Uni-Ulm Lecture EST3 ZSW Lead-Acid Batteries 1

Energy Science and Technology III
Lecture
Winter Term 2017/18
Lead Acid Batteries (LAB)

11 Jan. 2018
Mario Wachtler, Ludwig Jörissen

Zentrum für Sonnenenergie- und Wasserstoff-Forschung (ZSW)
Baden-Württemberg
180111 | University of Ulm | EST-III | LAB | MW
Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
-2-
Lead Acid Battery Development
The LAB’s history dates back to 1789, with its birthdate being debated being
either 1854 or 1859.
1854 1859 1973 Today
W.J. Sinsteden G. Planté F&E world record 40 Wh/kg
0.1 Wh/kg 9 Wh/kg Japan Storage 200 W/kg
70.5 Wh/kg 500 cycles (SFUDS*)
100 cycles Charging time
50% in 5 min
80% in 15 min
150 USD/kWh
*simplified federal urban driving schedule
The present lead acid battery is

the result of 150 years of
mostly empirical development!
-3-
Lead Acid Battery Development
Milestones
2000 Lead acid batteries ready to power the global communication highways.
1990 Lead acid batteries power the cellular telephone revolution.
1980 Stationary VRLA batteries based on AGM technology are developed.
1968 The maintenance free SLI battery is developed.
1965 Polypropylene SLI battery cases start to be used.
1958 Jache describes the gel VRLA battery.
1951 Lead calcium alloys are used in telephone exchange stationary lead acid batteries.
1918 Shimadzu describes the ball mill oxide.
1915 Willard introduces rubber separators.
1910 The iron-clad or tubular plate construction is introduced.
1907 A lead calcium alloy is patented.
1904 Red cedar wood is used as battery separator.
1882 Gladstone and Tribe describe the so called double-sulfate theory i.e. the basis of
operation of the lead acid battery. Tudor operates a lead acid battery factory in
Luxembourg.
1881 Faure discovers the pasted plate which yields a mayor breakthrough in capacity. A
lead antimony alloy is used the first time to give strength.
1859 Planté improves the capacity of the lead acid batteries with a technique still in use
today (Planté type plates).
1854 Sinsteden uses for the first time lead plates in sulfuric acid to store, i.e. accumulate,
electricity
1800 Volta demonstrates to Napoleon the Volta pile, a primary, non rechargeable battery.
1789 Galvani carries out his frog leg experiments.
-4-
General Properties
Pros:
 High cell voltage (~ 2 V)
 High safety at normal and at abuse conditions
 Long calendar life is possible in certain conditions (especially in charge sustaining
mode)
 Good power (100 – 200 W/kg, high-power LAB up to 1000 W/kg for short periods)
 Large system variety: sizes from 12 V, 0.5 Ah for camcorder batteries all the way up to
2 V 12.000 Ah for submarine battery cells.
 Good recycleability, since all components are rich in Pb
 Low costs (from 50 €/kWh)
Cons:
 Low specific energy (25 Wh/kg for stationary LAB to 45 Wh/kg for SLI LAB)
 Low cycle life for heavy cyclic duty
 Limited storage times
 Ventilation of storage room is required, since H2 and O2 may evolve
 Self discharge (approx. 3% per month at 20°C)
-5-
Types of Lead Acid Batteries
By Basic Design
Lead acid batteries (LAB)
Flooded LAB Valve-regulated lead acid battery

Vented LAB (VRLA)
(German: geschlossene Bleibatterie) Maintenance-free LAB
• Maintenance required (H2O refilling) Sealed battery
(German: verschlossene Bleibatterie)
• Immobilised electrolyte
• Maintenance-free
Continuous improvements:
• Low maintenance
• No maintenance Absorbant glass mat Gel-Type
(AGM) • Electrolyte immobilisation
• Electrolyte immobilisation as silica gel
in glass microfibre fleece
-6-
Types of Lead Acid Batteries
By Application
Industrial Batteries Traction Batteries SLI Batteries

(starting, lighting,
Applications: Applications: ignition)
Uninterrupted power Fork lifts, utility vehicles, (German: Starterbatterie)
supply (UPS) / reserve …
battery, other stationary Applications:
applications Optimised towards: Cars, motorcycles, …
cycle life Start-stop
Optimised towards:
calendar life in charge Market share: ~ 25% Optimised towards:
sustaining mode power and weight,
low price, high safety
Market share: ~ 25% good cold cranking
properties
Market share: ~ 50%
-7-
Contents
Introduction
Basic Reactions
Side Reactions
Electrolyte
Ageing Mechanisms
-8-
Basic Reactions
discharge
Anode (negative electrode): charge

- +
Pb  Pb2+ + 2e−
PbSO4 Pb2+ + SO42–  PbSO4
PbSO4
Solution Pb + SO42–  PbSO4 + 2e−
Pb Pb2+ SO42- Pb2+ SO42-
Cathode (positive electrode):
Diffusion
e-
e- PbO2 + 4H+ + 2e−  Pb2+ + 2H2O
Pb2+ + 2 e-  Pb
(PbO2 is non-stoichiometric, which explains high
Transfer conductivity)
Pb2+  Pb+4 + 2 e- (reaction probably occurs via soluble insertion
compound HxPbO2)
PbO2
2 H2O4 H+ +2 O2- Pb2+ + SO42–  PbSO4
PbO2 PbO2 + SO42– + 4H+ + 2e−  PbSO4 + 2H2O
Cell reaction:
Pb + PbO2 + 2SO42– + 4H+  2PbSO4 + 2H2O
-9-
Basic Reactions
discharge
Anode (negative electrode): charge
Solution-precipitation Pb  Pb2+ + 2e−

mechanism Pb2+ + SO42–  PbSO4
Pb + SO42–  PbSO4 + 2e−
“Double sulfate theory”

(during discharge PbSO4 Cathode (positive electrode):
is formed at both PbO2 + 4H+ + 2e−  Pb2+ + 2H2O
electrodes) (probably via soluble insertion compound
HxPbO2)
Pb2+ + SO42–  PbSO4

Electrolyte H2SO4 as active PbO2 + SO42– + 4H+ + 2e−  PbSO4 + 2H2O
material
 Acid concentration changes
during charge/discharge Cell reaction:
(can be used for state of Pb + PbO2 + 2SO42– + 4H+  2PbSO4 + 2H2O
charge indication via acid
density)
- 10 -
Electrode Potentials and Cell Voltage
Standard Electrode Potentials and Standard Electromotoric Force (EMF)
Positive electrode: E0(PbO2/PbSO4) = 1.690 V vs. SHE
Negative electrode: E0(PbSO4/Pb) = – 0.358 V vs. SHE
Cell EMF: ∆E = E0(PbO2/PbSO4) – E0(PbSO4/Pb) = 2.048 V
Actual Electrode Potentials and EMF
Exact electrode potentials and EMF depend on pH value and on concentration of

H2SO4!
Nominal Cell Voltage: ~ 2.0 V
- 11 -
Electrode Potentials and Nominal Cell Voltage
Anode: Pb + SO42–  PbSO4 + 2e−

0 RT aPbSO4 0 RT
EPbSO4 / Pb  EPbSO 4 / Pb
 ln  EPbSO / Pb  ln aSO 2
zF aPb  aSO 2 4
2F 4
 
4
  0.358  0.029 lg aSO 2 V

4
Cathode: PbO2 + SO42– + 4H+ + 2e−  PbSO4 + 2H2O

4 4
0 RT aPbO2  aSO42  aH  0 RT aSO42   aH 
EPbO2 / PbSO4  EPb / PbSO4  ln  EPb / PbSO4  ln 
zF aPbSO  aH2 O 2F aH2 O
 
4 2 2
 1.690  0.118pH  0.059 lg aH2O  0.029 lg aSO 2  V

4
Cell: Pb + PbO2 + 2SO42– + 4H+  2PbSO4 + 2H2O

2  a 
4
RT a RT 1
E  EPbO2 / PbSO4  E PbSO4 / Pb  EPbO  EPbSO   
0 0 SO H
2 / PbSO4 / Pb ln 4
ln
4
2F aH2 2O 2 F aSO 2
 
4
 2.048  0.118pH  0.059 lg aSO 2  0.059 lg aH 2O V

4
- 12 -
Electrode
Typical electrode thickness: <1 – 3 mm
High porosity required:

Negative electrode: Porous sponge Pb
(~50% porosity, ~0.5 m2/g active surface
area)
Positive electrode: porous PbO2 (~ 50%
porosity, ~5 m2/g active surface area)
With increasing discharge

 Decrease of electronic conductivity as
PbSO4 is an insulator (10-9 S/cm)
 Decrease of pore volume, since volume
of PbSO4 is higher than that of Pb and
PbO2, which hinders diffusion of
electrolyte
In reality only about 50% of active materials

are dischargeable
D.U. Sauer: Bleibatterien; OTTI-Seminar: Wiederaufladbare
Batteriesysteme; Ulm (Germany), 2010.
- 13 -
Contents
Introduction
Basic Reactions
Side Reactions
Electrolyte
Ageing Mechanisms
- 14 -
Side Reactions
Parasitic side reactions with slow kinetics:
 Gas formation reactions (electrolysis of H2O)

Oxygen evolution at positive electrode
2H2O  O2 + 4H+ + 4e−
Hydrogen evolution at negative electrode
2H+ + 2e−  H2
 Oxygen recombination at negative electrode

O2 + 4H+ + 4e−  2H2O
(this reaction is exploited in VRLA batteries)
(reaction is unimportant in flooded LAB due to slow O2 diffusion in electrolyte)
 Corrosion of positive current collector grid

Pb + 2H2O  PbO2 + 4H+ + 4e−
Side reactions result in self-discharge (conservation/buffer charging with low current is

recommended to maintain charge state)
- 15 -
Grid Corrosion
 Corrosion of positive current collector grid:

Pb + 2H2O  PbO2 + 4H+ + 4e−
 In acidic conditions and presence of sulfate:

Pb + PbO2 + 2H2SO4  2PbSO4 + 2H2O (via PbO intermediate layer)
PbSO4 is insulator, and increases charge transfer resistance between grid and
active material
Most important ageing mechanism of LAB Corrosion layer

(PbO2, PbSO4)
Intermediate layer
(PbO) Active mass
Strongly dependent on (PbO2)
 Alloy material and grid processing + H2SO4
 Temperature
 Acid concentration
 Potential
Grid (Pb)
- 16 -
Gas Formation Reactions
pH range for LAB

Both positive and negative
electrode operate outside the
thermodynamic stability window of
the aqueous electrolyte:
 Formation of O2 and H2
thermodynamic stability window of H2O
U / V vs. SHE
Pourbaix diagramme
(potential vs. pH)
- 17 -
Potentials and Kinetics of Side Reactions
Current voltage curves
Flooded
VRLA
Equilibrium potentials (dependent
on acid concentration)
Basic charge / discharge reactions of Pb and PbO2: fast kinetics (high current rates even at small deviations from
equilibrium potentials)
O2 and H2 evolution: high overvoltages required: low current rates at normal conditions, gradual current increase with
electrode polarisation (especially important at overcharge conditions)
Oxygen recombination (oxygen reduction): „limiting current“ (reaction rate is determined by rate of oxygen diffusion from
positive to negative electrode) D. Berndt, „Valve-Regulated Lead-Acid Batteries“; J. Power Sources 100 (2001) 29.
P.T. Moseley, D.A.J. Rand, in „Valve Regulated Lead-Acid Batteries“, Elsevier, 2004; (Fig. 1.5).
- 18 -
Contents
Introduction
Basic Reactions
Side Reactions
Electrolyte
Ageing Mechanisms
- 19 -
Working Principle of VRLA
Oxygen Recombination
gas channels
Recombination of O2 at negative electrode

Diffusion of O2 from positive to negative electrode required
Diffusion is slow in electrolyte, and fast in gas phase
R.F. Nelson, in „Valve-regulated Lead-Acid Batteries“, ed. D.A.J. Rand, P.T. Moseley, J. Garche, C.D. Parker, Elsevier 2004. p. 7.
- 20 -
Immobilised Electrolyte in VRLA
Electrolyte is immobilised as gel or in glass microfibre mat (AGM, absorbant

glass-fibre mat)
Cracks and pores are formed in gel or microfibre mat which allow fast O2
diffusion via gas phase
Gel-type electrolyte Electrolyte in AGM

Trapping (absorption) of H2SO4 in glass
fibre mat
Formation of gel from H2SO4 and pyrogenic

(fumed) SiO2
- 21 -
VRLA
Reduction of H2 evolution is required in VRLA
Negative electrode is over-dimensioned

 positive electrode is first fully charged and O2 evolution starts
 O2 diffuses to negative electrode
 due to recombination of O2 negative electrode is never fully charged, and H2
evolution remains negligible
Recombination does not work with 100% efficiency, therefore slowly gas
pressure builds up; if pressure becomes too high (approx. 100 - 150 mbar
overpressure) gas is released by short opening of valve ( valve-regulated
LAB)
- 22 -
Working Potential Ranges
Charge voltage ranges
Flooded
VRLA
In a VRLA both electrodes work at

D. Berndt, „Valve-Regulated Lead-Acid Batteries“; J. Power
more positive potentials than in a Sources 100 (2001) 29.
flooded LAB. P.T. Moseley, D.A.J. Rand, in „Valve Regulated Lead-Acid
Batteries“, Elsevier, 2004; (Fig. 1.5).
- 23 -
VRLA – Where the Name Comes from …
Resealable Valve
Resealable valve
1: Sealing edge
2: Synthetic-rubber plate
3: Spring
4: Flame-resistant porous
disc
5: O-ring gasket
- 24 -
Comparison of Gel and AGM-Technology
Immobilizing the electrolyte: Gel vs. AGM
SiO2 gel AGM

Immobilization: excellent fair
Resistance: high low
 Selection of design defined by applications
Preferred applications for gel types: standby, low rate cycling,

permits very high cells without danger of stratification.
Preferred applications for AGM types: wherever maintenance

is an argument against vented cells.
To be considered: cost, charging mode.
- 25 -
Contents
Introduction
Basic Reactions
Side Reactions
Electrolyte
Ageing Mechanisms
- 26 -
Electrolyte
Dilute H2SO4
Working concentrations:
Flooded LAB: charged 1.24 – 1.28 g/cm3 (33 – 37%, 4.2 – 4.8 M)
discharged: ~ 1.1 g/cm3 (~ 15%, ~ 1.6 M)
VRLA: charged 1.30 – 1.32 g/cm3 (40 – 42%, 5.2 – 5.5 M)
discharged: 1.05 – 1.1 g/cm3 (8 – 15%, 0.85 – 1.6 M)
Strong variations of freezing point with acid concentration
Acid concentration can be used for determination of state of charge (SOC)
Acid acts as active material, i.e. battery capacity determines minimum amount of
electrolyte which is required
- 27 -
Dilute H2SO4
Concentration Conversion Table
Concentration Density Concentration Concentration Refractive Relative
Wt.% g/cm3 g/L mol/L index viscosity
A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen; Leipheim and Munich (Germany), 2006.
- 28 -
Electrolyte Conductivity
as Function of Concentration and Temperature
Conductivity / -1cm-1
Selection of electrolyte concentration

and quantity has big influence
on cell performance!
Source: H. Bode, „Lead Acid Batteries“.

John Wiley & Sons, New York 1977, pg. 74
Per cent H2SO4 (by weight)  The Electrochemical Society, Pennington, NJ
- 29 -
Open Circuit Voltage (OCV)
as Function of Acid Density
Equilibrium voltage (OCV) / V
OCV according to
Nernst equation
Linear approximation
Acid density / g/cm3
- 30 -
Freezing Point
as Function of Electrolyte Density
In fully discharged state freezing point lies around -10°C.
Freezing point / °C  Risk of freezing in winter!
flooded Acid density / g/cm3
VRLA
(SOC = state of charge)
- 31 -
Low Temperature Performance of SLI Batteries
Battery performance decreases drastically at low temperatures.

Old (aged) batteries may not deliver the required cold cranking power.
Engine
load
Battery
capacity
http://www.varta-automotive.com/elearning/de/t1_3_1.html?1,2 (January 2013)
- 32 -
Contents
Introduction
Basic Reactions
Side Reactions
Electrolyte
Ageing Mechanisms
- 33 -
Ageing Mechanisms
Positive grid corrosion

Sulfation
Acid stratification
Compactation of negative electrode mass (Pb) during cycling:
 Loss of porosity and surface area
 Counter measure: mass expander additives
Dendritic Pb deposition
 If solubility of PbSO4 in electrolyte is too high, dissolution and deposition can occur at
separated places, resulting in dendric Pb deposition and danger of internal short
circuits.
Weakening of AM structure due to volume changes during charge/discharge
VPbSO4/VPb  2.6
VPbSO4/VPbO2  1.9
 Volume changes result in mechanical stress which weakens AM structure (AM may fall
out from grid and create short circuits)
 Measures against short circuits:
- Reservoir for detached electrode material at bottom of battery
- Pocket separators (separator pockets / bags)
- 34 -
Sulfation during Storage in Discharged State
 Sulfation = accumulation of PbSO4 which cannot be dissolved any longer

during charge
 Due to recrystallisation of PbSO4 to form large (inactive) crystals
 Especially when unused for long times in deeply discharged state
 Coarse grained PbSO4 can only be recharged with great difficulty
(“reconditioning”)
recrystallisation
Same volume
Half surface area
Large surface area required for charge reaction

SEM image of cycled positive electrode with large
inactive PbSO4, which do not contribute to the charge
D.U. Sauer: Bleibatterien; OTTI-Seminar: Wiederaufladbare process any longer.
Batteriesysteme; Ulm (Germany), 2010. Varta, Johnson-Controls
- 35 -
Sulfation During HRPSoC Operation
HRPSoC Operation = high-rate partial state of charge operation

 flat cycling at high current rates around a medium state of charge
 Typical requirement for HEV applications
At high rates negative electrode tends to form a dense PbSO4 layer at the surface, which
prevents complete discharge and results in increased electrode polarisation
• During discharge Pb reacts with sulfuric acid to give PbSO4
• At low rates sulfuric acid which is consumed in electrode bulk can be replenished by diffusion from
electrolyte bulk into electrode. Electrode is homogeneously discharged.
• At high rates sulfuric acid is consumed faster in electrode bulk than it can diffuse into the electrode.
Discharge reaction is concentrated on the surface. Dense PbSO4 layer at surface impedes diffusion of
sulfuric acid even more.
• During following charge electrode potential becomes more negative and hydrogen evolution
increases.
Low rate discharge High rate discharge Recharge following a high rate discharge
- 36 -
D.A.J. Rand, P.T. Moseley: Lead Acid Systems Overview, in J. Garche (ed.): Encycl. of Electrochem. Power Sources, Elsevier, Amsterdam, 2009, Vol. 4, p. 550.
Sulfation – Counter Measures
Avoiding sulfation during HRPSoC Reconditioning of sulfated

duty: electrodes:
 Add carbon additives (up to 2 wt.%)  Special charge programme to

to negative electrode reactivate (redissolve) PbSO4
 E.g.:
→ Use of VLRA in HEVs becomes  Charge slowly with low current (C/100 – C/20)
possible until heavy overcharge (2.6 V, up to 30%
overcharge, attention: strong gassing!)
 Procedure can be repeated several times (i.e.
battery can be cycled) if required.
- 37 -
UltraBattery
by SCIRO / Furukawa Batteries
Hybrid lead acid

battery / supercap
system with a
combined Pb / carbon
negative electrode
A. Cooper, J. Furukawa, L. Lam, M. Kellaway;

J. Power Sources 188 (2009), 642.
Improved high-rate performance: sufficient for moderate HEV applications

HEV prototype (Honda Insight)
- 38 -
Acid Stratification
heavy concentrated acid

light dilute acid
Formation of acid concentration profile − +
in cell during repeated charge / Discharge
(discharge). Low concentration in
upper part, high concentration in lower
part of cell. H2O
SO42-
Discharge process: H2SO4 is SO42-

consumed between plates,
dilute acid near electrode
moves upwards, concentrated acid
above electrodes sinks downwards, − +
good mixing of electrolyte. Charge
Charge process: H2SO4 is produced at

plates, sinks downwards, low H2O
SO42-
concentration acid near separator
moves upwards. SO42-
- 39 -
Acid Stratification
Results of acid stratification: Counter measures:
Electrode is preferentially charged in upper Overcharge of cell (charge up to 115%),

part and preferentially discharged in lower which results in heavy gassing, which mixes
part electrolyte (for flooded cells only, where gas
can escape)
In upper part of electrode
active material is only partially used due to Forced agitation / circulation by electrolyte
lack of H2SO4 pumping (e.g. via external electrolyte pump)
grid corrosion is accelerated due to lower
acid density VRLA batteries: immobilisation of
electrolyte counteracts vertical flow and
In lower part of electrode thus alleviates stratification problems.
electrode is overstressed (disintegration of
active material)
complete charge is increasingly difficult,
increased sulfation of negative electrode
 Accelerated ageing
- 40 -
Contents
Introduction
Basic Reactions
Side Reactions
Electrolyte
Ageing Mechanisms
- 41 -
Typical Discharge Voltage Curve
Spannungssack: due to
crystal nucleation, only
for fully charged cells Rapid voltage decrease due to
consumption of reactants and
Normal operation region: quasi-linear further increase of internal
voltage decrease (due to OCV decrease resistance
and increase of internal resistance)
Voltage / V
Time / h
- 42 -
Rate Capability
Capacity / normalised to nominal capacity

Voltage / V
High power LAB

(n = 1.12)
Standard LAB (n = 1.25)
Discharge capacity / Ah Discharge current / C-rate
n = Peukert parameter
Discharge time / h
High power LAB
(n = 1.12)
Standard LAB (n = 1.25)
A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen;

Leipheim and Munich (Germany), 2006.
Discharge current / C-rate
- 43 -
Rate Capability and Peukert’s Law
Ideal battery:
Capacity is independent of applied current.
Discharge time / h
Discharge time scales linearly with current. High power LAB
(n = 1.12)
(I.e. double current means half discharge time.)
Real battery: Standard LAB (n = 1.25)
Capacity decreases at high currents

Discharge time decreases stronger than for
ideal battery. Discharge current / C-rate
(I.e. double current means less than half A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen;
discharge time.) Leipheim and Munich (Germany), 2006.
Can be described by:
Peukert‘s Law (1897): t  I n  CN  INn 1 I … actual current

t … actual discharge time
n … Peukert coefficient (for practical batteries between 1.01 and 1.4)
t In  K CN … nominal capacity
IN … current at which nominal capacity was determined
K … Constant (for ideal batteries K = CN)

- 44 -
Practical vs. Theoretical Energy
167 Wh/kg
from 25 Wh/kg for stationary LAB

to 45 Wh/kg for SLI LAB
- 45 -
Contents
Introduction
Basic Reactions
Side Reactions
Electrolyte
Ageing Mechanisms
- 46 -
Plate Types
Planté type plate Faure: Grid plate Tubular plate

(high surface area) (for pasting) 1910
1859 1881
http://www.tpub.com/content/doe/hdbk1084/ (last access 01/2011):
- 47 -
Plate Types
Grid Plates
Use:
● Both as negative and positive plate
Design:
● Casted grids or expanded metal grids
● Low cost, high rate capability, lower cycle life as
active material is not well fixed
Manufacture:
● Grid plate made by casting (gravity casting or
injection molding).
● Flat pasted plates, some-times in combination
http://www.tpub.com/content/doe/hdbk with tubular grids, are standard in most
1084/ (last access 01/2011): application.
● Cast grids increasingly substituted by expanded
wrought grids (mainly for negative electrode).
● Very thin grids (pure Pb) are used for spirally
wound cells.
Applications:
● SLI batteries, automotive, marine, industrial
trucks, light duty traction, emergency back-up
systems
D. Pavlov: Lead-Acid Batteries, Elsevier, Amsterdam, 2011, p. 203.
- 48 -
Plate Types
Grid Plates
Cast grid Expanded

metal grid
- 49 -
AM Utilisation as Function of Current Collector Shape
[%] D A C
16
80
8
C 3.87g Pb = 1 Ah
60
conventional tubular
40 B
A
B 1 D
0,1
0,2
20
1 2 3 4 5 6
Average electron path way [mm] Expanded metal fibres
Increasing utilisation of active mass (AM) with P. Faber, in Power Sources 4, Proceedings of the 8th
International Symposium held at Brighton, Sept. 1972, pg.
decreasing length of electron path way (in AM) 525 – 540. D. H. Collins, ed., Oriel Press, 1973
- 50 -
Plate Types
Tubular Plates
Use:
 Especially for positive plates (in combination
with conventional negative plates)
Design:
 Metal tab surrounded by active material and
contained in cloth tube or separator tube
 Round shapes prefered in flooded LAB
 Rectangular shapes prefered for VRLA, due to
better contact with immobilised electrolyte layer
Manufacture:
 Grid made by casting or injection-molding of
http://www.tpub.com/content/doe/hdbk1084/ (last access 01/2011): spines attached to a connector bus and lug.
 Fiber glass sheaths or multi-tube gauntlets are
placed over the spines and filled with mass
powder or slurry.
Properties and applications:

 High capacity, long cycle life, smaller power,
expensive production
D. Pavlov: Lead-Acid Batteries, Elsevier, Amsterdam, 2011, p. 217.  EV, submarines, stationary application, etc.
- 51 -
Plate Types
Planté Type Plates
Design:
 Large surface area
Manufacture:
 Made by crimping or rolling lead strips into
rosettes inserted in holes of cast plates, or by
cutting grooves into lead plates, and
electrolytical formation.
Applications:
 Simple design and production, poor capacity,
high reliability, long life during float duties
 Standby emergency power, load levelling,
telephone exchange, signaling, uninterruptible
power systems (UPS), …
http://www.tpub.com/content/doe/hdbk1084/ (last access 01/2011):
- 52 -
Plate Manufacturing
+ H2SO4
+ O2 Paste
“Leady oxide” + additives “Basic lead sulfates”
Pb ingot
(ball mill or (PbO + Pb) (= xPbO•PbSO4•yH2O)
furnace) + PbO + Pb + H2SO4
may be added to
“Red lead oxide” positive electrode paste
Pb3O4
Curing
Pasting Flash drying at controlled temperature and humidity
Cured plate
onto Pb grid → Formation of hard porous mass (“skeleton”)
from paste particles
→ Oxidation of residual Pb
Soaking Formation Mounting

in H2SO4 (Charging) of plates into battery
Battery
→ Transformation of PbO to Charging to produce
basic lead sulfates and “spongy Pb” at negative electrode
(partially to) PbSO4 PbO2 at positive electrode
- 53 -
Electrode Additives
Increase of electronic conductivity

(low conductivity of active materials especially in discharged state)
 Carbon for negative electrode (0.2 – 3.0%)
 No suitable and stable additives for positive electrode, so far
Increase and stabilisation of electrode porosity (“expander materials”)
(especially negative electrode tends to lose porosity)
 Negative electrode: organic (lignin, < 1%), inorganic (TiOx)
 Positive electrode: fibres
Modifiers for PbSO4 crystallisation
 BaSO4 as crystallisation seeds
Avoidance of sulfation of negative electrode
 Carbon (0.5 to 2 wt.%)
Formation aids (help in formation process, especially of positive electrode)
 Carbon
 Pb3O4
- 54 -
Contents
Introduction
Basic Reactions
Side Reactions
Electrolyte
Ageing Mechanisms
- 55 -
Separators
Requirements: Materials:
 High mechanical stability  Usually microporous (0.2 – 1.0 µm

 Chemical stability (towards H2SO4 in pore size) corrugated separators
presence of O2)  PP, PE, polyester, glass microfibres
 No electronic conductivity  (Historical: cellulose, PVC)
 High porosity with suitable pore size
and pore structure
 Good wettability Types:
 Gas permeability
 Sheet separators (sheet between
electrodes)
 No separator is required for AGM  Pocket separators (bag around
LABs. electrode plate, prevents short
circuits by material falling off from
plate)
 Tube separators (tubes around
cylindrical electrodes)
- 56 -
Battery Housings
Materials:
 Mainly polymers: PP, polycarbonate, styrene-acrylonitrile (SAN) copolymer,
acrylonitrile-butadiene-styrene copolymer
 Polycarbonate and SAN are transparent and allow visual control of acid level
(flooded battery)
- 57 -
Components of Flooded LAB and VRLA
Component Flooded Cell Valve Regulated Cell
Cell container with Vent caps Resealable (Bunsen) vents

Electrolyte free Immobilized by AGM or SiO2
Separator Microporous, plastic PE, or glass fiber felt
Positive grid Pb-Sb Pb-Ca-Sn

Negative grid Low Sb Pb-Ca
- 58 -
Plate Sets in Stacked Cells
To achieve high capacities large electrodes are required.

Thickness of electrodes is limited.
Therefore in a cell several plates are switched parallel.

= Set of plates
+ −
- 59 -
Stacked Plate-Design (SLI, Start-Stop)
www.varta-automotive.de (last access: 01/2011)
- 60 -
Stacked Plate-Design
Maintenance-Free SLI Type
State-of-the-art SLI
Source:http://www.tpub.com/content/doe/hdbk1084/
- 61 -
Comparison of Typical SLI Batteries
E. Meissner: Automotive Batteries - Conventional, in: J. Garche (ed.): Encyclopedia of

Electrochemical Power Sources, Vol. 4, Elsevier, Amsterdam, 2009, pp. 829-850.
- 62 -
Gel-Type VRLA
(Hagen Drysafe)
HAGEN drysafe Battery

6V/4Ah(C20)
HPS-640
Dimensions:
LxWxH
70x48x102 (mm)
Weight: 0,82 kg
- 63 -
Cyclindrical AGM-VRLA
Thin Plate Spiral Wound Design (EXIDE)
AGM-VRLA-Battery with improved cyclability

(Source: Exide)
- 64 -
Cyclindrical Lead Acid Battery
Thin Plate Spirally Wound Design - OPTIMA 24 Ah/36V
Weight, kg 25
Impedance, mOhm (1 kHz @ 23 C) 14.6
DC Resistance, mOhm (400 A @ 23 C) 23.2
Reserve Capacity, Ah 18
C/20 Capacity, Ah 24
CCA, A (30 s @ 0F, > 21.6 V) 350
Maximum Continuous Discharge, A (25 C) 300
- 65 -
Bipolar Designs
?
e e
- -
? e Partition wall Positive ?
e -
- Active
?
Paste
Negative
Active
Paste
? ?
e- e- ?
Separator
2 + 2
V V
Monopolar 4 V Bipolar 4 V Pseudo-bipolar 4 V
Advantage: A.C. Loyns: Bipolar batteries, in J. Garche (ed.): Encyclopedia of Electrochemical

Power Sources, Vol. 4, Elsevier, Amsterdam, 2009, pp. 750-754.
Low ohmic internal resistance
Challenge:
How to get cells tight? Corrosion at positive side may result in leakage (which resembles a
short circuit)
- 66 -
Bipolar Battery
(Effpower)
Effpower
Hybrid Battery
12 V
Width 230 mm
Height 167 mm
Length 118 mm
Weight 3,9 kg
W/Kg 800
Source: EffPower
- 67 -
Contents
Introduction
Basic Reactions
Side Reactions
Electrolyte
Ageing Mechanisms
- 68 -
Long Life:
 Discharge LAB only as far as needed, avoid deep discharge
 Do not fully discharge LAB before recharging
 Recharge LAB as soon as possible after discharge
 If LAB is used in a cyclic duty around a middle state of charge (PSoC, partial
state of charge), fully recharge LAB regularly (at least once a month)
 The lower the temperature the higher the calendar life, but below -5°C risk of
freezing
 Storage: in fully charged state at low temperature (< 25°C), recharge battery
regularly (every 3 to 6 months)
Safety:
 Ventilate rooms with lead acid batteries (H2 and O2 evolution!)
 Avoid sparks and flames near lead acid batteries (H2 and O2 evolution!)
 LAB must be recycled
- 69 -
Further Reading
A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen; Leipheim and

Munich (Germany), 2006. (Book in German language).
D. Pavlov: Lead-Acid Batteries – Science and Technology; Elsevier, Amsterdam

(The Netherlands), 2011.
D. Berndt: Valve-regulated lead-acid batteries; J. Power Sources 100 (2001), 29.
Varta: Battery know-how / battery glossary: http://www.varta-

automotive.com/index.php?id=15&L=0 (last access: 01/2011)
J. Garche (ed. in chief): Encyclopedia of electrochemical power sources; Elsevier,

New York (USA), 2009, Vol. 4.
- 70 -
Acknowledgements
Parts of this lecture are based on a lecture by Andreas Jossen (TU München).
- 71 -
Thank you for your attention!
mario.wachtler@zsw-bw.de
www.zsw-bw.de
Zentrum für Sonnenenergie- und Wasserstoff-Forschung

Baden-Württemberg
Helmholtzstraße 8, 89081 Ulm
Stuttgart Widderstall Ulm Ulm

Photovoltaics
- 72 - & Solab Solar test-field Electrochemical Energy eLab (June 2011)
180111 |
Energy Policy & Energy CarriersUniversity of Ulm | EST-III | LAB | MW Technologies

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Energy Science and Technology III

Lead Acid Batteries (LAB)

Mario Wachtler, Ludwig Jörissen

*simplified federal urban driving schedule

The present lead acid battery is

Lead acid batteries (LAB)

Flooded LAB Valve-regulated lead acid battery

Industrial Batteries Traction Batteries SLI Batteries

Market share: ~ 50%

Anode (negative electrode): charge

PbO2 PbO2 + SO42– + 4H+ + 2e−  PbSO4 + 2H2O

Anode (negative electrode): charge

Solution-precipitation Pb  Pb2+ + 2e−

“Double sulfate theory”

Pb2+ + SO42–  PbSO4

Standard Electrode Potentials and Standard Electromotoric Force (EMF)

Positive electrode: E0(PbO2/PbSO4) = 1.690 V vs. SHE

Negative electrode: E0(PbSO4/Pb) = – 0.358 V vs. SHE

Cell EMF: ∆E = E0(PbO2/PbSO4) – E0(PbSO4/Pb) = 2.048 V

Actual Electrode Potentials and EMF

Exact electrode potentials and EMF depend on pH value and on concentration of

Nominal Cell Voltage: ~ 2.0 V

Anode: Pb + SO42–  PbSO4 + 2e−

  0.358  0.029 lg aSO 2 V

Cathode: PbO2 + SO42– + 4H+ + 2e−  PbSO4 + 2H2O

 1.690  0.118pH  0.059 lg aH2O  0.029 lg aSO 2  V

Cell: Pb + PbO2 + 2SO42– + 4H+  2PbSO4 + 2H2O

 2.048  0.118pH  0.059 lg aSO 2  0.059 lg aH 2O V

Typical electrode thickness: <1 – 3 mm

High porosity required:

With increasing discharge

In reality only about 50% of active materials

Parasitic side reactions with slow kinetics:

 Gas formation reactions (electrolysis of H2O)

 Oxygen recombination at negative electrode

 Corrosion of positive current collector grid

Side reactions result in self-discharge (conservation/buffer charging with low current is

 Corrosion of positive current collector grid:

 In acidic conditions and presence of sulfate:

Most important ageing mechanism of LAB Corrosion layer

pH range for LAB

thermodynamic stability window of H2O

Current voltage curves

Recombination of O2 at negative electrode

Electrolyte is immobilised as gel or in glass microfibre mat (AGM, absorbant

Gel-type electrolyte Electrolyte in AGM

Formation of gel from H2SO4 and pyrogenic

Reduction of H2 evolution is required in VRLA

Negative electrode is over-dimensioned

Charge voltage ranges

In a VRLA both electrodes work at

Immobilizing the electrolyte: Gel vs. AGM

SiO2 gel AGM

 Selection of design defined by applications

Preferred applications for gel types: standby, low rate cycling,

Preferred applications for AGM types: wherever maintenance

Strong variations of freezing point with acid concentration

Acid concentration can be used for determination of state of charge (SOC)

Selection of electrolyte concentration

Source: H. Bode, „Lead Acid Batteries“.

Equilibrium voltage (OCV) / V

Acid density / g/cm3

flooded Acid density / g/cm3

Battery performance decreases drastically at low temperatures.

http://www.varta-automotive.com/elearning/de/t1_3_1.html?1,2 (January 2013)

Positive grid corrosion