Separation and Purification Technology 324 (2023) 124490

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Separation and Purification Technology

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

Improved desalination via cell voltage extension and simultaneous energy

recovery of redox flow desalination using organic supporting electrolyte
Hyunjin Kim a, 1, Seonghwan Kim a, b, 1, Dayoung Ahn a, Choonsoo Kim a, *
a
Department of Environmental Engineering with Institute of Energy/Environment Convergence Technologies and Department of Future Convergence Engineering, Kongju
National University, 1223-24, Cheonan-daero, Cheonan-si 31080, Republic of Korea
b
Samsung Research, Samsung Electronics Company Limited, Republic of Korea

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

Keywords: Redox flow desalination (RFD) is a promising desalination technology based on a redox flow battery system with
Desalination intervening channels for water streams. However, the RFD system suffers from a low desalination capacity
Redox flow desalination because its operational cell voltage is limited to approximately 1.2 V to stably operate under a narrow potential
Organic electrolyte
window of water. Here, we report a novel strategy for improving the desalination performance of RFD by
Cell voltage extension
Energy recovery
introducing organic supporting electrolytes for redox reactions, allowing for an extension of the operational cell
voltage and effective energy recovery in the RFD system. Using an organic electrolyte (100 mM TEABF4 in
acetonitrile) for sustainable redox reactions (V(acac)-3/ V(acac)3 and V(acac)3/ V(acac)+ 3 ), the maximum cell
voltage was increased to 3.5 V. At an operating cell voltage of 3.0 V, the system exhibited a substantially
improved salt removal rate of 2670 µg/cm2/min. This is a 40-fold improvement compared with the salt removal
rate (68 µg/cm2/min) in the RFD system utilizing an aqueous supporting electrolyte (100 mM Fe(CN)3- 4-
6 /Fe(CN)6
in 100 mM NaCl). Moreover, with the energy recovery process, the RFD system recovered 30 % of the energy
used for desalination, reducing energy consumption even at a high operating cell voltage. The results suggest that
the adaptation of organic electrolytes in the RFD system can be a good approach to improve desalination per­
formance via the extension of cell voltage and energy recovery, and it can open new routes for water desalination
and environmental applications.

1. Introduction discharging (electrical energy extraction), a reverse redox reaction oc­

Redox flow desalination (RFD) is gaining wide interest as a prom­
ising desalination process for water treatment [1–10]. As a modification
of the conventional redox flow battery, the RFD system establishes an
intervening channel for the water stream separated from the cathode
and anode for redox reactions using ion exchange membranes [11,12].
Because they inhibit the mixing of the redox and water streams, the
redox reaction enables RFD systems to achieve water desalination with
simultaneous electrical energy storage [13–16] (Fig. 1). As a traditional
redox flow battery, the RFD employs a full-cycle operation with
charging and discharging [17]. During charging (electrical energy
storage), the redox reactions of the asymmetric redox couples occur at
the cathode and anode (Fig. 1A). During the redox reaction, the salt ions
are removed from the water stream (water desalination), and the
asymmetrical redox couples are stored as electrical energy. During
curs at the cathode and anode (energy recovery), and the water stream is
concentrated by the diffusion of salt ions from the cathode and anode.
Thus, the RFD system is energy-efficient owing to energy recovery
during water desalination.
Uniquely, instead of asymmetric redox couples on the cathode and
anode, the circulation of a single redox couple allows stable water
desalination with low specific energy consumption because of its low
operational cell voltage(Fig. 1B), although it is not operated with energy
recovery [18,19]. Therefore, desalination in an RFD system with a
symmetric redox couple is successfully driven without a water-splitting
reaction, resulting in less by-product production and less variation in the
pH of the water stream [20,21]. Additionally, under mild electro­
chemical conditions, it is not essential to employ highly stable and
expensive metal oxide electrodes (e.g., dimensionally stable anodes) as
there is a high diversity in the use of electrode materials (e.g., low-cost

* Corresponding author.
E-mail address: choonsoo@kongju.ac.kr (C. Kim).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.seppur.2023.124490
Received 16 May 2023; Received in revised form 26 June 2023; Accepted 30 June 2023
Available online 7 July 2023
1383-5866/© 2023 Elsevier B.V. All rights reserved.
H. Kim et al.
Fig. 1. Operation of the RFD system with asymmetric- and symmetric
redox flows.
carbonaceous electrodes) [22]. Another advantage is that scaling up the
RFD system is achievable with multicarbon electrode stacking, in
contrast to conventional unit-cell stacking in electrochemical desalina­
tion processes such as capacitive deionization and electrodialysis [23].
In this regard, techno-economic analysis proved the high potential of the
RFD system in terms of operating and capital costs and desalination
performance compared to conventional electrochemical desalination
processes [20,23,24].
Despite the remarkable advances in RFD systems in aqueous media,
their operation suffers from a limited operating cell voltage of approx­
imately 1.2 V due to the narrow electrochemical potential window of
water [25]. Therefore, the low operating cell voltage leads to a low salt
removal rate of 50–60 mg/g/h because the performance has an
approximately linear relationship with the maximum operating cell
voltage in the RFD system [1,18,20]. Moreover, for energy recovery in
an RFD system with an asymmetric redox couple, the low cell voltage
forces energy transfer to return to the RFD system (i.e., the concept of
round-trip energy recovery) because the system has poor efficiency in
energy transfer from the RFD system to a storage device (i.e., the concept
of one-way energy recovery) with a low cell voltage [26]. Consequently,
the RFD system requires sequential charging and discharging for round-
trip energy recovery, leading to the unfavorable intermittent production
of fresh water. Thus, one-way energy recovery in an RFD system is
desirable, leading to continuous desalination; hence, it is necessary to
Fig. 2. Schematic of RFD system and module for energy recovery (i.e., redox flow battery system) with redox flows containing organic supporting electrolyte for
desalination and energy recovery, respectively.
2
Separation and Purification Technology 324 (2023) 124490
extend the cell voltage. Fortunately, RFD operation is not limited to
aqueous media, and is well known for redox flow batteries with organic
supporting electrolytes [27–37]. Therefore, this study aimed to improve
the desalination performance of an RFD system by extending the oper­
ating cell voltage and energy recovery using an organic supporting
electrolyte. To demonstrate the performance of the RFD system (Fig. 2)
using an organic supporting electrolyte, our system comprised two res­
ervoirs for redox flow channels with organic supporting electrolytes
containing a redox couple and one reservoir for an intervening channel
with a water stream. In the redox flow channel, 10 mM vanadium(III)
acetylacetonate (V(acac)3) as a redox couple was introduced in aceto­
nitrile with 100 mM tetraethylammonium tetrafluoroborate (TEABF4)
as a supporting electrolyte for the positive and negative carbon elec­
trodes, respectively. On the other hand, NaCl solution was supplied to
the intervening channel to act as a water stream [38,39]. Desalination
performance was further assessed through a parametric investigation
using various parameters, including the operating cell voltage, flow rate,
and initial feedwater concentration. Moreover, the energy recovery was
evaluated with an additional module (i.e., a redox flow battery system)
for energy extraction sequentially combined with the RFD system.
2. Experimental
2.1. Description of cell configuration of RFD
As shown in Fig. 2, the cell configuration of the RFD system (for
desalination) consisted of two channels, including diluted and concen­
trated channels for water streams, as a modification of the cell design of
a conventional redox flow battery. In the out channels (denoted as redox
channels, 4 × 4 × 0.2 cm3), the commercial activated carbon electrode
(area: 3 cm × 3 cm with an average mass of 130 mg, ACC 5092-20,
Kynol) was placed with a titanium current collector. The detailed
characteristics of the carbon electrode are found in our previous study (a
specific surface area: 2000 m2/g, high-purity carbon content: >95 %,
thickness: 515 µm, and specific resistivity: 1.35 Ω⋅cm) [40]. A redox
flow (10 mM V(acac)3 as a redox couple and 100 mM TEABF4 as a
supporting electrolyte in acetonitrile) was supplied to the electrodes for
sustainable oxidation and reduction reactions in the redox channel. In
the channels diluted and concentrated with NaCl solution (4 × 4 × 0.2
cm3), the salt ions (Na+ and Cl− ) were removed and accumulated,
H. Kim et al.
respectively. The channels were separated by an arrangement of one
cation-exchange (CMX, Neosepta) and two anion-exchange (AMV,
Seleion) membranes to permit the transportation of selective ions and
prevent the mixing of flows. Additionally, the redox flow battery module
(for energy recovery) was sequentially combined with the RFD system to
extract the stored energy during the charging process. The energy re­
covery module was designed using the same specifications as the RFD
system, without the two intervening channels for water streams.
2.2. Desalination test of RFD
The desalination performance of the RFD system was examined at a
constant cell voltage (3.0 V) applied by a battery cycler (WBCS3000,
WonATech Co.) for 10 and 30 min using only a charging process for
desalination, that is, without a discharging process for energy recovery.
Using a peristaltic pump (07528-10, Masterflex L/S®), the feed solutions
were supplied to the diluted and concentrated channels (for water
stream) and the redox channels (for redox flow) at a flow rate of 60 mL/
min in batch mode comprising 50 mM NaCl solution (100 mL) for the
water streams and the redox flows of acetonitrile solution containing
redox couples of 10 mM V(acac)3 and supporting electrolyte of 100 mM
TEABF4 (100 mL). To confirm the effect of the organic supporting
electrolyte on desalination performance, desalination was tested at the
redox flow of an aqueous supporting electrolyte with 100 mM NaCl
solution (100 mL) containing a redox couple of 100 mM Na3Fe(CN)6/
Na4Fe(CN)6 and a comparative analysis was performed. Moreover, the
desalination performance was further investigated using various oper­
ating parameters, including a flow rate of 20 mL/min–80 mL/min, cell
voltage of 2.2 V–4.6 V, and initial feed concentration of 10 mM–300 mM
for the water stream.
To analyze standard desalination, including the salt removal ratio,
salt removal rate, concentration reduction, charge efficiency, and en­
ergy consumption (Eqs. (1)–(6), conductivity (F-54BW, HORIBA), and
pH (9615S-10D, HORIBA) of the effluent in the diluted channel of the
RFD system were measured using real-time monitoring.
Saltremoval(oraccumulation)ratio = Cn /C0
∑
k
Saltremovalcapacity = (Cn − C0 ) • ν • MNaCl • (tn − tn− 1 )/A
n=0
Saltremovalrate = Saltremovalcapacity/ttotal
Concentrationreduction = saltremovalratio × feedconcentration
(∫ )
SRC • A Idt
Chargeefficiency = / (5)
MNaCl F Fig. 3A shows the desalination characteristics of the RFD system with
∫ organic supporting electrolytes as assessed by the removal and accu­
t2
Energyconsumption =
V
Idt
moverall t1
where C0 and Cn are the initial and effluent concentrations (mM)
calculated from the conductivity measurements, ν is the volumetric flow
rate (L/min), MNaCl is the molecular weight of NaCl (58.44 g/mol), tn −
tn− 1 and ttotal are the time intervals (min) for measuring the conductivity
and total operational time (h), A is the effective area of the electrode
(cm2), and F is the Faraday constant (96,485 C/mol). V, I, and moverall are
the applied cell voltage (V), current (A), and total NaCl removal (mol)
during ttotal, respectively.
2.3. Energy recovery of RFD
Energy recovery was tested using a module of redox flow battery
system sequentially combined with the RFD system for desalination
(Fig. 2). It was conducted at a charging process with a constant current
of 4 mA/cm2 (cut-off voltage of 3.05 V) for desalination at the RFD
Separation and Purification Technology 324 (2023) 124490
system followed by a simultaneous discharging process with a constant
current of − 0.4 mA/cm2 (cut-off voltage of 0 V) for energy recovery at
the module of the redox flow battery. The flow rate was 60 mL/min in a
water stream of 50 mM NaCl solution and the redox flow of an aceto­
nitrile solution containing 10 mM V(acac)3 and 100 mM TEABF4. To
evaluate the energy recovery, the current, voltage, and energy effi­
ciencies were calculated using Eqs. (7)–(9):
∫t ∫t
Currentefficiency = Id dt/ Ic dt (7)
0 0
∫ t ∫ t
Voltageefficiency = Vd dt/ Vc dt (8)
0 0
Energyefficiency = Chargeefficiency × Voltageefficiency (9)
where Ic and Id, and Vc and Vd are the currents and voltages during the
charging and discharging processes, respectively.
2.4. Electrochemical analysis of redox couple in organic and aqueous
electrolytes
To determine the electrochemically stable potential window of the
organic electrolyte, we performed cyclic voltammetry (CV) measure­
ments using a custom-built system with two electrodes (Fig. S1 in
Supplementary Information, SI) using a potentiostat/galvanostat (Ver­
saSTAT 3, Princeton Applied Research). For measurements in organic
100 mM TEABF4 in acetonitrile, activated carbons (with an average
mass of 39 mg) were employed as the working and counter electrodes at
a scan rate of 1 mV/s. To determine the stable potential window, the S
value was calculated using Eqs. (10)–(11) [41,42]. Additionally, the
redox reaction in the organic electrolyte was analyzed by adding a redox
couple to 10 mM V(acac)3 in acetonitrile containing 100 mM TEABF4 at
a scan rate of 1–5 mV/s.
Sa = Qa /Qc − 1 (10)
(1) Sc = Qc /Qa − 1 (11)
where the S values of Sa and Sc are the anodic and cathodic limits,
(2)
respectively. Qa and Qc represent the accumulated and released charges,
respectively, as indicated by the CV curves.
(3)
3. Results and discussion
(4)
3.1. Desalination performance of RFD during the charging process
(6) mulation ratio, specific current profile. As shown in Fig. 3A, the specific
current substantially decreased during the initial charging process and
reached a pseudo-steady state as the operating time increased. This
behavior may be attributed to the capacitive properties of the porous
carbon electrode and the charge-transfer reaction of the redox couples.
During the early charging process, the redox couple is rapidly adsorbed
onto the carbon electrode with a large surface area, resulting in a rapid
decline in the specific current, which is the typical shape of a capacitive
current. However, with increasing elapsed time, the system became
governed by a charge-transfer-dominant mechanism, producing a stable
specific current. Accordingly, a significant decrease in the removal ratio
in the diluted channel is observed during early charging, followed by a
constant increase in the removal ratio, whereas the accumulation ratio
increases correspondingly in the concentrated channel. For example, 22
% of the salt was removed (removal ratio: C/C0 = 0.78) during salt
accumulation, up to 27 % (accumulation ratio: C/C0 = 1.27). The sum of
the removal and accumulation ratios was close to 2, indicating that the
removal and accumulation were well balanced. Regarding the
3
H. Kim et al. Separation and Purification Technology 324 (2023) 124490

Fig. 3. (A) Salt removal & accumulation ratio expressed as C/C0 and specific current profile of the RFD system and RFD operation with organic and aqueous
supporting electrolytes: (B) Removal ratio and (C) desalination performance metrics, including salt removal rate, charge efficiency, and energy consumption at the
diluted channel of the RFD system. The desalination was tested at 50 mM NaCl solution in diluted and concentrated channels with a cell voltage of 3.0 V and a flow
rate of 60 mL/min. In the redox channels, the redox flow of organic electrolyte was prepared with acetonitrile solution containing 10 mM V(acac)3 and 100 mM
TEABF4, while that of aqueous electrolyte was prepared with 100 mM NaCl containing a redox couple of 100 mM Na3Fe(CN)6/Na4Fe(CN)6.

desalination performance, the salt removal rate was approximately potential difference of approximately 2.2 V which is within the potential
2670 μg/cm2/min with a charge efficiency of approximately 99 % and window of 3.5 V) (Fig. S3B). Despite the high operating cell voltage (3.5
an energy consumption of 25 kJ/mol, which closely aligns with the V), the change in the pH in the diluted channel was negligible (Fig. S4).
accumulation rate of 2831 μg/cm2/min. These results suggest that the Considering that pH fluctuation is largely responsible for parasitic side
RFD system not only performs stably with the organic supporting elec­ reactions in aqueous media, such as carbon oxidation, oxygen reduction,
trolyte but also has a good balance between removal and accumulation or water splitting, it is assumed that the side reactions were suppressed
in the diluted and concentrated channels. Furthermore, the redox couple in the redox flow with an organic supporting electrolyte (redox flow
and the organic electrolyte were not detected in the diluted channel channels). This also aligns with the high charge efficiency of RFD with
during desalination, confirming negligible contamination (Fig. S2). the organic electrolyte compared to RFD with the aqueous electrolyte
Nevertheless, with the advancement of ion exchange membranes and (Fig. 3C). Interestingly, the use of organic electrolytes enables the RFD
newly synthesized redox couples, it is necessary to prevent system to significantly reduce energy consumption from 105 kJ/mol in
contamination. an aqueous electrolyte to 25 kJ/mol. Moreover, after long-term opera­
To confirm the improved desalination performance of the RFD sys­ tion evaluation (24 h), the solution of the dilution channel was inves­
tem with an organic supporting electrolyte, its performance was further tigated by HPLC analysis. As a result, no organic electrolyte was detected
analyzed and compared with that of the RFD system employing an (Fig. S5), implying that the stability of the long-term operation of the
aqueous supporting electrolyte (Fig. 3B and C). The results in Fig. 3B RFD system and the reliability caused by using organic electrolytes.
clearly show that the organic electrolyte significantly affected the
desalination performance, with the removal ratio greatly decreasing to
3.2. Parametric investigation of RFD
approximately 23 %, whereas the aqueous electrolyte showed a small
decrease of up to 5 %. This trend was better supported by standard
To comprehensively understand the desalination performance of the
desalination metrics (Fig. 3C). The RFD system with the organic elec­
RFD system with an organic supporting electrolyte, we conducted a
trolyte exhibited a higher salt removal rate (2670 μg/cm2/min) than the
parametric investigation using various operating parameters such as cell
system with the aqueous electrolyte (68 μg/cm2/min). The performance
voltage, flow rate, and feed concentration (Fig. 4). When the cell voltage
of the organic electrolyte corresponded to a 40-fold increase in the salt
was increased to 4.6 V, the removal was enhanced from 6 % to 15 % in
removal rate compared to that of the aqueous electrolyte. In terms of
the RFD system at a cell voltage of 2.2 V (Fig. 4A). The RFD system
productivity, at a salt removal ratio of 10 %, the aqueous electrolyte was
achieved a high salt removal rate of 1803 μg/cm2/min at a cell voltage
31.25 LMH (L/m2/h), while the organic electrolyte was 417 LMH,
of 4.6 V. This is 2.6 times higher than that at a cell voltage of 2.2 V,
showing the performance improvement of approximately 13 times.
demonstrating the approximately linear relationship between desalina­
Additionally, among the other salt removal rates of RFD systems re­
tion performance and the maximum operating cell voltage in the RFD
ported in the literature (Table S1), this value was significantly
system. Additionally, a charge efficiency of approximately 100 %
improved.
facilitated the inhibition of side reactions, even under a notably high cell
One key aspect in interpreting the improved salt removal rate is the
voltage (Fig. 4B). The energy consumption gradually increased from
increased operating cell voltage. Regarding the electrochemically stable
56 to 115 kJ/mol as the cell voltage increased, requiring new ap­
potential window (Fig. S3), the CV curves exhibited a nearly rectangular
proaches for effective desalination in RFD systems with less energy
shape in organic electrolyte within the potential of − 1.5 V–2.0 V.
consumption, such as the energy recovery process. Nonetheless, elec­
Considering the stable potential window of approximately 1.2 V in
trolyte degradation may occur at high cell voltages; thus, the cell voltage
aqueous media [43], this suggests that the stable potential window is
must be optimized.
around 3.5 V in organic electrolyte, confirmed further by the S-value
The variation in the flow rate had a significant effect on the desali­
below 0.1 for the criterion of electrochemical stability window
nation performance (Fig. 4C-D). At a high flow rate of 80 mL/min, the
(Fig. S3A). Consequently, the operating cell voltage could be extended
salt removal rate increased to 1168 μg/cm2/min compared to 326 μg/
to 3.5 V in the organic supporting electrolyte, which is three times
cm2/min at a flow rate of 20 mL/min. Particularly, the energy con­
higher than that in the aqueous electrolyte (cell voltage limit of
sumption of the RFD system was significantly reduced at high flow rates
approximately 1.2 V), allowing a significant improvement in the salt
(Fig. 4D), which may be due to the slow ion mobility in the organic
removal rate (Fig. 3). This is likely due to the extended potential window
electrolyte, which triggers a limited mass transfer of the redox couple
enabling full activation of the redox reactions (as indicated by the peak
onto the surface of the carbon electrodes [44]. This is confirmed by the

4
H. Kim et al. Separation and Purification Technology 324 (2023) 124490

Fig. 4. Salt removal ratio and desalination performance metrics, including salt removal rate, charge efficiency, and energy consumption) in the diluted channel of the
RFD system with organic supporting electrolyte with various operational parameters (cell voltage: 2.2–4.6 V (A–B), flow rate: 20–80 mL/min (C–D), and feed
concentration: 10–300 mM NaCl (E–F)). The black bar in panels B, D, and F shows the desalination performance of the RFD system obtained from Fig. 3 under
standard operational conditions (cell voltage of 3.0 V, flow rate of 60 mL/min, and feed concentration of 50 mM NaCl).

5
H. Kim et al.
atypical salt removal behavior at a low flow rate of 20 mL/min (i.e., no
exponential decrease), which is different from that at faster flow rates
(Fig. 4C). Therefore, the RFD system requires sufficient flow rate to fully
utilize the redox reaction.
The influence of feed concentration on the performance was further
investigated (Fig. 4E–F). Depending on the feed concentration (Fig. 4E),
the salt removal ratio varied between 2 % at a high feed concentration of
(300 mM NaCl) and 23 % at a low feed concentration (10 mM NaCl),
corresponding to salt removal rates of 1326 μg/cm2/min and 529 μg/
cm2/min, respectively (Fig. 4F). The following two major results were
obtained: First, when considering a high removal ratio at low feed
concentrations, the RFD system can be significantly more effective in
low-salinity media (i.e., brackish water). Additionally, the RFD system
revealed a constant energy consumption of approximately 74 kJ/mol
regardless of the feed concentration, which suggests that the RFD system
has a high potential to treat highly saline media (i.e., seawater or
wastewater). Secondly, a significant dependence of the feed concen­
tration on the salt removal rate was observed. This can be attributed to
the increased systematic resistance owing to the low ionic conductivity
at low feed concentrations and the induced concentration polarization
during operation. Thus, new strategies are required to improve the
system resistance in RFD systems, such as applying conducive resins for
a consistent salt removal rate.
3.3. Energy recovery of RFD with a semi-continuous desalination
Fig. 5 shows the energy recovery of the RFD system examined using
cell voltage profiles, the salt removal ratio (C/C0), and average con­
centration reduction at the end of the desalination phase (ΔC d) to
evaluate energy recovery in the RFD system. The energy recovery was
estimated through repeated desalination and energy recovery processes
in the RFD system combined with a redox flow battery module (as
depicted in Fig. 2). The repeated processes were as follows: First, the
RFD system initiated desalination by applying a constant current of 4
mA/cm2 to the RFD system when the redox flow battery module was in
the open-circuit potential mode (charging for desalination). Second,
when the cell voltage of the RFD system reached the cut-off voltage
(3.05 V), the RFD system switched to open-circuit potential mode,
sequentially followed by a constant current of − 0.4 mA2/cm2 applied to
the module with a cut-off voltage of 0 V (discharging for energy
recovery).
As shown in Fig. 5A, the shape of the voltage profiles was similar to
6
Separation and Purification Technology 324 (2023) 124490
the conventional charging and discharging processes of the RFD system.
As a one-way concept of energy recovery, charging led to salt removal in
the RFD system (desalination), whereas discharging extracted the
accumulated energy at the redox flows during desalination in the redox
flow battery module as an energy storage device (energy recovery).
However, when the module performed energy recovery, the RFD system
maintained salt removal even in the open-circuit mode (semi-desalina­
tion), which was supported by the fact that the salt removal ratio in the
RFD system was <1 during the discharging process at the module
(Fig. 5B). The overall salt removal estimated from the average concen­
tration reduction (ΔC d) was approximately 2.0 mM (Fig. 5C). This is
different from the concept of round-trip energy recovery, which results
in salt accumulation during discharge. It implies that our system oper­
ates through continuous desalination and simultaneous energy recovery.
This semi-continuous desalination in our system can be attributed to the
increased maximum cell voltage in the organic electrolyte, which im­
proves energy transfer efficiency from the RFD system to the redox flow
battery module. However, the energy efficiency of our system remained
at approximately 30 % (Table 1), which was responsible for the over­
potential and ohmic drops in the system owing to the solution resistance
and Donnan potential, among others. Therefore, to overcome this issue,
future studies should strive for the advancement of membranes specially
synthesized for the interface of organic and aqueous media or the
redesign of the RFD system and energy storage device.
4. Conclusions
In this study, we introduced a novel RFD concept using organic
supporting electrolytes to improve the maximum operating cell voltage
by extending the electrochemical stability window, and its performance
Table 1
Indicators of charge efficiency, voltage efficiency, and energy efficiency under
charge/discharge cycles.
Cycles Charge efficiency (%) Voltage efficiency (%) Energy efficiency (%)
1 26.4 19.2 5.1
2 55.2 37.2 20.5
3 60.8 40.9 24.8
4 64.0 42.9 27.5
5 66.3 44.5 29.5
6 66.9 45.2 30.2
Fig. 5. Energy recovery of the RFD system
examined by cell voltage profiles, salt removal
ratio (C/C0), and average concentration reduc­
tion at the end of the desalination phase (ΔC d)
during the repeated cycles of desalination and
energy recovery in the RFD system. The desali­
nation test was performed at the RFD system
under a constant current of 4 mA2/cm with a
cut-off voltage of 3.05 V, while the energy re­
covery was tested at the redox flow battery
module under a constant current of − 0.4 mA2/
cm with a cut-off voltage of 0 V (refer to the
scheme of Fig. 2). The water stream (50 mM
NaCl) and redox flow (10 mM V(acac)3 and 100
mM TEABF4 in acetonitrile) were fed with a flow
rate of 60 mL/min.
H. Kim et al.
improvement was demonstrated through a parametric investigation,
including cell voltage, flow rate, feed concentration, and simultaneous
energy recovery. With the adaptation of the organic electrolyte, our
system exhibited high desalination performance with a salt removal rate
of 2670 µg/cm2/min, charge efficiency of approximately 100 %, and
energy consumption of 25 kJ/mol at a stable cell voltage of 3.0 V. The
salt removal rate of the organic electrolyte was a 40-fold improvement
compared to that of the aqueous electrolyte. Moreover, the increased
maximum cell voltage enabled the RFD system to effectively extract up
to 30 % of the accumulated energy via a one-way concept of energy
recovery, leading to a semi-continuous desalination process in the RFD
system. These results suggest that the organic supporting electrolyte
offers a favorable platform for providing a more effective RFD system
with extended maximum cell voltage and simultaneous energy recovery.
Therefore, we believe that the introduction of organic supporting elec­
trolytes in RFD systems can serve as a guideline for future research to
further advance energy-efficient RFD systems and expand their appli­
cations in industrial practice.
CRediT authorship contribution statement
Hyunjin Kim: Conceptualization, Visualization, Investigation,
Writing – original draft. Seonghwan Kim: Investigation, Writing – re­
view & editing. Dayoung Ahn: Conceptualization, Visualization,
Investigation. Choonsoo Kim: Writing – review & editing, Supervision,
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.
Data availability
Data will be made available on request.
Acknowledgments
This work was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF), funded by
the Ministry of Education (NRF-2021R1I1A3040360), and by a research
grant from the Waste to Energy Recycling Human Resource Develop­
ment Project of the Korean Ministry of Environment (ME).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.seppur.2023.124490.
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