Technical Report from www.RERinfo.

ca




A Lead-Acid Battery Model for Hybrid System Modelling









Prepared by:
Michael Ross
2180 rue Valois
Montreal, Quebec
H1W 3M5
michael.ross@RERinfo.ca



Presented to:
Dave Turcotte
CANMET Energy Diversification Research Laboratory
Natural Resources Canada


Under contract #0-1238DT

2 March, 2001


Summary

A simple battery model for hybrid system simulation has been developed. Given battery
temperature and charge or discharge current, the model calculates the battery state-of-
charge, voltage, gassing current, heat evolution, and ageing. The model has been
implemented in Simulink.



CONTENTS
Introduction......................................................................................................................... 1
Inputs, Outputs and Capabilities......................................................................................... 1
The Model ........................................................................................................................... 2
Modelling State-of-Charge.............................................................................................. 2
Modelling Battery Voltage and Gassing Current ............................................................ 3
Modelling Ageing............................................................................................................ 5
Modelling Self-Discharge................................................................................................ 6
Modelling Heat Evolution ............................................................................................... 7
Modelling Gassing and Loss of Water ............................................................................ 7
Model Calibration............................................................................................................... 8
Model Implementation........................................................................................................ 8
Recommendations............................................................................................................... 8
References........................................................................................................................... 9
1

Introduction

The battery is one of the principal components of a hybrid power system. It is a complex
device, with non-linear behaviour and memory over the short-term, medium-term and
long-term. Any attempt to simulate hybrid power systems will require a model of the
battery. The simulation requirements will dictate the nature of the model used. For
optimising energy flows within a hybrid system, a relatively simple battery model should
suffice.

A lead-acid battery model has been developed for the hybrid system modelling being
done at CEDRL. It is a semi-empirical model, partly taken from the literature and partly
founded on basic electrochemistry. The model has been fit to measured data from two
lead-acid batteries, the Global Yuasa 45T15 tubular flooded-vented 2V cell and the GNB
Absolyte IIP 50A-05 12V battery. The model was originally written and fit to the
measured data in Matlab; subsequently it has been implemented in Simulink.

This report describes the inputs and outputs of the model, discusses its capabilities,
documents the mathematical relations in the model, overviews the fitting and validation
procedure, and recommends further developments to the model.

Inputs, Outputs and Capabilities

The inputs to the model are:
1) The current (positive for charge, negative for discharge, zero for open circuit)
2) The temperature of the battery (in C)

The outputs of the model are:
1) The battery voltage
2) The battery State-of-Charge (SOC), given in terms of the equivalent state-of-charge
for a discharge rate of C/20 at 25C.
3) A vector of maintenance requirements:
a) A battery replacement counter, which indicates how many battery lifetimes
(or the fraction thereof) have been used.
b) A watering counter, which indicates how many times the battery has required
watering (or the fraction thereof).
4) The heat evolved from the battery (in W, with positive indicate net heat production).
5) The battery gassing rate (in L/hr of hydrogen gas evolved).

In order for the model to generate these outputs, the user must specify a set of parameters
describing the battery bank to be modelled. This set of parameters consists of:
1) The nominal battery voltage (e.g., 12V, 24V, 48V, etc.)
2) The C/20 battery capacity at 25C (in Ah)
3) The battery technology (Global Yuasa Tubular or Absolyte IIP)
4) The self-discharge of the battery in one month (in terms of % of capacity at the outset
of the month), at a temperature specified by the user.
5) The float life of the battery (in years) at a temperature specified by the user.
2

6) The method by which the cycle life is to be estimated, linear or log-linear. The user
specifies two points on the cycles versus SOC curve (with SOC being given for a
C/20 rate at 25C). With the linear estimation method, these two points define a linear
relationship between cycle life and SOC. With the log-linear estimation, the two
points define a straight line when the natural logarithm of cyclelife is graphed against
SOC.
7) The cell water loss that necessitates watering (in kg).
8) The starting SOC for the simulation, given in terms of a C/20 rate at 25C.

The model accounts for certain elements of battery behaviour and ignores others. Note
that the model accounts battery self-discharge and for the effect of temperature (over a
range of approximately 5C to 35C) on battery capacity, gassing, self-discharge, and
resistance. Note, however, that the model does not account for stratification of the battery
nor changes in the battery operation due to ageing or sulfation.

The Model

Modelling State-of-Charge

State-of-charge is an ill-defined metric and using it within a battery model causes several
problems. Rather than deal with such problems as negative state-of-charge, state-of-
charge over 100%, etc., this battery model uses another metric of the energy stored within
the batterythe charge (i.e., number of Ah) that would have to be discharged from a
fully charged battery to bring it to its current state. This is an unambiguous metric that
has definite physical meaning.

Every time step, the Ah discharged variable is updated according to
( ) ( )
0
, max AhD dt I I I AhD
SD gas
+ =

where AhD is the number of Ah that would have to be discharged from a fully charged
battery to bring it to its current state;
I is the normalized charge current (in amps, negative for discharge);
I
gas
is the gassing current (in amps, calculated elsewhere in the model, zero or
positive on charge and zero on discharge);
I
SD
is self-discharge current (in amps, always positive);
t is time;
and AhD
0
is AhD at the beginning of the simulation.

This last variable is calculated from
0 0
SOC C C AhD
ref ref
=

where C
ref
is the reference cell capacity (i.e., the capacity of the cell to which the model
was fit) in Ah;
and SOC
0
is the initial state-of-charge specified by the user (in terms of C/20 at 25C).

The normalized charge current, I, is calculated by
3

sim
ref
sim
C
C
I I =

where I
sim
is the charge current input to the model (i.e., the charge current outside of the
battery model) in amps;
and C
sim
is the capacity of the battery specified for the simulation (in Ah).



Modelling Battery Voltage and Gassing Current

When the charge current, I, is negative, the battery is discharging and the cell voltage, V,
is calculated from a relation loosely based on [Copetti et al., 1993]:
( ) ( )
( )
( ) ( ) 25 1
0001 . 0 ) ( 1
1 25
4 2
3 1

|
|

\
|
+
+
+
+

+ =
T DaTr
AhR
DP
I
DP
DK
I
AhR DV T
T
V
DV V
DP DP
T
slope
OC
OC

where DV
oc
is a fit parameter roughly corresponding to the open-circuit voltage of the
battery when it is fully charged;
T is the battery temperature;
DV
slope
is a fit parameter roughly corresponding to the partial derivative of the
open circuit voltage with respect to state-of-charge;
AhR is the useable amount of charge remaining in the battery;
DK
T
is the discharge capacity of the reference cell at the temperature T, in Ah;
DP
1,2,3,4
are fit parameters;
and DaTr is a parameter describing the change in internal battery resistance with
temperature.

The variable DK
T
is calculated by:
( ) ( ) 25 1 + = T DaTc DK DK
T

where DK is a fit parameter corresponding to the discharge capacity of the reference cell
at an infinitesimal discharge current (i.e., the capacity of active material in the
cell) in Ah;
and DaTc is a parameter describing the change in the useable battery capacity with
temperature.

From this, AhR is calculated by:
T
DK
AhD
AhR =1

The partial derivative of the open circuit voltage with respect to temperature (in V/C) is
calculated based on a curve fit to data in [Vinal, 1955, p. 194]:
4

1000
0628981 . 9 966821 . 53 79444 . 120 18547 . 120 500655 . 44
8 6 4 2
SG SG SG SG
T
V
OC
+ +
=

where SG is the specific gravity of the battery (assumed fully mixed, i.e., no
stratification) measured at 25C and is calculated from
( )
DK
SG SG AhD
SG SG
empty full
full

=
where the subscripts full and empty refer to the battery being fully charged and fully
discharged.


When the charge current, I, is zero, the battery is open circuited and the cell voltage, V,
equals V
OC
and is calculated from a curve fit to data in [Vinal, 1955, p. 193]:
(SG)
.
(SG)- SG . - e . SG- . . - V
SG
OC
ln
9 0007776503 0
ln 0027 169 4836919 1 13606 174 22968 168 + =


When the charge current, I, is positive, the battery is charging and the cell voltage, V, is
calculated based on a relation adapted from [Copetti et al., 1993]:
( )
( )
( ) ( )
|
|
|
|
|
|
|
|

\
|

|
|

\
|
+
+
+
+ +

+ =
25 1
0001 . 0 1 1
25
,
min
4 2
3 1
max
T CaTr
AhC
CP
I
CP
CK
I
AhC CV T
T
V
CV
V
V
CP CP
slope
OC
OC

where V
max
is the maximum attainable voltage, i.e., the voltage that would occur with all
charge current being used in the gassing reaction;
CV
oc
is a fit parameter roughly corresponding to the open-circuit voltage of the
battery when it is fully discharged;
CV
slope
is a fit parameter roughly corresponding to the partial derivative of the
open circuit voltage with respect to state-of-charge;
AhC is the useable amount of charge remaining in the battery;
CK is a fit parameter corresponding to the capacity of the reference cell, in Ah;
CP
1,2,3,4
are fit parameters;
and CaTr is a parameter describing the change in internal battery resistance with
temperature.

The useable amount of charge remaining in the battery is calculated from:
CK
AhD
AhC =1

The gassing current, I
gas
, is based solely upon the voltage of the battery and the
temperature (the charge current and state-of-charge are only implicitly involved). The
5

rate of the gassing reaction is assumed to be described by the Tafel equation, which is
linearized at voltages just above the onset of gassing. Between the voltage of the onset of
gassing, V
gas
, and the voltage at which the linearization no longer applies, V
gas
+V
Tafel
,
there is a smooth transition between the linear and the exponential curves. This is
achieved by linearly weighting the two equations between these two points:

<
|
|

\
|
+
|
|

\
|

|
|

\
|


=
Tafel diff
Tafel
diff
V
Tafel
diff
Tafel
V
diff
Tafel diff
V
gas
V V
V
V
e CK
V
V
V
e CK V
V V e CK
I
diff
Tafelf
diff
0 1
3
3
3
1
1
1

where
1
and
3
are fit parameters.

The gassing current is actually based on V
diff
, the difference between the battery voltage
and the voltage at the onset of gassing, V
gas
:
( ) ( ) ( ) [ ] 25 1 , 0 max
2
= T CaTg V V
diff

where
2
is a fit parameter roughly corresponding to the voltage of the onset of gassing,
and CaTg is a parameter describing the change in gassing voltage with temperature.

The maximum attainable voltage given the charge current, V
max
, is found from solving for
V
diff
in the equation for I
gas
, with I
gas
=I, the charge current. This is an iterative process in
some cases.



Modelling Ageing

Three counters are used to estimate the number of battery lives used. The float life
counter holds the estimate of the fraction of the current batterys float life that has been
used. The cycle life counter holds the estimate of the fraction of the current batterys
cycle life that has been used. The overall life counter holds the number of battery lives
used (a counting number) plus the fraction of the current battery that has been used.
This fraction is estimated to be equal to whichever is greater of the float life and the cycle
life counters. Both the float life and cycle life counters are reset to zero, and one is added
to the overall life counter, whenever either the float life or the cycle life counter reaches
one. Note that this is similar to, but not exactly equivalent to, the approach used in the
WATSUN PV model [WATSUN Simulation Laboratory, 1997], which at each time step
decreases the remaining battery life by the greater of the cycle life ageing and float life
ageing in that time step.

It is generally considered that the float life of a lead-acid battery halves for every 8C
(for non- or low-antimonial grids) to 10C (for antimonial grids) rise in temperature
[Spiers et al., 1995]. Below 20C, float ageing is considered invariant with temperature
[Spiers et al., 1996]. Thus the time rate of float life ageing (with t in hours) can be
6

estimated from the following equation. This is integrated with respect to time to generate
the float life counter.
|
|

\
|

=
m
float
mT
float
float
dt
dAge
20
10 8760
1
,
10 8760
1
max


where m is 3.01x10
-2
for antimonial grids and 3.76x10
-2
for non- or low-antimonial
grids;
and
float
is calculated based on a float life (in years) and associated temperature
specified by the model user.

It is not clear how best to estimate the cycle life ageing. Some of the literature suggests
log-linear ageing curves [Linden, 1984] while manufacturers sometimes indicate linear
ageing curves (e.g., Global Yuasa). The model used here calculates that from time t to
time t+dt, the cycle life ageing will be equal to:
( ) ( )
t dt t
cycle
SOC Cycles SOC Cycles
dAge
1 1
2
1
=
+


This expression can be summed over time steps to determine the fraction of the batterys
cycle life that has been used. The state-of-charge is calculated from:
ref
C
AhD
SOC =1
With a linear cycle life ageing estimation method, the number of cycles to failure as a
function of SOC is given by:
( )
cyc cyc
SOC m SOC Cycles + =
whereas with a log-linear cycle life ageing estimation method, the number of cycles to
failure as a function of SOC is given by:
( )
SOC m
cyc
cyc
SOC Cycles 10 =
where m
cyc
and
cyc
are calculated based on the pair of points on the cycles versus SOC
curve specified by the user.

Note that if the user specifies a very flat cycle life curve, this approach will underestimate
the rate of cycle life ageing. That is, if the SOC has little effect on the number of cycles
before failure, this approach will not be appropriate. For most real batteries, and certainly
most lead-acid batteries, the above approach appears reasonable.



Modelling Self-Discharge

The rate of self-discharge rises exponentially with temperature; low- or no-antimony
grids have a lower rate of self-discharge than high antimony grids. The self-discharge
current is calculated by:
( )
( ) ( )
720
10 1 ln
T m
SD
ref SD
SD
AhD C I

=


7

where m
SD
is 0.027, and based on the slope of a graph given in [Linden, 1984, p.3-18]
and information given in [Spiers et al., 1998];
and
SD
is calculated based on the monthly self-discharge rate furnished by the user:
T m
month
SD
SD
SD
10
=
where SD
month
is the fraction of the batterys capacity that is discharged in one month at a
temperature of T.



Modelling Heat Evolution

Three sources of heat are modelled here:
1) Joule Heat: The heat due to the losses causing the overpotential, i.e., the current
multiplied by the entire polarisation overpotential.
2) Reversible Heat: The heat, liberated by the battery on charge and absorbed on
discharge, corresponding to the difference between the heat of reaction and the useful
work done.
3) Gassing Heat: The heat absorbed when water is electrolyzed in the gassing reaction
and the hydrogen and oxygen gasses thus produced escape the battery; it corresponds
to the difference between the heat of reaction and the electric work done to perform
the electrolysis.

On discharge, current is negative and the rate of heat generation (in Watts, with positive
indicating heat liberated from the battery) is calculated by:
( ) |

\
|

+ =
T
V
T I V V I P
OC
OC heat
15 . 273
The former term represents the joule heat and the latter term the reversible heat.

On charge, the rate of heat generation is calculated by:
( ) ( )
recomb gas gas
OC
OC heat
I V I
T
V
T I V V I P

+ + = 1
96500 2
10 44 . 48
23 . 1 15 . 273
*
3
*

where I
gas*
is the greater of I
SD
and I
gas
;
and
recomb
is the fraction of oxygen gas evolved that is recombined within the battery.

In the above equation, the first term represents the joule heat of the charge reaction, the
second the reversible heat of the charge reaction, the third the joule heat of the gassing
reaction, and the fourth the gassing heat.



Modelling Gassing and Loss of Water

The accumulated water loss from the battery, M
H2O
, expressed as a fraction of the
maximum permissible water loss, M
H2O
(in kg), is calculated from:
8

dt
I
M
O H
gas
O H
2
*
4
2
10 357 . 3


The rate of hydrogen gas evolution, in L/hr, is equal to the 0.4178I
gas*
.

Model Calibration

The model was calibrated, i.e., the fit parameters were determined, by a nonlinear least-
squares method. The current-voltage-SOC relations of the model were implemented as
MATLAB functions (one for charge and the other for discharge). These functions were
then repeatedly called by a MATLAB nonlinear least-squares method until the best fit
was achieved for a set of charge and discharge curves for Global Yuasa and Absolyte IIP
batteries. These curves were taken from battery testing done a CEDRL in 1997 and 1998.
Four curves were used, corresponding to roughly C/10, C/20, C/50, and C/200 rates. In
order to weight each curve equally, all curves were adjusted so that they had the same
number of data points.

One problem that arose in this fitting procedure was the lack of data at high voltages, i.e.,
in the gassing region. In order to fit the Global Yuasa battery in this region, the C/10 rate
curve was extended above 2.5 V based on curves for tubular batteries in [Copetti et al.,
199X]. For the Absolyte IIP 50A-05 battery, the gassing parameters were calculated
directly in order to achieve a gassing plateau of 15.5V (2.58V per cell) at a current of
11A (roughly C/10) and a temperature of 25C, with gassing starting at 2.28V per cell.
That is, under the above conditions, when all current is causing gassing, the battery
would be at 15.5V.

Another problem that arose was the lack of data at temperatures below 25C. Because
only a few curves were available, and these only at temperatures of 5C and 15C, the
temperature adjustment factors found in [Copetti et al., 1993] were used.

Model Implementation

The model was implemented in Simulink. It was tested and debugged using a series of
basic current and temperature cycling regimes. The only important consideration in the
operation of the model is that within the Simulink solver zero crossing checking must be
disabled.

Recommendations

1) The model works quite well and has a number of somewhat novel elements that are
arguably improvements on the models found in the literature. As it is presently
implemented, it could form the basis of a conference article. With further work it
might form the basis of a journal article. At minimum, a conference article should be
published.
2) Further battery testing should be done at temperatures below 25C, at high voltages,
and at high currents. Furthermore, the cycling behaviour of the battery should be
9

documented and compared with that predicted by the model in order to determine
how seriously stratification will affect the model accuracy.
3) A number of possible improvements to the model should be investigated:
Rather than fit the parameters DV
OC
, DV
slope
, CV
OC
, and CV
slope
to the curves, the
open circuit voltage should be calculated using the curve for V
OC
. This would
simplify the model, put it on a sound electrochemical foundation, and possibly
improve the low temperature charge performance of the model, particularly for
the Absolyte IIP battery.
Rather than apply a temperature correction term to the whole of the
overpotential part of the charge and discharge voltage relations, the temperature
correction should be applied to only the term with current in the denominator. It
may be possible to infer this relation from the change in resistivity of sulfuric acid
with temperature.
Change the form of the gassing equation, such that gassing commences at the
theoretical onset of gassing, rises linearly to a fit parameter describing the voltage
at which the exponential nature of the Tafel equation becomes evident. At this
voltage, the numerator of the exponent would be 0, not V
Tafel
, as it is now. This
would improve the models ability to predict battery efficiency.
Directly incorporate the gassing current into the voltage relation for charging.
That is, Igas should be subtracted from I for the term of the charge relation that
includes AhC in the denominator. This would improve the models performance
when the battery in nearly fully charged.
Attempt to account for stratification, perhaps by modelling the cell as three or
more parallel grids, in different concentration solutions of sulfuric acid.
After the above improvements, see if fit exponents can be replaced with more
physically justified exponents.
4) The model should be made available, in its Simulink implementation, on the Internet.
This would permit outside parties to comment on and suggest improvements to the
model.

References

Copetti, J.B., E. Lorenzo, and F. Chenlo. A General Battery Model for PV System
Simulation. Progress in Photovoltaics. Vol. 1, pp. 283-292 (1993).

Copetti, J.B., F. Chenlo, and E. Lorenzo. Comparison between Charge and Discharge
Batteries Models and Real Data for PV Applications. Source unknown. 199X.

Linden, David. Handbook of Batteries and Fuel Cells. New York: McGraw-Hill
Publishing Company, 1984.

Spiers, David J. and Asko D. Rasinkoski. Predicting the service lifetime of lead/acid
batteries in photovoltaic systems. Journal of Power Sources. Vol. 53, pp. 245-253
(1995).

10

Spiers, David J. and Asko A. Rasinkoski. Limits to Battery Lifetime in Photovoltaic
Applications. Solar Energy. Vol. 58, pp. 147-154 (1996).

Spiers, David and Jimmy Royer. Guidelines for the Use of Batteries in Photovoltaic
Systems. Neste Advanced Power Systems/Natural Resources Canada, 1998.

Vinal, George Wood. Storage Batteries (4
th
edition). New York: John Wiley & Sons,
1955.

Watsun Simulation Laboratory. Watsun-PV 6.0 Users Manual and Program
Documentation. Waterloo, Ontario: University of Waterloo, 1997.


Appendix: Changes to Battery Model

(2002/01/08)

When implemented in Simulink, the combination of charge controller and battery was not
stable when on float charge at low voltages (e.g., 2.2 to 2.3 V per cell). The battery
voltage was overly sensitive to charge current; this caused the variable time step solver to
reduce the time step, resulting in a slow simulation. Perturbations to the available charge
current (i.e., the output of the array) would often cause the simulation to halt with an
error message indicating an instability.

The way that the model deals with gassing was changed in order to make the model more
stable. At the low voltages typical of float charge, gassing now occurs at a low rate. This
means that the currents at low voltages are higher than before, making the battery voltage
less sensitive to small perturbations in the charge current.

The new expression for I
gas
on charge is:

( )

<

|
|

\
|

=

onset
onset
V V
SD
gas
V V
V V e CK e CK I I
I
onset
0
, min
3
2
3
2
1 1

where
1
,
2,
and
3
are fit parameters and
V
onset
is a constant describing the lowest voltage at which any gassing occurs. This
is set to 2.17V, which should be lower than any realistic float setpoint.

In effect, the new gassing curve is an exponential curve, with the curve shifted
downwards such that I
gas
intersects the I=0 axis at the voltage V
onset
. Since this ignores
the linearity of the Tafel curve at low voltages, this is somewhat less realistic than the
previous relation, in theory. In practice, it gives a good fit to the measured battery curves.

11

The low gassing current suggested by the model when the battery is on float is quite
realistic. Even though the gassing voltage for a lead acid cell is commonly given as 2.39
V at 25C, this is the voltage at which the exponential nature of the tafel curve becomes
evident. Electrolysis can begin at voltages as low as 1.2 V, and gassing can be observed
visually in batteries well below 2.39 V.

The equation for the battery voltage on charge has been changed slightly as well.
Whereas before the voltage was limited to V
max
, the voltage attained when all current was
used in gassing, now there is no limit on voltage but the gassing current is limited to the
total charge current, I-I
SD
. The current used to calculate the battery voltage is now I-I
SD
,
i.e., it is reduced by the self-discharge current. These changes result in more realistic
battery output, simplify the model, and make for more stable operation when combined
with the charge controller model in Simulink.

A change has also been made to how the self-discharge current is treated when
calculating the state of charge. Now this is calculated as:

( ) ( )
0
AhD dt I I I AhD
SD gas
+ + =

That is, self-discharge is considered to occur at all times, even during gassing. This is
physically justified, but leads to some peculiar behaviour when all the current is going
into gassing: state-of-charge reaches a plateau below a full state-of-charge. This minor
problem arises out of inadequacies in the way the gassing current is calculated, not in the
assumption that self-discharge occurs at all times.