STUDIA UBB CHEMIA, LVI, 1, 2011

ELECTROCHEMICAL BEHAVIOUR OF YBaCo4O7

IN NEUTRAL AQUEOUS SOLUTION

MIRCEA DAN*a, NICOLAE VASZILCSINa,

ANDREA KELLENBERGERa, NARCIS DUTEANUa

ABSTRACT. Considering the possibility to use YBaCo4O7 as oxygen sensor

in different environments, the study of electrochemical behaviour of this
compound was extended for neutral aqueous solution. Cyclic voltammetry and
electrochemical impedance spectroscopy have shown that the compound
behaviour in neutral solution is different than that in alkaline one. Compound
porosity was determined using BET technique and the results are in accordance
with thermogravimetric studies carried out in oxygen flow for YBaCo4O7
compound, emphasizing the oxygen intake / release by YBaCo4O7. Correlating
all these results, an electrochemical mechanism for YBaCo4O7 oxidation in
neutral aqueous solution has been proposed.

Keywords: mixed oxides, YBaCo4O7, electrochemical behaviour of YBaCo4O7,

cyclic voltammetry, electrochemical impedance spectroscopy,
BET technique.

INTRODUCTION
Recent studies have revealed special structural, electrical and magnetic
properties of Y-114 mixed cobalt oxide. Due to these properties the mixed
cobalt oxides can be used as membranes with high oxygen permeability,
oxygen sensors and also as cathodic material in fuel cells [1-5].
The compound YBaCo4O7, also named Y-114, has been extensively
studied since 2002 by Valldor et al. [6,7].
The electrochemical behaviour of Y-114 mixed oxide has been studied
in alkaline solutions [8] and had as starting point the electrochemical intercalation
the oxygen inside of transitional metal oxide network, presented by J.C. Grenier
et al. [9,10] as well as the experimental results regarding the electrochemical
cobalt behaviour studied by cyclic voltammetry and electrochemical impedance
spectroscopy [11].
The aim of the present paper is to study the electrochemical behaviour
of Y-114 mixed oxide in neutral aqueous solution (Na2SO4 0.5 mol L-1) and to
give an insight of its anodic oxidation mechanism. To the best of our knowledge,
there are no studies devoted to the electrochemical behaviour of YBaCo4O7
in aqueous neutral solutions.

a
University “POLITEHNICA”, Faculty of Industrial Chemistry and Environmental Engineering,
P-ta Victoriei, Nr.6, RO- 300006 Timisoara, Romania, * [email protected]
 MIRCEA DAN, NICOLAE VASZILCSIN, ANDREA KELLENBERGER, NARCIS DUTEANU

RESULTS AND DISCUSSION

Due to Y-114 structural and morphological complexity, the shape of
polarization curves depends on the working conditions; a critical parameter
is represented by the polarization rate.
Cyclic voltammograms recorded starting from -1.8 V versus Ag/AgCl
are depicted in Fig. 1. All these curves were recorded after a prior polarization
at -1.8 V (versus Ag/AgCl) for 300 seconds in order to remove the superficial
adsorbed oxygen.

0.012 4

0.010 A 3

0.008

0.006
8
0.004
I [A]

2
0.002
1 B
0.000
5
-0.002
6 9
-0.004
7
-0.006
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
E [V/Ag/AgCl]

Figure 1. Cyclic voltammograms (A-first cycle; B-fifth cycle) on YBaCo4O7 working

electrode in 0.5 mol L-1 Na2SO4 solution at 10 mV s-1 scan rate.

Analyzing the voltammograms presented in Fig. 1, one can observe the

appearance of an anodic peak (1) in the first cycle. This peak can be associated
with oxidation of superficial adsorbed hydrogen or of absorbed hydrogen inside
the mixed oxide network during cathodic polarization. At more positive electrode
potential an anodic wave (2) appears. This wave is associated with cobalt
oxidation (Co → CoII + 2e-). When the electrode potential becomes more
positive a second anodic wave (3) associated with oxidation of Co (II) ions
(CoII → CoIII + e-) can be observed. Like in alkaline media, anodic oxidation
of Co (II) ions consists in oxygen insertion into the mixed oxide crystalline
structure. When the electrode potential is over 1.17 V versus Ag/AgCl oxygen
evolution on electrode surface can be noticed.
On the backward scan a cathodic peak (5) associated with reduction
of Co (III) ions to Co (II) ions was noticed, followed by a small current plateau (6)
associated with reduction of Co (II) ions to Co. When the electrode potential
becomes more negative the hydrogen evolution reaction was observed (7).
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 ELECTROCHEMICAL BEHAVIOUR OF YBaCo4O7 IN NEUTRAL AQUEOUS SOLUTION

The insertion of oxygen ions into the Y-114 crystalline structure leads
to its compaction, resulting in the inhibition of redox processes at the Y-114 /
electrolyte solution interface. Therefore, the peak height and also the limiting
currents decrease during electrochemical polarization. In the fifth cycle, the
polarization curves details are fading, except the anodic wave (8) associated
with oxidation of Co (II) ions and also the reduction peak (9) associated with
the reduction of Co (III) ions to Co (II).

0.0015

0.0010

0.0005

0.0000
I [A]

-0.0005

-0.0010

-0.0015
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5
E [V/Ag/AgCl]

Figure 2. Cyclic voltammogram on YBaCo4O7 working electrode in

0.5 mol L-1 Na2SO4 solution at 5 mV s-1 scan rate.

When the cyclic voltammograms were recorded at lower polarization

rate ( 5 mV s-1), starting from open circuit potential (OCP) with polarization at
OCP for 300 s (Fig. 2), the first peak 1 (Fig. 1) corresponding to the oxidation
of Co to Co (II) was not obtained. The lower polarization rate, leads to higher
quantities of electricity crossing the interface during the experiment. A further
analysis of the CV shown in Fig. 2, reveals a net oxidation peak related to
the oxidation of Co (II) ions to Co (III) ions, instead of the plateau recorded at
higher polarization speed (Fig. 1). This process is controlled by the diffusion
of O2- ions inside of Y-114 mixed oxide and not by the diffusion of different
ionic species presented in the adjacent electrolyte solution. Quasi-irreversible
nature of the oxidation of Co (II) ions is distinguishable both by the higher
difference between potentials related with the oxidation and reduction peak
potentials and also by the attenuation with almost 50% of the reduction peak
height in comparison with the oxidation peak.

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 MIRCEA DAN, NICOLAE VASZILCSIN, ANDREA KELLENBERGER, NARCIS DUTEANU

When cyclic voltammograms were recorded at higher polarization

scan rate (100 mV s-1) the anodic wave associated with the oxidation of the
Co (II) ions is indistinct and overlapped over the oxygen evolution curve as
is depicted in Fig. 3.

0.008

0.006

0.004

0.002
I [A]

0.000

-0.002

-0.004

-0.006
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
E [V/Ag/AgCl]

Figure 3. Cyclic voltammogram (5 cycles) on YBaCo4O7 working electrode in

0.5 mol L-1 Na2SO4 solution at 100 mV s-1 scan rate.

The compound porosity was determined by the BET technique and

the results are presented in Table 1.

Table 1. BET surface area, pore diameter, and pore volume of the YBaCo4O7 sample

Parameter Value
BET Surface Area 0.3108 m² g-1
BJH Desorption average pore diameter (4V/A) 11.0584 nm
BJH Desorption cumulative volume of pores between 1.7000 nm -1
0.000786 cm³ g
and 300.0000 nm diameter

This will lead to large specific surface and provide channels favouring
adsorption and desorption of oxygen in time of electrochemical polarization.
Compared with dense bulk sample, this porous balls show fast oxygen adsorption
and desorption rates.
SEM images obtained for YBaCo4O7 bar electrode used in this work
are presented in Fig. 4. Analyzing the SEM images, a porous structure due to
crystallites agglomeration can be observed. This structure equalizes with a
large number of pores inside of ceramic electrode. Large pores amount lead to
a higher specific surface with channels which favour oxygen adsorption /
desorption process and lead to a high concentration of superficial active ions.
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 ELECTROCHEMICAL BEHAVIOUR OF YBaCo4O7 IN NEUTRAL AQUEOUS SOLUTION

Figure 4. SEM images of the YBaCo4O7 electrode’s surface before electrochemical

oxidation/reduction at 1000x(a) and 5000x(b) magnification

Based on all information presented above we are presenting a

mechanism for Co (II) to Co (III) global oxidation process in neutral aqueous
solution in Fig. 5.
This way the oxygen activity in the superficial layer becomes more
pronounced than oxygen activity in the bulk of mixed oxide. This activity
gradient determines to the oxygen diffusion from the surface of Y-114
compound into the mass of mixed oxide. Oxygen diffusion rate is much
lower in comparison with charge transfer or hydroxyl ions diffusion from the
electrolyte solution to the electrode surface.
Therefore, the electrochemical oxidation of Co (II) to Co (III) actually
consists in oxygen insertion into the crystalline structure of YBaCo4O7.
Consequently, during oxidation the crystalline network of Y-114 mixed
oxide becomes more compact (dense), so that oxygen diffusion is slower.
Furthermore, the oxidation process of Co (II) to Co(III) is not complete.
The constriction of the mixed oxide layer induces a slight irreversible
character to the oxidation of Co (II) ions, which leads to the disappearance of
the oxidation plateau (3) and also to the attenuation of the reduction peak (6)
in comparison with the oxidation peak (Fig. 1).
According with the presented mechanism, at anodic polarization,
after the OCP, the oxidation process is controlled by the charge transfer step;
this is supported by the electrochemical impedance spectra.
The electrochemical impedance spectra recorded for the YBaCo4O7
electrode during oxidation at E = 0.3 V in neutral solution are given in Fig.6.
The experimental complex plane plots show distinct features depending
on the frequency range. Thus, the final part of an incomplete semicircle can be
observed at high frequencies, between 100 kHz and 30.9 kHz, which is related
to a charge transfer process. A slightly curved line related to a Gerischer element
appears at intermediate frequencies, between 30.9 kHz and 141 Hz. Finally, a
large semicircle is observed at low frequencies, between 141 Hz and 1 mHz.
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 MIRCEA DAN, NICOLAE VASZILCSIN, ANDREA KELLENBERGER, NARCIS DUTEANU

Figure 5. Proposed mechanism for the electrochemical oxidation

of YBaCo4O7 in neutral solutions:
a) oxidation of Co2+ ions at electrode interface;
b) addition of water molecules at newly formed Co3+ cations;
c) elimination of H+ ions;
d) elimination of H2O and structural rearrangement of YBaCo4O7;
e) diffusion of oxygen ions; lines- preponderant ionic interaction.

Figure 6. Experimental Nyquist (a) and Bode (b) plots for YBaCo4O7 at E = 0.3 V in
0.5 mol L-1 Na2SO4. Inset: enlargement of the medium to high frequency domain.
Open symbols are experimental points and continuous lines are simulated
by the CNLS fitting according to the equivalent circuit.

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 ELECTROCHEMICAL BEHAVIOUR OF YBaCo4O7 IN NEUTRAL AQUEOUS SOLUTION

The experimental impedance data were modelled using the equivalent

circuit given in Fig. 7. It consists of an ohmic resistance ROhm in series with
a parallel connection of a constant phase element (CPE) and the charge
transfer resistance Rct followed by a Gerischer element (GE) and a parallel
connection of a Warburg element (W) and a resistance (R) in series with a
capacitor (C).

Rohm CPE GE W

Rct R C

Figure 7. Equivalent electric circuit for modelling oxygen insertion

into the YBaCo4O7 electrode in neutral solution.

The ohmic resistance includes the uncompensated solution resistance

and a contribution from the resistance of the YBaCo4O7 electrode. The
constant phase element replaces the double layer capacitance since it has
been observed that it describes more accurately the behaviour of real
electrochemical systems. The Gerischer element [13] is a diffusion element,
similar to the Warburg impedance, which has been proposed to describe
the alternating current response of an electrochemical system where a
chemical reaction is preceding or following the electrochemical reaction. In
its most simple form the impedance of a Gerischer element is given by:

ZGE = Z0 / (k + jω)1/2

where Z0 is the magnitude of the impedance at ω = 1 rad s-1 and k is a rate

constant parameter.
The experimental impedance data were fitted to the equivalent circuit
using a complex non-linear least squares procedure. The results of the fitting
are shown as continuous lines in Fig. 6 and the corresponding values of the
circuit elements, together with their standard errors are given in Table 2.
The high frequency part of the impedance spectra could be fitted
only if the ohmic resistance was imposed to a fixed value. However, if the
proposed model is used to simulate the response at high frequencies up to
108 Hz the whole semicircle is visible as a continuous line in the inset of
Fig. 6a. The constant phase angle parameter n has a value of 0.52 and is
considered to be related to surface inhomogeneities and porosity of the
electrode. Values around 0.9 are common for metal electrodes, while lower
values of 0.6 have been reported for porous electrodes [14].
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 MIRCEA DAN, NICOLAE VASZILCSIN, ANDREA KELLENBERGER, NARCIS DUTEANU

Table 2. Experimental values of the circuit elements during oxidation

of YBaCo4O7 in neutral solution

Parameter Value
ROhm [Ω] 25 (fixed)
T [F sn-1] 7.04 × 10-4 ± 2.54 × 10-4
n 0.52 ± 0.04
Rct [Ω] 10.07 ± 0.89
Z0 [Ω s1/2] 0.00344 ± 6.2 × 10-5
k [s-1] 1.72 ± 0.03
RW [Ω] 126.0 ± 2.2
τD [s] 1.855 × 10-6 ± 0.185 × 10-6
φ 0.5 (fixed)
R [Ω] 34.57 ± 0.71
C [F] 9.06 × 10-4 ± 0.17 × 10-4

CONCLUSIONS
Results obtained by cyclic voltammetry in neutral aqueous solution
showed that the YBaCo4O7 mixed oxide is sensitive to anodic or cathodic
polarization. Based on the experimental data we can conclude that the
electrochemical oxidation of Co(II) ions consist in oxygen insertion in the
mixed oxide structure. Because of that during oxidation the Y-114 crystalline
network becomes denser, so that oxygen diffusion rate is lowered.
The compaction of Y-114 during oxidation imposes a partial irreversible
character of this process, and as a consequence the oxidation leads to
disappearance of the oxidation plateau and also to the attenuation of the
reduction peak.
Based on the EIS spectra and the presented mechanism, the oxidation
process is controlled by the charge transfer step. Thus, a complete structural
characterization of the fully oxidized phase will be discussed in a forthcoming
paper.

EXPERIMENTAL SECTION
The YBaCo4O7 compound was obtained using a solid state reaction, by
mixing the precursor Y2O3, BaCO3 and CoO4/3 according to the stoichiometric
cation ratio. After decarbonisation at 1000°C the powder was pressed in bars
(2x2x10 mm). The bars were fired in air for 48h at 1200°C and then removed
rapidly from furnace and set to ambient temperature. [1,3,4,6,12].

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 ELECTROCHEMICAL BEHAVIOUR OF YBaCo4O7 IN NEUTRAL AQUEOUS SOLUTION

The electrochemical measurements were carried out using an Autolab

PGSTAT 302N equipped with electrochemical impedance spectroscopy (EIS)
module. The electrochemical cell was a conventional one-compartment, three-
electrode glass cell with a volume of 50 mL. Two graphite counter electrodes
were placed symmetrically next to the working electrode made of YBaCo4O7
pressed bar and a Ag/AgCl(sat) electrode was used as reference. All potentials
in this work are given versus the reference electrode. All electrochemical
measurements were performed in 0.5 mol L-1 Na2SO4 electrolyte solution.
Electrochemical impedance spectroscopy measurements were carried out
using the FRA module of Autolab 302N, in the frequency range from 0.1 Hz to
100 kHz and AC voltage amplitude of 10 mV. For each spectrum 60 points
were collected, with a logarithmic distribution of 10 points per decade. The
experimental electrochemical impedance data were fitted to the electrical
equivalent circuit by a complex non-linear least squares (CNLS) Levenberg –
Marquardt procedure using ZView – Scribner Associates Inc. software.
The surface area was determined according to the Brunauer-Emmet-
Teller (BET) method using a ASAP 2020 M (Micromeritics Instrument Corporation
USA).

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