Lead Acid Batteries (LAB)

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-
 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 2V to 12V.
 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)

- 4-
 Battery terminology

 Cell: is an electrochemical unit used to create electrical energy from stored chemical energy. A basic cell
consists of two electrodes with an electrolyte between them.

 Electrode: The electrodes are the basic elements within an electrochemical cell. There are two in each cell:
one positive and one negative electrode. The cell voltage is determined by the voltage difference between the
positive and the negative electrode.

 Electrolyte: is the medium that provides the conduction of ions between the positive and negative electrodes of
a cell.

 Separator: is required within a cell to prevent the anode and cathode shorting together. With cells being made
more compact, the space between the anode and cathode becomes much smaller and as a result the two
electrodes could short together causing a catastrophic and possibly explosive reaction. The separator is an ion-
permeable, electronically non-conductive material or spacer that is placed between the anode and cathode.

 Anode: is the electrode at which an oxidation reaction occurs. The positive electrode is the anode during
charging and the negative electrode is the anode during discharging.

 Cathode: is the electrode in a battery or other system at which a reduction reaction occur. The negative
electrode of the battery or cell is the cathode during charging and the positive electrode is the cathode during
discharging.

In order to prevent confusion, the anode and cathode is normally defined during the discharge cycle. In this way,
anode is used for the negative electrode; and cathode is the positive electrode in a cell or battery.

- 5-
 Battery terminology
 Capacity: The capacity of a battery or cell is defined as the amount of charge that it can deliver in a single
discharge. Battery capacity is normally specified in amp-hours (or milli-amp-hours).

 Charge rate or C-rate : is the charge or discharge current in Amperes as a proportion of the rated capacity. For
example, in the case of a 500 mAh battery, a C/2 rate is 250 mA and a 2C rate would be1 A.

 Energy Density: The volumetric energy storage density of a battery, expressed in Watt-hours per litre (Wh/l).

 Power Density: The volumetric power density of a battery, expressed in Watts per litre (W/l).

 Specific Energy: The gravimetric energy storage density of a battery, expressed in Watt-hours per kilogram
(Wh/kg).

 Specific Power: The specific power for a battery is the gravimetric power density expressed in Watts per
kilogram (W/kg).

 Cycle Life: is number of cycles that a cell or battery can be charged and discharged under specific conditions,
before the available capacity falls to a specific performance criteria - normally 80% of the rated capacity. Lithium
-ion cells currently have cycle life times of around 300-1000 cycles. The cycle life of a cell or battery is greatly
influenced by the type depth of the cycle and the method of recharging. Improper charge cycle cut-off,
particularly if the cell is over-charged reduces the cycle life.

 Cut-off voltage: As a battery is discharged it has a voltage curve that it follows - the voltage generally falling
over the discharge cycle. The cut-off voltage is the voltage at which the discharge is terminated by any battery
management system.
- 6-
- 7-
 Battery terminology

 Self-Discharge: It is found that batteries and cells will lose their charge over a period of time, and need re-
charging. It is normally expressed in a percentage of the rated capacity lost per month and at a given
temperature. The self-discharge rate of a battery or cell is very dependent upon the temperature.

 Constant-Current Charge: This refers to a charging process where the level of current is maintained at a
constant level regardless of the voltage of the battery or cell.

 Constant-Voltage Charge: - This definition refers to a charging process in which the voltage applied to a battery
is held at a constant value over the charge cycle regardless of the current drawn.

- 8-
 Types of Lead Acid Batteries
By Basic Design

Lead acid batteries (LAB)

Flooded LAB Valve-regulated lead acid battery

Vented LAB (VRLA)
• Maintenance required (H2O refilling) Maintenance-free LAB
Sealed battery
• 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

- 9-
 Types of Lead Acid Batteries By Application
(thickness of active materials)

Industrial Batteries Traction Batteries SLI Batteries

(starting, lighting,
ignition)
Applications: Applications: Applications:
Uninterrupted power Fork lifts, utility vehicles, Cars, motorcycles, …
supply (UPS) / reserve … Start-stop
battery, other stationary
applications

Optimised towards: Optimised towards: Optimised towards:

cycle life in charge cycle life power and weight,
sustaining mode low price, high safety
good cold cranking
properties

Market share: ~ 25% Market share: ~ 25% Market share: ~ 50%

- 10
-
 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

- 11
-
 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+ + 2H 2O
Pb2+ + 2 e-  Pb
Pb2+ + SO42–  PbSO4
Transfer
Pb2+  Pb+4 + 2 e- PbO2 + SO42– + 4H+ + 2e−  PbSO4 + 2H2O
PbO2

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

- 12
-
 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)
 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

 Electrode Potentials and Nominal Cell Voltage

Anode: Pb + SO42–  PbSO4 + 2e −

aPbSO4
E PbSO4 / Pb  E PbSO
0
4 /Pb

RT
ln  E PbSO
0
4 /Pb
RT ln a SO 2
zF aPb  a SO 2 2F 4

 
4

  0.358  0.029 lga SO 2 V

4

Cathode: PbO2 + SO4 2– + 4H+ + 2e−  PbSO4 + 2H2O

RT aPbO2 a SO42  a H RT aSO42 a H

4 4
EPbO / PbSO  E 0 / PbSO  ln  E Pb / PbSO4 
0
ln 
Pb
2 4 4 zF aPbSO  a2H O 2F aH2 O
 
4 2 2

 1.690  0.118pH  0.059 lgaH 2O  0.029 lga SO 2 V

4

Cell: Pb + PbO2 + 2SO 42– + 4H+  2PbSO 4 + 2H2Oa a

2
4
E  E E  E0  E0  RT ln SO4 H

RT
ln
1

PbO2 / PbSO4 PbSO4 / Pb PbO2 / PbSO4 PbSO4 / Pb 2
2F a 2F aSO 2
 
H 2O 4

 2.048 0.118pH  0.059lg a  0.059lg aH O V

SO42 2
Electrode Potentials and Nominal Cell Voltage
 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.
 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
 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)
 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)
 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)
 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).
 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
 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.
 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
 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)
 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.
P.T. Moseley, D.A.J. Rand, in „Valve Regulated Lead-Acid
flooded LAB. Batteries“, Elsevier, 2004; (Fig. 1.5).
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
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: low rate cycling

Preferred applications for AGM types: wherever maintenance

is an argument against vented cells.
 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
 Electrolyte

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
 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.
 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
 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)
A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen; Leipheim and Munich (Germany), 2006.
 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
 Ageing Mechanisms

Positive grid corrosion

Sulfation
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)
 Sulfation during Storage in Discharged State

 Sulfation = accumulation of PbSO4

 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
 Sulfation During high rate operation

At high rates negative electrode tends to form a dense PbSO4 layer at the surface:

• 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

180111 | University of Ulm | EST-III | LAB | MW

- 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:
 Add carbon additives (up to 2 wt.%)
to negative electrode
→ Use of VLRA in HEVsbecomes
possible
Reconditioning of sulfated
electrodes:
 Special charge programme to
reactivate (redissolve) PbSO4
 E.g.:
 Charge slowly with low current (C/100 – C/20)
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.
 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)
 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-
 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
 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
 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
A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen; Leipheim and Munich (Germany), 2006.
 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

Peukert’s Law relates battery capacity to

discharge rate:

Discharge time / h
High power LAB
(n = 1.12)
Cp = Ik t
Cp is the amp-hour capacity at a 1 A discharge Standard LAB (n = 1.25)
rate
I is the discharge current in Amperes
Discharge current / C-rate
t is the discharge time, in hours
k is the Peukert coefficient, typically 1.1 to 1.3
 Example

Lab batteries
k = 1.15
Cp = 63 A-hr

Prediction of Peukert
equation is plotted at left

What the manufacturer’s Nominal capacity: A-hrs @ 25˚C to 1.75 V/cell

data sheet specified:
1 hr 2 hr 4 hr 8 hr 24 hr

36 A-hr 45 A-hr 46 A-hr 49 A-hr 56 A-hr

Practical vs. Theoretical Energy

167 Wh/kg

E=2.05V
W= 642.52g
X=2

from 25 Wh/kg for stationary LAB

to 45 Wh/kg for SLI LAB
 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
 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.
 Plate Types
Grid Plates

Cast grid Expanded

metal grid
 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
 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.
 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):

 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
→ Transformation of PbO to
basic lead sulfates and
(partially to) PbSO4
(Charging) of plates into battery
Battery
Charging to produce
“spongy Pb” at negative electrode
PbO2 at positive electrode
 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
 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
 Manufacturing process

Oxide manufacture: Lead oxide is manufactured by one of two methods—a Barton Pot or a milling
process. In the Barton Pot process, air is blown over molten lead to produce a fine stream of lead
droplets. The droplets react with oxygen in the air to form the oxide, which consists of a core of lead
with a lead oxide (PbO) coating.
In the milling process, solid lead (which may range in size from small balls to complete pigs) is fed
into a rotating mill. The tumbling action of the lead generates heat and the surface of the lead
oxidizes. As the particles roll around in the drum, the surface layers of oxide are removed to expose
more clean lead for oxidation. The airstream carries the powder to a bag filter, where it is collected.

Grid production: Grids are produced mainly by casting (both automatic and manual) or, particularly
for automotive batteries, expansion from wrought or cast lead alloy.

Pasting: Battery paste is made by mixing the oxide with water, sulphuric acid and a range of
proprietary additives. The paste is pressed by machine or hand into the grid lattice, and the plates
are usually flash-dried in a high-temperature oven.
Pasted plates are cured by storing them in ovens under carefully controlled conditions of
temperature, humidity and time. Free lead in the paste converts to lead oxide.
 Manufacturing process

Formation, plate cutting and assembly: Battery plates undergo an electrical formation process in one
of two ways. In tank formation, plates are loaded into large baths of dilute sulphuric acid and a direct
current is passed to form the positive and negative plates. After drying, the plates are cut and
assembled, with separators between them, into battery boxes. Plates of like polarity are connected
by welding together the plate lugs.
In jar formation, the plates are electrically formed after being assembled into battery boxes.
 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)
 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)
 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

 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

+ −
Stacked Plate-Design (SLI, Start-Stop)

www.varta-automotive.de (last access: 01/2011)

 Stacked Plate-Design
Maintenance-Free SLI Type
State-of-the-art SLI

Source:http://www.tpub.com/content/doe/hdbk1084/
 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.
 Gel-Type VRLA
(Hagen Drysafe)

HAGEN drysafe Battery

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

AGM-VRLA-Battery with improved cyclability

(Source: Exide)
 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
 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)
 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
 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
 Recommendations for Usage

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
 Further Reading

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.