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 Journal of The Electrochemical Society, 153 共5兲 C357-C364 共2006兲 C357
0013-4651/2006/153共5兲/C357/8/$20.00 © The Electrochemical Society

Effects of Deposition Conditions on the Morphology of Zinc

Deposits from Alkaline Zincate Solutions
R. Y. Wang,a,*,z D. W. Kirk,a,** and G. X. Zhangb
a
Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Ontario,
Canada, M5S 3E5
b
Teck Cominco Metals, Limited, Mississauga, Ontario, Canada, L5K 1B4

The morphology of zinc deposits from alkaline zincate solutions was systematically investigated over a wide range of conditions.
Zinc deposit morphology was categorized as heavy spongy, dendritic, boulder, layerlike, and filamentous mossy. The formation of
dendritic, layerlike, and mossy deposits is under single-factor control, and these morphologies are defined as type I. The formation
of heavy spongy and boulder deposits is under multiple-factor control, and they are defined as type II. Within type I, dendrite
initiation and growth are both under diffusion control, while layer and mossy formation is under activation control. Based on the
effects of deposition conditions, morphology diagrams were constructed. These diagrams demonstrate that the control factors are
not independent, and no universal critical overpotential for a specific deposit morphology exists.
© 2006 The Electrochemical Society. 关DOI: 10.1149/1.2186037兴 All rights reserved.

Manuscript submitted September 30, 2005; revised manuscript received January 17, 2006.
Available electronically March 31, 2006.

Electrodeposition of zinc is important in electrowinning, electro-
galvanizing, and zinc rechargeable batteries.1 The morphology of
zinc deposits and its control play a critical role in the quality and
performance of the final products. Early morphology studies of zinc
deposition were driven by the application of zinc electrowinning,
where deposits were obtained from acidic chloride or sulfate solu-
tions. Later, interest in developing rechargeable zinc batteries as a
high-energy power source has stimulated sustained research on
deposition from alkaline zincate solutions. The cycle life of re-
chargeable zinc batteries has been found to be limited by the mor-
phological changes of the zinc electrode related to shape change,
dendritic formation, and loss of porosity.
Naybour2 reported three types of deposits, dendritic, layer-like
mixed with boulder, and mossy. Diggle and co-workers3 found that
below an overpotential of 85 mV, a spongy deposit formed, and
above 140 mV, a mixed spongy and dendritic deposit formed. A
critical overpotential for dendritic initiation was determined to be
75–85 mV. Diggle concluded that dendritic initiation was under dif-
fusion control, while the growth stage was under activation control.
Mansfeld and Gilman observed that at 200 mV, dendrites developed
from the electrode surface directly,4 rather than from the tips of
protrusions or pyramids.3 Moshtev and Zlatilova5 found the average
radius of curvature at the protrusion tips increased proportionally
with time. The effects of variables, including overpotential, electro-
lyte composition, and substrate orientation on the dendritic precur-
sors were investigated. Moshtev stated that the overpotential was the
critical variable rather than the current density 共cd兲 for deposit mor-
phology. Efforts have been made toward preventing dendritic forma-
tion by applying various charging methods,6-8 lowering zincate
concentration,9-14 and applying convection.15,16
Other deposit structures have also been studied to a more limited
extent. Bockris and co-workers17 attributed layerlike growth of zinc
at low overpotential to the bunching of monatomic steps into mac-
rosteps due to the higher surface energy of the edge plane than the
surface plane. At higher overpotential, nucleation occurred more
generally, giving rise to a uniform growth of boulder deposits. Based
on cyclic voltammogram 共CV兲 experiments, Lamping and
O’Keefe18 proposed that zinc followed a lateral growth mode at low
overpotential, but at high overpotential a vertical growth mode
dominated.
The formation of mossy deposits has been reported.2,6,17,19 Nev-
ertheless, before the development of the scanning electron micro-
scope 共SEM兲, there was difficulty in distinguishing mossy from
* Electrochemical Society Student Member.
** Electrochemical Society Active Member.
z
E-mail: rainey@chem-eng.utoronto.ca
heavy spongy deposits20 due to their similar appearance, i.e., black
powder. Jaksic21,22 studied the inhibition of mossy deposits and
found that copper catalyzed hydrogen reduction and triggered
spongy deposits; molybdenum, lead, and mercury suppressed or
eliminated mossy formation. Jaksic also claimed that mossy forma-
tion was an autocatalytic, mass-transfer-controlled process. Cachet23
attributed mossy formation to anodically dissolved zinc.
McBreen and Gannon24 examined 2–4% w/v 共weight/volume兲
addition of HgO, Ti2O3, PbO, CdO, In2O3, and Ga2O3
to pasted ZnO electrodes. These metals 共except for gallium兲 were
believed to deposit before zinc and act as a substrate. Those with
interatomic distances close to zinc yielded fine deposits. Other
additives that have been found to influence zinc morphology
include tin,25,26 antimony,18 lead,17,25-27 tetraethyl ammonium,27
perfluorosurfactants,28 polyoxylethylene,29 citrate,30 and fluorinated
surfactants.23
In spite of the numerous investigations on the morphology of
zinc deposits from alkaline solutions, there is still a lack of system-
atic characterization and understanding. It is the objective of this
study to investigate the complete range of morphological variations
with respect to the common deposition conditions. The results will
be presented in three papers. The aim of this paper is to characterize
and categorize the morphological features of zinc deposits. Attempt
is made to link the controlling mechanism to the deposit morphol-
ogy change. Understanding of the mechanisms involved in the for-
mation of various morphologies will be dealt in a following paper.
Experimental
The electrolyte was 7 mol L−1 共M兲 KOH solution saturated with
ZnO 共0.7 M兲. It was prepared by dissolving analytical reagent 共AR兲-
grade KOH pellets and ZnO powder in triple-distilled water. The
solution was stirred for 4 h accompanied by nitrogen bubbling to
remove oxygen. A gelled electrolyte was prepared by mixing
7% w/v potassium polyacrylate with 93% w/v 0.7 M zincate solu-
tion. The mixture was stirred at room temperature for 70 h, followed
by a few minutes vacuum to remove air bubbles trapped in the gel.
Polycrystalline zinc sheet was obtained from Alfar Aesar 共99.9%兲.
Zinc single crystals 共slowly cast, bulk zinc containing large grains,
courtesy of Teck Cominco兲 were obtained by cleavage of the zinc
sample at liquid nitrogen temperatures. In order to obtain the desired
surface area, foil electrodes were coated with epoxy 90HS 共Amer-
coat Canada兲, and single crystals were mounted in epoxy resin
共LECO兲.
In the study of the effects of deposition conditions, a rectangular
cell was modified to obtain a 267-mL Hull cell31 共Fig. 1兲. The rect-
angular cell was divided by a clear separator to keep the trapezoidal
shape of the Hull cell. For in situ microscopy, the electrolyte was
filled in both sides of the separator to avoid reflection from the
C358 Journal of The Electrochemical Society, 153 共5兲 C357-C364 共2006兲

of deposition. Filamentous mossy deposits have the appearance of

Figure 1. The modified Hull cell: 共1兲 separator, 共2兲 auxiliary cathode, 共3兲
cathode, 共4兲 anode, and 共5兲 microscope with CCD camera.
conventional angled Hull cell. Another modification was that an
auxiliary cathode was placed in front of the cathode and was pulled
up to expose one-quarter more of the cathode at each time interval.
Thus, deposits on the cathode were divided into four time regions.
The Hull cell was calibrated at each experimental condition. For
calibration, a cathode was sectioned into ten insulated pieces, and
the current passing through each piece was determined. The current
density 共cd兲 vs location plot was then used to interpret site-specific
cd. After deposition, boundaries dividing adjacent deposit mor-
phologies on a Hull cell cathode were identified using an optical
microscope 共Olympus SZ11兲, and the apparent cd at boundaries was
determined from the cd calibration plot.
The reference electrode was Hg/HgO. A Solartron 1280B unit
was used for current or potential control. In potential control, current
interrupt was used for IR compensation. Hitachi S4500 and S5200
SEM were used for scanning electron microscopy. A Philips
PW3710 diffractmeter was used for crystallographic determination.
A Coulter SA3100 was used to determine deposit Brunauer-Emmett-
Teller 共BET兲 surface area, using N2 as absorbent.
Results
Categorization of deposit morphology.— Zinc deposits were re-
ported as dendritic, layerlike, and mossy, developing at high, mod-
erate, and low cd, respectively.2 In this study, based on deposit crys-
tallinity and microstructure, zinc deposits were divided into five
categories: heavy spongy, dendritic, boulder, layerlike, and filamen-
tous mossy, as summarized in Table I.
As illustrated in Fig. 2, heavy spongy deposits are large boulder
agglomerates and highly branched dendrites, developing at very
high cd and after long deposition time. Dendrites are treelike and
can be hexagonal if deposition is slow. Boulders are typically hex-
agonal shape in discrete assemblies. Layer-by-layer growth on indi-
vidual boulder deposits can be seen from the image. Layerlike de-
posits are epitaxial growth and are typically found at the beginning
tangled whiskers with a typical diameter of 50–200 nm and lengths
that can exceed 5 ␮m.
Effect of surface preparation.— The initial deposition is greatly
affected by electrode surface conditions, such as surface roughness,
contamination, and oxidation condition. These conditions are also
critical to experimental reproducibility in electrochemistry. Deliber-
ately changing surface conditions can provide valuable information
for revealing deposition mechanisms. Prior to deposition, zinc elec-
trodes are usually degreased, mechanically ground, and acid-etched.
The effect of electrode preparation was demonstrated by studying
the effect of mechanical grinding and acid-etch.
Effect of grit size of Si carbide paper.— After grinding with
1200-grit Si carbide paper, half of the electrode surface was ground
with 180 grit. As a result, coarse and smooth surfaces were gener-
ated on the same electrode. As illustrated in Fig. 3a, at low cd,
mossy deposits tended to grow along grooves caused by grinding. At
high cd 共Fig. 3b兲, dendrites developed on both smooth and coarse
surfaces. The dendrites were relatively uniform in terms of number
and size over the entire electrode, indicating much less sensitivity to
surface roughness.
Effect of acid-etch.— After grinding with 1200-grit Si carbide
paper, half of the electrode was etched with 25% HNO3 for 10 s. At
low cd, electrodeposition produced large numbers of mossy deposits
on the unetched surface compared to few mossy deposits on the
etched surface 共Fig. 4a兲. At higher cd, the morphology was boulder
on both surfaces. Fewer but larger boulder deposits were found on
the unetched electrode surface than on the etched electrode surface
共Fig. 4b兲.
The effect of etching suggests that during mossy initiation, mi-
crozinc particles generated in mechanical grinding provide consid-
erable numbers of heterogeneous nucleation sites. The acid-etch dis-
solves these sites and reduces the opportunity for mossy deposits to
nucleate. At high cd, nucleation of boulder and dendritic deposits is
possible regardless of availability of nucleation centers. This result
is consistent with the grit size results. The abrasion sites in deep
grooves produced in mechanical grinding cannot totally be removed
in washing or acid etching, and thus act as nucleation centers in
mossy initiation. The above effects suggest mossy initiation is de-
termined by the nucleation process and thus is highly site-selective,
while dendritic and boulder formation is not selective.
Effect of substrates.— On substrates other than zinc, the crystal-
lographic misfit between the substrate and zinc deposit affects de-
posit morphology. As demonstrated in Fig. 5, at low cd, layerlike
deposits were not obtained on copper, nickel, or iron substrates.
Instead, boulder deposits followed by mossy deposits were found.

Table I. Categorization of Zn deposits.

Heavy spongy Dendritic Boulder Layerlike Mossy

Appearance 共unaided Black powder Metallic Gray metal Shiny metal Black powder
eye兲 crystal
Microstructure Agglomerate Fern, leaf, Granular Ridge, layerlike Filament,
共under microscope兲 large boulder hexagon boulder whisker
Adherence Nonadherent Nonadherent Adherent Adherent Nonadherent
Porosity Dispersed Dispersed Compact Compact Highly porous
nonporous nonporous
Crystallinitya Anisotropically Isotropically Anisotropically Epitaxial Isotropically
oriented oriented oriented oriented oriented
Growth cd Highest Very high Moderate Low Lowest
Nucleation site Nonselective Nonselective Selective Nonselective Highly
selectivity selective
Category Type II Type I Type II Type I Type I
a
Anisotropically oriented: deposits grow three-dimensionally; bulk and individual deposits are polycrystalline. Isotropically oriented: deposits grow
two-dimensionally; individual deposits are single crystals. 共To be discussed in a following paper.兲
 Journal of The Electrochemical Society, 153 共5兲 C357-C364 共2006兲
Copper and nickel crystals are face-centered cubic 共fcc兲 struc-
ture, for which the close-packed plane is 共111兲 with an interatomic
distance of 0.2556 nm for copper and 0.2492 nm for nickel.32 At
low cd, zinc deposits tend to grow at 具0001典. The
共0001兲Zn /共111兲Cu,or Ni fitting should be the best crystal face match.
Based on an interatomic distance of 0.2665 nm for the zinc basal
plane 共0001兲, copper has a closer interatomic distance, and Lamping
reported fine deposits were obtained.33 Because of larger misfit of
共0001兲Zn /共111兲Ni, zinc forms islands 共boulders兲 on nickel in accor-
dance with the Volmer–Weber model with negative misfit.34
Iron has a body-centered cubic 共bcc兲 structure and the 共110兲
plane is the close-packed plane with an interatomic distance of
0.2482 nm, which is smaller than that of the zinc basal plane. For
iron, 共0001兲Zn /共110兲Fe fitting at 具112̄0典Zn /具111典Fe direction was pro-
posed to have the least misfit.24,35,36 Similar to the growth on nickel,
zinc formed islands on top of iron in accordance with the Volmer–
Weber mode with negative misfit.34 Moreover, the exchange cd of
hydrogen reduction on iron is ten times higher than that on zinc.37
Much higher hydrogen evolution was observed on iron. Nucleation
C359
Figure 2. SEM images of five distinct Zn
deposit morphologies
was more selective. Only on grooves produced in mechanical grind-
ing did zinc crystals preferentially initiate, and crystals were few in
number but large in size.
Effect of impurities.— Lead, tin, and a number of other additives
have been found to be suppressors of dendrites.21 Their effects on
other morphologies, such as mossy, have not been examined in de-
tail. Some common impurities present in commercial zinc have been
investigated. Images of the deposits from deliberate addition of
these impurities to the zincate solutions are illustrated in Fig. 6.
The addition of indium, arsenic, lead, and bismuth caused re-
duced cd at constant potential 共Fig. 7兲, and reduced the roughness of
deposits correspondingly 共Fig. 6兲.
Addition of arsenic resulted in a similar cd–time curve as that of
no additive. However, after a steady-state growth period of layerlike
or boulder deposits, there was a rapid increment of cd, suggesting
the rapid increase of effective surface area. At this time, the growth
of mossy zinc was observed. Thus, addition of arsenic facilitates
mossy initiation.
In the presence of indium, bismuth, and lead additives, the cd
C360 Journal of The Electrochemical Society, 153 共5兲 C357-C364 共2006兲
Figure 3. Effect of grit size: 共a兲 10 mA cm−2, 5 min; 共b兲 40 mA cm−2,
5 min.
remained constant for long plating times 共Fig. 7兲, indicating that the
mossy formation was inhibited 共Fig. 6兲. Addition of indium did not
influence cd dramatically but did cause smooth large grain deposits.
Therefore, bismuth, indium, and lead are suppressors of den-
drites 共in agreement with previous literature兲 as well as inhibitors of
mossy deposits. Arsenic is unusual in that it is an accelerator for
mossy formation but has little effect on dendritic growth.
Effect of gelled electrolyte.— In a gelled electrolyte, the solution
viscosity is so high that diffusion control should dominate. Figure 8a
shows deposits obtained at a cd of 5 mA cm−2. Bulk deposits were
layerlike islands growing laterally, which is typical of a low-cd
growth mode.18 On the other hand, dendrites grew on top of the
layerlike islands vertically, which is typical of a diffusion-controlled
growth mode.18 In nongelled systems, only one of these two growth
modes dominates, but in the gelled electrolyte, both can be seen. In
addition, dendrites initiated from the edges of the islands and grew
laterally, which is similar to thin layer growth.38,39 Dendrites possi-
bly followed a horizontal diffusion direction because the vertical
diffusion path was blocked by hydrogen bubbles trapped in the
gelled electrolyte.
As shown in Fig. 8b, at 2 mA cm−2 mossy deposits developed on
layerlike deposits. This low cd causes very selective nucleation site
growth. For instance, whiskers were observed to develop preferen-
tially on the grain at the upper left corner in Fig. 8b. This grain
appears to be the basal plane.
Morphology diagram.— In addition to the qualitative character-
ization of the effects of surface preparation, substrate, additive, and
gelled electrolyte, the quantitative effects of cd, deposition time,
Figure 4. Effect of acid etch on Zn deposit morphology: 共a兲 13 mA cm−2,
5 min; 共b兲 30 mA cm−2, 20 min.
concentration of zincate and KOH, temperature, and stirring on de-
posit morphology were investigated to construct morphology dia-
grams. These diagrams not only graphically illustrate different mor-
phologies developing at different conditions, but also serve as a
quantitative reference for morphological control.
As demonstrated in Fig. 9, the change of the three most distinct
structures with time and cd, as well as with other deposition condi-
tions, is plotted. Heavy spongy is not included because the cd at
which it develops is out of the cd range studied. Layerlike and
boulder deposits are reported as a compact deposit.
Effect of zincate concentration.— From 0.7 M zincate solution
共in the middle of Fig. 9兲, dendrites develop at a cd higher than
32 mA cm−2. Mossy deposits form at a cd lower than 15 mA cm−2
and at a higher cd when time increases.
At a higher zincate concentration of 0.85 M, both boundaries
move to a higher cd, particularly for the dendritic-compact bound-
ary. At a lower zincate concentration of 0.35 M, both boundaries
move to a lower cd, leaving a much smaller room for the growth of
compact deposits.
Effect of temperature.— At a higher temperature of 50°C, den-
drites develop at a much higher cd of 63 mA cm−2, and mossy de-
posits develop onto compact deposits after about 30 min. At a lower
temperature of 0°C, a cd higher than 15 mA cm−2 induces dendritic
formation.
 Journal of The Electrochemical Society, 153 共5兲 C357-C364 共2006兲
Figure 5. Effect of substrate on Zn deposit morphology 共10 mA cm−2,
5 min兲 共a兲 on Cu, 共b兲 on Ni, and 共c兲 on Fe.
Effect of stirring.— Stirring significantly increases the cd at the
dendritic-compact boundary several times, which is consistent with
other works.15,16 The effect of stirring on mossy formation, however,
is negligible.
Effect of KOH concentration.— At a higher KOH concentration
of 10 M 共0.7 M zincate兲, dendrites develop at a lowered cd of
22 mA cm−2. Usually, dendrites develop first from the bottom of
electrodes where replenishment of ions is difficult and hence a
higher pH value is expected. 共Reduction of 1 M zincate ions re-
leases 4 M OH− ions, which increases pH value locally.兲 The cd at
the compact-mossy boundary also drops a few milliamperes.
C361
Discussion
The cd at dendritic-compact boundaries 共Fig. 9兲 was found to
increase linearly with increased zincate concentration, and the den-
dritic growth was always accompanied with visible hydrogen evo-
lution. The cd at the boundary 共measured apparent cd兲 is therefore
expected to be the limiting diffusion cd. This is in agreement with
the conclusion from Diggle.3 Substituting D = 1.21
⫻ 10 cm S 共estimated from CV experiments兲 into nFD/␦,
−5 2 −1
which is the slope determined according to the equation,
ilim = nFDC0 /␦, gives diffusion layer thickness ␦ = 0.046 cm. This
number is in good agreement with the value of 0.05 cm for unstirred
solution.40 It follows from morphology diagrams that dendritic ini-
tiation is favored at high cd, low zincate concentration, high KOH
concentration, unstirred solution, or highly viscous gelled electro-
lyte. All these effects confirm dendritic initiation is under diffusion
control, which is in agreement with other works.3,17,41 Vise versa,
compact and mossy growth cannot be under diffusion control.
A disagreement arises about what is the controlling mechanism
of dendritic growth. Bockris and other workers have concluded den-
dritic growth is under activation control,3,17,39 but this is not sup-
ported by our experimental results. First, long after dendritic initia-
tion, as shown in Fig. 9, deposition conditions are still consistent
with diffusion control. If deposition conditions are deliberately
changed to those favoring activation control, e.g., low cd, dendrites
should then still grow perpendicularly to the surface if dendritic
growth is under activation control. However, Fig. 10 demonstrates
that dendrites did not continue to grow vertically. Instead, nonden-
dritic, lateral, layer-by-layer growth dominated. Most importantly,
mossy deposits were found growing on the pre-existing dendrites.
These two deposit morphologies are not found with dendritic
growth. Thus, dendritic growth did not continue under activation
control conditions.
Secondly, dendrites initiate and grow perpendicularly to the sur-
face at a thermodynamically unfavorable crystal direction, 具112̄0典,
while lateral growth of activation control is in the more favorable
具0001典 direction.18 Generally, activation control conditions do not
provide sufficient energy for dendritic growth.
Finally, dendrites always grow following the diffusion path
which is perpendicular to the substrate surface, strongly suggesting a
growth mechanism of diffusion control.
From the above arguments it is concluded that dendritic growth
is not under activation control but diffusion control. The detailed
interpretation of this growth model will be included in a following
paper.
As noted earlier, the zinc deposit morphology depends critically
on deposition conditions. Accordingly, the growth mechanism must
be linked to certain deposition conditions at which the distinct mor-
phology develops. For layerlike deposits growing at low cd, the
deposits are oriented crystals. Since the deposition is likely under
single-factor control 共activation control兲, deposits grow epitaxially
to minimize activation energy. For higher cd, the concentration gra-
dient becomes significant and a mixed control of diffusion and ac-
tivation is found. Under this condition, there is competition between
the growth direction of the diffusion field and lateral layer growth.
Deposits are boulder and anisotropically oriented. After further in-
crease of cd to the point when the concentration gradient is domi-
nant, pure diffusion control takes place, and deposits grow in the
diffusion direction perpendicular to electrode surface. This single
controlling factor and the hexagonal close-packed 共hcp兲 crystal
structure of zinc form the dominant dendritic shape of zinc. Hydro-
gen is evolved but is not rapid due to the low hydrogen exchange cd.
At higher cd, the stirring effect of hydrogen evolution takes con-
trol. The controlling factor is diffusion plus convection, which
causes the local concentration gradient to oscillate. Deposits again
become anisotropically oriented, yielding the heavy spongy depos-
its.
At extremely low cd, nucleation overpotential plays a decisive
role. Deposit initiation becomes highly selective on specific nucle-
C362 Journal of The Electrochemical Society, 153 共5兲 C357-C364 共2006兲

Figure 6. SEM images of deposits in the presence of additives: 共a兲 100 ppm Bi, 50 mA cm−2; 共b兲 100 ppm Bi, 10 mA cm−2; 共c兲 100 ppm Pb, 50 mA cm−2; 共d兲
100 ppm Pb, 10 mA cm−2; 共e兲 100 ppm In, 50 mA cm−2; 共f兲 100 ppm In, 10 mA cm−2; 共g兲 100 ppm As, 50 mA cm−2; and 共h兲 100 ppm As, 10 mA cm−2, 0.7 M
zincate, 7 M KOH, 25°C, unstirred.
 Journal of The Electrochemical Society, 153 共5兲 C357-C364 共2006兲 C363

Figure 7. Plots of cd–time for Zn deposition at 40 mV.

ation sites. The deposition process is under mixed charge-transfer

and nucleation control, which disagrees with a simple mass-transfer
mechanism suggested by Jaksic.21 This leads to the anisotropic
mossy growth morphology. A detailed analysis will be presented in
a following paper.
The sequential change of crystallinity and other properties of
deposits reflects the change of the controlling mechanism. There-
fore, in addition to categorizing deposit structures according to their
physical appearance, it is revealing to categorize the deposit based

Figure 9. Morphology diagrams of Zn deposits.

on formation mechanism. As shown in Table I, dendritic and layer-

like deposits are attributed to type I, which form under a single-
factor control 共spongy deposits have similar formation mechanism
as layerlike兲; heavy spongy and boulder deposits are attributed to
type II, which develop under mixed control factors. This connection
of the controlling mechanism and morphology will improve our un-
derstanding of the morphology development with the change of
deposition conditions.

Figure 8. Effect of gelled electrolyte: 共a兲 5 mA cm−2, 0.5 h; 共b兲 2 mA cm−2, Figure 10. Mossy growth after dendritic initiation at 50 mA cm−2, 5 min
1 h. followed by 10 mA cm−2, 10 min.
C364 Journal of The Electrochemical Society, 153 共5兲 C357-C364 共2006兲
Conclusions
A diverse range of zinc deposits can be generated from alkaline
zincate solutions, which are grouped into five categories: heavy
spongy, dendritic, boulder, layerlike, and filamentous mossy.
Of type I deposits, dendritic initiation and growth are under dif-
fusion control while layer initiation is under activation control.
Morphology diagrams were developed to graphically and quan-
titatively delineate deposit morphology change from one type to
another under various deposition conditions. They also display the
variables that are correlated and which can be decisive on the final
structure of deposits.
A universal overpotential or cd that controls the initiation of
dendrites alone does not exist. Instead, any conditions that can drive
the reaction into diffusion control can trigger dendritic initiation.
Low temperature, low zincate, or high KOH concentration, no stir-
ring, and high viscosity can all dramatically reduce the minimum
dendritic initiation overpotential from 70–90 mV to 20–30 mV.
Acknowledgments
Financial support from Teck Cominco Metals, Limited, and Ma-
terials & Manufacturing Ontario is gratefully acknowledged.
Natural Sciences and Engineering Research Council of Canada
(NSERC) assisted in meeting the publication costs of this article.
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