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A Durable, Inexpensive and Scalable Redox Flow Battery Based on Iron

Sulfate and Anthraquinone Disulfonic Acid
To cite this article: Bo Yang et al 2020 J. Electrochem. Soc. 167 060520

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 Journal of The Electrochemical Society, 2020 167 060520

A Durable, Inexpensive and Scalable Redox Flow Battery Based on

Iron Sulfate and Anthraquinone Disulfonic Acid
Bo Yang,=,* Advaith Murali,= Archith Nirmalchandar,=,* Buddhinie Jayathilake,*
G. K. Surya Prakash,** and S. R. Narayanan***,z
Department of Chemistry, Loker Hydrocarbon Research Institute, University of Southern California, Los Angeles, California
90089, United States of America

A new redox flow battery system based on iron sulfate and anthraquinone disulfonic acid (AQDS) is shown here to have excellent
electrical performance, capacity retention, and chemical durability. While these redox couples, iron(II)/iron(III) and AQDS are well
known individually, their combination in a redox flow battery is shown here for the first time to provide unique benefits for large-
scale energy storage. Based on iron sulfate, a waste product of the steel industry, the active materials cost for this battery is
anticipated to be $66/kWh. Cycling studies of over 500 cycles in the symmetric cell configuration show a negligibly low capacity
fade rate of 7.6 × 10−5% per cycle. This symmetric cell also shows a notably high average coulombic efficiency of 99.63%. Using
a graphite felt electrode modified with multi-walled carbon nanotubes (MWCNTs), we could achieve a peak power density of
194 mW cm−2. The major voltage losses are ascribed to the ohmic resistance of the electrode and electrolyte. Despite the lower cell
voltage of the system relative to the vanadium flow battery, the iron–AQDS flow battery system presents a good prospect for
simultaneously meeting the demanding requirements of cost, durability and scalability for large-scale sustainable energy storage.
© 2020 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited. This is an open access
article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/
by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/
1945-7111/ab84f8]

Manuscript submitted December 13, 2019; revised manuscript received March 20, 2020. Published April 9, 2020. This was paper
408 presented at the Dallas, Texas, Meeting of the Society, May 26–May 30, 2019.
Supplementary material for this article is available online

The demand for large-scale energy storage.—The exponential
growth in solar and wind-based electricity generation has been
driving the need for energy storage systems at an unprecedented
scale. Even to store 20% of the electricity generated today by solar
and wind systems we will need an enormous storage capacity of
700 GWh.1 While the cumulative world battery production is
expected to reach about 370 GWh by 2020 due to the demand for
lithium-ion batteries in electric vehicles,2 we can expect further
exponential growth because of the global deployment of renewable
electricity generation systems. At the anticipated “mega” scale of
deployment, the principal requirements for successful storage tech-
nologies are durability, low cost and sustainability of materials.3,4
Rechargeable batteries in general, and redox flow batteries in
particular, have many advantages to fulfill this need.5–7
Levelized cost of energy storage.—The levelized cost of energy
storage (LCOS) is the metric used to rate the economic competitiveness
of energy storage systems. LCOS is calculated by simply dividing the
sum of the capital and operating costs of the system by the total energy
stored and delivered over the lifetime of the system. To achieve market
competitiveness, the LCOS target for large-scale energy storage
systems is 2.5 cents kWh−1, as suggested by the US Department of
Energy (DoE).8 To satisfy this LCOS target, a system costing $200/
kWh must store 8000 kWh over its lifetime. Assuming one charge/
discharge cycle per day, such an energy storage system must last at
least for 22 years. Consequently, the system should be based on
inexpensive and abundant materials that are available without geopo-
litical constraints, while also being sustainable and eco-friendly. Thus,
the battery industry is seeking cost-effective alternatives to common
battery materials such as lead, zinc, lithium, vanadium, chromium, etc.
Iron-based flow batteries.—Iron is particularly attractive as a
battery material because of its abundance, low cost and environmental
=
These authors contributed equally to this work.
*Electrochemical Society Student Member.
**Electrochemical Society Member.
***Electrochemical Society Fellow.
z
E-mail: sri.narayan@usc.edu
friendliness.3 Globally, over 1600 million metric tons of iron (steel) are
produced every year.9 There have been previous reports attempting to
use iron-based compounds as the positive electrolyte in redox flow
batteries. In these examples, the iron was deployed as the ferrocyanide/
ferricyanide couple,10,11 ferrocene/ferrocenium couple,12,13 or as iron-
phenanthroline complexes.14 The specific compositions mentioned
here entail significantly higher cost than desirable, and also present
the challenge of long-term chemical stability and durability.15,16
Although the aqueous “all-iron” flow battery uses only iron(II)
chloride that is relatively inexpensive,17,18 continuous operation has
to contend with multiple challenges leading to high system costs.
Firstly, the parasitic evolution of hydrogen at the negative
electrode18,19 requires additional sub-systems and reactors to capture
and recombine the hydrogen and maintain the acidity of the solutions.
Also, the kinetics of electrodeposition of iron is relatively slow,
necessitating operation at low current densities. These characteristics
lead to higher system costs despite the low materials costs.
Unfortunately, unlike the vanadium systems, reliable cost data is not
available for the iron chloride system to make comparisons. Iron-
Chromium redox flow batteries use iron(II) chloride at the positive
electrode,20 but are also faced with the challenge of hydrogen
evolution at the chromium electrode.21–23 More recently, Tucker
et al. proposed a low-cost single-use portable battery based on iron
(III) salts and metallic iron as an inexpensive power source for
developing countries emphasizing the non-toxic and inexpensive
nature of iron-based battery materials.24 Thus, despite the advantages
of iron, the large-scale exploitation of iron as an active material in
redox flow batteries has hitherto been a challenge.
Iron-AQDS flow battery.—We present here for the first time the
properties of a redox flow battery system based on iron that does not
suffer from the limitations of the iron-based batteries described above.
This flow battery uses aqueous solutions of iron(II)/iron(III) sulfate at
the positive electrode and a water-soluble organic redox couple,
anthraquinone/anthraquinol disulfonic acid (AQDS/AQDSH2) at the
negative electrode. Steel mills generate enormous amounts of iron
sulfate as the waste product of scale removal. Hence, iron sulfate is
available for as low as $0.10/kg25 and can be put to good use in this
battery. We and several others have studied the use of AQDS in flow
 Journal of The Electrochemical Society, 2020 167 060520
batteries26–29 and our research has shown that AQDS is one of the
most robust and efficient redox materials for repeatedly storing and
delivering charge at the negative electrode.30–32 In addition, the large-
scale manufacturing cost of AQDS is projected to be as low as
$3/kg.33,34 Therefore, the iron sulfate/AQDS system is particularly
promising as a low-cost solution for “mega”-scale energy storage.
Operating principle of the iron/AQDS flow battery.—A sche-
matic of the Iron/AQDS cell and the accompanying reversible
reactions at each electrode are shown in Fig. 1. Iron(II) and iron
(III) exist as aqua complexes in solution. The positive electrode is
based on the interconversion of the iron(II) and iron(III). At the
negative electrode, AQDS undergoes redox interconversion between
the quinone and hydroquinone forms and protons are added or
released. Sulfuric acid is the source of protons for this reaction, and
is also used on both sides of the cell. A high acid concentration (2 M
sulfuric acid) on the positive side ensures that the aqua complexes of
iron do not hydrolyze. Further, protons also serve to transport the
ionic current across the cell. Proton transport occurs through a
proton exchange membrane. For example, Nafion® 212 is a proton
exchange membrane that combines high proton conductivity and
durability. The reversible cell voltage for such an iron/AQDS cell
under standard state conditions is 0.62 V. We determined the charge-
transfer rate constants and the diffusion coefficients for the two
redox couples, and found these values to be suitable for achieving
high efficiencies and high current densities (Table I).
Experimental
Materials.—Ferrous sulfate heptahydrate (J. T. Baker, >99%),
1 M anthraquinone-2,7-disulfonic acid solution (Riverside Specialty),
Figure 1. Operating principle of the Iron/AQDS redox flow cell.
sulfuric acid (VWR, ACS grade) and deionized water (18 MOhm-cm)
was used in preparing the active material solutions for all the
experiments. Nafion® 212 and 117 proton exchange membranes (Ion
Power Inc.) were used as purchased. Electrodes (geometric area
25 cm2) were prepared by modifying graphite felt (PAN Graphite Felt,
3 mm thick, Graphite Store) with 10% (w/w) of multi-wall carbon
nanotubes (Flo Tube 9000, Cnano Technology). To prepare such
electrodes, typically 100 mg of carbon nanotubes were dispersed in
100 ml of isopropanol by ultrasonication for 2 h. Nafion® ionomer
(5 or 10 weight percent of the carbon nanotubes) was added to the
mixture of carbon nanotubes and isopropanol before sonication to
achieve a stable dispersion and also serve as a binder to attach the
carbon nanotubes to the graphite felt. The dispersion of carbon
nanotubes in isopropanol was then impregnated in the graphite felt
to the required loading level by repeatedly dropping small quantities of
the dispersion on to a heated graphite felt electrode. When the
isopropanol evaporated the carbon nanotubes were left behind in the
electrode with the Nafion®. The electrodes were then cured at 140 °C
in air to render the Nafion® insoluble and complete the attachment of
the carbon nanotubes to the graphite felt. Subsequently, the electrodes
were then oxidized in a 30% sulfuric acid solution to ensure full
wetting of the interior parts of the electrodes prior to cell assembly.
Methods of testing and analysis.—Rotating disk voltammetry
was conducted on a glassy carbon electrode (Pine Instruments) with a
platinum wire counter electrode and a mercury sulfate reference
electrode (Eo = 0.68 V vs NHE). Voltammetry experiments used a
scan rate of 50 mV sec−1 and electrode rotation speeds in the range of
400 to 3000 rotations per minute (rpm). Voltammetry and impedance
measurements (over the frequency range of 10 mHz to 100 kHz) were
made using a potentiostat (Versastat 300 with impedance analyzer).
 Journal of The Electrochemical Society, 2020 167 060520
Table I. Charge-transfer rate constants and diffusion coefficient for iron and AQDS redox couples as measured from linear sweep voltammetry at a
rotating disk electrode.
Redox couple Standard rate constant for electron transfer, 10−5 cm s−1
3+ 2+
Fe /Fe 7.3
AQDS/AQDSH2 15.2
Redox flow cells were assembled using custom-designed cell hard-
ware (Electrochem Inc.). For flow rates of electrolyte below
0.3 l min−1, we used a centrifugal magnetic drive pump (BC-2CP-
MD 12 VOLT DC, March Manufacturing Inc.). For flow rates greater
than 0.3 l min−1, a gear pump (Eclipse pump E02KLVF-X, Baldor
Motor CDP3310, SCR DC control BC140) was used. All full-cell
experiments were carried out at 23 °C. A blanket of argon gas was
maintained over the headspace of the reservoirs to avoid reaction with
oxygen. Charge/discharge studies, current-voltage measurements, and
long-duration cycling were conducted using a battery cycler (Maccor
4200 with 30 A capability). Charge capacity was determined by the
coulombs needed to reach a cut-off voltage of 1 V. Discharge capacity
was determined from the coulombs delivered until a cut-off voltage of
0.001 V. Coulombic efficiency was calculated for every cycle by
dividing the discharge capacity value by the value of charge capacity
immediately preceding the discharge. Therefore, coulombic efficiency
refers to a particular cycle.
Permeation studies.—To measure the permeation rate of iron(II)
and iron(III) through the proton exchange membrane, a permeation
cell was set up with two 30 ml glass reservoirs separated by a
circular piece of Nafion® 212 membrane with a permeation area of
2 cm2. On one side of the permeation cell we used 1 M iron(II) or iron
(III) sulfate in 1 M sulfuric acid, and the other side was a plain 1 M
sulfuric acid solution. Samples were withdrawn at fixed intervals from
the sulfuric acid side and analyzed for their concentration of iron by
rotating disk voltammetry at a glassy carbon disk electrode. The mass-
transport limited currents at 1500 rpm were converted to concentration
values. The diffusion coefficient (D) was calculated as per the
following equation (see SI-5) applied to the initial rate.
DCL (t) Dt = ADV-1d -1 (CH ‐CL)
Where CL is the concentration of test species in the “low” side, V is
the volume of the “high” concentration side, A is membrane area, δ is
membrane thickness, and CH is the concentration of test species on the
“high” concentration side. The apparent diffusion coefficient of the
permeating species was then obtained from the slope of CL vs time.
Results and Discussion
Cell configuration and overcoming the challenge of cross-
over.—A conventional redox flow battery operates in an “asym-
metric” configuration (Fig. 1) where each type of redox couple is
circulated past the appropriate electrode (positive or negative). In
such a case, the redox materials usually crossover from one electrode
to the other through the proton exchange membrane resulting in
fading of the cell’s capacity.31,35–37 We measured the apparent
diffusion coefficients of iron(II) and iron(III) through the Nafion®
212 membrane and found them to be comparable to their diffusion
coefficient in aqueous solutions (Table II). Therefore, it was not
surprising that crossover in the asymmetric cell caused a rapid
decrease of discharge capacity. Although iron(II) and iron(III)
readily crossed over, we found that AQDS did not show any
measurable permeation through the Nafion® 212 membrane, con-
sistent with our previous observations in aqueous all-organic redox
flow batteries.30,31 We attributed this inability of AQDS to crossover
to its relatively larger size compared to the benzoquinone derivatives
Diffusion coefficient, 10−6 cm2 s−1
Oxidized species Reduced species
3.43 5.74
3.40 1.64
that are found to crossover through Nafion®.31 Thus, the crossover of
iron(II) and iron(III) does lead to a capacity fade rendering the
asymmetric cell configuration unsuitable for long-term operation.
However, the permanent loss of capacity faced in the asymmetric
configuration can be completely avoided by operating the cell in the
“symmetric” or “mixed electrolyte” configuration.
In the symmetric cell configuration, we used an identical mixture
of iron sulfate and AQDS as the positive and negative electrolyte
solutions (Fig. 2a). At the positive electrode, during charging, only
iron(II) in the mixture gets oxidized to iron(III); AQDS present on
this side cannot be oxidized further at the potential of the positive
electrode (Fig. 2b). At the negative electrode, during charging,
AQDS is reduced to AQDSH2 as iron(II) cannot be reduced at the
potential at which AQDS is reduced. Similarly, during discharge, the
iron(III) is reduced to iron(II) at the positive electrode while AQDS
stays unaffected. AQDSH2 at the negative electrode is oxidized to
AQDS, while the iron(II) remains unchanged. At the end of several
cycles of discharge, any imbalance that may arise in the distribution
of iron between the two sides can be erased by mixing the
electrolytes and evenly splitting the solutions between the two
reservoirs. The effect of the “mix-and-split” protocol can also be
achieved by interchanging the leads of the cell periodically so as to
make the previously positive electrode the negative electrode.31,38,39
The mixed electrolyte configuration has also the benefit of main-
taining similar osmotic pressures on both sides of the cell thus
avoiding water transport across the cell. However, one negative
aspect of the mixed electrolyte system is the increased viscosity of
the solutions because both the redox couples are present in the same
solution at high concentrations. The additional material required for
the mixed electrolyte on both sides is less of a concern when the
active materials are as inexpensive as iron sulfate and AQDS.
In our previous studies on aqueous all-organic flow batteries, we
have shown that the permanent capacity fade caused by crossover
can be avoided by starting with a mixed-electrolyte or symmetric
cell configuration.31 In the present study, we started with equal
amounts of a mixture of iron sulfate and AQDS on both sides of the
cell, and repeatedly charged and discharged the cell to full capacity.
While the capacity of the “asymmetric” iron/AQDS cell cycled at
200 mA cm−2 showed a rapid decay as expected (Fig. 3a), the
capacity of the “symmetric” cell did not show any noticeable change
in capacity even after 500 cycles (Fig. 3b). The average capacity
fade rate was as low as 7.6 × 10−5% per cycle (or 1.2 × 10−4% per
hour). At this capacity fade rate, we can project a fade of 1.2% in
10,000 h of operation. These highly stable capacity values are a
proof of the inherent durability of the iron/AQDS redox battery.
These results showed that AQDS in a mixed electrolyte environment
is stable to oxidation by iron(III). Also, iron(III) that crossed over
underwent reversible electrochemical reactions with AQDSH2
during the cycling. Repeated cycling did not result in any changes
to the shape of the charge/discharge curves or produce any new
discharge plateaus thereby confirming the chemical stability of the
redox couples (See supplementary information SI-1 is available
online at stacks.iop.org/JES/167/060520/mmedia).
The average coulombic efficiency of the “symmetric” cell was
99.63%, over the 500 cycles (Fig. 3b), suggesting that the rate of
crossover of iron(II) and iron(III) was extremely low. Since the
diffusion coefficient of iron(II) through the membrane is higher
than that of iron(III), and since AQDS does not crossover, the
 Journal of The Electrochemical Society, 2020 167 060520
Table II. Apparent diffusion coefficients through nafion® 212 membrane.
Solutions used for permeation studies
1 M Iron(II) sulfate
0.5 M Iron(III) sulfate
1 M Iron(II) sulfate + 0.5 M AQDS
0.5 M Iron(III) sulfate + 0.5 M AQDS
Figure 2. (a) Schematic of the three types of electrolyte configurations studied, and (b) processes during the charging and discharging of symmetric cell with the
mix-and-split protocol.
mix-and-split protocol usually needed to reset the imbalance in
concentrations in a symmetric cell was not required during this
cycling test. These advantages arising from the fundamental proper-
ties of the iron/AQDS system are significant in avoiding additional
balance-of-plant costs. Subsequent to the repeated cycling experi-
ments, the cell was subject to other tests under various other
conditions and even after 1300 cycles of testing in various modes,
the cell did not suffer any noticeable change in capacity, further
testimony to the stability of the materials.
Since AQDS does not crossover through the Nafion® membrane,
we investigated the feasibility of a “semi-symmetric” configuration
in which we used an iron(II) solution as a positive electrolyte and an
Apparent diffusion coefficient cm2 s−1
3.33 × 10−6
1.33 × 10−6
2.33 × 10−6
1.00 × 10−6
equimolar mixture of iron(II) and AQDS solutions as the negative
electrolyte (Fig. 2a). Upon extended cycling we noticed that the
capacity began to fade albeit at 2.8 × 10−2% per hour (Fig. 3c)
tending to a lower fade rate with time. Once again, no crossover of
AQDS was detected. However the difference in the diffusion
coefficients of iron(II) in an aqueous solution vs iron(II) in
combination with AQDS solution, and also the difference in the
osmotic pressure between the positive and negative sides could
explain the higher fade rate of the semi-symmetric cell compared to
the symmetric configuration cell (Table II). Such differences in the
diffusion coefficients could arise from the higher viscosity of the
iron(II)-AQDS solutions compared to the plain iron(II) solutions.
 Journal of The Electrochemical Society, 2020 167 060520

Figure 3. (a) Coulombic efficiency and discharge capacity during cycling of asymmetric cell at 200 mA cm−2, with 1 M iron(II) sulfate and 2 M sulfuric acid,
200 ml on the positive side, and 1 M AQDS and 2 M sulfuric acid, 100 ml on the negative side. (b) Coulombic efficiency and discharge capacity during cycling
of symmetric cell at 200 mA cm−2, with mixed electrolyte consisting of 0.67 M iron(II) sulfate, 0.33 M AQDS and 2 M sulfuric, 150 mL in each reservoir, and
(c) Coulombic efficiency and discharge capacity during cycling at 100 mA cm−2 of semi-symmetric cell with 1 M iron(II) sulfate and 2 M sulfuric acid on the
positive side, and 1 M iron(II) sulfate with 2 M sulfuric acid and 0.5 M AQDS on the negative side, with 100 mL on both sides. Flow rate was 0.3 l min−1 in all
the experiments.

Also, some degree of association between iron(II) and AQDS cannot
be excluded.
For asymmetric cells, the crossover process causes a steady loss
in discharge capacity and imbalance of concentration of iron(II).
However, with symmetric cells, the iron ions crossover from the
positive electrode to the negative electrode and then diffuse back
even during a single charge half-cycle, equalizing the iron concen-
tration on both sides. Therefore, the discharge capacity does not
decline steadily from cycle to cycle, although the crossover process
lowers the coulombic efficiency of any particular cycle.
Current-voltage performance, ohmic losses and efficiency.—To
characterize the electrical performance of the iron/AQDS symmetric
cell, we measured the current-voltage curves. The electrodes in these
cells consisted of graphite felt coated with multi-wall carbon
nanotubes (MWCNT) that were prepared in-house as described in
the experimental section. The addition of 10 wt% of MWCNT
increased the active surface area of the electrodes by over 150 times
compared to the plain graphite felt electrode, increased the utiliza-
tion of active materials, and reduced the ohmic resistance presented
by the electrodes. Using the “forced flow” configuration for
electrolyte movement through the felt electrodes, we could achieve
current densities as high as 840 mA cm−2 at 100% state-of-charge
(Fig. 4a). The maximum power density for this cell was
134 mW cm−2 (Fig. 4b) Electrochemical impedance spectroscopy
(EIS) measurements on this cell were used to separate the ohmic,
charge-transfer and mass transfer contributions to the polarization
resistance (See supplementary SI-3 for results of EIS measurements
and details of how these values were determined). The charge-
transfer resistance decreases with increasing current and mass
transfer resistance contributions do not manifest until the current
approaches the limiting current for mass transport, while the ohmic
resistance is expected to not change much with current. Thus, the
decrease in cell voltage in range of current being tested, is largely
governed by ohmic resistance losses. We have plotted the current-
voltage curves after correcting the cell voltage for the ohmic
overpotential loss (Fig. 4a). This corrected cell voltage is indicated
as the “IR-corrected voltage.” The small difference between the IR-
corrected voltage and the open circuit voltage is consistent with the
low contribution of charge-transfer and mass transfer processes to
the internal resistance of the cell.
Ohmic losses arise from the use of a thick and porous graphite
felt electrode (2–3 mm thick) and the Nafion® 117 membrane (about
175 microns thick). While the graphite electrodes modified with
MWCNT exhibited a lower resistance compared to the unmodified
felt electrodes, our experiments varying the Nafion® content of these
electrodes suggested that there was scope for the optimization of the
MWCNT modified electrodes with respect to the amount of Nafion®.
To verify the impact of the ohmic contribution, we prepared
electrodes with a lower content of the Nafion® binder.
Specifically, the amount of Nafion® dispersant used in modifying
the felts was reduced from 10% to 5%. The use of 10% Nafion was
expected to yield a better dispersion of the carbon nanotubes and
more accessible area to the reactant flow compared to the 5% Nafion.
This difference was consistent with the differences in the mass
transport resistance values. When coupled with a Nafion® 117
 Journal of The Electrochemical Society, 2020 167 060520

Figure 4. (a) Current-voltage curves for symmetric cell with Nafion® 117 membrane, 10% Nafion® electrode, 1 M iron(II) sulfate with 0.5 M AQDS and 2 M
sulfuric acid, 100 mL on both sides, (b) power density curve for cell in cell in Fig. 4a. (c) Current voltage curve for semi-symmetric cell with Nafion® 212
membrane, 5% Nafion® electrode, 1 M iron(II) sulfate and 2 M sulfuric acid on the positive side and 1 M iron(II) sulfate with 2 M sulfuric acid and 0.5 M AQDS
on the negative side, and (d) power density of for cell in Fig. 4c.

membrane, the felt with 5% binder showed an ohmic resistance of 17
mOhms. This value was 6 mOhms lower than the Nafion 117
membrane coupled with the felt that had 10% binder. Furthermore,
by deploying a Nafion® 212 membrane that is just 50 microns thick,
we could lower the ohmic resistance by another 4 mOhms, down to
13 mOhms. These observations suggested that the Nafion® binder
being an electronic insulator prevented the multi-walled carbon
nanotubes from being electrically connected to the felt structure
thereby increasing the resistance of the electrode. Thus, the cell with
MWCNT-modified felt electrodes with 5% Nafion® binder resulted
in a marked increase in power density to 194 mW cm−2 and
reduction of the area specific ohmic resistance from 0.575 Ohm
cm2 to 0.325 Ohm cm2. The electrodes with 5% of Nafion® and
N212 membrane could support current densities as high as
1.16 A cm−2 compared to the 0.84 A cm−2 by the electrodes with
10% Nafion® and N117 membrane. Further reductions in the ohmic
contributions can be achieved by reducing the thickness of the felt
electrodes or by using carbon fiber paper electrodes, and by
increasing the temperature of the cell.
The round-trip energy efficiency of the symmetric cell was in the
range of 70%–75% at a constant current density of 100 mA cm−2
and at a utilization of 70% of the theoretical capacity (See
Supplementary Information, SI-2). The coulombic efficiency of the
iron/AQDS cell being very close to 100% avoids any significant
reduction in energy efficiency, unlike in the case of vanadium flow
batteries. The results in Figs. 4c and 4d suggest that achieving higher
power density without compromising energy efficiency will require
further reduction of the ohmic losses in the iron/AQDS cell. The
flow field and electrode combinations may also be modified further
to achieve greater utilization of the internal surface area of the
carbon paper electrodes as demonstrated by Perry et al.40
Furthermore, given the inherent stability of the active materials,
the cell may be operated at higher temperatures. With such design
optimization, the power densities can be increased further, although
such improvements were beyond the scope of the current study.
Low materials cost.—The most important features of the iron
sulfate/AQDS system are the durability and low cost of materials.
We have found no measurable change in the capacity of these cells
over 500 cycles in symmetric cells and no deterioration of active
material across long periods of cycling. Although the thermody-
namic cell voltage of 0.62 V is not as high as that for the vanadium
system, we project an active material cost (including acid), to be
about $54/kWh for the symmetric cell using acidic solutions of iron
sulfate and AQDS (see Supplementary Information SI-4 for calcula-
tions and assumptions). For systems that rely on long-duration
operation at low rates of charge and discharge, the cost of redox
materials is the dominant contributor to system cost. In comparison,
the materials cost is significantly lower than that of the materials cost
of state-of-art vanadium systems at $160–180/kWh,41,42
 Journal of The Electrochemical Society, 2020 167 060520
We recognize that the stack costs will be higher for the Fe-AQDS
system because of the lower voltage. Therefore, we have estimated
the power-related cost at twice that of the VRFB system. With
further reduction of the ohmic resistance contributions we can
project an operating voltage of 0.5 V for the Fe-AQDS cell. Thus,
at 0.5 V, the system cost for Fe-AQDS is projected to be 60% of the
cost of the VRFB system operating at 1.1 V. Thus, with further
increase in power densities combined with the attributes of low cost
and high durability, the iron sulfate/AQDS system could become a
unique and attractive candidate for meeting the LCOS target for
large-scale energy storage systems.
Conclusions
An iron/AQDS flow battery, based on relatively inexpensive
redox materials was found to be rechargeable over hundreds of
cycles with an extraordinarily low rate of decline in capacity. Such
low rates of capacity loss are not encountered with other flow
batteries based on organic redox couples. Using an electrolyte
mixture of iron sulfate and AQDS in a symmetric cell configuration
we could achieve a coulombic efficiency of 99.63% and avoid the
permanent capacity fade encountered in the asymmetric configura-
tion. Despite the oxidative properties of iron(III), AQDS was found
to be chemically stable in the mixed electrolyte solution. Current
densities as high as 1.16 A cm−2 could be supported at the
electrodes, demonstrating that the electrochemical reaction step
and the mass transport of reactants were fast. We could achieve
power densities as high as 194 mW cm−2 with an un-optimized cell
design. We found that the principal voltage losses arose from the
ohmic resistance of the electrode and electrolyte. Thus, the reduction
of ohmic resistance by almost 40%, achieved by altering the
composition of the carbon-nanotube modified electrodes resulted
in an increase of the discharge voltage leading to an increase in the
power density and energy efficiency. With these characteristics, the
iron/AQDS battery overcomes the challenges encountered with other
iron-based flow batteries. Despite the relatively lower cell voltage
for this system compared to the vanadium flow battery, the
extraordinary durability of the iron/AQDS battery combined with
the low cost of materials, presents a unique opportunity for further
optimization of electrodes, reactant concentrations, and cell config-
urations for meeting the requirements of “mega”-scale energy
storage applications.
Acknowledgments
The authors thank ARPA-E (Contract #DE-AR0000337) the
Loker Hydrocarbon Research Institute and the Department of
Chemistry, University of Southern California for financial support.
Conflict of Interest Statement
Authors SRN and GKS are principals in Battery Energy Storage
Technology LLC, a licensee of organic redox flow battery tech-
nology from the University of Southern California. We acknowledge
the University of Southern California’s financial interest in Battery
Energy Storage Technology LLC.
ORCID
S. R. Narayanan https://orcid.org/0000-0002-7259-3728
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