Available online at www.sciencedirect.
com Current Opinion in
ScienceDirect
Review Article
Aqueous organic flow batteries for sustainable energy
storage
Vinayak Krishnamurti, Bo Yang, Advaith Murali, Sairaj Patil,
G. K. Surya Prakash and Sri Narayan
Abstract
Aqueous Organic Redox Flow Batteries (RFBs) have the po-
tential to address the large-scale need for storing electrical
energy from intermittent sources like solar- and wind-based
generation. Unlike metal-based redox systems, small organic
molecules present the prospect of achieving sustainability, by
being synthesizable from abundantly available carbon dioxide,
water, nitrogen, sulfur, and renewable energy. This mini-review
focuses on the progress and challenges in designing water-
based RFBs based on small organic molecules that can
address the requirements of large-scale energy storage. Much
of the recent research in this area involves discovering new
molecular architectures via computational screening, under-
standing degradation, and cell configurations to address the
techno-economic challenges of extraordinary electrochemical
durability, recyclability, low cost of precursor materials, and
good solubility. Redox materials for the positive side of the cell
are notably few. Future research must continue to focus on
these techno-economic challenges through rapid materials
discovery.
Addresses
Department of Chemistry, Loker Hydrocarbon Research Institute,
University of Southern California, Los Angeles, CA, 90089, USA
Corresponding author: Narayan, Sri (sri.narayan@usc.edu)
Current Opinion in Electrochemistry 2022, 35:101100
This review comes from a themed issue on Environmental Electro-
chemistry (2022)
Edited by Ernesto Calvo and Artur Motheo
For complete overview about the section, refer Environmental Electro-
chemistry (2022)
Available online 15 July 2022
https://doi.org/10.1016/j.coelec.2022.101100
2451-9103/© 2022 Elsevier B.V. All rights reserved.
Keywords
Redox flow, Batteries, Energy storage, Sustainable energy storage,
Rechargeable stationary batteries, Energy storage systems.
Introduction
Solar and wind resources are adequate to meet the
global demand for zero-carbon energy many times over.
However, the principal challenge of intermittency of
www.sciencedirect.com
Electrochemistry
electricity generation from these resources necessitates
the deployment of sustainable energy storage systems at
a “mega-scale” [1]. To this end, redox flow batteries
(RFBs) present the potential for a scalable, safe, and
long-lasting energy storage solution [2]. In RFBs, energy
is stored in solutions of the redox-active materials held in
tanks. The electrical energy is regenerated when these
solutions flow through a stack of cells. The scale-up of
the energy content involves simply increasing the tank
size, and power production is increased by adding more
cell stacks. The physical separation of the large bulk of
the stored energy in the tanks away from the power-
producing stacks of cells is an inherent safety feature
that cannot be overemphasized when deploying electrical
energy storage systems at the mega-scale level.
All-vanadium-based RFBs exemplify the features of
such an energy storage system. Due to the favorable
electrochemical properties and relatively high stability
offered by vanadium redox chemistry, all-vanadium-
based RFBs have matured to individual deployments
of 1e10 MWh capacity [3]. Since these are stationary
deployments, the low energy density of these systems is
not a major concern. However, with the falling cost of
renewable electricity generation and the enormous scale
of energy storage required, vanadium RFBs face chal-
lenges of reducing material costs and ensuring sustain-
ability [4]. From the standpoint of commercialization,
vanadium RFBs serve, without doubt, as a springboard
for deploying new generation RFB-based energy storage
systems. However, the next generation technologies
must focus on inexpensive, safe, and sustainable mate-
rials [5]. To this end, redox-active small organic mole-
cules have emerged as promising materials because of
the variety of molecular structures that can be synthe-
sized and tuned for achieving optimal electrochemical
properties [6e8]. Furthermore, small organic molecules
present the ultimate prospect of achieving sustainabil-
ity, being synthesizable from abundantly available
carbon dioxide, water, nitrogen, sulfur, and renewable
energy. This mini-review focuses on the progress and
challenges in designing RFBs based on water-soluble
organic molecules. Organic RFBs may be classified
broadly as “Aqueous” and “Non-Aqueous”, based on the
solvent used for dissolving the redox-active molecules.
Current Opinion in Electrochemistry 2022, 35:101100
2 Environmental Electrochemistry (2022)
The benefits and challenges that ensue from the use of
these two types of solvents vary considerably.
Although water is an inexpensive and non-flammable
solvent, water can be chemically reactive toward certain
organic molecules and the kinetics of redox processes and
their corresponding voltage windows are affected by pH.
Non-aqueous solvents are typically aprotic and dipolar to
dissolve a wide range of organic molecules and ionic salts.
These solvents can make the electrolyte expensive simply
because of the large quantities required. Many of the
organic solvents are also volatile, toxic, and flammable.
However, they still hold some promise because of the
large voltage range accessible using various organic mol-
ecules in non-aqueous media. At least half-a-dozen re-
views, appearing between 2017 and 2022, survey the
properties of a growing list of redox organic molecules
suitable for RFBs [5,9e15]. In this mini-review, we will
focus on the significance of recent developments in the
Scheme 1
Summary of reported classes of redox-active molecules employed in organic and hybrid organic-inorganic RFBs.
Current Opinion in Electrochemistry 2022, 35:101100
field of aqueous organic RFBs in addressing the techno-
economic requirements for large-scale sustainable
energy storage. We have categorized water-based Organic
RFBs by their operating pH (acidic, neutral, and alkaline),
and whether they are dual-organic or hybrid organic-
inorganic systems [16]. We have summarized the
various molecular classes that have featured in the recent
literature along with the potential range reported
(Scheme 1). While listing every molecule tested was
beyond the scope of this mini-review, the molecular
classes listed in Scheme 1 summarize the state of the art.
Aqueous acidic organic RFBs
Acid-based aqueous organic RFBs typically employ so-
lutions of redox couples dissolved in 1e2 M sulfuric acid
with off-the-shelf proton-conducting polymer mem-
brane separators such as NafionÒ and FumasepÒ. This
www.sciencedirect.com

configuration closely resembles the vanadium RFBs
yielding a low ionic resistance. The quinone-based redox
couples with sulfonic acid substituents are among the
earliest water-soluble candidates investigated. These
systems include the first dual organic system of
anthraquinone and benzoquinone derivatives, the
hybrid organic/inorganic system with anthraquinone
(AQDS) derivatives and bromine (or hydrobromic acid)
and the lead/quinone system [6,7,17]. Sulfonated qui-
nones in the acid form (as opposed to the alkali salt
form) exhibit solubility of >1 M. Generally, the oxidized
forms tend to have lower solubility than the reduced
forms. Thus, polar and ionizable substituents such
aseOH, eNH2, eSO3H, and ePO3H are used to in-
crease solubility [18]. However, ionization in water as
determined by the pKa values markedly increases the
degree of solvation to promote solubility. By lowering
the crystal lattice energy, crystallization may be averted
and more of the redox material can be retained in so-
lution, as exemplified by the use of polyethylene glycol
substituents and asymmetric molecules [19]. Further-
more, the quinones undergo two-electron proton-
coupled electron transfer in acidic media to yield a high
specific capacity.
The challenges of reactivity with water via the
Michael-type reaction, crossover through the proton-
conducting membranes, and proto-desulfonation were
Scheme 2
Degradation mechanisms of commonly employed organic redox materials in aqueous media.
www.sciencedirect.com
Aqueous organic flow batteries Krishnamurti et al. 3
first recognized with benzoquinone-based positive side
materials of this type (Scheme 2) [17,20]. While
electron-withdrawing substituents increase the elec-
trode potential, they also increased the reactivity of the
molecule to nucleophilic reactions by water. The re-
actions may be deceptively slow, and thus the conse-
quences may not be observable during short-term
cycling [21]. By carefully balancing the electronic ef-
fects of the substituents, the degradation can be
suppressed [21]. Dimerization and quinhydrone for-
mation have been reported when utilizing AQDS at
concentrations over 0.5 M. While no irreversible
degradation results from this type of interaction,
reduced electrochemical utilization, and increase of
viscosity can be a disadvantage [22,23]. Most recently,
cyclohexanediones have shown promise as negative
electrode materials with a specific charge capacity of 4-
electron per molecule in an acid medium, although
chemical stability and crossover rates need further
investigation [24]. Phenothiazine-based molecules,
especially derivatives of methylene blue have shown
good solubility (>1M) and chemical stability in acidic
solutions and are good candidates for positive side
materials [25]. Crossover and operation at higher
temperatures still need to be investigated.
Proton-conducting membranes are found permeable to
benzoquinone derivatives, while crossover has not been
Current Opinion in Electrochemistry 2022, 35:101100
4 Environmental Electrochemistry (2022)
reported with anthraquinone derivatives [21,26]. To
minimize capacity fade, mixed electrolytes with mix-
and-split operating strategies combined with an ion-
exchange membrane of reduced permeability (PEEK
and PES over Nafion) have been successfully demon-
strated [21]. Under such conditions, the coulombic ef-
ficiency can be >99%. Some of the disadvantages of
deploying mixed solutions are reduced solubility of the
individual components, potential incompatibility of
materials, and the added cost from doubling the
required amounts of reactants. To mitigate crossover
effects, a promising strategy involves utilizing a
bifunctional molecule: a single molecule designed to
contain two non-equivalent redox centers (e.g., benzo-
quinone and anthraquinone). This approach enables the
same compound to function as both the positive and
negative electrode material [5]. The paucity of stable
positive electrode materials in acid has prompted the
use of inexpensive iron (II)/iron (III) sulfate. A sym-
metric cell with mixed electrolyte of AQDS and iron (II)
sulfate has shown excellent durability over hundreds of
cycles. In the absence of degradation pathways, such a
cell holds the prospect of being operable at elevated
temperatures (60  C) to achieve an increase in power
density [26].
Aqueous alkaline organic RFBs
Aqueous alkaline organic RFBs are attractive due to the
prospect of lowering the cost of the stack components
by using stainless steel instead of the graphite bipolar
plates needed for acidic systems. However, graphite
materials exhibit a high overpotential for hydrogen
evolution, a benefit that cannot be overemphasized for
the negative side. For the negative side of alkaline RFBs,
anthraquinone and its derivatives have shown promise
due to their solubility and chemical stability [27]. Sol-
ubility in alkaline media results from the ionization of
the eOH and eCOOH substituents [27,28]. Dihy-
droxyanthraquinone has been investigated extensively
in alkaline RFBs. Extended cycling resulted in irre-
versible capacity fade due to the formation of anthrone
under alkaline conditions. By restricting the state of
charge or by adding oxygen, the anthrone formation can
be avoided, a strategy that would be broadly applicable
to other anthraquinone derivatives [29]. Quinoxalines
and pyrazine are also reversibly oxidized and reduced in
alkaline media and are suitable as negative electrode
materials [29,30]. However, the chemical degradation of
alloxazine and pyrazine in alkaline media needs to be
contended with (Scheme 2). Phenazine and its de-
rivatives have received significant attention recently and
systematic theoretical studies have led to the identifi-
cation of high-concentration anolytes that can undergo
reversible cycling [31,32]. In phenazine derivatives, the
radical products of the redox reaction are stabilized by
the electron-delocalization resulting from the two ben-
zene rings flanking the redox center. This feature
Current Opinion in Electrochemistry 2022, 35:101100
renders the molecule resistant to dimerization and side
reactions. By substitution with hydroxy, carboxy, and
polyethyleneglycolic groups, the solubility can be
increased [31,32]. One of the latest successes in mo-
lecular engineering to enhance electrochemical revers-
ibility in aqueous alkaline media is exemplified by the
studies on 9-fluorenone derivatives [33]. By affixing
appropriate functional groups to the fluorenone rings,
the ketyl dianion (2e reduced form) form is stabilized,
leading to facile electrochemical interconversion be-
tween the alcohol and ketone forms.
Notably, there are no reports of organic redox couples for
the positive electrode that are chemically stable to
repeated cycling in alkaline media. The electron-defi-
cient positive materials are particularly prone to reaction
with a strong nucleophile such as the hydroxide ion.
Consequently, alkaline RFBs invariably use inorganic
ferrocyanide/ferricyanide as the positive electrode ma-
terial and that allows cell voltages as high as 1.4 V to be
attained. While the ferrocyanide redox couple is
assumed to be stable, a large excess of the ferrocyanide
positive material used in the cells would prevent
degradation from manifesting in the cell cycling results.
The chemical instability of the ferrocyanide redox
couple in strongly alkaline media caused by the disso-
ciation of cyanide ions is a drawback that needs to be
recognized and acknowledged [34]. In alkaline RFBs,
cation-exchange membranes such as NafionÒ allow for
the transport of potassium or sodium ions between the
positive and negative sides. Donnan exclusion of the
anionic species by the cation exchange membrane
minimizes the crossover of the redox materials [35].
Aqueous pH-Neutral organic RFBs
Organic RFBs that operate at neutral pH employ solu-
tions of sodium sulfate, sodium chloride, or a buffer as the
electrolyte. The neutral pH usually allows for improved
stability and chemical reversibility. Since the ionic con-
ductivity of the electrolyte is considerably lower than that
of the acidic and alkaline organic RFBs, higher polariza-
tion losses are expected for such cells. For the positive
electrode, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl radical
(TEMPO) and its derivatives have been found to be
promising. Sulfate and quaternary ammonium groups in
the 4-position are attractive for increasing solubility at
neutral pH [34]. A dual-ammonium functionalized
TEMPO molecule has been used as a positive side ma-
terial, and was found to be highly stable to cycling while
exhibiting low permeability through anion exchange
membranes [36]. Most recently, iron (II) complexes using
substituted bipyridyl ligands have shown promise as
positive side materials, improving on the key disadvan-
tages of ferrocyanide redox couples [37]. Ferrocenyl
alkylammonium salts have shown promise as positive side
materials. Their degradation can be controlled by altering
the substituent groups and changing the strength of the
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coordination. Viologen and its derivatives are suitable as
water-soluble negative electrolyte materials at neutral
pH, exhibiting good solubility and chemical reversibility.
The addition of two quaternary ammonium groups to the
viologen backbone has mitigated the formation of dimers,
while adding alkyl sulfonate groups has achieved good
cycling stability [38,39]. Viologen derivatives have been
cycled successfully with (ferrocenylmethyl)trimethy-
lammonium chloride on the positive side yielding stable
performance at high operating cell voltage [39]. Crossover
of redox materials is challenging to mitigate because of
membrane permeability to cationic materials. A combi-
nation of TEMPO and phenazine linked via a triethylene
glycol group has shown promise as a “combi-molecule”
suitable for neutral-pH redox-flow battery applications.
This “combi-molecule” is so named because it is consti-
tuted by combining molecular moieties that are sepa-
rately suitable for the positive and negative sides of the
cell. The bi-functional molecules are to be distinguished
from the combi-molecule in that the positive and negative
electrolyte functions are not explicitly realizable by
splitting the molecule, as exemplified by alizarin red. A
symmetric cell exhibited stable cycling over 1800 cycles
and a battery voltage of 1.2 V, indicating a promising di-
rection for avoiding crossover [40]. Similarly, by
combining a viologen unit to a TEMPO moiety, “combi-
molecule” type properties have been observed [41].
However, the solubility of such large molecules in
aqueous electrolyte presents a challenge.
Summary and outlook
Much of the research around aqueous organic RFBs are
still in the “mode of discovery” of new redox molecules
that can satisfy the competing requirements of excel-
lent electrochemical durability, cycle life, low cost, and
good solubility. More research would be needed to
discover viable organic redox materials for the positive
side of the cell along the lines of most recent findings
[37]. Computational screening methods such as DFT
and molecular dynamics have been increasingly used in
rational molecular design, particularly to raise solubil-
ity, suppress reactivity, and increase cell voltage
[28,33]. We anticipate that the electrochemical
screening of redox properties in non-aqueous media
and the application of molecular engineering can form
the initial basis for the selection and modification of
molecular properties suitable for aqueous media.
Among the strategies for improving stability, the
following appear particularly promising:
(1) Balancing the electronic factors affecting the mole-
cule’s properties by using a combination of electron-
withdrawing and electron-donating functional
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Aqueous organic flow batteries Krishnamurti et al. 5
groups. This will suppress nucleophilic addition
reactions such as Michael additions and proto-
desulfonation [21].
(2) Adding bulky substituents to sterically hinder or
prevent the addition of water and hydroxide to the
electrophilic centers, and also suppress dimerization
[42].
(3) Improving the kinetic stability of ionized forms of
redox-active molecules by tuning not only the
electronic and steric factors operating in the redox
molecule, but also by adjusting the pKa of the so-
lution to promote facile electrochemical intercon-
version [33].
(4) In the case of molecules where one or more oxida-
tion state is ionic, extended conjugation can be
utilized via molecular engineering to stabilize the
ionic form via delocalization of charge [42].
With the use of off-the-shelf ion-exchange membrane
separators, molecular size and anion exclusion appear to
be the only viable approach to minimize crossover.
Symmetric cells with mixed electrolyte is a practical
solution when the cost of materials is relatively low as
in the case of AQDS and iron (II) salts. To this end,
symmetric cells that use the bifunctional molecular
approach or the “combi-molecule” appear particularly
promising when the molecules are stable and soluble in
aqueous electrolyte. The possibility of using sustain-
able biomaterials and waste products as low-cost ma-
terials is an exciting prospect [43]. Scaled-up
demonstrations of hybrid organic-inorganic systems
have started to occur globally. From the techno-
economic viewpoint of finding a sustainable large-
scale energy storage solution based on aqueous
organic RFBs, future research must continue to focus
on achieving low material cost and extended chemical
durability through rapid materials discovery.
Acknowledgement
The authors acknowledge the financial support from the
US Department of Energy, Office of Electricity,
managed by Pacific Northwest National Laboratory. We
also acknowledge the support from the Loker Hydro-
carbon Research Institute at the University of South-
ern California.
Declaration of competing interest
The authors declare the following financial interests/
personal relationships which may be considered as po-
tential competing interests: Sri Narayan reports a rela-
tionship with Battery Energy Storage Technologies Inc.
that includes: board membership and equity or stocks.
Sri Narayan has patent #10,566,643 licensed to Battery
Current Opinion in Electrochemistry 2022, 35:101100
6 Environmental Electrochemistry (2022)
Energy Storage Technologies Inc. Sri Narayan has patent
#10,833,345 licensed to Battery Energy Storage Tech-
nology Inc.
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