Chemical Engineering Journal 394 (2020) 124954

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Chemical Engineering Journal

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

Highly efficient indoor light quasi-solid-state dye sensitized solar cells using T
cobalt polyethylene oxide-based printable electrolytes
Shanmuganathan Venkatesana, I-Ping Liua, Chih-Mei Tseng Shana, Hsisheng Tenga,
Yuh-Lang Leea,b,
⁎

a
Department of Chemical Engineering, National Cheng Kung University, Tainan 70101, Taiwan
b
Hierarchical Green-Energy Materials (Hi-GEM) Research Center, National Cheng Kung University, Tainan 70101, Taiwan

HIGHLIGHTS GRAPHICAL ABSTRACT

• Cobalt PEO printable electrolytes are

prepared for the indoor light DSSCs.
High performance cobalt polyethylene oxide (PEO) printable electrolyte for DSSCs operating under 200 lx T5
light illumination.
• The Rheological and electrochemical
properties of the electrolytes are stu-
died.
• A21.06%
cobalt cell achieves an efficiency of
under 200 lx T5 light illumi-
nation.
• Aciencies
bifacial cell achieves the best effi-
of 17.22% and 14.25%.
• The QS-DSSCs retain 98% of its initial
value after 1000 h test.

ARTICLE INFO ABSTRACT

Keywords: High-performance printable electrolytes (PEs) containing Co+2/Co+3 or I−/I3− redox-couple are prepared to
Cobalt electrolyte fabricate quasi-solid-state (QS) dye-sensitized solar cells (QS-DSSCs) for room light environment applications.
Poly ethylene oxide Polyethylene oxide (PEO) and poly(methyl methacrylate) (PMMA) are utilized to prepare PEs. Various para-
Printable electrolyte meters are regulated to obtain the optimal power conversion efficiencies (PCEs). For the I−/I3− system, the QS-
Indoor light
DSSCs using PEO and PEO/PMMA PEs achieve nearly identical PCEs (16.32% and 16.40%, respectively) under
Sub-module cells
Bi-facial cell
the optimal conditions. However, the PCEs obtained for the Co+2/Co+3 system are markedly higher and the cell
using PEO PE has a higher PCE (21.06%) than that using PEO/PMMA (18.14%). This difference is ascribed to the
different composition of Li+ and Co+3 around the photoelectrode. The presence of Li+ around the interface will
repel Co+3 away from the interface, decreasing the recombination of excited electrons to Co+3. According to the
molecular structure, PMMA has more lone pair electrons to coordinate with Li+ ions, which will decrease the
concentration of free Li+ more significantly than does by PEO. Therefore, the presence of PMMA will decrease
and increase, respectively, the Li+ and Co+3 concentrations at the photoelectrode/electrolyte interface, re-
sulting in more significant recombination of electrons to the Co+3. Consequently, the PCE of the PEO/PMMA cell
is lower than that of the PEO cell. This effect doesn’t occur in I−/I3− system because the concentration variation

⁎
Corresponding author at: Department of Chemical Engineering, National Cheng Kung University, Tainan 70101, Taiwan.
E-mail address: yllee@mail.ncku.edu (Y.-L. Lee).

https://doi.org/10.1016/j.cej.2020.124954
Received 21 January 2020; Received in revised form 31 March 2020; Accepted 2 April 2020
Available online 05 April 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
S. Venkatesan, et al.
of negatively charged ions did not affect significantly the electrons recombination at the interfacial. By using this
cobalt PE, a bifacial QS-DSSC can achieve PCEs of 17.22% and 14.25%, respectively, under front-side and back-
side illumination by 200 lx T5 light. A sub-module QS-DSSC using the cobalt PE can attain a PCE of 12.56%.
1. Introduction
Dye-sensitized solar cells (DSSCs) are suitable substitutes for clas-
sical photovoltaic devices because they are prepared using potentially
inexpensive materials and simple procedures [1,2]. They have a facile,
compact, colourful design with high power conversion efficiency (PCE)
[3]. As of today, the PCE of liquid-state cells has reached over 14% by
using organic dyes and cobalt liquid electrolytes (LEs) [4,5]. This PCE is
higher than the efficiencies of liquid-state cells using classical ruthe-
nium complex and porphyrin dyes [6,7]. As a result of the presence of
the LEs, high-efficiency DSSCs are always required to have perfect
sealing procedures to control for electrolyte leakage and solvent eva-
poration at elevated temperatures [8]. These problems have been
solved by using solid-state and gelated electrolytes instead of LEs
[9–12]. These kinds of electrolytes effectively reduce solvent leakage
but decrease the PCEs of the cells due to the poor conductivity char-
acteristics of these materials and insufficient penetration of solids into
the pores of the titanium dioxide (TiO2) [13].
Since several years ago, DSSC research has been focused on the
preparation of polymer gel electrolytes (PGEs) to overcome the lim-
itations associated with using liquid and solid electrolytes [14–16].
These PGEs were obtained by mixing different types of polymers into
the LEs. Several kinds of nanosized materials were also mixed to the
PGE to improve the PCE, and stability of the cells [14,17,18]. These
PGEs had high ionic conductivity and good pore-filling ability with the
photoelectrodes. The quasi-solid-state dye-sensitized solar cells (QS-
DSSCs) assembled using PGEs using an injection process had high PCEs
and long-term performance at high temperatures [19]. However, PGEs
and the injection process were not appropriate for the production of
large-area module cells. These kinds of DSSCs required a printing pro-
cess to introduce the electrolytes into the cells [20–23]. The solid-jelly-
like PGEs that were obtained were not suitable for printing on the
surface of electrodes because of the damage that would occur to their
jelly structure while carrying out the printing process. This issue was
eliminated by using polymer electrolyte pastes that were prepared
simply by altering the compositions of polymers into the LEs [20–22].
Electrolyte pastes with optimal viscosity were easily printed on the
surface of photoelectrodes either using a screen printing or doctor blade
technique. The cells using these printable electrolytes (PEs) had higher
PCEs than the cells using PGEs and LEs.
In the literature, iodide DSSCs using novel dyes are typically em-
ployed for room light applications [24–35]. The optimal conditions
utilized for these cells are different from those operating under one-sun
conditions. In contrast to one-sun conditions, only a very few electrons
are excited under room light illumination. These electrons are re-
combined easily with the redox couple, which seriously affects the Voc
of the cells [36]. Likewise, the formation of excited holes is decreased
under room light illumination, in which a small quantity of iodide is
sufficient to reduce the number of holes formed. As a result of these two
facts, the overall performance of the DSSCs is decreased. By regulating
the amount of iodide/triiodide (I−/I3−) in the electrolytes, the PCE of
the cell can be somewhat improved [26]. The light intensity is also
affected due to the amount of iodine in the electrolyte. This issue is
realized in the incident photon-to-current conversion efficiency (IPCE)
and electrochemical impendence spectroscopy (EIS) analysis of DSSCs.
In recent years, cobalt and copper electrolytes have been considered to
be suitable for the production of high-performance room light DSSCs
[37–43].
In this study, high-performance PEs containing cobalt2+/coablt3+
(Co /Co+3) or I−/I3− redox couple was prepared to fabricate QS-
+2
2
Chemical Engineering Journal 394 (2020) 124954
DSSCs for room light environment applications. Polyethylene oxide
(PEO) and poly(methyl methacrylate) (PMMA) were utilized as mate-
rial to prepare PEs from corresponding liquid electrolytes. The com-
ponents of the electrolytes and thicknesses of the photoelectrodes were
regulated to obtain a high PCE under room light conditions. The cells
using cobalt PEs (PEO 9 wt%) had much higher efficiency than the cells
using iodide PEs. The cobalt PEs were utilized for the preparation of
bifacial and sub-module cells, which also showed high PCEs under
200 lx T5 light illumination. The cobalt QS-DSSC had high stability as
compared to the corresponding liquid-state DSSC under 35 °C.
2. Material and methods
2.1. Materials
PEO (Mw = 400000), PMMA (Mw = 120,000), 1,3-dimethyl-imi-
dazolium iodide (DMII, > 98%), 3-methoxypropionitrile
(MPN, > 98%), 4-tert-butylpyridine (tBp, 96%), ammonium hexa-
florophosphate (NH4PF6, 99.99%), titanium diisopropoxide bis(acet-
ylacetonate) (TiAcAc, 75 wt% in isopropanol), tert-butanol, lithium
iodide (LiI, 99%), iodine (I2, 99%), and quinidine thiocyanate (GuSCN,
99%) were purchased from Sigma Aldrich. Nitrosonium tetra-
fluoroborate (NOBF4, 99%), 2,2′-bipyridine (bpy, 99%) and cobalt (II)
chloride hexahydrate (CoCl2·6H2O, 98%), were supplied by Alfa Aesar.
Lithium perchlorate (LiClO4, 98%) was acquired from Fluka. Methanol
(99.8%) and titanium (IV) chloride (TiCl4, 99.9%) was received from
Acros organics and J. T. Baker, respectively. Silver pastes were obtained
from Taiwan DSC PV Ltd. TiO2 pastes for the preparation of the main
layer (DSL 30 NR, 30 nm, PST-18 NR) and the scattering layer (PST-
400C, 400 nm) were obtained from Dyesol and Catalyst & Chemicals
Industries Co., Ltd. N719 (> 99%) and Y123 dye (> 98%) were re-
ceived from Solaronix and Dyenamo, respectively. Fluorine-doped tin
oxide glass (FTO) was received from the Hartford Glass Co., Ltd.
2.2. Preparation of the iodide and cobalt PEs
The preparation method for the electrolyte pastes used in the
printing process involved two steps: First, the iodide and cobalt LEs
were prepared. Second, polymers (PEO and PMMA) were introduced
into the LEs and heated under constant stirring. The composition of the
iodide LE is as follows: 0.01 M I2, 0.2 M DMII, 0.8 M tBp, and 0.1 M
GuSCN with an MPN solvent. Various amounts of DMII (0.2–1.0 M) and
tBp (0.2–1.0 M) were utilized for the optimization studies. For the
preparation of the cobalt LE, 0.11 M Co(bpy)3 (PF6)2, 0.025 M Co(bpy)3
(PF6)3, 1.2 M tBp, and 0.1 M LiClO4 were dissolved in MPN [42]. The
weight percentage of the PEO and PEO/PMMA for the PEs was 9 wt%.
PEO with weight ratios of 3, 6, and 12% was added to the LEs for the
optimization experiments.
2.3. Fabrication of the DSSCs.
The photoelectrodes and counter electrodes (CEs) were fabricated
on FTO substrate based on the procedures described in previous reports
[26,39]. To prepare a mesoporous TiO2 and Pt layer, first, the FTO
substrate was well cleaned serially in a detergent solution, ethanol, and
acetone using ultra-sonication. Then, the compact TiO2 film was made
on the cleaned FTO by immersing the FTO substrate in the TiCl4 solu-
tion. Thereafter, mesoporous TiO2 pastes, including DSL 30 NR (30 nm)
and PST-400C (400 nm), respectively were screen printed on the TiCl4/
FTO electrode to obtain the main TiO2 layer (4 µm) and scattering
S. Venkatesan, et al. Chemical Engineering Journal 394 (2020) 124954

(6 µm) layer. Various thicknesses of the TiO2 layers (4–10 µm) were
also coated on the FTO substrate for the optimization experiments. For
the performance comparison, TiO2 layers were also prepared using the
PST-18 NR and PST-400C pastes. TiO2 electrodes were heat-treated at
500 °C for 30 min and then cooled to 80 °C.
The cooled electrodes were sensitized by immersing in N719 and
Y123 dye solutions for 12 h followed by cleaning using ethanol. The dye
solutions were prepared following the procedures demonstrated in the
literature [37]. The active area of the dye-sensitized TiO2 was
0.4 × 0.4 cm2. A platinized conductive glass substrate with and
without pre-drilled holes was employed as the CEs for the DSSCs. The
platinum deposition was carried out using a sputter coater that oper-
ated at 40 mA for 15 and 105 s, respectively for obtaining the 10.1 and
12.1 nm thick Pt layers. The DSSCs were fabricated using the liquid,
PGE, and PE pastes by an injection and printing process, respectively.
For the DSSCs fabricated using the printing process, the entire area
except the TiO2 layer was covered using 30 µm thick Surlyn film (void
area of 0.5 × 0.5 cm2) via the hot pressing method, and the electrolyte
pastes were printed on the surface of the TiO2. After removing the
Surlyn film that was attached to the photoelectrode containing the
electrolyte pastes and CE were fabricated using another 25 µm thick
Surlyn film as a spacer to obtain a QS-DSSCs. When assembling the
devices using the injection method the photoelectrode and CE were first
attached using 25 µm thick Surlyn film. The LE and hot PGEs were then
injected through the predrilled holes into a gap between the two elec-
trodes using a vacuum pump.
The above-described procedures were also followed for the fabri-
cation of quasi-solid-state sub module cells. The rectangular TiO2 layer
and Pt layer were prepared along with silver lines on a well cleaned as
well as TiCl4 -treated FTO substrates. Before the dye-sensitization and
Pt deposition process, the silver line was covered using 60 µm thick
Surlyn film until these processes were completed. The PEs were coated
on the TiO2 layer, and this electrode was combined with the (CE) using
Surlyn film (60 µm thick) and the hot pressing method to obtain the
sub-module DSSCs. The active area of this was 11.21 cm2
(1.9 × 5.9 cm2).
2.4. Measurements
The rheological characteristics of the cobalt polymer electrolytes
were studied utilizing rheometer (model AR 200ex, stress control).
Thickness of the TiO2 layers were measured using an Alpha-Step D-500
stylus profiler. The electrolyte conductivity was estimated using EIS.
The ion diffusivity in the electrolytes was measured using cyclic
voltammetry (CV). To conduct these experiments, symmetric dummy
cells with an active area of 0.5 × 0.5 cm2 were prepared using LEs and
PEs sandwiched between two platinized FTO glasses (12.1 µm thick Pt
layer) with a 60 µm thick Surlyn spacer. CV experiments were carried
out using an Autolab potentiostat (PGSTAT 30) with a scan rate of
20 mV s−1 and a voltage range from −0.1 to +0.1 V. EIS curves were
recorded on the dummy cells using the potentiostat equipped with a
frequency response analyzer. The frequency ranges from 105 Hz to
10−2 Hz with an alternating current amplitude of 10 mV was applied
for the EIS measurements. The impedance parameters were extracted
by the fitting of EIS curves using Z-view software with the suitable
equivalent circuits. EIS measurements on liquid-state cells and QS-
DSSCs were studied in a potential range from 0.65 V to 0.85 V. The
IPCE spectra were recorded using a quantum efficiency measurement
system (QR-R3011, DC mode, Enlitech, Taiwan). The photocurrent
density-voltage (J-V) characteristics were recorded utilizing a Keithly
model 2400 source meter under 200 lx T5 light illumination. The T5
fluorescent lamp was kept in a box fixed with a holder that was at-
tached with a motor. The light brightness level was adjusted by moving
the location of the lamp holder. The Jsc, Voc, fill factor (FF) and PCE
values (Tables 1–3) were the average of four cells. The PCE of the room
light DSSCs were estimated using the following equations:
Jsc × Voc × fill factor (FF) ÷ incident power (Pin).
3. Results and discussion
3.1. Effects of DMII and tBp amounts on the performance of the iodide cells
Before preparing the cobalt PEs, the iodide PEs were prepared using
PEO and PMMA polymers. It has been proven already that the perfor-
mance of room light iodide DSSCs is dependent on the amount of iodine
in the electrolytes [26,31]. The room light DSSC using low amounts of
iodine had high PCEs. Apart from the iodine amount, the performance
of the DSSCs can be enhanced by regulating the amount of chemical
additives, in particular, DMII and tBp in the iodide LEs [14,44]. First of
all, various amounts of DMII were added into the LE containing 0.01 M
I2. The performance of the cells using these electrolytes was measured.
The J-V curves and the related parameters of liquid cells at 200 lx T5
light illumination are compared in Fig. S1a (ESI†) and Table 1. The Jsc
increased and Voc decreased with increases in the amount of DMII in the
LEs. The Jsc was higher for the liquid-state DSSC utilizing 1.0 M DMII
(24.80 µA cm−2) as compared to the 0.2 M DMII (23.48 µA cm−2). The
higher Jsc was ascribed to the higher IPCE of the DSSC utilizing 1.0 M
DMII rather than the 0.2 M DMII, as given in Fig. S1b (ESI†). The liquid-

Table 1
Photovoltaic data at 64 µW cm−2 (200 lx) for the iodide cells using N719 dye, various DMII concentrations, different tBp concentrations, various TiO2 layer
thicknesses and different polymers.
DSSC components Jsc (µA.cm−2) Voc (V) FF Pmax (µW.cm−2) PCE (%)

0.2 M DMII(a) 23.48 ± 0.11 0.608 ± 0.003 0.720 ± 0.003 10.28 ± 0.10 16.06 ± 0.16
0.4 M DMII(a) 23.81 ± 0.05 0.608 ± 0.002 0.700 ± 0.003 10.11 ± 0.08 15.83 ± 0.14
0.6 M DMII(a) 24.35 ± 0.03 0.598 ± 0.002 0.700 ± 0.003 10.15 ± 0.06 15.92 ± 0.09
0.8 M DMII(a) 24.71 ± 0.20 0.581 ± 0.004 0.700 ± 0.002 10.01 ± 0.16 15.70 ± 0.24
1.0 M DMII(a) 24.80 ± 0.04 0.587 ± 0.001 0.680 ± 0.002 9.97 ± 0.01 15.46 ± 0.03
0.2 M tBp(b) 23.74 ± 0.03 0.588 ± 0.002 0.720 ± 0.001 10.19 ± 0.05 15.70 ± 0.08
0.5 M tBp(b) 23.25 ± 0.02 0.592 ± 0.002 0.730 ± 0.002 10.08 ± 0.04 15.69 ± 0.06
0.8 M tBp (b) 23.16 ± 0.02 0.618 ± 0.004 0.730 ± 0.003 10.45 ± 0.05 16.32 ± 0.08
1.0 M tBp (b) 23.07 ± 0.03 0.616 ± 0.001 0.730 ± 0.001 10.32 ± 0.05 16.20 ± 0.08
2 + 4 µm(c) 21.22 ± 0.01 0.651 ± 0.002 0.714 ± 0.001 9.86 ± 0.03 15.41 ± 0.04
4 + 4 µm(c) 22.46 ± 0.01 0.634 ± 0.001 0.717 ± 0.003 10.22 ± 0.06 15.95 ± 0.09
6 + 4 µm(c) 23.66 ± 0.03 0.616 ± 0.011 0.720 ± 0.010 10.46 ± 0.04 16.40 ± 0.06
8 + 4 µm(c) 24.47 ± 0.08 0.586 ± 0.011 0.720 ± 0.010 10.33 ± 0.06 16.13 ± 0.08
PEO 9 wt% (d) 23.70 ± 0.11 0.604 ± 0.001 0.730 ± 0.001 10.45 ± 0.05 16.33 ± 0.10

(a)
0.01 M I2, 0.8 M tBp, 12.10 nm Pt film, 6 + 4 µm TiO2 layer.
(b)
0.01 M I2, 0.2 M DMII, 12.10 nm Pt film, 6 + 4 µm TiO2 layer.
(c)
9 wt% PEO/PMMA (7/3), 0.01 M I2, 6 + 4 µm TiO2 layer, 0.2 M DMII, 0.8 M tBp, 12.10 nm Pt film.
(d)
0.2 M DMII, 0.8 M tBp, 0.01 M I2, 6 + 4 µm TiO2 layer, 12.10 nm Pt film.

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S. Venkatesan, et al. Chemical Engineering Journal 394 (2020) 124954

Table 2
Photovoltaic data at 67. 56 µW cm−2 (200 lx) for the cobalt DSSCs using Y123 dye. RPt obtained from the cobalt DSSCs. Ion diffusivity and ionic conductivity in the
cobalt LE and PEO PEs.
Electrolytes(a) Jsc (µA.cm−2) Voc (V) FF Pmax (µW.cm−2) PCE (%) Rpt (Ω Conductivity × 10−4 Diffusivity × 10−6
.cm−2) (mS cm−1) (cm2 s−1)

Liquid 25.18 ± 0.12 0.754 ± 0.001 0.752 ± 0.001 14.29 ± 0.09 21.15 ± 0.14 34.00 1.03 1.74
3 wt% PEO (Injection) 25.27 ± 0.26 0.716 ± 0.001 0.779 ± 0.001 14.09 ± 0.14 20.85 ± 0.19 36.73 0.90 1.43
6 wt% PEO 24.41 ± 0.47 0.723 ± 0.021 0.786 ± 0.012 13.88 ± 0.22 20.54 ± 0.34 33.45 0.73 1.20
9 wt% PEO 25.10 ± 0.50 0.727 ± 0.022 0.779 ± 0.006 14.23 ± 0.60 21.06 ± 0.51 31.86 0.60 1.03
12 wt% PEO 23.30 ± 0.46 0.685 ± 0.041 0.790 ± 0.041 12.61 ± 0.42 18.67 ± 0.43 32.66 0.47 0.75
9 wt% PEO + PMMA (7/ 24.14 ± 0.47 0.664 ± 0.003 0.787 ± 0.004 12.61 ± 0.14 18.67 ± 0.002 60.20 0.59 0.97
3)

(a)
6 + 4 µm TiO2 layer, 12.1 nm Pt film, 0.11 M Co2+/0.025 M Co3+, 1.2 M tBp.

Table 3
(a)
Photovoltaic data for the cobalt bifacial QS-DSSCs using Y123 dye and 2–8 µm thick TiO2 layers.
Light intensity TiO2-layer thickness (nm) Front-illumination (rear-illumination)

Jsc (µA cm−2) Voc (V) FF (%) Pmax (µW cm−2) PCE (%)

69.49 µW cm−2 (200 lx) 2 µm 19.71 ± 0.03 0.712 ± 0.014 0.776 ± 0.008 10.89 ± 0.14 15.67 ± 0.22
(17.17) ± 0.19 (0.709) ± 0.10 (0.785) ± 0.004 (9.56) ± 0.28 (13.75) ± 0.14
4 µm 20.55 ± 0.08 0.705 ± 0.006 0.784 ± 0.003 11.37 ± 0.04 16.35 ± 0.18
(17.35) ± 0.26 (0.701) ± 0.008 (0.794) ± 0.005 (9.65) ± 0.25 (13.87) ± 0.28
6 µm 21.74 ± 0.135 0.690 ± 0.001 0.792 ± 0.002 11.89 ± 0.07 17.10 ± 0.103
(17.93) ± 0.305 (0.685) ± 0.002 (0.805) ± 0.003 (9.88) ± 0.165 (14.22) ± 0.236
8 µm 22.40 ± 0.04 0.674 ± 0.012 0.793 ± 0.001 11.97 ± 0.255 17.22 ± 0.371
(18.40) ± 0.28 (0.669) ± 0.013 (0.805) ± 0.003 (9.91) ± 0.30 (14.25) ± 0.50

(a)
PEO (9 wt%), 1.61 nm Pt film, 0.11 M Co2+/0.025 M Co3+, 1.2 M tBp.

state DSSC using 1.0 M DMII obtained a Voc value of 0.587 V. This value Fig. 1a, b. The DSSC utilizing 1.0 M DMII had higher capacitance than
was lower than that of the 0.608 V for the cell using 0.2 M DMII. The the DSSC utilizing 0.2 M DMII (Fig. 1a). This indicates a downward shift
interfacial charge-transfer resistance of the cells using these electrolytes in the TiO2 conduction band edge in the presence of 1.0 M DMII. This
was studied using EIS, for which the related results are presented in band edge shift was the reason for the high Jsc and low Voc in the

Fig. 1. Chemical capacitance and recombination resistance of the iodide liquid cells using different amounts of DMII (a, b) and tBp (c, d).

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S. Venkatesan, et al. Chemical Engineering Journal 394 (2020) 124954

corresponding DSSCs. For the recombination resistance at the photo-
electrode/electrolyte interface (Rct) presented in Fig. 1b, lower Rct va-
lues were obtained for the cells using 1.0 M DMII than were obtained
with the use of 0.2 M DMII. The lower Rct values implied high electron
recombination at the photoelectrode/iodide LE interface. Thus, the cell
using 1.0 M DMII obtained a low value of 0.587 V in comparison to the
other cells. The cells using 1.0 M DMII obtained a PCE of 15.46%. This
PCE was lower than that of the PCE of the cell using 0.2 M DMII
(16.06%). The low PCE was ascribed to the low Voc of the cells using a
high concentration of DMII. These results suggest that a low DMII
concentration (0.2 M) is optimal to achieve high PCEs under 200 lx T5
light illumination.
Secondly, different amounts of tBp (0.2–1.0 M) were utilized to
prepare the electrolytes, and the performance of the DSSCs using these
electrolytes was studied. Fig. S2a (ESI†) shows the J-V characteristics
and Table 1 displays the J-V parameters of the DSSCs. The PCE obtained
for the liquid DSSC utilizing 0.2 M tBp was 15.70%. This efficiency was
improved with increases in the amount of tBp and attained a high value
of 16.32% at 0.8 M of tBp. This was ascribed to the enhanced Voc of the
DSSC in the presence of 0.8 M tBp. The further increase in the amount
of tBp triggered a slight decrease in the PCE. The Jsc was higher for the
DSSC utilizing 0.2 M tBp than for the DSSC utilizing 0.8 M tBp. The
higher Jsc was ascribed to the higher IPCE of the DSSC utilizing 0.2 M
tBp (Fig. S2b) (ESI†). To determine how the presence of 0.8 M tBp
improved the Voc, EIS experiments were conducted for the liquid cells
utilizing low (0.2 M) and high (0.8 M) concentrations of tBp. The re-
lated results are given in Fig. 1c, d. In the liquid DSSC utilizing 0.8 M
tBp, the Rct values were higher than in the DSSC utilizing 0.2 M tBp
(Fig. 1d). This reveals that the Rct improved in the presence of a high
concentration of tBp. This was because a huge amount of tBp adsorbed
onto the surface of the photoelectrode, preventing the recombination
reaction between the triiodide ions and the electrons on the photo-
electrode [45]. Fig. 1c implies that the capacitance of the cells de-
creased in the presence of 0.8 M tBp. This result indicated that the
higher amount of tBp in the electrolyte increased the charge density of
the TiO2 conduction band, which is consistent with the high Voc value
acquired for the associated QS-DSSCs. Thus, the high Voc obtained for
the cells utilizing 0.8 M tBp contributed to the high PCE of the related
cells.
4 µm thick scattering layer.
An IPCE analysis was performed for the QS-DSSCs to determine the
reason for the enhancement of the Jsc with an increase in the thickness
of the main layer. The IPCE spectra measured for the QS-DSSCs using
photoelectrodes with 2–8 µm thick main layers are given in Fig. 2b.
These four cells exhibited different absorbance ranges in a wavelength
region ranging from 300 to 850 nm even though the N719 dye was
utilized for all four cells. For the QS-DSSC using the 2 µm thick main
layer, an IPCE value of 71.52% at a wavelength of 530 nm was ob-
tained. This value increased with increases in the thickness of the main
layer. For the cell using an 8 µm thick main layer, the IPCE value was
75.90%. This value was higher than the values obtained for the cells
using 4 and 6 µm thick main layers. The high IPCE was mainly ascribed
to greater dye absorption and light scattering in the presence of the
8 µm thick main layer. The IPCE values measured for these cells were
consistent with the Jsc values.
In this work, a 9 wt% PEO-based electrolyte paste was also pre-
pared, and the performance of the DSSC utilizing this electrolyte was
measured. A PCE of 16.33% was acquired for the cells utilizing the PEO
PE (Table 1). This PCE was similar to that of the PCEs for the DSSCs
utilizing the PEO/PMMA PEs (16.40%) and LEs (16.32%). This effi-
ciency of 16.40% was higher than the efficiency of the DSSCs utilizing
the PEO/PVDF PE system (15.39%) [26]. This result was also consistent
with the results reported for these QS-DSSCs operating under AM 1.5
conditions [20,21]. To further improve the PCE of room light DSSCs,
cobalt PEs were next prepared and utilized. As compared to the results
obtained for the iodide cells, entirely different results were obtained for
the cobalt QS-DSSCs, which will be described in the section 3.5.

3.2. Effect of various thicknesses of photoelectrodes on the performance of

the iodide QS-DSSCs

After regulating the concentrations of the DMII and tBp in the LEs,
iodide PEs were prepared. It has been reported that QS-DSSCs fabri-
cated using polymer blend electrolytes exhibited high PCEs under one-
sun conditions [20,21]. In light of these reports, PEO/PMMA (7/3, 9 wt
%) was introduced into LEs containing 0.01 M I2, 0.2 M DMII, 0.8 M
tBp, and MPN to prepare the PEs. These PEs were applied onto the
surface of photoelectrodes that with a 6–12 µm thick TiO2 layers
(Table 1). The performance of the cells utilizing these photoelectrodes
was evaluated. The J-V characteristics recorded under 200 lx T5 light
illumination are shown in Fig. 2a. The parameters derived from these
curves are given in Table 1. Voc displayed a significant decrease with
increases in the main layer thickness from 2 µm to 8 µm. This was
attributed to the higher electron recombination and small mass trans-
port in the thick main layers. It was also noticed that Jsc increased with
increases in the thickness of the main layer from 2 µm to 8 µm. The PCE
improved with thickness up to 6 µm and then began declining due to
the reduction in Voc. Even if a thick TiO2 layer has a higher surface area
and thereby enhanced dye loading and light scattering, it also induces
higher recombination resistance and thereby increases the electron
recombination reaction with triiodide ions on the TiO2 surface, leading
to a reduction in PCE. Among all the QS-DSSCs in this work, the highest
PCE obtained was 16.40%, for the main layer thickness of 6 µm. This Fig. 2. (a) J-V curves, and (b) IPCE of the QS-DSSCs using different thicknesses
suggested that the optimal thickness is a 6 µm thick main layer and a of the TiO2 main layer.

5
S. Venkatesan, et al.
3.3. Effect of TiO2 pore size on the penetration of the iodide PEs
In the above experiment, Dyesol TiO2 paste with a particle size of
30 nm was utilized to prepare the main layer, which was 10 nm larger
than the size of the particles used in a study reported in the literature
[26]. The penetration of the PEs into the pores of the TiO2 can be im-
proved by the use of large particle size. To prove this, electrolyte pe-
netration experiments were conducted as illustrated in the published
reports on this topic [19–22]. The results of the current study are shown
in Fig. S3 (ESI†). The 2 and 10 µm thick TiO2 main layers with particles
size of both 30 and 20 nm were printed separately onto platinum-
coated FTO glasses. The penetration of the PEO/PMMA PEs was as-
sessed by calculating the charge transfer resistance (RPt) at the interface
of platinum modified FTO/TiO2 (FTO/Pt/TiO2) and PE interface. It is
well known that QS-DSSCs with a high penetration of PEs will have a
low RPt as a consequence of the strong pore-filling of the PE with the Pt
film beneath the TiO2 film [19–22]. Fig. S3 (ESI†) shows the RPt values
acquired from the EIS analysis of the cells using these two TiO2 main
layers. The 2 µm thick TiO2 main layers using particle sizes of 30 and
20 nm had RPt values of 7.82 and 8.89 Ω cm2, respectively. These two
values increased with increases in the thickness of the TiO2 main layers
from 2 to 10 µm. However, the increase was not significant for the main
layer with a particle size of 20 nm, which exhibited poor PE penetra-
tion. In comparison, the RPt decreased significantly when the main layer
with a particle size of 30 nm was used, revealing much higher PE pe-
netration. Thus, the obtained RPt values were 11.79 Ω cm2 and
8.40 Ω cm2, respectively, for the 10 µm thick TiO2 main layer con-
taining particle sizes of 20 and 30 nm. These studies confirmed the
advantages of using a main TiO2 layer with a particle size of 30 nm in
terms of the contact of the PE into the pores of the photoelectrode.
3.4. Rheological properties of the cobalt PEO PEs
In a previous section, QS-DSSCs using iodide PEO and PEO/PMMA-
based PEs did not show marked differences in terms of PCEs under
room light conditions. The cells using iodide PEs obtained a maximum
PCE of ~16.40% (Table 1). To further increase the PCE, cobalt PEO PEs
were prepared by introducing various amounts of PEO (3–12 wt%) into
an MPN-based cobalt LE. The PEO was insoluble in the LE at room
temperature (RT). Therefore, the temperature of the mixtures was in-
creased to enhance the solubility of the polymers. The different con-
centrations of PEO were completely soluble when the temperature
reached 120 °C. The hot mixtures were cooled to RT to form the elec-
trolyte pastes for the printing process. The solidification results for the
cobalt LE with various concentrations of PEO at RT are given in Fig. S4
(ESI†). The solidification of the cobalt LE improved with increases in
the amount of PEO in the electrolyte. However, the amounts of the
polymers determined the viscous characteristics of the solidified elec-
trolyte that was formed. The 3 wt% PEO and LE formed a polymer gel
instead of a paste, which was more suitable for an injection process than
for a printing process. The 6, 9, and 12 wt% PEO, respectively formed
moderate, optimal and highly viscous pastes with LE. However, the
electrolyte pasted formed using 9 wt% PEO was the most convenient for
the printing process.
It has been reported that the viscosity of a polymer-based electrolyte
is a key factor that typically influences the outcome of the printing
process [20–23]. In this work, 6, 9, and 12 wt% PEO-based electrolyte
pastes exhibited changes in their performance during the printing
method. This was ascribed to the various viscosities of the polymer
electrolytes, as verified in the rheological experiments. Fig. 3 displays
the viscosity evaluated for the electrolyte pastes containing different
amounts of PEO. The 9 wt% PEO-based PE paste had a viscosity of
23.47 Pa s at a shear rate of 1.11 s−1. This value slowly decreased with
increases in the shear rate and reached a value of 6.83 Pa s at a high
shear rate of 92.47 s−1. Although the viscosity value decreased at a
high shear rate, the printing process was proven to be efficient with this
6
Chemical Engineering Journal 394 (2020) 124954
electrolyte paste. The results confirmed that the electrolyte paste with
9 wt% PEO was most appropriate for the printing process. For the
electrolyte pastes using 6 wt% and 12 wt% PEO, the viscosity values of
2.80 and 93.57 Pa s, respectively, measured at a shear rate of 1.11 s−1.
These values were significantly lower (~10 times) and higher (~4
times) than the value obtained for the electrolyte paste based on 9 wt%
PEO. These result indicated that the rheological properties of these two
electrolyte pastes were different from that of the 9 wt% PEO-based
electrolyte system. The viscosities of these electrolyte pastes also de-
creased with increases in the shear rate. These two electrolytes were
even able to coat on the photoelectrode, but they were more than two
times less efficient than the 9 wt% PEO-based PE paste for the printing
process. This is because of their inadequate viscosities as compared to
the 9 wt% PEO-based electrolyte.
3.5. Effects of cobalt PEO PEs on the performance of the QS-DSSCs
The photovoltaic performance of the cells using PGEs with 3 wt%
PEO and PEs with 6, 9 and 12 wt% of PEO was evaluated. For com-
parison, the performance of the cells using LE and PEs with 9 wt% PEO/
PMMA was also measured. The J-V curves of these DSSCs are displayed
in Fig. 4. The parameters derived from these curves are given in
Table 2. A PCE of 18.67% for the cells fabricated using PEs with 9 wt%
PEO/PMMA was obtained. This efficiency was considerably lower than
that of the DSSCs using cobalt LE (21.15%). Although the Jsc was
slightly decreased, a marked decrease in the Voc caused low PCE in the
QS-DSSC using the PE with 9 wt% PEO/PMMA. This result indicated
that the PE with PEO/PMMA was not favourable to increasing the DSSC
PCE values. For the QS-DSSC using the PE with 9 wt% PEO, a PCE of
21.06% was obtained. This PCE was remarkably higher than the PCE of
the cells utilizing the PEO/PMMA PE (18.67%). These results were
distinct from those obtained for the cells using iodide-based electro-
lytes. For the iodide PEs, the cells using PEs with 9 wt% PEO, and the
PEO/PMMA had similar PCEs of ~16.40%. The high efficiency of the
corresponding DSSC was attributed to the higher Jsc and Voc of the QS-
DSSCs using a cobalt PE with 9 wt% PEO. The PCE of 21.06% was
comparable to that of the PCE of the liquid version (21.15%). The PCEs
of this QS-DSSC using a PE with 6 wt% PEO (20.54%) and 12 wt% PEO
PEs (18.67%) were lower than those for the cells using a PE with 9 wt%
PEO (21.06%). This is because the lower Jsc and Voc of the related cells
caused a decrease in their PCEs. The PCE of the QS-DSSCs fabricated
using the PGE with 3 wt% PEO using the injection process had an ef-
ficiency of 20.85%, which was lower than the PCE of the cells using the
PE with 9 wt% PEO (21.06%).
To determine the cause for the high PCE of the QS-DSSCs using the
Fig. 3. Rheological properties of the cobalt PEs containing 6, 9, and 12 wt%
PEO.
S. Venkatesan, et al. Chemical Engineering Journal 394 (2020) 124954

amount of PEO and a minium value of 31.86 Ω cm2 was obtained at 9 wt

% PEO. A smaller RPt value indicates a lower charge transfer resistance at
the CE/PE interface which is helpful to get a higher PCE. The highest PCE
of the DSSC using 9 wt% PEO PE is consistent with the smallest RPt value
of the cell. However, this relationship is not consistent between cells
using LE and the PE (9 wt% PEO) which implies that other factors, in-
stead of Rpt, are more important in determining the PCE.
In this study, the cells using cobalt PEO/PMMA PEs had lower ef-
ficiencies than the cells using PEO PEs. The performance difference
between these two PEs systems in the DSSCs can be explained using the

Fig. 4. J-V curves of the cells using the cobalt LE, and PEs with various con-
centrations of PEO and 9 wt% PEO/PMMA.

PE with 9 wt% PEO, the ion diffusivity and conductivity of the PEs were
first measured from the CV and EIS curves, respectively (see Figs. S5 &
S6 in ESI†) [20,21]. For comparison, the ion diffusivity and con-
ductivity of other electrolytes were also measured. The results of these
studies are presented in Table 2. The ion diffusivity and conductivity of
the LE, respectively, were 1.74 × 10−6 cm2 s−1 and 1.03 × 10−4 S
cm−1. For the PE pastes, the ion diffusivity and conductivity of the
electrolyte decreased with increases in the amount of PEO. The PEs
with 9 wt% PEO had lower ion diffusivity and conductivity values than
the LE and electrolytes with 3 and 6 wt% PEO. Although the 9 wt% PEO
PE had appropriate levels of viscosity for the printing technique, it had
low potential to improve the ion diffusivity and electrolyte con-
ductivity. However, the PCE of the DSSCs with 9 wt% PEO did not
decrease due to the low ion diffusivity and conductivity of the elec-
trolyte. The Jsc and PCE of the QS-DSSCs using a PE with the best
amount of PEO were both similar to those for the liquid counterpart.
These outcomes specified that the ion diffusivity and conductivity of the
electrolytes were not the factors determining the PCEs of the QS-DSSCs
and indicated that there were a few other effects because of the 9 wt%
PEO PE participated in the improvement of the PCE of the QS-DSSCs.
An EIS analysis was carried out for the cells using LE and PEs with
the optimal concentration (9 wt%) of PEO and PEO/PMMA (7:3) PEs.
The chemical capacitance and Rct derived from the related EIS spectra
(see Fig. S7 in ESI†) of these devices are compared in Fig. 5. The DSSCs
using PEO/PMMA PEs had higher capacitance (Fig. 5(a)) and smaller
Rct (Fig. 5(b)), respectively, than those of the DSSCs using PEO PEs. The
higher capacitance of the PEO/PMMA cell implies a downward shift in
the conduction band edge by adding the PMMA (see Fig. 5(a)). Theo-
retically, this shift will lead to a higher Jsc for the PEO/PMMA cell.
However, a slightly lower Jsc was obtained as shown in Table 2.
Therefore, the lower Jsc of the PEO/PMMA cell should be ascribed to
the smaller Rct shown in Fig. 5(b), which is consistent with its shorter
electron lifetime demonstrated in Fig. 5(c). On the other hand, the
higher Rct value of the PEO cell indicates a higher charge recombination
resistance at the photoelectrode/PE interface. This is the main effect
leads to the higher Voc and higher PCE of the PEO cells. In comparison
to the PEO cell, the liquid-state cell had lower capacitance and higher
Rct. Since a lower capacitance is expected to result in a smaller Jsc, the
higher Jsc, Voc and PCE of the liquid cell is attributed to its higher
charge recombination resistance (higher Rct).
The charge transfer resistance at the electrolyte and counter electrode
(RPt) was derived from the EIS curves (Fig. S6 in the ESI†) for the cells
using LEs and PEs [20,46]. As shown in Table 2, the cells using LEs had
Fig. 5. (a) Chemical capacitance, (b) Rct and (c) electron lifetime obtained from
an RPt value of 34 Ω cm2. The RPt value become higher (36.73 Ω cm2)
the EIS analysis for the cells using cobalt LE, and cobalt PEs with 9 wt% PEO
when 3 wt% PEO PE was used, but decreses markedly with increasing and 9 wt% PEO/PMMA (7/3).

7
S. Venkatesan, et al. Chemical Engineering Journal 394 (2020) 124954

Fig. 6. A proposed model of Li+ and Co3+ distribution for DSSCs using liquid electrolyte (a), PEO PE (b) and PEO/PMMA PE (c).

mechanism proposed in Fig. 6. It is well known that cations and ad- 3.6. Stability of the cobalt QS-DSSCs
ditives are contained in the electrolytes, playing as different roles in
improving the performance of DSSCs [47–49]. The electrons excited The stability of the cells assembled utilizing the optimal amount of
under light illumination inject into the TiO2 film and thereby, the TiO2 PEO (9 wt%) was assessed under room light conditions. For compar-
film is negatively charged and an electrical double layer is formed on ison, the stability of the corresponding liquid cell was also assessed. The
the film surface [47]. In the electrolyte containing cobalt redox couple, two cells were subjected to a constant T5 light illumination of 200 lx at
the main cations are Li+ and cobalt redox couple, and the competing 35 °C. The differences in the PCEs during the stability test were nor-
adsorption of the cations ions will determine the situations of the malized as presented in Fig. 8. For the DSSC using a LE, the efficiency
electrical double layer and photoelectrodes [48]. Since Li+ has a was 98% of its initial value after 1000 h test. For the DSSC using the PE,
smaller size, it can easily penetrate into the TiO2 films than does by the the efficiency was enhanced gently with the testing time and achieved
cobalt ion (Fig. 6a). The presence of the Li+ ions on the photoelectrode an efficiency of over 100% after the same test period. The results in-
leads to a more positive electrical double layer which results in a higher dicated that the cells using PEs had a high stability as compared to LEs
repulsion force to the oxidized cobalt ion (Co+3), pushing them away under 200 lx room light illumination.
from the photoelectrode and thereby, reduce the recombination of ex-
cited electrons with the Co+3 ions (that is, increase the charge re- 3.7. Effects of cobalt PEO PEs on the performance of the bifacial QS-DSSCs
combination resistance, Rct). Therefore, the presence of Li+ is ad-
vantageous to the performance of DSSCs. Finally, the cobalt PEs with 9 wt% PEO were utilized to fabricate
In this study, the cells using PEO/PMMA PEs had lower Rct, shorter room light quasi-solid-state bifacial DSSCs. It is well known that the
electron lifetime and lower efficiencies in comparison to those of the transparency of a CE significantly affects the PCE of QS-DSSCs. For the
cells using PEO PEs and liquid electrolytes (Fig. 5b, c). This result can preparation of the highly transparent CE, a 1.61 nm thick Pt layer was
be ascribed to the lower Li+ concentration on the photoelectrode sur- coated instead of 12.10 nm thick Pt layer onto a FTO substrate. Various
face of the cell using PEO/PMMA PEs. According to the molecular bifacial QS-DSSCs were fabricated using PEO (9 wt%) PEs, Pt CE, and
structure, the PEO contains ether group (-C-O-C), and both ether and photoelectrodes with 2, 4, 6 and 8 µm thick TiO2 main layers. The
carbonyl (C=O) groups are involved in PMMA. Both the functional photovoltaic performance of these DSSCs was studied under front- and
groups contain lone pair electrons which have a strong tendency to backside-illumination of 200 lx. The J-V characteristics and the
coordinate with alkali metal ions such as Li+ (Fig. 6b, c) [50–54]
Therefore, the concentration of Li+ ions will decrease at the presence of
the polymers and, thereby, the Co+3 ions have a higher probability to
contact the photoelectrode (Fig. 6b, c), resulting in a lower cell per-
formance. Comparing the PEO and PEO/PMMA systems, PEO/PMMA
has more lone pair electrons to coordinate with the Li+ [51–54], which
decreases the Li+ concentration in the electrical double layer more than
does by PEO (Fig. 6b). Consequently, the local concentration of the
Co3+ near the photoelectrode was increased in the cell using PEO/
PMMA PE and the performance of the DSSC is lower than that using
PEO PE. For the liquid state cell, since no polymer is present in the
electrolyte, the coordination between Li+ and polymer did not occur
and, therefore, the liquid cell has higher recombination resistance and
high efficiencies than the gel-state DSSCs (Fig. 5b & Table 2).
Since the laboratory cells based on cobalt PEO PEs had high PCEs
and were stable, this electrolyte was also applied for the fabrication of a
sub-module QS-DSSC, which had an active area of 11.2 cm2. Fig. 7
shows the J-V curve and related parameters obtained for the sub-
module cell under 200 lx room T5 light illumination. The module cell
based on the cobalt PEO PEs obtained a high PCE of 12.58%. This result
proved the advantages of cobalt PEO PEs for the preparation of room Fig. 7. J-V characteristic of a sub-module QS-DSSC using cobalt PEO PE (9 wt%
PEO) under 200 lx T5 light illumination. The active and aperture area of the QS-
light cobalt QS-DSSC modules.
DSSC are 11.21 cm2 (1.9 × 5.9 cm2) and 19.5 cm2 (3 × 6.5 cm2), respectively.

8
S. Venkatesan, et al.
Fig. 8. The long-term stability of the cells using the cobalt LE and PEO PEs
(9 wt% PEO) under 200 lx T5 light illumination.
associated parameters, respectively, for the related cells are given in
Fig. S8 (ESI†) and Table 3. The PCE of the cell under front-side illu-
mination conditions increased with increases in the thickness of TiO2
main layer and attained a high value of 17.22% at a layer thickness of
8 µm. Although the Voc significantly decreased, a large increase in the
Jsc triggered a high PCE in these DSSCs. The remarkable red-shift in the
IPCE spectrum of the cell utilizing an 8 µm thick TiO2 main layer as
compared to the 2 µm thick layer (Fig. S9 in the ESI†) contributed to the
high Jsc of the related QS-DSSC. Cells using a photoelectrode with a
thick TiO2 main layer generally have easy contact with the electrolyte,
which increases the charge recombination at the interface. As a result of
this effect, the cell Voc is significantly reduced. At the same time, the
high active area and related dye loading of the photoelectrode usually
result in the absorption of a lot of photons, which assists the high Jsc of
the DSSCs. Nevertheless, under back-side illumination conditions, the
Jsc increased, and the Voc decreased with increases in the thickness of
the TiO2 main layer from 2 to 8 µm. The cells with an 8 µm thick TiO2
main layer achieved a high Jsc and a PCE of 18.40 µA/cm−2 and
14.25%, respectively.
4. Conclusion
In conclusion, the cobalt PEO PE was shown to be more suitable
than the iodide PEO/PMMA PE for assembling high-performance room
light QS-DSSCs. The optimal PEO PE had lower ion diffusivity and
conductivity than the corresponding LE. However, the PCE of the cells
utilizing this PE was similar to that of the cells using LEs under the
200 lx T5 light illumination. This PCE was also remarkably higher than
the PCE of the QS-DSSCs utilizing iodide PEs. The appropriate viscosity
of the PE paste, the high Rct, and low RPt of the cells helped to the high
efficiency of the corresponding DSSCs. The sub-module cell using the
cobalt PE had a high efficiency of 12.60%. The bi-facial QS-DSSCs using
9 wt% PEO had efficiencies of 17.60% and 14.58%, respectively, under
the 200 lx front and back-side illumination conditions. The cells based
on PEs had superior stability as compared to the cells based on the LEs
at 35 °C.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
This research was supported by the Hierarchical Green-Energy
Materials (Hi-GEM) Research Center, which works under the Ministry
of Education (MOE). This work was also supported by the Ministry of
9
Chemical Engineering Journal 394 (2020) 124954
Science and Technology (MOST 106-2221-E-006-197-MY3, MOST-107-
2119-M-006-001) in Taiwan.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2020.124954.
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