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Cite this: DOI: 10.1039/c6ta04405k

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One-step electrochemical deposition of Ni1
xMoxS

ternary suldes as an ecient counter electrode for
dye-sensitized solar cells
J. Theerthagiri,a R. A. Senthil,a M. H. Buraidah,b J. Madhavan,*a A. K. Arofb
and Muthupandian Ashokkumarc
Ternary suldes of Ni1
xMoxS lms with various compositions (x 0, 0.05, 0.1, and 0.2) were fabricated on
a uorine doped tin oxide (FTO) glass substrate by a simple one-step electrochemical deposition method.
The electrochemically deposited ternary suldes were utilized as a low-cost and highly ecient platinum
free counter electrode (CE) for dye-sensitized solar cells (DSSCs). The structure, surface morphology and
elemental composition of the electrochemically deposited ternary suldes were examined by using X-ray
diraction (XRD), high resolution scanning electron microscopy (HR-SEM) and energy dispersive X-ray
spectroscopy (EDS). A phthaloylchitosan (PhCh) based polymer electrolyte was used as an electrolyte for
DSSCs. Cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization studies
revealed that the Ni0.95Mo0.05S CE exhibited lower charge-transfer resistance at the CE/electrolyte
interface and higher electrocatalytic activity towards the regeneration of I
from I3
relative to other
compositions. The Ni0.95Mo0.05S ternary sulde oers a positive synergistic eect for the
electrochemical catalytic activity towards the reduction of I3
, which may be due to an increase in active
catalytic sites and low-charge transfer resistance and achieved a high power conversion eciency of

Received 27th May 2016

Accepted 14th September 2016

7.15% with a Voc of 0.65 V, a Jsc of 17.21 mA cm
2, and a FF of 0.64 with a PhCh-based polymer
electrolyte, which is comparable to that of the conventional Pt CE (7.20%). The present investigation

DOI: 10.1039/c6ta04405k

demonstrates that the electrochemically deposited Ni0.95Mo0.05S ternary sulde is a promising candidate

www.rsc.org/MaterialsA

as a low-cost and highly ecient CE in DSSCs.

Introduction
Dye-sensitized solar cells (DSSCs) have attracted signicant
attention for solar energy to electrical energy conversion
because of their low-cost, simple fabrication process, good
plasticity, transparency, ease of large scale production, environmental friendliness and high power conversion eciency.13
Typical DSSCs consist of a dye-sensitized TiO2 photoanode, an
I
/I3
redox electrolyte and a counter electrode (CE). The CE is
one of the indispensable components in DSSCs, which collects
electrons from an external circuit and catalyses the reduction of
triiodide (I3
) to iodide (I
) in the redox electrolyte. Generally,
platinum (Pt) is the most widely employed CE in DSSCs due to
its remarkable electrocatalytic activity towards the reduction of
I3
to I
ions. However, Pt is a noble metal and very expensive

Solar Energy Lab, Department of Chemistry, Thiruvalluvar University, Vellore-632

115, India. E-mail: jagan.madhavan@gmail.com; Fax: +91 416 2274748; Tel: +91
416 2274747

Centre for Ionics University of Malaya, Department of Physics, University of Malaya,

Kuala Lumpur 50603, Malaysia

School of Chemistry, University of Melbourne, Parkville Campus, Melbourne, VIC

3010, Australia

This journal is The Royal Society of Chemistry 2016

and it can easily undergo dissolution to PtI4 or H2PtI6 in the

liquid I
/I3
redox electrolyte, which strongly hinders the
commercialization of large scale production of DSSCs. This
issue has prompted many researchers to develop new Pt-free CE
materials with low-cost and high electrocatalytic activity for I3

reduction.
Nowadays, many other functional materials have been
employed to replace noble Pt CEs in DSSCs, such as carbon
materials,4,5 metal selenides,6,7 metal suldes,810 conducting
polymers11,12 and metal carbides and nitrides.13,14 Among
various transition metal compounds, metal suldes have drawn
immense attention due to their good electrocatalytic activity,
high conductivity, good stability, non-toxicity and high abundance.15 Many researchers have studied NiS based Pt free CEs
for DSSCs in recent years.1618 A variety of nickel sulde phases,
such as NiS, NiS2, Ni3S2, Ni3N4 and Ni9S8, have been formed
depending on the synthetic conditions.19 Hydrothermal and
electrochemical deposition methods are most widely used to
synthesize these nickel sulde phases. Nevertheless, a relatively
low conductivity of pure nickel sulde still limits its practical
applications due to the grain boundaries and defects between
the nickel sulde particles.20,21 To resolve this problem and
improve its conductivity and electrocatalytic activity, several

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strategies have been adopted such as coupling with other electrocatalytic materials10,17 and introducing some other materials
into nickel sulde phases.18,20 Liu et al.10 synthesized NiCo2S4 by
using a facile solvothermal route and used it as a CE for DSSCs.
The fabricated DSSC with the NiCo2S4 CE achieved a high power
conversion eciency of 6.14%, which is comparable to that of
the conventional Pt CE (6.29%). Zheng et al.22 developed
CoMoS4 and NiMoS4 by a facile solution reaction method and
they displayed good electrocatalytic activity towards the regeneration of I
from I3
. The power conversion eciencies of
DSSCs with CoMoS4 and NiMoS4 CEs were 4.95% and 5.27%,
respectively. Further, the eciencies were improved to 7.31%
and 7.14%, respectively by introducing graphite into CoMoS4
and NiMoS4, which were comparable with the eciency of the
Pt CE (7.46%). Chuang et al.23 fabricated a coral-like lm of
Ni@NiS on a conducting glass substrate by an electrochemical
method in a two step process. The DSSC with the coral-like
Ni@NiS CE showed a higher power conversion eciency of
7.84%, while the DSSC fabricated with the Pt CE achieved an
eciency of 8.11%. Banerjee et al.24 synthesized nickel cobalt
sulde directly on a FTO glass substrate by sulphurization of
nickel cobalt oxide, and subsequently utilized it as a CE for
DSSCs. The DSSC with nickel cobalt sulde showed an excellent
electrocatalytic activity towards the I
/I3
redox reaction, and
achieved a power conversion eciency of 6.9%, which is
comparable with that of the Pt CE (7.07%).
In the present investigation, we have developed ternary
suldes of Ni1
xMoxS with various compositions (x 0, 0.05,
0.1, and 0.2) on FTO glass substrates by a simple electrochemical deposition method using the cyclic voltammetry
technique. The electrochemical deposition method was chosen
in this work because of its simple procedure, easy scale up
possibility and large deposition area. The eect on electrocatalytic activity and power conversion eciency of DSSCs by
the addition of Mo into NiS as ternary suldes was also investigated. In this work, a phthaloylchitosan (PhCh) based polymer
electrolyte was used as an electrolyte for DSSCs. Although
a higher power conversion eciency for the DSSCs has been
achieved while employing liquid electrolytes (I
/I3
redox
couple) in DSSCs, they have several disadvantages such as short
term stability due to organic solvent evaporation and leakage,
diculty in sealing the device, electrode corrosion, etc., which
limits the commercialization of DSSCs. The usage of a polymer
electrolyte can overcome these problems.1 To the best of our
knowledge, this is the rst report describing the synthesis of
newer stoichiometric compositions of ternary metal suldes by
a simple one-step electrochemical route and investigating the
positive synergistic eect of various compositions of Ni1
xMoxS
towards the electrochemical catalytic reduction of I3
in DSSCs
fabricated with a polymer electrolyte.

Paper

acetonitrile, 2-propanol and absolute ethanol were purchased

from SDFCL, India. Chitosan and phthalic anhydride were
purchased from Merck-Germany. Carbowax was purchased
from Supelco, USA. Polyvinylidine diuoride (PVDF), ethylene
carbonate (EC), lithium perchlorate (LiClO4), lithium iodide
(LiI), tetrapropylammoniumiodide (TPAI), N3 dye [cis-diisothiocyanato-bis(2,20 -bipyridyl-4,40 -dicarboxylic
acid)
ruthenium(II)] and uorine-doped SnO2 (FTO) (7 U per square,
TCO22-7) conducting glass were purchased from Sigma Aldrich.
TiO2 nanoparticles (P25 and P90) were provided by Degussa,
Germany. Demineralised water was obtained from Nice chemicals, India. All reagents were used without further purication.
Electrochemical deposition of Ni1
xMoxS lms
Prior to the electrochemical deposition, the FTO glass substrate
was washed using a mild detergent solution followed by
deionized water, acetone and nally with isopropanol in an
ultrasonic bath for 15 min. The cyclic voltammetry technique
was used for the electrochemical deposition process. The
Ni1
xMoxS (x 0, 0.05, 0.1, and 0.2) ternary sulde lms were
electrochemically deposited on the FTO glass substrate using an
electrochemical workstation (CHI608E, CH Instrument, USA)
with a three electrode conguration system. The electrode
comprises a precleaned FTO glass substrate as a working electrode, Pt wire as a counter electrode and saturated aqueous
Ag/AgCl as a reference electrode. The electrochemical deposition solution was prepared by dissolving 0.78 g of NiCl2$6H2O/
Na2MoO4$2H2O and 3.80 g of H2HCSNH2 in 50 mL of deionized
water and stirred well for 15 min. The potential range of electrochemical deposition of Ni1
xMoxS ternary sulde lms was
from
0.9 to 0.7 V at a scan rate of 5 mV s
1 for 25 sweep cycles.
Finally, the electrochemically deposited NiS, Ni0.95Mo0.05S,
Ni0.9Mo0.1S, and Ni0.8Mo0.2S sulde lms were washed with
deionized water and dried at room temperature for 2 h. Also, we
tried to obtain a pure MoS lm under the same experimental
conditions and precursors for comparison studies, but there
was no coating of MoS on the FTO glass substrate.
The electrochemical deposition process of pure NiS has been
described in an earlier report by Hou et al.15 During hydrolyzation, thiourea (TU) is easily oxidized to form formamidine
disulde, which subsequently reacts with the metal ions (Ni2+)
to form the corresponding metal suldes (NiS). This process is
explained as follows: (reactions (1)(3)).

(1)

(2)

Experimental section
Materials
Nickel(II) chloride hexahydrate (NiCl2$6H2O), sodium molybdate dihydrate (Na2MoO4$2H2O), thiourea (CH2CSHCH2), nitric
acid (HNO3), iodine chips (I2), N,N-dimethylformamide (DMF),

J. Mater. Chem. A

reduction

Ni2 2TU/NiTU2 2 ! NiS

(3)

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Journal of Materials Chemistry A

Electrodeposition of ternary sulde, viz., Ni1
xMoxS, is

similar to that of pure NiS. Instead of a specic metal ion, metal
ion precursors, namely, Ni2+ and Mo6+, were taken in stoichiometric ratio in the electrolyte solution and deposition was
performed.
reduction

Ni2 Mo6 2TU ! Ni2 Mo4 SNiMoS

(4)

A similar mechanism has also been proposed by Tran et al.25

for the CoIIWIVSx ternary sulde system.
Preparation of the polymer electrolyte
An optimized phthaloylchitosan (PhCh) based polymer electrolyte was used in this investigation. The composition of the
polymer electrolyte contains 1.3 wt% PEO, 5 wt% phthaloylchitosan, 31.5 wt% DMF, 37.8 wt% ethylene carbonate,
22.7 wt% tetrapropylammonium iodide and 1.7 wt% iodine. In
brief, a mixture of 1.3 wt% PEO, 5 wt% phthaloylchitosan,
31.5 wt% DMF, 37.8 wt% ethylene carbonate and 22.7 wt% of
tetrapropylammonium iodide was taken in a closed glass
container. The contents were stirred well at 353 K for about 2 h
until a homogeneous viscous gel was formed. Then, the solution was allowed to cool down to room temperature. Iodine
(1.7 wt%) was then added to the polymer electrolyte and stirred
well until it becomes a homogeneous viscous solution.
Fabrication of DSSCs
A TiO2 photoanode was prepared as described in our previous
reports.26,27 In brief, a pre-cleaned FTO conducting glass was
used as a substrate for the photoelectrode and a two layer TiO2
coating onto the FTO glass substrate was performed. To obtain
a rst compact layer, 0.5 g of TiO2 (P90) powder was ground well
with 2 mL of 0.1 M HNO3 for about 30 min in an agate mortar
and pestle. The resulting TiO2 (P90) paste was spin coated at
2650 rpm for 60 s on the conducting side of the FTO glass
substrate followed by sintering at 450  C for 30 min. To obtain
a second porous layer of TiO2, 0.5 g of TiO2 (P25) was ground
well with 2 mL of 0.1 M HNO3, 0.1 g carbowax and 2 drops of
Triton-X 100. Then, the obtained TiO2 (P25) paste was coated
above the compact layer using a doctor blade technique followed by sintering at 450  C for 30 min. The TiO2 photoelectrode was dye-sensitized by immersing in 3 mM ethanolic
solution of N3 dye for 24 h. The sandwich conguration of
DSSCs was assembled using the dye-sensitized TiO2 photoelectrode and the as-prepared CEs. Prior to the assembly, the
polymer electrolyte described earlier was evenly spread on the
surface of the dye-sensitized TiO2 photoelectrode. In addition,
the Pt CE was prepared by drop casting plastisol solution on the
FTO glass substrate and sintered at 450  C for 30 min. The Pt CE
was used as a reference cell for comparison. The active area of
the DSSC was 0.2 cm2.
Characterization techniques
The X-ray diraction (XRD) patterns were recorded using
a Rigaku X-ray diractometer (Mini Flex II, Japan) with Cu Ka

This journal is The Royal Society of Chemistry 2016

in the 2q range of 2080 at a scan rate

radiation (l 1.5406 A)

1

of 5 min . The shape and morphology of the electrochemically deposited samples were examined by high resolution
scanning electron microscopy (HRSEM) with an FEI Quanta
FEG 200 system at an accelerating voltage of 20 kV. The
elemental composition analysis was performed by using energy
dispersive X-ray spectroscopy (EDS) equipped with HRSEM. The
electrocatalytic performance of the samples was evaluated by
cyclic voltammetry (CV) measurements. The CV was carried out
using a CHI608E electrochemical workstation (CHI, USA) in
a three-electrode system with a Pt-wire as the counter electrode,
non-aqueous Ag/AgCl as a reference electrode and electrochemically deposited ternary Ni1
xMoxS lms as a working
electrode. The electrolyte used in CV measurements consisted
of 0.1 M LiClO4, 10 mM LiI and 1 mM I2 in acetonitrile. The
electrolyte solution was N2-purged for 15 min before taking the
CV measurements. The CV curves were recorded in the potential
ranging from
0.6 to +1.2 V. The symmetrical cells (CE/polymer
electrolyte/CE) were fabricated to perform the electrochemical
impedance spectroscopy (EIS) and Tafel analysis. The EIS was
carried out using an AC-impedance technique in the frequency
range of 0.1 Hz to 1.0 MHz at an AC amplitude of 5 mV. The
Tafel curves were recorded in the potential range of
0.15 V to
0.15 V and the scan rate was 10 mV s
1.
The photovoltaic performances of DSSCs were evaluated by
recording photocurrent densityvoltage (JV) curves under
a white light irradiation of 100 mW cm
2 (AM 1.5) using a solar
simulator PEC-L01 (PECCELL Inc., Japan). The ll factor (FF)
and power conversion eciency (h) of DSSCs were calculated
according to the following eqn (5) and (6).28
FF
h %

Vmax  Jmax
Voc  Jsc

(5)

Vmax  Jmax
Voc  Jsc  FF
 100
 100
Pin
Pin

(6)

Where Vmax (mV) and Jmax (mA cm
2) are the voltage and current
density, respectively, at the point of maximum power output on
the JV curve, Pin is the incident light power, and Voc and Jsc are
the open circuit voltage (mV) and the short circuit current
density (mA cm
2), respectively.

Results and discussion

XRD studies
The XRD patterns of the pristine FTO glass substrate and the
electrochemically deposited NiS, Ni0.95Mo0.05S, Ni0.9Mo0.1S and
Ni0.8Mo0.2S lms are displayed in Fig. 1. The diraction peaks of
pure NiS (Fig. 1b) can be observed at 2q 30.3 , 45.8 , and 53.7 ,
which can be indexed to (100), (102) and (110) diraction planes
of the hexagonal phase of NiS (JCPDS no. 75-0613). These
diraction peaks are in good agreement with an earlier report by
Xiao et al.29 All other strong diraction peaks correspond to the
pristine FTO glass substrate. The XRD patterns of Ni0.95Mo0.05S,
Ni0.9Mo0.1S and Ni0.8Mo0.2S (Fig. 1ce) indicate that the XRD
pattern of NiS is not changed due to the incorporation of Mo
with no specic diraction peaks of Mo in the Ni1
xMoxS

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Paper

Fig. 1

XRD patterns of the (a) pure FTO glass substrate, as-deposited

(b) NiS, (c) Ni0.95Mo0.05S, (d) Ni0.9Mo0.1S and (e) Ni0.8Mo0.2S lms.

Fig. 2 Typical HR-SEM images of electrochemically deposited (a) NiS,

(b) Ni0.95Mo0.05S, (c) Ni0.9Mo0.1S and (d) Ni0.8Mo0.2S lms.

samples, possibly due to the low amount of Mo present in the

Ni1
xMoxS. However, small changes in the peak intensity of NiS
were observed which may be due to Mo atoms incorporated at
the interstitial positions or substitutional sites producing
considerable contraction and expansion of the lattice constants.

Ni0.95Mo0.05S composition on the surface of the FTO glass

substrate was conrmed from the EDS analysis.

Morphology and elemental studies

The surface morphology of the electrochemically deposited NiS,
Ni0.95Mo0.05S, Ni0.9Mo0.1S and Ni0.8Mo0.2S lms was examined by
HR-SEM, and the corresponding images are presented in Fig. 2.
The HR-SEM image of pure NiS (Fig. 2a) appeared spherical in
shape with some aggregated particles containing a large number of
irregular particles. The HR-SEM image of Ni0.95Mo0.05S, Ni0.9Mo0.1S
and Ni0.8Mo0.2S lms (Fig. 5bd) clearly shows that the spherical
shaped NiS does not change its morphology by the addition of Mo.
It can be seen that the Ni0.95Mo0.05S (Fig. 5b) is tightly packed
nanocrystals. The well connected surface morphology with tightly
packed nanocrystals promotes the eective electron transport from
their surface to the redox electrolyte in DSSCs.30 The Ni0.9Mo0.1S
and Ni0.8Mo0.2S show more agglomeration of particles by
increasing the content of Mo. Also, the HR-SEM studies conrmed
that the electrochemically deposited NiS, Ni0.95Mo0.05S, Ni0.9Mo0.1S
and Ni0.8Mo0.2S layers adhered well on the FTO glass substrate.
The good adhesion of the electrochemically deposited CE materials on the FTO substrate is a crucial factor for determining the
long-term stability and eciency of the fabricated DSSCs.
The elemental composition of the electrochemically deposited pure NiS and optimized Ni0.95Mo0.05S CE lms was ascertained by EDS analysis and the corresponding EDS spectra are
shown in Fig. 3. The EDS spectra clearly indicate that pure NiS
(Fig. 2a) consisted of Ni and S atoms, whereas Ni0.95Mo0.05S
(Fig. 2b) is composed of Ni, Mo and S atoms only. In addition,
the observed other peaks of Sn, O, Si and F are ascribed to the
FTO glass substrate,31 and no other impurity peaks are found.
The atomic ratio of elemental percentage of species detected by
EDS is mentioned in the inset of Fig. 3. The formation of

J. Mater. Chem. A

Electrocatalytic activity
The electrochemical activity of NiS, Ni0.95Mo0.05S, Ni0.9Mo0.1S,
Ni0.8Mo0.2S and Pt CEs towards the reduction of I3
to I
ions
was examined by cyclic voltammetry using a three electrode
system at a scan rate of 100 mV s
1. The cyclic voltammograms

EDS spectra of electrochemically deposited (a) NiS and (b)

Ni0.95Mo0.05S lms.

Fig. 3

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Journal of Materials Chemistry A

of dierent electrode materials for the I
/I3
redox species are

presented in Fig. 4. Two pairs of redox peaks (Ox-1/Red-1, Ox-2/
Red-2) can be observed for all the electrodes. The pair of redox
peaks observed at the le side (low potential) can be attributed
to the redox reaction shown in reaction (7), and the pair of redox
peaks observed at the right side (high potential) can be attributed to the redox reaction shown in reaction (8).32
I3
+ 2e
4 3I

(7)

3I2 + 2e
4 2I3

(8)

The CV curves of NiS, Ni0.95Mo0.05S, Ni0.9Mo0.1S, and

Ni0.8Mo0.2S were similar in shapes to that of Pt, suggesting
a similar electrocatalytic behaviour for the I
/I3
redox reaction.
The characteristics of peaks Ox-1 and Red-1 are at the focus of
our analysis because the CE is responsible for catalyzing the
reduction of I3
to I
ions in DSSCs.33 The peak current density
(IPC) and the peak-to-peak separation (EPP) are two important
parameters for evaluating the electrocatalytic activity of various
CEs.18 A higher IPC means a faster reaction rate whereas
a smaller EPP means a smaller over-potential and high electrocatalytic activity for the I
/I3
redox reaction.21 Hence, a higher
IPC and a smaller EPP are benecial for a CE to achieve high
electrocatalytic performance. The observed EPP values for
dierent CEs are presented in Table 1. It can be noted that the
Ni0.95Mo0.05S CE exhibited a higher IPC and a smaller EPP
(0.48 V) relative to other CEs. Also, the obtained IPC and EPP
values are closer to the values of Pt CEs. According to Gong
et al.,34 the electrocatalytic activity of the catalyst may also
depend on the stoichiometric ratio and total active surface area,
changing the stoichiometric ratio may improve the catalytic
activity. We have also evaluated the electrocatalytic activity of
dierent CE materials with the same total active surface area for
the reduction of I3
into I
ions. The observed CV results

Fig. 4 Cyclic voltammograms for various CEs at a scan rate of 100

mV s
1 in 10 mM LiI, 1 mM I2 and 0.1 M LiClO4 as a supporting electrolyte in acetonitrile.

This journal is The Royal Society of Chemistry 2016

Table 1

Electrochemical parameters for various CEs

Counter electrode

Rs (U cm2)

Rct (U cm2)

EPP (V)

NiS
Ni0.95Mo0.05S
Ni0.9Mo0.1S
Ni0.8Mo0.2S
Pt

13.02
10.11
11.00
12.02
11.42

105.18
57.49
73.20
89.78
53.38

0.87
0.48
0.59
0.73
0.67

demonstrate that the Ni0.95Mo0.05S CE possesses a stronger

catalytic behaviour compared to other CEs towards I3
reduction in DSSCs. This may be due to a higher synergistic eect
oered by the Ni0.95Mo0.05S, and the increase in active catalytic
sites. However, it can be noted that the electrocatalytic activity
decreases on increasing the Mo content to 10% and 20% and
this may be due to coverage of excess Mo on the NiS surface
which may shield ecient electron transport.
The cyclic voltammograms of the Ni0.95Mo0.05S CE at various
scan rates for the I
/I3
redox reaction are presented in Fig. 5a.
It can be seen that the IPC increases with an increase in scan
rate. Also, the cathodic and anodic peaks are gradually and
regularly shied towards negative and positive directions,
respectively which suggests that suldes at the inner sites
become reactive at a high scan rate.8 Fig. 5b shows a linear
relationship between the peak current density and the square
root of the scan rates. According to the Langmuir isotherm
principle, this linear relationship reveals that the transport of I

species on the surface of the CE is aected by the diusion
limitation of the redox reaction,35 and there is no specic

Fig. 5 (a) Cyclic voltammograms of the Ni0.95Mo0.05S electrode at

dierent scan rates, and (b) relationship between the redox peak
current and square root of the scan rate.

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interaction between the I
/I3
redox species and Ni0.95Mo0.05S

CE. The observed CV results indicate that the Ni0.95Mo0.05S CE
can be a promising CE in DSSCs.
Electrochemical impedance spectroscopy studies
The electrochemical impedance spectroscopy (EIS) measurements were carried out in symmetrical dummy cells fabricated
with two identical CEs to further understand the charge-transfer
process and evaluate the electrocatalytic activity of the synthesized CEs. The corresponding Nyquist plots of the symmetrical
dummy cells are shown in Fig. 6. The Nyquist plots were tted
with the Z-view soware and the relevant equivalent circuit
model is shown in the inset of Fig. 6. The intersection of the
high frequency intercept on the real axis (Z0 -axis) corresponds to
the series resistance (Rs), including the sheet resistance of two
identical CEs and the electrolyte resistance. The high frequency
region of the rst semicircle corresponds to the charge-transfer
resistance (Rct) and constant phase element (CPE) at the
CE/electrolyte interface,36 in which the Rct represents the electrocatalytic performance of CEs. The semicircle at low frequency
corresponds to the Nernst diusion impedance (Zw) of the
I
/I3
redox couple in the electrolyte.37 The obtained Rs and Rct
values are listed in Table 1. It can be seen that the Rs values of
the sulde electrodes are almost similar but slightly higher than
that of the Pt CE, and therefore the eect of Rs on the photovoltaic performance can be omitted.38 The Rct is mainly related
to the electrocatalytic activity for the reduction of I3
to I
ions,
and a lower Rct value means the superior electrocatalytic activity
of CEs, which is benecial for an increase in the FF of the
DSSCs. The Rct value of the Ni0.95Mo0.05S CE (57.49 U cm2) is
lower than that of other sulde CEs and very close to that of the
conventional Pt CE (53.38 U cm2). This indicates that the
Ni0.95Mo0.05S is as eective as a Pt CE for electrocatalytic
reduction of I3
. The observed lower Rct of Ni0.95Mo0.05S may be

Fig. 6 Nyquist plots for dummy cells fabricated with NiS,

Ni0.95Mo0.05S, Ni0.9Mo0.1S, Ni0.8Mo0.2S and Pt CEs. The inset gure is
the relevant equivalent circuit model.

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Paper

due to the positive synergistic eect by the introduction of Mo

into the NiS, which can increase the conductivity and accelerate
the regeneration of I
from I3
. It can be seen that the EIS
results are in good accordance with the results obtained from
CV measurements.
Tafel polarization studies
Tafel polarization measurements were performed with the
symmetrical dummy cell similar to the one used in EIS to
further elucidate the electrocatalytic activity of the various CEs.
The corresponding Tafel polarization curves are shown in Fig. 7.
In Tafel analysis, the exchange current density (Jo) and limiting
current density (Jlim) are closely related to the electrocatalytic
activity of the CEs.18,35 The Jo can be determined from the
intercept of the linear tting lines from the cathodic and anodic
polarization curves.39 The anodic and cathodic branches of the
Tafel curve for the Ni0.95Mo0.05S CE showed a larger slope than
other sulde CEs and closer to the Pt CE, indicating the higher
Jo value for the Ni0.95Mo0.05S CE, and thus suggesting its superior electrocatalytic activity for the reduction of I3
ions. The Jo
is inversely proportional to the Rct as expressed in eqn (9).
Jo RT/nFRct

(9)

where R is the gas constant, T is the temperature, n is the

number of electrons involved in the I3
reduction reaction and
Rct is the charge transfer resistance obtained from the EIS
spectrum. From the graph, it is noteworthy that the trends in Jo
values for the various CEs in the Tafel measurements are in
good agreement with the EIS measurements. In addition, the
information about Jlim can also be obtained with Tafel curves.
The Jlim is related to the diusion characteristics of the redox
couple. The highest Jlim demonstrates the faster diusion rate
of the I3
reduction in the electrolyte. The trends of Jlim would
be consistent with the Jo for all CEs. It can be concluded from
the CV, EIS and Tafel polarization measurements that the

Fig. 7 Tafel polarization curves of the fabricated symmetrical dummy

cells based on various CEs.

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Ni0.95Mo0.05S CE possesses a similar electrocatalytic activity to

Pt CE for regeneration of I
from I3
, and the above investigation demonstrates that the Ni0.95Mo0.05S CE can be expected to
show a reasonable power conversion eciency of the DSSCs.

Photovoltaic performances of the DSSCs

The photovoltaic performances of the fabricated DSSCs based
on various CEs were analysed under white light illumination of
100 mW cm
2 (AM 1.5) by recording the photocurrent density
voltage (JV) curves. The JV curves obtained for the fabricated
DSSCs with NiS, Ni0.95Mo0.05S, Ni0.9Mo0.1S, Ni0.8Mo0.2S and Pt
CEs are shown in Fig. 8. The resultant photovoltaic parameters
of DSSCs such as open-circuit voltage (Voc), short-circuit current
density (Jsc), ll factor (FF) and the overall power conversion
eciency (h) are summarized in Table 2. The photovoltaic
parameters of the DSSC fabricated with the pure NiS CE were
found to show a Voc of 0.68 V, Jsc of 12.71 mA cm
2, FF of 0.69
and h of 5.96%. It could be noticed that the addition of Mo into
the NiS CE led to a signicant enhancement in the power
conversion eciency of DSSCs. The DSSC based on the
Ni0.95Mo0.05S CE exhibited a higher power conversion eciency
of 7.15% with Voc of 0.65 V, Jsc of 17.21 mA cm
2, and FF of 0.64,
which is comparable to that of the Pt based reference cell
(7.20%). The enhanced power conversion eciency of the
Ni0.95Mo0.05S CE is mainly attributed to the improved Jsc and FF,
which could arise from the positive synergistic eect towards
the ecient reduction of I3
to I
ions, highly active catalytic
sites and lower Rct at the CE/electrolyte interface. The well
touched surface morphology of the Ni0.95Mo0.05S CE may also
increase the electrocatalytic regeneration of I
from I3
, which
is benecial for an ecient electron transport mechanism. The
optimized Ni0.95Mo0.05S and conventional Pt CE based DSSCs
with the PhCh-based polymer electrolyte were subjected to
a stability test. It was found that the fabricated DSSC with the
Ni0.95Mo0.05S CE and the PhCh-based polymer electrolyte

Fig. 8 Photocurrentvoltage curve of DSSCs fabricated with NiS,

Ni0.95Mo0.05S, Ni0.9Mo0.1S, Ni0.8Mo0.2S and Pt CEs.

This journal is The Royal Society of Chemistry 2016

Journal of Materials Chemistry A

Photovoltaic parameters of fabricated DSSCs with various

Table 2

CEs
Counter
Electrode

Voc
(V)

Jsc
(mA cm
2)

Fill factor

NiS
Ni0.95Mo0.05S
Ni0.9Mo0.1S
Ni0.8Mo0.2S
Pt

0.68  0.03
0.65  0.03
0.65  0.03
0.65  0.03
0.66  0.02

12.71 
17.21 
16.01 
12.60 
17.32 

0.69
0.64
0.60
0.64
0.63

0.04
0.07
0.15
0.18
0.02

 0.03
 0.04
 0.06
 0.05
 0.01

Eciency,
h (%)
5.96  0.01
7.15  0.01
6.24  0.01
5.24  0.01
7.20  0.01

exhibited about 84% of its initial performance over 5 days,

whereas the conventional Pt CE based DSSC exhibited about
91% of its initial performance over 5 days. This clearly indicates
that the Ni0.95Mo0.05S has a comparable stability to Pt. Hence,
the Ni0.95Mo0.05S CE can be a promising low-cost material with
high eciency for DSSCs.
The schematic illustration of the electron transfer mechanism taking place in the fabricated DSSC using the
Ni0.95Mo0.05S CE is shown in Fig. 9. When the cell is illuminated, the N3 dye is photoexcited and its electrons are transferred into the conduction band of the TO2 photoelectrode.
Subsequently, the photoexcited N3 dye molecules regenerate its
electrons from the redox mediator of the electrolyte and the I

ions of the redox mediator are oxidized into I3
ions (eqn (10)).
Then, the oxidized I3
ions get reduced to I
ions at the
Ni0.95Mo0.05S CE (eqn (11)).
3I
+ 2D+ / I3
+ 2D (regeneration of N3 dye)

(10)

I3
+ 2e
/ 3I
(regeneration of iodide ions)

(11)

Thus, the cycle is completed by the continuous ow of

electrons from the TO2 photoelectrode into the Ni0.95Mo0.05S CE
through an external circuit.

Fig. 9 The schematic representation of the DSSC based on the

Ni0.95Mo0.05S CE under illumination.

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Conclusions
In summary, ternary suldes of Ni1
xMoxS lms with various
compositions (x 0, 0.05, 0.1, and 0.2) were electrochemically
deposited on a FTO conducting glass substrate by using the
cyclic voltammetry technique. HR-SEM studies revealed the
shape and surface morphology of the samples. The elemental
composition of the electrochemically deposited ternary suldes
was ascertained by EDS studies. Subsequently, the electrochemically deposited ternary sulde lms were utilized as
a Pt-free low-cost CE for DSSCs. The CV, EIS and Tafel
measurements revealed that the Ni0.95Mo0.05S lm exhibited
low-charge transfer resistance and superior electrocatalytic
activity for the reduction of I3
to I
ions compared to other
CEs. The Ni0.95Mo0.05S oered a more synergistic eect for the
reduction of I3
, which may be due to highly active catalytic
sites and fast reaction kinetics for the I
/I3
redox reaction. The
DSSC fabricated with the Ni0.95Mo0.05S CE achieved a high
power conversion eciency of 7.15%, which is comparable to
that of the traditional Pt CE (7.20%). These results demonstrate
that the Ni0.95Mo0.05S CE could be one of the promising highly
ecient and low-cost CEs for DSSCs.

Acknowledgements
We gratefully acknowledge the nancial support from the
Department of Atomic Energy-Board of Research in Nuclear
Sciences (DAE-BRNS) (Grant No. 2013/37P/1/BRNS/10), Mumbai, India. Also, we acknowledge Mr Shahan Shah, Centre for
Ionics University of Malaya (CIUM), University of Malaya, 50603
Kuala Lumpur, Malaysia, for his support.

Notes and references

1 J. Theerthagiri, A. R. Senthil, J. Madhavan and T. Maiyalagan,
Recent progress in non-platinum counter electrode
materials for dye-sensitized solar cells, ChemElectroChem,
2015, 2, 928945.
2 C. Martna, M. Zi
oek and A. Douhal, Ultrafast and fast
charge separation processes in real dye-sensitized solar
cells, J. Photochem. Photobiol., C, 2016, 26, 130.
3 S. Thomas, T. G. Deepak, G. S. Anjusree, T. A. Arun, S. V. Nair
and A. S. Nair, A review on counter electrode materials in dyesensitized solar cells, J. Mater. Chem. A, 2014, 2, 44744490.
4 J. Zhao, J. Ma, X. Nan and B. Tang, Application of noncovalent functionalized carbon nanotubes for the counter
electrode of dye-sensitized solar cells, Org. Electron., 2016,
30, 5259.
5 M. Janani, P. Srikrishnarka, S. V. Nair and A. S. Nair, An indepth review on the role of carbon nanostructures in dyesensitized solar cells, J. Mater. Chem. A, 2015, 3, 17914
17938.
6 J. Theerthagiri, R. A. Senthil, K. Susmitha, M. Raghavender
and J. Madhavan, Synthesis of Ecient Ni0.9X0.1Se2 (XCd,
Co, Sn and Zn) Based Ternary Selenides for Dye-Sensitized
Solar Cells, Mater. Sci. Forum, 2015, 832, 6171.

J. Mater. Chem. A

Paper

7 P. Yanga and Q. Tang, Bifacial quasi-solid-state dyesensitized solar cells with metal selenide counter
electrodes, Electrochim. Acta, 2016, 188, 560565.
8 Z. Hu, K. Xia, J. Zhang, Z. Hu and Y. Zhu, Highly transparent
ultrathin metal sulde lms as ecient counter electrodes
for bifacial dye-sensitized solar cells, Electrochim. Acta,
2015, 170, 3947.
9 L. Sun, L. Lu, Y. Bai and K. Sun, Three-dimensional porous
reduced graphene oxide/sphere-like CoS hierarchical
architecture composite as ecient counter electrodes for
dye-sensitized solar cells, J. Alloys Compd., 2016, 654, 196
201.
10 J. Liu, C. Li, Y. Zhao, A. Wei and Z. Liu, Synthesis of NiCo2S4
nanowire arrays through ion exchange reaction and their
application in Pt-free counter-electrode, Mater. Lett., 2016,
166, 154157.
11 K. Saranya, M. Rameez and A. Subramania, Developments in
conducting polymer based counter electrodes for dyesensitized solar cells An overview, Eur. Polym. J., 2015, 66,
207227.
12 Z. Yang, T. Chen, R. He, H. Li, H. Lin, L. Li, G. Zou, Q. Jia and
H. Peng, A novel carbon nanotube/polymer composite lm
for counter electrodes of dye-sensitized solar cells, Polym.
Chem., 2013, 4, 16801684.
13 G. R. Li, J. Song, G. L. Pan and X. P. Gao, Highly Pt-like
electrocatalytic activity of transition metal nitrides for dyesensitized solar cells, Energy Environ. Sci., 2011, 4, 1680
1683.
14 J. Theerthagiri, R. A. Senthil, M. H. Buraidah, J. Madhavan
and A. K. Arof, Synthesis of a-Mo2C by carburization of aMoO3 nanowires and its electrocatalytic activity towards
tri-iodide reduction for dye-sensitized solar cells, J. Mater.
Sci. Technol., 2016, DOI: 10.1016/j.jmst.2016.03.003.
15 J. Huo, J. Wu, M. Zheng, Y. Tu and Z. Lan, Eect of ammonia
on electrodeposition of cobalt sulde and nickel sulde
counter electrodes for dye-sensitized solar cells,
Electrochim. Acta, 2015, 180, 574580.
16 Z. Hu, K. Xia, J. Zhang, Z. Hu and Y. Zhu, Highly transparent
ultrathin metal sulde lms as ecient counter electrodes
for bifacial dye-sensitized solar cells, Electrochim. Acta,
2015, 170, 3947.
17 J. Huo, J. Wu, M. Zheng, Y. Tu and Z. Lan, Flower-like nickel
cobalt sulde microspheres modied with nickel sulde as
Pt-free counter electrode for dye-sensitized solar cells,
J. Power Sources, 2016, 304, 266272.
18 X. Zuo, R. Zhang, B. Yang, G. Li, H. Tang, H. Zhang, M. Wu,
Y. Ma, S. Jin and K. Zhu, NiS nanoparticles anchored on
reduced graphene oxide to enhance the performance of
dye-sensitized solar cells, J. Mater. Sci.: Mater. Electron.,
2015, 26, 81768181.
19 H. Sun, D. Qin, S. Huang, X. Guo, D. Li, Y. Luo and Q. Meng,
Dye-sensitized solar cells with NiS counter electrodes
electrodeposited by a potential reversal technique, Energy
Environ. Sci., 2011, 4, 26302637.
20 W.
Maiaugree,
A.
Tangtrakarn,
S.
Lowpa,
N. Ratchapolthavisin and V. Amornkitbamrung, Facile
synthesis of bilayer carbon/Ni3S2 nanowalls for a counter

This journal is The Royal Society of Chemistry 2016

View Article Online

Paper

21

22

23

24

25

26

27

28

29

electrode of dye-sensitized solar cell, Electrochim. Acta, 2015,

174, 955962.
Y. Xiao, J. Wu, J. Lin, G. Yue, J. Lin, M. Huang, Y. Huang,
Z. Lan and L. Fan, A high performance Pt-free counter
electrode of nickel sulde/multi-wall carbon nanotube/
titanium used in dye-sensitized solar cells, J. Mater. Chem.
A, 2013, 1, 1388513889.
X. Zheng, J. Guo, Y. Shi, F. Xiong, W. H. Zhang, T. Ma and
C. Li, Low-cost and high-performance CoMoS4 and NiMoS4
counter electrodes for dye-sensitized solar cells, Chem.
Commun., 2013, 49, 96459647.
H. M. Chuang, C. T. Li, M. H. Yeh, C. P. Lee, R. Vittal and
K. C. Ho, A coral-like lm of Ni@NiS with coreshell
particles for the counter electrode of an ecient dye
sensitized solar cell, J. Mater. Chem. A, 2014, 2, 58165824.
A. Banerjee, K. K. Upadhyay, S. Bhatnagar, M. Tathavadekar,
U. Bansode, S. Agarkar and S. B. Ogale, Nickel cobalt sulde
nanoneedle array as an eective alternative to Pt as a counter
electrode in dye sensitized solar cells, RSC Adv., 2014, 4,
82898294.
P. D. Tran, S. Y. Chiam, P. P. Boix, Y. Ren, S. S. Pramana,
J. Fize, V. Artero and J. Barber, Novel cobalt/nickel
tungsten-sulde catalysts for electrocatalytic hydrogen
generation from water, Energy Environ. Sci., 2013, 6, 2452
2459.
J. Theerthagiri, R. A. Senthil, M. H. Buraidah, J. Madhavan
and A. K. Arof, Eect of tetrabutylammonium iodide
content on PVDF-PMMA polymer blend electrolytes for
dye-sensitized solar cells, Ionics, 2015, 21, 28892896.
J. Theerthagiri, R. A. Senthil, M. H. Buraidah, J. Madhavan
and A. K. Arof, Studies of solvent eect on the conductivity
of 2-mercaptopyridine-doped solid polymer blend
electrolytes and its application in dye-sensitized solar cells,
J. Appl. Polym. Sci., 2015, 132, 42489.
J. Theerthagiri, R. A. Senthil, M. H. Buraidah, J. Madhavan
and A. K. Arof, Synthesis of W, Nb and Ta doped a-Mo2C
and Their Application as Counter Electrode in Dyesensitized Solar Cells, Mater, Mater. Today, 2016, 3, S65S72.
Y. Xiao, C. Wang and G. Han, Eects of thiourea
concentration on electrocatalytic performances of nickel
sulde counter electrodes for use in dye-sensitized solar
cells, Mater. Res. Bull., 2015, 61, 326332.

This journal is The Royal Society of Chemistry 2016

Journal of Materials Chemistry A

30 J. Theerthagiri, R. A. Senthil, M. H. Buraidah,

M. Raghavender, J. Madhavan and A. K. Arof, Synthesis
and characterization of (Ni1-xCox)Se2 based ternary
selenides as electrocatalyst for triiodide reduction in dyesensitized solar cells, J. Solid State Chem., 2016, 238, 113
120.
31 N. Jiang, L. Bogoev, M. Popova, S. Gul, J. Yano and Y. Sun,
Electrodeposited nickel-sulde lms as competent
hydrogen evolution catalysts in neutral water, J. Mater.
Chem. A, 2014, 2, 1940719414.
32 X. Yang, J. Luo, L. Zhou, B. Yang, X. Zuo, G. Li, H. Tang,
H. Zhang, M. Wu, Y. Ma, S. Jin, Z. Sun and X. Chen, A
novel Pt-free counter electrode for dye-sensitized solar
cells: Nickel sulde hollow spheres, Mater. Lett., 2014, 136,
241244.
33 Z. Li, F. Gong, G. Zhou and Z. S. Wang, NiS2/Reduced
graphene oxide nanocomposites for ecient dye-sensitized
solar cells, J. Phys. Chem. C, 2013, 117, 65616566.
34 F. Gong, X. Xu, Z. Li, G. Zhou and Z. S. Wang, NiSe2 as an
ecient electrocatalyst for a Pt-free counter electrode of
dye-sensitized solar cells, Chem. Commun., 2013, 49, 1437
1439.
35 W. Wang, X. Pan, W. Liu, B. Zhang, H. Chen, X. Fang, J. Yao
and S. Dai, FeSe2 lms with controllable morphologies as
ecient counter electrodes for dye-sensitized solar cells,
Chem. Commun., 2014, 50, 26182620.
36 X. Yin, F. Wu, N. Fu, J. Han, D. Chen, P. Xu, M. He and Y. Lin,
Facile synthesis of poly(3,4-ethylenedioxythiophene) lm via
solid-state polymerization as high-performance Pt-free
counter electrodes for plastic dye-sensitized solar cells,
ACS Appl. Mater. Interfaces, 2013, 5, 84238429.
37 S. Yun, H. Pu, J. Chen, A. Hagfeldt and T. Ma, Enhanced
performance of supported HfO2 counter electrodes for
redox couples used in dye-sensitized solar cells,
ChemSusChem, 2014, 7, 442450.
38 F. Gong, H. Wang, X. Xu, G. Zhou and Z. S. Wang, In situ
growth of Co0.85Se and Ni0.85Se on conductive substrates as
high-performance counter electrodes for dye-sensitized
solar cells, J. Am. Chem. Soc., 2012, 134, 1095310958.
39 C. T. Li, C. P. Lee, Y. Y. Li, M. H. Yeh and K. C. Ho, A
composite lm of TiS2/PEDOT: PSS as the electrocatalyst
for the counter electrode in dye-sensitized solar cells,
J. Mater. Chem. A, 2013, 1, 1488814896.

J. Mater. Chem. A