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The next generation vanadium flow batteries with

high power density – a perspective
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Cite this: DOI: 10.1039/c7cp07456e

Wenjing Lu,ab Xianfeng Li *ac and Huamin Zhang *ac

Received 4th November 2017,
Accepted 24th November 2017
DOI: 10.1039/c7cp07456e
rsc.li/pccp
Vanadium flow batteries (VFBs) have received increasing attention due to their attractive features for
large-scale energy storage applications. However, the relatively high cost and severe polarization of VFB
energy storage systems at high current densities restrict their utilization in practical industrial
applications. Optimization of the performance of key VFB materials, including electrodes, electrolytes
and membranes, can realize simultaneous minimization of polarization and capacity decay. The power
density and energy density of VFBs are thus simultaneously enhanced. Moreover, relevant theoretical
mechanisms and foundations based on virtual investigations of VFB models and simulations can guide
these optimizations. The improved power density and energy density can reduce the cost of VFB energy
storage systems, accelerating their successful industrialization. In this perspective, modification methods
to optimize the performance of key VFB materials and investigations of models and simulations of VFBs
will be discussed. Therefore, the available ideas and approaches will be provided to direct further
improvements in the power density and energy density of VFB systems.

1. Introduction
Due to the continual increase in concerns regarding global environ-
mental pollution and the energy crisis, it is increasingly urgent to
a
Division of energy storage, Dalian Institute of Chemical Physics, propel the development and utilization of renewable energy sources.
Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, China.
However, renewable energy sources, such as solar and wind power,
E-mail: lixianfeng@dicp.ac.cn, zhanghm@dicp.ac.cn
b
University of Chinese Academy of Sciences, Beijing 100049, China
possess the undesirable features of high intermittence and instabil-
c
Collaborative Innovation Centre of Chemistry for Energy Materials (iChEM), ity. It is very difficult to realize reasonable and efficient use of
Dalian 116023, China renewable energy sources when generating electricity.1,2 At this time,

Wenjing Lu obtained her Bachelor’s Dr Xianfeng Li received his PhD in

degree (BSc) from Shandong Univer- Polymer Chemistry and Physics
sity in 2014. She is presently a PhD from Jilin University in 2006. He
student under the supervision of currently serves as a full professor
Prof. Xianfeng Li at Dalian and as head of the energy storage
Institute of Chemical Physics division at Dalian Institute of
(DICP). Her work involves mem- Chemical Physics (DICP), Chinese
brane structure design and research Academy of Science (CAS). His
on the performance of porous ion research interests include func-
conducting membranes for flow tional membranes for secondary
battery applications. battery applications. He is the
author of more than 150 peer-
Wenjing Lu Xianfeng Li reviewed papers with more than
3000 citations. He has received
several awards from the Chinese government, including the
National Technology Invention Award. He currently serves on the
editorial boards of ‘‘Scientific Reports’’ and ‘‘Journal of Energy
Chemistry’’.

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large-scale energy storage technologies have begun to play an

important role in ensuring a safe and reliable power supply.1
Large-scale energy storage technologies can store inconsecutive
electrical energy generated from renewable energy sources and
release continuous electricity, thus effectively tuning the instability
and discontinuity of renewable energy sources. Therefore, large-scale
energy storage technology is key in converting the role of renewable
energy sources from auxiliary to dominant.3,4
Among various large-scale energy storage technologies, such as
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pumped hydro storage, compressed air energy storage and battery

energy storage, vanadium flow batteries (VFBs) possess the out-
standing characteristics of high safety, large output power and
storage capacity, rapid response, long cycle life, high efficiency,
and environmental benignity.4–10 A VFB employs vanadium ions
with different valences as active species in different half-cell
electrolytes to store electrical energy converted from chemical
energy. The positive electrolyte uses the VO2+/VO2+ redox couple,
while the V2+/V3+ redox couple is utilized in the negative electro-
lyte. Using the same element in different half-cell electrolytes can
effectively ameliorate the cross-mixing of active species so as to
diminish self-discharge and capacity loss. Moreover, electrolytes
can be reused to reduce the system cost. The electrochemical
reactions occurring on the surfaces of the electrodes during the
charge–discharge process can be expressed as follows:11–13
Cathode:
Charge
VO2þ þ H2 O  e Ð VO2þ þ 2Hþ
Discharge
Anode:
Charge
V3þ þ e Ð V2þ
Discharge
Overall electrochemical reaction:
Charge
VO2þ þ H2 O þ V3þ Ð VO2þ þ V2þ þ 2Hþ
Discharge
Dr Huamin Zhang currently serves
as a full professor at Dalian Institute
of Chemical Physics (DICP), Chinese
Academy of Science (CAS). He is also
the CTO of Dalian Rongke Power
Co., Ltd. He received his PhD degree
from Kyushu University in 1988. His
research interests include energy
and energy storage, e.g. fuel cells
and flow batteries. He has co-
authored more than 260 research
papers published in refereed
Huamin Zhang journals and more than 150
patents. He has received numerous
awards from the Chinese govern-
ment, including the National
Technology Invention Award.
Fig. 1 Schematics of (a) an operating single VFB; (b) a VFB stack.
A VFB energy storage system is relatively complicated; it con-
sists of electrolyte storage units, a battery energy storage system
module, the battery stack, the battery management system, the
power conversion system, and the energy management system.
Among these, the battery stack is the kernel of the VFB energy
storage system; its area and number of single cells determine
the power rate of the system (Fig. 1b).11,14 Furthermore, the key
materials of a single VFB are the electrodes, membrane and
electrolytes (Fig. 1a). The number of single VFBs in a stack and
the effective area of the electrodes mainly dominate the output
power of a VFB system. Also, the energy density of a VFB is
defined by the concentration and volume of the electrolyte.14
The development of VFBs has been very rapid, and many
significant achievements have been realized. To date, many
VFB demonstration programs have already been realized,
including a 5 MW/10 MW h commercial demonstration system
in China and a 15 MW/60 MW h system in Japan.14,15 There-
fore, VFBs are the most promising technology for the applica-
tion of large-scale energy storage at present. The successful
industrial application of VFB energy storage systems will very
probably be accomplished in the near future. However, the
comparably high cost of VFBs seriously restricts their further
development.16,17 In addition, the low solubility and poor
stability of vanadium ions in supporting electrolytes impose a
major restriction on the energy density of VFB systems.11,16,18
Additionally, the increased current density contributes to more
severe polarization, which significantly reduces the power density
of VFB systems. The energy efficiency, which acts as the indicator
of the energy conversion ratio in the charge–discharge process,
will decrease accordingly. Moreover, the conductivity of
membranes at high current densities also affects the power
density of VFB systems to a large extent.19–21
In recent years, with the intent of improving the power
density and energy density of VFB systems, many investigations
concentrating on key VFB materials have been carried out. For
example, detecting surface treatments on electrodes to decrease
electrochemical polarization, introducing additives as precipi-
tation inhibitors in electrolytes to improve the vanadium-ion
concentration and thermal stability, carrying out structure
design and optimization to improve the selectivity and con-
ductivity of membranes, and designing more accurate and
effectual system models and simulations are available methods
to increase the power density and energy density of VFB
systems. This perspective will focus on the most recent

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achievements of these investigations and describe the develop-
ing future trends of VFB electrodes, electrolytes and mem-
branes. Additionally, studies of models and simulations of
VFB systems will be reviewed. Therefore, this perspective will
provide effective ideas and methods to direct further improve-
ments in the power density and energy density of VFB systems.
2. Strategies for improving the power
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density and energy density of VFB
systems
2.1 Electrode
Types of battery polarization include electrochemical or active
polarization, ohmic polarization and concentration polariza-
tion. These polarization phenomena are strongly affected by the
chemistry of the electrodes, the resistance of the electrolytes,
the performance of the membranes, etc., especially for electro-
chemical polarization.20–23 The dominant source of overpotential
in each region of a generalized polarization curve for a VFB is
shown in Fig. 2.24 The electrode surface is the place where the
redox reactions occur. Therefore, investigations on electrodes are
extremely significant for improving the power density of VFB
systems.20 A perfect electrode applied in VFBs should possess
high electrochemical activity and reversibility, high conductivity,
low resistance for mass transfer, excellent mechanical, thermal
and chemical stability, and low cost.20,25,26 Carbon materials,
particularly carbon felt and graphite felt, are currently the most
commonly used electrode materials.20,25,26 Their eminent three-
dimensional porous structures with high specific areas can
provide continuous and unhindered passage for the electrolyte,
promoting mass transfer and minimizing the concentration
polarization. The high specific area provides more active reaction
sites for the redox couples, thus improving the electrochemical
activity and reaction kinetics. The high conductivity can efficiently
decrease the ohmic polarization. Furthermore, the high mechan-
ical, thermal and chemical stability ensure maintenance of
stable battery performance under the strongly oxidizing and
Fig. 2 Generalized polarization curve for a VFB, indicating the dominant
source of overpotential in each region.24 Reprinted with permission from
ref. 24. Copyright Springer, 2011.
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acidic VFB operating conditions.19 In the following section, this
paper will concentrate on the modification methods of carbo-
naceous materials.
2.1.1 Minimization of the electrochemical polarization.
To further minimize the polarization induced by the intrinsic
deficiencies of carbonaceous electrodes, some modification
methods have been developed. For the purpose of reducing
electrochemical polarization, executing surface treatments on
electrodes to create more active species for reactions of VFB
redox couples is quite effective. Among these methods, some
can produce oxygen-containing or nitrogen-containing groups
as active sites to improve the electrocatalytic activity of carbonac-
eous electrodes, such as oxidization treatment, nitrogenization
treatment and thermal treatment.25,27–30 Introducing appropriate
electrocatalysts on the electrode surface is another method which
can eliminate the activation barrier for the redox conversion; these
electrocatalysts include conductive metals and metal oxides as well
as metal carbides, carbides, nitrides and carbonitrides.21,22,31–35
Wang et al. used bismuth (Bi) as the electrocatalyst on the
surface of a graphite felt electrode.21 Cleverly, they utilized
electrolytes containing Bi3+. Bi metal could thus be synchro-
nously electrodeposited on the negative electrode surface
during the process of VFB operation. This method is different
from the pretreatment procedures for other metal electrocata-
lysts. Bi could accelerate the kinetics of the V(II)/V(III) redox
reaction, especially under high power operation, and lead to
faster charge transfer. Finally, the energy efficiency, which is
mainly governed by the electrochemical and concentration
polarizations,19 of the VFB with Bi increased by 11% at a high
current density of 150 mA cm2 compared with the VFB without
Bi. Therefore, the power density and energy density increased
as well. However, the introduction of metals, metal oxides or
metal carbides will complicate the preparation process of
electrodes, increasing the cost of the electrode. Also, it is
usually difficult to ensure their uniform distribution, resulting
in their limited utilization in VFBs. Inversely, the utilization of
carbon materials (or carbides) increases gradually as a result of
their outstanding characteristics, as mentioned above. Recently,
Zoraida et al. employed graphene-modified graphite felt obtained
by electrophoretic deposition (EPD) as a VFB electrode material
(Fig. 3).36 The three dimensional cross-linked interconnected
porous structure with well distributed oxygenated active sites
contributed to the increased wettability of the electrode and
Fig. 3 (a) Nyquist plots recorded on different graphite felt electrodes in a
0.05 M VOSO4/1.0 M H2SO4 solution at 0.9 V (vs. Ag/AgCl/3.5 M KCl);
(b) charge/discharge profiles of the four VFB cells during operation.36
Reprinted with permission from ref. 36. Copyright Elsevier, 2017.
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increased the active area towards vanadium redox reactions.

Therefore, the graphene-modified graphite felt electrode exhibited
excellent performance towards VO2+/VO2+ redox reactions. Addi-
tionally, the charge transfer resistance of the resulting graphene-
modified graphite felt (GF-G) was much lower on both electrodes
(Fig. 3a). Also, a VFB using GF-G as the positive electrode (VRFB-4)
demonstrated the lowest overpotential compared with other VFBs
(Fig. 3b). Finally, the energy efficiency of the VFB using this
electrode was remarkably high, reaching 95.8% at 25 mA cm2.
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2.1.2 Minimization of the ohmic polarization. The ohmic

resistance of a battery generally originates from the electrical
resistance of the electrodes, blocked ion transport across the
electrolytes and membranes, and the contact resistance
between battery components.24 In other words, the ohmic
polarization of VFBs is largely derived from the bipolar, elec-
trode and membrane bulk resistance, the contact resistance
between the battery components and the resistance of the
electrolytes. For electrodes, high ohmic polarization is normally
caused by large thickness as well as insufficient diffusivity
of electrolyte circulation through their porous structures.
Compressing porous electrodes is an effective method to optimize
their pore structures, improving their electrical conductivity. A
high compression ratio can decrease the electrode thickness,
shortening the distance between the current collector and the
membrane for ions and electrons. The electrical conductivity of
the electrodes thus increases with decreasing thickness.37 Further-
more, the mechanical stability of the electrodes is enhanced by
their high compressing ratio as well.37–39 In addition, introducing
carbon materials (or carbides) into porous carbonaceous electro-
des to alter their pore structure, designing excellent flow-field
structures or flow channels, realizing better contact among all
battery components, and selecting electrode materials with proper
morphology can be applied to efficiently decrease the ohmic
polarization.37,39–42 Recently, Zhao et al. created a VFB with a
carbon nanoparticle-decorated graphite felt electrode placed in a
flow-field structure (Fig. 4a and b).39 The carbon nanoparticles
were treated with nitric acid and then coated on the electrode
surface. This method effectually improved the electroactive sur-
face area. Also, the reduced electrode thickness contributed to
decreased ohmic resistance and, thus, to increased power density
(Fig. 2 and 4c). The battery with a flow-by structure with a single
serpentine flow field displayed a lower ohmic loss and a higher
mass-transport current density than that with a flow-through
structure without flow fields. This result indicates that addition
of a flow field can decrease the difference in concentration
between the flow channel and electrode, thus decreasing the
battery polarization (Fig. 4c). Ultimately, the current density
was as high as 200 mA cm2 with an energy efficiency of 72.7%
(Fig. 4d).
2.1.3 Minimization of the concentration polarization. To
decrease the concentration polarization, rapid and unblocked
mass transport through the electrode is the pivotal aspect.
Therefore, the flowing behavior of electrolytes through the
porous structure of electrodes is extremely significant.28,43–45
Designing an optimal electrode configuration, tuning the flow
rate of electrolytes, and designing flow fields in the electrode
Fig. 4 Schematic of VFB components: (a) flow-through structure without
flow fields; (b) flow-by structure with a single serpentine flow field. (c)
Polarization curves of VFBs employing different electrodes (A: original
graphite felt in flow-through structure, B: 1.5 mm graphite felt in flow-
through structure, C: 1.5 mm graphite felt in flow-by structure, D2: 1.5 mm
graphite felt coated with 2 mg cm2 carbon nanoparticles in flow-by
structure); (d) rate performance at different current densities.39 Reprinted
with permission from ref. 39. Copyright Elsevier, 2016.
interior and on the electrode surface to accelerate the uniform
distribution of electrolytes are available strategies to minimize
battery concentration polarization.28,44,46 A more open pore
structure improves the flowing behavior of electrolytes. How-
ever, a lower specific surface area is obtained, resulting in
higher electrochemical polarization.43 The higher flow rate of
electrolytes leads to decreased concentration polarization,
resulting in higher discharge capacity and energy efficiency.
However, the parasitic pump loss is accordingly increased to a
certain degree.44,46 Therefore, optimizing only the flowing
behavior of electrolytes is relatively unserviceable.
The flow field between the current collector and the porous
electrode can help distribute the electrolyte more uniformly
with reasonable pumping power, thus effectually decreasing
the concentration polarization.44,47 As a result, designing the
flow field on electrodes is a very efficient and promising
method that is expected to attract increasing attention. Zhao
et al. analyzed and compared the performance of VFBs with and
without flow fields (Fig. 5a).44 Moreover, they also investigated
the effects of the flow rate on the battery polarization. Increasing
the flow rate of the electrolytes led to an obvious decrease in the
concentration polarization, particularly with flow fields (Fig. 2 and
5b–d). This phenomenon mainly arose from the more even ion
distribution in both the in-plane and through-plane directions.

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Fig. 5 (a) Schematics of the components of VFBs with flow-through
electrodes (up) without flow fields and (down) with serpentine flow fields,
including polarization curves of the VFBs with and without flow fields at the
flow rate of (b) 1.2 ml s1; (c) 2.5 ml s1; and (d) 5.0 ml s1. (e) Charge–
discharge performance of VFBs with and without flow fields.44 Reprinted
with permission from ref. 44. Copyright Elsevier, 2014.
Although the corresponding pumping power for the battery with a
higher flow rate was consequently higher, an optimized value was
obtained. Operating at the optimum flow rate, the VFB with flow
fields showed lower charge voltage and higher discharge voltage,
indicating the effects of flow fields on decreasing the battery
polarization (Fig. 5e).
In fact, the aforementioned approaches can address various
polarization behaviors of VFBs. Different types of battery polar-
ization are not affected by a single factor; the effects of these
solutions are thus correlated and synergetic.28,43 The design of
flow fields on electrodes and the optimization of the flowing
behavior of electrolytes can decrease the concentration polar-
ization. The introduction of carbon materials can also simulta-
neously address the issues of electrochemical polarization and
concentration polarization. To illustrate this, Manthiram et al.
utilized nitrogen-doped carbon nanotubes (N-CNTs) decorated
on graphite felts to act as an electrode material for VFBs
(Fig. 6).28 The uniform and dense distribution of N-CNT
networks on the surface of the graphite felt contributed to
the formation of a sufficiently porous electrode structure. The
existence of this structure propelled the mass transport of the
electrolytes. Also, the increased hydrophilicity resulting from
the addition of N-CNT may also help decrease the concentration
polarization. Additionally, the increased electrochemical surface
area induced by the ideal porous graphite substrate and doped
nitrogen atoms in the carbon lattice networks improved the
electrocatalytic activity of the electrodes. Decreased electro-
chemical polarization was thus realized. Therefore, the capacity
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Fig. 6 (a) Charge–discharge curves of VFBs with pristine GF (black), CNT/
GF (red), and N-CNT/GF (blue) electrodes and (b) columbic efficiency,
voltage efficiency, and overall energy efficiency values for the three
electrode materials.28 Reprinted with permission from ref. 28. Copyright
American Chemical Society, 2012.
and the energy efficiency were both increased by utilizing the N-
CNTs-decorated electrode materials (Fig. 6a and b).
In short, the most commonly used electrode materials in
VFB applications at present are felt materials, namely carbon
and graphite felts. To ensure the minimum polarization in
order to achieve higher power density, diverse modification
methods have already been carried out on carbon and graphite
felt electrodes. Among these methods, the introduction of
materials that can produce oxygen-containing and nitrogen-
containing groups as active sites is fairly effective. Also, this is
one of the most promising methods to improve the electro-
catalytic activity of electrodes. The electrochemical polarization
then decreases. Proper compression of electrodes can decrease
the thickness of the electrodes, thus increasing their conduc-
tivity. The ohmic polarization decreases as well. Moreover, the
design of flow fields on the surface and in the interior of
electrodes should receive increasing attention to decrease the
concentration polarization, thus decreasing the cost of the VFB
system. It is worth noting that a particular solution can often
address one or more polarization problems. Therefore, further
altering these modification methods of electrodes or seeking
other available methods to combine the advantages and avoid
the drawbacks of these methods can finally lead to optimal VFB
performance, contributing to higher power density and lower
cost of VFB systems. Moreover, selecting proper electrode
materials with excellent pore structures to avoid the intrinsic
deficiencies of felt electrodes may be another effective idea.
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2.2 Electrolyte
Apart from the flow rate of the electrolytes, as illustrated above,
the effects of other parameters relevant to electrolytes on the
power density of VFBs are actually slight. However, the low
solubility of vanadium ions in the supporting electrolyte and
the precipitation of toxic V2O5 at elevated temperature impose
severe restrictions on the energy density of VFBs.11,16,18,48–50
This is because the volume and concentration of the electro-
lytes determine the energy capacity of VFBs.11 As described
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above, VFB electrolytes employ vanadium ions with different
valences as active species, while an aqueous sulfuric acid
solution commonly serves as the supporting electrolyte. Com-
monly, the solubilities of V(II), V(III), and V(IV) ions in sulfuric
acid supporting electrolytes increase with increasing tempera-
ture or decreasing concentration of the sulfuric acid solution,
while the solubility of V(V) ions exhibits the opposite tendency.
Thus, the low solubility of vanadium ions mainly arises because
V(II), V(III), and V(IV) ions precipitate at low temperature, while
V2O5 ions precipitate at high temperature.15,48,51 The poor
solubility of vanadium ions in sulfate-based supporting elec-
trolytes restricts the energy density of the current VFB systems
to 30 to 40 W h L1, while their weak thermal stability
commonly leads to a narrow operating temperature range of
10 1C to 40 1C.17,51,52 To improve the energy capacity and
further reduce the cost of VFB systems, as well as to widen
the temperature range of VFB operation, variable optimizations
on electrolytes have also been carried out. When sulfate-based
solutions serve as supporting electrolytes, the solubility of
vanadium ions strongly depends on the concentration of the
sulfuric acid solution. As mentioned above, there may be a
tradeoff in the concentration of sulfate-based solutions for
higher solubility of vanadium ions.15,51 However, the effect of
optimizing the concentration of the sulfuric acid solution to
improve the solubility and thermal stability of vanadium ions is
poor. Currently, more effective modification methods are the
addition of proper additives as precipitation agents for vana-
dium ions in sulfate-based solutions and the use of mixed acid
solutions as supporting electrolytes.51–57
2.2.1 Using additives as precipitation inhibitors. When
sulfate-based solutions act as supporting electrolytes, precipita-
tion agents are commonly added to the positive electrolyte
because the finite solubility of vanadium ions largely arises
from the precipitation of V(V) ions. Generally, organic com-
pounds that can complex with or adsorb V(V) ions to suppress
the nucleation or crystallization of V2O5, can serve as electro-
catalysts to improve the reaction kinetics, or can decrease the
strength of the attraction forces between the particles to reduce
agglomeration should be preferentially chosen as precipitation
inhibitors.18,51,56,58 Compounds containing –OH, –SH, or –NH2
groups with ring or chain structures can effectively increase the
solubility of vanadium ions, thus inhibiting the precipitation of
V(V) and improving the electrochemical performance of the
electrolytes.15,57,59–62 There are two explanations for this phe-
nomenon: the first is that these additives act as complexing
agents. These ‘‘complexing agents’’ can not only absorb on the
surfaces of the nuclei to coordinate with V(V) ions and retard
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the crystal growth of V2O5, but can also adsorb to the surfaces
of electrodes and improve their electrochemical reversibility.
These additives generally include L-glutamic acid, glucose,
glycerol, n-propyl alcohol, methanesulfonic acid (MSA), and
aminomethylsulfonic acid (AMSA).60,62,63 The other explanation
is that the additives serve as dispersion agents which can
promote the dispersion of hydrated V(V) ions based on the
combination of columbic repulsion and steric hindrance. These
dispersion agents include inositol, phytic acid, D-sorbitol, tri-
shydroxymethyl aminomethane (Tris), methyl orange (MO), and
Triton X-100 (OP).50,60,61,64 In addition, sulfate-based additives
and some polymers can delay the precipitation of V2O5 on the
basis of the second explanation, such as sodium ligninsulfonate
(SL), sodium dodecyl sulfate (SDS), and polyvinyl alcohol (PVA).64
However, the amount of the additive must be optimized because
too much additive will damage the hydrated layer of V(V) ions,
affecting the mass transport and increasing the ohmic polariza-
tion of the battery along with capacity loss. It is more noteworthy
that the poor chemical stability of organic additives in strongly
oxidizing and acidic solutions normally leads to their unstable
presence in VFB electrolytes.57 Therefore, the utilization of
organic additives should be avoided as much as possible.
Another strategy is to introduce inorganic additives, such as
phosphate-based additives, chloride-based additives, amine-
based additives, and metal ions.51,56,57,65,66 The presence of
metal ions, such as Cr3+ and In3+, also accelerates the electro-
catalytic activity of electrolytes. The electrochemical reversibility
and kinetics of redox couples are thus improved, which is
analogous to the influence of introducing electrocatalysts on
electrodes.51,57,65,67 However, adding metal ions to positive elec-
trolytes to improve the concentration and thermal stability of
VFB electrolytes is relatively rare. On the other hand, NH4+,
PO43, HPO42 and H2PO4 can coordinate or ion-pair with
V(V) ions or can adsorb on their nucleation sites to prevent
the crystallization of V2O5, thus improving the electrochemical
activity of electrolytes.55,56,68 Their utilization is comparably
more effectual and common. Roznyatovskaya et al. previously
employed phosphoric acid as an additive to improve the thermal
stability of the catholyte by inhibiting the precipitation of V(V)
ions (Fig. 7a).66 The role played by phosphoric acid in stabilizing
the catholyte at elevated temperature was ascribed to the inter-
action between phosphoric acid and V(V) monomers or dimers,
which formed two different V(V)-phosphoric acid coordination
compounds (Fig. 7a). The precipitation of V2O5 was thereby
prolonged. Furthermore, M. Skyllas-Kazacos et al. utilized
inorganic phosphate-based additives in a sulfate-based electro-
lyte (KS11), containing 1 wt% of K3PO4+ and 1 wt% of SHMP
((NaPO3)6) (KS: K is K3PO4, and S is SHMP) to improve the
concentration of vanadium ions.69 The blocked precipitation
was attributed to the release of phosphate ions (PO43) from
K3PO4 and PO3 ions from SHMP; these are believed to be
adsorbed onto the nucleating ions or onto the growing crystals,
inhibiting the further formation of vanadium crystals as illu-
strated above. Also, the presence of phosphate-based additives
would not affect the reaction kinetics of the V(IV)/V(V) redox
couples. The electrolyte containing 4 M V(V) solution in 6 M
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Fig. 7 (a) Proposed pathways for V(V) precipitate formation in sulfuric acid
electrolyte;66 (b) effects of different blends of KS formulation on the
precipitation of V(V) solution at 40 1C; (c) effects of temperature on the
performance of formulation KS11 using 3 M V(V) and 4 M V(V) solutions in
6 M sulphate/bisulphate after 1000 h.69 Reprinted with permission from
ref. 66. Copyright Elsevier, 2017. Reprinted with permission from ref. 69.
Copyright Elsevier, 2017.
sulfate-based supporting electrolyte remained stable at 40 1C for
1000 h (Fig. 7b and c). Finally, a solution composed of 3.5 M V(V)
in 5.7 M sulfate-based solution with an additive (KS11) was
obtained and was found to be fairly promising for VFBs with
high energy density at high temperature.
The introduction of additives into negative electrolytes can
improve the stability of the electrolytes at low temperature by
preventing V(II) and V(III) ions from precipitating; these additives
include polyacrylic acid (PA), glycerol, ammonium phosphate,
ammonium sulfate, Flucon-100, sodium pentapolyphosphate,
and metal ions.48,53,70 Their acting mechanisms are analogous
to those of the additives in positive electrolytes. However, the
energy density of VFB systems is mainly confined by the pre-
cipitation of V2O5 at elevated temperature. Increasing numbers
of inorganic phosphate-based precipitation inhibitors will be
developed to be added to sulfate-based supporting electrolytes in
the near future, due to their aforementioned merits.
2.2.2 Employing mixed acid solutions as supporting
electrolytes. The utilization of mixed acid solutions as support-
ing electrolytes is another method to improve the solubility of
vanadium ions in supporting electrolytes and extend the tem-
perature range of VFB operation.45,49,66 Additionally, their use
can improve the electric conductivity and electrochemical
activity of electrolytes. In fact, the idea of utilizing mixed acid
solutions is similar to that of the introduction of additives in
electrolytes. As exhibited above, the presence of Cl, PO43,
HPO42, H2PO4, etc. can improve the concentration and thermal
stability of VFB electrolytes. Combining the aforementioned act-
ing mechanisms and relevant investigations, hydrochloric acid,
phosphoric acid, MSA, etc. have been used as additives in sulfate-
based supporting electrolytes, especially hydrochloric acid.51,54,71
Yang et al. have used sulfate-chloride mixed supporting electro-
lytes in VFBs; these can dissolve 2.5 M vanadium ions.54 A VFB
using a sulfate–chloride mixed supporting electrolyte realized
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Fig. 8 (a) Structures of V5+ complexes in sulfate and sulfate–chloride
mixed solutions, as predicted by quantum calculation. The pink, green, red,
and white spheres represent vanadium, chloride, oxygen, and proton ions,
respectively. (b) Performance of a VFB with a 2.5 M vanadium mixed
solution at 40 1C, 50 1C, 5 1C, and 0 1C.54 Reprinted with permission from
ref. 54. Copyright John Wiley and Sons, 2011.
dramatically increased energy capacity, and the novel electrolyte
could remain stable over a wide temperature range of 5 1C to
50 1C (Fig. 8). The main reasons are the formation of a stable
vanadium–chloride complex at elevated temperatures and the
decreased SO42 concentration. However, hydrochloric acid pos-
sesses the disadvantages of high volatility and high causticity, and
chlorine may be released during the charge–discharge process.
Due to these disadvantages, VFBs using sulfate-chloride mixed
supporting electrolytes suffer from serious issues of safety and
environmental friendliness. However, the effectiveness of other
mixed acid systems in improving the solubility of vanadium ions
cannot be compared with that of sulfate-chloride mixed systems.
Actually, preventing the release of chlorine is key to realize the
successful commercialization of mixed acid systems. Currently, in
the views of safety, reliability, stability and economy, sulfate acid-
based solutions are still the most commonly used supporting
electrolytes for the long term.
The ideas and acting mechanisms of adding precipitation
inhibitors and utilizing mixed acid supporting electrolytes are
analogous. In addition to these two methods, controlling the
state of charge (SOC) of the battery is sometimes employed.
This is because changes in the density and viscosity of the
electrolytes, which are closely related to their conductivity, can
Phys. Chem. Chem. Phys.

Perspective
be regarded as a function of the SOC (or the oxidation state of
vanadium ions). Therefore, variations in the SOC will influence
the solubility and stability of VFB electrolytes to a certain
degree.18,72 However, to avoid precipitation of V2O5, the SOC
must be decreased, which will cause a decrease in the energy
density.51 As a consequence, it is comparably difficult to prevent
capacity loss by controlling the SOC. However, the SOC is also
closely related to the imbalance of positive and negative half-cell
electrolytes, which can lead to a decrease in the efficiency and
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capacity of VFBs.73,74 Real-time measurement and analysis of the
SOC on each side of the VFB electrolyte enables in situ study of
the electrolyte, which is useful for estimating capacity loss and
achieving high system effectiveness.73,74
2.3 Membranes
The polarization induced by VFB membranes is mainly ohmic
polarization. Especially at higher current densities, serious
ohmic polarization caused by hindered and difficult mass trans-
port results in high voltage loss. Also, the ionic and contact
resistance between the membrane and electrode normally result
in ohmic polarization.47 At present, commercial perfuorinated
sulfonated membranes are still the most widely used mem-
branes in VFBs in light of the ready degradation of other types
of ion exchange membranes in the strong oxidized and acidic
environment of VFBs.75–77 However, due to the low ion selectivity
and high cost of perfuorinated sulfonated membranes, porous
membranes with low cost are among the most promising alter-
natives for industrial VFB application.78 In the past few years,
many modification methods have been carried out to optimize
the performance of porous membranes in VFBs. Also, currently,
the VFB performance of porous membranes is very high; thus, it
is difficult to further improve their energy efficiency.78 The main
challenge of porous membranes is their relatively low voltage
efficiencies at higher current densities (Fig. 9). In fact, the
columbic efficiency of VFBs using porous membranes normally
remains unchanged with increasing current density (Fig. 9).
Thus, the decreased voltage efficiency also leads to decreased
Fig. 9 Variations in porous membrane performance in VFBs at different
current densities.79 Reprinted with permission from ref. 79. Copyright
Royal Society of Chemistry, 2016.
Phys. Chem. Chem. Phys.
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energy efficiency at high current densities.79–83 This serious
voltage loss at high current densities constricts improvement
in the power density. Decreases in the cost of VFB systems will be
prevented as well.
The voltage efficiency of VFBs at high current densities is
closely related to their ion conductivity, or in other words, the
resistance of the membrane under VFB operating conditions.
Lower resistance can accelerate mass transport at high current
densities, resulting in lower ohmic polarization.84,85 In general,
larger pore size, higher pore interconnectivity, wider pore size
distribution, a thinner membrane and higher membrane
hydrophilicity contribute to higher ion conductivity of porous
membranes. However, there is a conflict between high con-
ductivity and high selectivity, and these methods commonly
lead to lower ion selectivity of membranes. When attempting to
improve the voltage efficiency, high columbic efficiency at
elevated current densities must be simultaneously ensured to
minimize capacity loss. In fact, modifying porous membranes
with the sole purpose of decreasing the battery voltage loss at
high current densities is impractical. To date, most modifica-
tions of porous membranes have aimed to balance the conflict
between high ion selectivity and high ion conductivity. A high
voltage efficiency at high current density is generally achieved
by improving the overall performance of porous membranes.
Also, optimizing the overall performance of porous membranes
achieves high ion selectivity, high ion conductivity and high
chemical stability at the same time. The energy efficiency, the
energy density and the power density can be accordingly
enhanced as well.
To date, structure design and optimization of porous
membranes has been the most effective method to improve
their comprehensive performance.78 These methods include
optimizing preparation parameters, introducing hydrophilic
inorganic-based nanoparticles or charged groups, studying
the formation mechanism of the porous membranes, and
selecting novel high-performance membrane materials.78,86–90
For a complete modifying process, when the membrane materials
have been selected, the preparation parameters should be first
optimized to tune the membrane pore structures preliminarily.
The initial performance of porous membranes determines
whether a modification method should be carried out or which
modification method should be employed. However, simple
optimization of the preparation parameters during the fabrication
process has finite effects on improving the membrane perfor-
mance. Also, the utilization of hydrophilic inorganic-based
nanoparticles often leads to higher membrane resistance.91,92
It is also difficult to maintain structure integration of nanoparticle-
decorated porous membranes over long cycling times. Addition-
ally, the introduction of charged groups can weaken the
chemical stability of porous membranes because of their ready
degradation.75–78,86,87 The studies on the formation mechanism
of porous membranes are too complex to be put into practice.
Moreover, identifying appropriate novel membrane materials
will require much time. Actually, a large number of modification
methods concentrate on offsetting the intrinsic drawbacks of
membrane materials. For example, the purpose of introducing
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Fig. 10 (a) Proton conducting mechanism of the prepared membranes.
(b) Scanning electron microscope image showing the morphology of the
membrane cross section; scale bar, 5 mm. (c) Cycling performance of a
VFB using PBI-34 and PBI-68 membranes at different current densities. (d)
Long-term stability test of a VFB assembled with a PBI-68 membrane at
various current densities.90 Reprinted with permission from ref. 90. Copy-
right Royal Society of Chemistry, 2016.
hydrophilic inorganic-based nanoparticles or charged groups is
normally to overcome the high hydrophobicity of membranes.
As a consequence, if the membrane material is very well chosen,
it is relatively facile to achieve high performance for VFBs
assembled with porous membranes. In this case, simple mod-
ification can enable preparation of a high-performance porous
membrane for VFBs.
Yuan et al. used polybenzimidazole (PBI) as a porous
membrane material for the first time (Fig. 10).90 The advant-
ages of PBI lie in its outstanding thermal, mechanical and
chemical stabilities as well as the high hydrophilicity conferred
by its amine groups (Fig. 10a). Furthermore, the presence of ion
exchange groups directly in the backbone of PBI will not sacrifice
the chemical stability of the membranes. Therefore, there is
almost no need to introduce any hydrophilic groups to improve
the membrane hydrophilicity or carry out other approaches to
enhance the membrane stability. They only optimized the casting
thickness during the process of vapor-induced phase inversion to
obtain sponge-like porous PBI membranes with highly excellent
performance in VFBs (Fig. 10b). The VFB assembled with the
optimal porous PBI membrane (PBI-68) demonstrated a columbic
efficiency of nearly 100%, a voltage efficiency of 78.47%, and an
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energy efficiency of 78.05% at a high current density of
200 mA cm2; these were all much higher than the corres-
ponding values of commercial Nafion 115 (Fig. 10c). Also, the
VFB could continually run for over 13 000 cycles, with no obvious
efficiency decline being observed (Fig. 10d). Due to this excellent
performance, the optimized porous PBI membrane was utilized
in a kW stack, and the stack performance indicated the high
reliability and practicality of the prepared membrane.
In summary, enhancing the overall performance of porous
membranes in VFBs, namely by realizing a perfect balance
between their selectivity and conductivity, is vital to maintain
high columbic efficiency and decrease voltage loss at high
current density. High energy density and power density can
thus be effectively achieved. Although the aforementioned
modification methods can address the deficiencies of porous
membranes to a very large degree, the disadvantages of these
methods also result in other problems. Therefore, the choice of
excellent membrane materials with outstanding features, such
as high stability, high hydrophilicity and low cost, is the most
significant aspect to realize the successful industrial applica-
tion of porous membranes in VFBs. The modifications of the
membranes should be as simple as possible.
2.4 Models and simulations of VFB systems
In general, the mechanisms and processes of VFB systems,
such as the ion transport mechanism and the capacity decay
mechanism, are very complex and obscure. Traditional laboratory
studies of these mechanisms and processes require great expense
of time and cost. Moreover, direct laboratory testing of the key
materials of VFBs is relatively complicated, time-consuming, and
not highly effective.93 The relevant mechanisms attained by
investigations on models and simulations of VFBs provide theo-
retical foundations to guide the design of VFBs and optimization
of their performance. To date, there has been considerable
investigation of models and simulations of VFBs to study the
various mechanisms and process existing in VFB systems, such as
their thermal behavior, the Donnan effect at the membrane/
electrolyte (M/E) interfaces, the effects of ion concentration on
the ion mobility, hydrogen evolution effects, the ion transport
mechanism across the membrane, the self-discharge process, and
dynamic performance in VFBs.94–100 Therefore, these models and
simulations can predict the performance of VFB systems to a
certain degree. The effects exerted by variations in the relevant
parameters on the performance of VFBs, such as the dynamic
diffusion coefficient of vanadium ions, the pressure drop,
the electrode thickness and the flow rate of electrolytes, can
be illustrated as well. Zhao et al. have developed a two-
dimensional, transient model to investigate the mechanisms
of ion transport across a commercially available porous separa-
tor in VFBs; they also studied the effects of these mechanisms
on battery performance (Fig. 11).98 Their purpose was to study
the relationship between the key properties of porous separators
and the performance of VFBs. After validating the effectiveness
and fidelity of the model, they investigated the effects of the pore
diameter, the separator thickness, and the operation conditions
(Fig. 11a–c). The results showed that the transport mechanism of
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Fig. 11 (a) Comparison of the simulated charge–discharge curve with
experimental data; (b) predicted changes in the total amount of vanadium
ions during the charge–discharge process at positive and negative half-cells
for porous separators with different pore sizes; (c) predicted changes in the
total amounts of vanadium ions during the charge–discharge process at
positive and negative half-cells with a 30 nm porous separator with different
operation modes and a 5 nm porous separator with different operation
modes.98 Reprinted with permission from ref. 98. Copyright Elsevier, 2016.
vanadium ions across available separators was dominated by
convection. Decreasing the pore size to less than 15 nm could
effectively minimize the convection-driven vanadium-ion crossover.
However, further reduction in migration- and diffusion-driven
vanadium-ion crossover could only be realized when the pore size
was reduced to a level close to the size of the vanadium ions. The
operating conditions, such as the pressure on each half-cell of a
VFB, played an important role in the vanadium-ion crossover rate
across the available separators. Based on these conclusions, porous
membranes with better performance can be designed and fabri-
cated by balancing the proton transport and transfer of vanadium
ions and by adjusting the operating conditions of VFBs.
Investigations on models and simulations of VFB systems are
useful in designing better flow fields on electrodes and optimizing
the flowing behavior of electrolytes.101,102 Additionally, these inves-
tigations can guide the creation of entirely novel VFB battery
structure designs, like the circular vanadium flow battery, to address
the issue of the low energy density of VFBs systems.103 The
discrepancies in the results derived from dynamic models and
experimental values are normally less than those using pure math-
ematical models or stationary models.99 In future, more effective
and more accurate models and simulations should be built to study
the various mechanisms and operating process of VFBs more deeply
and precisely. However, at all events, although variable models and
simulations can improve the convenience of experiments, the results
of these studies still need to be verified by laboratory tests in order to
truly utilize them in practical applications.
3. Summary and perspective
High cost is the main limitation for the successful industriali-
zation of VFBs in the field of large-scale energy storage.
Phys. Chem. Chem. Phys.
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Improvements in the current density of VFB systems lead to
severe polarization, contributing to lower power density.
The power density and energy density strongly depend on the
performance of key VFB materials, including the chemistry of
the electrodes, the concentration and stability of the electrolytes,
and the ion selectivity and ion conductivity of the membranes.
Of course, the cost of these key materials must be as low as
possible.
The chemistry of the electrodes largely affects the polariza-
tion of VFB systems, including electrochemical polarization,
ohmic polarization and concentration polarization. At present,
carbon felts and graphite felts are the most commonly used
electrode materials. To effectually improve the power density of
a VFB system, necessary modifications have been carried out on
felt materials. Carrying out surface treatments on electrodes
can produce more active sites for redox reactions of VFB
active species. The electrocatalytic reactivity of the electrodes
is thereby improved. Compression of porous electrodes to
decrease the thickness of the electrodes can improve their
conductivity, thus decreasing the ohmic polarization. Further-
more, the electrode materials must possess high mechanical
and chemical stability to maintain stable performance under
the strongly oxidizing and acidic VFB operation conditions.
Due to the low solubility and poor thermal stability of
vanadium ions in supporting electrolytes, VFB systems operate
with low electrolyte concentrations and in narrow temperature
ranges. These are the main reasons for the low energy density
of VFB systems. In other words, these issues restrict the
realization of low-cost VFB systems. The addition of inorganic
precipitation inhibitors is an effective method to improve the
concentration of vanadium ions in supporting electrolytes and
prevent vanadium ions from precipitating. The utilization of
mixed acid solutions and control of the SOC can also modify
the concentration and stability of electrolytes to a degree.
The performance of membranes affects not only the power
density but also the energy density of VFB systems. High ion
selectivity and high ion conductivity at high current densities
ensure simultaneous increase of the power density and energy
density. Also, high columbic efficiency and high voltage
efficiency at high current densities result in high energy effi-
ciency of VFB systems. Porous membranes are among the most
promising alternatives to the current commercial perfluori-
nated sulfonated membranes with both low ion selectivity
and high cost. Of course, some modification methods are still
required to enhance the performance of porous membranes in
VFBs. However, proper choice of membrane materials is the
most pivotal aspect and can eliminate unnecessary modifica-
tion processes to a large degree. Materials with high selectivity
and conductivity, high mechanical and chemical stability, high
hydrophilicity and low cost are preferred membrane materials.
In addition, to save time and cost, investigations on models
and simulations of VFB systems on various mechanisms and
processes may be necessary. The effects exerted by variations in
relevant parameters on the battery performance can be relatively
well clarified. Although there is a certain deviation between
the results arising from models and simulations and those
This journal is © the Owner Societies 2017

PCCP
originating from experiments, the results originating from these
models and simulations can theoretically effectively direct the
optimization of VFB performance.
In summary, the developing trends of VFB systems are low
cost and minimum polarization at high current densities.
Modifications of key VFB materials, along with investigations
on models and simulations of VFB systems, will effectively
optimize their overall performance. VFB systems will thus
achieve successful industrialization in large-scale energy storage
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applications in the future.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Financial support of our work by the China Natural Science
Foundation (Grant No. 21476224), the Outstanding Young
Scientist Foundation, Chinese Academy of Sciences (CAS),
Science and Technology Service Network Initiative (KFJ-EW-
STS-108) and National Youth Top-notch Talent Program and
Key project of Frontier Science, CAS (QYZDB-SSW-JSC032) is
greatly acknowledged.
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