Int. J. Hydrogen Energy. Vol. 13. No. 3, pp. 141-I511, 1988. 0360-3199/88 $3.1111+ 0.

1~1
Printed in Great Britain Pergamon Press pie.
International Association for Hydrogen Energy.

IMPROVED COMPONENTS FOR ADVANCED ALKALINE WATER

ELECTROLYSIS
J. DWlSEK, P. MAUNOWSKI,J. MERGELAr~OH. SCHMITZ
Institute of Applied Physical Chemistry, Nuclear Research Centre Jtilich, J tilich, F.R.G.

(Received for publication 3 November 1987)

Abstract--The industrial realization of an advanced electrolysis cell for alkaline water electrolysis is gradually
achieved and semitechnical cell units were constructed. The cells work with ceramic diaphragms and
galvanically-depositedRaney nickel electrodes. The working temperature is 100-120°C and total pressure between 1
and 5 bar. The average energy consumption at 0.4 A cm -2 and 100°C is 3.8 kWh m -3 hydrogen. The influence of cell
components on total cell performance data is discussed. The variation of manufacturing parameters on the quality of
single components (electrodes and diaphragm) is considered. Corrosion problems at operating conditions and their
elimination by using proper construction techniques were investigated.

INTRODUCTION uniform throughout the literature. According to our test

The application of suitable active electrodes is important
in order to achieve a low cell voltage in alkaline water
electrolysis.For thispurposeaseriesofcatalyticmaterials
for anodes as well as cathodes has been proposed and
examined. A survey of the activity of various electroca-
talysts for anodic oxygen evolution under comparable
conditions (10 M K O H , 100°C, current density 0.1 to 1.0
A cm -2) has been published recently [1]: the lowest
oxygen overvoltage was observed for Raney nickel
electrodes made by the K F A technique [2, 3], their
activity remaining unchanged for more than 13,000 h [4].
The Raney nickel electrodes made by the K F A
technique have also proved as very effective hydrogen
cathodes [2, 3]. A high catalystic activity for hydrogen
evolution from alkaline solutions has also been found for
some combined coatings on the basis of Ni (and/or Co)
with Mo (and/or W, V, etc.). The hydrogen overvoltage
on compact molybdenum and tungsten in acidic [5] as
well as basis solutions [6] is higher than on compact
nickel, however, it is well known that even very low
amounts of Mo (6+), as well as W (6+), Cr (6+), V
(5+), etc., in the brine cause a sharp decrease of
hydrogen overvoltage on sodium or potassium amalgam
cathodes during chlor-alkali electrolysis according to the
amalgam process (e.g. Balej and Paseka [7]). This fact
has been used for an in-situ activation of amalgam
decomposers by Mo (6+ )-salts [8]. The in-situ activation
of lower active or deactivated hydrogen cathodes by low
amounts of soluble salts of Mo (6+) and/or Co (Ni) (2+)
[9.10] is based on the same principle,
Both the directly effective electrodes and the elec-
trodes which must be secondarily in situ activated, need
an appropriate carrier basis. In our laboratory, Raney
nickel was selected for this purpose. Such electrode
materials have been familiar for a long time and have
also proved their worth, although this opinion is not
141
results, the Raney nickel electrodes can be very well
used for an alkaline water electrolysis. However, a
simple and easily realizable method for producing them
inexpensively was still lacking. In our opinion, the
Raney nickel electrodes used till now and produced out
of Ni/Al-alloys by sinter techniques have for economical
reasons small chances to be applied on a large technical
scale. For this reason, a new method, namely a galvanic
deposition of a Ni/Zn-alloy was developed up to the
technicalscale.
A further important requirement in order to carry out
an advanced alkaline water electrolysis is to increase the
working temperature from the conventional 80 up to
100-120°C, which causes a decrease of electrode over-
voltage, and also a decrease of ohmic losses throughout
the cell.
Under such conditions, a commonly used asbestos
diaphragm is no longer stable enough in a hot K O H
solution and in addition, for mechanical reasons, it is
usually several millimeters thick causing too high a
voltage throughout the cell.
Thiner asbestos diaphragms, for example 0.5 mm
thick, result in poor gas purities. Therefore, a develop-
ment of a new, proper separator is necessary.
A wide range of different materials on an organic,
inorganic and combined basis were tested. Especially
favourable seems the use of a fine porous, screen
supported diaphragm on an inorganic oxide basis which
is not hydrophobic and allows therefore a "zero gap"
construction of an electrolytic cell. Different oxidic
materials were investigated, considering primarily the
chemical stability in hot KOH.
NiO was chosen because of its excellent chemical
stability in hot K O H , unique physicalproperties and the
simple procedure of producing a diaphragm out of this
material [2, 11].
142 J. DIVISEK. P. MALINOWSKI, J. MERGEL AND H. SCHMITZ

3O

], o I I : "~..~ I I I I
E - I00 - 200 - 300 - 400 - 500 - 600 -700 - 800 - 900 - I000 - I I00 - t200

pH-2.5

_.o ....... \\
-9o 5oo,,., \',~ A/'~,z.-3,.
--120

Fig. 1. Current-voltage curves of alloy components.

ELECTROCATALYST PRODUCTION hibits the access of Ni2+-ions to the cathode. The supply
of the Zn2+-ions which are being discharged from the
Raney nickel produced by galvanic deposition is adsorption layer can only occur through diffusion from
applied as an electrocatalyst. Because of the deposition the bulk solution. When already in the adsorption
potential, Zn instead of AI is used as a leachable layer, discharged Zn2+-ions are not replaced quickly
component. As a second component which stays stable
after activation process, Ni, Co or Fe or their combina- enough, their inhibitory action decreases and the Ni
content in the alloy increases. This means, that during
tions can be deposited galvanically. In Fig. 1, the the simultaneous deposition of both ions, the rate of the
current-voltage curves of the alloy components Ni, Co
and Zn, measured on the rotating disk electrode are transport phenomena plays an important part in deter-
presented. With a simultaneous addition of Zn, the mining the alloy composition.
Without discussing all the practical consequences of
extensive inhibition of the Ni and Co deposition takes those phenomena, one of the resulting aspects is that the
place, Ni being stronger inhibited than Co. At the same
change of mass transport conditions obtained through
time,. the preferred
. . Zn deposition
. leads to Zn-rich,+alloys, changes of the Prandtl layer (hydrodynamic boundary
obtamed at such potentials, which m pure Zn- -solutton
correspond to anodic dissolution. This inhibition of the layer) is effective only in certain potential range espe-
cially at more negative potentials. This dependence is
cathodic discharge of Ni compared to this of Zn is well shown in Fig. 3.
known and described in the literature [12]. This abnor-
mal behaviour was interpreted in different ways. We
believe, that the theory of alloy formation with the Table 1. Activity ofelectrodeposited Ni-Zn alloys according to
decreased activity of single components [13] for the E(~) =-(RT/2F) ln az.(.~.oy)
Ni/Zn system is the most probable one. A direct
verification of this theory can be found in measurements xn~ Xz, In an~ In az,
of rest potentials of Ni/Zn alloys with a different
composition against pure Zn as a reference electrode in 0,00 1,00 0,0
an arbitrary solution of ZnZ+-ions (Fig. 2). Such 0.04 10.96 -258,996 - 1,532
measurements were carried out by different authors 0,06 0.94 -255,621 - 1,609
[14--16] and showed a defined qualitative dependence of 0,09 0,91 - 94,351 - 14,937
the rest potential value on the alloy composition. From 0,15 0,85 - 14,913 -24,576
these values, the activity of Zn in an alloy as referred to "0,20 0,80 - 13,343 -24,896
the activity of pure Zn (az, = 1) was calculated with the 0,30 0,70 - 4,762 -26.817
help of simplified Nernst equation [16]. It could be 0,40 0,60 - 4,312 -26,911
shown, that the Zn activity in the alloy has very low 0,50 0,50 - 3,122 -27,570
0.60 0.40 - 2.881 -27.960
values, especially in the range of the a and y phases 0.70 0.30 - 1.947 -29.869
(Table 1). It seems that the strong formation of the 0.8O 0.20 - 0.798 -33.289
intermetallic compounds is responsible for this effect. 0,85 0,15 - 0,541 -35.277
A further phenomenon during the simultaneous dis- 0,90 0,10 - 0,198 -37,133
charge of Ni and Zn ions and formation of Ni/Zn alloys is 0.95 0.05 - 0.070 -39.374
the strong specific adsorption of Zn-'+-ions which in- 1.00 0,00 --
 A D V A N C E D ALKALINE WATER ELECTROLYSIS 143

600 --

O
1.6 -

-'- 2
~ 1.5- I
200 LLI

2'
,'
I __ T
o 50 Joo 1.4
tool % Zn I I I
80 I00 120
Fig. 2. Rest potential of a cell (Ni-Zn)(s)/Zn2+(aq)/Zn(s) as a T (°C)
function of alloy composition.
Fig. 4. Temperature dependence of the/R-free voltage of a
zero-gapJmodel cell at j = 1 A c m - : (1,2) and j = 0.4 A c m -2
(1',2'). Anodes: Raney-nickel (KFA), cathodes: Ni/Mo
(therm.) (2,2'), Raney-nickel (KFA) (1,1'). Electrolyte: 10M
KOH.
I00 --

~ After 6150h
zo ~ loo k ~ ~, ~, ~
I • • -"'- i~-nm V

6o /,
0 I l t ._o t ekectrode
"o 20
O.OlO 0.01~ 0.020 0
e-

--~F,r (ore) ~ I I I 1 I
O 0 2OOO 4000 6000 8000 I0,000
Current denslty ( A . m -z)

ioo
Fig. 5. Time stability of a Raney-nickel cathode at 100°C in 10
M KOH (geometrical active area: 200 cm2).
O
/ o (~ g

~ ~0
~ o " ELECTROCATALYST PERFORMANCE
* "'///~ T h e c o m p a r i s o n of t h e catalytic activities b e t w e e n t h e
o o * R a n e y nickel c a t h o d e s a n d t h e n i c k e l - m o l y b d e n u m
O
, , , c a t h o d e s , b o t h of t h e m p r o d u c e d in o u r l a b o r a t o r y , is
o o.o~o o.ol5 o.ozo s h o w n in Fig. 4.
apt (cm) T h e m e a s u r e m e n t s were c a r r i e d o u t in a " s a n d w i c h "
cell with a " z e r o g a p " b e t w e e n the e l e c t r o d e s a n d t h e
d i a p h r a g m in o r d e r to o b t a i n p r a c t i c e - o r i e n t e d results.
Fig. 3. Alloy composition as a function of Prandtl layer at In all cases identical R a n e y nickel a n o d e s were used, so
different deposition potentials: (1) - 1150 mV. (2) - 9 0 0 m V , t h a t t h e s t a t e m e n t is c h a r a c t e r i s t i c only for t h e c a t h o d e s .
(3) - 1050 mV (vs SCE). T h e c u r r e n t densities w e r e 1 A cm -~" a n d 0.4 A cm -2
144 J. DIVISEK, P. MALINOWSKI, J. MERGEL AND H. SCHMITZ
400 -

N~ I ~E 200300-- ~ ............:...................21

I I I I I
0 2000 4000 6000 8000 I0,000
Currentdensity(A.m-z)
Fig. 6. Anodic overvoltage of different electrodes: (1) Raney-nickel (Ni/Zn), (2) spinel (Co30~, NiCo_,O4)
or perovskit (LaNiO3, L a o , s S r o . s C o O 3 ) , (3) perforated Ni plate or roughed expanded Ni gauze.

IOM KOH, IO0°C

400 200
400 400mA/cm 2 400mA/cm 2
v . w q

lOb on, 14h shut lob on, 14h shut

480 •- ' e - o • • °'"° •

0
460 --
"1-
"~ 440 --

E
-geo ..
p ~, 0 ,~e o I

- IO00 -
la.J
-~1020 ~...~ • a~.o.-~O~o..~.o/e~°~°''~°
°O ° • t .-..,~O~....O..,..,,e,..~O~O....,.O..~O~o o~O ~
-- 1 0 4 0 ,,~

-- 1 0 6 0 -
I I I I I I I I
0 900 1800 2700 3600 4500 5400 6300 7200
t(h)
Fig. 7. Time stability of Raney-nickel electrodes during the stimulated day/night cycle.

respectively. The nickel-molybdenum cathodes are bet-
ter than the Raney nickel ones at temperatures below
100°C. The Raney nickel cathodes have on the other
hand a more pronounced overvoltage-temperature de-
pendence so that at 100°C a cross point is reached and at
even higher temperatures the Raney nickel cathodes are
slightly better,
The long time stability of the cell voltage under
working conditions for 6000 h has been already demons-
trated [17].
The cathodic potential examination shown in Fig. 5
confirms the already demonstrated potential stability of
the cell. According to this measurement, the change of
the cathodic potential after 6000 h of operation time
amounted to 10 mV, although some corrosion produces
such as Fe, Cr or Mn were detected on the cathode
surface with help of E D A X analysis (energy dispersive
X-ray analysis). The anode shows similar long time
stability as the cathode.
A comparison of anodic activities of Raney nickel,
spinel and perovskite electrodes measured by Balej [1] is
shown in Fig. 6. Because of the high number of single
measurements that were carried out, full ranges instead
of single curves are given.
 ADVANCED ALKALINE WATER ELECTROLYSIS 145
IOM KOH, 100~3 continuous
operation
t
330 ~-- ~ _ ~
320 r-- • ~°~°~•~'•/•~•~•~•-I • o.~• • o..• • •
310 r /
o ~oo I" /
.= 2~o l-

r, -86o [-
-870h •-0- ..o-'* * °"•/0 *
E _cool_ .'• • ...•.•..•_•/
-890 r
-900 r
-910 r
--920 r
o-- t I I I I 1 I I

I 2OO
J 180
Etectrotyte 160
e/o~e~ ,e~O~O~O~' s•~°~° .,..._.___.__.o_._._....-.e -- 140 "~

I00 N
u 40 80 ~
30 Cothode -- 60
20 • • -- 40
I0 Anode --1 20
I U I "I J
0 900 1800 2700 3600 4500 5400 6300 7200
t (h)

Fig. 8. Rest potentials of Raney-nickel electrodes and zinc content in the electrodes and in the electrolyte
as a function of time.

I
The demonstrated results were obtained during con- to4:
tinuous performance, which was a standard procedure in
practice, and published in literature. One of the possible g
of carrying on the advanced water electrolysis in ~ "
waySthenear future could incorporate the use of solar '~ ~
energy. This operation mode requires a discontinuous ~"
day/night working cycle which represents an extremely E o• s ~ •
severe operating condition. For this reason, the Raney- ~ "~'~~ : . . . . .
nickel electrodes were tested at first in a monopolar cell "a
under simulated day/night cycle for 7000 h and the
results are shown in Fig. 7. O
The cell was operated for 1 0 h a t 4 0 0 m A c m -2and o• 2 _ , , t .... ~ , , ,
100°C in 10 M K O H and subsequently shut down for 14 h s 0o 5o
each day. Approximately 300 interruptions were carried p,w,
nlcket oxide
mot % Me•= (Me-TI, Zr) pure
tltonate
out during this operation.
Figure 8 shows the rest potentials of both electrodes Fig. 9. Corrosion rate as a function of composition for NiO
measured each day one hour before restarting the cell. diaphragms with ZrO2 and TiO2 additives (10 M KOH, 120°C,
The cathodic potential values can be correlated with the 20,000 h).
146 J, DIVISEK, P. MALINOWSKI. J. MERGEL AND H. SCHMITZ

NIO Diaphragm (btack spot)

06/8/50985

4000 3o~o ao'oo ,sbo ,o6o 560

~'(cm-O

Fig. 10. Infrared spectra of NiO with a thin layer containing excess of oxygen and of standard original
sample of NiO.

decreasing zinc concentration in the cathode. The where z < < 1.

stability of these potentials will be further improved. In a
bipolar cell, the catalyst must be protected by protective
voltage during shut-downs,
I N F L U E N C E O F A D D I T I V E S ON C H E M I C A L
S T A B I L I T Y O F NiO IN K O H
Besides pure NiO, the influence of some additives on
chemical stability of the diaphragm was investigated,
These additives were introduced to the original Ni
powder either as a metal powder or as an oxide
according to the following reaction schemes:
yz+ 1
x z Me + Ni + . - - - - - 7 - O~--, (Me,Or), (NiO)l (1)
. . . .
z MexOy + Ni + V2 02 ---, (MexOy)~ (NiO)l (2)
The mixed oxide formed possesses different prop-
erties than pure NiO structure (called "first generation"
diaphragm), mainly when the Gibbs energy A G of the
reaction:
Me~Oy + NiO ~ Me,Oy NiO (3)
has a negative value at manufacturing temperature of
1000°C so that a new chemical compound and not only a
mixture of substrates is formed, which can be clearly
identified with X-ray powder diffractometry. This differ-
ence can be demonstrated when using ZrO2 and TiO2 as
additives.
The Gibbs energy A G of the reaction:
ZrO2 + NiO ---, Z r O : NiO (4)
has a positive value at 1000°C, which implies that this
reaction does not take place during manufacturing
procedure. X-ray analysis identifies two separate
phases; namely those of NiO and ZrO2. For this reason
 ADVANCED ALKALINE WATER ELECTROLYSIS 147

~ I. Anode
[[ 2 DiaDhrogm-anodic side (bLack/gray spots]
II 3. Diaphragm-cathodicside (bLock/gray spots]
t I t 4" ~:th~de dlophrocjm

4.

.
Q
- /
/t \

A/'t
150 5SO 950 1350 1750

Roman shift (am-*)

Fig. 11. Raman spectra of the surface of different cell components.

the chemical stability of such doped NiO diaphragm
stays unchanged and is further determined by the
solubility of NiO in K O H since the solubility of pure
ZrO_- is comparable with this of NiO.
On the other hand, the Gibbs energy of the reaction:
TiO, + N i O - - , NiTiO3 (5)
has a negative value of A G l ( ~ ° = - 2 6 . 3 kJ m o l - l , so
that these two oxides react with each other during
diaphragm manufacturing procedure, forming a new
mixed oxide as determined by X-ray analysis. There-
fore, the solubility of NiO diaphragm can be influenced
by different additions of TiO2 as shown in Fig. 9.
Its stability reaches a maximum (minimum of the
corrosion rate) with an addition of 5 wt% TiO2 and
decreases with an increasing TiO2 content. Already with
20 wt% of TiO, the stability of such NiO-doped
diaphragm reaches this of a pure titanate (50 mol %
TiO2). The corrosion rate of pure NiO indicated on the
left-hand side of Fig. 9 corresponds to a total weight loss
of 2% after 20,000 h in 10 M K O H at 120°C.
This result was confirmed in another experiment
where under electrolysis conditions (10 M K O H , 120°C,
0.4 A cm -2, 15,000 h) the weight loss of pure NiO
diaphragm was negligible. The corrosion rate of pure
titanate is five times higher than that of pure NiO.
The further additives of such elements as Cr, Al or W
in metallic or oxidic form resulted in production of
corresponding mixed oxides but did not change the
overall properties of an NiO diaphragm.
I N F L U E N C E O F P R O D U C T G A S E S ON
P R O P E R T I E S O F NiO D I A P H R A G M
A n o t h e r possible property of the NiO diaphragm is
148 J. DIVISEK, P. MALINOWSKI, J. MERGEL AND H. SCHMITZ
~ , ~ oxidized layer is negligible. The results of the above
Ior
~oa
cl u,us~ | NiO particle of about 0.01--0.03 ~tm is affected by the
io6 ---¢-after t ozs-~oo
~
u I0 r . . L etectrotys|sJ
- ~,,.~ T NiOi.5-l.s. This was confirmed by the Laser-Raman
o ~
"~ ~ =05 - ~
~o6 U~d ) spectra representing the surface of the anode and of the
•r- [ ~ ~ a,ter jN=O
~= Io'
I°s etectrotyas
jo3 I I I I I I
z o 4o 60 eo loo
T I'C)
Fig. 12. Electrical resistance of NiO based diaphragms as a
function of temperature and composition,
the possible interaction of its surface with the product
gases, H2 and 02. It is well known that NiO can be
reduced with H2 under certain conditions (enhanced
temperature and PH2)- The reduction stability of NiO
was already presented [17]. The other influence of a NiO
diaphragm is the chemisorption of oxygen with its
subsequent mounting into the NiO-lattice. This reaction
produces in case of p-semiconductors (such as NiO)
electron vacancies which lead to an increase of electrical
conductivity.
Chemisorption of oxygen as a surface reaction takes
place even at electrolysis temperature of 100-120°C.
The following step, three-dimensional outward lattice
expansion and simultaneous formation and migration of
Ni vacancies, is related to higher temperatures.
The green NiO diaphragm becomes black after 20 h in
an open laboratory cell without separate electrode
compartments and with an anode in direct contact with a
diaphragm and a separated cathode. Gravimetric analy-
sis shows a clear weight increase of a black diaphragm,
After a short thermal treatment of 10 rain in air
atmosphere at 1000°C the desorption of 02 is complete
and the diaphragm reaches its original weight and green
colour,
In another experiment, the black NiO diaphragm was
treated with hydrochloric acid. Already after few
seconds, the diaphragm became green again, implying
that only the thin surface layer removed carried a surplus
oxygen. The weightdecreaseamounts to approximately
1.5-2 %. Analytical determination of oxygen content in
black NiO was carried out by hot extraction method
[18]. The results imply an oxygen excess yielding a
composition of NiO1.03-t.07 when related to the total
mass of NiO. The infrared spectra shown in Fig. 10
represent bulk analyses of the oxidized and unchanged
samples of NiO, respectively. The similarity of both
spectra points out that even the oxidized nickel oxide
consists in total volume of NiO and the total mass of the
experiments when considering the true diaphragm sur-
face, lead to a conclusion that only a very thin laver of an
oxidation, but its true composition is in the range of
Spectroscopy. Figure 11 shows Raman spectra of the
surface of ciifferent cell components. The first three
anodic and cathodic side of the diaphragm are identical
and contain only the peaks of Nil+3). The next spec-
trum presents the surface of the cathode and is charac-
teristic for metallic Ni. As comparison, the last spectrum
shows the surface of the NiO diaphragm in its original
state. It means, that under certain conditions the
diaphragm could be oxidized during the electrolysis
process.
The electrical resistivity of such oxidized samples
decreases as compared with green NiO as shown in Fig.
12. The temperature dependence points out the nonme-
tallic semiconducting nature of the samples.
The addition of oxides with cations of valence higher
than 2+ causes a destruction of electron vacancies.
Consequently, the oxidation process is largely inhibited.
For these reasons, the electrical conductivity of NiO
sample decreases when mentioned oxides are added.
Figure 12 shows also the electrical resistivity values of
such diaphragms of the DIS-100 series (DIS = DI-
aphragm Stabilized). As can be clearly seen, their
, electrical resistance is considerably higher than this of
pure NiO.
NiO B A S E D D I A P H R A G M AS A C O M P O N E N T
O F AN A D V A N C E D E L E C T R O L Y S I S CELL
In order to reach a cell voltage of 1.5 V at technical
current densities of approximately 0,5 A cm -z, the
diaphragm-electrodes configuration should be arranged
in a "sandwich" manner with a "zero-gap" distance
between the electrodes and the diaphragm. This con-
struction is possible when a thin, mechanically stable,
nonhydrophobic diaphragm is used, allowing a direct
contact with gas-evolving electrodes without any prac-
tical losses as shown in Fig. 13. The advantages of such
configuration and NiO diaphragm can be seen in re-
latively small ohmic losses resulting in small vottage loss
throughout the cell. In Fig. 14, when considering the
values of (U~e,- Um rre~) as a function of time, a voltage
loss of about 75 mV is measured with a current
interruption technique in a "sandwich" electrolytic cell
working in 10 M K O H at 100°C and a current density of
0 . 4 A c m -z. Approximately half ofthisvalue is ascribed
to the diaphragm, the rest being caused t h r o u g h a
gas-bubble effect and electrolyte resistivity. In this
experiment, the DIS-100 diaphragms were used as the
separator. The achieved totalcell voltage corresponds to
an energy consumption of 3.8 kWh m -3 hydrogen.
Depending on the construction materials more or less
 ADVANCED ALKALINE WATER ELECTROLYSIS 149
pronounced corrosion problems have to be considered
in a system when carrying out an advanced alkaline
water electrolysis.
Elimination of those problems can be achieved
through the specific technological construction form of
the electrolysis cell and through the application of the
construction materials with higher Ni content.
Considering the construction improvements, a special
microspacer technology was developed. The spacer
keeps the electrodes away at a distance of approximately
100-200 ~tm. This distance is, macroscopically speaking
so small that it cannot be practically differentiated from
the "zero-gap" construction and it also does not cause
any additional increase of the cell resistance.
Under this aspect, it seems very important that both
diaphragm and electrodes keep their dimension and
form stability in order to optimize the electrode distance
from the diaphragm. Form stable ceramic diaphragm on
NiO basis seems especially suitable for this purpose.
The second method to minimalize the corrosion
problems is the use of appropriate construction mate-
rials. It seems that steels with at least 20-30 wt% Ni are
necessary in order to carry out the advanced alkaline
water electrolysis at a temperature level of 100-120°C.
In combining both mentioned aspects, one obtains an
electrolytic cell built in a "sandwich" manner with a
"zero-gap" distance between the electrodes and the
diaphragm (practically 100-200 ~tm spacer) that works
over a long period of time with a constant cell voltage of
1.5-1.6 V at 100°C and 0.4 A cm -2.

Acknowledgements--The authors are grateful to Dr E. Koglin

for carrying out the Laser-Raman analyses and to Dr J.
Fig. 13. Zero-gap sandwich consisting of NiO diaphragm and Rottmann from the Institute of Reactor Materials for the
Raney-nickel electrodes (magnif. 60 ×). sample analyses by the hot extraction method.

1.60

1.58

1.56 ~ ~ ~

,.54

1.52
o>
¢ 1.50
U 1.4e \ \ [ ~ " ~ ~I~.,~. ~ ~ ~ 4~'"~"
I R - c l ~"r e c t ~

1.46

I.a4 I I I I
500 I000 1500 2000
Time (h}

Fig. 14. Cell voltage (total and /R-free) as a function of time (10 M KOH, 100°C, 0.4 A cm-2).
150 J. DIVISEK, P. MALINOWSKI, J. MERGEL AND H. SCHMITZ
REFERENCES
1. J. Balei, Int. J. Hydrogen Energy 10, 89 (1985).
2. J. Divisek, H. Schmitz and J. Mergel, Chem.-Ing.-Tech. 11.
$2,465 (1980).
3. J. Divisek, J. Mergel and H. Schmitz, Int. J. Hydrogen 12.
Energy 7, 695, (1982). 13.
4. J. Divisek, P. Malinowski, J. Mergel and H. Schmitz,
Electrolytic Hydrogen Production by Means of Improved
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