SCIENCE CHINA

Chemistry
• ARTICLES • October 2013 Vol.56 No.10: 1463–1469
doi: 10.1007/s11426-013-4904-y

Ionic liquid crystal-based electrolyte with enhanced charge

transport for dye-sensitized solar cells
PAN Xu, WANG Meng, FANG XiaQing, ZHANG ChangNeng, HUO ZhiPeng
& DAI SongYuan*
Key Laboratory of Novel Thin Film Solar Cells, Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031, China

Received January 18, 2013; accepted March 21, 2013; published online July 8, 2013

A room temperature ionic liquid crystal, 1-dodecyl-3-ethylimidazolium iodide (C12EImI), and an ionic liquid, 1-decyl-3-
ethylimidazolium iodide (C10EImI), have been synthesized, characterized and employed as the electrolyte for dye-sensitized
solar cells (DSSC). The physicochemical properties show that a smectic A (SmA) phase with a lamellar structure is formed in
C12EImI. Both C12EImI and C10EImI have good electrochemical and thermal stability facilitating their use in DSSC. The
steady-state voltammograms reveal that the diffusion coefficient of I3– in C12EImI is larger than that in C10EImI, which is at-
tributed to the existence of the SmA phase in C12EImI. Because the iodide species are located between the layers of imidazo-
lium cations in C12EImI, exchange reaction-based diffusion is increased with a consequent increase in, the overall diffusion.
The electrochemical impedance spectrum reveals that charge recombination at the dyed TiO2/electrolyte interface of a
C12EImI-based DSSC is reduced due to the increase in I3– diffusion, resulting in higher open-circuit voltage. Moreover, both
short-circuit current density and fill factor of the C12EImI based DSSC increase, as a result of the increasing transport of I3– in
C12EImI. Consequently, the photoelectric conversion efficiency of C12EImI-based DSSC is higher than that of the
C10EImI–based DSSC.

ionic liquid crystal, dye-sensitized solar cells, electrolyte, smectic A phase, exchange reaction

1 Introduction flammability, high ionic conductivity and wide electro-

chemical window [5]. However, compared with organic
solvent-based electrolytes, the large viscosity of ionic liq-
Dye-sensitized solar cells (DSSC) [1, 2], as a promising
uids drastically retards the physical diffusion of iodide spe-
inexpensive alternative to conventional inorganic photovol-
cies, resulting in the lower light-to-electricity conversion
taic devices, are currently attractive to both academic and
efficiency of DSSC [6, 7]. Thus, numerous efforts have
commercial interests. Impressive photoelectric conversion
been made to improve photovoltaic performance of DSSC
efficiency of higher than 12% has been obtained for DSSC
with ionic liquid-based electrolytes, such as exploring new
with organic solvent-based electrolytes [3]. However, the
kind of ionic liquids with low viscosity [8] or changing the
presence of liquid electrolytes in DSSC may result in some
structure of the ionic liquids [9].
practical limitations due to leakage [4]. In an effort to de-
It is widely accepted that the charge transport in ionic
velop stable electrolyte systems, ionic liquids have been
liquid-based electrolytes is different from that in the con-
screened as solvents due to their unique properties such as
ventional organic solvent-based electrolytes. Generally, the
chemical and thermal stability, negligible vapor pressure, no
diffusion of I3– in ionic liquid-based electrolytes is larger
than that would be expected on the basis of recorded viscos-
ity data and calculated Einstein–Stokes ratios [10]. A mech-
*Corresponding author (email: sydai@ipp.ac.cn)

© Science China Press and Springer-Verlag Berlin Heidelberg 2013 chem.scichina.com www.springerlink.com
1464 Pan X, et al.
anism has already been proposed as the reason for this en-
hanced I3– transport. It assumes that the I3– transport is cre-
ated by a combination of an ordinary diffusion process and
a Grotthuss-type charge-transfer mechanism due to the ex-
istence of high ionic strength [11–14]. This mechanism can
be described by the Dahms–Ruff equation [15, 16]:
kBT
Dapp  Dphys  Dex   kex 2 c '/ 6
6 r
where c’ is the total concentration of iodide species. From
equation (1), the diffusion of I3– in ionic liquids can be en-
hanced by increasing Dex in addition to lowing the viscosity
of the ionic liquids.
Recently, Yamanaka et al. have developed a new type of
electrolyte based on ionic liquid crystals (ionic liquids with
a smectic A phase), with the aim of improving the charge
transport of the I3–/I– redox couple [17, 18]. They have
found that 1-dodecyl-3-methylimidazolium iodide (C12MImI)
has a self-assembled bilayer structure owing to interdigitat-
ed alkyl chains of the imidazolium cations, resulting in the
formation of an imidazolium-type ionic liquid crystal. They
also proved that C12MImI with a smectic A phase can con-
tribute to the exchange reaction. As a result, the transport of
the I–/I3– redox couple in C12MImI was improved. This pro-
vides a way to improve the Grotthuss-type diffusion. How-
ever, the phase transition temperature from crystalline to
SmA and the viscosity of C12MImI are both relatively high,
which limits its application in DSSC. Thus, we have at-
tempted to make some modifications to the imidazolium
ring to lower both the phase transition temperature and the
viscosity, with the aiming of improving the photovoltaic
performance of DSSC.
In this paper, an ionic liquid crystal, 1-dodecyl-3-
ethylimidazolium iodide (C12EImI), and an ionic liquid
(C10EImI), 1-decyl-3-ethylimidazolium iodide (Figure 1)
were synthesized and characterized. The charge transport
mechanism of I–/I3– in C12EImI and C10EImI were studied,
as well as their application in DSSC.
2 Experimental section
2.1 Materials
All the reagents were purchased from Acros and used as
received.
Figure 1 Molecular structures of C12EImI and C10EImI.
Sci China Chem October (2013) Vol.56 No.10
2.2 Synthesis of C12EImI and C10EImI
C12EImI and C10EImI were synthesized by quaternization of
1-ethylimidazole (Acros, 98%) with 1-iodododecane
(C12H25I, Acros, 98%) and 1-iododecane (C10H25I, Acros,
98%). Taking C12EImI as an example: an equimolar mixture
of 1-ethylimidazole and 1-iodododecane was placed into a
58 mL Teflon lined, stainless steel autoclave and heated at
(1)
100 C for 12 h. The crude product was washed with diethyl
ether and then the resulting liquid was dried at 60 C under
vacuum for 12 h to remove any volatile solvents. Finally, a
pale yellow liquid was obtained with a yield of 78.6 %.
Identification was carried out by 1H-NMR in d6-acetone
(see Supporting Information).
2.3 DSSC assembly
The preparation of the DSSC was similar to previous re-
ports [19, 20]. The TiO2 film was 10 μm thick, and a 2-μm-
thick light scattering layer was used. The films were im-
mersed overnight in anhydrous ethanol solution with
5.0 × 10–4 M N719 dye. The total active electrode area of the
DSSC was 0.25 cm2.
2.4 Measurements
The thermal behavior of imidazolium salts was investigated
by differential scanning calorimetry (DSC) (Thermal Anal-
ysis DSC821) with a heating rate of 10 °C min–1 over a
temperature ranging from –50 to 100 °C under a nitrogen
flow rate of about 50 mL min–1 as protective gas. Thermo-
gravimetric analysis (TGA) was performed using a TG 209
F3 Tarsus. About 5–10 mg of the sample was kept in the
TG pan and heated at a heating rate of 10 °C min–1 from
20 °C to 500 °C in nitrogen gas.
Polarized optical microscope (POM) analyses were car-
ried out with a microscope equipped with crossed polarizers.
Images were recorded at a magnification of 100× as movies
with a digital camera at 293 K.
Electrochemical window measurements were carried out
by using an electrochemical workstation (CHI660A, CH
Instruments, Inc., USA). The working electrode was a
1-mm-radius Pt disk (CHI 102) and the auxiliary electrode
was a platinum wire. An Ag wire was used as a pseu-
do-reference electrode. The scan rate was 10 mV s–1. The
electrolyte was prepared by dissolving 0.1 M C12EImI (or
C10EImI) in 3-methoxylpropionitrile. Here C12EImI (or
C10EImI) is used as both supporting electrolyte and redox
species.
The diffusion coefficient (D) of I3– was calculated ac-
cording to the steady-state current in cyclic voltammetry
measurements with an electrochemical workstation
(CHI660A, CH Instruments, Inc., USA). In CV measure-
ments, the working electrode was a 5.0-μm-radius Pt disk
ultra-microelectrode (CHI107), and the auxiliary electrode