Electrochimica Acta 58 (2011) 238–246

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

A three-dimensional model for negative half cell of the vanadium redox flow
battery
Xiangkun Ma, Huamin Zhang ∗ , Feng Xing
Division of Advanced Energy Storage Batteries and Technologies, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

a r t i c l e i n f o a b s t r a c t

Article history: A stationary, isothermal, three-dimensional model for negative half cell of the vanadium redox flow
Received 4 June 2011 battery is developed, which is based on the comprehensive conservation laws, such as charge, mass
Received in revised form and momentum, together with a kinetic model for reaction involving vanadium species. The model is
15 September 2011
validated against the results calculated by the available two-dimensional model. With the given geometry
Accepted 15 September 2011
of the negative half cell, the distributions of velocity, concentration, overpotential and transfer current
Available online 24 September 2011
density in the sections that are perpendicular and parallel to the applied current are studied. It is shown
that the distribution of the electrolyte velocity in the electrode has significant impact on the distribution
Keywords:
Vanadium redox battery
of concentration, overpotential and transfer current density. The lower velocity in the electrode will cause
Three-dimensional model the higher overpotential, further result in the side reaction and corrosion of key materials locally. The
Transfer current density distribution development of the design of the vanadium redox flow battery is discussed, and the further research is
Overpotential distribution proposed.
© 2011 Elsevier Ltd. All rights reserved.

1. Introduction
Energy storage technology can provide a solution to solve the
balance problem between generation and consumption of power.
The use of energy storage for load leveling and peak shaving can
improve the utilization of generation, transmission, and distribu-
tion assets, and can allow utilities to defer investment in additional
electric facilities. Energy storage technology will play a very cru-
cial role in the delivery of electricity from renewable resources,
such as solar and wind, which typically suffer from intermittency
problems [1]. Among the technologies of energy storage, the vana-
dium redox flow battery is well suitable for relatively large-scale
utility application due to its advantages like long life, high perfor-
mance, active thermal management, and independence of energy
and power rating [2–6]. In order to realize the commercial appli-
cation of the vanadium redox flow battery, a number of challenges
have to be overcome, like scale-up and optimization which includes
flow geometries assemblage and operation conditions. Modeling
and simulation are cost-effective methods for resolving these prob-
lems, which can reduce the costs and long timescales associated
with laboratory-based research. The insight into the fundamental
processes inside the vanadium redox flow battery can be obtained
by modeling and simulation, which is helpful for optimizing the
∗ Corresponding author. Tel.: +86 411 84379072; fax: +86 411 84665057.
E-mail address: zhanghm@dicp.ac.cn (H. Zhang).
design and operating condition, and further accelerating the devel-
opment process.
Compared with the conventional battery such as lithium-ion
and lead-acid [7–10], a few of models were developed for the
vanadium redox flow battery in recent years. For example, You
et al. [11] presented a two-dimensional dimensionless mathemat-
ical model for a flow-through porous electrode, in which the effect
of mass transfer, ohmic resistance and electrode reaction kinet-
ics on the performance of porous electrode was investigated. A
transient, two-dimensional model was put forward by Shah et al.
[12]. The model was based on conservation principle, incorpo-
rating the fundamental models of transport and a kinetic model
for reactions involving vanadium species. The model studied the
effect of variation in concentration, electrode porosity and elec-
trolyte flow rate on the performance of cell, even taken into account
non-isothermal effect [13] which was done by adding an energy
equation and gas-evolving side reactions including oxygen [14] and
hydrogen [15] evolution. Based on the dynamic model developed
by Shah, You et al. [16] developed a simplified stationary model
through introducing SOC (state of charge). The effects of applied
current density, electrode thickness ratio and local mass transfer
coefficient on the performance of all-vanadium redox flow battery
were studied. Vynnycky [17] used asymptotic methods to deter-
mine the characteristic current density scale in terms of operating
conditions and cell component properties. A mathematical model
for the vanadium flow unit-cell is presented by Shah et al. [18]
which is designed to provide accurate, rapid solution at the unit-
cell scale. Up to now, the simulated research on the vanadium flow

0013-4686/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2011.09.042
 X. Ma et al. / Electrochimica Acta 58 (2011) 238–246 239

Fig. 1. A schematic diagram of the vanadium redox flow battery [16].

battery is mostly concentrated on the two-dimensional simulation

and seldom research takes into account for the influence of the cell
geometry. The three dimensional simulation possibly can provide
the information in more detail, and could be more helpful for the
research of the vanadium flow battery.
In this paper, based on the model presented by Shah et al. [12]
and You et al. [16], a stationary, isothermal, three-dimensional
model for negative half cell of the vanadium redox flow battery
is presented. The model is described by the comprehensive con-
servation laws like charge, mass and momentum, together with a
kinetic model for reaction involving vanadium species. With the
given geometry of the negative half cell, the distributions of veloc-
ity, concentration, overpotential and transfer current density in
the sections that are perpendicular and parallel to the direction
of the applied current is studied. The model is validated against
the results calculated by the available two-dimensional model. The
development of vanadium redox flow battery design is discussed.
2. Model assumption and equations
2.1. Model geometry and assumption
Fig. 1 shows a schematic diagram of a single vanadium redox
flow battery, which includes electrode, current collector, ion
exchange membrane and tanks equipped with electrolyte. A sul-
furic acid solution containing vanadium ions is used as the positive
and negative electrolyte, which is circuited to the battery cell. The
reaction in the positive and negative electrode is as following [19]:
Positive electrode : VO2+ + H2 O-e−  VO+
2 + 2H
+
Negative electrode : V3+ + e−  V2+
In this paper, the negative half cell which includes inflow chan-
nel, negative electrode and outflow channel is only considered,
which is as shown in Fig. 2.
The assumptions below have been made:
Fig. 2. Geometry of negative electrode with inflow/outflow channel.
(3) Physical properties of membrane and electrode are isotropic
and homogeneous. Non-isothermal condition and side reac-
tions are not taken into account.
(4) Transport of the charged species occurs by diffusion and con-
vection. The migration terms are ignored for simplification.
(5) There is no leakage of reactant or charge through the external
surfaces of the cell, no crossover of vanadium species through
the membrane.
2.2. Governing equations
A set of transport equations based on the principle of conser-
vation have been developed by Shah et al. [12] and You et al. [16]
for the electrode domain. The species of V2+ and V3+ are consid-
ered here. For each species, mass conservation equation which is
applied in the whole domain including electrode and channel can
be described as follows:
−
→
v ∇ ci − Dieff ∇ 2 ci = Si (4)
(1) where −
→
v is the flow velocity inchanneland electrode, ci represents
concentration of species, i ∈ V2+ ,V3+ , Si is the source term for
(2) eff
species i, defined in Table 1 and discussed in the sequel. Di is
effective diffusion coefficient, which is derived from the free-space
value, Di , by a Bruggemann correction [20]:
eff
Di = ε3/2 Di (5)

ε denotes the electrode porosity. Since charge entering the elec-

−
→
(1) The dilute-solution approximation is valid for simplification. trolyte, i e is balance by the charge leaving from the solid phase in
The flow is regarded as incompressible and laminar. the electrode, charge equation of conservation yields:
(2) The Nernst potentials of the negative electrode relate to SOC −
→ −
→
i s = − i e = S (6)
(state of charge) of electrolyte, which define the concentra-
tions of reactant and product at any time. The relationship
between charge (or discharge) time and SOC is described in Table 1
Eq. (3). Where t0 is the total charge (or discharge) time. S0 and Source terms for Eqs. (4) and (6).

Se represent the values of SOC at the beginning and the end of Source Negative electrode
charge (or discharge). The transient model can be simplified to
Si V2+ a*j/F
a stationary one: V3+ −a*j/F

t S s a*j
SOC = S0 + (Se − S0 ) (3) l −a*j
t0
240 X. Ma et al. / Electrochimica Acta 58 (2011) 238–246

where S denotes the source term for charge conservation, defined Eq. (13) will be switched to Darcy’s law. Secondly, the absolute mag-
−
→ −
→ nitude of the viscous term is too small to compare to the ones of
in Table 1. i e and i s are the ionic and electronic current densities,
respectively, which can be obtained by the Ohm’s law. The law can Darcy term and pressure term when slip boundary condition which
only be applied in the electrode domain: is satisfied by Darcy’s law applies to the walls. The order of viscous
−
→ term is only 1–10, whereas the orders of rests are up to 104 . The
eff
i s = −s ∇ s (7) effect of viscosity can be neglected.
−
→ Butler–Volmer expression is used for the transfer current
i e = −l ∇ l (8)
density in the electrode compartment, which describes the elec-
s and l , denote the electronic potential and ionic potential, trochemical reactions taking place on the surface of the porous
eff carbon electrode. The precise multi-step reaction mechanism is not
respectively. s is the effective electronic conductivity of the
porous electrode, which is related to the electronic conductivity known, but it has previously been demonstrated that the reversible
of solid material,  s , subject to a Bruggemann correction [20]: redox features are well captured by the Butler–Volmer formulation:
  ˛ F   ˛ F 
eff c s 3+ c s 2+
s = (1 − ε)3/2 s (9) j= ic0 V
exp −
c c
− V
exp
a c
(16)
cV3+ RT cV2+ RT
The ionic conductivity can be calculated by [21]:
where ˛a and ˛c are the anodic and cathodic transfer coefficient. ic0
l = 35.716 + 7.699 × SOC (10)
is the negative exchange current density, which can be calculated
For the velocity −→v in Eq. (4), it is appropriate to use Darcy’s by [16]:
law to describe the flow in the electrode which consists of porous
ic0 = Fkc (cV2+ )˛c (cV3+ )˛a (17)
carbon felt, since the Reynolds number, Re, based on the pore-size
length scale only arrives at Re ∼ 0.1–1. However, the flow in the where kc is the standard rate constant for negative reaction; c
inflow and outflow channel should be characterized by stationary denotes the overpotential for the negative electrode reaction which
incompressible Navier–Stokes (NS) equation: is defined as:
 
v = −p +  ∇ −
v · ∇ )−
(−
→ → →
v + (∇ −
→ c = s − l − Ec
T (18)
v) (11)
where Ec is the equilibrium potential for negative reaction, which
∇ ·−
→
v =0 (12)
is given by:
where  denotes density of the bulk solution and p is liquid absolute

RT cV3+
pressure. Ec = Ec0 + ln (19)
F cV2+
It is difficult to calculate a coupled Darcy–NS model since two
different scales are described for the models. Darcy’s law is modeled Ec0 denotes the equilibrium potential at standard condition, which
for the macroscopic application, while NS equation for microscopic is listed in Table 4.
one. At the interface between Darcy and NS domain, an inter- In order to calculate the surface concentration of vanadium ion:
face parameter must be specified which honors the continuity of c s 3+ and c s 2+ , the local mass transfer coefficient km is introduced to
mass and momentum over the interface. For the Darcy–NS system, V V
describe the effect of species transport between the bulk solution
various interface conditions have been presented in some paper
and the liquid–solid interface, therefore the local flux at the surface
[22–24]. They differ in terms of treatment of jump of tangential
of the negative electrode during charge will be:
component of the velocities across the interface. An easier method
to handle this situation is to employ Brinkman equation [25,26] N s 3+ = km (cV3+ − c s 3+ ) = kc (cV2+ )˛c (cV3+ )˛a
V V
which is modeled for coupled free flow and porous media flow.   ˛ F   ˛ F 
There is no need to formulate specific interface condition unlike the c s 3+ c c
c s 2+ a c
V V
× exp − − exp (20)
coupled Darcy–NS model. The Brinkman equation for single-phase cV3+ RT cV2+ RT
incompressible flow is written as follows:
 
−→v = −p + ∗ ∇ −
→
v + (∇ −
→
v )T (13) N s 2+ = km (cV2+ − c s 2+ ) = kc (cV2+ )˛c (cV3+ )˛a
V V
K   ˛ F   ˛ F 
c s 2+ c s 3+
∇ ·−
→v =0 (14) × V
exp
a c
− V
exp −
c c
(21)
cV2+ RT cV3+ RT
where K is the permeability of the porous electrode which is nor-
mally described by the Carman–Kozeny equation [27]: where km denotes the mass transfer coefficient, which is approxi-
mately calculated by [28]:
df2 ε3
km = 1.6 × 10−4 −
→
K= · (15) 0.4
v (22)
16kCK (1 − ε)2
The vanadium concentration at the surface of the negative sur-
df is the fiber diameter and kCK is the Carman–Kozeny constant,
face can be solved by combining Eqs. (20) and (21):
which depends on the type of media and is used as a fitting param-
eter.  is the physical viscosity of electrolyte, * is an effective PcV3+ + (1 + P)cV2+
c s 2+ = (23)
viscosity. Compared to the NS equation, the inertia term switches V 1+M+P
to Darcy term when electrolyte enters porous media. The continuity McV2+ + (1 + M)cV3+
of mass and momentum at the interface is settled automatically. c s 3+ = (24)
V 1+M+P
In contrast to Darcy’s law, the viscous term in the Brinkman
equation is an additional one which considers the effect of viscosity. where
However, there are two reasons to help us to ignore its effect: firstly, kc
 ˛ F 
(c 2+ )˛c −1 (cV3+ )˛a exp
a c
M= (25)
the Brinkman equation which derives from Darcy’s  
law is used km V RT
in the microscopic because its viscous term  ∇ v + (∇ −
∗ −
→ →
v )T is kc ˛c Fc
 
P= (c 2+ )˛c (cV3+ )˛a −1 exp − (26)
taken into account. After choosing * to equal to a very small value, km V RT
 X. Ma et al. / Electrochimica Acta 58 (2011) 238–246 241

2.3. Boundary conditions Table 2

Electrode property.

In galvanostatic operation of cell, the flux condition for potential Parameter Symbol Value Unit Origin
distribution of the porous electrode along the electrode/collector Porosity ε 0.929 – Ref. [29]
interface is written as follows: Specific surface area a 1.62 × 104 m2 Ref. [29]
Electronic conductivity s 1000 S m−1 Estimated
−s ∇ s · −
→
eff
n = −I (27) Carbon fiber diameter df 1.76 × 10−5 m Ref. [29]
Kozeny–Carman constant kCK 4.28 – Fitted
where I denotes the applied current density, − →
n denotes outward Length L 0.046 m Measured
unit normal vector. During charge, the current is assumed to enter Width W 0.03 m Measured
Thickness d 0.003 m Measured
the carbon felt uniformly. For discharge the signs are reversed.
There are zero charge flux conditions for all the other surfaces of
the electrode.
Table 3
Since the conservation of charge, the charge leaving the solid Electrolyte property.
phase is balanced by one entering the electrolyte. So the flux
condition for potential distribution of the electrolyte along the elec- Parameter Symbols Value Unit Origin
−3
trode/membrane interface is as follows: Viscosity  4.928 × 10 Pa s Measured
V2+ diffusion DV2+ 2.4 × 10−4 m2 s−1 Ref. [30]
−l ∇ l · −
→
n =I (28) coefficient
V3+ diffusion DV3+ 2.4 × 10−4 m2 s−1 Ref. [30]
For discharge the situations are reversed. Also, there are insu- coefficient
Initial vanadium c0 1500 mol m−3 Calculated
lated conditions for the rest of the electrode surfaces.
concentration
According to assumption 2, the concentration of reactant and Initial proton c0 4500 mol m−3 Calculated
n H+
product are related to SOC at any time. Therefore, the concentration concentration
−3
of vanadium species at the inlet of inflow channel can be treated Initial water cn0 H O 46,500 mol m Calculated
2
as constant at any given SOC. The concentration expressions of the concentration

vanadium species at inlet at any given SOC will be:


c in2+ = c 0 · SOC Table 4
V (29)
in Kinetic parameters.
c 3+ = c 0 · (1 − SOC)
V
Parameter Symbols Value Unit Origin
where c0 is the initial vanadium concentration of the negative half Negative standard reaction kc 1.7 × 10−7 m s−1 Ref. [6]
cell. In this paper, the operation is the same to You’s et al. [16]. rate constant
Therefore, the value of c0 is equal to 1500 mol m−3 . At the outlet of Cathodic transfer ˛c 0.5 – Assumed
coefficient: positive
the outflow channel, all the reactant diffusive fluxes are set to zero,
Cathodic transfer ˛c 0.5 – Assumed
in the so-called fully developed flow approximation: coefficient: negative
Equilibrium potential: Ec0 −0.255 V Ref. [31]
−Di ∇ ci · −
→
eff
n =0 (30) V2+ /V3+

All the other boundaries of electrode and inflow/outflow chan-

nel are set to walls, which mean no flux across the boundary:
3. Results and discussion
eff
v ci ) · −
(−Di ∇ ci + −
→ →
n =0 (31)
3.1. Validation of the model
For the conservation of momentum, velocity and pressure con-
ditions apply to the inlet of inflow channel and outlet of outflow
Fig. 3 shows the simulated negative electrode potentials
channel, respectively:
by two-dimensional model [16] and the ones by three-

v = Q /A (inlet) dimensional model at different SOC for applied current density
(32) of 40 mA cm−2 . The initial vanadium electrolyte was 1500 mol m−3
p = pout (outlet)
VOSO4 + 3000 mol m−3 H2 SO4 . The initial volume of negative elec-
where Q is the electrolyte flow rate, A is the cross-sectional area trolyte is 60 ml, which is consistent with You’s experimental
of the inlet channel. The outlet pressure is usually set to zero. The condition. It can be seen from the figure that the two simu-
no-slip boundary condition applies to the walls of inflow/outflow lated results are well-fitted. The comparison has demonstrated a
channel, but slip boundary condition for walls of electrode. The good degree of accuracy. The average of relative error is less than
electrolyte pressure satisfies a Neumann condition at the bound- 2.46%. The slight error between the results of two models may be
aries of electrode domain: attributed to effect of distribution of electrolyte flow rate compared
to that in two-dimensional model.
∇p · −
→
n =0 (33)

2.4. Numerical details and parameters Table 5

Basic operation parameters.
The conservation equations are solved by the COMSOL Parameter Symbols Value Unit
Multiphysics® package, which is based on the finite-element
Operating temperature T 298 K
method. A quadratic basis was used in all of the simulations, Volumetric flow rate Q 27 ml min−1
together with 108,285 elements. The relative error tolerance is Outlet pressure pout 0 Pa
set to 1 × 10−6 . The default set of parameter values is listed in Surface area of inlet channel A 6.534 × 10−6 m2
Tables 2–5. Applied current density I 40–80 mA cm−2
242 X. Ma et al. / Electrochimica Acta 58 (2011) 238–246
Fig. 3. Comparison of simulated negative half-cell potential values by two-
dimensional model and ones by three-dimensional model at different SOC for
applied current density of 40 mA cm−2 .
3.2. Distributions along electrode/current collector interface
The distribution of velocity in three-dimension is more com-
plex than two-dimension. Fig. 4 shows contour planes of velocity
in the electrode domain. The value of velocity in two-dimensional
simulation is almost constant in the electrode due to its simple
geometry which is a regular rectangle. However, it is entirely differ-
ent in three-dimension. The electrolyte enters the porous electrode
through inflow channel. The flow velocity will first decrease due
to the expanding space then increase when the electrolyte leaves
the domain. Most of electrolyte flow through electrode along the
inlet–outlet diagonal. At the two corners which corresponds to the
axis of (x = −0.015 m, y = −0.023 m) and (x = −0.015 m, y = 0.023 m),
respectively, the minimum of velocity occurs. In the region of {x > 0,
y > 0, z ∈ (− 0.003 m, 0)} and {x < 0, y < 0, z ∈ (− 0.003 m, 0)}, there is
a symmetric velocity distribution. Moreover, in the region of {x < 0,
y > 0, z ∈ (− 0.003 m, 0)} and {x > 0, y < 0, z ∈ (− 0.003 m, 0)}, a similar
symmetric pattern is found. The patterns are also projected to elec-
trode/current collector interface, which refers to Fig. 5. Note that
the velocity of z-direction component in most region of electrode,
whose order is up to 10−5 , is too low to compare with that of x and
y directions. It is only considered in the region close to the inlet
and outlet of electrode due to the normal directions of inflow and
outflow channel are both parallel to z-axis. If the area of electrode
is large enough and flow directions of electrolyte in the inflow and
Fig. 4. Contour planes of velocity in the electrode domain.
Fig. 5. Simulated velocity contour plots on electrode/current collector interface.
outflow channel are parallel to X–Y plane, z-direction component
in the whole electrode domain can be entirely neglected.
One of the major advantages for three-dimensional model is
that it can provides the detailed information about the distribu-
tions of concentration, overpotential and transfer current density
on electrode/current collector and electrode/membrane interface,
which cannot be obtained by two-dimensional model. Fig. 6 shows
contour plots for distributions of V3+ concentration, overpotential
and transfer current density on electrode/current collector inter-
face at 50% SOC for applied current density of 40 mA cm−2 . In
these plots, x-axis corresponds to the width of electrode and y-
axis corresponds to length. The inlet and outlet are located in the
regions of {x = − 0.015 m, y ∈ (0.02 m, 0.023 m)} and {x = 0.015 m,
y ∈ (− 0.023 m, − 0.02 m)}, respectively. Although there is a little
fluctuation in virtue of mesh grid density or numerical oscillations,
contour plots indicate the rule of parameter distributions in some
extent. The distribution of V3+ concentration looks like sector dif-
fusion from inlet to outlet. As we would expect, the concentration
at the inlet of electrode is the highest, while the concentration
in the region close to the top and left side which corresponds to
y = 0.023 m and x = −0.015 m is lower than other regions. More-
over, on the line of top and left side, the values both become
smaller towards the direction away from outlet. As the left side,
x = −0.015 m, is approached, V3+ concentration gradually decreases
and the gradient has the opposite trend due to the velocity com-
ponent that is vertical to the left side decreases. Moreover, the
contour plots close to left side are almost parallel to left side owing
to the gradient parallel to the left side varies slightly, which is
caused by the velocity component parallel to the left side increases
rapidly as the outlet approached. The distributional rules also apply
to concentration distribution in the region close to the top side,
y = 0.023 m. In the region close to the outlet, the concentration is
higher than one introduced above due to the fact that the concen-
tration located close to the two sides is mixed together with high
concentration which flow along inlet-outlet diagonal. It is clearly
that the overpotential is totally uneven. Since minimum of velocity
occurs in the top right corner and the bottom left corner as showed
in Fig. 5, the values of overpotential are bigger than ones in other
regions due to concentration overpotential. Such polarization may
cause the side reaction like hydrogen evolution and corrosion of
bipolar plate easier. The variation of overpotential becomes more
obviously, and trails off along the direction of inlet–outlet. The min-
imum value of that has almost the same location with the one of
V3+ concentration. In the region close to the inlet and outlet, where
the high value of velocity occurs, the transfer current density is
higher than others. Along the diagonal which connects inlet with
 X. Ma et al. / Electrochimica Acta 58 (2011) 238–246
Fig. 6. Contour plots for distributions of parameters on the electrode/current col-
lector interface: (a) V3+ concentration, (b) overpotential, and (c) transfer current
density.
outlet, the value of transfer current density decreases first, and then
increases. As left and top sides are approached, the value decreases
gradually but the degree of variation shows opposite tendency.
The distributional rules also apply to the overpotential distribu-
tion. They are both due to the concentration changes drastically in
243
Fig. 7. Simulated velocity spatial distribution on three parallel contour planes.
this region. The transfer current density in the top right corner and
bottom left corner, which correspond to (x = 0.015 m, y = 0.023 m)
and (x = −0.015 m, y = −0.023 m), is the lowest. It should be noted
that although the distributional patterns are obtained based on the
given cell geometry, the effect of velocity field on distributions of
concentration, overpotential and transfer current density is consis-
tent when the cell geometry is changed.
3.3. Distributions on three different contour planes
The velocity spatial distributions on three contour planes are
shown in Fig. 7. The corresponding contour plots on each plane are
demonstrated in Fig. 8. In these plots, z-direction and y-direction
corresponds to the thickness and height of the electrode respec-
tively. The electrode/current collector interface is represented by
the line, z = 0 and the electrode/membrane interface by z = −3 mm.
The plane referring to x = 0 locates in the middle of electrode, which
has a symmetrical line of velocity corresponding to y = 0. The veloc-
ity experiences little change on this plane, which is similar to the
velocity distribution calculated by the two-dimensional model [16].
However, the other two have different velocity distributions. The
plane at x = 0.01 is close to the inlet of electrode. The velocity in
the region corresponding to y < 0 is obviously higher than other
regions. The velocity decreases as the height increases from bot-
tom line, y = −0.023 m, along any line parallels to y-axis. The plane
at x = −0.01 m has the similar pattern, but the tendency of veloc-
ity distribution is opposite to the conclusion of plane at x = 0.01.
Moreover, the contour plots in all figures demonstrate that velocity
almost has the same value along any line parallels to z-axis.
Three planes were chosen to show distributions of V3+ concen-
tration, overpotential and transfer current density at 90% SOC for
applied current density of 80 mA cm−2 during charge. Fig. 9 shows
contour plots of V3+ concentration on three planes at 90% SOC.
The depletion of V3+ concentration on plane, x = 0 and x = 0.01 m,
decreases from the bottom surface along any line parallels to y-
axis except one on plane, x = −0.01 m. It shows special contours
due to its complex three-dimensional shell profile, resulted from
three-dimensional velocity distribution. The concentration dis-
tribution on the plane, x = 0 shows a similar pattern with one
simulated by two-dimensional model [16] due to the uniform
velocity field. On any line parallels to z-axis, the highest concen-
tration occurs near the intersection with the line, z = −1.9 mm, and
as electrode/collector interface is approached, the depletion of V3+
increases along these lines. In the opposite direction, there is the
same variation but at smaller degree because of the major reaction
244 X. Ma et al. / Electrochimica Acta 58 (2011) 238–246
Fig. 8. Simulated contour plots of velocity on three contour planes: (a) x = −0.01 m;
(b) x = 0; (c) x = 0.01 m.
occurs in the region close to the current collector. Compared with
the concentration on three planes, the minimum and maximum
concentration both occur on the plane, x = 0.01 m. The minimum
locates at the intersection of top surface of electrode, y = 2.3 cm,
and electrode/collector interface, z = 0 due to lower velocity. The
maximum is at the bottom surface of electrode close to the inlet.
The average depletion of V3+ concentration is lowest on the plane,
x = −0.01 m, on which the range of variation of transfer current
density is smallest.
Fig. 9. Comparison of simulated value of V3+ concentration on three contour planes
at 90% SOC: (a) x = −0.01 m; (b) x = 0; (c) x = 0.01 m.
Fig. 10 shows contour plots of transfer current density on three
planes at 90% SOC. The maximum current density occurs at the
intersection of bottom surface, y = −2.3 cm, and electrode/current
collector interface, z = 0, on plane, x = 0.01 m. There are some similar
characteristics among these three planes. Along direction parallels
to z-direction, the values increase as the electrode/collector inter-
face is approached from the line z = −1.9 mm. The same variation
occurs in the direction to electrode/membrane interface, but the
degree is smaller. In the region close to the top line, y = 0.024 m, the
gradient increases significantly due to variations of concentration
 X. Ma et al. / Electrochimica Acta 58 (2011) 238–246
Fig. 10. Comparison of simulated value of transfer current density on three contour
planes at 90% SOC: (a) x = −0.01 m; (b) x = 0; (c) x = 0.01 m.
and mass transfer resistance. Near the line, z = −1.9 mm the values
are smaller than other regions where high concentration and low
overpotential occur. The contour plots show great difference close
to the bottom region on these planes. The contours demonstrate
closed curve on plane x = −0.01 m, whereas disappear on other
planes, which is mainly caused by different velocity and overpo-
tential. The contours of overpotential on the slice also show the
similar corresponding curves.
Fig. 11 shows the corresponding contour plots of overpotential
on three planes at 90% SOC. Because of the fact that the plane at
245
Fig. 11. Comparison of simulated value of overpotential on three contour planes at
90% SOC: (a) x = −0.01 m; (b) x = 0; (c) x = 0.01 m.
x = −0.01 m is close to outlet, the values of velocity increase as the
height increases along any line parallels to y-axis which refers back
to Fig. 8(a). However, on the plane at x = 0.01 m, the distribution is
opposite due to the plane is close to inlet as shown in Fig. 8(c). In
the region, y > 0, on each plane, as inlet is approached, the value of
overpotential and the degree of variation become higher due to the
velocity getting smaller. However, in the region, y < 0, the variation
is opposite. So in Fig. 11 from (a) to (c), the closed curve looks
like moving towards the bottom surface of electrode. On three
planes, lower absolute value of over-potential occurs near the line,
z = −1.9 mm, where high concentration and low current density
246 X. Ma et al. / Electrochimica Acta 58 (2011) 238–246

locate. Both to the directions of electrode/membrane interface p the liquid pressure, Pa

and electrode/collector interface from the line, z = −1.9 mm, the R universal gas constant, J mol−1 K−1
absolute value of overpotential increases. It is necessary to prevent SOC state of charge
corrosion of current collector because the maximum absolute value S source term, mol m−3 s−1
of overpotential occurs in the region close to electrode/current T temperature, K
collector interface. v velocity in electrode and flow channel, m s−1
It is indicated that the electrode/current collector interface in z charge of the ionic species
Figs. 5 and 6 corresponds to the line, z = 0 in Figs. 8–11. The
distributions on electrode/collector interface are determined by Greek letters
intersection of contours and line, z = 0. It can be seen clearly that ˛ transfer coefficient
the corresponding variational rule of V3+ concentration, overpo- ε porosity of the carbon electrode
tential and transfer current density in Fig. 6 is consistent with the  overpotential, V
figures introduced above. s electronic potential, V
l ionic potential, V
4. Conclusions  ionic conductivity, S m−1
 density of bulk solution, kg m−3
A stationary, isothermal, three-dimensional model for negative  electronic conductivity, S m−1
half cell of the vanadium redox flow battery is developed. The model  dynamic viscosity, Pa s
is based on the fundamental laws of charge, mass and momentum
conservation, coupled with a kinetic model for reaction involving Subscripts
vanadium species. With the same condition the model is validated a anodic reaction quantity
against the results calculated by the available two-dimensional c cathodic reaction quantity
model. In the given geometry of the negative half cell the distribu- e  in electrolyte
ionic property 
tions of velocity, concentration, overpotential and transfer current i species i ∈ V2+ ,V3+
density in the sections that are perpendicular and parallel to the in inlet value
applied current are reported. It is shown that the velocity distribu- out outlet value
tion in the given geometry of cell has a symmetric pattern in the l electrolyte quantity
electrode domain. The lower velocity in the electrode will cause s solid or electronic property
the higher overpotential, which will result in the side reaction
and corrosion of key materials locally. In the region closed to the Superscripts
inlet and outlet, transfer current density has relatively high value eff effective value
where high velocity occurs. The distributions of concentration, in inlet value
overpotential and transfer current density along electrode/current s liquid–solid interface quantity
collector interface reveal the corresponding variational rules on the 0 equilibrium or initial value
intersections of slices and interface. The uniformity of the distri-
bution of velocity of electrolyte in the electrode is the key point References
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