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Solar Energy 115 (2015) 452470
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Review on polymer electrolyte in dye-sensitized solar cells (DSSCs)

M.S. Suait a,, M.Y.A. Rahman b,, A. Ahmad c,
a
Solar Energy Research Institute (SERI), Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
b
Institute of Microengineering and Nanoelectronics (IMEN), Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
c
School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia

Received 6 August 2014; received in revised form 17 February 2015; accepted 26 February 2015
Available online 30 March 2015

Communicated by: Associate Editor Frank Nuesch

Abstract

The dependence of dye-sensitized solar cells (DSSCs) on the liquid electrolytes set the limitation and restriction on the expending of
the DSSC module fabrication. Moreover, the reductions in its performances were observed as consequences from electron recombination
in semiconductorliquid electrolytes interfaces. This comes back to the question of the behavior of this type of cells, toward the
volatilization of redox-electrolytes solution at the semiconductor/electrolyte interface. A more complicated situation arises when the pho-
toanode is in contact with the volatilization of redox-electrolytes solution that aects the charge distribution at the semiconductorelec-
trolyte interface, and initiated photocorrosion on photoelectrode. The nding of ionic conductivity in polymer material complexed with
salt gives a breakthrough to the development of DSSC devices. This article reviews the various approached taken by dierent perspec-
tives in increasing the solid-state and quasi-solid DSSCs performances utilized solid and gel polymeric electrolytes. From there, a col-
lectives data of power conversion eciencies and roles played by solid and gel polymeric electrolytes in DSSC were tabularized.
Throughout the review process, we predicted that in coming years, polyionic liquids (polyILs) will dominant the polymer electrolyte
application in DSSCs due to its unique characteristics.
2015 Elsevier Ltd. All rights reserved.

Keywords: Dye-sensitized solar cell; Solid-state; Quasi-solid; Polyionic liquids; Polymer electrolyte

1. Introduction pollution, carbon dioxide emission and green house eects.

Nowadays, the world is facing a major crisis with
regards to the pollution of the earth and shortage of
sustainable, safe and environmental friendly energy
resources. Several concerns arise due to the utilization of
non-renewable energy resources from carbon based fuels,
shortage of available energy sources, and other factors
related to health and environmental issues such as air
Address: Solar Energy Research Institute (SERI), Universiti Kebang-
saan Malaysia, 43600 Bangi, Selangor, Malaysia (M.S. Suait).
E-mail addresses: mohdsukor@ukm.edu.my (M.S. Suait), mohd.
yusri@ukm.edu.my (M.Y.A. Rahman), azizan@ukm.edu.my
(A. Ahmad).
Therefore, eorts in lowering energy consumption and pro-
tecting the environment have gradually motivated all the
researchers in the world to explore the alternative energy
sources (Ahuja and Tatsutani, 2009). It is well known that
the best approach is to utilize renewable energy resources
(Twidell and Weir, 2012). Renewable energy resources
are generally dened as energy that comes from resources
which can be regenerated continuously such as sunlight,
wind, hydro, rain, waves and geothermal heat.
Renewable energy sources that gain their energy conver-
sion from the sun, such as solar cells, are expected to be
capable of supplying the endless energy for mankind. In
view of such concerns, solar energy is one of the most

http://dx.doi.org/10.1016/j.solener.2015.02.043
0038-092X/ 2015 Elsevier Ltd. All rights reserved.
 M.S. Suait et al. / Solar Energy 115 (2015) 452470
promising future energy resources considering its abun-
dance, cleanliness, safety and higher economic value that
allow energy generation in remote rural areas (Twidell
and Weir, 2012). The direct conversion of sunlight into
electric power by photovoltaic cell is of particular interest
because it has many advantages over most of the currently
used electrical power generation methods, and it is very
eective among all available renewable energy resources
(ABARE, 2010). Other attractive features are that the
photovoltaic cell is inexhaustible, does not lead to
secondary environmental pollution, has no exhaust that
produces green-house gases, and has zero nuclear waste
by-products. European Joint Research Centre predicted
that energy directly harvested from sunlight would be
20% of total energy consumption in 2050, and this value
could be over 50% by 2100 (European Commission, 2013).
In general, photovoltaic cell is a device that converts the
energy from sun light into electric energy by using an
unlimited source of clean energy which is the sunlight.
Additionally, photovoltaic cells do not require mechanical
movement or movable parts to generate electricity. They
are based on the concept of charge separation at a single
junction or hetero-junction between two dierent type (n-
and p-type) semiconductor or semiconductormetal
(Schottky) junctions (Singh et al., 2011). Therefore, photo-
voltaic cell can continuously work free from maintenance,
and for a longer period of time than other power genera-
tion technologies (Jiang and Yan, 2013). Photovoltaic cells
can be divided into dierent categories depending on their
working principles, production techniques, and materials
used (Chopra et al., 2004; Gong et al., 2012; Hagfeldt
et al., 2010; Jena et al., 2012; Jiang and Yan, 2013; Jun
et al., 2013; Kong et al., 2007; McGehee, 2011; Tian and
Cao, 2013; Wurfel and Wurfel, 2009; Wei, 2010). The most
commonly used photovoltaic cell are made of silicon (Si),
cadmium telluride (CdTe), copper indium selenide/sulde
(CIS), or multi-junction based materials, perovskite solar
cell and dye sensitized solar cells (DSSC).
As recorded by West (1974), the discovery of photo-elec-
trochemical cell (PEC) has been initiated by Becquerel
(1839) and led to the nding by Vogel in 1883 via the exten-
sion of photosensitivity to longer wavelengths through the
addition of a dye sensitizer to silver halide emulsions. Years
later, Moser (1887) enhanced the concept of dye from pho-
tography to photoelectrochemical cells using the dye ery-
throsine on silver halide electrodes. The interest in
photoelectrochemistry of semiconductors led to the discov-
ery of wet-type PEC by Gerischer (1966) and Gerischer and
Tributsch (1968). ORegan and Gratzel (1991) has then
extended the concept to the dye sensitized solar cells
(DSSC) or commonly known as Gratzel cell, by using
organic dye molecules as light absorber monolayer on the
nanocrystalline titanium dioxide (TiO2), mesoporous net-
work of wide band gap semiconductor. The DSSC technol-
ogy separates the main two functions in conventional
photovoltaic devices that use a donor and an acceptor type
of organic/inorganic materials to form a heterojunction in
453
favoring the separation of the exciton into two carriers.
Whereas, the charge generation in DSSC is conducted at
the semiconductordye interface and the charge transport
is done by the semiconductor and the electrolyte. The car-
riers transport properties can be improved by optimizing
the semiconductor and the electrolyte composition and
the spectral properties optimization can be done by mod-
ifying the dye alone (Nazeeruddin et al., 2011). This signi-
cant breakthrough quickly received more attention, due to
its high power conversion eciency under cloudy and arti-
cial light conditions, sustainable and low-cost starting
materials and also simple fabrication technology in com-
parison to classical silicon based, multi-junction and thin
lm solar cells (Mor et al., 2006; Lin et al., 2011b; Zhang
and Cao, 2011). It is environment-friendly, transparent
due to the characteristic of the materials, and especially
able to realize various colored solar cells. Due to these
characteristics, DSSC is noticed to be proper for building
integrated photovoltaic that uses solar cells as the outer
walls or glass windows of buildings. Ten years after the
introduction of DSSC, quantum-dots dye-sensitized solar
cell (QDSSC) was developed by replacing organic dye-sen-
sitizer in DSSC with inorganic sensitizer (Luther et al.,
2010). Inorganic sensitizer in QDSSC mainly utilize the
narrow bandgap metal chalcogenide compounds that are
more commonly reserved for suldes, selenides and tel-
lurides (Mora-Sero et al., 2009; Jun et al., 2013; Rhee
et al., 2013). The eorts in replacing the organic dye with
inorganic crystal seem to be very interesting challenge.
Nevertheless, the absences of organic dye in this kind of
device will drastically drop the eciency. The heart of this
type of photovoltaic cell is the junction created between a
semiconductor electrode and a liquid electrolyte, where
the charge transfer to electrolytes must be much faster than
the direct electronhole recombination rate in the semicon-
ductor in order to produce an ecient cell (Bisquert et al.,
2004).
This review highlights on the application of polymer
electrolytes membrane as an ionic conductor in DSSC.
Polymer electrolyte is chosen for use in DSSCs to overcome
the problem of leaking and sealing, ammability issues,
shape exibility and electrochemical stability faced by liq-
uid electrolyte. In addition, the presence of liquid elec-
trolytes posed challenges in integration of large area
modules, diculty in implementing tandem architectures,
possible desorption and photodegradation of the attached
dyes in DSSC, corrosion of counter electrode and pho-
todegradation of some components which lead to lower
lifetimes, performance and practical usage of the photovol-
taic cells (Armand et al., 1978; Kubo et al., 2002; Wu et al.,
2008a). To overcome such problem, polymer electrolyte
provided alternative materials to be utilized in DSSC
devices. However, the disadvantage of polymer electrolyte
is that it has lower ionic conductivity than that of liquid
electrolyte. Thus, the performance of solar based devices
utilizing polymer electrolyte is lower than the photovoltaic
cells utilizing liquid electrolyte. Currently, gel polymer
454 M.S. Suait et al. / Solar Energy 115 (2015) 452470
electrolyte has replaced solid polymeric electrolyte since its
ionic conductivity was higher than its solid form, in order
to improve the performance of DSSC. The objective of this
review is to give a broad view of the use of various types of
polymer electrolyte in DSSCs. The review also highlights
the performance of several DSSCs utilizing various types
of polymer electrolyte under 100 mW cm2 light illumina-
tions at room temperature ionic conductivities.
2. Structure of DSSC
The cell consists of two main electrodes, namely;
photoelectrode and counter electrode deposited onto the
thin layer of transparent conducting oxide (TCO). They
are separated by an electrolyte containing redox mediators
as shown in Fig. 1 (ORegan and Gratzel, 1991;
Nazeeruddin et al., 2011; Yu et al., 2012). In DSSCs, the
photovoltaic semiconductor material is then covered with
organic dye typically ruthenium based complex, or quan-
tum-dots materials (CdS, CdTe) as a photo absorber mate-
rial (Gratzel, 2001; ORegan and Gratzel, 1991). The
photovoltaic semiconductor material commonly metal
chalcogenides or metal oxides semiconductor is used mate-
rial for the photoelectrode (Kong et al., 2007; Sommeling
et al., 2006) which is deposited onto the TCO including
indium-doped SnO2 (ITO), uorine-doped SnO2 (FTO),
or aluminum-doped ZnO (AZO) substrate (Coutts et al.,
1999; Kong et al., 2007; Liu et al., 2010; Stadler, 2012), a
various types of electrolyte containing redox mediator such
as iodide based, thiocyanate based, and cobalt based elec-
trolytes (Fukui et al., 2006; Wu et al., 2007; Yella et al.,
2011) and a counter electrode lm at the back contact of
the photovoltaic cell as the catalyst surface (Thomas
et al., 2014).
Semiconductor materials such as metal chalcogenides
and metal oxides based photoelectrode have been under
extensive investigation due to their wide application in
energy storage and environmental remediation (Gong
et al., 2012; Gratzel, 2001). Semiconductor materials act
Fig. 1. Typical structure of dye-sensitized solar cell (ORegan and Gratzel,
1991; Yu et al., 2012).
as electron acceptor and electronic conduction path to
facilitate photoexcited electrons because of their conduc-
tive electronic structure, referred to as the valence band
(VB) and conduction band (CB) (Gong et al., 2012;
ORegan and Gratzel, 1991). The metal oxide semiconduc-
tors like TiO2, ZnO, SnO2, ZrO2 and Nb2O5 gained a lot of
attentions due to their wide bandgap. Besides these simple
oxides, ternary oxides, such as SrTiO3 and Zn2SnO4, have
been investigated, as well as coreshell structures, such as
ZnO-coated SnO2 (Hagfeldt et al., 2010). Since the discov-
ery of DSSC in 1991 by ORegan and Gratzel (1991),
mesoporous TiO2 made up of arrays of nanoparticles
photoelectrode has an unbeatable record of the highest
eciencies in DSSC till today (Jena et al., 2012;
Narayan, 2012). The n-type TiO2 photoelectrodes nanopar-
ticles oers some unique properties making it a feasible
semiconductor for DSSC such as (i) the low intrinsic con-
ductivity of the lm, (ii) the small size of the nanocrys-
talline particles does not support a built-in electric eld
and (iii) the electrolyte diuse into the porous lm all the
way to the back-contact created the semiconductor/elec-
trolyte interface essentially three-dimensional (Gratzel,
2003). TiO2 normally occurs in three crystal modications
structure, namely; rutile, anatase and brookite. While rutile
is the thermodynamically stable phase, anatase is preferred
for dye sensitized solar cells, due to its larger band gap
(Eg = 3.2 eV for anatase compared to Eg = 3.0 eV for
rutile, corresponding to an absorption edge of kg
390 nm and kg 410 nm, respectively) (Lee et al., 2011;
Schwanitz, 2008). The high refractive index of TiO2
(n = 2.5 for anatase) results in ecient diuse scattering
of the light inside the porous photoelectrode, which signi-
cantly enhances the light absorption (Cherubin, 2009). In
addition, mesoporous TiO2 photoelectrode has a high
internal surface area to support the monolayer of a dye
sensitizer and its conduction band edge lies slightly below
the excited state energy level (LUMO) positioned of many
dyes sensitizer. This condition is required for ecient elec-
tron injection in the conduction band of semiconductors to
transport across TiO2 lm by diusion toward the TCO
(Cherubin, 2009; Gratzel, 2003; Jena et al., 2012; Wei,
2010). The high dielectric constant of TiO2 (e = 80 for ana-
tase) provides good electrostatic shielding of the injected
electrons from the oxidized dye molecule attached to the
TiO2 surface, thus reduced their recombination before
reduction of the dye by the redox electrolyte (Cherubin,
2009; Narayan, 2012). However, the capabilities of TiO2
anatase phase to absorb solar spectrum in the range of
ultraviolet or near-ultraviolet radiation can only capture
about 4% of the solar light. Dye sensitization of wide
band-gap semiconductor surfaces by anchored dyes has
provided a successful solution to extending the absorption
range of the cells to long wavelength region (Chen et al.,
2011). The properties of semiconductor photoelectrode
lms also depend on the characteristics of transparent glass
electrodes coated substrate with a thin conductive layer,
known as transparent conducting oxide (TCO). TCO
 M.S. Suait et al. / Solar Energy 115 (2015) 452470
allows light to pass through to the active material beneath
(where carrier generation occurs) and acting as an ohmic
contact for charge carrier to transport out of the photovol-
taic devices (Acton, 2013). Dye sensitizer layer serves as the
solar energy absorber in DSSC which absorbs the solar
photons and produced electronhole pairs. Since the elec-
trons and holes in the dye layer have very small mobilities,
this layer must be very thin for the charge carriers to reach
the membranes within their lifetimes (Wurfel and Wurfel,
2009). The examination of numerous dyes with a variety
of chromophoric ligands has indicated that the main factor
for optimization solar photons harvesting was the signi-
cant light absorption in the ultraviolet (UV)visible
(VIS)near infrared (NIR) region. The ideal sensitizer
should absorb all light below a threshold wavelength of
about 920 nm (Kong et al., 2007). Many dierent types
of dyes have been extensively studied for DSSCs applica-
tion and it can be classied into two main types; organic
dyes and inorganic dyes according to the structure (Kong
et al., 2007). Organic dyes include natural organic dyes
such as coumarin (Hara et al., 2003a, 2003b; Liu et al.,
2012), perylene (Cappel et al., 2009; Zafer et al., 2007)
and synthetic dyes. While, inorganic complexes dyes
includes metal complex, such as polypyridyl complexes of
transition metals, metalloporphyrins, metallo-phathalo-
cyanines and inorganic quantum dots (CdS, CdSe, CZTS,
ZnTe) which has high thermal stability and chemical stabil-
ity as compared to organic dyes (Giribabu and Kanaparthi,
2013; Hagfeldt et al., 2010; Kalyanasundaram and Gratzel,
2009; Yella et al., 2011).
Counter electrode plays important roles in electrons
transfer, since charge transfer resistance from FTO surface
to the electrolyte is high, the use of a suitable catalyst helps
in the reduction of the charge transfer resistance at counter
electrode, and thus helps in pushing the reaction toward a
forward direction (Thomas et al., 2014). There are several
types of counter electrodes available such as platinum, car-
bon based materials, conducting polymer, nitrides and sul-
des based materials that are extensively studied by the
researchers (Hagfeldt et al., 2010; Jena et al., 2012;
Thomas et al., 2014). Platinum (Pt) is the most common
counter electrode used due to its high catalytic activity
and high power conversion eciency. However, Pt faces
a problem due to its excessive cost and its scarcity of
resources. Pt nanoparticles have excellent characteristic
properties like high surface area, high transmittance, low
charge transfer resistance, high electrical conductivity and
corrosion resistance, than any other noble metal (Lee
et al., 2010d). The nanoparticles provide a signicant
advantage in terms of reduced platinum loading coupled
with a slight increase in solar cell performance due to
higher surface to volume ratio for the nanoparticles.
(Jena et al., 2012). Alternatively to Pt counter electrode,
carbon and its allotropes based counter electrode provide
a broad range of selections such as carbon black
(Murakami and Gratzel, 2008), carbon nanoparticle (Lee
et al., 2008a), activated carbon (Imoto et al., 2003),
455
graphite, single, double and multi-walled carbon nanotube
(Lee et al., 2007; Nam et al., 2010; Zhang et al., 2010), gra-
phene (Zhang et al., 2011) and porous carbon (Xu et al.,
2013). Carbon based materials have an abundant and
inexpensive starting materials, with high corrosion resis-
tance and high reactivity for triiodide reduction (Hagfeldt
et al., 2010; Xu et al., 2011). However, carbon and its allo-
tropes have disadvantages in the poor electrocatalytic
activity but it can be compensated by increasing the active
surface area of the catalytic layer by depositing thick and
porous lms over the substrate (Jena et al., 2012). Other
low cost materials that have been reported are conducting
polymers; poly(3,4-ethylenedioxythiophene) (PEDOT)
based composite (Lee et al., 2010c, 2012; Maiaugree
et al., 2012; Wei et al., 2014), polyaniline (PANI) (Bay
et al., 2006; Tang et al., 2013) and polypyrrole (Ki
Hwang et al., 2014; Tang et al., 2013; Xia et al., 2011),
nitrides based (Wu et al., 2011) and recently suldes based
materials such as iron suldes, FeS2 (Chen et al., 2014;
Wang et al., 2013), copper suldes, CuS (Chen et al.,
2014), cobalt suldes, CoS (Kung et al., 2012; Tai et al.,
2013), Cu2ZnSnS4 (Bai et al., 2013; Xin et al., 2011; Xu
et al., 2012; Wozny et al., 2013; Zhang et al., 2014) has also
gained a lot of attention as a future counter electrode layer
in DSSC. However, back to the main concerns; all of them
have a poor electrocatalytic activity as compared to
nanoparticles Pt.
3. Principles operational
The principle of power generation in DSSC uses the
same electrochemical principles by generating electricity
upon illumination. It is very similar to that of photosynthe-
sis of plants, so it is often referred to as articial
photosynthesis. The sensitizing ruthenium based complex
dye molecules on wide-bandgap n-type semiconductor such
as TiO2, SnO2 or ZnO which is not only acting as support
for dye sensitizer, but also functions as electron acceptor
and electronic conductor (Nazeeruddin et al., 2011).
Fig. 2 illustrates electron transfer mechanism in DSSC.
Upon illumination of surface DSSC, the photo-sensi-
tized dye molecule on metal oxides semiconductor absorbs
the sunlight and excited from the ground state (D) at high
occupied molecular orbital (HOMO) to the excited state
(D*) at the lowest unoccupied molecular orbital
(LUMO), thus emitting photogenerated electrons (Eq. (1)).
TiO2 jD hm ! TiO2 jD 1

TiO2 jD ! TiO2 jD e 
2
The electrons from photoexcited dye are injected into the
mesoporous semiconductor networks lled with a liquid
redox electrolyte and rapidly transferred to the conduction
band (CB) of the semiconductor interfaces (ORegan and
Gratzel, 1991). At this point, the electrons and the holes
are separated; the electrons are located in the conduction
band and the holes are left in the oxidized dye (Gratzel,
456 M.S. Suait et al. / Solar Energy 115 (2015) 452470

Fig. 2. Working principle of DSSC operation (Hardin et al., 2012).

2003). Subsequently, the injected electrons in the conduc-
tion band of semiconductors are transported across TiO2
lm by diusion toward the transparent conductive oxide
substrate, and then to the external circuit resulting in a ow
of current (Wei, 2010). This process is ultrafast and initi-
ates conversion of light into electricity in DSSC. While,
the oxidized dye is regenerated to its neutral state by receiv-
ing ground-state electrons from redox mediators, usually
comprised of iodide/triiodide (I/I 3 ) in the electrolyte
and transports the positive charges to electrically con-
nected counter electrode (Gratzel, 2003). The sustainability
of light energy conversion is facilitated by regeneration of
the reduced dye sensitizer either via a reversible redox cou-
ple (I/I
3 ) or the electrons donation from a p-type semi-
conductor. The photoanode receives electrons from the
photo-excited dye sensitizer which is thereby oxidized to
D+ (Eq. (2)). The neutral dye sensitizer (D) can be regener-
ated by accepting electrons from I ion redox mediator via
the oxidation reaction of the redox species dissolved in the
electrolyte (Eqs. (3) and (4)) (Longo and de Paoli, 2003).
TiO2 jD e ! TiO2 jD 3 DSSC eciency. Others have attempted to develop highly
 porous and large surface area nanostructure lm consisting
TiO2 jD 3=2I ! TiO2 jD 1=2I
3 4
The mediator I 3 will then diuses toward the counter elec-
trode and regenerated by reduction reaction
(I  
3 + 2e ! I ) of the electrons circulated through the
external circuit (Eqs. (5) and (6)).
1=2I 
3 e ! 3=2I

5
I
3

2e ! 3I 
6 Lan et al., 2010; Lin et al., 2011a; Olsen et al., 2000; Wei
The eciency of a DSSC in the process of energy conver-
sion depends on the relative energy levels and the kinetics
of electron transfer processes at the liquid junction of the
sensitized semiconductorelectrolyte interface. For ecient
operation of the cell, the rate of electron injection must be
faster than the decay of the dye excited state. Also, the rate
of re-reduction of the oxidized sensitizer (or dye cation) by
an electron donor in the electrolyte (Eq. (4)) must be higher
than the rate of back reaction of the injected electrons with
the dye cation (Eq. (3)), as well as the rate of reaction of
injected electrons with the electron acceptor in the elec-
trolyte (Eq. (6)). Finally, the kinetics of the reaction at
the counter-electrode must also guarantee the fast
regeneration of charge mediator (Eq. (5)), or this reaction
could also become rate limiting in the overall cell perfor-
mance (Longo and de Paoli, 2003).
4. Background and development
Extensive research work is carried out to understand the
parameters that control the performance of DSSC in order
to improve its eciency. Numerous eorts have already
been made to optimize the redox electrolyte (Ejigu et al.,
2011; Lee et al., 2010a, 2010b; Wang et al., 2003, 2004)
and the dye absorbance (Cherubin, 2009; Narayan, 2012;
Nazeeruddin et al., 2001, 2003, 2005) in order to improve
of semiconductor with a wide band gap as working elec-
trode (Ghicov and Schmuki, 2009; Han et al., 2010; Mor
et al., 2006). Several attempts have been made to reduce
the resistivity while maintaining high level of transparency
the transparent conducting oxide (TCO) lm (Ali et al.,
2011; Kim et al., 2013a) and other researchers focused on
the development of counter electrode (Fang et al., 2004;
et al., 2007).
4.1. Electrolyte
Electrolyte plays one of the most important roles in
regeneration of the dye sensitizer from its oxidized state
 M.S. Suait et al. / Solar Energy 115 (2015) 452470
by receiving ground-state electrons from redox mediators
in DSSC (Gratzel, 2003). The chemical composition of
the electrolyte is a particularly crucial parameter in photo-
voltaic systems. The electrolyte needs to meet the require-
ments of having a long-term stability, including chemical,
optical, electrochemical, thermal and interfacial stability,
which does not cause desorption and degradation of the
dye from the oxide surface. The electrolyte must reduce
the oxidized dye rapidly and guarantee the fast diusion
of charge carriers between porous nanocrystalline layer
and the counter electrode in order to sustain the light
energy conversion (Bella and Bongiovanni, 2013). Several
types of electrolytes have been used in DSSCs, which can
be divided according to their physical properties such as
liquid electrolytes and polymer electrolytes.
The use of a liquid electrolyte oers an eective solution
to the problem of electroneutrality in heterogeneous con-
verters such as DSSCs. The non-porous structure of the
DSSC permits an increase in surfaces area with the assis-
tance of the ionic shielding by cations from a dissolved salt
in the liquid phase, which remains highly conducting under
all operating conditions. The charge carriers in the same
phase are rapidly separated into dierent phases at very
high interfacial contact (Bisquert et al., 2004). Various
types of metal-salts based liquid electrolytes and ionic liq-
uid are being used together with redox couple in DSSC
such as triiodide (I 
3 /I ) based, thiocyanate (SCN /

  
(SCN)3 (Oskam et al., 2001), SeCN /(SeCN)3 (Wang
et al., 2014) based, pseudo-halides (Br/Br 3 ) (Ferrere et
al., 1997) and cobalt (Mathew et al., 2014; Yella et al.,
2011) based electrolytes in various types of organic
solvents such as nitriles (i.e., acetonitrile (ACN), valeroni-
trile, pro-pionitrile, 3-methoxypropionitrile (MPN)) and
heterocyclic compounds (i.e., ethylene carbonate (EC),
propylene carbonate (PC), c-butyrolactone, N-methyl-2-
pyrrolidone (NMP)) (Fukui et al., 2006; Hagfeldt et al.,
2010; Kebede and Lindquist, 1999; Kong et al., 2007;
Lee et al., 2010b; Oregan and Gratzel, 1991; Sommeling
et al., 2006; Yella et al., 2011). The I 
3 /I electrolyte has
been extensively studied as the main electrolyte com-
position for DSSC research (Bay et al., 2006; Fukui
et al., 2006; Lee et al., 2010b; Nazeeruddin et al., 2003;
Oregan and Gratzel, 1991; Olsen et al., 2000;
Sommeling et al., 2006; Wu et al., 2011). According to
Ondersma and Hamann (2013), I 3 /I

possesses several
remarkable characteristics which have produced this
reliance:
 Ruthenium dyes such as N3 and N719 are regenerated
with near unity eciency by I (Cliord et al., 2007).
 Back electron transfer (recombination) from TiO2 to I 3
is remarkably slow, largely due to a complicated
multielectron transfer mechanism (Boschloo and
Hagfeldt, 2009; Rowley and Meyer, 2009). Slow recom-
bination results in long electron diusion lengths, L,
through the TiO2 allowing for near unity charge collec-
tion eciencies (Peter, 2007).
457
 I 
3 /I is highly soluble in an array of solvents and has a
high diusion coecient due to its small size allowing
for optimized concentrations of each species without
concern for reaching the solubility limits or diusion
limits.
 I
3 /I

has a relatively low light absorbance reducing
competitive absorbance with the dye.
 In addition, the I 
3 /I redox couple is very stable, and
not subject to decomposition under operation
conditions.
To date, the highest power conversion eciency of the
DSSC still depending on the liquid electrolytes by using
Cobalt (II/III) based redox species along with tert-butyl
pyridine (TBP), and LiClO4 in acetonitrile as a solvent
and zinc-porphyrin sensitizer (SM315) in order to improve
its performance up to 13% (Mathew et al., 2014).
Unfortunately, liquid electrolytes poses challenges in
integration of large area modules, diculty in implement-
ing tandem architectures, sealing issues, possible desorp-
tion and photodegradation of the attached dyes, which
lead to lower lifetimes of the performance and practical
use of the cells (Park et al., 2014; Suait et al., 2014; Wu
et al., 2008a). Alternatively, solvent-free room-temperature
ionic liquids (RTILs) such as alkyl imidazolium salt, tri-
alkyl methylsufonium salt and alkylpyridinium salt are
widely used in DSSC. RTILs are molten salts that have a
low volatility that can overcome one of the major draw-
backs of ammability solvent-based liquid electrolytes
(Matsumoto et al., 2001; Wang et al., 2003). In addition
to presenting several interesting properties, such as good
chemical and thermal stability and high ionic conductivity,
RTILs can act both as solvents and redox couples
(Kitamura et al., 2001). However, RTILs has disadvan-
tages of being uid and problem to immobilize them.
Therefore, replacing liquid electrolytes and RTILs based
electrolytes with polymer electrolytes oers a means of
eliminating the stated problem.
4.2. Polymer electrolyte
Polymer electrolyte is dened as polymer materials com-
plexed with salts (Fenton et al., 1973). Polar functional
group in the main polymeric chain acting as medium to sol-
vate the ionic species by intermolecular interaction. The
ionic transport occurs by diusion of dissociated ions and
transported through the free volume of the polymer matrix
(Bella and Bongiovanni, 2013). The nding of high ionic
conductivity (105 S cm1) at room temperature in the
polymeric material, polyethylene oxide (PEO) complex
with NaSCN salt by Fenton et al. (1973) gives a break-
through to the development of solid-state electrochemical
devices for energy storage such as rechargeable batteries,
photoelectrochemical/solar cell, supercapacitor, fuel cells
and electrochromic windows (Armand et al., 1978). Since
then, there have been substantial research activities toward
the preparation of various types of polymer electrolytes
458 M.S. Suait et al. / Solar Energy 115 (2015) 452470
having dierent combinations of polymer and salts (Di
Noto et al., 2011). Today, there are various families of
classical polymer electrolytes such as gel, plasticized, ionic
rubber polymer electrolytes and ion conducting polyelec-
trolytes. They consist of a variety of classical polymeric
materials from synthetics polymer and its blends to
bio-based polymer. Namely, PEO (Ren et al., 2002), poly
(methyl methacrylate) (PMMA) (Lee et al., 2010e; Yang
et al., 2008), polyethylene glycol (PEG) (Joseph et al.,
2006), poly(ethylene glycol) methyl ether methacrylate
(PEGMA) (Bella et al., 2013a, 2013b), polyacrylonitrile
(PAN) (Taslim et al., 2010; Rika et al., 2009; Rahman
et al., 2010), poly(vinyl chloride) (PVC) (Rahman et al.,
2004, 2007), and poly(vinylidene uoride-co-hexau-
oropropylene) (PVdF-HFP) (Kim et al., 2006; Lee et al.,
2008b; Priya et al., 2008; Noor et al., 2014). To date,
polysaccharides and modied polysaccharides based mate-
rials such as chitosan (Buraidah et al., 2010), cellulose
(Rudhziah et al., 2015) and carrageenan (Bella et al.,
2015) received the attention due to their higher ionic con-
ductivities at room temperature. In addition, two other
main families of hybrid inorganicorganic polymer
electrolytes are reported by Di Noto et al. (2011). They
are mono-phase and multi-phase polymer electrolytes.
The several types of inorganic ller have been included into
polymer electrolyte such as zircronia (ZrO2), titania (TiO2),
carbon-nanotubes and silica (SiO2) (Kim et al., 2004, 2006,
2008; Lee et al., 2008b, 2010b, 2010e). However, only a few
of the mentioned polymer electrolytes has been tested in
actual DSSCs. The rst report on utilizing of polymer
electrolyte in DSSC was found 20 years backs in 1995 by
Cao et al. (1995). The performance of DSSCs in term of
photovoltaic parameters utilizing polymeric electrolyte
are summarized in Table 1. The structure of the
DSSCs was TCO/TiO2-dye/electrolyte/platinum. In this
review, we divided polymer electrolytes application in
DSSC according to their main physical properties; (a) solid
polymer electrolytes which rise to solid-state DSSCs, and
(b) gel polymer electrolytes giving rose to quasi-solid
DSSCs.
4.2.1. Solid polymer electrolyte (SPE)
Solid polymer electrolytes which rise to solid-state
DSSCs were normally fabricated by solution casting of
polymer electrolyte solution onto a dye-adsorbed TiO2
photoelectrode directly. Kim et al. (2004), utilized low
molecular weight (Mw) poly(ethylene oxide dimethyl ether)
(PEODME, Mw = 500)/MPII/I2/fume SiO2 SPE in
improved solar cell eciency up to 4.5% by replacing
potassium iodide (KI) with 1-methyl-3-propylimidazolium
iodide (MPII) (Jsc was increased drastically from 0.4 to
9.5 mA cm2). Kang et al. (2005) obtained overall
conversion eciency of 0.01% for high Mw
PEO(Mw = 1.0  106 g mol1)KI/I2 based SPE DSSC.
The dramatic increases in eciency is observed upon the
addition of low Mw amorphous oligomer polypropylene
glycol (PPG) in PEO-KI/I2 up to 3.84% at 100 mW cm2
with Jsc of 11.2 mA cm2, Voc of 0.72 V and of 0.48. It
is obvious that the increase in the current density upon
the addition of oligo-PPG primarily arises from the
increased interfacial contact between the electrolyte and
the dye.
Another approach was done by placing membrane on
top of sensitized TiO2. Buraidah et al., 2010 reported that
the electrolyte membranes consisting of biopolymer
complexed with ammonium and ionic liquid chitosan
NH4Ibuthyl-methyl-imidazolium-iodide (BMII) at
(27.5:22.5:50.0) percentage ratios exhibit conductivity of
3.43  105 S cm1 at room temperature. The photovoltaic
parameters such as Jsc of 0.07 mA cm2 and Voc of 0.23 V
were obtained from the IV curves of photoelectrochemical
systems utilized anthocyanin pigment extracted from black
rice. Bella et al. (2015) demonstrated high power conversion
eciency of modied polysaccharide based solid polymer
electrolytes; carboxymethyl (CM)-kappa caraageenan-
NaI/I2-EC up to 2.06% with ionic conductivity value of
5.53  102 S cm1 at room temperature. Interestingly to
note that, after 250 h under thermal stress (60 C) for sta-
bility test, the cell showed a reduction of its initial photo-
conversion eciency of only 6%. Blending of CM
k-carrageenan and CM cellulose-NH4I/I2 biopolymer
electrolytes has been reported by Rudhziah et al. (2015).
They found that the ionic conductivity increased with
increasing NH4I concentration to achieve the highest room
temperature ionic conductivity of 2.32  103 S cm1
However, the power conversion eciency of solid biopoly-
mer electrolyte only reached 0.13% of eciency. Suait
et al. (2014) reported the use of bio-based polyurethane
(PU) solid polymeric electrolyte complexed with 0.5 M
lithium iodide (LiI) to 0.05 M iodine (I2), in a DSSC of
FTO/TiO2/PU-LiI-I2/Pt with N719 dye. The PU solid
polymer electrolyte was synthesized via in-situ polymeriza-
tion technique and casted on Teon mold via solution cast-
ing technique before the membrane was placed on top of
sensitized TiO2. Even though the conductivity achieved
up to 104 S cm1, the photovoltaic parameters of the
solid-state DSSC utilizing PU-LiI/I2 reported by Suait
et al. (2014) are very low due to the weak contact between
the semiconductorelectrolytes interfaces (SEI). By taking
the advantages of fast curing properties of our bio-based
PU, the fabrication technique is improved via in-situ poly-
merization of PU-LiI prepolymer electrolyte solution
directly on TiO2 photoelectrode. The power conversion
eciency increased drastically up to 2.03% as showed in
Fig. 3. The results are comparable to standard DSSC pre-
pared using commercial electrolytes, Iodolytes by
Solaronix Company. Even though, the Jsc is increased
along with eciency, the Voc are found to be lower than
the standard DSSC due to the absence of electric additives
such as pyridine based, 4-tert-butylpyridine (TBP), thio-
cyanate based, guanidinium thiocyanate (GSCN) and
iodide based ionic liquid, 1-methyl-3-propylimidazolium
iodide (MPII), tetrabutylammonium iodide (TBAI) (Wu
et al., 2008a).
 M.S. Suait et al. / Solar Energy 115 (2015) 452470 459

Table 1
Performances of several DSSCs utilizing polymer electrolyte under 100 mW cm2 light illumination.
Electrolyte r g (%) Jsc Voc (V) FF A (cm2) I (mW/cm2) References
(103 S cm1) (mA cm2)
Solid polymer electrolyte
PEODME/MPII/I2/SiO2 x 4.50 9.50 0.65 NA 0.13 100 Kim et al. (2004)
PEO-KI/I2 0.002 0.01 0.06 0.68 0.26 NA 100 Kang et al. (2005)
PEO-PPG-KI/I2 0.03 3.84 11.2 0.72 0.48 NA 100 Kang et al. (2005)
PULiI/I2 0.74 0.003 0.06 0.14 0.26 1.00 100 Suait et al. (2014)
Gel polymer electrolyte

(i) classical technique

PEOEC/PCLiI/I2 (N3 dye) 5.20 3.60 2.80 0.58 0.60 NA 27 Ren et al. (2002)
PVdF-HFPMPII (Z-907 dye) NA 5.30 11.69 0.67 0.71 0.15 100 Wang et al. (2002)
PAN-co-S/NaI-I2TBP 2.37 2.75 4.53 0.69 0.53 0.80 60 Lan et al. (2006)
TEOS-PEGLiI/I2C6DMIITBP (N3 dye) NA 4.10 9.20 0.74 0.61 NA 100 Joseph et al. (2006)
PVdF-HFPTiO2LiI/I2 NA 4.25 9.91 0.70 0.60 0.16 NA Kim et al. (2006)
PMMA-EC/PC/DMCNaI/I2 6.89 4.78 10.07 0.78 0.61 0.25 100 Yang et al. (2008)
PVdF-HFPTBAI/I2TBP (N3 dye) 5.71 3.71 10.96 0.71 0.48 0.25 100 Lee et al. (2008b)
PVdF-HFPSiO2TBAI/I2TBP (N3 dye) 7.18 5.97 14.04 0.71 0.60 0.25 100 Lee et al. (2008b)
PULiI/I2BMImITBP 9.80 6.10 14.11 0.74 0.50 NA 100 Lee et al. (2010d)
PVdF-HFPEC/PCNaI (natural dye) 0.15 0.72 2.63 0.47 0.58 0.16 100 Noor et al. (2014)
Bio-polymer electrolytes
CM-cellulose/PEONaI/I2MPIITBP NA 5.18 10.03 0.75 0.69 0.78 100 Bella et al. (2013d)
AEIIPCAgaroseNMPI/I2GuNCS NA 5.45 11.71 0.72 0.65 0.28 100 Hsu et al. (2013)
AgaroseKI/I2 9.02 0.54 3.27 0.67 0.24 0.25 100 Singh et al. (2013)
MPII/EMISCNmicro-celluloseLiI/I2TBP NA 3.33 3.27 0.67 0.24 0.22 100 Salvador et al. (2014)
SPE ChitosanNH4I/I2BMII (anthocyanin) 0.03 NA 0.07 0.23 0.22 0.16 100 Buraidah et al. (2010)
SPE CM k-CarrageenanNaI/I2EC 55.3 2.06 7.60 0.50 NA 0.78 100 Bella et al. (2015)
SPE CM k-Carrageenan/CM 2.32 0.13 0.42 0.50 0.64 1.00 100 Rudhziah et al. (2015)
CelluloseNH4I/I2

(ii) swelling technique

PAA-PEGNaI/I2TBP (N3 dye) 3.24 3.2 8.3 0.71 0.54 0.50 100 Lan et al. (2007)
PVdF-HFPEC/PCLiI/I2C6DMIITBP 102 7.3 15.57 0.76 0.62 0.16 100 Priya et al. (2008)
BEMA:PEGMA(70:30)NaI/I2 NA 5.41 16.0 0.58 0.58 0.22 100 Bella et al. (2013b)
PEGMA:PEGDA:NaI (70:30)NaI/I2 NA 3.23 12.59 0.50 0.51 0.22 100 Bella et al. (2013a)
PEGMA:PEGDANaI/I2 NA 2.70 10.96 0.50 0.49 0.22 100 Bella et al. (2013a)
PEGMA:BIPDANaI/I2 NA 2.11 8.89 0.48 0.49 0.22 100 Bella et al. (2013a)
PEGMA:BIEDANaI/I2 NA 1.80 8.19 0.44 0.50 0.22 100 Bella et al. (2013a)
PEGMA:DEGDMANaI/I2 NA 1.30 6.65 0.40 0.49 0.22 100 Bella et al. (2013a)
PEGMA:PEGDA (80:20)NaI/I2 NA 4.41 17.46 0.50 0.52 0.22 100 Bella et al. (2014a)
PEGMA-PEGDAMg-MOFNaI/I2 NA 4.80 12.60 0.69 0.55 Bella et al. (2013c)
BEMA:PEGMA(70:30)MFCMPIINaI/I2 7.03 15.20 0.76 0.61 0.78 100 Bella et al. (2014b)
Polyionic Liquid electrolyte

(i) Polypyridinium ion based DSSC

PNM4VPINMPIKI/I2 6.41 5.64 13.44 0.68 0.62 0.25 100 Wu et al. (2008b)
Poly(MVPI)/I2EMImDCN 0.01 0.65 3.04 0.70 0.30 0.25 100 Singh et al. (2010)
PEOM-P4VPILiI/I2 0.03 3.00 11.10 0.49 0.55 0.40 100 Seo et al. (2012)

(ii) Polyimidazolium ion based DSSC

PEO-co-BImI/I2SiO2 NA 5.25 11.6 0.73 0.66 0.15 100 Kim et al. (2008)
Poly(VIm-co-PEO)LiI/I2EC/PC 2.89 7.60 16.90 0.58 NA 0.20 100 Wang et al. (2008)
PBVImTFSILiI/I2PMII/EMITFSITBP 0.41 4.40 10.57 0.61 0.68 0.10 100 Zhao et al. (2011)
(N3 dye)
PBVImTFSI(ILsTiO2)TBPGuNCS/ 0.85 5.26 11.66 0.66 0.68 0.1 100 Chen et al. (2012a)
EMISCNEMII/PMII/I2 (N3 dye)
Poly[BVIm][HImTFSI]NBBGNCS/ 5.83 5.92 12.92 0.68 0.68 0.28 100 Chen et al. (2012b)
EMISCNEMII/PMII/I2 (N3 dye)
Poly(VImI-co-PEGMA)/ PEOLiI/I2DMAP 0.07 3.46 5.60 0.63 0.52 0.25 100 Zhang et al. (2012)
Poly(MAtri(EO)ImTFSILiI/I2TBP 0.65 1.74 NA NA NA NA 100 Bui et al. (2014)
(N3 dye)
(continued on next page)
460 M.S. Suait et al. / Solar Energy 115 (2015) 452470

Table 1 (continued)
Electrolyte r g (%) Jsc Voc (V) FF A (cm2) I (mW/cm2) References
(103 S cm1) (mA cm2)
Poly(EAHImI) (N3 dye) 0.36 5.29 9.75 0.84 0.67 0.20 100 Wang et al. (2012)
PEBII/MPII (organized TiO2 by 0.80 5.85 17.00 0.64 0.54 0.40 100 Chi et al. (2011)
PVC-g-POEM template)
PEBII 0.20 5.93 18.10 0.64 0.51 0.40 100 Chi et al. (2011)
PEBII-co-POEM 0.22 4.50 17.00 0.63 0.54 0.40 100 Chi et al. (2012)
PEBII-co-POEM/MPII NA 7.00 17.80 0.69 0.57 0.40 100 Chi et al. (2012)
PEBII 0.20 7.10 13.80 0.84 0.61 NA 100 Ahn et al. (2012)
PEBII (TiO2 from Dyesol) 0.20 4.60 10.00 0.84 0.54 NA 100 Ahn et al. (2012)
PEBII (TiO2 nanosheets on SnO2 0.2 7.70 17.40 0.77 0.58 0.40 100 Ahn et al. (2013b)
nanotubes + organized TiO2)
PEBII (Honey comb like TiO2) 0.2 7.40 17.20 0.74 0.58 0.16 100 Ahn et al. (2013a)
PEBII (SnO2 hollow sphere + TiO2 0.2 8.20 18.20 0.76 0.60 0.40 100 Ahn et al., 2014
nanosheet + organized TiO2)
PEBII (Pine tree like TiO2) 0.2 8.00 17.70 0.74 0.62 0.20 100 Roh et al. (2014)
PEBII (organized TiO2 by PS-g-P2VP 0.20 4.00 9.10 0.80 0.54 0.16 100 Kim et al. (2013b)
template)

12
PU-Li/I2 (casting membrane)
4.2.2. Gel polymer electrolyte (GPE) PU-Li/I2 ( in-situ polymerization)
The quasi-solid state, or gel state, is a particular state of 10
Current Density (mA cm ) Liquid electrolyte (Iodolyte AN-50)
-2

matter, neither liquid nor solid, or conversely both liquid

8
and solid (Wu et al., 2008a). Generally, a classical gel poly-
mer electrolyte (GPE) is dened as a system which consists 6
of a dissolved polymer network (polymer host) with stoi-
chiometric ratios of electrolytes composition gellify by 4
plasticizer, co-polymerization, organic gelators, inorganic
(ceramic llers), heat induced, UV-cured and cross-linker. 2
Whereas, the other categories of GPE is prepared by swel-
0 0.004%
ling the polymeric membrane in the liquid electrolyte with a 2.03% 2.95%

redox mediator-based electrolytes solution as illustrated in
Fig. 3. By this method, the liquid electrolyte is trapped in
the polymer matrix network and a stable gel is obtained
(Bella and Bongiovanni, 2013; Bella et al., 2013b).
Classical GPE consists of small fractions of low molar
mass polar polymeric matrix in large amount of organic
plasticizer (e.g. ethylene carbonate (EC) or propylene car-
bonate (PC)) with polar aprotic organic solvent (e.g.
ACN, THF). The plasticizer lower the glass transition tem-
perature of the polymer by introducing a degree of disorder
in the crystalline phase, increasing its segmental mobility
and free volume of the system (Nogueira et al., 2004).
Ren et al. (2002) reported the use of the plasticized gel
polymeric electrolyte, (PEO1500 and PEO2000) with
200 wt.% EC/67 wt.% PC and 20 wt.% LiI/5 wt.% I2 in
DSSC. They found high Mw of heat-induced cross-linking
(60 C) PEO (2000 g mol1) in plasticized dominant elec-
trolytes gives higher photocurrent (2.8 mA cm2), and
power conversion eciency (3.6%) under 27 mW/cm2
white light illumination as compared to low Mw PEO with
1500 g mol1. Wang et al. (2002) from Gratzel group
reported the utilization 10 wt.% PVdF-HFP in MPII liquid
electrolyte as a gel polymeric electrolyte in DSSC (redox
electrolyte composition was not mention). They observed
high power conversion eciency up 5.3% with Jsc of
11.69 mA cm2, Voc of 0.67 V and of 0.71 using Z-907
0.0 0.2 0.4 0.6 0.8 1.0
Voltage (V)
Fig. 3. IV curves of PU-LiI/I2.
dye. Lan et al. (2006), prepared gel polymer electrolyte
by trapping a liquid electrolyte of binary organic solvent
mixture, 60/40% ratio of EC/PC containing dissolved
0.5 M NaI and 0.05 M I2 by heat-induced cross-linking at
85 C in polymer cages based on 20 wt.% poly(acryloni-
trile-co-styrene) (PAN-co-S). The system gives rise to the
maximum ionic conductivity of 2.37  103 S cm1 at
30 C. A quasi-solid state DSSC was fabricated by drop-
ping the gel of PAN-co-S/NaI + I2 and its overall energy
conversion eciency of light-to-electricity of 2.46% was
achieved under irradiation of 60 mW cm2. With the addi-
tion of 0.5 M TBP, the power conversion eciency
increased up to 2.75% but Jsc was found to reduce around
0.40 mA cm2 from the control electrolytes and Voc
increased from 0.47 to 0.53 mV. Yang et al. (2008) synthe-
sized PMMA and prepared gel polymer electrolyte consist
of 12 wt.% PMMA in homogeneous plasticized liquid elec-
trolyte solution of EC/PC/DMC(4:2:1) 0.5 M TBP and
varied NaI (0.20.8 M)/0.06 M I2. The quasi-solid DSSC
possessed a good long-term stability, light-to-electrical
energy conversion eciency of 4.78% at 0.6 M to
 M.S. Suait et al. / Solar Energy 115 (2015) 452470
0.06 M mol ratio of NaI/I2 and optimum ionic conductiv-
ity of 6.89  103 S cm1. The value are comparable to
control liquid electrolytes prepared without the presence
of PMMA with the Voc, Jsc, FF and overall power conver-
sion eciency of 0.732 V, 10.72 mA cm2, 0.61 and 4.79%,
respectively. The Jsc of DSSC with PMMA was found to be
lower than control liquid electrolyte. The Jsc decrease after
gelation is mainly due to the decrease of conductivity of the
electrolyte. On the other hand, the Voc was found to be
increased, which results from the suppression of dark cur-
rent by polymer chains covering the surface of TiO2 elec-
trode. Lee et al. (2008b) varied a series weight percentage
of PVdF-HFP (less than 10 wt.%) in 0.4 M TBAI, 0.04 M
I2 and MPN as GPE in N3 dye based DSSC. They found
the overall energy conversion eciency reduced from
3.93% to 2.68% with 9 wt.% of PVdF-HFP and the conduc-
tivity dropped from 6.10  103 to 5.18  103 S cm1. By
further increment of polymeric host to plasticizer ratios
reduced the conductivity and ion mobility drastically, thus
lower the eciency. Noor et al. (2014) also prepared GPE
containing 48% (PVDF-HFP) 32% NaI 20% (EC/PC)
(utilizing natural dyes) gives room temperature conductiv-
ity of 1.53  104 S cm1 and produced power conversion
eciency of 1.85% at 30 mW/cm2 illumination and reduced
to 0.72% at 100 mW cm2 illumination. PVdF-HFP has
received great attention as one of the promising host poly-
mers for polymer electrolytes because of its excellent
mechanical strength by reducing highly crystalline PVdF
with copolymerized of HFP (Noor et al., 2014) and its
photoelectrochemical stability under potential application
(Kim et al., 2006).
In order to improve physical and mechanical stability of
the gel polymer electrolytes, organic or inorganic gelators
were included as gelling agent to form composite gel poly-
mer electrolyte. An interesting class of organic gelators is
represented by natural organic molecules such as polysac-
charides and biomacromolecules such as chitosan, chitin,
cellulose, agarose, and arrowroot. Cellulose is the most
common natural polymer and it is considered as an almost
inexhaustible source of raw material, which can satisfy the
increasing demand for environmentally friendly and bio-
compatible products. The quasi-solidication of a liquid
electrolyte by means of a combined system consisting of
PEO and carboxymethyl cellulose sodium salt (CMC)
was done by Bella et al. (2013d). They achieved a maxi-
mum light-to-electricity conversion eciency of 5.18%
(Jsc = 10.03 mA cm2, Voc = 0.75 V, FF = 0.69) for the
gel-polymer electrolyte obtained using a CMC/PEO ratio
of 0.09, and an amount of liquid electrolyte equal to
55 wt%. Interestingly, after 250 h the DSSCs based on
the CMC/PEO gel-polymer electrolyte retained the 82
98% of the initial eciency value, indicating that the cells
exhibited remarkable long term stability. Study by Hsu
et al. (2013) shows the eciency was enhanced from
4.72% to 5.25% with the addition of 0.5 wt.% Agarose in
MPII liquid electrolyte and the best eciency was achieved
by using the 1-allyl-3-methylimidazolium (AEII)-Agarose
461
gel electrolyte at 5.45%. Another approach on Agarose
based gel electrolyte was done by Singh et al. (2013).
They prepared dierent stoichiometric ratios of Agarose
powder to KI dissolved in D2 water. They found that the
optimum conductivity of (60:40 wt.%) Agarose-KI/I2
based DSSC gives 0.54% eciency with Jsc of
3.27 mA cm2, Voc of 0.67 V and FF of 0.24. Salvador
et al., 2014 prepared gel electrolytes composed of dierent
volume percentage ratios of the two ionic liquids (with and
without iodide as anion), 2 wt.% of LiI, I2 (10 wt.% of the
whole iodide weight) and 36 wt.% of cellulose microcrys-
talline powder. 10 wt.% of TBP was also added as an addi-
tive to increase the open-circuit voltage (Voc). An
optimization of the photovoltaic performance of cellulose
gel-based DSSCs was obtained at 3.33% eciency by moni-
tored at 50/50 volume percentage ratio between the two
ionic liquids MPII and EMISCN, the 5 wt.% of the
micro-cellulose, 2 wt.% of LiI, I2 (10 wt.% of the whole
weight of iodide) and 10 wt.% of TBP. The time and the
temperature of the heating step is found to be necessary
to improve the gel penetration into the mesoporous TiO2
layer.
The introduction of inorganic ceramic llers into poly-
mer electrolyte system increased the ionic conductivity
and makes the electrolyte more amorphous to promote
more ion dissociation from the organic salt for the charge
transfer in the electrolyte (Ahmad et al., 2008). Kim et al.
(2006) discovered power eciency of 4.25% in comparison
to control system at 3.85% with inclusion of 10 wt.% TiO2
in PVdF-HFP:NMP (15:85 weight ratio) and 1.0 M LiI/
0.1 M I2 redox-electrolytes solution. The Voc was found
to increase from 0.58 to 0.61 V by increasing TiO2 llers.
Drastic change in overall energy conversion eciency with
the presence of ceramic llers are also been observed by
Lee et al. (2008b). They found higher overall energy con-
version eciency of 5.97 wt.% with 1 wt.% silica nanopar-
ticles as organic ller in 5 wt.% PVdF-HFP, 0.8 M TBAI,
0.12 M I2 and 0.1 M TBP in MPN in comparison to con-
trol liquid electrolyte system. Another ceramic llers inclu-
sion technique has been done by Joseph et al. (2006) in
preparing composite gel polymer electrolyte for quasi-
solid-state DSSC with an overall solar energy conversion
eciency of 4.10%. The gel was prepared by in-situ sol
gel technique of tetraethyl orthosilicate (TEOS) with
PEG200 in 7 ml redox electrolyte containing 0.1 M LiI,
0.05 M I2, 0.6 M 1-hexyl-2,3-dimethylimidazolium iodide
(C6DMII) and 0.5 M TBP in MPN. The hybrid TEOS-
PEG gel electrolyte was prepared by mixed 3 ml of
TEOS, 0.4 ml of glacial acetic acid as a catalyst in the
hydrolysis process and 0.5 ml of water (52% of the stoichio-
metric value required for the hydrolysis of TEOS) together
with 0.3 ml of low molecular weight PEG for mechanical
strength and ion transfer. However, a few preliminary
experiments with the unsealed cells showed about 30%
reduction in Jsc values, but the Voc remained the same,
after 48 h of assembling the cells. The formation of silica
network is believed to hold the electrolytes structure but
462 M.S. Suait et al. / Solar Energy 115 (2015) 452470
from our personal experiences, this types of gel is lacking in
exibility and durability of the gel and not able to stand the
pressure between both working and counter electrode of
DSSC.
An interesting study by Lee et al. (2010d) showed that
the use of UV-cured PU (010 g) along with 10 g of liquid
electrolytes consists of 0.1 M LiI/0.05 M I2 liquid elec-
trolytes, 0.60 M 1-butyl-3-methylimidazolium iodide
(BMImI), and 0.50 M TBP in MPN resulted in high con-
ductivity of 9.80  103 S cm1 with 6.10% eciency of
quasi-solid DSSC at 8 g urethane acrylate precursor in
10 g liquid electrolytes. The results are comparable to stan-
dard liquid electrolyte cells with 6.60% power conversion
eciency. Interestingly, this technique utilized photo-poly-
merization of aliphatic urethane acrylate in liquid elec-
trolyte by UV-cured process into polyurethane network
of gel polymer electrolyte. The stable and exible gel could
be obtained through this method.
Apart from classical GPE preparation technique, there
is another version of gel polymer electrolyte prepared by
swollen technique of polymeric membrane into liquid elec-
trolytes as shown in Fig. 4. Lan et al. (2007) reported the
use of copolymerization technique between poly(acrylic
acid) (PAA) and PEG produced 3.19% overall energy con-
version eciency when soaked in 0.5 M NaI/0.05 M I2
0.5 M TBP in c-butyrolactone (with N3 dye sensitizer). It
is well known that PAA is a type of superabsorbents, which
can absorb a large amount of water and retained the
absorbed water even under some pressure. However, pris-
tine PAA is not a good absorbent for organic solvents used
in liquid electrolytes. In order to have an ecient absor-
bent ability of PAA superabsorbent in liquid electrolyte,
they modied PAA with the amphiphilic PEG to form
homogeneous hybrid without phase disengagement. After
soaking the polymeric membrane of PAAPEG in liquid
electrolyte, a stable polymer gel electrolyte is formed by
retaining large amount of liquid electrolyte and shows
moderate value of ionic conductivity and good chemical
stability (Lan et al., 2007). They also investigate the stabil-
ity of polymer gel electrolyte by observing the ionic con-
ductivity as functions of storage time at 30 C. They
found that the ionic conductivity has a slight decrease dur-
ing the rst 20 h, and then remains constant over the rest of
the measured time. This is because the liquid electrolyte in
the surface layer of polymer gel electrolyte during the rst
20 h is found to be unstable and easy to volatilize. The
highest ambient ionic conductivity of polymer gel elec-
trolyte reaches 3.24  103 S cm1, and the constant value
is about 3.06  103 S cm1, as compared to liquid elec-
trolyte prepared (0.5 M NaI, 0.05 M I2, 0.5 M TBP in c-bu-
tyrolactone) is 6.7  103 S cm1. So aforementioned
phenomenon can be concluded that liquid electrolyte is
well encapsulated in the network of the hybrid without
leakage problem and obtains a moderate value of ambient
ionic conductivity (Lan et al., 2007). Priya et al., 2008 uti-
lized the same swelling technique in preparing quasi-solid
state DSSC. By introducing electrospinning technique to
Fig. 4. Preparation of quasi-solid polymer electrolyte by swelling
technique. (Bella et al., 2013b).
prepare PVdF-HFP membrane (16 wt.% PVdF-HFP in
(70/30) mixtures of acetone/N,N-dimethylacetamide) and
then activated the membrane in liquid electrolyte consist
of 0.6 M C6DMII, 0.1 M LiI, 0.05 M I2, and 0.5 M TBP
in EC/PC (1:1 wt.%), they obtained high power conversion
eciency up to 7.30% with Jsc of 15.57 mA cm2, Voc of
0.76 V and of 0.62.
Extensive study on utilizing photopolymerization
approached in quasi-solid state DSSC was conducted by
Bella et al. (2013b). They reported power conversion e-
ciency of quasi-solid-state DSSC at 5.41% using polymeric
membrane of bisphenol A ethoxylate dimethacrylate
(BEMA) to PEGMA (35:65) in the liquid electrolyte with
a redox mediator-based solution consist of 0.375 M NaI/
0.0375 M I2 in ACN. According to their studies, BEMA
was utilized to form a three-dimensional network and the
addition of PEGMA as a co-monomer will inuences the
propagation reaction and changes the architecture of the
polymeric matrix; thus, aecting its properties. In their
investigation, the amount of BEMA was varied between
20 and 50 wt.% and they found that the membranes were
not self-standing below 20 wt.% BEMA (power conversion
eciency of 4.73%), while above 50 wt.% (power conver-
sion eciency of 3.97%) they were rigid and hard to man-
age in assembling the cells. By performed dynamic
mechanical analysis and measured the storage (elastic)
modulus of the polymer networks at the rubbery plateau,
they calculate the cross-linking density of the networks
and relate the ability of BEMA:PEGMA ratio in inuenc-
ing the amount of liquid electrolyte trapped in the mem-
branes during swelling. They observed that, the cross-
linking density increases linearly with the amount of
BEMA. It means that when the difunctional monomer
increases, the network obtained becomes tighter. The
weight concentration of the liquid electrolyte stored in
the low cross-link membranes was found to increase as a
function of BEMA amount up to certain value, but then
decreases drastically. This may be due to the fact that,
the increased of cross-linking density means the cross-
linked polymeric network is too dense to store a fair
 M.S. Suait et al. / Solar Energy 115 (2015) 452470
amount of liquid electrolyte. On the other hand, below
35 wt.% of BEMA the network is very loose and is no
longer able to trap the electrolyte (Bella et al., 2013b). In
other work, they copolymerized monofunctional PEGMA
with various difunctional acrylate monomer by UV-cured
photopolymerization at (70:30) ratios and swelled in
0.5 M NaI/0.05 M I2 in ACN (Bella et al., 2013a). Under
irradiation, difunctional forms a three-dimensional poly-
mer network and monofunctional monomer will contribute
to the propagation of the polymeric chain and transformed
the polymer matrix architecture. They found that the
degree of cross-link density of the membranes inuence
the amount of liquid electrolyte uptake. Thus, aected
the eciency of the quasi-solid DSSCs (from 1.3% to
2.7%) because they depend on how much liquid electrolyte
is possible to trap in the gelpolymer membranes. From
their results as shown in Fig. 5, they concluded that, at high
degree of cross-link density values, the polymeric network
is too dense to take in and store a fair amount of liquid
electrolyte. On the other hand, low degree of cross-link
density values lead to a very loose network, that is no
longer able to eectively trap the liquid electrolyte. The
trends was followed and improved by the addition of
0.5 M NaI in the mixture of monofunctional and difunc-
tional acrylate monomer before irradiation. They observed
high power conversion eciency up 3.23% with Jsc of
12.56 mA cm2, Voc of 0.50 V and of 0.51. Further
optimization was achieved at (80:20) PEGMA to
PEGDA ratio after variation of several weight ratios at
the same concentration of the prepared electrolyte (Bella
et al., 2014a). By optimization process, they improved the
power conversion eciency up to 4.41% with Jsc of
17.46 mA cm2, Voc of 0.50 V and of 0.52. Afterward,
an improvement of power conversion eciency up to
4.80% were obtained by introduction of metalorganic
frameworks (Mg-MOF) compound as a llers by ad hoc
synthesized in UV-cured acrylic monomers and swelled in
electrolytes composition of 0.3 M NaI, 0.03 M I2, 0.2 M
MPII and 0.35 M TBP in ACN (Bella et al., 2013c). By
changing to the bio-polymer organic llers based on
microbrillated cellulose into BEMA:PEGMA (30:70%
ratio), the eciency increased drastically to 7.03%. The rise
was ascribed to the partial crystalline structure of the MFC
network of bers, resulting in a multiplanar light scattering
grating. As a consequence, photons which passed
unharmed through the photoanode were recovered and
reected back to the N719 dye molecules, thus increasing
the sensitizer excitation and, as a consequence, the charge
photo-injection (Bella et al., 2014b).
4.3. New insight: polyionic liquid polymer electrolyte
(PolyILs)
Recently, a growing interest has been given to immobi-
lized RTILs via polymerization reaction as new class of
polymer electrolytes; polyionic liquids (polyILs)
(Watanabe et al., 1993, 1995; Nakai et al., 1998; Ito and
463
Fig. 5. Variation of the power conversion eciency and the amount of
liquid electrolyte uptake as a function of crosslink density for various UV-
cured polymer electrolyte membranes (Bella et al., 2013a).
Ohno 1998). Few successful works have been carried out
to prepare highly conductive IL-based polymer gels by vari-
ous methods as described by Lu et al. (2009). They can be
classied into three major types: (1) doping of polymers
with ILs, (2) in-situ polymerization of vinyl monomers in
ILs, and (3) polymerization of polymerizable ILs (contain-
ing vinyl groups). The success has diverted researches atten-
tion in DSSC application from conventional polymer
electrolytes to polymerization of RTILs based electrolytes.
Polyionic liquids (polyILs) took the advantages of the weak
attraction of tethered quaternary nitrogen cations on poly-
meric segment with free anions in resulting higher mobility
of I anions to transport. The weak attraction was inu-
ences by weak basicity of quaternary nitrogen atoms, the
conjugation eect of the amine ring, and the large steric hin-
drance of the polymer backbone (Wu et al., 2008b). They
are a new class of polymers that combine both the novel
properties of ILs and improved mechanical durability and
dimensional control resulting from polymerization (Zhao
et al., 2011).
Earlier work on polyILs based DSSC utilized classical
GPE concept which consist of dissolved small fractions of
polyILs matrix in large amount of organic plasticizer/or-
ganic solvent and/or with the presence of gelling agent.
Fig. 6 illustrated main types of poly(ionic liquid)-based elec-
trolytes for DSSC. Kim et al. (2008) polymerized dichloro
PEO oligomers and functionalized with butylimidazole to
prepare PEO based bis-imidazolium iodide salt (PEOm-
BImI). The gel polymer electrolyte of PEOm-BImI in
MPN (1:1) were prepare at various Mw of PEO to I2 molar
ratios with the presence of 5 wt.% hydrophilic fumed SiO2
nanoparticles as gelating agent in DSSC. They obtained
high energy-conversion eciency of 5.25% under AM 1.5
illumination with Voc = 733 mV, Jsc = 10.71 mA cm2 and
FF is 0.67 for PEO13-BImI/0.15 M I2. Wang et al. (2007)
reported the maximum power conversion eciency of
7.6% by solidication of the liquid electrolyte containing
0.5 M LiI, 0.05 M I2 in EC/PC (80/20) with 10 wt.%
464 M.S. Suait et al. / Solar Energy 115 (2015) 452470
n LiI/I2TBP liquid electrolyte prepared; 5.3% power con-
n
N by introducing 15 wt.% TiO2 functionalized on 1-methyl-
N N
I-
-
I imidazolium bis(triuoromethanesulfonyl)imide) (Poly
R R
Polyimidazolium ion based ILs Polypyridinium ion based ILs
Fig. 6. Main types of poly(ionic liquid)-based electrolytes for DSSC.
poly(ethylene glycol) methacrylate-co-methylimidazole
chloride P(MOEMImCl). P(MOEMImCl) were obtained
via polymerization of methyl imidazole based polymers
having PEO oligomers segment. Zhang et al. (2012),
synthesized poly(N-propyl-vinylimidazolium iodide-
co-poly(ethylene glycol) methyl ether methacrylate)
(poly(VImI-co-PEGMA)) copolymer by reacting a mixture
of PEGMA and vinylimidazolium in AIBN/chloroform.
Afterward, the poly(VImI-co-PEGMA) was reacted with
excess of 1-iodopropane to quaternize the copolymer struc-
tures in order to obtained polyILs. The polyILs copolymer
and its blend with poly(ethylene oxide) (PEO) were then
used to prepare the polymer electrolytes containing 3 g of
polymer, 0.5 g of LiI, 0.32 g of I2, and 0.1 g of DMAP were
dissolved in acetonitrile. The blend electrolytes thus pre-
sented the highest ionic conductivity among the prepared
electrolytes with ionic conductivity of 7.40  105 S cm1.
The poly(VImI-co-PEGMA)/PEO blend electrolyte
achieves the highest energy conversion eciency of 3.46%
with Jsc of 5.60 mA cm2, the Voc of 632 mV, and the FF
of 0.52. They also found that the impedance results
indicated the improved photovoltaic performance of the
blend electrolyte was originated from the increased ionic
diusion coecient and the prevented downward move-
ment of the conduction band edge of TiO2.
Before, Zhao et al. (2011) has obtained 4.40% eciency,
Jsc = 10.57 mA cm2 Voc = 0.61 V and FF is 0.68 from
solvent-free (25 wt.%) poly(1-butyl-3-vinylimidazolium
(PolyBVIm TFSI) dissolved in PMII/EMITFSI (13:7) ionic
liquids (ILs) based electrolytes contained 0.1 M I2, 0.1 M
LiI, 0.5 M TBP for quasi-solid-state DSSC. The gel
polymer electrolyte was initiated by heat-induced cross-link
at 80 C. The obtained eciency of PolyBVImTFSIPMII/
Fig. 7. Polymerization procedures of [PBVIm][TFSI] (Chen et al., 2012a).
EMITFSILiI/I2TBP is comparable to PMII/EMITFSI
version eciency, Jsc = 11.27 mA cm2 Voc = 0.65 V and
FF is 0.68. The eciency was then improved up to 5.26%
3-[(triethoxysilyl)propyl] imidazolium chloride (TMICl)
ILs precursors in 0.1 M I2, 0.5 M TBP, 0.1 M GNCS,
EMII/PMII/EMISCN (6:6:7) and 25 wt.% poly(1-butyl-3-
[BVIm][TFSI]) based electrolytes. Fig. 7 shows the
polymerization procedures of [PBVIm][TFSI] (Chen
et al., 2012a). Moreover, the report produced a very
convincing results, revealing that the thermostability of
modied IL-TiO2 nanoparticles gel electrolyte based
devices is better than the unmodied TiO2 nanoparticles
and pure poly(ILs). They showed that cell containing 15
wt% IL-TiO2/[PBVIm][TFSI] based electrolyte retained
almost 100% of the initial eciency even after about
1200 h, while the cell without IL-TiO2 and fume TiO2 only
maintained 85% and 88% of the initial eciency, respec-
tively. Years later, the same group reported the new
improvement up to 5.92% eciency by dissolved 25 wt.%
of polymerized poly(1-butyl-3-(1-vinylimidazolium-3-
hexyl)-imidazolium bis(triuoromethanesulfonyl)imide)
(Poly[BVIm][HImTFSI]) in 0.1 M I2, 0.5 M N-butylben-
zimidazole (NBB), 0.1 M GNCS, EMII/PMII/EMISCN
(6:6:7) liquid electrolyte (Chen et al., 2012b). They
obtained high energy-conversion eciency of 5.92%
under AM 1.5 illumination with Voc = 0.68 V, Jsc =
12.92 mA cm2 and FF is 0.68. Recently, Bui et al.
(2014), took an opposing approach by polymerizing the
methacrylate end group and tri(ethylene oxide) group with
anion segment of TFSI and let a free imidazolium counter
cation instead of anion as discussed above. The device gave
the low conversion eciency of up to 1.74%.
Apart from imidazolium ions based polyILs, there is
other types of polyILs that been tested in quasi-solid
DSSC; pyridinium ions. The work has been initiated by
Wu et al. (2008b) via synthesized of poly(N-alkyl-4-vinyl-
pyridine) iodine (PNR4VPI) by bulk polymerization reac-
tion of 4-vinyl-pyridine to form poly(4-vinyl-pyridine)
(P4VP) and followed by various quarternization initiated
by dierent alkyl iodide group in methanol solution to
convert the pyridine groups into pyridinium ions.
The increased conductivities of the polymer electrolytes
with the increase of the mole ratio of I2/I- and
further increment were obtained by the addition of
 M.S. Suait et al. / Solar Energy 115 (2015) 452470
0.6 M N-methyl-4-vinylpyridine iodine (NMPI) at
6.41  103 S cm1 in PNR4VPI-ethanol solution. They
also found that the increased in N-alkyl chain length
decreased the conductivity value. The fabricated DSSC
gives power conversion eciency of 3.61% with
Voc = 0.47 V, Jsc = 12.58 mA cm2 and FF is 0.61. By
immersing the surface of dye-sensitized TiO2 lm in KI,
the photoelectric performance of DSSC was improved to
5.64%, Jsc to 13.44 mA/cm2, and Voc to 0.68 V.
Approach in utilizing polyILs in solid-state DSCC has
been initiated by Singh et al. (2010). They synthesized
poly(N-methyl 4-vinylpyridine iodide) (PMVPI) blended
with 1-ethyl 3-methylimidazolium dicyanamide
(EMImDCN) in deionized water solution. The maximum
ionic conductivity value of 9.12  106 S cm1 was
obtained at 40 wt.% IL concentration and energy conver-
sion eciency of 0.65% were obtained with the presence
of I2. Seo et al., 2012 synthesized Poly(oxyethylene
methacrylate)poly(4-vinyl pyridine) (POEMP4VP)
comb-like copolymers via atom transfer radical polymer-
ization at various ratios and then quaternized with
1-iodopropane to convert the pyridine groups into pyri-
dinium ions. They obtained the power conversion eciency
up to 3.00% with Jsc of 11.10 mA cm2, Voc of 0.49 V, of
0.55 and ionic conductivity of 3.30  105 S cm1.
Due to the lack in power conversion eciency, the
approached turn back to imidazolium ions based polyILs
for solid-state DSSC. Wang et al. (2012), performed a syn-
thesized on poly(1-alkyl-3-(acryloyloxy)hexylimidazolium
iodide) (PEAHImI) for solid-state DSSC prepared by solu-
tion casting technique by using ACN. PEAHImI exhibits
the highest ionic conductivity (3.63  104 S cm1) at
room temperature with power conversion eciency of
5.29%, the Voc of 0.84 V, the Jsc of 9.75 mA cm2 without
the addition of iodine. Surprisingly, the incorporation of
iodine into polyILs resulted in the decrease of both the
Voc and the photocurrent density due to the visible light
adsorption by iodine and the enhancement of the recom-
bination between conduction band electrons and the
triiodide.
Chi et al. (2011) investigated the plasticization of
poly((1-(4-ethenylphenyl)methyl)-3-butyl-imidazolium
iodide) (PEBII, Mw = 15,000 g/mol) with MPII as solid-
state electrolyte on the improved electrode/electrolyte
interfaces using commercialized TiO2 paste by Solaronix
(Ti-Nanoxide T) on organized mesoporous TiO2 thin
lm-coated FTO glass using a doctor-blade technique, fol-
lowed by sintering. The synthesis procedure of PEBII
based electrolytes for was illustrated in Fig. 8 (Ahn et al.,
2012). The addition of MPII in PEBII resulted in an
increase in ionic conductivity from 0.20  103 to
0.80  103 S cm1. The solid electrolyte was prepared by
drop-cast onto the photoanode for several times and the
cells were placed in a vacuum oven for a day to induce
complete evaporation of the solvent. However, a reduction
in power conversion eciency was obtained when MPII
was introduced from 5.93% to 5.85%, which might be
465
due to the increased electron recombination, as proven
by the impedance analysis. In 2012, they reported the
copolymerization of EBII monomer with poly(oxyethylene
methacrylate) (PEOM) via free radical polymerization has
increased the eciency up to 7.00% with the presence of
MPII (Chi et al., 2012). Ahn et al., 2012 improved
solid-state DSSC up to 7.10% eciency with Jsc of
13.80 mA cm2, Voc of 0.84 V and of 0.61. By synthesized
organized TiO2 with combination of iodide free PolyILs,
PEBII and approximately 1.5-fold greater than that of
commercially available TiO2 paste by Dyesol (4.60% and
reduction in Jsc to 10.00 mA cm2), indicating the impor-
tance of an organized mesoporous structure. The crack
free, 6 lm micrometer-thick, organized mesoporous
TiO2 lms were prepared via an ecient one-pot procedure
using the spindle-shaped, preformed TiO2 nanoparticles
and the PVC-g-POEM graft copolymer as building blocks
and a structure-directing agent, respectively (Ahn et al.,
2012). Further improvement up to 7.70% were observed
by introducing 10 wt.% TiO2 nanosheets and SnO2 nan-
otubes on organized mesoporous TiO2 lms as a light scat-
tering layer without scarifying surface area and electron
transport properties (Ahn et al., 2013b). Later, various
architectures of TiO2 were tested by same group resulting
in high power conversion eciency of 7.40% for honey
comb-like TiO2 (Ahn et al., 2013a), 8.2% for with the pres-
ence of SnO2 hollow sphere and TiO2 nanosheet double
shell nanostructures on organized TiO2 (Ahn et al., 2014)
and 8.00% for pine tree-like TiO2 architectures (Roh
et al., 2014). After changing the template self-organized
TiO2 with anionically polymerized polystyrene-b-poly
(2-vinyl pyridine) (PS-b-P2VP) block copolymer, they
obtained lower power conversion eciency of 4.00% with
Jsc of 9.10 mA cm2, Voc of 0.80 V and of 0.54 (Kim
et al., 2013b).
Fig. 8. poly(ionic liquid)-PEBII based electrolytes for solid-state DSSC
(Ahn et al., 2012).
466 M.S. Suait et al. / Solar Energy 115 (2015) 452470
5. Outlook
This review highlights the utilization of various polymer
electrolyte membranes in dye-sensitized solar cells (DSSCs)
and its performances. The devices structure and working
principle of DSSC is also presented. So far, the highest
power conversion eciency of polymeric based electrolytes
in DSSC was given by iodine free poly((1-(4-ethenylphe-
nyl)methyl)-3-butyl-imidazolium iodide) (PEBII) polymer
electrolytes developed by Professor J.H. Kim group in
Yonsei University, South Korea. Surprisingly, the conver-
sion values of their solid-state DSSC surpass all the quasi-
solid DSSC. The advantages in free volume of PEBII which
inuenced by segmental motion of the tethered cation is
key factor in high conversion values as compared to other
types polyimidazoliums based polyILs. From our perspec-
tive, we believe that in coming years, polyILs as an iodine
free electrolyte will be dominant as electrolyte in DSSCs.
Thus, increasing the possibility of eliminating I2 compo-
nents as redox mediators in DSSC; subsequently will raise
the cell durability, photocurrent, electron life times and
reducing the photocorrosion eects of counter electrode
by iodine radical.
Acknowledgements
The authors would like to extend their gratitude toward
Universiti Kebangsaan Malaysia for allowing this research
to be carried out. Last but not least, we would like to
acknowledge all of the supports that have been given
throughout the process of this manuscript. This work is
supported by the Fundamental Research Grant Scheme,
FRGS/1/2011/TK/UKM/02/39 and Research University
Grant, UKM-GUP-2011-228.
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