Recent Progress in Non-Platinum Counter Electrode Materials For Dye Sensitized Solar Cells

DOI: 10.1002/celc.
201402406
Reviews
Recent Progress in Non-Platinum Counter Electrode

Materials for Dye-Sensitized Solar Cells
Jayaraman Theerthagiri,[a] Arumugam Raja Senthil,[a] Jagannathan Madhavan,*[a] and
Thandavarayan Maiyalagan[b]
ChemElectroChem 2015, 2, 928 945
928
2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Reviews
Dye-sensitized solar cells (DSSCs) have gained increasing attention with regard to photovoltaic devices, because of their low
cost and simple fabrication methods; they are mostly investigated in indoor light-harvesting and portable applications. The
focus has been on three main parameters of photovoltaic devices, that is, lifetime, and cost effectiveness. A DSSC consists of
four prominent components including a photoanode, a photosensitizer, a redox electrolyte, and a counter electrode. The
counter electrode is a crucial component, in which triiodide is
reduced to iodide by electrons flowing through the external
circuit. An effective approach to improve the performance of
a counter electrode is to enhance the power conversion efficiency and to reduce the cost of the device. Platinum-coated
conducting glass electrodes give the best performance, but

their high cost and the scarcity of platinum restricts large-scale
application in DSSCs. This has prompted researchers to develop low-costing platinum-free electrodes for DSSCs. In this
review, we focus mainly on counter electrode materials for the
electrocatalytic redox reaction for the I/I3 electrolyte, and
apart from this, other counter electrode materials for iodinefree redox electrolytes are discussed. Different counter electrode materials are highlighted in different categories such as
carbon materials, conducting polymers, oxide and sulfide materials, transition-metal nitrides and carbides, and composite
materials. The stability of counter electrodes in DSSCs is also
presented.
1. Introduction
portant criteria that must be considered in selecting a polymer

include good conductivity and stability. The conductivity of an
electrolyte mainly depends on the concentration of the salt
containing the mobile species as well as the extent up to
which the salt is dissociated, which thus makes all dissociated
ions available for conduction.[11] However, the dissociation of
salts depends on the dissociation constant of the salt, the
donor number of the solvent, the dielectric constant of the solvent, and the nature of the salt. In polymer electrolytes, however, the conductivity arises from rapid segmental motion and
the interaction between the cations and the donor atom of
the main structure.
The sensitizing dye should possess the following requirements for efficient energy conversion: The absorption spectrum of the dye should cover the whole visible region and the
near-infrared portion of the solar spectrum. The excited state
of the dye should be higher in energy than the conduction
band edge of the n-type semiconductor, so that an efficient
electron-transfer process can take place between the excited
dye and the conduction band of the semiconductor.[12, 13] The
most common high-performing dyes reported so far are the
ruthenium-centered polypyridyl complexes, including N3,
N719, and N749 (black dye), in addition to other dyes, such as
porphyrins,[14, 15] phthalocyanines,[16] and metal-free organic
dyes.[17, 18]
The counter electrode is an indispensable component in
DSSCs, as it injects electrons into the electrolytes to catalyze
the reduction reaction (I3 to I) after charge injection from the
photooxidized dye. Conventional conductive glasses, such as
indium-doped tin oxide (ITO) or fluorine-doped tin oxide (FTO)
without a catalyst present a low rate of reduction for the counter electrode, and thus, the counter electrode must be coated
with a catalytic material to accelerate the reaction.[19, 20] In this
regard, platinum (Pt) is preferred due to its superior conductivity and high electrocatalytic activity. However, platinum is
a very expensive, scarce noble metal and it undergoes slow
dissolution due to the corrosive I3 /I redox electrolyte, which
deteriorates its long-term stability. These drawbacks restrict
large-scale applications of Pt electrode in DSSCs.[4, 21] Hence, it
is important to develop alternative noble-metal-free materials
that are capable of replacing platinum as electrocatalysts. The
The solar cell is a promising renewable energy device that converts sunlight into electricity; it has broad potential to contribute to the solution for the future energy problem that humanity faces.[1] Nowadays, solar energy technology is gaining tremendous popularity due to its numerous advantages, which
include its ability to operate without noise, toxicity, or greenhouse gas emission. Among various solar cells, dye-sensitized
solar cells (DSSCs) demonstrate specific advantages over other
photovoltaic devices, because of their high efficiency, low cost,
simple fabrication procedures, environmental friendliness,
transparency, and good plasticity. Though DSSCs perform well
under laboratory conditions relative to other solar cells, parameters such as efficiency, lifetime, and cost determine their commercial applications. The major components of conventional
DSSCs include a nanocrystalline semiconductor oxide, a dye
sensitizer, a redox electrolyte, and a counter electrode (CE).[2, 3]
Recently, extensive studies of the individual components of
DSSCs have been performed to reduce production costs and
to achieve high cell performance. The cell performance depends on many factors such as surface morphology, particle
size, photoelectrode thickness of TiO2, and the nature of the
dye. An overall solar conversion efficiency of more than 12 %
has been achieved by employing liquid electrolytes (I/I3
redox couple) in DSSCs. However, the use of liquid electrolytes
causes many problems in DSSCs such as short-term stability
due to organic solvent evaporation and leakage, difficulty in
sealing the device, electrode corrosion, and limited solubility
of inorganic salts such as KI, NaI, and LiI.[4, 5]
To overcome these disadvantages, many researchers have
focused on alternatives such as the gelation of solvents,[6, 7]
polymers incorporating I/I3 redox couple materials,[8, 9] or replacing the liquid electrolytes with other solid materials.[10] Im[a] J. Theerthagiri, A. R. Senthil, Dr. J. Madhavan
Solar Energy Lab, Department of Chemistry
Thiruvalluvar University, Vellore-632 115 (India)
E-mail: jagan.madhavan@gmail.com
[b] Dr. T. Maiyalagan
Materials Science and Engineering Program
The University of Texas at Austin, Austin, TX 78712 (USA)
www.chemelectrochem.org
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Reviews
power conversion efficiency of DSSCs does not increase in proportion to an increase in the thickness of the platinum film,
and it is possible to obtain a high power conversion efficiency
with a very thin platinum film of 2 nm. Such results suggest
that production costs can be somewhat reduced by reducing

the amount of platinum used.
However, a more promising way to reduce the cost of
DSSCs is to explore other low-costing materials that possess
reasonably good catalytic activity.[22] The general requirement
of a photoelectrode material is that it should have a maximal
optical function to absorb solar energy in the visible region
with a high catalytic function. The electrocatalytic activity of
the material can be improved by increasing the specific surface
area, so the material must be prepared with nanoscale dimensions. This is because nanosized materials show different physical and chemical properties than bulk materials.[23]
The cell performance of a DSSC can be evaluated by the fill
factor (FF) and the overall solar light to electrical energy conversion efficiency (h), which can be calculated according to
Equations (1) and (2):[13, 24]
Mr. Jayaraman Theerthagiri received

his MSc degree in chemistry from the
Ramakrishna Mission Vivekananda College, Mylapore, Chennai, in 2011. He is
currently a PhD student at the Thiruvalluvar University, Vellore. His current
research is focused on the synthesis of
counter electrode materials for DSSCs,
polymer electrolytes, and photocatalysis for energy and environmental
applications.
Mr. Arumugam Raja Senthil received
his MSc degree in chemistry from the
Thiruvalluvar University, Vellore, in
2012. He is currently a PhD student at
the Thiruvalluvar University, Vellore.
His current research is focused on
polymer electrolytes for electrochemical device applications.
FF
h %
Vmax Jmax
V Jsc FF
100 oc
100
Pin
Pin
In this review, the recent progress in the replacement of the

platinum counter electrode with other cheaper materials for
DSSCs is presented. The platinum-free counter electrode materials are categorized into carbon materials, conducting polymers, inorganic metal oxides and metal sulfides, transitionmetal nitrides and carbides, and composite materials, and the
advantages of these platinum-free catalysts for DSSCs are also
highlighted.
2. Dye-Sensitized Solar Cells: General

Mechanism
A schematic diagram of a conventional DSSC and the individual components of the cell are shown in Figure 1. DSSCs are
typically composed of electrodes (anode and cathode), a dye
(D) as a sensitizer, and the I/I3 redox couple containing the
electrolytes.
The excited-state level of a dye should be higher in energy
than the conduction band edge of the semiconductor, so that
efficient electron transfer from the excited dye to the conduction band of the semiconductor oxide will take place. The
energy level of the oxidized state of the dye must be more
positive than the HOMO level of the redox potential of the
electrolyte for regeneration of the dye. Regeneration of the
oxidized dye from the redox species of the electrolytes should
be faster than recombination of the oxidized dye with an electron in the TiO2 photoanode. The semiconductor oxide must
be mesostructured to achieve a surface area that is large
enough to allow sufficient dye to harvest the incident light.
Dr. Thandavarayan Maiyalagan received his PhD degree in physical

chemistry from the Indian Institute of
Technology, Madras, and completed
postdoctoral programs at the Newcastle University (UK) and at the University of Texas, Austin (USA). His main research interests concern new materials
and their electrochemical properties
for energy conversion and storage devices, electrocatalysts, fuel cells, and
biosensors.
in which Jsc is the short-circuit current density [mA cm2], Voc is

the open-circuit voltage [V], Pin is the incident light power, and
Jmax [mA cm2] and Vmax [V] are the current density and voltage
at the point of maximum power output in the current versus
voltage (JV) curves.
Dr. Jagannathan Madhavan is currently

working as an Assistant Professor in
the Department of Chemistry, Thiruvalluvar University, Vellore, India. He received his PhD degree from the Department of Energy, University of
Madras, in 2007 and worked as a postdoctoral fellow at the School of
Chemistry, University of Melbourne,
Australia from 2008 to 2010. His current research interests include dyesensitized solar cells, photocatalysis,
polymer electrolytes, and nanomaterials for energy and environmental remediation.
Vmax Jmax
Voc Jsc
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Reviews
Carbonaceous materials are quite attractive to replace the platinum electrode in DSSCs due to their high electronic conductivity, large surface area, corrosion resistance towards iodine,
high reactivity for triiodide reduction, and low cost. Several
carbonaceous materials such as graphene, carbon nanotubes,
activated carbon, graphite, and carbon black have been successfully employed as counter electrodes.[3638]
In 1996, Kay and Grtzel first explored a graphiticcarbon
black mixture as a counter electrode material and achieved
a power conversion efficiency of 6.7 %.[39] Thereafter, intensive
research efforts have been focused on carbon materials. The
power conversion efficiency and the fill factor of DSSCs are
strongly dependent on the thickness of the carbon layer. It has
been reported that the fill factor increases as the carbon layer
thickness increases up to 10 mm.[40] Glassy carbon with low
crystallinity shows high electrocatalytic activity for the reduction of triiodide in the redox reaction. The enhanced electrocatalytic activity of glassy carbon can be attributed to increased
graphene stacks and active sites in glassy carbon.[41] Lee et al.
fabricated DSSCs by using nanosized carbon as a counter electrode material and reported a power conversion efficiency of
7.56 %. After storing the devices in the dark at room temperature for 60 days, the carbon counter electrode retained 84 % of
its initial efficiency.[42]
The optical and electrochemical properties of the carbon
counter electrode are dramatically affected by the composition
and concentration of the precursor used. The optimized
carbon counter electrode exhibits high transparency and sufficient catalytic activity for I3 reduction.[43] Veerappan et al. have
employed colloidal graphite as an efficient counter electrode
for triiodide reduction in DSSCs. Advantages of colloidal graphite are that it may act dually as a substrate as well as an electrocatalyst so that it can be successfully replaced by both the
transparent conducting oxide (TCO) and platinum.[44]
Electron injection [Eq. (4)]:

4
Dye regeneration [Eq. (5)]:

5
Regeneration of iodine [Eq. (6)]:

I3 2 e ! 3 I
For efficient regeneration of the electrolyte, the chargetransfer resistance of the catalyst in the counter electrode and
the diffusion constant of triiodide are very important.
The reactions involved in the reduction mechanism of I3 are
described by Zhang et al. [Eqs. (7)(9)]:[25]
I3 sol $ I2sol I sol
7
3.1. Carbon-Based Materials
Photoexcitation [Eq. (3)]:
2 D 3 I ! I3 2 D
I* e ! I sol
3. Platinum-free Counter Electrode Materials
Among semiconductor oxides, TiO2 is widely studied due to its

high charge transport and its ability to suppress charge
recombination.[12, 13]
Upon illumination of the cell, an electron generated by the
sensitizer is transferred to the conduction band of the oxide
semiconductor wherein the sensitizer is anchored. Then, the
sensitizer is regenerated by the iodide ions from the electrolyte
(iodide/triiodide redox couple dissolved in an organic solvent),
and I3 in the electrolyte is reduced by the electron reaching
the counter electrode through back contact. The cycle is completed by electron migration between the TiO2 semiconductor
and the counter electrode.
D* ! D e CB
in which * represents the free site on the electrode surface

and sol indicates the solvent of the electrolyte solution phase.
The equilibrium reaction (step 7) is usually fast. The subsequent iodine reduction reaction (steps 8 and 9) occurs at the
liquidsolid interface, that is, I2 dissociates into two surface I
atoms (I*) upon adsorption on the electrode surface, and the
removal of I* through one-electron transfer to produce solvated I(sol) determines the overall electrocatalytic activity.
In this review, we focused on Pt-free, low-costing counter
electrode materials for DSSC applications. Detailed review articles on the individual components of DSSCs and an overview
of the energetics of the electron-transfer processes involved in
DSSCs have already been reported by various researchers.[2635]
Figure 1. Energy-level diagram of a DSSC. VAC = vacuum energy level,

CB = conduction band, VB = valence band.
D hn ! D*
I2sol 2* ! 2 I*
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Reviews
roles in efficiency.[48] Wang et al. have prepared a counter electrode for DSSCs by using nitrogen-doped mesoporous carbon
(NMC). The NMC counter electrode can achieve a power conversion efficiency of 7.02 % with the liquid I/I3 redox couple;
this is comparable to the power conversion efficiency of a Pt
counter electrode (7.26 %) under the same test conditions. This
result clearly indicates that the NMC electrode is an alternative
low-costing material for the Pt counter electrode in DSSCs.[49]
Jian et al. have investigated a DSSC by using a nonionic surfactant Triton X-100 modified mesoporous carbon (MC) counter
electrode. Such an electrode-based cell can reach a maximum
power conversion efficiency of 5.65 %.[50]
Among the carbon polymorphs, graphene-based materials
have captured more attention in Pt-free DSSCs. Graphene is
a compound that has two dimension atomically thick sp2carbon atoms arranged in a hexagonal honeycomb lattice
structure. Graphene has been demonstrated to be a promising
counter electrode material for DSSCs due to its excellent conductivity, high electrocatalytic activity, and remarkable transparency over the entire solar spectrum.[51]
Roy-Mayhew et al. have reported that the charge-transfer resistance of functionalized graphene is 10 times greater than
that of platinum, as there is no applied bias, and the charge
transfer resistance approaches that of platinum at an applied
bias of 0.5 V. Also, they have studied the effect of tuning the
catalytic functional groups on functionalized graphene sheets
and have shown that increasing the number of oxygen-containing functional groups results in an increase in the catalytic
activity of the material.[52] The low number of oxygen functionalities in the graphene electrode
mainly affects the redox kinetics
and the charge-transfer resistance. The low current density is
mainly attributed to a high
charge-transfer resistance for the
I3 /I redox reaction.[53] Yue et al.
have investigated a Pt/graphene
film as a counter electrode in
DSSCs and compared its power
conversion efficiency with that
of a traditional platinum counter
electrode. The Pt/graphenebased
DSSC
can
achieve
a higher power conversion efficiency (7.88 %) than the Pt counter electrode (6.51 %). This is because of its higher conductivity
and lower charge-transfer resistance on the electrode/electrolyte
interface for the I3 /I redox reaction.[54] The lower cost of graphene-based counter electrode
materials has attracted largescale applications in DSSCs.
The combination of graphene
Figure 2. SEM images of different carbon materials such as activated carbon (Ca), carbon black (Cb), conductive
with a polymer produces an efcarbon (Cc), carbon dye (Cd), carbon fiber (Cf), carbon nanotube (Cn), mesoporous carbon (Com), discarded toner
of a printer (Cp), and fullerene (C60).[47]
fective counter electrode, for
Veerappan et al. have fabricated a DSSC with a spray-coated
carbon counter electrode, and they investigated the impact of
spraying time of the carbon paste on the performance of the
glass/plastic-coated carbon counter electrodes. The spraycoated carbon counter electrode on glass and plastic can achieve a power conversion efficiency of more than 6.0 %, and the
highest power conversion efficiency of 6.2 % is obtained with
a spraying time of 420 s.[45] Chen et al. have prepared a carbon
black coated graphite counter electrode with a thickness of
0.2 mm by a spin-coating method; it shows a maximum power
conversion efficiency of 6.46 %, which is higher than the efficiency (6.37 %) of a thermally deposited Pt/FTO counter electrode.[46] Wu et al. have fabricated a DSSC by using different
types of carbon-based counter electrodes, such as mesoporous
carbon, activated carbon, carbon black, conductive carbon,
carbon dye, carbon fiber, carbon nanotube, discarded toner of
a printer, and fullerene. All of these carbon materials possess
good electrocatalytic activity for triiodide reduction in DSSCs,
and the corresponding SEM images of these materials are
shown in Figure 2. However, mesoporous carbon shows catalytic activity that is comparable to that of Pt. The mesoporous
carbon counter electrode shows a power conversion efficiency
of 7.5 % by using the I/I3 redox couple.[47]
Sebastin et al. synthesized carbon nanofibers (CNFs) at different temperatures ranging from 550 and 750 8C, and these
CNFS have been used as a counter electrode for DSSCs. CNFs
synthesized at 550 8C show higher conversion efficiency than
CNFs synthesized at other temperatures. These authors report
that the surface area and crystallinity of the materials play key
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which graphene is responsible for the high catalytic activity
and the polymers act as a conducting support material.[55] The
combination of the high crystallinity of graphene with the
high surface area of carbon black results in a material with low
interfacial transfer resistance and high catalytic activity; this
material shows the highest power conversion efficiency of
5.99 %.[56] Kim et al. have used three different polymorphs of
carbon for counter electrodes in DSSCs, including graphene,
single-walled carbon nanotubes (SWCNTs), and a graphene
SWCNTs composite (Figure 3). Of these three catalysts, the gra-
Table 1. Photovoltaic characteristics of DSSCs with different carbonbased counter electrodes.

Sample
Jsc [mA cm2]
Voc [V]
FF
h [%]
Ref.
glassy carbon
carbon
colloidal graphite
carbon nanotube
C60 (fullerene)
carbon dye
carbon nanofiber
N-doped carbon
Vor-ink P3
Vor-ink P10
graphene/Pt
graphene/carbon
graphene
SWCNTs
SWCNTs-GO[a]
16.50
10.52
12.7
13.25
11.60
13.38
7.4
15.46
8.14
7.77
14.56
15.07
13.1
13.0
12.7
0.71
0.72
0.794
0.80
0.75
0.80
0.71
0.71
0.70
0.71
0.75
0.70
0.70
0.71
0.70
0.645
0.60
0.62
0.65
0.32
0.69
0.42
0.64
0.66
0.70
0.68
0.57
0.63
0.52
0.56
7.56
6.07
6.2
7.0
2.8
7.5
2.17
7.02
3.75
3.83
7.43
5.99
5.87
4.97
5.17
[41]
[42]
[44]
[47]
[47]
[47]
[48]
[49]
[51]
[51]
[54]
[56]
[57]
[57]
[57]
[a] GO = graphene oxide.
polyaniline (PANI), polypyrrole (PPy), and poly(3,4-ethylenedioxythiophene) (PEDOT) have been adopted as counter electrodes
for DSSCs.
Over the last decade, PANI has been one of the most intensively studied conducting polymers due to its easy synthesis,
high conductivity, good environmental stability, and interesting
redox properties.[59, 60] Li et al. have reported that an increase in
the surface area of the PANI electrode improves its catalytic activity. It has a lower charge-transfer resistance and a higher
electrocatalytic activity for the I3 /I redox reaction than the
platinum electrode. The overall energy conversion efficiency of
DSSCs with a PANI counter electrode is 7.15 %, which is higher
than that with the platinum electrode (6.90 %).[61] The thickness, surface morphology, and electrocatalytic activity of the
electrochemically synthesized PANI counter electrode have
been investigated by Lin et al. After optimization of the
sweep-segment number in cyclic voltammetry, the 27-sweep
segment PANI counter electrode shows good electrocatalytic
activity for triiodide reduction. The energy conversion efficiency obtained by using this PANI counter electrode is 5.92 %.[62]
To improve the electrocatalytic and photovoltaic properties of
DSSCs, Ameen et al. have investigated sodium fluoroacetate
(SFA)-doped PANI and compared the results with those obtained by using undoped PANI and a platinum counter electrode.[20] The superior photovoltaic properties (e.g. h, Jsc, Voc,
and incident photon-to-current efficiency) of the SFA-PANIbased cell have been attributed to its high conductivity and
electrocatalytic activity. Another report on PANI-CSA (polyanilinecamphorsulfonic acid) as a counter electrode for DSSCs is
also interesting. The performance of the porous PANI-CSA
nanostructured counter electrode with optimized surface
roughness is comparable to that of a conventional DSSC with
a platinum counter electrode.[63] Xiao et al. have prepared polyaniline nanofibers to replace the Pt counter electrode in
DSSCs; the PANI nanofibers show excellent electrocatalytic activity for the I3 /I redox reaction. A power conversion efficiency of 6.21 % can be achieved by using the PANI nanofiber
Figure 3. A multifunctional nanocarbon-based interlayer used in DSSCs and

the JV curves with (c) and without (g) TiCl4 treatment, as well as with
SWCNH interlayers of 15 (c) and 30 nm (c).[37]
phene-deposited SWCNT electrode shows the highest power

conversion efficiency (5.87 %), and thus, graphene is the most
suitable material for the counter electrode in DSSCs.[57] The
photovoltaic characteristics of DSSCs with different carbonbased counter electrodes are shown in Table 1.
Carbon materials are low-costing counter electrode catalysts
in DSSCs; however, the main drawback of carbon-based counter electrodes is that these materials require large dosage to
attain the targeted catalytic activity. Then, a poor connection
between the carbon film and the substrate limits the longterm use of carbon-based counter electrodes.
3.2. Conducting Polymers
In recent years, research efforts have been directed towards
conducting polymers due to their potential uses as conducting
substrates, hole conductors, and counter electrode materials
for DSSCs. Conducting polymers are promising candidates for
counter electrode materials in DSSCs due to their unique properties, such as high conductivity, low cost, good stability, and
high catalytic activity for I3 reduction.[58] Polymers such as
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counter electrode; this is close to the efficiency achieved by
using the Pt counter electrode (6.39 %).[64] Li et al. have investigated the effect of doping several anions such as SO42, ClO4 ,
BF4 , Cl , and TsO (Ts = tosyl) into the PANI film. Among
them, the SO42-doped PANI film shows a higher reduction current for the reduction of I3 and a lower charge-transfer resistance than the Pt counter electrode. The PANI-SO4 counter electrode in DSSCs shows a conversion efficiency of 5.6 %.[65] The
sodium dodecyl sulfate (SDS)-doped PANI film exhibits the
highest conductivity, and this leads to a higher catalytic reduction of I3 . DSSCs assembled with PANI-SDS as a counter electrode show a photocurrent conversion efficiency of 7.0 %,
which is comparable to that of a conventional Pt counter electrode (7.4 %).[66]
Wu et al. have synthesized polypyrrole (PPy) nanoparticles
coated with a conducting FTO glass to construct a PPy counter
electrode for DSSCs. The overall power conversion efficiency of
DSSCs with the PPy counter electrode is 7.66 %, which is
higher than that of the platinum counter electrode (6.90 %).[24]
Jeon et al. have synthesized PPy nanoparticles and have fabricated a PPy-layered FTO glass as a counter electrode for DSSCs
by the drop-casting method by using a PPy-dispersed colloidal
solution. The power conversion efficiency of these DSSCs can
reach a maximum of 7.73 %, which is the highest efficiency to
date with the use of PPy as a counter electrode.[58] A polypyrrole nanotube film has been employed as a novel counter electrode to substitute the expensive Pt counter electrode in
DSSCs. A PPynanotube membrane has also been used to replace the Pt counter electrode and the FTO plate; a power
conversion efficiency of 5.27 % can be obtained for the DSSC
assembled with this PPynanotube membrane.[67] The Tafel polarization curves and the JV curves of a characteristic DSSC
fabricated by using Pt/FTO and a PPy counter electrode are
shown in Figure 4. It is clear from this figure that the Tafel
zone of the Pt electrode is higher than that of the PPy counter
electrode, which indicates that the exchange-current density of
Pt is higher than that of the PPy electrode and that the catalyt-
ic activity of Pt is superior to that of the PPy electrode. Veerender et al. have used a free-standing PPy film as a substratefree and Pt-free counter electrode for DSSCs, and their results
have revealed that the PPy film exhibits remarkable catalytic
activity for the I3 /I redox reaction with a DSSC efficiency of
3.5 %.[68] A fabric counter electrode prepared by coating PPy on
a cotton-fabric-coated Ni substrate shows comparable catalytic
activity towards the reduction of I3 .[69] The structure and properties of PPy are greatly influenced by anion doping. Dodecylbenzenesulfate-doped PPy shows the highest electrocatalytic
activity for the I3 /I redox reaction, and thus, PPy films could
replace Pt counter electrodes in DSSCs.[70]
PEDOT is an another kind of conducting polymer that has attracted much attention due to its ease of processing, remarkable stability, electrical conductivity, and catalytic capability.[71]
A low-costing and low-temperature method to fabricate the
high-performance PEDOT counter electrode for DSSCs has
been successfully developed by Yin et al. The overall power
conversion efficiency of the PEDOT counter electrode based
DSSC is 7.04 %, which is comparable to that of the platinum
counter electrode (7.35 %).[72] Sudhagar et al. have reported
that the overall power conversion efficiency of DSSCs with PEDOT:PSS (PSS = polystyrene sulfonate) can be increased by the
addition of catalytic sulfide materials. A PEDOT:PSS DSSC
shows efficiency of 3.8 %; the efficiency increases to 5.4 % in
CoS/PEDOT:PSS DSSC, which is comparable to the efficiency of
the conventional platinum counter electrode (6.1 %).[73]
PEDOT:PSS/carbon counter electrode materials possess
a large surface area, high conductivity, small sheet resistance,
and good redox properties. DSSCs fabricated with this counter
electrode reach an energy conversion efficiency of 4.11 %. Their
simple nature and their low cost allow carbon conductive
paste PEDOT:PSS to be used as a credible alternative counter
electrode in DSSCs.[74] Yue et al. have reported that PEDOT:PSS/
PPy films have low surface resistance and good catalytic performance for the I3 /I redox electrolytes. The energy conversion efficiency of DSSCs based on PEDOT:PSS:PPy counter electrodes is 7.60 %, and this efficiency is comparable to that of
DSSCs based on platinum electrodes. Figure 5 shows the photocurrentvoltage curves of
DSSCs with PPy, PEDOT:PSS, and
PEDOT:PSS/PPy counter electrodes.[75] Kwon and Park have
synthesized PEDOT with different
conductivities ranging from 100
to 690 S cm1 by a simple polymerization method and optimized
the
conductivity
(340 S cm1) of the PEDOT counter electrode exhibiting high
performance for the I3 reduction.[76] Further, a PEDOT counter
electrode has also been synthesized by the aqueous galvanoFigure 4. a) Tafel curves of symmetrical cells based on Pt/FTO and PPy electrodes and b) JV characteristic curves
of DSSCs fabricated by using Pt/FTO and PPy counter electrodes.[67]
static polymerization technique
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a plain FTO plate and are widely studied in DSSCs. Several
quantum dots such as CdS, CdSe, CdTe, CuSnI2, CuS, PbS, and
InAs have been used as sensitizers of nanocrystalline TiO2,
which is used in the construction of quantum-dot-sensitized
solar cells.[78, 79] CoS deposited as a quasitransparent layer on
FTO glass is more electrocatalytic than the bulk platinum electrode for the reduction of triiodide. CoS and CuS have been
used as counter electrodes in DSSCs. A maximum solar conversation efficiency of 2.7 % is obtained with a CuS counter electrode, whereas the platinum counter electrode shows an efficiency of only 0.51 % in combination with polysulfide electrolytes.[80] Wang et al. have demonstrated that CoS is highly efficient in the reduction of triiodide to iodide in DSSCs; also, it
possesses remarkable stability and thermal stress, which make
it an extremely interesting candidate as a replacement for platinum in DSSCs.[81] Wu et al. have introduced MoS2 and WS2 into
DSSC systems as counter electrode catalysts, and these sulfides
show excellent catalytic activities for the generation of the
conventional I/I3 redox couple. These counter electrodes achieve high power conversations of 7.59 and 7.73 %, respectively,
which are close to the photovoltaic performance of DSSCs
with a platinum counter electrode.[82] The corresponding JV
curves are shown in Figure 6. The MoS2 counter electrode synthesized by using a low-temperature wet chemical process exhibits a competitive power conversion efficiency of 7.01 %. The
MoS2 counter electrode holds promise as a replacement for expensive Pt-based counter electrodes in DSSCs. A DSSC fabricat-
Figure 5. The JV curves of DSSCs assembled with PPy, PEDOT:PSS, and PEDOT:PSS/PPy counter electrodes.[75]
with different polymerization times. The catalytic activity of the

counter electrode varies with the polymerization time. Upon
increasing the polymerization time the reaction rate also increases with a higher catalytic reduction of I3 . PEDOT synthesized by this technique shows a higher power conversion efficiency of 6.46 % than the Pt counter electrode (6.33 %) under
the same test conditions.[77] The photovoltaic characteristics of
DSSCs with different conducting polymers as counter electrodes are shown in Table 2. PEDOT exhibits high conductivity,
Table 2. Photovoltaic characteristics of DSSCs with different conducting

polymers as counter electrodes.
Sample
Jsc [mA cm2]
Voc [V]
FF
h [%]
Ref.
PANI nanofibers
SFA-PANI
PPy
PPy
HCl-PPy
PANI
PANI
PANI-SDS
PPy-nanotube
PEDOT
PEDOT:PSS/C
10.94
13.62
15.01
11.0
15.5
14.60
13.29
14.0
13.10
16.26
7.5
0.68
0.74
0.740
0.785
0.778
0.714
0.72
0.72
0.71
0.710
0.83
0.54
0.53
0.69
0.64
0.64
0.69
0.61
0.59
0.56
0.61
0.66
4.0
5.5
7.66
7.773
7.73
7.15
5.92
7.0
5.27
7.04
4.11
[20]
[20]
[24]
[58]
[58]
[61]
[62]
[66]
[67]
[72]
[74]
Figure 6. The JV curves of DSSCs with MoS2 and WS2 counter electrodes.[82]
high catalytic activity, and good adhesion to FTO conductive

substrates; even though PEDOT is more expensive than other
conducting polymers, it can be electrodeposited within a limited area of the electrode. So far, upon analyzing various known
conducting polymers, PPy is of special interest due to its ease
of synthesis, excellent stability in air, low cost, and high polymerization yield.
ed by using the Pt-counter electrode shows a power conversion efficiency of 7.31 %, which is close to the 7.01 % shown by
the MoS2 counter electrode.[83] Yang et al. have studied different phases of NiS as counter electrodes for DSSCs. a-NiS and
b-NiS can be synthesized by a solvothermal route, and their
performance has been compared in terms of power conversion
efficiency in DSSCs. The performance of DSSCs with an a-NiS
counter electrode is much better than that of DSSCs with a bNiS counter electrode.[84]
More recently, researchers have focused on binary and ternary metal sulfide materials as counter electrodes to further im-
3.3. Metal Sulfide Materials

The construction of an efficient cathode is important for all
types of electrochemical cells. Metal sulfides are considered
good choices, as these electrocatalysts are deposited on
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prove the activity of metal sulfides in DSSCs. Lin and Chou
have synthesized NiCo2S4 as a highly efficient counter electrode in Pt-free DSSCs and an impressive efficiency of 6.14 %
has been achieved; this value is comparable to the efficiency
of the Pt-based DSSC (6.29 %).[85] Zheng et al. have fabricated
DSSCs with different ternary metal sulfides such as CoMoS4
and NiMoS4 and porous chalcogels of CoMoS4 and NiMoS4.
They have reported that these ternary compounds show
power conversion efficiency that is similar to that of DSSCs fabricated with noble Pt counter electrodes.[86] The I3 /I redox reaction, electrochemical impedance plot, Tafel polarization, and
JV curves of DSSCs with ternary metal sulfides of CoMoS4,
NiMoS4, CoMoS4-C, and NiMoS4-C in addition to those of Pt
counter electrodes are shown in Figure 7. This figure evidences
that the cathodic and anodic peak current densities of
CoMoS4-C and NiMoS4-C are higher than those of CoMoS4 and
NiMoS4, which is due to the addition of graphite; this indicates
that graphite can improve the catalytic activity of triiodide reduction. Furthermore, the mean time current density is lower
than that for the Pt counter electrode. The Nyquist plot shows
that the series resistance (Rs) with CoMoS4 and NiMoS4 electrodes is 14.0 and 15.8 W, respectively. Both values are higher
than the Rs value of the Pt electrode (8.2 W), which may be
due to the lower conductivity of the electrode. The value of Rs
does not decrease even after the addition of graphite.
Mali et al. have synthesized Cu2ZnSnS4 nanofibers by electrospinning by using polyvinylpyrrolidone (PVP) and cellulose acetate (CA) as solvents. The fabricated DSSC shows an efficiency
of 3.10 and 3.90 % for the PVP-Cu2ZnSnS4- and CA-Cu2ZnSnS4based counter electrodes, respectively.[87] CuSbS2 and CuInS2
nanocrystals have also been used as counter electrodes to replace the expensive Pt counter electrode in DSSCs.[88, 89] CuInS2
nanocrystals can be synthesized from a simple one-spot route,
and the DSSC fabricated by using this material can achieve
a conversion efficiency of 5.77 %. Hence, these low-costing materials are suitable as replacements for the Pt counter electrode
in DSSCs. The photovoltaic characteristics of DSSCs with different metal sulfide based counter electrodes are shown in
Table 3.
3.4. Metal Oxide Materials
Metal oxides are also best-opted materials to replace the Pt
counter electrode in DSSCs due to their low cost, good thermal properties, and high catalytic activity. Some semiconductor
oxides have been shown to increase the catalytic activity for
the reduction of triiodide to iodide. Wang et al. have studied
the catalytic activity of ZnO with a conductive polymer that exhibits excellent photovoltaic performance with a maximum
power conversation efficiency of 8.17 %.[90] Tantalum oxide
(TaO), a non-platinum counter electrode, shows impressive
platinum-like electrocatalytic activity for triiodide reduction in
DSSCs. The TaO counter electrode in DSSCs shows a high
power conversion efficiency of 6.48 %, which is better than the
power conversion efficiency of the platinum counter electrode.[91] A DSSC with NiO as the counter electrode has been
Figure 7. a) The I3 /I redox peaks of the CoMoS4, NiMoS4, CoMoS4-C, NiMoS4-C and Pt counter electrodes. b) Electrochemical impedance plots (Rct = chargetransfer resistance ZN = N element series circuit, and CPE = constant phase element). c) Tafel polarization curves of symmetrical cells. d) JV curves of characteristic DSSCs fabricated with ternary sulfide and Pt counter electrodes.[86]
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than the Pt counter electrode, which shows a power conversion efficiency of 8.78 %.[97] Hou et al. have used first-principles
quantum-chemical calculations for the electrocatalytic activity
of potential semiconductor counter electrodes and have reported that a-Fe2O3 can be used as a new counter electrode
catalyst for DSSCs.[98] a-Fe2O3 exhibits adsorption energy of
iodine that is almost identical to that of a Pt counter counter
electrode at the acetonitrile/electrode interface (shown in
Figure 9). The photovoltaic characteristics of DSSCs fabricated
with different metal oxides as counter electrodes are presented
in Table 4.
Table 3. Photovoltaic characteristics of DSSCs with different metal sulfides as counter electrodes.
Sample
Jsc [mA cm2]
Voc [V]
FF
h [%]
Ref.
CoS
CuS
MoS2
WS2
a-NiS
b-NiS
NiCo2S4
CA-Cu2ZnSnS4
PVPCu2ZnSnS4
CuSbS2
11.2
13.9
12.52
12.94
11.42
9.80
14.11
8.42
6.83
5.58
0.52
0.55
0.63
0.64
0.68
0.68
0.72
0.57
0.57
0.74
0.32
0.35
0.63
0.64
0.67
0.63
0.60
0.65
0.64
0.54
1.9
2.7
4.9
5.2
5.2
4.2
6.1
3.9
3.1
2.6
[80]
[80]
[82]
[82]
[84]
[84]
[85]
[87]
[87]
[88]
fabricated by Feihl et al.[92] Of various weight ratios investigated, 10 % by weight of NiO nanoparticles in ethanol paste
shows better efficiency than other samples. The NiO electrode
also has good homogeneity, transparency, and consumes suitable light harvest with good conductivity. NbO2 and WO2 have
also been used as counter electrodes in DSSCs.[93, 94] Cheng
et al. have reported the use of hydrogen-treated commercial
WO3 as a counter electrode to replace the Pt counter electrode. The triiodide reduction reaction is fast if hydrogen-treated commercial WO3 is used as the counter electrode. The
mechanism of the triiodide reduction reaction by using hydrogen-treated commercial WO3 and commercial WO3 is shown in
Figure 8. The power conversion efficiency of hydrogen-treated
WO3 is 5.43 %, whereas commercial WO3 without hydrogen
treatment shows a power conversion efficiency of only
0.63 %.[95]
Figure 9. The calculated adsorption energy of the iodine atom of various

semiconductor materials.[98]
Table 4. Photovoltaic characteristics of DSSCs fabricated with different

metal oxide counter electrodes.
Figure 8. Mechanism of the triiodide reduction by using commercial WO3

and hydrogen-treated WO3 electrodes.[95]
Jsc [mA cm2]
Voc [V]
FF
h [%]
Ref.
V2O3
Nb2O5
MoO2
ZnO
TaO
Ta2O5
H-WO3
C-WO3
SnO2
SnO2-d
W18O49
10.19
9.98
7.84
10.4
12.59
13.01
15.46
6.71
18.71
17.21
17.14
0.78
0.80
0.76
0.39
0.77
0.75
0.74
0.50
0.43
0.53
0.70
0.63
0.60
0.40
0.18
0.67
0.42
0.47
0.21
0.35
0.52
0.66
5.40
4.84
2.40
0.77
6.48
4.08
5.43
0.63
2.88
4.81
7.94
[2]
[2]
[2]
[90]
[91]
[91]
[95]
[95]
[96]
[96]
[97]
3.5. Transition-Metal Nitrides and Carbides

The catalytic activity of carbides was first explored between
1960 and 1970.[99] This led to similar findings for other early
transition-metal carbides and nitrides. However, the development of nitride research began after the 1980s due to its technological interest and applications. Nitrogen is located in the
periodic table of the elements between carbon and oxygen.
Nitrides are close to oxides and carbides with more or less significant ionic, covalent, and metallic character. The synthesis of
transition-metal nitrides provides interesting challenges because of the insertion of nitrogen into the interstitial sites of
the metals. The potential applications of transition-metal ni-
Two different phases of SnO2 have been used as counter

electrodes for DSSCs by Pan et al.[96] They have reported that
d-phase SnO2 shows a low charge-transfer resistance and
higher polarization current density. The power conversion efficiency is 4.81 %, whereas the SnO2 phase shows power conversion efficiency of only 2.88 %. Zhou et al. have demonstrated
W18O49 nanofibers as a superior electrocatalyst due to the
abundance of oxygen vacancies that offer sufficient active sites
for the reduction of I3 into I . The W18O49 nanofiber counter
electrode shows an efficiency of 8.58 %; this is slightly lower
Sample
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significantly by combining with N-doped graphene oxide.[21]
Transition-metal carbides, such as molybdenum and tungsten
carbides, are potential substitutes for platinum counter
electrodes in DSSCs because of their low cost and high electrocatalytic performance in triiodide reduction. Furthermore, it
has been reported that the catalytic activity can be increased
by the addition of P25 into Mo2C and WC particles.[108] Highly
active Mo2N and W2N have been synthesized and used as
counter electrodes in DSSC systems for the reduction of triiodide. Mo2N and W2N counter electrodes can achieve power
conversation efficiencies of 6.38 and 5.81 %, respectively, and
these efficiencies are about 91 and 83 %, respectively, of the
photovoltaic performance of DSSCs fabricated by using a platinum counter electrode.[109] Wu et al. have prepared vanadium
nitride (VN) peas by a simple urea-precursor route and used
these peas as a counter electrode in a DSSC for the traditional
redox couple, that is, the reduction of I3 into I . The VN peas
show a higher power conversion efficiency (5.57 %) than the Pt
counter electrode (3.69 %) in the new organic redox couple thiolate/disulfide(T/T2).[110] Mesoporous WC shows an excellent
solar conversion efficiency if used as a counter electrode in
DSSCs. Jang et al. have synthesized mesoporous WC through
a polymer-derived (WC-PD) and a microwave-assisted (WCMW) route. The power conversion efficiencies of WC-PD and
WC-MW counter electrodes are 6.61 and 7.01 %,
respectively.[111]
He et al. have reported that a TiC counter electrode shows
a higher power conversion efficiency than the conventional Pt
counter electrode in DSSCs with a Co2 + /Co3 + polypyridyl
redox mediator. The TiC counter electrode can achieve an efficiency of 7.74 %, whereas the conventional Pt counter electrode shows an efficiency of only 7.51 %.[112] Wu et al. have investigated TiC as a counter electrode material and have reported that the efficiency of TiC is 6.40 %, whereas the Pt-based
counter electrode shows only 7.16 % efficiency under the same
test conditions. Also, the efficiency of the DSSC can be increased from 6.40 to 7.68 % upon introducing small amounts
of Pt into TiC, and this value is higher than the efficiency of
the Pt counter electrode.[113] Zhong et al. have investigated
TiCSiCC as a counter electrode to replace the expensive Pt
electrode, and the DSSC fabricated by using the TiCSiCC
counter electrode shows an efficiency of 5.7 %.[114] Figure 11
shows the JV curves of some transition-metal carbides and nitrides.[2] The photovoltaic characteristics of DSSCs assembled
with different transition-metal carbides and nitrides counter
electrodes are shown in Table 5.
Transition-metal nitrides and carbides have unique properties in that they show material diversity, are low costing, and
have high catalytic activity; furthermore, they can be prepared
by simple synthesis and can be easily modified in comparison
to carbon materials, organic polymers, inorganic oxides, and
sulfides.
trides and carbides have been widely explored in materials

chemistry due to their unique physical and chemical properties, that is, their high chemical stability, high wear resistance,
electronic conductivity, and magnetic properties. In general,
transition-metal nitrides are conventionally produced by using
metals, metal halides, or metal oxides that are thermally converted into nitrides by using high-temperature treatment with
N2 or NH3(g) or into carbides by carbonation with CH4(g).
Transition-metal nitrides and carbides are considered to be
potential substitutes for platinum due to their platinum-like
electrocatalytic activity. Nitrides and carbides have a wide
range of applications; they can be used in dehydrosulfurization
and dehydrogenation, they can be used as supercapacitors
and in hydrotreating and hydrogenation, and they show good
photocatalytic activity.[100102] Vanadium nitride is used as a catalyst for n-butane dehydrogenation, and its catalytic activity is
similar to that of platinum-based catalysts.[103] An oil refinery
catalytic process such as hydrotreating of heavy vacuum gas
oil (HVGO) uses Mo2N and W2N to remove impurities such as
oxygen, sulfur, and unsaturated hydrocarbons.[104] Molybdenum
nitride is used for hydrodesulfurization in the petroleum industry.[105, 106] It is not surprising that certain metal nitrides and carbides may replace platinum as counter electrodes in DSSCs.
Wu et al. have studied several carbide and nitride materials in
DSSCs as counter electrode catalysts.[2] A comparison of the
power conversion efficiencies of DSSCs with different carbide
and nitride catalysts is shown in Figure 10.
A TiC counter electrode with an optimal film thickness of
20 mm can achieve a high power conversion efficiency of
6.46 %, which matches the performance of DSSCs prepared
with a platinum counter electrode.[22] Jiang et al. have reported
TiN nanotube arrays as counter electrodes, the photovoltaic
performances of which are comparable to those of a conventional platinum counter electrode; they have also suggested
the replacement of electrocatalytically active materials as
a better option than the noble metal platinum in fuel cells.[107]
Zhang et al. have developed several nitride-based catalysts for
the reduction of triiodide in DSSC systems and have reported
that the catalytic activity of nitride materials can be improved
3.6. Composite Materials

Composites are made by combining two or more materials
that can then be used as efficient catalysts for DSSCs. These
Figure 10. Distribution graph showing the power conversion efficiencies of

I3 /I DSSCs.[2]
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Lee et al. have investigated
the effect of inserting graphene
between PEDOT in counter electrodes in DSSCs. A graphene/
PEDOT film without TCO and
platinum were also used as
counter electrodes in DSSCs. The
power conversion efficiency with
Pt/FTO can reach 6.68 %, whereas graphene/PEDOT and PEDOT
show efficiencies of 6.26 and
5.62 %, respectively.[120] Yue et al.
have investigated a graphene/
PEDOT:PSS composite as a counter electrode for the replaceFigure 11. JV curve of a) some transition-metal carbides and b) some transition-metal nitrides for I3 /I in
DSSCs.[2]
ment of the expensive Pt counter electrode in DSSCs. The graphene/PEDOT:PSS composite has low charge-transfer resistTable 5. Photovoltaic characteristics of DSSCs assembled with different
ance on the electrode/electrolyte interface and also possesses
metal carbide and metal nitride counter electrodes.
high electrocatalytic activity for the I3 /I redox reaction. The
Sample
Jsc [mA cm2]
Voc [V]
FF
h [%]
Ref.
graphene/PEDOT:PSS counter electrode shows high efficiency
VC
10.94
0.803
0.56
4.92
[2]
of 7.86 %, which is higher than the Pt counter electrode
VN
11.74
0.788
0.64
5.92
[2]
(7.31 %).[121] Li et al. have prepared a TiS2/PEDOT:PSS composite
NbN
9.81
0.798
0.47
3.68
[2]
as the counter electrode for DSSCs. In the TiS2/PEDOT:PSS comTiC
13.30
0.788
0.62
6.50
[2]
posite structure, TiS2 is distributed in the polymer matrix of PETiN
12.83
0.796
0.61
6.23
[2]
MoN
14.11
0.774
0.58
6.437
[21]
DOT:PSS, which leads to high conductivity and high electrocaTiC
13.12
0.77
0.64
6.46
[22]
talytic activity for the redox reaction of the I3 /I couple. An efTiN nanotube
15.78
0.760
0.64
7.73
[107]
ficiency of 7.04 % can be obtained by using TiS2/PEDOT:PSS,
Mo2N
0.74
0.60
6.38
6.38
[109]
and this is comparable to the efficiency of a Pt counter elecW2N
12.96
0.78
0.57
5.81
[109]
VN peas
15.06
0.73
0.66
7.29
[110]
trode (7.65 %).[122] Song et al. have fabricated a DSSC by using
WC
14.17
0.76
0.65
7.01
[111]
a SiO2/PEDOT-PSS composite as the counter electrode. The
TiC-SiC-C
11.13
0.78
0.65
5.7
[114]
SiO2/PEDOT-PSS counter electrode shows electrocatalytic activity that is comparable to that of a Pt counter electrode for the
reduction of I3 into I , and a power conversion efficiency of
new materials show better performance than the conventional
5.66 % can be obtained with a DSSC fabricated with SiO2/
platinum counter electrode. Recently, some platinum-based
PEDOT-PSS as the counter electrode.[123] Nitrogen-doped
composites such as Pt/carbon nanotubes, Pt/graphene, and Pt/
carbon and an iron-carbide nanocomposite show remarkable
polymer have been introduced as counter electrode catalysts
electrocatalytic activity for the reduction of I3 into I . A total
in DSSCs, and these composites show superior electrocatalytic
conversion efficiency of 7.36 % has been observed for a DSSC
activitythan the traditional Pt counter electrode.[115117] The
fabricated with this composite material; this value is higher
transition-metal compounds TiC, WO2, and VN have been inthan that obtained with a conventional Pt counter electrode
corporated with platinum and used as counter electrode cata(7.15 %).[124] A hydrothermally synthesized MoS2-C hybrid has
lysts for DSSCs. These materials show photovoltaic perserved as a low-costing Pt-free counter electrode for DSSCs
formance that is almost 20 % higher than that of the unitary
due to the special structure and high surface area of the MoS2materials.[118] However, to reduce the cost of DSSCs utilizing Pt,
C composite. It is able to achieve a high power conversion effiwe have to explore other low-costing materials with high cataciency of 7.69 %, which is higher than the efficiency achieved
lytic activity to replace platinum- and platinum-based compoby the Pt counter electrode (6.74 %).[125] Yang et al. have reportsite catalysts. Joshi et al. have reported an efficient DSSC by
ed a comparative study between 1D and 2D graphene bridges
using a cheap carbon/TiO2 composite as an alternative to the
and have shown that the 2D graphene bridge composite is
platinum counter electrode for triiodide reduction.[119] In the
better than the 1D materials. As a result, graphene introduced
carbon/TiO2 composite, carbon acts as the catalyst and TiO2
as 2D bridges enhances photoinduced charge transport in
functions as a binder. A solar-to-energy conversion efficiency
DSSCs and also lowers recombination.[126] The differences beof about 5.5 % has been reported by using this carbon/TiO2
tween the 1D and 2D nanomaterial composite electrodes are
composite, and moreover, this composite shows device pershown in Figure 12.
formance that is comparable to that of platinum counter elecThe photovoltaic efficiency of DSSCs with the improved gratrodes in terms of Jsc, Voc, and h under similar fabrication
phene structure counter electrode is still lower than that of
procedures.
DSSCs with a standard platinum counter electrode. To further
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Figure 12. Model of 1D (a, b) and 2D (c, d) nanomaterial composite electrodes.[126]
improve the cell performance, a graphene structure incorporated with tungsten nanoparticles in ethanol has been used as
a counter electrode. The graphenetungsten composite structure counter electrode can achieve an overall photovoltaic efficiency of 5.88 %.[3] Nagarajan et al. have assembled a PEDOT-reinforced exfoliated graphite composite counter electrode in
DSSCs. The PEDOT/EFG (EFG = exfoliated graphite) electrode
shows high energy conversion efficiency of 5.7 %, whereas the
conventional platinum counter electrode shows energy conversion efficiency of 4.4 %.[127] A TiNcarbon nanocomposite
counter electrode exhibits outstanding energy conversion efficiency of 6.71 %, which is higher than that observed for DSSC
devices fabricated by using pure TiN nanoparticles, carbon,
and conventional platinum counter electrodes. The outstanding performance of TiN embedded in amorphous carbon is
a result of low charge-transfer resistance and good chemical
stability.[23] CoS-coated multiwalled carbon nanotubes (CoS/
MWCNTs) have also been employed as a counter electrode for
DSSCs due to the superior catalytic activity of CoS and the specific surface of MWCNTs. This electrode exhibits excellent catalytic activity and a higher energy conversion efficiency (6.96 %)
than pure platinum, MWCNT, and CoS counter electrodes.[128]
A MWCNTs/PPy composite has been used as a counter electrode to replace the expensive Pt counter electrode in DSSCs.
The MWCNTs/PPy composite shows an efficiency of 3.78 %, and
the efficiencies of MWCNTs and PPy are 0.72 and 2.68 %, respectively. The performance of MWCNTs/PPy is high relative to
that of the MWCNTs and PPy counter electrodes, and the corresponding cyclic voltammetry (CV) curves (Figure 13) reveal
that the MWCNTs/PPy composite shows superior catalytic activity for the I3 /I redox reaction. This may be due to the
higher conductivity of the MWCNTs/PPy composite due to the
addition of PPy into the MWCNTs.[129] Niu et al. have prepared
an axlesleeve-structured MWCNTs/PANI composite and used it
as a counter electrode to replace the Pt electrode. This composite shows an efficiency of 7.21 %, which is comparable to that
of the Pt counter electrode (7.59 %).[130] Wang et al. have investigated a composite catalyst of rosin carbon/Fe3O4 with stunning morphology and applied it as a counter electrode in
DSSCs. The DSSC assembled by using this composite shows
a high power conversion efficiency of 8.11 %, which is comparable to that of the traditional
sputtered Pt counter electrode.[131] The photovoltaic characteristics of DSSCs assembled
with different composite counter
electrodes are shown in Table 6.
The commercial mass production of DSSCs will need a large
amount of platinum, which is
very expensive and not abundantly available. Therefore, composite materials can be viewed
as promising alternatives to the
platinum counter electrode in
DSSCs.
Figure 13. CV curves for the I3 /I redox reaction using Pt, PPy, MWCNTs, and
MWCNTs/PPy composite counter electrodes.[129]
4. Counter Electrodes for Iodine-Free Redox

Electrolytes
The iodide/triiodide redox couple electrolytes are the most
ubiquitous and the most efficient in DSSCs. Also, researchers
have introduced some new redox couples, including Co3 +
/Co2 + , SCN/SCN3 , Br/Br3 , Fe3 + /Fe2 + , and T2/T , in
DSSCs.[132136] Low-costing Pt-free counter electrode materials
have been proven to be promising catalysts for the regeneration of iodine-free redox electrolytes. Tian and Sun have explained the drawbacks of I/I3 electrolytes and iodine-free
redox couple electrolytes in detail.[137] Mathew et al. have achieved 13 % efficiency for a DSSC by using a Co3 + /Co2 + redox
shuttle.[138] Swami et al. have investigated a CoS counter electrode for the regeneration of cobalt-based redox electrolytes
and have achieved an efficiency as high as 6.72 %.[132] Dao et al.
have prepared a Au nanoparticle/graphene nanohybrid by
a dry plasma reduction method and used it as a counter electrode in DSSCs fabricated with the Co3 + /Co2 + redox electrolyte.[139] Maiaugree et al. have developed a NiSO4/PEDOT:PSS
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sun et al. during analysis from light soaking at 5560 8C and
only a minor decrease is observed in the open-circuit voltages
(i.e. 5080 mV) due to a shift in the conduction band towards
more positive potentials.[143]
A decrease in the fill factor at high light levels is due to an
increase in the series resistance of the cell. There is no evidence of dye degradation, no loss of iodine, and no loss of catalytic activity of the Pt-based counter electrode. However, storage at 80 8C results in a 1020 % decrease in performance with
ionic-liquid- or solvent-based electrolyte systems. Syrrokostas
et al. have synthesized Pt counter electrodes by two different
methods, namely, electrochemical deposition and thermal decomposition of hexachloroplatinic acid (H2PtCl6) solution. They
then stored the DSSCs fabricated with these electrodes in the
air and electrolyte solution for up to 70 days and then checked
their stability by cyclic voltammetry tests. They observed degradation from a decrease in the triiodide reduction peak current density and an increase in the activation energy. The current density of the counter electrode decreases by about 15
to 25 % of the initial value if it is stored in air, whereas it decreases by 40 % if it is stored in the electrolyte. Degradation
of the stability can be attributed to the dissociation of Pt when
stored in the electrolyte.[144]
Yun et al. have studied the chemical stability of counter electrodes by using X-ray photoelectron spectroscopy. They have
reported that Cu and Au films scarcely dissolve as their respective sulfides. The Al film gradually loses its metallic properties
in iodine-based liquid electrolytes. On the other hand, for the
conducting polymer-based counter electrode, the PEDOT:PSS
film adsorbs the organic molecules in the electrolytes,[145] and
the degradation mechanism of the metal and the conducting
polymer counter electrodes in the iodine-based electrolyte is
shown in Figure 14. Murakami et al. have reported that a counter electrode prepared with a heating process shows better re-
Table 6. Photovoltaic characteristics of DSSCs fabricated with different

composite counter electrodes.
Sample[a]
Jsc [mA cm2]
Voc [V]
FF
h [%]
Ref.
GO-tungsten
MoN nitrogen-doped GO
N-doped GO
TiN-carbon
PEDOT:PSS
CoS/PEDOT:PSS
PEDOT:PSS:PPy
Pt/WO2
Pt/WO2/TiO2
carbon/TiO2
GO/PEDOT:PSS
TiS2/PEDOT:PSS
SiO2/PEDOT:PSS
Fe3C@N-C
PEDOT:EFG
MWCNTs/PPy
MWCNTs/PANI
carbon/Fe3O4
12.21
14.62
12.14
14.36
13.2
12.53
14.27
12.91
12.54
12.53
15.7
13.06
13.5
14.97
10.2
14.83
16.08
16.01
0.73
0.772
0.821
0.697
0.65
0.73
0.75
0.78
0.83
0.70
0.77
0.68
0.72
0.74
0.77
0.77
0.78
0.75
0.66
0.70
0.58
0.67
0.62
0.69
0.71
0.68
0.70
0.57
0.65
0.60
0.58
0.66
0.72
0.65
0.57
0.68
5.88
7.998
5.80
6.71
5.40
6.31
7.60
6.94
7.23
5.50
7.86
5.46
5.66
7.36
5.78
7.42
7.21
8.11
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composite film counter electrode for the regeneration of the

organic T2/T electrolyte.[136] Another report by Al-Mamun et al.
describes the preparation of a silver nanowiregraphene counter electrode for the Co3 + /Co2 + redox mediator electrolyte for
DSSCs, and a power conversion efficiency of 2.44 % has been
noted; this value is comparable to the power conversion efficiency of the Pt-based counter electrode (2.55 %).[140] Mu and
Ma have reported that the TiC counter electrode shows higher
efficiency than the Pt counter electrode in DSSCs with a Co3 +
/Co2 + redox electrolyte. The power conversion efficiency using
TiC as the counter electrode is 4.13 % and that of the Pt-based
counter electrode is only 2.91 %.[141]
Pt-free counter electrode materials are cheap and suitable
for the regeneration of both the
iodide/triiodide redox couple
and iodine-free redox couples.
Hence, the development of new
counter electrode materials has
attracted immense attention in
recent years.
5. Stability of Counter
Electrodes
The commercialization of DSSCs
predominantly depends on the
long-term stability of the fabricated cell, and this may be affected by factors such as degradation of the dye, evaporation
or leakage of the solvent, and
the dissociation of the counter
electrode in the corrosive
iodide/triiodide
electrolyte.[142]
The long-term stability of DSSCs
has been investigated by HarikiChemElectroChem 2015, 2, 928 945
Figure 14. Schematic diagram explaining the degradation mechanism of metal and conducting polymer counter
electrodes in the iodine-based liquid electrolyte.[145]
941
Reviews
sults than a counter electrode prepared without a heating process.[146] Storing the device in the dark at room temperature
enhances both the open-circuit voltage and the fill factor but
reduces the short-circuit current density.[142]
Degradation of the electrode is expected to occur in DSSCs
prepared with these kinds of counter electrodes, and this affects their long-term stability. The stability of the counter electrode may be determined by cyclic voltammetry. The value of
the peak current is largely determined by mass transport. The
potential difference between the oxidation and reduction peak
currents is indicative of electrocatalytic activity. A reaction with
the I3 mechanism has a potential difference of 68 mV.[147] Yue
et al. have investigated the stability of a Pt/graphene counter
electrode by using cyclic voltammetry. They performed 30 continuous cycle scans of the Pt/graphene counter electrode at
a scan rate of 10 mV s1.[54] Figure 15 represents the 30 continuous cycles of the Pt/graphene counter electrode at a scan rate
of 10 mV s1 and the relationship between the number of
cycles and the maximum redox peak current densities, which
shows a good linear relationship after 30 cycles. It is clear from
Figure 14 that the unchanged curve shape and the constant
redox peak current densities are indicative of excellent electrochemical stability of the Pt/graphene counter electrode.
The counter electrode used for the I3 reduction should possess high catalytic activity, high conductivity, and stability. Also,
it is important to realize that apart from cell composition, the
purity of the starting materials and the processing conditions
play important roles in the stability of the fabricated DSSCs.
6. Summary
DSSCs are the focus of recent attention owing to their ability
to convert sunlight into electricity at a low cost. A DSSC is
composed of an electrode (photoanode, generally a TiO2coated fluorine-doped tin oxideplate used as the anode and
photocathode), a dye as the sensitizer, and I3 /I redox electrolytes. At present, the major focus of DSSCs is to decrease the
cost and to increase the photo-to-current conversion efficiency.
The electrolyte plays an important role in improving the efficiency of the device by increasing the conductivity of the
redox couple. From a cost point of view, the dye and counter
electrode are the focus. For the dye, Rubipyridyl complexes
generally show high efficiency, but they are expensive. For the
counter electrode part, platinum gives the best performance,
but it is also expensive and its rarity limits its practical application in DSSCs. It has been suggested that the expensive platinum counter electrode in DSSCs could be replaced by alternative materials.
Apart from the dye and the electrolyte, it is important to develop alternative materials capable of replacing platinum as
the electrocatalyst. In DSSCs, the counter electrode is a crucial
component, in which triiodide is reduced to iodide by electrons flowing through the external circuit. We have seen
a series of platinum-free counter electrode materials in DSSCs
such as carbon materials, conducting polymers, inorganic
oxides and sulfides, transition-metal nitrides and carbides, and
composite materials. Among these materials, conducting polyChemElectroChem 2015, 2, 928 945
Figure 15. a) 30 continuous cycles of the Pt/graphene counter electrode at

a scan rate of 10 mV s1, and b) the relationship between the number of
cycles and maximum redox peak current densities.[54]
mers show promise as alternatives to platinum-free counter

electrodes in DSSCs. Transition-metal nitrides and carbides
have a wide range of applications in many fields, and many of
these materials demonstrate excellent catalytic activity for the
reduction of triiodide ions. Intense investigation should be
done to develop novel counter electrodes for DSSCs, and
a new concept or design strategy is needed in this field. While
developing or designing counter electrode materials, the researcher should remember that electrodes should be cheap,
environmentally friendly for clean technology, and exhibit
a wide range of applications.
Acknowledgements
We gratefully acknowledge financial support from the Department of Atomic Energy- Board of Research in Nuclear Sciences
(DAE-BRNS) and the Department of Science and TechnologySci942
Reviews
ence and Engineering Research Board (DST-SERB). Also, we acknowledge Dr. Krishna Rao Ragavendran, Department of Physics,
University of Malaya, for his support.
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945

Recent Progress in Non-Platinum Counter Electrode Materials For Dye Sensitized Solar Cells

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DOI: 10.1002/celc.

Recent Progress in Non-Platinum Counter Electrode

ChemElectroChem 2015, 2, 928 945

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

conducting glass electrodes give the best performance, but

portant criteria that must be considered in selecting a polymer

ChemElectroChem 2015, 2, 928 945

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

that production costs can be somewhat reduced by reducing

Mr. Jayaraman Theerthagiri received

In this review, the recent progress in the replacement of the

2. Dye-Sensitized Solar Cells: General

Dr. Thandavarayan Maiyalagan received his PhD degree in physical

in which Jsc is the short-circuit current density [mA cm2], Voc is

Dr. Jagannathan Madhavan is currently

ChemElectroChem 2015, 2, 928 945

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Electron injection [Eq. (4)]:

Dye regeneration [Eq. (5)]:

Regeneration of iodine [Eq. (6)]:

3.1. Carbon-Based Materials

Photoexcitation [Eq. (3)]:

3. Platinum-free Counter Electrode Materials

Among semiconductor oxides, TiO2 is widely studied due to its

in which * represents the free site on the electrode surface

Figure 1. Energy-level diagram of a DSSC. VAC = vacuum energy level,

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ChemElectroChem 2015, 2, 928 945

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Table 1. Photovoltaic characteristics of DSSCs with different carbonbased counter electrodes.

Jsc [mA cm2]

[a] GO = graphene oxide.

Figure 3. A multifunctional nanocarbon-based interlayer used in DSSCs and

phene-deposited SWCNT electrode shows the highest power

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

with different polymerization times. The catalytic activity of the

Table 2. Photovoltaic characteristics of DSSCs with different conducting

Jsc [mA cm2]

high catalytic activity, and good adhesion to FTO conductive

3.3. Metal Sulfide Materials

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ChemElectroChem 2015, 2, 928 945

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Jsc [mA cm2]

Figure 9. The calculated adsorption energy of the iodine atom of various

Table 4. Photovoltaic characteristics of DSSCs fabricated with different

Figure 8. Mechanism of the triiodide reduction by using commercial WO3

Jsc [mA cm2]

3.5. Transition-Metal Nitrides and Carbides

Two different phases of SnO2 have been used as counter

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

trides and carbides have been widely explored in materials

3.6. Composite Materials

Figure 10. Distribution graph showing the power conversion efficiencies of

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 12. Model of 1D (a, b) and 2D (c, d) nanomaterial composite electrodes.[126]