J Mater Sci

Energy
E N E R G Y Mmaterials
ATERIALS

Honeycomb-like polypyrrole/multi-wall carbon

nanotube films as an effective counter electrode
in bifacial dye-sensitized solar cells
Honggang Li1,2, Yaoming Xiao1,2,* , Gaoyi Han1,2,*, and Miaoyu Li1,2

1
Institute of Molecular Science, Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry, Innovation
Center of Chemistry and Molecular Science, Shanxi University, Taiyuan 030006, People’s Republic of China
2
Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University, Taiyuan 030006, People’s
Republic of China

Received: 10 March 2017 ABSTRACT

Accepted: 7 April 2017
Ó Springer Science+Business
Media New York 2017
Honeycomb-like polypyrrole/multi-wall carbon nanotube (PPy/MWCNT) film
demonstrates as an efficient and semitransparent counter electrode (CE) in
bifacial dye-sensitized solar cell (DSSC), which is first fabricated on fluorine-
doped tin oxide glass by a facile method using a sacrificial template of poly(-
methyl methacrylate) (PMMA). The results from ultraviolet–visible spec-
trophotometer and cyclic voltammetry measurements testify that the
honeycomb-like PPy/MWCNT film possesses high transparency for the back-
side illumination and wonderful electrocatalytic activity for the reduction of
triiodide (I3-) to iodide (I-) in the bifacial DSSC. Electrochemical impedance
spectroscopy results indicate that the honeycomb-like nanostructure combining
with the MWCNT decreases the resistance of the PPy/MWCNT film for the
transfer of electrons from the external circuit back to the redox electrolyte. The
bifacial DSSC based on the honeycomb-like PPy/MWCNT CE achieves 7.07 and
4.11% of the front and rear efficiencies, respectively, which are higher than those
of the bifacial DSSC based on the flat PPy CE (5.78 and 3.07%, respectively).

Introduction a redox electrolyte containing iodide/triiodide (I-/

A great deal of scientific and technical interest has
been placed since the dye-sensitized solar cell (DSSC)
was first introduced by Grätzel and his co-workers in
1991 [1–3]. The DSSC typically consists of a dye-sen-
sitized TiO2 photoanode, a counter electrode (CE), and
I3-) redox couple. The CE must have a superior cat-
alytic activity for the reduction of I3- to I-, which is
usually made of platinum (Pt) on the F-doped tin oxide
(FTO) glass substrate due to its superior electrocat-
alytic properties and high electrical conductivity [4].
However, Pt is extremely expensive [5], and it is
unstable in the I-/I3- redox couple electrolyte [6].

Address correspondence to E-mail: ymxiao@sxu.edu.cn; han_gaoyis@sxu.edu.cn

DOI 10.1007/s10853-017-1082-x

Therefore, developing an effective, economic, and
stable Pt-free CE for the practical application of DSSCs
is still imperative [7]. Carbon-based materials [8–10],
metal sulfides [11–15], metal nitrides [16, 17], and
conducting polymers have been attempted to replace
Pt catalyst in the DSSC [18–22]. Among them, the
polypyrrole (PPy) thin film has been considered as one
of the most promising CE materials due to its low cost
and highly catalytic activity in the DSSC [23, 24].
However, the PPy’s conductivity is unsatisfactory for
the transfer of electrons in the CE. Moreover, multi-
wall carbon nanotubes (MWCNTs) are honored as
excellent electron transfer materials with large surface
area and excellent mechanical strength [25], but their
catalytic activity for I3- reduction is undesirability [26].
To solve above-mentioned problems, several
research groups combined the highly conductive
MWCNT with the electrocatalytic PPy, which obvi-
ously improved the photoelectric conversion effi-
ciency of DSSCs [27–29]. For example, Peng et al.
prepared PPy/MWCNT CE and applied in the flexible
DSSC with a conversion efficiency of 4.04% by the
chemical polymerization and drop-casting method
[27]. Moreover, the CE with honeycomb architecture
has been used to improve its conductivity and catalytic
activity in DSSCs [30, 31]. Presently, we prepared
poly(3,4-ethylenedioxythiophene) (PEDOT) with
honeycomb nanostructure through the monodis-
persed template of poly(methyl methacrylate)
(PMMA), which exhibited high catalytic performance
and low resistance. Furthermore, the honeycomb
nanostructure enhanced the CE’s transparency, which
could be employed in the bifacial DSSC [31]. Polyani-
line and PEDOT are the most important transparent
materials in the bifacial photovoltaic device [32, 33].
However, according to the best of our knowledge, the
research about utilizing low-cost PPy film as the
transparent CE for the bifacial DSSC is relatively few.
In this paper, we replaced the high-cost PEDOT by
PPy and introduced the MWCNT to further enhance
the PPy’s conductivity. A honeycomb-like PPy/
MWCNT CE on the FTO surface was first prepared for
the bifacial DSSC by using the sacrificial template of
monodispersed PMMA nanospheres. The electrocat-
alytic activity and transparency of the honeycomb-like
PPy/MWCNT CE were measured by cyclic voltam-
metry (CV) and ultraviolet–visible (UV–Vis) spec-
trophotometer. The internal resistances of DSSC under
illumination and dark conditions were evaluated by
electrochemical impedance spectroscopy (EIS). And
J Mater Sci
the photon-to-current conversion efficiencies of the
bifacial DSSC were investigated under front and rear
illuminations of 100 mW cm-2 (AM 1.5G).
Experimental
Materials
Pyrrole (Py) was purchased from Sigma-Aldrich. Multi-
wall carbon nanotubes (MWCNTs, purity [ 99.5%;
average diameter 40–60 nm; length [ 10 um) were
purchased from Chengdu Organic Chemicals Co., Ltd.,
Chinese Academy of Sciences. Methyl methacrylate
(MMA) and 2,20 -Azobis (2-methylpropionamidine)
(Analysis purity grade) were purchased from Shanghai
Chemical Agent Ltd., China. Dye N719 [cis-di(thio-
cyanato)-N,N0 -bis(2,20 -bipyridyl-4-carboxylicacid-4-te-
trabutyl-ammonium carboxylate) ruthenium (II)] was
purchased from Dyesol, Australia. The above agents
were used without further purification.
Synthesis of the PMMA template
The PMMA was prepared as described previously
[34]. Briefly, 50 g MMA was dissolved in 450 mL
distilled water under stirring at 400 rpm for 30 min
in nitrogen atmosphere. After the temperature was
heated up to 70 °C, 0.12 g of 2,20 -Azobis (2-methyl-
propionamidine) dihydrochloride in 25 mL distilled
water was added. Then the mixture was stirred for
6 h. Finally the original PMMA template solution
with a concentration of 10 wt% was achieved.
Fabrication of the honeycomb-like PPy/
MWCNT CE
By refluxing raw MWCNT in a 3:1 mixture of H2SO4
(98%) and HNO3 (78%) at 120 °C for 15 min, the
functionalized MWCNT was achieved. Then the
functionalized MWCNT was filtered off, washed
thoroughly with deionized water, and suspended in
a mixture solution of acetone and ethanol with 1:1 in
volume ratio by ultrasonication for 2 h. Finally, the
functionalized MWCNT suspension with a concen-
tration of 1 mg mL-1 was obtained.
The fabrication procedures for various CEs are
outlined in Scheme 1. To increase the hydrophilic
property of the FTO substrate (12 X sq-1, NSG,
Japan), it was first pre-treated by sonication for 1 h in
J Mater Sci
Scheme 1 Schematic diagram
of the fabrication procedures
of the a f-PPy, b f-PPy/
MWCNT, c h-PPy, and h-PPy/
MWCNT CEs, respectively.
a cleaning solution (H2O:NH4OH:H2O2 = 5:1:1 (vol-
ume ratio)). Then 5.0 lL as-prepared MWCNT sus-
pension was spin-coated on the pre-treated FTO
substrate at 1000 rpm for 10 s then at 2500 rpm for
30 s. After the solvent evaporation, the MWCNT/
FTO substrate was formed. Then the PMMA template
solution (10.0 lL) was spin-coated onto the
MWCNT/FTO substrate under the same spin-coating
parameters. After that, the PMMA/MWCNT film on
the FTO substrate was obtained by treating it in oven
at 60 °C for 30 min.
The electrodeposition of PPy was carried out with a
computer-controlled Autolab potentiostat (Type III)
containing 10 mM pyrrole, 20 mM sodium dodecyl
sulfate, and 20 mM lithium perchlorate [31]. A PMMA/
MWCNT/FTO, a Pt wire, and a saturated Ag/AgCl
were used as the working electrode, counter electrode,
and reference electrode, respectively. The CV electro-
polymerization of PPy on the PMMA/MWCNT film
was measured at a potential window of -0.4 to 0.8 V for
6 cycles at a scan rate of 0.05 V s-1. The obtained PPy/
PMMA/MWCNT film was rinsed in distilled water and
dried at 60 °C. After that, the PPy/PMMA/MWCNT
film was immersed in chloroform for 3 h to dissolve
away the PMMA. Finally the honeycomb-like PPy/
MWCNT (h-PPy/MWCNT) CE was achieved.
For comparison, the flat PPy (f-PPy), flat PPy/
MWCNT (f-PPy/MWCNT), and honeycomb-like PPy
(h-PPy) were also prepared as the same conditions of
h-PPy/MWCNT CE without the MWCNT or without
the PMMA template. Moreover, the amount of
MWCNT spin-coated on the pre-treated FTO substrate
was optimized by adjusting the volume of the MWCNT
suspension (10.0, 5.0, and 3.3 lL), and the finally
obtained h-PPy/MWCNT CEs were defined as h-PPy/
MWCNT-1, h-PPy/MWCNT-2, and h-PPy/MWCNT-
3 CEs, respectively. The results were demonstrated in
‘‘Supporting Information.’’
Preparation of the dye-sensitized TiO2
photoanode
The TiO2 anode was prepared as described previ-
ously [7]. In brief, a layer of TiO2 colloid with an area
of 0.4 9 0.4 cm2 was coated on FTO substrate and
dried in air. Then the TiO2 film was calcined in a
muffle furnace at 450 °C for 30 min to obtain the TiO2
nanocrystal anode film. After being cooled down to
80 °C, the resultant anode was thoroughly immersed
in a 0.25 mM solution of the dye N719 in absolute
ethanol for 24 h. The dye-sensitized TiO2 photoanode
was obtained.
Assemblage of the DSSC
The sandwich-type DSSC was fabricated by injecting
the electrolyte solution between the dye-sensitized
TiO2 photoanode and h-PPy/MWCNT CE. The
electrolyte solution in the DSSCs contains 0.05 M
iodine, 0.10 M tetramethyl ammonium iodide, 0.10 M

potassium iodide, 0.10 M lithium iodide, 0.10 M
tetrabutyl ammonium iodide, 0.10 M guanidine
thiocyanate, and 0.50 M 4-tert-butyl-pyridine in
acetonitrile.
Characterizations and measurements
Field emission scanning electron microscopy (FE-SEM,
JEOL-JSM-7001F) was used to characterize the mor-
phology of the CE. Fourier transform infrared (FTIR)
measurements (BRUKER TENSOR 27) for the CEs were
taken with KBr as pellet. UV–Vis transmittance spectra
were measured on an Agilent 8453 UV–Vis diode array
spectrophotometer. UV–Vis diffuse reflectance tests
were obtained on UV–Vis Spectrophotometer Evolu-
tion 220 (Thermo Fisher Scientific Inc., USA) with an
integrating sphere accessory ringing from 300 to
800 nm and a reference of standard BaSO4 powder. The
electrocatalytic activity was measured by Autolab
potentiostat (Type III) using a Pt wire as a reference
electrode, a Pt sheet as a counter electrode, and the as-
prepared CE as a working electrode. CV tests were
conducted in a supporting electrolyte (10 mM LiI,
1.0 mM I2, and 0.1 M LiClO4 in acetonitrile) from
-0.6 V to 0.8 V (vs. Pt) at a scan rate of 50 mV s-1.
Photon-to-current conversion efficiencies of the DSSCs
were evaluated by measuring the current–voltage (J–V)
curves on a computer-controlled CHI660D under rear
and front illuminations, and the incident light intensity
was 100 mW cm-2 (AM 1.5 G). EIS measurement of
the DSSC was obtained at frequencies ranging from 0.1
to 105 Hz with 5 mV of AC amplitude by a Zennium
electrochemical workstation (Zahner) in the ambient
temperature. When carried out without light in the
dark condition, EIS measurements should be with a
corresponding bias potential of the open-circuit volt-
ages based on the front illumination. When evaluated
under rear and front illuminations, EIS measurements
were carried out under 100 mW cm-2 (AM 1.5 G) with
a corresponding bias potential of the open-circuit
voltages based on the rear and front illuminations,
respectively. The resultant impedance spectra were
simulated by using Z-view software.
Results and discussion
In the PPy curve (Fig. 1a), the peak located at
3415 cm-1 corresponds to the N–H stretching vibra-
tion. The peaks at 1529 and 1436 cm-1 are
J Mater Sci
characteristics of the in-plane vibrations of pyrrole
ring. The C–N stretching, C–H deformation vibration,
and C–H wagging vibration are observed at 1288,
1037, and 773 cm-1, respectively. The presence of
strong bands at about 1157 and 965 cm-1 indicates
the formation of doped PPy [35]. The low absorption
band at 663 cm-1 is ascribed to C–H out of plane
bending of pyrrole moiety in PPy [23]. Figure S1 a is
on behalf of the MWCNT sample. The C=C stretching
of the aromatic group is observed at 1573 cm-1 [36].
The peaks at around 1211, 1706, and 1376 cm-1 are
ascribed to the C=O stretching vibrations and
hydroxyl groups (-OH) bending deformation of the
carboxylic groups (-COOH) from the acid-oxidized
MWCNT surface [37]. FTIR spectra of f-PPy/
MWCNT (Fig. 1b) and h-PPy/MWCNT (Fig. 1d)
show that the above characteristic peaks of PPy and
MWCNT were all existed, which indicated that the
PPy/MWCNT composites were successfully pre-
pared by electrodeposition. In Fig. S1 b, the C=O of
the PMMA is observed at the bond stretching fre-
quency 1732 cm-1. The peaks at 2995 and 2955 cm-1
are, respectively, assigned to the CH3 stretching
vibration and CH3 asymmetrical stretching vibration
of the PMMA. Peaks at 1242, 1150, and 754 cm-1 are
attributed to the asymmetric CH2 transformation,
CH2 twisting, and CH2 rocking vibration of the
PMMA, respectively [38]. In the h-PPy (Fig. 1c) and
h-PPy/MWCNT (Fig. 1d), there is no characteristic
peak of the PMMA, which implied that the PMMA
template was removed completely away from the
PPy film.
Figure 2a shows that the PPy film consisting of PPy
nanoparticles is flat and compact, which was elec-
trodeposited homogeneously on the FTO surface.
Based on Fig. S2, the FE-SEM images of the PMMA/
MWCNT film, the average diameter of the MWCNT
is about 50 nm and that of the PMMA is about
200 nm. After the electrodeposition of PPy on the
MWCNT (Fig. 2b), the MWCNT is wrapped with the
PPy nanoparticles and the total diameter is about
170 nm; thus, the PPy thin film around the MWCNT
is about 60 nm in thickness. When introducing the
PMMA template into the PPy film, then removing the
PMMA template, honeycomb-like nanostructure with
200 nm of the hole’s diameter was formed regularly
(Fig. 2c). Combining the MWCNT with the PMMA
template, honeycomb-like PPy/MWCNT film was
obtained (Fig. 2d). Moreover, Fig. S3a–c represents
FE-SEM images of the honeycomb-like PPy/
J Mater Sci
Figure 1 FTIR spectra of a f-PPy, b f-PPy/MWCNT, c h-PPy, and
d h-PPy/MWCNT, respectively.
MWCNT CEs based on different volume of the
MWCNT suspension (10.0, 5.0, and 3.3 lL, respec-
tively). According to the results (Figs. S4, S5;
Table S1, Supporting Information), the h-PPy/
MWCNT-2 CE showed the best performances.
Therefore, the amount of MWCNT spin-coated on the
Figure 2 FE-SEM images of a f-PPy, b f-PPy/MWCNT, c h-PPy, and d h-PPy/MWCNT CEs with a bar of 100 nm, respectively.
pre-treated FTO substrates for the f-PPy/MWCNT
and h-PPy/MWCNT CEs was 5.0 lL in the main text.
The UV–Vis transmittance and diffuse reflectance
spectra of the bare FTO substrate, f-PPy, f-PPy/
MWCNT, h-PPy, and h-PPy/MWCNT films on the
FTO substrates are shown in Fig. 3, respectively. The
bare FTO substrate indicates a total transmittance
and diffuse reflectance of about 80 and 35% in the
visible range. The transmittance decreases to 55%,
and the diffuse reflectance reduces to 15% after
electrodeposition the flat PPy on the bare FTO sub-
strate (Fig. 3A-a, 3B-a). The introduction of the
MWCNT into the flat PPy film would further reduce
the transmittance and diffuse reflectance to 45 and
13% (Fig. 3A-b, 3B-b). However, introducing of
PMMA template into the PPy film, then removing the
PMMA template, the honeycomb-like nanostructure
could observably enhance the transmittance and
diffuse reflectance to 65 and 20% (Fig. 3A-c, 3B-c).
After combining the MWCNT with the PMMA tem-
plate, honeycomb-like PPy/MWCNT film showed a
moderate transmittance and diffuse reflectance of 60
and 18% (Fig. 3A-d, 3B-d). The results indicate that
 J Mater Sci

Figure 3 A, B UV–Vis transmittance and diffuse reflectance spectra of the bare FTO substrate, a f-PPy, b f-PPy/MWCNT, c h-PPy, and d
h-PPy/MWCNT CEs, respectively.

the increased light absorption is mainly attributed to

the enhanced transparency and slightly ascribed to
the light scattering.
Cyclic voltammetry (CV) is a powerful tool to
investigate the CE’s electrocatalytic activity [5, 21]. In
theory, the catalytic activity is positively correlated
with the cathodic reduction peak current density,
while it is negatively correlated with the peak sepa-
ration between the anodic and cathodic peaks (Epp)
[39, 40]. Based on the CV curves of different PPy CEs
(Fig. 4), the cathodic reduction peak current densities
for the four samples are in the order of h-PPy/
MWCNT [ h-PPy [ f-PPy/MWCNT [ f-PPy. Epp
values of all PPy-based CEs follow the order of f-PPy
(1041 mV) [ f-PPy/MWCNT (998 mV) [ h-PPy Figure 4 CV curves of a f-PPy, b f-PPy/MWCNT, c h-PPy, and
(971 mV) [ h-PPy/MWCNT (873 mV). The results d h-PPy/MWCNT CEs at scan rates of 50 mV s-1.
indicate that the h-PPy/MWCNT CE has the best
electrocatalytic activity for the I3-/I- redox species
than that of other CEs, and this is due to that the Nyquist plots of DSSCs based on the f-PPy, f-PPy/
honeycomb-like nanostructure can expose abundant MWCNT, h-PPy, and h-PPy/MWCNT CEs under
catalytic surface and plentiful contact area with the dark condition with the bias potential of the actual
electrolyte. Moreover, the MWCNT in the PPy film measured open-circuit voltages based on the front
can enhance the CE’s conductivity for the electron illumination. The high-frequency intercept on the real
transport and further enhance the surface area of the axis represents the series resistance (RS). The three
h-PPy/MWCNT CE. However, the MWCNT can arcs are assigned to impedance related to the charge
absorb incident light resulting in less diffuse reflec- transport at the CE/electrolyte interface (RCT(CE)),
tion with the increasing of MWCNT. Therefore, the TiO2/dye/electrolyte interface (RCT(TiO2)), and the
catalytic and photoelectric properties both increased carrier transport by ions within the electrolyte (W),
and then decreased with the increasing of MWCNT. respectively. The CPE(CE) and CPE(TiO2) are con-
EIS measurement was taken to analyze the inter- stant phase elements of RCT(CE) and RCT(TiO2) in the
facial resistance of the DSSC. Figure 5a gives the equivalent circuit, respectively, which represent the
J Mater Sci

Figure 5 A Nyquist plots of the DSSCs based on (a) f-PPy, (b) f-PPy/MWCNT, (c) h-PPy, and (d) h-PPy/MWCNT CEs, respectively;
B Nyquist plots of the DSSC based on the h-PPy/MWCNT CE under dark condition, rear and front illuminations, respectively.

Table 1 EIS results of DSSCs based on different PPy CEs

DSSC RS (X cm2) RCT(CE) (X cm2) CPE(CE) (mF cm-2) RCT(TiO2) (X cm2) CPE(TiO2) (mF cm-2) W (X cm2)

a-dark 2.58 0.32 0.89 12.32 0.83 2.72

b-dark 2.10 0.30 0.93 11.04 0.84 1.71
c-dark 2.03 0.28 0.96 9.22 0.86 1.68
d-dark 1.90 0.19 0.95 5.76 0.86 0.80
d-rear 1.87 0.18 0.92 3.60 0.86 0.77
d-front 1.85 0.15 0.91 2.26 0.84 0.75

capacitance at the interface between the electrode and
electrolyte. An ideal capacitance has an exact semi-
circle with a CPE value of 1. The inset of Fig. 5a is the
equivalent circuit model for the DSSC [41, 42]. The
resultant EIS parameters are fitted and listed in
Table 1. RS and RCT(CE) values of DSSCs measured
under dark conditions decrease orderly. The DSSC
with the h-PPy/MWCNT CE shows the lowest RS
and RCT(CE) values of 1.90 and 0.19 X cm2, respec-
tively. The results demonstrate that the honeycomb-
like nanostructure and the MWCNT both reduce the
interfacial resistance of the DSSC. This is owing to
that the electrolyte filling in the honeycomb-like
nanostructure can provide more electron transport-
ing path than that of the flat and compact structure,
and can reduce the electron transporting distance.
Moreover, the MWCNT enhances the conductivity of
the h-PPy/MWCNT CE. The above three most
important factors result in an effective and rapid
electron transporting ability of the h-PPy/MWCNT
CE, which would further improve the performance of
DSSC especially the fill factor [43]. Furthermore, the
CPE(CE) and CPE(TiO2) values of the h-PPy/
MWCNT CE are higher than those of the f-PPy CE,
suggesting that the former has a higher porosity than
that of the latter, resulting in a larger catalytic surface.
EIS measurements measured under rear or front
illumination with a bias potential of the open-circuit
voltage are quite different from that of under dark
condition [44, 45]. Figure 5b illustrates the impedance
characteristics of the same DSSC based on the h-PPy/
MWCNT CE under dark condition, rear and front
illuminations, respectively. Values of RS and RCT(CE)
measured under dark condition, rear and front illu-
minations are similar, which suggests the h-PPy/
MWCNT CE has similar electrochemical properties
under the three conditions. However, RCT(TiO2) val-
ues are quite different under the three conditions, this
might be owing to the different electron density, and
recombination rate was caused by the different light
intensity [44, 45]. The higher light intensity, the larger
electron density and recombination rate, and then,
the lower RCT(TiO2) value. RCT(TiO2) value measured
under front illumination is lower than that of under
 J Mater Sci

Figure 6 Photocurrent density–voltage characteristics of DSSCs under A front and B rear illuminations; DSSCs based on (a) f-PPy, (b) f-
PPy/MWCNT, (c) h-PPy, and (d) h-PPy/MWCNT CEs, respectively.

Table 2 Epp from the CV

curves, photovoltaic DSSC Epp (mV) Illumination JSC (mA cm-2) VOC (mV) FF g (%)
performances of DSSCs based
a 1057 Front 15.53 759 0.49 5.78
on different PPy CEs under
Rear 7.35 732 0.57 3.07
full front and rear sunlight
b 996 Front 16.05 770 0.50 6.18
illuminations (100 mW cm-2,
Rear 7.53 746 0.60 3.37
AM 1.5 G), respectively
c 971 Front 16.34 758 0.51 6.32
Rear 8.27 727 0.57 3.43
d 873 Front 17.50 762 0.53 7.07
Rear 9.30 736 0.60 4.11

rear illumination and much lower than that of under
dark condition, and this is due to that the dark color
of the iodic electrolyte and the incomplete trans-
parency of the CE resulted in a lower light intensity
to the TiO2 photoanode from the backside illumina-
tion than that of from front illumination.
Figure 6a, b shows the recorded photovoltaic
characteristics of DSSCs based on different PPy CEs
under full sunlight illumination (100 mW cm-2,
AM 1.5 G) from front and rear sides, respectively.
The photovoltaic results are summarized in Table 2.
The DSSC employing h-PPy/MWCNT CE achieves
the highest conversion efficiencies than those of
DSSCs with other CEs under both front and rear
illuminations. The enhanced short-circuit current
density (JSC) values of both front and rear illumina-
tions are owing to the increased catalytic activity of
the honeycomb-like PPy/MWCNT CE. Moreover,
another factor for the observably increased JSC value
from backside illumination is the enhanced trans-
mittance of the honeycomb-like PPy/MWCNT CE.
The increased open-circuit voltage (VOC) values
might be attributing to the enhanced JSC and the
honeycomb-like nanostructure with the introduction
of MWCNT. The enhanced fill factor (FF) values are
owing to the reduced values of RS, RCT(CE), and
RCT(TiO2) by employing the honeycomb-like PPy/
MWCNT CE. Therefore, the front and rear efficien-
cies of the bifacial DSSCs show an order of f-PPy \ f-
PPy/MWCNT \ h-PPy \ h-PPy/MWCNT. The
bifacial DSSC based on the h-PPy/MWCNT CE
yields impressive conversion efficiencies of 7.07 and
4.11% from front and rear illuminations, respectively,
which are higher than those of the DSSC based on the
f-PPy CE (5.78 and 3.07%, respectively).
Conclusions
In summary, we introduced an effective, low-cost,
semitransparent, and honeycomb-like PPy/MWCNT
CE for the bifacial DSSC, which was fabricated by a
J Mater Sci
facile method using a sacrificial template of PMMA.
The honeycomb-like nanostructure not only enhanced
the electrocatalytic activity for the reduction of I3- to
I-, but also increased the transmittance of the CE for
the utilization of sunlight. The introduction of
MWCNT further improved the CE’s conductivity for
the electron transporting from the external circuit back
to the redox electrolyte. The impedance behaviors
were quite different under different light intensity,
which were caused by the dark color of the iodic
electrolyte and the incomplete transparency of the CE.
As a result, the low-cost bifacial DSSC based on the
h-PPy/MWCNT CE yielded front and rear efficiencies
of 7.07 and 4.11%, respectively, which were higher
than those of the bifacial DSSC based on f-PPy CE (5.78
and 3.07%). Although the efficiencies in this paper
were not high, the facile template method could be
widely applied to prepare other cost-effective and
transparent CEs for the application of bifacial solar
cells and tandem devices in the future.
Acknowledgments
The authors appreciate funding from National Nat-
ural Science Foundation of China (61504076,
21574076, and U1510121) and National Natural Sci-
ence Foundation of Shanxi Province (2015021129 and
2014011016-1).
Electronic supplementary material: The online
version of this article (doi:10.1007/s10853-017-1082-
x) contains supplementary material, which is avail-
able to authorized users.
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