CA1179730A - Snap-in sealing and insulating member for galvanic cells - Google Patents
Snap-in sealing and insulating member for galvanic cellsInfo
- Publication number
- CA1179730A CA1179730A CA000405244A CA405244A CA1179730A CA 1179730 A CA1179730 A CA 1179730A CA 000405244 A CA000405244 A CA 000405244A CA 405244 A CA405244 A CA 405244A CA 1179730 A CA1179730 A CA 1179730A
- Authority
- CA
- Canada
- Prior art keywords
- sealing
- insulating member
- diameter
- combination
- downwardly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- H01M50/30—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
SNAP-IN SEALING AND INSULATING MEMBER FOR GALVANIC
CELLS
ABSTRACT OF THE DISCLOSURE
In a sealed galvanic seal having an anode, a cathode, and a cylindrical can into which the principal components of the cell are assembled, a sealing and insulating member is provided at the top end of the cathode can, and is held in sealing relationship to the can by a crimp formed over the top edge thereof. The sealing and insulating member is formed with an upper portion having a diameter which is substantially the same as the inside diameter of the can in the region above the bead, and has an inwardly directed shoulder in the periphery of the member to a diameter which is substantially the same or slightly less than the diameter of the can at the bead. Below the shoulder, there is a downwardly and outwardly extending skirt formed in the lower portion of the sealing and insulating member, the maximum diameter of which is located substantially at the lowest extremity thereof, and which is greater than the diameter of the can at the bead. The sealing and insulating member may be snap-fitted into the can prior to crimping, and held in place without the necessity to pre-crimp. Moreover, by such an assembly, there is a greater internal volume provided in the cathode can.
File No. PAT2018
CELLS
ABSTRACT OF THE DISCLOSURE
In a sealed galvanic seal having an anode, a cathode, and a cylindrical can into which the principal components of the cell are assembled, a sealing and insulating member is provided at the top end of the cathode can, and is held in sealing relationship to the can by a crimp formed over the top edge thereof. The sealing and insulating member is formed with an upper portion having a diameter which is substantially the same as the inside diameter of the can in the region above the bead, and has an inwardly directed shoulder in the periphery of the member to a diameter which is substantially the same or slightly less than the diameter of the can at the bead. Below the shoulder, there is a downwardly and outwardly extending skirt formed in the lower portion of the sealing and insulating member, the maximum diameter of which is located substantially at the lowest extremity thereof, and which is greater than the diameter of the can at the bead. The sealing and insulating member may be snap-fitted into the can prior to crimping, and held in place without the necessity to pre-crimp. Moreover, by such an assembly, there is a greater internal volume provided in the cathode can.
File No. PAT2018
Description
~'7 ~IELD OF THE INVENTlON
This invention relates to sealed galvanic cells, such as primary alkaline cells and others, ancl particularly relates to a sealing and insulating member for such cells. The sealing and insulat-ing members according to this invention are particuLarly ciesigneci to have a snap-in fitment to the cathocie can, by which the placement of the member in the correct position may be assureci. The sealing and insulating members may have a rupturable vent membrane, as requirecl, anci may be formed from a variety of materials including especially polypropylene ancl co-polymers thereof.
BACKGROUND O~ T~E INVENTI~N
The general construction of sealed, cylindrical galvanic cells is such that the principal components, an anode and a cathode, are assembled into a can, together with the appropriate separators, electrolyte, etc. Generally, the can into which the principal cell components are assembled is a cathode can -- i.e., the can, and usually the closed bottom encl thereof, forms a cathocle contact for the cell -- ancl the cell is closed by a member placed in the top enci of the can. Such member is generally a sealing ancl insuLating melnber, by whicl the cell is sealecl so as to preclucie electrolyte leakage therefrom, and so that the anocie contact of the cell is insulated frorn the can at the opposite encl thereof from its closed bottom end. 1~ 7'3 ~3~) However, the sealing and insulating member for the sealed galvanic cell may serve several purposes, and ideally it is designed so that sealing of the galvanic cell during and after discharge operations and/or during or after severe temperature cycling, is assurecl. Vrdinary cornmercial gaLvanic cells such as primary alkaline cells and others are, indeed, tested to determine whether the sealing will remain integral following discharge or reverse polarity connections, or temperature cycling; but the severity of the cell tests rnay vary, depending upon the type of cell.
Moreover, it is often desired that a sealed galvanic cell should be provided having a rupturable vent membrane in the sealing member, such that if extreme pressures develop beyond a predetermined limit within the seal, the membrane will rupture and thereby permit a controlled release of gas -- and, usually, some of the cell components -- without the danger that the cell may rupture or mechanically fail in an uncontrolled manner.
Still further, it is always desireable that the material of the sealing and insulating member which is placed at the top of the cathode can should be substantially inert to the cell components that are within that can.
In general, however, not all of the above requirements have been met by any one sealing and insulating member. ~ne of the severe problems that is encountered in the provision of a sealing and insulating rnernber is that, norrnally, it would be expected that a material having substantial mechanical rigidity and tensile strength, and having a co-efficient of thermal ~ 3 ~
expansion very similar to those of stee~ -- the material of which the galvanic cell can would normally be produced --should be used. Such materials generally comprise nylon, but vinyl and polyethylene may be considered and have been used.
A co-pencling Canaclian patent application, Serial No.
393,134, filecl ~ecember 23, 19~1, clescribes a sealing ancl insulating member for galvanic cells which is formecl of polypropylene and co-polymers thereof, contrary to the usual expectations that woulcl be drawn from the prior art thclt nylon, polyvinyl chloricle or A~ which are recognized at "engineering plastics" -- shoulcl be usecl.
Certain of the properties of polypropylene ancd co-polymers thereof permit the provision of sealing and insulating members which have rupturable membranes formed therein during the moulding operation of the members.
Another property which provides a further, unexpected advantage over the prior sealing and insulating members of the co-pending application referred to above, is that polypropylene and co-polymers thereof may be stressed in some areas of a moulded member in such a manner that sealing and insulating members may be formed having a downwardly and outwardly extending skirt in their lower portion such that they may be snap fitted into the cathode can. This snap fitmellt is achievecl by forcing the lower end of the downwarclly ancl outwarclly extending skirt past the bead that is formed near the top of the can, and thereby assuring that the sealing ancl insulating 26 member is positioned in the correct place within the can prior to crimping.
-~ 7~ 7q~
Certain prior art patents show ceLl structures having moulded plastic sealing and/or insulating members placed therein, but all o~ the prior art tends to lead away from the snap-fitting sealing and insulating member formed of polypropyLene and/or co-polymers thereof. For example, ~ELDHAK~, Canadian patent '34'3,652, issued June 1~, 1974, shows a container having a hard plastic closure which has a diameter larger than the ~iameter of the container opening, wt~ere the sealing of the can radially compresses the closure to a diameter which is smaller than that of the container, by pushing the closure through a reducing die. Thereafter, the closure is permitted to expand into contact with the container with such force that the upper edge of the containe-r is slightly deformed outwardly. Hard nylon is generally used, or other cold-flow resistant plastics such as hard polyethylene may also be used.
RALSTON et al, U.S. Patent 3,663,301, issue~ May 16, 1972 to the predecessor corporation of the present assignee, teaches an electrochmical cell wherein an annular border of the plastic disc top is disposed so as to provide a tight seating fit in the can, using the bead of the can as a seat. However, there is no downwardly and outwardly extending skirt, and in any event the plastic material that is used is nylon.
lEVY, U.S. patent 4,075,398, issued lebruary 21, 197~, provides a closure for a tubular cell envelope which is pressed into the can, and which has indentations formed in the can to provide for proper axial location of the end cap. Lt is stated that a plastic material which is both resilient yet resistant ~ 7~ .h to creep shoul~ be used; and that by force-fitting the end cap into the mouth of the can, a predictable and tight-fitting relationship can be obtained. Levy specifically states, however, that polypropylene is relatively unsatisfactory, especially in high-quality sealed cells which are to be used under extreme temperature conditions.
RIEDL, United States patent 4,124,73~, shows a sealing element which may be made of a synthetic resin material which has rubber-elastic properties, where the sealing element has a self-loc~ing engagement when positioned over the top of the cell can. A flanged portion of the sealing element is pushed into the can, where the crimped top of the can bears iTl sealing configuration against a horizontally extending bearing protrusion. The crimp in the top of the cell can must be turned over to an extent of at least 14~ degrees and up to 19~
degrees. Riedl specifies that there may be no cutting of the cell cup rim into the material of the sealing member, even before it reaches its final position, because the interior semi-circular configuration of the cell cup rim concentrically compresses the bearing protrusion which then extends beheath the crimped rim in a sealing and self-limiting manner, but only after it reaches its final position. The greater portion of the sealing element remains above the can, and no furLher crimping or sealing operation takes place. Ln other words, the entire sealing operation Eor the cell comes solely as a conse(luence of the placement of the element into the can.
British patent 1,420,324, published January 7, 1~76, shows yet a further cell structure where the rim of the can is turned '37~
inwardly, such as by rolling the edge, to engage within an annular depression which is formed in the sealing element at the end of the can. A groove is thereafter rolled in the outer wall of the can, resulting in an inwardly directed annular ridge which is pressed into and grips the sealing element so as to improve the seal between the element and the can, and so as to locate the sealing element in a positive manner.
~ n providing a sealed galvanic cell according to the present invention -- for example, alkaline primary cells, lithium manganese dioxide cells, and others -- we have discovered that the provision of a sealing and insulating member which may be positively fitted without pre-crimping to the can, assures that the sealing member is in the correct position for crimping. Moreover, by properly locating the sealing member according to the present invention, by snap fitting the sealing member into the mouth of the can, more uniform manufacturing results are obtained. Still further, a greater internal volume of the can may be provided, whereby additional active material may be placed in the can so as to thereby improve or increase the energy capacity of the cell.
Because the thermal co-efficient of expansion of polypropylene and co-polymers thereof is quite different than that of steel, unlike that of nylon which is much closer to that of steel, provision must be made that the sealing and insulating members maintain their sealing integrity durillg severe temperature cycling, storage at very high or very low temperatures, deep discharge, or combinations of those severe operating and/or storage conditions for the cell. Thus, after ~5~ 7~
the sealing and insulating member of this invention is snap-fitted into the cell and has been secured in the cell by crimping, generally there is a portion of the upper portion of the sealing and insulating member below the crimp and/or against the bead which has been stressed beyond the elastic limit of the material, and another portion of the upper portion of the sealing and insulating member at the periphery thereo between the bead and the crimp which is not stressed beyond the elastic limit thereof. At the same time, so as to preclude an inward migration of the central portion of the sealing and insulating member during the crimping operation, we have discovered that the present invention by which the sealing and insulating member is snap-fitted into the can assures that the central portion of the member will generally have a slight change of elevation upwardly with respect to the bottom of the can.
All of these features, and others, are accomplished by the provision of a cylindrical sealed galvanic cell having, in combination, an anode, and a cathode placed in a generally cylindrical can which has a closed bottom end and an opened top end, where there is an inwardly extending bead formed near the top end of the can, and into which is also placed a sealing and insulating member at the top end of the can. The sealing and insulating member is held in sealing relationship to the can, after final assembly, by a crimp which is formed at the top 26 edge of the can, with the top edge of the can exten~ing over the top periphery of the member. The upper portion of the member is fonned having a diameter which is substantially the same as the inside diameter of the can in the region above the bead. An inwardly directed shoulder is formed in the periphery of the member, below the upper portion, to a diameter which is substantially the same or slightly less than the diameter of the can at the bead. The shoulder is subtended by a downwardly and outwardly extending skirt which is formed in the lower portion of the sealing and insulating member, where the maximum diameter of the skirt portion is located substantially at the lowest extremity thereof, and is greater than the diameter of the can at the bead. The sealing and insulating member is snap-fitted into the can with the upper portion above the bead and the lower skirt portion below the bead, after which the crimping action to seal the can takes place.
Indeed, one of the advantages of the present invention is that after the sealing and insulating member has been snap-fitted into the cathode can, there is reasonable assurance that there will be no spillage or evaporation of the components of the cell, while the cell waits for the final crimping operation to take place.
The snap-in feature, in addition to keeping the sealing and insulating member from floating up, also locates the top accurately with respect to the top of the can for the crimping operation. That is, the sealing and insulating membe-r does not float or ride up in the can before crimping or during the crimping operation, as it might otherwise have done. ~ecause the internal usable volume which is available for active material, is increased within the cell by increasing the 9~
internal heigilt, more active material may be placed in the cell.
There is thus provided a galvanic cell and a sealing and insulating member therefore which may have a variety of precise configurations, depending upon the size and type of cell being sealed, where all of the desired characteristics described above, and others, may be accomplished.
_RIEF DESCRIPTION OF THE DRAWINGS
These, and other features and objects of the invention are, however, more fully described hereafter in association with the accompanying drawings, in which:
Figure 1 is a plan view of a typical sealing and insulating member according to the present invention;
Figure 2 is a cross-sectional view of the member of figure 1, in the direction of arrows 2-2;
Figure 3 is a cross-section of another typical sealing and insulating member according to the present invention; and
This invention relates to sealed galvanic cells, such as primary alkaline cells and others, ancl particularly relates to a sealing and insulating member for such cells. The sealing and insulat-ing members according to this invention are particuLarly ciesigneci to have a snap-in fitment to the cathocie can, by which the placement of the member in the correct position may be assureci. The sealing and insulating members may have a rupturable vent membrane, as requirecl, anci may be formed from a variety of materials including especially polypropylene ancl co-polymers thereof.
BACKGROUND O~ T~E INVENTI~N
The general construction of sealed, cylindrical galvanic cells is such that the principal components, an anode and a cathode, are assembled into a can, together with the appropriate separators, electrolyte, etc. Generally, the can into which the principal cell components are assembled is a cathode can -- i.e., the can, and usually the closed bottom encl thereof, forms a cathocle contact for the cell -- ancl the cell is closed by a member placed in the top enci of the can. Such member is generally a sealing ancl insuLating melnber, by whicl the cell is sealecl so as to preclucie electrolyte leakage therefrom, and so that the anocie contact of the cell is insulated frorn the can at the opposite encl thereof from its closed bottom end. 1~ 7'3 ~3~) However, the sealing and insulating member for the sealed galvanic cell may serve several purposes, and ideally it is designed so that sealing of the galvanic cell during and after discharge operations and/or during or after severe temperature cycling, is assurecl. Vrdinary cornmercial gaLvanic cells such as primary alkaline cells and others are, indeed, tested to determine whether the sealing will remain integral following discharge or reverse polarity connections, or temperature cycling; but the severity of the cell tests rnay vary, depending upon the type of cell.
Moreover, it is often desired that a sealed galvanic cell should be provided having a rupturable vent membrane in the sealing member, such that if extreme pressures develop beyond a predetermined limit within the seal, the membrane will rupture and thereby permit a controlled release of gas -- and, usually, some of the cell components -- without the danger that the cell may rupture or mechanically fail in an uncontrolled manner.
Still further, it is always desireable that the material of the sealing and insulating member which is placed at the top of the cathode can should be substantially inert to the cell components that are within that can.
In general, however, not all of the above requirements have been met by any one sealing and insulating member. ~ne of the severe problems that is encountered in the provision of a sealing and insulating rnernber is that, norrnally, it would be expected that a material having substantial mechanical rigidity and tensile strength, and having a co-efficient of thermal ~ 3 ~
expansion very similar to those of stee~ -- the material of which the galvanic cell can would normally be produced --should be used. Such materials generally comprise nylon, but vinyl and polyethylene may be considered and have been used.
A co-pencling Canaclian patent application, Serial No.
393,134, filecl ~ecember 23, 19~1, clescribes a sealing ancl insulating member for galvanic cells which is formecl of polypropylene and co-polymers thereof, contrary to the usual expectations that woulcl be drawn from the prior art thclt nylon, polyvinyl chloricle or A~ which are recognized at "engineering plastics" -- shoulcl be usecl.
Certain of the properties of polypropylene ancd co-polymers thereof permit the provision of sealing and insulating members which have rupturable membranes formed therein during the moulding operation of the members.
Another property which provides a further, unexpected advantage over the prior sealing and insulating members of the co-pending application referred to above, is that polypropylene and co-polymers thereof may be stressed in some areas of a moulded member in such a manner that sealing and insulating members may be formed having a downwardly and outwardly extending skirt in their lower portion such that they may be snap fitted into the cathode can. This snap fitmellt is achievecl by forcing the lower end of the downwarclly ancl outwarclly extending skirt past the bead that is formed near the top of the can, and thereby assuring that the sealing ancl insulating 26 member is positioned in the correct place within the can prior to crimping.
-~ 7~ 7q~
Certain prior art patents show ceLl structures having moulded plastic sealing and/or insulating members placed therein, but all o~ the prior art tends to lead away from the snap-fitting sealing and insulating member formed of polypropyLene and/or co-polymers thereof. For example, ~ELDHAK~, Canadian patent '34'3,652, issued June 1~, 1974, shows a container having a hard plastic closure which has a diameter larger than the ~iameter of the container opening, wt~ere the sealing of the can radially compresses the closure to a diameter which is smaller than that of the container, by pushing the closure through a reducing die. Thereafter, the closure is permitted to expand into contact with the container with such force that the upper edge of the containe-r is slightly deformed outwardly. Hard nylon is generally used, or other cold-flow resistant plastics such as hard polyethylene may also be used.
RALSTON et al, U.S. Patent 3,663,301, issue~ May 16, 1972 to the predecessor corporation of the present assignee, teaches an electrochmical cell wherein an annular border of the plastic disc top is disposed so as to provide a tight seating fit in the can, using the bead of the can as a seat. However, there is no downwardly and outwardly extending skirt, and in any event the plastic material that is used is nylon.
lEVY, U.S. patent 4,075,398, issued lebruary 21, 197~, provides a closure for a tubular cell envelope which is pressed into the can, and which has indentations formed in the can to provide for proper axial location of the end cap. Lt is stated that a plastic material which is both resilient yet resistant ~ 7~ .h to creep shoul~ be used; and that by force-fitting the end cap into the mouth of the can, a predictable and tight-fitting relationship can be obtained. Levy specifically states, however, that polypropylene is relatively unsatisfactory, especially in high-quality sealed cells which are to be used under extreme temperature conditions.
RIEDL, United States patent 4,124,73~, shows a sealing element which may be made of a synthetic resin material which has rubber-elastic properties, where the sealing element has a self-loc~ing engagement when positioned over the top of the cell can. A flanged portion of the sealing element is pushed into the can, where the crimped top of the can bears iTl sealing configuration against a horizontally extending bearing protrusion. The crimp in the top of the cell can must be turned over to an extent of at least 14~ degrees and up to 19~
degrees. Riedl specifies that there may be no cutting of the cell cup rim into the material of the sealing member, even before it reaches its final position, because the interior semi-circular configuration of the cell cup rim concentrically compresses the bearing protrusion which then extends beheath the crimped rim in a sealing and self-limiting manner, but only after it reaches its final position. The greater portion of the sealing element remains above the can, and no furLher crimping or sealing operation takes place. Ln other words, the entire sealing operation Eor the cell comes solely as a conse(luence of the placement of the element into the can.
British patent 1,420,324, published January 7, 1~76, shows yet a further cell structure where the rim of the can is turned '37~
inwardly, such as by rolling the edge, to engage within an annular depression which is formed in the sealing element at the end of the can. A groove is thereafter rolled in the outer wall of the can, resulting in an inwardly directed annular ridge which is pressed into and grips the sealing element so as to improve the seal between the element and the can, and so as to locate the sealing element in a positive manner.
~ n providing a sealed galvanic cell according to the present invention -- for example, alkaline primary cells, lithium manganese dioxide cells, and others -- we have discovered that the provision of a sealing and insulating member which may be positively fitted without pre-crimping to the can, assures that the sealing member is in the correct position for crimping. Moreover, by properly locating the sealing member according to the present invention, by snap fitting the sealing member into the mouth of the can, more uniform manufacturing results are obtained. Still further, a greater internal volume of the can may be provided, whereby additional active material may be placed in the can so as to thereby improve or increase the energy capacity of the cell.
Because the thermal co-efficient of expansion of polypropylene and co-polymers thereof is quite different than that of steel, unlike that of nylon which is much closer to that of steel, provision must be made that the sealing and insulating members maintain their sealing integrity durillg severe temperature cycling, storage at very high or very low temperatures, deep discharge, or combinations of those severe operating and/or storage conditions for the cell. Thus, after ~5~ 7~
the sealing and insulating member of this invention is snap-fitted into the cell and has been secured in the cell by crimping, generally there is a portion of the upper portion of the sealing and insulating member below the crimp and/or against the bead which has been stressed beyond the elastic limit of the material, and another portion of the upper portion of the sealing and insulating member at the periphery thereo between the bead and the crimp which is not stressed beyond the elastic limit thereof. At the same time, so as to preclude an inward migration of the central portion of the sealing and insulating member during the crimping operation, we have discovered that the present invention by which the sealing and insulating member is snap-fitted into the can assures that the central portion of the member will generally have a slight change of elevation upwardly with respect to the bottom of the can.
All of these features, and others, are accomplished by the provision of a cylindrical sealed galvanic cell having, in combination, an anode, and a cathode placed in a generally cylindrical can which has a closed bottom end and an opened top end, where there is an inwardly extending bead formed near the top end of the can, and into which is also placed a sealing and insulating member at the top end of the can. The sealing and insulating member is held in sealing relationship to the can, after final assembly, by a crimp which is formed at the top 26 edge of the can, with the top edge of the can exten~ing over the top periphery of the member. The upper portion of the member is fonned having a diameter which is substantially the same as the inside diameter of the can in the region above the bead. An inwardly directed shoulder is formed in the periphery of the member, below the upper portion, to a diameter which is substantially the same or slightly less than the diameter of the can at the bead. The shoulder is subtended by a downwardly and outwardly extending skirt which is formed in the lower portion of the sealing and insulating member, where the maximum diameter of the skirt portion is located substantially at the lowest extremity thereof, and is greater than the diameter of the can at the bead. The sealing and insulating member is snap-fitted into the can with the upper portion above the bead and the lower skirt portion below the bead, after which the crimping action to seal the can takes place.
Indeed, one of the advantages of the present invention is that after the sealing and insulating member has been snap-fitted into the cathode can, there is reasonable assurance that there will be no spillage or evaporation of the components of the cell, while the cell waits for the final crimping operation to take place.
The snap-in feature, in addition to keeping the sealing and insulating member from floating up, also locates the top accurately with respect to the top of the can for the crimping operation. That is, the sealing and insulating membe-r does not float or ride up in the can before crimping or during the crimping operation, as it might otherwise have done. ~ecause the internal usable volume which is available for active material, is increased within the cell by increasing the 9~
internal heigilt, more active material may be placed in the cell.
There is thus provided a galvanic cell and a sealing and insulating member therefore which may have a variety of precise configurations, depending upon the size and type of cell being sealed, where all of the desired characteristics described above, and others, may be accomplished.
_RIEF DESCRIPTION OF THE DRAWINGS
These, and other features and objects of the invention are, however, more fully described hereafter in association with the accompanying drawings, in which:
Figure 1 is a plan view of a typical sealing and insulating member according to the present invention;
Figure 2 is a cross-sectional view of the member of figure 1, in the direction of arrows 2-2;
Figure 3 is a cross-section of another typical sealing and insulating member according to the present invention; and
2 Figure 4 is a cross-section of the same member after it has been sealed by crimping the top of a galvanic cell can.
DESCRIPTION OF THE PREFERRED EM~ODIMENTS
As noted, the present invention relates particularly to 26 sealed galvanic cells, the principal components of which are an anode, a cathode, and a generally cylindrical cathode can into which those components, together with electrolyte, separators, 73~
~tc., are placed. In keeping with the general practice, it is assume~ that the cylindrical cathode can is closed at its bottom end and open at its top end. Those matters being universally accepted and general, they are not specifically identified in the accompanying drawings.
Referring, now, to Figures 1 and 2, there is shown a typical sealing and insulating member according to the present invention, and which is not unlike a sealing and insulating member according to this invention that may be utilized in sealed alkaline primary cells of the "~" size. Such cells are generally used in flashlights, electric toys and games, and the like.
The sealing and insulating member 10, shown in ~igures 1 and 2, has a generally central portion 12, an upper peripheral portion 14, and a lower portion 16. On th underside of the member 10, there is formed a circular rib 18, concentric with the periphery of the member.
The outer portion of the upper surface of the member 10, at 20, is conveniently ormed so that it is relatively flat, so as to accommodate the crimp which will later be made in the can into which the member is fitted; and at a position inwardly of the outer section 20, there is formed a vent membrane 22. The thickness of the vent membrane 22 is considerably thinner than the cross-section of any other pcrtion of the sealing and insulating member 10.
For purposes of orientation of the member 10, if required, 26 a portion of the central portion 12 may be removed, as at 24.
There is also formed, in the central portion 12, a downwardly ~'7~ 7 ~ ~
extending cavity 2~, and an upwardly extending cavity 28 in the underside of the central portion 12. The cavity 26 is terminated at its bottom by a plug portion 30, as discussed hereafter.
Of particular interest in the embodiment of the sealing and insulating member as shown in Figures 1 and 2, is the inwardly directed shoulder 32 formed in the outer periphery below the upper portion 14; and it is noted that the shoulder 32 is subtended by a downwardly and outwardly extending skirt 34 which is formed -in the lower portion 16 of the member 10.
It will be appreciated that the diameter of the upper portion 14 of the member 10 is substantially the same as the inside diameter of the cathode can into which it will be fitted, where the inside diameter being referred to is that which is above the preformed inwardly extending bead near the top end of the can. Likewise, it will be appreciated that the shoulder 32 extends inwardly to a diameter which is substantially the same or slightly less than the diameter of the cathode can, at the bead. The downwardly and outwardly extending skirt 34 which is formed in the lower portion 16 of the member 10 has its maximum diameter located substantially at the lowest extremity thereof, and it is greater than the diameter of the cathode can at the bead. That is, as can be seen, the maximum diameter of the skirt 34 is greater than the inner cliameter of the sho~llder 32.
Generally, however dependent on certain specifics of the 26 design of the cathode can into which it will be fitted, the maximum diameter of the skirt portion 34 does not exceed the maximum diameter of the upper portion 14 of the member 10. The ~ ~ 76~
cross-section of the skirt portion 34 decreases in thickness below the shoulder 32, towards the lowest extremity of the skirt.
Referring to Figures 3 and 4, another typical embodiment of a sealing and insulating member according to the present invention, is shown. The member 36 is not unlike that which may be utilized in sealed alkaline prirnary cells of the "AA"
size. In the member 36, there is formed an upper portion 38 and a lower portion 40, and a central portion 42 having a downwardly extending recess 44 and an upwardly extending recess 46 formed therein. A thin membrane portion 48 is again provided, much as the membrane portion 22 of the embodiment of Figures 1 and 2, for the purposes described hereafter. Also, as before, the recess 44 is terminated at its bottom by a plug portion 50.
Referring to the sealing and insulating member 36, it will be noted that there is formed in the outer periphery thereof, below the upper portion 38, a shoulder 52, below which there is a downwardly and outwardly extending skirt portion 54 in the lower portion 40 of the member. The cross-section of the skirt portion 54 is substantially constant, below the shoulder 52. It will also be noted that, on the underside of the member 36, there is a circular recess 56, as discussed hereafter.
Having particular regard to Figure 4, the effect of the crimping action of a can with respect to a sealing and insulating member according to the present invention, is shown.
26 In Figure 4, the sealing and insulating member is that of Figure 3, but it may easily be that of Figures 1 and 2, or any 1~l'7~73~
other specific configuration of sealin~ and insulating member which adopts and provides the features of the present invention.
In any event, it will be noted in Figure 4 that a can 60 is provided, only the upper portion of which is shown. ~ear the top of the can 6U, there is formed a bead 62; and the upper portion of the can 60 above the crimp 62 generally has the same diameter, prior to crimping, as the lower portion of the can below the bead 62. However, prior to crirnping, the extreme upper portion of the can may be slightly flared outwardly, as indicated at 64. After the crimp is formed, as at 66, a portion of the top of the sealing and insulating member is covered.
It will be clear, from Figure 4, that prior to crimping, the installation of the sealing and insulating member 36 into the can 60 is such that the member is forced downwardly, causing the skirt portion 54 to flex inwardly as the lower extremity thereof passes the bead 62, after which the skirt portion 54 regains its original configuration because it has been stressed to an extent which is well below the elastic limit of the material of which the member is formed. However, the limit to which the member 36 is permitted to intrude downwardly into the can 60 is determined by the interference of the shoulder 52 with the bead 62. rhus, a relatively secure and assured placement of the member 36 (or any member accord:ing to the present invention) in the can 60 (or any can into whici the member is designed to be fitted) is assurecl, by exerting sufficient force against the sealing and insulating member :~ ~l 7~3~73~
until it "snaps" into the can in a specific relationship to the bead of the can.
Indeed, by achieving the proper placement of the sealing and insulating member within the can for each cell that is manufactured, with predictability, it is evident that a greater usable volume within the can may be assured and designed for.
This allows for the provision of more active material within the cell, thereby increasing its electrical capacity, or energy storage capacity. Moreover, the downwardly and outwardly extending skirt portion of the sealing and insulating member according to this invention provides the inverted-U
configuration with an upwardly extending cavity on the underside of the member, whereby an overall thinner cross-section of the member in its upper portion may be achieved. This results in a greater internal volume within the cell with no loss of structural strength of the sealing and insulating member; and may also result in the use of a smaller quantity of plastics material resin for the production of the member.
For example, having regard to the sealing and insulating member 36 shown in Figures 3 and 4, it is evident that the separator within the cathode can to which the sealing and insulating member will be fitted may extend upwardly into the cavity 56 on the underside of the member. Likewise, a separator in a cell into which a member 1~, as shown in ligures 1 and 2, 26 may be fitted, may extend upwardly to the underside of the member outwardly of the circular rib 18. ~loreover, because it is known by virtue of the interference of the shoulder 32 or 52 ~ ~7s~7~
with the bead 62 (or otherwise) how far the seaLing and insulating member will intrude into the can prior to crimping, placement of more electrolyte or other active material in the can is possible.
The effect of crimping is shown in Figure 4, where stress distribution within the material of the upper portion 3~ of the member 36, at the outer periphery thereof, is indicated by the groups of arrows shown at 6~ an~ 70. The crirnping ~orce which is required to create the crimp at 66 causes portions of the outer peripheral area of the upper portion 38 to be stressed to varying amounts, whereby the distributed forces set up a stress gradient which is such that at least a first portion of the peripheral portion is stressed to an extent greater than the elastic limit of the material from which the sealing and insulating member has been formed. At other portions, the amount of stress is less than the elastic limit.
Generally, the highly stressed portions occur at the upper corner beneath the crimp, and may also occur at the lower corner, above the shoulder 52, above the bead 62 of the can 60.
Likewise, there may be some flexing of the material of the sealing and insulating member, other than the material of the downwardly and outwardly depending skirt portion in the lower portion of the member, such that a change of elevation may occur. Because of the general configuration of the sealing an(l insulating member, of any of the figures shown, the change oE
elevation of the central portion of the member is upwards with respect to the bottom of the can, as shown by the dastled line 72 in Figure 4.
~7~ 3~
In any event, the crimping Eorce by which the crimp is formed in the top of the can is such that the upper portions of the can near the top edge thereof are cold worked, so that upon release of the crimping forces by removal of the can from the crimping die, the crimp remains and thus the stress distribution within the rnaterial of the sealing and insulating member also remains. Of course, the stress distribution within the material, as discussed above, has caused at least a portion of the outer periphery of the sealing and insulating member to 10 be stressed beyond its elastic limit, and at least another portion is such that it has not been stressed beyond its elastic limit.
These latter characteristics are important when it is realized that, not only does the sealing and insulaing member act to seal the can after crimping, it must continue to seal the can when the cell is subjected to extrerne temperature variations and/or charging or discharging characteristics --leaving aside, for the moment, the question of pressure relief venting.
Thus, as is discussed in the co-pending application referred to above, by proper dimensioning and proportioning of at least a portion of the periphery of the sealing rnember, it is possible that the seal may be secure at all temperatures.
~or example, if the cell is subjected to extremely cold temperatures, the sealing and insulating member may shrink to a 26 greater extent than the can, but a seal is assured because of the characteristics referred to above. Likewise, if the cell is subjected to extremely high temperatures, the seal is again ~ 7 ~
assured, although at a different portion of the periphery of the sealing and insulating member.
When the material to be used for production of the sealing and insulating member according to the present invention is a homo-polymer of polypropylene, or a co-polymer of polypropylene, especially with polyethylene, it has been foun~
that the best results are obtained when the melt index of the polypropylene is between 4 and 30, preferrably between 9 and 14.
The melt index or melt flow index is an indication oE the average molecular weight and melt viscosity of polypropylene.
Resins which have low melt flow indexes provide greater toughness, whereas resins which have higher melt flow indexes have a better mould fill out, with possibly shorter mould cycles and a higher gloss on the moulded product.
In any event, it is to be noted that homo-polymers and co-polymers of polypropylene are very practical for moulding the thin membrane 22 or 48 of the specific embodiments illustrated, or other thin membranes according to the present invention. There is no necessity to provide fracture lines or specifically designed cross-sections, but pressure relief venting is assured. Moreover, very close tolerance as to the thic~ness of the relief membrane may be designed for and assured.
It is generally considered to be desirable that, if the 2 pressure relief membrane is to burst, the membrane should burst sufficiently well that there would be no secondary clogging of the vent passages within which the membranes are formed, by any 1~7.~ 7~
of the other cell component materials which may flow through the vent passage if the pressure venting has occurred. Such other components may especially be parts of the separator or anode material within the cell, as well as electrolyte.
As previously mentioned, the downwardly extending recesses 26 or 44 are terminated at their bottom by a plug 30 or 50 respectively. That plug serves a particular purpose, and is more particularly described in the co-pending application re~erred to above. However, for a fuller understanding of the present invention, the following discussion is made.
It is known that, in order to complete the assembly of a galvanic cell, a current collector is placed into the cell, normally by driving it through a portion of the sealing and insulating member. Very often, the current collector has the general form and shape of a nail. Because the normal geometry of the cell is such that the current collector member is placed in the centre thereof, in an axial direction, the downwardly extending recess 26 or 44 accommodates the member.
Placement of the current collector member, such as by a press or knocking it with a hammer, occurs after the crimping action, in other words after the cell has been completely sealed. Indeed, it is sometimes desirable that the cells are built in one manufacturing plant and are shipped to another plant for final manufacturing steps to occur, such as placement of the current collector, and jacketing of the cell. Ln any 26 event, when the current collector is placed by driving it against the plug portion 30 or 50, a controlled fracture around the plug portion will occur because of the fact that the upper ~ 7~
portion of the plug portion is formed such that it is thinnest in its cross-section around the periphery of the plug.
~loreover, the underside of the plug portion terminates at an upwardly extending recess 28 or 46, which is greater in diameter than the diameter of the downwardly extending recess.
Thus, a clean fracture of the plug portion is assured because there is an induced fracture line or stress concentrater line, from the extreme outer edge of the upper surface of the plug portion 30 or 50, to the sides of the upwardly extending recess below the plug portion.
The various configurations of sealing and insulating members according to the present invention may have differing specific features. For example, as noted in L~igure 2, the central portion of the member may extend below the skirt portion; whereas, as noted in Figure 3, it may extend downwardly to substantially the same extent as the skirt portion.
Likewise, the upper surface or at least a portion of the upper surface of the member may be sloped downwardly and outwardly from the centrally disposed portion, such as is shown in Figure 3 or the central portion of Figure 2 inwardly from the outer upper peripheral portion 20.
~ 7 ~
Materials that have been contemplated, and of which sealing and insulating members according to the present inventlon have been moulded, include the following filled or unfilled resins: polypropylene, polyethylene, cv-polymers of polypropylene with polyethylene, and polysulfone, acrylonitrile-butadiene-styrene terpolymer.
However, polypropylene and co-polymers of polypropylene with polyethylene, where the melt index of the polypropylene is between 4 and 30, and preferrably between 9 and 14, have yielded particularly acceptable results.
For example, batches of alkaline primary cells have been assembled, having sealing and insulating members with a configuration substantially as shown in Figure 3, made from differing materials.
In one test, samples were made of nylon and of a polypropylene homo-polymer available from Shell Chemical Company and identified either as Shell SM6100 or SY6100, or Shell polypropylene 5820. ~ylon members were manufactured which had vent passages that were sealed with a hot melt wax.
However, those members tended in out-of-cell venting tests to vent at much higher pressures at lower temperatures than the polypropylene members having a thin membrane moulded therein.
For example, at 25 degrees C, the polypropylene membranes having a thickness of .004 inches tended to vent at approximately 680 p.s.i., whereas the hot melt nylon members vented at more than 1500 p.s.i. In all cases, the line pressure for the test was 2000 p.s.i. and the rate of pressure build up was 250 p.s.i. per minute. Moreover, when the cells were
DESCRIPTION OF THE PREFERRED EM~ODIMENTS
As noted, the present invention relates particularly to 26 sealed galvanic cells, the principal components of which are an anode, a cathode, and a generally cylindrical cathode can into which those components, together with electrolyte, separators, 73~
~tc., are placed. In keeping with the general practice, it is assume~ that the cylindrical cathode can is closed at its bottom end and open at its top end. Those matters being universally accepted and general, they are not specifically identified in the accompanying drawings.
Referring, now, to Figures 1 and 2, there is shown a typical sealing and insulating member according to the present invention, and which is not unlike a sealing and insulating member according to this invention that may be utilized in sealed alkaline primary cells of the "~" size. Such cells are generally used in flashlights, electric toys and games, and the like.
The sealing and insulating member 10, shown in ~igures 1 and 2, has a generally central portion 12, an upper peripheral portion 14, and a lower portion 16. On th underside of the member 10, there is formed a circular rib 18, concentric with the periphery of the member.
The outer portion of the upper surface of the member 10, at 20, is conveniently ormed so that it is relatively flat, so as to accommodate the crimp which will later be made in the can into which the member is fitted; and at a position inwardly of the outer section 20, there is formed a vent membrane 22. The thickness of the vent membrane 22 is considerably thinner than the cross-section of any other pcrtion of the sealing and insulating member 10.
For purposes of orientation of the member 10, if required, 26 a portion of the central portion 12 may be removed, as at 24.
There is also formed, in the central portion 12, a downwardly ~'7~ 7 ~ ~
extending cavity 2~, and an upwardly extending cavity 28 in the underside of the central portion 12. The cavity 26 is terminated at its bottom by a plug portion 30, as discussed hereafter.
Of particular interest in the embodiment of the sealing and insulating member as shown in Figures 1 and 2, is the inwardly directed shoulder 32 formed in the outer periphery below the upper portion 14; and it is noted that the shoulder 32 is subtended by a downwardly and outwardly extending skirt 34 which is formed -in the lower portion 16 of the member 10.
It will be appreciated that the diameter of the upper portion 14 of the member 10 is substantially the same as the inside diameter of the cathode can into which it will be fitted, where the inside diameter being referred to is that which is above the preformed inwardly extending bead near the top end of the can. Likewise, it will be appreciated that the shoulder 32 extends inwardly to a diameter which is substantially the same or slightly less than the diameter of the cathode can, at the bead. The downwardly and outwardly extending skirt 34 which is formed in the lower portion 16 of the member 10 has its maximum diameter located substantially at the lowest extremity thereof, and it is greater than the diameter of the cathode can at the bead. That is, as can be seen, the maximum diameter of the skirt 34 is greater than the inner cliameter of the sho~llder 32.
Generally, however dependent on certain specifics of the 26 design of the cathode can into which it will be fitted, the maximum diameter of the skirt portion 34 does not exceed the maximum diameter of the upper portion 14 of the member 10. The ~ ~ 76~
cross-section of the skirt portion 34 decreases in thickness below the shoulder 32, towards the lowest extremity of the skirt.
Referring to Figures 3 and 4, another typical embodiment of a sealing and insulating member according to the present invention, is shown. The member 36 is not unlike that which may be utilized in sealed alkaline prirnary cells of the "AA"
size. In the member 36, there is formed an upper portion 38 and a lower portion 40, and a central portion 42 having a downwardly extending recess 44 and an upwardly extending recess 46 formed therein. A thin membrane portion 48 is again provided, much as the membrane portion 22 of the embodiment of Figures 1 and 2, for the purposes described hereafter. Also, as before, the recess 44 is terminated at its bottom by a plug portion 50.
Referring to the sealing and insulating member 36, it will be noted that there is formed in the outer periphery thereof, below the upper portion 38, a shoulder 52, below which there is a downwardly and outwardly extending skirt portion 54 in the lower portion 40 of the member. The cross-section of the skirt portion 54 is substantially constant, below the shoulder 52. It will also be noted that, on the underside of the member 36, there is a circular recess 56, as discussed hereafter.
Having particular regard to Figure 4, the effect of the crimping action of a can with respect to a sealing and insulating member according to the present invention, is shown.
26 In Figure 4, the sealing and insulating member is that of Figure 3, but it may easily be that of Figures 1 and 2, or any 1~l'7~73~
other specific configuration of sealin~ and insulating member which adopts and provides the features of the present invention.
In any event, it will be noted in Figure 4 that a can 60 is provided, only the upper portion of which is shown. ~ear the top of the can 6U, there is formed a bead 62; and the upper portion of the can 60 above the crimp 62 generally has the same diameter, prior to crimping, as the lower portion of the can below the bead 62. However, prior to crirnping, the extreme upper portion of the can may be slightly flared outwardly, as indicated at 64. After the crimp is formed, as at 66, a portion of the top of the sealing and insulating member is covered.
It will be clear, from Figure 4, that prior to crimping, the installation of the sealing and insulating member 36 into the can 60 is such that the member is forced downwardly, causing the skirt portion 54 to flex inwardly as the lower extremity thereof passes the bead 62, after which the skirt portion 54 regains its original configuration because it has been stressed to an extent which is well below the elastic limit of the material of which the member is formed. However, the limit to which the member 36 is permitted to intrude downwardly into the can 60 is determined by the interference of the shoulder 52 with the bead 62. rhus, a relatively secure and assured placement of the member 36 (or any member accord:ing to the present invention) in the can 60 (or any can into whici the member is designed to be fitted) is assurecl, by exerting sufficient force against the sealing and insulating member :~ ~l 7~3~73~
until it "snaps" into the can in a specific relationship to the bead of the can.
Indeed, by achieving the proper placement of the sealing and insulating member within the can for each cell that is manufactured, with predictability, it is evident that a greater usable volume within the can may be assured and designed for.
This allows for the provision of more active material within the cell, thereby increasing its electrical capacity, or energy storage capacity. Moreover, the downwardly and outwardly extending skirt portion of the sealing and insulating member according to this invention provides the inverted-U
configuration with an upwardly extending cavity on the underside of the member, whereby an overall thinner cross-section of the member in its upper portion may be achieved. This results in a greater internal volume within the cell with no loss of structural strength of the sealing and insulating member; and may also result in the use of a smaller quantity of plastics material resin for the production of the member.
For example, having regard to the sealing and insulating member 36 shown in Figures 3 and 4, it is evident that the separator within the cathode can to which the sealing and insulating member will be fitted may extend upwardly into the cavity 56 on the underside of the member. Likewise, a separator in a cell into which a member 1~, as shown in ligures 1 and 2, 26 may be fitted, may extend upwardly to the underside of the member outwardly of the circular rib 18. ~loreover, because it is known by virtue of the interference of the shoulder 32 or 52 ~ ~7s~7~
with the bead 62 (or otherwise) how far the seaLing and insulating member will intrude into the can prior to crimping, placement of more electrolyte or other active material in the can is possible.
The effect of crimping is shown in Figure 4, where stress distribution within the material of the upper portion 3~ of the member 36, at the outer periphery thereof, is indicated by the groups of arrows shown at 6~ an~ 70. The crirnping ~orce which is required to create the crimp at 66 causes portions of the outer peripheral area of the upper portion 38 to be stressed to varying amounts, whereby the distributed forces set up a stress gradient which is such that at least a first portion of the peripheral portion is stressed to an extent greater than the elastic limit of the material from which the sealing and insulating member has been formed. At other portions, the amount of stress is less than the elastic limit.
Generally, the highly stressed portions occur at the upper corner beneath the crimp, and may also occur at the lower corner, above the shoulder 52, above the bead 62 of the can 60.
Likewise, there may be some flexing of the material of the sealing and insulating member, other than the material of the downwardly and outwardly depending skirt portion in the lower portion of the member, such that a change of elevation may occur. Because of the general configuration of the sealing an(l insulating member, of any of the figures shown, the change oE
elevation of the central portion of the member is upwards with respect to the bottom of the can, as shown by the dastled line 72 in Figure 4.
~7~ 3~
In any event, the crimping Eorce by which the crimp is formed in the top of the can is such that the upper portions of the can near the top edge thereof are cold worked, so that upon release of the crimping forces by removal of the can from the crimping die, the crimp remains and thus the stress distribution within the rnaterial of the sealing and insulating member also remains. Of course, the stress distribution within the material, as discussed above, has caused at least a portion of the outer periphery of the sealing and insulating member to 10 be stressed beyond its elastic limit, and at least another portion is such that it has not been stressed beyond its elastic limit.
These latter characteristics are important when it is realized that, not only does the sealing and insulaing member act to seal the can after crimping, it must continue to seal the can when the cell is subjected to extrerne temperature variations and/or charging or discharging characteristics --leaving aside, for the moment, the question of pressure relief venting.
Thus, as is discussed in the co-pending application referred to above, by proper dimensioning and proportioning of at least a portion of the periphery of the sealing rnember, it is possible that the seal may be secure at all temperatures.
~or example, if the cell is subjected to extremely cold temperatures, the sealing and insulating member may shrink to a 26 greater extent than the can, but a seal is assured because of the characteristics referred to above. Likewise, if the cell is subjected to extremely high temperatures, the seal is again ~ 7 ~
assured, although at a different portion of the periphery of the sealing and insulating member.
When the material to be used for production of the sealing and insulating member according to the present invention is a homo-polymer of polypropylene, or a co-polymer of polypropylene, especially with polyethylene, it has been foun~
that the best results are obtained when the melt index of the polypropylene is between 4 and 30, preferrably between 9 and 14.
The melt index or melt flow index is an indication oE the average molecular weight and melt viscosity of polypropylene.
Resins which have low melt flow indexes provide greater toughness, whereas resins which have higher melt flow indexes have a better mould fill out, with possibly shorter mould cycles and a higher gloss on the moulded product.
In any event, it is to be noted that homo-polymers and co-polymers of polypropylene are very practical for moulding the thin membrane 22 or 48 of the specific embodiments illustrated, or other thin membranes according to the present invention. There is no necessity to provide fracture lines or specifically designed cross-sections, but pressure relief venting is assured. Moreover, very close tolerance as to the thic~ness of the relief membrane may be designed for and assured.
It is generally considered to be desirable that, if the 2 pressure relief membrane is to burst, the membrane should burst sufficiently well that there would be no secondary clogging of the vent passages within which the membranes are formed, by any 1~7.~ 7~
of the other cell component materials which may flow through the vent passage if the pressure venting has occurred. Such other components may especially be parts of the separator or anode material within the cell, as well as electrolyte.
As previously mentioned, the downwardly extending recesses 26 or 44 are terminated at their bottom by a plug 30 or 50 respectively. That plug serves a particular purpose, and is more particularly described in the co-pending application re~erred to above. However, for a fuller understanding of the present invention, the following discussion is made.
It is known that, in order to complete the assembly of a galvanic cell, a current collector is placed into the cell, normally by driving it through a portion of the sealing and insulating member. Very often, the current collector has the general form and shape of a nail. Because the normal geometry of the cell is such that the current collector member is placed in the centre thereof, in an axial direction, the downwardly extending recess 26 or 44 accommodates the member.
Placement of the current collector member, such as by a press or knocking it with a hammer, occurs after the crimping action, in other words after the cell has been completely sealed. Indeed, it is sometimes desirable that the cells are built in one manufacturing plant and are shipped to another plant for final manufacturing steps to occur, such as placement of the current collector, and jacketing of the cell. Ln any 26 event, when the current collector is placed by driving it against the plug portion 30 or 50, a controlled fracture around the plug portion will occur because of the fact that the upper ~ 7~
portion of the plug portion is formed such that it is thinnest in its cross-section around the periphery of the plug.
~loreover, the underside of the plug portion terminates at an upwardly extending recess 28 or 46, which is greater in diameter than the diameter of the downwardly extending recess.
Thus, a clean fracture of the plug portion is assured because there is an induced fracture line or stress concentrater line, from the extreme outer edge of the upper surface of the plug portion 30 or 50, to the sides of the upwardly extending recess below the plug portion.
The various configurations of sealing and insulating members according to the present invention may have differing specific features. For example, as noted in L~igure 2, the central portion of the member may extend below the skirt portion; whereas, as noted in Figure 3, it may extend downwardly to substantially the same extent as the skirt portion.
Likewise, the upper surface or at least a portion of the upper surface of the member may be sloped downwardly and outwardly from the centrally disposed portion, such as is shown in Figure 3 or the central portion of Figure 2 inwardly from the outer upper peripheral portion 20.
~ 7 ~
Materials that have been contemplated, and of which sealing and insulating members according to the present inventlon have been moulded, include the following filled or unfilled resins: polypropylene, polyethylene, cv-polymers of polypropylene with polyethylene, and polysulfone, acrylonitrile-butadiene-styrene terpolymer.
However, polypropylene and co-polymers of polypropylene with polyethylene, where the melt index of the polypropylene is between 4 and 30, and preferrably between 9 and 14, have yielded particularly acceptable results.
For example, batches of alkaline primary cells have been assembled, having sealing and insulating members with a configuration substantially as shown in Figure 3, made from differing materials.
In one test, samples were made of nylon and of a polypropylene homo-polymer available from Shell Chemical Company and identified either as Shell SM6100 or SY6100, or Shell polypropylene 5820. ~ylon members were manufactured which had vent passages that were sealed with a hot melt wax.
However, those members tended in out-of-cell venting tests to vent at much higher pressures at lower temperatures than the polypropylene members having a thin membrane moulded therein.
For example, at 25 degrees C, the polypropylene membranes having a thickness of .004 inches tended to vent at approximately 680 p.s.i., whereas the hot melt nylon members vented at more than 1500 p.s.i. In all cases, the line pressure for the test was 2000 p.s.i. and the rate of pressure build up was 250 p.s.i. per minute. Moreover, when the cells were
3~'b assembled~ there was an average increase of useable volume within cells having sealing elements according to the present invention, of about 2.0%.
In another test, a tota~ of 104 sealing and insulating memberS made of Shell polypropylene S~16100 were tested for out-of-cell venting pressure, foLlowing annealment of the members at l50 degrees C for 2.5 hours. They were then tested at 21 degrees C, and of the entire batch, 8 vented at 60~ to 650 p.s.i. 49 vented at 651 to 700 p.s.i. 43 vented at 701 to 750 p.s.i. and 4 vented at 751 to 800 p.s.i. In other words, the pressure distribution was reasonably even on either side of 700 p.s.i. with no cell venting either lO0 p.s.i. a~ove or below the stated pressure of 700 p.s.i.
There has been described a sealing and insulating member for galvanic cells, and several different embodiments of sealing and insulating members have been illustrated, where each member in any event comprises an upper portion which is defined in the outer periphery of the member above an inwardly directed shoulder, where the diameter of the upper portion is Substantially the same as the inside diameter of the cathode can into which the member will be fitted, measured above the bead formed in the can near the top thereof; and where the inwardly directed shoulder extends to a diameter which is substantially the same or slightly less than the diameter of the can at the bead. The sealing and insulating member is 26 defined in its lower portion beneath the shoulder by a downwardly and outwardly extendi1lg skirt, where the maximum diameter of .he skirt is located substantially in the lowest ~ 7S~7~
extremity thereof, and is greater than the diameter of the can at the bead. Thus, a sealing and insulating member is provided which has a snap-fitting relationship to the can, whereby accurate placement of the member within the can is assured. A
greater internal volume within the can may be provided, so that additional active rnaterial may be placed in the cell.
Further, the snap-in feature of sealing and insulating members according to the present invention assures that the top may be pre-assembled to cells into which the active material has been loaded, without the need of pre-crimping, and with the assurance that the sealing and insulating member will not float up in the cell during the crimping operation. However, a controlled change of elevation of the central portion of the sealing and insulating member away from the bottom of the cell during the crimping operation, may be provided for. For example, during assembly of cells having sealing and insulating members with a configuration such as is shown in the aforementioned co-pending application, it has been found to be desireable that the element is held in place by a downward pressure against the element during the crimping operation.
However, during the crimping operation on cells having elements according to this invention, the downward pressure against the element may be reduced or eliminated, without any loss of electrolyte from the cell due to the crimping pressure.
Because proper dimensioning of the sealing and insulating member assures that stress distribution in the peripheral material of the member will occur, so that there will be a portion that has been stressed above the elastic limit and a ~ 7~7~
portion that has not been stressed beyond the elastic lirnit of the material, integrity of the cell against electrolyte leakage, during and following temperature cycling and deep discharge, is assured. Moreover, controlled venting rather than uncontrolled rupture, such as in reverse polarity or charging conditions of the cell, is also assured.
Finally, when homo-polymers and co-polymers of polypropylene are used, including the preferred homo-polymer identified as Shell SM6100, considerable cost savings in the production of sealing and insulating members according to the present invention are achieved.
Other embodiments than those referred specifically above, and other materials than those mentioned, may of course be used, and other sealed galvanic systems other than those referred to may utilize the present invention, without departing from the spirit and scope of the appended claims.
In another test, a tota~ of 104 sealing and insulating memberS made of Shell polypropylene S~16100 were tested for out-of-cell venting pressure, foLlowing annealment of the members at l50 degrees C for 2.5 hours. They were then tested at 21 degrees C, and of the entire batch, 8 vented at 60~ to 650 p.s.i. 49 vented at 651 to 700 p.s.i. 43 vented at 701 to 750 p.s.i. and 4 vented at 751 to 800 p.s.i. In other words, the pressure distribution was reasonably even on either side of 700 p.s.i. with no cell venting either lO0 p.s.i. a~ove or below the stated pressure of 700 p.s.i.
There has been described a sealing and insulating member for galvanic cells, and several different embodiments of sealing and insulating members have been illustrated, where each member in any event comprises an upper portion which is defined in the outer periphery of the member above an inwardly directed shoulder, where the diameter of the upper portion is Substantially the same as the inside diameter of the cathode can into which the member will be fitted, measured above the bead formed in the can near the top thereof; and where the inwardly directed shoulder extends to a diameter which is substantially the same or slightly less than the diameter of the can at the bead. The sealing and insulating member is 26 defined in its lower portion beneath the shoulder by a downwardly and outwardly extendi1lg skirt, where the maximum diameter of .he skirt is located substantially in the lowest ~ 7S~7~
extremity thereof, and is greater than the diameter of the can at the bead. Thus, a sealing and insulating member is provided which has a snap-fitting relationship to the can, whereby accurate placement of the member within the can is assured. A
greater internal volume within the can may be provided, so that additional active rnaterial may be placed in the cell.
Further, the snap-in feature of sealing and insulating members according to the present invention assures that the top may be pre-assembled to cells into which the active material has been loaded, without the need of pre-crimping, and with the assurance that the sealing and insulating member will not float up in the cell during the crimping operation. However, a controlled change of elevation of the central portion of the sealing and insulating member away from the bottom of the cell during the crimping operation, may be provided for. For example, during assembly of cells having sealing and insulating members with a configuration such as is shown in the aforementioned co-pending application, it has been found to be desireable that the element is held in place by a downward pressure against the element during the crimping operation.
However, during the crimping operation on cells having elements according to this invention, the downward pressure against the element may be reduced or eliminated, without any loss of electrolyte from the cell due to the crimping pressure.
Because proper dimensioning of the sealing and insulating member assures that stress distribution in the peripheral material of the member will occur, so that there will be a portion that has been stressed above the elastic limit and a ~ 7~7~
portion that has not been stressed beyond the elastic lirnit of the material, integrity of the cell against electrolyte leakage, during and following temperature cycling and deep discharge, is assured. Moreover, controlled venting rather than uncontrolled rupture, such as in reverse polarity or charging conditions of the cell, is also assured.
Finally, when homo-polymers and co-polymers of polypropylene are used, including the preferred homo-polymer identified as Shell SM6100, considerable cost savings in the production of sealing and insulating members according to the present invention are achieved.
Other embodiments than those referred specifically above, and other materials than those mentioned, may of course be used, and other sealed galvanic systems other than those referred to may utilize the present invention, without departing from the spirit and scope of the appended claims.
Claims (13)
1. In combination, a cylindrical sealed galvanic cell, having an anode, a cathode, and a generally cylindrical can into which the principal components of the cell are placed, said can having a closed bottom end and an open top end, and said can having an inwardly extending bead formed near the top end thereof; and further comprising:
a sealing and insulating member at the top end of said cathode can, said member being held in sealing relationship to said can by a crimp formed at the top edge of said can, with said top edge of the can extending over the top periphery of said member;
where said sealing and insulating member is formed with an upper portion having a diameter which is substantially the same as the inside diameter of said can in the region above said bead;
and having an inwardly directed shoulder in the periphery of said member to a diameter which is substantially the same or slightly less than the diameter of said can at said bead;
said shoulder being subtended by a downwardly and outwardly extending skirt formed in the lower portion of said member, where the maximum diameter of said skirt portion is located substantially at the lowest extremity thereof, and is greater than the diameter of said can at said bead.
a sealing and insulating member at the top end of said cathode can, said member being held in sealing relationship to said can by a crimp formed at the top edge of said can, with said top edge of the can extending over the top periphery of said member;
where said sealing and insulating member is formed with an upper portion having a diameter which is substantially the same as the inside diameter of said can in the region above said bead;
and having an inwardly directed shoulder in the periphery of said member to a diameter which is substantially the same or slightly less than the diameter of said can at said bead;
said shoulder being subtended by a downwardly and outwardly extending skirt formed in the lower portion of said member, where the maximum diameter of said skirt portion is located substantially at the lowest extremity thereof, and is greater than the diameter of said can at said bead.
2. The combination of claim 1, where said downwardly and outwardly extending skirt has a cross-section which decreases in thickness below said shoulder towards its lowest extremity.
3. The combination of claim 1, where said downwardly and outwardly extending skirt has a substantially constant cross-section below said shoulder.
4. The combination of claim 1, 2 or 3, where said sealing and insulating member is formed with a centrally disposed portion having a thickness greater than the surrounding material, and having a downwardly extending recess subtended at its bottom by an integrally formed plug portion which is thinnest in cross-section around its periphery; and where the underside of said plug portion terminates at an upwardly extending recess having a planar top surface and downwardly and outwardly extending sides, the diameter of said planar top surface of said upwardly extending recess being greater than the diameter of said downwardly extending recess.
5. The combination of claim 1, 2 or 3, where said sealing and insulating member is formed with a centrally disposed portion having a thickness greater than the surrounding material, and having a downwardly extending recess subtended at its bottom by an integrally formed plug portion which is thinnest in cross-section around its periphery; and where the underside of said plug portion terminates at an upwardly extending recess having a planar top surface and downwardly and outwardly extending sides, the diameter of said planar top surface of said upwardly extending recess being greater than the diameter of said downwardly extending recess; where said centrally disposed portion extends downwardly to substantially the same extent as said skirt portion.
6. The combination of claim 1, 2 or 3 wherein said sealing and insulating member is formed so that the crimping action by which said crimp is formed at the top edge of said can, crimping said top edge against said member, causes a slight change of elevation of the central portion of said member upwardly with respect to the bottom of said can.
7. The combination of claim 1, 2 or 3, wherein at least a first portion of the thickness of the peripheral material of said upper portion of said sealing and insulating member is stressed by the crimp formed at the top edge of said can to an amount greater than the elastic limit of the material thereof, and at least a second portion of the thickness of the peripheral material of said upper portion of said sealing and insulating member is stressed by said crimp to an amount less than the elastic limit of said material.
8. The combination of claim 1, 2 or 3 wherein said sealing and insulating member is formed so that the crimping action by which said crimp is formed at the top edge of said can, crimping said top edge against said member, causes a slight change of elevation of the central portion of said member upwardly with respect to the bottom of said can; and wherein at least a first portion of the thickness of the peripheral material of said upper portion of said sealing and insulating member is stressed by the crimp formed at the top edge of said can to an amount greater than the elastic limit of the material thereof, and at least a second portion of the thickness of the peripheral material of said upper portion of said sealing and insulating member is stressed by said crimp to an amount less than the elastic limit of said material.
9. The combination of claim 1, 2 or 3, where a current collector member extends through a central portion of said sealing and insulating member and into said anode; and said sealing and insulating member is formed with at least one portion of the upper surface thereof, other than at the place where said current collector extends through the material thereof, with a thickness less than the surrounding material so as to provide a rupturable vent area of said member in the event that pressure within said sealed galvanic cell reaches a predetermined level.
10. The combination of claim 1, 2 or 3, where said sealing and insulating member has at least one circular rib, concentric with the periphery, formed in at least one side of said member.
11. The combination of claim 1, 2 or 3, where the material of said sealing and insulating member is chosen from the group consisting of the following filled or unfilled resins, namely polypropylene, polyethylene, co-polymers of polypropylene with polyethylene, polysulfone, and acrylonitrile-butadiene-styrene terpolymer.
12. The combination of claim 1, 2 or 3, where the material of said sealing and insulating member is chosen from the group consisting of polypropylene and co-polymers of polypropylene with polyethylene, and the melt index of said polypropylene is between 4 and 30.
13. The combination of claim 1, 2 or 3, where the material of said sealing and insulating member is chosen from the group consisting of polypropylene and co-polymers of polypropylene with polyethylene, and the melt index of said polypropylene is between 9 and 14.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000405244A CA1179730A (en) | 1982-06-16 | 1982-06-16 | Snap-in sealing and insulating member for galvanic cells |
| ZA833839A ZA833839B (en) | 1982-06-16 | 1983-05-26 | Snap-in sealing and insulating member for galvanic cells |
| AU15299/83A AU569470B2 (en) | 1982-06-16 | 1983-06-02 | Snap-fit seal and vent for primary cell |
| BE0/210947A BE896976A (en) | 1982-06-16 | 1983-06-06 | IMPROVEMENTS ON GALVANIC BATTERIES |
| DE19833320714 DE3320714A1 (en) | 1982-06-16 | 1983-06-08 | SEALED GALVANIC CELL |
| IT48460/83A IT1167442B (en) | 1982-06-16 | 1983-06-09 | CLAMPING AND SEALING ELEMENT FOR GALVANIC CELLS |
| ES1983281985U ES281985Y (en) | 1982-06-16 | 1983-06-15 | IMPROVEMENTS INTRODUCED IN HERMETIC GALVANIC BATTERIES |
| FR838309877A FR2529016B1 (en) | 1982-06-16 | 1983-06-15 | IMPROVEMENT WITH GALVANIC BATTERIES |
| BR8303176A BR8303176A (en) | 1982-06-16 | 1983-06-15 | GALVANIC CELL CYLINDRICAL SEAL |
| JP58108518A JPS598265A (en) | 1982-06-16 | 1983-06-15 | Battery device with snap engaging type insulating sealing member |
| GB08316257A GB2122021B (en) | 1982-06-16 | 1983-06-15 | Snap-in sealing and insulating member for galvanic cells |
| MX197673A MX153435A (en) | 1982-06-16 | 1983-06-16 | IMPROVEMENTS TO SHUTTER SEAL FOR ELECTRIC BATTERY |
| US06/688,262 US4670362A (en) | 1982-06-16 | 1984-12-31 | Snap-in sealing and insulating member for galvanic cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000405244A CA1179730A (en) | 1982-06-16 | 1982-06-16 | Snap-in sealing and insulating member for galvanic cells |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1179730A true CA1179730A (en) | 1984-12-18 |
Family
ID=4123018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000405244A Expired CA1179730A (en) | 1982-06-16 | 1982-06-16 | Snap-in sealing and insulating member for galvanic cells |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4670362A (en) |
| JP (1) | JPS598265A (en) |
| AU (1) | AU569470B2 (en) |
| BE (1) | BE896976A (en) |
| BR (1) | BR8303176A (en) |
| CA (1) | CA1179730A (en) |
| DE (1) | DE3320714A1 (en) |
| ES (1) | ES281985Y (en) |
| FR (1) | FR2529016B1 (en) |
| GB (1) | GB2122021B (en) |
| IT (1) | IT1167442B (en) |
| MX (1) | MX153435A (en) |
| ZA (1) | ZA833839B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1230921A (en) * | 1983-07-08 | 1987-12-29 | Manuel R. Malay | Low profile seal |
| DE3437039A1 (en) * | 1983-11-04 | 1985-05-23 | Duracell International Inc., Tarrytown, N.Y. | SEALING PART WITH MINERAL FILLERS FOR GALVANIC CELLS |
| US4720672A (en) * | 1984-06-27 | 1988-01-19 | Jon Turino | Testability system |
| GB2218564B (en) * | 1988-05-05 | 1991-05-15 | Duracell Int | Injection molded top |
| US5389465A (en) * | 1992-05-21 | 1995-02-14 | Hawker Energy Products, Inc. | Snap fit battery case and method |
| US5672443A (en) * | 1994-04-15 | 1997-09-30 | Phillips Plastics Corporation | Battery sealing cap |
| US5776631A (en) * | 1995-12-06 | 1998-07-07 | Eveready Battery Company, Inc. | Safety snap-through seal for galvanic cells |
| US6010802A (en) | 1996-01-22 | 2000-01-04 | Rayovac Corporation | Current collector assembly |
| US6001504A (en) * | 1998-03-11 | 1999-12-14 | Duracell Inc. | Prismatic battery housing |
| US6025090A (en) * | 1998-05-15 | 2000-02-15 | Duracell Inc. | End cap assembly for an alkaline cell |
| USD413858S (en) * | 1998-05-29 | 1999-09-14 | Sony Corporation | Rechargeable battery |
| US6042967A (en) * | 1998-07-29 | 2000-03-28 | Duracell Inc | End cap seal assembly for an electrochemical cell |
| KR100300405B1 (en) * | 1998-09-10 | 2002-06-20 | 김순택 | A cap assy of second battery |
| US6274267B1 (en) | 1999-07-30 | 2001-08-14 | Moltech Power Systems, Inc. | Seal for electrochemical cell |
| US6671187B1 (en) | 1999-09-24 | 2003-12-30 | Wilson Greatbatch Ltd. | Protection device having a sleeve and method of assembling a battery with a protection device and an electrical component |
| US6437239B1 (en) | 1999-09-24 | 2002-08-20 | Wilson Greatbatch, Ltd. | Protection device and method of determining exposure temperature |
| US6205034B1 (en) | 1999-09-24 | 2001-03-20 | Wilson Greatbatch Ltd. | Protection device for protecting an electrical component and method of assembling a battery with a protection device and an electrical component |
| US6317335B1 (en) | 1999-09-24 | 2001-11-13 | Wilson Greatbatch Ltd. | Stiffened protection device for protecting an electrical component |
| US6426867B1 (en) | 2000-05-05 | 2002-07-30 | Wilson Greatbatch, Ltd. | Protection device having tapered ribs and method of assembling a battery with a protection device and an electrical component |
| US20080085450A1 (en) * | 2006-10-05 | 2008-04-10 | Depalma Christopher L | End cap seal assembly for an electrochemical cell |
| US20080102365A1 (en) * | 2006-10-31 | 2008-05-01 | Yoppolo Robert A | End cap seal assembly for an electrochemical cell |
| US20080102366A1 (en) * | 2006-10-31 | 2008-05-01 | Anglin David L | End cap seal for an electrochemical cell |
| US20080166626A1 (en) * | 2007-01-05 | 2008-07-10 | Yoppolo Robert A | End cap seal assembly for an electrochemical cell |
| US20080220316A1 (en) * | 2007-03-06 | 2008-09-11 | Berkowitz Fred J | End cap seal assembly for a lithium cell |
| JP7005288B2 (en) | 2017-11-02 | 2022-01-21 | 株式会社ニューフレアテクノロジー | Dust collector |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2149169A (en) * | 1934-11-30 | 1939-02-28 | Gelardin Albert | Dry cell |
| US3623915A (en) * | 1969-07-11 | 1971-11-30 | Ching Koon Pun | Electric dry cells |
| US3663301A (en) * | 1970-04-09 | 1972-05-16 | Mallory & Co Inc P R | Leak-proof primary cell |
| US3754997A (en) * | 1971-06-16 | 1973-08-28 | Mallory & Co Inc P R | Electric battery cell with a plastic top having a spring pressure seal |
| GB1420324A (en) * | 1972-06-20 | 1976-01-07 | Mindex Battery Works Ltd | Dry cell batteries |
| US4020241A (en) * | 1976-03-29 | 1977-04-26 | Union Carbide Corporation | Galvanic cell having a resealable vent closure |
| DE2619178B2 (en) * | 1976-04-30 | 1978-08-17 | Varta Batterie Ag, 3000 Hannover | Galvanic primary element |
| US4075398A (en) * | 1976-10-26 | 1978-02-21 | Esb Incorporated | Means of providing pressure relief to sealed galvanic cell |
| US4079172A (en) * | 1977-03-30 | 1978-03-14 | Union Carbide Corporation | Galvanic cell having a high pressure vent closure |
| US4112200A (en) * | 1977-06-30 | 1978-09-05 | Union Carbide Corporation | Galvanic cell having a primary radial seal and a secondary resealable vent closure |
| JPS5855619B2 (en) * | 1977-11-30 | 1983-12-10 | 富士電気化学株式会社 | Sealing gasket body for explosion-proof batteries |
| US4146681A (en) * | 1977-12-23 | 1979-03-27 | Union Carbide Corporation | Seal closure for a galvanic cell |
| IN151904B (en) * | 1978-05-31 | 1983-09-03 | Hitachi Maxell | |
| US4191806A (en) * | 1978-08-28 | 1980-03-04 | Esb Incorporated | Pressure vent for a sealed primary cell |
| DE2941757C2 (en) * | 1979-10-16 | 1982-06-16 | Varta Batterie Ag, 3000 Hannover | Closure arrangement for galvanic elements and process for their production |
| JPS56132765A (en) * | 1980-03-19 | 1981-10-17 | Matsushita Electric Ind Co Ltd | Manufacture of sealing body for battery |
| JPS56132764A (en) * | 1980-03-19 | 1981-10-17 | Matsushita Electric Ind Co Ltd | Manufacture of sealing body for battery |
| JPS5718682U (en) * | 1980-07-02 | 1982-01-30 | ||
| CA1164936A (en) * | 1981-12-23 | 1984-04-03 | Charles Markin | Sealing and insulating member for galvanic cells |
-
1982
- 1982-06-16 CA CA000405244A patent/CA1179730A/en not_active Expired
-
1983
- 1983-05-26 ZA ZA833839A patent/ZA833839B/en unknown
- 1983-06-02 AU AU15299/83A patent/AU569470B2/en not_active Expired
- 1983-06-06 BE BE0/210947A patent/BE896976A/en not_active IP Right Cessation
- 1983-06-08 DE DE19833320714 patent/DE3320714A1/en active Granted
- 1983-06-09 IT IT48460/83A patent/IT1167442B/en active
- 1983-06-15 FR FR838309877A patent/FR2529016B1/en not_active Expired - Lifetime
- 1983-06-15 GB GB08316257A patent/GB2122021B/en not_active Expired
- 1983-06-15 ES ES1983281985U patent/ES281985Y/en not_active Expired
- 1983-06-15 JP JP58108518A patent/JPS598265A/en active Granted
- 1983-06-15 BR BR8303176A patent/BR8303176A/en not_active IP Right Cessation
- 1983-06-16 MX MX197673A patent/MX153435A/en unknown
-
1984
- 1984-12-31 US US06/688,262 patent/US4670362A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| GB2122021A (en) | 1984-01-04 |
| AU1529983A (en) | 1983-12-22 |
| IT1167442B (en) | 1987-05-13 |
| JPH0534777B2 (en) | 1993-05-24 |
| ZA833839B (en) | 1984-02-29 |
| IT8348460A0 (en) | 1983-06-09 |
| MX153435A (en) | 1986-10-08 |
| FR2529016A1 (en) | 1983-12-23 |
| BR8303176A (en) | 1984-01-31 |
| GB2122021B (en) | 1985-11-13 |
| US4670362A (en) | 1987-06-02 |
| AU569470B2 (en) | 1988-02-04 |
| DE3320714C2 (en) | 1992-07-30 |
| FR2529016B1 (en) | 1994-06-03 |
| DE3320714A1 (en) | 1983-12-22 |
| ES281985Y (en) | 1985-11-16 |
| BE896976A (en) | 1983-10-03 |
| JPS598265A (en) | 1984-01-17 |
| GB8316257D0 (en) | 1983-07-20 |
| ES281985U (en) | 1985-04-16 |
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Legal Events
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| MKEC | Expiry (correction) | ||
| MKEX | Expiry |