Professional Documents
Culture Documents
1 s2.0 S0378775316303664 Main PDF
1 s2.0 S0378775316303664 Main PDF
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 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.
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
92
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
93
Fig. 2. (a) AFM image of a single sheet of graphene (b) FE-TEM image of single graphene layers (c) the corresponding line diagram.
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
94
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
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.
96
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.
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
(2)
98
Table 2
IeV characteristic of the Pt and HC-GCF counter electrode based DSSCs.
CE
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.
References
[1] B. O'regan, M. Gr
atzel, Nature 353 (1991) 737e740.