Journal of Power Sources 319 (2016) 90e98

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Flexible and conductive cotton fabric counter electrode coated with

graphene nanosheets for high efciency dye sensitized solar cell
Iftikhar Ali Sahito a, c, Kyung Chul Sun b, Alvira Ayoub Arbab a, c, Muhammad Bilal Qadir a,
Yun Seon Choi a, Sung Hoon Jeong a, *
a
b
c

Department of Organic and Nano Engineering, Hanyang University, Seoul 133-791, Republic of Korea
Department of Fuel Cells and Hydrogen Technology, Hanyang University, Seoul 133-791, Republic of Korea
Department of Textile Engineering, Mehran University of Engineering and Technology, Jamshoro 76062, Pakistan

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

A unique graphene coated-fabric

counter electrode is prepared for
DSSCs.

It shows very low surface resistance
of only 7 U sq1 with excellent
exibility.

It shows a very low charge transfer
resistance of only 1.2 U.

This fabric counter electrode gives a
photovoltaic conversion efciency of
6.93%.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 8 January 2016
Received in revised form
10 March 2016
Accepted 5 April 2016
Available online 16 April 2016

Textile fabric based electrodes due to their lightweight, exibility and cost effectiveness, coupled with
the ease of fabrication are recently given a huge attention as wearable energy sources. The current dye
sensitized solar cells (DSSCs) are based on Platinized-Fluorinated Tin oxide (Pt-FTO) glass electrode,
which is not only expensive, but also rigid and heavyweight. In this work, a highly conductive-graphene
coated cotton fabric (HC-GCF) is fabricated with a surface resistance of only 7 U sq1. HC-GCF is used as
an efcient counter electrode (CE) in DSSC and the results are examined using photovoltaic and electrochemical analysis. HC-GCF counter electrode shows a negligible change of resistance to bending at
various bending positions and is also found extremely resistant to electrolyte solution and washing with
water. Cyclic voltammogram, Nyquist and the Tafel plots suggest an excellent electro catalytic activity
(ECA) for the reduction of tri-iodide I
3 ions. Symmetrical cells prepared using HC-GCF, indicate a very
low charge transfer resistance (RCT) of only 1.2 U, which is nearly same to that of the Pt with 1.04 U.
Furthermore, a high photovoltaic conversion efciency (PCE) of 6.93% is achieved using HC-GCF counter
electrode using polymer electrolyte.
2016 Elsevier B.V. All rights reserved.

Keywords:
Fabric
Graphene
Counter electrode
Electro conductivity
DSSC

1. Introduction
Dye sensitized solar cells (DSSCs) have attained astonishing interest since the last ten years, based on the extremely important
* Corresponding author.
E-mail address: shjeong@hanyang.ac.kr (S.H. Jeong).
http://dx.doi.org/10.1016/j.jpowsour.2016.04.025
0378-7753/ 2016 Elsevier B.V. All rights reserved.

energy crises, to shift towards renewable energy sources [1e3].

However, expensive and rare Platinum (Pt) metal, used at the
counter electrode (CE) in a typical DSSCs, limits its practical
application. Moreover, lack of exibility, limited availability of the
Fluorinated Tin oxide (FTO) glass, used in DSSC and its high cost
makes it the most expensive part used in DSSC [4]. Therefore, it is

I.A. Sahito et al. / Journal of Power Sources 319 (2016) 90e98

extremely important to discover unique materials, which are truly

capable of replacing Pt in terms of electro conductivity and electro
catalytic activity (ECA) towards the reduction of tri-iodide I
3 ions
and on the other hand are also exible, organic and cost effective.
Recently, a momentous focus is shifted towards the use of Ptfree materials and their composites, in quest of exploring their
unique properties to be used at the counter electrode in a DSSC
[5,6]. Researchers have used conducting polymers [7e9], carbon
materials [10e14] and transition metals based inorganic materials
[15,16], Pt-free or low-Pt alloys have also received a growing interest as counter electrode materials in DSSCs, and efciencies of
more than 8% have been achieved using them [17e21]. Yet, the
carbon nanotubes (CNT) proved to be most successful and have also
given more than 10% efciencies by using different techniques such
as their enzymatic dispersion [22], however commercially available
CNT and the metals used in alloys are expensive. Moreover, to
replace the FTO glass and to prepare a exible electrode for DSSC,
polyethylene naphthalate (PEN) or polyethylene terephthalate
(PET), coated with a very thin layer of Indium Tin oxide (ITO), have
also been used [23]; however, not only their conductive coating is
sensitive to bending, but also these conductive transparent sheets
are not cost effective. Therefore, unique and novel structured
electro conductive textiles (e-textiles), with a range of fabrication
techniques have gained a lot of attention very recently. Commonly
used textiles including, nylon [24], polyester [25], and cotton
[26,27], have found their use as exible and cost effective substrates
for the preparation of conductive fabrics, by use of carbon materials
and conducting polymers. Amongst these, biodegradable nature of
the cotton favors its use in future compared to other bers. On the
other hand, amongst the carbon materials, the two-dimensional
graphene with an extremely high electrical conductivity has revolutionized the research recently [28] coupled with the production
of graphene in large quantities.
Here in, we present a novel and unique, highly conductivegraphene coated cotton fabric (HC-GCF) as CE for DSSC. Previously, we have shown to increase the adsorption of graphene oxide
nanosheets (GONs) on the cotton fabric by cationizing it [29].
Briey, both the cotton fabric and GONs carry negative surface
charge, therefore, the coating may not be as even and longer lasting
as required. Yet through a simple and well-known process of cationization, the surface charge of the cotton fabric was altered,
which resulted in self-assembly of GONs on its surface, giving
higher amount of loading of GONs and consequently a high electrical conductivity was achieved. This novel and exible CE is not
only cheaper compared to Pt, but also it does not require any high
temperature treatment, which is required in the case for activation
of Pt. This electrode can be easily prepared in bulk using a simple,
dip and dry technique followed by chemical reduction. Therefore,
we believe, that HC-GCF electrode will be considered as a strong
candidate to replace Pt in future for the further development of low
cost, exible and efcient cells.
2. Experimental
2.1. Materials
Graphite powder was kindly provided by Asbury Carbons (USA)
(particles size < 100 mm). Sulfuric acid (H2SO4), potassium permanganate (KMnO4), hydrogen peroxide (H2O2), hydrochloric acid
(HCL), hydrazine monohydrate (N2H4), Bovine Serum Albumin
(BSA) and nitric acid (HNO3) were purchased from Sigma-Aldrich
(USA). FTO glass (TEC 8, Pilkington Co.), N719 (cis-diisothiocyanato-bis(2,20-bipyridyl-4,40-dicarboxylato) ruthenium(II) bis(tetrabutylammonium), Solaronix), chloroplatinic acid hexahydrate
(Sigma-Aldrich Co.), Surlyn as spacer (60 mm, Dupont Co.) and

91

Polyethylene oxide (PEO) were used as received, 1-Butyl-3methylimidazoliumiodide (BMII), iodine (I2), Lithiumiodine (LiI),
4-tert-butylpyridine (TBP) and anhydrous acetonitrile were purchased for the composition of electrolytes by Aldrich Co. For
reproducibility, standard cotton fabric (SCF), ISO 105/F, was purchased from Korean Apparel Testing and Research Institute (KATRI).
Briey, it was 100% cotton, weight of the fabric was 115 g m2 with
warp 35/cm and weft 31/cm.
2.2. Synthesis of graphene oxide nanosheets
Graphene oxide nanosheets (GONs) were synthesized from
graphite powder by the modied Hummer's method [30,31].
Briey, 5 g of graphite powder was added to 200 mL of concentrated H2SO4 in an ice bath with continuous stirring for 30 min.
KMnO4 (25 g) was added slowly at temperature no higher than
10  C. Afterwards, the mixture was allowed to react at 35  C for 4 h
with vigorous stirring. To stop the reaction, the temperature was
dropped to 10  C, with the use of ice, and 250 mL of DI water was
added slowly. Later, 5 mL of H2O2 (30%) was added and then, the
mixture was stirred for 30 more min. Then, this mixture was kept
for 2 h followed by rinsing the supernatant, with 10% HCl and then
DI water. At that time, 250 mL of water was added to the resulting
product to form dispersion and sonicated for 30 min. Un-exfoliated
GO was removed by centrifugation for 5 min at 10,000 rpm and to
obtain an inorganic salts free GONs, dialysis of the solution was
realized for two weeks.
2.3. Cationization of fabric and coating of graphene oxide
nanosheets
For the adsorption of GONs onto the cotton fabric, a 1.0% solution of GONs was diluted from the stock solution and bath sonicated for 30 min. The surface charge of the fabric was modied by
cationization process, which consists of padding the fabric in
0.15 g L1 BSA solution for 5 min, followed by washing it and then
drying at 70  C for 30 min. After this process, the cotton fabric was
cationized, having a positive surface charge. This modication was
the basis for the higher attachment of GONs by weight on cotton
surface, creating a self-assembly to form an even layer on the fabric.
Afterwards, the fabric was soaked in GONs dispersion for 30 min at
80  C, making it easier for GONs to attach on the surface of fabric by
evaporating water in the dispersion slowly. This dip and dry cycle
was repeated until there was no change in the sample weight gain.
2.4. Reduction of graphene oxide nanosheets into graphene
nanosheets
Chemical reduction method is the most suitable one according
to the nature the cotton fabric. The fabric was chemically reduced,
using hydrazine monohydrate solution to convert coated GONs to
GNs. 100 mM hydrazine monohydrate solution was heated at 90  C
and the fabric was treated in it for 25 min inside a sealed ask. After
that, the fabric was washed with plentiful amount of deionized
water until the pH of the washing water became neutral. The
resulting GNs coated cotton fabric (GCF) was dried at 100  C in oven
for 15 min.
2.5. Preparing photo anode
To prepare the photo anode, Titania nanotubes (TNT) and TiO2
pastes were prepared and coated on the FTO glass according to our
previous work [3,32]. Holed and prewashed FTO glass
(15  15 mm2) was immersed in TiCl4 solution (40 mM) for 30 min
at 70  C and washed with water and ethanol. After washing, the

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I.A. Sahito et al. / Journal of Power Sources 319 (2016) 90e98

substrate was annealed at 500  C for 30 min. Pre-treated FTO glass

was coated with P25 as the main layer and TNT paste as the scattering layer by the same process using the doctor blade method. A
25 mm thick scotch tape was used to maintain the thickness of the
paste and position. After coating, both P25 and TNT lms, the TiO2
lms were heated in ve steps of 70  C, 325  C, 375  C, 450  C, and
500  C for 30, 5, 5, 15 and 15 min respectively, using the high
temperature furnace (Lab house Co.). In the post treatment, the
coated and sintered TiO2 lms were again immersed in TiCl4 solution (40 mM in water) for 30 min at 70  C. After washing with
water and ethanol, the lms were annealed at 500  C for 30 min
again to reduce the grain boundary and increase the uptake of the
sensitizer molecules. The annealed TiO2 lms were immersed in
dye solution (0.3 mM, in ethanol) rapidly and kept in an airtight
glass-container at room temperature under dark and dry condition
for 18 h. Dye-adsorbed photo anodes were washed to remove the
non-adsorbed dye by using ethanol and dried under nitrogen ow.
2.6. Preparing counter electrode and fabrication of fabric based
DSSC
In order to prepare the exile fabric based counter electrode, the
as prepared highly conductive GNs coated fabric was laminated
onto a common PET transparent plastic sheet by the help of the two
sided tape. This electrode was placed over the photo-electrode,
keeping a 60 mm surlyn in between the two electrodes and
pressed at 80  C so that the surlyn melts thereby sealing the cell. It
is important to mention here that cotton fabric being hydrophilic in
nature, can absorb the liquid electrolyte, leaving behind the cell
inactive. Therefore, to supplement the possession of electrolyte in
between the electrodes, we provided the counter electrode with
the PET support so that the fabric can withhold the electrolyte and
hinder its evaporation from back side. Another strategy was to
place a non-woven porous PET membrane between the two electrodes which was aimed at absorbing the electrolyte and keeping it
available between the electrodes [33,34]. Additionally, polymer gel
electrolyte was used instead of liquid electrolyte, as the liquid
electrolyte can evaporate rather easily compared to the polymer gel
electrolyte. The polymer gel electrolyte was composed of 0.6 M
BMII, 0.05 M I2, 0.1 M LiI, 0.5 M TBP in acetonitrile and then adding
5 wt% of PEO in it and stirred until it dissolved completely. The
electrolyte was injected into the drilled one-hole FTO glass and the
hole was sealed with a cover glass and surlyn. The cell fabrication
steps are explained more effectively in the schematic diagram,
shown in Fig. 1.
3. Characterization
Field emission-transmission electron microscopy (FE-TEM, JEOL
JEM-2010) was used to investigate the presence of single layers
GONs and the dimensional information of the GONs was obtained
by atomic force microscope (AFM), XE-70, Park Systems in a tapping mode. Surface morphology of the fabric samples was investigated using Field Emission-Scanning Electron Microscope (FESEM) model, (JEOL JSM-6700F) at accelerating voltage of 15 kV. The
Raman spectra were measured using a Raman microscopy system
(NRS-3100, JASCO, Japan). Intensities of carbon and oxygen functional group peaks, at the surface of fabric were measured through
X-ray photoelectron spectroscopy (XPS) using Multilab ESCA 2000
system VG from Thermo scientic, USA, using mono-chromatized
Al Ka radiation with energy step size of 0.05 eV. Transmittance
spectra were obtained by using UV-1650PC spectrophotometer
(Shamadzu Co.). Electrical resistance at the surface of cotton fabric
was measured using a standard four-point probe head system
method by means of RM3000 resistivity test unit by Jandel

Engineering, Switzerland. The catalytic activity (ECA) of the electrodes was measured by using a three-electrode system in an
argon-purged electrolyte (0.01 M LiClO4, 10 mM LiI, and 1 mM I2
acetonitrile solution) with ultimate electrochemical workstation
(Bio Logic Co). The photovoltaic performance of the DSSC devices
was evaluated using K101-Lab 20 (Mac Science Co) source
measuring unit. A solar simulator with 160 W Xenon arc lamp was
used as light source (Spectral match; 0.75e1.25, Non-uniformity of
irradiance; 2%, Temporal instability; 2%). The light intensity
was calibrated with a KIER-calibrated Si solar cell (Mc science Co).
Photovoltaic parameters of the cells were measured under masked
frame. In order to investigate the electrochemical properties of GCF,
series resistance (RS) and Charge Transfer Resistance (RCT) were
measured with electrochemical impedance spectroscopy (EIS) using frequency range of 0.05 Hze300 kHz under 100 mW cm2 using
ultimate electrochemical workstation (Bio Logic Co). Incident
photon-to-current conversion efciency (IPCE) was measured as a
function of wavelength from 350 to 730 nm using a specially
designed IPCE system for dye-sensitized solar cells (PV measurements, Inc.). A 75 W xenon lamp was used as the light source for
generating monochromatic beams. Calibration was performed using a silicon photodiode, which was calibrated based on the NISTcalibrated photodiode G425 standard. The IPCE values were
measured under halogen bias light at a low chopping speed of
10 Hz.
4. Results and discussion
Fig. 2(a) shows a layer of GONs accompanied with its corresponding line diagram in Fig. 2(c). As can be seen, the line prole of
the GONs shows an average height of around 1.7 nm, which is a
characteristic of the single layer of GO. A sufciently oxidized form
of graphite results in single layers of GONs, therefore, in order to
conrm their existence, FE-TEM techniques was used. Fig. 2(b)
represents FE-TEM image of single layers of GONs, which can be
easily seen, having typical folded structure.
In the current approach of preparing HC-GCF and as reported
earlier, the fabric was rst coated with BSA to alter the surface
charge of the cotton fabric from negative to positive and then the
fabric was padded in negatively charge GONs. Fig. 3(a) and (b)
shows the FE-SEM images of the pure cotton fabric both in low and
high magnication, respectively. However, when the fabric is
coated with BSA, the surface of the bers in the cotton fabric
showed a wrinkled coating on their surface, which is more clearly
visible in the high resolution image in Fig. 3(d). Afterwards, the
fabric was coated with GONs and then reduced by hydrazine
monohydrate to convert it into HC-GCF. A highly uniform coating of
GNs, covering the entire surface of fabric can be seen in low
magnication image and same can also be seen in the cross
sectional view of the fabric, revealing an extremely smooth coating
of GNs after surface modication of the cotton fabric.
In order to ensure the effectiveness of the reduction process and
to investigate the relative existence of the carbon, oxygen and nitrogen functional groups, we performed the XPS test. Fig. 4(a)
shows the XPS survey spectra of untreated fabric coated with,
GONs, GNs and BSA treated fabric with GNs coating. As presented in
spectra of GONs coated fabric, the O1s peak can be seen dominating, compared to the C1s peak, which indicates the presence of
abundant oxygen-containing defect sites throughout the basal
plane and the edges of GO [35]. Conversely, when GONs was
reduced to GNs, it showed higher intensity of C1s, with a decreased
O1s intensity. This indicates the restoration of graphitic network to
induce high electrical conductivity at the surface of the fabric.
Moreover, the spectra of the cationized sample treated with BSA
shows the nitrogen peak, also conrming the existence of nitrogen

I.A. Sahito et al. / Journal of Power Sources 319 (2016) 90e98

93

Fig. 1. Schematic diagram of DSSC preparation with GCF counter electrode.

Fig. 2. (a) AFM image of a single sheet of graphene (b) FE-TEM image of single graphene layers (c) the corresponding line diagram.

in BSA treated samples.

To explore deeper inside the reduction of graphene oxide to
graphene, C1s core level spectra were deconvoluted and are

presented in Fig. 4(c) and (d) respectively. C1s spectra of GONs and
GNs were mainly composed of the various oxidation states,
including: CeC at 284.6 eV, CeO at 286.6 eV, C]O at 287.7 eV, and

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I.A. Sahito et al. / Journal of Power Sources 319 (2016) 90e98

Fig. 3. FE-SEM images of (a) untreated cotton fabric at low and (b) high magnication, (c) BSA treated cotton fabric at low and (d) high magnication, (e) GNs coated fabric (f) cross
sectional view of GNs lm coated on fabric.

C(O)O at 288.7 eV, strongly indicating the presence of oxygencontaining groups, such as hydroxyl, epoxy, carbonyl, and carboxylic acid on the surface or edge of the GONs [36]. After the reduction
all the peaks showing oxygen groups can be clearly seen to
decrease, suggesting the restoration of graphitic structure and a
high electrical conductivity on the surface of the fabric. Fig. 4(b)
shows the Raman spectra of the GONs and GNs and the typical D, G
and 2D peaks can be seen in both the spectra. In the spectrum of
GONs coated cotton fabric, the typical G band corresponding to the
rst-order scattering of the E2g mode is at 1596 cm1. This is due to
the in-phase vibration of the graphite lattice and D band at
1340 cm1 for the disorder band caused by the graphite edges,
indicating a reduction in the size of the in-plane sp2 domains,
possibly due to the extensive oxidation [37]. An increase in the ID/IG
ratio of the spectra is from GONs to GNs is visible, which was
changed from 0.78 to 1.1 after the reduction process. This change
suggests a decrease in the average size of the sp2 domains upon
reduction of the exfoliated GO [38]. The change can be explained if
the new graphitic domains are created that are smaller in size to the
ones present in GO before reduction, yet more numerous in

number. Increase in the 2D peak intensity is also noticeable in the

GNs spectrum, which indicates a defect rich structure due to
presence of nitrogen, which may have helped to increase ECA of the
HC-GCF.
During the cells fabrication, the compatibility of the materials to
be used in contact to one another has to be considered and therefore, the reaction between electrolyte and the HC-GCF counter
electrode was observed using UVeVis spectroscopy. Fort this purpose the HC-GCF was kept in the electrolyte solution for 48 h and
the transmittance % of the electrolyte solution, before and after
immersion, is plotted against the wavelength ranging from 260 to
800 nm, as given in Fig. 5(a), and showed almost same transmittance throughout this range. This suggests the HC-GCF was
chemically resistant to electrolyte and there was no effect on the
coating of the HC-GCF. Fig. 5(a), also shows the transmittance
spectra of the HC-GCF resistance to washing, where the two
spectra, before and after immersion in water, show now change in
transmittance %, suggesting that the electrode was stable even after
several washing cycles.
Additionally, the HC-GCF was washed by the DI water several

I.A. Sahito et al. / Journal of Power Sources 319 (2016) 90e98

95

Fig. 4. (a) XPS survey spectra of GONs and GNs (b) Raman spectra of GONs and GNs (c) C1s core level spectra of GONs and (d) C1s core level spectra of GNs.

Fig. 5. (a) Transmission spectra of the electrolyte solution and water before and after immersion of the HC-GCF in them (b) Percentage change in surface resistance of HC-GCF
against different bending states.

times and showed no traces of the coating in the DI water, as shown

in the Supplementary Information Fig. S1.

In order to assure the use of the use of HC-GCF as a exible

electrode, the change in resistance was measured against different

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I.A. Sahito et al. / Journal of Power Sources 319 (2016) 90e98

bending positions. The results showed and excellent bendability

with negligible change in resistance percentage over a cycle of
various bending positions, as shown in Fig. 5(b). The HC-GCF was
bent from position 1 to 4 and then back to position 1, yet there was
negligible change in resistance. The change in resistance % was
found maximum at bending position 4, however, it was lower than
1.5%. With such low change in surface resistance at different
bending angles, it can be said that the HC-GCF electrode showed
excellent performance to be used as exible electrode materials.
Together with change in resistance %, current passage through the
HC-GCF was also measured against time and the results are presented in the Fig. S2 in the Supplementary Information. The current
was recorded at a constant voltage of 1 V, and the results showed
identical current value at all bending positions, proving that there
was no change in the conductance of current by the HC-GCF at
various bending positions.
Fig. 6(a) shows the cyclic voltammogram (CV) curves of the Pt
coated on FTO glass and GNs coated on cotton fabric, at a scan rate
of 20 mV.s1 to investigate their ECA, in a three electrode electrochemical cell. In this experiment, the HC-GCF or Pt electrodes were
set as working electrodes (WE) in the cells respectively, Pt wire was
used as CE and Ag/AgCl, as a reference electrode. Both, the HC-GCF
and Pt electrodes exhibited a pair of anodic and cathodic peaks as
shown in Fig. 6(a). The reaction rate of the catalyst for the reduction
of (I
3 ) ions in the electrolyte is inuenced by the cathodic peak
current density [ICP] in a CV curve. A higher [ICP] absolute value
infers a better ECA for the catalytic material. The peak to-peak
distance [EPP] and the absolute value of over potential [EAP] are
inversely proportional to the standard electrochemical rate constant of a redox reaction and ECA of the samples [39].
The HC-GCF showed a peak current density [ICP]
of 0.42 mA cm2, whereas
the Pt electrode
a
showed 0.79 mA cm2 (The details of the values obtained are
mentioned in Table 1), which indicates that the Pt electrode provides better ECA towards the reduction of tri-iodide ions. Also HCGCF showed an anodic peak current [IAP] of 1.02 mA cm2, whereas
the Pt electrode showed 0.82 mA cm2, which suggest that the HCGCF electrode provides higher electro conductivity compared to Pt.
It can also be observed that the [EAP] value of HC-GCF is 0.32 V,
which is slightly higher than Pt electrode with 0.27 V.
On the other hand the [EPP] value of Pt is also slightly less than
that of HC-GCF and as mentioned earlier, both these parameters are
inversely correlated with ECA, therefore it can be said that the Pt
shows better ECA, however the change was only marginal. It can be

noted that the Pt electrode provided higher ECA towards the

reduction of tri-iodide, nevertheless, the HC-GCF provided sufcient ECA, which was only slightly less than the Pt electrode, to
prove its candidacy to be used as CE material in DSSC. External
quantum efciency (EQE) % or the IPCE of the prepared cells was
measured in the range between 400 and 800 nm wavelengths.

EQE

Electrons out
Photons in

(1)

Fig. 6(b) shows a typical IPCE curve of the DSSC based on N719. It
of importance to note that both the IPCE curves are almost same for
both DSSCs based on HC-GCF and Pt-FTO counter electrodes. As the
photo anode in both the cells was same therefore, there is negligible difference in the IPCE curves of both types of cells.
The internal kinetics of the cells were analyzed by measuring
the interfacial electrochemical behavior of the two types of CEs,
using the symmetrical dummy cell structure. The structure was
comprised of the two identical electrode, Pt or HC-GCF, sandwiched
together with the polymer electrolyte lled inside [40]. Fig. 7(a)
shows the Nyquist plots for the Pt and HC-GCF symmetrical cells
respectively. The Nyquist plots were simulated using EC-lab
software and the equivalent circuit used for tting the EIS spectra is
given as inset.
Generally, the Nyquist plot of the dummy cell is comprised of an
ohmic series resistance (RS), showing the sheet resistance of the
electrode itself in the high frequency region. Then, the rst semicircle presents the charge transfer resistance (RCT) of the electrode/
electrolyte interface, in the medium frequency region and Nernst
diffusion impedance (Zd) of the I  =I3 redox couple, in the low
frequency region [41]. RS and RCT can be represented as intersection
of high frequency semicircle at real axis and radii of high frequency
semicircle, respectively. The value of RS, as given in Table 1, shows
that the electrode resistance is nearly same in both types of electrodes. It may also be noted that the HC-GCF electrodes provided a
slightly lower RS value compared to Pt. On the other hand the RCT
value, which has an inverse relation to the reduction of triode, is
slightly lower in the case of Pt, producing a smaller semicircle.
Though, the HC-GCF results in a marginally higher RCT value,
though it is extremely sufcient for a CE material to be used in a
DSSC, proving the excellent ECA. These results are consistent with
the CV results.
To support the investigation on interfacial charge transfer
properties of CE/electrolyte of the HC-GCF compared to Pt, Tafel
polarization curves were obtained using the dummy cells

Fig. 6. (a) Cyclic Voltammogram for fabric electrode and Pt electrode at a scan rate of 20 mV.s1 in 10 mM LiI, 1 mM I2 acetonitrile solution containing 0.1 M LiClO4 as the supporting
electrolyte (b) External quantum efciency of DSSCs prepared using HC-GCF and Pt-FTO counter electrodes.

I.A. Sahito et al. / Journal of Power Sources 319 (2016) 90e98

97

Table 1
Electrical and electrochemical characteristics of Pt and GCF electrode.
Counter electrode

RS [U]

RCT [U]

Zd [U]

ICP [mA]

IAP [mA]

ECP [V]

EAP [V]

EPP [V]

HC-GCF
Pt-FTO

7.2
7.5

1.24
1.04

1.271
1.371

0.42
0.79

1.02
0.82

0.02
0.03

0.32
0.27

0.31
0.24

Fig. 7. (a) Nyquist plots of symmetrical cells prepared using Pt and HC-GCF counter electrode (b) Tafel plot of symmetrical cells based on Pt and HC-GCF counter electrodes.

mentioned earlier, and the curves are presented in Fig. 7(b). The
scan rate for this measurement was 10 mV s1. A Tafel curve is a plot
of the log of the current density vs. the applied voltage. It is usually
divided into three parts: A polarization zone appearing at the lower
potential, then and a steep slope can be observed at the middle,
called a Tafel zone, deciding the ECA of the electrode, followed by a
diffusion zone at higher voltage. It can be observed from the curves
that the limiting diffusion current density (Jlim) was higher in the
case of HC-GCF, with the value of 1.82 mA cm2, however, the Pt
produced slightly lower Jlim value of 1.56 mA cm2. On the other
hand exchange current density (J0) value, calculated from the
intersection of the linear cathodic and anodic Tafel polarization
curves also showed the similar trend as of Jlim. It is important to
mention here that the Jo is inversely proportional to RCT of the
electrode using the relation:

Jo

RT
;
nFRCT

towards the reduction of tri-iodide ions.

Fig. 8 shows the overall photovoltaic performance, currentevoltage (IeV curve), of the DSSCs prepared using conventional Pt and the HC-GCF counter electrodes, which were evaluated
under AM 1.5 illumination (1 sun, 100 mW cm2). The obtained cell
parameters of the short-circuit current (JSC), open-circuit voltage
(VOC), ll factor (FF) and overall conversion efciency (PCE) are
summarized in Table 2.
It was observed that the DSSC based on Pt-FTO showed PCE of
8.44% with the FF of 78.52, VOC of 0.67 V and JSC of 15.88 mA cm2,
whereas, the HC-GCF counter electrode based cells resulted in a
close PCE of 6.93%, with FF of 70.92, VOC of 0.66 V and a JSC of
14.75 mA cm2. As a result, the HC-GCF reaches 82.11% of the PCE of
Pt. The repeatability data of the cells based on HC-GCF counter
electrode is given in Supplementary Information. A slightly lower

(2)

where, R is the gas constant, T shows temperature, n accounts for

the number of electrons involved in the reaction and F is the Faraday's constant. A lower Jlim value reveals that Pt has a marginal
edge over the HC-GCF in terms of better ECA, nevertheless the HCGCF electrode provide sufcient ECA.
Graphene in its oxidized form is composed of lattice defects
together with many oxygen-containing functional groups, such as
hydroxyls, carbonyls, and epoxides. During chemical reduction
process all of them are not removed completely, however, thermal
reduction at elevated temperature is the best practice to remove
almost all of the oxygen containing groups. Cotton fabric intrinsically cannot bear high temperature and therefore, some of the
oxygen species still remain on the surface of rGO. However, on the
other hand, it has been demonstrated previously [42e44] that the
oxygen species provide active catalytic sites for the oxygen reduction reaction to increase the catalytic and therefore photovoltaic
performance of a DSSC. In case of HC-GCF, the oxygen species,
shown in XPS spectra in Fig. 4(a), together with a high surface of the
cotton fabric itself may have helped provide a high catalytic activity

Fig. 8. Polarization curves of Pt and HC-GCF counter electrode based cells.

98

I.A. Sahito et al. / Journal of Power Sources 319 (2016) 90e98

Table 2
IeV characteristic of the Pt and HC-GCF counter electrode based DSSCs.
CE

JSC [mA cm2]

VOC [V]

FF (%)

PCE %

Pt-FTO
HC-GCF

15.88
14.75

0.67
0.66

78.52
70.92

8.44
6.93

JSC of 14.75 mA cm2 and a minor decrease in VOC value may be due
to a higher RCT of the HC-GCF counter electrode. Because of the
geometry of the fabric, it may provide better microporous structure
compared to the Pt, yet the rmness of the fabric is inferior when
compared to the solid Pt coated on FTO. Due to the geometry of the
fabric, it is compressible, which may be a possible reason for not
providing intact mechanical contact with the clips in contact for
measuring photovoltaic properties and thus a decreased FF was
observed. Keeping in mind the low temperature preparation of the
proposed CE, its cost effectiveness, exibility and organic nature,
HC-GCF can be considered as in innovative and stable CE for various
application including fabric based energy storage and energy conversion devices.
5. Conclusions
A highly conductive, exible, mechanically strong and stable,
and fully organic cotton fabric counter electrode for dye sensitized
solar cell (DSSC) was prepared, coated with graphene nanosheets
(GNs). The adsorption of negatively charged graphene oxide
nanosheets (GONs) was enhanced by cationizing the cotton fabric,
which resulted in a highly conductive-graphene coated cotton
fabric (HC-GCF). The surface resistance was measured to be lower
than that of Pt, with a value of only 7 U sq1. The conversion of
GONs into GNs was investigated using X-ray photoelectron spectroscopy, Raman spectroscopy and Wide angle X-ray diffraction
techniques. The HC-GCF showed excellent resistance against electrolyte and water and also to bending at various bending angles.
The coated fabric showed no change in resistance at various
bending cycles and conducted the same current also. The electrochemical analysis, including cyclic voltammogram (CV), Nyquist
plots and Tafel plots suggested sufcient electro catalytic activity
(ECA) towards the reduction of tri-iodide ions in the electrolyte. An
extremely low charge transfer resistance (RCT) of 1.24 U and an
overall conversion efciency of 6.93% with polymer electrolyte,
together with low temperature preparation, low cost, easy availability, exibility and bio-degradable nature suggests that this
fabric electrode can be an excellent and innovative candidate for
the future generation of DSSCs.
Acknowledgement
We are very thankful to Asbury Carbons (USA) for technical
consultation and for providing us graphite powder free of cost.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jpowsour.2016.04.025.
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