Department of Lead-Acid Batteries

Institute of Electrochemistry and Energy Systems (IEES)

Bulgarian Academy of Sciences, Sofia, Bulgaria

Strap Grid Tubular Plate –

a New Positive Plate for Lead-Acid Batteries

D. Pavlov, G. Papazov, B. Monahov

 Changes in Plate Thickness on Cycling

During discharge PAM and NAM expand in volume and during charge
they shrink.

1,8
After certain number of
Relative plate thickness

Positive plate
cycles:
1,6
 plates lose porosity
1,4 PAM because of degradation
shedding
of expander – capacity
1,2
Negative plate
declines.
1,0 Loss of expander
properties  plates expand, PAM
0,8 loses its integrity and
0 20 40 60 80 100 120 140 parts of it shed off.
Cycles Capacity declines.

Expansion of PAM on cycling is often the reason for battery failure.

The life of the battery can be prolonged by limiting PAM expansion.

Fig. 2
 Methods for Suppression
of the Positive Plate Expansion

I. By active block compression

In this case AGM or glass mat
separators are used.
PAM
NAM
PbO2 AGM
Pb However:
AGM separators contract.
The electrolyte quantity
between the plates
decreases.
Negative plates shrink
and lose capacity and
charge acceptance.

Fig. 3
 Methods for Suppression
of the Positive Plate Expansion

II. Enclosing the PAM into tubes

Tubular plates are very thick

Gauntlet  coefficient is quite high

Low charge acceptance
Spine
Low power

PAM High energy and capacity

Long cycle life

This design of the positive plates is not suitable for electric vehicle batteries.

Fig. 4
In an attempt to improve the power output and charge acceptance
a new tubular plate design was developed at our Department in IEES (CLEPS)

Strap Grid Tubular Plate Design (STGP)

The shape of the tubes was changed from cylindrical to flattened
elliptic or rectangular. The spine was replaced by a strap.

Gauntlet Strap PAM

Gauntlet

Spine

PAM

Fig. 5
Differences Between the Two Tubular Plates

Tubular plate SGT Plate

8.4 mm in diameter 3.5 mm plate thickness

2.5 mm PAM thickness 1 mm PAM thickness
3.0 mm spine diameter 1 mm strap thickness
 = 2.0 - 2.4 g PAM/cm2  = 0.8 - 0.9 g PAM/cm2

Fig. 6
Why does the shape of the tube exert a strong
influence on parameters of the positive plate
The specific surface area of PAM
SLI plate with 100g PAM is from 3 to 8 m2/g PAM. Assume
PAM Grid
3-7 m 2/g 40-70 m 2/g an average value of 5 m2/g. An SLI
Grid bar plate with 100 g of PAM has a surface
Corrosion layer (CL)
area of about 500 m2. The grid of such
Active mass
a plate has a surface area of between
collecting layers
(AMCL)
40 and 70 cm2 assume 50 cm2.
During plate discharge, the current
generated on an active-mass surface
of 500 m2 is concentrated in a layer of
the positive active mass and passes
through a 50 cm2 grid surface area.
PAM Grid
500 m 2 SPAM / S PAM = 106 50 cm 2 This results in a 106-fold increase in
current density.

WPAM is PAM weight WPAM

  0.8  1.0g / cm2
Sgrid - collector grid surface Sgrid
Fig. 7
Influence of the grid-bar shape and plate design
on uniformity of current distribution
over the grid surface

a
id - non-uniform
PAM

b id - uniform Tube

PAM
PAM

AMCL
CL Grid
Grid

Fig. 8
 SGTP Production Technology

1. 4BS paste is prepared at 90oC.

2. The paste is diluted with H2O to d = 1.80 g/cm3.

3. Die-cut or cast strap grids are inserted into the gauntlets.

4. The tubes are filled with 4BS suspension under pressure.

5. The plates are subjected to curing and formation.

Fig. 9
The investigations were performed
with batteries containing:
3 SGT plates + 4 negative plates per cell
AGM separators
VRLAB type

The batteries were tested for

PV systems (IEC 61427)
electric vehicle (ECE-15)
hybrid electric vehicle (ECE-15 HEV)

Fig. 10
Battery Tests for PV System Applications
Standard ICE 61427

50 cycles at low
state of charge
18 (90%DOD)
40oC
16
Voltage, V

14
12
10
8
0 500 1000 1500 2000
Time, h
Fig. 11a
Battery Tests for PV System Applications
Standard ICE 61427
100 cycles at
high state of
18 charge
(25%DOD)
40oC
16
Voltage, V

14
12
10
8
0 500 1000 1500 2000
Time, h
Fig. 11b
Battery Tests for PV System Applications
Standard ICE 61427

Low state High state of charge

18 of charge

40oC
16
Voltage, V

14
12
10 One gross cycle - 1100 hours

8
0 500 1000 1500 2000
Time, h
Fig. 11c
 Test Results of PV Batteries
at Partial State of Charge
End-of-discharge and end-of-charge voltage on Batteries have
cycling at 90% DOD. undergone 11 gross
cycles or 12100h

16 The batteries have

stable voltage
performance and
14
End voltage, V

Charge good charge

acceptance
Discharge
12 throughout the low
state of charge
U charge I U discharge I
10 U charge II U discharge II cycles.
U charge III U discharge III
U charge IV U discharge IV
U charge V
U charge VI
U discharge V
U discharge VI
Batteries with pasted
8 plates and expanded
0 10 20 30 40 50
grids have cycle life
Cycles 2 200 – 3 300 h.
Fig. 12
 Battery Test Following EV. Standard ECE-15.

25 Each cycle consists of

Urban part
20
two parts:
repeated 4 times

15 one urban part

Discharge
which is repeated
Power, kW

10
4 times without
5 rest period
0

-5
Charge

-10
0 100 200 300 400 500 600

Time, sec

Fig. 13a
 Battery Test Following EV. Standard ECE-15.

25 Each cycle consists of

Urban part Suburban part
20
two parts:
repeated 4 times

15 one urban part

Discharge
which is repeated
Power, kW

10
4 times without
5 rest period
0 followed by one
-5 suburban part.
Charge

-10
0 100 200 300 400 500 600 Total cycle duration –
Time, sec 20 min.

Fig. 13b
 Battery Test Following EV. Standard ECE-15.

25 Each cycle consists of

Urban part Suburban part
20
two parts:
repeated 4 times

15 one urban part

Discharge
which is repeated
Power, kW

10
4 times without
5 rest period
0 followed by one
-5 suburban part.
Charge

-10
0 100 200 300 400 500 600 Total cycle duration –
Time, sec 20 min.

Fig. 13c
 Capacity and ECE Energy during Cycling
of a SGTP Battery
PbSnCa die-cut strap grids. Two charge modes were used.
At I1U2 charge
300 35 mode with Fch = 108%
30 the energy output
250 Ah decreases and
ECE energy, Wh

25 stays at a low level.

Capacity, Ah
200
Wh
20 At I1U2I3 charge
150
15 mode with Fch = 118%
100
10
the energy output
I1 U2 I1 U2 I3 preserves its initial
50 5
I1 = 0.4C10 I1 = 1.5C10 value.
0 0 The life of
1 200 400 600 800 1000 the battery is
Cycles 990 ECE-15 cycles.

The SGTP battery fails due to strap corrosion and softening of the active mass.

Fig. 14
 ECE Cycling for Hybrid
Electric Vehicle Applications

120 At the beginning

100

Generator off Car generator is off

SOC, %

80
60
40
Battery is discharged down to 40%
20
0
1 ECE cycle – 20% discharge
0 1 2 3 4 5 6 7 8 9 10

Cycles 20
Urban part Suburban part
15 repeated 4 times

When SOC reaches 40%, Power, kW 10 Discharge

the car generator is 5

switched on… 0

-5
Charge
-10
Generator on after 60% DOD

-15
0 100 200 300 400 500 600

Time, sec
Fig. 15a
 ECE Cycling for Hybrid
Electric Vehicle Applications

120 When SOC reaches 40%,

100
the car generator is
SOC, %

80
60 Generator on switched on…
40
40%
20
0
0 1 2 3 4 5 6 7 8 9 10

Cycles 20
Urban part Suburban part
15 repeated 4 times

….an additional charge current 10 Discharge

is added to the ECE discharge
Power, kW

5
and charge pulses.
0

-5
Charge
-10
Generator on after 60% DOD
-15
0 100 200 300 400 500 600

Time, sec
Fig. 15b
 ECE Cycling for Hybrid
Electric Vehicle Applications

120
100
Generator on
SOC, %

80
60
40
After every 10 cycles the battery
20
40% is subjected to a full charge
0
0 1 2 3 4 5 6 7 8 9 10
Cycles 20
Urban part Suburban part
15 repeated 4 times

During the next 7 HEV cycles 10 Discharge

the battery and the engine
Power, kW

5
operate in parallel and the
battery is slowly charged. 0

-5 4% charge
per cycle
-10 Charge
Generator on after 60% DOD
-15
0 100 200 300 400 500 600

Time, sec
Fig. 15c
 Test Results of ECE-HEV Cycling

25
Urban part Suburban part Peak
20 repeated 4 times power
20%
15
Power, kW

Discharge
10

-5
Charge
-10
0 100 200 300 400 500 600

Time, sec

The peak power was measured during the cycle test of the battery

Fig. 15d
 Peak Power Changes during ECE HEV
Cycling of SGTP Battery
The peak power in the first 3 ECE
1200 0.4C 1.5C 1.5C 2C 1.5C
108% 118 110 108% 118% cycles was measured before the
1000 charge generator was switched on.
Peak power, W

800 By varying the charge current and

600
charge factor it was established
that the optimum charging mode is:
400 A B C D E

200 P1 P2 P3
I1 = 1.5C A

0 U2 = 15.2 V
0 1000 2000 3000 4000 5000 6000
I3 = 0.05C A
Cycles
35 Fch = 118%
30
The battery has a cycle life of 5 500
Capacity, Ah

25
20 hybrid cycles which correspond to
Capacity C2
15 a distance run of about 55 000 km.
10
Softening of PAM and intergranular
5
corrosion of the grid limit the
0
0 1000 2000 3000 4000 5000 6000
battery life.
Cycles
Fig. 16
 Summary

Cycle life SGTP batteries when tested

according to:
a) Photovoltaic test protocol -
longer than 8 gross cycles (8 800 h).
b) Electric vehicles ECE-15 algorithm -
990 ECE cycles.
c) ECE – hybrid electric vehicle test -
5 500 HEV cycles.

Fig. 17
The phenomena that limit cycle life are:

a) Strap corrosion
b) Softening of PAM in some
parts of the tubes
c) Residual sulphation of the
plates

Fig. 18
 Degradation of PAM Structure
and Strap Grid Corrosion

Cycling according to the ECE-15 test protocol

Cycles 1 100 200 380 600 1000
Test cells

PAM characterization

Optical
Porosity XRD analysis SEM BET Wet analysis
metallography

Fig. 19
Volume / cm3.g-1 0,035
0,03 1 cycle Differential Pore Volume as
0,025
0,02
0,015
a Function of Pore Radius
0,01
0,005 for PAM Samples after
0
-3 -2 -1 0 1 2 3
1, 100, 200 and 380 Cycles
Volume / cm3.g-1

0,035
0,03 100 cycles
0,025
0,02 During cycling the pore volume
0,015
0,01 increases from 0.12 to 0.17 cm3/g.
0,005
0
This value is limited by the tube
-3 -2 -1 0 1 2 3
volume. It is below the critical
Volume / cm3.g-1

0,035
200 cycles
0,03
0,025
value of 0.28 cm3/g for PAM
0,02 disintegration during expansion.
0,015
0,01
0,005 After formation PAM contains
0
-3 -2 -1 0 1 2 3
mainly macropores with radii of
Volume / cm3.g-1

0,035
0,03 380 cycles about 1 μm. During cycling the
0,025 share of macropores, along which
0,02
0,015 the H2SO4 and H2O move fast into
0,01
0,005
the volume of PAM, decreases and
0
-3 -2 -1 0 1 2 3
the share of the pores with medium
Log (pore radius,m m) size radii increases.
Fig. 20
Abs. Intensity, c.p.s.
G PAM AMCL CL
15000 Changes in the Content of
 -PbO 2 -PbO2, PbSO4 and -PbO2
0.350 nm
10000
Phases in PAM as a Function
of Distance from the Strap
Surface after 380 Cycles
5000
6 5 4 3 2 1

The PAM of fully charged plates

Abs. Intensity, c.p.s.

1500
G PAM AMCL CL
consists mainly of -PbO2. Its amount
1000
decreases in the interior of the plate
and near the corrosion layer it is half
500

PbSO 4 that on the plate surface.

0.300 nm
6 5 4 3 2 1
0 Though the plate is fully charged the
Abs. Intensity, c.p.s.

1500 interior of the plate contains substantial

G PAM AMCL CL
quantity of PbSO4 crystals which cause
1000
 -PbO 2 / tet-PbO
the capacity of the plate to decline.
0.311 nm
500 The corrosion layer and its interface
with the active mass contains -PbO2
0
6 5 4 3 2 1 obtained as a result of the oxidation of
Distance from strap surface, a.u.
the lead straps.
Fig. 21
 Micrographs of the Structure of the Inner
PAM Layers Adjacent to the Corrosion Layer

Some amounts of
PbSO4 crystals have
remained unoxidized
to PbO2 though the
battery was fully
charged. We called
this phenomenon
“residual sulphation”.
There must be some
reason for the
impeded oxidation of
PbSO4 to PbO2!

Fig. 22
 Mechanism of Impeded Oxidation of PbSO4
to PbO2 in the Inner Layer of the Plate

On oxidation of PbSO4 to PbO2 H2SO4

1. PbSO4 + 2H2O  PbO2 + H2SO4 + 2H2+ + 2e-
is formed in the pores of PAM.

2. The solubility of PbSO4 as a function of Diffusion of H2SO4 out of the plate is

H2SO4 concentration a slow process and CH2SO4 increases
6.0 with the charging time.
5.0
The solubility of PbSO4 depends on
SPbSO4/mg.l-1

4.0
the CH2SO4. On increase of the CH2SO4
3.0 from 1.12 to 1.30 s.g the solubility of
2.0 PbSO4 decreases 5 times.
1.0
In the inner PAM layers of the plate
the rate of PbSO4 oxidation slows
1.00 1.10 1.20 1.30 1.40 1.50
CH2SO4, s.g. down with increase of CH2SO4. Some
V.Danel, V. Plichon, Electroch. Acta Vol. 27 No 6 (1982) 771 PbSO4 crystals remain unoxidized,
G.W.Vinal, D.N.Craig, J.Res.Natnl.Bur.Stand. 22 (1939) 55 which limits the capacity of the plate.

Fig. 23
The residual sulphation of the positive plate
depends on:

a) PAM density
b) Distribution of the pore volume by pore radius
c) Concentration and volume of the H2SO4 solution
d) Charging mode
e) Additives to the electrolyte

Many desulphation additives have appeared on the

market recently. The advertisements claim that they
extend the battery life and the power output.

Fig. 24
 Some Differences are Observed between the
PAM Structure on the Side of the Plate Surface
and on the Side of the Corrosion Layer
Soft zones Hard zones
Near the plate surface
the PAM features many
soft powdery zones
which grow in volume
towards the plate
interior.
Close to the strap
interface hard zones are
formed with membrane
surface layer and
several large caverns.

The aggregates of the powdery structure often lose contact between

each other. As a result – parts of PAM are excluded from the current
generation process and the capacity of the plate decreases.
Fig. 25
Intergranular Corrosion

Some of the cells that failed had

cracked straps due to
intergranular corrosion.
The thin layer of (Pb1-xSn1-x)3Ca
compound, formed on
segregation of Sn and Ca from
the lead grains to the grain
boundaries, corrodes faster than
the lead grains and cause the
straps to crack.

Fig. 26
 Conclusions
SGTP can operate at partial state of charge and
can be successfully used for PV battery applications.

SGTP have high power and fairly long cycle life and
can be used for EV battery applications.

A mechanism of residual sulphation of the plate

is proposed.

The technology for SGTP production is analogous to

that used for wet filling of cylindrical tubular plates. We
changed only the filling material. Instead of red lead
and leady oxide we filled the tubes with 4BS crystals.

Fig. 27
 Acknowledgement

The research team of the

Lead-Acid Batteries Department at CLEPS
wants to acknowledge with gratitude
the financial support provided by
ALABC/EALABC and INCO(Brite-Euram Project)
and the European Commission (ABLE Project)
for implementation of the present research.

Fig. 28
Thank you for your attention!