G. MUTHURAMAN et al.: ENHANCED STABILITY AND ELECTROCHEMICAL PERFORMANCE OF A BaTiO3/PbO2 ...
211–215
ENHANCED STABILITY AND ELECTROCHEMICAL
PERFORMANCE OF A BaTiO3/PbO2 ELECTRODE VIA A LAYER
OBTAINED WITH LAYER ELECTRODEPOSITION
IZBOLJ[ANA STABILNOST IN ELEKTROKEMIJSKA
ZMOGLJIVOST ELEKTRODE BaTiO3/PbO2, IZDELANE Z
ELEKTRODEPOZICIJO PLAST NA PLAST
Govindan Muthuraman, Kannan Karunakaran, Il Shik Moon
Department of Chemical Engineering, Sunchon National University, #255 Jungangno, Suncheon 540-742, Jeollanam-do, Republic of Korea
ismoon@sunchon.ac.kr
Prejem rokopisa – received: 2014-08-18; sprejem za objavo – accepted for publication: 2015-03-24
doi:10.17222/mit.2014.200
Herein, the electrodeposition of BaTiO3 and PbO2 on Ti using the layer-by-layer method under different current densities (CDs)
and times, was investigated. The weight difference in the deposited BaTiO3 explains the BaTiO3 weight decrease by one order
with the increasing CD from 0.025 A cm–2 to 0.125 A cm–2 and also follows the same trend during the PbO2 deposition. The
PbO2 deposition at different CDs demonstrates that the deposited PbO2 weight increases by one order with the increasing CD.
Also, cyclic voltammetry results explain the low and moderate deposition CDs and the time suitably shows the PbO2 redox
behavior. According to SEM and XRD, a CD of 0.05 A cm–2 affects the formation of crystalline BaTiO3 and PbO2 more than
higher or lower CDs. Finally, the BaTiO3 and PbO2 layer-by-layer electrode electrodeposited at a moderate CD showed a better
stability than the electrode including only PbO2. The use of BaTiO3 is promising for the stability of the PbO2 electrode
preparation.
Keywords: BaTiO3, PbO2, electrodeposition, layer by layer, electrode stability
Preiskovana je bila elektrodepozicija BaTiO3 in PbO2 na Ti, z uporabo metode plast na plast, pri razli~nih ~asih in gostotah toka
(CD). Razlike v te`i BaTiO3 razlo`ijo nara{~anje te`e BaTiO3 za red velikosti zaradi nara{~anja CD, od 0,025 A cm–2 do 0,125
A cm–2. Podoben trend je bil opa`en tudi pri nana{anju PbO2. Pri nana{anju PbO2, razli~ni CD ka`ejo nara{~anje te`e
nanesenega PbO2 za red velikosti z nara{~anjem CD. Tudi cikli~na voltametrija razlo`i majhen in srednji CD in ~as ustrezno
ka`e redoks vedenje PbO2. SEM in XRD z 0,05 A cm–2 vodita nastanek kristalini~nega BaTiO3 in PbO2 bolj kot vi{ji in ni`ji
CD. Kon~no se ka`e bolj{a stabilnost elektrode elektronane{enega BaTiO3 in PbO2 plast na plast pri zmernih CD, kot pa pri
PbO2 elektrodi. Uporaba BaTiO3 je obetajo~a za stabilnost priprave PbO2 elektrode.
Klju~ne besede: BaTiO3, PbO2, elektro nana{anje, plast na plast, stabilnost elektrode
1 INTRODUCTION
PbO2 clearly emerges as an attractive material used as
an anode for a direct oxidation of organic compounds
due to its high oxygen-evolution potential, low price,
relative stability under the high positive potentials
required, stability at high temperatures and ease of pre-
paration.1–3 Its high overpotential for O2 evolution allows
the application of potentials to about 2.0 V versus a satu-
rated calomel electrode (SCE) in an acidic medium
without vigorous O2 evolution.4 The PbO2 electrodes
have some disadvantages, i.e., they corrode at high rates
under reducing conditions and in some acids, and they
have poor mechanical properties. Its composites with
various oxides (e.g., Al2O3, RuO2, and TiO2) are
known4–6 for a high catalytic activity and stability.
Among many ways of preparation, such as the sol-gel
technology, the plasma-chemical method, etc., the
electrochemical synthesis is the most promising method,
easy to implement, allowing the technological para-
meters to be varied smoothly for a better control of the
composition and properties of the resulting composi-
tes.4–6
The - and -types of PbO2, applied layer by layer on
metal anodes have been widely used in electrolysis.7,8
Generally, titanium is not a viable substrate for practical
electrodes in electrodepositing non-ferrous metals. Alu-
minum is relatively cheap and has a good conductivity.
The electrode material obtained by electrodepositing
lead dioxide on an A1 substrate has huge market pros-
pects. A stress-free intermediate -PbO2 coating is pro-
duced with electrodeposition from an alkaline lead bath9
and it plays the role of the binder on the top -PbO2
coating, improving the service life of the electrode. A
non-conducting ceramic material has also been used as
the substrate to achieve a high stability of PbO2 with the
fluorine resin as the co-dopant on the upper layer.10
In the present investigation, perovskite-type BaTiO3
is applied to Ti as the lower layer using the hydrothermal
electrodeposition method. As the top/upper layer, PbO2
is to applied. The effects of the thickness of both layers
are controlled with the current density and the deposition
Materiali in tehnologije / Materials and technology 50 (2016) 2, 211–215 211
UDK 544.6:544.032.1:669.058 ISSN 1580-2949
Original scientific article/Izvirni znanstveni ~lanek MTAEC9, 50(2)211(2016)
time to achieve the electrode stability and activity. Thus,
the main work of this paper deals with the layer-by-layer
deposition of BaTiO3 and PbO2 and its influence on the
PbO2 electrode stability and electrochemical application
as a sandwich-type electrode.
2 EXPERIMENTAL DETAILS
2.1 Electrodeposition
Electrolysis was performed using a DC power supply,
BS 32C (0–100 V, 0–50 A) from the Korea Switching
Company, Korea, using the constant-current mode (the
galvanostatic mode). Before the electrolysis start, the
anode was initially immersed in the electrolyte for 1 min
to stabilize its surface state. The deposition was per-
formed in two steps: in the first step, BaTiO3 was formed
as the lower coating on a pretreated Ti electrode at 65 °C
using a current-density range of 0.025–0.125 A cm–2 for
15–60 min. The BaTiO3 deposited electrode was washed
after its deposition in hot ammonia water adjusted to pH
11 to minimize the BaCO3 formation. It was then rinsed
in purified Millipore water and cleaned in ethanol with
an ultrasonic cleaner for 1 min. Then, -PbO2 was
deposited as the upper layer using a current-density (CD)
range of 0.025–0.125 A cm–2 for 15–60 min in a 0.1 M
HNO3 medium at 65 °C.
2.2 Analysis
Cyclic-voltammetry (CV) measurements were per-
formed using a VersaSTAT3 from Princeton Applied
Research, USA. The electrochemical cell was a three-
electrode cell with a working electrode, a platinum-plate
counter electrode and an Ag/AgCl reference electrode.
The working electrode was prepared with the electro-
deposition method. Scanning electron microscopy of the
prepared PbO2 electrodes was carried out with Zeiss
EVO MA10 to investigate the surface morphology of the
films. The XRD patterns of the as-prepared PbO2 sam-
ples were obtained from an X’PERT-PRO X-ray
diffractometer with Cu-K radiation ( = 0.1540598
nm). The electrolysis was done using a DC power supply
from KSC, Korea, with an applied CD of 0.3 A cm–2 in 1
M H2SO4.
3 RESULTS AND DISCUSSIONS
3.1 Selection of deposition conditions
As the CD and time are the key factors to control the
deposition, the initial work was done to identify the
suitable deposition time and CD for the first and second
layers of BaTiO3 and PbO2, respectively. First, the
BaTiO3 layer was deposited using four different CDs of
(0.025, 0.05, 0.1, 0.125) A cm–2 with four different
durations such as (15, 30, 45, 60) min, by keeping the
PbO2 (the second layer) deposition parameters (CD =
0.05 A cm–2, 30 min duration) constant. As mentioned in
the experimental section, the BaTiO3 and PbO2 deposi-
tions were done in different solutions and the obtained
results are tabulated in Table 1. It is seen from the 1st
row and 4th column of Table 1 that the weight of the
deposited BaTiO3 shows no consistency with different
deposition times (15–60 min) within a single CD (0.025
A cm–2); a similar inconsistency is also shown for the
PbO2 deposition, the 5th column. However, with the in-
creasing CD during the BaTiO3 deposition from 0.025 to
0.125 A cm–2, shown in the 1st to the 4th rows, the
deposited BaTiO3 weight is reduced by one order from
0.01 to 0.001 (the 5th column).
Table 1: Deposited-electrode weight difference in each step of:
1) BaTiO3 and 2) PbO2 at different current densities and times
Tabela 1: Razlika v masi nane{ene elektrode za vsako stopnjo:
1) BaTiO3 in 2) PbO2 pri razli~nih gostotah tokov in ~asih
BaTiO3 coating PbO2 coating Electrode weightdifference (g)
CD@
(A cm–2)
Time
(min)
CD@
(A cm–2)
Time
(min) BaTiO3 PbO2
0.025
15
0.05
30 0.0222 0.2837
30 0.0181 0.2929
45 -0.0034 0.3043
60 0.024 0.3041
0.05
15
0.05
30 -0.0027 0.0649
30 0.0052 0.2681
45 0.0055 0.2969
60 -0.0087 0.2997
0.1
15
0.05
30 0.0094 0.0908
30 0.0054 0.0217
45 -0.0089 0.0338
60 -0.0076 0.0800
0.125
15
0.05
30 0.0032 0.0702
30 -0.0372 *
45 0.0629 *
60 0.0397 0.0456
0.025 30 0.025
15 0.0159 -0.0318
30 0.0091 -0.0133
45 0.0084 0.1065
60 0.0167 0.4092
0.025 30 0.05
15 -0.0594 0.2779
30 0.0105 0.2188
45 -0.0180 0.0140
60 -0.0065 0.5551
0.025 30 0.1
15 0.1020 0.1611
30 -0.0423 0.3547
45 -0.0137 0.4100
30 -0.0362 0.2384
0.025 30 0.125
15 * *
30 * *
45 * *
60 * *
*Dissolution of electrode, @CD = current density, lower than the
original weight
In a similar way, the deposited PbO2 weight also
decreases by one order with the increasing CD (the 6th
column – from 0.1 to 0.01). At the same time, the results
are different if the PbO2 deposition CD is varied at a
G. MUTHURAMAN et al.: ENHANCED STABILITY AND ELECTROCHEMICAL PERFORMANCE OF A BaTiO3/PbO2 ...
212 Materiali in tehnologije / Materials and technology 50 (2016) 2, 211–215
fixed CD and time of the BaTiO3 deposition (5th to 8th
rows of Table 1) where the weight of BaTiO3 is main-
tained constant but the deposited PbO2 weight is
increased by one order with the increasing CD (the 6th
column of the 5th to 8th rows in Table 1). It is maintained
on the basis of the results that the formation of BaTiO3
on the Ti electrode influenced further deposition of
PbO2, which means that the conductivity was lower
when BaTiO3 completely covered the electrode due to
the dielectric properties of BaTiO3. A similar trend
applied to the PbO2 deposition carried out at a high CD
and a fixed, low CD of the BaTiO3 deposition where a
complete dissolution of the deposited film was observed.
Further, through a CV analysis, the electron-transfer
behavior of the deposited electrode can be inferred on
the basis of PbO2 redox properties. Figure 1a shows the
PbO2 redox response to the effects of various CDs and
times of the BaTiO3 deposition, where no redox peaks
for PbO2 are observed except for two CD variations in
the BaTiO3 deposition: 0.025 (45 min) A cm–2 and 0.05
(45 min) A cm–2. In all the remaining conditions, only a
charge transfer like the CV response is observed. In the
case of the variation in the PbO2 deposition, 60 min and
0.025 A cm–2 or 0.05 A cm–2, CD only shows redox
peaks that resemble PbO2,11 as shown in Figure 1b.
Under another two conditions, a CD of 0.1 A cm–2 over
45 min and 60 min deposition times, the PbO2 deposition
indicates a low oxidation current. All the remaining
conditions show a charging current like the CV response
without any redox peaks as not enough PbO2 is exposed
on the electrode surface. This is well correlated with the
deposited weight of PbO2 in the 1st, 2nd and 7th rows of
the 6th column of Table 1, where only the deposited
PbO2 weight is higher than in the other conditions.
3.2 Morphological characterization
SEM images of the BaTiO3 and PbO2 deposited at
different conditions are depicted in Figure 2. The first
layer of BaTiO3 shows no distinctive difference in the
SEM image and it looks almost like a needle structure in
micrometer size, as shown in Figure 2a. Both layers
deposited at 0.025 A cm–2 show a densely deposited
PbO2 layer (Figure 2b). There is a defect in the PbO2
G. MUTHURAMAN et al.: ENHANCED STABILITY AND ELECTROCHEMICAL PERFORMANCE OF A BaTiO3/PbO2 ...
Materiali in tehnologije / Materials and technology 50 (2016) 2, 211–215 213
Figure 1: CV results for electrodeposited BaTiO3/PbO2 using
different current densities and times in a 0.1 M phosphate buffer
solution at a scan rate of 20 mV s–1: a) variation in BaTiO3 deposition
current density and time with fixed current density and time (0.05
A cm–2, 30 min) of PbO2 deposition, b) variation in PbO2 deposition
current density and time with fixed current density and time (0.025
A cm–2, 30 min) of BaTiO3 deposition
Slika 1: Rezultati cikli~ne voltametrije elektro nane{enega BaTiO3/
PbO2, pri uporabi razli~nih gostot tokov in ~asov, v 0,1 M fosfatni
puferski raztopini pri hitrosti skeniranja 20 mV s–1: a) spreminjanje
gostote toka in ~asa nana{anja BaTiO3 od stalne gostote toka in ~asa
(0,05 A cm–2, 30 min) pri nana{anju PbO2, b) spreminjanje gostote
toka in ~asa nana{anja PbO2 pri stalni gostoti toka in ~asa (0,025 A
cm–2, 30 min) nana{anja BaTiO3
Figure 2: SEM images of BaTiO3 and PbO2 electrodes, deposited at
different CDs and times: a) BaTiO30.1(45 min), b) BaTiO30.025(30 min)/
PbO20.025(60 min), c) BaTiO30.025(30 min)/PbO20.1(60 min), d) BaTiO30.05(45 min)/
PbO20.05(30 min), e) BaTiO30.1(45 min)/PbO20.05(30 min)
Slika 2: SEM-posnetki BaTiO3 in PbO2 elektrod, nane{enih pri raz-
li~nih CD in ~asih: a) BaTiO30,1(45 min), b) BaTiO30,025(30 min)/
PbO20,025(60 min), c) BaTiO30,025(30 min)/PbO20,1(60 min), d) BaTiO30,05(45 min)/
PbO20,05(30 min), e) BaTiO30,1(45 min)/PbO20,05(30 min)
coating if the PbO2 deposition CD increased to 0.1
A cm–2 (Figure 2c). The film cracking is more dominant
if both layers were deposited at a CD of 0.05 A cm–2
(Figure 2d). The film cracking is more enhanced if the
BaTiO3 layer was deposited at 0.1 A cm–2 (Figure 2e).
When both layers were deposited at a low CD of 0.025
A cm–2, there is a smooth layer with smaller particles.
Figure 3a shows the XRD patterns of the BaTiO3
deposited electrodes using different CDs and times with
a fixed PbO2 deposition. With the applied CD of 0.05
A cm–2, the BaTiO3 peak reflections are less intense at 2
values of about 31.03, 38.58, 41.88, and 55.47 (VRC#
01-075-0213) along with the Ti reflections. Additionally,
BaCO3 also appeared on the surface, with a 2 peak at
about 23.85 (VRC# 00-044-1487) that might have
occurred after the deposition of BaTiO3 due to high pH.12
The BaTiO3 peak intensity increased when the deposition
CD increased to 0.1 A cm–2 as shown on curve b in
Figure 3a. The lowest CD (0.025 A cm–2) caused a
decrease in the crystallinity of BaTiO3, which turned to
the amorphous phase; see a broad peak between 2 of
20–35 on curve c of Figure 3. In the case of the PbO2
deposition, the deposited electrode using various CDs
and times shows peaks for the PbO2 formation (VRC#
01-076-0564) as shown in Figure 3b. The only
difference found is a peak-intensity decrease at a 2
value of about 28.49 when the PbO2 is deposited at 0.1
A cm–2 and 0.05 A cm–2 (60 min and 30 min) on the top
of the BaTiO3 deposition using the 0.025 A cm–2 and 0.1
A cm–2 CDs in the 30 min and 45 min durations (Figure
3b, curves b and d).
It is evident from the results that the 2 of 28.49
belongs to the (111) plane13, whose peak intensity is
reduced, which means that the -PbO2 formation is
predominant at this given condition. As seen on curve b
in Figure 3a, the BaTiO3 formation is more prominent at
the 0.05 A cm–2 CD, which means that the BaTiO3
concentration increases the -PbO2 formation during the
PbO2 deposition. It is well known that the -PbO2
formation enhances the catalytic activity tremendously.14
3.3 Stability analysis
In order to apply the prepared electrodes, the
selectively prepared electrodes obtained their stability in
1 M H2SO4 due to an enhanced CD of 0.3 A cm–2, as
depicted in Figure 4. An electrode that was prepared at a
CD of 0.05 A cm–2 (45 min) for BaTiO3 and at 0.05
A cm–2 (30 min) for the PbO2 deposition showed a 3.9 V
cell voltage up to 110 h (Figure 4, curve a); and after the
potential sharply increased to 22 V the prepared elec-
trode was decomposed. In the case of the increase in the
BaTiO3 deposition at the CD of 0.1 A cm–2 when the
G. MUTHURAMAN et al.: ENHANCED STABILITY AND ELECTROCHEMICAL PERFORMANCE OF A BaTiO3/PbO2 ...
214 Materiali in tehnologije / Materials and technology 50 (2016) 2, 211–215
Figure 4: Electrolysis of different electrodes in 1 M H2SO4 at
accelerated current density of 0.3 A cm–2: a) BaTiO30.05(45 min)/
PbO20.05(30 min), b) BaTiO30.1(45 min)/PbO20.05(30 min), c) BaTiO30.025(30 min)/
PbO20.025(60 min), d) BaTiO30.025(30 min)/ PbO20.1(60 min), e)
PbO20.025(60 min)
Slika 4: Elektroliza razli~nih elektrod v 1 M H2SO4 pri pospe{eni
gostoti toka 0,3 A cm–2: a) BaTiO30,05(45 min)/PbO20,05(30 min), b)
BaTiO30,1(45 min)/PbO20,05(30 min), c) BaTiO30,025(30 min)/PbO20,025(60 min),
d) BaTiO30,025(30 min)/PbO20,1(60 min), e) PbO20,025(60 min)
Figure 3: a) XRD patterns of current-density and time variation
(mentioned in the figure) of BaTiO3 deposition, b) XRD patterns of
BaTiO3/PbO2 prepared at various current densities and times: a)
BaTiO30.025(30 min)/PbO20.025(60 min), b) BaTiO30.025(30 min)/
PbO20.1(60 min), c) BaTiO30.05(45 min)/PbO20.05(30 min), d) BaTiO30.1(45 min)/
PbO20.05(30 min)
Slika 3: a) Rentgenogram spreminjanja gostote toka in ~asa pri
nana{anju BaTiO3, b) rentgenogram BaTiO3/PbO2, pripravljenega pri
razli~nih gostotah toka in ~asih: a) BaTiO30,025(30 min)/PbO20,025(60 min),
b) BaTiO30,025(30 min)/PbO20,1(60 min), c) BaTiO30,05(45 min)/ PbO20,05(30 min),
d) BaTiO30,1(45 min)/PbO20,05(30 min)
other conditions stayed the same, the decomposition of
the electrode occurred at around 40 h, which means that
the stability was reduced with the increasing CD (Figure
4, curve b).
In the case of the lowest CD (0.025 A cm–2) used for
both the BaTiO3 and PbO2 depositions for 30 min and 60
min, respectively, the stability increased to 180 h (Figure
4, curve c). By keeping the BaTiO3 CD of 0.025 A cm–2
and changing the PbO2 CD to 0.1 A cm–2 over 60 min,
the stability of the prepared electrode tremendously
decreased to 20 h, as observed in Figure 4, curve d.
Finally, only the PbO2 electrode deposited at the CD of
0.025 A cm–2 in 60 min, showing a stability of 48 h
(Figure 4, curve e) explains a high influence of the
BaTiO3 layer on the stability of the PbO2 electrode.
4 CONCLUSIONS
We successfully investigated an electrodeposition of
BaTiO3 and PbO2 on Ti using the layer-by-layer method
under different conditions. The weight measurement
confirms that the BaTiO3 and PbO2 formation is opti-
mum at a moderate CD of 50 A cm–2 and a deposition
time of 30–45 min. In addition, CV results confirm the
same finding through the redox behavior of PbO2. SEM
and XRD results further prove that a moderate CD leads
to crystalline BaTiO3 and -PbO2 rather than -PbO2.
The layer-by-layer deposition of BaTiO3 and PbO2
makes PbO2 more stable than it would be if there was
only PbO2. A further application of the selectively pre-
pared electrode is in progress.
Acknowledgements
This work was supported by the National Research
Foundation of Korea (NRF), funded by the Korea Govern-
ment (MEST) (Grant No. 2014R1A2A1A01001974).
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