Journal of Power Sources 506 (2021) 230192

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Journal of Power Sources

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

A two-dimensional analytical unit cell model for redox flow battery

evaluation and optimization
Yunxiang Chen a ,∗, Jie Bao b , Zhijie Xu a , Peiyuan Gao a , Litao Yan b , Soowhan Kim b , Wei Wang b
a
Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, 99354, USA
b
Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA, 99354, USA

HIGHLIGHTS GRAPHICAL ABSTRACT

• A two-dimensional analytical unit cell

model is proposed and widely validated.
• Activation, equilibrium, and pump en-
ergy losses are dominant sources of en-
ergy losses.
• A guideline for reducing activation, equi-
librium, and pump energy losses is pro-
posed.
• Electrode microstructure design depends
on an optimal porosity predicted by the
model.
• The model differs vastly from its 0-
dimension version in energy losses and
efficiency.

ARTICLE INFO ABSTRACT

Keywords: Cell performance optimization is important for improving the system efficiency of a redox flow battery. To gain
Redox flow battery better insights into key controlling factors of system efficiency, this work first proposed a theoretical model
Cell voltage model for a unit cell by extending a two-dimensional analytic model to a full cell. The model is then used for cell
Energy losses
performance optimization after validating it with experimental and numerical modeling data. With the results,
Validation and optimization
the activation, equilibrium, and pump energy losses are identified as the dominant battery energy losses. A
Mass transport
Electrode microstructure design
guideline for reducing these sources is also proposed. Following the guideline, the mass transport coefficient is
shown as a key control factor of equilibrium energy loss and Coulombic efficiency (CE). Approaches are then
proposed to improve CE and system efficiency. The mass transport also controls pump rate optimization by
reducing equilibrium energy loss. An optimal electrode porosity design can further improve a battery’s system
efficiency based on an optimal porosity predicted by our model. The model also demonstrates distinct behaviors
and overestimation in system efficiency when reduced to a zero-dimensional model. With the model, the
guideline, and new insights, this work provides a reliable and efficient tool for the evaluation and optimization
of redox flow batteries.

1. Introduction energies from solar and wind power to existing electric grids [1–
6]. Among existing RFBs [6,7], the vanadium redox flow battery
Redox flow batteries (RFBs) represent an economically viable en- (VRFB) is the most mature and has been commercially constructed
ergy storage technology that can integrate intermittent renewable at megawatt scale [8,9]. Despite such progress, massive deployment

∗ Corresponding author.
E-mail address: yunxiang.chen@pnnl.gov (Y. Chen).

https://doi.org/10.1016/j.jpowsour.2021.230192
Received 22 January 2021; Received in revised form 13 May 2021; Accepted 20 June 2021
Available online 25 June 2021
0378-7753/© 2021 Elsevier B.V. All rights reserved.
Y. Chen et al.
of RFBs across the globe has not yet been achieved due to the high
costs of design, manufacture, and operation of battery systems [10–
12]. Though organic redox electrolytes are believed to significantly
reduce the costs [13–15], their chemical instability and low solubility
render their large-scale applications in the near term [15]. Therefore,
for given redox materials, optimizing the battery performance in terms
of voltage and system efficiency is the most effective approach for cost
reduction [16]. As the voltage of a single cell unit is the basis for the
stack- and system-scale optimization [6,17,18], developing a reliable
unit cell model is necessary for accurate prediction, evaluation, and
optimization of the performance of RFBs at cell, stack, and system
scales.
Performance at the cell scale is mainly determined by reaction
kinetics, mass transport, and pump consumption [6,16]. Specifically,
the reaction kinetics are affected by the reaction rate constant and
the distributions of current density and active species concentrations
at electrode interfaces. The mass transport is usually determined by
the relative importance of electrolyte advection and diffusion at the
electrode interface, which is further controlled by the local distribu-
tion of flow velocity and active species concentrations. The velocity
distribution also determines the pressure drop between the cell inlet
and outlet, which controls pump energy consumption. Due to the
important roles of the local distribution of flow, concentrations, and
current density, two-dimensional (2D) and three-dimensional (3D) nu-
merical models that solve the coupled conservation laws of mass,
charge, momentum, and energy with artificial or scanned electrode
microstructure are the most suitable tools for understanding and im-
proving cell performance [6,17,19]. For instance, the first 2D transient
model was introduced by [20] who studied the 2D distribution of
current density, concentrations, and electronic and ionic potentials
using a porous media assumption. Later, similar models were used
to study the effects of heat transfer [21], applied current density,
porosity, mass transfer [22], hydrogen [23] and oxygen [24] evo-
lution, cross-over and water transport [25], and parameter selection
on cell performance [26]. By solving the flow in an X-ray computed
tomography scanned electrode using a lattice Boltzmann method and
solving the concentration and charge transport using a finite volume
method, [27] introduced the first 3D pore-scale model for RFB and
studied the effects of flow rate, electrode microstructure, and inlet
state of charge (SoC) on cell performance [28]. Using a similar method
with artificial electrodes, [29] further studied the oxygen evolution
and the relationship between porosity and permeability, specific area,
and effective diffusivity. The results demonstrate the significant impact
of pore size and distribution on permeability, specific area, and gas
evolution.
Though 3D models are accurate for predicting flow and transport
processes, their scales are usually limited at millimeter scale due to
high computational costs [27,29], which questions the efficacy of using
these models to predict and optimize the cell performance at cell and
larger scales [30]. The 2D numerical models are less expensive than
the 3D models, however, their computational time still limits their ef-
fectiveness for cell-scale prediction and optimization [23]. Due to these
issues, the most commonly used numerical models for cell performance
prediction and optimization are zero-dimensional (0D) models that
assume the distributions of flow, concentration, and current density are
uniform within the electrode [31–33]. This assumption is usually valid
at low current density, high active species concentration, and high flow
rate [33]; however, it is questionable at low pump rate and the end of
discharging [34]. Such a limitation is attributed to the large concen-
tration gradient of active species at electrode interfaces at a low flow
rate, which affects both the mass transport coefficient and discharging
time [34], and therefore the cell performance. Besides, existing 0D
models usually manifest large arbitrariness in parameter calibration.
For example, [31] fitted a value of 420 m−1 for the specific area to
match the measured cell voltage. Such a value does not affect the
2
Journal of Power Sources 506 (2021) 230192
accuracy of the cell voltage, but significantly underestimates the pres-
sure drop [35,36], and therefore overestimates the system efficiency
when used for predicting cell performance. An improper selection of the
specific area also affects the local current density and thus changes the
relative importance of equilibrium potential and activation potential to
the cell voltage. Estimating the effects of mass transport coefficient on
cell voltage and performance is another source of arbitrariness. Though
the mass transfer coefficient can generally be estimated by empirical
formulas linking a Sherwood number to Reynolds number and Schmidt
number [16,29,37–42], the fitted coefficients and exponents vary a
lot, which could result in large uncertainty in cell voltage prediction,
especially at the end of discharge [41,43].
To resolve the above issues and maintain the accuracy as 2D and
3D models and the computational efficiency as 0D models, this work
integrates a 2D analytic solution to active species concentrations, a
new mass transport coefficient model, and a new porosity-specific
area relationship [34] to create a new unit cell voltage model (Sec-
tion 2). Such a model is then calibrated with cell voltage data from
two experiments performed at Pacific Northwest National Laboratory
(PNNL), a 2D porous media model [26] and an experiment reported
in the literature [31], to test its wide applicability under different
conditions (Section 3). The model’s calibration performance, evaluation
of sources of potential losses and energy losses, and suggestions for cell
performance optimization are included in Section 4.
2. Model equations
Existing cell voltage models assume uniform concentrations within
electrodes, which results in less accurate predictions of equilibrium,
activation, and concentration potentials that are affected by the con-
centration gradient at the electrode–electrolyte interface [31–33]. By
leveraging a new 2D analytical model for concentrations from our
previous work [34], this paper aims to derive an analytical unit cell
model that enables better predictions of these potentials.
2.1. Potentials
Previous studies show that the cell voltage (𝐸𝑐 ) of an aqueous RFB
can be represented by six components (Eq. (1)), including the formal
potential of redox couples (𝐸 0 ), chemical potentials of active species
𝑎 ), chemical potentials from water and proton (𝐸 ), activation po-
(𝐸𝑒𝑞
𝑝𝑤
tentials due to charge and mass transfer resistance (𝐸𝑎𝑐𝑡 ), concentration
potentials due to concentration gradients at electrode interface (𝐸𝑐𝑜𝑛 ),
and potential losses due to electron transport in current collectors and
electrodes and proton transport in the membrane (𝐸𝑜ℎ𝑚 ) [31,41,44–
46]. The summation of the first two terms is the equilibrium potential
attributed to vanadium ions, i.e., 𝐸𝑒𝑞 = 𝐸 0 + 𝐸𝑒𝑞
𝑎 , while the summation
of the first three terms is the open-circuit cell voltage, i.e., 𝐸𝑜𝑐𝑣 =
𝐸𝑒𝑞 + 𝐸𝑝𝑤 [31].
𝐸𝑐 = 𝐸 0 + 𝐸𝑒𝑞
𝑎
+ 𝐸𝑝𝑤 + 𝐸𝑎𝑐𝑡 + 𝐸𝑐𝑜𝑛 + 𝐸𝑜ℎ𝑚 (1)
For a vanadium flow battery, the formal potential is calculated by
the difference of formal potential of VO+ 2
/VO2+ (𝐸𝑃0 ) in the positive
3+ 2+ 0
electrode and that of V /V (𝐸𝑁 ) in the negative electrode, i.e., 𝐸 0 =
𝐸𝑃0 − 𝐸𝑁0 .
The chemical potentials of active species for a VRFB can be de-
termined by the chemical potential difference due to reactions of
VO+ 2
/VO2+ and V3+ /V2+ in the positive and negative electrodes, which
can be mathematically quantified by Eq. (2).
( 𝑐𝑤 ) ( 𝑐𝑤 )
𝑅𝑇 𝑅𝑇
𝑎
𝐸𝑒𝑞 = ln 5𝑤 − ln 3𝑤 (2)
𝐹 𝑐4 𝐹 𝑐2
where 𝑅, 𝑇 , and 𝐹 denote ideal gas constant, temperature, and Faraday
constant. 𝑐5𝑤 , 𝑐4𝑤 , 𝑐3𝑤 , and 𝑐2𝑤 represent concentrations of VO+
2
, VO2+ ,
3+ 2+
V , and V at the electrode surface (see Section 2.2).
Y. Chen et al. Journal of Power Sources 506 (2021) 230192

Fig. 1. A sketch of a unit flow battery cell. The cell voltage is measured as the voltage difference at the two red dots at current collector–electrode interfaces. c and s denote
microchannels and adjacent solids. 𝑐5𝑤𝑖 , 𝑐5𝑤 , and 𝑐5𝑐 denote the concentration of vanadium VO+2 at the wall of cell entrance, and at the wall and centerline of the cell outlet. The
solid black arrow lines denote charge and the dashed black arrows denote discharge.

As proton and water are generated or consumed in the positive by Eq. (7) [41]. The formulas for mass transfer rate (𝑘𝑚𝑁 and 𝑘𝑚𝑃 ) are
electrode, the resultant chemical potentials should be included in cell introduced in Section 2.2.
voltage and can be quantified by Eq. (3) with 𝑐𝐻𝑃 and 𝑐𝑤𝑃 denot-
|𝛥𝑐𝑁 | = |𝐼|∕(𝐹 𝑘𝑚𝑁 ); |𝛥𝑐𝑃 | = |𝐼|∕(𝐹 𝑘𝑚𝑃 ) (7)
ing the concentrations of proton and water in the positive electrode,
respectively [46]. The ohmic potentials are attributed to electron transport resis-
( 𝑐2 ) tances in current collectors and electrodes and proton transport in the
𝑅𝑇
𝐸𝑝𝑤 = ln 𝐻𝑃 (3) membrane, which can be estimated by Eq. (8) [31,46,47].
𝐹 𝑐𝑤𝑃
2𝐿𝑐 𝐿 2𝐿𝑒
The activation potentials are potential losses caused mainly by 𝐸𝑜ℎ𝑚 = 𝐼0 + 𝐼0 𝑚 + 𝐼0 (8)
charge transfer resistance, whose net contribution to the cell voltage 𝜎𝑐 𝜎𝑚 𝜖 3∕2 𝜎𝑒
can be quantified by Eq. (4). where 𝐼0 denotes a nominal current density, calculated by 𝐼0 = 𝐼𝑡 ∕(𝐵𝐻)
( ) ( ) during charging and 𝐼0 = −𝐼𝑡 ∕(𝐵𝐻) during discharging. 𝐵 and 𝐻
𝑅𝑇 𝐼 𝑅𝑇 −𝐼
𝐸𝑎𝑐𝑡 = sinh−1 √ − sinh−1 √ (4)
𝛼𝐹 𝛼𝐹 denote the width and height of the electrode (see Fig. 1). Symbols
2𝐹 𝑘𝑝𝑜𝑠 𝑐4𝑤 𝑐5𝑤 2𝐹 𝑘𝑛𝑒𝑔 𝑐2𝑤 𝑐3𝑤
𝐿𝑐 , 𝜎𝑐 , 𝐿𝑚 , 𝜎𝑚 , and 𝜎𝑒 represent current collector thickness, current
where 𝛼, 𝑘𝑝𝑜𝑠 , 𝑘𝑛𝑒𝑔 denote reaction transfer coefficient, standard reac- collector electronic conductivity, membrane thickness, membrane elec-
tion rate constant in positive electrode, and that in negative electrode, tronic conductivity, and electrode conductivity, respectively. Previous
respectively. 𝐼 is the local current density calculated by 𝐼 = 𝐼𝑡 ∕(𝑉𝑒 𝐴𝑠 ) work shows that 𝜎𝑚 = (0.5139𝜆 − 0.326) exp[1268 ∗ (1∕303 − 1∕𝑇 )] with
for charging and 𝐼 = −𝐼𝑡 ∕(𝑉𝑒 𝐴𝑠 ) for discharging [34]. Symbols 𝐼𝑡 , 𝜆 = 22 [48], while electrode electronic conductivity (𝜎𝑒 ) is provided by
𝑉𝑒 , and 𝐴𝑠 represent the applied current, the volume of positive or the manufacture (www.sglcarbon.com). See the values of parameters in
negative electrode, and the specific area of electrodes, respectively. For Table 1.
√
a given porosity 𝜖, the specific area is estimated as 𝐴𝑠 = 4𝛼𝐴 ( 𝜖 − 𝜖)∕𝑏𝑠
with 𝛼𝐴 and 𝑏𝑠 denoting a correction factor and average fiber size, 2.2. Concentrations
respectively [34]. The correction factor accounts for the effects of
simplifying a real electrode into multiple microchannels on specific To compute the cell voltage, this section derives solutions to the
area. A value of 1 for 𝛼𝐴 means no correction. concentrations and mass transfer rate as required in Section 2.1. It is
The concentration potentials are attributed to the concentration important to mention that the following equations are derived without
gradient at the electrode interface. As analytical solutions to bulk considering cross-over of active ions and side reactions, which assumes
concentrations of VO+ 2
(𝑐5𝑐 ), VO2+ (𝑐4𝑐 ), V3+ (𝑐3𝑐 ), and V2+ (𝑐2𝑐 ) inside indi- the total concentrations of vanadium ions in positive and negative are
vidual pores have been derived in our previous work (see Section 2.2), independent of time. With such an assumption, the concentrations of
the concentration potential can be estimated by Eqs. (5) and (6) for VO+ 2
, VO2+ , V3+ , and V2+ at electrode interface are given by Eqs. (9)
charging and discharging, respectively [41]. and (10) [34].
( |𝛥𝑐𝑁 | )( |𝛥𝑐𝑃 | ) [ ]
𝑐 𝑅𝑇 5 𝐼𝑃
𝐸𝑐𝑜𝑛 =− ln 1 − 𝑐 1− (5) 0
𝑐5𝑤 = 𝑐45 SoC + ( 𝑃
− 2𝛾)𝐼𝑐𝑑 ∕𝛽 + 2 𝑐𝑢 𝐻∕𝛽 ; 𝑐4𝑤 = 𝑐45
0
− 𝑐5𝑤 (9)
𝛼𝐹 𝑐3 𝑐4𝑐 16 𝑏
( |𝛥𝑐𝑁 | )( |𝛥𝑐𝑃 | ) [ 𝐼 𝑁 ]
𝑑 𝑅𝑇 5
𝐸𝑐𝑜𝑛 = ln 1 − 𝑐 1− (6) 0
𝑐2𝑤 = 𝑐23 SoC + ( 𝑁
− 2𝛾)𝐼𝑐𝑑 ∕𝛽 + 2 𝑐𝑢 𝐻∕𝛽 ; 𝑐3𝑤 = 𝑐23
0
− 𝑐2𝑤 (10)
𝛼𝐹 𝑐2 𝑐5𝑐 16 𝑏
0 and 𝑐 0 denote the total initial concentrations of active
where |𝛥𝑐𝑃 | and |𝛥𝑐𝑁 | are used to estimate the concentration difference where 𝑐45 23
at the interface. In general, such a difference is determined by the species in positive and negative electrode. SoC and 𝛾 represent the state
mass transfer rate near the electrode interface and can be calculated of charge and a constant accounting for the entrance effect. 𝑏 denotes an

3
Y. Chen et al. Journal of Power Sources 506 (2021) 230192

average pore size in the electrode, which is determined by 𝑏 = 4𝜖∕𝐴𝑠 if starting the discharging process. The discharging stage stops at time 𝑡𝑑
simplifying a real electrode as multiple microchannels [34]. 𝛽 is a fitted when one of the concentrations of ions reaches 0 (i.e., a limiting current
parameter to account for the effects of simplifying an actual electrode density scenario). It is necessary to mention that the ending SoC (SoC𝑒 )
into multiple channels [34] and 𝛽 = 1 means no correction. The none- and the waiting time 𝑡𝑤 need to be determined from experiments or a
dimensional parameters 𝐼𝑐𝑑 𝑃 = 𝐼𝑏∕(𝐹 𝑐 0 𝐷 ), 𝐼 𝑁 = 𝐼𝑏∕(𝐹 𝑐 0 𝐷 ), 𝐼 𝑃 = battery’s typical working conditions.
45 5 𝑐𝑑 23 2 𝑐𝑢
0 𝑢𝑃 ), 𝐼 𝑁 = 𝐼∕(𝐹 𝑐 0 𝑢𝑁 ) denote the relative importance of the
𝐼∕(𝐹 𝑐45 0 𝑐𝑢 23 0
driving current density to the diffusion and advection in controlling 3. Experiments and parameters
species concentrations in positive and negative electrodes. Symbols 𝐷5
and 𝐷2 represent diffusivities of VO+ 2
and V2+ , respectively. Symbols To test the efficacy of the proposed cell voltage model under various
𝑢𝑃0 and 𝑢𝑁0
are the average electrolyte velocity and can be calculated conditions, two experiments were performed at PNNL, a computational
by 𝑢𝑃0 = 𝜔𝑃 ∕(𝐵𝐿𝑒 𝜖) and 𝑢𝑁 0
= 𝜔 𝑁 ∕(𝐵𝐿 𝑒 𝜖) with the pump rate for fluid dynamics (CFD) model [26] and experiment data from existing
positive and negative electrode denoted by 𝜔𝑃 and 𝜔𝑁 (see details literature [31], were selected for validation. For convenience these
in [34]). Usually, the pump rates in positive and negative electrode are cases are denoted by A, B, C, and D, respectively. Case A uses graphite
identical and thus 𝜔 = 𝜔𝑃 = 𝜔𝑁 is used to represent the pump rates for felt electrodes and a Nafion® 115 cation exchange membrane with
convenience. vanadium mixed acid electrolyte (2 M VOSO4 + 5 M HCL). Case B uses
Similarly, the bulk concentrations of VO+ 2
, VO2+ , V3+ , and V2+ inside air-heated graphite felt electrodes and a Nafion® 112 cation exchange
individual pores can be determined as Eqs. (11) and (12) [34]. membrane; the electrolyte is 2 M VOSO4 + 5 M HCL plus a small
5 𝑃 0 𝑐 amount of acetic acid. Case C uses carbon felt electrodes and a Nafion®
0
𝑐5𝑐 = 𝑐5𝑤 − 𝐼 𝑐 ; 𝑐 = 𝑐45 − 𝑐5𝑐 (11) 114 cation exchange membrane with vanadium mixed electrolyte (1 ∼
16𝛽 𝑐𝑑 45 4
5 𝑁 0 𝑐 0
1.5 M vanadium + 4 M H2 SO4 ). Case D uses the same electrodes and
𝑐2𝑐 = 𝑐2𝑤 − 𝐼 𝑐 ; 𝑐 = 𝑐23 − 𝑐2𝑐 (12) electrolyte composition as case C though the amount of vanadium is 1
16𝛽 𝑐𝑑 23 3
∼ 1.6 M and the membrane is Nafion® 115. Details of cases C and D
For proton (𝑐𝐻𝑃 ) and water (𝑐𝑤𝑃 ) concentrations in the positive
can be found in [20,26], and [31].
electrode, we assume that their concentrations are uniform within the
To drive the present model, two types of parameters are required.
electrode [31]. With such an assumption, their solutions can be given
The first type can be determined from the battery sizes, operation
as Eqs. (13) and (14) (see derivations in Appendix).
conditions, and basic physical properties of electrode and electrolyte
0 (2 − 𝑛𝐻 )𝐼𝑡 [ (1 + 𝜖𝛿)𝜔𝑃 𝑡 (1 + 𝜖𝛿)𝜔𝑃 𝑡 ] (parameters without superscripts 𝑎 and 𝑏 in Table 1). The second
𝑐𝐻𝑃 = 𝑐𝐻𝑃 + + 1 − exp(− ) (13)
2
𝜔𝑃 (1 + 𝜖𝛿) 𝐹 𝑉𝑡 𝜖𝑉𝑒 type, including reaction rate constant in positive (𝑘𝑝𝑜𝑠 ) and negative
0 (1 + 𝑛𝑑 )𝐼𝑡 [ (1 + 𝜖𝛿)𝜔𝑃 𝑡 (1 + 𝜖𝛿)𝜔𝑃 𝑡 ] (𝑘𝑛𝑒𝑔 ) electrodes, mass transport coefficient (𝛽), and proton transport
𝑐𝑤𝑃 = 𝑐𝑤𝑃 − + 1 − exp(− ) (14)
2
𝜔𝑃 (1 + 𝜖𝛿) 𝐹 𝑉 𝜖𝑉𝑒 coefficient (𝑛𝐻 ), is difficult to measure in experiments and thus needs
𝑡
0 0 calibration (parameters with superscript 𝑎 in Table 1). The model and
where 𝑐𝐻𝑃 and 𝑐𝑤𝑃 denote the initial concentrations of proton and
parameters used for the 4 cases have been implemented in Matlab and
water in the positive electrode. 𝑛𝐻 is a fitted parameter to estimate
the code is available upon request.
proton flux through membrane. 𝑛𝑑 is the water drag coefficient. 𝛿 =
𝑉𝑒 ∕𝑉𝑡 is the ratio of electrode volume (𝑉𝑒 ) to the tank volume (𝑉𝑡 ).
4. Results and discussion
Regarding the mass transfer rate, some work suggested it is mainly
determined by average flow velocity [16,29,37,38,40–42], others argue
4.1. Model performance
that it is affected by both flow velocity and pore size [39]. However, our
previous work suggests flow velocity, diffusion, pore size, and electrode
In order to examine the model’s capability in predicting the charg-
height all affect the mass transfer rate for a realistic flow battery [34].
ing and discharging voltage curve, Fig. 2 shows a comparison of the cell
To evaluate the effect of mass transport rate on cell voltage, this work
voltage curves from our model (red lines) and those from experiments
calculates the mass transfer rate as 𝑘𝑚𝑃 = 𝛽𝑘𝑇𝑚𝑃 and 𝑘𝑚𝑁 = 𝛽𝑘𝑇𝑚𝑁 for
(black diamonds) and CFD modeling (black squares). The results show
its value in the positive and negative electrode. The formula of 𝑘𝑇𝑚𝑃
that the average difference in cell voltage over all cases is less than
and 𝑘𝑇𝑚𝑁 denote a theoretically derived mass transport rate as shown
0.014 V. This proves that our model is able to accurately reproduce
in Eqs. (15) and (16) [34].
the cell voltage curve with different electrode, membrane, electrolyte,
𝑢0
𝑘𝑇𝑚𝑃 = (15) and operation conditions.
(5∕16 − 2𝛾)𝑃 𝑒𝑃 + 2𝐻∕𝑏 − 4∕(3𝑃 𝑒𝑃 ) More importantly, the fitted parameters for the four distinct cases
𝑢0
𝑘𝑇𝑚𝑁 = (16) are in consistent ranges. For instance, the calculated specific area
(5∕16 − 2𝛾)𝑃 𝑒𝑁 + 2𝐻∕𝑏 − 4∕(3𝑃 𝑒𝑁 )
is 57.8 ∼ 59.4 mm−1 for all cases (𝐴𝑏𝑠 in Table 1), which falls in
Here 𝑢0 = 𝑢𝑃0 = 𝑢𝑁 0
= 𝜔∕(𝐵𝐿𝑒 𝜖), 𝑃 𝑒𝑃 = 𝑢0 𝑏∕𝐷5 , and 𝑃 𝑒𝑁 = the commonly measured range of electrodes [7]. The mass transport
𝑢0 𝑏∕𝐷2 . The parameter 𝛽 is a fitted parameter that quantifies the effects coefficients fall between 0.69 ∼ 1.22 (𝛽 𝑎 in Table 1), which means
of simplifying an actual electrode to multiple channels. It is worth that estimating the mass transport coefficient using Eqs. (15) and (16)
mentioning that the mass transport formula provided by [34] does not is reliable for real electrodes even though these formulas are derived
require fitted parameters; however, it can still predict similar values to from a simplified condition. For the reaction rate constants, the fitted
those by [41] and [40] for flow-through cells with a velocity range 0 parameters are around a 2 ∼ 5 times difference for cases A, C, and D.
∼ 5 cm/s. The differences between B and A (ca. 6 ∼ 22 times) are higher, but
Noting that the concentrations for vanadium ions (Eqs. (9) through still smaller than the diverse ranges from observations [50]. The ratio
(12)) are functions of SoC, while concentrations of proton and water of the reaction rate constants between positive and negative electrodes
(Eqs. (13) and (14)) are dependent of time (𝑡), Eq. (17) links SoC to (ca. 6 ∼ 18) also falls in the range (ca. 0.24 ∼ 44) of observations [50].
time based on charge and mass conservation [31]. Though the proton transfer coefficient is treated as a fitted parameter,
𝐼𝑡 𝐼𝑡 it has little effect on the overall accuracy of cell voltage and battery
SoC𝑐 = SoC𝑠 + 𝑡; SoC𝑑 = SoC𝑒 − (𝑡 − 𝑡𝑒 − 𝑡𝑤 ) (17) performance because the proton-water potential accounts for less than
0
𝐹 𝑉𝑡 𝑐23 0
𝐹 𝑉𝑡 𝑐23
1% of the total energy losses. Details are discussed in Section 4.2.
where SoC𝑐 and SoC𝑑 denote the SoC for charging and discharging. In addition, the fitted parameters agree with the commonly ac-
The charging stage starts at SoC𝑠 and stops at SoC𝑒 at the time 𝑡𝑒 = cepted understanding of how different physical and chemical treat-
0 (SoC − SoC )∕𝐼 . The battery then waits for time 𝑡
𝐹 𝑉𝑡 𝑐23 𝑒 𝑠 𝑡 𝑤 before ments affect the battery properties. For example, with a small amount

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Y. Chen et al. Journal of Power Sources 506 (2021) 230192

Table 1
Parameters used for each case.
Symbol Meaning Unit A B C D
𝑇 Temperature K 298 298 300 297
𝐻 Cell height m 0.05 0.05 0.1 0.1
𝐵 Cell width m 0.02 0.02 0.1 0.1
𝐿𝑐 Collector thickness m 0.015 0.015 0.006 0.005
𝐿𝑚 Membrane thickness m 1.27e−4 5.08e−5 1.8e−4 1.25e−4
𝜖 Porosity 1 0.67 0.67 0.68 0.67
𝛼𝐴 Specific area coefficient 1 1 1 1 1
𝜔 Pump rate m3 s−1 3.33e−7 3.33e−7 1.00e−6 1.00e−6
𝐼𝑡 Applied current A 0.75 0.5 10 10
𝐼0 Nominal current density A m−2 750 500 1000 1000
𝑐20 Initial concentration of V2 mol m−3 0 0 27 60
0
𝑐23 Total concentration of V2/V3 mol m−3 2000 2000 1080 1200
𝑐50 Initial concentration of V5 mol m−3 0 0 27 60
0
𝑐45 Total concentration of V4/V5 mol m−3 2000 2000 1080 1200
0
𝑐𝐻𝑃 Positive initial H+ concentration mol m−3 5000 5000 1200 4200
0
𝑐𝐻𝑁 Negative initial H+ concentration mol m−3 3000 3000 1200 4200
0
𝑐𝑊 𝑃
Positive initial H2 O concentration mol m−3 47530 47530 4200 42300
𝑉𝑡 Tank volume m3 4.5e−5 4.0e−5 2.5e−4 2.232e−4
SoC𝑠 Charging start SoC 1 0 0 0.025 0.05
SoC𝑒 Charging end SoC 1 0.8 0.95𝑐 0.8015 0.7934
𝑘𝑎𝑝𝑜𝑠 Positive rate constant m s−1 9.0e−8 2.0e−6 3.2e−8 1.65e−8
𝑘𝑎𝑛𝑒𝑔 Negative rate constant m s−1 5.0e−9 3.2e−8 2.5e−9 3.0e−9
𝛽𝑎 Mass transport coefficient 1 1.1 1 1.22 0.69
𝑛𝑎𝐻 Proton transport coefficient 1 1 2 3 5
𝑘𝑏𝑚𝑃 Positive mass transport rate m s−1 2.85e−6 2.60e−6 1.03e−6 5.67e−7
𝑘𝑏𝑚𝑁 Negative mass transport rate m s−1 2.73e−6 2.48e−6 1.01e−6 5.59e−7
𝐴𝑏𝑠 Specific area mm−1 59.4 59.4 57.8 59.4
𝑏𝑏 Pore size μm 45.1 45.1 47.0 45.1

Values of superscript 𝑎 are fitted parameters; values with superscript 𝑏 are calculated from 𝛽 𝑎 and 𝛼𝐴 ; and the value with superscript 𝑐 is 0.8
for case B when calculating data in Tables 2 and 3. Other symbols used but not listed include: fiber size 𝑏𝑠 = 10 μm [7,31], cell thickness
𝐿𝑒 = 4 mm, conductivity of current collector (𝜎𝑐 = 91 000 S m−1 ) and electrode (𝜎𝑒 = 333 S m−1 ), pump efficiency 𝛼𝑃 = 0.8 [36], formal
0
potentials in positive and negative electrode 𝐸𝑃0 = 1.004 V, 𝐸𝑁 = −0.255 V [20], ideal gas constant 𝑅 = 8.314 J mol−1 K−1 , Faraday constant
𝐹 = 96485.33 C mol−1 , reaction transfer coefficient 𝛼 = 0.5, entrance effect constant 𝛾 = 0.033 [49], water drag coefficient 𝑛𝑑 = 2.5 [46],
diffusivities of V2/V3 (𝐷2 = 𝐷3 = 2.4e−10 m2 s−1 ), V4/V5 (𝐷4 = 𝐷5 = 3.9e−10 m2 s−1 ), water (𝐷𝑤 = 2.3e−9 m2 s−1 ), and proton (𝐷𝐻 =
1.4e−9 m2 s−1 ), water viscosity 𝜇 = 1e-3 Pa s [20], Kozeny–Carman constant 𝐾𝑐 = 5.55 [20].

of acetic acid added to the electrolyte, case B shows larger reaction rate
constants compared to those in case A. Further, the usage of different
acid in cases A/B and cases C/D results in larger differences in the
reaction rate constants which are affected by electrolyte composition.
Due to these agreements, the present model can likely provide clues for
better electrolyte molecule synthesis and composition design.
4.2. Sources of cell voltage and energy losses
In order to understand the relative contribution of each potential
component to the cell voltage as discussed in Section 2.1, Fig. 3 shows
how individual components, such as equilibrium potential, activation
potential, concentration potential, ohmic losses, and proton-related
potential, vary with time during charging and discharging. The results
show that the equilibrium potential (solid green lines) is the biggest
contribution of the total cell voltage (red lines), and it shows approx-
imately a symmetric behavior during charging and discharging. The
proton and water potential (magenta lines) is the second important
contribution for cases A and B, while activation potential (solid blue
lines) stands for the second place for cases C and D. The concentration
potential (solid black lines) is small during charging and most of the
time during discharging, but becomes highly important at the end of
discharging. The ohmic potential (cyan lines) is relatively small com-
pared to equilibrium and activation potentials for the current densities
(500 ∼ 1000 A/m2 ) considered here. Though not shown in Fig. 3, the
open-circuit cell voltage (𝐸𝑜𝑐𝑣 = 𝐸𝑒𝑞 + 𝐸𝑝𝑤 ) has a similar trend as the
equilibrium potential. However, its magnitude is always lower than cell
voltage (𝐸𝑐 ) during charging and higher than that during discharging.
The energy consumed or generated from individual potentials is
another way to understand their relative importance. Here we calculate
the energy from each component by Eq. (18).
𝑡𝑏
𝑒𝑥 = 𝑖 ⋅ 𝐸𝑥 𝑑𝑡
∫𝑡𝑎
𝐸𝑥 denotes 𝐸𝑒𝑞 , 𝐸𝑎𝑐𝑡 , 𝐸𝑐𝑜𝑛 , 𝐸𝑜ℎ𝑚 , and 𝐸𝑝𝑤 ; and the 𝑒𝑥 denotes 𝑒𝑒𝑞 , 𝑒𝑎𝑐𝑡 ,
𝑒𝑐𝑜𝑛 , 𝑒𝑜ℎ𝑚 , and 𝑒𝑝𝑤 , respectively. During charging, 𝑡𝑎 = 0, 𝑡𝑏 = 𝑡𝑒 , and
𝑖 = 𝐼𝑡 ; during discharging, 𝑡𝑎 = 𝑡𝑒 +𝑡𝑤 , 𝑡𝑏 = 𝑡𝑑 , and 𝑖 = −𝐼𝑡 (see definition
of 𝑡𝑒 and 𝑡𝑑 in Section 2.2). The energy consumed by pump during
charging and discharging is 𝑒𝑃 = 2𝑃𝑤 (𝑡𝑏 − 𝑡𝑎 ) with the pump power and
electrode permeability calculated as 𝑃𝑤 = 𝜔2 𝜇𝐻∕(𝐿𝑒 𝐵𝐾𝛼𝑃 ) [36] and
𝑏2 𝜖 3
𝐾 = 16𝐾 𝑠(1−𝜖)2 [35], respectively. Therefore, the total energy consumed
𝑐
(positive value) or generated (negative value) in the battery system is
∑
𝑒𝑠 = 𝑒𝑃 + 𝑒𝑥 for charging and discharging. Table 2 lists the value
of duration time (𝑡𝑏 − 𝑡𝑎 ), 𝑒𝑥 , 𝑒𝑃 , and 𝑒𝑠 for charge, discharge, and full
cycle for various cases. Though these values are determined from the
model in the present work, most of them are measurable and could
be used to verify the model’s predictive capability. For instance, by
timing the charge/discharge time and measuring electronic resistance
from electrodes, current collectors, and membrane under a constant
applied current, the ohmic energy losses can be estimated. Meanwhile,
a measurement of the time series of open-circuit potential can ap-
proximately determine the energy losses associated with equilibrium
potential considering that proton energy loss is negligible. Further,
measurements of the energy provided or consumed by external power
source, load device, and pumps can determine the system energy loss.
Nevertheless, measurements of activation and concentration energy
losses are still challenging.
The cases A to D in Table 2 show that the net (full cycle) energy
loss due to equilibrium potentials is much smaller than that due to
activation loss even though their absolute values are the highest during
charging and discharging. We argue that such a low net energy loss
from equilibrium potential is due to the symmetric behavior of the
equilibrium potential curve. The ratio of discharging time to charging
time, equivalent to the Coulombic efficiency (CE) for a constant current
density, is a proper parameter to quantify the symmetric behavior. To
(18) further understand the role of a CE, Table 3 lists the relative ratio of

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Y. Chen et al. Journal of Power Sources 506 (2021) 230192

Fig. 2. A comparison of cell voltage from the present model with those obtained from PNNL experiments (A and B), CFD modeling (C), and experiment reported in the literature
(D). Parameters used in each case are listed in Table 1. More details of C and D can be found in [20,26], and [31].

Table 2
Energy consumption and generation from individual components.
No. 𝛽 𝐴𝑠 Type Time 𝑒𝑒𝑞 𝑒𝑎𝑐𝑡 𝑒𝑐𝑜𝑛 𝑒𝑜ℎ𝑚 𝑒𝑝𝑤 𝑒𝑃 𝑒𝑠
Unit h kJ kJ kJ kJ kJ kJ kJ
Charge 2.57 8.54 0.83 0.01 0.29 1.18 0.65 11.50
A 1.1 59.4 Discharge 2.54 −8.41 0.82 0.03 0.29 −1.16 0.64 −7.80
Full cycle 5.11 0.13 1.65 0.04 0.58 0.02 1.28 3.70
Charge 3.43 7.59 0.14 0.01 0.15 1.00 0.86 9.75
B 1.0 59.4 Discharge 3.40 −7.50 0.14 0.02 0.15 −0.99 0.85 −7.34
Full cycle 6.83 0.09 0.27 0.03 0.30 0.01 1.71 2.41
Charge 0.56 25.21 5.05 0.21 1.45 2.77 0.46 35.15
C 1.22 57.8 Discharge 0.52 −23.15 4.72 0.42 1.35 −2.62 0.42 −18.84
Full cycle 1.08 2.06 9.78 0.63 2.80 0.15 0.88 16.30
Charge 0.53 24.12 4.86 0.35 1.08 2.54 0.48 33.34
D 0.69 59.4 Discharge 0.48 −21.20 4.38 0.57 0.97 −2.32 0.43 −17.18
Full cycle 1.01 2.92 9.24 0.92 2.05 0.22 0.91 16.25
Charge 0.53 24.12 4.86 0.35 1.08 2.54 0.48 33.43
D1 1.0 59.4 Discharge 0.48 −21.20 4.38 0.57 0.97 −2.32 0.43 −17.18
Full cycle 1.01 2.92 9.24 0.92 2.05 0.22 0.91 16.25
Charge 0.53 24.02 4.87 0.22 1.08 2.54 0.48 33.20
D2 2.0 59.4 Discharge 0.51 −22.45 4.67 0.44 1.02 −2.48 0.46 −18.32
Full cycle 1.04 1.57 9.54 0.66 2.10 0.07 0.94 14.88
Charge 0.53 23.90 4.88 0.10 1.08 2.54 0.48 32.98
D3 5.0 59.4 Discharge 0.53 −23.64 4.96 0.23 1.08 −2.62 0.48 −19.52
Full cycle 1.07 0.26 9.84 0.33 2.16 −0.08 0.97 13.46

Unit of 𝐴𝑠 is 1/mm.

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Y. Chen et al. Journal of Power Sources 506 (2021) 230192

Fig. 3. The variations of total cell voltage (𝐸𝑐 ), equilibrium potential (𝐸𝑒𝑞 ), activation potential (𝐸𝑎𝑐𝑡 ), concentration potential (𝐸𝑐𝑜𝑛 ), ohmic potential (𝐸𝑜ℎ𝑚 ), and proton and water
potential (𝐸𝑝𝑤 ), with respect to time for cases A to D.

Table 3
Relative contribution of individual components to total energy loss.
No. 𝛽 𝐴𝑠 𝑒𝑒𝑞 ∕𝑒𝐿 𝑒𝑎𝑐𝑡 ∕𝑒𝐿 𝑒𝑐𝑜𝑛 ∕𝑒𝐿 𝑒𝑜ℎ𝑚 ∕𝑒𝐿 𝑒𝑝𝑤 ∕𝑒𝐿 𝑒𝑃 ∕𝑒𝐿 CE EE SE
A 1.1 59.4 0.04 0.45 0.01 0.16 0.00 0.35 0.99 0.78 0.68
B 1.0 59.4 0.04 0.11 0.01 0.13 0.00 0.71 0.99 0.92 0.75
C 1.22 57.8 0.13 0.60 0.04 0.17 0.01 0.05 0.93 0.56 0.54
D 0.69 59.4 0.18 0.57 0.06 0.13 0.01 0.06 0.90 0.53 0.51
D1 1.0 59.4 0.11 0.64 0.04 0.14 0.00 0.06 0.95 0.57 0.55
D2 2.0 59.4 0.02 0.73 0.02 0.16 −0.01 0.07 1.00 0.62 0.59
D3 5.0 59.4 0.01 0.75 0.01 0.17 −0.01 0.07 1.00 0.63 0.60

Unit of 𝐴𝑠 is 1/mm.

each energy loss relative to the total energy loss in a charge–discharge
cycle. The results of cases A to D in Table 3 show that the CE decreases
from 0.99 to 0.90 with the value of 𝑒𝑒𝑞 ∕𝑒𝐿 increasing from 4% to 18%.
This result together with the equilibrium potential curves (solid green
lines) in Fig. 3 means that, with increasingly obvious asymmetry from
cases A to D, the CE decreases and the net energy loss from equilibrium
potential increases. Though the net equilibrium potential is non-zero,
it is necessary to mention that such an energy loss is not caused by
the equilibrium potential itself, but attributed to the concentration
gradients within the electrode. The reason for a lower CE in cases C
and D will be further discussed in Section 4.3.
Though the proton and water potential ranks second or third in
cell voltage, its contribution to the total energy loss is negligible (see
𝑒𝑝𝑤 ∕𝑒𝐿 in Table 3 cases A to D) due to a good symmetry in its potential
curve and a small magnitude compared to the equilibrium potential
(magenta lines in Fig. 3). In contrast, the activation potential ranks

7
Y. Chen et al.
second or third among all potentials, its contribution to the net energy
loss is up to 45% ∼ 60% (see 𝑒𝑎𝑐𝑡 ∕𝑒𝐿 in Table 3 of A, C, and D). Such a
dominant contribution is attributed to the anti-symmetric behavior in
its potential curve and its moderate high magnitude compared to other
potential components. Though the activation energy loss dominates the
total energy losses in cases A, C, and D, case B is dominated by pump
energy consumption (see 𝑒𝑃 in Table 2 and 𝑒𝑃 ∕𝑒𝐿 in Table 3). For the
concentration and ohmic potentials, though their values are relatively
smaller compared to other potentials during charging and most of the
time during discharging, they together can contribute to 14% ∼ 21%
of the total energy losses.
Based on the above results and discussion, we propose a guideline
to identify the key sources of energy losses from a cell voltage curve
as follows. First, a CE value less than 0.93 (a battery similar to cases C
and D) suggests the energy loss associated with concentration gradients
may be important and optimization should be conducted to improve
the CE and thus reduce the overall energy loss. Second, if CE is already
close to 1 (a battery similar to A and B), the energy loss due to pump
consumption should be examined and pump optimization should be
conducted if the pump loss is important or if the system efficiency (SE)
is much lower than the energy efficiency (EE). Finally, if both a high
CE and low pump consumption are confirmed, optimization of reaction
kinetics should be improved in order to reduce the contribution of
activation loss. Optimization of ohmic losses is the final option if
reducing electrode electronic resistance and membrane thickness is
possible. Sections 4.3 to 4.5 further discuss potential approaches to
optimize energy losses from equilibrium potential, pump consumption,
and activation potential using our model.
It is necessary to mention that the above guidelines are proposed
based on a battery operation perspective. Such a viewpoint emphasizes
that the overall battery performance depends on both operation condi-
tions and material properties. For given battery design and materials,
optimization for operation conditions to improve CE and minimize
pump consumption is relatively easier than changing key material prop-
erties such as reaction rate constant and electronic resistance. However,
if the energy losses associated with material properties dominate the
overall energy losses, the order of optimization should be changed
accordingly. For example, optimization for ohmic losses should be the
priority at high current density because ohmic losses are shown as
dominant loss [51].
4.3. Cell performance optimization: mass transport
As mentioned in Section 4.2, a lower CE means a higher asymmetry
in the equilibrium potential, which results in a higher energy loss due
to the high magnitude of equilibrium potential. Therefore, the main
approach to reduce the equilibrium potential energy is to increase the
CE. Here we further argue that CE is controlled by the concentration
gradients along flow direction and the normal direction of electrode–
electrolyte interface. By definition, the CE is the ratio of discharging
time to charging time for a constant current density. For a given
start and end charging SoC (i.e., SoC𝑠 and SoC𝑒 ), the charging time
is determined as 𝑡𝑐 = 𝐹 𝑉𝑡 𝑐230 (SoC - SoC )/𝐼 , while the discharging
𝑒 𝑠 𝑡 loss is mainly attributed to the increased CE (blue solid line), which
time is 𝑡𝑑𝑐 = 𝐹 𝑉𝑡 𝑐230 (SoC - SoC∗ )/𝐼 . Here SoC∗ is the minimum
𝑒 𝑠 𝑡 𝑠
SoC, which is calculated as SoC∗𝑠 = max[SoC𝑠 , SoC2𝑚 , SoC5𝑚 ] with SoC2𝑚
and SoC5𝑚 denoting the SoC that makes 𝑐2𝑤 = 0 and 𝑐5𝑤 = 0 during
discharge, respectively. According to Eqs. (9) and (10), SoC2𝑚 and SoC5𝑚
are further limited by the mass transport coefficient 𝛽. Therefore, the
CE is determined by the mass transport coefficient. Though this work
does not consider cross-over and side reactions, it is necessary to
mention that these processes affect the total vanadium concentrations,
and thus the charge/discharge time and CE. With such a perspective,
the calibrated coefficient 𝛽 represents the combined effects from mass
transport, cross-over, and side-reactions.
As case D (Table 3) has the lowest CE and highest energy loss from
equilibrium potential, three extra cases, named D1, D2, and D3, with
8
Journal of Power Sources 506 (2021) 230192
different mass transport coefficients are designed to understand how
the mass transport coefficient changes CE and cell performance. Fig. 4
illustrates how the cell voltage curve changes with SoC and time at
four mass transport coefficients based on case D. The results show that
the minimum discharge SoC shifts from around 0.13 to 0.05 when
𝛽 increases from 0.69 to 5, and the end discharging time increases
from around 64 min to 67 min. With such a change, it was observed
that the CE increases from 0.90 to 1.0, the equilibrium energy loss
decreases from 2.92 kJ to 0.26 kJ, and the concentration energy loss
decreases from 0.92 kJ to 0.33 kJ, while ohmic- and proton-related
energy losses have little changes (see full cycle of cases D and D1 to D3
in Table 2). These changes also increase the SE from 51% to 60% (see
SE in Table 3). Though increasing the mass transport coefficient reduces
the energy loss from equilibrium and concentration potentials, the
results also show that increasing 𝛽 from 2.0 to 5.0 does not significantly
improve the energy loss and SE. Therefore, a good guideline for mass
transport optimization is trying to increase the mass transport but not
too much.
Though it is straightforward to increase the mass transport coef-
ficient using our model, obtaining a better flow battery design such
that the mass transport coefficient is higher is another story. As the
improvement of energy losses due to increased mass transport is mainly
attributed to improved CE, increasing 𝛽 is equivalent to decreasing
𝑃 , 𝐼 𝑃 𝐻∕𝑏, 𝐼 𝑁 , and 𝐼 𝑁 𝐻∕𝑏 according to Eqs. (9) to (12). Therefore,
𝐼𝑐𝑑
𝑐𝑢 𝑐𝑑 𝑐𝑢
decreasing the local current density and average pore size and/or
increasing total active species concentration, active species diffusivity
and pump rate can likely improve the mass transport rate. Our model
can act as a tool to design how these parameters should change in order
to achieve a desired cell performance.
4.4. Cell performance optimization: pump rate
As the pump energy occupies 71% of the total energy loss for case B
(Table 3), pump optimization is the most effective approach to improve
the cell performance of B. The pump optimization usually involves
changing pump rate 𝜔. A higher pump rate means higher pump energy
consumption because it is proportional to 𝜔2 , while a higher pump rate
also means a faster mass transport, which results in higher CE and lower
energy losses from equilibrium potential and concentration potential.
Pump optimization is designed to identify the pump rate that minimizes
the total energy losses and thus the maximum SE.
Using the parameters of case B, Fig. 5 shows the absolute (a) and
relative (b) energy losses from individual components with a pump
rate varying between 0 and 20 mL/min. The results show that the
SE peaks at around 7 mL/min with a value of around 87%, which is
12% higher than that in case B where the pump rate is 20 mL/min
(Fig. 5b). Fig. 5a further shows that the maximum SE is reached
when the total energy loss, a summation of total cell energy loss 𝑒𝑐
(blue diamond line) and pump energy consumption 𝑒𝑃 (cyan line),
reaches the trough. The trough is mainly attributed to the reduced
energy losses from the equilibrium potential (blue solid line), although
energy losses from concentration and proton potentials also contribute
to it. Meanwhile, Fig. 5b suggests the reduced equilibrium energy
significantly reduces the percentage of equilibrium potential loss in the
total energy losses. As the CE signifies the effect of mass transport,
the above analyses suggest it is the improved mass transport due to
increased pump rate that improves the cell performance.
However, with increasing pump rate, the improvement of cell per-
formance due to improved mass transport becomes less important as the
pump energy consumption gradually dominates the overall energy loss
(see cyan lines in Fig. 5a–b). This suggests that a pump optimization is
especially useful when the mass transport coefficient is low like case D
(see calculated mass transport rate 𝑘𝑏𝑚𝑃 and 𝑘𝑏𝑚𝑁 in Table 1), which is
equivalent to a scenario of low CE or low pump rate. This conclusion
can be demonstrated by Fig. 5b where the SE increases from 75% to
87% with the pump rate increasing from 1 mL/min to 7 mL/min.
Y. Chen et al. Journal of Power Sources 506 (2021) 230192

Fig. 4. The variations of cell voltage with respect to SoC (a) and time (b) at four mass transport coefficients (𝛽). Parameters used for 1.0, 2.0, and 5.0 cases are identical to those
used in 0.69 case (Table 1 case D) except for the value of 𝛽.

Fig. 5. The variations of absolute and relative energy losses predicted by the present model for case B at different pump rates (a, b), the present model for case A at different
porosities (c, d), and a 0D model for case B at different pump rates (e, f). 𝑒𝑥 , 𝑒𝑐 , and 𝑒𝐿 denote six energy loss sources, total cell energy loss, and total system energy loss,
respectively.

4.5. Cell performance optimization: activation loss and electrode structure
When energy losses from both equilibrium potential and pump
consumption have been optimized to a low level, like case A in Table 3,
reducing the energy loss from activation potential becomes important.
The most straightforward approach to reduce the activation energy loss
is to develop new active materials and electrolyte to make the reaction
rate constants higher. Though developing a new active material is time
consuming, changing the composition of electrolyte is feasible and
could achieve higher reaction rate constants as demonstrated in case
B when compared to case A (see rate constants in Table 1).

9
Y. Chen et al.
For a given active material and electrolyte composition, adjusting
the electrode structure properties, e.g., porosity and specific area, could
also improve the cell performance. However, such an improvement
is not straightforward due to three competing processes. Specifically,
increasing the specific area reduces the local current density and thus
reduces the activation energy loss. However, a higher specific area usu-
ally means smaller porosity which results in higher pressure drop [29,
35,36,52] and ohmic potential [31]. Therefore, an optimization of
electrode porosity or specific area is required to minimize total energy
losses. Considering
√ that the specific area is linked to porosity through
𝐴𝑠 = 4( 𝜖 − 𝜖)∕𝑏𝑠 [34], we only study how porosity affects the cell
voltage and overall performance. It is worth mentioning that the above
relationship is similar to 𝐴𝑠 = 4(1−𝜖)∕𝑏𝑠 [52] when the porosity is close
to 1 and its applicability for real electrodes has been demonstrated by
a pore-scale study [29].
Following the above formula, Fig. 5c shows that the cell voltage
increases with increasing porosity during charge, while decreasing with
porosity during discharge. This is consistent with the results from a
2D numerical model [20]. In addition, it shows little change to the
cell voltage when increasing the porosity from 0.5 to 0.67, but varies
around 0.05 V when the porosity increases from 0.8 to 0.9. This
suggests that the porosity affects cell voltage in a non-linear manner
and such a non-linearity is likely attributed to the competing effects of
porosity on activation potential and ohmic potential.
To further understand the role of porosity in changing cell perfor-
mance, Fig. 5d shows the variations of energy loss components (left
axis) and battery inefficiencies (CE and SE in right axis) with respect
to porosity. As reducing the activation energy loss is the optimization
goal, we analyze the reversed 𝑥-axis, i.e., from 0.9 to 0.5. The result
shows that the activation energy loss (green line) is decreased when
decreasing the porosity. Meanwhile, both pump consumption (cyan
line) and ohmic energy loss (black line) increase. Due to these three
competing processes, the overall battery energy loss (red line) and the
SE (dashed blue line) reach their extrema at an optimal porosity of
0.8. It is quite clear that the improvement of the battery performance
is mainly achieved by reducing the activation energy loss through
increasing the specific area when the electrode porosity is higher than
the optimal porosity. By contrast, the battery performance could be im-
proved through reducing the pump consumption and ohmic energy loss
by increasing the electrode porosity when it is lower than the optimal
value. As the optimal porosity determines the strategy of improving the
battery performance, the present model, which can estimates its value,
is of great practical worth for better electrode structure design.
4.6. Comparison with a 0D cell voltage model
As 0D modeling has been widely used to predict the cell voltage
and evaluate cell performance [31,46], we evaluate the difference
between the present model and a 0D model. A 0D model assumes that
the concentrations of active species are uniform everywhere, which
is equivalent to set 𝛽 = +∞ in the present model. Fig. 5e–f shows
the absolute and relative contribution of each energy loss by setting
𝛽 = 1010 for case B. The results show that the activation and ohmic
energy losses do not change with pump rate, and energy losses from
equilibrium, concentration, and proton potentials are almost 0. There-
fore, an optimized pump rate is not observed in a 0D model compared
to what is observed in a 2D model (Fig. 5a–b). Such a difference can
be explained as follows: (a) the uniform distributions of concentrations
mean that the equilibrium potential depends only on SoC, which results
in a fully symmetric potential curve during a charge–discharge cycle;
(b) the uniform distributions of concentrations also mean that the
charging time equals the discharging time, which means CE = 1; (c) the
uniform distributions of concentrations mean that the concentrations
at the electrode interface and in the bulk are identical, which means
concentration loss is zero; and (d) as all concentrations depend only
on SoC, the activation potential only changes with SoC but not with
10
Journal of Power Sources 506 (2021) 230192
the pump rate. For these reasons, a uniform concentration distribution
used by the 0D model results in very different energy losses, CE, and SE
features compared to those from a 2D model which considers the con-
centration gradients along flow direction and at electrolyte–electrode
interface.
In addition, due to the inability to predict the equilibrium energy
loss, the 0D model significantly underestimates the overall energy loss
at low flow rate, which results in significant overestimation of the SE
at low flow rate. For example, the 0D model predicts the total energy
loss and the SE at a flow rate 1 mL/min as around 0.6 kJ and 93%
(Fig. 5e,f), while the present model gives values as 2.3 kJ and 75%
(Fig. 5a,b). With the increasing of the flow rate, the 0D model tends to
give similar prediction as the present model.
5. Conclusions
This work proposed an analytical model for evaluating cell voltage
and battery performance based on a 2D analytical solution to concen-
trations for RFBs. Such a model demonstrates a good agreement of
the cell voltage with experimental and CFD modeling data and the
calibrated model parameters are consistent in various conditions of
electrode structure, electrolyte composition, and operation conditions.
With the validated results, the equilibrium, activation, and pro-
ton/water potentials are identified as the key components of cell volt-
age, while the activation energy loss, equilibrium energy loss, and
pump energy consumption are identified as the dominant energy losses
of the battery system. A guideline of optimizing the key energy losses
is proposed. Further analyses show that the mass transport process
controls the CE and the energy loss from equilibrium potential. A pump
rate optimization can improve the SE of the cell through improving the
mass transport, increasing the CE, and significantly reducing energy
loss from equilibrium potential. Further improvement of cell perfor-
mance can be achieved by using either new active species/electrolyte
composition or better electrode structure design. Such a battery de-
sign depends on the relative magnitude of the electrode porosity to
an optimal porosity obtained from the present model. Specifically,
increasing the specific area is recommended if the electrode porosity
is higher than the optimal porosity, otherwise increasing the porosity
is a better option. The comparison of the present model with its 0D
version demonstrates a very different prediction of the energy losses
when a uniform concentration assumption is invoked and a significant
overestimation of the SE is observed using a 0D model.
Based on the accuracy of the present model, the insights of sources
of energy losses, and the guideline for cell performance optimization,
the present model provides a reliable and efficient tool for flow battery
design, evaluation, and optimization.
CRediT authorship contribution statement
Yunxiang Chen: Conceptualization, Methodology, Software, Vali-
dation, Analyses, Investigation, Writing. Jie Bao: Discussion, Supervi-
sion, Project administration, Funding acquisition, Data curation. Zhijie
Xu: Discussion, Supervision, Project administration, Funding acquisi-
tion, Data curation. Peiyuan Gao: Analyses, Discussion. Litao Yan: Ex-
periments, Discussion. Soowhan Kim: Discussion. Wei Wang: Project
administration, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Y. Chen et al.
Acknowledgments
This research was supported by Energy Storage Materials Initiative
(ESMI), which is a Laboratory Directed Research and Development
Project at Pacific Northwest National Laboratory (PNNL). PNNL is a
multiprogram national laboratory operated for the U.S. Department of
Energy (DOE) by Battelle Memorial Institute under Contract no. DE-
AC05-76RL01830. The authors thank the two anonymous reviewers
and editor for their constructive feedback of this work.
Appendix. Concentrations of proton and water
As the concentrations of proton and water in the positive electrode
are required to predict the potentials from water and proton, their
analytical solutions are derived in this section. The processes that
control the transport of proton include the proton exchange between
electrolyte tank and the electrode, the generation or consumption of
proton from chemical reaction in positive electrode, and the transport
of proton through membrane. Similar to [31], we assume the proton
concentration is uniform within the electrode. Denoting 𝑐𝐻𝑃 and 𝑐𝐻𝑅
as the proton concentration in the positive electrode and tank, their
mass conservation can be written as Eqs. (19) and (20).
𝑑(𝜖𝑉𝑒 𝑐𝐻𝑃 ) 𝐼 𝐼
= 𝑢𝑃0 𝐵𝐿𝑒 𝜖(𝑐𝐻𝑅 − 𝑐𝐻𝑃 ) + 2 𝑡 − 𝑛𝐻 𝑡 (19)
𝑑𝑡 𝐹 𝐹
𝑑(𝑉𝑡 𝑐𝐻𝑅 )
= −𝑢𝑃0 𝐵𝐿𝑒 𝜖(𝑐𝐻𝑅 − 𝑐𝐻𝑃 ) (20)
𝑑𝑡
where the last two terms in Eq. (19) denote the amount of proton
generated from chemical reaction and transported from the membrane.
A reference value for 𝑛𝐻 is 1 if the concentration gradient of proton at
the membrane–electrolyte interface is zero and water velocity through
the membrane is zero. For an actual flow battery, such a value requires
measurements or fitting form model.
Dividing Eq. (20) by 𝑉𝑡 and Eq. (19) by 𝜖𝑉𝑒 and then subtracting
the resulted Eq. (19) from Eq. (20), an equation for 𝑐𝐻𝑅 − 𝑐𝐻𝑃 is given
by Eq. (21).
𝑃 254–266, http://dx.doi.org/10.1016/j.apenergy.2014.06.077.
𝑑(𝑐𝐻𝑅 − 𝑐𝐻𝑃 ) 𝑢 𝐵𝐿𝑒 𝑉 (2 − 𝑛𝐻 )𝐼𝑡
=− 0 (1 + 𝜖 𝑒 )(𝑐𝐻𝑅 − 𝑐𝐻𝑃 ) − (21)
𝑑𝑡 𝑉𝑒 𝑉𝑡 𝜖𝑉𝑒 𝐹
An analytical solution to Eq. (21) is given by Eq. (22) with an initial
0
condition (𝑐𝐻𝑅 − 𝑐𝐻𝑃 )𝑡=0 = 𝑐𝐻𝑅 0
− 𝑐𝐻𝑃 = 0.
(2 − 𝑛𝐻 )𝐼𝑡 [ 𝜔𝑃 (1 + 𝜖𝛿)𝑡 ]
𝑐𝐻𝑅 − 𝑐𝐻𝑃 = 1 − exp(− ) (22)
𝜔𝑃 (1 + 𝜖𝛿)𝐹 𝑉𝑒 𝜖
where 𝜔𝑃 = 𝑢𝑃0 𝐵𝐿𝑒 𝜖 and 𝛿 = 𝑉𝑒 ∕𝑉𝑡 . Substituting Eq. (22) to Eq. (19),
a solution to 𝑐𝐻𝑃 can be given as Eq. (13) with an initial condition
𝑐𝐻𝑃 |𝑡=0 = 𝑐𝐻𝑃
0 .
The solution to water in the positive electrode can be derived sim-
ilarly, although the value 2 and 𝑛𝐻 are replaced by -1 and 𝑛𝑑 because
1 mole of water is consumed when 2 mole of proton is generated and
the water transport flux through the membrane is different from that
of proton. The water drag is selected as 𝑛𝑑 = 2.5 [46,48].
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