Journal of Energy Storage 61 (2023) 106622

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Journal of Energy Storage

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Research papers

Redox flow batteries: Pushing the cell voltage limits for sustainable
energy storage
Rahul Thamizhselvan a, c, Raghupandiyan Naresh a, c, Ramachandran Sekar b, c,
Mani Ulaganathan d, *, Vilas G. Pol e, *, Pitchai Ragupathy a, c, e, **
a
Electrochemical Power Sources Division, CSIR-Central Electrochemical Research Institute, Karaikudi-630 003, Tamil Nadu, India
b
Electroplating and Metal Finishing Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630 003, Tamil Nadu, India
c
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
d
Department of Sciences, Amrita School of Physical Sciences, Amrita Vishwa Vidyapeetham Coimbatore-641 112, India
e
Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Electrode kinetics of zinc at the anode in an alkaline medium holds a great prospective for energy storage systems
Alkaline electrolyte due to low redox potential of Zn(OH)2− 4 /Zn redox couple (− 1.26 V vs SHE), high capacity, good stability, in­
High cell voltage volves two electron transfer, high reversibility, eco-friendly and low cost. Undoubtedly, enlarging the voltage of
Energy efficiency
the flow cell is the ultimate goal for enhancing the energy density of the system. Here, we demonstrate the
Polyiodide
Redox flow battery
increase in the operating cell voltage of Zinc-Polyiodide (ZnI2) flow battery by meticulously switching the
anolyte from an acidic/neutral to an alkaline medium. Very interestingly, swapping the electrolyte from neutral
to an alkaline medium shows drastic increase in the voltage window from 1.37 V (neutral) to 1.89 V (alkaline) for
ZnI2 redox flow battery (RFB). Furthermore, the developed advanced hybrid ZnI2 electrolyte highly improved the
rate capability of the RFB, even at 100 mA cm− 2, exhibiting a round trip efficiency of 98 % and the corresponding
energy efficiency is about 46 %. On the other hand, the ZnI2 flow cell with the given electrolyte condition
delivered a maximum coulombic (96 %), voltage (83 %) and energy efficiency (77 %) at 20 mA cm− 2. Moreover,
the alkaline based ZnI2 RFB performed stably over 90 cycles at 30 mA cm− 2. At the same time, 50 cycles at 50
mA cm− 2 have also been tested. This reported cycle life is ever maximum cyclability achieved for alkaline based
metal halides RFBs. Thus, a creative protocol of switching the anolyte pH from acid/neutral to alkaline medium
offers an efficient route to attain high cell voltage and high energy density device when paired with high positive
redox potential species.

1. Introduction
Globally, there is a gradual rise in energy demand by 1.8 % annually,
it will be expected to reach 50 % by 2050 as traditional-based fossil fuels
undergo fast depletion [1]. This scenario can be effectively overcome by
utilizing renewable energy sources for electricity generation, as
renewable resources offer the cleanest and most viable solution for
sustainable energy. However, the intermittent nature of renewable
sources seriously interrupts the continuous supply of electricity [2–8]. In
this regard, an efficient implementation of energy storage technology is
highly desirable for ameliorating system’s reliability and sustainability
[6,7,9]. Redox flow batteries (RFBs) possess a number of the claim such
as long cyclability, ease of operation, flexibility in battery design, eco-
friendly and easy scalability and hence it is considered to be a premier
stationary energy storage technology [10–13]. The capacity of RFBs
depends on the volume or concentration of redox-active species present
in the electrolyte. In contrast, power density is determined by the area of
the active electrode or by the number of cells of the battery [2,6,7]. So
that, the energy and power density can be independently varied in RFBs,
as this enthusiastic feature helps to facilitate the scalability of RFBs to
large scale storage of electricity. Further, to enhance cell voltage and
energy density, the non-aqueous based RFBs are quite attractive due to

* Corresponding authors.
** Correspondence to: P. Ragupathy, Electrochemical Power Sources Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630 003, Tamil Nadu,
India.
E-mail addresses: m_ulaganathan@cb.amrita.edu (M. Ulaganathan), vpol@purdue.edu (V.G. Pol), ragupathyp@cecri.res.in (P. Ragupathy).

https://doi.org/10.1016/j.est.2023.106622
Received 20 August 2022; Received in revised form 18 December 2022; Accepted 3 January 2023
Available online 24 January 2023
2352-152X/© 2023 Published by Elsevier Ltd.
R. Thamizhselvan et al. Journal of Energy Storage 61 (2023) 106622

wider electrochemical potential window (~4 V), better rate capability,

use of variety of organic redox molecules, abundance of starting mate­
rials and cost-effective [14,15]. On the other hand, all vanadium RFBs
have gained significant attention and commercialized globally owing to
their long cyclability and the use of vanadium precursors in both anolyte
and catholyte reduces the risk of cross-contamination of electrolytes.
However, vanadium RFB suffers from certain critical issues such as low
cell voltage (1.26 V), which leads to low energy density (<25 Wh L− 1 in
practical) and use of acid as supporting electrolyte also triggers
hydrogen evolution reaction (HER) at anode which affects the
coulombic efficiency of the battery. On the other hand, zinc based RFBs
has been overwhelmingly attracted as a suitable alternative candidate
for stationary energy storage applications due to the low potential of
Zn2+/Zn redox potential (− 0.76 V vs SHE), high stability of metallic
zinc, risk free and high theoretical capacity (820 mA h g− 1, 5854 mA h
L− 1) [16]. So far, various zinc-based flow batteries have been reported
such as Zn/Br2 [10], Zn/Ce [17], Zn/Mn [18], Zn/I2 [19–24] and Zn/
TEMPO [25]. Among these, Zn/Br2 RFB is widely recognized and
commercialized due to its unique characteristics such as high cell
voltage (1.84 V), high specific energy density (~55 Wh Kg− 1 in prac­
tical) and long cyclability (>2000) [26]. However, certain critical issues
found in Zn/Br2 RFB include sluggish kinetics of Br− /Br2 redox couple,
self-discharge of bromine and high corrosive nature of bromine alto­
gether restricting strictly the further development in the system. Thus, it
necessitates developing an efficient alternative for catholyte to over­
come the aforesaid bromine-based issues. By replacing 2Br− /Br2 redox
couple with I− /I−3 redox couple has recently been developed as an
appealing alternative catholyte in flow batteries. Owing to its high
abundance of iodine in the ocean, moreover, iodine is far less corrosive,
volatile, hazardous than bromine species and relatively low cost [27].
When the iodine (I2) is generated at the cathode during charging of the
flow cell, it forms extremely soluble triiodide ions (I−3 ) by spontaneously
reacting with the iodide ions (I− ) in the electrolyte [23]. The detailed
electrochemical reactions that occur at the cathode are shown in the
equations below

2I− ↔ I2 + 2e− E0 = 0.621 V vs SHE (1)

Fig. 1. Schematic illustration of working principle of advanced hybrid alkaline
based ZnI2 RFB.
−
I2 + Cl ↔ I2 Cl −
(2)

I2 Cl− ➔3/2 I2 + e− (3)
The schematic illustration of working principle of ZnI2 RFB is
depicted in Fig. 1. The I2Cl− /I− redox kinetics are significantly faster
than Br2/Br− redox couple. Furthermore, the former ZnI2 RFB shows an
output voltage of 1.30 [28]. Yet, the observed voltage for ZnI2 RFB
system is relatively lower than conventional ZnBr2 RFB system (1.84 V)
which substantially affects the energy density of the battery. Therefore,
development of high voltage of zinc based RFB system is urgently
required to improve the energy density of the RFB.
Recently, alkaline electrolyte-based zinc RFBs have great interest as
an anode due to the low redox potential of Zn(OH)2− 4 /Zn redox couple
(− 1.26 V vs SHE), low cost and two- electron transfer [20]. If the Zn
(OH)2−4 /Zn redox couple (as an anolyte) pairs with any species with
higher positive redox potential (as catholyte), then the open circuit cell
voltage (OCV) of the cell will drastically increase to a large extent, as it is
beneficial to attain high energy density. According to Pourbiax diagram,
an electrolyte’s pH highly determines the species redox potential [20].
For example, zinc redox couple exhibits a huge difference in the redox
potential while switching from an acidic/neutral to an alkaline medium
as given below.
/
In acidic neutral medium : Zn2+ + 2e− ↔ Zn E = − 0.763 V vs SHE
○
(3)
In alkaline medium : Zn(OH)4 2− + 2e− ↔ Zn + 4OH− E
○
Hence, this strategy opens an efficient route to construct high cell
voltage RFBs by simply switching the electrolyte environment from an
acidic/neutral to an alkaline medium. By applying this strategy, Zhang
et al. demonstrated a hybrid alkaline based ZnI2 RFB with 0.47 V alle­
viated potential by simply tuning the anolyte from an aqueous to an
alkaline medium and the flow cell delivered an energy density of 330.5
Wh L− 1 [20]. However, the acetate-based precursors used in the report
have a greater coordinating ability towards metal ions, therefore it may
strictly affect the plating and stripping process of zinc during the charge
discharge process; as a result, the cell voltage may be highly affected
which in turn decrease the energy density of the system. Besides that,
zinc foil was adopted as an electrode in the ZnI2 system, however
dissolution of zinc over a period of time severely affects the capacity of
the battery and 2D structure of zinc foil also limits the areal capacity,
which altogether affects the performance of the battery. Since at the
anode, the Zn plating and striping plays a crucial role, here in the present
work, for improving the cell performance, oxide-based precursor have
been employed in the anolyte which can help to stabilize the revers­
ibility of the zinc during the GCD process. In addition, we employed high
surface area 3D graphite felt as anode and cathode, which significantly
helps to attain high areal capacity and efficient plating/stripping of zinc.
On the other hand, supporting additives have been used in the catholyte
for stabilizing the conductivity of the electrolyte.
In the present work, with the help of Pourbiax phenomenon, an

alkaline based Zinc-Polyiodide flow battery is successfully demonstrated

(4) by adopting I− /I2Cl− redox couple as catholyte and alkaline Zn(OH)2− 4 /
= − 1.260 V vs SHE

2
R. Thamizhselvan et al.
Zn redox couple as anolyte. The designed ZnI2 RFB cell establishes a
potential difference of 1.88 V, much higher than the 1.36 V obtained for
the ZnI2 flow cell at the neutral electrolyte medium. As mentioned
above, the I− /I2Cl− redox couple is identified as a better replacement for
2Br− /Br2 redox couple because the I− /I2Cl− has emerged as an efficient
species due to corrosive free, high reversibility and involves two-
electron transfer reaction. The detailed electrochemical reaction that
occurs in ZnI2 RFB are described as follows:
At anode;
Zn(OH)4 2− + 2e− ↔ Zn + 4OH− E = − 1.26 V vs SHE (Alkaline medium)
○
(5)
At cathode;
−
(6)
○
2I ↔ I2 E = + 0.621 V vs SHE
Net cell reaction
Zn + I2 + 4OH− ↔ Zn(OH)4 2− + 2I− Ecell = 1.88 V (7)
During the charging process, iodide ions (I ) in the catholyte get
− catholyte (1 M KI + 1 M NH4Cl) was stored separately in a container,
oxidized to form elemental iodine (I2), which then immediately reacts
with free I− to give trihalide ions I2Cl− , whereas zincate (Zn(OH)2−
4 ) in
the anolyte gets reduced to form metallic zinc (Zn) which then subse­
quently deposited on the electrode. During discharging process, reverse
reactions proceeds and vice versa. The alkaline based zinc-polyiodide
flow cell performs better over a wide range of current densities (20 to
100 mA cm− 2) and exhibits a coulombic efficiency of 96 %, and an
energy efficiency of 73 % at 40 mA cm− 2. Even at a high current density
of 100 mA cm− 2, the ZnI2 flow cell shows 97 % of coulombic efficiency.
Furthermore, the flow cell exhibits a stable performance over 90 cycles
with 90.67 % of coulombic efficiency. Therefore, this simple protocol
aids in attaining a high cell voltage RFB system by simply switching an
anolyte (zinc species) pH from acid/neutral to alkaline medium and
greatly impacts the energy density of the RFB.
2. Experimental methods
2.1. Materials
Zinc oxide (Merck, >98.5 %), Sodium hydroxide (Thomas Baker, 98
%), Potassium iodide (Rankem, 99.5 %), Potassium chloride (SRL, 99.5
%), Ammonium chloride (Thermo Fischer Scientific, 99 %), Zinc chlo­
ride (Alpha Aesar, >98 %) were purchased and used as received. The
Graphite Felt (GF) with 5 mm thickness was purchased from SGL Car­
bon, SIGRACELL®, Germany. The Nafion-117 membrane was purchased
from Dupont, USA and used as an ion exchange membrane.
2.2. Electrolyte preparation
The electrolyte was prepared using double distilled (DI) water and
the electrolyte formulations used in the flow cell study includes 50 mL of
0.25 M ZnO + 5 M NaOH serve as anolyte and 50 mL of 1 M KI + 1 M
NH4Cl serve as catholyte. The ZnO and KI acts as active species whereas
NaOH and NH4Cl are used as supporting electrolyte, respectively.
2.3. Electrochemical studies
The electrochemical properties of anolyte and catholyte were
investigated using cyclic voltammetry (CV) and electrochemical
impedance spectroscopy (EIS) techniques in a three-electrode cell
configuration. The given area of GF was attached with the glassy carbon
rod current collector (GC, thickness 50 mm) and used as working elec­
trode; Ag/AgCl and platinum foil were used as reference and counter
3
Journal of Energy Storage 61 (2023) 106622
electrodes, respectively. The EIS was performed to explore the interfa­
cial charge transfer properties of an anolyte at a frequency range be­
tween 10 kHz to 0.1 Hz with AC perturbation of 10 mV in an open circuit
potential. All the electrochemical characterizations for the half cells are
carried out using Biologic instrument, France (model: VSP-300
potentiostat).
2.4. Flow cell assembly
Scribner redox flow cell test system (Model: 857, USA) was used to
evaluate the charge-discharge performance of the flow cell. The flow cell
was constructed as described below: two graphite plates with a grooved
portion of 3 mm depth have been employed as supporting electrode. The
GF of size 3 cm × 3 cm was directly used as primary electrode (such as
anode and cathode) without any pre-treatment process. The GF elec­
trodes i.e., anode and cathode were placed on the grooved portion of the
graphite plate which was separated by Nafion-117 membrane which act
as an ion exchange membrane. The Nafion-117 membrane was activated
prior to flow cell assembly by immersing Nafion-117 in the mixture of
sulfuric acid (H2SO4) and hydrogen peroxide (H2O2). The electrolyte
consists of 50 mL of each anolyte (0.25 M ZnO + 5 M NaOH) and
which was pumped in to respective the flow cell compartment at flow
rate of 30 mL min− 1 with the help of peristaltic pump. Copper was used
as a current collector on both sides. The galvanic charge-discharge
(GCD) study was performed at different current densities from 20 to
100 mA cm− 2; for curiosity, at each current density there are five cycles
were recorded and high frequency resistance (HFR) was recorded by the
Scribner instrument automatically during GCD operation.
2.5. Physical characterizations
Surface morphological of the electrode after GCD performance was
explored by scanning electron microscope (SEM, model: Tescan VEGA
3). Raman spectroscopy (LabRAM HR Evolution, Horiba; laser wave­
length: 532 nm) was employed to explore defects on the surface of the
felt during the GCD process.
3. Results and discussion
Cyclic voltammetry measurements were recorded at a scan rate of 5
mV s− 1 for understanding the electrochemical properties of anolyte and
catholyte. As shown in Fig. 2 (a), the Zn(OH)2− 4 /Zn redox couple depicts
a lower negative redox potential of − 1.51 V vs. Ag/AgCl than Zn2+/Zn
redox couple of − 1.08 V vs. Ag/AgCl, which is about 0.43 V higher than
that of Zn2+/Zn redox potential obtained at the neutral medium. It is
seen that Zn(OH)2− 4 /Zn redox couple exhibits a higher anodic peak
current density of 96.22 mA cm− 2 than Zn2+/Zn redox couple of 33.02
mA cm− 2. It indicates the better plating/stripping of zinc in an alkaline
medium. Thus, Zn(OH)2− 4 /Zn redox species combined with I /I3 redox
− −
species (0.34 V vs Ag/AgCl) exhibits the largest potential difference of
1.8 V, which is much better than the ZnI2 in a neutral medium and
merely closer to the conventional Zn–Br2 system (1.84 V). The CV
measurement for the catholyte 0.1 M KI was recorded in a potential
window of 0 to 0.8 V vs Ag/AgCl at 5 mV s− 1. The CV curve showed the
redox peak, oxidation (at 0.68 V vs Ag/AgCl) and reduction (at 0.37 V vs
Ag/AgCl) correspond to I− to I−3 and I−3 to I− . However, NH4Cl was used
as a supporting electrolyte with the main KI electrolyte to increase the
conductivity and electrochemical performance of the catholyte. The
addition of chloride ions acts as a complexing agent and form iodine-
chloride ions complexation, which release iodide ions, hence the ca­
pacity of the system is enhanced and also stabilized the redox reaction
[23,29]. The CV for catholyte composition (such as 0.05 M KI + 1 M
NH4Cl) shows the I− to I2 redox reaction, which comprises of two anodic
peaks at 1.01 V and 1.39 V vs Ag/AgCl which corresponds to the con­
version of I− to I2 with an intermediate formation of I2Cl− (Fig. 2b)
R. Thamizhselvan et al.
Fig. 2. (a) Cyclic voltammogram of anolyte (0.1 M ZnO + 3 M NaOH, 0.05 M ZnCl2 + 1 M KCl) and catholyte (0.1 M KI) recorded at a scan rate of 5 mV s− 1, (b)
Cyclic voltammogram catholyte of 0.05 M KI + 1 M NH4Cl, (c) and (d) CV curve recorded at different scan rates.
[23,29,30]. Similarly, two cathodic peaks were observed during the
reverse scan at 0.4 V and − 0.01 V vs. Ag/AgCl corresponding to the
conversion of I2 to I− . The CV curves have also been recorded at different
scan rates 5 to 9 mV s− 1 for Zn(OH)2− 4 /Zn redox couple to reveal the
further electrode kinetics. It was observed that the peak current density
of the system linearly increases with increase of scan rate from 5 to 9 mV
s− 1 and the peak position is also shifted towards the high potential due
to the increased electrode polarization at the electrode at a high scan
rate. Moreover, the linear variation of the peak current density for the
square root of the scan rate indicates the diffusion-controlled electrode
kinetics. The CV curves recorded at different scan rates are shown in
Fig. 2 (c) and (d). The diffusion-coefficient values of the anolyte and the
catholyte at a given electrode condition were estimated by employing
Randles Sevick equation. The diffusion-coefficient (D) values of 4.87 ×
10− 6 and 6.31 × 10− 6 cm2 s− 1 corresponding to the anodic and cathodic
reaction of Zn(OH)2− 4 /Zn conversion reaction were obtained. On the
other hand, in the presence of ammonium chloride, the I− /I2 shows two
redox processes, the corresponding diffusion coefficient (D) values are
estimated for both redox processes separately. The first redox reaction
shows the diffusion coefficient values of 7.018 × 10− 5 and 7.147 × 10− 5
for anodic and cathodic reaction respectively; whereas, the D values of
9.086 × 10− 5 and 8.082 × 10− 5 corresponding to second redox reactions
respectively. This enhanced multiple redox behaviour and the signifi­
cant increased diffusion co-efficient values suggest the improved ki­
netics of redox reactions. The obtained diffusion coefficient values are
almost similar to the previously reported work [31].
4
Journal of Energy Storage 61 (2023) 106622
An alkaline based ZnI2 flow cell was constructed by using 0.25 M
ZnO + 5 M NaOH as anolyte and 1 M KI + 1 M NH4Cl as catholyte. A
Nafion-117 membrane with an active area of 9 cm2 was adopted in the
flow cell configuration. The redox flow cell performance was evaluated
by GCD profile at different current densities (20 to 100 mA cm− 2). It is
worth noting that, alkaline based ZnI2 RFB shows an enhanced discharge
plateau cell voltage of 1.89 V than neutral ZnI2 RFB 1.30 V at 20 mA
cm− 2. This significant increase in the discharge plateau cell voltage is
due to the switching of zinc electrolyte pH from neutral Zn2+/Zn redox
couple (− 0.76 V vs SHE) to alkaline Zn(OH)2− 4 /Zn redox couple (− 1.26
V vs SHE). It is seen that the alkaline Zn(OH)2−4 /Zn redox couple has a
lower redox potential than a neutral Zn2+/Zn redox couple. As shown in
Fig. 3 (a), the GCD profile of ZnI2 shows a better improvement in the
charging (1.91 V) and discharging (1.70 V) voltage which is 0.54 V and
0.57 V greater than that of neutral ZnI2 RFB (charging: 1.37 V and
discharging: 1.13 V) system. This simple strategy is beneficial to render
high cell voltage and high energy density RFB systems. Also, HFR value
for an alkaline based ZnI2 RFB is found to be avg. 480 mΩ (charging) and
avg. 501 mΩ (discharging), which is comparatively lower than that of
neutral ZnI2 RFB (charging avg. 585 mΩ and discharging avg. 548 mΩ)
as shown in Fig. S1 (a). Further, alkaline based ZnI2 RFB exhibits an
excellent rate performance at various current densities, as shown in
Fig. 3b. The alkaline based ZnI2 RFB delivered a maximum capacity of
25 mA h at 100 mA cm− 2 and the detailed capacity plot at various
current densities are shown in Fig. S1 (b). For instance, the reliability
five cycles were recorded at each current rate and their corresponding
R. Thamizhselvan et al. Journal of Energy Storage 61 (2023) 106622

Fig. 3. (a) Comparison of neutral and alkaline based zinc-polyiodide redox flow battery performance at the current density of 20 mA cm− 2, (b) Charge discharge
profile of an alkaline based zinc-polyiodide RFB recorded at different current density, (c) Voltage drop vs current density plot, (d) Polarization and power curves of
the zinc polyiodide RFB observed at different current density and (e) CE, VE and EE vs cycle number plot evaluated at different current density.

charge-discharge profiles are shown in Fig. S2. However, there is a
gradual rise in voltage drop noted on increasing the current density from
20 to 100 mA cm− 2 as shown in Fig. 3c, this can be attributed due to the
increased polarization at high current densities. Moreover, ZnI2 flow cell
shows a stable performance with >95 % coulombic efficiency at all
current densities. This high efficiency is attributed to the catholyte
composition (such as 1 M KI + 1 M NH4Cl) used here. A similar effect
was observed for the NH4Br based supporting electrolyte [32]. The
presence of halide ions (X− = Cl− or Br− ) unlocks the capacity of iodine
(I2) forming I2X− as result it provide increased number of iodide ions and
hence, increases the capacity of the system [23]. Even at a high current
density of 100 mA cm− 2, the flow cell shows a coulombic efficiency of
97 % as shown in Fig. 3 (e). Moreover, the cell shows the voltage effi­
ciency of ~70 % at 60 mA cm− 2, which is a much better than that of
previously reported work (70 % at 20 mA cm− 2) [20]. The polarization
study was performed for the alkaline based ZnI2 redox flow battery by
charging the cell at 20 mA cm− 2 for 1 h and the flow cell was subjected
to different current densities starting from 0 to 0.24 A cm− 2 for every 10
s to obtain polarization curves. It was observed that the power density
increases linearly with the current density, while the equivalent cell
voltage decreases as shown in Fig. 3 (d). The alkaline based ZnI2 RFB
delivered a maximum power density of 1.51 W cm− 2 at 0.17 A cm− 2.
Here at 0.1 A cm− 2, the cell delivered a specific capacity of 4.5 Ah L− 1
and the corresponding energy density is found to be 6.975 Wh L− 1
(volume of electrolyte: 50 mL; discharge voltage: 1.55 V current density:
0.1 A cm− 2 for 15 mins). This low energy density value is mainly
attributed to the low state of charge (SOC). Since the flow cell is tested
only 15 mins GCD process, the expected state of charge is very less.
To realize the cycling stability of ZnI2 RFB, extended long charge-
discharge cycling performance was tested at 30 mA cm− 2 for about
90 cycles as shown in Fig. S3 (a). Initially, the flow cell shows an avg. CE
of 91.09 %, VE of 77.32 % and EE of 70.42 % for the first five cycles and
then exhibited a stable performance over 70 cycles with an avg. CE of 95
%, VE of 78.40 % and EE of 74.5 % as shown in Fig. 4 (a). The ZnI2 RFB
delivered a maximum discharge capacity of 6.67 mA h at 30 mA cm− 2
for 15 min charge-discharge process and accordingly, the material uti­
lization was estimated to be 89 %. The theoretical capacity for the
alkaline based ZnI2 (1 M) system is 2.68 Ah which is similar to the
previously reported work [20]. The capacity retention is about 100 % up
to 70 cycles at current density of 30 mA cm− 2. At the end of 90th cycle,
the capacity retention is decreased to 84 %. Moreover, the cycling per­
formance for ZnI2 RFB in the given condition is much higher than the
previously reported work [20]. However, after 70th cycle, efficiency loss
was observed considerably. It is possibly due to an increase in the in­
ternal resistance of the cell caused by the formation of thick iodine (I2)
film on the electrode surface, restricting further electro-oxidation of

5
R. Thamizhselvan et al.
Fig. 4. Long cycling performance of an alkaline based zinc-polyiodide RFB system operated at (a) 30 mA cm−
time interval.
iodide (I− ) [33]. As a result, it increases the charge-discharge over­
potential, which is well correlated with the full cell HFR plot as shown in
Fig. S3 (b). It is also believed that fading in efficiency may also be
attributed to the electrolyte starvation, where the water transfer was
observed during the cell operation (11 mL of water transferred from
catholyte to anolyte was observed). The water transfer from the elec­
trolyte was encountered (catholyte to anolyte) after 70 cycles which
leads to starvation of the electrolyte and reduces the coulombic effi­
ciency of the cell. In addition, the flow cell was cycled at a current
density of 50 mA cm− 2 as shown in Fig. S3 (c), the corresponding cycling
ability plot is shown in Fig. 4 (b). The flow cell exhibits an excellent
cycling performance for about 50 cycles with avg. CE, VE and EE of 94
%, 72 % and 67.1 % respectively and the system delivered a maximum
6
Journal of Energy Storage 61 (2023) 106622
2 2
and (b) 50 mA cm− for 15 min charge discharge
discharge capacity of 11.29 mA h at 50 mA cm− 2 reveals a significant
improvement in cycling performance of alkaline based ZnI2 flow cell
when compared to previously reported work [20]. The material utili­
zation and capacity retention were 90 % and 100 % respectively up to
50 cycles. However, the HFR value gradually increases over time, as
seen in Fig. S3 (d). The detailed overview reports related to ZnI2 based
RFBs are mentioned in Table S2.
To further evaluate the characteristic of zinc deposition, negative felt
from the flow cell was disassembled after 90 cycles and investigated by
SEM analysis. Fig. 5a-c shows the SEM images of pristine, negative felt
on neutral and alkaline based ZnI2 RFB respectively. A considerable
amount of zinc is observed on both neutral and alkaline on the negative
felt. In general, the zinc deposition and dissolution depends on the
R. Thamizhselvan et al.
Fig. 5. SEM images of (a) bare rayon felt, (b) Rayon felt obtained from neutral ZnI2 system, (c) Rayon felt obtained from the alkaline based zinc-polyiodide system,
(d) EDAX spectrum of cycled electrode, (e) Nyquist plot obtained from the cycled electrolyte and (f) Raman spectrum of cycled electrode.
nature of the substrate used and medium of the electrolytes [34]. As seen
in Fig. 5c, the zinc deposition in alkaline medium is significantly higher
than that of neutral medium due to the variation in nucleation process.
The EDAX analysis confirms the presence of zinc (2.68 %) and oxygen
(31.36 %) content in the felt as shown in Fig. 5d. A peak at 440 cm− 1 in
Raman spectra also confirms the presence of zinc on the felt as shown in
Fig. 5f. The EIS analysis was performed to investigate the electrode/
electrolyte interfacial resistance of electrolyte after cycling, the corre­
sponding Nyquist plot and equivalent circuit (inset) are shown in Fig. 5e.
It is observed that the ohmic resistance (Ro) is caused by the contact
resistance between electrolyte and electrodes, current collectors and
electrolyte resistance i.e., the migration of ions creates resistance to
current flow through electrolyte and the charge transfer resistance (Rct)
arises due to the Faradaic process i.e., the resistance against the process
of electron transfer from one phase (e.g., electrode) to another (e.g.,
liquid). The obtained ohmic resistance and charge transfer resistance
values are 0.9 and 1.1 Ω respectively. The equivalent circuit comprises
of ohmic resistance (Ro), charge transfer resistance (Rct), constant phase
element (Q) and Warburg impedance (W). The detailed EIS parameters
are given in Table S1 (a).
4. Conclusion
In summary, we have successfully demonstrated a high cell voltage
alkaline based zinc-polyiodide redox flow battery by systematically
changing the electrolyte environment from neutral/acid to alkaline
medium. The redox potential of the electrolyte highly depends on the pH
of the solution, which is significantly fine-tuned the cell voltage of the
flow cell. Therefore, the alkaline based zinc-polyiodide RFB exhibits a
higher cell voltage of 1.8 V, which is 500 mV more than the conventional
ZnI2 in neutral medium (1.3 V). Also, the newly designed cell can
perform at a wide range of current densities (20 to 100 mA cm− 2). More
importantly, even at a high current density of 100 mA cm− 2 the alkaline
7
Journal of Energy Storage 61 (2023) 106622
based zinc-polyiodide redox flow cell shows 97 % of coulombic effi­
ciency. Further, the assembled alkaline based zinc-polyiodide RFB ex­
hibits better cycling over 90 cycles with CE of 90 % and EE of 67 %. Such
advanced design of redox couples opens a new avenue in developing
high-performance, low cost and environmentally benign redox flow
battery technology.
CRediT authorship contribution statement
Rahul Thamizhselvan: Investigation, Writing – original draft.
Raghupandiyan Naresh: Investigation. Sekar Ramachandran: Investi­
gation and Supervision. M. Ulaganathan: Review& editing and Super­
vision. Vilas G. Pol: Review & editing, Resources and supervision. P.
Ragupathy: Conceptualization, Writing – review & editing, Resources,
Supervision and funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Unique Contribution Number: CECRI/PESVC/Pubs/2022-065.
Data availability
The data that has been used is confidential.
Acknowledgments
Dr. P. Ragupathy and Mr. Rahul Thamizhselvan would like to
acknowledge CSIR, New Delhi for the financial support through
Focussed Basic Research (FBR), project number: MLP0322. Dr. P.
Ragupathy thanks CSIR and CECRI in India for the award of Raman
R. Thamizhselvan et al.
Research Fellowship to carry out this work at Purdue University, Indi­
ana, USA. VP thanks to Davidson School of Chemical Engineering for the
support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.est.2023.106622.
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