CA2188131A1 - Rechargeable lithium battery construction - Google Patents
Rechargeable lithium battery constructionInfo
- Publication number
- CA2188131A1 CA2188131A1 CA002188131A CA2188131A CA2188131A1 CA 2188131 A1 CA2188131 A1 CA 2188131A1 CA 002188131 A CA002188131 A CA 002188131A CA 2188131 A CA2188131 A CA 2188131A CA 2188131 A1 CA2188131 A1 CA 2188131A1
- Authority
- CA
- Canada
- Prior art keywords
- cell
- elements
- collector
- battery
- cells
- 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.)
- Abandoned
Links
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0431—Cells with wound or folded electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
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- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- 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
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- 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
- H01M6/30—Deferred-action cells
- H01M6/32—Deferred-action cells activated through external addition of electrolyte or of electrolyte components
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- H01M6/30—Deferred-action cells
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A rechargeable lithium ion battery comprises a plurality of interleaved flexible electrolytic cells, each of which is a unitary planar laminated structure comprising polymeric anode (13), cathode (17), and intermediate electrolyte layers (15) disposed between electrically conductive anode (11) and cathode collector foil (19) elements. One of the collector foils (19) of a cell has an open grid structure to allow penetration of electrolyte solution into the cell layer while the other is substantially more continuous to provide supporting strength to the cell. At least a pair of cells (54, 58) having respective continuous foil anode and cathode collectors are interleaved in spiral-folded fashion to present the collector foils at the outer surface of the resulting structure to provide terminal contacts for the resulting high-capacity low-profile battery.
Description
W0 95/31836 r~v~ c ~ 6 21 8813~
Rechargeable Lithium Baetery Construction ., .
Rr~T~TE8~ APPLICATION
This application is a continuation-in-part of U. 5 . Patent Application S.N. 08/160, 018, filed 30 November 1993, the 10 disclosure of which is incorporated herein by reference. That prior application is assigned to the assignee of this application .
R~r~('.RQrmTn OF T~TP INVENTION
The present invention relates to electrolytic cells comprising polymeric composition eleGtrode and electrolyte members a~d to a methoa of economically making such cells. In particular, the invention relates to rechargeable lithium battery cells comprising an electrode-intermediate polymeric separator element containing an electrolyte solution through which lithium ions from a source electrode material move between cell electrodes during the charge/discharge cycles of 25 the cell. The invention is particularly useful for making such cell s in which the ion source electrode is a lithium compound or otker material capable of intercalating lithium ions, and where an ~ nter-electrode membrane comprises a plasticized polymeric mat_ix made ionically conductive by t~he incorporation of an 30 organic solution of a dissociable lithium salt which provides ion c mobility.
WO ~)513103G 2 1 8 8 1 3 1 r~.,~ / /G
.
Ear~y rechargeable lithiu.~ cells utilized lithi~m meta' .
electrodes as the ion source in conjunction with positive electrodes comprising ~compounds çapable of intercalating the lithium ions within their structure during discharge of the 5 cell. Such cells relied, fQr the most part, on porous separator struçture~ or membranes which physically entrained a measure of fluid electrolyte, ~usually in the form of a solution of a lithium compound, and which also ~provided a means f~r preventing destructive contact between the electrodes of ~ the 10 cell. Sheets or membranes ranging from glass fiber filter paper or cloth to microporous polyolefin film or nonwoven fabric were saturated with solutions of a~lithium compound, such as LiCl04, LiPF6, or LisF4, in an organic so~vent, e . g ., propylene carbonate, diethoxyethane~ or dimethyl carbonate, to form such 15 electrolyte/separator elements. The fluid electrolyte bridge thus established between the electrodes provided the necessary Li~ ion mobility for conductiYities in the range of about 10-3 S/cm .
2G Subse~uent developments, such as described in U. S . Pat .
5,29~,318 have provided electrolytic battery cells which have both positive and negatiYe electrodes comprising compounds capable of intercalating ions and include strong, non-porous, flexible polymeric electrolytic cell separator membrane =
materials which contain lithium salt electrolyte solutions and remain functional over~ temperatures ranging well below room temperature. These eleçtrolyte membranes are çmployed either as separator elements with TnrrB~In; r~rl l y assembled battery cell components or in composite battery cells ronstructed of -3G successively coated ~ayers of ~electrode and electrolyte ~
compositions . In each of these implementations, however, ~the -- 2 -- =
W0 95~31836 P~ .1 / /6 polymeric electrolyte/separator elements often contain the lithium electrolyte salts at the time of ceIl assembly and, due to the hygroscopic nature of those salts, necessitate extraordinary environmental conditions during cell assem'oly.
~ Iore recent developments have provided a manner of utilizing these improved polymeric electrDlyte membrane and electrode compositions which substantially eliminates the need for special environmental controls during cell manufacture.
10 Typically, the polymeric electrode and electrolyte/separator layers are thermally bonded to form a laminated cell structure which ensures optimum interlayer reactivity and enables the postponement of sensitive electrolyte incorporation until the final stages ol battery construction or even later in its 15 application as an activating fluid.
The laminated layer structure of these cells also provides a ready means for incorporating electrical current.
collector elements, usually as additional outer conductive 20 layers or foils which can add further strength to the cell assembly. In order to provide optimum access of activating electrolyte solution to the electrode and separator layers, it is preferred that at least one of these outer collector layers, when comprising a normally impermeable material such as metal 25 foil, be of an open grid or mesh structure, perforated, or otherwise similarly formed to allow fluid permeation.
Batteries of various size, capacity, and voltage range can readily be fashioned from the layered cell structùre by 30 overlaying a number of cells or manifolding a single cell of ex~ended dimension. Although manifolding is useful in its Wo 9~/3l836 2 l D ~3 l 3 ~ PCP/US95/05776 economy of operations and ability to provide directly, i . e, without additional insulating~ elements, a proper arrangement of respective eLectrod~ cDllectDrs, ~the folding of a perforate or grid collector tends to result ill-the stress fracture or rupture -5 of that weaker element which may ultimately lead to a significant interrupti~on of curre=Ilt flow to a battery term.inal.
The present form of battery constructio:Q provides a means for alleviating such stresses and, additionally, simplifies the production of battery packages in a variety of si7es, 10 capacities, and voltages.
STJIvn\T~RY OF ~T-TP IN~ TIOT~ _=
Improved electrolytic cell ~electrode and separator elements l]t;li7in~T polymeric materials preferably comprise the combination of a poly(vinylidene fIuoride~ copolymer matrix and a compatible organic plasticizer which maintains a homogeneous 20 composition in the fDrm of a flexible, self-supportlng film.
The copolymer: comprises about 75 to 92% by weight ~linylidene fluoride~VdF) and 8 to 25% hexafluoropropylene ~IIFP), a range in which the latter co-monomer limits the crystallinity of the final copolymer to a degree which ensures good fiim strength 25 while enabling the retention of about ~Q tD 60% of preferred solvents for lithium electrolyte salts. Within this range of solvent content, the 5 to 7 . 5% salt ultimately comprising a --hybrid electrolyte membrane yields an effective room temperature ionic conductivity of about :bO-4 to 10=-3 S/cm, yet 30 the ~-hr~n~ exhibits no evidence of solvent exudation which might lead ~to cell leakage or~ loss.of conductivity.
WO 9~/3~836 ~ 1 8 ~ l 3 ~ PCT/IJS95/05776 Electrolytic cells, such as rechargeable battery cells, are generally constructed by means of~ the lamination of electrode and e].ectrolyte cell elements which are individually prepared, by coating, extrusion, or otherwise, from 5 compositions comprising the noted PVdF copolymer materials. For example, in the construc_ion of a lithium-ion battery, a current collector layer of aluminum foil or grid is overlaid with a positive electrode film or membrane separately prepared as a coated layer of a dispersion of intercalation electrode 10 composition, e.g., a LiMn2O4 powder in a plasticized copolymer matrix solution, which is dried to form the membrane. An electrolyte/separator membrane formed as a dried coating of a composition comprising a solution of the VdF :HFP copolymer and a plasticizer is then overlaid upon the positive electrode 15 film. A negative electrode membrane fQrmed as a dried coating of a powdered carbon dispersion in a plasticized copolymer matrix solution is similarly overlaid upon the separator membrane layer, and a copper collector foil or grid is laid upon the negative electrQde layer to complete the cell assembly. This 20 asse~nbly is then heated under pressure to provide heat-fused bonding between the plasticized copolymer matrix components and to the collector foils or grids tQ thereby effect the lamination of the cell elements into a unitary flexible battery cell s tructure .
At this stage the laminated structure comprises a signi'icant measure of homogeneously distributed organic plast cizer, particularly in the separator membrane stratum, yet - s devoid of hygroscopic electrolyte salt ~s a result, the 30 ~inactive~ battery cell may be stored at ambient cQnditions, either before or after being shaped or further processed, Wo s~J31836 ~ 1 8 81 31 r~u..,5,v5ll6 without concern for electrolyte deterioration due ~o reaction with atmospheric moisture Orly when an electrolyte salt solutiorl is i~troduced. to activat;e the battery cell need there ::
be concern for r--;nt~;ninr anhydrous conditions, as may oe .-5 ef fectively achieved in an atmosphere of ~ry, inert gas .
-When it is desired to so activate a ~oattery in the f inalstage of manufacture or prior to subsequent use, t~e Iamlnate cell structure is immersed in or ~otherwise contacted with an 10 elctrolyte salt sQlution which penetrates the permeable collector element and ~imbibes into the VdF:HFP copolymer membrane matrix to provide substantially the same~ ionic .:
conducti~ity enhancement ~s achieved by a preformed hybrid electrolyte/separator film containing such an electrolyte: salt 15 solution_ In order to facilitate the absorption of electrolyte solution1 lt is preferred.that a substantial portion of the plasticizer be previously removed from the copolymer matrix This may be readily accomplished at any time following t~e laminating operation by immersio~ of the cell lamInate in a 20 copolymer-inert, low-boilinrJ solvent, such: as diethyl ether or~
hexane, which will selctively leach the plasticizer without significantly affecting th~e copoIymer matrix of t~e ceII~~
element strata. The extracting so~vent may then be simply evaporated to yield a dry, inactive battery cell.=The laminate 25 structure may be stored in plasticized form for an extenaed period of time prior to activation. : =
A battery-forming process utilizi~g the laminated polyme~
ma~erials is readily adapta'ol ~c batch or cantinuous ::
30 operation, since the electrode ~nd ~1 rrtrnlyte layer elements, as well as the collector :grids~and foilst~may~oe snaped or sized WO 9513~836 2 1 8 8 ~ 3 1 PCTiUSg5/05776 prio~ to laminate assembly or they may be laminated from confluent webs of polymer layer materials for later shaping or manifolding. A particular advantage lies in the fact that, - unlike those cells of previous practices re~uiring ultimate 5 element integration, the functional electrolytic cell resulting from the lamination of the layer elements need only be sized and multiplexed, as desired, to obtain completed batteries.
The present invention provides a manner of such cell 10 multiplexing which improves the implementation of the resulting batteriesr as well as alleviating a previous disadvantage associated with manipulation of the more fragile perforated foil or grid collector elements of the cell. This problem, a fracturing of the collector element, is attributable primarily 15 to t:t_e abrupt bending of that element when situated at the exterior surface of a manifold, or accordion-pleated, battery structure. The invention provides a remedy by utilizing grid or perorate foils as the respective positive and negative collectors of a pair of laminated cells which are then 20 multiplexed in a double-lead concentric fold, or " jelly-roll~, assembly which maintains the grid collectors at the interior of the roll, while the complementary solid foil collectors remain at the exterior. In this manner, the stronger foil collectors resist the folding stresses and lend further support to the 25 assembly, while the effect of any fold-induced fracture of a grid collector is mitigated by the conductive continuity maintained by contact between the grid and the matching contiguous solid foil o like polarity in the other assembly cell. Residing at the exterior surfaces of the folded battery 30 structure, the solid foil collectors iurther ultimately present high-conductivity surfaces which readily receive the respective wog~c/3l836 2 1 8 8 1 3 1 P.~ ,.l 'll6 battery contacts. Numerous l~attery arrangements with varlous functional advantages :are furtXer made po5sible by the ~asic =
double-lead cell fo_aiIIg cons~truction of tEis invention. ~
~.
RF~TFF rlF~rPTPTION OF T~F DRAwTNG
The present invention will be described with reference to the accompanying drawing of which: ~ ~
FIG. l is a diagrammatic vlew of a typical Iaminated lithium-ion battery cell structure utilized in the present invention; : : ~
FIG. 2 is a alagrammatic representation of a laminating process for preparing=a battery cell structure of FIG. 1 ~ ~-FIG. 3 is a diagrammatic se~tional view of a multicell battery structure utilizing the basic cell elements of F~IG. l;
FIG. ~ is a diagrammatic sectional view of a manifQld battery structure utilizing the basic cell elements of FI~. 1;
FIG. 5 is a diagrammatic~:sectional view of a double-lead folded celI: battery cons~ruct~iorl~of the present invention;
FIG. 6 is an enIarged vi:ew~~of the ba~tery construction section taken from FIG. 5 at phantom enclosure 60; ~: -~
wo 05l3l83(i 2 1 8 8 ~ 3 I PCT/US9~/0~776 FIG. 7 is a sectional view of a compact battery construction according to FIG. 5 showing an enclosure and terminal contact structure embodiment;
FIG. 8 is a sectional view~of the compact battery construction of FIG. 7 showing another embodiment of an enclosur~ and terminal contact structure;
FIG. 9 is a sectional view of the compact battery construction of FIG. 7 showing yet another embodiment of an enclosure and terminal contact structure;
FIG. 10 is a sectional view of the compact battery construction of FIG. 7 showing still another embodiment of an enclosure and ~Prrn;nAl contact structure;
FIG. 11 is a sectional view o~ an increased voltage battery utilizing a series couple of the FIG. 7 compact battery construction FIG. 12 is a graph tracing recycIing voltage as a function of time for lithium-ion battery cells according to FIG. 7 and FIG. 11; and FIG. 13 is a graph of capacity as a function of the number of charge/discharge cycles for lithium-ion battery cells according to FIG. 7 and FIG. 11.
_ g Wo gsl31836 2 1 8 8 T 3 1 r~ /6 nF ';C~PTION ~F ~HE INVENTION
A laminated rechargeable bat~ery cell structure useful ir.
5 the present invention as depictea in ~IG, 1 cQmprises an electrically-cQnductive _ollectQr foil or ~rid ll / such as copper, nickel, nickel-plated metal, or high-nickel stairlless steel, upon which is laid a rlegative electrode membrane 13 comprising an intercalatable material, such as carbon or 10 graphite, or a low-YoLtage lithium insertion comFound, such as WO2, MoO2, or Al, dispersed in a plasticized pQlymeric binde~
matrix. An electrolyte/separator~ film membrane 15 of plasticized VdF:H~P copolymer is=positïorled upon electrQde element 13 ard is covered with a positive electrode membrane 1 15 comprising a composition of a finely-divided lithium intercalation compound, such as LiMn204, LiCoO2, or LiNiO~, in a plasticized polymeric ~binder matrix. Ar, aluminum collector foil or grid 19 completeg~ the assembly which is then pressed betweer platens (not shown) under heat and pressure to sQften and bond 2 0 the polymeric components and laminate the membrane and collector layers. As previously noted, at least one of the cell collector foils is preferably preformed as a permèable grid to facilitate the flow of activating solution i~to the cell.
Simply for ease and cQnsistency of ilIustration, ~the posltive 25 collectQr is depicted in the first ~ew Figures as such a grid.
Separator membrane element 15 is generally prepared from a composition comprising ~he earlier-n~ted 75 ~o q21 vinylidene fluoride: 8 to 259~s hexafluoropropylenè copolymer ~available 30 com.~erclally frQm Atochem North America as Kynar F1EX) ard an organic plasticizer. Such a copolymer composition is also -- 1(1 -~ Wos~13183G 2 ~ 8 81 31 r l/V~ _~A-776 preferred foL the preparation of the electrode membrane elements, since subsec~uent laminate interface compatibili~:y is ensured. The plasticizer may be one of the various organic compounds commonly used as solvents for electrolyte salts, 5 e.g, propylene carbonate or ethylene carbonate, as well as mixtures of these compounds. E~igher-boiling plasticizer compounds, such as dibutyl phthalate~ dimethyl phthalate, diethyl phthalate, and tris butoxyethyl phosphate are particularly suitable. Inorganic filler adjuncts, such as fumed lO silica, fumed alumina, or silanized fumed silica, may be used to enhance the physical strength and melt viscosity of a separator membrane and to increase the subsequent level of electrolyte solution absorption.
Any common procedure for castmg or forming films or membranes of polymer compositions may be employed in the preparation of the present membrane materials. Where casting or coating of a fluid composition is used, e.g., with meter bar or doctor blade apparatus, the viscosi~y of the composition will 2(~ normally be reduced by the addition of a readily evaporated casting solvent, such as acetone, tetrahydrofuran (THE), or the like. Such coatings are normally air-dried at moderate temperature to yield self-supporting films of homogeneous, plasticized copolymer compositions. A membrane material, 25 particularly for use as a separator element, may also be formed by allowing the copolymer in commercial form, i . e ., bead or powder, to swell in a proportionate amount of plastici~er and then pressing the swollen mass between heated ~e.g, about llO~
~o 150~C) plates or rollers, or extruding the mixture.
Wo 95/3183G PCr/US9~/05776 Lamination of assembled cell structurçs may~similarIy be accr~mpl ' q~Prl by commonly-used apparatus~ Preshaped or si~zed assemblies may be simply pressed ~or a short while between_metal plates weighted at abo~t 3 x 10~ t=o 5 x= lOg~ Pa in an oven at a temperature of about 110 to 150~. Where continuous webs= of component membranes are available~ the operation may be carried out using heated rill PntlPr roller~_~ In ~ucn a ~ laminate battery assembly method, as depicted in FIG. 2, a copoer-collector foil 21 and a negative electrode elelILent 23 are arranged in overlay fashion, preferably between buffer sheets o~ rn;nllm foiI (not shown), and are passed through the rolls 215 of a commerclal card-sealir,g laminator at a temperature of about 110 to 150~.
A treated aluminum co Llector grid 29 and a positive elec~rode element 27 are simi~arly laminated to provide a pair of ~~
electrode/collector battery elements 22, 24. An electrolyte/
separator element 25 is then inserted between the electrQde/
collector pair 22, 24 and the resulting assembly is passed through the 1 ~rn; n~trr device at a=roll temBerature~ of ahout 110 to 150C. with somewhat less pressure to obtain the laminate battery cell structure. , , . = ~
The foregoing procedure may be employed to prepare cells of higher cap~city by duplicating within the cell ~structure the appropriate electrode and electrolyte elements. Such a multiplex configuration is depicted in FIG. 3 and comprises copper collector 31, negative electrode layer elements 33, electrolyte/separator eleme~ts 35, positive electrode elements 37, ana aluminum collector grid=elements 39. Tabs 32, 34 of the collPrtrr Pl P~Pnts form respectiYe common ~terminals for the battery structure. Subser~-uent lamination, extraction, and activation with electrolyte solution produces a battery cell or Wo ~/31836 PC rn~95~05776 about twice the capacity of the basic cell hown in FIG. 1.
Battery cells of proportionately greater capacity can readily be constructed by repeating, as desired, the se~uences of cell elements as desired Consideration should, of course, be given to the anticipated increase in processing time occasioned by the increased mass of material through which extraction and activation fluids will pass.
SubseS~uent to lamination, the battery cell material may be stored under normal conditions with the retained plasticizer for any length of time prior to final battery processing and activation =The laminate may be die-punched into coins for use in the ~m; 1 i ~:r "button" batteries or elongated sheets of the f lexible laminated cell material may be rolled with an interposed insulator or manifolded, as depicted in FIG. 4, to yield a compact, high-density structure to be sealed in a protective enclosure with activating electrolyte solution.
The manifold cell of FIG 4, shown there as only partially folded for clarity of illustration, may typically be prepared in the following éxemplary manner. A negative electrode coating composition was prepared by stirring in a lid-co~ered glass vessel a mixture of 7 . 0 g commercial microcrystalline graphite (about 5 ~Im), 2.0 g 88:12 VdF:HFP copolymer (Atochem Kynar FLEX
2822), 3.12 g dibutyl phthalate, 0.37 g Super-P conductive carbon, and about 28 g acetone. The resulting paste may be degassed by briefly applying a reduced pressure to the mixing vessel. A portion of the composition was coated on a glass plate with a doctor blade device gapped at about 0 . 66 mm. The coated layer was allowed to dry within the coating enclosure under moderately flowing dry air at room temperature for about lO min W09~l3l~36 2 1 8 8 1 3 1 PCTIUS95/05776 to yield-a `tollgh, elastic film which was readily s.rippea from the glass plate. The film was about 0 .16 I[m thick~ with a dry basis weight o~ about ~0 . 23 kg/rrl~ 'and was easily cut into=
negative electrDde element 43 of about 600=.x 40 Irm.
~ -A 620 x 4Q ~m copper collector foil 41 was trimme~ ~t Qne end to form a tab 44 which would subseguently serve as a convenient battery trrminAl~ To enhance the ensuing adherence ~
to its ~sc~ri~tr~ electrode eleme~lt, foil 41 was dip-coated in 2 0.59~ aGeto~le srl-ltinn ~of ~he FLEX 2822 VQ~:XFP copolymer~ ai~--dried, and oven-heated at about 339 to 35QC fDr 5-20 se~conds.
The heating step may be eliminated by using a dip coating solution of about 396 each. o the~VdF_HFP copolymer and dibutyl phthalate, or a coating Qf ethylene-acrylic acid ~copolymer primer composition (e.g., Morton 50-C-12~. The resulting~
negative oil Gol 1 rrtrr 41 was thqn laminated with negative electrode membrane 43 in the desGrihed manner to form a negative electrodeJcollector Gell Sl~h;3ss~rnhly~
A similarly sized positive electrode/rrl 1 frtrr 5~lh~ss~mhl y was formed by laminating an acetone-cleaned and polymer dip-coated open mesh aluminum grid 49 of about 5D llm thickness (e.g., a MicroGrid precision expanded foil marketed by ~elker Corporation) to a positive electrode membrane .47 prepared from 2 stirred homogeneous mixture of 10~5 g of Li1 xMn2O4, where ~ ~ ~ < 1 (e.g., Li1 OsMn2O4 prepared in~a manner described in U~. Patent 5,196,279), sieved through 53 llm, 1.61 g of the YdF:~FP copolymer (FL~X 2322t, 1.63 g dibutyl phthalate, 0 . 5 g Super-P~ conductive carbon, and about 16 g acetone The composition was coated at a blade gap o3~ about 1.1 mm to yield ~n C~ rrtrQde iil~ ~1lth dry basis weight of about Wo 9~/3lg3~ r~ ,.'C5/ l~
. 2188131 0 . 6 kg/m2 .
The electrode/collector subassembly pair were laminated, as in the procedure depicted in FIG. Z~ with a 600 x 40 mm strip 5 of an electrolyte~separator element 4~_ The membrane coating solution for element 45 was prepared by suspending 2 . 0 g of the VdF:HFP copolymer (FLEX 2822) in about lO g of acetone and 2.0 g of dibutyl phthalate (DsP) and warming the mixture to about 50C
with occasional agitation to facilitate dissolution. A portion 10 of the solution was coated on a glass plate with a doctor blade devlce gapped at about 0 . 5 mm and air dried for about 10 min to yield the tough, elastic electrolyte/separator mel[brane 45 which was about 85 ~lm thick with a dry basis weight of about 0.1 kg/m2. The sheet was then folded in zig-~ag fashion as depicted 15 in FIG. 4 and pressed into a tight manifold structure in which only respective outer portions of the separate continuous positive and negative collector surfaces 49, 41 were in contact .
The manifold battery structure was then immersed in stirred diethyl ether three times for about 10 minutes each during which the ether solvent penetrated between the structure surfaces and through the grid of collector 49 to extract a substantial portion of the DBP plasticizer. The manifold battery cell was thereafter activated in preparation for charge~discharge cycling by immersion under a substantially moisture-free atmosphere in a lM electrolyte solution of LiPF6 in 50:50 ethylene carbonate (EC) :dimethyl carbonate (DMC) for at least 20 minutes during which the laminated cell imbibed about 3196 of its extracted weight. Following a mild wiping with absorbent materials to re~ove surface electrolyte, the Wo9~/31836 2 1 8 8 i 3 1 - Pcr~S95/05776 activated battery structure was hermetirally heat-sealed,= but for the extending terminal tabs 42, 44, in a close-fitting envelope ~not shown) of moisture-proDf .barrier material, such as polyolefin/aluminum~ foil~polyester laminate C~7lr~tinrJ
5 commercially used ~r foodstuff enclosures.
The battery structures Df the present invention may be activated with any of the numerous compositiDns used as 15iguid electrolyte solutiDns.~ Notably, the el~ctrolyte solutions may 10 comprise such organic solvents as dimethyl r~rhnn~tr, ethylene carbonate, diethoxyethane, diet.hyl carbonate, propylene carbonate, di~ethoxyethane, dipropyl carbonate, and mixtures thereof. Also, in the formulation of the activating electrolyte solutions, other useful lithium salts, ;nrll1~inr LiCl04, LiN(CF3So2)2, LiBF4, LiCF3So3, LiAsF6, and LiSbF6, may be employed in solution concentratiDns of between about 0 . 5 and 2M. Of particular utility are the exceptional ethylene carbonate/dimethyl carbonate com}?ositions of LiPF6 and mixtures with LiBF4 descrihed in U,S. Pat. 5,192, 629.
During the manifolding operation, it was noted that the abrupt bendirg of open mesh collector grid 49 at each of the structure folds caused a number of i=r~ctures of the relatively weak grid material in those are-as - Although such fractures were 25 r~f little conseguence' at the ~ i nt~rnAl folds 48 due to the contiguity of the facing surfaces of grid 49, fractures at exterior folds 46 reslllted in deleterir.us disruptions i~ the continuity of that collector.. element. In response to this problem, the following fIexible.=battery cell asse~bly of the 3 0 present invention was~ developed .
W0 9~131836 r. ~ 6 ~ 2 ~ 88 ~ ~ I
This advantageous cell assembly is shown in FIG. 5 in partly-expanded diagrammatic form to facilitate illustration of the novel arrangement of the cell elements within the structure. Further in this vein, the elements of a cell, for example cell 54, have been shown merely as a foil collector 51, a grid collector 52, and, disposed between the coll ectors, an element 53 which is in fact the previously described combination of positive electrode/elec~trolyte membrane/negative electrode. As further indicated, the assembly may be of any desired composite length and, as well, may be of any number of folds or wraps.
The purpose of the present cell arrangement is, primarily, to avoid the external folding stresses on open mesh collector grid materials which ultimately lead to ele~Lent fracture. A~ additional advantage is enjoyed, however, in the disposition of solid foil collector elements at the exterior of the cell where they lend strength and protection and provide a ubi~uitous receptor surface for the application of electrical 2 0 terminals, leads, and contacts .
As depicted in FIG. 5, a cell of the present invention comprises a pair of subcells 54, 58 which are, in essence, inverse images of one another. That is, the negative collector pf subcelI 54 is solid foil 51, while that of subcell 58 is grid 55. On the other hand, the positive collector of subcell 54 is grid 52, while that of subceIl 58 is solid foil 56. This key arrangement may be viewed more clearly in the enlarged section 60 of the structure shown in FIG. 6. There, subcell 64 negative collector foil 61 of, ~or example, copper contacts subcell 68 negative grid 65~ also of copper. The complementary subcell Wo9~131836 21881 3l r~ C./l6 positive oîl and grid,col;lecto~s~62, 66 Qf, ~Qr example,~
aluminum will likewise be in contact in alternating layer.s of the folded construction.
To orm the new cell construction, the subcells are overiaid so that one pair of like~ collectors,~ e g., negative elements 51, 55, are in co~itact, and the elongate~double-layer composite is ol ed, in a double L~ad "~elly roll~` fashion,~ with the exterior solid foil element at all times constituting the exterior D the :folded: structure. As is evident in: FIG. 5~, the innermost subcell of the f,olded pair is si~ed to extend beyond the other ir, order, thereby, to b~e situated at the exterior of the structure:for at least a portIon, pre~erably about half, of.
its circumference. In ~his manner, the ~rid elements are~:~
sub~ected only to interior foldin~ stresses and are supported by solid foils o 1i~e~po~arity, yet substantial solid foll surfaces of both polarities are presented at= the surface of the f inal battery cell ~ ~
2 0 In the ~ollowing Figures depicting completed battery constructions of the invention, each of the subcells has-been further reduced~t~ :a slngle eleme-nt or ease and clarity of illustration. Thus, in FI{~. 7, ~or instance, elements 74, 78 correspond to subcells,54, 58 of E~G 5.and~should be understood to comprise all of the collector,- electrode, and electrolyte layers of a complete c~ell, as exempliied in FIG..1 ~he~
comp~essed sell depictlon of the folded ~tr~ in these latter Figures more ~closely resemble the actual state of ~ the battery elements.
3 0 ~
n the embodimen-t shown~ ~IG. 7~ ~he olded cell ~ =
W09513~83G 218813 1 r~ .. "6 comprising subcell elements 74, 7~ may be treated in the manner described with respect to the folded cell of FIG. 4 prior to being sealed in enclosure 72. In particular, the folded construction may be extracted of plasticizer and activated with electrolyte solution. Alternatively, the folaed c~ll may be activated without prior extraction or an extracted cell may be sealed in the enclosure with a predet~rm;nf~l amount of activating electrolyte solution which will be imbibed substantially entirely into the cell. In this latter process, the activating solution may be in~ected through the enclosure envelope of a previously sealed battery with subsequent heat-healing at the point of injection.
As shown in particular in FIG. 7, this embodiment comprises the double-lead folded cell struct`ure of complementary elements 74, 78 sealed within two sheets of commercially-available moisture-proof enclosure film 72 typically comprising an outer 15 ~m polyester or polyamide film, a 50 ~Lm aluminum foil, and an inner 15 11m polyester film bearing about a 90 ~m layer of heat-seal adhesive. In addition to forming an hermetic cohesive seal, the adhesive provides good bonding to metal at temperatures in the range of about 100-125C. In an iniæial sealing step, the enclosure sheets 72, with punched electrode access holes 75, are adhered to the foil .electrode surfaces 71, 76 of cell elements 74, 78, thus sealing the exposed areas of the electrodes from the interior of the final enclosure which is then completed by sealing the sheets together at their edges 73. Conductor leads 79 may thereafter be affixed to the respective exposed cell electrodes by means of solder 77 or other conductive adherent, such as silver=filled epoxy .
Wo 95/31836 2 1 8 8 1 3 1 PCT/US95/05776 A VariatiQn in the protective packaging of tne folaed cell is shown in FIG 8 where a single sheet of encloSur~=~
material a2, wh~ch might be a preformed bag, i5 employed. :Here, - conductors=89~ may be affixed to respective electrode sur~aces of complement`ary cell ,elements ~4=, 88 wi~h solder 87, 86 De~ore the cell is inserted i~to ,the b~with a measure o~ e:Lect~rolyte solution, lf so processed, and, Lf conductors 89 lack individual insulation, with an adhered irsulation ~ilm 85.
Heat-sealing the mouth area 83 o the enclosure ser.ves also to separate and insulate conductors 89. = = = - =
Yet another variation from~ the battery struc~ture of FIG.
7 is shown in FIG. 9 where firm contacts 96, 97 of, or example, copper pads are respectivFly affixed with solder ~r coneluctive adhesive tD electrode surfaces 99, 91 acces5ible ~hrough holes 95 in envelope material 92 . Such- a battery is thereby adapted for direct contact~ertion into a llt; l; 7;n~J devlice. The embodiment o~ FIG. lQ provides similar terminal pads which are located on the same surace Df the battery package. An insulat-ng ~ilm 105 enables the use of a simple a:dhered conductor foil 109 to.sDrL~vey current between cell element 108=
and terminal 106, while ~Grn;n~l 107 is adhered directly to cel:l element 104.
The voltage output of a ba=ttery of the.present construction may readily be increased by series multiplexing of a plurality of the basic folaed-cell structure of FIG 5. As sho~7n in FIG. 11~ the negative electrode element 114 o~ a first olded :cell lI0 is~placed in. electrical cQntact with the positive electrode al,eme~t 113 Qf a similar cell,111 prior to sealing the series couple at the cell surfaces a~d closure areas wo ~131836 2 1 8 8 1 3 ~ PCT/US9~0~776 113 of envelope materials~ 112 with the desired a~.ount of activating electrolyte. The battery vQltage is thus doubled with the two-cell structure shown. In addition to the earlier-noted affixing of conductors 119 with solder connections 116, 5 117, the depicted battery package includes a commercially-available current- and thermal-protective P~C switch 115, such as the Poly-Switch device manufactured by RayChem Corp. of Menlo Park, CA. As a compact alternative to the use of a separate protection switch device, the present flexible, 10 multilayer construction may include an additional layer within a cell structure, for instance between an electrode and collector layer, which comprises the thermally-sensitive composition of a ~TC switch.
Activated batteries of FIGs. 11 and 7 were tested by cycling over ranges of ~-9 V and 2-4 . 5 V, respectively, at a rate of 40 m~ which was maintained constant within 1%.
Multicycle traces of the resulting data are shown in FIG. 12 where 122, 123 and 124, 125 are the respective discharge and 20 charge traces The traces of cell capacity over extended charging cycles are shown in FIG. 13 where 132 traces the subs~antially constant capacity of the higher voltage battery of FIG 11, whlle similar performance of the single cell battery o~ FIG.7 is shown at trace 135. . -While the above description has=related in large measurethe preparation of a number of battery assemblies, other variants are likewise to be included within the scope of the invention as set out in the appended c~aims.
Rechargeable Lithium Baetery Construction ., .
Rr~T~TE8~ APPLICATION
This application is a continuation-in-part of U. 5 . Patent Application S.N. 08/160, 018, filed 30 November 1993, the 10 disclosure of which is incorporated herein by reference. That prior application is assigned to the assignee of this application .
R~r~('.RQrmTn OF T~TP INVENTION
The present invention relates to electrolytic cells comprising polymeric composition eleGtrode and electrolyte members a~d to a methoa of economically making such cells. In particular, the invention relates to rechargeable lithium battery cells comprising an electrode-intermediate polymeric separator element containing an electrolyte solution through which lithium ions from a source electrode material move between cell electrodes during the charge/discharge cycles of 25 the cell. The invention is particularly useful for making such cell s in which the ion source electrode is a lithium compound or otker material capable of intercalating lithium ions, and where an ~ nter-electrode membrane comprises a plasticized polymeric mat_ix made ionically conductive by t~he incorporation of an 30 organic solution of a dissociable lithium salt which provides ion c mobility.
WO ~)513103G 2 1 8 8 1 3 1 r~.,~ / /G
.
Ear~y rechargeable lithiu.~ cells utilized lithi~m meta' .
electrodes as the ion source in conjunction with positive electrodes comprising ~compounds çapable of intercalating the lithium ions within their structure during discharge of the 5 cell. Such cells relied, fQr the most part, on porous separator struçture~ or membranes which physically entrained a measure of fluid electrolyte, ~usually in the form of a solution of a lithium compound, and which also ~provided a means f~r preventing destructive contact between the electrodes of ~ the 10 cell. Sheets or membranes ranging from glass fiber filter paper or cloth to microporous polyolefin film or nonwoven fabric were saturated with solutions of a~lithium compound, such as LiCl04, LiPF6, or LisF4, in an organic so~vent, e . g ., propylene carbonate, diethoxyethane~ or dimethyl carbonate, to form such 15 electrolyte/separator elements. The fluid electrolyte bridge thus established between the electrodes provided the necessary Li~ ion mobility for conductiYities in the range of about 10-3 S/cm .
2G Subse~uent developments, such as described in U. S . Pat .
5,29~,318 have provided electrolytic battery cells which have both positive and negatiYe electrodes comprising compounds capable of intercalating ions and include strong, non-porous, flexible polymeric electrolytic cell separator membrane =
materials which contain lithium salt electrolyte solutions and remain functional over~ temperatures ranging well below room temperature. These eleçtrolyte membranes are çmployed either as separator elements with TnrrB~In; r~rl l y assembled battery cell components or in composite battery cells ronstructed of -3G successively coated ~ayers of ~electrode and electrolyte ~
compositions . In each of these implementations, however, ~the -- 2 -- =
W0 95~31836 P~ .1 / /6 polymeric electrolyte/separator elements often contain the lithium electrolyte salts at the time of ceIl assembly and, due to the hygroscopic nature of those salts, necessitate extraordinary environmental conditions during cell assem'oly.
~ Iore recent developments have provided a manner of utilizing these improved polymeric electrDlyte membrane and electrode compositions which substantially eliminates the need for special environmental controls during cell manufacture.
10 Typically, the polymeric electrode and electrolyte/separator layers are thermally bonded to form a laminated cell structure which ensures optimum interlayer reactivity and enables the postponement of sensitive electrolyte incorporation until the final stages ol battery construction or even later in its 15 application as an activating fluid.
The laminated layer structure of these cells also provides a ready means for incorporating electrical current.
collector elements, usually as additional outer conductive 20 layers or foils which can add further strength to the cell assembly. In order to provide optimum access of activating electrolyte solution to the electrode and separator layers, it is preferred that at least one of these outer collector layers, when comprising a normally impermeable material such as metal 25 foil, be of an open grid or mesh structure, perforated, or otherwise similarly formed to allow fluid permeation.
Batteries of various size, capacity, and voltage range can readily be fashioned from the layered cell structùre by 30 overlaying a number of cells or manifolding a single cell of ex~ended dimension. Although manifolding is useful in its Wo 9~/3l836 2 l D ~3 l 3 ~ PCP/US95/05776 economy of operations and ability to provide directly, i . e, without additional insulating~ elements, a proper arrangement of respective eLectrod~ cDllectDrs, ~the folding of a perforate or grid collector tends to result ill-the stress fracture or rupture -5 of that weaker element which may ultimately lead to a significant interrupti~on of curre=Ilt flow to a battery term.inal.
The present form of battery constructio:Q provides a means for alleviating such stresses and, additionally, simplifies the production of battery packages in a variety of si7es, 10 capacities, and voltages.
STJIvn\T~RY OF ~T-TP IN~ TIOT~ _=
Improved electrolytic cell ~electrode and separator elements l]t;li7in~T polymeric materials preferably comprise the combination of a poly(vinylidene fIuoride~ copolymer matrix and a compatible organic plasticizer which maintains a homogeneous 20 composition in the fDrm of a flexible, self-supportlng film.
The copolymer: comprises about 75 to 92% by weight ~linylidene fluoride~VdF) and 8 to 25% hexafluoropropylene ~IIFP), a range in which the latter co-monomer limits the crystallinity of the final copolymer to a degree which ensures good fiim strength 25 while enabling the retention of about ~Q tD 60% of preferred solvents for lithium electrolyte salts. Within this range of solvent content, the 5 to 7 . 5% salt ultimately comprising a --hybrid electrolyte membrane yields an effective room temperature ionic conductivity of about :bO-4 to 10=-3 S/cm, yet 30 the ~-hr~n~ exhibits no evidence of solvent exudation which might lead ~to cell leakage or~ loss.of conductivity.
WO 9~/3~836 ~ 1 8 ~ l 3 ~ PCT/IJS95/05776 Electrolytic cells, such as rechargeable battery cells, are generally constructed by means of~ the lamination of electrode and e].ectrolyte cell elements which are individually prepared, by coating, extrusion, or otherwise, from 5 compositions comprising the noted PVdF copolymer materials. For example, in the construc_ion of a lithium-ion battery, a current collector layer of aluminum foil or grid is overlaid with a positive electrode film or membrane separately prepared as a coated layer of a dispersion of intercalation electrode 10 composition, e.g., a LiMn2O4 powder in a plasticized copolymer matrix solution, which is dried to form the membrane. An electrolyte/separator membrane formed as a dried coating of a composition comprising a solution of the VdF :HFP copolymer and a plasticizer is then overlaid upon the positive electrode 15 film. A negative electrode membrane fQrmed as a dried coating of a powdered carbon dispersion in a plasticized copolymer matrix solution is similarly overlaid upon the separator membrane layer, and a copper collector foil or grid is laid upon the negative electrQde layer to complete the cell assembly. This 20 asse~nbly is then heated under pressure to provide heat-fused bonding between the plasticized copolymer matrix components and to the collector foils or grids tQ thereby effect the lamination of the cell elements into a unitary flexible battery cell s tructure .
At this stage the laminated structure comprises a signi'icant measure of homogeneously distributed organic plast cizer, particularly in the separator membrane stratum, yet - s devoid of hygroscopic electrolyte salt ~s a result, the 30 ~inactive~ battery cell may be stored at ambient cQnditions, either before or after being shaped or further processed, Wo s~J31836 ~ 1 8 81 31 r~u..,5,v5ll6 without concern for electrolyte deterioration due ~o reaction with atmospheric moisture Orly when an electrolyte salt solutiorl is i~troduced. to activat;e the battery cell need there ::
be concern for r--;nt~;ninr anhydrous conditions, as may oe .-5 ef fectively achieved in an atmosphere of ~ry, inert gas .
-When it is desired to so activate a ~oattery in the f inalstage of manufacture or prior to subsequent use, t~e Iamlnate cell structure is immersed in or ~otherwise contacted with an 10 elctrolyte salt sQlution which penetrates the permeable collector element and ~imbibes into the VdF:HFP copolymer membrane matrix to provide substantially the same~ ionic .:
conducti~ity enhancement ~s achieved by a preformed hybrid electrolyte/separator film containing such an electrolyte: salt 15 solution_ In order to facilitate the absorption of electrolyte solution1 lt is preferred.that a substantial portion of the plasticizer be previously removed from the copolymer matrix This may be readily accomplished at any time following t~e laminating operation by immersio~ of the cell lamInate in a 20 copolymer-inert, low-boilinrJ solvent, such: as diethyl ether or~
hexane, which will selctively leach the plasticizer without significantly affecting th~e copoIymer matrix of t~e ceII~~
element strata. The extracting so~vent may then be simply evaporated to yield a dry, inactive battery cell.=The laminate 25 structure may be stored in plasticized form for an extenaed period of time prior to activation. : =
A battery-forming process utilizi~g the laminated polyme~
ma~erials is readily adapta'ol ~c batch or cantinuous ::
30 operation, since the electrode ~nd ~1 rrtrnlyte layer elements, as well as the collector :grids~and foilst~may~oe snaped or sized WO 9513~836 2 1 8 8 ~ 3 1 PCTiUSg5/05776 prio~ to laminate assembly or they may be laminated from confluent webs of polymer layer materials for later shaping or manifolding. A particular advantage lies in the fact that, - unlike those cells of previous practices re~uiring ultimate 5 element integration, the functional electrolytic cell resulting from the lamination of the layer elements need only be sized and multiplexed, as desired, to obtain completed batteries.
The present invention provides a manner of such cell 10 multiplexing which improves the implementation of the resulting batteriesr as well as alleviating a previous disadvantage associated with manipulation of the more fragile perforated foil or grid collector elements of the cell. This problem, a fracturing of the collector element, is attributable primarily 15 to t:t_e abrupt bending of that element when situated at the exterior surface of a manifold, or accordion-pleated, battery structure. The invention provides a remedy by utilizing grid or perorate foils as the respective positive and negative collectors of a pair of laminated cells which are then 20 multiplexed in a double-lead concentric fold, or " jelly-roll~, assembly which maintains the grid collectors at the interior of the roll, while the complementary solid foil collectors remain at the exterior. In this manner, the stronger foil collectors resist the folding stresses and lend further support to the 25 assembly, while the effect of any fold-induced fracture of a grid collector is mitigated by the conductive continuity maintained by contact between the grid and the matching contiguous solid foil o like polarity in the other assembly cell. Residing at the exterior surfaces of the folded battery 30 structure, the solid foil collectors iurther ultimately present high-conductivity surfaces which readily receive the respective wog~c/3l836 2 1 8 8 1 3 1 P.~ ,.l 'll6 battery contacts. Numerous l~attery arrangements with varlous functional advantages :are furtXer made po5sible by the ~asic =
double-lead cell fo_aiIIg cons~truction of tEis invention. ~
~.
RF~TFF rlF~rPTPTION OF T~F DRAwTNG
The present invention will be described with reference to the accompanying drawing of which: ~ ~
FIG. l is a diagrammatic vlew of a typical Iaminated lithium-ion battery cell structure utilized in the present invention; : : ~
FIG. 2 is a alagrammatic representation of a laminating process for preparing=a battery cell structure of FIG. 1 ~ ~-FIG. 3 is a diagrammatic se~tional view of a multicell battery structure utilizing the basic cell elements of F~IG. l;
FIG. ~ is a diagrammatic sectional view of a manifQld battery structure utilizing the basic cell elements of FI~. 1;
FIG. 5 is a diagrammatic~:sectional view of a double-lead folded celI: battery cons~ruct~iorl~of the present invention;
FIG. 6 is an enIarged vi:ew~~of the ba~tery construction section taken from FIG. 5 at phantom enclosure 60; ~: -~
wo 05l3l83(i 2 1 8 8 ~ 3 I PCT/US9~/0~776 FIG. 7 is a sectional view of a compact battery construction according to FIG. 5 showing an enclosure and terminal contact structure embodiment;
FIG. 8 is a sectional view~of the compact battery construction of FIG. 7 showing another embodiment of an enclosur~ and terminal contact structure;
FIG. 9 is a sectional view of the compact battery construction of FIG. 7 showing yet another embodiment of an enclosure and terminal contact structure;
FIG. 10 is a sectional view of the compact battery construction of FIG. 7 showing still another embodiment of an enclosure and ~Prrn;nAl contact structure;
FIG. 11 is a sectional view o~ an increased voltage battery utilizing a series couple of the FIG. 7 compact battery construction FIG. 12 is a graph tracing recycIing voltage as a function of time for lithium-ion battery cells according to FIG. 7 and FIG. 11; and FIG. 13 is a graph of capacity as a function of the number of charge/discharge cycles for lithium-ion battery cells according to FIG. 7 and FIG. 11.
_ g Wo gsl31836 2 1 8 8 T 3 1 r~ /6 nF ';C~PTION ~F ~HE INVENTION
A laminated rechargeable bat~ery cell structure useful ir.
5 the present invention as depictea in ~IG, 1 cQmprises an electrically-cQnductive _ollectQr foil or ~rid ll / such as copper, nickel, nickel-plated metal, or high-nickel stairlless steel, upon which is laid a rlegative electrode membrane 13 comprising an intercalatable material, such as carbon or 10 graphite, or a low-YoLtage lithium insertion comFound, such as WO2, MoO2, or Al, dispersed in a plasticized pQlymeric binde~
matrix. An electrolyte/separator~ film membrane 15 of plasticized VdF:H~P copolymer is=positïorled upon electrQde element 13 ard is covered with a positive electrode membrane 1 15 comprising a composition of a finely-divided lithium intercalation compound, such as LiMn204, LiCoO2, or LiNiO~, in a plasticized polymeric ~binder matrix. Ar, aluminum collector foil or grid 19 completeg~ the assembly which is then pressed betweer platens (not shown) under heat and pressure to sQften and bond 2 0 the polymeric components and laminate the membrane and collector layers. As previously noted, at least one of the cell collector foils is preferably preformed as a permèable grid to facilitate the flow of activating solution i~to the cell.
Simply for ease and cQnsistency of ilIustration, ~the posltive 25 collectQr is depicted in the first ~ew Figures as such a grid.
Separator membrane element 15 is generally prepared from a composition comprising ~he earlier-n~ted 75 ~o q21 vinylidene fluoride: 8 to 259~s hexafluoropropylenè copolymer ~available 30 com.~erclally frQm Atochem North America as Kynar F1EX) ard an organic plasticizer. Such a copolymer composition is also -- 1(1 -~ Wos~13183G 2 ~ 8 81 31 r l/V~ _~A-776 preferred foL the preparation of the electrode membrane elements, since subsec~uent laminate interface compatibili~:y is ensured. The plasticizer may be one of the various organic compounds commonly used as solvents for electrolyte salts, 5 e.g, propylene carbonate or ethylene carbonate, as well as mixtures of these compounds. E~igher-boiling plasticizer compounds, such as dibutyl phthalate~ dimethyl phthalate, diethyl phthalate, and tris butoxyethyl phosphate are particularly suitable. Inorganic filler adjuncts, such as fumed lO silica, fumed alumina, or silanized fumed silica, may be used to enhance the physical strength and melt viscosity of a separator membrane and to increase the subsequent level of electrolyte solution absorption.
Any common procedure for castmg or forming films or membranes of polymer compositions may be employed in the preparation of the present membrane materials. Where casting or coating of a fluid composition is used, e.g., with meter bar or doctor blade apparatus, the viscosi~y of the composition will 2(~ normally be reduced by the addition of a readily evaporated casting solvent, such as acetone, tetrahydrofuran (THE), or the like. Such coatings are normally air-dried at moderate temperature to yield self-supporting films of homogeneous, plasticized copolymer compositions. A membrane material, 25 particularly for use as a separator element, may also be formed by allowing the copolymer in commercial form, i . e ., bead or powder, to swell in a proportionate amount of plastici~er and then pressing the swollen mass between heated ~e.g, about llO~
~o 150~C) plates or rollers, or extruding the mixture.
Wo 95/3183G PCr/US9~/05776 Lamination of assembled cell structurçs may~similarIy be accr~mpl ' q~Prl by commonly-used apparatus~ Preshaped or si~zed assemblies may be simply pressed ~or a short while between_metal plates weighted at abo~t 3 x 10~ t=o 5 x= lOg~ Pa in an oven at a temperature of about 110 to 150~. Where continuous webs= of component membranes are available~ the operation may be carried out using heated rill PntlPr roller~_~ In ~ucn a ~ laminate battery assembly method, as depicted in FIG. 2, a copoer-collector foil 21 and a negative electrode elelILent 23 are arranged in overlay fashion, preferably between buffer sheets o~ rn;nllm foiI (not shown), and are passed through the rolls 215 of a commerclal card-sealir,g laminator at a temperature of about 110 to 150~.
A treated aluminum co Llector grid 29 and a positive elec~rode element 27 are simi~arly laminated to provide a pair of ~~
electrode/collector battery elements 22, 24. An electrolyte/
separator element 25 is then inserted between the electrQde/
collector pair 22, 24 and the resulting assembly is passed through the 1 ~rn; n~trr device at a=roll temBerature~ of ahout 110 to 150C. with somewhat less pressure to obtain the laminate battery cell structure. , , . = ~
The foregoing procedure may be employed to prepare cells of higher cap~city by duplicating within the cell ~structure the appropriate electrode and electrolyte elements. Such a multiplex configuration is depicted in FIG. 3 and comprises copper collector 31, negative electrode layer elements 33, electrolyte/separator eleme~ts 35, positive electrode elements 37, ana aluminum collector grid=elements 39. Tabs 32, 34 of the collPrtrr Pl P~Pnts form respectiYe common ~terminals for the battery structure. Subser~-uent lamination, extraction, and activation with electrolyte solution produces a battery cell or Wo ~/31836 PC rn~95~05776 about twice the capacity of the basic cell hown in FIG. 1.
Battery cells of proportionately greater capacity can readily be constructed by repeating, as desired, the se~uences of cell elements as desired Consideration should, of course, be given to the anticipated increase in processing time occasioned by the increased mass of material through which extraction and activation fluids will pass.
SubseS~uent to lamination, the battery cell material may be stored under normal conditions with the retained plasticizer for any length of time prior to final battery processing and activation =The laminate may be die-punched into coins for use in the ~m; 1 i ~:r "button" batteries or elongated sheets of the f lexible laminated cell material may be rolled with an interposed insulator or manifolded, as depicted in FIG. 4, to yield a compact, high-density structure to be sealed in a protective enclosure with activating electrolyte solution.
The manifold cell of FIG 4, shown there as only partially folded for clarity of illustration, may typically be prepared in the following éxemplary manner. A negative electrode coating composition was prepared by stirring in a lid-co~ered glass vessel a mixture of 7 . 0 g commercial microcrystalline graphite (about 5 ~Im), 2.0 g 88:12 VdF:HFP copolymer (Atochem Kynar FLEX
2822), 3.12 g dibutyl phthalate, 0.37 g Super-P conductive carbon, and about 28 g acetone. The resulting paste may be degassed by briefly applying a reduced pressure to the mixing vessel. A portion of the composition was coated on a glass plate with a doctor blade device gapped at about 0 . 66 mm. The coated layer was allowed to dry within the coating enclosure under moderately flowing dry air at room temperature for about lO min W09~l3l~36 2 1 8 8 1 3 1 PCTIUS95/05776 to yield-a `tollgh, elastic film which was readily s.rippea from the glass plate. The film was about 0 .16 I[m thick~ with a dry basis weight o~ about ~0 . 23 kg/rrl~ 'and was easily cut into=
negative electrDde element 43 of about 600=.x 40 Irm.
~ -A 620 x 4Q ~m copper collector foil 41 was trimme~ ~t Qne end to form a tab 44 which would subseguently serve as a convenient battery trrminAl~ To enhance the ensuing adherence ~
to its ~sc~ri~tr~ electrode eleme~lt, foil 41 was dip-coated in 2 0.59~ aGeto~le srl-ltinn ~of ~he FLEX 2822 VQ~:XFP copolymer~ ai~--dried, and oven-heated at about 339 to 35QC fDr 5-20 se~conds.
The heating step may be eliminated by using a dip coating solution of about 396 each. o the~VdF_HFP copolymer and dibutyl phthalate, or a coating Qf ethylene-acrylic acid ~copolymer primer composition (e.g., Morton 50-C-12~. The resulting~
negative oil Gol 1 rrtrr 41 was thqn laminated with negative electrode membrane 43 in the desGrihed manner to form a negative electrodeJcollector Gell Sl~h;3ss~rnhly~
A similarly sized positive electrode/rrl 1 frtrr 5~lh~ss~mhl y was formed by laminating an acetone-cleaned and polymer dip-coated open mesh aluminum grid 49 of about 5D llm thickness (e.g., a MicroGrid precision expanded foil marketed by ~elker Corporation) to a positive electrode membrane .47 prepared from 2 stirred homogeneous mixture of 10~5 g of Li1 xMn2O4, where ~ ~ ~ < 1 (e.g., Li1 OsMn2O4 prepared in~a manner described in U~. Patent 5,196,279), sieved through 53 llm, 1.61 g of the YdF:~FP copolymer (FL~X 2322t, 1.63 g dibutyl phthalate, 0 . 5 g Super-P~ conductive carbon, and about 16 g acetone The composition was coated at a blade gap o3~ about 1.1 mm to yield ~n C~ rrtrQde iil~ ~1lth dry basis weight of about Wo 9~/3lg3~ r~ ,.'C5/ l~
. 2188131 0 . 6 kg/m2 .
The electrode/collector subassembly pair were laminated, as in the procedure depicted in FIG. Z~ with a 600 x 40 mm strip 5 of an electrolyte~separator element 4~_ The membrane coating solution for element 45 was prepared by suspending 2 . 0 g of the VdF:HFP copolymer (FLEX 2822) in about lO g of acetone and 2.0 g of dibutyl phthalate (DsP) and warming the mixture to about 50C
with occasional agitation to facilitate dissolution. A portion 10 of the solution was coated on a glass plate with a doctor blade devlce gapped at about 0 . 5 mm and air dried for about 10 min to yield the tough, elastic electrolyte/separator mel[brane 45 which was about 85 ~lm thick with a dry basis weight of about 0.1 kg/m2. The sheet was then folded in zig-~ag fashion as depicted 15 in FIG. 4 and pressed into a tight manifold structure in which only respective outer portions of the separate continuous positive and negative collector surfaces 49, 41 were in contact .
The manifold battery structure was then immersed in stirred diethyl ether three times for about 10 minutes each during which the ether solvent penetrated between the structure surfaces and through the grid of collector 49 to extract a substantial portion of the DBP plasticizer. The manifold battery cell was thereafter activated in preparation for charge~discharge cycling by immersion under a substantially moisture-free atmosphere in a lM electrolyte solution of LiPF6 in 50:50 ethylene carbonate (EC) :dimethyl carbonate (DMC) for at least 20 minutes during which the laminated cell imbibed about 3196 of its extracted weight. Following a mild wiping with absorbent materials to re~ove surface electrolyte, the Wo9~/31836 2 1 8 8 i 3 1 - Pcr~S95/05776 activated battery structure was hermetirally heat-sealed,= but for the extending terminal tabs 42, 44, in a close-fitting envelope ~not shown) of moisture-proDf .barrier material, such as polyolefin/aluminum~ foil~polyester laminate C~7lr~tinrJ
5 commercially used ~r foodstuff enclosures.
The battery structures Df the present invention may be activated with any of the numerous compositiDns used as 15iguid electrolyte solutiDns.~ Notably, the el~ctrolyte solutions may 10 comprise such organic solvents as dimethyl r~rhnn~tr, ethylene carbonate, diethoxyethane, diet.hyl carbonate, propylene carbonate, di~ethoxyethane, dipropyl carbonate, and mixtures thereof. Also, in the formulation of the activating electrolyte solutions, other useful lithium salts, ;nrll1~inr LiCl04, LiN(CF3So2)2, LiBF4, LiCF3So3, LiAsF6, and LiSbF6, may be employed in solution concentratiDns of between about 0 . 5 and 2M. Of particular utility are the exceptional ethylene carbonate/dimethyl carbonate com}?ositions of LiPF6 and mixtures with LiBF4 descrihed in U,S. Pat. 5,192, 629.
During the manifolding operation, it was noted that the abrupt bendirg of open mesh collector grid 49 at each of the structure folds caused a number of i=r~ctures of the relatively weak grid material in those are-as - Although such fractures were 25 r~f little conseguence' at the ~ i nt~rnAl folds 48 due to the contiguity of the facing surfaces of grid 49, fractures at exterior folds 46 reslllted in deleterir.us disruptions i~ the continuity of that collector.. element. In response to this problem, the following fIexible.=battery cell asse~bly of the 3 0 present invention was~ developed .
W0 9~131836 r. ~ 6 ~ 2 ~ 88 ~ ~ I
This advantageous cell assembly is shown in FIG. 5 in partly-expanded diagrammatic form to facilitate illustration of the novel arrangement of the cell elements within the structure. Further in this vein, the elements of a cell, for example cell 54, have been shown merely as a foil collector 51, a grid collector 52, and, disposed between the coll ectors, an element 53 which is in fact the previously described combination of positive electrode/elec~trolyte membrane/negative electrode. As further indicated, the assembly may be of any desired composite length and, as well, may be of any number of folds or wraps.
The purpose of the present cell arrangement is, primarily, to avoid the external folding stresses on open mesh collector grid materials which ultimately lead to ele~Lent fracture. A~ additional advantage is enjoyed, however, in the disposition of solid foil collector elements at the exterior of the cell where they lend strength and protection and provide a ubi~uitous receptor surface for the application of electrical 2 0 terminals, leads, and contacts .
As depicted in FIG. 5, a cell of the present invention comprises a pair of subcells 54, 58 which are, in essence, inverse images of one another. That is, the negative collector pf subcelI 54 is solid foil 51, while that of subcell 58 is grid 55. On the other hand, the positive collector of subcell 54 is grid 52, while that of subceIl 58 is solid foil 56. This key arrangement may be viewed more clearly in the enlarged section 60 of the structure shown in FIG. 6. There, subcell 64 negative collector foil 61 of, ~or example, copper contacts subcell 68 negative grid 65~ also of copper. The complementary subcell Wo9~131836 21881 3l r~ C./l6 positive oîl and grid,col;lecto~s~62, 66 Qf, ~Qr example,~
aluminum will likewise be in contact in alternating layer.s of the folded construction.
To orm the new cell construction, the subcells are overiaid so that one pair of like~ collectors,~ e g., negative elements 51, 55, are in co~itact, and the elongate~double-layer composite is ol ed, in a double L~ad "~elly roll~` fashion,~ with the exterior solid foil element at all times constituting the exterior D the :folded: structure. As is evident in: FIG. 5~, the innermost subcell of the f,olded pair is si~ed to extend beyond the other ir, order, thereby, to b~e situated at the exterior of the structure:for at least a portIon, pre~erably about half, of.
its circumference. In ~his manner, the ~rid elements are~:~
sub~ected only to interior foldin~ stresses and are supported by solid foils o 1i~e~po~arity, yet substantial solid foll surfaces of both polarities are presented at= the surface of the f inal battery cell ~ ~
2 0 In the ~ollowing Figures depicting completed battery constructions of the invention, each of the subcells has-been further reduced~t~ :a slngle eleme-nt or ease and clarity of illustration. Thus, in FI{~. 7, ~or instance, elements 74, 78 correspond to subcells,54, 58 of E~G 5.and~should be understood to comprise all of the collector,- electrode, and electrolyte layers of a complete c~ell, as exempliied in FIG..1 ~he~
comp~essed sell depictlon of the folded ~tr~ in these latter Figures more ~closely resemble the actual state of ~ the battery elements.
3 0 ~
n the embodimen-t shown~ ~IG. 7~ ~he olded cell ~ =
W09513~83G 218813 1 r~ .. "6 comprising subcell elements 74, 7~ may be treated in the manner described with respect to the folded cell of FIG. 4 prior to being sealed in enclosure 72. In particular, the folded construction may be extracted of plasticizer and activated with electrolyte solution. Alternatively, the folaed c~ll may be activated without prior extraction or an extracted cell may be sealed in the enclosure with a predet~rm;nf~l amount of activating electrolyte solution which will be imbibed substantially entirely into the cell. In this latter process, the activating solution may be in~ected through the enclosure envelope of a previously sealed battery with subsequent heat-healing at the point of injection.
As shown in particular in FIG. 7, this embodiment comprises the double-lead folded cell struct`ure of complementary elements 74, 78 sealed within two sheets of commercially-available moisture-proof enclosure film 72 typically comprising an outer 15 ~m polyester or polyamide film, a 50 ~Lm aluminum foil, and an inner 15 11m polyester film bearing about a 90 ~m layer of heat-seal adhesive. In addition to forming an hermetic cohesive seal, the adhesive provides good bonding to metal at temperatures in the range of about 100-125C. In an iniæial sealing step, the enclosure sheets 72, with punched electrode access holes 75, are adhered to the foil .electrode surfaces 71, 76 of cell elements 74, 78, thus sealing the exposed areas of the electrodes from the interior of the final enclosure which is then completed by sealing the sheets together at their edges 73. Conductor leads 79 may thereafter be affixed to the respective exposed cell electrodes by means of solder 77 or other conductive adherent, such as silver=filled epoxy .
Wo 95/31836 2 1 8 8 1 3 1 PCT/US95/05776 A VariatiQn in the protective packaging of tne folaed cell is shown in FIG 8 where a single sheet of encloSur~=~
material a2, wh~ch might be a preformed bag, i5 employed. :Here, - conductors=89~ may be affixed to respective electrode sur~aces of complement`ary cell ,elements ~4=, 88 wi~h solder 87, 86 De~ore the cell is inserted i~to ,the b~with a measure o~ e:Lect~rolyte solution, lf so processed, and, Lf conductors 89 lack individual insulation, with an adhered irsulation ~ilm 85.
Heat-sealing the mouth area 83 o the enclosure ser.ves also to separate and insulate conductors 89. = = = - =
Yet another variation from~ the battery struc~ture of FIG.
7 is shown in FIG. 9 where firm contacts 96, 97 of, or example, copper pads are respectivFly affixed with solder ~r coneluctive adhesive tD electrode surfaces 99, 91 acces5ible ~hrough holes 95 in envelope material 92 . Such- a battery is thereby adapted for direct contact~ertion into a llt; l; 7;n~J devlice. The embodiment o~ FIG. lQ provides similar terminal pads which are located on the same surace Df the battery package. An insulat-ng ~ilm 105 enables the use of a simple a:dhered conductor foil 109 to.sDrL~vey current between cell element 108=
and terminal 106, while ~Grn;n~l 107 is adhered directly to cel:l element 104.
The voltage output of a ba=ttery of the.present construction may readily be increased by series multiplexing of a plurality of the basic folaed-cell structure of FIG 5. As sho~7n in FIG. 11~ the negative electrode element 114 o~ a first olded :cell lI0 is~placed in. electrical cQntact with the positive electrode al,eme~t 113 Qf a similar cell,111 prior to sealing the series couple at the cell surfaces a~d closure areas wo ~131836 2 1 8 8 1 3 ~ PCT/US9~0~776 113 of envelope materials~ 112 with the desired a~.ount of activating electrolyte. The battery vQltage is thus doubled with the two-cell structure shown. In addition to the earlier-noted affixing of conductors 119 with solder connections 116, 5 117, the depicted battery package includes a commercially-available current- and thermal-protective P~C switch 115, such as the Poly-Switch device manufactured by RayChem Corp. of Menlo Park, CA. As a compact alternative to the use of a separate protection switch device, the present flexible, 10 multilayer construction may include an additional layer within a cell structure, for instance between an electrode and collector layer, which comprises the thermally-sensitive composition of a ~TC switch.
Activated batteries of FIGs. 11 and 7 were tested by cycling over ranges of ~-9 V and 2-4 . 5 V, respectively, at a rate of 40 m~ which was maintained constant within 1%.
Multicycle traces of the resulting data are shown in FIG. 12 where 122, 123 and 124, 125 are the respective discharge and 20 charge traces The traces of cell capacity over extended charging cycles are shown in FIG. 13 where 132 traces the subs~antially constant capacity of the higher voltage battery of FIG 11, whlle similar performance of the single cell battery o~ FIG.7 is shown at trace 135. . -While the above description has=related in large measurethe preparation of a number of battery assemblies, other variants are likewise to be included within the scope of the invention as set out in the appended c~aims.
Claims (10)
1. A rechargeable battery construction comprising a plurality of flexible electrolytic cell positive electrode elements, negative electrode elements, and separator elements, each of said elements being of polymeric composition, arranged in continuous concentrically overlapping layers c h a r a c t e r i z e d i n t h a t a) said elements are arranged to form at least two cells of which each cell comprises a positive electrode element, a negative electrode element, and a separator element disposed therebetween; and b) the respective like-polarity electrodes of each cell are disposed contiguously within said construction.
2. A battery construction according to claim 1 c h a r a c t e r i z e d i n t h a t each of said electrodes comprises an electrolytically active composition element and an electrically conductive collector element.
3. A battery construction according to claim 2 c h a r a c t e r i z e d i n t h a t the respective collector elements of said like-polarity electrodes are disposed contiguously within said construction.
4. A battery construction according to claim 3 c h a r a c t e r i z e d i n t h a t one of the respective collector elements of each said like-polarity electrodes is permeable to a fluid electrolyte.
5. A battery construction according to claim 4 c h a r a c t e r i z e d i n t h a t said permeable collector elements comprise the cell layers disposed closest to the interior of said concentrically overlapping arrangement.
6. A battery construction according to claim 5 c h a r a c t e r i z e d i n t h a t a respective one of the opposite-polarity collector elements of the cells is disposed at the outer surface of said concentrically overlapping arrangement.
7. A rechargeable battery construction comprising a plurality of electrolytic cells of which each cell comprises a positive electrode member, a negative electrode member, and a separator member disposed therebetween, said members having flexible, self-supporting, polymeric matrix film composition and being bonded to contiguous members of said cell at respective interfaces to form a unitary flexible laminate cell, c h a r a c t e r i z e d i n t h a t a) each of said electrode members comprises an electrolytically active composition element and an electrically conductive collector element;
b) at least one of said collector elements of each cell is permeable to a fluid electrolyte;
c) the respective like-polarity collector elements of at least two of said cells are disposed contiguously within said construction;
d) the members of said two cells are formed into a structure having a continuous concentrically overlapping layer arrangement;
e) said permeable collector elements comprise the cell layers disposed closest to the interior of said overlapping arrangement structure; and f) a respective one of opposite-polarity collector elements of said cells is disposed at the outer surface of said structure.
b) at least one of said collector elements of each cell is permeable to a fluid electrolyte;
c) the respective like-polarity collector elements of at least two of said cells are disposed contiguously within said construction;
d) the members of said two cells are formed into a structure having a continuous concentrically overlapping layer arrangement;
e) said permeable collector elements comprise the cell layers disposed closest to the interior of said overlapping arrangement structure; and f) a respective one of opposite-polarity collector elements of said cells is disposed at the outer surface of said structure.
8. A battery construction according to claim 7 c h a r a c t e r i z e d i n t h a t said overlapping arrangement structure is hermetically sealed within a moisture-proof barrier material enclosure.
9. A battery construction according to claim 8 c h a r a c t e r i z e d i n t h a t said construction comprises means individually communicating electrically between said opposite-polarity collector elements and the exterior of said enclosure.
10. A battery construction according to claim 9 c h a r a c t e r i z e d i n t h a t a) said construction comprises at least two of said overlapping arrangement structures sealed within said enclosure;
b) respective opposite-polarity collector elements of said structures are in electrical communication; and c) the respective complementary opposite-polarity collector elements outermost in said construction are in electrical communication with the exterior of said enclosure.
b) respective opposite-polarity collector elements of said structures are in electrical communication; and c) the respective complementary opposite-polarity collector elements outermost in said construction are in electrical communication with the exterior of said enclosure.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/241,255 US5478668A (en) | 1993-11-30 | 1994-05-11 | Rechargeable lithium battery construction |
| US241,255 | 1994-05-11 | ||
| PCT/US1995/005776 WO1995031836A1 (en) | 1994-05-11 | 1995-05-10 | Rechargeable lithium battery construction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2188131A1 true CA2188131A1 (en) | 1995-11-23 |
Family
ID=22909921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002188131A Abandoned CA2188131A1 (en) | 1994-05-11 | 1995-05-10 | Rechargeable lithium battery construction |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5478668A (en) |
| EP (1) | EP0759209A4 (en) |
| JP (1) | JPH09506208A (en) |
| AU (1) | AU2477895A (en) |
| CA (1) | CA2188131A1 (en) |
| IL (1) | IL113667A (en) |
| TW (1) | TW281806B (en) |
| WO (1) | WO1995031836A1 (en) |
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-
1994
- 1994-05-11 US US08/241,255 patent/US5478668A/en not_active Expired - Lifetime
-
1995
- 1995-05-09 TW TW084104586A patent/TW281806B/zh active
- 1995-05-09 IL IL113667A patent/IL113667A/en active IP Right Grant
- 1995-05-10 EP EP95919086A patent/EP0759209A4/en not_active Ceased
- 1995-05-10 JP JP7529223A patent/JPH09506208A/en active Pending
- 1995-05-10 CA CA002188131A patent/CA2188131A1/en not_active Abandoned
- 1995-05-10 AU AU24778/95A patent/AU2477895A/en not_active Abandoned
- 1995-05-10 WO PCT/US1995/005776 patent/WO1995031836A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US5478668A (en) | 1995-12-26 |
| TW281806B (en) | 1996-07-21 |
| IL113667A0 (en) | 1995-08-31 |
| IL113667A (en) | 1997-06-10 |
| EP0759209A1 (en) | 1997-02-26 |
| JPH09506208A (en) | 1997-06-17 |
| EP0759209A4 (en) | 1997-06-04 |
| AU2477895A (en) | 1995-12-05 |
| WO1995031836A1 (en) | 1995-11-23 |
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| EEER | Examination request | ||
| FZDE | Discontinued |