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Estimation of the Capacity of Nickel-Cadmium Batteries by Measuring


Impedance using Electrolyte-Deficient Battery Characteristics

Naoki KAT0 and Katsuhiko YAMAMOTO

N T I Interdisciplinary Research Laboratories


3-9-11 Midori-cho, Musashino-shi, Tokyo, 180 Japan

Abstract

This paper describes a method of testing trickle- Commercial A C


Power Source
charged nickel-cadmium (Ni-Cd) batteries. The main
causes of deterioration are shown to be short-circuit
and electrolyte leakage. In the former case, the
batteries are easily tested by measuring the voltage. In
the latter case, we show that measuring the impedance
is an effective way to test the condition of batteries
because its logarithm is linearly related to the
capacity, and this relationship can be obtained easily
and quickly from characteristics of electrolyte-
deficient batteries. Fig. 1 Schematic of battery testing system

that had been used with trickle-charging for over five


1. Introduction years in emergency lighting equipment. We shall refer
to these as "used batteries".
Trickle-charged Ni-Cd batteries are widely used to
provide standby power during power failures of Figure 2 shows battery capacity versus weight for
commercial AC supplies. Telecommunication systems used batteries. The batteries that fall within the circle
in the near future will require many storage batteries". had very low impedance and their open circuit
Battery testing techniques will therefore become more voltage (OCV)was nearly zero. Therefore, in this case,
and more important. The usual method for testing the the cause of deterioration was certainly a short-circuit
condition of a storage battery is to measure how long between electrodes. For the other batteries, the
the battery continues to discharge at a constant capacity tended to be lower when the weight was
current. However, this method has several
disadvantages. For example, it is laborious and takes a
long time, or if a power failure occurs during the
measurement, the battery cannot supply the
emergency demand for power. Consequently, there is
a need for a new method that can quickly test a
battery while it is fully charged.

Figure 1 is a schematic of our battery testing system.


The battery testing circuit is remotely controlled to
enable it to measure the battery characteristics and
send the data to the operator.
Our approach was to estimate the capacity of Ni-Cd
batteries from electrically measurable characteristics.
Therefore, we tried to find characteristics that are
related to capacity.

Normalized Weight, W
2. Cause of Deterioration under Trickle-Charging Fig. 2 Relationship between Q and W for used
batteries. Q is normalized by nominal capacity; W is
We investigated the deterioration of Ni-Cd batteries normalized by maximum weight.

0-7803-2750-01951 $4.00@ 1995 IEEE 772


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lighter. Furthermore, some of these batteries had white curves in Fig. 5 are similar and can be expressed by
surface discoloration (carbonate) due to electrolyte
leakage. These batteries partially recovered their Q=aXln(Zrm=o)+b (1)
capacity when fresh electrolyte was injected into the
battery case. In this case, the main cause of where a and b are constants, and the correlation
deterioration appeared to be electrolyte leakage. To coefficients for used and for electrolyte-deficient
investigate this, we made "electrolyte-deficient batteries were 0.968 and 0.962, respectively. These
batteries", which had less than the standard amount of results confirm that electrolyte leakage was the main
electrolyte, and compared their characteristics with cause of deterioration.
those of the used batteries.

The variation in capacity of the electrolyte-deficient -4


batteries is shown in Fig. 3. The size and nominal E
N" -3
capacity were different from those of' the used
batteries, but the manufacturer was the saime. Figure 3
Y

a
i-2
shows a similar pattern to Fig. 2.
p-1
.*E:
"mo 0
E
1.4 pN
1.2 z 2
?!
ss
.*
U
1.0 g 3
4
3 0.8 0 1 2 3 4 5 6 7 8
3 Normalized Real Part, Z RC
U
0.6 Fig. 4 Complex plane impedance of (a) 100%
N
.i electrolyte amount and (b) 50% electrolyte amount
3 0.4 for electrolyte-deficient batteries. Z R ~and Z I m are
normalized by the impedance where the imaginary
z 0.2 part is zero for (a).

0
0 20 40 60 80 100
Normalized Electrolyte Amount, V(%)
Fig. 3 Variation of Q with V for electrollyte-deficient
batteries. V is normalized by the standaird amount of
electrolvte.

A Cole-Cole plot of the impedance spectra for the


electrolyte-deficient batteries is shown in Fig. 4. The
measurement was performed in the fully-charged state
with no bias current, using a computer controlled
frequency response analyzer (Solartron 1250) and a
galvanostat (Solartron 1286). The plot shifted to the
right and the semi-circle became larger as battery
capacity decreased, showing that electrolyte leakage "
raises impedance. Therefore, there should be 1 10 100 1000
correlation between capacity and impedance. Normalized Impedance, ZIm=O
Fig. 5 Relationship between Q and ZIm=O for (A)
used and (B) electrolyte-deficient batteries. Q is
Figure 5 shows the relationship between capacity Q divided by the maximum capacity of used batteries.
and impedance ZIm-0, the real part where the Z I ~ = Ois divided by their minimum impedance.
imaginary part is zero (refer to Fig. 4), for the used
batteries and for the electrolyte-deficiient batteries.
Physically, ZIm=O corresponds to the totad resistance of
the electrodes and the separator with electrolyte. The 3. Battery Testing Method
frequency of ZIm=O, where the imaginary part is zero,
ranges from 50 Hz to 5 kHz. As battery capacity There are two main causes of deterioration in
decreases, the frequency of ZIm=O incre,ases. The two trickle-charged batteries: short-circuits and electrolyte

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leakage. When the deterioration is caused by a We investigated the validity of these assumptions for
short-circuit, the condition of the Ni-Cd batteries can two types of electrolyte-deficient batteries. Type 0
be determined by measuring the voltage because a was the same type as referred to in Fig. 5(B). Type 0
large voltage drop is observed. When the deterioration was made by the same manufacturer, but it was
is caused by electrolyte leakage, the battery capacity smaller with lower nominal capacity.
can be estimated by measuring ZIm=O and by using
eq.(l). Since voltage and impedance are easy to Figure 7 shows the measured relationship between
measure with fully-charged batteries, these methods capacity and ZIm=O for both types, and the calculated
are promising for the testing system shown in Fig. 1. relationship for type @ using eq.(3). The calculated
However, for practical use, two problems remain. One relationship agrees well with the measured
is that it is necessary to establish a quantitative relationship of type @ . This shows that our
relationship between battery capacity and ZIm=O. The assumptions were valid.
other is that an elaborate electronic circuit is needed
to measure ZIm=O because the real and the imaginary
parts of impedance must be obtained separately at
various frequencies and the point where the imaginary
part is zero must be found.
Our solutions to these two problems are described in
Sections 4 and 5.

4. Relationship between Capacity and ZIm=O

In order to get a quantitative relationship between


battery capacity and ZIm=O, it is necessary to
investigate deteriorated batteries. The usual method of
obtaining deteriorated batteries is to charge and
discharge them at high temperature. However, this is
laborious and takes a long time (at least half a year).
I
I ,
, : .
I
Moreover, the deterioration modes under these z, zb mZ,
m Z b (log scale)
Normalized Impedance, Z Im=O
conditions are not necessarily the same as those in
Fig. 6 Assumptions to get linear correlation between
normal use. If characteristics of electrolyte-deficient Q and Z I m a (m and n are constants).
batteries could be used instead, this would allow a 0for electrolyte-deficient batteries
quantitative relationship to be obtained quickly and 0for used batteries obtained by 0
easily. Therefore, we investigated whether the
relationship between capacity and ZIm=O for
electrolyte-deficient batteries also applies to batteries
that have deteriorated in normal use. We use the
following equation:

Q=a, x I n(ZIm=o)+b,, (2) 0 2.0


where a, and b, are constants, and we assume that
A
.U
3
0
41.5
(i) the change in impedance with decreasing capacity U
is independent of battery size and nominal capacity
for trickle-charged batteries made by the same
z 1.0
:,

manufacturer (see Fig. 6). z


3

LI

0.5
(ii) the relationship obtained is the same type as eq.(2).

If the capacity and ZIm=O of used batteries that have 0


not deteriorated are Q, and Z,, and the capacity of the 1 10 100 1000
electrolyte-deficient batteries with 100% electrolyte Normalized Impedance, Z Im=O
amount is Q,, the following equation gives the Fig. 7 Comparison of real relationship (-) with
‘ relationship for the used batteries (refer to relationship calculated from type 0 for type 0
electrolyte-deficient batteries The graph of
(e..).
APPENDIX). type 0 is the same as Fig. 5 (B).
Q=a, X(Q,/Q,)x I n(Zrm=o/Z,)+Q, (3)

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Figure 8 shows the relationship for the used batteries (2) Pulse Charge Estimating Method
and the relationship calculated from type (D batteries.
In this calculation, the values of Q, and t z b are not We measured impedance by the, "pulse charge
clear, so we used the average values of data within the estimating method2'" using a current pulse generator
circle in Fig. 5 for Q, and Z,. The two relationships (Hokuto Denko HC-113), a digital oscilloscope
show good agreement. In particular, the values of (Yokogawa DL-1300), a current probe amplifier
ZIm=O where the capacity is 50-60% (the standard (Tektronix AM502A), and a high frequency active
value of replacing the deteriorated batteries with new probe (Universal Probes ASPSOO).
ones) are almost the same. Therefore, by using the
characteristics of electrolyte-deficient batteries, we can Figure 10 shows a conceptional diagram of the
quickly obtain the quantitative relationship between battery voltage change A V(t) caused by a pulsed
capacity and ZIm=O for batteries that have deteriorated. charging current I. The battery impedance R is
defined as AV(t,)/I.

1.o
0.9
c) 0.8
8
'g 0.7
g
g 0.6
c 0.5
0
.cds0.4
3

0.3
3 0.2
0.1
1 10 100 1000
Normalized Impedance, Zrm=al 0.1 1 10 100 1000 10000
Fig. 8 Comparison of real relationship (->I for used Frequency (Hz)
batteries (same graph as Fig. 5(A)) with rellationship Fig. 9 Relationship between frequency and correlation
calculated from electrolyte-deficient battexies (*.*) coefficient in eq.(4) for used and for electrlyte-
(from Fig. 5 (B)). deficient batteries.

5. Simple Impedance Measurement


I I I
(1) Measurement at a Fixed Frequency

Measuring ZIm=O at various frequencies requires a


complicated battery testing circuit. Therefore, we
investigated the measurement of impedance at one
fixed frequency.

Figure 9 shows the relationship between the


measurement frequency and the correlation coefficient
of the following equation for used and for
l , I
0 ti t2
electrolyte-deficient batteries. Time, t
Fig. 10 Conceptional diagram of battery voltage
Q=ax In(Z(f))+b (41 change caused by a pulsed charging current.

where f is frequency, Z(f) is the absolute value of the


real part and the imaginary part, and a and b are Figure 11 shows the relationship between the battery
constants. Both types of batteries showed a high capacity and the impedance R. The linear relationship
correlation coefficient of around.0.95 from 110 Hz to 1 is almost the same as shown in Fig. 5(A). The
kHz. Therefore, we can estimate battery capacity by correlation coefficient of eq.(l) is 0.960 when ZIm=O is
measuring Z(f) in this range with only a small loss in replaced with R. This method can be simplified, so it
accuracy compared to measuring ZIm-0. leads to a simple battery testing circuit.

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100

U 2.0
U
.
s3
E 50
5 1.5
0
v

a
0
U
z s
3 1.0 s
cd
31
E
n

Z 0.5

0 0.1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Electrolyte Amount (g)
dig. 11 Relationship between Q and R for usec Fig. 12 Dependence of separator impedance at 1 kHz
batteries as determined by the pulse charge estimatinj on electrolyte amount.
method. R is normalized by the minimun impedance.

6.Amount of Electrolyte and Impedance of Separator

We investigated why battery capacity is linearly


related to the log of the impedance. Electrolyte
leakage causes a decrease in the amount of electrolyte
in the electrodes and the separator. The Ni-Cd
batteries we investigated use a polypropylene
separator, and the electrodes tend to absorb
electrolyte from the separator when the amount of
electrolyte decreases. Therefore, the increase in
battery impedance due to electrolyte leakage is
probably caused mainly by the increase in separator
impedance.
Fig. 13 Experimental setup for measuring the
impedance of a separator.
Figure 12 shows how impedance depends on the
amount of electrolyte at 1 kHz obtained by
experiment (Fig. 13). The electrolyte was distributed
homogeneously. The linear relationship between deficient batteries. Instead of measuring ZIm=O at
impedance and log of the amount of electrolyte was various frequencies, fixing the frequency in the rang
observed in the range from 0.1 to 0.5 g. This result from 10 Hz to 1 kHz or using a pulse charge
suggests that battery impedance depends on separator estimating method is effective for practical use
impedance. We are now investigating whether the because they allow the use of simplified battery
condition of the separator in this range corresponds to testing circuit. We think that battery capacity is
the condition of the separator in the range where cell linearly related to the log of the battery impedance
capacity changes linearly with log of the impedance. because the impedance depends mainly on the
separator impedance.

7. Conclusions In this research, the characteristics of a single Ni-Cc


battery were investigated. Since batteries are usuallj
The main causes of deterioration of trickle-charged connected in series or parallel, we are now studyin8
Ni-Cd batteries were proved to be short-circuits and how to test such batteries.
electrolyte leakage. In the latter case, correlation was
found between battery capacity and impedance and
this allowed us to estimate the capacity by measuring Acknowledgements
the impedance, ZIm=O. Furthermore, we obtained a
quantitative relationship for batteries that have We would like to thank Drs. Ichiro Yamada, Toshirc
deteriorated in actual use. This was quickly and easily Hirai, and Tsutomu Ogata and Mr. Noboru Asano fo
calculated from the characteristics of electrolyte- their support on this research.
11R
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References

[ 11 N. Dalarsson, "A Recommendation for Centralized


Powering of Local Network Elements", Proceedings of
INTELEC'94, pp. 108-114.

[2] Y. Konya, T. Takeda, K. Takano, M. Kohno, K.


Yotsumoto, and T. Ogata, "A Deterioration Estimating
System for 200-Ah Sealed Lead-Acid Batteries",
Proceedings of INTELEC'94, pp. 256-262.

4ppendix (refer to Fig. 6)

The equation for electrolyte-deficient batteries is

Q=al Xln(ZIm=o)+bl---(l ) (eq. 0in Fig. 6)

.*. Qa=alXln(Za)+bl---(2),

Qa/n=al X In(mZ,)+bl---(3)

2)-(3)

(l-l/n)Qa=al Xln(l/m)---(4).

The equation for used batteries is presented as

Q=a2XIn(Z1m=o)+b2---(5)

'. Q b=a2 x ln(zb)+b2---(6),

Qb/n=a,X In(mZ,)+b2---(7)

6)-(7)

(1 -1 /n)Qb=a2xin(1/m)---(8)

4)i(8)

Qa/Qb'a1/a2---(9).

+om eq. (5), (61, (9), the following equation is obtained


or used batteries.

)=a1 (eq. 0in Fig. 6


x(Qb/Q,)x~n(ZIm=O/Z~)+Q~---(~~)

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