Electrochimica Acta 151 (2015) 306311

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

From seaweeds to biopolymeric electrolytes for third generation solar

cells: An intriguing approach
Federico Bella a,b, *, Nadhratun N. Mobarak c , Fatihah N. Jumaah c , Azizan Ahmad c
a
Center for Space Human Robotics @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129 Torino, Italy
b
Department of Applied Science and Technology - DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Torino, Italy
c
School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul
Ehsan, Malaysia

A R T I C L E I N F O A B S T R A C T

Article history: Renewable energy systems represent a milestone of third millennium applied scientic research. As a
Received 8 August 2014 viable, economic and environmentally friendly alternative to the solid electrolytes currently used in dye-
Received in revised form 7 November 2014 sensitized solar cells (DSSCs), here we propose a biopolymer derived from seaweeds, which undergoes a
Accepted 10 November 2014
process of selective carboxylation to improve its transport properties. Subsequently, a chemometric
Available online 11 November 2014
approach is used to tune the amount of salts and additives, and the highest ever measured ionic
conductivity for a biopolymeric solid electrolyte has been reached (5.53
102 S cm1). To make this
Keywords:
material suitable for DSSC application, an innovative sublimation process has been developed to allow a
Dye-sensitized solar cell
Polymer electrolyte
molecule-by-molecule activation of the electrolyte, and an efciency of 2.06% (stable in aging tests) was
Iodine measured in a rst device prototype. Green chemistry, low cost materials, multivariate-based
Green preparation methods and activation via spontaneous sublimation make this investigation a concrete
Carrageenan starting point for the new generation of solid electrolytes for DSSCs.
2014 Elsevier Ltd. All rights reserved.

1. Introduction the low durability of the photovoltaic performance, mainly due to

Nowadays the overall increase in energy consumption and the
continuously growing energy demand have paved the way to huge
interest towards new types of energy supply [1]. Renewable
energies are gradually facing the industrial and pre-industrial
scale-up; among all, solar energy seems to be one of the most
promising, as well as convertible into electricity by means of
electronic devices based on different technologies [2,3]. Even
though the photovoltaic (PV) market is currently dominated by
silicon technology, which provides high sunlight conversion
efciency, the use of expensive raw materials and highly energy
consuming process technologies are relevant drawbacks. Con-
versely, the dye-sensitized solar cell (DSSC) is emerging as a
leading alternative solar harvester [4], being a low-cost device and
suitable for large area production [5,6]. At present, the highest
photovoltaic conversion efciency is 13.0% [7].
In view of technological renement and device scale-up, a
thorough investigation of the commonly used liquid electrolyte
(i.e., a I/I3-based acetonitrile solution) is necessary. In particular,
* Corresponding author. Tel.: +39 0110903448.
E-mail address: federico.bella@polito.it (F. Bella).
the evaporation and leakage of the organic solvent, must be
avoided. In order to solve this awkward problem, many research
groups proposed the use of ionic liquids [8], nanoparticles [9],
gelling agents [10], p-type semiconductors [11] and polymer gels
[12] and membranes [13,14], as reported in our recent review
article [15]. In particular, polymeric materials are those on which
the scientic community is intensively focusing its efforts [16,17].
In addition to signicant efciency and durability, another
aspect to be considered when proposing a new non-liquid
electrolyte concerns the cost and environmental impact of the
selected materials [18,19]. This topic is often neglected in the
literature: for example, the recently published 15% efciency for a
perovskite solar cells was obtained in the presence of a perovskite
synthesized from very toxic and expensive lead salts, and required
the use of a carcinogenic solvent (g-butyrolactone) [20]. It is
intuitive to think that this is not a realistic approach for a
technology that must be cheap and environmentally friendly. In
contrast, the use of easily accessible natural source materials could
provide a better strategy. In this regard, cellulose, its derivatives
and other biomatrices have recently been successfully used for the
preparation of quasi-solid electrolytes for DSSCs [2124].
In this communication, we propose k-carrageenan (kC), a linear
sulfated polysaccharide extracted from seaweeds, as a new matrix

http://dx.doi.org/10.1016/j.electacta.2014.11.058
0013-4686/ 2014 Elsevier Ltd. All rights reserved.
 F. Bella et al. / Electrochimica Acta 151 (2015) 306311
for the preparation of completely solid electrolytes for DSSCs. Well
known as catalytic reagent for sugar hydrolysis [25], HPV infection
inhibitor [26] and used in the preparation of hydrogels for drug-
delivery [27] and superabsorbent materials [28], to the best of our
knowledge kC has never been used in the eld of solar energy
harvesting. We performed a specic chemical modication to
increase kC ionic conductivity, followed by the optimization of its
performance by means of an innovative chemometric approach.
The activation of the electrolyte was carried out by an indigenous
process of iodine sublimation. After having identied the optimal
conditions for its preparation, the solid electrolyte was successfully
tested in DSSC devices, and an efciency equal to 2.06% (stable in
aging tests) was achieved.
2. Experimental
2.1. Materials
k-carrageenan was commercially obtained from Takara Corpo-
ration Sdn. Bhd. (Sabah, Malaysia). Eucheuma cottonii seaweeds are
typically found below the low tide mark to the upper subtidal zone
of a reef, growing on sand to rocky seaoor areas along a coral reef,
where water movement is slow to moderate. The molecular weight
of kC was 1.41
106 Da [29], which is a particularly good value (in
terms of mechanical and electrical properties) for biopolymers in
DSSCs [30].
Sodium hydroxide, isopropanol, monochloroacetic acid, sodi-
um iodide and iodine were supplied by Sigma-Aldrich. All
materials were used without further purication.
Conducting glass plates (FTO glass, Fluorine doped Tin Oxide
over-layer, sheet resistance 7 V/sq, purchased from Solaronix)
were cut into 2  2 cm2 sheets and used as a substrate for the
deposition of a TiO2 porous lm from a paste (DSL 18NR-AO,
Dyesol) and for the fabrication of platinized counter-electrodes.
Sensitizing dye cis-diisothiocyanato-bis(2,20 -bipyridyl-4,40 -dicar-
boxylato) ruthenium(II) bis(tetrabutylammonium) (N719, Ruth-
enizer 535 bis-TBA) was purchased from Solaronix.
2.2. Preparation of carboxymethyl-k-carrageenan (CkC)
CkC was prepared using kC as precursor. kC, sodium hydroxide,
isopropanol and water were mixed together and alkalized at 50  C
for 1 h. Monochloroacetic acid was dissolved in isopropanol in the
ask and added to the reaction mixture. It was left to stir for 4 h at
50  C and then terminated by adding alcohol. The solid was ltered
and rinsed with ethanol and vacuum dried at room temperature.
2.3. Preparation of CkC membranes
CkC solutions were prepared by dissolving CkC in a 1 vol%
aqueous acetic acid solution. After complete dissolution, the
solutions were cast in Petri dishes and left to form a membrane. In
case that the addition of NaI and EC was required, they were
introduced before the casting, and the system was stirred at room
temperature for a further hour. The transparent membranes were
obtained after drying at RT for 72 h. Then, they were transferred
into a desiccator for drying.
2.4. Characterization of CkC membranes
Attentuated total reectance - Fourier transform infrared
spectroscopy (ATR-FTIR) analysis was carried out using Perkin
Elmer Spectrum 2000 in the range of 4000 to 400 cm1 with
scanning resolution of 4 cm1. This analysis was conducted to
307
observe changes of functional groups before and after modication
[31].
13
C nuclear magnetic resonance (NMR) analyses were per-
formed in order to conrm the structure of k-carrageenan
derivatives using Bruker Avance III 600 MHz, where kC and CkC
were dissolved in the solvent D2O.
Elemental analysis was carried out using FlashEA 1112 Elemen-
tal Analyzer, in order to determine the element content and the
degrees of substitution in k-carrageenan derivatives.
The alternating current (AC) electrochemical impedance
spectroscopy (EIS) measurement was carried out using a high
frequency response analyzer (HFRA, Solartron 1260) and an
electrochemical interface (SI 1286) in the frequency range of
1 Hz10 MHz with 10 mV amplitude. The polymer electrolyte was
sandwiched between the stainless steel ion-blocking electrodes
with a surface contact area of 2.0 cm2. The bulk resistance (Rb) was
determined from the equivalent circuit analysis by using the Zview
analyzer software. The conductivity values (s ) were calculated by
1
the equation s t
R1
b
A , where t is the lm thickness (cm) and
A is the active area of the electrode (cm2). The EIS analysis were
performed at room temperature.
The morphologies of the polymer electrolytes were examined
by a Scanning Electron Microscope (SEM) Philip XL 30 model.
2.5. DSSC fabrication and characterization
As regards the preparation of photoanodes, FTO covered glasses
were rinsed with acetone and ethanol in an ultrasonic bath for
10 min. A TiO2 paste layer with a circular shape was deposited on
FTO by doctor-blade technique and dried at 100  C for 10 min on a
hot plate. Then, a sintering process at 520  C for 30 min allowed the
formation of a nanoporous TiO2 lm with a mean thickness of
8 mm, measured by prolometry (P.10 KLA-Tencor Proler). Finally,
photoelectrodes were soaked into a 0.4 mM N719 dye solution in
ethanol for 12 h at room temperature, and then rinsed in ethanol to
remove the unadsorbed dye.
Counter electrode FTO glasses were cleaned with the same
rinsing method described above and a 5 nm Pt thin lm was
deposited by thermal evaporation.
A solid state DSSC was assembled by positioning the polymer
electrolyte membrane onto the sensitized photoanode. Then, the
two electrodes were clipped together and a cyanoacrylate glue was
used as a sealant. This sandwich-type cell was pressed with two
binder clips for few seconds, which were then removed when the
glue took hold.
The active area of the cell was 0.78 cm2 and the photovoltaic
measurements were performed with a 0.22 cm2 rigid black mask.
Photocurrent-photovoltage (I-V) electrical characterizations under
AM1.5 illumination (100 mW cm2) were carried out using a class A
solar simulator (91195 A, Newport) and a Keithley 2440 source
measure unit. The experimental results reported in this manuscript
are the average of three replicates.
3. Results and discussion
Our experimental work consisted of a few steps, starting from
the raw material, kC, extracted from Eucheuma cottonii seaweeds
by a low cost industrial process operated by Takara Corporation
Sdn. Bhd. (Sabah, Malaysia). Since in our previous fundamental
studies we found that oxygen atoms of kC backbone can form
coordinated bonds with cations (i.e., the counterions of the I/I3
redox mediator: Na+) [32], in this work we expected that the
introduction of oxygen-containing substituent groups in the kC
chain would have provided more sites for cations to coordinate,
thus increasing the ionic conductivity with respect to the raw
material. Accordingly to Suns reaction [33], we converted kC into
308 F. Bella et al. / Electrochimica Acta 151 (2015) 306311

CkC: the process consisted of the deprotonation of the hydroxyl
groups of kC by a strong base (NaOH), followed by the reaction
between kC alkoxides and monochloroacetic acid. Character-
izations useful to demonstrate the successful completion of the
process, namely elemental analysis (Table A1), 13C NMR (Fig. A1)
and ATR-FTIR (Fig A2), are reported in Appendix A.
kC and CkC 75 mm-thick membranes were prepared by casting
technique. Positive conrmation that the chemical modication on
kC, by increasing the amount of oxygen, had affected the electrical
properties was obtained by means of ionic conductivity measure-
ments (see EIS spectra in Fig. A3): the conductivity of CkC
(3.40
105 S cm1) was about two orders of magnitude greater
than that of kC (5.34
107 S cm1). Here, it is necessary to specify
that, even though a salt was not yet added to kC, the conductivity
value could be measured. This can be explained considering that
kC can be categorized as anionic polyelectrolyte, since it has -SO3
groups in its chemical structure. Performing the chemical
modication on kC, the resulting substitution of -OH groups with
-COO groups increased the anionic character of the polymeric
backbone, besides increasing the number of active sites which led
to the increase of ionic conductivity.
Although the chemical modication of kC led to a signicant
increase in the ionic conductivity, it was still necessary to add the
iodine-based redox mediator so that the CkC-based biopolymeric
membranes could act as solid electrolytes for DSSCs. In a rst
attempt, we added sodium iodide (NaI) and iodine (I2) during the
casting process, but the iodine sublimated in the fume hood during
the samples drying, thus making the membrane useless for our
purposes. For this reason, we decided to separately introduce NaI
and I2.
As regards NaI introduction, it is well known that the salts
concentration affects the ionic conductivity of the electrolyte and
the photovoltaic performance of the device [34,35]. Moreover, the
addition of salts is often accompanied by that of plasticizers (i.e.,
ethylene carbonate, EC): by interacting with the polymer chains
at a molecular level, reducing the crosslinking density and
lowering the glass-transition temperature of the polymeric
network, plasticizers increase the mobility of the redox mediator
in the polymer matrix [36]. Furthermore, it has been demon-
strated that plasticizers promote salt dissociation and favor cell
stability by increasing salt solubility (as a consequence, more dye
cations are regenerated by I ions) [37]. With the aim of
indentifying the optimal amounts of NaI and EC to be introduced
by the casting process, we investigated a large experimental
domain (NaI 1545 wt%, EC 1530 wt%) adopting a chemometric
approach. We planned a D-optimal design of experiment (DoE),
which is a powerful mathematical multivariate analysis method
useful to optimize functional materials, simultaneously deter-
mining variables as others are modied [17]. While most of the
research in DSSCs consists of monovariate analysis, even when
this procedure leads to error due to interactions between the
variables, the DoE approach (recently introduced by us in this
eld, [38]) simultaneously studies different variables to obtain an
empirical mathematical equation for the built model, as well as a
response map that considers the inuence of parameters [39].
For the D-optimal DoE, 8 experiments were performed: the two
variables (NaI, EC) were codied in three levels, and three central
point replicates were used to evaluate the experimental reproduc-
ibility. The complete design matrix is summarized in Table 1,
together with the experimental response (ionic conductivity, s ).
Experiments were carried out in random order to provide
protection against the effects of lurking variables, and results
were analyzed using the software MODDE (version 7.0.0.1,
Umetrics). The DoE was evaluated through analysis of variance
(ANOVA, see Figs. A45), and the calculated regression coefcient
R2 = 0.94 emphasized the high signicance of the chemometric
model. The set of experiments allowed to achieve a maximum ionic
conductivity of 5.53
102 S cm1 (at room temperature) with a
CkC-based biopolymeric electrolyte membrane containing 45 wt%
NaI and 30 wt% EC, as showed in the tted response surface
reported in Fig. 1. Larger amounts of salt and plasticizer were
investigated, but it was not possible to obtain self-standing and
homogeneous membranes; conversely, the proposed membranes
showed a very good distribution of all their components (see SEM
image in Fig. A6). To the best of our knowledge, we can state that
the value of ionic conductivity measured is the highest ever
obtained in the eld of green polymer electrolytes, to the point to
be truly comparable to that of the intrinsically conductive
polymers [40,41].
The last step of the preparation procedure of the biopolymeric
electrolyte membranes was the introduction of iodine. Here we
propose a rapid and easy way for the introduction of this
component, exploiting its best known feature: sublimation. As
far as this process may seem simple and obvious, it is even more
surprising to note that it has never been exploited in this eld.
Therefore, CkC-based membranes (already containing NaI and EC)
were placed in a simple sublimation chamber with some grains of
I2, whose gas-solid phase transition occurred at room temperature,
as reported in Fig. 2. It is relevant to point out that once sublimated
within the membranes, iodine did not come out, but it remained
effectively trapped in the biopolymeric network. The ability of I2 to

Table 1
Experimental matrix of variables (NaI, EC) and corresponding experimental
response (ionic conductivity, s ) for the D-optimal DoE. s values after sublimation
process (s subl) are also reported. Short circuit current density (Jsc), open circuit
voltage (Voc), ll factor (FF) and efciency (h) values of the corresponding DSSCs are
listed.

NaI EC s s subl Jsc Voc FF h

(wt%) (wt%) (S cm1) (S cm1) (mA cm2) (V) (%)
15 15 4.99
104 9.83
105 4.00 0.52 0.52 1.09
45 15 2.75
102 1.65
103 6.70 0.51 0.53 1.82
30 15 5.10
103 1.21
103 5.20 0.52 0.53 1.42
15 30 5.08
104 4.88
104 5.10 0.52 0.52 1.39
45 30 5.53
102 3.25
103 7.60 0.51 0.53 2.06
30 30 1.92
102 1.42
103 6.80 0.52 0.53 1.87
30 30 1.90
102 1.51
103 6.82 0.51 0.53 1.84
30 30 1.97
102 1.40
103 6.77 0.52 0.53 1.80 Fig. 1. Response surface showing the effect of NaI and EC weight concentration on
the ionic conductivity of CkC-based biopolymeric electrolyte membranes.
 F. Bella et al. / Electrochimica Acta 151 (2015) 306311
permeate a three-dimensional polymeric structure is very
interesting, and was used by Shenoy et al. to prepare conductive
polyurethane foams used in electrostatic imaging and biological
sensors [42]. It was therefore easily conceivable that I2 interacted
with the components already present in the membranes. In
particular, two types of interaction were identied.
The rst was the weak interaction IO between iodine and
oxygen atoms of the carboxylic units of the biopolymeric
framework: this interaction, reected on the shift of the FTIR
peak at 1604 cm1 (related to the asymmetric vibration of
carboxylate anions,COO) towards higher frequencies (Fig. A7),
was previously detected also by Zhdankin et al. for other purposes,
and investigated by means of single-crystal X-ray diffraction (XRD)
and NMR analysis [43]. This conrms that iodine tends to strongly
Fig. 2. From seaweeds to CkC-based biopolymeric electrolyte membranes:
preparation procedure.
309
Fig. 3. Photocurrent-photovoltage curve for the best DSSC fabricated with CkC-
based biopolymeric electrolyte membrane. Inset: normalized light-to-electricity
conversion efciency of the device versus conservation time under 60  C in dark
conditions.
adsorb on polymeric matrices, and the type of interaction depends
on the selected material. For example, Ramelow et al. showed that,
on poly(ethylene glycol dimethacrylate), the dopant attack
occurred on the CH2CH2 bond rather than on the -CH3 bond
[44].
On the other hand, the second interaction that was observed is
well known in the eld of DSSCs, and it is related to the reaction
between I2 and NaI:
I2 I $I
3 (1)
whose chemistry was thoroughly investigated and modeled by
Boschloo and Hagfeldt [45]. This reaction leads to a decrease of I
charge carriers concentration, simultaneously with the formation
of I3 ions. Taking into account that the heavier I3 ions have a
lower mobility than I ones [46,47], a conrmation that the
reaction between NaI and I2 occurred was obtained from ionic
conductivity measurements after sublimation. As it can be seen
from Table 1, all values of ionic conductivity of the CkC-based
membranes decreased of about one order of magnitude after I2
sublimation. Anyway, if compared to those reported in the
literature [48], these conductivity values can ensure the well-
functioning of DSSCs assembled with the proposed solid polymer
electrolytes, for which - in absence of solvents - the effective
charge transport can be rationalized by a Grotthuss-type electron
exchange mechanism (polyiodide bond exchange mechanism)
[49].
Part of the experimental work focused on the optimization of
sublimation conditions, and this will be the subject of a
forthcoming paper. It can be anticipated that the amount of salts
and plasticizers introduced in the membranes greatly affects the
quantity of iodine that can be trapped in the membranes: this is
also evident at the bottom of Fig. 2, observing the different color
intensities assumed by membranes containing various amounts of
NaI and EC. Within the experimental range considered in this work,
it was calculated - by gravimetric methods - a 11:1 molar ratio
between NaI and I2, which is roughly in line with that traditionally
adopted in DSSC electrolytes [45]. However, further and rened
spectroscopic investigations are necessary (and in progress) to
study the I2-concentration/DSSC-performance relationship adopt-
ing different sublimation conditions.
Truly solid DSSCs were sealed by placing each soft biopolymeric
electrolyte membrane between a N719-sensitized photoanode and
310 F. Bella et al. / Electrochimica Acta 151 (2015) 306311
a Pt-cathode. Under 1 sun of simulated irradiaton, the overall light-
to-electricity conversion efciency (h), ll factor (FF), open-circuit
voltage (Voc) and short-circuit current density (Jsc) values were
obtained through the current-voltage characteristics of the solar
cells. The values of these photovoltaic parameters are listed in
Table 1. As can be noted, Voc and FF values were almost constant
over the considered experimental domain, while large differences
were found in Jsc, which varied between 4.00 and 7.60 mA cm2.
This variation was certainly related to the different ionic
conductivities measured for CkC-based biopolymeric electrolyte
membranes, in their turn dependent on the amount of EC and NaI
amounts used for their preparation. Overall, the best cell showed a
2.06% sunlight conversion efciency, in the presence of 45 wt% NaI
and 30 wt% EC; its photocurrent versus photovoltage characteristic
is reported in Fig. 3. In order to perform a preliminary stability test,
this solid DSSC was kept at 60  C for 250 h and checked every 30 h.
As can be noted in the inset of Fig. 3, after 250 h the cell showed a
reduction of its initial photo-conversion efciency of only 6%.
This interesting result showed that there was no loss of iodine from
the solid electrolyte, even under thermal stress.
4. Conclusions
In conclusion, we have presented an innovative preparation
strategy for producing performant solid polymer electrolytes having
seaweeds in their roots. Through a chemical modication carried out
in aqueous solvent, the conductivity of CkC-based biopolymeric
electrolyte membranes reached 5.53
102 S cm1, which currently is
the highest value ever measured for a biopolymeric electrolyte. The
activation of the membranes was performed in two steps. In the rst
one, the introduction of iodide and plasticizer was tuned by means of
a multivariate chemometric approach. The second step, namely the
introduction of iodine, was conducted by means of a simple, cheap
and never experienced before sublimation process at ambient
temperature and pressure. The rst prototype of solid DSSC
assembled with the membrane which showed the highest conduc-
tivity value provided an efciency of 2.06%, stable in aging tests
carried out under thermal stress.
These present ndings pave the way to an intense and relevant
research on these green materials, which - as shown - have great
potential for application in electronic devices. In addition, they are
proposed as a viable alternative to the currently leading
perovskites-based solid electrolytes in DSSCs, produced with
highly expensive and heavily toxic (and sometimes carcinogenic)
precursors. Applied energy must pass through these routes of
exploitation of widely available biomaterials, converting them into
functional materials for the production of electricity by simple
processes [50,51].
Acknowledgements
F.B. sincerely thanks Dr. Cinzia Citti (Universit del Salento) for
proofreading.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at 10.1016/j.electacta.2014.11.058.
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