EIecrroekimicn

Acra, Vol. 40, No. 13 14, pp. 2449.2453. 1995

Copyright
0 1995 Elsevier Science Ltd.
Printed in Great Britain. All rights reserved
0013~4686/95 $9.50 + 0.00

0013-4686(95)00212-x

ALKALINE POLY(ETHYLENE
OXIDE) SOLID POLYMER
ELECTROLYTES.
APPLICATION
TO NICKEL SECONDARY
BATTERIES
J. F. FAWARQUE~,S. GUINOT,N. Bouzw, E. SALMONand J. F. PENNEAU*
Laboratoire dElectrochimie Industrielle, CNAM-2, rue ContG-75003 Paris, France
* EDF-Dkpartement des Etudes et de la Recherche, Les Renardihres-77250 Moret-sur-Loing, France
6 April 1995)

(Received

Abstract-Water-containing and anhydrous alkaline PEO-based solid polymer electrolytes have been
prepared, involving two different technologies. They exhibit a high ionic conductivity, and values up to
10e3 Scm- are obtained for some compositions at room temperature. Conductivity studies and thermal
analysis are presented, and the conductivity vs. temperature behaviour of each type of solid polymer
electrolyte studied is discussed. Preliminary results are reported concerning the cyclability of cells involving a nickel positive electrode, and a cadmium or a zinc negative electrode.

Key words: alkaline

batteries.

solid polymer

electrolyte,

poly(ethylene

INTRODUCTION

should be addressed.

nickel secondary

EXPERIMENTAL

Solid polymer electrolytes are ionic conductive solutions of salts in a polymeric solvent, typically
poly(ethylene oxide) (PEO). The study of such new
electrolytes was initiated by Wright et aI.[l] who
carried out the first conductivity measurements of
polymer-salt complexes, and concretised by Armand
et aI.[2-31, who was the first to recognise the real
practical potential use of PEO-based electrolytes.
The diversity and the complexity of the current
research in the field of polymer electrolytes can be
explained by their attractive advantages as compared to conventional solid or liquid electrolytes.
For example, problems like chemical and electrochemical instability, corrosion and gas emission, can
be avoided in such polymer-based systems, which
can in addition be easily processed due to their plasticity. This undoubtedly makes solid polymer electrolytes real good candidates for applications like
batteries and other electrochemical
devices[4].
Among numerous
systems, lithium-based
solid
polymer electrolytes have been the most extensively
studied materialsC3, 51. We present here a new
family of solid polymer electrolytes, whose specificity
lies in their composition, based on PEO and potassium hydroxide (KOH). Several compositions have
been prepared, and two have been mainly studied,
an anhydrous one and a water-containing one. The
thermal and conductivity properties of those two
compositions have been investigated. As an application, a prospective study of the cyclability of nickel
secondary batteries, namely nickel/cadmium
and
nickel/zinc, is reported here.

t To whom correspondence

oxide), ionic conductivity,

Commercial
PEO 20.000 (Fluka av.mol. wt.
2 x 104), KOH (Fluka), and methanol (Merck) were
used as starting materials for solid polymer electrolytes preparation. The water-containing composition
was prepared by direct mixing of PEO, KOH and
H,O, at approximately 90C. The anhydrous composition was prepared by the conventional solvent
casting method. Equivalent amounts of PEO and
KOH were dissolved in methanol, and were mechanically stirred for several hours at room temperature,
so that the solvent was allowed to evaporate slowly.
After casting on an appropriate support, the last
traces of solvent were removed under vacuum. The
ionic conductivity of both compositions was determined by using the UCcomplex impedance method.
A typical button cell composed of two expanded
nickel grid electrodes was used for the measurements, which were carried out over the frequency
range of 0.1 Hz to 2 x lo6 Hz using a Schlumbezger
1250 Frequency Response Analyser and 1286 Electrochemical Interface controlled by a Compaq
microcomputer. All analysed cells were previously
kept at 80C for 20min and then allowed to cool at
room temperature, to ensure good contact between
the electrolyte and the electrodes. Two or even three
series of measurements were performed for each of
these two complexes in different button cells, and the
samples were heated and cooled five times and data
collected on heating. With an acceptable reproducibility, the fifth heating cycle data are reported
here. Fifth heating-cooling cycle measurements at a
frequency value of 104Hz are also presented. All
impedance measurements were made after half an
hour temperature stabilisation. The total ionic conductivity was calculated using equation (1), where 1
and A are the thickness of the electrolyte and the

2449

J. F. FAUVARQUE et al.

2450

area of the electrodes respectively, and R, is the

resistance of the electrolyte estimated from UCimpedance data.
a(Scm-)

l(cm)
R&2) x A(cm2)

(1)

A SETARAM 101 differential scanning calorimeter

(DSC) was used to determine the melting temperature and other thermal characteristics of the two
compositions, using stainless steel sealed pans. The
samples were heated at a rate of 3Cmin- , over a
temperature range of 0-100C in nitrogen atmosphere. Each sample was run three times over the
temperature range previously indicated. The temperatures reported are onset temperatures.
RESULTS AND DISCUSSION

Water-containing composition of 60% wt.% PEO,

30wt.% KOH and lOwt.% H,O
The Arrhenius plot of the total ionic conductivity
is shown in Fig. la, exhibiting an unusual behaviour
of the electrolyte. Indeed, three domains can be
-2.5 ,
a

l*
l*
.

.
.

2.7

3.1

2.9

3.3

3.5

(IXOfO/K-I

observed on the curve log (a) vs. f (l/T), in the

overall temperature range. Two domains, from room
temperature to 60C and from 65C to the maximum
temperature, show a linear increase of the conductivity with increasing temperature, which is the
normal situation expected for a PEO-based solid
polymer electrolyte. A third domain, in the temperature range of 60-65C, surprisingly shows a very
important decrease of the conductivity. This transition is not the usual one accounted for PEO-based
solid polymer electrolytes, such as Arrhenius type.
Figure lb shows typical impedance plots for the electrolyte, at three different temperatures from the three
different domains.
DSC curves of this water-containing composition
are shown in Fig. 2, exhibiting two endothermic
peaks. The one at 66C could be attributed to the
melting, either of the crystalline phase of PEO or of
another crystalline phase existing in the electrolyte.
The other at 36C has not been clearly identified yet.
Further investigations such as X-ray analysis are
under progress.
The unusual conductivity vs. temperature behaviour of the 6Owt.% PEO, 30wt.% KOH and
lOwt.%
H,O composition has also been observed
on cooling cycle, as illustrated by Fig. 3, which
shows the temperature dependence of the total ionic
conductivity for a heating/cooling cycle, before and
after quenching, data being collected at a frequency
of lo4 Hz. One may notice that an hysteresis phenomenon in Gonductivity takes place below the melting
temperature
of the sample. Furthermore,
the
quenched sample exhibits, on heating, a lower conductivity value than the non-quenched sample, from
room temperature to 60C.
Such results can be explained by the following
hypothesis: at room temperature, two phases coexist,
one being crystalline PEO, and the other, more concentrated in KOH than 30wt.%, being the conducting phase. In the melting temperature range of the
crystalline PEO (60-65C), the sudden decrease of
the conductivity can thus be related to an homogeni-

.
.

.
.

.
.

5ooo

endo

IcaxJ

15W

2cccM

Z/Ohms

Fig. 1. (a) Temperature

dependence of the total ionic conductivity of a 6Owt.% PEO, 30wt.% KOH and lOwt.%
H,O solid polymer electrolyte. (b) Impedance
plots of a
PEO 6Owt.%, 30wt.%
KOH and lOwt.%
H,O solid
polymer electrolyte between two nickel electrodes, at different temperatures:
(a) 24C (A) 64C, (0) 94C. Frequency
range: 0.1 Hz to 2 MHz.

20

40

60

Temperature

80

loo

(C)

Fig. 2. DSC trace of a 6Owt.% PEO, 30wt.% KOH and

10 wt.% H,O solid polymer electrolyte at a heating rate of
3C min- (onset temperatures).

Polymer

electrolytes.

Application

2451

to nickel batteries

l.

.
.
i

2.5

2.7

3.1

23
looo/r

3.3

2.5

3.5

2.7

239

3.1

3.3

3.5

(mom/K-l

(l/K)

Fig. 4. Variation of the total ionic conductivity

vs. reciprocal temperature
of a 50 wt.% PEO and 50 wt.% KOH solid
polymer electrolyte.
-2,5
b

KOH in the composition. As far as we know, no

value higher than 10-3Scn-1
at room temperature
has already been obtained for alkaline PEO-based
solid polymer electrolytes.
Application: prospective study of the cyclability of
nickel secondary batteries in the water-containing
composition of 60 wt.% PEO, 30 wt.% KOH and

-5.5
2.5

2.7

2.9
Iccwr

3.1

3.3

3.5

(l/K

Fig. 3. Temperature
dependence of the total ionic conductivity of a 6Owt.% PEO, 30wt.% KOH and lOwt.% H,O
solid polymer electrolyte
(data collected at a frequency
f = lo4 Hz); (a) before quenching; (b) after quenching.

zation in KOH concentration. This is consistent with

experiments
previously
heating/cooling
the
described. Indeed, it is well known that the crystallinity of a polymeric sample is less after quenching. This has also been confirmed by experiments
carried out with plasticized compositions showing
that the decrease in conductivity over the temperature range 6t-65C is less important and that
this effect is more pronounced as the amount of plasticizer increases.

lOwt.% H,O
The Nickel/Cadmium
6Owt.% PEO, 30wt.%
KOH and lOwt.% H,O solid polymer electrolyte
secondary battery tested was manufactured
by
assembling vertically 11 cadmium and 12 nickel circular electrodes. Each positive electrode (thickness:
7.5 x 10e4m and area 6.16cm) is based on nickel
hydroxide Ni(OH),, and has a theoretical capacity
of 250Ahcme2. Each negative electrode (thickness:
5.5 x 10e4m and area 6.16cm2) is based on
cadmium electro-deposited on a nickel-plated iron
and has a theoretical
capacity
of
support,
550Ahme2. The separator is a polyamide knitted
sheet (thickness: 4 x 1O-4 m). The limiting electrode

Anhydrous composition of 50 wt.%PEO and 50 wt.%

KOH
Figure 4 shows a plot of log (a) vs. l/T for this
composition. This curve also exhibits three domains.
However, in the 60-65C temperature zone, the fall
of the conductivity value is much less pronounced.
These results are consistent with the previously suggested hypothesis, and with the DSC analysis reported in Fig. 5, from which the crystallinity was
determined; it was found to be lower than that of the
6Owt.% PEO, 30wt.% KOH and lOwt.% H,O
composition. On the other hand, conductivity values
of the anhydrous composition are much higher, and
such good conductivity over the whole temperature
range can be related to the high concentration of

endo

I
64 C

-1
0

20

40

60

80

100

Temperature (C)
Fig. 5. DSC curve for a 50wt.% PEO and 50 wt.% KOH
solid polymer

electrolyte
at a heating
(onset temperatures).

rate of 3Cmin-t

2452

J. F. FAUVMQUE et al.

is the positive one, and the element has thus a theoretical capacity of 1.7Ah (based on observed data in
an aqueous KOH solution). The reactions involved
in the cycling process of the element are the following:
Ni(OH), + OH-

charge and discharge curves are represented in Fig.

6a and b, respectively, showing a well-defined
plateau at 1.1 V for the discharge, and at 1.35 V for
the charge. Cycling experiments have been performed between 0.8 V and 1.6 V, at a current density
value of 2.2Am-*. The average capacity of the
element obtained up to now is 1.1 Ah, ie about 65%
of the theoretical capacity previously mentioned.
Thus, the actual capacity of the element is assumed
to be 1.1 Ah. These prospective results indicate the
rather good cyclability of both nickel and cadmium
electrodes in the 60wt.% PEO, 30wt.% KOH and
lOwt.% H,O solid polymer electrolyte. Cycling life
of this secondary battery is still under evaluation.
Prototypes of higher capacity will be subsequently
investigated, and the study will be extended to the

NiOOH + e- + H,O

dirsbarge
charge

Cd(OH), + 2e- L

Cd+20H-

discharge

Cell testing was done using a computer controlled

constant current cycler. The cycling performance for
polymer electrolyte Nickel/Cadmium cell, illustrated
by the faradic yield vs. number of cycles, and typical

1.8
a

1,7
1-6
>

1.5

194

1.3

1,2

1,l

0.9
68

10

20

30

40

Time ! h

196
a

1.5
1,4
> 1,3

0.8
0,7
66

10

15

20

2.5

30

35

Time I h

-i
0

10

15

20

25

Cycle number

Fig. 6. (a) Typical charge and discharge curves of a 60 wt.% PEO, 30 wt.% KOH and 10 wt.% H,O solid
polymer electrolyte Nickel/Cadmium cell. (b) Faradic yield vs. cycle number for a 60 wt.% PEO, 30 wt.%
KOH and 10 wt.% H,O solid polymer electrolyte Nickel/Cadmium cell.

Polymer electrolytes.

Application

2453

to nickel batteries

of 160 Ah rne2. The reactions involved in the cycling

process of the element are the following:
clWpe
NiOOH + e- + H,O
Ni(OH), + OH- L
discharpe
charge

ZnO + 2e- + H,O ,I

Zn + 20H-

disclurpe

Cell testing was performed using a CEAMID-6

type chrono-amperostat.
This element exhibits a
good discharge behaviour, even under a rate of C/8.
It was tested in cycling experiments under the following conditions: charge rate = C/16, discharge
depth = 81% of the capacity, discharge rate = C/8.
Its internal resistance value is 6 Q. At present, one of
such cells has been cycling for 60 cycles, without any
short-circuit (major problem encountered in aqueous
media). A decrease of capacity has been observed
from the 47th cycle on. The characteristic curves for
charge and discharge of the nickel and zinc electrodes prove their good cyclability, with faradic
yields up to 87%. All these results are presented on
Fig. 7ad

Time I h

I
10

15

20

25

Time / h

CONCLUSION
100,

.Q
J

40.
20.
OTd
10

*a .

20

30

40

50

l*,,
60

Fig. 7. (a) Typical charge and discharge curve of a 60 wt.%

PEO, 30wt.% KOH and lOwt.% H,O solid polymer
electrolyte-Nickel
electrode. (b) Typical charge and discharge curve of a 6Owt.% PEO, 30wt.% KOH and
lOwt.% H,O solid polymer electrolyte-Zinc electrode. (c)
Typical charge and discharge curve of a 6Owt.% PEO,
30 wt.% KOH and 10 wt.% H,O solid polymer electrolyteCell voltage. (d) Variation of the capacity vs. cycle number
for a 60 wt.% PEO, 30 wt.% KOH and 10 wt.% H,O solid
polymer electrolyte.

cyclability

of other

nickel

secondary

batteries,

such

as Nickel/Metal hydride.
A Nickel/Zinc 60wt.% PEO, 30wt.% KOH and
lOwt.% H,O solid polymer electrolyte secondary
battery has been elaborated and tested in such
medium. It has been manufactured by assembling a
central circular zinc electrode, between two nickel
electrodes.
The negative
electrode
(thickness:
2 x 10W4m and area 5 x 10m4m2) is an expanded
zinc grid, welded on each side on a cadmium drilled
sheet as collector, and has a theoretical capacity of
820Ahm-.
The positive electrodes (thickness:
10m4m and area 5 x 10-4m2) are made of nickel
hydroxide Ni(OH), , and have a theoretical capacity

It was presented a new class of solid polymer electrolytes, based on PEO and KOH, exhibiting an
unusual conductivity
vs. temperature behaviour
which can be attributed to the existence of two
phases within the electrolyte, one of these being the
conducting, high concentrated phase. At the same
time, both compositions have significant ionic conductivity values, at room temperature as well as at
high temperature. The water-containing
one can
easily be used in nickel secondary batteries, regarding the good cyclability of Nickel/Zinc and Nickel/
Cadmium cells.
Acknowledgements--The
authors thank the Agence de
IEnvironnement et de la Ma&rise de IEnergie (Ademe) and
ElectricitC de France (EDF) for financial support.

REFERENCES
1. D. E. Fenton, J. M. Parker and P. V. Wright, Polymer
14, 589 (1973).
2. M. B. Armand, J. M. Chabagno and M. J. Duclot,
Second International Conference on Solid Electrolytes, St
Andrews, paper 6.5 (1978).
3. M. B. Armand, J. M. Chabagno and M. J. Duclot, in
Fast Transport in Solids (Edited by P. Vashishta), p.
131-136, North-Holland, New-York (1979).
4. Polymer Electrolytes Reviews, Vols 1 and 2 (Edited by
J. R. MacCallum and C. A. Vincent). Elsevier Applied
Science, London (1987) and (1989).
5. M. Armand, W. Gorecki and R. Andreani, Second Int.
Symp. on Polymer Electrolytes (Edited by B. Scrosati), p.
91-97, Elsevier, Amsterdam (1990).