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Introduction
Definition
At the University of Kassel, the late H.-J. Euler [l] performed theoreti-
cal and experimental work for the better understanding of sinter processes.
In his thesis, Metzendorf [2], one of Eulers students, correlated the limit of
mass utilization to the interruption of the electronic paths. After the death of
Euler, one of us (A. W.) continued his work and supplemented it by electro-
chemical experiments. This work, performed by Willer and Riickborn, has
die
sample of
lrnglhI
recently been published [5]. The doctoral thesis of Willer [3] was related to
the sinter behaviour of copper powder, whereas the diploma thesis of Riick-
born [4] was directed towards the behaviour of cobalt powder. Figure 1 shows
the experimental device for the measurement of the average specific conduc-
tivity of a pressed metal powder sample during compression. As shown in Fig.
Fig. 3. Experimental
212
Icmpcralurc I l
so0. -0.20 SO .
400 -0.30. 40
MO- _OAO 30
200. -0.50 20
I
0 0.50 1.00 1.50 2.00 150 3.00 3.50 LOO 4.50 5.00
1m.I h
Fig. 4. Specific resistance and dilatation of a pressed cobalt powder specimen as a function of
temperature.
160
5
g 120
9
0
4
g 40
g 0
0 100 200 300 LOO 500
tunporotur. / c
V, = 4nR3/3 (6)
For a porosity, P:
n3VK=l-P (7)
Substituting eqn. (6) in eqn. (7) gives:
wL = 2nw, (9)
and, consequently, the specific resistance of the total aggregate, Q, is:
wH = R/4h (11)
Using this expression in combination with eqns. (8) and (10) yields:
R = R*(R&,/2a) I2 (14)
215
For h 6 R, the third term in the brackets of eqn. (18) can be neglected
against the second one. Therefore, according to eqn. (18a) the potential in
the neck zone deviates, by the second power of the R/h ratio, from the
potential of the sphere.
216
3 corny. 6 thcrmosm,
Fig. 7. Electrochemical cell for measurement of ohmic resistance of pressed powder specimens.
Figure 7 shows a test cell design for the determination of the electronic
resistance of a pressed powder sample during an electrochemical treatment
consisting of dipping in the electrolyte and electrochemical reduction. Such
measurements have been performed 4th copper samples as well as with
cobalt samples. The results can be described as follows: at the moment when
a pressed-powder sample of cobalt is dipped in the KOH electrolyte, the
OF------ lASO
65 -. .A00
f 60 - . 350
g 55-e .-PO0 ;
:
y 50 - -250 f
s
2 z
,o AS-. .- 200
.r
g
150
1
LO-
z
35.. 100
Fig. 8. Electronic resistance and potential of a pressed copper powder sample as function of time
after soaking in KOH at room temperature.
217
. 75
6 LO
P
E 35
d . 50 ;
: %I f
e25 . 25
g 8
2 20
.I a--:. 0 p
f IS
Fig. 9. Electronic resistance and potential of pressed copper powder samples during cathodic
reduction as function of reduction charge.
Battery engineers are aware that PbOa electrodes sometimes are only
partly dischargeable, despite the fact that at the beginning of the experi-
ment all of the active material consists of PbO,. This feature has been
observed in antimony-free electrodes [7] and has therefore been called the
antimony-free effect (AFE). There has been no real understanding of the
AFE so far. One hypothesis claimed the growth of a lead sulphate layer as
the reason for the AFE [8, lo].
Some years ago, it was stated [9] that the lead sulphate layer is not
the reason, but the result, of the AFE and that the true cause can only
be a changing current distribution from cycle to cycle. In this sense,
the cause of the AFE was postulated as a changing conductivity of the
cycled PbO, [ 91. From eloflux experiments [ 121, it was possible to diagnose
the AFE and to develop a therapy against it. It was shown that the AFE
would be better named a relaxable insuflicient mass utilization (RIMU)
because the phenomenon is independent of the absence or presence of
antimony. With the aid of the aggregate-of-spheres model, it is possible to
explain very easily the mechanism involved in the AFE in terms of a RIMU
process [ 131.
1.3
>
2 1.1
f
9 0.9
............ p(:
Y
--- Ptl
-.-'- Pbwire
%
; a7 - grid
0 20 LO 60 w m 120 lb0
b) I / minules
Fig. 11. (a) Potential, (b) electronic reeistance of a PM), electrode during discharge.
p 120
ll-c_
E 20.
L
0 0.
IL 11 20 23 26 29 32
0) cycle number
14 I7 20 23 26 26 32
b) cych numbor
Fig. 12. (a) Material utilization, (b) electronic resietance of active material of a Faure PbO,
electrode ae a function of cycle number [ 111.
221
Fig. 13. Correlation between active mass utilieation and electronic resistance of active PM),.
Both the capacity and the resistance remain stable during cycling if a
good cycle regime is applied to the electrode. If the electrode is exposed to a
bad cycle regime, however, the conductance of the active material decreases
simultaneously with the mass utilization. This behaviour is shown in Fig. 12
where curve (a) represents the material utilization and curve (b) depicts the
material resistance as a function of the cycle number. Finally, Fig. 13
demonstrates the correlation between the active-mass utilization and the
electronic resistance of the active material of the PbO, electrode. Treatments
that help to recover a good utilization of material also simultaneously
decrease the ohmic resistance of the active material [ll].
Few fundamental data are known that allow the developed theory to be
applied to the lead dioxide electrode. New information may be obtained,
however, from the following calculations.
The estimated radius, R, agrees with scanning electron microscopic and BET
measurements. The value of the surface (interfacial) tension, Q, has been
selected in accordance with data reported for solids [15,16] that are correct
in their order of magnitude. With such values for the various parameters, the
223
Conclusions
References
10 D. Pavlov, The lead-acid cell, in B. D. McNicol and D. A. J. Rand (ede.), Power &mrCee for
Electric Vehicles, Elsevier, Amsterdam, 1964.
11 W. Borger, U. Hulhneine, H. Laig-H8rstebrock and E. Meisener, 16th Znt. Power Source8
Symp., Bournemouth, 1988.
12 J. Bohmann, U. Hullmeine, E. Vase and A. Winsel, Active material structure related to cycle
life and capacity, ZLZRO Project LE-277, Final Rep., Dec. 1%2.
13 U. Hullmeine, E. Vose and A. Winsel, J. Power Sources, 25 (1969) 27- 47.
14 J. P. Pohl and H. Rickert, Electrochemistry of lead dioxide, in S. Trasatti (ed.), Electrode8 of
Conductive Metallic Oxides, Elsevier, Amsterdam, 1960.
15 Handbook of Chemistry and Physics, CRC-Press, Cleveland, 56th edn., 1975.
16 L. Mandelcom, Non-Stoichiometric Compounds, Academic Press, New York, 1964.