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    3 views64 pages

    Us 6197445

    Uploaded by

    EMRULLAH DESTEGÜL

    Copyright:

    © All Rights Reserved
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    of 64
    2) United States Patent Ward et al. 'US006197445BL US 6,197,445 BL Mar. 6, 2001 a0) Patent No.: (45) Date of Patent: (54) AIR DEPOLARIZED ELI cH ;CTROCHEMICAL (75) Inventors: Michael Andrew Ward, Belvidere, IL (US); Robert Brian Dopp, Marietta, GA (US); Joseph Lynn Passan Middleton, WI (US); Gregory Seott Moy, Madison, WI (US); John Edward Oltman, Mount Horeb, WI (US) (73) Assignee: Rayovae Corporation, Madison, WI (us) Subject to any disclaimer, the term of this is extended or adjusted under 35 C. 154(b) by 0 days. (*). Notice: (21) Appl. No: 09/263,122 (22) Filed: Mar. 5, 1999 Related U.S. Application Data (60) Provisional application No. 60/077,037, filed on Mar. 6, 1908, and provisional application No, 6/001,384, filed on Jul 1, 1998, (1) Incl? HOIM 2/00; HOLM 2/02 (2) US.CL 429/163; 429/164, 429/171; 429/185; 429/27; 429/34 429/163, 164, ‘20/171, 185, 162, 82, 86, 27, 4 (58) Field of Seareh 56) References Cited USS, PATENT DOCUMENTS. Re. 31413 10/1983 Jaggaré 42927 404 10/1974 Porter et al 136/86 A 121974 Jammet 086 A (List continued on next page.) FOREIGN PATENT DOCUMENTS 1849783 3/1988 (AT) HoIMi492 (List continued on next page.) OTHER PUBLICATIONS “What is a Battery?” Rayovae Corp., pp. 6-7, 1995." Axegui, J., et al. “Universal application of the zine-ait system in batteries.” Progress in Batteries and Solar Cells, vol. 5, 1984, pp. 136-138, Abstract. (List continued on next page.) Primary Examiner—Stephen Kalatut Assistant Examiner—Angela J. Martin (74) Attorney, Agent, or Firm—Thomas D. Wilhelm 67 ABSTRACT ‘An elongate, generally tubular, air depolarized electro chemical cell (10) comprising a cathode (14), including an ‘tir cathode assembly (26), extending about the tubular circumference, and along the tubular length, of the cell (10), ‘an anode (12), a separator (16) between the anode (12) and the cathode (14), electrolyte, a top closure member (177, 200), and a bottom closure member (114, 202). The cathode assembly (26) is fixedly held, by a friction fit, in a slot (116) at the bottom of the cell. The slot can be developed, for ‘example, by inner (110) and outer (114) walls of a cathode can (28), by inner (226) and outer (224) walls of a bottom closure member (202), or by an outer wall (114) of a cathode ccan (28) and an opposing outer wall of a plug (128) on the interior of the cell, Preferably, bottom closure structure of the cell (10) and receives a bottom edge portion (44) of the cathode current collector (82), and makes electrical contact with the bottom edge portion (44), preferably at an inner surface (60) of the cathode current collector. A diffusion member (36) of the cathode assembly (26) is preferably ‘compressed as a seal, at the bottom ofthe cell (10), between an outer side wall (39) of the cell and the remainder of the cathode assembly (26). The diffusion member (36) is also used at least as an assist in sealing the cell (10) against electrolyte leakage from the anode cavity (137) and past the cathode assembly (26). Various embodiments comprehend crimping the outer side wall against the cathode assembly ‘and thereby developing a crimping bias inthe outer side wall which holds the cathode assembly in the slot, by friction, between the outer and inner side walls 12 Claims, 24 Drawing Sheets ym sh 102 ste de LLL US 6,197,445 BI Page 2 US. PATENT DOCUMENTS 2125954 6/1993 (Ca) nom02 2177303 * 10/94 (CA) Homo 881,959 5/1975 Thiet al 13686 aap SBIAT 11985 (ED) Homa 3897265 7/1975 Saggaid 13080 A 950 SAL 9/1993 (EP) HaLM2n2 B563519 6/1976 Lovie 136386 A 211980 Ur) ais 3977901 $1996 Buvzell Les A oh Soma Somn2i1 8/1977 Wiacek 29336 + Fsa0 HOIMI12)04 4084726 * 11977 Sauer ea 29068 7.421069 > 21982 OP) ona 4105880 "8/1978. Kondesch se 5p.a32s75 + 21982 OP) Wo une SUSS44 1071978 Peybylae 227 Syeanea = 101082 OFF nae 411891526 2/1980 Crctameyer ah 213 Sean640 31983 OB aM 22002 41981 Zatsky 77 Seanesel hoa GD Homa (11982. Gibbard snr Seaaza9 1983 GP) HoLM90 {8/1982 Oliman ea wn 42927—S8.002188 3/1983 UP) HOIM/12)05 ‘= 1/1983 Dopp 291623. 58-053159 3/1983 (IP) HOLM/4/90_ + 41983. Youhids ea. 42927 = Ssosisoo —atses OPS aint 91983. Smianich S92 SROBTIBL 5/1983. UP) Won HoIM206 + 211984 Wincek 2977S 1067S 1983 UP) HaLM96 © 31984 Gira sar Seas h1983 UP) HOIMI205 5 HRAS8S Sar S8:128578 81983 UP) an “ HIM206 + “41986. MeEvoy S8:161273 9/1983 UB) HoIMi1205 {S198 Olina ea 58:165252 9/1983 UP) HOUMA {S987 Oliman ea SS.198861 1/1983 (IP) “on HOM 4667714 © 8/1987 Okman ea o-t7s2 3/1985 GP) Hounnn 4,791,034 12/1988 61-2279 1/1986 (IP) ‘HOIM/12/06 4g2008 “ios 62202470 9/1987 UP) Sonn “ HOIM/I206 44s28.959 5/1980 Taney oa ‘ox02i70 31988 GP) oiMii206 4842953 6/1989 Ros, I 63200672 121988 UP) HOIM/1205 4895.205 11990 Chey 2230049 "91990 UP) Pavers 41994296 1/1990 Borbely ea. Sours ir Uy HOIMII205 4,950,561 8/1990 Niksa et al... 414754 1/1992 (IP) HOLM/2/16- 495786 911990 Cheiky 4173591992 UB) HoLMii/i6 S185218 2/1993 Brokman ea 162378 6/102 UD) HOIMI1206 1,190,833 3/1993 Goldstein et al. 4206443 7/1992 (IP) srrsve vow HOLM/2/02 5279905 1/1994 Mansfield Je 4312771 1/1992 GP) HoIMi125 Sa00578 41994 Ohashi et 47402 "2/1993 IP) HOIM/1200 SIMU8711 5/1904 Pasanl et 52902521993 (IP) “ooenvonnns HOIM/05 5328.77 7/1904 Bene Taos 5/1993 GP) “ HDIMIL208 5302577 11/1994 Pedi sans 51993 UP) HOIMIL200 5,366,822 11/1994 Korall et al. 5-258782 10/1993 (IP) senso oe HOTM/12/06 Sasa 1/1993 Pawan et sions “Sose GP) OLDIGaI00 5,415,949 5/1995 Stone et al. 8.195229 7/1996 (JP) ‘HOIM/12/06 S451.473 9/1995 Oltman et al L-185835—— 7/1999 (IP) arn oe HOTM/12/06, 5158988 10/1995 Pat wonzses 6/1992 {WO} HoIMi205 SS67538 10/1996 Oliman ea . Ss7017 11/1996 Morita tal ‘0/162 OTHER PUBLICATIONS 5582950 12/1996 Olan ea 2977 ae 5582952 12/1996 Oliman eal “"aaott6 Bender, Steven F, et al. “Zine/Air Cells” Handbook of Ss01s41 "1/1997 Oltmaa ‘20171 Batteries, New York: McGraw-Hill, Ine, 1995. pp. 31997 cus et ojos 134-135, 91997 Buns 26231 Costenoble, Us et al, Galvanic Primary Element. Oct. 16, + 311998, Dopp 180 loo 26 20 Le—— 39 130W US 6,197,445 BL Mar. 6, 2001 Sheet 16 of 24 U.S. Patent LA FIG,3 U.S. Patent Mar. 6, 2001 Sheet 17 of 24 FIG. 31B US 6,197,445 B1 26 150 156 158 160 161A 161B U.S. Patent Mar. 6, 2001 Sheet 18 of 24 US 6,197,445 BL °. a oS ao 8 im 1 2 q 3 = <~—n a to rs oO | i a i t+ = a a al o ON 4 e ~ © a oS o_t an a ° h o—h a K © a—~ ey a —F © Gd nN t+ © a a) 2 “oe le a a © <—o a a ~<—_« N a ~ ; ; a 4 5 a 24 154 189 152 170 US 6,197,445 B1 Sheet 19 of 24 Mar. 6, 2001 U.S. Patent Ky 807 pet a> 2% ee "Old Mar. 6,2001 Sheet 20 of 24 US 6,197,445 B1 U.S. Patent FIG, 34A U.S. Patent Mar. 6, 2001 Sheet 21 of 24 US 6,197,445 BL 242 208 108 36 214 210A—NI a 16] 204 36 34 FIG. 34C 37 U.S. Patent Mar. 6, 2001 Sheet 22 of 24 US 6,197,445 BL q AH U.S. Patent Mar. 6, 2001 Sheet 23 of 24 US 6,197,445 BL 242 U.S. Patent Mar. 6, 2001 Sheet 24 of 24 US 6,197,445 BL FIG. 39A US 6,197,445 BL 1 AIR DEPOLARIZED ELECTROCHEMICAL CELLS. ‘This application claims priority from provisional appli ‘cation Ser. No. 60/077,037, filed Mar. 6, 1998, Ser. No. (60/091 384 filed Jul. 1, 1998, both of which are incorporated herein by reference in their entireties. ‘The U.S. Government has a paid-up license in this invention and the right in limited circumstances to require the patent owner to license others on reasonable terms as provided for by the terms of one or more of Contract Nos, DAALO1-95-C.3543, DAABO7-96-C-G026, and DAABO7- 97-€.G027 awarded by Department of the Army. BACKGROUND ‘This invention relates to air depolarized eletrochemical ccs. This invention is related specifically to metal-at it ‘depolarized electrochemical els, especially elongate elin- drial eels. Elongate cells are described hetein with respect to calls having the size generally known a5 “AA” Botton cells, abo illustrated herein, are commercially produced in smaller sizes having lesser heigh-o-diameter ratios, and are generally directed toward se in hearing aids, and computer applications. Such butlon cells generally feature overall contained cell volume of less than 2 em and for the hearing aid cells less than 1 em*. ‘The advantages of air depolarized cells have been known as farback asthe 19th centry. Generally, an air depolarized ‘cl draws oxygen from air ofthe ambient environmen, for tse as the cathode active material, Because the cathode active material need not be eared in the cel, the space in the cell hat would have otherwise been required for carrying cathode active material can, in general, be utilized for ‘containing anode active material. ‘Accordingly, the amount of anode active material which can be contained in an ait depolarized cell is generally significantly greater than the amount of anode active mate- tial which can be contained ina 2-clectode cell of the same Coverall size. By “2-clectode” cell, we mean an clectro- ‘chemical cel wherein the entire charge ofboth anode active material and cathode aetive material ae contained inside the cel structure when the cell is received by the consumer. Generally for a given ell size, and similar mass, an ae depolarized cell can provide a significantly greater number ‘of wat-hours of electromotive force than cana similarly Sized, and similar mass, 2electode cell using the same, of 4 similar, material as the anode eletoactive material. Several attempts have been made to develop and market commercial applications of meta-air cells. However, until ahout the 1970's, such cells were prone to leakage, and other types of failure. In the 1970's, metal-ar button cells were successfully introdueed for use in hearing aids, as replacement for electrode cells. The ells so introduced were generally ‘cliable, and the incidence of leakage had generally been controlled to an extent sufficient to make such cells com- mercially acceptable By the mid 1980's, znc-air cells became the standard for hearing aid use, Since that time, significant effort has been made foward improving metalair hearing ad cells. Such clon has been directed toward «number of issues. For ‘example, efforts hive been directed toward ineeasing clec- trochemieal capacity of the cell, ioward consistency of performance from cll to cell, toward contol of electrolyte leakage, toward providing higher voltages desired for nower 0 as os ss 4s ss 2 heating aid appliance technology, toward higher limiting current, and toward controlling movement of moistre into and out of the cel, and the ik ‘An important factor in button cell performance is the ability to consistently conirol_movement of the centeal portion of the eathode assembly away from the bottom wall Of the cathode can during final cell assembly. Such move ment of the central portion of the cathode assembly is commonly known as “oming.” ‘Another important factor in button cell performance isthe electrical contact between the cathode curent collector and the cathode ean or other cathode terminal. Conventional cathode current collectors comprise ‘woven wire screen structure wherein ends of such wites provide th electrical contact between the eahode current collector and the inner surface of the cathode can, While meta-ar button ccs have found wide-spread use in hearing appliances, and some use as back-up batteries in computes, air depolarized cells have, hisiorically, not had ‘widespread commercial application for other end uses, orn other than small button cel sizes. ‘The air depolarized button cells readily available as items of commerce for use in hearing aid appliances are generally limited to sizes of no more than 0.6 cm” overall volume. In view of the superior ratio of “watt-hour capacity/mass” of tir depolarized cells, it would be desirable to provide air depolarized electrochemical cells in additional sizcs and configurations, and for other applications. It would espe cially be desirable to provide air depolarized electrochemi- cal cells which ate relatively much larger than button cells For example, it woul! he desirable to provide such cells in AA" size a6 well a8 inthe slandard button cel sizes SUMMARY OF THE INVENTION Its an object of the invention to provide an elongate air depolarized electrochemical cell having a novel bottom structures and bottom closures for the cel. It is another object of the invention to provide an air depolarized electrochemical cell wherein an elongate cath- ‘ode extends into a slot between outer and inner side walls of bottom closure member, including optionally a bottom portion of a cathode can, ‘A further object of the invention is to provide an air depolarized electrochemical cell wherein an air permeable diffusion member extends downwardly into a slot between the cathode assembly and an outer side wall of the bottom closure member ‘A still further object is to provide an air depolarized electrochemical cell having a crimp extending about a circumference of the outer side wall of the bottom closure member of the cell, ILis yet another object to provide a method of fabricating an air depolarized electrochemical cell including running & crimping tool against a circumference of the outer side wall of the bottom closure member while backing up the erimp- ing tool with a back-up tool disposed against the inner side wall, and thereby crimping the outer side wall against the combination ofthe cathode assembly and the inner side wall It is a still further object 10 so develop a crimp bias crimping the outer side wall of the bottom closure member, optionally a cathode can, along a height of the outer side wall corresponding to substantially the full height of the inner side wall, ‘The invention comprehends an air depolarized electro- chemical cell, having a length, @ top, and a bottom, The cell US 6,197,445 BL 3 ‘comprises a cathode, including an air cathode assembly, ‘extending slong the length of the cell; an anode, including clectroactive anode material disposed inwardly, inthe cell, Of the cathode assembly; a separator between the anode and the cathode assembly; electrolyte dispersed in the anode, the ‘cathode, and the separator; a top closure member closing the top of the cell; and a bottom closure member closing the bottom of the cell, the bottom closure member having an ‘outer side wall, a lowest extremity of the bottom closure ‘member, and an inner side wall extending upwardly from the Jowest extremity, defining a slot between the outer and inner side walls, the outer side walls applying a crimping bias against the cathode assembly and thereby developing a friction ft holding the cathode assembly in the slot between the outer and inner side walls. In preferred embodiments, the crimping bias on the outer ‘side wall extends about the bottom closure member along substantially the full height of the inner side wall In prefereed embodiments, a cavity is defined inwandly of | the inner side wall. The cavity has a bottom opening at the lowermost extremity and a closed top, a bottom wall at an upwardly disposed portion of the botiom closure member, the crimping bias in the outer side wall being located on the ‘outer side wall mid-way between the closed top and the bottom opening of the cavity as measured on the opposing inner side wall In some embodiments, the bottom closure member further ‘comprises an arcuate bottom wall disposed inwardly of said inner side wall and applying a bias urging the inner side wall against the cathode assembly. Optionally, the arcuate bottom wall extends downwardly from the inner side wall, at an acute angle, toward a central portion of the bottom wal. In preferred embodiments, the cel includes a liquid-tight ‘eal in the slot, preferably between the outer side wall and the cathode assembly, scaling the cell against leakage of electrolyte around the cathode assembly at the bottom closure member, Preferably, the cathode assembly is in electrical contact ‘with the bottom closure member at the inner side wall In some embodiments, the air cathode assembly com- prises catalytically active material between a cathode current collector and an air diffusion member, the air diffusion member defines a compressed liquid seal in the bottom ‘closure member, and the cell further comprises second seal in the bottom closure member, defined by a generally rnon-compressible seal member. The second seal is prefer- ably Tocated between the outer side wall and the air diffusion member, and may have a seal leg extending under the cathode current collector, In some embodiments, the bottom closure member is ‘comprised in a cathode can extending from the bottom of the cell along a substantial portion of the length of the cell A second family of embodiments of the invention com- prebends a method of fabricating an air depolarized elec- trochemical cell, having a length, a top, and a bottom, The cell comprises a cathode, including an air cathode assembly, extending along the length of the cell, an anode, including celectroactive anode material disposed inwardly, inthe cell, ‘of the cathode assembly, a separator between the anode material and the cathode assembly, electrolyte dispersed in the anode, the cathode, and the separator, a top closure member closing the top of the cell, and a bottom closure ‘member closing the bottom of the cell. The bottom closure member has an outer side wall, a lowest extremity, and an inner side wall extending upwardly from the lowest extrem- ity, A sot is defined between the outer and inner sice walls, as os ss 4s ss 6s 4 ‘The method comprises running a crimping tool against a circumference of the outer side wall of the bottom closure ‘member while backing up the erimping tool with a back-up tool disposed against the inner side wall, and thereby erimp- ing the outer side wall against the combination of the cathode assembly and the inner side wall. Preferably the crimping of the outer wall against the cathode assembly and the inner side wall brings the inner side wall into secure electrical contact with a bottom portion ff the cathode curtent collecter. ‘Also preferably, the crimping of the outer side wall against the cathode assembly and the inner side wall includes compressing the air diffusion member at the crimped portion of the outer side wall, whereby the air diffusion member operates a8 a liquid seal sealing against leakage of electrolyte around a bottom edge portion of the cathode assembly and out of the cel In preferred embodiments, the cell has a bottom wall disposed inwardly of the inner side wall, and the method further comprises, after running the crimping tool against the combination of the cathode assembly and the inner side , forming a central portion of the bottom wall dowawardly, optionally to a height substantially below a top of the inner side wall, optionally forming the central portion downwardly in an arcuate configuration, and optionally to a height corresponding toa the lowest extremity of the bottom closure member. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a pictorial view of an elongate cylindrical ‘metal-air cell ofthe invention FIG. 2 shows a cross-section of the cell, taken at 22 of | FIG.1 FIG. 3A is an enlarged representative cross-section of the side wall and bottom wall structures atthe bottom of the cell, including the air cathode, and is taken at dashed circle 3A in FIG. 2. FIG, 3B is an enlarged representative eross-section of the side wall and grommet and other seal structures at and adjacent the top ofthe cel, also showing the air eathocle, and is taken at dashed circle 3B in FIG. 2. FIG, 4 shows a representative cathode current collector used in air cathode assemblies of the invention. FIGS. 4A, 4B, 4C illustrate respectively 2 continuous- ‘weld butt joint, a spot weld butt joint, and a joint formed by welding interdigitated wires or fingers. FIG. 5 shows a representative perforated metal sheet useful for making the cathode current collector of FIG. 4. FIG, $A shows a representative perforated metal cathode current collector for use in a button cell, and having a generally imperforate contact zone. FIG, 3B shows a representative edge view of the cathode current collector of FIG. SA. FIG. SC shows a metal strip illustrating an array of patterns of circular etched precussors of cathode current collectors, from which current collectors of FIG. SA can be made. FIG. SD shows a representat depolarized button cell employ tor of FIGS. SA and SB. FIG. 6 shows an enlarged portion of a comer of the metal sheet of FIG. §, illustrating hexagonal perforations. FIG. 7 is an enlarged representative eross-section of the air cathode illustrated in FIG, 3A fe cross-section of an. air ‘ cathode current collee- US 6,197,445 BL 5 FIG. 8 is a representative pictorial view of an elongate cylindrical cathode eurreat collector having circular perfo- rations. FIG. 9 is a representative pictorial view of an elongate cylindrical cathode current collector having square perfora- tions. FIG. 10 isa representative pictorial view of cylindrical cathode current collector of te invention, and active carbon. catalyst secured to the current collector. FIG. 11 isa representative elevation view of apparatus for forming a sheet of the active carbon catalyst. FIGS. 12 and 12A are representative pictorial views, with parts cut away, ofan active carbon sheet and a stack of sich sheets being formed into a eross-bonded composite of such sheets. HIG. 13 is a representative pictorial view ofthe assembled air cathode, including cathode current collector, active car bon catalyst, and diffusion member. FIG. 14 is a representative pictorial view of a stack of pressure rolls used for assembling the active carbon catalyst, and the diffusion member, to the cathode current collector, FIG. 14A is a representative orthogonal view illustrating alternative apparatus and methods for assembling the active carbon eallyst, and the diffusion member, to the eathode current collector. FIG. 18 i graph illustrating the effect of rolling pressure ‘on cathode voltage. FIG. 16 is an enlarged longitudinal eross-section, with paris cut away, of an aie cathode useful in assembling an ‘elongate cell ofthe invention. FIG. 17s an enlarged transverse cross-section, with parts ‘cut away, of an air cathode useful in assembling an elongate cell of the invention FIG. 18 isa cross-section of a top portion of a cell of the invention illustrating @ stop groove in the cathode ean, FIG. 19 is 2 representative cross-section of a drawn, or

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