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Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 6549
www.rsc.org/materials COMMUNICATION
Flexible conductive threads for wearable dye-sensitized solar cells†
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Shaocong Hou, Zhibin Lv, Hongwei Wu, Xin Cai, Zengze Chu, Yiliguma and Dechun Zou*
Received 22nd December 2011, Accepted 8th February 2012
DOI: 10.1039/c2jm16773e

Flexible conductive threads were successfully fabricated on cheap
insulating commercial thread substrates using a dip-coating method
with conductive polymer PEDOT:PSS. The PEDOT:PSS
improved the conductivity and catalytic performance of the threads.
For the first time, threads were utilized to fabricate fiber-shaped
dye-sensitized solar cells with 4.8% efficiency.
Recently, flexible/wearable electronics have been drawing more and
more attention for their advantages in combined electronics and
fabrics.1 Weaving using fiber electric devices as building blocks is one
of the attractive potential methods for fabricating flexible and
wearable electric devices.2 To date, fiber electronics have taken
important steps forward,2–4 such as the successful fabrication of fiber
sensors, fiber field-effect transistors, and fiber actors. However, some
obstacles have been encountered, one of which is energy harvesting/
storage because all energy-consuming devices need energy to main-
tain their normal electronic functions.5 Thus, fiber energy converters,
such as thermoelectric converter,6 piezoelectric converter,7 and
photoelectric converter,8,9 have been proposed to address the issues
above.
Fiber electrodes play an important role as indispensable compo-
nents to fiber devices in both collecting electron/hole carriers and
loading functional materials. Excellent conductivity is a basic
requirement and is desirable for fiber electrodes. Fiber electrodes
should possess electrocatalytic performance aside from good flexi-
bility, lightweight, and human/fiber interface comfortability for
electrochemical devices, such as dye-sensitized solar cells
(DSSCs).10–14 Metal wires are the most common fiber electrodes with
good conductivity, however, their flexibility needs to be improved
and their weight needs to be reduced. Considering the wide appli-
cation of flexible, light, and comfortable natural or synthetic polymer
fibers in the textile field, they would be ideal electrodes for wearable
electronics if they are endowed with conductivity via surface modi-
fication with other conductive materials. Conductive polymer is
especially suitable for modifying polymer fiber compared with metal
and metal oxide inorganic conductive materials, because it shows
better compatibility with a polymer fiber substrate.15 Thus, the
all-polymer electrode could not only obtain good conductivity, but
also preserve the physical and comfort properties of the fiber
substrate. So far, the highest conductivity of 100 S cm 1 is achieved by
coating PEDOT/PSS on the polyamide monofilament,16 while that of
dip-coated conductive threads are less than 10 S cm 1.17
In the current study, all-polymer conductive threads were
successfully prepared via dip-coating methods using a DMSO doping
commercial PEDOT:PSS solution with a low-cost commercial and
textile-used thread. The final conductive thread possessed good
conductivity (109 S cm 1), catalytic performance to I /I3 redox
shuffler, and flexibility. Moreover, the conductive thread was used for
the first time as a counter electrode for the fiber-shaped DSSC and
showed good photovoltaic performance.
The commercial polyester threads used in the current study
comprised 15 mm diameter high-oriented monofilaments that were
twisted together. The thread loosened and the diameter was not well
defined because of crude industrial technology. However, the
PEDOT:PSS treatment improved the appearance of the conductive
thread, as shown in Fig. 1. The monofilaments were adhered close
together by PEDOT:PSS and formed a composite thread with
a diameter of approximately 300 mm. The surface of the thread was
well covered with the PEDOT:PSS film and the parallel veinlet on the
film caused by the monofilaments undersurface was easily observed.
The continuous and completed PEDOT:PSS film favors good

Beijing National Laboratory for Molecular Sciences, Key Laboratory of

Polymer Chemistry and Physics of Ministry of Education, College of
Chemistry and Molecular Engineering, Peking University, Beijing,
China. E-mail: dczou@pku.edu.cn; Fax: +86-10-62759799; Tel: +86-10-
62759799 Fig. 1 Morphology of the conductive thread. (a and b) SEM images of
† Electronic supplementary information (ESI) available: Additional the conductive thread and (c and d) cross-section SEM images of the
experimental details. See DOI: 10.1039/c2jm16773e conductive thread.

This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 6549–6552 | 6549

conductivity. Fig. 1c and d show the cross-section SEM images of the
conductive thread. The PEDOT:PSS conductive polymer bound the
monofilaments together, and a conductive network, which enhanced
the conductivity of the thread and increased the surface area of the
conductive polymer, was formed inside the thread. Moreover, the
PEDOT:PSS film surrounding the monofilaments was in the nano-
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metres range, which was too thin to be determined using the current
experimental instruments. However, the flexibility of the thread was
preserved because of the thin but robust film. Therefore, the
conductive thread could be bended or knotted, while the conductivity
and mechanical properties sacrificed a little, which are the basic
requirements for weaving the thread into textile electronics.3
The dipping–coating times could be used to easily adjust the
PEDOT:PSS loading on the thread. The PEDOT:PSS loading was
found to increase linearly with dipping–coating times, whereas the
resistance of the thread linearly decreased, as shown in Fig. 2a. Only
0.316 mg of PEDOT:PSS per centimetre of the thread was observed
when the thread was dipped 10 times. However, the resistance was
reduced to 13 U cm 1, i.e., 109 S cm 1. The fabrication of the highly
conductive threads is an important step in the fiber electronics field.18
Cyclic voltammetry (CV) was used to investigate the catalytic
performance of the conductive threads to I /I3 . Fig. 2b shows the
CV curves of three conductive threads with different PEDOT:PSS
loadings. Two couples of obvious redox current peaks show the high
catalytic performance of the conductive thread ascribing to PEDOT
modification. The I /I3 and I2/I3 catalytic redox reactions caused
the left and right peaks, respectively.19 The peak currents significantly
increased when the PEDOT:PSS loading increased from 0.104 mg
cm 1 to 0.206 mg cm 1, indicating that high loading improves cata-
lytic performance. The peak currents slightly increased when the
PEDOT:PSS loading was further increased to 0.316 mg cm 1. The
surface area of the PEDOT:PSS reasonably produced a positive
effect on the total catalytic surface and thus on the catalytic perfor-
mance.20 The surface of the PEDOT on the thread will lightly increase
after completely covering the surface of monofilaments using
a special amount of PEDOT:PSS. However, further increase in
PEDOT:PSS does not increase the surface.
Fig. 2 (a) PEDOT mass loading and the resistance of the conductive
thread vs. dipping time in the fabrication process; (b) CV curves of the
conductive thread with different PEDOT mass loadings; (c) CV curves of
the conductive thread in continuing 50 scanning cycles at 100 mV s 1; (d)
CV curves of the conductive thread at different scanning rates.
6550 | J. Mater. Chem., 2012, 22, 6549–6552
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Fifty continuous CV cycles were conducted in acetonitrile solution
containing I /I3 to validate the catalytic stability of the conductive
thread (Fig. 2c). The curve of the 13th cycle had a lower redox current
compared with the curve of the first CV cycle, indicating a strong
interaction between the PEDOT:PSS and the components in the
solution in the previous 13 cycles.22 However, the CV curves,
including peak potential and current, were almost similar to one
another in the following 37 cycles, demonstrating that the conductive
thread had good electrochemical stability.
Fig. 2d shows the CV curves of the conductive thread at different
scanning rates. The linear relationship between the peak current
and square root of the scanning rate was obtained to explore the
electrochemical dynamics process of the thread. According to results
in the literature,21 the transport of I on the surface of the conductive
thread may have caused the redox species diffusion-limited process.
The electrochemical properties described above show the potential
application of conductive threads in DSSCs.
The fiber-shaped dye-sensitized solar cells were fabricated
(as shown in Fig. 3a) using conductive threads as counter electrodes
to illustrate their potential application in optic-electronics. Fig. 3b
shows the photovoltaic performances of the solar cells and their
parameters are summarized in Table 1. Using conductive thread
loading of 0.104 mg cm 1 PEDOT:PSS, the corresponding device had
the following good performances: open-circuit voltage (Voc), short-
circuit voltage (Jsc), filled factor (FF), and photoelectron conversion
efficiency (PCE) reached 0.699 V, 11.3 mA cm 2, 0.56, and 4.46%,
respectively. FF increased to 0.63 or 0.67 when the loading increased
to 0.206 mg cm 1 or 0.316 mg cm 1, respectively, whereas Voc and Jsc
had a slight change. The final PCE grew up to 4.54% or 4.82%,
respectively. The results are comparable to those of DSSCs using
platinized carbon fiber as counter electrodes.14 Our conductive
polymer threads show both lower cost and better resistant to shear
force than carbon fiber-based CEs.
The electrochemical impedance was determined in situ under dark
condition to clarify the relationship between the conductive thread-
based counter electrode and the device performance. Fig. 3c and
d show the Nyquist curves of three devices with different
PEDOT:PSS loadings. Each curve contained three arcs, including the
Fig. 3 (a) Photo of the fiber solar cell; (b) I–V curves of fiber-shaped
solar cells using conductive thread electrodes with different PEDOT mass
loadings and (c and d) EIS curves of fiber-shaped solar cells using
conductive thread electrodes at 0.68 V under dark conditions.
This journal is ª The Royal Society of Chemistry 2012

Table 1 EIS and I–V parameters of devices with different CEs
Loading/mg cm 1
Rs/U RCE/U Voc/V Jsc/mA cm 2
FF h (%)
1 0.104 218 19.2 0.699 11.3 0.56 4.46
2 0.206 77.1 15.0 0.680 10.6 0.63 4.54
3 0.316 73.2 12.5 0.676 10.7 0.67 4.82
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left high-frequency arc corresponding to the electron transport
process through the counter electrode/electrolyte interface, the middle
arc corresponding to the carrier-recombining process through the
photoanode/electrolyte interface, and the right low-frequency arc
corresponding to the diffusion process of redox species in the elec-
trolyte.23 The series ohm resistance of the device (Rs), the electron
transport resistances of the counter electrode/electrolyte interface
(RCE), and the carrier-recombined resistances of the counter elec-
trode/electrolyte interface (RWE) were obtained via electrochemical
circle fitting. The Rs and RCT of the devices using a conductive thread
with 0.104 mg cm 1 of PEDOT:PSS were 218 and 19.2 U, respec-
tively. According to the literature,24 Rs and RCT, which have negative
effects on FF, contribute to the total resistance of the device and thus
to PCE. Low RCT is consistent with the good catalytic performance
of the conductive thread. However, high Rs, which is mainly attrib-
uted to the high resistance of the conductive thread, is detrimental to
device performance. The Rs greatly dropped to 77.1 U and the RCT
also decreased to 15.0 U, when the PEDOT:PSS loading increased to
0.206 mg cm 1. Thus, small Rs and RCT could reduce the total series
ohm resistance and then improve the FF. The Rs and RCT minimally
dropped and thus the FF was improved, when the PEDOT:PSS
loading was further increased to 0.316 mg cm 1.
The power output of the fiber DSSCs should be easy to adjust to
satisfy different power-consuming wearable electronic devices. The
illuminated area of the fiber DSSCs is proportional to device length.
Moreover, the photovoltaic performances of the devices with
different lengths were investigated, as shown in Fig. 4. The short-
circuit current linearly increased with the device length, indicating
that the desirable current output could easily be obtained by changing
the device length. However, the Voc and FF slightly decreased mainly
because of the series ohm resistance, leading to the decrease in PCE.
The resistance of the conductive thread increased with length, thus,
a larger voltage drop occurred at the counter electrode, leading to the
lower Voc. The PCE of the 5.5 cm long fiber DSSC was maintained at
3.8%. To reduce the adverse effect of series ohm resistance on device
performance, it is important to further improve the conductivity of
the PEDOT:PSS film, which is our following work in future.
The conductivity of the conductive polymer PEDOT is highly
dependent on its doping with organic molecule, such as the DMSO in
Fig. 4 (a) I–V curves of the fiber-shaped DSSCs with different device
lengths and (b) the photovoltaic parameters vs. the device length.
This journal is ª The Royal Society of Chemistry 2012
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the current study.25 Volatilizing or dissolving in solvent may result in
changes in doped concentration, as well as in the conductivity of
PEDOT, during staining via organic solvent or washing processes.
The conductive threads were soaked in different solvents for a day
and then dried to clarify their resistance to solvents. Water, aceto-
nitrile, and liquid electrolyte containing I /I3 were chosen for
considering the actual environment and application in liquid-state
DSSCs. The conductivity of the conductive threads sacrificed a little
when treated with water and their conductivity dropped by approx-
imately 10% and 20% when treated with acetonitrile and electrolyte,
respectively. These results show that the current experimental
conductive threads have good resistance to the solvents above and
thus their high stability is key to their actual application in a complex
environment.18 These conductive threads treated with solvents were
further used to fabricate fiber DSSCs (4, 5, and 6) as described above.
Fig. 5 shows the photovoltaic and electrochemical properties of the
DSSCs. Device 4 had a higher filled FF (0.69) and PCE (5.18%)
compared with device 3, whereas devices 5 and 6 had lower PCE
(4.05% and 4.39%, respectively) because of lower Jsc and FF. The Voc
of device 6 was larger by 40 mV than that of device 3, indicating the
interaction between the redox species and the PEDOT changed the
redox potential on the surface of the conductive thread.22
EIS was used to explain the effect of solvent treatment on the
properties of counter electrodes and corresponding devices. The three
phase peaks in the Bode plots (Fig. 5b) from right to left correspond
to the electron transport process through the counter electrode/elec-
trolyte interface, carrier recombination process photoanode/electro-
lyte interface and diffusion process in electrolyte, respectively. The
right peak of devices 4, 5, and 6 slightly shifted to low frequency and
shows that the characteristic time for electron transport increased
compared with that of device 3, indicating a smaller electron trans-
port speed through the PEDOT:PSS/electrolyte interface. The results
have verified some changes in the electrochemical properties of the
conductive threads after solvent treatment. Fig. 5c and d show the
Nyquist plots of devices 3 to 5, and the corresponding parameters are
summarized in Table 2. The order of Rs, from low to high, was
devices 4, 1, 5, and 6, which is consistent with the resistance of the
corresponding conductive threads. The RCE of devices 4, 5, and 6
increased to 21.4, 47.2, and 76.6 U, respectively, compared with
Fig. 5 I–V (a), Bode (b), and Nyquist (c and d) curves of the fiber-
shaped solar cells using conductive thread electrodes soaked in water,
acetonitrile, and electrolyte.
J. Mater. Chem., 2012, 22, 6549–6552 | 6551
 View Article Online

Table 2 EIS and photovoltaic parameters of the fiber-shaped DSSCs 3 L. B. Hu, M. Pasta, F. La Mantia, L. F. Cui, S. Jeong,
using conductive thread electrodes soaked in different solvents (H2O, H. D. Deshazer, J. W. Choi, S. M. Han and Y. Cui, Nano Lett.,
ACN, and electrolyte) 2010, 10, 708.
4 D. Marculescu, R. Marculescu, N. H. Zamora, P. Stanley-Marbell,
Solvent Rs/U RCE/U Voc/V Jsc/mAcm 2
FF h (%) P. K. Khosla, S. Park, S. Jayaraman, S. Jung, C. Lauterbach,
W. Weber, T. Kirstein, D. Cottet, J. Grzyb, G. Troster, M. Jones,
4 H2O 48.4 21.4 0.700 10.77 0.69 5.18 T. Martin and Z. Nakad, Proc. IEEE, 2003, 91, 1995.
5 ACN 73.2 47.2 0.670 9.76 0.62 4.05 5 H. Nishide and K. Oyaizu, Science, 2008, 319, 737.
Published on 29 February 2012. Downloaded by University of Minnesota - Twin Cities on 31/05/2013 09:51:09.

6 Electrolyte 81.9 76.6 0.715 10.13 0.61 4.39
device 3, indicating that the catalytic performances of the counter
electrodes were weakened, probably because of the corrosion effects
of the solvents, especially polar organic solvents, to the PEDOT:PSS
film. The resistance of the PEDOT:PSS film to solvent could be
improved by doping the conductive polymer with macromolecules,
such as PEO, or via cross-linking, which will be the next study to be
conducted.
All polymer conductive threads were successfully fabricated via
dip-coating with commercial threads and PEDOT:PSS solution. It is
a universal method to fabricate conductive threads on insulating
thread substrates (such as cotton, wool, and silk threads) with other
conductive polymers (such as polyaniline and polypyrrole). The good
conductivity, catalytic performance, and stability of these conductive
threads show their potential applications in electronic devices, espe-
cially in electrochemical devices. Moreover, these conductive threads
are flexible and robust enough to be weaved into textiles.
Acknowledgements
This work was jointly supported by MOST (2011CB933300), NSFC
(50833001), and MOE (309001), China.
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6552 | J. Mater. Chem., 2012, 22, 6549–6552 This journal is ª The Royal Society of Chemistry 2012