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ScienceDirect
Solar Energy 107 (2014) 692699
www.elsevier.com/locate/solener

Eect of iodine intercalation in nanosized layered double

hydroxides for the preparation of quasi-solid electrolyte
in DSSC devices
Maria Bastianini a,b, Riccardo Vivani a, Morena Nocchetti a,, Daniele Costenaro b,
Chiara Bisio b,c,, Frederic Oswald d, Toby B. Meyer d, Leonardo Marchese b
b

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-

M. Bastianini et al. / Solar Energy 107 (2014) 692699

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

In the present work, a nanosized LDH, in nitrate form,

was intercalated with growing amounts of iodine, adapting
a previously published procedure (Bastianini et al., 2012),
and the resulting materials were used as additives for the
preparation of quasi-solid electrolytes, which were tested
in DSSC devices. A positive eect of the high concentration
of entrapped iodine on the DSSC performances was
observed.
2. Experimental
2.1. Materials preparation
2.1.1. Synthesis of nanosized LDH
Nanosized LDH containing nitrate anions in the interlayer region (hereafter named n-LDH-NO3) was synthesized by adapting the urea method already reported in
the literature (Costantino et al., 1998). 500 mL of 1 M solution of Zn(II) and Al(III) having molar fraction Al(III)/
Al(III) + Zn(II) equal to 0.30 was prepared dissolving
104 g (350 mmol) of Zn(NO3)26H2O and 56 g of
Al(NO3)39H2O (150 mmol) in a mixture of water and ethylene glycol 1:2 (v/v). 36 g (600 mmol) of solid urea were
then added to reach a urea/Al molar ratio of 4. The clear
solution was heated, under stirring, at reux temperature
for 6 h. The obtained gelatinous material was recovered
by centrifugation and washed twice with deionized water.
Finally, the material was stored as colloidal dispersion in
300 mL of water and ethylene glycol 1:2 (v/v). In order
to determine the solid amount per volume unit, a known
volume of dispersion was washed twice with de-ionized
water to remove the ethylene glycol and weighed after drying in an oven at 80 C. The dispersion contained 72 mg of
n-LDH per mL. 7 mL of the dispersion of n-LDH in nitrate
form (0.5 g of n-LDH-NO3) was washed two times with
deionized water and equilibrated with 50 mL of CO2-free
aqueous solution containing 1.3 g of KI (7.8 mmol) and
0.86 g (3.4 mmol) of I2. The suspension was kept under
magnetic stirring for 1 day under nitrogen atmosphere.
The arising material (hereafter named n-LDH-I2) was
washed two times with deionized water and dried over in
an oven at 40 C. Nanosized LDH containing iodide (nLDH-I) and the I2/I couple (n-LDH-I2/I) have been prepared according to methods reported elsewhere (Bastianini
et al., 2012).
2.1.2. Cell assembly
A 12 lm thick lm TiO2 particles (Ti-Nanoxide T/SP,
Solaronix) was screen-printed on a uorine-doped SnO2conducting glass electrode (7 X/cm2, TCO22-7, Solaronix)
and used as photoelectrode. After sintering at 773 K,
TiO2 electrodes were dye-coated by immersing them into
a 0.5 mM solution of cis-diisothiocyanato-bis[2,20 -bipyridyl-4,40 dicarboxylato] ruthenium[II] bis[tetrabutylammonium] dye (N719, Ruthenizer 535-bisTBA, Solaronix) and
5.0 mM of chenodeoxycholic acid (Solaronix) in methanol
(CH3OH 99.8% Aldrich 67-56-1, M.W. = 32.042) at room

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M. Bastianini et al. / Solar Energy 107 (2014) 692699

temperature for 16 h. Counter electrodes were prepared by

applying a drop of H2PtCl6 (Platisol T, Solaronix) on a
uorine-doped tin oxide glass, followed by sintering at
748 K for 15 min. The electrodes were separated by a
60 lm-thick hot melt polymer (Meltonix 1170-60PF,
Solaronix) and sealed up by heating. Reference cells were
prepared by introducing 3-methoxypropionitrile-based
electrolyte (Iodolyte Z-50, Solaronix) through the hole
drilled on the counter electrode with the help of a vacuum-chamber. The cell was then sealed with a hot melt
polymer sheet and a thin glass cover by heating. The eect
of addition of n-LDH to the liquid electrolytes was tested
by preparing cells (ve cells for each sample) using quasisolid electrolytes prepared as indicated below.
The DSSC devices were submitted to accelerated aging
test for 1200 h in a solar simulator with a light intensity
of 100 mW/cm2 (full sun, AM 1.5 G) at 333 K and ambient
relative humidity, following the ISOS-L-2 protocol (Reese
et al., 2011).
Before exposition all devices were secondary sealed with
epoxy glue and covered with a UV cut-o lter (up to
400 nm).
The DSSC devices were submitted to accelerated aging
test for 1200 h in a solar simulator with a light intensity
of 100 mW/cm2 (full sun, AM 1.5 G) at 333 K. Before
exposition all devices were secondary sealed with epoxy
glue and covered with a UV cut-o lter (up to 400 nm).

apparatus, in air ow and heating rate of 10 C/min. This

technique allowed also the determination of iodide and triiodide content.
Diuse reectance UVVis (DR UVVis) spectra were
recorded using a Perkin Elmer Lambda 900 spectrometer.
The spectrophotometer is equipped with an integrating
sphere accessory and using a hand-made quartz cell. Before
the analysis, the samples were dispersed in anhydrous
BaSO4 (10 wt%).
The morphology of the LDH particles was investigated
using a 1525 FEG LEO Field Emission Gun Scanning
Electron Microscope (FE-SEM) after depositing the samples on a stub and after coating with chromium.
Particle size analysis was performed by photocorrelation
spectroscopy with a ZETASIZER NANO ZS (MALVERN INSTRUMENTS). Before the analysis the samples
were dispersed (5 wt%) in 3-methoxypropionitrile solvent
and stirred for 16 h at room temperature.
Photocurrent densityvoltage curves characterization
was carried out at 1.5 AM illumination using a Keithley
2400 source measure unit. A SolarSim-150, Solaronix
served as light source and its intensity was adjusted with
a Si reference (IXYS XOB 17-04x3) for 1 sunlight intensity
of 100 mW/cm2.
The accelerated aging tests were carried out in a light
soaker (Sunirad A-65, Solaronix) with a light intensity of
100 mW/cm2 (AM 1.5 G) 24 h/day at 333 K.

2.1.3. Preparation of quasi-solid electrolytes

Quasi-solid electrolytes were prepared by dispersing
5 wt% of n-LDH samples in 3-methoxypropionitrile electrolyte (Iodolyte Z-50, Solaronix) and stirred for 16 h at
room temperature. After this time, the dispersions were
injected in the DSSC test cell through the hole drilled on
the counter electrode with the help of a vacuum-chamber.
The cell was then sealed with a hot melt polymer sheet
and a thin glass cover by heating.

3. Results and discussion

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

LDH in nitrate form having nanometric dimensions

(n-LDH-NO3) was used as starting material for the intercalation of increasing amount of iodine and used to produce quasi-solid electrolyte based DSSC. The approach
to obtain n-LDH-NO3 was adapted from a procedure
for the preparation of nanometric LDH in chloride form
(n-LDH-Cl) in a single step (Bastianini et al., 2012). More
specically, n-LDH-NO3 was successfully obtained from
solutions of zinc nitrate and aluminum nitrate and using
a mixture of water and ethylene glycol as reaction solvent, urea/Al(III) molar ratio of 4 and time of reaction
of 6 h.
The content of Zn, Al, nitrate and hydration water of
the n-LDH-NO3 sample, obtained by elemental analysis,
ion chromatography and thermogravimetry, respectively,
allowed assessing that the solid has the following formula
[Zn0.74Al0.26(OH)2](NO3)0.260.5H2O. The XRPD pattern
of the sample (Fig. 1a) shows an interlayer distance of
, thus conrming the presence of nitrate ions in the
8.92 A
interlayer region. The morphology of LDH particles was
analyzed by FE-SEM (Fig. 2). n-LDH-NO3 sample is constituted by hexagonal platelets of diameter of about 200 nm
arranged to form aggregates in which face-to-face and
edge-to-edge connections are mainly present.
In a previous paper it was reported that the intercalation
of triiodide, or more generally polyiodides, into LDH-Cl
via ion-exchange failed, very likely the low charge density

M. Bastianini et al. / Solar Energy 107 (2014) 692699

695

Table 1
Composition of the n-LDH containing increasing amount of iodine.
Sample

n-LDH-I
n-LDH-I2/I
n-LDH-I2

Fig. 1. XRPD pattern of (a) n-LDH-NO3 and (b) n-LDH-I2 samples.

of the guest species and the small interlayer distance of the

) made the process thermodynamically unfahost (7.85 A
vorable. On the other hand, in the present paper the intercalation of polyiodide was successfully attained starting
from n-LDH in nitrate form. The nitrate anions, having
lower anity for the matrix and determining a larger gal ) than chloride anions (Reichle, 1986),
lery height (8.92 A
allowed direct triiodide and higher polyiodides ionexchange. For the sake of simplicity, the global iodine content of this sample will be considered in the following as I2.
In particular, n-LDH-I2 pure phase was obtained equilibrating n-LDH-NO3 with a CO2-free aqueous solution
containing iodine and an excess of potassium iodide. The
recovered solid was dark brown and exhibit a characteristic
metallic luster typical of polyiodide species. The XRD diffraction pattern of n-LDH-I2, reported in Fig. 1b, shows
, due to the fact that the
only the 006 reection at 4.22 A
electron density of 003 metal hydroxide planes is close to
that of the 006 interlayer planes and the former diraction
eect is virtually extinct as already observed (Bastianini
et al., 2012).
The peak at 28.3 2 theta can be tentatively assigned to
the 121 reection of very low amount of crystalline orthorhombic iodine (PDF# 043-0304) present on the surface.

[Zn0.74Al0.26(OH)2](A)0.26x(I)x(I2)yzH2O
A

I2/I molar ratio (%)

Cl
Cl
NO3

0.18
0.18
0.26

0
0.11
0.40

0.43
0.57
0

0
61
154

In order to have samples with increasing iodine content,

n-LDH containing iodide (n-LDH-I) and the couple I2/I (nLDH-I2/I) were prepared as previously described
(Bastianini et al., 2012).
The compositions of all the samples were determined by
thermogravimetric analysis and ion chromatography
(Table 1). In the n-LDH-I2 sample the percentage of intercalated iodine referring to the iodide (I2/I molar ratio)
reaches the very high value of 154% indicating that the

iodine is also presents as higher polyiodides (i.e. I
5 , I7 ,
etc.).
DR-UVVis reectance spectra of intercalated samples
are reported in Fig. 3.
The spectrum of n-LDH-I sample shows a band centered at ca. 250 nm, assigned to I species (Fig. 3 curve
a). The DR-UVVis spectra of n-LDH-I/I2 and n-LDHI2 samples (Fig. 3, curves b and c) show two intense bands
at about 290 nm and 380 nm, corresponding respectively to
the spin- and symmetry-allowed r ! r and p ! r transitions of the linear I
3 species (Svensson and Kloo, 2003).
Moreover an absorption at 250 nm due to I species is also
detected in both n-LDH-I/I2 and n-LDH-I2 samples. The
additional broad absorption in the 5001000 nm range in
the spectrum of the n-LDH-I2 sample can be assigned to
pentaiodide ions. Polyiodide species are also present in
the n-LDH-I/I2 sample: the DR-UVVis spectrum shows,
in fact, a broad tail at high wavelength.
The ability of n-LDH to form colloidal dispersions into
methoxyproprionitrile (MPN) was evaluated through
photocorrelation spectroscopy (dynamic light scattering,
DLS). Dispersions of n-LDH samples at 5 wt% in MPN
solvent were stirred for 16 h and analyzed: Fig. 4 shows
the particle dimensions of the suspensions measured over
time when the stirring is stopped.

Fig. 2. Typical FE-SEM micrographs of n-LDH-NO3 sample at dierent magnications.

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M. Bastianini et al. / Solar Energy 107 (2014) 692699

12

Kubelka-Munk Function [a.u.]

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

Cell potential [V]

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-).

Dispersion of n-LDH-I and n-LDH-I2/I samples in

MPN is characterized by the presence of large aggregates
of ca. 44.5 lm, that are not stable over time. Indeed,
DLS analysis indicates that in the rst hour the larger
aggregates are deposited on the bottom of the cuvette
and only particles having dimensions less than 500 nm
remain in the suspension. The n-LDH-I2 sample shows
smaller aggregates (ca. 1.2 lm) with respect to the other
samples, probably due to the lipophilic character derived
from the presence of high amount of iodine that allows a
more ecient dispersion in the lipophilic MPN.
The photocurrentvoltage (JV) curves obtained from
the electrical characterization of DSSC devices prepared
with n-LDH dispersions based electrolyte are reported in
Fig. 5. They are compared with results obtained on a reference cell prepared with a standard Z-50 electrolyte (without
n-LDH addition).

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.

M. Bastianini et al. / Solar Energy 107 (2014) 692699

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

The open circuit voltage (Voc) increases signicantly

when n-LDH-I and n-LDH-I2/I solids are added to Z-50
electrolyte, nevertheless the photocurrent (Jsc) for these
devices stays low leading to a poor conversion eciency,
about half of reference cell. The cell prepared by using nLDH-I2 as additive shows a reduced Jsc with respect to the
reference, whereas both Voc and ll factor (FF) are slightly
higher than the device assembled with pure Z-50 electrolyte.
The theoretical Voc value in DSSC is determined by the
dierence between the Fermi energy of the TiO2 electrode
and the redox potential of triiodide/iodide in the electrolyte. It was also shown that the basicity of hydrotalcite
modies the surface potential of TiO2 and, as a consequence, the entire conduction band of the TiO2 lm shifts
with the surface potential and enhances the Voc of devices
with nanoclay gel electrolytes (Wang et al., 2013b). The
phenomenon was also observed in a study of the eect of
the addition of 4-tert-butylpyridine (TBP) in a liquid electrolyte, which has often been reported to act as a base in
DSSC (Boschloo et al., 2006). As for the clay, it was

proposed that this material acts as a buering layer, thus

preventing the electrolyte from being too acidic. The results
indicated that the buering eect is more pronounced for nLDH-I and n-LDH-I2/I samples, probably because they
deposited on the photoanode more than the n-LDH-I2
sample (see also DLS particle size analysis).
It is thus inferred that increasing I2/I molar ratio of the
n-LDH samples dispersed in the electrolyte, increases conversion eciency (from 54.5% relative eciency of n-LDHI to ca. 95% of n-LDH-I2, respectively). However, other
measurements are needed to investigate the real eect of
these solids when added to the electrolyte, such as the diffusion coecient of I
3 species and the redox behavior of

the I
/I
couple.
3
The time evolution of normalized photovoltaic parameters are reported in Fig. 6: the comparison between the reference cell and the DSSC devices containing the dispersion
of n-LDH-I2 sample is especially enlighten.
Data collecting during the light soaking accelerated test
indicated that photoconversion eciency of the cells with
120
2

Normalized Jsc [mA/cm ]

Normalized Voc [V]

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

Normalized Efficiency [%]

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).

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M. Bastianini et al. / Solar Energy 107 (2014) 692699

the pure electrolyte decreases of ca. 8.20% after 1200 h of

exposition (Fig. 6AD). A similar trend was observed with
device assembled with suspension of n-LDH-I2 samples: it
is relevant that the addition of n-LDH-I2 sample to the
electrolyte is not detrimental to the overall cell stability.
This is an interesting result with technological implications of industrial relevance in that today several companies are using liquid electrolytes for the preparation of
DSSC modules, and this entails a number of technological
problems, as for instance the lling of the devices by injection or by vacuum systems, that slow the manufacture. The
use of additives to avoid this problem was largely reported
in the literature for laboratory scale test cells, nevertheless
some examples on the possible upscaling of this approach
for the preparation of DSSC modules were already proposed (Hinsch et al., 2008; Kalyanasundaram, 2010). Our
work demonstrates that it is possible to nd suitable materials to prepare a quasi-solid electrolyte with similar performances (in terms of overall eciency and stability of
devices) of the reference liquid electrolyte, and this is
relevant for the potential applications in DSSC industrial
production process, especially because screen-printing
techniques can be employed for the module preparation.
4. Conclusions
Three samples of nanometric LDH containing increasing amount of iodine have been prepared. The intercalation
process of iodine described in a previous paper has been
improved, and led to materials containing I, I
3 and polyiodide species. The result has been achieved starting from a
LDH in nitrate form and performing the ion exchange in
aqueous solutions.
The introduction of n-LDH particles in the Z-50 electrolyte does not lead to a signicant increase of device conversion eciency with respect to the reference cell, and
samples containing a low amount of iodine are not suitable
for the preparation of devices with high conversion eciency. Nevertheless, a high concentration of intercalated
iodine has a benecial eect on the DSSC performances,
and in the case of sample n-LDH-I2 the device appears similar to that of DSSC devices prepared with pure reference
Z-50 electrolyte. A step forward the preparation of gel electrolytes is therefore made, though more work is needed to
optimize the electrolyte composition for better performances of DSSC devices.
Acknowledgements
The nancial supports of the FP7 European research
Projects INNOVASOL, Innovative Materials for
Future Generation Excitonic Solar Cells and GLOBASOL Global solar spectrum harvesting through highly
ecient photovoltaic and thermoelectric integrated cells
are gratefully acknowledged.

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