B254 Journal of The Electrochemical Society, 150 共6兲 B254-B261 共2003兲

0013-4651/2003/150共6兲/B254/8/$7.00 © The Electrochemical Society, Inc.

Microstructure and Electrochemical Properties of

IrO2 -Ta2 O5 -Coated Titanium Anodes
L. K. Xua,b and J. D. Scantleburyc,z
a
Qingdao Corrosion and Protection Laboratory, Luoyang Ship Material Research Institute (LSMRI)
Qingdao, 266071, China
b
School of Material Science and Engineering, Tianjin University, Tianjin, 300072, China
c
Corrosion and Protection Centre, University of Manchester Institute of Science and Technology (UMIST)
Manchester, M60 1QD, UK

The microstructure and electrochemical properties of IrO2 -Ta2 O5 coated titanium anodes have been studied using scanning
electron microscopy, energy dispersive X-ray analysis, and electrochemical impedance spectroscopy 共EIS兲 polarization and accel-
erated life test. The morphologies of IrO2 -Ta2 O5 anodes consist of dried mud-cracks surrounded by compact areas with superficial
agglomerates except for 10% Ir (Ir:Ta ⫽ 10:90 in mole ratio兲 anode. The composition of oxide coating is inhomogeneous with
IrO2 segregation in the agglomerates. EIS study indicates that 30% Ir is a critical concentration for IrO2 -Ta2 O5 coating to achieve
metallic conductivity. The anode with 50-70% Ir is found to have not only the largest electrochemically active surface area but also
the highest electrochemical activity, with 70% Ir anode also presenting the highest stability.
© 2003 The Electrochemical Society. 关DOI: 10.1149/1.1569479兴 All rights reserved.

Manuscript submitted March 8, 2002; revised manuscript received December 16, 2002. Available electronically April 11, 2003.

Cathodic protection has been extensively proven to be an effec-
tive method to protect metallic structures from corrosion in electro-
lytes like seawater, brackish water, and soil. In an impressed current
cathodic protection system, the auxiliary anode acts as a very im-
portant component to achieve desired and reliable performance. A
lot of materials have been used as impressed current anodes, includ-
ing graphite, high silicon cast iron, lead-silver alloy, platinized tita-
nium and niobium and mixed metal oxide 共MMO兲 anodes.1-4 Each
of these anode materials has its characteristics. MMO anode is a
composite material, which consists of a conductive and electrocata-
lytic mixed metal oxide layer coated on a valve metal substrate.
Usually, titanium is the substrate due to its reasonable cost, while
the oxide active layer can be tailored and modulated to meet the
requirements for different applications. Since MMO anode has high
performance characteristics over other anodes,5,6 it has attracted in-
tense interest from both researchers and cathodic protection engi-
neers.
Research work and applications about MMO anode in cathodic
protection have been carried out in the U.S. Army Construction
Engineering Research Laboratory since the early 1980s.7,8 The ce-
ramic oxide anode developed early by this laboratory consists of a
lithium ferrite composition plasma sprayed on to a titanium sub-
strate. These ceramic anodes were replaced later by MMO anodes
with RuO2 and/or IrO2 as active elements, because the latter has the
merits of a very low electrical resistance and a very low consump-
tion rate.
Dimensionally stable anode 共DSA兲 with RuO2 -TiO2 oxides
coated on titanium was invented at the end of the 1960s, which led
to a technological revolution in the chloralkali industry due to its
excellent catalytic activity for chlorine evolution and good electro-
chemical stability.9 But this DSA anode will have a limited service
life in the case of oxygen evolution due to the corrosion of active
component of RuO2 . A lot of oxides such as IrO2 , PtOx , SnO2 ,
Co3 O4 , Nb2 O5 , ZrO2 , Ta2 O5 , etc, and some oxide mixtures have
been used to improve the anodic stability and service life.10-15
Although the first test application of an MMO anode in cathodic
protection engineering can be traced back to 1971 and it has been
widely used in the past decades,5 the composition of the active layer,
the microstructure, the manufacturing details, quality control stan-
dard, and their correlations with the electrochemical performance of
this anode have not been known clearly from the published
literature.16 However, it is very important and necessary to get a
z
E-mail: scantlebury@umist.ac.uk
better understanding of the chemistry, the structure, and the proper-
ties of this material in order to exert successful application and for
further development. It has been known that IrO2 has a much better
stability than RuO2 in the anodic electrolysis.10,15,17 IrO2 -Ta2 O5
mixed metal oxide-coated titanium anode was reported to be one of
the best anodes for oxygen evolution environment and has a very
long service life even under harsh operation conditions.12,18-20 In
this work, MMO anodes with IrO2 -Ta2 O5 active layer were studied
as impressed current anodes. This is because service life is always
the main concern for the technological application. Various analyti-
cal and electrochemical techniques including scanning electron mi-
croscopy 共SEM兲, energy dispersive X-ray analysis 共EDX兲, electro-
chemical impedance spectroscopy 共EIS兲, polarization, and
accelerated life test have been used to probe the microstructure and
electrochemical properties of IrO2 -Ta2 O5 coated titanium anodes.
Experimental
Electrode preparation.—The electrodes with a variable compo-
sition of IrO2 -Ta2 O5 active layer were prepared by a thermal de-
composition method. Commercial 99.5 wt % titanium plates with a
size of 120 ⫻ 60 ⫻ 1.5 mm as the substrates of the electrodes were
degreased in acetone and then etched in boiling 10 wt % oxalic acid
solution for 2 h to get uniform surface roughness. The precursor of
H2 IrCl6 and TaCl5 salts dissolved in butanol containing 20 vol %
concentrated hydrochloric acid in the required mole ratio was ap-
plied to the substrate by brushing. The metal Ir:Ta mole ratio in the
precursor was changed from 10:90 to 90:10. The nominal composi-
tions of the coating are taken as 10, 30, 50, 70, and 90% Ir in mole
ratio, respectively. The applied coating was dried at 100°C in air for
10 min, and then fired at 500°C for 10 min. The operation of coat-
ing, drying and firing was repeated six times to achieve the desired
loading of oxides. The electrode was finally annealed at the same
temperature for 1 h for complete oxidation of the coating. The load-
ing of the oxides estimated by the weight increase of the sample
after the finish of preparation was 0.75-1.07 mg cm⫺2 . The prepared
sample plate was then cut into pieces of 15 ⫻ 15 ⫻ 1.5 mm for
electrochemical tests and surface analysis.
Electrochemical measurement.—The test sample was mounted in
a flat Teflon holder with a round exposed area of 1 cm2 . All of the
electrochemical measurements were carried out in a single compart-
ment cell, taking platinum foil as a counter electrode and saturated
calomel electrode 共SCE兲 as a reference electrode. A Luggin capillary
with saturated KCl salt bridge was used to minimize the errors due
to ohmic drop in the electrolyte. Solutions were prepared using

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 Journal of The Electrochemical Society, 150 共6兲 B254-B261 共2003兲
Figure 1. SEM morphologies of IrO2 -Ta2 O5 anodes with different compo-
sitions: 共a兲 10% Ir, 共b兲 30% Ir, 共c兲 50% Ir, 共d兲 70% Ir, and 共e兲 90% Ir.
deionized water and reagent-grade chemicals. The tests were made
usually at room temperature except for the accelerated life test
where the solution temperature was controlled at 30 ⫾ 1°C with a
water thermostat. Electrochemical techniques such as potentiody-
namic polarization, EIS, and accelerated life test were applied to
characterize the oxide electrodes. Potentiodynamic polarization tests
were made in 0.5 mol dm⫺3 Na2 SO4 solution using an ACM Instru-
ments potentiostat/galvanostat which was controlled by a PC with
auto Tafel logging software at a sweep rate of 0.33 mV s⫺1 . The
internal resistance 共iR兲 drop was corrected by measuring the solu-
tion resistance with EIS at high frequency domain. Electrochemical
impedance measurement was taken in 0.5 mol dm⫺3 Na2 SO4 solu-
tion using ACM Instruments EIS system controlled by EIS logging
software. The frequency range was from 30 kHz to 10 mHz. The
amplitude of the ac sine signal was 10 mV 共p/p兲. The impedance
data were fitted to appropriate equivalent circuits using ZView
analysis software.
Accelerated life test 共ALT兲 was generally used to evaluate the
stability of the mixed metal oxide electrodes because the oxide an-
ode can have a very long service life under the normal conditions of
electrolysis in industry, for example, DSA in the chloralkali industry
having a lifetime of ⬃10 years,21 and MMO anode for impressed
current cathodic protection in concrete having a life of over 20
years.6 The accelerated test was conducted at a current density of
2 A cm⫺2 in 1 mol dm⫺3 H2 SO4 solution. The cell voltage between
the working electrode and the counter electrode was recorded with a
chart recorder. The time when the cell voltage reached 20 V was
taken as the accelerated life of the oxide electrode.
Microstructure analysis.—The morphology and surface compo-
sition of the oxide electrodes were analyzed by SEM and EDX. An
AMRAY 1810-type SEM equipped with a Link ISIS microanalyzer
was used. The operating voltage of electronic beam was 20 keV for
morphological observation and 16 keV for EDX analysis.
Results and Discussion
Microstructure.—The morphological micrographs of untested
samples of IrO2 -Ta2 O5 anodes are shown in Fig. 1. It can be seen
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B255
that 10% Ir anode presents dried mud-crack groups surrounded by
compact areas. The dried mud-crack feature is very typical for ther-
mally prepared oxide anodes,22-25 and was thought to be caused by
the mechanical stress due to the difference of thermal expansion
coefficients of the oxides and the substrate22,23,26 and the thermal
shock stress from cooling in air to ambient temperature. The crack
groups are not connected with each other and are distributed uni-
formly with a size of about 20 ␮m, which seem to be related to the
surface roughness of the titanium substrate after etching. Some pits
with a diam of about 1 ␮m can be seen in the compact areas. With
the increase of IrO2 content, an obvious change of morphology takes
place. For 30% Ir anode, in addition to cracks and compact areas,
there appear some white agglomerates, which are mainly precipi-
tated on the compact regions. With more IrO2 in the oxide mixture,
cracks become smaller and the numbers of agglomerates increase
with more agglomerates connecting to form networks along the
boundaries of the crack groups. For a 70% Ir anode, the numbers of
agglomerates decrease somewhat, but the network is more complete.
The anode with 90% Ir has less but bigger cracks with less agglom-
erates.
The above morphologies of IrO2 -Ta2 O5 oxide anodes generally
agree with the results in the literature,12,20,27 but are different from
those reported by J. Krysa et al.28 and Yu. E. Roginskaya et al.29
where no agglomerates, but only dried mud cracks, appear. This is
perhaps due to the difference of pretreatment of titanium substrate
and the preparation procedures. It has been known that the morphol-
ogy of an oxide anode is strongly dependent on the substrate mate-
rials, the composition of oxide coating, the surface treatment of
substrate, the nature of precursor, the physical and chemical proper-
ties of individual oxides, and the preparation procedures26,30,31 Any
of these factors can make a significant change of the oxide anode
morphology.
EDX was used to analyze the composition of small areas on the
outer surface of the oxide anode. For a 10% Ir anode, weak iridium
but strong tantalum and titanium peaks were probed on the spectra,
indicating very low iridium content on the coating surface. The dis-
tribution of tantalum is not uniform with more on the crack areas.
For 30% Ir anode, iridium peaks became obvious. In the agglomer-
ates, the iridium peak was higher than the tantalum peak suggesting
the enrichment of iridium, while the tantalum peak was much higher
than the iridium peak in the crack area 共Fig. 2兲. With the increase of
IrO2 content, the ratio of Ir/Ta peaks increase further in the agglom-
erates, meaning more IrO2 segregation. Such segregation seems to
be the specific feature of oxide anodes containing IrO2 , which has
also been observed in IrO2 -TiO2 , 32 IrO2 -TiO2 -SnO2 , 26
IrO2 -TiO2 -PtOx 33 and IrO2 -TiO2 -CeO2 34 systems. This inhomoge-
neity of composition is also a typical surface characteristic of oxide
anodes, even the anode with 100% IrO2 showing varied iridium
density in different areas.32
Titanium peaks are found in the EDX spectra of all the
IrO2 -Ta2 O5 oxide anodes though no titanium was added in the pre-
cursor on purpose. Similar cases were also reported in the oxide
anodes of Ir0.3Ce0.7O2 , 34 IrO2 , 32 and Ir0.3Sn0.7O2 . 26 The appearance
of a titanium signal can be attributed to the dissolution of titanium
substrate by the acidic action in the precursor, and/or the diffusion
from the substrate into the oxide layer during the thermal prepara-
tion, and probably the contribution of titanium substrate due to the
radiation penetration in some thin areas.26 The titanium peak is gen-
erally stronger in the compact area than in the crack area, which is
perhaps due to the thinner coating on the ridges of a rough surface
of the substrate.
The EDX spectra also show the presence of little chlorine species
in the oxide coating, which is typical for oxide anodes using chlo-
ride salts in the precursor. This may result from the incomplete
decomposition of the precursor salts.35 It was reported that chlorine
species may exist as chloride inclusion in the oxides,34 or be trapped
in the coating.31,32
 B256 Journal of The Electrochemical Society, 150 共6兲 B254-B261 共2003兲
Figure 2. Energy dispersive X-ray spectra of 30% Ir anode: 共a兲 in agglom-
erates, and 共b兲 in crack area.
Electrochemical impedance spectroscopy.—EIS is a technique
used to analyze the impedance response of a system at different
frequencies by imposing a small amplitude sine wave disturbance on
the electrochemical system at a constant dc bias. It has been widely
used in the studies of passivation of metals, inhibitors, semi-
conducting oxide films, organic coatings, batteries, and so on.36-38
Since EIS can provide information on the oxide matrix and the
interface of oxides/solution, it has also become a useful tool to char-
acterize the mixed metal oxides coated titanium electrodes39,40
Figure 3 shows the impedance spectra of 10% Ir anode in
0.5 mol dm⫺3 Na2 SO4 solution at different dc voltages. The Nyquist
plots present two semicircles, indicating two time constants. The
small semicircle observed at high frequency domain, which is al-
most independent of the applied dc bias, reflects the impedance of
the oxide matrix, while the semicircle at low frequency domain can
be attributed to the electrochemical reaction of oxygen evolution
occurring at the interface between the oxide layer and the electro-
lyte. With the increase of applied dc voltage from 1150 to 1350 mV,
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the charge transfer resistance associated to oxygen evolution de-
creased markedly, suggesting that the oxygen evolution was more
rapid and intensive at higher potential. Note that the origins of the
semicircles are not on the real axis, which is the typical feature of
porous electrode and is attributable to the roughness of the electrode
surface.41,42
Figure 4 presents the Bode plots of other IrO2 -Ta2 O5 oxide an-
odes recorded at 1150 mV in 0.5 mol dm⫺3 Na2 SO4 solution. As
compared with EIS of a 10% Ir anode, the impedance spectra of
these anodes show only one time constant, with the semicircle at
high frequency domain in Nyquist plot disappearing. This means
that the nature of the oxide matrix of the electrodes has been
changed with increasing the IrO2 content in the oxide mixtures. EIS
has been used to study the mechanism of oxygen evolution on vari-
ous electrode materials. Simple impedance spectra with only a
single, often depressed semicircle were often reported,32,33,40,43,44
although oxygen evolution is known to occur by multistep reaction
mechanisms that might generally produce complicated EIS. The im-
pedance behavior of oxygen evolution for IrO2 -Ta2 O5 anodes in
0.5 mol dm⫺3 Na2 SO4 solution is in agreement with the above re-
sults.
An equivalent circuit shown in Fig. 5 has been used to fit the EIS
data according to the structure of the oxide electrode. R s , R f , and
R ct are resistors related to the ohmic resistance of the electrolyte, the
oxide matrix resistance, and the charge transfer resistance of oxygen
evolution reaction, respectively. CPE1 and CPE2 are constant phase
elements in place of the capacitance of the oxide film and the double
layer 共dl兲 capacitance. The use of a CPE instead of a capacitance
element is thought to be a good approximation approach to describe
a practical electrode with different degrees of surface roughness,
physical nonuniformity, and energetic inhomogeneities, or a nonuni-
form distribution of surface reaction sites.45-47 CPE is a frequency
dependent capacitance, the impedance of which can be expressed as
Z CPE ⫽ 关 Q 共 j␻ 兲 n兴 ⫺1 关1兴
Where ␻ is the angular frequency, Q is a frequency independent
constant, and n is a power factor related to the depression angle. An
n value of zero corresponds to a pure resistor. A unity value of n
corresponds to a pure capacitor. An n value of 0.5 corresponds to
Warburg impedance.
For CPE2 coupled with the charge transfer resistance R ct , the dl
capacitance C dl can be calculated by the following equation48
⫺1 n 2⫺1 1/n 2
C dl ⫽ 关 Q 2 共共 R s ⫹ R f兲 ⫺1 ⫹ R ct 兲 兴 关2兴
Figure 3. EIS of 10% Ir anode in
0.5 mol dm⫺3 Na2 SO4 solution at differ-
ent applied potentials. Unit for Z⬘ , Z⬙ ,
and 兩Z兩: ⍀ cm2 . Phase angle theta: deg.
共a兲 Nyquist plot, and 共b兲 Bode plot.
 Journal of The Electrochemical Society, 150 共6兲 B254-B261 共2003兲
Figure 4. EIS of IrO2 -Ta2 O5 oxide anodes in 0.5 mol dm⫺3 Na2 SO4 solution. E ⫽ 1150 mV 共SCE兲. Unit for 兩Z兩: ⍀ cm2 . phase angle theta: deg. 共a兲 30% Ir,
共b兲 50% Ir, 共c兲 70% Ir, and 共d兲 90% Ir.
The fit results of Bode plots with the above equivalent circuit are
also shown in Fig. 4. The deviation between the experimental data
and the simulation result is small, suggesting that the used equiva-
lent circuit is suitable to represent the electrochemical system. In
fact, the equivalent circuit in Fig. 5 has been widely employed to
describe the impedance behavior of mixed metal oxides-coated tita-
nium electrode.39,40
The change of the oxide film resistance with the composition of
IrO2 -Ta2 O5 anodes is shown in Fig. 6. The film resistance droped
abruptly from 7.3 ⍀ to 0.06 ⍀ cm2 when Ir content increased from
10 to 30%. With Ir content over 30%, R f changed little in the range
of 0.02-0.06 ⍀ cm2 . As a matter of fact, R f was so small that the
semicircle at high frequency in EIS disappeared. The film resistance
originated from both the mixed metal oxide coating and the inter-
Figure 5. Equivalent circuit model for EIS analysis of mixed metal oxide
anodes.
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B257
layer between the oxide coating and the substrate. The latter is a thin
oxide film of IrO2 -doped TiO2 /Ti2 O3 formed on titanium substrate
due to the thermal preparation procedure.39 The small film resistance
of the anodes with over 30% Ir suggests that the mixed metal oxide
coatings had metallic conductivity and the interlayers of IrO2 -doped
titanium oxides were very thin. Little change of R f for the oxide
anodes with more than 30% Ir indicates that there existed a critical
Ir content in the oxide mixtures. When the Ir content is below this
value, the oxide coating will be dominated by the poorly-conductive
component Ta2 O5 , and will show very low conductivity. However,
with Ir content higher than the critical value, the conductivity will be
controlled by the active component IrO2 , presenting metallic con-
ductivity. This may possibly be explained by the microstructure of
IrO2 -Ta2 O5 coating using the percolation theory.12 It has been found
that the IrO2 -Ta2 O5 coating is a mixture of oxide crystal (IrO2 ) and
amorphous phase (Ta2 O5 ). To become electroconductive, the oxide
coating must have enough clusters of IrO2 to form a conductive
network connecting the electrolyte with the substrate.49 Once the
network is formed, the resistance of the oxide coating will drop
dramatically and changes little even with more IrO2 content. It was
also reported in the literature that IrO2 -TiO2 and RuO2 -TiO2 oxide
films have a critical concentration amounting to 25-30% IrO2 or
 B258 Journal of The Electrochemical Society, 150 共6兲 B254-B261 共2003兲
Figure 6. Change of the film resistance with the Ir content in the
IrO2 -Ta2 O5 oxide anodes.
29
RuO2 to achieve metallic conductivity, which is agreeable with the
result for IrO2 -Ta2 O5 electrodes.
For the 10% Ir anode, the high film resistance may be mainly
attributed to the poor conductivity of the oxide coating with too
small amount of conductively active component, although the
poorly doped titanium oxide interlayer also has a contribution. Simi-
lar impedance behavior was also reported for Ru-Ti-Sn ternary ox-
ide electrodes in 1mol dm⫺3 NaCl solution.50 It was found that
Ru0.2Ti0.8O2 electrode had a film resistance of 17 ⍀ cm2 , while
Ru0.2Ti0.1Sn0.7O2 electrode showed little film resistance, which was
thought to be the result of the improvement of conductivity due to
the substitution of SnO2 for TiO2 .
An n value of 0.7 for 10% Ir anode and n values of 0.8-0.9 for
other oxide anodes have been found, which suggests that the CPE
for oxygen evolution on IrO2 -Ta2 O5 anodes has the nature of a
capacitor. Figure 7 shows the dependence of dl capacitance on the
composition of the oxide anodes. With the increasing of Ir content,
the dl capacitance increases from an initial value of 5.9 mF cm⫺2 at
10% Ir to a maximum of ⬃55 mF cm⫺2 at 50-70% Ir, and then
decreases to 33 mF cm⫺2 at 90% Ir. This variation of C dl with com-
position is consistent with that of voltammetric charge q * taken
from cyclic voltammetry measured at a sweep rate of 20 mV s⫺1 in
0.5 mol dm⫺3 Na2 SO4 solution.51 The charge q * was obtained by
the integration of the anodic part of the voltammetric curves be-
tween 0 and 1.0 V 共SCE兲. The relationship between C dl and q * is
shown in Fig. 8, presenting a linear result. This means that the C dl
Figure 7. Change of the dl capacitance with the Ir content in the IrO2 -Ta2 O5
oxide anodes.
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Figure 8. The relationship between dl capacitance and voltammetric charge
of IrO2 -Ta2 O5 oxide anodes.
given by EIS can also reflect the electrochemically active surface
area 共EASA兲 of oxide electrode. The maximum of C dl at 50-70% Ir,
suggesting the largest EASA, can be attributed to the interaction
between the oxide components. The cyclic voltammetry study
showed that the ‘inner’ surface makes a large contribution to the
EASA of IrO2 -Ta2 O5 anodes.51 Because the anode with 50-70% Ir
has more IrO2 agglomerates and less cracks in the microstructure,
the large EASA may possibly result from the fine crystallites which
produce more grain boundaries to enlarge the inner surface area.
The change of charge transfer resistance with the composition of
the oxide anodes is demonstrated in Fig. 9. The reciprocal of R ct
represents the electrochemical activity for oxygen evolution on the
surface of the anode. The R ct for 10% Ir anode is 470 ⍀ cm2 , much
higher than other oxide anodes, indicating its poor electrochemical
activity. The reciprocal of R ct increases with IrO2 content at first,
and reaches a maximum at 50-70% Ir, then decreases. This is quite
similar to the behavior of C dl vs. composition, which means that the
electrochemical activity has an intimate relation with the EASA of
the oxide electrodes. The electrochemical activity of oxide elec-
trodes depends on both the electrocatalytic effect and the geometric
factor. Since both q * and C dl can be used to represent the real
surface area of the oxide electrode,49,52 the reciprocal of R ct divided
by q * or C dl will present the truly electrocatalytic effect. Fig. 10
gives the dependence of 1/(R ctq * ) and 1/(R ctC dl) on IrO2 content in
the oxide mixture. The electrocatalytic activity increased with Ir
content continuously and changed slowly after reaching 70% Ir. This
proves that the maximum electrochemical activity at 50-70% Ir
comes from both the large EASA and its good electrocatalytic effect.
Figure 9. Change of the charge transfer resistance with the Ir content in the
IrO2 -Ta2 O5 oxide anodes. E ⫽ 1150 mV 共SCE兲.
 Journal of The Electrochemical Society, 150 共6兲 B254-B261 共2003兲 B259

Figure 12. Tafel slopes of IrO2 -Ta2 O5 oxide anodes in 0.5 mol dm⫺3
Na2 SO4 solution.

Figure 10. Change of normalized charge transfer resistance with Ir content

in IrO2 -Ta2 O5 oxide anodes. E ⫽ 1150 mV 共SCE兲. kinetic parameter for the electrochemical reaction, and independent
of the surface area of the electrode, the change of Tafel slope rep-
resents the difference of the electrochemical reaction mechanism.
The electrodes with more than 30% Ir may have the same mecha-
Polarization behavior.—Potentiodynamic polarization behavior
nism. It has been found that the 70% Ir anode has a Tafel slope of
of IrO2 -Ta2 O5 oxide anodes was measured in 0.5 mol dm⫺3 Na2 SO4
48 mV dec⫺1 in the low overpotential region and 120 mV dec⫺1 in
solution at a sweep rate of 0.33 mV s⫺1 in the range of oxygen
the high overpotential region in 1 mol dm⫺3 H2 SO4 solution. There-
evolution. The typical polarization curves with iR correction are
fore, the large Tafel slope of ⬃112 mV dec⫺1 in the Na2 SO4 solu-
shown in Fig. 11. Note that the current density is expressed with
tion is caused by the support electrolyte. Oxygen evolution on the
respect to geometric surface area. It is found that the Tafel lines are
almost linear in the low overpotential region and the slope becomes thermal IrO2 has also been reported to become increasingly difficult
increasingly steep in the high overpotential range. The region of in neutral solution.57
To compare the electrocatalytic activity, the current density at a
Tafel linearity extends to ⬃0.06, ⬃5, and ⬃3 mA cm⫺2 for
constant potential derived from polarization curves as a function of
IrO2 -Ta2 O5 anodes with 10% Ir, 70% Ir, and 90% Ir, respectively.
composition is shown in Fig. 13. It has a very similar shape as that
The increase of the Tafel slope in the high overpotential region is
in Fig. 9, showing a maximum electrochemical activity at the com-
usually attributed to the gas bubble formation and pore clogging
position of 50-70% Ir. With the increase of the polarization poten-
which may block some EASA, a new rate-determining step pre-
tial, the oxygen evolution reaction became intensive, and the differ-
dominating in the region of high current density, or a change of
ence of electrochemical activity for anodes with different Ir content
electrochemical reaction mechanism.53,54 Similar behavior of oxy-
increased. Figure 14 shows the dependence of normalized current
gen evolution with two Tafel slopes has also been reported for
density by voltammetric charge q * on Ir content in the coating. It
RuO2 -TiO2 electrodes in 0.5 mol dm⫺3 H2 SO4 and 1 mol dm⫺3
also presents that the anode with 50-70% Ir has highest electrocata-
NaOH solutions,54 Ru0.3Ti( 0.7⫺x ) Snx O2 anodes in 1 mol dm⫺3 lytic effect. At higher overpotential, the electrocatalytic activity in-
HClO4 solution,55 RuO2 -TiO2 electrodes, and SnO2 -CuCo2 O4 elec- creased very fast with increasing Ir content until 50% Ir, then it
trodes in NaOH solutions,56 and Co3 O4 and NiCo2 O4 electrodes in changed slowly. This means that the electrochemical activity of
KOH solutions.53 IrO2 -Ta2 O5 anodes depends on both electrocatalytic effect and the
The Tafel slopes of the oxide electrodes at low overpotential number of surface active sites. At higher IrO2 content, the geometric
region as a function of composition are shown in Fig. 12. It can be contribution from electrochemically active surface area becomes
seen that the Tafel slope is high for 10% Ir anode. With increasing Ir predominant. Figures 14 and 10 show similar results although the
content, the Tafel slope goes down sharply from 150 mV dec⫺1 at
10% Ir to 116 mV dec⫺1 at 30% Ir, and changes a little with more Ir
content. The average Tafel slope is 112 mV dec⫺1 , close to 2.303
(2RT/F) for the anodes with 30-90% Ir. Since Tafel slope is a

Figure 11. Potentiodynamic polarization curves of IrO2 -Ta2 O5 anodes in Figure 13. Change of polarization current density with Ir content in
0.5 mol dm⫺3 Na2 SO4 solution. 0.5 mol dm⫺3 Na2 SO4 solution.

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 B260 Journal of The Electrochemical Society, 150 共6兲 B254-B261 共2003兲
Figure 14. Change of normalized polarization current density with Ir con-
tent in 0.5 mol dm⫺3 Na2 SO4 solution.
electrocatalytic activity of the electrode has been described in dif-
ferent way.
Anode stability.—For technological application, electrode stabil-
ity and service life are always the main concern. Accelerated life test
at high current density was used to evaluate the stability of
IrO2 -Ta2 O5 anodes. The accelerated lifetime vs. composition is
shown in Fig. 15. It can be seen that the lifetime increases slowly
with increasing Ir content at the beginning, and rises abruptly after
50% Ir, then goes down a little, presenting highest stability at 70%
Ir. Considering the variation of electrochemical activity with com-
position, it can be found that the anode with 70% Ir has the opti-
mized combination of activity and stability, which is consistent with
the results in the literature.12,19,20
The stability of electrode is intimately related to its failure
mechanism. For mixed metal oxide anodes, the deactivation mecha-
nisms are generally attributed to the consumption of active compo-
nent in the oxide mixture, and/or the passivation of the substrate
behind the mixed oxide layer,58,59 which depends on the morphol-
ogy and phase structure. The maximum stability at 70% Ir may be
due to not only the synergistic interaction between IrO2 and Ta2 O5
oxides, in which the inert element can stabilize the active compo-
nent and provide protection for the substrate surface, but also the
largest EASA at this composition which can lower the actual current
density in the stability test.
Conclusion
1. The morphologies of IrO2 -Ta2 O5 anodes present dried mud
cracks surrounded by compact areas with superficial crystalline ag-
glomerates except for 10% Ir anode where no agglomerate is pre-
Figure 15. The accelerated lifetime of IrO2 -Ta2 O5 oxide anodes in
1 mol dm⫺3 H2 SO4 solution at a current density of 2 A cm⫺2 .
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cipitated. The composition of IrO2 -Ta2 O5 coating was inhomoge-
neous with iridium segregation in the agglomerates.
2. EIS study indicates that the film resistance of the oxide coating
dropped dramatically with Ir content over 30% and changed little
with further increase of Ir content. 30% Ir is a critical concentration
for IrO2 -Ta2 O5 anodes to possess metallic conductivity.
3. The dl capacitance C dl derived from EIS and the voltammetric
charge q * measured from cyclic voltammetry have a linear relation-
ship, suggesting that both C dl and q * can represent the electro-
chemically active surface area of the oxide anodes.
4. IrO2 -Ta2 O5 anode with 50-70% Ir has both the largest elec-
trochemically active surface area and the highest electrochemical
activity. The former is attributed to the more IrO2 agglomerates and
possibly the fine crystallites in the matrix. The latter resulted from
not only large EASA but also good electrocatalytic effect.
5. IrO2 -Ta2 O5 anodes show a Tafel slope of about 112 mV dec-1
in 0.5 mol dm⫺3 Na2 SO4 solution at low overpotential region inde-
pendent of the Ir content except for 10% Ir anode with a Tafel slope
of 150 mV dec⫺1 . The anode with 70% Ir also demonstrated the
highest stability, agreeing with the results in the literature.
Acknowledgment
L. K. Xu would like to thank China Scholarship Council for
financial support, and Mr. T. Y. Wang of LSMRI for his assistance in
sample preparation.
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