example, asphalt or polyamide. Alternatively, either one of the can or cover may be coated with a mateπal that functions as both an electπcal insulator and anti-corrosion layer, while the other of these two components may be coated with a mateπal that functions only as an anti-corrosion layer. In this manner, the electπcal insulation would be provided where needed (i.e., between the cover/can interface), while the surfaces partially defining the void area in the internal volume of the cell will still be protected from the corrosive effects of the electrochemical mateπals within the cell Furthermore, by utilising different mateπals, mateπals may be selected that are lower in cost or exhibit optimal characteπstics for the intended function. To assist in the sealing of the cover to the can, a conventional sealant may be applied to the bottom surface of the peπpheral edge of the cover.
Once the collector has been attached to the cover and the electπcal insulation coating has been applied, the cover is placed over the open end of the can. Preferably, the can has an outward extending flange formed at its open end. Furthermore, the cover preferably has a slightly curved peπpheral edge that conforms to the shape of the flange. Once the cover has been placed over the open end of can, a seaming chuck may be used to form a double seam closure.
For example, m one embodiment a seaming chuck is placed on the cover, such that an annular downward extending portion of the seaming chuck is received by an annular recess formed in the cover. Next, a first seaming roll is moved in a radial direction toward the peπpheral edge of the cover. As the first seaming roll is moved toward the peπpheral edge and flange, its curved surface causes the peπpheral edge to be folded around the flange. Also, as the first seaming roll moves radially inward, the seaming chuck, can, and cover are rotated about a central axis, such that the peπpheral edge is folded around the flange about the entire circumference of the can Furthermore, as the fust seaming roll continues to move radially inward, the flange and peπpheral edge are folded downward After the peπpheral edge and the flange have been folded into this position, the first seaming roll is moved away from the can, and a second seaming roll is then moved radially inward toward the flange and penpheral edge The second seaming roll has a different profile than the first seaming roll The second seaming roll applies sufficient force against the flange and peπpheral edge to press and flatten the folded flange and peπpheral edge against the exteπor surface of the can, which is supported by the seaming chuck As a result of this process, the peπpheral edge of the can is folded around and under the flange and is cπmped between the flange and the exteπor surface of the walls of the can A hermetic seal is thus formed by this process
To illustrate the hermetic nature of this type of seal, a D sized can constructed m accordance with this embodiment of the present invention was filled with water as was a D sized can constructed with a conventional seal, such as that illustrated in Figure 1. The two cans were maintained at 71°C and weighed over time to determine the amount of water lost from the cans. The conventional construction lost 270 mg per week, and the construction in accordance with the present invention did not lose any weight over the same time peπod. These results were confirmed using KOH electrolyte, with the conventional construction losing 50 mg per week and the inventive construction again not losing any weight
As will be apparent to those skilled m the art, the beverage can-type construction utilises minimal space m the battery inteπor, reduces the number of process steps required to manufacture a battery, and significantly reduces the cost of mateπals and the cost of the manufactuπng process. Furthermore, the thickness of the can walls may be significantly reduced, for example to 150 μm (6 mils) or less. As a result, the internal volume available for containing the electrochemically active mateπals may be increased. For example, for a D sized battery according to the second preferred embodiment, the percentage of the total battery volume that may be used to contain the electrochemically active mateπals may be as high as 97 volume percent, while collector assembly volume may be as low as 1 6 volume percent The volumes of batteries of othei sizes are included in the table shown in Figures 10A and 10B
In a variation of the second preferred embodiment, the battery can is first formed as a tube with two open ends The tube may for example be extruded, seam elded, soldered or cemented, using conventional techniques The tube may be formed for example of steel, aluminium, or plastic The tube defines the side walls of the can A first open end of the tube is then sealed by secuπng a cover thereto using the beverage can sealing technique outlined above, with the exception that no electπcal insulation is required between this cover and the side walls A positive contact terminal may be welded or otherwise secured to the outer surface of the cover The battery may then be filled and the cover of a collector assembly may be secured to the second open end of the can in the same manner as descπbed above. Alternatively, the cover of the collector assembly may be sealed to the tube before the tube is filled and sealed to the other cover
Accordingly, in an example of the second embodiment, a battery is provided that compπses a can for containing electrochemically active mateπals including at least positive and negative electrodes and an electrolyte, the can having a first end, an open second end, side walls extending between the first and second ends, and an end wall extending across the first end, the can further having a flange that extends outward from the open second end of the can towards the first end, a cover for sealing the open end of the can, the cover having a peπpheral edge that extends over and around the flange and is cπmped between the flange and an exteπor surface of the side walls of the can; and electπcal insulation provided between the flange and the peπpheral edge of the cover and between the can and the peπpheral edge The electπcal insulating mateπal is preferably provided in the form of a coating deposited directly on at least one of the can and the outer cover. A pressure relief mechanism is formed in a surface of the can for releasing internal pressure from with the can when the internal pressure becomes excessive. In a third preferred embodiment, an electrochemical cell is provided that includes a collector assembh which closes and seals the open end of a can The collector assembly includes a collector, such as a nail, disposed in electπcal contact with an electrode, for example the negative electrode Also included in the collector assembly is a cover having an aperture preferably formed centrally in the cover. The collector is disposed in and extends through the aperture in the cover. A dielectπc insulating mateπal is disposed between the collector and the cover to provide dielectπc insulation therebetween Accordingly, the collector nail is electπcally isolated from the cover. The pressure relief mechanism is present in a surface of the can.
The dielectπc insulating mateπal may be an organic macromolecular mateπal, such as an organic polymer. Suitable mateπals include epoxy, rubber, and nylon. Other dielectπc mateπals may be used that are resistant to the electrolyte used. For alkaline cells, preferably the dielectπc mateπal is resistant to attack by potassium hydroxide (KOH) and is non-corrosive in the presence of potassium hydroxide. The dielectπc insulating material may be assembled to the collector assembly as explained further below.
The cover of the collector assembly is connected and sealed to the open top end of the can, preferably by forming a double seam closure by a beverage can-type sealing technique. Accordingly, the can preferably has an outward extending flange formed at its open end. Furthermore, the cover preferably has a slightly curved peπpheral edge that conforms to the shape of the flange. Once the cover has been placed over the open end of can, a seaming chuck may be used to form a double seam closure, as descπbed above for the second preferred embodiment. While a double seam can-to-cover closure is preferred, it should be appreciated that other can-to-cover closures may be employed in accordance with the third preferred embodiment.
In a vanation of the third preferred embodiment, the battery can is first formed as a tube with two open ends. The tube may for example be extruded, seam welded, soldered or cemented, using conventional techniques. The tube may be formed for example of steel, aluminium, or plastic. The tube defines the side walls of the can. A first open end of the tube is then sealed by secuπng a cover thereto using the beverage can sealing technique outlined above A positive contact terminal may be welded or otherwise secured to the outer surface of the cover The battery may then be filled and the cover of a collector assembly may be secured to the second open end of the can in the same manner as descπbed above Alternatively, the cover of the collector assembly may be sealed to the tube before the tube is filled and sealed to the other cover
The electrochemical cell according to the third preferred embodiment allows for a direct connection between the can and the cover, which preferably provides a pressure seal therebetween, but does not require electπcal isolation between the cover and the side walls of the can. Instead, the collector, preferably a nail, is dielectπcally insulated from the cover such that the negative and positive terminals of the electrochemical cell are electπcally isolated from one another While there is no requirement of maintaining electπcal isolation between the can and the cover, it is preferred that a sealant be applied at the closure joining the can to the cover to assist in the sealing of the cover to the can. A conventional sealant may be applied to the bottom surface of the peπpheral edge of the cover. In a beverage can construction, once the sealing procedure is complete, the sealant migrates to the positions shown in Figure 8D It should be appreciated that the sealed closure along with the insulating mateπal should be capable of withstanding internal pressure build-up greater than the venting pressure at which the pressure release mechanism releases pressure.
To provide an acceptable outer battery terminal in accordance with well accepted battery standards, the electrochemical cell preferably further includes an outer cover in electπcal contact with the collector. The outer cover may be welded by spot weld or otherwise electπcally connected to the collector To ensure proper electπcal insulation between the outer cover and the inner cover, preferably a dielectπc mateπal such as annular pad is disposed between the outer cover and the inner cover. Suitable dielectπc mateπals include nylon, other elastomeπc mateπals, rubber, and epoxy, which may be applied on the top surface of the inner cover or on the bottom surface of the outer cover Accordingly, an acceptable standard battery terminal may be provided, preferably as the negative terminal, at the collector end of the electrochemical cell The assembly of an electrochemical cell according to the third preferred embodiment is illustrated in the assembly view of Figure 12 and is further illustrated in the flow diagram of Figure 13. The preferred method of assembly includes providing a can formed with a closed bottom end and open top end, and disposing into the can the active electrochemical materials including the negative electrode, the positive electrode, and an electrolyte, as well as the separator and other cell additives. Once the active electrochemical cell materials are disposed within the can, the can is ready for closure and sealing with the collector assembly.
Prior to closing the can, the collector assembly is assembled by first disposing the collector, preferably a nail, within an aperture formed in the cover, preferably along with a ring or disc of insulating material, so that the collector is disposed in the opening of the insulating ring. The insulating ring is preferably formed of a material which provides dielectric insulation and can be heated to reform and settle between the cover and the collector, for example epoxy. Alternatively, other organic macromolecular dielectric insulation materials may be used in place of epoxy, such as a rubber grommet, an elastomeric material, or other dielectric materials that may form adequate insulation between the collector and the cover.
Preferably, a recess is formed in the top surface of the cover, centred about the aperture. Accordingly, the ring of insulating material may be disposed in the recess on top of the cover and the top head of a collector nail may be disposed thereabove. Thus, the insulating ring may assembled to the collector nail and cover, and the insulating ring heated to a temperature sufficiently high enough to melt the ring such that the ring reforms and flows into the aperture in the cover to provide continuous dielectric insulation between the collector nail and the cover. For a ring made of epoxy, a temperature of 20°C to 200°C for a time of a few seconds to twenty-four hours may be adequate to reform and cure the insulating material. Once the dielectric material forms adequate insulation between the collector nail and the cover, the insulated material is preferably cooled. During the heating and cooling steps, the collector nail is centred in the aperture such that the nail does not contact the cover. Thereafter, preferably an electrical dielectric insulating pad such as an annular dielectric pad is disposed on top of the cover so as to extend radially outward from the perimeter of the nail. A conductive negative cover is then preferably disposed on top of the collector nail and pad, and is welded or otherwise formed in electrical contact with the collector nail.
Once the collector assembly is fully assembled, the collector assembly is then connected to the can to sealingly close the open end. Can closure preferably employs a double seam closure, although other suitable can closure techniques may be used. In addition, preferably a second cover is connected to the closed end of the can, preferably overlying a pressure relief mechanism.
For a D sized battery according to the third preferred embodiment, the percentage of the total battery volume that may be used to contain the electrochemically active materials may be as high as 96 volume percent, while collector assembly volume may be as low as 2.6 volume percent. The volumes of batteries of other sizes are included in the table shown in Figures 10A and 10B.
Accordingly, in an example of the third embodiment, an electrochemical cell is provided that comprises a can for containing electrochemically active materials including at least positive and negative electrodes and an electrolyte, the can having an open end, a closed end, and side walls extending between the open and closed ends; a cover positioned across the open end of the can and connected to the can, the cover having an aperture extending therethrough; a current collector extending through the aperture in the cover and extending internally within the can to electrically contact one of the positive and negative electrodes; and an insulating material disposed between the collector and the cover for electrically insulating the collector from the cover and creating a seal between the collector and the cover. A pressure relief mechanism is formed in a surface of the can for releasing internal pressure from within the can when the internal pressure becomes excessive. In addition, the electrochemical cell preferably includes a first contact terminal electrically coupled to the collector and a dielectric mateπal disposed between the first contact terminal and the cover for electπcally insulating the cover from the first contact terminal
In a further embodiment, the can may be formed to have the protrusion for the positive battery terminal formed directly in the closed end of the can In this manner, the void space existing between the closed end of the can and the positive outer cover may be used to contain electrochemically active mateπals or otherw lse provide space for the collection of gases, which otherwise must be provided within the cell Although the increase in cell volume obtained by forming the protrusion directly in the bottom of the can is not provided in the table in Figure 10A, it will be appreciated by those skilled in the art that the internal volume is typically one percent greater than the volumes listed for the cells listed in the table which are formed with a separate cover
In a further embodiment, a pπnt layer may be applied directly onto the exteπor surface of the battery can to provide a label. By applying the label directly onto the exteπor of the can as a pπnt layer, rather than with a label substrate, the internal volume of the cell may be further increased since one does not have to account for the thickness of a label substrate to construct a cell that meets the ANSI or other exteπor size standards By "directly" is meant that no label substrate is present between the pπnt layer and the external surface of the battery can. Current label substrates have thicknesses on the order of 75 μm (3 mils). Because such label substrates overlap to form a seam running along the length of the battery, these conventional labels effectively add about 250 μm (10 mils) to the diameter and of 330 μm (13 mils) to the cπmp height of the battery. As a result, the battery can must have a diameter that is selected to accommodate the thickness of the label seam m order to meet the ANSI or other size standards. However, by pπntmg a lithographed label directly on the exteπor surface of the can, the diameter of the can may be correspondingly increased approximately 250 μm (10 mils). Such an increase in the diameter of the can significantly increases the internal volume of the battery. Thus, the internal volume of the battenes with substrate labels could be further increased, for example by 2 percent (1.02 cc) for a D sized battery, 2.6 percent (0.65 cc) for a C sized battery, 3.9 percent (0 202 cc) for an A A sized cell and 5 5 percent (0 195 cc) for an AAA sized battery, if the labels were pπnted directly on the exteπor of the can
Labels may also be pnnted on the can using transfer pπnting techniques in which the label image is first pπnted on a transfer medium and then transferred directly onto the can exteπor Distorted lithography may also be used whereby intentionally distorted graphics are pπnted on flat mateπal so as to account for subsequent stress distortions of the flat mateπal as it is shaped into the tube or cylinder of the cell can
Pπor to pπnting the lithographed label, the exteπor surface of the can is preferably cleaned To enhance adherence of the pπnt to the can, a base coat of pπmer may be applied to the exteπor surface of the can The pπnt layer is then applied directly on top of the base coat on the can by known lithographic pπnting techniques The label may further compπse an electπcally insulating overcoat A varnish overcoat is preferably applied over the pπnt layer to cover and protect the pπnt layer, and also to serve as an electπcally insulating layer The pπnted label may be cured with the use of high temperature heating or ultraviolet radiation techniques.
With the use of the pπnted label, the thickness of the label may be significantly reduced compared with a conventional label on a substrate, to a maximum thickness of approximately 13 μm (0 5 mils) In a particular embodiment, the pπnted label has a base coat layer of a thickness in the range of about 2 5 to 5 μm (0.1 to 0 2 mil), a pπnt layer of a thickness of approximately 2.5 μm (0.1 mil), and a varnish overcoat layer of a thickness in the range of about 2.5 to 5 μm (0.1 to 0.2 mil).
By reducing the label thickness, the can is able to be increased m diameter, thereby offeπng a further increase in available volume for active cell mateπals while maintaining a predetermined outside diameter of the battery
As will be appreciated, through the use of the constructions noted above, a battery can may be made with thinner walls, on the order of 100-200 μm (4-8 mils), since the construction techniques outlined below do not require the thicker walls that are required in conventional batteπes to ensure a sufficient cπmp and seal Furthermore, a label may be lithographed directly onto the exteπor surface of the battery can By making the can walls thinner and lithographing the label directly onto the exteπor of the can, the internal volume of the cell may be further increased since one does not have to account for the thickness of the label substrate to construct a cell that meets the ANSI exteπor size standards
While the present invention has been descπbed above as having pπmary applicability to alkaline batteπes, it will be appreciated by those skilled in the art that similar benefits may be obtained be employing the inventive constructions in batteπes utilising other electrochemical systems For example, the inventive constructions may be employed in pπmary systems such as carbon-zmc and lithium based batteπes and in rechargeable batteπes, such as NiCd, metal hydπde, and Li based batteπes. Furthermore, certain constructions of the present invention may be used in raw cells (i.e., cells without a label as used m battery packs or multi-cell batteπes) Additionally, although the present invention has been descπbed above in connection with cylmdπcal batteπes, certain constructions of the present invention may be employed m constructing pπsmatic cells.
The present invention will now be further descπbed by reference to the embodiments shown in Figures 4A to 13
An electrochemical battery 300 constructed in accordance with a first preferred embodiment of the present invention is shown in Figures 4A through 4C. A pressure relief mechanism 370 is formed in the closed end 314 of can 312. The pressure relief mechanism 370 is formed by providing a groove 372 m the bottom surface of can 312, as shown in Figures 5 and 6. The groove is formed as an arc of approximately 300 degrees. The shape formed by the groove is slightly open so that the pressure relief mechanism has an effective hinge. The size of the area circumscπbed by the groove 372 is selected such that upon rupture due to excessive internal pressure, the area withm the groove 372 may pivot at the hmge withm the positive protrusion of outer cover 311 without interference from outer cover 311 The pressure relief mechanism 370 is positioned beneath outer cover 311 so as to prevent the electrochemical mateπals from dangerously spraying directly outward from the battery upon rupture
The open end of can 312 is sealed by placing either a nylon seal 330 having a J- shaped cross section or a nylon seal 330' having an L-shaped cross section in the open end of can 312, inserting a negative outer cover 345 having a rolled back peπpheral edge 347 within nylon seal 330 or 330', and subsequently cπmpmg the outer edge 313 of can 312 to hold seal 330 or 330' and cover 345 in place To help hold seal 330 or 330' in place, a bead 316 is formed around the circumference of the open end of can 312 Nylon seal 330 or 330' is coated with asphalt to protect it from the electrochemically active mateπals and to provide a better seal
Referring particularly to Figures 4A and 4C, the annular nylon seal 330 is shown configured with a J-shaped cross section which includes an extended vertical wall 332 at the outermost peπmeter thereof, a shorter vertical wall 336 at the radially inward side of the seal and has a hoπzontal base member 334 formed between the vertical walls 332 and 336 As shown m Figure 4B, the J-shaped nylon seal 330 is configured absent the short vertical section 336 to form a plain L-shaped cross section
With particular reference to Figure 4C, the assembly of the electrochemical cell shown in Figure 4A is illustrated therein. The cy ndπcal can 312 is formed with side walls defining the open end and bead 316 for receiving internally disposed battery mateπals pπor to closure of the can Disposed withm can 312 are the active electrochemical cell mateπals including the positive and negative electrodes and the electrolyte, as well as the separator, and any additives Together, the outer cover 345, with the collector nail 340 welded or otherwise fastened to the bottom surface of cover 345, and annular nylon seal 330 are assembled and inserted into the open end of can 312 to seal and close can 312. The collector nail 340 is preferably welded via spot weld 342 to the bottom side of outer cover 345 Together, collector nail 340 and cover 345 are engaged with seal 330 to form the collector assembly, and the collector assembly is inserted in can 312 such that the rolled back peripheral edge 347 of outer cover 345 is disposed against the inside wall of annular seal 330 above bead 316 which supports seal 330. The collector assembly is forcibly disposed within the open end of can 312 to snugly engage and close the can opening. Thereafter, the outer edge 313 of can 12 is crimped inward to axially force and hold seal 330 and outer cover 345 in place. Referring back to Figure 4B, the inside surface of outer cover 345 and at least a top portion of collector nail 340 are further shown coated with an anti-corrosion coating 344.
An electrochemical battery 400 constructed in accordance with a second preferred embodiment of the present invention is shown in Figures 7 through 9. A negative outer cover 445 is secured to the open end of can 412 using a beverage can- type sealing technique. The method of making a battery having the construction shown in Figure 7 is described below with reference to Figures 8A-8D. Prior to attaching negative outer cover 445 to the open end of can 412, a collector nail 440 is welded to the inner surface of cover 445. Next, as shown in Figure 8 A, the inner surface of cover 445, as well as the peripheral portion of the upper surface of cover 445, is coated with a layer 475 of electrical insulation material. The portion of collector nail 440 that extends within the void area between the bottom of cover 445 and the top surface of the negative electrode/electrolyte mixture 120, is also coated with the electrical insulation.
Additionally, the inner and outer surfaces of can 412 are also coated in the region of the open end of can 412. Thus, negative outer cover 445 is electrically insulated from can 412.
To assist in the sealing of outer cover 445 to can 412, a sealant 473 is applied to the bottom surface of peripheral edge 470 of cover 445. Once the sealing procedure is complete, sealant 473 migrates to the positions shown in Figure 8D.
Once collector nail 440 has been attached to outer cover 445 and the electrical insulation coating has been applied, outer cover 445 is placed over the open end of can 412 as shown in Figure 8B. Can 412 has an outward extending flange 450 formed at its open end. Further, outer cover 445 has a slightly curved peripheral edge 470 that conforms to the shape of flange 450 Once outer cover 445 has been placed over the open end of can 412, a seaming chuck 500 is placed on outer cover 445, such that an annular downward extending portion 502 of seaming chuck 500 is received by an annular recess 472 formed in outer cover 445. Next, a first seaming roll 510 is moved in a radial direction toward the peπpheral edge 470 of outer cover 445 As first seaming roll 510 is moved toward peπpheral edge 470 and flange 450, its curved surface causes peπpheral edge 470 to be folded around flange 450. Also, as first seaming roll 510 moves radially inward, seaming chuck 500, can 412, and outer cover 445 are rotated about a central axis, such that peπpheral edge 470 is folded around flange 450 about the entire circumference of can 412 Further, as first seaming roll 510 continues to move radially inward, flange 450 and peπpheral edge 470 are folded downward to the position shown in Figure 8C.
After peπpheral edge 470 and flange 450 have been folded into the position shown in Figure 8C, first seaming roll 510 is moved away from can 412, and a second seaming roll 520 is then moved radially inward toward flange 450 and peπpheral edge 470. Second seaming roll 520 has a different profile than first seaming roll 510. Second seaming roll 520 applies sufficient force against flange 450 and peπpheral edge 470 to press and flatten the folded flange and peπpheral edge against the exteπor surface of can 412, which is supported by seaming chuck 500. As a result of this process, the peπpheral edge 470 of can 412 is folded around and under flange 450 and is cπmped between flange 450 and the exteπor surface of the walls of can 412, as shown in Figures 7 and 8D. A hermetic seal is thus formed by this process.
A vaπation of the beverage can construction is shown in Figure 9. In the illustrated embodiment, the battery can is first formed as a tube with two open ends. The tube defines the side walls 614 of can 612. A first open end of the tube is then sealed by secuπng an inner cover 616 thereto using the beverage can sealing technique outlined above, with the exception that no electπcal insulation is required between inner cover 616 and side walls 614. A positive outer cover 618 is welded to the outer surface of inner cover 616. The battery is then filled and a negative outer cover 645 secured to the second open end of can 612 in the same manner as descπbed above. An electrochemical battery 700 constructed with a feed through collector in accordance with a third preferred embodiment of the present invention is shown in Figures 11 through 13. Similar to the electrochemical cell 400 with beverage can-type construction shown in Figure 7, electrochemical cell 700 includes an electrically conductive can 712 having a closed end 314 and an open end in which a low volume collector assembly 725 and outer negative cover 750 are assembled. Electrochemical cell 700 includes a positive electrode 115 in contact with the interior walls of can 712 and in contact with a separator 117 that lies between a positive electrode 115 and a negative electrode 120.
Electrochemical cell 700 includes a pressure relief mechanism 370 formed in the closed end 314 of can 712, which allows for employment of low volume collector assembly 725. The pressure relief mechanism 370 is formed as a groove as described herein in connection with Figures 4A, 4B, 5, and 6. In addition, a positive outer cover 311 is connected to the closed end of can 712 and overlies the pressure relief mechanism 370. The assembly and location of positive outer cover 311 is provided as shown and described herein in connection with Figure 4A.
Electrochemical cell 700 includes a collector assembly 725 which closes and seals the open end of can 712. Collector assembly 725 includes a collector nail 740 disposed in electrical contact with the negative electrode 120. Also included in the collector assembly 725 is a first or inner cover 745 having a central aperture 751 formed therein. The collector nail 740 is disposed and extends through the aperture 751 in inner cover 745. A dielectric insulating material 744 is disposed between collector nail 740 and first cover 745 to provide dielectric insulation therebetween. Accordingly, the collector nail 740 is electrically isolated from inner cover 745.
Inner cover 745 in turn is connected and sealed to the open top end of can 712. Inner cover 745 is sealed to can 712 by forming a double seam closure at the peripheral edges 450 and 470 as explained herein in connection with Figures 7-9. The collector nail 740 is dielectrically insulated from inner cover 745 such that the negative and positive terminals of the electrochemical cell are electπcally isolated from one another A sealant is applied at the closure joining the can to the cover to adequately seal the can. as explained in connection with the battery shown and descπbed herein in connection with Figures 7-8D
Electrochemical cell 700 further includes an outer cover 750 in electπcal contact with collector nail 740 Outer cover 750 is welded by spot weld 742 to collector nail 740 A dielectπc mateπal as annular pad 748 is disposed between outer negative cover 750 and inner cover 745 Accordingly, an acceptable standard battery terminal is provided at the negative end of electrochemical cell 700
The assembly of electrochemical cell 700 is illustrated in the assembly view of Figure 12 and is further illustrated in the flow diagram of Figure 13 The method 770 of assembly of electrochemical cell 700 includes providing can 712 formed with a closed bottom end and open top end Step 774 includes disposing into can 712 the active electrochemical mateπals including the negative electrode, the positive electrode, and an electrolyte, as well as the separator and other cell additives Once the active electrochemical cell mateπals are disposed within can 712, can 712 is ready for closure and sealing with the collector assembly 725 Pπor to closing the can, the collector assembly is assembled by first disposing the collector nail 740 within aperture 751 formed m inner cover 745 along with a πng of insulating mateπal according to step 776 Collector nail 740 is disposed in the opening 742 of insulating πng 744 which may include a πng or disk of epoxy which provides dielectπc insulation and can be heated to reform and settle between the inner cover 745 and collector nail 740 Also shown formed in inner cover 745 is a recess 755 formed m the top surface and centred about aperture 751 Ring 744 of insulating mateπal is disposed in recess 755 on top of inner cover 745 and the top head of collector nail 740 is disposed thereabove In step 778, the insulating πng 744 is assembled to collector nail 740 and cover 745 and the insulating πng 744 is heated to a temperature sufficiently high enough to melt πng 744 such that πng 744 reforms and flows into the aperture 751 in cover 745 to provide continuous dielectπc insulation between collector nail 740 and inner cover 745 Once dielectπc mateπal 744 forms adequate insulation between collector nail 740 and inner cover 745, the insulated mateπal is preferably cooled in step 780 During the heating and cooling steps 778 and 780, the collector nail 740 is centred in aperture 751 such that nail 740 does not contact cover 745 Thereafter, in step 782, an electπcal dielectπc insulating pad 748 such as an annular dielectπc pad is disposed on top of inner cover 745 and extends radially outward from the peπmeter of nail 740 In step 784, disposed on top of collector nail 740 and pad 748 is a conductive negative cover 750 which is welded m electπcal contact with collector nail 740 Once the collector assembly is fully assembled, the collector assembly is then connected to the can to seahngly close the open end as provided in step 786. The can closure employs a double seam closure. In addition, the assembly method 770 includes step 788 of connecting a second outer cover to the closed end of the can overlying the pressure relief mechanism 370.
EXAMPLE
The total battery volume, collector assembly volume, and internal volume available for electrochemically active mateπal for each battery are determined by viewing a Computer Aided Design (CAD) drawing, a photograph, or an actual cross section of the battery which has been encased in epoxy and longitudinally cross- sectioned. The use of a CAD drawing, photograph, or actual longitudinal cross section to view and measure battery dimensions allows for inclusion of all void volumes that might be present in the battery. To measure the total battery volume, the cross-sectional view of the battery taken through its central longitudinal axis of symmetry is viewed and the entire volume is measured by geometπc computation To measure the internal volume available for electrochemically active mateπals, the cross-sectional view of the battery taken through its central longitudinal axis of symmetry is viewed, and the components making up the internal volume, which includes the electrochemically active mateπals, void volumes and chemically inert mateπals (other than the collector nail) that are confined within the sealed volume of the cell, are measured by geometπc computation. Likewise, to determine volume of the collector assembly, the cross- sectional view of the battery taken through its central longitudinal axis of symmetry thereof is viewed, and the components making up the collector assembly volume, which include the collector nail, seal, inner cover, and any void volume defined between the bottom surface of the negative cover and the seal, are measured by geometπc computation The container volume may likewise be measured by viewing the central longitudinal cross section of the battery and computing the volume consumed by the can, label, negative cover, void volume between the label and negative cover, positive cover, and void volume between the positive cover and the can
The volume measurements are made by viewing a cross section of the battery taken through its longitudinal axis of symmetry This provides for an accurate volume measurement, since the battery and its components are usually axial symmetπc. To obtain a geometπc view of the cross section of a battery, the battery was first potted in epoxy and, after the epoxy solidified, the potted battery and its components were ground down to the central cross section through the axis of symmetry More particularly, the battery was first potted in epoxy and then ground short of the central cross section. Next, all internal components such as the anode, cathode, and separator paper were removed in order to better enable measurement of the finished cross section The potted battery was then cleaned of any remaining debπs, was air dπed, and the remaining void volumes were filled with epoxy to give the battery some mtegπty before completing the gπndmg and polishing to its centre The battery was again ground and polished until finished to its central cross section, was thereafter traced into a drawing, and the volumes measured therefrom.
Pπor to potting the battery in epoxy, battery measurements were taken with callipers to measure the overall height, the cπmp height, and the outside diameter at the top, bottom, and centre of the battery. In addition, an identical battery was drsassembled and the components thereof were measured. These measurements of components of the disassembled battery include the diameter of the current collector nail, the length of the current collector nail, the length of the current collector nail to the negative cover, and the outside diameter of the top, bottom, and centre of the battery without the label present.
Once the battery was completely potted in epoxy and ground to centre through the longitudinal axis of symmetry, the cross-sectional view of the battery was used to make a drawing. A Mitutoyo optical comparator with QC-4000 software was used to trace the contour of the battery and its individual components to generate a drawing of the central cross section of the battery. In doing so, the battery was securely fixed in place and the contour of the battery parts were saved in a format that could later be used in solid modelling software to calculate the battery volumes of interest. However, before any volume measurements were taken, the drawing may be adjusted to compensate for any battery components that are not aligned exactly through the centre of the battery. This may be accomplished by using the measurements that were taken from the battery before cross sectioning the battery and those measurements taken from the disassembled identical battery. For example, the diameter and length of the current collector nail, and overall outside diameter of the battery can be modified to profile the drawing more accurately by adjusting the drawing to include the corresponding known cross-sectional dimensions to make the drawing more accurate for volume measurements. The detail of the seal, cover, and crimp areas were used as they were drawn on the optical comparitor.
To calculate the volume measurements, the drawing was imported into solid modelling software. A solid three-dimensional volume representation was generated by rotating the contour of the cross section on both the left and right sides by one-hundred- eighty degrees (180°) about the longitudinal axis of symmetry. Accordingly, the volume of each region of interest is calculated by the software and, by rotating the left and right sides by one-hundred-eighty degrees (180°) and summing the left and right volumes together an average volume value is determined, which may be advantageous in those situations where the battery has non-symmetrical features. The volumes which include any non-symmetrical features can be adjusted as necessary to obtain more accurate volume measurements.
Figures 10A and 10B show volumes of various different types of battery constructions that are more fully disclosed in US 60/102,951 filed 2 October 1998 and US 60/097,445 filed 21 August 1998. As shown in Figure 10A in the rows referenced "Pressure Relief in Can Bottom" and "Pressure Relief in Can Bottom With Thin Walls," a D sized battery constructed using the construction shown in Figure 4A, has an internal volume that is 93 5 volume percent when the can walls are 250 μm (10 mils) thick, and an internal volume that is 94.9 volume percent when the can walls are 200 μm (8 mils) thick As shown in Figure 10B, a D sized battery constructed using the construction shown in Figure 4A, has a collector assembly volume that is 2 percent of the total volume when the can walls are 250 μm (10 mils) thick and 200 μm (8 mils) thick As shown in Figure 10A in the row referenced "Beverage Can-Type Construction", a D sized battery constructed using the construction shown m Figure 11, had an internal volume that was 97.0 volume percent when the can walls were 200 μm (8 mils) thick As shown in Figure 10B, a D sized battery constructed using the construction shown in Figure 7 had a collector assembly volume that was 1 6 percent of the total volume when the can walls were 200 μm (8 mils) thick. As shown Figure 10A in the row referenced "Beverage Can With Feed Through Collector", a D sized battery constructed using the construction shown in Figure 11, had an internal volume that was 96 0 volume percent when the can walls were 200 μm (8 mils) thick As shown in Figure 10B, a D sized battery constructed using the construction shown in Figure 11 had a collector assembly volume that was 2.6 percent of the total volume when the can walls were 200 μm (8 mils) thick. The C, AA, and AAA sized batteπes having similar construction also exhibited significant improvements in internal volume efficiency, as is apparent from the table in Figure 10A.
Furthermore, using these techniques to measure and calculate battery volumes, it was found that the internal volume of the batteπes with substrate labels could be further increased 2 percent (1.02 cc) for a D sized battery, 2.6 percent (0.65 cc) for a C sized battery, 3.9 percent (0.202 cc) for an AA sized cell, and 5.5 percent (0.195 cc) for an AAA sized battery, if the labels were pπnted directly on the exteπor of the can.

Claims

CLAIMS:
1. An electrochemical cell comprising: a can for containing electrochemically active materials including positive and negative electrodes and an electrolyte, the can having an open end, a closed end with an end wall extending across the closed end, and side walls extending between the open and closed ends; a first cover positioned across the open end; and a pressure relief mechanism formed in a surface of the can.
2. An electrochemical cell according to claim 1, wherein the end wall is integrally formed with the side walls of the can.
3. An electrochemical cell according to claim 1, wherein the can is formed as a tube with the end wall being a cover secured across the closed end.
4. An electrochemical cell according to any preceding claim, wherein the pressure relief mechanism is formed in the end wall of the can.
5. An electrochemical cell according to claim 4, wherein the pressure relief mechanism is formed by coining a surface of the end wall of the can.
6. An electrochemical cell according to claim 4 or claim 5, wherein the pressure relief mechanism includes a hinged portion that pivots out from the end wall of the can upon rupture.
7. An electrochemical cell according to any of claims 4 to 6, wherein the pressure relief mechanism includes an arc-shaped groove formed in a surface of the end wall of the can.
8. An electrochemical cell according to claim 7, wherein the arc-shaped groove is formed as a 300 degree partial circle.
9. An electrochemical cell according to any of claims 4 to 8, wherein a second cover is positioned on the end wall of the can to be in electrical contact therewith and to extend over the pressure relief mechanism.
10. An electrochemical cell according to claim 9, wherein the second cover includes a centrally disposed contact terminal protrusion, and wherein the pressure relief mechanism is formed in the end wall of the can in a region underlying the protrusion.
11. An electrochemical cell according to claim 9 or claim 10, wherein the second cover is electrically coupled to the positive electrode to serve as a positive external battery terminal and the first cover is electrically coupled to the negative electrode to serve as a negative external battery terminal.
12. An electrochemical cell according to any preceding claim, wherein an insulator is disposed between the can and the first cover for electrically insulating the can from the first cover.
13. An electrochemical cell according to claim 12, wherein the insulator is a coating of insulating material deposited on at least one of the can and the first cover.
14. An electrochemical cell according to any preceding claim, wherein the cell is a cylindrical cell.
15. A method of preparing an electrochemical cell comprising the steps of: forming a can having an open end and a closed end; forming a pressure relief mechanism in a surface of the can; dispensing electrochemically active materials in the can; and sealing a first cover across the open end of the can.
16. A method according to claim 15, wherein the step of sealing includes providing a layer of electrical insulation between the can and the first cover.
17. A method according to claim 15 or claim 16, wherein the step of forming the can includes the substeps of forming a tube to define side walls of the can, and securing a cover across an open end of the tube to define an end wall across the closed end of the can.
18. A method according to any of claims 15 to 17, wherein the step of forming a pressure relief mechanism comprises forming a groove.
19. A method according to claim 18, wherein the groove is formed by moulding.
20. A method according to any of claims 15 to 19, further comprising the step of attaching a second cover to the closed end of the can such that the second cover extends over the pressure relief mechanism.
PCT/US1999/018667 1998-08-21 1999-08-16 Battery construction having pressure release mechanism WO2000011736A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2000566907A JP4323722B2 (en) 1998-08-21 1999-08-16 Battery configuration with pressure relief mechanism
EP99943719A EP1108269B1 (en) 1998-08-21 1999-08-16 Battery construction having pressure release mechanism
AU56757/99A AU5675799A (en) 1998-08-21 1999-08-16 Battery construction having pressure release mechanism
AT99943719T ATE253258T1 (en) 1998-08-21 1999-08-16 DESIGNING A BATTERY WITH SAFETY VENTILATION
CA002340387A CA2340387A1 (en) 1998-08-21 1999-08-16 Battery construction having pressure release mechanism
DE69912454T DE69912454T2 (en) 1998-08-21 1999-08-16 CONSTRUCTION OF A BATTERY WITH SAFETY VENTILATION

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US9744598P 1998-08-21 1998-08-21
US60/097,445 1998-08-21
US10295198P 1998-10-02 1998-10-02
US60/102,951 1998-10-02
US09/293,225 US6632558B1 (en) 1998-08-21 1999-04-16 Battery construction having pressure release mechanism
US09/293,225 1999-04-16

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WO2000011736A1 true WO2000011736A1 (en) 2000-03-02

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EP (1) EP1108269B1 (en)
JP (1) JP4323722B2 (en)
CN (1) CN1169245C (en)
AT (1) ATE253258T1 (en)
AU (1) AU5675799A (en)
CA (1) CA2340387A1 (en)
DE (1) DE69912454T2 (en)
TW (1) TW442991B (en)
WO (1) WO2000011736A1 (en)

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EP1108269A1 (en) 2001-06-20
ATE253258T1 (en) 2003-11-15
JP4323722B2 (en) 2009-09-02
EP1108269B1 (en) 2003-10-29
CN1323455A (en) 2001-11-21
CN1169245C (en) 2004-09-29
CA2340387A1 (en) 2000-03-02
AU5675799A (en) 2000-03-14
JP2003534625A (en) 2003-11-18
TW442991B (en) 2001-06-23
US6632558B1 (en) 2003-10-14
DE69912454D1 (en) 2003-12-04
DE69912454T2 (en) 2004-08-19

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