32 ‘THE POSITIVE GRID IN STATIONARY LEAD-ACIO BATTERIES M€ FORM. [ATAT BELL LABORATORIES MURRAY HILL, NEW JERSEY 07974 ABSTRACT ‘The hight oxidizing ad acsic environment experienced by the positive pata intelacommurication lead acibattariassoverly Tits the choice of positve rid materials. Cure. gids a ‘made Wom pure lead or lad based alloys. although long ived batteries have been obtsined using pure aad grids with complex designs, the need for thick grids coupled withthe figh denety of loedveauts in bataios with low energy dona.” Energy ‘density improvements coud be achieved thinner lead grids oF ‘tin grids made fom less danse matorals coud bo employed. “Many approaches to controling the corsion and growth rato of lead-bosed grids as wall as tothe uso of alterativematorals have been roperted inthe ltaretra. Th papa provides ani depth evaluation of the strengths and weaknesses of these approaches based on the charactristics associated with avila (9 mater inrmooUCTION ‘Tha majority of ead ac battrias used for telecommurications tbackup power Inthe United States employs pasted. pate technology. in his approach to battery dasign the actve ‘material ofboth the postive and ative plates ished Inthe Intoratices of grida. Grids have two principle functions: they evans among. the power plat, th fo, and the ‘ctve materiel of tho pate. The optimum gid material shoud be strong and a metalic conductor. it ohoud also form alow resistance bond with the active material and be sabe, 008 £0 handle ia manufacture, and ‘cost \dentiication of mata thet meets al of these requirements hos been dilficut, especialy for the positive plate which functions in 8 highiy oizng environment. In stlionery led acid batteries, postive plate potentials of 1.8 V vs SHE a common. The thermodynamic instabity of water at this Dotental imposes another requrement. In order to miniize ‘s2-icharge ofthe postive plate and to promote high recharge Inieney. tho gid materiel must be a por elotrocatalyst for ‘xygen evolution, allowing ges production ony et very low Positive gids for telecommunications batters are curently ‘made trom pure lead and lead alloys, primary those based on the Pb-Ce system. Theso metals possess savera! of the required characteristics, including electron conductivity, active ‘material Bond formation, and cost. However, tha se has feauived ‘substantial design compromises. becouse they are tute ductle and subjct to corosion wider battery Use ‘conditions. ‘Tho corrosion process produces a stongly adherent layer of ‘lectro-conducting led oxdes on the gid srlace according 10 the reaction Po +H, = POO, + 2ne + 2H ‘The actual stucture ofthe cortosion fim is complox (1). The ‘ute ogion ofthe fim consists primary of porous beta PDO, tntla the densa inner region compres elet/on conducting ubsteichiomrc lead ondes as wellas some alpha POO,. THs inner fim protects the gid toa large extent by provenng direct Contact between land sulwric ass. However, corrosion IS hot stopped completly. iis beloved that oxygen fae reicals, hd atoms guin access tothe grid by cifusing, tough Vacancies inthe latce of the protective layer (2). These ‘oxygen species ore intermadiates erated during the oxygen that occurs the gd in paral with ‘Because the cercosion products are considerably less dense than the underving lead from which they are formed, tensle [Svesaos are coated a the mota-oxie interface. Lead yields {nde the infuence of thase sreses, resulting in changos in ‘rd dimension (3). If daformation (growth) i severe, contact Botwoon the grid and the active materal can be lst. Islation ‘of the activa materal from the eectvon conducting network ‘aveeso decrease cal copacy ‘To dete, stationary battery ie has boon maximized by the use Of pure ised in conjunction with bolanced gid designs (4 5. ‘Ths combination rasute im grid growth that is both low a Unvform. Ruptures inthe protective fim coused by growth te txpected tobe smal, uniformly dlstibute, and easy repaired by new fm formation. Howover, pur lead gigs ae cific to ‘manufacture end must be supported within the cell to prevent In contrast ids made trom leadcacium alloys ae stronge but they tend to corrode. more rapsly than pure tad ris 8d their corrosion rates «senate funtion of tele mevosucte (6.7). The grater hardness of Po-Ca alloy is achoved by the development et two-ohases, ® preciptate of PD,Ca dispersed in» Pb-Ce sold solution (8). Unless uniform dispersions of ‘small particies Toealzed and severa corosion can accu (8 localize at mrodets. set as. stress concentrators (10). ‘Ronurterm daormaton of the weakened gid i tho osu are produced during. manufacture, ghly [Although the use of pure lead grids of complex design has ‘successfully minimized the impact of grid corosion and growth ‘on cel if, thas been at th cost of specific energy. Specie ‘energy, expressed as Wh kg", Is ealelted from the total ‘energy svalable tom the battery under specified discharge ‘conditions end its total weight. "The gids used in longrved Stavonary batteries are typialy 0.1 £00.35 inches thick. The ‘asultng large grid cross anctonal are is cetical with respect to 1 eed gis esstanco to growth. However, grids ‘loments end do nat contribute sigiiconty toh inthe batery. On the other hand, boceuse ofthe high density Oot ad, they make up about 25 to 36 % ofa calls waight ‘An additional source of low onargy density avises fom the use of thick pltes becouse ofthe nature ofthe discharge reaction. Bitusion of the bislfete species into the pores of the plate reas 203e4ou $6.00 © 654 IEEE32 ‘becomes less efficient with increasing plat thickness. thas teen demonstrted that wikzation of the postive active mate ina single plato increases by abovt 20.% whon the active ‘motel is dvded equally botwoon two plates of hal the snl Plata thicknoss (11) Cleatty, energy density could be increased signticanty it thinner lead ids could be usod forthe positive pate. Even [renter gains could be achieved if thin gids of loss donse Materials could be employed, Several approaches (0 improving energy densty Uvough gid modification have bean described inthe Harotue. Techniques can be gororally diviged Into those that employ load asthe butk gid matal and those thet Use alternative materials LEAD AND LEAD ALLOY GRIDS ‘Tha Use of ead oF one ofits aloys takes advantage of in-place rmanafectuing and ocycling tachngue socisted with losd. Strong setve land igh oxygen evolution overpotontl However, with lead, improvements in energy density ae mites forthose obtained by thinning the gi. Thin grids are abl oly ifehe corosion and strength issues associated with ad con 00 ‘addressed. ‘The mojoty of fort this agord has boon in the ‘evelopment of stronger and more corrosion resistant loys, In Spite of consdarete roseerch, nod progress has basn meade ints afoe. Lead-ealcium alloys stil predominate in commercial systems and wil not be discussed here liprovad corrosion resistance has been achieved by the use of factve materal and loctoyte adctves. The most thoroughly Studied of thes are cobalt slate and phosphoric 8d» SEM fhotomierographs. show that the presence of cobalt sllte feads to. denser corrosion fins, the resuing dacreaes in Borosity making the lm more protactvel12).Cabat rons leo Tower the oxygen evelution overpotential (13). thes been “suggested that the intermedates nthe oxygen reaction combine ‘more readily, decaasing thas residence time onthe corrosion layer surace. The small: surface concentration decreases the fue of intermediates at tha metal onde layer Sgnifcant increase. in saldscharge and. poor recherge bfficieny that are brought about by enhanced oxygen evolution. Phosphoric acid also reduces the rate of gid corosion by producing lower sstace area ceroson layer (14). The Fesuling lower reactivity of the POO, with respect to Conversion to FOSOs during discharge preserves the d onporous maiphalogy ofthe protective aye.” Uatortn phosphoric acid also lowers the actvty of the PDO, active ‘materalin a smiar manner, leading to capacty losses of up 2 ‘ow cis) Thinner grids ean also bo used if lad-based mato are _srengthened toimsrove thei resistance to growth Composites Bt Toad with Hors of alumina, carbon, and quartz havea boon feportod (16,17). Ths technology is limited bythe abity of the fibers o be wet by molten lead. Inthe abeance ofa song bond atthe fbermeta interface ile strength improve ‘ehiowad snd catastrophe covosion has boon observed ot th ‘metalfiber interface, "On the other hand, gid strengths has boon increased by casting melton metal around a titanium (7 tre praform (18). Even in the absence of wetting. the Bresence of welded nodes in the preform lessens” gd Setrmation Coatings have also been applied to lead and ead alloy grids to ‘crease th corrosion rate. Tha approach introduces alot ‘the addtional composites expected with nan lead materials 36 Coatings must adhere wel both tothe oad substrate and tothe Scive matarl, bo chemically and slctechemicaly stable, favo onygen evtution cheractoraties simar to the PDO, Covosion layer formed on leed, and finaly be protective ofthe lead subatrate.. Based on tho mechanism for gid corrosion ‘Gocussed above, © protective layer most act as bares not fniy for sulle acid but also for the difusion of oxygen ‘one ofthe coating ystems that hasbeen proposed is besed on hlorosufonate ethylene polymars mixed ith graphite or carbon formate them conduetwe( 19). Orgaic mater ar not long ved at postive plate potentials Tha cxdation rests inthe production of sostc sci. one of the most. aggressive Compounds known with respect toad. Acetate anon severly “tack both the gid andthe positive active mater catastrophic plate flr. ‘Amore promising costing materi, 69Pb0,, has rcenty bean ‘oscrted inthe Meratre (20). Bacauseitis chemical simi {fe postive plate ondes, ths eloctor-conducting perovskite “pours to form astieng bend with bath tho ative material and the ond. However, ie chomislly unstable in suluric acid, ‘Socemposing to form 8350, and PEO, 8x50, is en insulator ed formation of continuous fimo ths salt could lead to ‘Solaton ofthe active materi em the gid. Application of an futer coating of Pb to form a layered structure appears t0 Stabitze the system. Accelerated toting resuts svggest 9 gnlicent improvement in ged Me undar leat conditions as & feault of this costing NON-LEAD GRIDS “The selection of nome! matorials for positive gris is mited primarily by the severity ofthe positive plate environment and Erereauierent for low rats of exygon evolution. Mot of the ‘designs proposed have employed. Tl as the gid meter ‘Aimough iis only hall as conducive as Pb, itis about 40 {imos 06 bord and'1/3 a8 densa (21). Grid thickness can be renee to provide both adequate conductvty end 2 Sgnitcant gain in oneray Sensi ‘A catical tector that must be considered when using Tis its Dassivation at anode potentials. The surface oxi fim tat forms is recttying, causing curent flow to go to 200 fayimptotcaly. To keep te reastance of the gidactve ‘mater interface low, Tr must bo protcted with a sable herent, eactron conducting costing. The earlest approsch ‘desorbed inthe potent hterature waves converting the sutace ‘fT motel tate nitride by reaction n a rategen stmosphore (22), Teri nitride te qute table in sulwie sci ond has & fesisuvity. of 2.2: 10-* obm.cm. However, the nitide aso ‘oxidizes at anodic potentils. Flesh plating with gold protects the ride, but tho gald Ist slowly forms a nomconducting tude at the potentials of the poskwe plats. Although this System inet viable, the approach which t describes has sat 3 precedent for th uso af br and mullayered grid structures. In fact, to moet the needs of active matorial asin and siow fnygen evelution, most gid designs have included inal ostng of PbO, oof ead metal which oxdzes to PEO, ding Formation ofa strong bond with Ts difieutt. Good adhesion fof Ined. to Ti has been achieved by paral cfusion of an Slectroplated eed layer inte tho” substrate at elavated Temperatures (23). This techeique must ba caied out in a tmosohere of lead vapor to prevent the loss of led frm the Surface, An adherent lead costing Mas also boon produced sing © nickel conversion coating (24). Nekel Mas beendeposited by precharging the ttanium with hydrogen (08 ekel bath produces intr, seas pleted with “The use of chemical etching toroughen the Ti surface has been Shown to improve adhesion Song. bonding of an Imermadate thermal decomposition FuD; and outer PEO, layer fave boon achieved with tie approach (28). Deposits of tieciron conducting ruthoniam dloxie are qute stable when txposed to acd at positive pate potentials. However, the very sod rate ot which oxygen evolved on tis eno raqures a ‘ssionel outer layer of electrodeposited POO, to eliminate Interference with the performance of the positive plata on charge and open cuit. ‘The loss of conductivity at the Tsui acid interface andthe re for 8 PDO, working surface have also been adcressed tisng a geomet approach (26). A porous Ti matrix hes been filed wits lad to produce a load-itanin network with a mixec motel outer surface. The formation of PbO, atthe lead rgions Gt the, motal-acd. interface blocks the” pores. to furor ponotroton of the eectalyte, leaving the lead titariam Ierfocesin the interior conductive. The Ti portion ofthe outer ‘Sivface passivates in contact wit the 0c, but tis no longer foqured fer electron eonduction whieh eccurs trough the PoOyPbT path “The concept of» mutilayer structure has also been extended to Irotas other then Ti, Taylor (27) has proposed the use of Uectrochemcaly stable metals such es Hb, Te, and W, with an termediate Av coating and an exterior dense PDO; layer. He ‘Sse Inches haloum and sconum as well asthe borides. ities and carbides of to Group VV. and Vi tension metals Us candidate materials. Wil has expanded on ths concept { 2) and has extended it 1 ‘minum, copper and fon (29). ponevation of the sactraiye results io the formation of @ Pacsivating onde, which although not conductive, covers oly Boat traction of the metargold interface. In the later case the reactive metas, # exposed to the sltion through pinhoes, oottackod by sectroyte, Stace reactive metas typical form Sototle reacton products, thoy can dramatically iter the ‘Sectrochomical bolance of the cal._In both approaches, pinholes inthe coatings can also result in delamination ofthe Protective coatings leading to. the loss of grd-active material Eontact and subsoquent cell fre (One of the more interesting materials suggested for postive (dss based on oxides of taruum 30). These Magne ase, Mibstichiometne ondes (0, are electron conducting for» {ise to 1.96, At sul higher values of x, the oxde Becomes an insulto,, while at lower veles, fis unstable In cid. Recent Studies of the Behavior of redox coupes in aqueous acs ot Mognol\ phase 710, alectrodes Nave shown thst, above 2 potentl of 1-2 V ve SHE, electron waster becomes highly reversible (91). A costing of PEO, has been shown forest th electrochemical ativty observed on this maton at lower potentials. ‘SUMMARY AND CONCLUSIONS. itis obvious that many aporosches to cicumventing postive ‘id corrosion have beon proposes. Some have addressed the Corrosion behavior and soltnss of lead directly using addtves, reinforcements, and coatings. Impeoverant in eneray density esta trom the abiity to use thinner plates. Others have Substituted hghter and stronger materi "loa. impeowing ‘nergy density by vsing thinner grids constuctad from los 37 a2 dense matrials. However, inno casa has spl material eon \Goratiod winch meats at of the ertra for posite gid im» lead acd battery. 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