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Solar Energy 107 (2014) 692699
www.elsevier.com/locate/solener
a
Dipartimento di Chimica, Universita` di Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy
Dipartimento di Scienze e Innovazione Tecnologica and Centro Interdisciplinare Nano-SiSTeMI, Universita` del Piemonte Orientale A. Avogadro, via
T. Michel 11, 15121 Alessandria, Italy
c
ISTM-CRN Istituto di Scienze e Tecnologie Molecolari, via G. Venezian 21, Milano, Italy
d
Solaronix SA, Rue de lOuriette 129, CH-1170 Aubonne VD, Switzerland
Received 23 December 2013; received in revised form 29 May 2014; accepted 11 June 2014
Available online 9 July 2014
Communicated by: Associate Editor Frank Nuesch
Abstract
A nanosized layered double hydroxide (n-LDH) was intercalated with growing amount of iodine and the resulting materials used as
additives for the preparation of quasi-solid electrolytes for dye-sensitized solar cells (DSSC). The inuence of the amount of iodine on
solar cell performances was tested by dispersing 5 wt% of intercalated LDH in a methoxypropionitrile-based liquid electrolyte and using
the obtained dispersion for DSSC assembly. The electrochemical characterization of the devices showed that the addition of increasing
amount of iodine intercalated LDH has a positive eect on solar cell photoenergy conversion. In addition, time stability of devices
prepared with non-liquid electrolyte were taken into consideration.
2014 Elsevier Ltd. All rights reserved.
Keywords: Dye-sensitized solar cells; Quasi-solid electrolyte; Layered double hydroxide; Nanoparticles; Iodine
1. Introduction
Dye-sensitized solar cells (DSSCs) are currently attracting widespread scientic and technological interest as a
high-eciency and low-cost alternative to conventional
inorganic photovoltaic devices (ORegan and Gratzel,
1991). The classical components of the DSSC are: (i) a
Corresponding authors. Tel.: +39 0755855562; fax: +39 075585566
(M. Nocchetti). Tel.: +39 0131360262; fax: +39 0131360250 (C. Bisio).
E-mail addresses: morena.nocchetti@unipg.it (M. Nocchetti), chiara.
bisio@mfn.unipmn.it (C. Bisio).
http://dx.doi.org/10.1016/j.solener.2014.06.014
0038-092X/ 2014 Elsevier Ltd. All rights reserved.
TiO2 nanocrystalline lm deposited on a SnO2:F transparent conductive glass as the working electrode; (ii) a ruthenium bipyridyl derivative adsorbed and chemically
anchored on TiO2 nanocrystals; (iii) an electrolyte (nor
mally based on the I
3 /I redox couple); and (iv) a platinized SnO2:F glass as the counter electrode (Nazeeruddin
et al., 1993). Above 11.3% energy conversion eciency
has been achieved in DSSC with an organic liquid based
electrolyte containing I/I
3 as the redox couple (Gao
et al., 2008).
Unfortunately, the liquid electrolyte normally used for
the preparation of DSSC devices shows several technolog-
ical problems such as solvent evaporation, leakage of volatile solvent and environmental toxicity. Many eorts have
been made to solve these problems by using plasticized
polymers, where small amounts of liquids are added to
polymer/salt complexes, and gel electrolytes, where electrolyte solutions are incorporated into a polymer matrix
(Kang et al., 2005; Nogueira et al., 2001; Suzuki et al.,
2004; Stergiopoulos et al., 2002).
Relevant eorts have been made for the preparation of
gel (or quasi-solid) ionic electrolytes by using silica nanoparticles (Wang et al., 2003), or silica with structural porosity (Yang et al., 2006), carbon nanoparticles and nanotubes
(Usui et al., 2004), TiO2 nanoparticles (Usui et al., 2004)
and layered materials as additives (Park et al., 2008; Tsui
et al., 2011; Costenaro et al., 2013).
Among layered compounds, layered double hydroxides
(LDHs) are promising materials in a wide range of applications because of their easy manipulation to obtain functional materials. As a matter of fact, in the last two
decades there has been a rapid growth in the number of scientic papers and industrial patents on LDH.
LDHs are represented by the general formula [M(II)1x
M(III)x(OH)2][Ax/n mH2O], where M(III) cations are typically
Al, Cr, Fe, Ga and M(II) can be Mg, Zn, Ni, Co, Cu. A is
an exchangeable anion of ionic valence n, and x is the
M(III) molar fraction. The x value generally ranges from
0.2 to 0.4 and determines the positive layer charge density
and the ion exchange capacity (IEC) of the material
(Triro` et al., 1991; Rives, 2001; Jones and Newman,
1998; Leroux and Taviot-Gueho, 2005; Oh et al., 2009).
The insertion, via ion exchange reactions, of selected inorganic or organic anions allows the preparation of materials
for applications in the eld of polymeric nanocomposites
(Costantino et al., 2009a, 2009b, 2011; Aloisi et al., 2010;
Leroux et al., 2012; Swanson et al., 2013; Merchan et al.,
2013), heterogeneous catalysis (Vaccari, 1999; Turco
et al., 2004; Montanari et al., 2010; Silva et al., 2009;
Busca et al., 2010), photo-chemistry (Latterini et al.,
2007; Costantino et al., 2013), photocatalysis (Gunjakar
et al., 2011; Gomes Silva et al., 2009) and decontamination
purposes (Aimoz et al., 2012). Moreover, several strategies
have been proposed to exfoliate LDHs in two-dimensional
nanosheets in order to obtain ordered thin lms (Ma et al.,
2006; Gardner et al., 2001; Woo et al., 2011; Yan et al.,
2011) especially for optical devices (Bendall et al., 2010;
Yan et al., 2011). Recently, a composite material based
on LDH nanoparticles and a mixture of conductive polymers (i.e. poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) or PEDOT:PSS) was used as electrically and
optically active buer layer in organic photovoltaic solar
cells. The authors demonstrated around 10% improvement
in power conversion eciency (Bolognesi et al., 2013). Few
works report on the use of LDHs to obtain quasi solid electrolytes to improve DSSC eciency (Wang et al., 2013a,
2013b): LDHs in nitrate, carbonate and sulfate form are
capable of solidifying the electrolyte against leakage and
increase the solar cell eciency.
693
694
2.2. Instrumentation
The Zn and Al content of the solid was obtained by
Inductively Coupled Plasma-Optical Emission Spectrometer (ICP-OES) Varian 700-ES series after dissolving the
samples in HNO3.
Iodide content was obtained by ion-chromatography
(IC): complete I and I
3 deintercalation was achieved by
equilibrating 100 mg of sample in 20 mL of 1 M Na2CO3
solution for 12 h. The supernatant solution was then analyzed with a Dionex 2000 ion chromatographer.
X-ray powder diraction (XRPD) patterns were collected with a Philips XPERT PRO MPD diractometer
operating at 40 kV and 40 mA, step size 0.0170 2Theta
degree and step scan 20 s, using the Cu Ka radiation and
an XCelerator detector.
Water and nitrate content of the solids was obtained by
coupled thermogravimetric (TGA) and dierential thermal
(DTA) analyses performed with a Netzsch STA 449C
695
Table 1
Composition of the n-LDH containing increasing amount of iodine.
Sample
n-LDH-I
n-LDH-I2/I
n-LDH-I2
[Zn0.74Al0.26(OH)2](A)0.26x(I)x(I2)yzH2O
A
Cl
Cl
NO3
0.18
0.18
0.26
0
0.11
0.40
0.43
0.57
0
0
61
154
696
0.1
a
Photocurrent [mA/cm 2 ]
10
b
c
200
400
600
800
1000
1200
1400
Wavelength [nm]
5000
Dimension [nm]
4000
3000
2000
1000
0
100
200
c
b
0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Fig. 3. DR-UVVis spectra of n-LDH-I (a), n-LDH-I2/I (b) and n-LDHI2 (c) samples.
d
8
300
400
Time [min]
Fig. 4. Particle sizes of the n-LDH samples dispersed in 3-methoxypropionitrile measured at increasing time after having stopped the stirring of
the dispersion. n-LDH-I (curve -j-), n-LDH-I2/I (curve -o-) and n-LDHI2 (curve -4-).
Fig. 5. JV curves of the DSSC devices prepared with dierent electrolytes: Z-50 reference electrolyte (curve a), quasi-solid electrolytes prepared
by adding to Z-50 5 wt% of n-LDH-I (curve b), n-LDH-I2/I (curve c) and
n-LDH-I2 samples (curve d).
The open circuit voltage (Voc), short circuit photocurrent density (Jsc), ll factor (FF), photoenergy conversion
eciency (g) and relative photoenergy conversion eciency
(Rel. g) of prepared devices are reported in Table 2.
The introduction of n-LDH-I and n-LDH-I2/I solids in
the Z-50 electrolyte leads to a decrease of photoenergy conversion eciency compared with reference electrolyte.
Indeed, the eciency for the reference cell is 5.32%, while
for the devices containing n-LDH-I, n-LDH-I2/I and nLDH-I2 samples are 2.90%, 3.43%, and 5.05%, respectively.
The addition of hydrotalcite samples containing dierent anionic species led to a signicant modication of Jsc
parameter. Indeed, passing from n-LDH-I to n-LDH-I2
sample, the Jsc value progressively increases from 5.56 to
9.57 mA/cm2 (Table 2). It is known that photocurrent
strongly depends on the speed of charge transport in the
electrolyte and, especially in quasi-solid electrolytes, is
based on physical diusion (Wang et al., 2013b). Previous
literature works on DSSC cells based on hydrotalcite solids
exchanged with dierent anions suggested that the channels
of the hydrotalcite network are responsible for the diusion
process and that a strong repulsion between the anions and
the redox couple may inuence the charge transport properties. It was thus reported that the diusion coecient of
triiodide ion shows strong dependence on the type of intercalated anion (Wang et al., 2013a). It was also shown that
nitrate ion, which has a slightly higher ion anity than
iodide, did not aect the photocurrent collection that
remained similar to that of the liquid electrolyte. Our data
indicated that the Jsc values progressively increased with
the concentration of triiodide species in the interlayer
region, and became similar to that produced in the case
of reference cell prepared by using the liquid electrolyte
alone. This suggests that an high amount of triiodide species favors the injection process and the diusion process
of the redox couple toward the TiO2 photoanode.
697
Table 2
Characteristic of DSSC devices prepared by using standard Z-50 electrolyte and adding to the Z-50 electrolyte n-LDH samples dispersed in 5 wt%. The
relative eciency (Rel. g (%)) is calculated by dividing the conversion of each cell prepared by using n-LDH samples by the eciency of the reference cell.
Sample
Jsc (mA/cm2)
Sd
Voc (V)
Sd
FF
Sd
g (%)
Sd
Rel. g (%)
Z-50
n-LDH-I
n-LDH-I2/I
n-LDH-I2
11.30
5.56
6.58
9.57
0.07
0.29
0.18
0.09
0.732
0.844
0.827
0.764
0.003
0.008
0.004
0.001
0.64
0.62
0.63
0.69
0.01
0.03
0.00
0.00
5.32
2.90
3.43
5.05
0.02
0.06
0.06
0.05
100.00
54.51
64.53
94.83
120
100
80
60
40
20
Z-50
n-LDH-I2
100
80
60
40
20
Z-50
n-LDH-I2
200
400
600
800
1000
1200
200
B
400
800
1000
1200
Time [h]
Time [h]
120
100
80
60
40
20
Z-50
n-LDH-I2
0
0
200
C
400
600
Time [h]
800
1000
1200
120
Normalized FF
600
100
80
60
40
20
Z-50
n-LDH-I2
0
0
200
400
600
800
1000
1200
Time [h]
Fig. 6. Temporal evolution of photovoltaic parameters (Voc, Jsc, FF and g) of DSSC with Z-50 and electrolytes added with n-LDH-I2 samples on solar
soaking at (60 C, AM 1.5 full sunlight).
698
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