CA1196375A - Lithium batteries - Google Patents
Lithium batteriesInfo
- Publication number
- CA1196375A CA1196375A CA000423693A CA423693A CA1196375A CA 1196375 A CA1196375 A CA 1196375A CA 000423693 A CA000423693 A CA 000423693A CA 423693 A CA423693 A CA 423693A CA 1196375 A CA1196375 A CA 1196375A
- Authority
- CA
- Canada
- Prior art keywords
- copper
- separator
- lithium
- anode
- sheet
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/42—Grouping of primary cells into batteries
- H01M6/46—Grouping of primary cells into batteries of flat cells
- H01M6/48—Grouping of primary cells into batteries of flat cells with bipolar electrodes
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Electrical cells and batteries comprising cathodes formed as slurries of MnO2 and carbon in an organic solution of electrolyte in contact with a copper substrate, and sheet lithium anodes adhered to either a conductive plastic or a roughened copper substrate.
Electrical cells and batteries comprising cathodes formed as slurries of MnO2 and carbon in an organic solution of electrolyte in contact with a copper substrate, and sheet lithium anodes adhered to either a conductive plastic or a roughened copper substrate.
Description
63~5 This invention relates to electrical batteries, and particularly to a novel lithium battery of one or more cells.
Lithium batteries have been long known to have potentially superior qualities, such as tolerance for low temperature, high energy density, and long shelf life, but have hitherto been adopted for use only in limited quantities and for highly specialized applications. As pointed out~`in an .
article entitled "Focus On Lithium Batteries: High Energy For Critical Needs", Electronic ~esign, December 10, 1981, pp.
183-198, at page 183, the reasons for this limited acceptance have been simple, but compelling; conventional lithium batteries are very expensive, and have a reputation for being dangerous.
The conventional approach to the design and con-struction of lithium batteries revolves about a conception of the battery as a single cell encapsulated in a metal con-tainer, as of nickel plated steel, and comprising a lithium disc formed integral with a grid of nickel plated steel, or stainless steel, as a current collector. The cathode is a solid pressed pellet of any of vari~us reductants held in a metal cup, as by a metal ring. Such a construction is described, for example, in U.S. Patent No. 3,853,627. This arrangement has manifest advantages in protecting the cell from mechanical damagei in preventing interactions between potentially reactive components of the atmosphere, such as 2 N2, CO2, H2 and H2O, and the chemically active cell compo-nents; and in ameliorating to some degree the consequences of pressure generated within the cell, either by volatile electrochemical constituents such as SO2, or by gases formed '~ ~
in secondary reactions bet~een cell components and contaminants that are Eormcd during storage or are not adequat&ly excluded or removed during cell manu~acture.
~lowever, the provisions made in this way to ensure cell integrity have signi-ficant attendant disadvantages; notable among these are the complexity and consequent cost of the construction, and the potential for explosion caused by excessive internal gassing, internal contaminants, misuse or improper disposal techniques. The potential for explosions is inherent in the use of the rigid metal cell container; i.e., in the very expedient adopted to minimize the probability of potentially explosive reactions.
Recent advances in lithium batteries are described in the Following copending Applications for Letters Patent, by Alan H. Bruder and assigned to the assignee of this invention.
Canadian Application Serial No. 419,745 for Lithium Batteries With Organic Slurry; U.S. Patent Serial No. 4,429,026 for Laminar Multicell Lithium Batteries.
The objects of this invention are to simplify the constructions and improve the reliability of lithium batteries.
The use of organic slurry cathodes, as described in the above cited Canadian Applications Serial No. 419,745, has been found to alleviate many of the problems encountered with pressed bound cathode pellets, the conventional alternative. Basically, the organic slurry cathode comprises a slurry of
Lithium batteries have been long known to have potentially superior qualities, such as tolerance for low temperature, high energy density, and long shelf life, but have hitherto been adopted for use only in limited quantities and for highly specialized applications. As pointed out~`in an .
article entitled "Focus On Lithium Batteries: High Energy For Critical Needs", Electronic ~esign, December 10, 1981, pp.
183-198, at page 183, the reasons for this limited acceptance have been simple, but compelling; conventional lithium batteries are very expensive, and have a reputation for being dangerous.
The conventional approach to the design and con-struction of lithium batteries revolves about a conception of the battery as a single cell encapsulated in a metal con-tainer, as of nickel plated steel, and comprising a lithium disc formed integral with a grid of nickel plated steel, or stainless steel, as a current collector. The cathode is a solid pressed pellet of any of vari~us reductants held in a metal cup, as by a metal ring. Such a construction is described, for example, in U.S. Patent No. 3,853,627. This arrangement has manifest advantages in protecting the cell from mechanical damagei in preventing interactions between potentially reactive components of the atmosphere, such as 2 N2, CO2, H2 and H2O, and the chemically active cell compo-nents; and in ameliorating to some degree the consequences of pressure generated within the cell, either by volatile electrochemical constituents such as SO2, or by gases formed '~ ~
in secondary reactions bet~een cell components and contaminants that are Eormcd during storage or are not adequat&ly excluded or removed during cell manu~acture.
~lowever, the provisions made in this way to ensure cell integrity have signi-ficant attendant disadvantages; notable among these are the complexity and consequent cost of the construction, and the potential for explosion caused by excessive internal gassing, internal contaminants, misuse or improper disposal techniques. The potential for explosions is inherent in the use of the rigid metal cell container; i.e., in the very expedient adopted to minimize the probability of potentially explosive reactions.
Recent advances in lithium batteries are described in the Following copending Applications for Letters Patent, by Alan H. Bruder and assigned to the assignee of this invention.
Canadian Application Serial No. 419,745 for Lithium Batteries With Organic Slurry; U.S. Patent Serial No. 4,429,026 for Laminar Multicell Lithium Batteries.
The objects of this invention are to simplify the constructions and improve the reliability of lithium batteries.
The use of organic slurry cathodes, as described in the above cited Canadian Applications Serial No. 419,745, has been found to alleviate many of the problems encountered with pressed bound cathode pellets, the conventional alternative. Basically, the organic slurry cathode comprises a slurry of
2 -6~5 MnO2 and carbon in a solution of a lithium salt in an organic solvent~ In order to obtain the requisi-te solubility and ionic actiVity for the lithium salts used as electrolytes in lithium systems, organic solvents of considerable solvent po~er, such as propylene carbonate, 1,2 dimethoxyethane, and the like, are conventionally employed. As noted in the above cited Canadian Application Serial No. 419,715, such solven-ts appear to have the ability to permeate the conductive plastic intercell connectors used to isolate the active cell components electrochemically while providing a low impedance path for electronic conduction. This permeation is not sufficiently marked to be characterized by any appreciable solvation or swelling of the conductive plastic, and has in fact been deduced to occur only from the phenomenon of an impedance buildup in batteries in which a conductive plastic boundary was employed to separate an organic slurry cathode from a lithium anode.
As described in the above cited Canadian Application Serial No.
419,715, this tendency can be prevented by sandwiching a metal solvent barrier between layers of conductive plastic, to form a solvent impermeable intercell connector. However, it has now been found that over a period of time at normal temperatures, or much more rapidly at elevated temperatures in the neighbor-hood of 120F, the solvents used in the organic slurry cathode show a tendency to weaken or destroy the adhesive bond between conductive plastic laminae, in contact with the slurry and used for electrochemical isolation, and adjacent metal foil laminae used either as solvent barriers or, for their electrical con-ductivity and mechanical strength, as external electrical terminals.
There are great practical difficulties involved in the resolution of the problem posed by an unavorable interaction between the organic solvent employed in the cathode slurry and the conductive plastic-metal interface. At this inter~ace, a conductive plastic adhesive is employed, because an adequate degree of adhesion between the conductive plastic and the metal foil, of aluminum, tinned steel or the liXe, cannot otherwise be attained, The desired degree of adhesion is attained by including small amounts of reactive functional groups in the adhesive to promote adhesion to the metal foil layer. These groups are speculated to be selectively affected by the potent organic solvent.
The alternative; of eliminating the conductive plastic and placing the cathode slurry directly in contact with the metal foil terminal, is only superficially attractive because the various functions well perormed by the conductive - plastic are antithetic to the normal metallic nature. In par-ticular, the conductive plastic is relied upon for adhesion to the cathode slurry sufficient to provide a low impedance electronic bond; for adhesion to adjacent thermoplastic com-ponents sufficient to provide a liqui.d impermeable seal around the periphery of the wet active cell components; and to provide electrochemical isolation between the electrochemi-cally active components of the cells and external metallic components or adjacent active cell components. Most of the metals fail in one or all of these desired attributes, and only such exotic and inordinately expensive metals as gold, silver and platinum are sufficiently inert electrochemically to warrant the appellation "inert". Some of the stainless steels are sufficiently inert to warrant consideration from 1~9~375 that standpoint alone, but lack adequate adhesive properties and are too costly for use in most applications. ~inned steel, while readi~y available and sealable, is not su~fi-ciently inert, tending to form destructive couples with the MnO2 in the cathode. Such metals as aluminum and zinc are far too active for consideration.
In accordance with this invention, it has been found that copper, while too active for use in a conventional lithium-MnO2 cell, can be employed as the substrate in con-tact with an organic slurry cathode comprising MnO2 if theassembled cell is subjected to a preliminary discharge, soon after electrochemical assembly; i.e., within a few minutes or hours after electrochemical assembly of the cell. Preferably, the copper used as the substrate in contact with the slurry in accordance with the invention is extended out into the seal area surrounding the active components of the cell or cells, to preclude or inhibit the migration of the organic solvent in the cathode slurry into regions in which it might cause prob-lems. In addition, the copper employed is preferably a copper foil having one or preferably both surfaces treated by conven-tional techniques to promote adhesion to adjacent substrates, as in the manners described in United States Patents Nos. 3,220,897; 3,293,109; and 3,699,018; for example.
Thus in a first aspect this invention provides a battery comprising a cathode slurry of manganese dioxide and carbon in a solution of a lithium salt in an organic solvent in contact with a copper substrate, and a lith-um anode, said battery having an OCV below the value at which the copper sub-strate will be oxidized by the manganese dioxide in the presence of the lithium.
;3~5 In a second aspect this invent:ion pro~ides a :Laminar battery, comprising a thin 1at sheet o:E me~al, a nodular layer of copper covering one surface of said metal sheet, a cathode slurry deposit of MnO~ and carbon in a solution of a lithium salt in an organic solvent on ana in intimate contact with a central region of said nodular copper layer, a separator axtending over sai~ cathode slurry deposit, a lithium anode in contact with a central region of said separator on a side of ~aid separator opposite said cathode slurry deposit, and means forming a sealed compartment about said anode, said cathode slurry deposit, and said separator.
In a third aspect this invention provides an anode assembly, comprising a sheet of lithium foil laminated to and permeating the interstices of a central region of the surface of a substrate of nodulated copper foil.
In a fourth aspect this invention provides an inter-cell assembly for a laminar battery, comprising a thin sheet of metal having opposed surfaces of nodulated copper, and a sheet of lithium foi~ laminated to a central region of one of said nodulated copper surfaces.
In a fifth aspect this invention provides a laminar battery, comprising a first thin sheet of metal foil having a nodualted copper surface formed on one side thereo~, a deposi.t of a slurry of MnO2 and carhon in a solution of a lithium salt in an organic solvent on a central region of ~aid nodular surface, a separator over and in contact with said slurry deposit, a lithium foil anoae in contact ~ith said separator on a side of said separator opposite said slurry deposit, said anode being laminated to a central region of a nodular copper surface formed on a second thin sheet of metal foil confront-- 5a -
As described in the above cited Canadian Application Serial No.
419,715, this tendency can be prevented by sandwiching a metal solvent barrier between layers of conductive plastic, to form a solvent impermeable intercell connector. However, it has now been found that over a period of time at normal temperatures, or much more rapidly at elevated temperatures in the neighbor-hood of 120F, the solvents used in the organic slurry cathode show a tendency to weaken or destroy the adhesive bond between conductive plastic laminae, in contact with the slurry and used for electrochemical isolation, and adjacent metal foil laminae used either as solvent barriers or, for their electrical con-ductivity and mechanical strength, as external electrical terminals.
There are great practical difficulties involved in the resolution of the problem posed by an unavorable interaction between the organic solvent employed in the cathode slurry and the conductive plastic-metal interface. At this inter~ace, a conductive plastic adhesive is employed, because an adequate degree of adhesion between the conductive plastic and the metal foil, of aluminum, tinned steel or the liXe, cannot otherwise be attained, The desired degree of adhesion is attained by including small amounts of reactive functional groups in the adhesive to promote adhesion to the metal foil layer. These groups are speculated to be selectively affected by the potent organic solvent.
The alternative; of eliminating the conductive plastic and placing the cathode slurry directly in contact with the metal foil terminal, is only superficially attractive because the various functions well perormed by the conductive - plastic are antithetic to the normal metallic nature. In par-ticular, the conductive plastic is relied upon for adhesion to the cathode slurry sufficient to provide a low impedance electronic bond; for adhesion to adjacent thermoplastic com-ponents sufficient to provide a liqui.d impermeable seal around the periphery of the wet active cell components; and to provide electrochemical isolation between the electrochemi-cally active components of the cells and external metallic components or adjacent active cell components. Most of the metals fail in one or all of these desired attributes, and only such exotic and inordinately expensive metals as gold, silver and platinum are sufficiently inert electrochemically to warrant the appellation "inert". Some of the stainless steels are sufficiently inert to warrant consideration from 1~9~375 that standpoint alone, but lack adequate adhesive properties and are too costly for use in most applications. ~inned steel, while readi~y available and sealable, is not su~fi-ciently inert, tending to form destructive couples with the MnO2 in the cathode. Such metals as aluminum and zinc are far too active for consideration.
In accordance with this invention, it has been found that copper, while too active for use in a conventional lithium-MnO2 cell, can be employed as the substrate in con-tact with an organic slurry cathode comprising MnO2 if theassembled cell is subjected to a preliminary discharge, soon after electrochemical assembly; i.e., within a few minutes or hours after electrochemical assembly of the cell. Preferably, the copper used as the substrate in contact with the slurry in accordance with the invention is extended out into the seal area surrounding the active components of the cell or cells, to preclude or inhibit the migration of the organic solvent in the cathode slurry into regions in which it might cause prob-lems. In addition, the copper employed is preferably a copper foil having one or preferably both surfaces treated by conven-tional techniques to promote adhesion to adjacent substrates, as in the manners described in United States Patents Nos. 3,220,897; 3,293,109; and 3,699,018; for example.
Thus in a first aspect this invention provides a battery comprising a cathode slurry of manganese dioxide and carbon in a solution of a lithium salt in an organic solvent in contact with a copper substrate, and a lith-um anode, said battery having an OCV below the value at which the copper sub-strate will be oxidized by the manganese dioxide in the presence of the lithium.
;3~5 In a second aspect this invent:ion pro~ides a :Laminar battery, comprising a thin 1at sheet o:E me~al, a nodular layer of copper covering one surface of said metal sheet, a cathode slurry deposit of MnO~ and carbon in a solution of a lithium salt in an organic solvent on ana in intimate contact with a central region of said nodular copper layer, a separator axtending over sai~ cathode slurry deposit, a lithium anode in contact with a central region of said separator on a side of ~aid separator opposite said cathode slurry deposit, and means forming a sealed compartment about said anode, said cathode slurry deposit, and said separator.
In a third aspect this invention provides an anode assembly, comprising a sheet of lithium foil laminated to and permeating the interstices of a central region of the surface of a substrate of nodulated copper foil.
In a fourth aspect this invention provides an inter-cell assembly for a laminar battery, comprising a thin sheet of metal having opposed surfaces of nodulated copper, and a sheet of lithium foi~ laminated to a central region of one of said nodulated copper surfaces.
In a fifth aspect this invention provides a laminar battery, comprising a first thin sheet of metal foil having a nodualted copper surface formed on one side thereo~, a deposi.t of a slurry of MnO2 and carhon in a solution of a lithium salt in an organic solvent on a central region of ~aid nodular surface, a separator over and in contact with said slurry deposit, a lithium foil anoae in contact ~ith said separator on a side of said separator opposite said slurry deposit, said anode being laminated to a central region of a nodular copper surface formed on a second thin sheet of metal foil confront-- 5a -
3'~S
ing saia first sheet, and a thermoplastic frame between and laminated to said first and second sheets around the peripheries thereo~ surroundin~ said anode, said cathode slurry deposit, and said separator.
In a sixth aspect this invention provides a multicell battery comprising cells each having a lithium anode and a MnO2 cathode spaced by a separator and communicating electrochemically through a solution of a lithium salt in an organic solvent, in which the cells are e~ectrochemically isolated and electronically connected together through metal intercell connectors each having opposed nodu~ar copper sur-faces in contact with an anode and a cathode of different adjacent cells.
In a seventh aspect this invention provides an inter-cell connector assembly for a laminar battery, comprising a sheet of aluminum having a layer of copper adhered to opposite surfaces and a surface layer of noaulated copper formed on the outer surface of each of said copper layers, and a layer o~
lithium laminated to a central region of one of said nodulated copper surfaces.
In an eighth aspect this inventi.on provides an laminar battery, comprising a thin flat sheet of metal, a nodular layer of copper covering one surface of said metal sheet, a cathode slurry deposit of MnO2 and carbon in a solution of a lithium salt in an organic solvent on and in intimate contac~ with a central region of said nodular copper layer, a separator extending over said cathode slurry deposit, a lithium anode in contact with a central region of said sepa-rator on a side of said separator opposite said cathode slurry deposit, and means forming a sealed compartment about said - 5b -. ~
. "
;3~7S
anode, said cathode slurry deposit, and said separa-tor, said anode comprising a sheet of lithium oil laminated to and per-meating the interstices of a central region of the surface of a substrate of nodulated copper foil.
In a ninth aspect this invention prov.ides an inter-cell assembly for a laminar battery, comprising a thin sheet of aluminum having opposed surfaces formed integral with layers of copper having external nodulated surfaces, and a sheet of lithium foil laminated to a central region of one of said nodulated copper surfaces.
In a tenth aspect this invention provides a multicell battery comprising cells each having a lithium anode and a MnO~ cathode spaced by a separator and communicating electrochemically through a solution of a lithium salt in an organic solvent, in which the cells are electrochemically isolated and electronically connected together through metal intercell connectors each having nodular copper surfaces, one of said surfaces being in contact with an anode and the other of said surfaces being in contact with a cathode of different adjacent cells, said intercell connectors having peripheries extending beyond the borders of said anodes and said cathodes and being sealed together through intermediate closed loops of thermoplastic material.
In the eleventh aspect this invention provides a laminar battery, comprising a thin flat sheet of metal having at least one external copper surface, a cathode slurry deposit of MnO2 and carbon in a solution of a lithium salt in an organic solvent on and in intimate contact with a central region of said copper surface, a separator extending over said cathode slurry deposit, a lithium anode in contact with a _ 5c -:
63~5 central region of said separator on a side of said separator opposite said cathode slurry deposit, and means forming a sealed compartment about said anode, said cathode slurry deposit, and said separator, said battery having been electrically drained promptly after electrochemical assembly to an OCV below the value at which said copper surface will be oxidized by said MnO2 in the presence of lithium.
In a twelfth aspect this invention provides a laminar battery, comprising a first thin sheet of metal foil having at least one external copper surface, a deposit of a slurry of MnO2 and carbon in a solution of a lithium salt in an organic solvent on a central region of said copper surface, a separator over and in contact with said slurry deposit, a lithium foil anode in contact with said separator on a side of said separator opposite said slurry deposit, said anode being laminated to a central region of a nodular copper surface formed on a second thin sheet of metal foil confronting said first sheet, and a thermoplastic frame between and laminated to said first and second sheets around the peripheries thereof surrounding said anode, said cathode slurry deposit, and said separator, in which~said battery has been electrically drained to an OCV below the value at which copper will be oxidized by MnO2 in the presence of lithium before any substantial oxidation of copper has occurred.
Lithium anodes for use with cathode slurries on copper substrates in accordance with the invention may be of conventional constructions. Alternatively, in accordance with a novel aspect of the invention, preferred anodes may be constructed by laminating lithium directly to a surface of a a-copper foil treated to promote adhesionl with the result that a laminar battery containing no conductive plastic components may be constructed.
The practice o~ the invention will best be understood in thP light o-f the following description, together with the accompanying drawings, of various illustrative embodiments thereo.
In the drawings, Fig. 1 is a schematic plan sketch of a cathode end plate suitable for use in the construction of batteries in accordance with the invention;
Fig. 2 is a schematic diagrammatic elevational sketch, with parts shown in cross section, and on an exagger-ated vertical scale relative to the horizontal scale, of the end plate of Fig. 1 as seen su~stantially along the lines 2-2 in Fig. l;
Fig. 3 is a schematic plan sketch of a frame useful in the construction of batteries in accordance with khe invention;
Fig. 4 is a schematic diagrammatic elevational cross-sectional sketch, on a vertical scale enlarged relative to horizontal scale~ showing the frame of Fig. 3 as seen sub-stantially along the lines 4-4 in Fig. 3;
Fig. 5 is a schematic plan view of a separator useful in constructing cells in accordance with the invention, shown approximately to a scale useful with the components of Figs. 1 and 3;
Fig. & is a schematic plan sketch of an intercell assembly useful in the manufacture of batteries in accordance with the invention;
Fig. 7 is a diagrammatic schematic elevational sketch, in cross section, with vertical dimensions greatly 3 ~637~i;
exaggerated relative to horizontal dimensions, showing a cross section through the intercell assembly of Fig. 6 substantially as seen along the lines 7-7 in Fig. 6 Fig. B is a schematic elevational cross-sectional sketch similar to that of Fig. 7, showing an alternative cross-sectional configuration of an intercell assembly useful in the practice of the invention;
Fig. 9 is a cross-sectional elevational schematic diagrammatic sketch similar to Figs. 7 and 8, showing another alternative cross-sectional construction for the intercell connector useful in accordance with the invention;
Fig. 10 is a schematic plan sketch of an anode end plate useful in the practice of the invention;
Fig. 11 is a diagrammatic schematic elevational cross-sectional view, with vertical dimensions exaggerated relative to the horizontal dimensions, illustrating the laminar construction of the anode end plate of Fig. 10 as seen substan-tially along the lines 11-11 in Fig. 10;
Fig. 12 is a diagrammatic schematic elevationai cross-sectional sXetch similar to Fig. 11, showing an alterna-tive construction for the anode end plate of Fig. 10;
Fig. 13 is a diagrammatic elevational cross-sectional sketch, with vertical dimensions greatly exaggerated with re-spect to horizontal dimensions, and on an enlarged scale relative to Figs. 1-11, of a two-cell battery in accordance with the invention;
Fig. 14 is an electron micrograph of the surface of a conventional bright copper foil; and Fig. 15 is an electron micrograph of the surface of a copper foil treated to promote adhesion in accordance with the preferred embodiment of the invention.
1~96375 Figs. 1 and 2 show a cathode end plate 1 comprising a main body portion 2 and, preferably, a projecting tab portion 3 adapted to be folded around the battery upon final assembly so that both terminals o the battery can be accessible from the same side, as is conventional in the flat battery art. As shown in Fig. 2, the end plate 1 comprises an external layer 4 of a suitable metal for making contact with desired electrical circuitry, and preferably of aluminum or the like, for example, aluminum 1-1/2 mils in thickness, on which a layer of copper 5 is deposited by conventional techniques. This base layer of copper may be about 200 microinches, i.e., about 0.2 mils in thickness. Over this copper base layer S is deposited a layer of coral or nodular copper 6, as by any of the techniq~es dis-cussed in the above cited U.S. Patents Nos. 37220,897, 3,293,109 or 3,699,018. U.S. Patents Nos. 4,073,699,
ing saia first sheet, and a thermoplastic frame between and laminated to said first and second sheets around the peripheries thereo~ surroundin~ said anode, said cathode slurry deposit, and said separator.
In a sixth aspect this invention provides a multicell battery comprising cells each having a lithium anode and a MnO2 cathode spaced by a separator and communicating electrochemically through a solution of a lithium salt in an organic solvent, in which the cells are e~ectrochemically isolated and electronically connected together through metal intercell connectors each having opposed nodu~ar copper sur-faces in contact with an anode and a cathode of different adjacent cells.
In a seventh aspect this invention provides an inter-cell connector assembly for a laminar battery, comprising a sheet of aluminum having a layer of copper adhered to opposite surfaces and a surface layer of noaulated copper formed on the outer surface of each of said copper layers, and a layer o~
lithium laminated to a central region of one of said nodulated copper surfaces.
In an eighth aspect this inventi.on provides an laminar battery, comprising a thin flat sheet of metal, a nodular layer of copper covering one surface of said metal sheet, a cathode slurry deposit of MnO2 and carbon in a solution of a lithium salt in an organic solvent on and in intimate contac~ with a central region of said nodular copper layer, a separator extending over said cathode slurry deposit, a lithium anode in contact with a central region of said sepa-rator on a side of said separator opposite said cathode slurry deposit, and means forming a sealed compartment about said - 5b -. ~
. "
;3~7S
anode, said cathode slurry deposit, and said separa-tor, said anode comprising a sheet of lithium oil laminated to and per-meating the interstices of a central region of the surface of a substrate of nodulated copper foil.
In a ninth aspect this invention prov.ides an inter-cell assembly for a laminar battery, comprising a thin sheet of aluminum having opposed surfaces formed integral with layers of copper having external nodulated surfaces, and a sheet of lithium foil laminated to a central region of one of said nodulated copper surfaces.
In a tenth aspect this invention provides a multicell battery comprising cells each having a lithium anode and a MnO~ cathode spaced by a separator and communicating electrochemically through a solution of a lithium salt in an organic solvent, in which the cells are electrochemically isolated and electronically connected together through metal intercell connectors each having nodular copper surfaces, one of said surfaces being in contact with an anode and the other of said surfaces being in contact with a cathode of different adjacent cells, said intercell connectors having peripheries extending beyond the borders of said anodes and said cathodes and being sealed together through intermediate closed loops of thermoplastic material.
In the eleventh aspect this invention provides a laminar battery, comprising a thin flat sheet of metal having at least one external copper surface, a cathode slurry deposit of MnO2 and carbon in a solution of a lithium salt in an organic solvent on and in intimate contact with a central region of said copper surface, a separator extending over said cathode slurry deposit, a lithium anode in contact with a _ 5c -:
63~5 central region of said separator on a side of said separator opposite said cathode slurry deposit, and means forming a sealed compartment about said anode, said cathode slurry deposit, and said separator, said battery having been electrically drained promptly after electrochemical assembly to an OCV below the value at which said copper surface will be oxidized by said MnO2 in the presence of lithium.
In a twelfth aspect this invention provides a laminar battery, comprising a first thin sheet of metal foil having at least one external copper surface, a deposit of a slurry of MnO2 and carbon in a solution of a lithium salt in an organic solvent on a central region of said copper surface, a separator over and in contact with said slurry deposit, a lithium foil anode in contact with said separator on a side of said separator opposite said slurry deposit, said anode being laminated to a central region of a nodular copper surface formed on a second thin sheet of metal foil confronting said first sheet, and a thermoplastic frame between and laminated to said first and second sheets around the peripheries thereof surrounding said anode, said cathode slurry deposit, and said separator, in which~said battery has been electrically drained to an OCV below the value at which copper will be oxidized by MnO2 in the presence of lithium before any substantial oxidation of copper has occurred.
Lithium anodes for use with cathode slurries on copper substrates in accordance with the invention may be of conventional constructions. Alternatively, in accordance with a novel aspect of the invention, preferred anodes may be constructed by laminating lithium directly to a surface of a a-copper foil treated to promote adhesionl with the result that a laminar battery containing no conductive plastic components may be constructed.
The practice o~ the invention will best be understood in thP light o-f the following description, together with the accompanying drawings, of various illustrative embodiments thereo.
In the drawings, Fig. 1 is a schematic plan sketch of a cathode end plate suitable for use in the construction of batteries in accordance with the invention;
Fig. 2 is a schematic diagrammatic elevational sketch, with parts shown in cross section, and on an exagger-ated vertical scale relative to the horizontal scale, of the end plate of Fig. 1 as seen su~stantially along the lines 2-2 in Fig. l;
Fig. 3 is a schematic plan sketch of a frame useful in the construction of batteries in accordance with khe invention;
Fig. 4 is a schematic diagrammatic elevational cross-sectional sketch, on a vertical scale enlarged relative to horizontal scale~ showing the frame of Fig. 3 as seen sub-stantially along the lines 4-4 in Fig. 3;
Fig. 5 is a schematic plan view of a separator useful in constructing cells in accordance with the invention, shown approximately to a scale useful with the components of Figs. 1 and 3;
Fig. & is a schematic plan sketch of an intercell assembly useful in the manufacture of batteries in accordance with the invention;
Fig. 7 is a diagrammatic schematic elevational sketch, in cross section, with vertical dimensions greatly 3 ~637~i;
exaggerated relative to horizontal dimensions, showing a cross section through the intercell assembly of Fig. 6 substantially as seen along the lines 7-7 in Fig. 6 Fig. B is a schematic elevational cross-sectional sketch similar to that of Fig. 7, showing an alternative cross-sectional configuration of an intercell assembly useful in the practice of the invention;
Fig. 9 is a cross-sectional elevational schematic diagrammatic sketch similar to Figs. 7 and 8, showing another alternative cross-sectional construction for the intercell connector useful in accordance with the invention;
Fig. 10 is a schematic plan sketch of an anode end plate useful in the practice of the invention;
Fig. 11 is a diagrammatic schematic elevational cross-sectional view, with vertical dimensions exaggerated relative to the horizontal dimensions, illustrating the laminar construction of the anode end plate of Fig. 10 as seen substan-tially along the lines 11-11 in Fig. 10;
Fig. 12 is a diagrammatic schematic elevationai cross-sectional sXetch similar to Fig. 11, showing an alterna-tive construction for the anode end plate of Fig. 10;
Fig. 13 is a diagrammatic elevational cross-sectional sketch, with vertical dimensions greatly exaggerated with re-spect to horizontal dimensions, and on an enlarged scale relative to Figs. 1-11, of a two-cell battery in accordance with the invention;
Fig. 14 is an electron micrograph of the surface of a conventional bright copper foil; and Fig. 15 is an electron micrograph of the surface of a copper foil treated to promote adhesion in accordance with the preferred embodiment of the invention.
1~96375 Figs. 1 and 2 show a cathode end plate 1 comprising a main body portion 2 and, preferably, a projecting tab portion 3 adapted to be folded around the battery upon final assembly so that both terminals o the battery can be accessible from the same side, as is conventional in the flat battery art. As shown in Fig. 2, the end plate 1 comprises an external layer 4 of a suitable metal for making contact with desired electrical circuitry, and preferably of aluminum or the like, for example, aluminum 1-1/2 mils in thickness, on which a layer of copper 5 is deposited by conventional techniques. This base layer of copper may be about 200 microinches, i.e., about 0.2 mils in thickness. Over this copper base layer S is deposited a layer of coral or nodular copper 6, as by any of the techniq~es dis-cussed in the above cited U.S. Patents Nos. 37220,897, 3,293,109 or 3,699,018. U.S. Patents Nos. 4,073,699,
4,088,544; and 4,113,576 teach methods of making copper foil having a roughened, toothed or nodulated surface of the kind here preferred which may advantageously be considered in the selection of conventional materials for use in the practic~ of the invention. The surface of the copper so ormed comprises minute projections which serve to aid in adhering the surface 6 to adjacent substrates, and in particular to adjacent thermo-plastic ~rame materials and to a cathode slurry deposit on the surface 6 in a manner to be described. A plain copper surface, ~5 rather than the nodular copper surface 6, can be employed if desired, but if so, additional care must be exercised to insure adequate adhesion to adjacent thermoplastic sealing components to be described, and a somewhat higher electrical impedance between the surface of the end plate 1 and the organic slurry 30 , adherent thereto may be anticipated.
~L19~5 Figs. 3 and 4 show a frame 7 useful in the assembly of batteries in accordance with the invention. As shown in Fig. 3, the frame 7 comprises a generally rectangular member formed with a central aperture 8 within which to receive electrochemical components of the cell in a manner to be described below. The frame 7 may be of any conventional thermoplastic material, preferably one which is adhesive or can be rendered adhesive by the application of heat, pressure or a suitable solvent, and in the present particularly preferred embodiment comprises a central layer 8, for example, of 5 mils in thickness, comprising a poly(vinyl chloride, vinyl acetate) containing about 85~ vinyl chloride and 15~ vinyl acetate by weight based on the weight of copolymer. On th~ surfaces of the vinyl layer 8 are deposited adhesive layers 9 and 10, which in accordance with the presently preferred embodiment may comprise Versalon 1140 hot melt polyamide adhesive, as made and sold by General Mills, Inc., of Minneapolis, Minnesotaj or other suitable polyamide or other adhesive known to the art.
Fig. 5 shows a separator useful in combination with the other components to be describedO The separator 11 may be of àny conventional material, of approximately 2-10 mils in thickness. Separators suitable for use in lithium batteries are well known in the art, among those to be considered being poly-olefins such as polypropylene, polyethylene, copolymers of propylene and ethylene, mixtures of polyolefins with rubbers such as styrene-butadiene rubber, and the like, together with additives such as TiO2 and the like. A suitable microporous polypropylene separator is sold under the trademark Celgard by Celanese Plastics Co., of Greer, So. Carolina. A presently preferred material is a 2-ml. microporous polyolefin separator * Trade ~lark ~lg6375 material of the kind described in U.S. patent No. 4,2B7,276, which incorporates a non-ionic wetting agent.
Fig. 6 i~hows an intercell assembly generally designated 12 which essentially comprises a copper sheet 13On which is laminated a lithium anode 14 of lithium foil, for example, about 2 mils in thickness. The preferred construction of the intercell assembly 12 is shown in Fig. ~ as comprising a central layer 15 of copper, on either side of which are formed nodularized surfaces 16 and 17 of copper prepared in the manner described above to have minute projections suitable for adhering to adjacent substrates. The lithium anode 14 may be laminated directly to one side 16 o this copper structure by the aid of pressure, for example, in the vicinity of 2000 lbs/in.2, which may be applied by calender rolls, or by an hydraulic press or the liXe. The thicknesses of the copper constituents of the intercell assembly 12 are not especially critical, but, for Pxample, in accordance with the preferred embodiment the central layer 15 of copper was approximately one mil in thickness, and the nodulated layers 16 and 17 on either side were each about 0.3 mils in thickness.
Fig. 8 shows an alternative construction 12a for the intercell assembly 12 of Fig. 6, in which the middle substrate comprises a central layer 18 of aluminum, from 1 to 2 mils in thickness, on each side of which are deposited layers 19 and 20 of thin soft copper. Over the layers of copper 19 and 20 are deposited nodular layers of copper 21 and 22, respectively, in the manner described above, and on one of the nodular layers 21 the lithium anode 14a is laminated in the manner described above.
Fig. 9 shows still another alternative construction 12b for the intercell assembly 12, in which, as in the embodi-63~75 ment of Figure S, the structure comprises an aluminum substrate 23, which Eor this purpose can be about 2 mlls in thickness, on one side of which is deposited a layer of copper 24. The layer of copper 24 is preferably, but not necessarily, provided with a nodular surface. On the other side of the aluminum layer 23 is a layer 25 of a conductive plastic adhesive primer, -to which a layer 26 of conductive plastic, for example of 2 to 6 mils in thickness, is laminated. The lithium anode 14b comprises a lithium foil laminated to the conductive plastic layer 26. For this purpose, as described in that application, the lithium surface adjacent the conductive plastic substrate should be freshly prepared.
This precaution is not necessary in the case of the laminations of the lithium foils 14 and 14a in the structures of Figures 7 and 8, because the forcible interfacing of the lithium foil with the nodular surface of the copper in those constructions creates so much additional surface that any surface impurities present on the lithium foil make no difference to the strength and electrical conductivity of the laminar bond achieved.
Figure 10 shows an anode end plate 30 suitable for use in the con-struction of laminar batteries in accordance with the invention, which essentially comprises a metal plate 31 to which is laminated a lithium anode 32. With reference to Figure 11, showing the present preferred construction, the metallic substrate 31 comprises an outer layer 33 of aluminum, for example, of 1-1/2 mils in thickness, on which is electrically deposited a layer of about .2 to .4 mils in thickness of soft copper 34. On the copper surface 34 is deposited a layer of modular copper 35~ of the kind descrlbecl above, to which -the llthlum ,anode 32 is lamin~lted by pressure RS described above.
Figure 1~ sho~s an alternate construction 30a for the anode end plate 30. This structure takes the form of an aluminum terminal plate 40, for e~ample of 2 mils in thickness, coated with a conductive plastic primer adhesivelayer 41 and thereby adhered to a conductive plastic layer 42, for example of 2 to 6 mils in thickness. The lithium anode 32a may be laminated directly to the surface of the conductive plastic layer 42 without an intermediate adhesive so long as the surface of the lithium adjacent the conductive plastic substrate 42 is freshly exposed just prior to the lamination.
Figure 13 shows a two-cell lithium battery constructed in accordance with the preferred embodiment of the invention. The substitution of the alternate components described above for those presently preferred components to be described in connection with Figure 13 will become apparent to those skilled in the art as the description proceeds.
Figure 13 shows a two cell battery. As will be apparent to those skilled in the art, a single cell battery could be made in the same way by eliminating intercell parts, and batteries of more than two cells could be assembled by simply multiplying the necessary intercell components.
~hile it is not necessary to the practice of the invention, it is convenient to assemble the battery on an insulating base sheet 50 coated with a suitable layer of adhesive 51. The base sheet may be of any suitable materials, but is preferably of the materials more fully shown and described in 36;3~7~;
U.S. Patent No. 4rO86,400, comprising a lamina~e of kraft paper, a thermoplastic liquid-impervious resin overlying the paper, and an overlayer on the resin of a heat sealing adhesive.
As shown, the base sheet 50, 51 is provided with an aperture 52 to expose the aluminum metal end terminal collector sheet 33 forming a portion of an anode collec~or assembly 30 of the kind described above in connection with Figs. 10 and 11.
The metal terminal sheet 33 is preferably laminated to a selected region surrounding the aperture 52 of the adhesive coating 51 on the insulating sheet 50, and to the peripheral borders of the adhesive soating 51 on the sheet 50, but is not necessarily, and preferably is not, laminated to the insulating sheet in other regions.
As indicated in Fig. 13, a first insulating frame 7 of thermoplastic material such as that described above in connection with Figs. 3 and 4 is laminated to the ~orders of the toothed side 35 of the copper upper layer oE the anode terminal assembly sheet 3, as by heat and pressure, to form a seal surrounding the lithium anode 32 that is laminated to the toothed surface of the copper layer 35 as described above. A
separator 11, of the type described above in connection with Fig. 5, is preferably only locally tacked to the periphery of the frame 7 around the borders of the aperture 8 and the frame 7, to allow communication of gases during later vacuum sealing of the battery in a manner to be described.
Over the separator 11 is deposited a first cathode stratum 53 comprising an organic cathode slurry of manganese dioxide and carbon, which may be of any of the formulations described below, or of such equivalent composltions as will ~96~37~
occur to those skilled in the art, and which is in conductive contact with the lower copper surface 17 of an intercell connector assembly 12 such as that described above in connection with Fiqs. 6 and 7. As shown, the boundaries of the intercell connector 12 extend well into the seal area at the periphery of the frame 7, to minimize and inhibit the flow of any electrolyte solvent from the cathode slurry 53 into other regions of the battery. Overlying the borders of the intercell connector assembly metal sheet 12 is a second frame 7, adhered to the copper side 16 of the intercell connector assembly 12, and provided with an integrally laminated lithium anode 14 as described aboYe in connection with Figs. 6 and 7.
A second ~hermoplastic frame 7 is applied over the periphery of the nodulated copper layer 16 of the intercell connector assembly 12, and a second separator 11 is applied over the lithium anode 14 and selectively adhered to portions of the borders of the frame 7 surrounding the aperture 8 in frame 7. A second cathode slurry deposit 54 is applied over the separator llo The battery assembly is then completed by the addition of a cathode end plate assembly 3, such as that described above in connection with Fi.gs. 1 to 2, which is sealed around the periphery of the upper side of the thermo-plastic frame 7 with the toothed side 6 of the copper substrate serving to promote adhesion by intimate interfacial contact with the thermoplastic adhesive, not saparately shown in Fig.
13, overlying the body of the frame 7. As illlustrated, the tab 3 formed on the cathode end plate assembly may be folded around the battery to present a positive terminal on the same side as the negative terminal exposed through the aperture 52 in the insulating base sheet.
3~5 Upon assembly in the manner generally described abovel which can proceed in more detail as described in the above cited copending applications, the components are prefer-ably heat-sealed about the peripheries under vacuum in the manner described in the above cited Canadian application Serial No. 419,745 and United States Patent 4,429,026. The processes as described in those applications, as are other operations in the manufacture and assembly of a battery com-prising lithium and organic slurry cathode components, are preferably carried out in a dry atmosphere. The peripheral seals described above are preferably not made in the order in which the components are assembled, but are made following assembly of the components as the battery is being evacuated during the sealing process.
Following assembly of the battery as described above, the battery is preferably subjected to an electrical drain by connecting its terminals across a suitable resistor to drain from one to three percent of the available energy capacity in the manner described in the above cited Canadian application Serial No. 419,745. This process serves to stabilize the battery against gassing, but is also essential to stabilize the battery against unwanted electrochemical couplings developed between the copper in contact with the organic cathode slurry and the MnO2 in the cathode slurry. This matter will be dis-cussed in more detail below.
Cathode slurry deposits such as those shown a-t 53 and 54 in Figure 13 are preferably formed as a slurry of manganese dioxide and carbon particles in an electrolyte solution in an organic solvent containing a lithium salt as the ionically con-ductive species. Suitable cathode slurry compositions com-prise from 50 to lO0 parts bv weight or propylene carbonate and from 0 to 50 parts by weight oE 1,2 dimethoxyethaneJ basecl on the ~eight of solvent, as the organic solvent, ~ith LiAsF6 in concentrations of from 0.05 to 2.00 molal, or LiC10~ in concentrations oE from 0.65 to 1.97 molal, as the electrolyte. The electrolyte solutlon may comprise from 35 to 59 percent by weight, based on the weight oE slurry, of a dispersion in a sollltion of hlnO2 and carbon black in weight ratios oE hlnO2/carbon black of from 8:1/24:1.
Various preferred and other suitable compositions of this kind are described in detail in the above cited Canadian Application No. 419,745. Other composi-tions that may be preferred for the lower flash point oE the solvent employed comprise the same range of ratios of MnO2 and carbon in an electrolyte solution of the chosen lithi~lm salt in ~-butyrolactone. Typical compositions suitable for the purpose may include from 45 to 50 parts by weight of ~-butyrolactone, in which from 6 to 12 parts by weight of LiAsF6 are dissolved, as the organic electrolyte, in which the manganese dioxide and carbon are dispersed in sufficient quantities to form a readily extrudable mixture. As is well known in the art, the particular ratio of MnO2 to carbon is optimized in dependence on the intended current drain environment of the battery, with higher propor-tions of hlnO2 favoring increased capacity, and higher ratios of carbon favoring lower impedance within the bounds stated.
Higher concentrations of the lithium salt in the electrolyte tend to decrease internal impedance, but the relatively high cost of ~he lithium salt may dictate a preference for a somewhat lower concentration than that electrically optimum. A particular composition that is entirely suitable comprises 103.68 gms. of hinO2, 4.32 gms. of carbon, 45.0 gms. ~f y-butyrolactone, and 6 gms. of LiAsF6. Such a composition has shown the ability to deliver 1440 milliampere hours to a cutoff voltage o 3.0 volts, and 1312 milliampere hours to 5.0 volts, in two cell batteries of the type described .. . . . . . . . . . . .
above containing:10 grams of cathode slurry per cell.
While it is not desired to be bound by any theoreti-cal explanation, it is speculated that the stability of batteries constructed as described above with arganic slurry cathodes on copper substrates can be rationalized on the following basis:
The exact reaction potentials obtained in practical electrochemical systems are difficult to obtain and are somewhat interdependent. However, in general for the systems here considered the overall cell reaction for a freshly assembled battery can be expressed as:
(1) Li + MnO2 ---> (Li+)(MnO2~3 ~3.62 volts The lithium reduction potential is given by (2) Li++ e~ -> Li -3.1 volts Adding reactions (1) and (2), (3) Li++ e~ +MnO2 - > (MnO2~Li+) ~0,52 volts The oxidation potential of copper is given by (4) 1/2 Cu > e~ + 1/2 Cu+2 -0.36 volts Adding reactions (3) and (4),
~L19~5 Figs. 3 and 4 show a frame 7 useful in the assembly of batteries in accordance with the invention. As shown in Fig. 3, the frame 7 comprises a generally rectangular member formed with a central aperture 8 within which to receive electrochemical components of the cell in a manner to be described below. The frame 7 may be of any conventional thermoplastic material, preferably one which is adhesive or can be rendered adhesive by the application of heat, pressure or a suitable solvent, and in the present particularly preferred embodiment comprises a central layer 8, for example, of 5 mils in thickness, comprising a poly(vinyl chloride, vinyl acetate) containing about 85~ vinyl chloride and 15~ vinyl acetate by weight based on the weight of copolymer. On th~ surfaces of the vinyl layer 8 are deposited adhesive layers 9 and 10, which in accordance with the presently preferred embodiment may comprise Versalon 1140 hot melt polyamide adhesive, as made and sold by General Mills, Inc., of Minneapolis, Minnesotaj or other suitable polyamide or other adhesive known to the art.
Fig. 5 shows a separator useful in combination with the other components to be describedO The separator 11 may be of àny conventional material, of approximately 2-10 mils in thickness. Separators suitable for use in lithium batteries are well known in the art, among those to be considered being poly-olefins such as polypropylene, polyethylene, copolymers of propylene and ethylene, mixtures of polyolefins with rubbers such as styrene-butadiene rubber, and the like, together with additives such as TiO2 and the like. A suitable microporous polypropylene separator is sold under the trademark Celgard by Celanese Plastics Co., of Greer, So. Carolina. A presently preferred material is a 2-ml. microporous polyolefin separator * Trade ~lark ~lg6375 material of the kind described in U.S. patent No. 4,2B7,276, which incorporates a non-ionic wetting agent.
Fig. 6 i~hows an intercell assembly generally designated 12 which essentially comprises a copper sheet 13On which is laminated a lithium anode 14 of lithium foil, for example, about 2 mils in thickness. The preferred construction of the intercell assembly 12 is shown in Fig. ~ as comprising a central layer 15 of copper, on either side of which are formed nodularized surfaces 16 and 17 of copper prepared in the manner described above to have minute projections suitable for adhering to adjacent substrates. The lithium anode 14 may be laminated directly to one side 16 o this copper structure by the aid of pressure, for example, in the vicinity of 2000 lbs/in.2, which may be applied by calender rolls, or by an hydraulic press or the liXe. The thicknesses of the copper constituents of the intercell assembly 12 are not especially critical, but, for Pxample, in accordance with the preferred embodiment the central layer 15 of copper was approximately one mil in thickness, and the nodulated layers 16 and 17 on either side were each about 0.3 mils in thickness.
Fig. 8 shows an alternative construction 12a for the intercell assembly 12 of Fig. 6, in which the middle substrate comprises a central layer 18 of aluminum, from 1 to 2 mils in thickness, on each side of which are deposited layers 19 and 20 of thin soft copper. Over the layers of copper 19 and 20 are deposited nodular layers of copper 21 and 22, respectively, in the manner described above, and on one of the nodular layers 21 the lithium anode 14a is laminated in the manner described above.
Fig. 9 shows still another alternative construction 12b for the intercell assembly 12, in which, as in the embodi-63~75 ment of Figure S, the structure comprises an aluminum substrate 23, which Eor this purpose can be about 2 mlls in thickness, on one side of which is deposited a layer of copper 24. The layer of copper 24 is preferably, but not necessarily, provided with a nodular surface. On the other side of the aluminum layer 23 is a layer 25 of a conductive plastic adhesive primer, -to which a layer 26 of conductive plastic, for example of 2 to 6 mils in thickness, is laminated. The lithium anode 14b comprises a lithium foil laminated to the conductive plastic layer 26. For this purpose, as described in that application, the lithium surface adjacent the conductive plastic substrate should be freshly prepared.
This precaution is not necessary in the case of the laminations of the lithium foils 14 and 14a in the structures of Figures 7 and 8, because the forcible interfacing of the lithium foil with the nodular surface of the copper in those constructions creates so much additional surface that any surface impurities present on the lithium foil make no difference to the strength and electrical conductivity of the laminar bond achieved.
Figure 10 shows an anode end plate 30 suitable for use in the con-struction of laminar batteries in accordance with the invention, which essentially comprises a metal plate 31 to which is laminated a lithium anode 32. With reference to Figure 11, showing the present preferred construction, the metallic substrate 31 comprises an outer layer 33 of aluminum, for example, of 1-1/2 mils in thickness, on which is electrically deposited a layer of about .2 to .4 mils in thickness of soft copper 34. On the copper surface 34 is deposited a layer of modular copper 35~ of the kind descrlbecl above, to which -the llthlum ,anode 32 is lamin~lted by pressure RS described above.
Figure 1~ sho~s an alternate construction 30a for the anode end plate 30. This structure takes the form of an aluminum terminal plate 40, for e~ample of 2 mils in thickness, coated with a conductive plastic primer adhesivelayer 41 and thereby adhered to a conductive plastic layer 42, for example of 2 to 6 mils in thickness. The lithium anode 32a may be laminated directly to the surface of the conductive plastic layer 42 without an intermediate adhesive so long as the surface of the lithium adjacent the conductive plastic substrate 42 is freshly exposed just prior to the lamination.
Figure 13 shows a two-cell lithium battery constructed in accordance with the preferred embodiment of the invention. The substitution of the alternate components described above for those presently preferred components to be described in connection with Figure 13 will become apparent to those skilled in the art as the description proceeds.
Figure 13 shows a two cell battery. As will be apparent to those skilled in the art, a single cell battery could be made in the same way by eliminating intercell parts, and batteries of more than two cells could be assembled by simply multiplying the necessary intercell components.
~hile it is not necessary to the practice of the invention, it is convenient to assemble the battery on an insulating base sheet 50 coated with a suitable layer of adhesive 51. The base sheet may be of any suitable materials, but is preferably of the materials more fully shown and described in 36;3~7~;
U.S. Patent No. 4rO86,400, comprising a lamina~e of kraft paper, a thermoplastic liquid-impervious resin overlying the paper, and an overlayer on the resin of a heat sealing adhesive.
As shown, the base sheet 50, 51 is provided with an aperture 52 to expose the aluminum metal end terminal collector sheet 33 forming a portion of an anode collec~or assembly 30 of the kind described above in connection with Figs. 10 and 11.
The metal terminal sheet 33 is preferably laminated to a selected region surrounding the aperture 52 of the adhesive coating 51 on the insulating sheet 50, and to the peripheral borders of the adhesive soating 51 on the sheet 50, but is not necessarily, and preferably is not, laminated to the insulating sheet in other regions.
As indicated in Fig. 13, a first insulating frame 7 of thermoplastic material such as that described above in connection with Figs. 3 and 4 is laminated to the ~orders of the toothed side 35 of the copper upper layer oE the anode terminal assembly sheet 3, as by heat and pressure, to form a seal surrounding the lithium anode 32 that is laminated to the toothed surface of the copper layer 35 as described above. A
separator 11, of the type described above in connection with Fig. 5, is preferably only locally tacked to the periphery of the frame 7 around the borders of the aperture 8 and the frame 7, to allow communication of gases during later vacuum sealing of the battery in a manner to be described.
Over the separator 11 is deposited a first cathode stratum 53 comprising an organic cathode slurry of manganese dioxide and carbon, which may be of any of the formulations described below, or of such equivalent composltions as will ~96~37~
occur to those skilled in the art, and which is in conductive contact with the lower copper surface 17 of an intercell connector assembly 12 such as that described above in connection with Fiqs. 6 and 7. As shown, the boundaries of the intercell connector 12 extend well into the seal area at the periphery of the frame 7, to minimize and inhibit the flow of any electrolyte solvent from the cathode slurry 53 into other regions of the battery. Overlying the borders of the intercell connector assembly metal sheet 12 is a second frame 7, adhered to the copper side 16 of the intercell connector assembly 12, and provided with an integrally laminated lithium anode 14 as described aboYe in connection with Figs. 6 and 7.
A second ~hermoplastic frame 7 is applied over the periphery of the nodulated copper layer 16 of the intercell connector assembly 12, and a second separator 11 is applied over the lithium anode 14 and selectively adhered to portions of the borders of the frame 7 surrounding the aperture 8 in frame 7. A second cathode slurry deposit 54 is applied over the separator llo The battery assembly is then completed by the addition of a cathode end plate assembly 3, such as that described above in connection with Fi.gs. 1 to 2, which is sealed around the periphery of the upper side of the thermo-plastic frame 7 with the toothed side 6 of the copper substrate serving to promote adhesion by intimate interfacial contact with the thermoplastic adhesive, not saparately shown in Fig.
13, overlying the body of the frame 7. As illlustrated, the tab 3 formed on the cathode end plate assembly may be folded around the battery to present a positive terminal on the same side as the negative terminal exposed through the aperture 52 in the insulating base sheet.
3~5 Upon assembly in the manner generally described abovel which can proceed in more detail as described in the above cited copending applications, the components are prefer-ably heat-sealed about the peripheries under vacuum in the manner described in the above cited Canadian application Serial No. 419,745 and United States Patent 4,429,026. The processes as described in those applications, as are other operations in the manufacture and assembly of a battery com-prising lithium and organic slurry cathode components, are preferably carried out in a dry atmosphere. The peripheral seals described above are preferably not made in the order in which the components are assembled, but are made following assembly of the components as the battery is being evacuated during the sealing process.
Following assembly of the battery as described above, the battery is preferably subjected to an electrical drain by connecting its terminals across a suitable resistor to drain from one to three percent of the available energy capacity in the manner described in the above cited Canadian application Serial No. 419,745. This process serves to stabilize the battery against gassing, but is also essential to stabilize the battery against unwanted electrochemical couplings developed between the copper in contact with the organic cathode slurry and the MnO2 in the cathode slurry. This matter will be dis-cussed in more detail below.
Cathode slurry deposits such as those shown a-t 53 and 54 in Figure 13 are preferably formed as a slurry of manganese dioxide and carbon particles in an electrolyte solution in an organic solvent containing a lithium salt as the ionically con-ductive species. Suitable cathode slurry compositions com-prise from 50 to lO0 parts bv weight or propylene carbonate and from 0 to 50 parts by weight oE 1,2 dimethoxyethaneJ basecl on the ~eight of solvent, as the organic solvent, ~ith LiAsF6 in concentrations of from 0.05 to 2.00 molal, or LiC10~ in concentrations oE from 0.65 to 1.97 molal, as the electrolyte. The electrolyte solutlon may comprise from 35 to 59 percent by weight, based on the weight oE slurry, of a dispersion in a sollltion of hlnO2 and carbon black in weight ratios oE hlnO2/carbon black of from 8:1/24:1.
Various preferred and other suitable compositions of this kind are described in detail in the above cited Canadian Application No. 419,745. Other composi-tions that may be preferred for the lower flash point oE the solvent employed comprise the same range of ratios of MnO2 and carbon in an electrolyte solution of the chosen lithi~lm salt in ~-butyrolactone. Typical compositions suitable for the purpose may include from 45 to 50 parts by weight of ~-butyrolactone, in which from 6 to 12 parts by weight of LiAsF6 are dissolved, as the organic electrolyte, in which the manganese dioxide and carbon are dispersed in sufficient quantities to form a readily extrudable mixture. As is well known in the art, the particular ratio of MnO2 to carbon is optimized in dependence on the intended current drain environment of the battery, with higher propor-tions of hlnO2 favoring increased capacity, and higher ratios of carbon favoring lower impedance within the bounds stated.
Higher concentrations of the lithium salt in the electrolyte tend to decrease internal impedance, but the relatively high cost of ~he lithium salt may dictate a preference for a somewhat lower concentration than that electrically optimum. A particular composition that is entirely suitable comprises 103.68 gms. of hinO2, 4.32 gms. of carbon, 45.0 gms. ~f y-butyrolactone, and 6 gms. of LiAsF6. Such a composition has shown the ability to deliver 1440 milliampere hours to a cutoff voltage o 3.0 volts, and 1312 milliampere hours to 5.0 volts, in two cell batteries of the type described .. . . . . . . . . . . .
above containing:10 grams of cathode slurry per cell.
While it is not desired to be bound by any theoreti-cal explanation, it is speculated that the stability of batteries constructed as described above with arganic slurry cathodes on copper substrates can be rationalized on the following basis:
The exact reaction potentials obtained in practical electrochemical systems are difficult to obtain and are somewhat interdependent. However, in general for the systems here considered the overall cell reaction for a freshly assembled battery can be expressed as:
(1) Li + MnO2 ---> (Li+)(MnO2~3 ~3.62 volts The lithium reduction potential is given by (2) Li++ e~ -> Li -3.1 volts Adding reactions (1) and (2), (3) Li++ e~ +MnO2 - > (MnO2~Li+) ~0,52 volts The oxidation potential of copper is given by (4) 1/2 Cu > e~ + 1/2 Cu+2 -0.36 volts Adding reactions (3) and (4),
(5) 1/2 Cu + MnO2 + Li~ (Li+)(MnO2~)~1/2 Cu+2 +.16 volts Reaction (5) will proceed spontaneously, and would be highly undesirable from the standpoint of battery stability.
However, the reaction in question will proceed rather slowly, so that the battery will be fully operative whether or not any steps are taken to inhibit the reaction for purposes not requiring extended shelf lie.
Following the preliminary electrical draining of the battery carried out in accordance with the preferred embodiment of the invention, the overall cell reaction can be expressed as:
(la) Li ~ MnO2 ~-~ (Li~)(MnO2 ) +3.2 volts The potential associated with the sum of reactions (la) and (2) is now (3a) Li~ ~ e~ ~ MnO2 -~ (MnO2)(Li~) ~0.1 volts In~order or this system to react with copper, the copper would have to be reduced, or become electrically positive with respect to the MnO2, which will not occur spontaneously. Thus, the result of the pre-drain operation i5 to make the copper cathodic relative to the MnO~, rather than anodic, resulting in a stable electrochemical system.
From the above discussion, it will be~
apparent that it is not necessary to drain the battery to an OCV (open circuit voltage) of 3.2 volts in order to stabilize it against the copper substrate; any OCV of 3.46 or below would suffice for this purpose. Actually, since the exact potentials involved in a real system are somewhat system dependent, a re precise criterion is that the OCV should be reduced to a value at which the copper will not be oxidized by the MnO2 in the presence of lithium. From the standpoint of inhibiting gassing, however, it is preferred to drain the battery to about the 3.2 volt level.
Fig. 13 shows the surface of a typical one ounce per square foot bright copper foil. This surface does not adhere well to most substrates without the aid of a specific adhesive;
e.g., such as the conductive plastic adhesive employed in 3 1~6375 embodimen~s such as that described above in connection with Fig. 12. The difference between this surface and that of a nodulated or toothed surface of the kind here preferred is illustrated in Fig. 15, which is an electron micrograph of the nodulated surface of a preferred form of copper foil as-made and sold by Califoil, Inc. of San Diego, Cali~ornia. Figs. 14 and 15 both were made at a magnification of 3000X; the projections, or nodules, in Fig. 15 accordingly occur at a spatial requency of about 30,000 per linear inch.
While the invention has been described with respect to the details of specific illustrative embodiments, many changes and variations will occur to those skilled in the art upon reading this description, and such may obviously be made without departing from the scope of the invention.
Having thus described the invention, what is claimed is:
However, the reaction in question will proceed rather slowly, so that the battery will be fully operative whether or not any steps are taken to inhibit the reaction for purposes not requiring extended shelf lie.
Following the preliminary electrical draining of the battery carried out in accordance with the preferred embodiment of the invention, the overall cell reaction can be expressed as:
(la) Li ~ MnO2 ~-~ (Li~)(MnO2 ) +3.2 volts The potential associated with the sum of reactions (la) and (2) is now (3a) Li~ ~ e~ ~ MnO2 -~ (MnO2)(Li~) ~0.1 volts In~order or this system to react with copper, the copper would have to be reduced, or become electrically positive with respect to the MnO2, which will not occur spontaneously. Thus, the result of the pre-drain operation i5 to make the copper cathodic relative to the MnO~, rather than anodic, resulting in a stable electrochemical system.
From the above discussion, it will be~
apparent that it is not necessary to drain the battery to an OCV (open circuit voltage) of 3.2 volts in order to stabilize it against the copper substrate; any OCV of 3.46 or below would suffice for this purpose. Actually, since the exact potentials involved in a real system are somewhat system dependent, a re precise criterion is that the OCV should be reduced to a value at which the copper will not be oxidized by the MnO2 in the presence of lithium. From the standpoint of inhibiting gassing, however, it is preferred to drain the battery to about the 3.2 volt level.
Fig. 13 shows the surface of a typical one ounce per square foot bright copper foil. This surface does not adhere well to most substrates without the aid of a specific adhesive;
e.g., such as the conductive plastic adhesive employed in 3 1~6375 embodimen~s such as that described above in connection with Fig. 12. The difference between this surface and that of a nodulated or toothed surface of the kind here preferred is illustrated in Fig. 15, which is an electron micrograph of the nodulated surface of a preferred form of copper foil as-made and sold by Califoil, Inc. of San Diego, Cali~ornia. Figs. 14 and 15 both were made at a magnification of 3000X; the projections, or nodules, in Fig. 15 accordingly occur at a spatial requency of about 30,000 per linear inch.
While the invention has been described with respect to the details of specific illustrative embodiments, many changes and variations will occur to those skilled in the art upon reading this description, and such may obviously be made without departing from the scope of the invention.
Having thus described the invention, what is claimed is:
Claims (13)
1. A battery comprising a cathode slurry of manganese dioxide and carbon in a solution of a lithium salt in an organic solvent in contact with a copper substrate, and a lithium anode, said battery having an OCV below the value at which the copper substrate will be oxidized by the manganese dioxide in the presence of the lithium.
2. A laminar battery, comprising a thin flat sheet of metal, a nodular layer of copper covering one surface of said metal sheet, a cathode slurry deposit of MnO2 and carbon in a solution of a lithium salt in an organic solvent on and in intimate contact with a central region of said nodular copper layer, a separator extending over said cathode slurry deposit, a lithium anode in contact with a central region of said separator on a side of said separator opposite said cathode slurry deposit, and means forming a sealed compartment about said anode, said cathode slurry deposit, and said separator.
3. An anode assembly, comprising a sheet of lithium foil laminated to and permeating the interstices of a central region of the surface of a substrate of nodulated copper foil.
4. An intercell assembly for a laminar battery, comprising a thin sheet of metal having opposed surfaces of nodulated copper, and a sheet of lithium foil laminated to a central region of one of said nodulated copper surfaces.
5. A laminar battery, comprising a first thin sheet of metal foil having a nodulated copper surface formed on one side thereof, a deposit of a slurry of MnO2 and carbon in a solution of a lithium salt in an organic solvent on a central region of said nodular surface, a separator over and in contact with said slurry deposit, a lithium foil anode in contact with said separator on a side of said separator opposite said slurry deposit, said anode being laminated to a central region of a nodular copper surface formed on a second thin sheet of metal foil confronting said first sheet, and a thermoplastic frame between and laminated to said first and second sheets around the peripheries thereof surrounding said anode, said cathode slurry deposit, and said separator.
6. A multicell battery comprising cells each having a lithium anode and a MnO2 cathode spaced by a separator and communicating electrochemically through a solution of a lithium salt in an organic solvent, in which the cells are electrochemically isolated and electronically connected together through metal intercell connectors each having opposed nodular copper surfaces in contact with an anode and a cathode of different adjacent cells.
7. An intercell connector assembly for a laminar battery, comprising a sheet of aluminum having a layer of copper adhered to opposite surfaces and a surface layer of nodulated copper formed on the outer surface of each of said copper layers, and a layer of lithium laminated to a central region of one of said nodulated copper surfaces.
8. A laminar battery, comprising a thin flat sheet of metal, a nodular layer of copper covering one surface of said metal sheet, a cathode slurry deposit of MnO2 and carbon in a solution of a lithium salt in an organic solvent on and in intimate contact with a central region of said nodular copper layer, a separator extending over said cathode slurry deposit, a lithium anode in contact with a central region of said separator on a side of said separator opposite said cathode slurry deposit, and means forming a sealed compartment about said anode, said cathode slurry deposit, and said separator, said anode comprising a sheet of lithium foil laminated to and permeating the interstices of a central region of the surface of a substrate of nodulated copper foil.
9. The battery of claim 8, in which said sealing means comprises a closed loop of thermoplastic material surrounding said anode, said cathode slurry deposit, and said separator and having opposed surfaces in which the peripheries of the nodulated surfaces of said metal sheet and said copper foil substrate are embedded.
10. An intercell assembly for a laminar battery, comprising a thin sheet of aluminum having opposed surfaces formed integral with layers of copper having external nodulated surfaces, and a sheet of lithium foil laminated to a central region of one of said nodulated copper surfaces.
11. A multicell battery comprising cells each having a lithium anode and a MnO2 cathode spaced by a separator and communicating electrochemically through a solution of a lithium salt in an organic solvent, in which the cells are electrochemically isolated and electronically connected together through metal intercell connectors each having nodular copper surfaces, one of said surfaces being in contact with an anode and the other of said surfaces being in contact with a cathode of different adjacent cells, said intercell connectors having peripheries extending beyond the borders of said anodes and said cathodes and being sealed together through intermediate closed loops of thermoplastic material.
12. A laminar battery, comprising a thin flat sheet of metal having at least one external copper surface, a cathode slurry deposit of MnO2 and carbon in a solution of a lithium salt in an organic solvent on and in intimate contact with a central region of said copper surface, a separator extending over said cathode slurry deposit, a lithium anode in contact with a central region of said separator on a side of said separator opposite said cathode slurry deposit, and means forming a sealed compartment about said anode, said cathode slurry deposit, and said separator, said battery having been electrically drained promptly after electrochemical assembly to an OCV below the value at which said copper surface will be oxidized by said MnO2 in the presence of lithium.
13. A laminar battery, comprising a first thin sheet of metal foil having at least one external copper surface, a deposit of a slurry of MnO2 and carbon in a solution of a lithium salt in an organic solvent on a central region of said copper surface, a separator over and in contact with said slurry deposit, a lithium foil anode in contact with said separator on a side of said separator opposite said slurry deposit, said anode being laminated to a central region of a nodular copper surface formed on a second thin sheet of metal foil confronting said first sheet, and a thermoplastic frame between and laminated to said first and second sheets around the peripheries thereof surrounding said anode, said cathode slurry deposit, and said separator in which said battery has been electrically drained to an OCV below the value at which copper will be oxidized by MnO2 in the presence of lithium before any substantial oxidation of copper has occurred.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US372,158 | 1982-04-26 | ||
| US06/372,158 US4977046A (en) | 1982-04-26 | 1982-04-26 | Lithium batteries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1196375A true CA1196375A (en) | 1985-11-05 |
Family
ID=23466948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000423693A Expired CA1196375A (en) | 1982-04-26 | 1983-03-16 | Lithium batteries |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4977046A (en) |
| EP (1) | EP0092834B1 (en) |
| JP (1) | JPS58198864A (en) |
| CA (1) | CA1196375A (en) |
| DE (1) | DE3377558D1 (en) |
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| US4824744A (en) * | 1984-09-14 | 1989-04-25 | Duracell Inc. | Method of making cell anode |
| JP2754563B2 (en) * | 1988-04-30 | 1998-05-20 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| US5180642A (en) * | 1992-02-24 | 1993-01-19 | Medtronic, Inc. | Electrochemical cells with end-of-service indicator |
| GB9305440D0 (en) * | 1993-03-17 | 1993-05-05 | Dowty Electronic Components | Lithiated manganese oxide |
| US5792576A (en) * | 1996-11-08 | 1998-08-11 | Gould Electronics Inc. | Limited rechargeable lithium battery based on a cathode slurry |
| US5837397A (en) * | 1996-11-08 | 1998-11-17 | Gould Electronics Inc. | Laminar (flat or paper-type) lithium-ion battery with slurry anodes and slurry cathodes |
| US5747103A (en) * | 1997-04-10 | 1998-05-05 | Voxcom, Inc. | Method and apparatus for printign lithium patterns on a press |
| US6243192B1 (en) | 1997-04-28 | 2001-06-05 | Timer Technologies, Llc | Electrochemical display and timing mechanism with migrating electrolyte |
| GB2324884A (en) * | 1997-04-28 | 1998-11-04 | Wisconsin Label Corp | Electrochemical display and timing mechanism with migrating electrolyte |
| US6285492B1 (en) | 1998-07-02 | 2001-09-04 | Timer Technologies, Llc | Interactive electrochemical displays |
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| US8722235B2 (en) | 2004-04-21 | 2014-05-13 | Blue Spark Technologies, Inc. | Thin printable flexible electrochemical cell and method of making the same |
| US8029927B2 (en) | 2005-03-22 | 2011-10-04 | Blue Spark Technologies, Inc. | Thin printable electrochemical cell utilizing a “picture frame” and methods of making the same |
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| US7432197B2 (en) * | 2006-01-27 | 2008-10-07 | Micron Technology, Inc. | Methods of patterning photoresist, and methods of forming semiconductor constructions |
| JP4635978B2 (en) * | 2006-08-02 | 2011-02-23 | ソニー株式会社 | Negative electrode and secondary battery |
| CN101802848A (en) * | 2007-07-18 | 2010-08-11 | 蓝色火花科技有限公司 | Integrated electronic device and methods of making the same |
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| US8916312B2 (en) * | 2010-04-20 | 2014-12-23 | GM Global Technology Operations LLC | Bipolar plate assembly with thermoplastic sealant and method therefor |
| US8486567B2 (en) * | 2010-05-10 | 2013-07-16 | Gas Technology Institute | Batteries, fuel cells, and other electrochemical devices |
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| US9715130B2 (en) | 2014-08-21 | 2017-07-25 | Johnson & Johnson Vision Care, Inc. | Methods and apparatus to form separators for biocompatible energization elements for biomedical devices |
| US9899700B2 (en) | 2014-08-21 | 2018-02-20 | Johnson & Johnson Vision Care, Inc. | Methods to form biocompatible energization elements for biomedical devices comprising laminates and deposited separators |
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| US10627651B2 (en) | 2014-08-21 | 2020-04-21 | Johnson & Johnson Vision Care, Inc. | Methods and apparatus to form biocompatible energization primary elements for biomedical devices with electroless sealing layers |
| US9923177B2 (en) | 2014-08-21 | 2018-03-20 | Johnson & Johnson Vision Care, Inc. | Biocompatibility of biomedical energization elements |
| US9383593B2 (en) | 2014-08-21 | 2016-07-05 | Johnson & Johnson Vision Care, Inc. | Methods to form biocompatible energization elements for biomedical devices comprising laminates and placed separators |
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| US10361404B2 (en) | 2014-08-21 | 2019-07-23 | Johnson & Johnson Vision Care, Inc. | Anodes for use in biocompatible energization elements |
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| US10381687B2 (en) | 2014-08-21 | 2019-08-13 | Johnson & Johnson Vision Care, Inc. | Methods of forming biocompatible rechargable energization elements for biomedical devices |
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| US3293109A (en) * | 1961-09-18 | 1966-12-20 | Clevite Corp | Conducting element having improved bonding characteristics and method |
| GB1362661A (en) * | 1970-12-21 | 1974-08-07 | Esb Inc | Electric batteries formed of stacked lamina-type cells |
| US3699018A (en) * | 1971-07-12 | 1972-10-17 | Northern Engraving Co | Method of electrodepositing coral copper on copper foil |
| US3985574A (en) * | 1973-05-18 | 1976-10-12 | Compagnie Generale D'electricite | Electrochemical elements in thin layers |
| US4150200A (en) * | 1974-12-16 | 1979-04-17 | Polaroid Corporation | Flat battery with novel slurry form electrode |
| US4113576A (en) * | 1976-06-17 | 1978-09-12 | Hutkin Irving J | Method of making a thin-copper foil-carrier composite |
| JPS5580276A (en) * | 1978-12-13 | 1980-06-17 | Matsushita Electric Ind Co Ltd | Manufacturing method of cell |
| JPS6041829B2 (en) * | 1979-01-06 | 1985-09-19 | 株式会社日立製作所 | Manufacturing method of positive electrode for non-aqueous electrolyte battery |
| JPS5686463A (en) * | 1979-12-18 | 1981-07-14 | Toshiba Battery Co Ltd | Organic solvent battery |
| US4328288A (en) * | 1980-07-25 | 1982-05-04 | Duracell International Inc. | Method for improving stability of Li/MnO2 cells |
-
1982
- 1982-04-26 US US06/372,158 patent/US4977046A/en not_active Expired - Fee Related
-
1983
- 1983-03-16 CA CA000423693A patent/CA1196375A/en not_active Expired
- 1983-04-25 EP EP83104046A patent/EP0092834B1/en not_active Expired
- 1983-04-25 JP JP58072771A patent/JPS58198864A/en active Granted
- 1983-04-25 DE DE8383104046T patent/DE3377558D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0092834B1 (en) | 1988-07-27 |
| US4977046A (en) | 1990-12-11 |
| EP0092834A1 (en) | 1983-11-02 |
| JPH0425672B2 (en) | 1992-05-01 |
| DE3377558D1 (en) | 1988-09-01 |
| JPS58198864A (en) | 1983-11-18 |
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