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Ionic liquid electrolytes for dye-sensitized solar cells

Mikhail Gorlov and Lars Kloo*
Received 31st October 2007, Accepted 7th February 2008
First published as an Advance Article on the web 18th March 2008
DOI: 10.1039/b716419j

The potential of room-temperature molten salts (ionic liquids) as solvents for electrolytes for
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dye-sensitized solar cells has been investigated during the last decade. The non-volatility, good solvent
properties and high electrochemical stability of ionic liquids make them attractive solvents in contrast
to volatile organic solvents. Despite this, the relatively high viscosity of ionic liquids leads to
Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J

mass-transport limitations. Here we review recent developments in the application of different ionic
liquids as solvents or components of liquid and quasi-solid electrolytes for dye-sensitized solar cells.

1. Introduction Generally, a DSSC consists of a photoanode (WE) with a thin

Solar radiation has a great potential as source of energy. Solar
energy is typically referred to as a source of “renewable” energy,
although it for practical reasons rather should be regarded as an
inexhaustible source for energy conversion. Nevertheless, for this
reason a large number of academic and industrial research groups
investigate the possibility to construct new photovoltaic devices (as
alternatives to the well-developed, but relatively expensive, silicon
solar cells) for the conversion of solar energy to electricity or
alternatively to fuels. After the discovery of a principally new type
of solar cells, dye-sensitized solar cells (DSSCs), by O’Regan and
Grätzel in 1991,1 much effort was invested to make this type of
molecular devices more efficient and stable. Up to now, maximum
light-to-electricity conversion efficiency of 11% at full sunlight
(100 mW/cm2 ) have been recorded.2 Moreover, long-term stability
tests (prolonged illumination and thermal stress) show promising
results.2
layer of nanostructured wide band-gap semiconductor attached
to the conducting substrate (TiO2 has been almost exclusively
used as a semiconductor in high performance DSSCs) and a
monolayer of organometallic or organic dye D adsorbed onto
the nanoparticles of the semiconductor (Fig. 1). Photoexcitation
of the dye molecules (eqn (1)) is followed by ultrafast injection
of the electrons into the conduction band of the semiconductor
(eqn (2)). The electrons are withdrawn to an external circuit and
returned to the system by reduction of an oxidized component of
the electrolyte redox couple RC+ (eqn (3)). The oxidized dye D+ is
finally regenerated by the reduced component of the redox couple
RC (eqn (4)).
D/TiO2 + hm → D*/TiO2 (1)
D*/TiO2 → D+ /TiO2 + e− /TiO2 (2)
RC+ + e− /CE → RC (3)

Inorganic Chemistry, Department of Chemistry, The Royal Institute of D+ /TiO2 + RC → D/TiO2 + RC+ (4)
Technology (KTH), Stockholm, Sweden

Mikhail Gorlov was born in Saint
Petersburg, Russia and received
his PhD in Chemistry from the
Saint Petersburg State Institute
of Technology in 2002. He was a
postdoctoral fellow (2003–2004)
at the Royal Institute of Technol-
ogy (KTH), Stockholm, Swe-
den, and he is currently a re-
searcher at the Inorganic Chem-
istry Department, KTH. His re-
search interest focuses on the
syntheses of new ionic liquids and
Mikhail Gorlov their application as electrolyte
media for dye-sensitized solar
cells.
Lars Kloo received his PhD in In-
organic Chemistry at Lund Uni-
versity, Sweden, in 1990, and
moved to his current position as
Professor in Inorganic Chemistry
at the Royal Institute of Tech-
nology (KTH) in Stockholm in
1998. During 1991–95 he was,
for shorter or longer periods, a
visiting scientist in other labora-
tories in the UK, USA and New
Zealand. His interest in ionic
liquids dates back to the end of
Lars Kloo the 1980s, when he started to use
such media both as electrolytes and for inorganic synthesis of new
organometallic and inorganic compounds and materials.

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Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J
Fig. 1 Schematic structure of a dye-sensitized solar cell.
Up to now, the most efficient DSSCs are based on nanostruc-
tured TiO2 as a semiconductor, ruthenium(II) bipyridyl complexes
as sensitizers, and electrolytes consisting of volatile organic
solvents with an iodide/triiodide redox couple.2
In spite of the promising efficiency and long-term stability
of DSSCs, there are several factors limiting their industrial
application, such as:
• ruthenium(II) dyes are expensive and sensitive to water and
oxygen;
• the use of iodide/triiodide as redox couple limits the perfor-
mance (open-circuit voltage) of the device;
• the use of volatile organic electrolytes makes encapsulation of
DSSCs difficult.
Attractive alternatives to volatile organic solvents are non-
volatile, room-temperature ionic liquids (ILs). Ionic liquids pos-
sess high chemical and thermal stability, relative non-flammability
and wide electrochemical window.3 Ionic liquids are composed
of aromatic or non-aromatic organic cations and various anions
(Fig. 2).
Fig. 2 Examples of the cationic and anionic parts of ionic liquids.
Ionic liquids based on imidazolium salts have been widely used
as solvents for DSSCs. However, the relatively high viscosity of this
type of imidazolium ionic liquids appears to limit their use because
of transport limitations: diffusion coefficients of the redox-couple
components (I3 − ) in ionic liquid electrolytes are about 1–2 orders
of magnitude lower than those in volatile organic solvents. As a
consequence, the efficiency of the reduction of oxidized dye D+ by
the reduced form of the redox couple is limited, especially at high
illumination intensities, thus decreasing the overall performance
of the DSSCs.
In general, ionic liquids were studied in DSSCs first of all as
non-volatile solvents for electrolytes, in contrast to commonly used
organic solvents, such as acetonitrile. An alternative way to solve
2656 | Dalton Trans., 2008, 2655–2666
View Online
the problem of slow diffusion of ions in viscous solvents such
as ILs is to use organic or inorganic hole-conductor materials.
Unfortunately, low hole-conductivity, formation of crystals in the
cell and poor semiconductor-electrolyte interface interaction so
far has limited their use.
It is important to note that in spite of high volatility of organic
solvents such as nitriles, many IL electrolytes are diluted with
organic solvents. The decrease of viscosity is not the only factor.
Thus, it was found8 that a high concentration of imidazolium
iodides leads to effective quenching of the dye molecules (eqn (5)):
D*/TiO2 + 2 I− → D− /TiO2 + I2 − • (5)
−
Moreover, a reduced D does not effectively inject electrons into
the semiconductor. According calculations, approximately 25% of
the ruthenium dye Z907Na undergoes reductive quenching in the
presence of pure 1-propyl-3-methylimidazolium iodide (PMImI).8
In spite of these difficulties, much progress has been achieved
in the synthesis of low-viscosity ILs and their application as
solvents for electrolytes in DSSCs. In this review, we summarize
the recent progress in the application of ionic liquids as solvents
or components of liquid and quasi-solid electrolytes for dye-
sensitized solar cells. The results from literature are also in a
compressed form summarized in Tables 1 and 2, where the former
table is dedicated to results for ILs as pure electrolytes, whereas
the latter contains results from quasi-solid electrolytes based on
ILs.
2. Ionic liquids as solvents for electrolytes
2.1. Electrolytes based on imidazolium ionic liquids
Room-temperature ionic liquids based on imidazolium cations
(Table 1) were realized to be promising solvents, alternative to
volatile organic solvents, such as nitriles, more than ten years
ago.4 Room-temperature molten salt systems based on 1-hexyl-
3-methylimidazolium iodide (HMImI) in combination with the
ruthenium-based dye N-3, Ru(L)2 (SCN)2 (L = 2,2 -bipyridyl-
4,4 -dicarboxylic acid, Fig. 3), have been used to scrutinize the
performance characteristics, the stability and the mass-transfer
effects in DSSCs.4
Fig. 3 Structures of the ruthenium-based N-3 and Z-907 dyes.
Cell performance showed high stability, with an estimated
sensitizer turnover in excess of 50 million. An investigation
has been carried out on the physical–electrochemical properties
of HMImI and its mixtures with organic solvents, such as
acetonitrile, and with other lower viscosity ILs, such as 1-ethyl-
3-methylimidazolium triflate (EMImTf). On the basis of the
measurements of diffusion coefficients of I3 − in pure HMImI,
it was proposed that electron exchange, a Grotthus-type charge
This journal is © The Royal Society of Chemistry 2008
 View Online

carrier mechanism, influences the overall transport with increasing

Ref.

10

18
4
4
5
5

12
13
14
17

20
21
21
6
7
iodine concentration.4 This may be represented as follows:

I3 − + I− → I− –I2 · · · I− → I− · · · I2 –I− → I− + I3 −

Z-907Na
Z-907Na

D-149
N-719
Z-907
Z-907
Z-907

K-19

K-60

K-19
K-19
Later, it was confirmed that triiodide might be transferred to the
Dye

N-3
N-3
N-3
N-3

N-3
counter electrode not only by diffusion, but also by a Grotthus-
like, non-diffusional hopping mechanism.5 The effect of the
Light intensity, mW/cm2

viscosity of IL electrolyte has been investigated on the performance

of DSSCs (Fig. 4). Both the short circuit photocurrent and
conversion efficiency increase with decreasing viscosity of the
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ILs. A conversion efficiency of 2.1% was observed for a cell of

EMImF·2.3HF in combination with the ruthenium-based N-3
dye at 100 mW/cm2 light intensity.5
Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J

100
100
100
100
100
100
100
100
99
100
100
100
100
100
100
100
g, %

0.36

6.67
4.54
6.27
7.05
2.1

7.0
6.6
7.4
7.0
8.0

6.8
2.4
4.8
—
—

0.717
0.727
0.764
0.698
0.699

0.676

Fig. 4 Ionic liquids used in ref. 5.

0.69
0.72
0.56
0.80
0.72

0.41
0.72

0.62
0.71
0.71
FF

Imidazolium iodide ionic liquids have a relatively high viscosity,

V oc , V

0.531

0.746
0.707
0.752
0.736
0.747

0.612
0.538
0.678
0.707

and, as consequence, mass-transport limitation problems restrict

0.57
0.65
0.50

0.64
0.71
0.7

the use of these ILs as solvents for electrolytes. A large progress

was achieved through the use of mixtures of imidazolium iodides
and low-viscosity ionic liquids. Thus, an ionic liquid electrolyte
J sc , mA/cm2

composed of 1-propyl-3-methylimidazolium iodide (PMImI) and

1-ethyl-3-methylimidazolium thiocyanate (EMImSCN) was used
13.54
13.55

9.54

16.13

13.07
13.99
9.5
11.8
5.8
0.9
13.3
12.8
12.8

15.1
9.2

13.6

in combination with the Z-907 dye (Fig. 3).6 The electrolyte

contained a co-adsorbed spacer, 3-phenylpropionic acid, which
increases the photocurrent. Efficiencies of the cells are found to
D(I3 − ), cm2 /s

3.4 × 10−7
4.3 × 10−6
7.6 × 10−7
2.95 × 10−7
4.4 × 10−7
6.3 × 10−7
3.42 × 10−7

3.2 × 10−7

2.48 × 10−7

1.9 × 10−7
3.0 × 10−7

be 7.0 and 7.7% at 1.0 or 0.1 sun illumination, respectively. The

viscosity of EMImSCN is 21 cP and the diffusion coefficient of
triiodide is 2.95 × 10−7 cm2 /s, which is 1.6 times higher than that
—

—
—

in the pure PMImI electrolyte.

Different additives have been used in ionic liquid electrolytes in
0.2 M I2 , 0.5 M NMBI, 0.12 M GuanSCN in PMImI/EMImSCN (65 : 35 v/v)
0.2 M I2 , 0.5 NMBI, 0.1 GuanSCN in AllylEImI/AllylEImTFSI (13 : 7 v/v)

order to enhance photocurrent or photovoltage. The use of organic

0.2 M I2 , 0.14 M GuanSCN, 0.5 M TBP in PMImI/EMImSCN (13 : 7 v/v)

0.2 M I2 , 0.5 NMBI, 0.1 GuanSCN in PMImI/EMImB(CN)4 (13 : 7 v/v)

nitrogen-containing heterocycles, such as tert-butylpyridine61–63

and N-alkylbenzimidazoles,64 results in an improvement of the
0.8 M PMImI, 0.15 M I2 , 0.1 M GuanSCN, 0.5 M NMBI in MPN

open-circuit voltage. It is believed that these compounds, being

0.1 M I2 , 0.1 LiI, 0.45 NMBI in PMImI/EMImDCN (13 : 7 v/v)

Lewis bases, are absorbed onto the surface of the semiconductor.

0.1 M HMImI2 Br, 0.1 M GuanSCN, 0.5 M NMBI in HMImI

0.2 M I2 in PMImI/EMImTFSI/EMImTf (2 : 2 : 1, v/v/v)

As a consequence, the conduction band edge of the semiconductor

is shifted, thus improving the photovoltage. N-Donor additives
may also react with components of the electrolytes. For instance,
I2 , 0.5 M NMBI in PMImI/EMImTCM (1 : 1 v/v)

it was recently found that N-methylbenzimidazole (NMBI) forms

30 mM I2 , 0.9 M DMHImI in EMIm-F·2.3HF

a crystalline product in organic and ionic liquid electrolytes;

30 mM I2 , 0.9 M DMHImI in EMImTFSI

this crystalline material was identified to be (NMBI)6 (NMBI-

Table 1 Liquid electrolytes based on ILs

5 mM I2 , 10% HMImI, 90% EMImTFSI

H+ )2 (I− )(I3 − ).65 Another important additive, controlling the self-

5 mM I2 , 10% HMImI, 90% EMImTf

assembly of the dye molecules, is guanidinium thiocyanate.60

0.2 M I2 , 0.5 M NMBI in PMImI

Guanidinium cations are absorbed together with the dye molecules

thus facilitating the formation of a compact monolayer.
0.5 M I2 , 0.1 CuI in HMImI
Composition of electrolyte

An ionic liquid electrolyte composed of PMImI, 1-ethyl-

3-methylimidazolium dicyanamide (EMImDCN), and lithium
HMImI : I2 (10 : 1)

iodide was combined with an amphiphilic polypyridyl ruthenium-

based sensitizer, Z-907, to obtain a solar cell based on a solvent-
free electrolyte that had an efficiency of 6.6% at 100 mW/
cm2 , and >7.1% at lower light intensities.7 Two electrolytes
were investigated: electrolyte A (0.1 M I2 , 0.45 M NMBI
in PMImI/EMImDCN, 13 : 7 by volume) and electrolyte

This journal is © The Royal Society of Chemistry 2008 Dalton Trans., 2008, 2655–2666 | 2657

B containing lithium iodide (0.1 M I2 , 0.1 LiI, 0.45 M NMBI
in PMImI/EMImDCN, 13 : 7 by volume). Laser transient ab-
sorbance measurements revealed that a significant enhancement of
the device efficiency, after adding LiI to the ionic liquid electrolyte,
could be ascribed to an increase in the electron injection yield and
dye regeneration rate.7 In addition, the diffusion coefficient of
triiodide in electrolytes A and B is found to be 4.4 × 10−7 cm2 /s,
which is 2.3 times higher than that in the pure PMImI electrolyte.
A 7.4% power conversion efficiency at air mass (AM) 1.5
full sunlight was reached with a solar cell employing a binary
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ionic liquid electrolyte composed of PMImI and 1-ethyl-3-
methylimidazolium tricyanomethanide (EMImTCM) in combina-
tion with the amphiphilic ruthenium complex NaRu(4-carboxylic
acid-4 -carboxylate)(4,4 -dinonyl-2,2 -bipyridine)(NCS)2 , coded
Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J
as Z-907Na.8 The viscosity of EMImTCM is 18 cP at 22 ◦ C,
which is much lower than the viscosity of PMImI (880 cP). The
electrolyte, based on PMImI/EMImTCM (1 : 1 by volume) also
contained an organic additive, 1-N-methylbenzimidazole, playing
the role of Lewis base and thus interacts with the TiO2 surface.
The photovoltaic parameters J sc , V oc , FF and g measured at 100
mW/cm2 were found to be 12.8 mA/cm2 , 752 mV, 0.764 and 7.4%,
respectively. Ultramicroelectrode voltammetric, nanosecond laser
transient absorbance, and photovoltaic measurements show that
a high iodide concentration is required for dye regeneration to
compete efficiently with charge recombination.8
Ionic liquids based on the 1-ethyl-3-methylimidazolium cation
were investigated by Dai et al.9 The effect of three different anions,
tricyanomethanide, dicyanamide and thiocyanate (Fig. 5), on the
performance of dye-sensitized solar cells were studied. Both the
short circuit photocurrent and conversion efficiency increased with
decreasing viscosity of the ionic liquids. A conversion efficiency
of 2.1% at 30 mW/cm2 light intensity was observed when the
ruthenium-based dye N-3 was used as sensitizer for the cell
containing the tricyanomethanide IL, which has lowest viscosity
among the three ILs. The efficiencies of 0.7 and 1.7% at the
same light intensity were observed in the case of dicyanamide
and thiocyanate ILs, respectively, as electrolyte.9
Fig. 5 Low-viscosity ionic liquids used as solvents.
A stable dye-sensitized solar cell was obtained using a new
binary IL electrolyte system based on PMImI and 1-ethyl-3-
methylimidazolium tetracyanoborate.10 Photoanodes containing
Z-907(Na) sensitized titanium dioxide were fabricated and DSSCs
resulted in a photovoltaic conversion efficiency of 6.4%, increased
to 7.0% (measured at 100 mW/cm2 light intensity) when 3-
phenylpropionic acid was used as a co-adsorbent/co-sensitizer.10
A highly efficient nanocrystalline DSSCs (8% efficiency at a light
intensity of 99 mW/cm2 ), based on an amphiphilic ruthenium
sensitizer [Ru(4,4 -dicarboxylic acid-2,2 -bipyridine)(4,4 -bis(p-
hexyloxystyryl)-2,2 -bipyridine)(NCS)2 ], coded as K-19 (Fig. 6),11
and a robust electrolyte (PMImI/3-methoxypropionitrile mixture)
2658 | Dalton Trans., 2008, 2655–2666
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Fig. 6 The structure of the K-19 dye.
were reported. Long-term stability tests showed that device
degradation was negligible following 1000 h of visible light soaking
at 60 ◦ C.12
Imidazolium salts containing the interhalogen anions IBr2 −
or I2 Br− have been synthesized and used as components of
IL electrolytes for encapsulated monolithic dye-sensitized solar
cells.13 Indications of an equilibrium between different forms of
XY2 − anions in solution are observed, which may indicate the
presence of different redox-active species in the electrolyte. Overall
light-to-electricity conversion efficiencies up to 6.4%, 5.0% and
2.4% at 100 mW/cm2 were achieved by using electrolytes based
on interhalogen ionic salts and c-butyrolactone, glutaronitrile or
native ionic liquids as solvents, respectively. In terms of stability,
the cell performance lost 9–14% of the initial efficiency after
1000 hours illumination at 35 mW/cm2 .
In order to improve the performance of DSSCs containing
ionic liquid electrolytes, various blocking layers may be used
on the photoanode. Thus, thin Nb2 O5 films act as a potential
blocking layer when deposited between an F-doped tin oxide
layer and a nanocrystalline TiO2 layer, improving V oc and the
conversion efficiency of dye-sensitized TiO2 solar cells with
HMImI electrolytes in combination with the ruthenium-based
sensitizer Z-907.14–16 Using Nb2 O5 films, the efficiency may be
enhanced from 2.8% (no blocking layer) up to 4.8% measured
at 100 mW/cm2 .
In order to improve properties of ionic liquids, the cationic
part may also be modified. Thus, allyl-functionalized imida-
zolium salts, such as 1-allyl-3-ethylimidazolium iodide and 1-
allyl-3-propylimidazolium iodide, have been prepared and used
in electrolytes for DSSCs.17 These salts have melting points close
to room temperature and show properties of supercooled fluids if
heated above their melting points. DSSCs containing electrolytes,
based on allyl-functionalized imidazolium salts, in combination
with the new ruthenium-based sensitizer K-60 (Fig. 7) show an
efficiency up to 6.8% at 100 mW/cm2 as well as good long-term
stability.17
Ionic liquid electrolytes were tested not only in combination
with ruthenium-based dyes, but also together with metal-free
organic sensitizers. Thus, the mixture of three imidazolium-
based ionic liquids, PMImI, EMImTf and EMImTFSI (TFSI =
bis(trifluoromethanesulfonyl)imide), were used in conjunction
with the organic indoline-based dye D-149 (Fig. 8).18 It was found
that the thickness of the nanocrystalline TiO2 film affects the
photovoltaic characteristics due to limitations of the diffusion
of I3 − ions. Viscosities and diffusion coefficients of I3 − in the
acetonitrile electrolyte are 1.4 cP s and 1.63 × 10−5 cm2 /s and
This journal is © The Royal Society of Chemistry 2008

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Fig. 7 The structure of the K-60 dye.
Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J
Fig. 8 The structure of the indoline-based dye D-149.
in the ionic liquid electrolyte the corresponding values are 118 cP
s and 2.48 × 10−7 cm2 /s. Photovoltaic parameters for the IL-based
electrolyte at 100 mW/cm2 are V oc = 612 mV, I sc = 16.13 mA/cm2 ,
FF = 0.676, g = 6.67%.18
Imidazolium ionic liquid electrolytes have also been used
in combination with the organic dyes shown in Fig. 9.19 The
multicolored solar cells were connected in series, and an efficiency
of 2.1% at 1 sun radiation was achieved. The total semiconductor
area was 25 cm2 . The authors note that the length of the alkyl
chain in imidazolium iodides, as well as the concentration of I2 ,
plays a crucial role in this system. BMImI was found to be the best
IL solvent; the optimal molar ratio BMImI : I2 was deduced to be
100 : 2.19
Metal ions present in an IL electrolyte affect the performance
of the DSSC. It was found that the addition of a small amount of
CuI to an HMImI-based electrolyte leads to an enhancement of
efficiency from 3.5% to 4.5%, probably because of adsorption of
Cu+ onto the TiO2 porous film.20
Fig. 9 Organic dyes used in combination with ILs electrolytes.
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View Online
A recent study was performed in order to compare imida-
zolium ILs electrolytes and organic volatile solvents containing
electrolytes.21 Three electrolytes were studied: electrolyte 1 (mix-
ture of PMImI–EMImSCN as solvent, 0.5 M NMBI and 0.12
guanidinium thiocyanate (GuanSCN) as additives, and 0.2 M I2 ),
electrolyte 2 (PMImI as solvent, 0.5 M NMBI as additive, and
0.2 M I2 ), electrolyte 3 (3 : 1 (v/v) mixture of acetonitrile and
valeronitrile, 0.6 M PMImI, 0.5 M 4-tert-butylpyridine (TBP) as
additive, and 0.03 M I2 ). The K-19 dye was used as sensitizer
(Fig. 6). Important general conclusions were made on the basis of
impedance spectroscopy studies: the authors note21 that the main
limiting factors in the IL-based solar cells in comparison to volatile
nitrile-based cells are the higher rate of recombination and lower
rate of injection of charge (probably due to competitive absorption
of light by I3 − , slower dye regeneration, faster self-recombination
of the dye and a shift of the conduction band of TiO2 ).
The use of the ionic liquid crystal, 1-dodecyl-3-
methylimidazolium iodide with iodine as an electrolyte for
dye-sensitized solar cells leads to a high short-circuit photocurrent
density and a high light-to-electricity conversion efficiency. This is
probably caused by a self-assembled structure of the imidazolium
cations, resulting in a high conductivity of the electrolyte.22,23
The authors note that the diffusion coefficient of triiodide D in
C12 MImI/I2 (4.2 × 10−8 cm2 /s) is larger than that of C11 MeImI/I2
(3.2 × 10−8 cm2 /s), whereas the viscosity of C12 MeImI/I2 is
2.5 times larger than that of C11 MeImI/I2 .
2.2. Other types of ionic liquids
Apart from alkylimidazolium ionic liquids, other types of room-
temperature molten salts have been tested as electrolytes. Thus,
trialkylsulfonium ILs of the general formula (R2 R S)I have been
prepared and successfully used as solvents for the electrolytes.24–26
An efficiency up to 3.7% at 0.1 sun was reached with methyldibutyl-
sulfonium iodide (B2 MS)I as electrolyte in combination with the
ruthenium-based dye N-719.24 Electron transport and recombina-
tion in DSSCs based on trialkylsulfonium ILs electrolytes were
investigated.25 It was found that the most viscous IL electrolytes
show a limitation of the photocurrent due to a low diffusion
coefficient of I3 − . The electron lifetime was dependent on the type
of cation in IL.25
Metal-iodide-doped trialkylsulfonium iodides and polyiodides
have also been studied.26 Copper and silver iodides were used
as metal-containing additives. The highest over-all conversion
Dalton Trans., 2008, 2655–2666 | 2659
 View Online

efficiency of 3.1% at 0.1 sun was achieved with a (B2 MS)I–AgI–I2

Ref.

31

36

52
41
42

45

47
49
30
35

37

40
39

43
44

46

50

53
54
56
58
electrolyte.26
Asymmetric phosphonium ionic liquids have been prepared and

N-719

N-719
N-719

N-719
N-719

N-719
Z-907
Z-907
Z-907
K-19

TBA
Dye

N-3

N-3
N-3

N-3
N-3

N-3
N-3
N-3

N-3
N-3

N-3
used as electrolyte components for DSSCs.27,28 Isobutyltrihexyl
phosphonium iodide (IH3 PI) shows the highest ionic conductivity

Light intensity, mW/cm2

at room temperature; the overall performance of solar cells
with the ruthenium-based sensitizer N-3 and PC–AN electrolyte
containing IH3 PI–I2 was found to be 5.9% at 8.9 mW/cm2 light
intensity.28
Tetraalkylammonium iodides (NR2 R 2 )I (R and R varied
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from CH3 to C6 H13 ) have been synthesized and studied as

99.2

51.9
electrolytes for DSSCs.29 Under illumination at 10 mW/cm2

100

100

100
100

100
96

100
100

100
100

100
100
100

100
100

100
100
100
intensity, the highest power conversion efficiency of 2.4% was

2.7–3
obtained with dimethyldihexylammonium iodide (M2 H2 N)I–I2
Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J

g, %

2.61

5.01
3.34

2.93
7.13
5.4
4.4
6.3

0.6
3.1

5.3
6.1
6.1
5.3

4.5

6.7

3.2
3.1
3.8
—
(10 : 1) electrolyte containing TBP as additive, which may
be compared to an efficiency of 5.4% obtained from similar

0.507

0.408
0.712

0.669

0.666
0.709
0.753

0.735
0.62

0.62

0.52
0.55
0.70

0.73

0.67

0.66

0.69
0.70
0.66
FF
cells with 3-methoxypropionitrile based electrolyte tested under

—
identical conditions. The best efficiency obtained with a soft solid

V oc , V

0.706

0.562
0.665
0.730

0.650
0.672
0.603

0.635

0.618
electrolyte, (E2 H2 N)I–I2 (10 : 1) with TBP, was 2.3%.29

0.60

0.63
0.64

0.65

0.57

0.69

0.66
0.66
0.6
—

—
Pyridinium ILs containing the interhalogen anions IBr2 − or
I2 Br− have been prepared and used as solvents or components of

J sc , mA/cm2
electrolytes for DSSCs.13 Glutaronitrile-based electrolytes with the
[BPy]I/[BPy]IBr2 redox couple have shown a 4.5% efficiency at 1

13.43

1.88

9.53
6.80
11.38
11.29

12.75
11.56

6.77
12.7

12.5

12.9

11.8

7.8

20.0
9.1
7.5
8.6
sun illumination.

10

—
D(I3 − ), cm2 /s

8.9 × 10−7
3.59 × 10−7

1.45 × 10−7
2.89 × 10−7
1.9 × 10−7
3.6 × 10−6
1.9 × 10−7

2.2 × 10−6
3. Quasi-solid electrolytes
—

—
—

—
—
—
—

—
—
—
—
—
In spite of great advantages with the use of ionic liquid electrolytes,
it may still be desirable to replace a liquid electrolyte by a solid

CH3 CO2 H, TMOS, 0.5 M PMImI, 0.04 mM NMBI, 20 mM I2 in PC/Triton X-100 (molar ratio 4 : 1)
or gel-like electrolyte. The main motives for such a replacement
Gelator (2 wt%), 0.2 M I2 , 0.12 M GuanSCN, 0.5 M NMBI in PMImI/EMImSCN (65 : 35 v/v)

arise from concerns regarding manufacturing procedures and

long-term stability when a liquid electrolyte is used. A large

3 M TMS-PMImI, 30 M HCOOH, 3 M TMOS, 0.5 M NMBI, 1.4 M PMImI, 0.44 M I2

number of publications during the last decade was devoted to
0.1 M I2 , PVP (1.5 wt%), TBMB (4.5 wt%), PMImI (80 wt%), propionitrile (20 wt%)

the development of new solid or quasi-solid materials which may

be used as electrolytes for DSSCs. Most of these materials are
0.3 M I2 , PVP (2 wt%), HOOC(CH2 )16 COOH (4 wt%), H2 O (5 wt%) in PMImI

based on ionic liquids (Table 2). Three general approaches were

introduced: the use of gelators, the use of inorganic materials
0.3 LiI, 0.5 M I2 , 0.5 M NMBI, 10 wt% of gelators (see text) in HMImI

PVDF-HFP (5 wt%), 0.6 M DMPImI, 0.1 M I2 , 0.5 M NMBI in MPN

0.5 M I2 , 0.45 M NMBI, SiO2 (5 wt%) in PMImI/MPN (v : v = 13 : 7)

for solidification of liquid electrolytes, and polymerization in IL

media. However, one should in these cases formally no longer
I2 (10 wt% of PMImI) in PHB/PMImI ([-O-] : PMImI = 10 : 1)

regard the ionic liquid as an ionic liquid; instead, it is essentially

0.35 M I2 , 0.02 M LiI, 0.5 M TBP, agarose (1 wt%) in PMImI

an electrolyte based on an organic salt dispersed in the polymer

0.3 LiI, 0.03 M I2 , 0.5 M TBP, a-ZrP (6 wt%) in PMImDP

or gel used, which in reality differs little in its function from any
other, inorganic or organic, salt except in terms of solubility and
PEO, KI (20 wt%), I2 (10 wt% of KI) in EMImSCN

I2 /MBPyrrI/succinonitrile (1 : 5 : 100 molar ratio)

co-solvent properties.
0.5 M I2 , 0.45 M NMBI, SiO2 (5 wt%) in PMImI
Table 2 Quasi-solid electrolytes based on ILs

Gel electrolytes consisting of ionic liquids, such as PMImI, and

I2 , TBAI, EMImI, EC : PC (4 : 1 v/v), PEG

different gelators are reported. The gelling agents are composed

40 g/l of gelator, I2 (8.7 wt%) in HMImI

of poly(vinylpyridine) (PVP) and HOOC(CH2 )n COOH (n = 4, 7,

1 M LiI, 0.5 M I2 in PEO(750)MImCl

PEODME, SiO2 (9 wt%), I2 , PMImI

10, 14). Gelation is caused by the reaction between PVP and the
PVDF-HFP (10 wt%), I2 in PMImI

Poly(MHH), 0.2 M I2 in HMImI

dicarboxylic acid.30
Composition of the electrolyte

The resulting gel electrolytes were tested in combination

I2 (10 wt%) in TMS-PMImI

with the ruthenium-based N-3 dye. The efficiency of the ionic

liquid electrolyte before gelation was 5.2%. After gelation, the
efficiency decreased to 3.4% (HOOC(CH2 )12 COOH) and 4.4%
(HOOC(CH2 )16 COOH), respectively. This decrease in perfor-
mance is associated with a decrease in diffusion properties of
the redox-active species: the diffusion coefficient of I3 − in gelated
electrolytes is about 10–20% lower than that in the corresponding
ionic liquid electrolyte before gelation.

2660 | Dalton Trans., 2008, 2655–2666 This journal is © The Royal Society of Chemistry 2008
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Scheme 1 Gelation processes in IL electrolytes.

A similar approach was described in refs. 31–34. PMImI

Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J

was solidified with PVP and 1,2,4,5-tetra(bromomethyl)benzene

(TBMB) according Scheme 1, right. Solar cells containing gel
electrolytes and the N-3 dye were tested. The solidification
was carried out by heating the cells after the gel electrolyte
precursors were inserted into the cell in order to assure sufficient
contact between the gel electrolyte and the nanoporous TiO2 .
An anomalous phenomenon was noted: the performance of gel
electrolytes usually decreases when the amount of gelators is
increased, but when 1,2,4,5-tetra(bromomethyl)benzene provides
the three-dimensional ionomer gel, the photocurrent density
increases from 6 mA/cm2 to 10 mA/cm2 (at 100 mW/cm2 ) when
the amount of the gelator is increased from 1.5% to 4.5%. This
observation was explained by a decrease of interfacial resistance
between the gel and the electrodes.31
An amphiphilic organogelator (Fig. 10) was used in low
concentrations (2%) in order to solidify electrolytes based on
PMImI and EMImSCN ionic liquids.35 The sol–gel transition
temperature was 108 ◦ C. The diffusion coefficient of I3 − in the
IL electrolyte PMImI/EMImSCN and the corresponding gelled
electrolyte was found to be 3.95 × 10−7 cm2 /s and 3.59 ×
10−7 cm2 /s, respectively. DSSCs containing gel electrolytes in
combination with the K-19 dye (Fig. 6) showed an efficiency of
6.3% at full sunlight irradiation. Long-term stability experiments
(light soaking accelerated stress at 60 ◦ C for 1000 h) showed
promising results.35
Fig. 10 Amphiphilic organogelator used in ref. 35.
Polymer electrolytes based on HMImI and crosslinked gelation
agents have been prepared and used for quasi-solid DSSCs.36
The polymer electrolytes contained iodine, NMBI, LiI and two
constituents in HMImI. The first constituent is a polypyridyl-
pendant poly(amidoamine) dendritic derivative (PPDD), shown
in Fig. 11. The second constituent is a multifunctional halogen
derivative, such as 1,4-dibromobutane or PEO with iodine atoms
on the chain ends. It was shown that PPDDs may be used for
solidification of ionic liquid electrolytes by in situ polymerization.
As sensitizer, the ruthenium-based dye N-3 was used. The
efficiencies of the cells were in the interval 2.7–3.0% at
100 mW/cm2 . Gel electrolytes may retain over 90% of the ionic
liquid electrolyte performance.36
Fig. 11 Gelation agents used in ref. 36,
An ionic polymer electrolyte was prepared by in situ thermal
polymerization of (hexa)(oxyethylene)methacrylate dissolved in
HMImI.58 Quasi-solid state DSSCs based on this electrolyte and
the ruthenium dye TBA N-3 were made without any sealing.
The performance of the cells was 3.8% at 1 sun illumination. A
reference organic liquid electrolyte, based on methoxyacetonitrile,
showed 6.5% efficiency. The long-term stability, however, is much
better for the polymer electrolyte: cells, which retained 90% of the
initial efficiency after 80 days at room temperature.58
Poly(ethylene oxide) (PEO) has been used as polymer matrix
for polymer electrolytes.37 Thus, polymers PEO : KI : I2 were
doped with the EMImSCN ionic liquid. Solar cells prepared with
the polymer electrolytes and the ruthenium-based sensitizer N-3
show efficiencies up to 0.6% at 100 mW/cm2 irradiation.37,38
A polymer material based on PEO and imidazolium chloride,
1-oligo(ethylene oxide)-3-methylimidazolium chloride (Fig. 12)
has also been used as a matrix for electrolytes for DSSCs. The
influence of PEO molecular weight and imidazolium group of the
ionic liquid on the different characteristics of the electrolyte (ionic
conductivity, diffusion coefficients of the redox species) as well
as over-all performance of the solar cells were investigated.39 In
combination with the sensitizer N-3, a maximum performance
of 3.1% was reached at 100 mW/cm2 irradiation by using
electrolyte with PEO(750)MImCl. It is important to note that the
polymeric electrolyte based on PEO(750) showed a much lower
efficiency of 1.9% than that of the imidazolium-based electrolyte
PEO(750)MImCl.
Fig. 12 Structure of PEO(X)MImCl.

This journal is © The Royal Society of Chemistry 2008 Dalton Trans., 2008, 2655–2666 | 2661

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Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J
Fig. 13 Quasi-solid electrolytes composed of ionic liquids and a-ZrP in ref. 40.
Quasi-solid electrolytes based on 1-propyl-3-methy-
limidazolium dihydrogenphosphate (PMImDP), iodide-triiodide
ILs and a-zirconium phosphate (a-ZrP) have been described
(Fig. 13).40 In combination with the ruthenium-based sensitizer
N-719, the photoenergy conversion efficiency of the cells
containing 6% a-ZrP increases by a factor of >2 to 2.61%, as
compared to DSSCs without a-ZrP. This difference is explained
by interaction between the additive tert-butylpyridine and a-ZrP
leading to an enhancement of the diffusion coefficient of I3 −
and, as a consequence, photocurrent. The highest diffusion
coefficient of I3 − (2.89 × 10−7 cm2 /s) and photocurrent density
(1.02 mA/cm2 ) are reached at an optimal concentration of a-ZrP
(6%).40
Grätzel et al. reported the preparation of an ionic liquid
polymer gel composed of PMImI and poly(vinylidenefluoride-co-
hexafluoropropylene) (PVDF-HFP).41 It was employed as quasi-
solid-state electrolyte in solar cells in combination with the Z-
907 dye showing an over-all conversion efficiency of 5.3% at
100 mW/cm2 illumination.41 The calculated diffusion coefficient
of I3 − was 1.9 × 10−7 cm2 /s.
Similar electrolytes based on 1-propyl-2,3-dimethylimidazolium
iodide and PVDF-HFP (5 wt%) (Fig. 14) show an overall
conversion efficiency of 6.1% at 100 mW/cm2 illumination in
conjunction with the Z-907 dye.42 The authors note that the I− /I3 −
redox couple can diffuse freely in the liquid domains surrounded by
the three-dimensional network of the PVDF-HFP (the diffusion
coefficient of I3 − was 3.6 × 10−6 cm2 /s). It should be noted that
these DSSCs show very high long-term stability under thermal
stress and light soaking.42
Fig. 14 Composition of the gel electrolyte used in ref. 42.
Imidazolium ionic liquids and fumed silica nanoparticles were
used for the preparation of quasi-solid state electrolytes.43,44 Thus,
gel electrolytes, based on PMImI and SiO2 nanoparticles (12 nm
particle size, 5 wt%) were prepared by sonication of an SiO2 -
2662 | Dalton Trans., 2008, 2655–2666
View Online
PMImI mixture. The calculated diffusion coefficient of I3 − was
1.9 × 10−7 cm2 /s. DSSCs with the Z-907 dye and gel electrolyte
show a light-to-electricity conversion efficiency up to 6.1% at 1
sun irradiation.43
A similar approach to solidify IL electrolytes was published by
Zhao et al.: fumed silica nanoparticles (5 wt%, 10 nm particle size)
were mixed under sonication with the IL electrolyte (PMImI/3-
methoxypropionitrile mixture, 13 : 7 by volume) to produce
a stable quasi-solid state electrolyte.44 DSSCs based on this
electrolyte and the N-3 dye show an overall conversion efficiency
of 5.3% at 100 mW/cm2 illumination.
TiO2 -based, dye-sensitized, quasi-solid-state solar cells
have been constructed by employing a nanocomposite
organic/inorganic gel electrolyte made by the sol–gel method.
The nanocomposite gel is based on the product of solvolysis
of tetramethoxysilane (TMOS), while its organic subphase is a
mixture of a surfactant (Triton X-100), propylene carbonate,
iodine, and PMImI (Fig. 15). Improved results were obtained by
adding NMBI. The dye N-3 was used in combination with the
gel electrolytes. A maximum efficiency of 5.4% was achieved at
96 mW/cm2 illumination.45
Fig. 15 Composition of the organic/inorganic gel electrolyte in ref. 45.
Fumed silica nanoparticles (9 wt%) were used to solidify an
electrolyte based on imidazolium or potassium iodides, iodine
and poly(ethylene oxide dimethyl ether) (PEODME, M w =
500 g/mol).46 Amorphous silica nanoparticles with a surface
area of 255 m2 /g were introduced into the system in order to
create a three-dimensional network. In combination with the N-3
sensitizer an efficiency of 4.5% at 100 mW/cm2 was achieved.
Dye-sensitized solar cells using ionic liquids, 1-alkyl-3-
methylimidazolium iodide (alkyl: C3 –C9 ), were fabricated with and
without a low molecular weight gelator (Fig. 16).47,48
This journal is © The Royal Society of Chemistry 2008
 View Online

fabricated.50 The diffusion coefficient of I3 − was relatively high

(2.2 × 10−6 cm2 /s). An efficiency up to 6.7% at 51.9 mW/cm2
was reported (the ruthenium-based dye N-719 was used); at
full sun irradiation the efficiency decreases to 5%, probably due
to the inefficient charge screening of electron transport in the
nanocrystalline film.50
Fig. 16 Gelator and IL-composed gel electrolyte used in refs. 47 and 48. A new approach to the preparation of quasi-solid DSSCs was
proposed by Kato et al.51 TiO2 nanoparticles were modified with
An energy conversion efficiency of 5.0% was obtained from
imidazolium salts (Fig. 18). The main difference between the
a quasi-solid-state DSSC using HMImI. The gelation of these
previously described gel electrolytes and this system is that the
ILs demonstrated a better high-temperature durability without
Downloaded by University Institute of Chemical Technology (UICT) on 13 September 2012

imidazolium cations are bound to TiO2 nanoparticles via Ti–O–

decreasing the solar cell efficiency. The short-circuit currents (J SC )
CO bonds. The length of the alkyl chains plays an important role
obtained from these DSSCs were about 70% of that obtained
in such gel-like electrolytes. In combination with the N-3 dye, an
from DSSCs using an organic liquid electrolyte. Viscosities of
efficiency up to 5% at 1 sun irradiation was achieved.51
Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J

the IL electrolytes decreased with increasing I3 − concentration

and alkyl chain length. The JSC values measured increased with
increasing I3 − concentration up to 0.7–1.4 M, depending on the
alkyl chain length. The J SC values measured showed the same
tendency as estimates from a model in which the redox couple is
transported by diffusion in the electrolytes. These results suggest
that the slower diffusion of I3 − to the counter electrode limits the
J SC values and that a larger amount of I3 − would be required to
maintain efficiency. However, increasing the concentration of I3 − to
more than 0.7–1.4 M resulted in a decrease in J SC . At the optimized
concentration of I3 − , the influence of the light absorption of I3 − was
estimated to cause 13% of the decrease in photocurrent. In order
Fig. 18 TiO2 nanoparticles modified with imidazolium salts used in
to the estimate the electron diffusion length in the TiO2 electrode,
ref. 51.
the electron diffusion coefficient (D) and electron recombination
lifetime s were determined, showing a faster D and a shorter s in the
IL electrolyte than in an organic electrolyte (OE). The higher D was Ionic gels have also been prepared from agarose (Fig. 19),
caused by the higher concentration of cation in the IL electrolyte. natural polysaccharide, and 1-alkyl-3-methylimidazolium salts.52
However, the lower s was caused by the higher concentration of The gels showed sufficient mechanical strength even though a very
I3 − and showed a dependence on concentration. Thus, the electron small amount of agarose was added (1.0–1.5 wt%). The photon
diffusion lengths (L) in the DSSC using the IL electrolyte were to electron conversion efficiency of the DSSCs containing ionic
shorter than that using the OE. The shorter L also reduced the gel electrolyte was 2.93% at a light intensity of 100 mW/cm2 . The
J SC of the IL electrolyte just as an increase in I3 − concentration. efficiency of the cells with a gel electrolyte is just slightly lower than
In addition, an increase of alkyl chain length increased s. This that of the corresponding liquid electrolyte based on an PMImI
result explains the highest efficiency observed in HMImI. During ionic liquid.52
the durability test of the DSSC at high temperature, a decrease
of the efficiency of the cell using IL electrolyte was observed in
1000 h. The change of I3 − concentration with time revealed that the
gelation of the electrolyte depresses a decrease of I3 − concentration
caused by sublimation of I2 . The authors note that a depression of
the sublimation of I2 is an important factor to improve the high-
temperature durability in non-volatile ionic liquid electrolytes.47,48
Supramolecular electrolytes based on PMImI, I2 and
poly(ethylene glycol) with hydrogen bonding (PHB) (Fig. 17) have Fig. 19 Structure of agarose.
been described.49 Efficiencies up to 3.3% were achieved by using
these electrolytes in combination with a N-719 ruthenium dye.
Quasi-solid electrolytes based on the EMImI ionic liquid and
polyethyleneglycol (PEG) were successfully used in combination
with the ruthenium-based N-3 dye as sensitizer and titanium
phthalocyanine (TiOPc) as co-adsorbent (Fig. 20).53 An impressive
efficiency of 7.13% was achieved (J sc = 20.0 mA/cm2 , V oc = 0.69 V,
FF = 0.52). The DSSC device using TiOPc displays a higher
Fig. 17 Component of supramolecular electrolytes used in ref. 49. power conversion efficiency than those without TiOPc, most likely
because of a decrease in electron transfer distance at the interface
Highly efficient, all-solid-state solar cells, containing elec- adsorption between the TiO2 film and the polymer electrolyte.
trolytes with succinonitrile as solid solvent and N-methyl-N- Trimethoxysilane derivatives of PMImI (TMS-PMImI) have
butyl-pyrrolidinium iodide/triiodide as redox mediator have been been synthesized (Fig. 21).54 Mixed with iodine, it was used

This journal is © The Royal Society of Chemistry 2008 Dalton Trans., 2008, 2655–2666 | 2663

Downloaded by University Institute of Chemical Technology (UICT) on 13 September 2012
Fig. 20 Structure of the titanium phthalocyanine complex used in ref. 53.
Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J
Fig. 21 Trimethoxysilane IL used in the gel electrolyte of ref. 54.
as a gel electrolyte in DSSCs through sol–gel condensation
offering in practice solid-state devices with overall efficiencies
of 3.2%. The specific conductivity of the gel electrolyte was
increased by the addition of iodine and also by an increase
in temperature. Variations to the cell performance were also
examined by the addition of organic and inorganic acids to the
electrolyte.54
Different nanocomposites have been prepared on the basis
of imidazolium ILs. An organic–inorganic material (Fig. 22)
was synthesized by the sol–gel route using TMS-PMImI as
precursor.55,56 Overall light-to-electricity conversion efficiency up
to 3.1% was achieved using this material in combination with the
ruthenium-based dye N-3.
Fig. 22 Nanocomposite used in the refs. 55 and 56.
Plastic and solid-state DSSCs based on carbon nanotubes and
imidazolium ILs were recently fabricated.57 The highest conversion
efficiency recorded was 2.3% under a simulated sunlight intensity
of 23 mW/cm2 .
Nanocomposite gel electrolytes were prepared by dispersion of
different inorganic materials, such as carbon nanotubes, other
carbon nanoparticles or titanium dioxide nanoparticles, into
EMImTFSI.59 In all cases, the performance of the DSSCs based
on such nanocomposite gel electrolytes was higher (up to 5% at
100 mW/cm2 ) than that of cells based on a pure ionic liquid
electrolyte (4.2% at 100 mW/cm2 ), despite lower viscosity of
the latter electrolyte systems. It was shown by impedance
2664 | Dalton Trans., 2008, 2655–2666
View Online
measurements that the resistance of non-doped ionic liquid
electrolytes is higher than that of the ionic nanocomposite gel
electrolytes.59
Concluding remarks and future prospects
The unique properties of ionic liquids embracing negligible volatil-
ity, very high thermo- and electrochemical stability, the ability to
dissolve a wide range of organic and inorganic compounds attract
much attention of research groups working in the dye-sensitized
solar cell field. Ionic liquids may be denoted “tunable” solvents
– their physico-chemical properties can be varied by modification
the anionic and/or cationic components. Relatively low viscosity
and hydrophobicity, desirable for solar cell applications, may
be achieved using this approach. It has been shown that ionic
liquids are not only perfect solvents for liquid electrolytes in
DSSCs, but also irreplaceable components of gel-like or quasi-
solid electrolytes.
When reading the summary of DSSC performance in this
review, a mild warning is at place. More specifically, the absolute
efficiency values given in Tables 1 and 2 should be taken with
some reservation. By optimization of the conditions of efficiency
determination, the values can be increased by at least 1–2%.
Factors, such as solar cell area, quality of glass and type of
conducting glass as well as counter electrodes and light filtering
and masking are all important. Since it is normally not known to
which degree such optimizations have been made, differences of
a few percent in reported efficiencies may be insignificant in the
sense that they do not communicate any information regarding
the inherent properties of the components used or tested.
The long-term instability of DSSCs remains one of the most
important factors limiting their industrialization. In general, one
can see two reasons for long-term instability of DSSCs: (a)
poor encapsulation of the cell leading to the evaporation of
the electrolyte, and (b) chemical processes taking place in the
electrolyte or at the solid/liquid interfaces leading to a degradation
of the dye, components of the electrolyte or surface of the counter
electrode. The use of ionic liquid exclude the first problem, whereas
the nature of undesired chemical processes depends on the specific
total system employed.
Here, we also see the future developments of electrolytes in
general, and ionic liquids in particular, for the use in DSSCs. It
is notable that the DSSCs studied so far essentially as the same
as those optimised for use with a volatile organic solvent as the
base ingredient for the electrolytes. The replacement of the organic
solvent for electrolytes based on ionic liquids might be regarded
as an ad hoc modification. Very little effort has been devoted to
the optimisation of the electrode materials or sensitizing dye to
this new class of electrolytes. Therefore, the initial studies that
constitute the major part of this review are mainly devoted to
the fundamental properties of ionic liquids; a first generation of
investigations.
The future, later generation studies, will have to address the
specific interactions between the ionic-liquid electrolytes and the
working as well as counter electrodes. Such investigations are likely
to not only include additives or dopants to the electrolytes, but also
a search for completely new and adapted dyes, redox agents as well
as electrode materials in order to fully exploit the potentials of the
ionic liquid electrolytes and their derivatives.
This journal is © The Royal Society of Chemistry 2008
 View Online

List of acronyms 11 P. Wang, C. Klein, R. Humphry-Baker, S. M. Zakeeruddin and M.

Grätzel, J. Am. Chem. Soc., 2005, 127, 808.
12 P. Wang, C. Klein, R. Humphry-Baker, S. M. Zakeeruddin and M.
Grätzel, Appl. Phys. Lett., 2005, 86, 123508/1.
13 M. Gorlov, H. Pettersson, A. Hagfeldt and L. Kloo, Inorg. Chem., 2007,
DSSC Dye-sensitized solar cell 46, 3566.
IL Ionic liquid 14 J. Xia, N. Masaki, K. Jiang, Y. Wada and S. Yanagida, Chem. Lett.,
PMImI 1-Propyl-3-methylimidazolium iodide 2006, 35, 252.
BMImI 1-Butyl-3-methylimidazolium iodide 15 J. Xia, N. Masaki, K. Jiang and S. Yanagida, J. Photochem. Photobiol.,
HMImI 1-Hexyl-3-methylimidazolium iodide A, 2007, 188, 120.
EMImTf 1-Ethyl-3-methylimidazolium triflate 16 J. Xia, N. Masaki, K. Jiang and S. Yanagida, J. Phys. Chem. C, 2007,
EMImSCN 1-Ethyl-3-methylimidazolium thiocyanate 111, 8092.
17 Z. Fei, D. Kuang, D. Zhao, C. Klein, W. H. Ang, S. M. Zakeeruddin,
Downloaded by University Institute of Chemical Technology (UICT) on 13 September 2012

EMImDCN 1-Ethyl-3-methylimidazolium dicyanamide

EMImTCM 1-Ethyl-3-methylimidazolium tricyanomethanide M. Grätzel and P. J. Dyson, Inorg. Chem., 2006, 45, 10407.
EMImTFSI 1-Ethyl-3-methylimidazolium 18 S. Ito, S. M. Zakeeruddin, R. Humphry-Baker, P. Liska, R. Charvet, P.
bis(trifluoromethanesulfonyl)imide Comte, M. K. Nazeeruddin, P. Pechy, M. Takata, H. Miura, S. Uchida
C12 MImI 1-Dodecyl-3-methylimidazolium iodide and M. Grätzel, Adv. Mater., 2006, 18, 1202 .
Published on 18 March 2008 on http://pubs.rsc.org | doi:10.1039/B716419J

BPy n-Butylpyridinium 19 H. Otaka, M. Kira, K. Yano, S. Ito, H. Mitekura, T. Kawata and F.

DMHImI 1,2-Dimethyl-3-hexylimidazolium iodide Matsui, J. Photochem. Photobiol., A, 2004, 164, 67.
EMImB(CN)4 1-Ethyl-3-methylimidazolium tetracyanoborate 20 L. Chen, B. Xue, X. Liu, K. Li, Y. Luo, Q. Meng, R. Wang and L.
PMImDP 1-Propyl-3-methylimidazolium Chen, Chin. Phys. Lett., 2007, 24, 555.
dihydrogenphosphate 21 F. Fabregat-Santiago, J. Bisquert, E. Palomares, L. Otero, D. Kuang,
MBPyrrI N-methyl-N-butylpyrrolidinium iodide S. M. Zakeeruddin and M. Grätzel, J. Phys. Chem. C, 2007, 111, 6550.
GuanSCN Guanidinium thiocyanate 22 N. Yamanaka, R. Kawano, W. Kubo, T. Kitamura, Y. Wada, M.
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