Effects of Oxygen Reduction on Nickel Deposition from

Unbuffered Aqueous Solutions : I . Deposition Process

and Deposit Structure
C. Q. Cui and Jim Y. Lee

J. Electrochem. Soc. 1994, Volume 141, Issue 8, Pages 2030-2035.

doi: 10.1149/1.2055055

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 Effects of Oxygen Reduction on Nickel Deposition from
Unbuffered Aqueous Solutions
I. Deposition Process and Deposit Structure

C. Q. Cut and Jim Y. Lee*

Department of Chemical Engineering, National University of Singapore, Singapore 05t I

ABSTRACT
In nickel deposition in the presence of dissolved oxygen, oxygen reduction occurred prior to nickel deposition, resulting
in the formation of poorly conductive Ni(OH)2 at the electrode surface. The presence of Ni(OH)2 suppressed the adsorption
of intermediate Ni(OH)ads, and the nucleation and crystal growth of nickel was inhibited as a result. The effects of oxygen
reduction on deposition, however, decreased with increasing NiCI2 concentration in the depositing solutions. This is
attributed to the increased competitiveness of Ni(OH)aas adsorption relative to Ni(OH)2 formation at high NiCl2 concentra-
tion. Nickel deposits of better uniformity and smaller grain size were produced in the presence of oxygen. However, a
porous nickel structure was not obtained under the experimental conditions. This disparity from the reactive deposition of
porous cobalt is explained in terms of a charge-transfer controlled electrode kinetics for nickel deposition and the stability
of Ni(OH)2 at the electrode surface.

Reactive deposition is a novel method for producing
highly porous metal structures by introducing oxygen into
the solution during electrodeposition. 1 Systematic studies
on cobalt deposition in the presence of oxygen were pio-
neered at the University of EssexY It was found that the
Co(OH)2 colloid layer formed upon 02 reduction at the elec-
trode surface inhibited the nucleation and crystal growth
of cobalt. The dynamic state of the colloid layer was di-
rectly responsible for the formation of a highly porous
cobalt deposit. Therefore, reactive deposition has the po-
tential to become a technologically important method of
producing highly porous metal structures and ultrafine
metal particles.
Porous nickel deposits a n d powders are strategic materi-
als that have found applications in the manufacturing of
catalysts, alkaline batteries, anticorrosion paints, mag-
netic storage media, and othersJ '~ As electrodeposition is
one of the most c o m m o n methods for preparing high sur-
face area nickel and nickel-alloy materials, it is of interest
to explore whether reactive deposition can further improve
the control and the quality of the existing process. The
electrodeposition of nickel has always been a favorite sub-
ject of research in fundamental studies.6-I~Examination of
the effects of oxygen reduction on nickel deposition will
provide additional insights into the basic mechanism of
nickel deposition.
The similarities in chemical and electrochemical proper-
ties between nickel and cobalt underwrite certain a priori
confidence in the application of reactive deposition to
nickel. W e have initiated a program for examining the reac-
tive deposition of nickel in detail and for evaluating the
suitability of this technique in the practical production of
fine nickel deposits. In this firstpart of a continuing series
of reports, the deposition on glassy carbon from unbuffered
aqueous chloride solutions is described. Emphasis is placed
on the macroscopic effects of oxygen reduction on the dep-
osition proper and on the morphology and structure of
the ensuing nickel deposits. Further work will concentrate
on the changes in electrode interracial details that have
given rise to some unsatisfying performances in this first
attempt.
Experimental
Electrochemical measurements were performed in a con-
ventional three-electrode cell using a computer-controlled
EG&G Princeton Applied Research (PAR) Mode] 273 po-
tentiostat/galvanostat. A 5 mm diam rotating glassy car-
bon (GC) disk electrode with a surface area of 0.196 cm 2
was used as the working electrode. The counter- and refer-
ence electrodes were a large area nickel foil (BDH) and a
* Electrochemical Society Active Member.
2030 J. Electrochem. Soc., Vol. 141, No. 8, August 1994 9 The Electrochemical Society, Inc.
saturated calomel reference electrode (SCE), respectively.
Particular care was taken to polish the GC disk electrode
with diamond paste, followed by thorough cleansing with
deionized water in an ultrasonic bath. The electrode, after
being dried on a tissue, was immediately used in the exper-
iments. The reproducibility of experimental results was
greatly improved by such pretreatment.
All chemicals used were of the AR grade. 1M KC1 was
used as the supporting electrolyte to reduce the ohmic drop
between the Luggin capillary of the reference electrode and
the working electrode. NiC12 - 6H~O was dissolved into the
electrolyte to various concentrations (0.05 to 0.5M) for
nickel deposition. In this work, the reduction of oxygen
was carried out in solutions saturated with dissolved oxy-
gen in order to avoid the stirring and shielding interference
of flowing oxygen. As a result, the electrolyte for reactive
deposition was purged with pure 02 for about 10 min prior
to the experiment. For comparative studies that required
an Q - f r e e electrolyte, the solutions were purged by N2 for
the same amount of time instead. In all cases the gas was
fed through a sintered glass plug directed right at the work-
ing electrode. A rotameter provided the necessary measure-
ment of the gas flow rate.
All experiments were carried out at room temperature.
All voltammetric experiments made use of sweeps starting
0.0
0.5
o
1.5
2.0
I I I i 1 I I
-1.2 -I.0 -0.8 -0.6 -0.4 -0,2 0
POTENTIAL, V vs SCE
Fig. 1. Voltammetric curves of nickel deposition on GC disk elec-
trode at 10 mV/sfrom O.05M NiCI2 in 1M KCI in the absence of
dissolved oxygen in the range of 0 V to different cathodic potential
limits.
J. Electrochem. Soc., Vol, 141, No. 8, August 1994 9 The Electrochemical Society, Inc. 2031

f r o m 0 V in the c a t h o d i c direction for the s t u d y of nickel

deposition. F o r the m e a s u r e m e n t of c u r r e n t - t i m e t r a n -
sients u n d e r p o t e n t i o s t a t i c excitations, the p o t e n t i a l was s0.00
stepped f r o m - 0 . 5 V w h e r e the n u c l e a t i o n of nickel w o u l d If} the presence ~f dissolved o~,yges

not occur. Ni was also d e p o s i t e d on c o p p e r foil (99.99%,

BDH) from 0.25M NiCI2 in 1M KC1 in the presence of either
f l o w i n g N2 or O2 (50 m l / m i n ) a n d the m o r p h o l o g y of the
deposits was e x a m i n e d on a J E O L - 3 3 0 X s c a n n i n g electron
microscope,
Results and Discussion
Voltammetric characteristics.-- The v o l t a m m o g r a m s of
nickel d e p o s i t i o n f r o m 0.05M NiC12 in 1M KC1 in the ab-
sence of o x y g e n at 10 mV/s are g i v e n in Fig. 1. The p o t e n t i a l
was scanned f r o m 0 V to different c a t h o d i c limits (indicated
by dashed lines). U n d e r such conditions, the v o l t a m m e t r i c
curves s h o w e d v i r t u a l l y zero c a t h o d i c current on the for-
w a r d scan u n t i l the onset of n u c l e a t i o n of nickel w h i c h
o c c u r r e d a r o u n d - 0 . 9 V. In the c a t h o d i c scan, two nickel
r e d u c t i o n peaks (I, II) a p p e a r e d p r i o r to the p r e d o m i n a n c e
of h y d r o g e n evolution. The o b s e r v a t i o n is similar to the
deposition on vitreous c a r b o n and Pd electrodes. 11'12A n a l y -
ses of ac i m p e d a n c e in nickel electrodeposition h a v e
suggested t h e presence of an a d s o r b e d i n t e r m e d i a t e such
as Ni(OH)a~. a'0'13 The i n t e r m e d i a t e is f o r m e d in the first
electron t r a n s f e r r e a c t i o n of Ni(OH) § to Ni(OH)ad~ and its
f o r m a t i o n is b e l i e v e d to be the r a t e - d e t e r m i n i n g step in
deposition 7,~44~
Ni 2+ + H20 = N i O H + + H § [1]
Ni(OH) § + e --> Ni(OH)~d~ [2]
In the electrolyte of 0.05M NiCI2 + 1M KC1 w h e n the current
of the first r e d u c t i o n p e a k (I) was correlated w i t h the elec-
t r o d e r o t a t i o n speed and the scan rate, the f o r m a t i o n of the
a d s o r b e d h y d r o x y l a t e d nickel c o m p l e x was best d e s c r i b e d
as q u a s i - r e v e r s i b l e a n d was u n d e r the m i x e d control of
b o t h electron t r a n s f e r a n d mass transfer. Ni(OH)a~ was
s u b s e q u e n t l y r e d u c e d to nickel m e t a l via two p a r a l l e l reac-
tion p a t h w a y s
Ni(OH),d, + Ni 2+ + 2e --->Ni + Ni(OH),d~ [3]
Ni(OH),~ + e --->Ni + OH [4]
A crossover of the c a t h o d i c a n d anodic currents was ob-
served w h e n the scan was r e v e r s e d at the foot of the two
r e d u c t i o n peaks. This feature is a n a l o g o u s to nickel deposi-
tion on vitreous c a r b o n 1~a n d is c h a r a c t e r i s t i c of a m e c h a n -
ism of n u c l e a t i o n and t h r e e - d i m e n s i o n a l growth. The h y -
d r o x y l a t e d nickel c o m p l e x N i ( O H ) ~ t h e r e f o r e f u n c t i o n e d
as b o t h a r e a c t i o n i n t e r m e d i a t e and as a catalyst associated
w i t h a p r o p a g a t i n g k i n k site in nickel deposition. 8
D u r i n g the deposition, protons (or water) were s i m u l t a -
neously d i s c h a r g e d to lead e v e n t u a l l y to the p r e d o m i n a n c e
of h y d r o g e n evolution. It has b e e n established t h a t the p r o -
d u c t i o n of h y d r o g e n atoms, H,~, is responsible for the pas-
sivation in nickel deposition at low p o t e n t i a l s due to the
f o r m a t i o n of n i c k e l - h y d r o g e n i n t e r m e t a l l i c compounds"
H20 + e --~ H~d~ + O H - [5]
2H,~ --> Hz [6]
~ 20. oo
2
g.9~
-1o.oo In the absenceOFdissolved oxygen
I I i I I I
-o.150 -0.250 -0.350 -0.450 -0.550 -0.650
E Iv)
Fig. 2. Voltammetric curves at 10 mV/s prior to the deposition from
0.25M NiCI2in 1M KCIwith and wi~out dissolved oxygen.
p o u n d s in the deposits h a d given rise to a distinguishable
green tint
Ni 2+ + 2 O H - = Ni(OH)2 [8]
S i m i l a r to the reactive deposition of cobalt, 2 oxygen re-
d u c t i o n p r e c e d e d nickel deposition in electrolytes rich in
dissolved o x y g e n (see Fig. 2). At the scan rate of 10 mV/s,
the current for oxygen r e d u c t i o n b e g a n to increase at
- 0 . 1 3 V and d e v e l o p e d into a p e a k at - - 0 . 5 0 V. This in
contrast to the current increase in only KC1 w h i c h w o u l d
only p r o d u c e a current plateau, z In u n b u f f e r e d n e u t r a l so-
lutions, oxygen r e d u c t i o n is k n o w n to occur by either the
f o u r - e l e c t r o n or the t w o - e l e c t r o n ]pathway
02 + 2H20 + 4e = 4 OH [9]
02 + H20 + 2e = H()2 + O H - [10]
The increase in the interracial p H as a result of o x y g e n
r e d u c t i o n f a c i l i t a t e d the f o r m a t i o n of nickel h y d r o x i d e at
the electrode via r e a c t i o n 8. The poorly c o n d u c t i v e Ni(OH)2
in t u r n c u r t a i l e d the o x y g e n reduction, resulting in a p e a k
in the v o l t a m m o g r a m of o x y g e n reduction.
Figure 3 shows the v o l t a m m e t r i c curves of nickel deposi-
tion on GC disk electrode at 10 mV/s f r o m 0.05M NiC12 in
1M KC1 in the presence of dissolved o x y g e n and different
cathodic p o t e n t i a l limits (indicated by a dashed line). In
c o m p a r i s o n w i t h the case w i t h o u t ,oxygen, the nickel depo-
sition is obviously i n h i b i t e d due to more facile f o r m a t i o n of
the poorly c o n d u c t i v e Ni(OH)2 at the electrode surface. In
the presence of oxygen, n u c l e a t i o n b e g a n at the p o t e n t i a l of
- 1 . 3 0 V, w h i c h was 400 mV more n e g a t i v e t h a n n u c l e a t i o n
0.25
0.75
z.25

t
Ni(OH),~ + Hads + e --->N i - H + H [7]
Therefore, in c o n t r a s t to reversing t h e c a t h o d e going sweep
a f t e r only the first r e d u c t i o n peak, in w h i c h case a c a t h o d i c ~, 1.75
p e a k was f o r m e d in t h e reverse scan, t h e reveraI of p o t e n -
tial a f t e r the second p e a k led to a relatively flat current 2.25
response because of h y d r o g e n p a s s i v a t i o n (see Fig. 1). P a s -
sivation was even m o r e severe if the p o t e n t i a l reversal was I I I I I I I
m a d e in the region of active h y d r o g e n evolution, in w h i c h -1.5 -1.3 -1.1 -0.9 -0.7 -0.5 -0.3
case -the c a t h o d i c current after reversal was v i r t u a l l y zero.
The i n h i b i t i o n in this case also c a m e f r o m the f o r m a t i o n of
POTENTIAL, V vs $CE
p o o r l y c o n d u c t i v e Ni(OH)2 as a result of the increase in
local p H in the electrode proximity. This was most e v i d e n t Fig. 3. Voltammetric curves of nickel deposition on GC disk elec-
in samples from a p r o l o n g e d deposition in w h i c h the accu- h'ode from 0.05M NiCI2 in 1M KCI in the presence of dissolved
m u l a t i o n of Ni(OH)2 or similar h y d r o x y l a t e d nickel corn- oxygen in the potential range of 0 V to - 1.45 or - 1.6 V at 10 mV/s.
2032 J. Electrochem. Soc., Vol. 141, No. 8, August 1994 9 The Electrochemical Society, Inc.

in the absence of oxygen. In addition, the first reduction O.375 I I I I I v

03.25 -In i~
Ill
/
peak associated with the formation of adsorbed hydroxy-
the presence of dissolved oxygen
lated complex Ni(OH)~d~ (reaction 2) also disappeared in the
presence of oxygen. The finding is similar to nickel deposi- 0.275 - In the absence o f d i s s o l v e d oxygen

tion from chloride solutions with brighteners such as 4- 0.225

ethylphenol and 4-nonylphenol ~7 in which the presence of
additives also eliminated the first reduction peak. The inhi-
bition had been attributed to the competitive adsorption of OA~
organic additives which lowered the surface coverage of
the adsorbed hydroxylated nickel complex. In reactive
deposition by O2, the formation of the adsorbed intermedi- 0.0250"075 ~ ~ ~ ~ //7
ate had to compete with the facile formation of Ni(OH)2 at
the electrode surface. The suppression in adsorbed inter- -0.025 __0100 I I I
mediate formation led to the inhibition in eventual nickel OJO0 -0.300 -0,500 -0,700 -0.900 -~.iO0 -t.300
deposition. The deposition of nickel from the 0.05M NiC12 E (V}
solution in the presence of oxygen was therefore predomi-
nantly controlled by the effectiveness of the first charge
transfer, reaction 2, the overall deposition of nickel was 2,BOO I I ~ I I I

made more irreversible due to more Ni(OH)2 being formed

2,400 ------ In the presence o f d i s s o l v e d oxygen
in the presence of oxygen.
Ni(OH)2 at the electrode could be reduced via the follow- 2,000 In ~he absence o f d i s s o l v e d oxygen A ~/~-~
ing reaction, 1 i, if the potential sweep continued further in
the cathodic direction
~.2oo 1
Ni(OH)2 + 2e --->Ni + 2 O H - []1]
0.B00
The e x t e n t of r e a c t i o n 11 in nickel d e p o s i t i o n in the pres-
ence of o x y g e n r e d u c t i o n was e s t i m a t e d f r o m the cross- 0.400 _ ~ J / /
o v e r p o t e n t i a l s in the v o l t a m m e t r i c curves. F o r depositions
0,000 ..... --~
t h a t f o l l o w reversible or q u a s i - r e v e r s i b l e kinetics, the
crossover p o t e n t i a l is closely associated w i t h t h e equi-
l i b r i u m p o t e n t i a l of m e t a l deposition. If h y d r o g e n evolu-
tion did not occur to a large e x t e n t in nickel deposition so
t h a t the c u r r e n t in the reverse scan was not fully inhibited,
-0,400
0AO0 -0.1~00 I
-0.300 I
-0.5o0
E
I
-o.?0o I
-0.900
(v}
-!/100 -d.300

Fig. 4. Voltammetric curves of nickel deposition on GC disk elec-

the crossover p o t e n t i a l was d e t e r m i n e d f r o m Fig. 3 to be trode at 10 mV/s from 0.1M (a, top) and 0.SM NiCI2 (b, bottom) in
- 1 . 1 0 V, a v a l u e m u c h more n e g a t i v e t h a n the s t a n d a r d 1M KCI with or without dissolved oxygen.
e q u i l i b r i u m p o t e n t i a l of - 0 . 9 0 V for r e a c t i o n 11. On the
contrary, the crossover p o t e n t i a l u n d e r similar conditions
was - 0 . 7 2 V w h e n O2 was e x c l u d e d f r o m the solution. cleation potentials between depositions with and without
Therefore, the possibility of the e l e c t r o c h e m i c a l r e d u c t i o n oxygen decreased. The diminishing effect of oxygen reduc-
of Ni(OH)2 (reaction 11) could not be e x c l u d e d in nickel tion on nickel deposition could be attributed to a more
d e p o s i t i o n in the presence of oxygen. However, it was fur- competitive adsorption 'of Ni(OH)ad~ at high Ni concentra-
t h e r f o u n d t h a t nickel deposition in the presence of O2 was tions. The formation of Ni(OH)ads (reaction 2) was promoted
i n d e p e n d e n t of the electrode r o t a t i o n speed, s h o w i n g the by the increase in NiC12 concentration. The formation of
c h a r a c t e r i s t i c of a c h a r g e - t r a n s f e r controlled process. All Ni(OH)2 at the electrode surface, on the other hand, was
evidence, therefore, p o i n t e d to the p r e s e n c e of a h i g h l y sta- rate limited by the diffusion of dissolved oxygen, and was
ble Ni(OH)2 phase at the electrode surface. In the r e a c t i v e
hardly affected by changes in the nickel concentration. The
d e p o s i t i o n of cobalt, the Co(OH)2 layer f o r m e d at the elec-
increasing presence of Ni(OH)~ds led finally to a detectable
t r o d e surface can be b r o k e n d o w n effectively by gas sparg-
reduction peak in 0.5M NiCl2. As stated earlier, the hydrox-
ing and by electrode rotation. 3 S u c h is not the case in the
ylated nickel complex Ni(OH)ads functioned both as a reac-
r e a c t i v e d e p o s i t i o n of nickel b e a u s e of the h i g h e r stability
of Ni(OH)2. As a result, the c h a r a c t e r i s t i c localized n u c l e - tion intermediate and as a catalyst associated with a prop-
ation and l i m i t e d crystal g r o w t h processes in cobalt r e a c - agating kink site,8 its formation was in close relation with
tive deposition was not a t t a i n a b l e in nickel deposition f r o m the nucleation potential. The descending cathodic shift in
u n b u f f e r e d solutions in the presence of oxygen. The inac- nucleation potential in the presence of oxygen with in-
tivity of Ni(OH)2 f o r m e d u p o n o x y g e n r e d u c t i o n at the elec- creasing NiCI2 concentration indicated a more proficient
trode was therefore deleterious to the f o r m a t i o n of porous formation of the adsorbed intermediate, and the restora-
nickel deposits by r e a c t i v e deposition. tion of deposition to normality.
F i g u r e 4 c o m p a r e s the v o l t a m m e t r i c curves of nickel In nickel deposition in the presence of oxygen, the
d e p o s i t i o n at 10 mV/s f r o m v a r i o u s NiC12 c o n c e n t r a t i o n s crossover potential in the voltammetric curves was also
w i t h a n d w i t h o u t dissolved oxygen. F r o m Fig. 4a, t h e n u - substantially changed with increasing NiCl2 concentration
c l e a t i o n p o t e n t i a l in the presence of dissolved o x y g e n was in the solutions. In 0. IM NiCI2, the crossover potential was
o b v i o u s l y m o r e n e g a t i v e t h a n t h a t in the absence of dis- -0.78 V in the presence of oxygen when the first reduction
solved o x y g e n for the 0.1M NiC12 solution. In addition, the peak was not apparent. The crossover potential was shifted
first r e d u c t i o n p e a k c o r r e s p o n d i n g to the f o r m a t i o n of the
h y d r o x y l a t e d nickel c o m p l e x (reaction 2) also d i s a p p e a r e d
in the p r e s e n c e of dissolved oxygen. However, w h e n the Table I. Characteristics of nickel deposition on glassy carbon
NiCI2 c o n c e n t r a t i o n was i n c r e a s e d to 0.5M, the first r e d u c - from voltammetry at 10 mV/s in the presence and absence
tion p e a k r e a p p e a r e d in deposition w i t h dissolved oxygen,
of dissolved oxygen.
as was similar to the case w i t h o u t dissolved oxygen. At a
Nucleation potential Crossover potential
h i g h nickel c o n c e n t r a t i o n the f o r m a t i o n of Ni(OH)2 at the (v) (v)
electrode f r o m o x y g e n r e d u c t i o n seemed to exercise little
i n f l u e n c e on the deposition proper. Table I lists the n u c l e - Solutions No O2 Dissolved O2 No O2 Dissolved O2
ation p o t e n t i a l s a n d the c r o s s - o v e r potentials of nickel de-
p o s i t i o n f r o m solutions w i t h different NiC12 c o n c e n t r a t i o n s 0.05MNiC12 + 1MKC1 -0.96 -1.30 -0.70 -1.10
0.10M NiC12 + 1M KC1 -0.94 -1.13 -0.62 -0.78
in the presence or absence of oxygen. As the NiC12 concen- 0.25M NiC12 + 1M KC1 -0.94 -0.98 -0.62 -0.65
t r a t i o n in the solutions was increased, the difference in n u - 0.50M NiC12 + 1M KCI -0.94 -0.95 -0.62 -0.62
J. Electrochem. Soc., Vol. 141, No. 8, August 1994 9 The Electrochemical Society, Inc. 2033
.200 I I I , I i I
l" 2.000

li -l.lV I~ the absence of dissolved oxygen

'~\ No D~ssolved Oxygen
.500 \
0.
'~.~]00
O00 tI 'i ,. ,_~.,ov \
\

i\i \ ".I \
~.200

0.B00
\

....

o2oo
!
. ! ~ .
I
9v
................
~ ' - ~
0400 /
0.000 0,000 "~
f I I I I I I
__I01.00 I I I
-5.000 5.000 ~.5.00 25,00 35.00 45.00 55.00 t0.00 30.00 50.00 70 i O0 I
90.00
t (s} t (s)

Fig. 5. Current transients of potentiostatic deposition obtained from Fig. 7. Current h'ansients from the potentiostatic deposition at
0.1M NiCI2 in 1M KCI in ~ e absence of dissolved oxygen at different -0.9 V from 0.5M NiCI~ in 1M KCI w i ~ and Mthout dissolved
potentials. oxygen.

to - 0.62 V in 0.5M NiC12 where the first reduction peak was straight line of slope 3 (n). The value of n is indicative of a
also clearly visible. The descending cathodic shifts in the progressive three-dimensional nucleation and crystal
crossover potentials therefore mirrored closely the changes growth process that was under interracial electron transfer
in the nucleation potential as they were both manifested by control. 19 Furthermore, the same i - t '~ dependence from
the increase in the adsorption coverage of Ni(OH)~d~ with the rising part of the peak also persisted even with increas-
increasing NiC12 concentration. The positive shifts in both ing NiC12 concentration up to 0.5M. This was different from
nucleation potential and crossover potential would eventu- the nickel deposition from 0.5M NiCI2 on vitreous carbon
ally remove any difference in nickel deposition with and electrode, 17where an instantaneous three-dimensional nu-
without oxygen at high NiCI~ concentration. cleation and crystal growth was claimed.
Figure 7 compares the current transients of potentio-
Potentiostatic current-time transients.--Analysis of the
current transient in potentiostatic deposition on a foreign static depositions from 0.5M NiC12 in 1M KC1 with and
substrate is often used to delineate the kinetics of two- and without oxygen. A longer induction period for nucleation is
evidently required for deposition in the presence of dis-
three-dimensional nucleation and crystal growth, the sur-
solved oxygen. The inhibition effect on nucleation is simi-
face morphology of the deposit, and the influence of addi-
lar to that in a Watts nickel bath with added organic
tives and so on. ~8'19Figure 5 shows the current-time tran-
brighteners. 17 In the present case, the longer induction for
sients at different deposition potentials obtained from a
nucleation was caused by the facile formation of surface
0.1M NiC12 + 1M KC1 solution without dissolved oxygen. As
Ni(OH)2 from oxygen reduction. Ni(OH)2 suppressed the
was typical in regular nucleation and growth processes,
adsorption of the hydroxylated nickel complex that was
two current maxima with different time constants ap-
precursory to the nucleation of nickel. Table II lists the
peared at low potentials. However, the first peak was not
induction times from chloride solutions of different NiC12
noticeable at higher potentials due to the rapid increase in
concentrations in the presence and absence of oxygen. The
the initial current transient and the limitations of the elec-
induction time was defined as the time taken to reach the
trochemical instrumentation. The first peak could be inter-
current m ax i m u m in the current transient and was indica-
preted in terms of a monolayer deposition of nickel via
tive of the ease of nickel nucleation. In all cases the induc-
two-dimensional nucleation and crystal growth in the com-
tion time decreased with increasing NiC12 concentration. In
pany of hydrogen evolution. The monolayer deposition, not
addition, the difference in induction time between deposi-
unlike normal electrocrystallization, was progressive at
tions with and without oxygen also diminished with the
low potentials and instantaneous at high potentials.~7'2~ The increase in NiC12 concentration. The diminishing effect of
more salient feature of nickel electrocrystallization,
02 under high Ni concentration was therefore of the same
namely, the second peak, was analyzed by examining the nature as that in voltammetric deposition. The high Ni con-
i - t = dependence of the rising response. Figure 6 shows the centration promoted the formation of the hydroxylated
logarithmic plot of current vs. time, which has resulted in a nickel complex (reaction 2) whereas the formation of
Ni(OH)2 was not benefited by such increases because it was
i limited by the diffusion of dissolved oxygen.
Similar to deposition without oxygen, an i - t 3 depend-
-0.9V ence was also found in the presence of oxygen. The electro-
crystallization of nickel in the presence of oxygen therefore
also proceeded via the progressive three-dimensional nu-
cleation and crystal growth process under interfacial elec-
tron transfer control. The presence of Ni(OH)2 at the sur-
0,1
face did not alter the electrocrysta][lization characteristics
of nickel, just as in the case of the reactive deposition of
w
cobalt. 3

Table II. A comparison of induction time for nucleation for

for nickel deposited potentiostoticallyat - 1.0 V
in the presence and absence of dissolved oxygen.
0.01

I0 20 30
, Induction tirae (tin), s
Solutions No O2 Dissolved 02 Difference (At~)
TItlE, sec
0.10M NiC12 + 1M KC1 8.23 -- --
Fig. 6. Lcmjarithmic plot of current vs. time from the rising part of 0.25M NiCle + 1M KC1 2.30 8.82 4.52
Fig. 5 at a deposition potential of - 0 . 9 V. 0.50M NiC12 + 1M KC1 2.28 5.22 2.94
2034 J. Electrochem. Soc., Vol. 141, No. 8, August 1994 9 The Electrochemical Society, Inc.
Fig. 8. Surface morphology of nickel deposited from 0.25M NiCI2 in 1M KCI in flowing N2 in the absence of oxygen (A) and flowing O2
(B) at 50 ml/min. The deposition was carried out potentiostatically at -1.1 V for 60 s.
Scanning electron microscopy.--The micrographs in
Fig. 8 show representative surface morphology of nickel
deposited from 0.25M NiCI~ in 1M KC1 with either flowing
N2 or 02 at 50 ml/min. The deposition was carried out po-
tentiostatically at -1.1 V for 60 s. Irrespective of the pres-
ence or absence of oxygen, the nickel surface was popu-
lated by cracks commonly indicative of high stresses in the
deposits. The presence of cracks on the nickel surface has
been attributed to the precipitation of the hydroxylated
nickel complex and the evolution of hydrogen during depo-
sition. Likewise, more pronounced cracks were found in
the deposition in the presence of oxygen due to precipita-
tion of the poorly conductive Ni(OH)2 during deposition. Of
more significance was the observation of many cubic crys-
tal grains of variable size on the surface of the deposit
obtained without dissolved oxygen. Deposition in the pres-
ence of oxygen, however, produced a more uniform crystal
surface with virtually no remnants of such growth sites.
The result strongly suggests that the presence of Ni(OH)2 at
the electrode surface inhibited the nucleation and crystal
growth of nickel to a large extent, and as a result deposits
of improved uniformity and finer grains were formed in the
presence of oxygen.
The deposit surface morphology was largely determined
by the electrocrystallization process. Irrespective of the
presence or absence of oxygen, a dense structure of the
deposit was formed as a result of three-dimensional pro-
gressive nucleation and crystal growth under interracial
electron transfer control. The deposition mechanism was
markedly different from the reactive deposition of cobalt in
which a highly porous structure was produced. 3 It was
stated that reactive cobalt deposition occurred similarly
via a three-dimensional progressive nucleation and crystal
growth process which was, however, under the mixed con-
trol of both mass transfer and electron transfer. 21 With the
inhibition effects of the dynamically instable Co(OH)2
colloid layer at the electrode surface, localized nucleation
and limited crystal growth prevailed in cobalt reactive
deposition and were directly responsible for the formation
of porous structure. 3 The localized nucleation and limited
crystal growth process was hardly reached in nickel depo-
sition because the inhibiting Ni(OH)2 layer at the electrode
surface was highly stable. A porous nickel deposit may be
possible if the stability of the Ni(OH)2 layer can be reduced
through a decrease in the interracial pH from oxygen
reduction, or through an increase in the concentration
polarization of Ni deposition. These ideas will be explored
in a followup study.
Conclusions
Nickel was deposited on glassy carbon electrode in u n -
buffered chloride solutions without dissolved oxygen via
the adsorbed intermediate Ni(OH)a~. The electrocrystal-
lization showed characteristics of progressive three-di-
mensional nucleation and crystal growth under interfacial
electron transfer control that was not even changed in the
presence of oxygen. Oxygen reduction, however, did occur
prior to nickel deposition, resulting in the formation of
poorly conductive Ni(OH)2 layers at the electrode surface.
The presence of Ni(OH)2 suppressed the adsorption of
Ni(OH)ads , and the nucleation and crystal growth of nickel
was inhibited as a result. The effects of oxygen reduction on
deposition diminished with increasing NiCl~ concentration
in the solutions, due mostly to increased competitiveness of
Ni(OH)ad, adsorption relative to Ni(OH)2 formation that
was not benefited by the increase in Ni concentration. The
Ni(OH)2 layer at the electrode surface was highly stable
and rendered the deposition of nickel more irreversible.
Nickel deposits of better uniformity and smaller grain
structure were produced in the presence of oxygen. How-
ever, a porous nickel structure was not obtained. This is
markedly different from the reactive deposition of cobalt in
the presence of oxygen. The disparity was attributed to a
different deposition kinetics for Ni (charge-transfer con-
trolled) and the stability of the Ni(OH)2 layer at the elec-
trode surface. These factors did not provide a conducive
environment for localized nucleation and limited crystal
growth that was instrumental in the reactive deposition of
porous cobalt. A porous nickel structure may be possible if
the interracial pH from oxygen reduction can be decreased
to impart dynamic instability to the Ni(OH)2 layer.
Acknowledgments
The authors would like to express their gratitude to Mr.
S. K. Tung for the SEM examination of nickel deposits. The
work is financially supported by The University research
grant (RP 920616), National University of Singapore.
Manuscript submitted Dec. 29, 1993; revised manuscript
received March 15, 1994.
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Incorporation of Impurity Metal Ions in

Electrolytic Manganese Dioxide
Hiroki Tamura,* Kenji Ishizeki, Masaichi Nagayama, *'~ and Ryusaburo Furuichi
Faculty of Engineering, Hokkaido University, Sapporo 060, Japan

ABSTRACT
The amounts of impurity metal ions incorporated into electrolytic manganese dioxide (EMD) during its preparation
were measured as a function of metal ion concentrations and current densities. The amount of incorporated ions increased
in proportion to the concentration in solution and at a fixed concentration it was different from ion to ion: Ni 2. < Zn 2. <
Co2. < Cu z*< Fe 3. < Pb 2+.The specific surface area of the formed EMD was larger for impurity ions with higher incorporation
affinity. Further, the adsorption of ions on the surface of a ready-made manganese dioxide sample (IC12) was examined,
and modeling of the adsorption behavior was attempted. The amounts of adsorbed ions at a fixed concentration in solution
and pH 0.7 (where EMD is produced) were obtained by the ion-adsorption model. There was a strong correlation between
the amount incorporated and the amount of adsorption, suggesting a mechanism in which EMD is eontaminated through
adsorption on its new growing surface. The increase in specific surface area of EMD with contaminants was interpreted to
be due to a suppression of the growth of EMD at the adsorbed foreign ion sites, resulting in EMD with many defects or
smaller particle sizes. The opposite effect of current density on incorporation for the two groups of metal ions was
discussed.

Manganese dioxide for battery use is produced mainly by
electrolysis of manganese sulfate solutions, and the
product is called electrolytic manganese dioxide (EMD).
This EMD is contaminated during production due to incor-
poration of various kinds of impurity ions from the elec-
trolyte solutions.
Contaminants, especially heavy metal ions, in the m a n -
ganese dioxide cathode accelerate the corrosion of the zine
anode, evolve hydrogen, and reduce the shelf life of dry
batteries. 1 This corrosion can be inhibited by amalgamat-
ing the zinc anode with mercury, but mercury addition has
been b a n n e d for environmental reasons. The production of
high purity EMD is, thus, very critical for batteries, and
removal of impurities from manganese ore leaehates has
been attempted. 2
Incorporated foreign ions in EMD also affect the electro-
chemical properties of the EMD cathode. It is reported that
with increasing potassium ion content, the ~/-MnO2 content
decreases, while the content of the less active ~-MnO~ in-
creases. ~ As a result, the cathode potential becomes lower,
and cathodic current densities decrease. Good battery per-
formance, however, has been achieved with Fe3+-containing
EMD. 4 Improvement of the charge-discharge characteris-
tics of EMD by inclusion of nickel and titanium ions has
been reported, ~ and the modification of manganese oxides
by introducing foreign cations to become fully recharge-
able has been proposed. 6
It is important to know the incorporation behavior of
ions into EMD to obtain very pure EMD free from impurity
ions or to he able to dose EMD with ions to improve its
* Electrochemical Society Active Member.
a Present address: Nippon Chemicon Co., Ltd., Higashigotanda
1-11-15-15, Shinagawa-ku, Tokyo 141, Japan.
electrochemical properties. Little is known, however, about
the quantitative aspects of incorporation.
In this investigation, kinds and amounts of incorporated
ions in EMD were studied as a function of the composition
of electrolyte solutions and the anodic current density. The
incorporation behavior of ions was compared with the ad-
sorption behavior of ions on manganese dioxide, character-
ized by the method developed by the authors. 7-12 Correla-
tion between incorporation and adsorption was found, and
the mechanism of incorporation is discussed based on the
experimental findings.
Experimental
Materials.--Reagent grade sulfates of Mn 2§ Pb 2~, Fe2§
Cu 2§ Co S§ Z n 2§ and Ni 2. were used. without further purifi-
cation. The cathode was a 6 mm diam spectrophotometric
graphite rod, and the anode was a 15 cm 2 t i t a n i u m plate.
Preparation of EMD.--The electrolyte solutions were
500 cm 3of 0.85 mol dm -3 MnSO4-0.40 mol dm -3 H2SO4 mix-
tures (pH 0.7), to which Pb 2§ Fe 2§ Cu 2§ Co S§ Zn z*, and Ni 2.
ions were added as sulfates at ion concentrations from
0.1 to 100 mg dm -3. The anodic oxidation of Mn 2. was
carried out at 97~ with constant currents from 0.075 to
0.15 A (anodic current densities 0,5 to 1.0 A dm -2) under
stirring. The amount of charge was fixed at 5.4 • 103 C,
which yielded about 2.5 g of MnO~, and the time for elec-
trolysis was 10 to 20 h depending on the current. The ac-
companying changes in electrolyte concentrations were
less than 10%. The cathode was separated from the bulk
solution with a porcelain tube to prevent reduction of the
added metal ions.
Analyses of EMD.--The deposited EMD was removed
mechanically from the anode, ground in a porcelain mortar,
washed thoroughly with distilled water until the washing