CA1185318A - Assembly of air-depolarized cells - Google Patents
Assembly of air-depolarized cellsInfo
- Publication number
- CA1185318A CA1185318A CA000413220A CA413220A CA1185318A CA 1185318 A CA1185318 A CA 1185318A CA 000413220 A CA000413220 A CA 000413220A CA 413220 A CA413220 A CA 413220A CA 1185318 A CA1185318 A CA 1185318A
- Authority
- CA
- Canada
- Prior art keywords
- cathode
- air
- assembly
- cell
- cathode electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
- H01M50/109—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure of button or coin shape
-
- 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
Abstract
ASSEMBLY OF AIR-DEPOLARIZED BUTTON CELLS
ABSTRACT
An air-depolarized button cell, such as a zinc-air cell, is assembled by placing a layer of hydrophobic microporous material, preferably polytetrafluoroethylene (PTFE) with catalytic cathode thereon in a cathode can having an air hole on the bottom thereof. A ring is placed above the cathode electrode, is force fitted within the cathode can, and is pushed downwardly against the cathode electrode structure sufficiently as to cause some compression of the PTFE layer beneath the cathode electrode in the area beneath the ring. By providing this compressed portion of the PTFE
layer, the cathode can is rendered substantially leak-proof, before assembly of the cell.
ABSTRACT
An air-depolarized button cell, such as a zinc-air cell, is assembled by placing a layer of hydrophobic microporous material, preferably polytetrafluoroethylene (PTFE) with catalytic cathode thereon in a cathode can having an air hole on the bottom thereof. A ring is placed above the cathode electrode, is force fitted within the cathode can, and is pushed downwardly against the cathode electrode structure sufficiently as to cause some compression of the PTFE layer beneath the cathode electrode in the area beneath the ring. By providing this compressed portion of the PTFE
layer, the cathode can is rendered substantially leak-proof, before assembly of the cell.
Description
~ 3540 IELD 0~ THE INVENTION
This inventlon relates to air-depolari~ed button cells, parti-cularly zinc-air ~ells. Specifically, thls inventlon relates to the a6sembly of such cells, includin~ provision for rendering the cathode can of a cell sub~tantially leak-proof prlor eo final as~embly of ehe cell.
BACKGROUND OF TH~ INVENTION
The assembly of zinc-air button cells, on a commercial or ma~s production basis, of button cells according eo the prior art as discussed hereafter, may glve rise to slgnlficant failure rates of the cell6 due to faulty or ineffective cealing of the cells and resultant electrolyte leak-age. ~lso, it is desirable to provide zinc-air button cell~ where contact areas of both the cathode and the ~node extend 61ightly above ~he periphery of the cell at the respective end thereof.
It is also advanta~eous, if pos6ible, to utilize ~andard button cell ~sse~bly techniques such as those used for 6ilver or mercury button cells, rather than to develop special methods of handlin~ and equipment specifically for assembly of ~inc-air cells - apart from the usual consider-ations of the materlals being handled. In other words, it ~ay ~ometimes be desirable and advantageous to place the electrode in the c~thode can of a button cell, during assembly, at some point prior to assembly of the anode 3 cap into the cathode can and the crimping of ehem together so as to effect a ~eal. Howe~er, the requi6ite unse~led na~ure of 6uch cells (aper~ures are necesfiary for air access) frequently causes leaka~e of the electrolyte from the cathode can, before assembly~ by leaka~e of the electrolyee around the cathode and 6eepage of the electrolyte toward and out the alr access hole or holes in the cathode can.
~2--S3~L~
~-3540 The prior art ha6 generally noS sddressed it~elf Co the que6tion of providing a leak-pr~of seal in the cathode can at ~uch a time that the cathode can is assured to be leak proof prior to a~sembly of the cell.
Generally, total dependance on the crimping action of the ca~hode can over the ~node cap i6 relied up~n for ~eallng the cell. One approach, however, has been fourld whereby ehe seal i6 accomplished prlor ~o the addition of ~he electrolyte and cell closure, h~wever the construceion iB ~omewhat compli-cated and requires a ~pecial form of cathod can.
Przybyla and Smith, in United States Patent No. 4,066,~22 i~sued January 3~ 1978, assigned to a common ~s6ignee herewieh, have taught ln one embodiment of the invention of that patent, a bu~ton cell wherein 8 layer of hydrophobic mirroporous material is placed in the bottom of the cathode can, and i6 compre6sed by forcin~ down over the hydrophobic microporous m~terial at the periphery thereof a metal rlng which has an interference fit within the cathode can, and which, when forced downwardly, compresse~ the hydro-phobic microporous material. At this point, the cathode can has been sub6tantially 6ealed, prior to the introduction thereinto of any other components.
However, Przybyla et al. al50 require that the cathode can be fiuch 0 that the central portlon of the bottom thereof i6 recessed upwardly, 90 that the lowermo~t portion Df the cathode can, and therefore ~he princlpal con-tact area of the positive terminal for the cell, is at ~he periphery ther~of.
Further, a 6econd metal sing is then placed into ~he cell over the gas depolarlzable electrode, to assure electric contact of the electrode to the fir6t ring and thence to the cathode can.
In another patent is6ued to Przybyla and Smith, U.S. Patent No.
4,118,544, in a similar ~tructure the ~econd ring is removed. However, proper electrlcal contact i~ therefore dependent upon pre6sure from the in6ulating grommet which is not as desirable.
~ ~53~ 3540 The Przybyl~ et al. ~tructures, therefore, require ~ conflgur&tion of element~ which reduces the u~eable ~olume ~f the cell, and requlres at least one ~dditional element ln one e~bodiment w~ich further reduces the useable volume of the cell or p~sltive electrlcal contact between cathode and container is dependent upon the re~illency of the insulating ~rommet which is not desirable. ~ever~hel~s6, the Przybyla et ~1. structures ~ssure the leak-proof ~6se~bly of the cells, at lea~t to the extent that electro-lyte placed within the c~thode can will not le~k pa~t the cathode and through the air ~cce~s opening6.
Such a6surance i~ not possible ln the struc~ure taught by Jaggard in U.S. Patent No. 3,897t265 issued July 1975. Tha~ patent ~peciflcally requires that the gro~met placed bet~een the anode and c~thode CUp5 serves the function of an insulator between the ~etal cup~, a sealing me~ber both between the ~etal cups and as a compression means for compressing the cathode as~embly against the cathode cup ko inhibit electrolyte leaka~e out of the alr access openings.
However, the sealing of the cathode as~embly occurs during the final seal$ng of ~he cell snd not during intermediary steps during which electrolyte is sub6tantially free to e6cape from the air access holes.
~0 Additionally, the compression from the ~eal~ng me~ber merely inhibit~ elec-trolyte leakage but does not ~ubstantially prevent it. In this re6pect it i6 noted that Jaggard provide6 an electrolyte absorbent me~ber or blotter beyond the "cathode" seal ad~acent the ~lr ~cce~s openings.
Sauer et al., in U.S. Patent No. 4,054,726 is6ued October 18, 1977 al60 teach a zinc-a$r button cell, the principal feature of whi~h iB the incluslon within the anode, which is ~inc powder, of a compres6ible expan-6ion body or bodies. aowever, one feature of the a6se~bly of ~he Sauer et al. cell i6 that, not unlike the Jaggard cell, the clo~-ng force which occurs when the csthode can ls crimped over the grommet and anode cup, 53~3 caufies sufflcient force against the ed~e portion of a hydrophobic layer placed into the cell beneath the ~lr-depolarizable electrode, and the shoulder por~ion of the cathode can at the perlphery ehereof~ 60 as to preclude electrolyte leakage around the edge of the hydrophoblc layer. In the Sauer et al. ~tructure, there i~ included a ring-like element having an L-shaped conflguration, with the vertical leg of the L extending downwardly past the edges of the air-depolari~a~le cathode electrode and forming part of the electrode ~tructure, for purposes of assurin~ electrical contact of the cathDde 6tructure to the metal cathode can. The 6ealing of the Sauer et al. ~tructure is, however, as stated above, solely by virtue of the crimping ac~ion of the cathode csn against the other element~ of the cell, during final assenbly. Additionally, a6 in Jaggard, the seal between the cathode assembly and the cathode can is effected only by compre~sion of the resllient sealin~ ~ember.
In any cell a6sembly procedure where the electrolyte i6 placed into the ~node cap, assembly of the wetted anode cap into the c~thode can ~ay be difficult; and on the other hand, aæsembly of the cath~de can over the anode cap may be difficult, except as the electrode structure within the cathode can is reasonably secured therein.
~ccordingly, lt may be convenient to follow more conventional button cell a6sembly procedures and techniques, flS practiced ln respect of silver and mercury cells, by charging some of ~he electrolyte into a sealed cathode can, and the remainder of the electrolyte into the anode cap. This i8 followed by Qs6embly of the cathode can onto the anode cap, which assem-bly i6 then crimped. However, because of the air access aper~ur4s in the cathode can of air depolarized cells the cathode can 1~ ~enerally not 6ealed.
A8 a result, electrolyte char~ing of the cathode frequently cause6 leakage during cell as~embly.
~5~
~-3540 It 1B an ob~ct vf the present invention to provide a method of asse~bly by which electrolyte might be char~ed lnto the cathode can, with assurance that the electrolyte will no~ leak from the cathode can even though there is an air ecce6~ openlng thereln.
It ls a further ob~ect of the present invention to provide an air-- depolarized cell ætructure having i~pro~ed cathode elsctric~l eontact and c&thode 6eal with enhanced volumetric capacity.
BRIEF DESCRIPTION OF THE DRAWINGS
~ he pre6ent invention i8 more fully described hereafter, and its ~o advantages explained, in as60cia~ion with the accompanying dr~wingR, in which:
Figure 1 is a partial cross-6ection of a typical air-depolarizable button cell, 6howin~ the principal components thereof and the applicatlon of the pre6ent invention thereto;
Figure 2 is a partlal cross-6ection showing an alternative embodi-ment of the cathode can; and F~gure 3 is a partlal cross-~ec~ion 6howing yet a further embodi-ment of the cathode can.
~-3540 THE I~VENTION
G~nerally, the present l~vention co~prlse6 an as6e~bly of alr-depolarized button cells where the cathode can provides a pos$tive terminal for the cell, and an anode cap provides & negatlve termlnal for the cell, with at least one air access open~ng in the cathode can, nnd a grommet between the metalllc cup~ to electrically insulate ~hem from each o~her.
Within the cell there is an ~node, and ~n air-depolariza~le cathode electric ~tructure, with an electricslly lnsulating and electrolyte sb60rbing layer between them, and a layer of hydrophobic microporous m~erial beneath the cathode electrode and contacting the bottom of the cathode can. The improve-ment ~o the prior art i6 provided by the ~ddition of a rin~ element which is placed in the cathode can above the air-depolarizable cathode electrode 6tructure and beneath the electrolyte absorbing separator; where the ring element i6 force fitted to the cathode can ~nd i8 pushed against the cathode electrode with sufficlent force that the hydrophobic microporous material beneath the cathode electrode iB circumferentially at least partially com-pressed, at least ln par~ of the area thereof beneath the ring, 60 as to .
a6sure an electrolyte leak-proof structure. Furthermore, at the 6ame time~
positive electricsl contact i8 effected between the compressed ca~hode and the cathode can vla the ring element which i8 ln inttmate contact with bothO
~0 In sccordance with the present invention, rapld assembly of the cathode can and the snode cap is not necessary, sfter the electrolyte has been charged into the cathode can if that procedure is being followed, since there will be no electrolyte leakage around the air-depolariza~le ca~hode structure and the peripheral edges of the hydrophobic microporous layer beneath the electrode structure.
-53~
DESCRIPTION OF T~IE PREFERRED EMBODIMENTS
With s2eclflc refer~ce to the d~ffwln~6, Fi~ure 1 depicts an asse~bly for an air-depolarized button cell 10, where a palr of met~llic cups whlch are lntended f~r nesti~g one in~o the other are used. The first is a csthode can 12, which provides the positive terminal for the cell 10, ~ and the second is ~he anode cap 14, which provides ~he negati~e ~erminal for the cell 10. A~ least one air access opening 16 1~ provided in the cathode can 12, 60 th t gas communication from ~he exterior of the cell 10 to the air-depolarizable electrode structure 22 i6 assured, as discussed hereafter.
The cathode can 12 and anode cap 14 are electrlcally insulated from each o other by a grommet 18; and the g~ommet prov~des a seal against electrolyte leakage from the cell 10 outwardly between the walls of the anode cap 14 and the cathode can 12.
Within the cell there i6 an anode 20 and an air-depQlarizable cathode electrode structure 22. A void 24 is ~hown abo~e the anode 20 and is discussed hereaf~er.
The air-depolarizable cathode electrode ~tructure 22 compri~es a current collector matrix 26 and a c~talyz~d cathode mix 28 whlch is intimately associated with the matrix 26. Above the cathode 6tructure 22, and between it and the anode 20, there i8 an electrolyte ~bsorbing separator layer, ~0 whlch preferably c~pri~e~ an absorber 30 and a barrier 32.
Beneath the cathode electrode structure 22 is a layer 34 of hydro-phoblc microporou6 ~aterial. PrePerably, that material is polytetrafluoro-ethylene (~TFE~ (or p~lychlorotrifluoroethylene (PCTF~)), which may be ei~her cintered or unsintered; and preferably the hydrophoblc layer 34 is bonded to the cathode structure 22 so es to provide a composite cathode laminate.
The bottom of the cathode can 12 is dished d~wnwardly, at 36, leaving a peripheral shoulder 38. Within ~he dished portion 36 of the cathode can there is placed a diffusion disc 40 above the air access opel~-o ing(s) 16.
~ ~ ~53~3 ~-3540 The ~node 20 may be either a pre~sed pellet (generally compriRing zinc amalgam), into which there ~ay ~1BO be added ~ trace of a gelling agent ~uch a~ carboxymethylcellulose; or the anode 20 may comprise fi poured zlnc amal~am powder. When tbe anode is a pres6ed zinc pellet, lt extend6 to ~he dotted line 42, and when the anode is a poured zinc powder lt will fill the ~ anode cap 14 to the wallfi thereof. The void 24 16 provlded within the cell, 80 a6 to permit the anode to expand duri~g discharge of the cell.
Above the cathode 6truc~ure 22, ~nd beneath ~he barrier 32 and absorber 30, there iB provlded a ring element or menber 44. The ring ele-ment 44 provide6 greater elec~rlcal con~act between the cathode ~tructure 22 ~nd the cathode can 12 and provides a means of as6uring that ~he cathode can 12 and the element6 as6embled into lt are leak-proof. The ring 44 ls force fitted into the cathode can 12; i.e., there i6 an lnterference fit between ~he ring 44 and the interior wall of the cathode can 12, and the ring 44 is pu~hed or assembled a~ainst the cathode structure 22 with 6ufficient force thPt the hydrophobic nicroporou6 layer 34 beneath the cathode 6tructure 22 i6 circumferentially at les6t partially compressed ln the area substantially beneath the ring 44. The amount of compression of the hydrophobic micro-porou6 layer 34 i6 Kenerally ~uch that the thickness of the microporous ~0 material 34 aft~r the compresslon is in the order of 30-80% of its initial thicknees. By such compre6Rion, there is no path provided by which elec-trolyte placed on the upper surface of ehe c~thode structure 22 can seep past the cathode structure and hydrophobic layer 34 to the area beneath the hydrophobic layer 34. That iB, ~he electrolyte cannot 6eep past the com-pres~ed ~rea of the hydrophobic layer 34. Thi6 leak-proof geal is assured by virtue of the force fit of the rlng 44 within the cathode can 12, ~o that once placed it will ~ot move out of place.
Preferably, the ring element 44 ha~ Rn L-~hsped cros6-~ection, ~ith the vertical leg of the L extending 8W8y from ~he electrode 6tructure 0 22, and the horizontal leg of the L extending inwardly from ~he wall of the cathode can 12 across the upper surface of ~he cathode ~tructure 22.
_g_ ~-3540 In the preferred e~bcdiment, ~he hori~ontal lag of the L-~haped cross section of ring 44 ls l~nger than the ~ertical leg. Thi6 ~6 not limiting, however, ~nd other cross-sectionc such as ctraight, triangular or circul~r may be po6sible, providing that there is an interference flt between the outer dlameter of the ring 44 ~nd the inner dlameter of the csthode can 12.
Obviously, the L-sheped confi~urstlon provides the ~tiffe~t ring for the volume taken up by lt.
It will ~l~o be Doted that, when ehe ring elemen~ 44 ls pushed again6t the cathode 6truc~ure 22 there is æome compression of the cathode gtructure 22 in the area beneath the ring 44 to ensure p~sitive electrical contact therewith ~nd there is forced trsnsmis~ion ~hrough the cathode structure 44 to cause compres6ion of the hydrophobic layer 34. The com-pressivn of ~he hydrophobic layer 34 may be aided by the provision of the shoulder portion 38, above the dished portion 36 of the botto~ of the cathode csn 12. Several alternative embodiments of the shoulder portion of the cathode can 12 sre sho~n in Figures 2 ~nd 3, whereby a ridge 46 ls formed in the shoulder portion 38 of the cathode can 12 as shown in Figure 2 or a pair of concentric rid~es 48 iB formed in the shoulder portion 38 as shown in Figure 3.
In order to a6sure the interference fit of the ring 44 into the cathode can 12, normally $t is formed so that its outside diameter ls, before as6embly into the cathode can, sli~htly greater ehan the inside dia-meter of the cathode can.
The purpoRe of the diffusion disc 40, in the bottom of the cathode can 12, i~ to as6ure that air entering the can through the air access open-ing 16 ls diffused across the botto~ of the composite cathode/hydrophobic layer laminate, to thereby s6fiure air access to the worklug area of the cathode. Likewi6e, the placement of the anode 20 above the cathode struc-ture 22 ensures that the anode fully faces the cathode, whln the cell is 3) operating.
5~
By adop~in~ ~he ring element 44 as used in the a6~e~bly of ilver oxide cellæ for ~enerally different purposes, conventional button cell s66embly techniques ~nd methods can be used ln maklng the air depolarized cells of the pr~sent invention. In particular, the necessity for special tool6, sizing dies, ~nd the like i6 pre~luded, ~nd there is no ~pecial - handling technique for a6sembling the anode cap lnto the cathode can, ~o as ~o preclude electrolyte leskage. ~urther, duri~g a~embly of cells accor-ding to thi6 lnvention, there i~ no chance for ~lectrolyte to be forced;
i.e., pumped, past the hydrophobic layer ln the bottom of the cathode can and out the ~ir a~cess hole.
By thi6 invention, the~e has been eliminated the requirement for reliance upon the sealing pressure of the ~ealing grommet ~o as to preclude leakage of electrolyte psst the cathode structure to the air access openin~s of the cell. Still further, additional rings for ensurin~ positive elec-trical contact or other ~tructure have been substantially eliminated, ~o that the interior volume of the cell can be dedicated to active materials, thereby increasing the capaclty of the cell.
A 6pecific example follows, showing utilization of thP present invention in the a6se~bly of a zinc-air cell.
5;~
~356~0 ~L~
__ .
A 3uliber of a~in~ir l~utl:~ ~oll~ e~ch h~vln~ 0.455 i~lches (1.16 ~) OoD~ ant 0.210 l~ch~4 ~0.53 e~ h~ r ~rc d~ bled, 1~ ~hlch the ~hode c~n ~LB formed Df nicl~ p3~tet ~t~el h~ g 3~ral8ht ~alls~ before Z~ee~
with ~rl In~lde dlametor of 0.~34 ~che~ (1.10 cm). The ~od~ c~p 18 ~1 ~ts~dard tr1clad ~terlal ~copper/~t~el/~ickel), e~lth a ~nn~n dl~eter of 0.405 i~che~ 03 ~n). ~ ~ylo~ 3ro~et lo pl~ced ~e~ee~ the c~t~de can ~nd s~de Cl~p- A b~nded ~th~de/ PTF~ ~tructure ~ pl~c~d ln the cath~de c~n, ~er a ~lffu~ion ~l~c of f~lter ~sper, ~lth the ~hicl~ne~s of the b~ded cathode lamirlate ~ei~g 0.022 încbe~ ~Q.056 ~3D). The ~otal thlck~ess of tbe l~arrler and ~b~rber l~yer~ ~8 O.Oû5 to 0.003 ~llche~ (0.013 t~ 0.020 cm~. The ria~ ~le~ent 18 or~ed sf pure Ric~el wiLth ssl outer dillmeter of 0.436 lnches (1.11 cm3 bef~re ~s~e~ibly into the cithode aa~ d ~n l~ner d~a~eter be-P~een t~e 12~ner edge~ of th~ b,oris~Gneal ~te~dlng le~6 of 0.34û ~nche~ (0.86 cm). I~ wlll be ~;o~ed that the ~cternal diame~cer of the r~ng e~cceed6 ~he lnternal ~l~meter ~f the c~th~de csn by ~proxlma~ely 0.002 inche~ ~about O . 00 j CDI) -~ he anode iB cDmprised c~f a compressed pelle~ f =l~amated zlnc powder, ~nd the elactrolgte 1~ ~ pot~sslum ~ydro~clde ~g0~) læolut~on.
~ he hydrophoblc c~brane iB unslnt~red P~FE, ~lth a thickne~s of 0.010 lnche~ (0.025 cm). Vpon ~3se~bly lnto she cell, the thickne~6 of the PTFE i~yer ~8 reduced by ~ppro~im3tel~ 50X in ~he srea beneeth the rlng and ~b~ve the ~h~ulder of the ca~hode c~n. All of the cells ~s6e~bled, accor-tlng ts the ~bDve9 ~e~onstrate e~c~llen~ oper~lng ch~r~cterl6tl~6, ~nd do ~ot leak during ~e~ly, ~tors~e or oper~tion.
It should be noted that the ring element ~ight convenlently be nickel, or nickel plated 6teel, or other ~uitable material. It iB noted that the present invent~on i6 particularly adaptable to and lntended for use ln alr-depolarized button cell6, and particularly a6 set forth in the appended cl&im6.
This inventlon relates to air-depolari~ed button cells, parti-cularly zinc-air ~ells. Specifically, thls inventlon relates to the a6sembly of such cells, includin~ provision for rendering the cathode can of a cell sub~tantially leak-proof prlor eo final as~embly of ehe cell.
BACKGROUND OF TH~ INVENTION
The assembly of zinc-air button cells, on a commercial or ma~s production basis, of button cells according eo the prior art as discussed hereafter, may glve rise to slgnlficant failure rates of the cell6 due to faulty or ineffective cealing of the cells and resultant electrolyte leak-age. ~lso, it is desirable to provide zinc-air button cell~ where contact areas of both the cathode and the ~node extend 61ightly above ~he periphery of the cell at the respective end thereof.
It is also advanta~eous, if pos6ible, to utilize ~andard button cell ~sse~bly techniques such as those used for 6ilver or mercury button cells, rather than to develop special methods of handlin~ and equipment specifically for assembly of ~inc-air cells - apart from the usual consider-ations of the materlals being handled. In other words, it ~ay ~ometimes be desirable and advantageous to place the electrode in the c~thode can of a button cell, during assembly, at some point prior to assembly of the anode 3 cap into the cathode can and the crimping of ehem together so as to effect a ~eal. Howe~er, the requi6ite unse~led na~ure of 6uch cells (aper~ures are necesfiary for air access) frequently causes leaka~e of the electrolyte from the cathode can, before assembly~ by leaka~e of the electrolyee around the cathode and 6eepage of the electrolyte toward and out the alr access hole or holes in the cathode can.
~2--S3~L~
~-3540 The prior art ha6 generally noS sddressed it~elf Co the que6tion of providing a leak-pr~of seal in the cathode can at ~uch a time that the cathode can is assured to be leak proof prior to a~sembly of the cell.
Generally, total dependance on the crimping action of the ca~hode can over the ~node cap i6 relied up~n for ~eallng the cell. One approach, however, has been fourld whereby ehe seal i6 accomplished prlor ~o the addition of ~he electrolyte and cell closure, h~wever the construceion iB ~omewhat compli-cated and requires a ~pecial form of cathod can.
Przybyla and Smith, in United States Patent No. 4,066,~22 i~sued January 3~ 1978, assigned to a common ~s6ignee herewieh, have taught ln one embodiment of the invention of that patent, a bu~ton cell wherein 8 layer of hydrophobic mirroporous material is placed in the bottom of the cathode can, and i6 compre6sed by forcin~ down over the hydrophobic microporous m~terial at the periphery thereof a metal rlng which has an interference fit within the cathode can, and which, when forced downwardly, compresse~ the hydro-phobic microporous material. At this point, the cathode can has been sub6tantially 6ealed, prior to the introduction thereinto of any other components.
However, Przybyla et al. al50 require that the cathode can be fiuch 0 that the central portlon of the bottom thereof i6 recessed upwardly, 90 that the lowermo~t portion Df the cathode can, and therefore ~he princlpal con-tact area of the positive terminal for the cell, is at ~he periphery ther~of.
Further, a 6econd metal sing is then placed into ~he cell over the gas depolarlzable electrode, to assure electric contact of the electrode to the fir6t ring and thence to the cathode can.
In another patent is6ued to Przybyla and Smith, U.S. Patent No.
4,118,544, in a similar ~tructure the ~econd ring is removed. However, proper electrlcal contact i~ therefore dependent upon pre6sure from the in6ulating grommet which is not as desirable.
~ ~53~ 3540 The Przybyl~ et al. ~tructures, therefore, require ~ conflgur&tion of element~ which reduces the u~eable ~olume ~f the cell, and requlres at least one ~dditional element ln one e~bodiment w~ich further reduces the useable volume of the cell or p~sltive electrlcal contact between cathode and container is dependent upon the re~illency of the insulating ~rommet which is not desirable. ~ever~hel~s6, the Przybyla et ~1. structures ~ssure the leak-proof ~6se~bly of the cells, at lea~t to the extent that electro-lyte placed within the c~thode can will not le~k pa~t the cathode and through the air ~cce~s opening6.
Such a6surance i~ not possible ln the struc~ure taught by Jaggard in U.S. Patent No. 3,897t265 issued July 1975. Tha~ patent ~peciflcally requires that the gro~met placed bet~een the anode and c~thode CUp5 serves the function of an insulator between the ~etal cup~, a sealing me~ber both between the ~etal cups and as a compression means for compressing the cathode as~embly against the cathode cup ko inhibit electrolyte leaka~e out of the alr access openings.
However, the sealing of the cathode as~embly occurs during the final seal$ng of ~he cell snd not during intermediary steps during which electrolyte is sub6tantially free to e6cape from the air access holes.
~0 Additionally, the compression from the ~eal~ng me~ber merely inhibit~ elec-trolyte leakage but does not ~ubstantially prevent it. In this re6pect it i6 noted that Jaggard provide6 an electrolyte absorbent me~ber or blotter beyond the "cathode" seal ad~acent the ~lr ~cce~s openings.
Sauer et al., in U.S. Patent No. 4,054,726 is6ued October 18, 1977 al60 teach a zinc-a$r button cell, the principal feature of whi~h iB the incluslon within the anode, which is ~inc powder, of a compres6ible expan-6ion body or bodies. aowever, one feature of the a6se~bly of ~he Sauer et al. cell i6 that, not unlike the Jaggard cell, the clo~-ng force which occurs when the csthode can ls crimped over the grommet and anode cup, 53~3 caufies sufflcient force against the ed~e portion of a hydrophobic layer placed into the cell beneath the ~lr-depolarizable electrode, and the shoulder por~ion of the cathode can at the perlphery ehereof~ 60 as to preclude electrolyte leakage around the edge of the hydrophoblc layer. In the Sauer et al. ~tructure, there i~ included a ring-like element having an L-shaped conflguration, with the vertical leg of the L extending downwardly past the edges of the air-depolari~a~le cathode electrode and forming part of the electrode ~tructure, for purposes of assurin~ electrical contact of the cathDde 6tructure to the metal cathode can. The 6ealing of the Sauer et al. ~tructure is, however, as stated above, solely by virtue of the crimping ac~ion of the cathode csn against the other element~ of the cell, during final assenbly. Additionally, a6 in Jaggard, the seal between the cathode assembly and the cathode can is effected only by compre~sion of the resllient sealin~ ~ember.
In any cell a6sembly procedure where the electrolyte i6 placed into the ~node cap, assembly of the wetted anode cap into the c~thode can ~ay be difficult; and on the other hand, aæsembly of the cath~de can over the anode cap may be difficult, except as the electrode structure within the cathode can is reasonably secured therein.
~ccordingly, lt may be convenient to follow more conventional button cell a6sembly procedures and techniques, flS practiced ln respect of silver and mercury cells, by charging some of ~he electrolyte into a sealed cathode can, and the remainder of the electrolyte into the anode cap. This i8 followed by Qs6embly of the cathode can onto the anode cap, which assem-bly i6 then crimped. However, because of the air access aper~ur4s in the cathode can of air depolarized cells the cathode can 1~ ~enerally not 6ealed.
A8 a result, electrolyte char~ing of the cathode frequently cause6 leakage during cell as~embly.
~5~
~-3540 It 1B an ob~ct vf the present invention to provide a method of asse~bly by which electrolyte might be char~ed lnto the cathode can, with assurance that the electrolyte will no~ leak from the cathode can even though there is an air ecce6~ openlng thereln.
It ls a further ob~ect of the present invention to provide an air-- depolarized cell ætructure having i~pro~ed cathode elsctric~l eontact and c&thode 6eal with enhanced volumetric capacity.
BRIEF DESCRIPTION OF THE DRAWINGS
~ he pre6ent invention i8 more fully described hereafter, and its ~o advantages explained, in as60cia~ion with the accompanying dr~wingR, in which:
Figure 1 is a partial cross-6ection of a typical air-depolarizable button cell, 6howin~ the principal components thereof and the applicatlon of the pre6ent invention thereto;
Figure 2 is a partlal cross-6ection showing an alternative embodi-ment of the cathode can; and F~gure 3 is a partlal cross-~ec~ion 6howing yet a further embodi-ment of the cathode can.
~-3540 THE I~VENTION
G~nerally, the present l~vention co~prlse6 an as6e~bly of alr-depolarized button cells where the cathode can provides a pos$tive terminal for the cell, and an anode cap provides & negatlve termlnal for the cell, with at least one air access open~ng in the cathode can, nnd a grommet between the metalllc cup~ to electrically insulate ~hem from each o~her.
Within the cell there is an ~node, and ~n air-depolariza~le cathode electric ~tructure, with an electricslly lnsulating and electrolyte sb60rbing layer between them, and a layer of hydrophobic microporous m~erial beneath the cathode electrode and contacting the bottom of the cathode can. The improve-ment ~o the prior art i6 provided by the ~ddition of a rin~ element which is placed in the cathode can above the air-depolarizable cathode electrode 6tructure and beneath the electrolyte absorbing separator; where the ring element i6 force fitted to the cathode can ~nd i8 pushed against the cathode electrode with sufficlent force that the hydrophobic microporous material beneath the cathode electrode iB circumferentially at least partially com-pressed, at least ln par~ of the area thereof beneath the ring, 60 as to .
a6sure an electrolyte leak-proof structure. Furthermore, at the 6ame time~
positive electricsl contact i8 effected between the compressed ca~hode and the cathode can vla the ring element which i8 ln inttmate contact with bothO
~0 In sccordance with the present invention, rapld assembly of the cathode can and the snode cap is not necessary, sfter the electrolyte has been charged into the cathode can if that procedure is being followed, since there will be no electrolyte leakage around the air-depolariza~le ca~hode structure and the peripheral edges of the hydrophobic microporous layer beneath the electrode structure.
-53~
DESCRIPTION OF T~IE PREFERRED EMBODIMENTS
With s2eclflc refer~ce to the d~ffwln~6, Fi~ure 1 depicts an asse~bly for an air-depolarized button cell 10, where a palr of met~llic cups whlch are lntended f~r nesti~g one in~o the other are used. The first is a csthode can 12, which provides the positive terminal for the cell 10, ~ and the second is ~he anode cap 14, which provides ~he negati~e ~erminal for the cell 10. A~ least one air access opening 16 1~ provided in the cathode can 12, 60 th t gas communication from ~he exterior of the cell 10 to the air-depolarizable electrode structure 22 i6 assured, as discussed hereafter.
The cathode can 12 and anode cap 14 are electrlcally insulated from each o other by a grommet 18; and the g~ommet prov~des a seal against electrolyte leakage from the cell 10 outwardly between the walls of the anode cap 14 and the cathode can 12.
Within the cell there i6 an anode 20 and an air-depQlarizable cathode electrode structure 22. A void 24 is ~hown abo~e the anode 20 and is discussed hereaf~er.
The air-depolarizable cathode electrode ~tructure 22 compri~es a current collector matrix 26 and a c~talyz~d cathode mix 28 whlch is intimately associated with the matrix 26. Above the cathode 6tructure 22, and between it and the anode 20, there i8 an electrolyte ~bsorbing separator layer, ~0 whlch preferably c~pri~e~ an absorber 30 and a barrier 32.
Beneath the cathode electrode structure 22 is a layer 34 of hydro-phoblc microporou6 ~aterial. PrePerably, that material is polytetrafluoro-ethylene (~TFE~ (or p~lychlorotrifluoroethylene (PCTF~)), which may be ei~her cintered or unsintered; and preferably the hydrophoblc layer 34 is bonded to the cathode structure 22 so es to provide a composite cathode laminate.
The bottom of the cathode can 12 is dished d~wnwardly, at 36, leaving a peripheral shoulder 38. Within ~he dished portion 36 of the cathode can there is placed a diffusion disc 40 above the air access opel~-o ing(s) 16.
~ ~ ~53~3 ~-3540 The ~node 20 may be either a pre~sed pellet (generally compriRing zinc amalgam), into which there ~ay ~1BO be added ~ trace of a gelling agent ~uch a~ carboxymethylcellulose; or the anode 20 may comprise fi poured zlnc amal~am powder. When tbe anode is a pres6ed zinc pellet, lt extend6 to ~he dotted line 42, and when the anode is a poured zinc powder lt will fill the ~ anode cap 14 to the wallfi thereof. The void 24 16 provlded within the cell, 80 a6 to permit the anode to expand duri~g discharge of the cell.
Above the cathode 6truc~ure 22, ~nd beneath ~he barrier 32 and absorber 30, there iB provlded a ring element or menber 44. The ring ele-ment 44 provide6 greater elec~rlcal con~act between the cathode ~tructure 22 ~nd the cathode can 12 and provides a means of as6uring that ~he cathode can 12 and the element6 as6embled into lt are leak-proof. The ring 44 ls force fitted into the cathode can 12; i.e., there i6 an lnterference fit between ~he ring 44 and the interior wall of the cathode can 12, and the ring 44 is pu~hed or assembled a~ainst the cathode structure 22 with 6ufficient force thPt the hydrophobic nicroporou6 layer 34 beneath the cathode 6tructure 22 i6 circumferentially at les6t partially compressed ln the area substantially beneath the ring 44. The amount of compression of the hydrophobic micro-porou6 layer 34 i6 Kenerally ~uch that the thickness of the microporous ~0 material 34 aft~r the compresslon is in the order of 30-80% of its initial thicknees. By such compre6Rion, there is no path provided by which elec-trolyte placed on the upper surface of ehe c~thode structure 22 can seep past the cathode structure and hydrophobic layer 34 to the area beneath the hydrophobic layer 34. That iB, ~he electrolyte cannot 6eep past the com-pres~ed ~rea of the hydrophobic layer 34. Thi6 leak-proof geal is assured by virtue of the force fit of the rlng 44 within the cathode can 12, ~o that once placed it will ~ot move out of place.
Preferably, the ring element 44 ha~ Rn L-~hsped cros6-~ection, ~ith the vertical leg of the L extending 8W8y from ~he electrode 6tructure 0 22, and the horizontal leg of the L extending inwardly from ~he wall of the cathode can 12 across the upper surface of ~he cathode ~tructure 22.
_g_ ~-3540 In the preferred e~bcdiment, ~he hori~ontal lag of the L-~haped cross section of ring 44 ls l~nger than the ~ertical leg. Thi6 ~6 not limiting, however, ~nd other cross-sectionc such as ctraight, triangular or circul~r may be po6sible, providing that there is an interference flt between the outer dlameter of the ring 44 ~nd the inner dlameter of the csthode can 12.
Obviously, the L-sheped confi~urstlon provides the ~tiffe~t ring for the volume taken up by lt.
It will ~l~o be Doted that, when ehe ring elemen~ 44 ls pushed again6t the cathode 6truc~ure 22 there is æome compression of the cathode gtructure 22 in the area beneath the ring 44 to ensure p~sitive electrical contact therewith ~nd there is forced trsnsmis~ion ~hrough the cathode structure 44 to cause compres6ion of the hydrophobic layer 34. The com-pressivn of ~he hydrophobic layer 34 may be aided by the provision of the shoulder portion 38, above the dished portion 36 of the botto~ of the cathode csn 12. Several alternative embodiments of the shoulder portion of the cathode can 12 sre sho~n in Figures 2 ~nd 3, whereby a ridge 46 ls formed in the shoulder portion 38 of the cathode can 12 as shown in Figure 2 or a pair of concentric rid~es 48 iB formed in the shoulder portion 38 as shown in Figure 3.
In order to a6sure the interference fit of the ring 44 into the cathode can 12, normally $t is formed so that its outside diameter ls, before as6embly into the cathode can, sli~htly greater ehan the inside dia-meter of the cathode can.
The purpoRe of the diffusion disc 40, in the bottom of the cathode can 12, i~ to as6ure that air entering the can through the air access open-ing 16 ls diffused across the botto~ of the composite cathode/hydrophobic layer laminate, to thereby s6fiure air access to the worklug area of the cathode. Likewi6e, the placement of the anode 20 above the cathode struc-ture 22 ensures that the anode fully faces the cathode, whln the cell is 3) operating.
5~
By adop~in~ ~he ring element 44 as used in the a6~e~bly of ilver oxide cellæ for ~enerally different purposes, conventional button cell s66embly techniques ~nd methods can be used ln maklng the air depolarized cells of the pr~sent invention. In particular, the necessity for special tool6, sizing dies, ~nd the like i6 pre~luded, ~nd there is no ~pecial - handling technique for a6sembling the anode cap lnto the cathode can, ~o as ~o preclude electrolyte leskage. ~urther, duri~g a~embly of cells accor-ding to thi6 lnvention, there i~ no chance for ~lectrolyte to be forced;
i.e., pumped, past the hydrophobic layer ln the bottom of the cathode can and out the ~ir a~cess hole.
By thi6 invention, the~e has been eliminated the requirement for reliance upon the sealing pressure of the ~ealing grommet ~o as to preclude leakage of electrolyte psst the cathode structure to the air access openin~s of the cell. Still further, additional rings for ensurin~ positive elec-trical contact or other ~tructure have been substantially eliminated, ~o that the interior volume of the cell can be dedicated to active materials, thereby increasing the capaclty of the cell.
A 6pecific example follows, showing utilization of thP present invention in the a6se~bly of a zinc-air cell.
5;~
~356~0 ~L~
__ .
A 3uliber of a~in~ir l~utl:~ ~oll~ e~ch h~vln~ 0.455 i~lches (1.16 ~) OoD~ ant 0.210 l~ch~4 ~0.53 e~ h~ r ~rc d~ bled, 1~ ~hlch the ~hode c~n ~LB formed Df nicl~ p3~tet ~t~el h~ g 3~ral8ht ~alls~ before Z~ee~
with ~rl In~lde dlametor of 0.~34 ~che~ (1.10 cm). The ~od~ c~p 18 ~1 ~ts~dard tr1clad ~terlal ~copper/~t~el/~ickel), e~lth a ~nn~n dl~eter of 0.405 i~che~ 03 ~n). ~ ~ylo~ 3ro~et lo pl~ced ~e~ee~ the c~t~de can ~nd s~de Cl~p- A b~nded ~th~de/ PTF~ ~tructure ~ pl~c~d ln the cath~de c~n, ~er a ~lffu~ion ~l~c of f~lter ~sper, ~lth the ~hicl~ne~s of the b~ded cathode lamirlate ~ei~g 0.022 încbe~ ~Q.056 ~3D). The ~otal thlck~ess of tbe l~arrler and ~b~rber l~yer~ ~8 O.Oû5 to 0.003 ~llche~ (0.013 t~ 0.020 cm~. The ria~ ~le~ent 18 or~ed sf pure Ric~el wiLth ssl outer dillmeter of 0.436 lnches (1.11 cm3 bef~re ~s~e~ibly into the cithode aa~ d ~n l~ner d~a~eter be-P~een t~e 12~ner edge~ of th~ b,oris~Gneal ~te~dlng le~6 of 0.34û ~nche~ (0.86 cm). I~ wlll be ~;o~ed that the ~cternal diame~cer of the r~ng e~cceed6 ~he lnternal ~l~meter ~f the c~th~de csn by ~proxlma~ely 0.002 inche~ ~about O . 00 j CDI) -~ he anode iB cDmprised c~f a compressed pelle~ f =l~amated zlnc powder, ~nd the elactrolgte 1~ ~ pot~sslum ~ydro~clde ~g0~) læolut~on.
~ he hydrophoblc c~brane iB unslnt~red P~FE, ~lth a thickne~s of 0.010 lnche~ (0.025 cm). Vpon ~3se~bly lnto she cell, the thickne~6 of the PTFE i~yer ~8 reduced by ~ppro~im3tel~ 50X in ~he srea beneeth the rlng and ~b~ve the ~h~ulder of the ca~hode c~n. All of the cells ~s6e~bled, accor-tlng ts the ~bDve9 ~e~onstrate e~c~llen~ oper~lng ch~r~cterl6tl~6, ~nd do ~ot leak during ~e~ly, ~tors~e or oper~tion.
It should be noted that the ring element ~ight convenlently be nickel, or nickel plated 6teel, or other ~uitable material. It iB noted that the present invent~on i6 particularly adaptable to and lntended for use ln alr-depolarized button cell6, and particularly a6 set forth in the appended cl&im6.
Claims (11)
1. In an air-depolarized cell assembly, comprising a pair of cups nesting one into the other, the first being a cathode can providing a positive terminal for the cell, and the second being an anode cap pro-viding a negative terminal for the cell; at least one air access opening in said cathode can providing gas communication from the exterior to the interior of said cell; a grommet between said cups for electrically insu-lating them; an anode, an air-depolarizable cathode electrode structure, an electrolyte absorbing separator layer between them, and a layer of hydrophobic microporous material beneath said cathode electrode and con-tacting the bottom of said cathode cup; the improvement comprising a ring element in place in said cathode can above said air-depolarizable cathode electrode and beneath said electrolyte absorbing separator layer, said ring element in force-fit engagement against said cathode electrode such that said hydrophobic microporous material beneath said cathode electrode is circumferentially, at least partially compressed in the area beneath said ring.
2. The assembly of claim 1, wherein said ring element has a substantially L-shaped cross-section; where the vertical leg of said L
extends away from said cathode electrode, and the horizontal leg of said L extends inwardly away from the wall of said cathode can.
extends away from said cathode electrode, and the horizontal leg of said L extends inwardly away from the wall of said cathode can.
3. The assembly of claim 2, where the outside diameter of said ring member, before assembly into said cell, is slightly greater than the inside diameter of said cathode can.
4. The assembly of claim 1, where the bottom of said cathode can has at least one ridge formed therein near the periphery thereof.
5. The assembly of claim 1, where the thickness of said hydro-phobic microporous material, after said ring member is put into place, is 30-80% of its initial thickness.
6. The assembly of claim 1, where said electrolyte absorbing separator layer comprises a barrier layer and an absorber layer.
7. The assembly of claim 1, further comprising a porous dif-fusion disc placed in said cathode can beneath said hydrophobic microporous material.
8. The assembly of claim 7, where the bottom of said cathode can is dished downwardly, and said diffusion disc in place in said dished portion.
9. The assembly of claim 1, where said air-depolarizable cathode electrode and said hydrophobic microporous material are bonded together.
10. The assembly of claim 1, where said hydrophobic microporous material is chosen from the group consisting of sintered polytetrafluoro-ethylene and unsintered polytetrafluoroethylene.
11. A method for constructing a air-depolarized cell comprising cathode cup with at least one aperture therein and a nesting anode cup wherein a layer of a hydrophobic microporous material is placed within said cathode cup contacting the bottom thereof and wherein layers of an air-depolarizable cathode electrode structure and an electrolyte absorbing separator are sequentially placed thereafter into said cathode cup and said cathode cup thereafter being filled with electrolyte prior to nesting of said anode cup and an anode active material into said cathode cup and the sealing of said cell, characterized in that said method comprises, prior to said filling with electrolyte, the step of placing a ring element in said cathode can above said air-depolarizable cathode electrode and beneath said electrolyte absorbing separator layer into force fitting engagement against said cathode electrode such that said hydrophobic microporous material is circumferentially, at least partially compressed in the area beneath said ring whereby leakage from said cathode cup during the subsequent addition of electrolyte is prevented.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31532181A | 1981-10-26 | 1981-10-26 | |
| US315,321 | 1981-10-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1185318A true CA1185318A (en) | 1985-04-09 |
Family
ID=23223872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000413220A Expired CA1185318A (en) | 1981-10-26 | 1982-10-12 | Assembly of air-depolarized cells |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1185318A (en) |
| GB (1) | GB2109622B (en) |
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| US5804327A (en) * | 1995-05-05 | 1998-09-08 | Rayovac Corporation | Thin walled electrochemical cell |
| US5904998A (en) * | 1995-05-05 | 1999-05-18 | Rayovac Corporation | Metal-air cathode can and electrochemical cell made therewith |
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| US6248463B1 (en) | 1997-05-05 | 2001-06-19 | Rayovac Corporation | Metal-air cathode can and electrochemical cell made therewith |
| US6261709B1 (en) | 1998-03-06 | 2001-07-17 | Rayovac Corporation | Air depolarized electrochemical cell having mass-control chamber in anode |
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| DE3314624A1 (en) * | 1983-04-22 | 1984-10-25 | Varta Batterie Ag, 3000 Hannover | AIR OXYGEN CELL |
| GB2154049A (en) * | 1984-02-09 | 1985-08-29 | Venture Tech Ltd | Electrochemical cell |
| CH654718GA3 (en) * | 1984-02-20 | 1986-03-14 | ||
| DE3413257C2 (en) * | 1984-04-07 | 1986-10-16 | Varta Batterie Ag, 3000 Hannover | Galvanic primary element |
| DE3425171A1 (en) * | 1984-07-09 | 1986-01-16 | Varta Batterie Ag, 3000 Hannover | Airborne oxygen cell |
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1982
- 1982-10-12 CA CA000413220A patent/CA1185318A/en not_active Expired
- 1982-10-14 GB GB08229409A patent/GB2109622B/en not_active Expired
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| CN106098978B (en) * | 2016-08-17 | 2018-09-21 | 徐嘉陵 | A kind of zinc-air battery structure and packaging technology |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2109622B (en) | 1985-05-22 |
| GB2109622A (en) | 1983-06-02 |
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