3278

J. Electrochem. Soc., Vol. 136, No. 11, November 1989 9 The Electrochemical Society, Inc.

pacity is acceptable, these films are capable of even higher

discharge currents.

Conclusion
From these studies it appears that high-quality amorphous m o l y b d e n u m sulfide films can be prepared by
chemical vapor deposition. The density of films prepared
close to 200~ corresponds well to the density of bulk MoS3
prepared by classical techniques. As the temperature of
film preparation is increased, there is a rapid increase in
density, corresponding to a loss of sulfur, as expected. For
both the bulk and thin film MoS3, it seems impossible to be
certain of the exact stoichiometry. However, the density
and FTIR results support that the materials are the same.
The films can be readily deposited on various substrates,
including simple aluminum foil. The films are very flexible
and, even when deposited on A1 foil, the adherence is remarkably good. Un d e r our deposition conditions we obtain packing densities of approximately 60%. The films can
easily be prepared even in our small research reactor with
surface areas of several hundred square centimeters. The
growth rate has not been optimized, but the rates described in this work (1000/~Jmin) are sufficient for most
applications. If indeed one of the main problems of the application of MoS3 as a cathode material is the intrinsic resistivity of the material, this problem has been diminished
but not eliminated by thin film preparation. The careful
control of temperature has allowed us to minimize the resistivity of the films, and the m i n i m u m occurs when the
stoichiometry is close to MoS3. We are continuing our
work on thin films of MoS3 to obtain resistivities substantially lower than the lowest observed, of 90 k~-cm. It is our
feeling that the only possible method of lowering the
resistance is to heavily dope the material.
The thin film work has allowed us to rapidly analyze several materials electrochemically and to observe the intrinsic limits of MoSs without binders or additives. The electrochemical behavior of thin films prepared in the
temperature range of 200~176
closely parallels the results obtained for bulk MoS3; however, superior long-term
cycling behavior was demonstrated. Two-thirds of the
original cycling capacity was maintained after 100 deep
discharge cycles at a rate of 0.2 mA/cm 2, with almost all of
this loss occurring during the first 6 cycles. In addition, in-

creasing the current density by a factor of 20 caused only

moderate change in the voltage characteristics. The electrochemical films show promising properties for use in
high surface area, high rate batteries, and for solid electrolyte, thin film batteries.

Acknowledgments
We would like to thank A. M. Williams for the molybden u m analysis, and J. J. Auborn for many helpful discussions. This work was supported in part by the Strategic
Defense Initiative Organization and managed by the Office
of Naval Research.
Manuscript submitted Nov. 28, 1988; revised manuscript
received March 27, 1989.

Polytechnic University assisted in meeting the publication costs of this article.

REFERENCES
1. A. J. Jacobson, R. R. Chianelli, S.M. Rich, and M. S.
Whittingham, Mater. Res. Bull., 14, 1437 (1979).
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"Proceedings of the 30th Power Sources Symposium," p. 68, The Electrochemical Society, Atlantic
City, N J, J u n e 7-10, 1982.
3. P. B. Harris, G. L. Holleck, J. Buzby, J. Avery, L. Pitts,
and K. M. Abraham, ONR Technical Report No. 9,
ONR Contract No. N00014-77-C-0155 (1982).
4. E. J. Plitcha and M. Salomon, J. Power Sources, 13, 319
(1984).
5. J. J. Auborn, Y. L. Barberio, K. J. Hanson, D.M.
Schleich, and M. J. Martin, This Journal, 134, 580
(1987).
6. D. M. Schleich and M. J. Martin, J. Solid State Chem.,
64, 359 (1986).
7. C. H. Chang and S. S. Chan, J. Catal., 72, 139 (1981).
8. J. R. Ferraro, "Low-Frequency Vibrations of Inorganic
and Coordination Compounds," p. 117, Plenum
Press, New York (1971).
9. W. P. Griffith, J. Chem. Soc., 5248 (1964).
10. D. Dolphin and A. Wick, "Tabulation of Infrared Spectra Data," p. 540, Wiley-Interscience, New York
(1977).
11. S. Sourisseau, O. Gorochov, and D. M. Schleich, To be
published.
12. M. A. Py and R. R. Haering, Can. J. Phys., 61, 76 (1983).

Electrodeposition of Silver under Direct and Pulsed Current

Y. Fukunaka, T. Yamamoto, and Y. Kondo*
Department of Metallurgy, Kyoto University, Kyoto, Japan
ABSTRACT
Electrodeposition of Ag ions on a vertical plane cathode immersed in stagnant 0.5M AgNO~ and 0.5M AgNO3-0.5M
HNO3 solutions was carried out under direct and pulsed current. The morphological variations with electrolytic conditions were examined by measuring the average diameters of the electrodeposits using the intercept method. The ratio of
the particle diameter obtained in a AgNO3-HNO3 solution under pulsed electrolysis to that under direct current at the
same average current density was m i n i m u m near 50-60 mA/cm 2. It was further enhanced with a decrease in the duty cycle
when the pulse-on time and the charge density were maintained at 1 ms and 9 C/cm 2, respectively. The concentration profiles of Ag ions in AgNO3 solution were also measured by holographic interferometry. In these experiments, the duplex
diffusion layer model proposed by Ibl (18) was found to adequately describe the phenomena provided that the pulse-on
time was sufficiently long. Based on the concentration profile measurements, it was deduced that the appearance of the
m i n i m u m ratio of particle diameter was closely related to the depletion of the surface concentration of Ag + ions during the
pulse~on time, that is, to the concept of limiting current pulse.
It is well known that industrial silver electrorefining in
nitrate solution has certain disadvantages such as the need
for scrapers and a large distance between electrodes due to
dendrite formation. A number of studies have been reported (1-4) on research to find ways to overcome these difficulties.
*Electrochemical Society Active Member.

Many papers (5-11) have also been published on electrocrystallization. From the standpoint of technological importance, the studies on polycrystalline substrate (7, 10, 11)
are noteworthy. Fisher observed that nitric acid had an inhibiting effect on the silver deposition (7, 10). Vereecken
and Winand (11) studied the effect of electrolyte composition, temperature, current density, and duration on morphology. They qualitatively summarized the nature of the

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d. Electrochem. Soc., Vol. 136, No. 11, November 1989 9 The Electrochemical Society, Inc.
d e p o s i t as a f u n c t i o n of b o t h t h e ratio of c u r r e n t d e n s i t y to
c o n c e n t r a t i o n of t h e b u l k e l e c t r o l y t e a n d t h e c o n c e n t r a t i o n of t h i o u r e a .
A n o t h e r w a y to i m p r o v e t h e q u a l i t y of d e p o s i t is to a p p l y
a p u l s e d e l e c t r o l y s i s t e c h n i q u e in w h i c h a v e r y h i g h current density can be instantaneously applied and a very
t h i n d i f f u s i o n l a y e r is f o r m e d n e a r t h e c a t h o d e surface.
T h e s e r e s u l t s s h o w t h a t t h e p h y s i c a l p r o p e r t i e s of electrod e p o s i t e d film c a n b e d r a s t i c a l l y i m p r o v e d .
T h e effects of p u l s e d c u r r e n t o n t h e p h y s i c a l p r o p e r t i e s
of e l e c t r o d e p o s i t s o f silver w e r e r e p o r t e d b y D i n i (12) a n d
P a v l o v i c et ak (13). T h e v a r i a t i o n s i n b o t h t h e m o r p h o l o g y
a n d c r y s t a l s t r u c t u r e of silver e l e c t r o d e p o s i t e d i n a silver
a m m o n i a c o m p l e x b a t h a n d silver c y a n i d e b a t h as a funct i o n of t h e p u l s e d c u r r e n t d e n s i t y a n d p u l s e - o n t i m e w e r e
e x a m i n e d b y F u k u m o t o et al. (14). M o r e o v e r , t h e effect of
t h e c a t h o d i c o v e r p o t e n t i a l o n t h e n u c l e a t i o n rate o f silver
in AgNO3 s o l u t i o n w a s s t u d i e d u s i n g t h e p o t e n t i o s t a t i c
double pulse method. The two-dimensional nucleation
m o d e l w a s a p p l i e d to t h i s p h e n o m e n a b y L a n et al. (15).
I n s p i t e of m u c h w o r k o n t h e e l e c t r o d e p o s i t i o n o f silver
as m e n t i o n e d a b o v e , t h e g r o w t h m e c h a n i s m of t h e p r e c i p i t a t e d p a r t i c l e o n t h e c a t h o d e s u r f a c e at r e l a t i v e l y h i g h
o v e r p o t e n t i a l is n o t well u n d e r s t o o d . T h i s is p a r t l y bec a u s e of o u r p o o r k n o w l e d g e o n t h e ionic m a s s t r a n s f e r
r a t e o f A g ions. T h e p r e v i o u s p a p e r (16) d e a l t w i t h t h e
i o n i c m a s s t r a n s f e r of Ag i o n s a s s o c i a t e d w i t h n a t u r a l
c o n v e c t i o n a l o n g a v e r t i c a l silver c a t h o d e u n d e r d i r e c t curr e n t electrolysis. I n t h e p r e s e n t p a p e r , t h e m o r p h o l o g i c a l
v a r i a t i o n s o f silver w i t h c u r r e n t d e n s i t y a n d c h a r g e d e n sity will b e r e p o r t e d . T h e effect of t h e p u l s e s c h e d u l e o n
m o r p h o l o g i c a l v a r i a t i o n s a n d i o n i c m a s s t r a n s f e r r a t e s will
be examined by comparing the results obtained in direct
c u r r e n t electrolysis.

Experimental
T h e e l e c t r o l y t i c cell w a s m a d e of acrylic r e s i n plates. T h e
i n n e r d i m e n s i o n w a s 30 m m h i g h , 30 m m w i d e , a n d 10 m m
t h i c k . T w o e l e c t r o d e s 30 m m h i g h , 10 m m wide, a n d
0.5 m m t h i c k w e r e p r e p a r e d f r o m a rolled silver plate. A
p o l i s h e d c a t h o d e w a s e t c h e d in 30% HNO3 s o l u t i o n for a
few seconds. The electrodes were coated with PVC, except
for t h e p a r t b e t w e e n 5-15 m m f r o m t h e l o w e r e d g e of t h e
e l e c t r o d e s so t h e effective s u r f a c e area w a s 10 10 m m .
The electrodeposition was carried out under galvanostatic
conditions.
A c a t h o d e of 1 m m w i d t h w a s e m p l o y e d w h e n t h e conc e n t r a t i o n profiles of A g + i o n s f o r m e d n e a r t h e c a t h o d e
were measured by the holographic interferometry techn i q u e . T h i s w a s n e c e s s a r y to r e d u c e t h e o p t i c a l p a t h
l e n g t h u n d e r v e r y h i g h c u r r e n t d e n s i t y i n o r d e r to m e a s u r e
t h e r e f r a c t i v e i n d e x profile v e r y close to t h e c a t h o d e surface. T h e e l e c t r o l y t i c cell for t h e s e m e a s u r e m e n t s was
m a d e of P y r e x glass p l a t e s of 3 m m t h i c k n e s s w i t h i n n e r
d i m e n s i o n s o f 40 m m h i g h , 25 m m wide, a n d 1 m m thick.
T h e e f f e c t i v e s u r f a c e area of t h e c a t h o d e i n s t a l l e d i n t h i s
e l e c t r o l y t i c cell w a s 1 10 m m .
T h e c o m p o s i t i o n s of e l e c t r o l y t e s are s h o w n in T a b l e I.
The electrodeposition with pulsed current was mainly
c o n d u c t e d i n 0.5M AgNO3-0.5M HNO3 solution, b e c a u s e
u n i f o r m i t y of c u r r e n t d e n s i t y d i s t r i b u t i o n w a s o b t a i n e d
e v e n at t h e h i g h e r c u r r e n t d e n s i t y . H o w e v e r , t h e i o n i c
m a s s t r a n s f e r r a t e s w e r e s t u d i e d o n l y i n 0.5M AgNO3 solution, b e c a u s e o p t i c a l a n d p h y s i c a l p r o p e r t i e s o n AgNO3HNO3 s o l u t i o n are n o t k n o w n .

Results and Discussion

Electrodeposition of silver under direct current.--It is
i m p o r t a n t to u n d e r s t a n d t h e m o r p h o l o g i c a l v a r i a t i o n of
s i l v e r e l e c t r o d e p o s i t e d u n d e r d i r e c t c u r r e n t b e f o r e t h e effect of p u l s e d e l e c t r o l y s i s is d i s c u s s e d . F i g u r e 1 s h o w s t h e
m o r p h o l o g i c a l v a r i a t i o n of t h e e l e c t r o d e p o s i t o b t a i n e d i n
0.5M AgNO3 a q u e o u s s o l u t i o n as a f u n c t i o n of c u r r e n t d e n sity a n d c h a r g e d e n s i t y . As m e n t i o n e d i n t h e p r e v i o u s
p a p e r (16), t h e o h m i c d r o p of e l e c t r o l y t e w a s s i g n i f i c a n t
d u r i n g e l e c t r o d e p o s i t i o n of silver a n d it w a s difficult to obt a i n g o o d r e p r o d u c i b i l i t y i n m e a s u r e m e n t of t h e polarizat i o n curve. T h e r e f o r e , e l e c t r o l y s i s w a s c a r r i e d o u t u n d e r

3279

Table I. Physical propertiesof AgN03 solution

0.5M AgNO3

DI = 1.4 x 10 ~(cm2/s)
a = 130.5 (cm3/mol)
u = 0.965 x 10-2 (cm2/s)
*t, = 0.482 (-)

0.5M AgNO3-0.5M HNO~

D~ = 1.7 x 10 5(cm2/s)(ll)
a(~-r - ~/a2~2)= 88.9 (cm3/mol)
v = 1 x 10-2 (cm2/s)
*t, = 0

(-)

the galvanostatic conditions. SEM pictures above

60 m A / c m 2 w e r e d i s c a r d e d b e c a u s e of s i g n i f i c a n t differe n c e in m o r p h o l o g y b e t w e e n t h e c e n t r a l a n d e d g e p a r t o f
the cathode caused by nonuniformity in current density.
With increasing current density under a charge density
o f 9 C / c m 2, t h e n u m b e r of p r e c i p i t a t e d p a r t i c l e s o n t h e silver cathode became significantly larger and the diameter
of t h e p a r t i c l e s w e r e c o n s i d e r a b l y r e d u c e d . T h i s o c c u r r e d
b e c a u s e of a n i n c r e a s e i n t h e a c t i v e s u r f a c e a r e a c a u s e d b y
a larger cathodic overpotential. The precipitated particles
o b s e r v e d at t h e l o w e r c u r r e n t d e n s i t y s h o w t h e e x i s t e n c e
of a level p r o b a b l y c o r r e s p o n d i n g to a l o w e r i n d e x of p l a n e
like (111), as P a n g a r o v (17) p o i n t e d out. F u r t h e r i n c r e a s e s
in t h e c u r r e n t d e n s i t y i n d u c e t h e h i g h e r o v e r p o t e n t i a l . A t
t h e s a m e time, t h e p r e c i p i t a t e d p a r t i c l e s s h o w less o f a
level a n d t h e i r s h a p e s b e c o m e s o m e w h a t r o u n d .
As e l e c t r o d e p o s i t i o n p r o g r e s s e s at a c u r r e n t d e n s i t y of
30 m A / c m 2, it is clearly s e e n t h a t t h e initially p r e c i p i t a t e d
p a r t i c l e s o n t h e c a t h o d e are g r a d u a l l y g r o w i n g . T h e n u m b e r of p r e c i p i t a t e d p a r t i c l e s are s u b s t a n t i a l l y c o n s t a n t duri n g e l e c t r o d e p o s i t i o n , as l o n g as t h e c h a r g e d e n s i t y is n o t
e x c e s s i v e . H o w e v e r , c o n t i n u a l e l e c t r o d e p o s i t i o n r e s u l t s in
a d e n d r i t i c s t r u c t u r e as s e e n in t h e p i c t u r e .
T h e v a r i a t i o n in t h e m o r p h o l o g y of e l e c t r o d e p o s i t s obt a i n e d i n AgNO~-HNO3 s o l u t i o n is s h o w n in Fig. 2. T h e effects of c u r r e n t d e n s i t y a n d c h a r g e d e n s i t y o n t h e m o r p h o l o g y a r e q u a l i t a t i v e l y s i m i l a r to t h o s e i n AgNO3
solution. H o w e v e r , t h e a d d i t i o n of HNO3 to t h e e l e c t r o l y t e
i n d u c e s a l a r g e r polarization, as p o i n t e d o u t i n a p r e v i o u s
p a p e r (16) a n d r e s u l t s in m o r e s p h e r o i d a l s h a p e d p a r t i c l e s
e s p e c i a l l y at l o w e r c u r r e n t densities.
T h e p a r t i c l e d i a m e t e r d e c r e a s e s w i t h i n c r e a s e in c u r r e n t
d e n s i t y a n d t h e w h o l e area o f t h e c a t h o d e b e c o m e s
c o v e r e d w i t h p r e c i p i t a t e d particles. A t a h i g h e r c u r r e n t
d e n s i t y o f 100 m A / c m 2, t h e e l e c t r o d e p o s i t f o r m s n e e d l e s h a p e d particles, e v e n at a c h a r g e d e n s i t y of 9 C/cm 2. T h e
l i m i t i n g c u r r e n t d e n s i t y i n 0.5M AgNO3-0.5M HNO3 solu-

Fig. 1. Morphology of silver electroplated under various kinds of

electrolytic conditions in O.5M AgN03 solution.

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J. Electrochem. Soc., Vol. 136, No. 11, N o v e m b e r 1989 9 The Electrochemical Society, Inc.

3280

duces the particle size by 20-30%. A c c o r d i n g to the polarization curves (16), the overpotential in 0.5M AgNO3 - 0.5M
HNO3 is t w i c e as large as that in 0.5M AgNO3 solution at
the s a m e current density b e l o w 100 m A / c m 2. This h i g h e r
o v e r p o t e n t i a l i n d u c e s a finer size of precipitated particles.
No net p r o d u c t i o n of precipitated particles d u r i n g elect r o d e p o s i t i o n was n o t i c e d in Fig. 1 and 2. If the n u m b e r of
precipitated particles on the c a t h o d e is substantially constant, the average d i a m e t e r of the precipitated particle
should be proportional to the c u b e root of the charge density. The d e p e n d e n c e of the average particle d i a m e t e r on
the charge density is s h o w n in Fig. 4. The a s s u m p t i o n of no
net p r o d u c t i o n of precipitated particles during e]ectrodeposition appears to be valid as long as the charge density is
less t h a n 9 C/cm 2, since linearity b e t w e e n the average particle d i a m e t e r and the c u b e root of the d u r a t i o n of electrolysis (charge density) is o b s e r v e d in both electrolytes u n d e r
t h e p r e s e n t e x p e r i m e n t a l conditions.

Electrodeposition of silver under pulsed current.--Figure

Fig. 2. Morphology of silver electroplated under various kinds of

electrolytic conditions in 0.5M AgNO3-0.SM HNO3 solution.

tion is a b o u t 65 m A / c m 2 (16), and therefore silver ions are

preferentially t r a n s p o r t e d to particular deposits on the
c a t h o d e u n d e r a v e r y high c o n c e n t r a t i o n overpotential.
It is recognized f r o m these two p h o t o g r a p h s that the
shape of the e l e c t r o d e p o s i t e d particles does not significantly v a r y with c o n v e n t i o n a l electrolytic c o n d i t i o n s such
as electrolyte composition, current density, and charge
density. F u r t h e r m o r e , the v a r i a n c e in the d i a m e t e r of the
p r e c i p i t a t e d particles is not e x t r e m e l y large. Thus, it was
d e c i d e d to m e a s u r e the average size of particles using the
i n t e r c e p t method.
T h e m e a s u r e d diameters are plotted against the current
density in Fig. 3. T h e y are significantly r e d u c e d w i t h increase in current density b e l o w 30 m A / c m 2, while t h e variation w i t h current density b e c o m e s smaller a b o v e
60 m A / c m ~, as long as the charge density is m a i n t a i n e d at
9 C/cm 2. It is also clearly seen that t h e addition of HNO~ re-

40

30

C/cm2

-t

5 s h o w s the m o r p h o l o g y o b t a i n e d u n d e r p u l s e d c u r r e n t in
0.5M AgNO3-0.5M H N Q solution. The charge density and
the pulse-on t i m e w e r e m a i n t a i n e d at 9 C/cm 2 and i ms, respectively. As m e n t i o n e d previously, the d i a m e t e r of elect r o d e p o s i t is d e c r e a s e d to a b o u t 10 ~m at 60 m A / c m 2 w i t h
increase in current density, and a needle-like electrodeposit is f o r m e d at 100 m A / c m 2 w h e n silver is e l e c t r o d e p o s i t e d
u n d e r direct current. H o w e v e r , pulsed electrolysis has
c o n s i d e r a b l y i m p r o v e d the quality of e l e c t r o d e p o s i t i o n
e v e n at a d u t y cycle of 0.5. The particle size is r e d u c e d
a b o v e an average current d e n s i t y of 30 m A / c m 2, and no form a t i o n of needle-like electrodeposit is o b s e r v e d at
100 m A / c m 2. F u r t h e r r e d u c t i o n in d u t y cycle i n t r o d u c e s
m u c h finer precipitated particles u n i f o r m l y distributed on
t h e cathode surface for cases a b o v e 30 m A / c m 2. H o w e v e r ,
at a d u t y cycle of 0.005, s o m e larger particles with 15 ~m
d i a m are precipitated u n d e r an average current density of
30-60 m A / c m 2.
The m o r p h o l o g y of e l e c t r o d e p o s i t e d particles b e c o m e s
v e r y c o m p l i c a t e d at a l o w e r average current d e n s i t y of
3 m A / c m 2. Moreover, a regular w a v y pattern w h o s e w i d t h
is a b o u t 100trm appears on the cathode surface at
r = 0.005. This is p r o b a b l y due to e l e c t r o d e p o s i t i o n of precipitates along a scratch m a r k on the cathode. This phen o m e n a was not r e p r o d u c i b l e and a structure r e s e m b l i n g a
b a m b o o grass leaf of 70 ~m d i a m and less t h a n 1 ~m in
t h i c k n e s s was s o m e t i m e s observed. S i n c e the m o r p h o l o g y
at 3 m A / c m 2 is not reproducible, these results will be
omitted.
T h e relationship b e t w e e n the average d i a m e t e r and t h e
p u l s e current density is s h o w n in Fig. 6. The data measu r e d u n d e r direct current is i n c l u d e d in the s a m e figure to
d e m o n s t r a t e that t h e l o g a r i t h m of the average d i a m e t e r decreases linearly with increase in the l o g a r i t h m of the direct
c u r r e n t d e n s i t y o v e r 10 m A / c m 2. When p u l s e plating is carried out at an average current density of 3 m A / c m 2, no substantial d e p e n d e n c e in the average d i a m e t e r on the pulse
50

20

o 0.5~
~0

AgNO~

& 0,SM AgNO3-0,5M HNO3

~ 3o
10
2O

10
0

30

60
90
i (mAIcm 2 )

120

Fig. 3. Effect of current density on the diameter of electrodeposited

particle.

t113(s,3)

10

Fig. 4. Dependence of electrodeposited particle diameter on the duration time of electropleting.

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J. Electrochem. Soc., Vol. 136, No. 11, November 1989 9 The Electrochemical Society, Inc.

,o

3281

'It

30

60
iav (mA/crn2 )

0.8

0.6
C~

o4
0-2

90

120

Fig. 7. Effect of average current density on dp/dDc (0.5M AgNO30.5M HNO3, To, = 1 ms, q = 9 C/cm2).

Fig. 5. Morphology of silver plated by pulsed electrolysis in 0.5M

A g N O r 0 . S M HNO3 solution (q = 9 C/cm2).

c u r r e n t d e n s i t y is noticed. H o w e v e r , the data obtained at

an a v e r a g e c u r r e n t density over 30 m A / c m 2 s h o w a clear
size r e d u c t i o n effect with increase in the pulse c u r r e n t
density, a l t h o u g h it is less significant in c o m p a r i s o n w i t h
the case of direct current.
Thus, the ratios of the particle d i a m e t e r o b t a i n e d u n d e r
p u l s e d c u r r e n t to that u n d e r direct current are plotted
against t h e average current density in o r d e r to e m p h a s i z e
the essential effects caused by pulse plating. F i g u r e 7 demonstrates that a m i n i m u m ratio at the s a m e d u t y cycle is att a i n e d at a r o u n d 50-60 m A / c m 2. Moreover, it shows that the
smaller the d u t y cycle, a m o r e significant r e d u c t i o n occurs
in particle diameter.
F r o m t h e s e results, it is well u n d e r s t o o d that the p r i m a r y
function of the pulse electrolysis is to raise the cathode
overpotential, which enhances nucleation which in turn
results in a smoother surface. With increase in the average

c u r r e n t density from 60 to 100 m A / c m 2, the c o n t r i b u t i o n of

t h e c o n c e n t r a t i o n polarization to the g r o w t h of the electrod e p o s i t e d particle b e c o m e s p r e d o m i n a n t to d i m i n i s h t h e
size r e d u c t i o n effect i n d u c e d by t h e larger cathodic overpotential.
Ionic mass transfer rate associated with the eLectrodeposition under pulsed current.---In order to e x a m i n e the
ionic mass transfer rate associated w i t h the electrocrystallization, the c o n c e n t r a t i o n profile of Ag + ions was meas u r e d by holographic interferometry. The m e a s u r e m e n t s
w e r e c o n d u c t e d only in 0.5M AgNO3 solution, since no
data is available on the relationship b e t w e e n the refractive
i n d e x and c o m p o s i t i o n s of electrolyte acidified w~th
HNO3. F i g u r e 8 r e p r e s e n t s the i n t e r f e r o g r a m r e c o r d e d 45s
after the start of the electrolysis u n d e r an average current
d e n s i t y of 60 m A / c m 2, w i t h a pulse p e r i o d of 2s and a d u t y
cycle of 0.5. A v e r y steep refractive i n d e x g r a d i e n t is seen
n e a r the vertical plane cathode. When t h e pulse-on t i m e is
as long as ls, it is possible to o b s e r v e oscillation of the int e r f e r o g r a m near the c a t h o d e surface w i t h pulse s c h e d u l e
w h e n u s i n g a 16 m m m o v i e camera. B e y o n d t h e oscillating
layer, substantially steady c o n c e n t r a t i o n profiles are
formed. This is qualitatively identical to the d u p l e x diffusion layer m o d e l (Fig. 9) p r o p o s e d by Ibl (18). U n d e r s u c h
conditions, the surface c o n c e n t r a t i o n of Ag ions at t h e
e n d of the pulse-on t i m e c o n v e r g e s to a certain v a l u e and a
quasi-steady state is established.
The surface c o n c e n t r a t i o n established u n d e r direct current can be e x p r e s s e d by
Shx = 0.628 (Ra*x) lj~

[1]

as l o n g as t h e current density distribution is u n i f o r m along

the vertical plane cathode (16, 19, 20). F r o m this equation,

1.5
'

x~

'

~'(3~0~)

"~o (~xv, r)=(3,0,5)

o(3,0.02)

O.5M A g N O 3 - 0 5 M H N O ~

TON=1ms

9 Clcm 2

::L
v 1.0
r'(--)

key

0.5

13

0.5

01

0.02

0,005

--X--

'

DC

'

'

;.

log ip (mAlcrn 2)

Fig. 6. Effect of the pulsed current density on the overage diameter

Fig. 8. Interferogram recorded at 45s after the start of pulsed plating

in O.5M AgNO3 solution (io, = 60 mA/cm 2, r = 0.5, T = ls).

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J. Electrochem. Soc., Vol. 136, No. 11, N o v e m b e r 1989 9 The Electrochemical Society, Inc.

3282

C*

to t h e s u r f a c e c o n c e n t r a t i o n b u t to a v a l u e close to t h e
b o u n d a r y v a l u e b e t w e e n t h e oscillating layer a n d t h e virtually s t e a d y layer i n v o l v e d in t h e d u p l e x d i f f u s i o n layer
m o d e l , as d e m o n s t r a t e d in Fig. 9.
F o r p u l s e p l a t i n g w i t h a s m a l l e r d u t y cycle r, Ibl (18) prop o s e d t h e f o l l o w i n g r e l a t i o n s h i p b a s e d o n a s i m p l e diffusion model

c;

5p = ~/2DTon (1 - r)

9 s.

Cothode

-'k.-.=

ipr
C'o= Co - ~ ( ~ N C$

[3]

[4]

8p)

7 -- ~ ( z F ) 2 ( C ' e ) 2 D

[5]

4(ip) 2

Fig. 9. Duplex diffusion layer model

t h e s u r f a c e c o n c e n t r a t i o n o f Ag ions w a s c a l c u l a t e d at a n
a v e r a g e c u r r e n t d e n s i t y w i t h t h e p h y s i c a l p r o p e r t i e s listed
in T a b l e I. It is d e p i c t e d b y a solid line in Fig. 10. M o r e o v e r ,
t h e m a s s t r a n s f e r rate u n d e r t h e l i m i t i n g c u r r e n t d e n s i t y is
g i v e n b y (16, 21, 22)
Sh= = 0.499 (Ra=) 1/4

[2]

I f t h e r e is n o e s s e n t i a l c h a n g e in t h e effective s u r f a c e area,
t h e c a l c u l a t e d l i m i t i n g c u r r e n t d e n s i t y for t h e p r e s e n t situa t i o n is 115 m A / c m 2. T h e solid line r e p r e s e n t i n g Eq. [1] is
e x t r a p o l a t e d to t h i s l i m i t i n g c u r r e n t d e n s i t y b y t h e d o t t e d
line as t h e r e is n o c o r r e l a t i o n e q u a t i o n at s u c h h i g h c u r r e n t
density.
T h e s u r f a c e c o n c e n t r a t i o n d u r i n g p u l s e p l a t i n g w a s estim a t e d . T h e o b s e r v e d s u r f a c e c o n c e n t r a t i o n s at t h e e n d o f
t h e p u l s e - o n t i m e o f l s are l o c a t e d on t h e solid line. T h e
s u r f a c e c o n c e n t r a t i o n at t h e e n d o f t h e p u l s e - o n t i m e o f l s
at a d u t y cycle o f 0.5 can b e a p p r o x i m a t e d b y t h e v a l u e pred i c t e d u n d e r a d i r e c t c u r r e n t d e n s i t y e q u i v a l e n t to t h e
s a m e a v e r a g e c u r r e n t d e n s i t y , as l o n g as t h e d r i v i n g force
o f n a t u r a l c o n v e c t i o n is small. H o w e v e r , t h e s u r f a c e conc e n t r a t i o n s u n d e r a p u l s e - o n t i m e o f 1 m s a n d at s m a l l e r
d u t y cycle are l o c a t e d a b o v e t h e line, e s p e c i a l l y at h i g h e r
a v e r a g e c u r r e n t d e n s i t y . U n d e r s u c h a p u l s e s c h e d u l e , it is
c o n s i d e r e d t h a t t h e t h i c k n e s s o f t h e oscillating layer is
a b o u t 2 I~m, w h i c h is less t h a n t h e p r e s e n t r e s o l u t i o n
p o w e r o f at m o s t 5-10 p.m b a s e d o n d i f f r a c t i o n t h e o r y (19).
It is t h e r e f o r e c o n c l u d e d t h a t t h e m e a s u r e d c o n c e n t r a t i o n
o f A g ion u n d e r t h e p u l s e s c h e d u l e o f s h o r t e r p u l s e - o n
time and higher pulse current density does not correspond

key

O.S

0.4

Ton

ra

0.5 l s

0.5

O n c e t h e d i f f u s i o n layer t h i c k n e s s 3N is given, t h e oscillating d i f f u s i o n layer t h i c k n e s s , 5p, a n d t h e b o u n d a r y v a l u e

b e t w e e n t h e s e t w o d i f f u s i o n layers, C'e, c a n b e calculated.
T h e n , t h e so-called t r a n s i t i o n time, ~, at w h i c h t h e interfacial c o n c e n t r a t i o n d r o p s p r e c i s e l y to zero at t h e e n d o f t h e
p u l s e - o n time, is a s s e s s e d .
U n d e r t h e a s s u m p t i o n t h a t t h e d i f f u s i o n layer t h i c k n e s s ,
~N, c a n b e e v a l u a t e d f r o m t h e c o r r e l a t i o n at t h e a v e r a g e
c u r r e n t d e n s i t y , t h e b o u n d a r y values, C'~, are calculated,
as s h o w n in Table II. We see t h e r e is c o n s i s t e n c y b e t w e e n
t h e c a l c u l a t e d C'e, a n d t h e o b s e r v e d c o n c e n t r a t i o n C~TM
w h e n t h e d u t y cycle is s m a l l a n d t h e p u l s e c u r r e n t d e n s i t y
is n o t too high. S i n c e t h e d u p l e x d i f f u s i o n layer m o d e l is
a p p l i c a b l e to e s t i m a t e t h e b o u n d a r y v a l u e C'~ in 0.5M
AgNOa s o l u t i o n w h e n t h e ionic m a s s t r a n s f e r rate associa t e d w i t h n a t u r a l c o n v e c t i o n d u r i n g o f f t i m e is n o t significant, this t e c h n i q u e is f u r t h e r e x t e n d e d to t h e case of 0.5M
AgNO3-0.5M HNO3.
T h e s u r f a c e c o n c e n t r a t i o n o f A g + ion e s t a b l i s h e d u n d e r
d i r e c t c u r r e n t is d e m o n s t r a t e d in Fig. 10. T h e l i m i t i n g curr e n t d e n s i t y for t h i s s o l u t i o n is 61.6 m A / c m 2 f r o m Eq. [2],
w h i l e 65 m A / c m e w a s o b t a i n e d f r o m t h e polarization m e a s u r e m e n t . Table III s h o w s t h e b o u n d a r y v a l u e C', a n d t h e
t r a n s i t i o n t i m e ~ c a l c u l a t e d for t h e p u l s e - o n t i m e o f 1 m s in
0.5M AgNO3-0.5M HNO3 solution. T h e p u l s e - o n t i m e is v e r y

Table II. Comparison between the observed surface concentration

and the calculated values (0.5M AgNO3)
T

ip
r
(A/cm2) (-)

ls
ls
ls
1 ms
1ms
1 ms
1ms
l ms

0.5
0.5
0.5
0.5
0.02
0.02
0.05
0.05

0.003
0.03
0.06
0.03
0.003
0.03
0.06
0.1

~N
(cm)

5p
(cm)

0.0217 - 0.0137 - 0.0119 - 0.0137 0.0001

0.0217 0.0002
9.0137 0.0002
0.0119 0.0002
0.0117 0.0002

Ce~
(M)

Cte
(M)

(M)

0.470
0.338
0.223
0.338
0.475
0.355
0.278
0.117

---0.344
0.475
0.346
0.233
0.101

0.475
0.344
0.229
0.344
0.475
0.344
0.229
0.06a

el s

aCl~ was taken from Fig. 1O. Except for this value, C1~was calculated from Eq. [1].

1 ms

0.05 1ms
0

"6
E 0.3

Table III. Calculated boundary value C'e under pulsed plating in

0.SM AgNO3-0.SM HNOa

0.02 1 ms
-

ip

0.2

(~1

0.006
0.06
0.12
0.06
0.15
1.5
1.2
2.0

Lay
(A]cm2)

~- ~. ", %. % , - . ~
o ~ ,,,
% -.\
t
30

F
60

t
90

\
120

Jay (mA/cm 2)
Fig. 10. Effect of average current density on surface concentration of
Ag + ions (0.5M AgNO3).

(A/cm 2)

(~)

iav
(A/cm2)

8N
(cm)

:~
( )

C'e
(M)

C]s
(M)

0.06
0.12
0.2
0.03
0.3
0.6
1
0.15
1.5
3
5
6
12
20

0.5
0.5
0.5
0.1
0.1
0.1
0.1
0.02
0.02
0.02
0.02
0.005
0.005
0.005

0.03
0.06
0.1
0.003
0.03
0.06
0.1
0.003
0.03
0.06
0.1
0.03
0.06
0.1

0.0140
0.0122
0.0110
0.0223
0.0140
0.0122
0.0110
0.0223
0.0140
0.0122
0.0110
0.0140
0.0122
0.0110

0.0001
0.0001
0.0001
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002

0.246
0.057
-0.460
0.248
0.061

0.243
0.053
-0.459
0.243
0.053

(ms)
2 x 103
28.1
0
3 10a
85
1.3
0

0.460 0.459 1.2 103

0.248 0.243 3.4
0.061 0.053 0.05
0

0.248 0.243 0.21

0.061 0.053 0.003
--0

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J. Electrochem. Soc., Vol. 136, No. 11, November 1989 9 The Electrochemical Society, Inc.
short, so the difference between C'~ and the surface concentration predicted by Eq. [1] at an average current density is minor. However, the calculated transition time, ~, is
less than the pulse-on time of 1 ms for many cases.
Thus, the critical condition under which the transition
time is reduced to be less than the pulse-on time of 1 ms is
demonstrated by a dotted line in Fig. 7. Above this dotted
line corresponding to the limiting current pulse characterized by T = ~, the pulse plating technique can be adequately applied to produce finer precipitates, while less
substantial i m p r o v e m e n t due to pulse plating is expected
below it. This dotted line crosses near the m i n i m u m point
of each curve at a particular duty cycle, except for
r = 0.005. Therefore, it will provide a good basis for the determination of the o p ti m u m scheduling of pulse plating.

Summary
Ag ~ ions were electrodeposited on a plane vertical silver
cathode installed in 0.5M AgNO3 and 0.5M AgNOa-0.5M
HNO3 solutions under direct and pulsed current. It was
found, through the experiments under direct current, that
Ag ions were preferentially electrodeposited on the surface of particles that had initially precipitated onto the
cathode and that the particle diameter was proportional to
the cube root of the charge density and decreased with increase in current density. The addition of HNO3 induced a
higher polarization and made a spheroidal shape of the
precipitated particle.
Pulse plating was conducted mainly in 0.5M AgNO30.5M H N Q solution and the average diameter was measured. Comparing this data with data obtained under direct
current showed that the effect of pulsed current on the
ratio of the diameters obtained by both processes was
most significant near the average current density of
50-60 mA/cm 2. Moreover, this effect was enhanced with reduction of the duty cycle, that is, with corresponding increase in pulse current density.
By measuring the surface concentration o f A g ions with
holographic interferometry, the qualitative soundness of
the duplex diffusion layer model proposed by Ibl was no*
ticed. Based on the duplex diffusion model, the transition
time at which the surface concentration of Ag ions is depleted to zero at the end of the pulse-on time was evaluated. This concept of limiting current pulse was reasonably compared with the experimental observation on the
ratio of precipitated particle diameter under pulsed current to that under direct current. The soundness of the
present way of estimating the limiting current pulse must
be further examined in many other metals and alloys in
order to provide a reasonable method to provide o p t i m u m
scheduling on pulse plating.

Acknowledgment
Part of this work was performed under financial aid
given to Y. F. by The Institute of Space and Astronautical
Science, to which the authors are grateful.
Manuscript submitted Nov. 28, 1988; revised manuscript
received April 21, 1989.

h:yoto University assisted in meeting the publication

costs of this article.

C*
CS
D1
d
iav
ip
q

LIST OF SYMBOLS
concentration in the bulk solution (mol/cm 3)
surface concentration of Ag ions (mol/cm 3)
diffusivity of Ag ion (cm2/s)
particle diameter (cm)
average current density (A/cm 2)
pulsed current density (A/cm 2)
amount of electricity (C/cm 2)

3283

Ra~

Rayleigh n u m b e r = gax301(-)
vD1

Ra*=

modified Rayleigh n u m b e r -

duty cycle ( - )

Sh=

Sherwood n u m b e r -

Ton
t
*t,
x
~N

pulse-on time (s)

time (s)
transfer n u m b e r ( - )
height from the lower edge of cathode (cm)
densification coefficient (cm3/mol)
diffusion layer thickness (cm)

~p

thickness of oscillating diffusion layer (cm)

01

concentration difference between the cathode surface and bulk electrolyte (mol/cm 3)
kinematic viscosity (cm2/s)
transition time (s)
density of bulk electrolyte (g/cm 3)
density of electrolyte at the cathode surface (g/cm 3)

v
p*
pS

gaiav(1 - *t,)x 4

zlFvD12

(-)

*h)x
(-)
zlFDl~l

ia~(1

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of Electrochemistry," Vol. 2, J. O'M. Bockris, B. E.
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