Materials Science in Semiconductor Processing 63 (2017) 190–195

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Materials Science in Semiconductor Processing

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

Low-cost counter electrodes based on nitrogen-doped porous carbon MARK

nanorods for dye-sensitized solar cells
⁎
Guiqiang Wang , Chao Yan, Shuo Hou, Wei Zhang
School of New Energy, Bohai University, Jinzhou 121013, China

A R T I C L E I N F O A BS T RAC T

Keywords: Nitrogen-doped porous carbon nanorods (N-PCNRs) with high accessible surface area are prepared by
Nitrogen doping carbonization of polyaniline (PANI) nanorods and subsequent chemical activation, and explored as the counter
Porous carbon nanorods electrode in dye-sensitized solar cells (DSCs). SEM and TEM images demonstrate that the nanorod morphology
Counter electrode of PANI is preserved after pre-carbonization and chemical activation treatment. The unique combination of the
Dye-sensitized solar cells
porosity with high accessible surface area, nitrogen doping, and nanorod structure endows the N-PCNR
electrode with an excellent electrocatalytic activity for the I3- reduction, which is illuminated by the
electrochemical measurements. Under simulated AM 1.5 illumination (100 mW cm−2), the DSC based on N-
PCNR counter electrode achieves a conversion efficiency of 7.01%, which is nearly close to that of the cell based
on Pt counter electrode (7.25%).

1. Introduction current performances of these carbonaceous materials are still lower

Since reported by Grätzel's group in 1991, dye-sensitized solar cells
(DSCs) have attracted wide-spread attention and been considered as
one of the most promising alternative to Si solar cells due to their low
cost, simple fabrication process, relatively high conversion efficiency,
and good stability [1–5]. In general, a DSC is consisted of a dye-
sensitized TiO2 photoanode, an electrolyte containing I-/I3- redox
couple, and a catalytic counter electrode. The counter electrode plays
an important role in determining the photovoltaic performance of
DSCs in term of collecting the electrons from external circuit and
catalyzing the reduction of I3- at the electrolyte/counter electrode
interface. Therefore, the ideal counter electrode should possess high
electrical conductivity and good electrocatalytic activity for the reduc-
tion of I3- [6]. So far, the most comment materials used for the counter
electrode of DSCs is Pt due to its excellent conductivity and superior
electrocatalytic performance [7–10]. However, the scare reserve in
nature and the associated high price hinder its large-scale application
in DSCs. Therefore, some cost-effective alternatives to Pt in the counter
electrode of DSCs have been extensively studied, such as polyaniline
[11–15], carbon-based materials [16], and metal sulfide [17].
Recently, many efforts have been made to replace Pt using
carbonaceous materials such as carbon nanotubes [18,19], porous
carbon [20–22], graphene [23–25], carbon fibers [26], and carbon
black [27] in the counter electrode of DSCs owing to their low cost,
good electrocatalytic performance, and high conductivity. However, the
than that of Pt and should be further improved for practical application
in DSCs. The electrocatalytic performance of carbonaceous materials
relies heavily on their morphology and microstructure, which greatly
influences the effective electrocatalytic surface area and the electrolyte
diffusion within the catalyst layer. It has been reported recently that the
nitrogen-doping and porous structure of carbonaceous materials can
enhance their conductivity, surface hydrophilicity, and electrocatalytic
activity, respectively, and then are of great benefit to the counter
electrode application in DSCs [28–30]. Xue et al. [31] prepared a
nitrogen-doped 3D graphene foam and demonstrated its application as
an efficient electrocatalyst to replace Pt in the counter electrode of
DCSs, leading to a conversion efficiency up to 7.07%. Li et al. [32]
reported the synthesis of nitrogen-doped macro/mesoporous carbon
with 3D interconnected open-pore structure as the efficient counter
electrode material. The nitrogen-doped macro/mesoporous carbon
showed a high conversion efficiency of 7.27%, which was even slightly
better than that of Pt electrode. These results indicate that nitrogen-
doped carbon nanomaterial with suitable porous structure is an ideal
low-cost counter electrode material in DSCs.
In this work, nitrogen-doped porous carbon nanorods (N-PCNRs)
with high accessible surface area were prepared by carbonization of
polyaniline (PANI) nanorods and subsequent chemical activation, and
employed as the Pt-free counter electrode in DSCs. The one-dimen-
sional nanorod structure provides direct pathway for the electron
transport and then enhances the electron transport within the N-

⁎
Corresponding author.
E-mail address: wgqiang@bhu.edu.cn (G. Wang).

http://dx.doi.org/10.1016/j.mssp.2017.02.018
Received 29 November 2016; Received in revised form 8 February 2017; Accepted 13 February 2017
Available online 21 February 2017
1369-8001/ © 2017 Elsevier Ltd. All rights reserved.
G. Wang et al.
Fig. 1. Process used for the preparation of nitrogen-doped porous carbon nanorods (N-PCNRs).
PCNR layer. The nitrogen-doping as well as the porosity with high
accessible surface area provides numerous electrocatalytic active sites
for I3- reduction. This combination of characteristics means that N-
PCNR electrode possesses an excellent electrocatalytic activity for the
reduction of I3-. The assembled DSC with N-PCNR counter electrode
exhibits a high conversion efficiency of 7.01%, which is very close to
that of the cell with Pt counter electrode.
2. Experimental
2.1. Preparation of N-PCNR electrodes
PANI nanorods were firstly prepared by polymerization of aniline in
aqueous solution using ammonium persulfate (APS) as the initiator.
Briefly, 10 g of aniline and 7 g of citric acid were mixed in 500 mL of
distilled water. 20 g of ammonium persulfate was dissolved in 150 mL
of distilled water. Then, ammonium persulfate solution was added into
the mixture solution of aniline and citric acid with vigorous stirring.
The resulting solution was left standing at about 3 °C for 20 h. The
obtained dark green sample was filtered and washed with distilled
water, and then dried under vacuum at 50 °C.
The as-prepared PANI nanorods were pyrolyzed at 600 °C under
nitrogen atmosphere for 3 h to obtained nitrogen-doped carbon
nanorods (N-CNRs). N-PCNRs were prepared by activating N-CNRs.
In brief, 3 g of N-CNRs were mixed with 9 g of KOH in aqueous
solution by stirring and subsequent sonication, followed by evaporation
at 90 °C. Then, above mixture was transferred into a tube furnace for
activation at 800 °C under nitrogen atmosphere with duration of 2 h.
The obtained product was rinsed with 1 M HCl solution and distilled
water until the pH value of effluent reached about 7, and then dried at
80 °C in air.
150 mg of as-prepared N-PCNRs were ground with 10 mL isopro-
panol and 10 μL tetrabutyl titanate in a mortar to obtain N-PCNRs
paste. The N-PCNR electrodes were fabricated by spraying the N-PCNR
paste onto pre-cleaned fluorine-doped tin oxide (FTO) glass, followed
by sintering at 400 °C for 15 min. N-CNR electrodes were also
prepared through the same procedure. The thickness of the carbon
catalyst layer was about 9 µm, which was controlled by the spray time.
2.2. Fabrication of DSCs
TiO2 electrodes were prepared by coating 9 µm-thick TiO2 film on
FTO glass using doctor-blade method and then sintering at 450 °C for
30 min. The TiO2 electrodes sensitized with N719 dye were used as the
photoanodes. A solution containing 0.5 M 1-hexyl-3-methylimidazo-
lium iodide, 0.2 M LiI, 0.05 M I2, and 0.4 M 4-tert-butylpyridine in 3-
methoxypropionitrile was used as the electrolyte. The DSC was
fabricated by clapping a photoanode, an electrolyte, and a counter
electrode into a sandwich structure.
2.3. Measurements and characterization
The morphology of samples was observed by scanning electron
microscopy (SEM, Hitachi S-4800) and transmission electron micro-
scopy (TEM, JEOL JEM2010). The surface area and pore structure of
the samples were measured by a Micromeritics ASAP 2020 instrument
191
Materials Science in Semiconductor Processing 63 (2017) 190–195
using N2 sorption at 77 K. X-ray photoelectron spectroscopy (XPS)
analysis was carried out on an ESCAlab 220I-XL spectrometer with Al
Kα radiation. Electrochemical measurements were carried out on
Solartron1255/1287 system. Electrochemical impedance spectroscopy
(EIS) was conducted with symmetric thin-layer cells in the frequency
range of 0.1–105 Hz at 0 V bias and 10 mV amplitude. Cyclic voltam-
metry (CV) measurements were performed in a three-electrode system
using a Pt wire as counter electrode and Ag/AgCl electrode as reference
electrode in acetonitrile solution containing 0.01 M LiI, 0.001 M I2,
and 0.1 M LiClO4. The scan rate is 50 mV s−1. The photocurrent-
voltage curves of DSCs were recorded by a Keithley 2400 source meter
under a simulated AM 1.5 illumination at 100 mW cm−2.
3. Results and discussion
N-PCNRs were prepared by carbonization of PANI nanorods at
600 °C and subsequent chemical activation at 800 °C (see Fig. 1). PANI
is an ideal precursor for preparing nitrogen-doped carbonaceous
materials due to its high content of nitrogen and uniformly distributed
nitrogen atoms in its framework. In addition, PANI with different
morphologies, such as nanofiber, nanotube, and nanosphere, can be
easily prepared by controlling the synthesis conditions [33–35], and
these original morphologies can be preserved even after high-tempera-
ture treatment. Accordingly, nitrogen-doped carbon nanorods (N-
CNRs) were prepared from PANI nanorods through high-temperature
carbonization. By activating N-CNRs, N-PCNRs were prepared. Fig. 2
displays SEM and TEM images of original PANI nanorods, N-CNRs,
and N-PCNRs. As shown in Fig. 2a and b, the PANI exhibits a nanorod-
like morphology with rough surface. The diameters of PANI nanorods
are in the range of 150–200 nm and the lengths range from 0.5 to
3 µm. After carbonization and chemical activation treatment, the
nanorod morphology is preserved except that the aspect ratio of
nanorod decrease slightly as shown in Fig. 2(c–f). The high-resolution
TEM image shown in Fig. 2g demonstrates that N-CNRs possess a
smooth surface. During the chemical activation, KOH corroded carbon
nanorods at high temperature to develop new pores on the surface of
carbon nanorods. Therefore, the as-prepared N-PCNRs exhibit the
well-developed pore structure as shown in Fig. 2h.
The pore structure and surface area of N-CNRs and N-PCNRs were
determined by N2 sorption measurements. Fig. 3 shows the N2
adsorption-desorption isotherms and pore-size distribution curves of
N-CNRs and N-PCNRs. As displayed in Fig. 3a, the isotherms of N-
CNRs are of type I, and the adsorption branch nearly overlap with
desorption branch over a wide range of relative pressure. In addition,
the nitrogen adsorption capacity of N-CNRs is small. These results
demonstrate that N-CNRs are poorly porous. The Brunauer-Emmett-
Teller (BET) surface area and pore volume of N-CNRs are 116.3 m2 g−1
and 0.10 cm3 g−1, respectively. N-PCNRs presents a combined type I/
IV isotherms with an obvious hysteresis loop at the relative pressure
0.4–0.8, demonstrating a characteristic of both the mesoporosity and
the microporosity. The pore-size distribution curve shown in Fig. 3b
further demonstrates that N-PCNRs have both micropores and well-
developed mesopore. The significant increase in the nitrogen uptake in
the entire pressure range for N-PCNRs is a result of the increase in
porosity created by chemical activation. The BET surface area and pore
volume of N-PCNRs are 2580.5 m2 g−1 and 1.36 cm3 g−1, respectively,
G. Wang et al.
Fig. 2. SEM and TEM images for PANI nanorods (a and b), N-CNRs (c and d), and N-PCNRs (e and f); the high-resolution TEM images of N-CNRs (g) and N-PCNRs (h).
which are much higher than those of N-CNRs.
XPS measurements were conducted to determine the element
compositions and states of N-CNRs and N-PCNRs. Fig. 4 exhibits
XPS survey spectra and N 1 s peaks for N-CNRs and N-PCNRs. As
expected, XPS survey spectra of N-CNRs and N-PCNRs (Fig. 4a) show
three peaks at binding energy of 288.1, 400.1, and 533.2 eV, corre-
sponding to C 1 s, N 1 s, and O 1 s, respectively. The elemental content
calculated from XPS survey spectra are summarized in Table 1. The
nitrogen and oxygen contents of N-CNRs are 8.67 at% and 9.77 at%,
respectively, while the nitrogen and oxygen contents of N-PCNRs are
2.03 at% and 14.62 at%, respectively. Clearly, the chemical activation
leads to a decrease in nitrogen content and an increase in oxygen
content. The N 1 s peak for N-CNRs can be deconvoluted into three
peaks centered at binding energy of 398.6, 400.1, and 401.2 eV
(Fig. 4b), assigning to pyridinic nitrogen (N-6), pyrrolic nitrogen (N-
5), and quaternary nitrogen (N-Q), respectively [36]. The deconvolu-
tion of N 1 s peak for N-PCNRs (Fig. 4c) displays three peaks at the
same binding energies, however, with different relative contributions.
From Table 1, it can be seen that after chemical activation, the relative
content of N-6 increase greatly, while the relative content of N-Q
decrease considerably. This indicates that N-6 and N-5 are predomi-
nant in N-PCNRs. N-6 and N-5 locate at the edge of the graphene layer,
and then can provide the electrochemically active sites to improve the
electrocatalytic performance of carbon materials [37].
EIS measurements were employed to characterize the electrocata-
lytic activity of N-CNR and N-PCNR electrodes for the I3- reduction.
Volume absorbed (cm g STP)
1500
-1
1200
3
900
600
300
0 0.0
0.0 0.2 0.4
Relative pressure (P/P0)
Fig. 3. N2 adsorption-desorption isotherms (a) and pore-size distribution curves (b) of N-CNRs and N-PCNRs.
Materials Science in Semiconductor Processing 63 (2017) 190–195
The cross-section SEM image of N-PCNR electrode in Fig. 5 shows that
the carbon catalyst layer has a thickness of about 9 µm. In order to
eliminate the effect of TiO2 photoanode, the symmetric thin-layer cells
consisting of two identical electrodes were used for EIS measurements.
Fig. 6a displays Nyquist plots of the symmetric cells based on N-CNR
and N-PCNR. For comparison, the Nyquist plot for Pt electrode was
also exhibited in Fig. 6a. Pt electrodes were prepared by thermal
decomposition of H2PtCl6 on FTO glass at 390 °C for 15 min. From
Fig. 6a, it can be seen that all Nyquist plots show two semicircles in the
high and low frequency regions, corresponding to the charge-transfer
process at the electrode/electrolyte interface and Nernst diffusion
process in the electrolyte, respectively. The corresponding equivalent
circuit is shown in the inset in Fig. 6a, in which Rs is the ohmic series
resistance, Rct is the charge-transfer resistance, CPE is the constant
phase element, ZN is the Nernst diffusion impedance. The EIS
parameters are obtained by fitting Nyquist plots and listed in
Table 2. Rct is a significant parameter to evaluate the electrocatalytic
activity of the electrode for the reduction of I3-. The smaller Rct value
is, the higher electrocatalytic activity could be. As shown in Table 2, Rct
for Pt, N-CNR, and N-PCNR electrodes are 1.6, 8.9 and 2.2 Ω cm2,
respectively. Clearly, the electrocatalytic activity of N-PCNR electrode
is much higher than that of N-CNR electrode, and nearly close to that
of Pt electrode. This greatly enhanced electrocatalytic activity of N-
PCNR electrode can be attributed to the unique porous nanorod
structure. As shown in Fig. 6b, the nanorod structure can provide a
direct pathway for fast electron transport, and the porosity with high
a 1.0
b
Pore volume (cm g )
-1
0.8
3
0.6
N-CNRs
N-CNRs 0.4 N-PCNRs
N-PCNRs
0.2
0.6 0.8 1.0
2 4 6 8 10
Pore size (nm)
192
G. Wang et al. Materials Science in Semiconductor Processing 63 (2017) 190–195

C 1s a c
b

Intensity (a .u.)

Intensity (a .u.)
O 1s
Intensity (a .u.)

N 1s N-5
N-CNRs

N-Q
N-6 N-5
N-PCNRs N-6

N-Q

0 200 400 600 800 1000 393 396 399 402 405 392 394 396 398 400 402 404 406
Binding energy (eV) Binding energy (eV) Binding energy (eV)
Fig. 4. (a) XPS scanning spectra of N-CNRs and N-PCNRs; deconvoluted N 1 s peaks of N-CNRs (b) and N-PCNRs (c).

Table 1 Table 2
Oxygen and nitrogen content in N-CNRs and N-PCNRs determined by XPS. EIS parameters of the symmetric thin-layer cells with Pt, N-CNR, and N-PCNR
electrodes and photovoltaic parameters of DSCs with Pt, N-CNR, and N-PCNR counter
Sample C content (at%) O content (at%) N content (at%) electrodes.

Total N-6 N-5 N-Q Electrode Rct (Ω Rs (Ω CPE (μF Voc (V) Jsc (mA FF η (%)
cm2) cm2) cm−2) cm−2)
N-CNRs 81.56 9.77 8.67 2.89 3.73 2.05
N-PCNRs 83.35 14.62 2.03 0.96 0.81 0.26 N-CNR 8.9 16.8 23.6 0.678 15.01 0.58 5.91
N-PCNR 2.2 17.1 41.2 0.702 15.85 0.63 7.01
Pt 1.6 16.5 5.8 0.698 15.98 0.65 7.25

doping, and the nanorod structure endows the N-PCNR electrode with
an excellent electrocatalytic activity. The Rs values of Pt, N-CNR, and
N-PCNR electrode do not vary significantly, demonstrating a good
binding of carbon nanorods with FTO substrate and a fast electron
transport through carbon nanorods network. As expect, N-PCNR
electrode exhibits the highest CPE value among the three electrodes
due to the largest surface area.
Cyclic voltammetry (CV) measurements were also carried out using
a three-electrode system to examine the electrocatalytic activity of the
electrodes. Fig. 7 shows CV curves for Pt, N-CNR, and N-PCNR
electrodes. Two pair redox peaks can be observed in CV curves. The
pair at more positive potentials is assigned to the redox reaction of I3-/
I2 couple (3I2 +2e ↔ 2I3-), and the pair at more negative potentials is
attributed to the redox reaction of I3-/I- (I3- +2e ↔ 2I-). The function of
Fig. 5. The cross-section SEM image of N-PCNR electrode. the counter electrode in a DSC is to catalyze the reduction of I3- to I-.
Therefore, the characteristics of the negative pair are usually employed
accessible surfaces area as well as the nitrogen doping of N-PCNRs to evaluate the electrocatalytic activity of the counter electrode. From
provides more electrocatalytic active sites. Therefore, it is the combina- Fig. 7, it can be observed that the peak current densities of N-PCNR
tion of the porosity with high accessible surface area, the nitrogen electrode are higher than those of the N-CNR electrode and comparable

10
2Rct ZN
a
2Rs
8
-Z'' (o hm cm )
2

6 1/2Cdl N-CNR
N-PCNR
Pt
4

0
35 42 49 56 63
2
Z' (ohm cm )
Fig. 6. (a) Nyquist plots of the cell based on Pt, N-CNR, and N-PCNR electrodes; (b) diagram of the electrochemical reaction process in N-CNRs and N-PCNRs. The inset in (a) is the
equivalent circuit.

193
G. Wang et al.
Current density (mA cm )
-2
2 4. Conclusions
Pt
N-PCNR
N-CNR
0 and successfully investigated as the efficient counter electrode for
-2
-1.0 -0.5 0.0 0.5 1.0
Voltage (V)
Fig. 7. CV curves of Pt, N-CNR, and N-PCNR electrodes obtained by a three-electrode
system at scan rate of 50 mV s−1.
20
Current density (mA cm )
-2
16
12
8 Pt
N-PCNR
N-CNR
4 based redox electrolyte exceeding 12 percent efficiency, Science 334 (2011)
PANI
0 sensitized solar cells, Chem. Rev. 115 (2015) 2136–2173.
0.0 0.2 0.4 0.6 0.8
Voltage (V)
Fig. 8. Photocurrent density-voltage curves of the DSCs with Pt, N-CNR, N-PCNR, and
PANI electrodes measured under simulated AM 1.5 illumination.
to those of the Pt electrode. This indicates that the electrocatalytic
activity of N-PCNR electrode is higher than that of N-CNR electrode
and comparable to that of Pt electrode, displaying that N-PCNRs can be
used as an efficient counter electrode material for application in DSCs.
The current density-voltage curves of DSCs fabricated with Pt, N-
CNR, and N-PCNR counter electrodes are displayed in Fig. 8. The
corresponding photovoltaic parameters, such as the open-circuit
voltage (Voc), the short-circuit current density (Jsc), the fill fact (FF),
and the conversion efficiency (η), are summarized in Table 2. The DSC
fabricated with N-CNR counter electrode exhibits a Voc of 0.678 V, a
Jsc of 15.01 mA cm−2, a FF of 0.58, and a conversion efficiency of
5.91%. When N-PCNR is used as the counter electrode, the photo-
voltaic parameters of the corresponding DSC are Voc=0.702 V,
Jsc=15.85 mA cm−2, FF=0.63, and η=7.01%. Obviously, the photovol-
taic performance of the DSC with N-PCNR counter electrode is much
better than that of the cell with N-CNR counter electrode, and very
close to that of the device with Pt counter electrode. This enhanced
photovoltaic performance can be assigned to the excellent electrocata-
lytic activity of N-PCNR electrode for I3- reduction derived from
combination of the porosity with high accessible surface area, nitrogen
doping, and nanorod structure. Previous works indicated that PANI
can be employed as the Pt-free counter electrode in DSCs [11,17].
Therefore, we also fabricated the PANI nanorod electrode-based DSC
and measured its photovoltaic performance. As shown in Fig. 8, the
conversion efficiency of DSC with N-PCNR counter electrode is much
higher than that of the cell with PANI counter electrode (5.11%). These
results demonstrate that N-PCNRs could be a promising cost-efficient
194
Materials Science in Semiconductor Processing 63 (2017) 190–195
alternative to Pt in the counter electrode of DSCs.
N-PCNRs with high accessible surface area were prepared by
carbonization of PANI nanorods and subsequent chemical activation
DSCs. The as-prepared N-PCNR electrode exhibited an excellent
electrocatalytic activity for I3- reduction and showed a very close
photovoltaic performance to Pt electrode in terms of Voc, Jsc, FF,
and η, which was attributed to the ideal combination of the porosity
with high accessible surface area, nitrogen doping, and nanorod
structure. This work could provide a promising strategy for designing
a low-cost and high-performance counter electrode material in DSCs.
Acknowledgement
This work was supported by National Natural Science Foundation
of China (grant number 21273137) and Liaoning Science &
Technology Project (grant number 201601011)
References
[1] B. O’Regan, M. Grätzel, A low-cost, high-efficiency solar cell based on dye-
sensitized colloidal TiO2 film, Nature 353 (1991) 737–739.
[2] S. Mathew, A. Yella, P. Gao, R. Humph ry-Baker, B. Curchod, N. Ashari-Astani,
I. Tavernrlli, U. Rothlisberger, M.K. Nazeeruddin, M. Grätzel, Dye-sensitized solar
cells with 13% efficiency achieved through the molecular engineering of porphyrin
sensitizers, Nat. Chem. 6 (2014) 242–247.
[3] A. Yella, H. Lee, H. Tsao, C. Yi, A. Chandiran, M.K. Nazeeruddin, E.E. Diau, C. Yeh,
S.M. Zakeeruddin, M. Grätzel, Porphyrin-sensitized soalr cells with cobalt (III/II)-
629–634.
[4] J. Wu, Z. Lan, J. Lin, M. Huang, Y. Huang, L. Fan, G. Luo, Electrolyte in dye-
[5] J. Halme, P. Vahermaa, K. Miettunen, P. Lund, Device physics of dye solar cells,
Adv. Mater. 22 (2010) E210–E234.
[6] N. Papageorgiou, Counter-electrode function in nanocrystalline photoelectro-
chemical cell configurations, Coord. Chem. Rev. 248 (2004) 1421–1446.
[7] H. Elbohy, A. Aboagye, S. Sigdel, Q. Wang, M.H. Sayyad, L. Zhang, Q. Qiao,
Graphene-embedded carbon nanofibers decorated with Pt nanoneedles for high-
efficiency dye-sensitized solar cells, J. Mater. Chem. A 3 (2015) 17721–17727.
[8] V. Dao, H. Choi, Pt nanourchins as efficient and robust counter electrode materials
for dye-sensitized solar cells, ACS Appl. Mater. Interfaces 8 (2015) 1004–1010.
[9] M. Yeh, S. Chang, L. Lin, H. Chou, R. Vittal, B. Hwang, K. Ho, Size effect of Pt
nanoparticles on the electrocatalytic ability of the counter electrode in dye-
sensitized solar cells, Nano Energy 17 (2015) 241–253.
[10] K. Lee, L. Lin, C. Chen, V. Suryanarayanan, C. Wu, Preparation of high
transmittance platinum counter electrode at an ambient temperature for flexible
dye-sensitized solar cells, Electrochim. Acta 135 (2014) 578–584.
[11] W. Hou, Y. Xiao, G. Han, D. Fu, R. Wu, Serrated, flexible and ultrathin polyaniline
nanoribbons: an efficient counter electrode for dye-sensitized solar cell, J. Power
Sources 322 (2016) 155–162.
[12] Y. Xiao, G. Han, Y. Li, M. Li, Y. Chang, High performance of Pt-free dye-sensitized
solar cells based on two-step electropolymerized polyaniline counter electrodes, J.
Mater. Chem. A 2 (2014) 3452–3460.
[13] Y. Xiao, W. Wang, S. Chou, T. Lin, J. Lin, In situ electropolymerization of
polyaniline/cobalt sulfide decorated carbon nanotube composite catalyst towards
triiodide reduction in dye-sensitized solar cells, J. Power Sources 266 (2014)
448–455.
[14] Y. Xiao, J. Lin, J. Wu, S. Tai, G. Yue, T. Lin, Dye-sensitized solar cells with high-
performance polyaniline/multi-wall carbon nanotube counter electrode electro-
polymerized by a pulse potentiostatic technique, J. Power Sources 233 (2013)
320–325.
[15] Y. Xiao, J. Lin, W. Wang, S. Tai, G. Yue, J. Wu, Enhanced performance of low-cost
dye-sensitized solar cells with pulse-electroplymerized polyaniline counter elec-
trode, Electrochim. Acta 90 (2013) 468–474.
[16] S. Yun, A. Hagfeldt, T. Ma, Pt-free counter electrode for dye-sensitized solar cells
with high efficiency, Adv. Mater. 26 (2014) 6210–6237.
[17] M. Wu, T. Ma, Platinum-free catalysts as counter electrodes in dye-sensitized solar
cells, ChemSusChem 5 (2012) 1343–1357.
[18] G. Wang, J. Zhang, S. Kuang, S. Zhuo, Nitrogen-doped porous carbon prepared by a
facile soft-templating process as low-cost counter electrode for high-performance
dye-sensitized solar cells, Mater. Sci. Semicond. Process. 38 (2015) 234–239.
[19] Y. Jo, J. Cheon, J. Yu, H. Jeong, C. Han, Y. Jun, S. Joo, Highly interconnected
ordered mesoporous carbon-carbon nanotube nanocomposite: pt-free high efficient
durable counter electrode for dye-sensitized solar cells, Chem. Commun. 48 (2012)
8057–8059.
[20] B. Zhao, H. Huang, P. Jiang, H. Zhao, X. Huang, P. Shen, D. Wu, R. Fu, S. Tan,
G. Wang et al.
Flexible counter electrodes based on mesoporous carbon aerogel for high-perfor-
mance dye-sensitized solar cells, J. Phys. Chem. C 115 (2011) 22615–22621.
[21] G. Wang, C. Huang, W. Xing, S. Zhuo, Micro-meso hierarchical porous carbon as
low-cost counter electrode for dye-sensitize solar cells, Electrochim. Acta 56 (2011)
5459–5463.
[22] P. Srinivasu, A. Islam, S. Singh, L. Han, M.L. Kantam, S.K. Bhargava, Highly
efficient nanoporous graphitic carbon with tunable textural properties for dye-
sensitized solar cells, J. Mater. Chem. 22 (2012) 20866–20869.
[23] J.D. Roy-Mayhew, I.A. Aksay, Graphene materials and their use in dye-sensitized
solar cells, Chem. Rev. 114 (2014) 6323–6348.
[24] W. Yang, X. Xu, Y. Gao, Z. Li, C. Li, W. Wang, Y. Chen, G. Ning, L. Zhang, J. Kong,
Y. Li, High-surface-area nanomesh graphene with enriched edge sites as efficient
metal-free cathodes for dye-sensitized solar cells, Nanoscale 8 (2016)
13059–13068.
[25] H. Wang, Y. Hu, Graphene as counter electrode materials for dye-sensitized solar
cells, Energy Environ. Sci. 5 (2012) 8182–8188.
[26] P. Joshi, L. Zhang, Q. Chen, D. Galipeau, H. Fong, Q. Qiao, Electrospun carbon
nanofibers as low-cost counter eelctrode for dye-sensitized solar cells, ACS Appl.
Mater. Interfaces 12 (2010) 3572–3577.
[27] T.N. Murakami, S. Ito, Q. Wang, M.K. Nazeeruddin, P. Liska, R. Humphery-Baker,
P. Comte, M. Grätzel, Highly efficient dye-sensitize solar cells based on carbon
black counter electrodes, J. Electrochem. Soc. 153 (2006) A2255–A2261.
[28] S. Hou, X. Cai, H. Wu, X. Yu, M. Peng, K. Yan, D. Zou, Nitrogen-doped graphene for
dye-sensitized solar cells and the role nitrogen states in triiodide reduction, Energy
Environ. Sci. 6 (2013) 3356–3362.
[29] L. Song, Q. Luo, F. Zhao, Y. Li, H. Lin, L. Qu, Z. Zhang, Durally functional, N-doped
195
Materials Science in Semiconductor Processing 63 (2017) 190–195
porous graphene foams as counter electrodes for dye-sensitized solar cells, Phys.
Chem. Chem. Phys. 16 (2014) 21820–21826.
[30] M. Chen, L. Shao, Y. Liu, T. Ren, Z. Yuan, Nitrogen-doped ordered cubic mesoprous
carbons as counter electrodes for dye-sensitized solar cells, J. Power Sources 283
(2015) 305–313.
[31] Y. Xue, J. Liu, H. Chen, R. Wang, D. Li, J. Qu, L. Dai, Nitrogen-doped graphene
foams as metal-free counter electrodes in high-performance dye-sensitized solar
cells, Angew. Chem. 124 (2012) 12290–12293.
[32] L. Li, C. Wang, J. Liao, A. Manthiram, Dual-template synthesis of N-doped macro/
mesoporous carbon with an open-pore structure as metal-free catalysts for dye-
sensitized solar cells, J. Power Sources 300 (2015) 254–260.
[33] H. Guan, L. Fan, H. Zhang, X. Qu, Polyaniline nanofibers obtained by interfacial
polymerization for high-rate supercapacitor, Electrochim. Acta 56 (2010) 964–968.
[34] Z. Huang, E. Liu, H. Shen, X. Xiang, Y. Tian, C. Xiao, Z. Mao, Preparation of
polyaniline nanotubes by a template-free self-assembly method, Mater. Lett. 65
(2011) 2015–2018.
[35] Z. Lei, M. Zhao, L. Dang, A. Lo, N. Yu, S. Liu, Structure evolution and
electrocatalytic application of nitrogen-doped carbon shell synthesized by pyrolysis
of near-monodisperse polyaniline nanospheres, J. Mater. Chem. 19 (2009)
5985–5995.
[36] D. Hulicova, J. Yamashita, Y. Soneda, H. Hatori, M. Kodama, Supercapacitors
prepared from melamine-based carbon, Chem. Mater. 17 (2005) 1241–1247.
[37] L. Chen, X. Zhang, H. Liang, M. Kong, Q. Guan, P. Chen, Z. Wu, S. Yu, Synthesis of
nitrogen-doped porous carbon nanofibers as an efficient electrode material for
supercapacitors, ACS Nano 6 (2012) 7092–7102.