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ington, D.C. (1961). 26. G. W. Dini, Metal Finish., 61(7), 52 (1963).

14. H. A. Laitinen, C. H. Liu, and W. S. Ferguson,
Anal. Chem., 30, 1266 (1958).
15. G. Torsi and G. Mamantov, J. Electroanal. Chem.
Interracial Electrochem., 30, 193 (1971).
16. G. W. Jernstedt, Proc. Am. Electroplating Soc., 36,
63 (1949), and 37, 151 (1950).
17. G. W. J e r n s t e d t et al., U.S. Pat. 2,451,340 (1948);
2,451,341 (1948); 2,470,775 (1949); 2,524,912
(1960) ; 2,575,712 (195I) ; 2,636,850 (1953);
2,678,909 (1954).
18. J. Teres, M.S. Thesis, Ohio S t a t e U n i v e r s i t y (1950).
19. N. W. Hovey, J. L. Griffin, and A. Krohn, This
Journal, 102, 470 (1955).
20. G. T. Bakhvalov, Izv. Vyssh. Uchebn. Zaved.
Tsvetn. MetalL, 3, 136 (1958).
21. P. M. Walker, N. E. Bentley, and L. E. Hall, Trans.
Inst. Metal. Finish., 32, 349 (1955).
22. N. A. Marchenko, L N. Lekhovitskyi, a n d A. N.
Buyanova, Zhur. Priklad. Khim., 31, 1511 (1958).
23. A. M. Yampolsky, Electroplating Metal Finishing,
16 (3), 76 (1963).
24. A. Hickling and H. P. Rothbaum, Trans. Inst. Metal
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25. G. A. Conn, Plating, 56(9), 1038 (1969).
27. G. T. Bakhvalov, "New Technology of E l e c t r o d e p o -
sition of Metals," Izd. Met., (in Russian) (19@6).
28. M. Ceresa, in "Electroplating Engineering H a n d -
book," 3rd ed., A. K. Graham, Editor (1971).
29. D. Rossi, Galvanotechnics, 793 (1953).
30. V. I. Cherenko et al., Elektrokhimiya, 4, 519 (1968).
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of Electrochemistry," Vol. 7, B. E. Conway and
J. O'M. Bockris, Editors, P l e n u m Press (1972).
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42, 364 (1977).
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(1967).
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ibid., 115, 507 (1968), and 116, 1503 (1969).
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ham, Editors, A c a d e m i c Press (1976).

Electrodes for Alkaline Water Electrolysis

D. E. Hall*
Inco Research & Development Center, Incorporated, Sterling Forest, Su~ern, New York 10901

ABSTRACT
Electrodes for a l k a l i n e w a t e r electrolysis have been m a d e b y a p p l y i n g high
specific surface a r e a coatings of nickel or n i c k e l - i r o n alloy to steel or nickel
substrates. The coatings are a p p l i e d as p o l y s i l i c a t e - b a s e d paints contain-
ing particles of the desired metals. The coating is sintered into a porous
s t r u c t u r e which is b o n d e d firmly to the substrate. The p r e s e n t electrode
p r e p a r a t i o n m e t h o d has been used to coat a v a r i e t y of s u b s t r a t e forms,
such as flat plates or w i r e screens, a n d is c o m p a t i b l e w i t h c o m m e r c i a l
alkaline electrolysis equipment. The r e s u l t i n g electrodes w e r e found to
be p a r t i c u l a r l y effective as anodes for oxygen evolution. The efficiency
of the electrodes was g r e a t l y influenced b y coating microstructure. This
microstructure, in turn, could be controlled b y a d j u s t i n g the sintering
conditions. Electrochemical o p e r a t i n g characteristics of the electrodes in 30
w / o K O H at 80~ were determined. C o m p a r a b l e o x y g e n evolution efficiencies
w e r e o b t a i n e d w i t h coatings m a d e from n i c k e l powders, n i c k e l flake, a n d
n i c k e l - i r o n a l l o y powder.

H y d r o g e n has been p r o d u c e d c o m m e r c i a l l y b y alka- defined as the ratio of its r e a l surface a r e a to its a p -

line w a t e r electrolysis for m a n y years. Recent indica-
tions are t h a t significant i m p r o v e m e n t s can be m a d e
in the electrolysis efficiency of practical cells (1). Thus,
despite advances in other electrochemical h y d r o g e n
production methods (2), much r e s e a r c h continues to
be done in a l k a l i n e w a t e r electrolysis to i m p r o v e effi-
ciency and develop m o r e d u r a b l e cell m a t e r i a l s (3).
T h e r e are s e v e r a l approaches to i m p r o v i n g the effi-
ciency of a l k a l i n e w a t e r electrolysis. Raising the elec-
trolysis t e m p e r a t u r e , for example, lowers the voltage
r e q u i r e d to m a i n t a i n a g~Ven cell c u r r e n t density (4).
I m p r o v e m e n t s in cell design, s e p a r a t o r structures, a n d
materials, etc., will also contribute to b e t t e r cell p e r -
formance. W h a t e v e r advances a r e made, it will r e m a i n
necessary to develop electrodes, c o m p a t i b l e w i t h the
system design and o p e r a t i n g conditions, which will give
the lowest possible overpotentials. This can be achieved
b y two methods, which can sometimes be combined for
m a x i m u m benefit. In the first, c a t a l y t i c a l l y active m a t e -
rials such as NiCo204 (5) are a p p l i e d to the electrode
surface. The second m e t h o d involves g r e a t l y increasing
the electrode surface a r e a (i.e., its "roughness factor,"
* Electrochemical Society Active Member.
Key words: alkaline water electrolysis, electrodes.
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parent, or geometric, a r e a ) , t h e r e b y l o w e r i n g the real
c u r r e n t d e n s i t y a n d the associated activation over-
potential.
Efficiency gains, as a rule, m u s t be b a l a n c e d against
the a d d i t i o n a l capital cost i n c u r r e d (6). F o r this r e a -
son, w o r k continues to be done to minimize o x y g e n
and h y d r o g e n overpotentials on i n e x p e n s i v e electrode
m a t e r i a l s such as nickel (7) and nickel alloys (8, 9),
which are the least expensive electrode m a t e r i a l s c u r -
r e n t l y k n o w n that can be used as b o t h anodes a n d
cathodes. These m a t e r i a l s function most efficiently
when f a b r i c a t e d as high surface a r e a electrode forms.
Because the electrode structures used in c o m m e r c i a l
a l k a l i n e electrolyzers vary, it is desirable to have a
m e t h o d of increasing the surface area w i t h o u t r e g a r d
to w h e t h e r the electrode is a c o r r u g a t e d or fiat plate,
w i r e cloth, or a combination of these or o t h e r s t r u c -
tures. This p a p e r reports the d e v e l o p m e n t of such elec-
trodes, in which a high surface a r e a coating is a p p l i e d
to m e t a l substrates, using a p a i n t containing p a r t i c u l a t e
nickel or n i c k e l - i r o n alloys. A l t h o u g h nickel, nickel-
iron alloy, and steel substrates have all b e e n used to
p r e p a r e electrodes, the p r e s e n t p a p e r is concerned
m a i n l y w i t h coatings on steel sheets a n d nickel screen.
 Vol. 128, No. 4 WATER ELECTROLYSIS
The coated steel sheets a r e i n t e n d e d for use p r i m a r i l y
in low t e m p e r a t u r e (T -----80~ electrolysis c h a r a c t e r -
istic of today's c o m m e r c i a l practice.
Experimental
Electrode coatings w e r e p r e p a r e d using p o l y s i l i c a t e -
b a s e d paints, in w h i c h t h e m e t a l p a r t i c l e s described
b e l o w w e r e suspended. The p a r e n t n i c k e l powders,
k n o w n c o m m e r c i a l l y as Inco T y p e 123 and Inco Type
287, are high p u r i t y p o w d e r s p r e p a r e d b y the t h e r m a l
decomposition of n i c k e l t e t r a c a r b o n y l (10). These p o w -
ders a r e r e f e r r e d to in this p a p e r as "Ni 123" a n d
"Ni 287," respectively. T h e i r surfaces are h i g h l y s p i k y
and angular. T h e specific surface a r e a of Ni 123 is
~0.4 m2/g and t h a t of Ni 287 is ~0.6 m2/g. Using these
values, a t y p i c a l N~ 123 coating 50% dense a n d 100 ~m
t h i c k w o u l d p r o v i d e a m a x i m u m surface roughness
factor of about 180 to a coated electrode. A n i c k e l - i r o n
a l l o y p o w d e r (37% Ni), s i m i l a r in s t r u c t u r e to Ni 123,
and a nickel flake p r o d u c e d b y b a l l m i l l i n g Ni 123
p o w d e r were also used.
The coatings w e r e a p p l i e d to flat panels of A I S I 1008
steel which h a d b e e n s a n d b l a s t e d to i m p r o v e coating
adhesion. The m e t a l - c o n t a i n i n g paints w e r e s p r e a d
o v e r the steel surfaces w i t h d r a w b a r s ; coating t h i c k -
ness was v a r i e d b y using d r a w b a r s w i t h different gauge
w i r e wrappings. Coatings w e r e also a p p l i e d to n i c k e l
w i r e screen, an electrode f o r m found in some c o m -
m e r c i a l electrolysis units. The nickel screen was 20
mesh , w i t h a w i r e d i a m e t e r of 0.38 millimeters. Screens
w e r e i m m e r s e d in the polysilic,ate p a i n t a n d then
s h a k e n to r e m o v e a n y excess p a i n t w h i c h filled the
spaces b e t w e e n a d j a c e n t wires. R o l l e r - a n d s p r a y -
coating of screens w e r e also used.
The coatings w e r e d r i e d and then sintered in a
c r a c k e d a m m o n i a a t m o s p h e r e at selected t e m p e r a t u r e s
b e t w e e n 760 ~ a n d 980~ for 5-60 min. Exact sintering
conditions f o r p a r t i c u l a r electrodes are given in the
text. Coating thicknesses w e r e d e t e r m i n e d from p h o t o -
m i c r o g r a p h s of polished electrode cross sections. Coat-
ings less t h a n ~,125 ~m thick w e r e uniform; t h i c k e r
coatings on the flat steel panels showed broad, s h a l l o w
striations caused b y the w i r e w r a p p i n g s on the d r a w -
bars. The a v e r a g e thickness was used for analysis of
the e x p e r i m e n t a l results.
Electrodes w e r e m a d e f r o m t h e coated steel panels
and n i c k e l screens b y cutting t h e m to a p p r o p r i a t e
size a n d t a c k - w e l d i n g a nickel w i r e to each. The w i r e
was i n s u l a t e d w i t h e p o x y resin. The b a c k and edges
of each coated steel p a n e l w e r e also coated, w i t h e p o x y
l a p p e d over the front (coated) side of the p a n e l to
p r e v e n t direct contact of the u n c o a t e d steel w i t h the
electrolyte solution d u r i n g electrochemical e x p e r i -
ments. The geometric areas of finished electrodes w e r e
t y p i c a l l y 3-7 cm 2.
The structures of the electrode coatings w e r e e x -
a m i n e d using p h o t o m i c r o g r a p h s of polished electrode
cross sections. In addition, t h e coating surface s t r u c -
t u r e and the morphologies of i n d i v i d u a l coating p a r -
ticles w e r e c h a r a c t e r i z e d b y scanning electron m i c r o s -
copy.
E l e c t r o c h e m i c a l m e a s u r e m e n t s . r a T h e electrochemical
cell used for c u r r e n t vs. p o t e n t i a l m e a s u r e m e n t s was a
straight-walled cylindrical polypropylene beaker with
a Teflon cover m a c h i n e d to fit. The cell, containing 30
w e i g h t p e r c e n t ( w / o ) K O H electrolyte, was i m m e r s e d
in a w a t e r b a t h which m a i n t a i n e d the cell t e m p e r a t u r e
at 80 ~ ___ 0.5~ A l a r g e p l a n a r n i c k e l c o u n t e r e l e c t r o d e
was positioned facing the w o r k i n g electrode, at a dis-
tance of a b o u t 3 cm f r o m it. A s a t u r a t e d calomel elec-
t r o d e (SCE) was used as the reference electrode. The
SCE was i n s e r t e d into a Luggin probe, the tip of which
was positioned at the center of the w o r k i n g electrode.
O v e r p o t e n t i a l s w e r e d e t e r m i n e d f r o m c u r r e n t vs. po-
t e n t i a l d a t a using the r e v e r s i b l e h y d r o g e n electrode
p o t e n t i a l vs. SCE in 30 w / o K O H at 80~ (9) a n d the
theoretical w a t e r electrolysis voltage at 80~ (11).
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741
The e x p e r i m e n t a l c u r r e n t d e n s i t y vs. o v e r p o t e n t i a l
d a t a w e r e then corrected for the effects of ohmic r e -
sistance using a c o m p u t e r m e t h o d d e v e l o p e d b y L e R o y
et al. (12). The Tafel slopes a n d e x c h a n g e c u r r e n t
densities r e p o r t e d b e l o w a r e b a s e d on the resistance-
corrected data. The o v e r p o t e n t i a l corrections p r o d u c e d
b y the p r o g r a m w e r e t y p i c a l l y 10-20 mV a t c u r r e n t
densities of 200 m A c m -2.
C u r r e n t d e n s i t y vs. e l e c t r o d e p o t e n t i a l m e a s u r e -
ments w e r e m a d e galvanostatically. A constant c u r r e n t
d e n s i t y of 200 m A cm -2 was i m p o s e d on each electrode
for ~ 6 hr. A t r o u g h l y 1 h r intervals, electrode p o t e n -
tials w e r e m e a s u r e d at s e v e r a l c u r r e n t densities f r o m
600 to 0.5 m A c m - 2 in descending order. The last set
of m e a s u r e m e n t s from each electrode was used for the
d a t a analysis given in this paper. Potentiostatic m e a -
surements of log i vs. E w e r e also m a d e for s e v e r a l 2.0
cm2 electrodes, in slow p o t e n t i a l - s w e e p experiments.
Because of the similarities of results from the g a l v a n o -
static a n d potentiostatic e x p e r i m e n t s , o n l y the f o r m e r
are discussed here.
Results
Nickel and Nickel-Iron Alloy Anode Coatings
Coating s t r u c t u r e . - - T h e coatings p r e p a r e d from Ni
123, Ni 287, and n i c k e l - i r o n a l l o y p o w d e r s consist of
porous n e t w o r k s w i t h unit p a r t i c l e d i a m e t e r s c h a r a c -
teristic of the p o w d e r s used to m a k e them. F i g u r e l a
shows the surface s t r u c t u r e of a t y p i c a l coating on a
m i l d steel sheet. The cross section of this coating,
shown in Fig. lb, indicates t h a t the s t r u c t u r e is quite
u n i f o r m from the base of the coating to its surface.
P o r o s i t y pockets w i t h d i a m e t e r s s e v e r a l times l a r g e r
than the particles themselves are s p r e a d e v e n l y t h r o u g h
the coatings.
Nickel flake coatings, a p p l i e d to m i l d steel panels,
have a l a m i n a r s t r u c t u r e in which the flakes a n d the
porous channels b e t w e e n t h e m are p r e f e r e n t i a l l y
o r i e n t e d p a r a l l e l to the steel base. This s t r u c t u r e is
shown in Fig. lc.
E l e c t r o c h e m i c a l c h a r a c t e r i s t i c s . - - O v e r p o t e n t i a l s for
o x y g e n evolution (~o2) at the high surface a r e a n i c k e l
anode coatings on steel sheets are less t h a n or equal
to those at nickel anode forms such as n i c k e l - p l a t e d
steel (13), n i c k e l cloth, and nickel s i n t e r (7). Typical
c u r r e n t density vs. o v e r p o t e n t i a l d a t a for the o x y g e n
evolution r e a c t i o n (OER) at two types of nickel
p o w d e r - c o a t e d steel electrodes are plotted in Fig. 2.
Tafel slopes of ~o2 vs. log i plots w e r e g e n e r a l l y 30-40
m V / d e c a d e for the electrodes studied in this work;
slopes g r e a t e r t h a n 40 m V / d e c a d e were, however, o b -
t a i n e d at some electrode coatings sintered at the h i g h e r
end of the 760~176 t e m p e r a t u r e r a n g e used. The
a v e r a g e slope of ~35 m V / d e c a d e is c o n s i d e r a b l y lower
t h a n Lu and S r i n i v a s a n ' s v a l u e of 62 m V / d e c a d e at
smooth n i c k e l electrodes tested u n d e r identical condi-
tions (14).
The efficiency of nickel screen anodes was also i m -
p r o v e d significantly b y the nickel p o w d e r coatings. F o r
example, a coating ,~40 ~m thick was s i n t e r e d onto
nickel screen at 760~ for 30 min. The o x y g e n evolution
overpotentials at c u r r e n t densities of 100 and 200 m A
cm - 2 w e r e a b o u t 80 mV l o w e r t h a n on uncoated
nickel screen anodes.
Nickel flake coatings, sintered at 760~ for 60 rain
onto mild steel sheets h a d a l a m i n a r structure, as d e -
scribed above and shown in Fig.. lc. Despite this p r e -
f e r r e d o r i e n t a t i o n of pore channels p e r p e n d i c u l a r to
the direction of e l e c t r o l y t e p e n e t r a t i o n and gas e v o l u -
tion, the nickel flake anode coating p e r f o r m e d well.
The Tafel slope was 33 m V / d e c a d e a n d overpotentials
w e r e c o m p a r a b l e to those o b t a i n e d at Ni 123 (Table I)
a n d Ni 287 p o w d e r coatings.
N i c k e l - i r o n alloy anode coatings on m i l d steel sheets,
sintered at 760~ for 60 min, h a d c u r r e n t d e n s i t y vs.
o v e r p o t e n t i a l characteristics which w e r e n e a r l y equal
 742 J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y April 1981

Fig. 1. (a, top left) Ni 123 coating on mild steel, sintered at

760~ for 60 min (Fischer subsieve of Ni 123 powder = 3-7 ~m)
3000X; (b, top right) cross section of same coating, 3 0 0 X ; (c,
bottom left) cross section of Ni flake coating, 300 X .

to those o b t a i n e d w i t h similar Ni 123 coatings, as shown m a k e up the coating n e t w o r k , is sensitive to sintering

in Table I.
EfJect of sintering conditions on coating microstruc-
ture and anode efficiency.--The sintering conditions of
the electrode coatings, as expected, w e r e found to
have a significant effect on their o x y g e n evolution
efficiencies and microstructures. The overall s t r u c t u r e
of the porous network, shown in Fig. l a and lb, is not
g r e a t l y changed over a b r o a d r a n g e of sintering times
and temperatures. However, the coating microstructure,
i.e., the m o r p h o l o g y of the i n d i v i d u a l particles w h i c h
9 Nl 287
9 NI 123
0,25
conditions. A t low sintering t e m p e r a t u r e s , m u c h of the
particle m o r p h o l o g y is p r e s e r v e d ; however, as one
would expect, as the s i n t e r i n g t e m p e r a t u r e is raised
or the sintering time is increased, the p a r t i c l e surfaces
tend to spheroidize and the contact areas b e t w e e n
a d j a c e n t particles increase. The result is a r e d u c t i o n
in electrode surface area. This can be seen b y c o m -
p a r i n g the coating structures in Fig. 3.
To d e t e r m i n e the effects of coating m i c r o s t r u c t u r e
on the efficiency of o x y g e n evolution, nine Ni 1 2 3
electrode coatings on m i l d steel panels w e r e p r e p a r e d
as described in Table II. Coatings w e r e all a p p l i e d
using the same d r a w b a r ; the a v e r a g e thickness was
~60 #m. A f t e r sintering and p r i o r to electrode f a b r i c a -
tion, a portion of each coating was tested for adhesion
w i t h a simple t a p e test, in w h i c h cellophane t a p e was
a p p l i e d firmly to the coating and then p u l l e d away.
Coatings 5-9 successfully resisted the test, b u t succes-

# Table I. Fe-37Ni alloy, Ni flake, and Ni 123 anode coatings.

0,20
Comparison of current density vs. potential characteristics.
All coatings sintered at 760~ for 60 min
0.15

Coating 702 ( V ) at ( m A em-~)

Electrode thickness,
010 I , , I i , I i i composition #m 1 10 100 200 400
lO-a i0-2 I0-I lO o

i, A r -~
Fe-37Ni 38 0.17 0.20 0.24 0.25 0.26
Fe-37Ni 58 0,16 0,20 0.23 0.24 0.25
Fig. 2. Current density vs. overpotential for oxygen evolution in Fe-37Ni 107 0.16 0.19 0,23 0.24 0.25
30 w/e KOH at 80~ Ni 123 anode coating: 85 ~m thick, sintered Ni 123 36 0.16 0.19 0.22 0.23 0.24
at 870~ for 10 min. Ni 287 anode coating: 85 ~m thick, sintered Ni 123 64 0.16 0.19 0.23 0.24 0.25
Ni 123 112 0.14 0.18 0.21 0.22 0.23
at 760~ for 60 min. Ni flake 84 0.16 0.19 0.22 0.23 0.24

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 VoL 128, No. 4 WATER ELECTROLYSIS 743

Table II. Sintering conditions of Ni 123 electrode coatings on I I

mild steel sheets used to determine the effect of coating
microstructure on electrocatalytic efficiency 760~ I 870oC l 980oC
I TIME (rain): I
Elec- Temp, Time,
trade ~ min Microstructure (by SEM) 5 ~o 3ol 5 io 3oI 5 io ~o
I
1 760 5 "~ Most of Ni 123 structure pre- 0.30 I
2 760 1O f served. Some rounding of sur.
face spikes.
3 760 30 Substantial rounding of spikes.
0.28
4 870 5 "( Spikes lost, but particles are
5 870 10 J still angular.
6 870 30 "~ Ni 123 structure lost. Particles > 0.26
7 980 5 ~ are rounded, indistinct; inter-
8 980 10 particle contact areas are
9 980 30 large.
o o

s i v e l y i n c r e a s i n g a m o u n t s of n i c k e l p o w d e r w e r e r e -
m o v e d from coatings 4 ( m i n i m a l ) t h r o u g h 1 ( s u b s t a n -
t i a l ) . Because the r e l a t i o n s h i p of this test to the m e -
chanical s t a b i l i t y r e q u i r e m e n t s for p r a c t i c a l electro-
l y z e r anodes was not known, all coatings w e r e used as
anodes. A clear relationship b e t w e e n coating m i c r o -
s t r u c t u r e and o v e r p o t e n t i a l at a constant c u r r e n t d e n -
sity was o b t a i n e d (Fig. 4). I n c r e a s i n g the t e m p e r a t u r e
a n d / o r t i m e of the s i n t e r i n g operation, i.e., r e d u c i n g
the effective anode s u r f a c e area, caused a g r e a t e r t h a n
70 m V o v e r p o t e n t i a l increase at 200 m A c m - 2 and an
associated increase in Tafel slope b e t w e e n coatings 2
a n d 9. A n o d e 1 was an exception; it was mechanic.ally
u n s t a b l e u n d e r conditions of vigorous o x y g e n evolution.
Thus some coating m a t e r i a l was lost, causing a r e d u c -
tion in surface a r e a and a consequent increase in o v e r -
potential.
Effect of coating thickness on anode e ~ c i e n c y . - - T h e
porous, open s t r u c t u r e of the n i c k e l coatings suggests
the likelihood that the i n t e r i o r surfaces of the anode
coatings catalyze the o x y g e n evolution r e a c t i o n to some
extent. This was i n v e s t i g a t e d using Ni 123 a n d Ni 287
coatings covering a w i d e r a n g e of thicknesses. The
coatings w e r e p r e p a r e d on m i l d steel panels using
i d e n t i c a l sintering conditions (760~ 60 m i n ) . Despite
some fluctuations in the data, Fig. 5A shows t h a t an
increase in Ni 123 coating thickness f r o m 23 to 150 ~m
causes some reduction in ~o2 at a given c u r r e n t density.
F o r Ni 287 coatings (Fig. 5B), the change in ~o2 w i t h
thickness is s o m e w h a t smaller.
A n increase in coating thickness also causes an
increase in the exchange c u r r e n t density. A t the Ni 123
coated anodes described in Fig. 5A, for example, io
r a n g e d from 2.8 X 10 - s A cm -2 at the 23 ~m thick
coating to 1.9 10 - 7 A c m - ~ at the 150 ~m t h i c k
coating. The d a t a from these e x p e r i m e n t s w e r e com-
p a r e d to the b e h a v i o r e x p e c t e d a s s u m i n g t h a t the e n -
tire coating thickness h a d equal e l e c t r o c a t a l y t i c ac-
tivity, w h i c h was d e t e r m i n e d as follows.
0.22
0.20
0Js I I
I I I I I I I I I
I 2 3 4 5 6 7 8 9
ANODE
Fig. 4. ~1o2 at selected current densities, for Ni 123 coatings on
mild steel (from Table II). Effect of coating mierostructure changes
caused by variation of sintering conditions.
If the entire m i c r o s t r u c t u r a l surface of the coating
catalyzes the OER w i t h e q u a l effectiveness, the effective
surface a r e a of the electrode, Aeff, is p r o p o r t i o n a l to
the coating thickness. The e x c h a n g e c u r r e n t d e n s i t y
p e r unit effective surface a r e a is a constant, c h a r a c t e r -
istic of the e l e c t r o d e m a t e r i a l a n d the r e a c t i o n w h i c h
t a k e s place. Thus, the e x p e r i m e n t a l l y m e a s u r e d e x -
change c u r r e n t will be p r o p o r t i o n a l to coating t h i c k -
ness (x)
io = M x + B [1]
M is the slope of a plot of e x c h a n g e c u r r e n t d e n s i t y
vs. coating thickness. The B t e r m includes e x c h a n g e
c u r r e n t on accessible portions of the s u b s t r a t e surface
(if a n y ) and on the e x t r a m i c r o s t r u c t u r a l a r e a a v a i l -
able in the top l a y e r of s i n t e r e d particles; at l a r g e x
( c o m p a r e d to the surface roughness of the s u b s t r a t e
a n d the coating unit p a r t i c l e d i a m e t e r ) , B should be
m u c h less t h a n Mx.
U n d e r conditions of n e t c u r r e n t flow, t h e Tafel r e -
lationship ~ _-- a + b log i obtains. Strictly, t h e c u r r e n t
density in this equation is based on effective surface
area, a n d thus ~l o: log (//Aeff), w h e r e I is the total

Fig. 3. Hi 123 coatings on mild steel, sintered for 30 min at (o, left) 760~ and (b, right) 980~ 3000
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 744 J. E$ectrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y April 1981

0.26 effective surface a r e a of a p a r t i c u l a r electrode w i t h a

high roughness factor. This would, of course b e e x -
200mAcro -2
pected u n d e r conditions of copious gas evolution, r e -
0.24 sulting in areas w h e r e e l e c t r o d e - e l e c t r o l y t e contact is
lost. However, it is a p p a r e n t l y also true w h e n gas
blockage is n o t a m a j o r consideration, i.e., w h e n the
> 0.22 c u r r e n t d e n s i t y is low: the l i n e a r region of the Tafel
plot e x t r a p o l a t e d to o b t a i n the io value at the s i n t e r e d
cJ nickel p l a q u e anode e x t e n d e d f r o m 10-2 A c m - 2 d o w n
o 0.20 to almost 10-~ A cm -2 [Fig. 6 of Ref. (7)].
Overpotentials at 200 m A cm - 2 w e r e used in Eq. [2],
to assess coating i n t e r i o r p a r t i c i p a t i o n in the o x y g e n
0.18 evolution reaction d u r i n g copious gas formation. G o o d -
Ni 123 ness-of-fit was less s a t i s f a c t o r y t h a n w i t h Eq. [1];
I I I i I I I
correlation of Ni 287 coating d a t a w i t h Eq. [2] was
0.16
0 20 40 60 80 IO0 120 t40 poor. F o r Ni 123 coatings, the regression was significant
COATING THICKNESS,~m at about the 90% level; the coefficient D was 24 m V /
decade. If the entire coating m i c r o s t r u c t u r e p a r t i c i p a t e d
40 80 120 160 200 240 P80 e q u a l l y in the oxygen evolution reaction, the e x p e c t e d
I ~ I I I ] I decrease in ~1o2 w o u l d be e q u a l to the Tafel slope a t
Ni 123 anode coatings, or ~35 m V / d e c a d e . Thus, t h e r e
0.24
~ ~ , ~ 2 0 0 mA cm -2 B
is p r o b a b l y some pore blockage b y evolved gas, which
increases the o b s e r v e d o v e r p o t e n t i a l b y r e d u c i n g the
0.22
active anode surface a r e a a n d increasing the r e s i s t -
> ance loss w i t h i n the coating pores. This p r o b l e m is
c~ a p p a r e n t l y m o r e severe w i t h the Ni 287 coatings e x -
0 amined, and m a y be due to t h e c h a i n l i k e s t r u c t u r e of
~" 0.20
Ni 287 powder, although this was not e v i d e n t f r o m
SEM p h o t o m i c r o g r a p h s of the coatings.
O. IS
Nickel Powder Cathode Coatings
Ni 287
The electrochemical b e h a v i o r of n i c k e l cathode
0.16 coatings on m i l d steel sheets was i n t e r p r e t e d using
criteria s i m i l a r to those a p p l i e d to anodes in the p r e -
Fig. 5. ~]o2 at selected current densities: effect of coating
ceding sections. A t n o r m a l o p e r a t i n g c u r r e n t densities
thickness. All coatings sintered at 760~ for 60 rain. (A) Ni 123
(2.00 m A c m - 2 ) , cathode o v e r p o t e n t i a l s w e r e 0.1-0.2V
coatings on mild steel sheets, (B) Hi 287 coatings on mild steel
h i g h e r t h a n corresponding anode o v e r p o t e n t i a l s for
sheets.
the same coatings. Tafel slopes on Ni 123 cathode coat-
ings w e r e 130-175 m V / d e c a d e , while io v a r i e d f r o m
current. Aeff is p r o p o r t i o n a l to coating thickness, a n d 1.6 X 10 -4 to 3.4 X 10 -4 A cm -2. On Ni 287 coatings,
thus Tafel slopes r a n g e d from 134 to 167 m V / d e c a d e , w i t h
~]o~ ----C -- D log x [2] most b e t w e e n 134-144 m V / d e c a d e . The exchange c u r -
w h e r e D is the slope of a plot of ~]o2 vs. -- log x, and r e n t d e n s i t y v a r i e d f r o m 8.8 10 -5 to 4.2 10 - 4 A
C is a constant. This equation, like Eq. [1], will be cm -2. The h i g h e r exchange c u r r e n t densities a r e com-
valid for coating thicknesses g r e a t e r t h a n s e v e r a l unit
particle diameters. 20
Regression fits of e x p e r i m e n t a l d a t a from the anodes
of Fig. 5 to Eq. [1] a n d [2] were used to d e t e r m i n e
how effectively the coating interiors w e r e utilized. F o r
Eq. [1], t h e "goodness-of-fit" (F value) i n d i c a t e d t h a t
the regressions were significant at the 99% level for
16-
both Ni 123- and Ni 287-coated anodes. A t Ni 123-
coated anodes, an increase of 10 gm in the coating
thickness p r o d u c e d an a v e r a g e 1.4 10 - s A cm - 2
increase in io (Fig. 6); for Ni 287 anode coatings, the
corresponding io increase was smaller, a b o u t 3.5 X N
10 . 9 A c m - 2 . I 12
It is interesting to compare the above results w i t h E
u
d a t a from A p p l e b y et al., who found [Fig. 7 of Ref.
(7)] that io at 90~ was ,~55 times h i g h e r on a 150 ;~m CO
I
thick sintered nickel plaque t h a n on a smooth nickel O
surface. Using the io value at smooth nickel o b t a i n e d
b y those authors ( ~ 7 10 -10 A c m - 2 ) , this increase O
is then about 3.8 X 10 - s A cm-2, o r r o u g h l y 2.6 X
10-3 A c m - 2 for each 10 ~m of sintered nickel t h i c k -
ness. This value is c o m p a r a b l e to t h a t r e p o r t e d a b o v e $
for Ni 287 coatings. 4
The nickel sinter used b y A p p l e b y et aZ. h a d an
a v a i l a b l e electrode surface area, according to BET
measurements, of 140 cm 2 p e r square c e n t i m e t e r of t h e
sintered plaque. If all of this a r e a w e r e e l e c t r o c h e m i - / 9
cally active, one w o u l d expect the exchange c u r r e n t 0 I I I
d e n s i t y m e a s u r e d on the p l a q u e to be 140 times h i g h e r 0 40 80 120 160
than on the smooth nickel electrode. It is n o t e w o r t h y
COATING THICKNESS, /.Lm
that this is n e a r l y t h r e e times higher t h a n the ,~55-fold
increase in io a c t u a l l y obtained, i n d i c a t i n g t h a t the Fig. 6. Exchange current densities vs. thickness of Ni 123 coat-
BET surface a r e a m a y s u b s t a n t i a l l y o v e r e s t i m a t e the ings on mild steel. Points: experimental. Line: best fit of Eq. [1].
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 VoW. I28, Ro. 4
parable to those observed by A p p l e b y et aZ. (7) on
screen-reinforced sintered nickel under similar con-
ditions. However, the hydrogen evolution overpoten-
rials at higher current densities reported by those
authors are significantly lower (by >70 mV at 10 mA
cm -2) than observed on high surface nickel coatings
in the present work. The explanation for this behavior
m a y lie in the fact that gas m a y exit only from the
front face o f the coatings on steel sheets rather than
from both faces in the case of porous sintered nickel.
This should be relatively more important in He evolu-
tion than in O2 evolution, due to the twofold difference
in gas volume produced at equal current densities.
However, when Ni 123 coatings were applied to Ni
cathode screens, no significant overpotential reduction
was obtained.
There is a trend toward higher overpotentials at
coatings with reduced microstructural surface area,
caused by more severe sintering conditions, as shown
in Fig. 7. However, this trend did not include the most
highly sintered cathode (No. 9), which showed an un-
expected decrease in ~H2. No explanation for this be-
havior was evident from photomicrographs of the coat-
ings. It is possible that this increase in efficiency at the
nickel coating with the smoothest surface morphology
is a result of easier gas release from coating pores;
the fact that similar behavior was not observed for O2
evolution may be due to the smaller size of evolving
H2 gas bubbles. It is also noteworthy that coating No. 1
failed in anodic operation but not as a cathode. This
indicates that cavitation forces which may rupture the
sintered coating structure may be more dependent on
gas bubble size "(larger for O~) than on total gas vol-
ume (larger for H2).
Appleby and co-workers (7) suggested that the in-
terior of screen-reinforced sintered nickel was largely
accessible for the hydrogen evolution reaction, as a
760~ 8TO~
TIME (rnin):
5 I0 30 5 I0 301
200mAcm "z
, 1
0.45
0.40
I electrode coating interior for hydrogen evolution than
0.35
>
o.~o I I
i Io
0.25
0.~0
0,1 5 I I I I I I
I 2 ~ 4 5 6
CATHODE
Fig. 7. ~1~'2 at selected current densities, for Ni 123 coatings on
mild steel (from Table II). Effect of coating microstructure changes
caused by variation of sintering conditions.
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WATER ELECTROLYSIS 745
consequence of the small bubble size of evolved H2.
Using the technique applied above to anode coatings,
the electrochemical activity of the inner surfaces of
Ni 287 cathode coatings was investigated as part of
the present work. A regression analysis of the hydro-
gen evolution data for Ni 287 coatings from ~20 to
290 ~m thick showed that each 10 ~m increase in coat-
ing thickness produced a 1.1 10 .5 A cm -2 increase
in io. For one decade of increase in coating thickness,
~H2 at 200 mA cm -2 was reduced by 55 mV. This is
less than half of the overpotential reduction expected
if the entire surface of the coating were catalyzing the
reaction equally. Similarly, Appleby et aI. (7) point
out that the apparent exchange current density for the
hydrogen evolution reaction at their sintered nickel
electrode was only 30 times higher than at smooth
nickel. This is substantially below its roughness factor
of 140, as measured by the BET technique.
Discussion
The electrodes described in the present paper are
prepared by applying particulate metal coatings to
metal substrates. The use of a paint-like suspension of
the metal particles makes it possible to achieve uni-
form coatings of controlled thickness using a variety
of coating techniques. This electrode fabrication
method, which appears to be we]./suited for preparing
anodes for alkaline water electrolysis, has two main
advantages: (i) the coating technique can be used
to add considerable surface roughness to existing elec-
trode structures of many kinds; (ii) the materials and
procedures used to prepare the electrodes are rela-
tively inexpensive. Both of these factors are in keep-
ing with the capital cost restraints on commercial
alkaline electrolysis equipment.
The efficiencies of the coated electrodes and their
microstructures, can be varied significantly by chang-
ing the coating preparation conditions. The interior
surfaces of both anode and cathode coatings participate
I in the electrode reactions to some extent; thus, over-
I 980oC potentials can be reduced by increasing the electrode
coating thickness. However, the use of thick anode
{
coatings to improve electrolysis efficiency is of doubtful
5 I0 30 value on economic grounds, since the overpotential
reduction obtained is small. This would be true even
I under ideal conditions, in which the overpotential r e -
duction for a tenfold increase in coating thickness is
given by the Tafel slope, which is only ~35 mV, as
shown earlier.
Although the electrode structure developed in the
present work is less suitable for hydrogen evolution
than for oxygen evolution, the cathode overpotential
reduction with increased coating thickness is larger.
This is not due to the more effective utilization of the
for oxygen evolution, but is rather a consequence of
the difference in Tafel slopes for the two processes.
The optimum electrode coating microstructure, for
any given cell and set of operating conditions, is that
which gives adequate strength and stability while
maintaining the highest possible surface roughness
factor. The present work indicates that different coat-
ing strengths are necessary, depending on whether the
coated electrodes are used as anodes or cathodes. The
efficiency improvements which can result from choos-
ing proper sintering conditions are large enough to be
significant. In addition, sintering no more than nec-
essary for adequate mechanical integrity of the coating
minimizes sintering costs.
I The use of steel substrates with porous coatings as
I 1 I anodes in alkaline electrolysis raises questions regard-
7 8 9
ing their durability, since unprotected mild steel c o r -
r o d e s rapidly under anodic service. None of the elec-
trodes used in this work showed evidence of corrosive
failure in six-hour electrolyses. A report of the operat-
ing characteristics and corrosion resistance of nickel
 746 ?. Electrochem. Sot.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY April 1981

powder-coated mild steel-based anodes in 1200 hr
tests will be made in a future publication.
Acknowledgments
Electrode coatings were prepared by W. A. Petersen
and J. A. Travis. Their cooperation in this work is
gratefully acknowledged. Electrode polarization data
were obtained with the skillful assistance of A. M.
Rapun. Permission to publish this work was granted
by MPD Technology, Incorporated of Wyckoff, New
Jersey, holders of commercial rights to the electrodes
described in this paper.
Manuscript submitted July 14, 1980; revised manu-
script received ca. Nov. 20, 1980.
Any discussion of this paper will appear in a Dis-
cussion Section to be published in the December 1981
JOURNAL. All discussions for the December 1981 Dis-
cussion Section should be submitted by Aug. 1, 1981.
Publicatio~ costs of this article were assisted by
Inco Research & Development Center, Incorporated.
REFERENCES
1. A. J. Appleby and G. Cr~py, in "Electrode Mate-
rials and Processes for Energy Conversion and
Storage," J. D. E. McIntyre, S. Srinivasan, and
F. G. Will, Editors, p. 382, The Electrochemical
Society Softbound Proceedings Series, Princeton,
N.J. (1977).
2. J. H. Russell, in "Industrial Water Electrolysis,"
S. Srinivasan, F. J. Salzano, and A. R. Landgrebe,
Editors, p. 77, The Electrochemical Society Soft-
bound Proceedings Series, Princeton, N.J. (1978).
3. A.J. Smith and J. D. Hatfield, ibid., p. 143.
4. M. H. Miles, G. Kissel, P. W. T. Lu, and S. Srini-
vasan, This Journal, 123, 332 (1976).
5. A. C. C. Tseung and S. Jasem, Electrochim. Acta,
22, 31 (1977).
6. D. P. Gregory, K. F. Blurton, and N. P. Biederman,
in "Industrial Water Electrolysis," S. Srinivasan,
F. J. Salzano, and A. R. Landgrebe, Editors, p. 54,
The Electrochemical Society Softbound Proceed-
ings Series, Princeton, N.J. (1978).
7. A. J. Appleby, G. Cr~py, and J. Jacquelin, Int. J.
Hydragen Energy, 3, 21 (1978).
8. J. M. Gras and' M. Pernot, in "Electrode Mate-
rials and Processes for Energy Conversion and
Storage," J. D. E. McIntyre, S. Srihivasan, and
F. G. Will, Editors, p. 425, The Electrochemical
Society Softbound Proceedings Series, Prince-
ton, N.J. (1977).
9. M. H. Miles, Electroanal. Chem. InterJacial Elec-
trochem., 60, 89 (1975).
1O. "Inco Nickel Powders: Properties and Uses," The
International Nickel Company, Inc. (1975).
11. F. J. Salzano, Editor, "Hydrogen Storage and Pro-
duction in Utility Systems," 3rd Quarter Progress
Report, Brookhaven National Laboratory, (BNL
19520), October 1974.
12. R. L. LeRoy, M. B. I. Janjua, R. Renaud, and U.
Leuenberger, This Journal, 126, 1674 (1979).
13. R. L. LeRoy, M. B. I. Janjua, R. Renaud, and U.
Leuenberger, in "Industrial Water Electrolysis,"
S. Srinivasan, F. J. Salzano, and A. R. Landgrebe,
Editors; p. 63, The Electrochemical Society Soft-
bound Proceedings Series, Princeton, N.J. (1978).
14. P. W. T. Lu and S. Srinivasan, This Journal, 125,
265 (1978).

An SEM Study of the Nature of the Electrochemical

Deposit in Reversible Electrodeposition Displays
H. J. Stocker, L. G. VanUitert, T. C. Loomis, and F. B. Koch*
Bell Laboratories, Murray Hill, New Jersey 07974

ABSTRACT
SEM-x-ray spectroscopic studies of display cells based on reversible elee-
trodeposition (RED's) conclusively show that the deposit is composed of ele-
mental silver, regardless of its color (gold, gray, black, red-brown, etc.) A
gold deposit is shown to consist of finely dispersed (colloidal) silver particles,
while the black deposit consists of a spongy type of deposit of elemental silver.
This fact means that the mechanism of operation of these dispersive displays
is due to collective electromagnetic scattering effects of colloidal silver. Con-
firming evidence that TiOz particles form in-depth contacts is also presented.

Display cells based on reversible electrodeposition
(RED's) are under active study (I, 2).
Experimental cells are constructed of two parallel
plates of indium-tin oxide (ITO) coated glass. The
intervening space is filled with a paste electrolyte con-
sisting of silver iodide (AgI), tetralkylammonium
iodide (RN4I), and a solvent (dimethylformamide or
DMF). The use of the tetralkylammonium iodide per-
mits the use of high silver concentrations in organic
solvent based electrolytes (2). Sometimes a mixture
of TiO2 powder and fine ZEOLITE particles (molecular
SIEVE) is added to the mixture. The function of the
TiO~ is twofold: one, it serves as an opacifier (white
background) and second it extends the electrical con-
tact into the interior of the cell, thus enlarging the
volume in which the electrochemical reactions take
place. The molecular sieve is added in an empirically
* Electrochemical SocietyActive Member.
Key words: spectroscopy, electrodeposition, deposits.
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determined proportion to adjust the conductivity of
the mixture for maximum contrast. The functions of
these components are more fully described in Ref. (2).
Upon application of voltage pulses of 1-2V magnitude
and several hundred millisecond durations, coloration
is observed at the cathode. A variety of colors, includ-
ing gray, black, gold, green-gold, red, red-brown,
light-blue, and navy blue reproducibly result from
plating in these experimental display cells. Several
colors may be observed in the same display cell, de-
pending on driving conditions. For instance, a brief
high amplitude pulse (duration 0.1 sec) in a DMF/
AgI/TBAI/TiO2-SIEVE cell (TBAI is tetrabutyl am-
monium iodide) produces a bright red color, while a
low amplitude pulse of 1 sec duration produces a dark
gray color. Similarly, in cells without the TiO2/SIEVE
filler, a golden color can often be observed with a l o w
driving current, while a gray to black deposit develops
if the cell is driven harder.