Estimation of the Capacity of Nickel-Cadmium Batteries by Measuring

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Estimation of the Capacity of Nickel-Cadmium Batteries by Measuring

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Impedance using Electrolyte-Deficient Battery Characteristics

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

Abstract

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

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.

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.

26-3

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.

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.

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

113

26-3

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.

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:

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

:,

3

LI

0.5

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

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)

774

26-3

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.

I I I

(1) Measurement at a Fixed Frequency

complicated battery testing circuit. Therefore, we

investigated the measurement of impedance at one

fixed frequency.

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.

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.

775

26-3

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.

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.

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

26-3

References

Powering of Local Network Elements", Proceedings of

INTELEC'94, pp. 108-114.

Yotsumoto, and T. Ogata, "A Deterioration Estimating

System for 200-Ah Sealed Lead-Acid Batteries",

Proceedings of INTELEC'94, pp. 256-262.

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

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

2)-(3)

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

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

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).

or used batteries.

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

777

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