12/21/2014

Battery5WhatTakesPlaceDuringDischarge

PreviousChapter

TableofContents

NextChapter

CHAPTER5
WHATTAKESPLACE
DURINGDISCHARGE
Consideredchemically,thedischargeofastoragebatteryconsistsofthe
changingofthespongyleadandleadperoxideintoleadsulphate,andthe
abstractionoftheacidfromtheelectrolyte.Consideredelectrically,the
changesaremorecomplex,andrequirefurtherinvestigation.Thevoltage,
internalresistance,rateofdischarge,capacity,andotherfeaturesmust
beconsidered,andtheeffectsofchangesinoneupontheothersmustbe
studied.Thisproceedingissimplifiedconsiderablyifweconsidereach
pointseparately.Theabstraction.oftheacidfromtheelectrolytegivesus
amethodofdeterminingtheconditionofchargeordischargeinthe
battery,andmustalsobestudied.

VoltageChangesDuringDischarge.Attheendofacharge,andbefore
openingthechargingcircuit,thevoltageofeachcellisabout2.5to2.7
volts.Assoonasthechargingcircuitisopened,thecellvoltagedrops
rapidlytoabout2.1volts,withinthreeorfourminutes.Thisisduetothe
formationofathinlayerofleadsulphateonthesurfaceofthenegative
plateandbetweentheleadperoxideandthemetalofthepositiveplate.
Fig.21showshowthevoltagechangesduringthelasteightminutesof
charge,andhowitdropsrapidlyassoonasthechargingcircuitisopened.
Thefinalvalueofthevoltageafterthechargingcircuitisopenedisabout
2.152.18volts.ThisismorefullyexplainedinChapter6.Ifacurrentis
drawnfromthebatteryattheinstantthechargeisstopped,thisdropis
morerapid.Atthebeginningofthedischargethevoltagehasalreadyhad
http://www.powerstream.com/1922/battery_1922_WITTE/batteryfiles/chapter05.htm

1/5

12/21/2014

Battery5WhatTakesPlaceDuringDischarge

arapiddropfromthefinalvoltageoncharge,duetotheformationof
sulphateasexplainedabove.Whenacurrentisbeingdrawnfromthe
battery,thesuddendropisduetotheinternalresistanceofthecell,the
formationofmoresulphate,andtheabstractingoftheacidfromthe
electrolytewhichfillstheporesoftheplate.Thedensityofthisacidishigh
justbeforethedischargeisbegun.Itisdilutedrapidlyatfirst,buta
balancedconditionisreachedbetweenthedensityoftheacidinthe
platesandinthemainbodyoftheelectrolyte,theacidsupplyintheplates
beingmaintainedatalowereddensitybyfreshacidflowingintothemfrom
themainbodyofelectrolyte.Aftertheinitialdrop,thevoltagedecreases
moreslowly,therateofdecreasedependingontheamountofcurrent
drawnfromthebattery.TheentireprocessisshowninFig.22.

Leadsulphateisbeingformedonthesurfaces,andinthebodyofthe
plates.Thissulphatehasahigherresistancethantheleadorlead
peroxide,andtheinternalresistanceofthecellrises,andcontributesto
thedropinvoltage.Asthissulphateformsinthebodyoftheplates,the
acidisusedup.Atfirstthisacidiseasilyreplacedfromthemainbodyof
theelectrolytebydiffusion.Theacidinthemainbodyoftheelectrolyteis
atfirstcomparativelystrong,orconcentrated,causingafreshsupplyof
acidtoflowintotheplatesasfastasitisusedupintheplates.This
resultsintheacidintheelectrolytegrowingweaker,andthis,inturn,
leadstoaconstantdecreaseintherateatwhichthefreshacidflows,or
diffusesintotheplates.Furthermore,thesulphate,whichismorebulky
thantheleadorleadperoxidefillstheporesintheplate,makingitmore
andmoredifficultforacidtoreachtheinterioroftheplate.Thisincreases
therateatwhichthevoltagedrops.
Thesulphatehasanothereffect.Itformsacoveroverthe
activematerialwhichhasnotbeenactedupon,andmakes
itpracticallyuseless,sincetheacidisalmostunableto
penetratethecoatingofsulphate.Wethushavequantities
ofactivematerialwhichareentirelyenclosedinsulphate,
therebycuttingdowntheamountofenergywhichcanbe
takenfromthebattery.Thustheformationofsulphate
throughouteachplateandtheabstractionofacidfromthe
electrolytecausethevoltagetodropataconstantly
increasingrate.
Theoretically,thedischargemaybecontinueduntilthe
voltagedropstozero,butpractically,thedischargeshould
bestoppedwhenthevoltageofeachcellhasdroppedto
1.7(onlowdischargerates).Ifthedischargeiscarriedon
beyondthispointmuchofthespongyleadandlead
peroxidehaveeitherbeenchangedintoleadsulphate,or
havebeencoveredupbythesulphatesoeffectivelythat
theyarealmostuseless.Platesinthisconditionrequirea
verylongchargeinordertoremoveallthesulphate.
Thelimitingvalueof1.7voltspercellappliestoa
http://www.powerstream.com/1922/battery_1922_WITTE/batteryfiles/chapter05.htm

2/5

12/21/2014

Battery5WhatTakesPlaceDuringDischarge

continuousdischargeatamoderaterate.Ataveryhigh
currentflowingforonlyaveryshorttime,itisnotonly'safe,
butadvisabletoallowabatterytodischargetoalower
voltage,theincreaseddropbeingduetotherapiddilution
oftheacidintheplates.
Thecellvoltagewillrisesomewhateverytimethe
dischargeisstopped.Thisisduetothediffusionoftheacid
fromthemainbodyofelectrolyteintotheplates,resulting
inanincreasedconcentrationintheplates.Ifthedischarge
hasbeencontinuous,especiallyifatahighrate,thisrisein
voltagewillbringthecelluptoitsnormalvoltagevery
quicklyonaccountofthemorerapiddiffusionofacidwhich
willthentakeplace.
Thevoltagedoesnotdependupontheareaoftheplate
surfacebutuponthenatureoftheactivematerialsandthe
electrolyte.Hence,althoughtheplatesofacellare
graduallybeingcoveredwithsulphate,thevoltage,
measuredwhennocurrentisflowing,willfallslowlyandnot
inproportiontotheamountofenergytakenoutofthecell.
Itisnotuntiltheplatesareprettythoroughlycoveredwith
sulphate,thusmakingitdifficultfortheacidtoreachthe
activematerial,thatthevoltagebeginstodroprapidly.This
isshownclearlyinFig.22,whichshowsthatthecell
voltagehasdroppedonlyaverysmallamountwhenthe
cellis50%discharged.Withcurrentflowingthroughthe
cell,however,theincreasedinternalresistancecausesa
markeddropinthevoltage.Opencircuitvoltageisnot
useful,thereforetodeterminehowmuchenergyhasbeen
takenfromthebattery.

SearchSite
Home
PolymerMolding
Batteries&Packs
BatteryChargers
PowerSupplies
DC/DCConverters
Automotive
CCTV/Security
SpotWelders
Inverters
CustomProducts
Technical
Resources
Surplus
Consulting

AcidDensity.Theelectrolyteofaleadstoragebatteryisa
mixtureofchemicallypuresulphuricacid,andchemically
purewater,theacidformingabout30percentofthe
volumeofelectrolytewhenthebatteryisfullycharged.The
pureacidhasa"specificgravity"of1.835,thatis,itis1.835
timesasheavyasanequalvolumeofwater.Themixture
ofacidandwaterhasaspecificgravityofabout1.300.As
thecelldischarges,acidisabstractedfromtheelectrolyte,
andtheweightofthelattermustthereforegrowless,since
therewillbelessacidinit.Thechangeintheweight,or
specificgravityoftheelectrolyteisthebestmeansof
determiningthestateofdischargeofacell,providedthat
thecellhasbeenusedproperly.Inorderthatthevalueof
thespecificgravitymaybeusedasanindicationofthe
amountofenergyinabattery,thehistoryofthebattery
mustbeknown.Suppose,forinstance,thatinrefillingthe
batterytoreplacethewaterlostbythenaturalevaporation
whichoccursintheuseofabattery,acid,oramixtureof
acidandwaterhas'beenused.Thiswillresultinthe
specificgravitybeingtoohigh,andtheamountofenergyin
thebatterywillbelessthanthatindicatedbythespecific
gravity.Again,ifpurewaterisusedtoreplaceelectrolyte
whichhasbeenspilled,thespecificgravitywillbelower
thanitshouldbe.Inabatterywhichhasbeendischarged
tosuchanextentthatmuchoftheactivematerialhasbeen
coveredbyalayeroftoughsulphate,orifaconsiderable
amountofsulphateandactivematerialhasbeenloosened
fromtheplatesandhasdroppedtothebottomofthecells,
itwillbeimpossibletobringthespecificgravityofthe
electrolyteupto1.300,eventhoughalongchargeisgiven.
There.must,therefore,beareasonabledegreeof
certaintythatabatteryhasbeenproperlyhandledifthe
specificgravityreadingsaretobetakenasatrueindication
oftheconditionofabattery.Whereabatterydoesnotgive
satisfactoryserviceeventhoughthespecificgravity
readingsaresatisfactory,thelatterarenotreliableas

http://www.powerstream.com/1922/battery_1922_WITTE/batteryfiles/chapter05.htm

3/5

12/21/2014

Battery5WhatTakesPlaceDuringDischarge

indicatingtheamountofchargeinthebattery.

Blog
PowerHumor
ContactUs
SiteMap
ViewCart

AdjustableDC/DC
converterforcars

Aslongasadischargecurrentisflowingfromthebattery,
theacidwithintheplatesisusedupandbecomesvery
muchdiluted.Diffusionbetweenthesurroundingelectrolyte
andtheacidintheplateskeepsupthesupplyneededin
theplatesinorderto,carryonthechemicalchanges.
Whenthedischargeisfirstbegun,thediffusionofacidinto
theplatestakesplacerapidlybecausethereislittle
sulphatecloggingtheporesintheactivematerial,and
becausethereisagreaterdifferencebetweenthe
concentrationofacidintheelectrolyteandintheplates
thanwillexistasthedischargeprogresses.Asthesulphate
beginstoformandfilluptheporesoftheplates,andas
moreandmoreacidisabstractedfromtheelectrolyte,
diffusiontakesplacemoreslowly.
Ifabatteryisallowedtostandidleforashorttimeaftera
partialdischarge,thespecificgravityoftheelectrolytewill
decreasebecausesome,oftheacidintheelectrolytewill
graduallyflowintotheporesoftheplatestoreplacethe
acidusedupwhilethebatterywasdischarging.
Theoreticallythedischargecanbecontinueduntilallthe
acidhasbeenusedup,andtheelectrolyteiscomposedof
purewater.Experiencehasshown,however,thatthe
dischargeofthebatteryshouldnotbecontinuedafterthe
specificgravityoftheelectrolytehasfallento1.150.Asfar
astheelectrolyteisconcerned,thedischargemaybe
carriedfartherwith'safety.Theplatesdeterminethepoint
atwhichthedischargeshouldbestopped.Whenthe
specificgravityhasdroppedfrom1.300to1.150,somuch
sulphatehasbeenformedthatitfillstheporesintheactive
materialontheplates.Fig.23showsthechangeinthe
densityoftheacidduringdischarge.

ChangesattheNegativePlate.Chemically,theactionatthenegative
plateconsistsonlyoftheformationofleadsulphatefromthespongylead.
Theleadsulphateisonlyslightlysolubleintheelectrolyteandis
http://www.powerstream.com/1922/battery_1922_WITTE/batteryfiles/chapter05.htm

4/5

12/21/2014

Battery5WhatTakesPlaceDuringDischarge

precipitatedassoonasitisformed,leavinghydrogenions,whichthengo
totheleadperoxideplatetoformwaterwithoxygenionsreleasedatthe
peroxideplate.Thesulphateformsmorequicklyonthesurfaceofthe
platethanintheinnerportionsbecausethereisaconstantsupplyofacid
availableatthesurface,whereastheformationofsulphateintheinterior
oftheplaterequiresthataciddiffuseintotheporesoftheactivematerials
toreplacethatalreadyusedupintheformationofsulphate.Inthe
negativeplate,however,thesulphatetendstoformmoreuniformly
throughoutthemassofthelead,becausethespongyleadismoreporous
thantheleadperoxide,andbecausetheacidisnotdilutedbythe
formationofwaterasinthepositiveplate.
Changesatthe,PositivePlate.Inafullychargedpositive
platewehaveleadperoxideastheactivematerial.Thisis
composedofleadandoxygen.Fromthisfactitisplainly
evidentthatduringdischargethereisagreaterchemical
activityatthisplatethanatthenegativeplate,sincewe
mustfindsomethingtocombinewiththeoxygeninorder
thattheleadmayform.leadsulphatewiththeacid.Inan
idealcell,therefore,thematerialwhichundergoesthe
greaterchangeshouldbemoreporousthanthematerial
whichdoesnotinvolveasgreatachemicalreaction.In
reality,however,theperoxideisnotasporousasthe
spongylead,anddoesnotholdtogetheraswell.
Thefinalproductsofthedischargeofapositiveplateare
leadsulphateandwater.Theleadperoxidemustfirstbe
reducedtolead,whichthencombineswiththesulphate
fromtheacidtoformleadsulphate,whiletheoxygenfrom
theperoxidecombineswiththehydrogenoftheacidto
formwater.Thereis,therefore,agreateractivityatthis
platethanattheleadplate,andtheformationofthewater
dilutestheacidinandaroundtheplatesothatthe
tendencyisforthechemicalactionstoberetarded.
Thesulphatewhichformsondischargecausestheactive
materialtobulgeoutbecauseitoccupiesmorespacethan
theperoxide.Thiscausestheleadperoxideatthesurface
tobeginfalling,tothebottomofthejarinfinedustlike
particles,sincetheperoxidehereholdstogethervery
poorly.

PreviousChapter

TableofContents

NextChapter

[Home][PowerStream][SiteMap]
[TechResources][PolicyandPrivacy]
[ContactUs]
GoogleAuthorVerification

PowerStreamTechnology
1163South1680West
OremUtah84058
Phone:8017649060Fax:8017649061

Copyright2000,2002,2003,2004,2005,2006,2008,2009,2010,2011,
2012,2013,2014
LundInstrumentEngineering,Inc.Allrightsreserved.byMarkW.Lund

http://www.powerstream.com/1922/battery_1922_WITTE/batteryfiles/chapter05.htm

5/5