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Eddie Nahúm Armendáriz-Mireles1

Photocurrent generation by dye-sensitized Enrique Rocha-Rangel2


solar cells using natural pigments Frida Caballero-Rico1
José Alberto Ramı́rez-de-León1

Manuel Vázquez3

1 Knowledge Management Center, Autonomous University of Tamaulipas,


Victoria, Tamaulipas, México
2 Department of Manufacturing of Advanced Materials, Polytechnic
University of Victoria, Victoria, Tamaulipas, México
3 Department of Analytical Chemistry, Faculty of Veterinary Science,
University of Santiago de Compostela, Lugo, Spain

Abstract
The development of photovoltaic panels has improved the their sensitizing effect on titanium dioxide. The results showed
conversion of solar radiation into electrical energy. This paper the great potential of natural pigments for use in solar cells.
deals with the electrical and thermal characteristics (voltage, The best results were obtained with the blackberry pigment,
current, and temperature) of photovoltaic solar cells sensitized reaching a value of 7.1 mA current, open-circuit voltage (Voc )
with natural pigments (dye-sensitized solar cell, DSSC) based of 0.72 V in 2 cm2 , and fill factor (ff) of 0.51 in the DSSC. This
on a titanium dioxide semiconductor. Several natural pigments performance is well above than that currently offers by actual
(blackberry, beets, eggplant skin, spinach, flame tree flower, cells. 
C 2015 International Union of Biochemistry and Molecular Biology,

papaya leaf, and grass extracts) were evaluated to determine Inc. Volume 00, Number 0, Pages 1–6, 2015

Keywords: sensitized, solar cell, electrical characterization, DSSC, natural


pigment, TiO2 semiconductor

1. Introduction the first solar cell, using selenium as a dielectric material.


Energy efficiency was only 1%. The continuous development
In the past few decades, clean technologies have been de-
of photovoltaic panels has improved the conversion of solar
veloped for producing energy, replacing gradually traditional
radiation into electrical energy [5]. Nowadays, this technology
methods of generating energy from nonrenewable resources
has greater importance than others for energy generation.
(oil, natural gas, and coal) by other renewable resources (wind,
Additionally, monitoring is essential for optimal performance.
hydro, and solar) [1]. Nowadays, the use of renewable and
The principle of operation of a solar cell is based on a light-
sustainable natural resources has become a global energy pri-
sensitive material absorbing solar energy and converting it
ority. Solar energy is considered as a source of endless energy.
into electrochemical energy [6]. Solar cells have been classified
Therefore, the use of this radiation has led to the development
by their evolution, according to their temporal development,
of new devices for such purposes [2].
technology, and energy efficiency:
The photovoltaic effect was first discovered by Becquerel
in 1839, when he observed an increase in current in one of
the electrodes of an electrolytic cell connected to two platinum
plates exposed to sunlight [3, 4]. In 1883, Charles Fritts built r First-generation cells: These are based on monocrystalline
silicon wafers, with limited theoretical efficiency and high
cost.
Abbreviations: DSSC, dye-sensitized solar cell; EU, European Union; ff, fill r Second-generation cells: These are thin-film panels, poly-
factor; TiO2 , titanium dioxide..
∗ Address
crystalline and amorphous silicon, with limited theoretical
for correspondence: M. Vázquez (PhD), Department of Analytical
efficiency and low cost.
Chemistry, Faculty of Veterinary Science, University of Santiago de r Third-generation cells: These are sensitized and organic
Compostela, Lugo 27002, Spain. Phone: +34 982822420;
Fax: +34 982822420; e-mail: manuel.vazquez@usc.es. panels. This technology is in a testing stage. Several strate-
Received 2 September 2015; accepted 8 October 2015 gies have being applied to achieve substantial efficiency
DOI: 10.1002/bab.1449 gains [7]. One such strategy is manufacturing multifunc-
Published online in Wiley Online Library tional cells, thermoelectric cells, dye-sensitized solar cells
(wileyonlinelibrary.com) (DSSCs), or cells built with organic materials [8, 9].

1
Biotechnology and
Applied Biochemistry

Sensitized by natural coloring cells are third-generation sensitizer in DSSC with high efficiency of up to 11–12%.
solar cells. They are known as DSSC or Grätzel type, in honor However, the ruthenium compounds are expensive, even less
of their inventor. These cells have great economic potential due abundant, and carcinogenic. Therefore, natural dyes are of
to the low price of raw materials and labor input required to great interest for use as sensitizers in DSSC [3, 15].
manufacture, compared to silicon-based solar cells [10]. The objective of this study was to characterize electrical
The processes of light absorption and electron transfer and thermal DSSC by several natural dyes based on titanium
in DSSC cells are performed separately, which means lower dioxide (TiO2 ) as a semiconductor using a data acquisition
manufacturing costs [11]. Their development has been of great system designed to monitor the variables voltage, current,
interest because their operation imitates natural photosynthe- and temperature to assess the efficiency of the cells and to
sis. In 2012, a study of the properties of spinach to generate determine the most efficient dye.
electricity combining a photosynthetic plant protein with a sili-
con semiconductor was published. This type of cell was called
biohybrid [12]. In a natural dye-sensitized cell, the pigment is 2. Materials and Methods
responsible for capturing sunlight. This pigment in combina- Solar cells were manufactured, characterized, and monitored
tion with a nanocrystalline titanium dioxide semiconductor and based on a process called “artificial photosynthesis” using
an electrolyte is the main part of this double solar energy solar cells produced with simple materials: paste TiO2 , dyes
capture. chlorophyll and anthocyanin (natural pigments), electrolyte
In natural sensitizers, purely organic dyes with good (iodine [I2 ] and potassium iodide, KI), and conductive glass [16].
photovoltaic performance are clean and low-cost sources for We focused on this type of solar cell to understand the behavior
DSSC, although their efficiency is much lower than industrial of chlorophyll and anthocyanin, which are present in plants
requirements [13]. Most leaves of green plants are rich in and fruit, respectively, and their relationship to the transfer
chlorophyll and the application of such natural colorant has of electrons. One of the main reasons for this relationship is
been investigated frequently in many related studies [14]. the anchor property of pigment (chlorophyll and anthocyanin)
The working ranges of DSSC are as follows: with the semiconductor. The characterization of the DSSC and
a common silicon cell was presented through electrical and
(1) Titanium dioxide: Absorbs less than or equal to 400 nm in thermal readings of variables, such as the open-circuit voltage
the spectrum. (VOC ), short circuit current (ISC ), and the cell temperature (TCEL ).
(2) Silicon: Absorbs from 300 to 1100 nm in the spectrum. The LabVIEW platform (National Instruments Corporation,
(3) Gallium nitride: Absorb wavelengths that are less than Austin, TX, USA) was used to characterize both environmental
silicon. conditions through which monitoring and data acquisition
were performed to analyze the efficient use of the solar cells for
Solar panels made from the materials described above power generation. The characterization of the solar panels was
depend on manufacturing processes that employ not clean conducted by developing an integrated circuit whose purpose
energy. Silicon and gallium arsenide have to be extracted was the conversion of parameters such as voltage, current,
from the earth’s crust and then they are transformed through and temperature, which are suitable to be read. The electrical
different processes to place them on the panel, not to mention signals were processed using the computer with LabVIEW
the polluting waste from companies that manufacture the software in which data were stored and statistical analysis was
panels. carried out.
In 2010, it was estimated that the European Union Two pieces of glass working functioning as electrodes were
(EU) would generate more than 7,000 tons of solar waste. used for the construction of the DSSC; on the surface of the
It is estimated that in 2020–2025 there will be a signif- glass, a thin film of graphite was deposited to make them
icant increase in waste, since the first large-scale pho- conductive. The redox couple KI/I dissolved in ethylene glycol
tovoltaic plants date from the 1990s (http://www.belt.es/ was used as an electron conducting means. Natural pigments
noticiasmdb/home2 noticias.asp?id = 9817). It is expected were used as solar energy absorbers and eventually nanosized
that an estimated 130,000 tons of this type of waste will be TiO2 particles were used as a medium where the coloring
produced by 2030 [2]. Therefore, even in this technology-clean (chlorophyll and anthocyanin) is anchored.
operation, it is required to minimize the environmental impact During the first study, photosynthetic pigments based
and if during the process there are better returns, the task will on anthocyanin present in blackberries, beets, beetroot, and
have been accomplished. The aim would be to have a clean eggplant skin were tested. The extraction of natural pigments
technology from manufacturers for disposal of wastes. from the materials used was as follows. An aliquot of 10 g of
The process of converting sunlight into electricity takes the selected substance was weighed on an analytical balance,
place in DSSC based on the sensitizing of a semiconductor. and then each sample was ground in a porcelain mortar and a
Therefore, numerous inorganic, organic, and hybrid dyes have mallet of the same material. Each crushed sample was mixed
been used as sensitizers in DSSC. Among synthetic inorganic with 50 mL of distilled water at room temperature in a dark
dyes, a ruthenium compound was effectively used as molecular room. Solid wastes from the solution were filtered through a

2 Photocurrent Generation by DSSCs Using Natural Pigments


(A) Electric diagram obtained using LabVIEW, from
FIG. 1 the National Instruments Corporation, software
that is used for lectures and the acquisition of
experimental data. (B) Graphic interface obtained
using the LabVIEW software that is used for
lectures and the acquisition of experimental data.

filter paper to acquire a pure natural pigment solution. Then, absorption and electron transfer in the cells. In addition, it
extracts of blackberry, beets, eggplant skin, and beetroot were was used to show how photosynthesis is mimicked. In another
mixed with ethylene glycol in a volume ratio of 1:1 to serve as experiment, DSSC was tested using artificial light produced
a blend of natural pigments [17]. by a halogen lamp. The cells were tested under controlled
For the extraction of chlorophyll from green plants such conditions to determine the standard curve as shown in the
as spinach, flame tree flower, papaya leaf, and grass, 10 g of literature [17].
each plant was separately mixed with 200 mL of distilled water. Parameters such as voltage, temperature, and irradiation
They were heated for 20 Min to extract chlorophyll through were recorded remotely as signals to be read from data
hydraulic indirect heating in boiling water. Solid waste in the acquisition card (NI cDAQ-9184, NI-9211, NI-9215; National
solution was filtered through a filter paper to obtain a solution Instruments Corporation) and therefore using a computer
of pure natural pigments. Then, the extracted fluids were with the LabVIEW software (Fig. 1A). A graphic interface was
mixed in the ratio of 1:1 to serve as a natural pigment [15]. created to control and store data, as shown in Fig. 1B.
The following materials, tools, and equipment were used to The results of experimental parameters were analyzed
characterize and monitor the manufacturing of the solar cells: using the current flow behavior and the amount of voltage
conductive glasses Rs < 10  (Delta Technologies Limited, with respect to temperature of the DSSC cell. The maximum
Loveland, CO, USA), electrolyte iodine KI in ethylene glycol, values of current and voltage generated by the photovoltaic
Degussa P25 titanium dioxide, graphite powder (Solaronix SA, panel standard were recorded between 13:00 and 14:00, the
Aubonne, Switzerland), a variable resistor (potentiometer) of time when the sun is highest in the sky and perpendicular
500  (Fluke Inc, Everett, WA, USA), a digital multimeter card to the photovoltaic panels. At this point, the cell reached a
(NI cDAQ-9184, NI-9211, NI-9215) for the platform LabVIEW, temperature of 47 ◦ C. This may relate to the voltage generated
computer, and temperature gauge NI USB-TC01 thermocouple immediately with the presence of the sun regardless of its
type ”J” (National Instruments Corporation, Austin, TX, USA). position relative to the photovoltaic panels and the transmitted
The artificial light source was a halogen lamp, 100 W heat radiation. Meanwhile, power is highly dependent on the relative
source (heat gun), nitric acid (10 mL with deionized water, pH position of the sun to the photovoltaic panels and the radiation
3–4) (Quimica Noreste, Monterrey, Mexico), security materials transmitted by the generated voltage decreases. The behavior
(latex gloves and glasses), and other accessories (clamps, was similar to that found in the literature [18].
containers, and spoons). Blackberry, beets, eggplant skin, In Fig. 2, it can be seen that the voltage is higher with
beetroots, spinach leaves, flame tree flower, papaya leaf, and blackberry than with the other pigments. This can be due to
grass extracts were used as natural pigments. the high anthocyanin levels. Figure 3 shows the measurements
of voltage and current (V × I) for the DSSC. Current is plotted
in short circuit, Isc , and open-circuit voltage, Voc . The DSSC of
3. Results and Discussion blackberry illuminated with artificial light based on halogen
The DSSC was tested under the following real conditions: (1) light reproduces conditions similar to sunlight radiation. The
the shade; (2) sunlight. An initial experiment was conducted curve shown in Figure 3 compares very well with that reported
to determine the influence of sunlight in the process of light in the literature [19].

Biotechnology and Applied Biochemistry 3


Biotechnology and
Applied Biochemistry

Photovoltaic performance parameters in solar cells


TABLE 1 sensitized with natural pigment obtained in this work

Open-circuit Photo current


photo voltage density Fill factor
Dye (Voc , V) (Jsc , mA cm2 ) (ff)

Blackberry 0.72 7.10 0.51


Spinach 0.53 0.41 0.53

Flame tree flower 0.50 0.55 0.53


Pawpaw leaf 0.44 0.60 0.53

Voltage, temperature, and irradiation under solar Skin of eggplant 0.38 1.60 0.40
FIG. 2 light generated by DSSC manufactured with
natural pigments.
Beet 0.32 0.67 0.52

Beetroot 0.29 0.32 0.40


Grass 0.20 0.30 0.40

The efficiencies ranging from 0.6% to 2.6% using a mixture


of xanthophyll and chlorophyll were due to energy transfer
of pigment mixed with cosensitized TiO2 [13]. The use of
chlorophyll pigments from granada leaf, mulberry extracts,
and mixture of chlorophyll and anthocyanin ranged from
0.55% to 0.72% [21]. Anthocyanin extracts of jabotica showed
a successful conversion of visible light into electricity [22]. In
The curve of V–I of the DSSC manufactured with
FIG. 3 a natural pigment extracted from black rice, the VOC ranged
blackberry pigment under artificial light.
from 0.551 to 0.412 V. The extract of black rice showed a
photosensitized effect, which is due to the interaction between
the carbonyl and hydroxyl of the molecule of anthocyanin and
To make a comparative analysis of the anthocyanin present the surface of TiO2 [14]. Red sicilian orange juice and extract
in some plants and fruits, DSSC with natural pigments such as of purple eggplant shells as natural DSSC sensitizers yielded
blackberries, beets, eggplant skin, and beet was characterized 0.66% and VOC = 0.325 V [23]. The efficiency and stability of
by making voltage measurements (Fig. 2). The tendency of the devices based on natural sensitizers such as blackberry and
the pigments is to decrease their efficiency as temperature blueberry and skin jabotica were investigated by Kimpa et al.
increases by the heat produced by the 100-W halogen bulb. [24]. The performance using blackberry was 0.52%, and it was
However, there are chemical factors that determine the antho- 0.61% using blueberry.
cyanin stability during processing and storage when subjected Natural pigments from the flame tree flower, papaya leaf,
to temperatures above 75 ◦ C, as reported in the literature [20]. and mixtures were used as sensitizers for DSSCs [25]. The
Table 1 shows the results of our work using different photoelectrochemical performance of the color extract of the
natural pigments to understand the behavior of chlorophyll flame tree flower showed an open-circuit voltage (VOC ) of
and anthocyanin in plants and fruits and their relationship 0.50 V, a fill factor (ff) of 0.588, and a conversion efficiency of
to the transfer of electrons. One of the main reasons for this 0.20%. The conversion efficiency of the DSSC prepared with
relationship is the anchor property of anthocyanin with the papaya leaf extract was 0.20%, with 0.50 V VOC and 0.605 ff.
semiconductor. The conversion efficiency of the pigment mixture of the flame
The results in Table 2 show the parameters obtained in tree flower and papaya leaf was 0.27%, with 0.518 V VOC and
studies by other researchers, which address various natural 0.69 ff.
sensitizers (rose bengal, eosin Y, skin of jabotica, fluorescein It was observed in the conversion efficiencies that both
sodium, blueberry, black rice, spinach, ipomoea, flame tree the short-circuit current density and fill factor of the cells are
flower, pawpaw leaf, mulberry, skin of eggplant, sicilian or- improved using the mixed pigments. DSSC manufactured using
ange). These studies showed values of 0.72 V for rose bengal rose bengal pigments for sensitization of TiO2 nanocrystals
and 0.59 V for the blackberries sample. yielded a VOC = 0.89 V and ff = 0.53 [26,27].

4 Photocurrent Generation by DSSCs Using Natural Pigments


Photovoltaic performance parameters in solar cells sensitized with natural pigment reported in the literature
TABLE 2

Open-circuit photo Photo current Fill factor


Dye voltage (Voc , V) density (Jsc , mA cm2 ) (ff) Reference

Rose bengal 0.72 8.73 0.44 [25]

Eosin Y 0.69 6.10 0.42 [12]


Skin of jabotica 0.66 2.60 0.62 [21]

Fluorescein sodium 0.65 3.65 0.38 [12]


Blueberry 0.59 1.00 0.61 [23]

Black rice 0.55 1.14 0.52 [13]


Spinach 0.55 0.46 0.51 [20]

Ipomoea 0.54 0.91 0.56 [20]


Flame tree flower 0.50 0.67 0.58 [24]

Pawpaw leaf 0.50 0.64 0.60 [24]


Mulberry 0.49 6.10 0.52 [23]

Skin of eggplant 0.35 3.40 0.40 [22]


Sicilian orange 0.34 3.84 0.50 [22]

In our work, the manufacture of DSSC based on blackberry 4. Conclusions


juice improved the conversion of solar radiation into electricity
The prototype developed demonstrates that it is possible
through a conductor of titanium dioxide. It yielded voltage up to
to obtain the output voltage levels of the DSSCs through
0.72 V and an efficiency of 0.51%. This situation is attributed to
a variation in its construction using blackberry pigments,
the high concentrations of anthocyanin combined with graphite
since the output voltage levels at 0.72 V in 2 cm2 is well
in a liquid form, which acts as the conveyor of electrons that are
above currently offered by the DSSCs in the presence of a
generated by the process of photosynthesis, producing output
semiconductor. In these experiments, natural conversion of
that is well above currently offered by DSSC as mentioned
light is used to show improvement in efficiency with the
above.
combination of the anthocyanin present in blackberry. These
During the first phase of experimentation, it was directly
results show the potential of research to get better results
confirmed that it is possible to measure the voltage using
without the need of semiconductors. It is also important
natural pigments with these equipments such as the voltmeter
to advance in DSSC prototypes without semiconductors for
or virtual laboratory. During this stage, natural pigments of
the development of a cell that can compete with the silicon
green plants from spinach, flame tree flower, papaya leaf,
cell.
and grass were selected as sensitizers for the preparation
of DSSC. These green plants have the natural mechanism of
converting solar energy into electrons (chlorophyll). Berries,
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6 Photocurrent Generation by DSSCs Using Natural Pigments