Lead

 ba'ery  
 Original  Plantè  ba'ery(1859)  

A  total  of  about  three  hundred  million  lead-­‐acid  ba'eries  are  made  every  year.  These  
range  in  size  from  2  Wh  cells  to  100  Wh  starHng,  lighHng  and  igniHon  (SLI)  systems,  
and  to  40  MWh  load  levelling  modules.  The  great  success  of  this  system  is  due  to  a  
number  of  favourable  factors  such  as  the  relaHvely  low  cost  and  availability  of  the  
raw  materials  (lead  and  sulphur),  ease  of  manufacture,  long  cycle  life  
 generality  
•  The  lead-­‐acid  cell  can  be  represented  schemaHcally  as  having  a  negaHve  
electrode  of  porous  lead  (lead  sponge)  and  a  posiHve  electrode  of  lead  
dioxide,  PbO2,  both  immersed  in  an  aqueous  soluHon  of  sulphuric  acid:  
         
 

As  the  cell  is  discharged,  sulphuric  acid  is  consumed  and  water  is  formed.  
Consequently   the   electrolyte   composiHon   and   density   vary   from   about   40%   by  
weight  of  H2SO4  (1.30  kg/dm  )  at  full  charge,  with  an  associated  OCV  of  2.15  V  at  
25°  to  about  16%  by  weight  of  H2S04  (1.10  kg/dm  3)  when  fully  discharged,  with  an  
OCV   of   1.98   V.   The   change   in   electrolyte   specific   gravity   provides   a   convenient  
method  of  determining  the  state  of  charge  of  a  cell.  OCV    depends  on  the  sulphuric  
acid   (and   water)   acHvity   and   temperature   and   may   be   predicted   with   accuracy  
from  thermodynamic  free  energy  values.  
 Voltage  

In  tradiHonal  'wet'  lead-­‐acid  cells  the  recharge  reacHons  become  less  

efficient  as  the  cell  approaches  85-­‐90%  state  of  charge,  and  the  posiHve  
electrode  begins  to  evolve  oxygen.  At  the  negaHve  electrode,  hydrogen  
ions  react  to  form  hydrogen  gas,  resulHng  in  water  loss.  
In  Valve  regulated  lead-­‐acid  (VRLA)the  oxygen  diffuses  from  the  posiHve  to  the  negaHve  
plate  where  it  oxidizes  the  lead,  prevenHng  it  from  reaching  a  potenHal  where  hydrogen  
will  evolve.  
Water  loss  
Voltage  
Voltage  
 PosiHve  electrode  

Rate  determining  reacHon:  

 PosiHve  electrode  
•  An  important  feature  of  the  posiHve  electrode  discharge  concerns  the  
nature  of  the  PbSO4  deposit  since  the  formaHon  of  dense,  coherent  layers  
can  lead  to  rapid  electrode  passivaHon.  Lead  dioxide  exists  in  two  
crystalline  forms,  rhombic  (α-­‐)  and  tetragonal  (β-­‐),  both  of  which  are  
present  in  freshly  formed  electrode  structures.  Since  PbSO4  and  α-­‐PbO2  
are  isomorphic,  crystals  of  lead  dioxide  of  this  modificaHon  tend  to  
become  rapidly  covered  and  isolated  by  lead  sulphate  
As  the  la'er  is  the  thermodynamically  
more  stable  of  the  two,  some  transformaHon  of  α-­‐  
into  β-­‐PbO2  may  occur  
during  the  life  of  a  ba'ery  
AddiHons  of  small  quanHHes  of  Hn  
are  made  to  the  lead  to  improve  its  
coaHng  properHes,  while  anHmony,  
calcium  or  selenium  are  added  to  form  
alloys  with  be'er  stress  resistance.  
AnHmony  (1.5-­‐8%)  greatly  improves  the  
mechanical  properHes  of  grids  and  
connector  bars,  but  also  increases  their  
electrical  resistance,  accelerates  the  
self-­‐discharge  of  the  cell,  
 PosiHve  electrode  
Use  of  lead-­‐calcium  or  low  anHmony  grids  with  
as  li'le  as  1%  anHmony  
is  increasing  to  reduce  water  loss.  

Tubular  plates  allow  deep  

discharge  
fine  mesh  grids  or  coarse  grids  covered  with  perforated  lead  foil  are  used  in  posiHve  
plate  manufacture.    When  the  paste  is  reduced  under  carefully  controlled  condiHons,  
highly  porous  sponge  lead  is  formed  consisHng  of  a  mass  of  acicular  (needle-­‐like)  
crystals  which  give  a  high  electrode  area  and  good  electrolyte  circulaHon.    
On  deep  cycling,  however,  and  especially  at  high  rates,  the  original  morphology  
tends  to  alter  to  give  larger  crystal  grains  which  have  a  lower  overall  area  
and  which  are  more  easily  passivated  by  PbSO4  layers.    
Surface-­‐acHve  materials  such  as  ligno-­‐sulphonic  acid  derivaHves  are  known  as  
expanders  and  are  thought  to  act  by  lowering  the  surface  energy  of  the  lead,  
so  making  the  formaHon  of  large  crystals  less  energeHcally  favourable.  
 Separators  
•  Separators  are  porous  insulaHng  sheets  which  are  placed  
between  the  electrodes  of  opposite  polarity  to  prevent  
contact  and  short  circuit  between  them.  They  also  act  as  a  
barrier  to  the  transport  of  acHve  material  between  the  
plates,  mechanically  support  the  posiHve  acHve  mass  (so  
reducing  shedding)  and  prevent  dendrite  formaHon.  
•  present-­‐day  ba'eries  almost  all  use  separators  made  from  
syntheHc  polymers  or  glass  filters.  The  porosity  
characterisHcs  of  these  substances  can  be  controlled  to  
within  close  tolerances  during  the  manufacturing  process.  
•  Very  efficient  thin  separators  are  required  for  high  energy  
density  ba'eries.  
Final  ba'ery  
Almost  all  lead-­‐acid  ba'ery  cases  are  
rectangular  (prismaHc)  in  shape.  
 Acid  lead  ba'ery:  as  it  works  
•  The  pracHcal  capacity  of  all  such  ba'eries  is  also  dependent  on  the  
temperature  of  operaHon  and  is  found  to  drop  very  rapidly  at  
temperatures  below  0°  
•  As  the  system  is  thermodynamically  unstable  with  respect  to  
hydrogen  and  oxygen  evoluHon,  lead-­‐acid  cells  are  subject  to  self-­‐
discharge:  

+  

-­‐  

The  rates  of  these  processes  are  dependent  on  temperature,  electrolyte  
volume  and  concentraHon,  and  most  importantly,  impurity  content.  If  
anHmony  is  leached  out  of  the  posiHve  grid  it  may  be  deposited  on  the  
negaHve  plate  where  it  catalyses  reacHon  ,  because  of  its  relaHvely  
low  hydrogen  overvoltage.  (volcan  plot)  
 sulphaHon  
 
•  If  a  lead-­‐acid  ba'ery  is  lee  for  a  prolonged  
period  in  an  uncharged  state  or  is  operated  at  
too  high  temperatures  or  with  too  high  an  
acid  concentraHon,  the  lead  sulphate  deposit  
is  gradually  transformed  by  recrystallizaHon  
into  a  dense,  coarse-­‐grained  form.  This  
process  is  known  as  sulphaHon  
 Manteinance  free  ba'ery  (MFB)  
•  Over  the  past  25  years,  the  introducHon  of  ba'eries  described  as  
'maintenance-­‐  free'  (MF)  has  had  an  important  impact  on  the  market.    
•  no  addiHon  of  water  to  the  electrolyte  is  required  over  a  normal  service  
life  of  2-­‐5  years.  
Standard  lead-­‐acid  ba'eries  lose  a  small  amount  of  water  by  evaporaHon,  but  
the  major  mechanism  for  water  loss  is  by  electrolysis  to  form  hydrogen  and  
oxygen.      The  presence  of  small  quanHHes  of  foreign  elements  lowers  the  
overvoltages  for  these  processes  and  leads  to  an  accelerated  water  loss:    
•  it  has  been  shown  that  the  elements  anHmony,  arsenic,  cobalt,  
manganese,  nickel,  plaHnum  and  tellurium  all  have  a  deleterious  effect,  
even  at  low  levels.    
 MFB  
•  Two  general  approaches  have  been  taken  in  the  development  of  
MF  ba'eries:  
•  -­‐  reducHon  of  the  rate  of  gas  formaHon  within  the  normal  operaHng  
condiHons  of  the  ba'ery;  
•  -­‐  promoHon  of  gas  recombinaHon.  
•  modified  posiHve  grid  and  strap  alloys  in  which  the  proporHon  of  
anHmony  is  substanHally  reduced  or  eliminated  and  replaced  by  
calcium  or  by  a  group  of  several  metals  (e.g.  stronHum/Hn/
aluminium).  Calcium  alloy  grids  have  greatly  improved  behaviour  so  
far  as  hydrogen  evoluHon  is  concerned,  but  the  calcium  alloys  have  
relaHvely  poor  processing  characterisHcs  leak-­‐proof  enclosures  with  
a  one-­‐way  vent  to  release  excess  gas  pressure  and  are  someHmes  
referred  to  as  'semisealed’  systems  
Modern  ba'eries  
PosiHve  and  negaHve  plates  are  
usually  made  using  a  
'honeycomb'  grid  
support  filled  with  acHve  
material.  The  separators  are  
thin  films  of  porous  
highly  insulaHng  materials  
which  also  retain  the  
electrolyte.  Usually  they  
contain  a  non-­‐woven  glass  
microfibre  mat  which  is  heat  
and  oxidaHon  
resistant.