Electrochimica Acta 309 (2019) 283e299

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

Mitigating capacity decay and improving charge-discharge

performance of a vanadium redox flow battery with asymmetric
operating conditions
M.Y. Lu a, W.W. Yang a, *, Y.M. Deng a, W.Z. Li a, Q. Xu b, **, Y.L. He a
a
Key Laboratory of Thermo-Fluid Science and Engineering of Ministry of Education, School of Energy and Power Engineering, Xi'an Jiaotong University,
Shaanxi, 710049, PR China
b
Institute for Energy Research, Jiangsu University, Zhenjiang, 212013, PR China

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

Article history: A two-dimensional transient model with considering vanadium ion crossover was presented to examine
Received 2 November 2018 the influence of asymmetric electrolyte concentrations and operation pressures strategies on the char-
Received in revised form acteristics of capacity decay, vanadium ions crossover and charge-discharge performance of a vanadium
24 March 2019
redox flow battery during battery cycling. It was indicated that for asymmetric electrolyte operating
Accepted 6 April 2019
Available online 10 April 2019
concentrations, with increasing the initial concentration of positive electrolyte while keeping initial
concentration of negative electrolyte unchanged, the discharge capacity decay behavior during battery
cycling can be effectively mitigated due to the reason that the imbalance of vanadium ions crossover is
Keywords:
Vanadium redox flow battery
alleviated by the increased diffusion flux of VO2þ/VOþ 2 couple from positive to negative side. Also, the
Asymmetric operating conditions overall charge-discharge performance of the battery is greatly improved due to the reduced potential
Discharge capacity decay losses of both electrode reactions. Moreover, it was shown that the discharge capacity decay can also be
Vanadium ions crossover suppressed by increasing the outlet pressure of positive electrode, which is attributed to the reason that
Charge-discharge performance the imbalance of vanadium ions crossover can be eliminated with the increased vanadium osmotic
convection driven by pressure gradient. However, asymmetric operation pressures showed little impact
on batter charge-discharge voltages.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction physical properties of battery components and materials for charge

Redox flow battery (RFB) has been regarded as a promising
energy storage technology for the stabilization of grid electricity
supplies, emergency power backup, and intermittent renewable
power systems such as solar and wind power, due to its virtues of
long cycle-life, high efficiency and flexibilities of energy and power
ratings [1e4]. Although great progress has been made in advancing
RFB technology, especially the all-vanadium redox flow battery
(VRFB) technology, the problems associated with battery perfor-
mance in term of system capacity, power and efficiency, and the
difficulties in optimizing battery structures and operating strate-
gies are still remained and need to be resolved.
Technically, the performance of VRFB depends not only on
* Corresponding author.
** Corresponding author.
E-mail addresses: yhxjtu@163.com (W.W. Yang), 87180817@qq.com (Q. Xu).
transport and electro-catalysis, but also on the management of
complex flow and species transport processes inside the cell. To
boost the VRFB performance, researchers have paid their attentions
on improving electrolyte properties for high vanadium ions solu-
bility and stabililty, and advancing the electrode properties for high
electrochemical reversibility and electrochemical activities and
designing new membranes for lower crossover of vanadium ions
and water transfer across the membrane and lower resistance
simultaneously in the VRFB [5e12]. Besides, for given battery
component materials, the increase of battery performance also
relies on optimzing the battery structure and operating strategies
[4,13e24], and addressing the critical transport issues in theVRFBs
[25,26].
One major mass transport isssue in the VRFB is the vanadium
ions crossover [27e31]. The unbalanced transport properties of
different vanadium ions in the membrane result in the imbalance of
electrolyte during battery cycling. Consequently, the half-cell with
less amount of vanadium ions becomes the dominant factor

https://doi.org/10.1016/j.electacta.2019.04.032
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
284 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299
limiting the battery discharge capacity. To resolve this, practically,
the electrolytes in both tanks need to be periodically rebalanced by
remixing to recover the battery capacity [32e35].
Currently, there have been many fundamental studies on
revealing the transport mechanisms of vanadium ions through the
membrane. One major transport mode of vanadium ions crossover
is molecular diffusion driven by concentration gradient through the
membrane. Some researchers [36,37] measured the diffusion co-
efficients of four different vanadium ions (V2þ ; V3þ ; VO2þ ; VOþ2 ) in
the membrane. It was indicated that the diffusivities of various
vanadium ions are different, which was believed to be the main
reason that causes the electrolyte imbalance [38,39]. Kumbur and
coworkers [40e42] also presented a two-dimensional model to
investigate the mechanism of convective transport of vanadium
ions and its impact on the total flux of vanadium ions crossover.
Their study showed that the convective transport of vanadium ions
is composed of the osmotic convection and the electro-osmotic
convection and that the convective transport occurs in the same
direction as applied current [40]. Since electro-osmotic convection
yields zero net effect on vanadium ions crossover for an entire
cycle, the difference in net convective transport is only governed by
the osmotic convection [41,42]. Later, Yang and Ye [43] found that
Hþ concentration gradient across the membrane gives rise to the
migration and electro-osmotic convection of vanadium ions. In
addition to above studies, some researchers also found that
migration is in the same direction as the applied current and mit-
igates the crossover flux of negative electrode species and in-
tensifies that of positive electrode species during charging
conditions and the opposite happens during discharging conditions
[44,45].
Based on the understanding of the mechanisms of vanadium
ions crossover, many researchers have put forward various oper-
ating strategies for alleviating the vanadium crossover and the
associated battery capacity decay [41,46e50]. For example, the
studies by Kumbur and his coworkers [46] indicated that applying
asymmetric current operating strategy (i.e., increasing charge cur-
rent while keeping the discharge current constant) can suppress
the capacity decay due to the reduction of net convective transport
of vanadium ions across the membrane. The reduced net convective
transport of vanadium ions was mainly attributed to the fact that
increasing charging current increases the magnitude of the electro-
osmotic convection during charging process, which in turn, com-
pensates for the convective crossover due to the osmosis process.
Besides, it was indicated that the asymmetric flow rates and
asymmetric electrolyte viscosities can also effectively reduce the
capacity decay resulting from the minimization of osmotic con-
vection [46]. Also, Yang and his coworkers [47] proposed to apply
asymmetric concentration operating conditions (i.e., decreasing the
initial concentration of negative electrolyte while increasing the
initial concentration of positive electrolyte) to mitigate capacity
decay. They found that high concentration gradient of vanadium
ions between two half-cells is beneficial to mitigating the imbal-
ance of vanadium crossover. However, in their study, the electrolyte
volumes in both half-cells are kept the same. As a result, the initial
discharge capacity is actually decreased due to the decreased total
amount of vanadium ions in negative half-cell with fixed electro-
lyte volume. Besides, Xi et al. [48] showed that the appropriate
strategies of adding negative electrolyte solution can suppress the
battery capacity decay. It was indicated that the multiple addition
strategy is superior to the strategy of adding the same amount of
negative electrolyte once at the beginning. Moreover, Dong and his
coworkers [49] found that the battery capacity decay can be alle-
viated by adding a soluble draw solute into the catholyte, which can
counterbalance the osmotic pressure between the negative and
positive half-cell. Furthermore, Wang et al. [50] found that by
regulating the gas pressures in the negative and positive electrolyte
tanks, the capacity can be also stabilized. However, the influence of
outlet pressure of positive electrode on transport mechanisms of
vanadium ion across the membrane, characteristics of electrolyte
imbalance and the variation of capacity during cycling is still not
fully understood.
In this work, a two-dimensional, isothermal, transient model
with considering vanadium ion transport in the membrane is
presented for a VRFB. Emphasis is located on examining the influ-
ence of asymmetric electrolyte concentrations and asymmetric
operation pressures on the capacity decay behavior, mechanism of
vanadium ions crossover and the charge-discharge voltages of a
VRFB during cycling. Notice that the asymmetric electrolyte con-
centration strategy (i.e., keeping higher vanadium concentration in
the positive half-cell than that in negative half-cell) herein can
maintain the same initial discharge capacity of the battery by
keeping the same initial amount of vanadium ions in both half-
cells. This study will provide fundamental information for opti-
mizing the asymmetric operating strategies such that the battery
capacity decay can be mitigated and the charge-discharge perfor-
mance can be improved.
2. Mathematical model
Consider a 2-D simulation domain as indicated in Fig. 1a which
represents the core of VRFB with flow-through electrode. Typically,
it consists of a negative carbon plate, a negative porous electrode, a
membrane, a positive porous electrode and a positive carbon plate.
The electrolytes consisting of vanadium ion couples dissolved in
sulfuric acid solution are stored in the respective electrolyte tanks
and circulated through the battery. In Fig. 1a, x-axis represents the
direction across the thickness of the membrane, while y-axis is the
electrolyte flow direction. During the charge and discharge pro-
cesses of the VRFB, the reactants are depleted while the products
are generated by the electrochemical reactions, which causes the
concentration variation of each kind of vanadium ions along the
flow direction. Generally, the battery reactions in the electrodes can
be expressed as:
)
V 3þ þ e charge discharge V 2þ negative (1)


!
)
VO2þ þ H2 O charge discharge VOþ 
2 þ e þ 2H
þ
positive


!
(2)
During the battery cycling, vanadium ions can also permeate
through the membrane by the mechanisms of diffusion, convection
and migration, which results in the side reactions as illustrated in
Fig. 1b. When VO2þ and VOþ 2 ions permeate through the membrane
to the negative electrode, the following side reactions can occur,
VO2þ þ V2þ þ 2Hþ /2V3þ þ H2 O (3)
VOþ
2 þ 2V
2þ
þ 4Hþ /3V3þ þ 2H2 O (4)
Simutaneously, the transport of V2þ and V3þ ions from the
negative electrode to the positive electrode leads to the following
side reactions,
V2þ þ 2VOþ þ
2 þ 2H /3VO
2þ
þ H2 O (5)
V3þ þ VOþ
2 /2VO
2þ
(6)
 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299 285

(4) The physical properties of the electrode and membrane are

isotropic and homogeneous.
(5) The electrolyte solution is well mixed inside the tank during
the battery operation.
(6) Possible side reactions such as hydrogen and oxygen evolu-
tions and the accompanying gas bubble formation in the
electrodes are not considered.
(7) No VO2þ and VOþ 2 ions can exist in the negative half-cell, and
no V2þ and V3þ can exist in the positive half-cell.
(8) SO2
4 ion doesn't exist in the membrane, because it is
assumed that the dissociation of HSO 4 is fully compressed by
the fixed charge in the membrane.
(9) Water transfer carried by hydrogen ions and vanadium ions
across the membrane is neglected.

2.1. Model formulations

2.1.1. Transport in the electrodes

During battery operation, V2þ =V3þ vanadium ion couple and the
species Hþ , HSO 2
4 and SO4 exist in the negative half-cell,
whileVO2þ =VOþ þ 
2 vanadium ion couple andH , HSO4 and SO4
2

ions exist in the positive half-cell. Mathematically, the mass con-

servation of each species i (exceptSO2
4 ) inside the corresponding
electrode can be formulated by
 
v εcele
i !ele
þ V$ N i ¼ Si (7)
vt

whereε is the electrode porosity, cele i

is the bulk concentration of
species i in the electrode, Si is the general source term, representing
the generation rate of species i as listed in Table 1. In Eq. (7), the
!ele
term N i is the mole flux of species i in the porous electrode, which
is described by a modified Nernst-Plank equation

!ele ele eff F

Vfele þ !
ele
N i ¼ Deff ele
i Vci  zi ci Di v l cele
i (8)
Fig. 1. Schematic of VRFB structure and the illustrations of vanadium ions crossover RT l
and related reactions in VRFB.
wherezi is the charge state of species i, fele
l
is the ionic potential in
the electrolyte phase, F is Faraday's constant, R is the universal gas
The above side reactions can cause the depletion of main active
constant and T is the cell temperature. Herein, the term Deff i de-
vanadium ions in the corresponding electrode.
notes the effective diffusion coefficient of species i defined by
Generally, the 2-D simulation domain can save the computa-
Bruggemann correction, i.e., Deff ¼ ε3=2 D .!
ele
tional time without losing much accuracy. To further simplify the i v i represents the su-
l
model, the following assumptions are also involved in model perficial velocity vector of electrolyte in the porous electrode,
formulations: which can be calculated by using Darcy's law

(1) All domains in the VRFB are treated as isothermal. !ele kele ele
vl ¼ Vpl (9)
(2) The electrolyte flow is regarded as incompressible. ml
(3) The dilute solution approximation is used for the species
transport in the simulation. whereml is the average dynamic viscosity of the electrolyte and pele
l
is the hydraulic pressure of electrolyte in the electrode. kele is the

Table 1
Sources terms for mass, momentum and species conservation equations.

Source term Description Positive electrode Negative electrode

2þ 3 1
SV2þ V concentrations equation (mol m s ) i=F
SV3þ V3þ concentrations equation (mol m3 s1)  i=F
SVO2þ VO2þ concentrations equation (mol m3 s1) i=F
SVOþ VOþ
2 concentrations equation (mol m
3 1
s )  i=F
2

S Hþ Proton concentrations equation (mol m3 s1)  2i=F

Sele Velocity continuity equation (kg m3 s1) ði$Mw Þ=ðF$Le Þ 0
l
286 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299

hydraulic permeability of the porous electrode, which can be fmem

l
is the ionic potential in the membrane. The electrolyte ve-
decided by Kozeny-Carmon equation [40]. locity !
mem
v is the macroscopic moving velocity vector which can
be determined by Schlogl's equation [40].
4r 2p ε3
kele ¼ (10) P !
CKC ð1  εÞ2 ! mem kp kf F zi Dmem
i Vcmem
v ¼  Vpmem  cf F Vfmem þ i
mw mw
l
seff;mem
where rp is the mean radius of the pores in the porous electrode, l

and the term CKC denotes Kozeny-Carman constant. (17)

The concentration of SO2
ion can be simply estimated by
4 where kp is the hydraulic permeability of the membrane, mw is the
considering electrically neutral condition of the electrolyte
viscosity of water, kf is the electro-kinetic permeability, fmem
l
is the
solution.
As for the flow of electrolyte solution through the porous elec- ionic potential in the membrane, Dmem
i is the diffusion coefficients
trode, it is simulated by considering the overall mass conservation of species i in the membrane, cmem
i is the concentration of species i
law and Darcy's law in a porous medium. Mathematically, the mass in the membrane and seff;mem
l
is the effective conductivity of the
continuity of the electrolyte flow in the porous electrode can be k
membrane. The first term m p Vpmem represents the osmosis of
given by w

water across the membrane driven by pressure gradient across the

  P mem mem !
V$ rl !
ele
vl ¼ Sele
l (11) k
membrane. The second termm f cf F Vfmem þ
F zi Di Vci
is
w l sl
eff;mem

where Sele
is the general mass generation rate of liquid water, as the electro-osmotic convection caused by the viscous interactions
l
listed in Table 1. Combining Eq. (9), Eq. (10) and Eq. (11), we have between the liquid and the mobile ions [40]. Since the directions of
the following equation pressure gradient, electrolyte potential gradient and concentration
gradient are mainly along x direction across the membrane, the
4r 2p ε3 liquid velocity vector is thus along x direction only. Also, it should
 rl V2 pele ¼ Sele (12) be noted that the flux continuity condition is applied at the inter-
ml CKC ð1  εÞ2 l l
face between the electrode and membrane. Details can be found
The transfer of charged ions in the electrolyte solution results in elsewhere [40].
the ionic current density, which can be given by The transport of charged species across the membrane results in
the ionic current density in the membrane. Since there is no charge
!ele X !ele consumption or generation inside the membrane region, the
Jl ¼F zi N i (13)
charge conservation equation in the membrane can be described as
i

Physically, the charge entering (or leaving) the electrolyte phase !mem
Vjl ¼0 (18)
is also balanced by the charge leaving (or entering) the solid
electron-conducting phase. The conservation of charge can then be As for the ionic current density in the membrane is described by
expressed as using Ohm's law:

!ele !ele !mem

V$ J l ¼ V$ J s ¼ j (14) Jl ¼ seff;mem
l
Vfmem
l (19)

wherej represents the volumetric current density of the electro- where seff;mem
l
is the effective conductivity of the membrane,
chemical reaction in each electrode. In Eq. (14), the electronic which can be calculated by
current density in the solid matrix of the porous electrode is
described by using Ohm's law: F 2 X mem mem
seff;mem
l
¼ zi Di ci (20)
RT
!ele i
J s ¼ sele ele
s Vfs (15)
The properties of the Nafion 117 membrane utilized in the
where sele simulation are also provided in Table 2.
s is the bulk conductivity of the electrode.
Notice that the physical properties of the electrode materials
used in the simulations are listed in Table 2. 2.1.3. Charge transfer in the current collector
The transport of electronic current in the current collector can
2.1.2. Transport in the membrane be simply modeled by Ohm's law that describes the relationship
between electronic potential gradient and the electronic current
In the membrane, the transports of species including V2þ ; V3þ ;
density:
VOþ
2 ; VO
2þ
and Hþ ions are considered. The transfer flux of each
species i is determined by the Nernst-Planck equation, which !cc
j s ¼ scc cc
s Vfs (21)
considers the transport mechanisms of molecular diffusion, con-
vection and migration.

!mem F
Vfmem þ !
mem mem
Ni ¼ Dmem
i Vcmem
i  zi cmem
i Dmem
i v ci 2.2. Boundary and initial conditions
RT l
(16)
2.2.1. Boundary conditions for species transport
whereDmem is the diffusion coefficient of species i in the mem- The concentrations of VO2þ =VOþ
2 at the interface x ¼ x2 and the
i
brane, cmem
i is the concentration of each species i in the membrane, concentrations of V2þ =V3þ at the interface x ¼ x3 are all set to be
 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299 287

Table 2 Table 3
Geometric parameters and physicochemical properties. Flux continuity conditions for the species transport at the interfaces x ¼ x2 and x ¼
x3 .
Symbol Description Value
The interface of two Species Flux continuity condition
ε Electrode porosity 0.93 [40]
electrodes and membrane
rp Mean pore radius (mm) 50.3 [40]
As Specific surface area of the porous electrode (m2 m3) 3.5Ⅹ104 [40] Negative electrode side Hþ ! !ele
 n $ N Hþ ¼  ðN eler eler eler
Hþ  2N VO2þ  4N VOþ Þ
CKC Kozeny-Carmen Coefficient 180 [40] at x ¼ x2 (see Fig. 1a) 2

hcell Electrode height (m) 0.035 V3þ ! !ele

 n $ N V2þ ¼  ðN eler
V2þ
 N eler
VO2þ
 2N eler
VOþ Þ 2
wcell Electrode width (m) 0.0285
VO2þ ! !ele
Electrode thickness (m) 0.004  n $ N V3þ ¼  ðN eler þ 2N eler þ 3N eler
VOþ Þ
Lele V3þ VO2þ 2

Lcc Current collector thickness (m) 0.006 HSO ! !ele

4
 n $ N HSO4 ¼  N eler
HSO
Electronic conductivity of electrode (S m1)
4
sele
s
66.7 [40]
Positive electrode side at Hþ ! !ele
scc Electronic conductivity of current collector (S m1) 1000 [40]  n $ N Hþ ¼ N eler eler
Hþ  2N V2þ
s x ¼ x3 (see Fig. 1a)
m Average dynamic viscosity of negative electrolyte (Pa 0.0025 [43] VO2þ ! !ele
 n $ N VO2þ ¼ N eler
VO2þ
þ 3N eler
V2þ
þ 2N eler
V3þ
s)
mþ VOþ ! !ele
Average dynamic viscosity of positive electrolyte (Pa 0.005 [40] 2  n $ N VOþ2 ¼ N eler eler eler
VOþ  2N V2þ  N V3þ
2
s) HSO ! !ele
mw Average dynamic viscosity of water (Pa s) 0.001 [3]
4
 n $ N HSO4 ¼ N eler
HSO 4

r Average density of negative electrolyte (kg m3) 1300 [43]

rþ Average density of positive electrolyte (kg m3) 1350 [40]
rw Density of water (kg m3) 999 [40]
Mw Molar mass of water (g mol1) 18  
V2þ diffusion coefficient (m2 s1) 2.4Ⅹ1010 [14] v ctank V tank ð ð  
Dele
V2þ i  out out 
V 3þ 2
diffusion coefficient (m s 1
) 2.4Ⅹ10 10
[14] ¼ wcell vl ci dl  vin c
l i
in
dl (23)
Dele
V3þ vt
Dele VO2þ diffusion coefficient (m2 s1) 3.9Ⅹ1010 [14]
VO2þ
Dele VOþ 2 1
2 diffusion coefficient (m s ) 3.9Ⅹ1010 [14] where V tank is the volume of the tank in each half-cell, V tank and
VOþ 2

Dele Hþ diffusion coefficient (m2 s1) 9.312Ⅹ109 [52] vV tank in Eq. (23) can be acquired by solving the following equation:
Hþ vt
Dele HSO 2 1
4 diffusion coefficient (m s ) 1.33Ⅹ109 [40]
HSO4

SO2 2 1
1.065Ⅹ109 [40] vV tank  
Dele 4 diffusion coefficient (m s )
SO2 ¼ wcell Lele vout  vin (24)
vt l l
4

k Reaction rate constant for negative reaction (m s1) 7.0Ⅹ108 [40]

kþ Reaction rate constant for positive reaction (m s1) 2.5Ⅹ108 [40]
a Negative charge transfer coefficient 0.45 [40]
At the outlet of the battery (i.e.y ¼ hcell ), the gradients of the
aþ Positive charge transfer coefficient 0.55 [40] species concentration are all set to be zero:
E0; Standard reduction potential at negative electrode (V) 0.255 [15]
ele !
E0;þ Standard reduction potential at positive electrode (V) 1.004 [15] Deff
i Vci $ n ¼ 0 (25)
Lmem Membrane thickness (mm) 203 [15]
cf Fixed acid concentrations (mol L1) 1.99 [40] At the electrode/current collector interface (i.e., x ¼ x1 ; x ¼ x4 )
zf Fixed acid charge 1 and the upper and bottom walls of membrane region, the
kf Electro-kinetic permeability in the membrane (m2) 1.13Ⅹ1020 [42]
impermeable-wall condition for species and mass transfer are
kp Hydraulic permeability in the membrane (m2) 1.58Ⅹ1018 [42]
Dmem V2þ membrane diffusion coefficient (m2 s1) 9.435Ⅹ1012
specified, i.e.,
V2þ
[43]
! !
Dmem V3þ membrane diffusion coefficient (m2 s1) 5.93Ⅹ1012 [40] N i$ n ¼ 0 (26)
V3þ
Dmem VO2þ membrane diffusion coefficient (m2 s1) 5.0Ⅹ1012 [40]
VO2þ
Dmem
VOþ
VOþ 2 1
2 membrane diffusion coefficient (m s ) 1.17Ⅹ1012 [40]
2
þ 1
Dmem
Hþ
H membrane diffusion coefficient (m s 2
) 3.35Ⅹ109 [42]
Dmem
HSO HSO 2 1
4 membrane diffusion coefficient (m s ) 4.0Ⅹ1011 [42]
4 2.2.2. Boundary conditions for charge transport
At x ¼ x0 , the electronic potential in solid phase is set to be zero,
i.e.

zero, which is attributed to the assumption that the side reactions fele
s ¼0 (27)
occur immediately. As aforementioned, the permeation of vana-
At x ¼ x5 , the current density condition is applied, i.e.
dium ions across the membrane results in the unwanted side re-
actions. Herein, the species generation or consumption by side ! !cc
reactions resulting from the vanadium crossover is treated as the  n $ j s ¼ Iapp (28)
flux boundary conditions for certain species at the electrode/ At the electrode/current collector interfaces (i.e. x ¼ x1 ; x ¼ x4 ),
membrane interface. Details can be found in Table 3. the continuity of electronic current density is applied, i.e.,
At the inlet of the battery (i.e. y ¼ 0), the concentrations of each
species for both electrodes are given based on the supplying con- !cc ! !ele !
j s $n ¼ J s $n (29)
ditions, i.e.,
The ionic current density is set to be zero.
At the electrode/membrane interfaces (i.e., x ¼ x2 , x ¼ x3 ), the
cele
i ¼ ctank
i (22) electronic current density is set to be zero. Ionic potential conti-
nuity condition is applied:
where ctank
i is the transient concentration of species i in the tank.
During battery operation, the transient concentration of species fmem
l ¼ fele
l (30)
i in the tank can be simulated based on the mass balance equation:
288 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299

At y ¼ 0 and y ¼ hcell , both electronic and ionic current are set to Table 4
Initial conditionsand operating parameters.
be zero:
Symbol Description Value
! !cc V2þ initial concentrations in negative electrolyte (mol L1)
 n $ j s ¼ 0 x0 < x < x1 ; x4 < x < x5 c0;ele
V2þ
0.156
! !ele (31) c0;ele V3þ initial concentrations in negative electrolyte (mol L1) 0.884
 n $ j l ¼ 0 x1 < x < x2 ; x3 < x < x4 V3þ
! !mem
2þ 1
c0;ele VO initial concentrations in positive electrolyte (mol L ) 0.884
n$ j l ¼ 0 x2 < x < x3 VO2þ
c0;ele VOþ 1
2 initial concentrations in positive electrolyte (mol L ) 0.156
VOþ2

c0;ele Hþ initial concentrations in negative electrolyte (mol L1) 4.4475

Hþ ;

c0;ele Hþ initial concentrations in positive electrolyte (mol L1) 5.0975

Hþ ;þ

c0;ele HSO 1
4 initial concentrations in negative electrolyte (mol L ) 2.6685
2.2.3. Boundary conditions for fluid flow HSO 4 ;

At the inlet of electrode, the velocity along y-direction is set, c0;ele HSO
4 initial concentrations in positive electrolyte (mol L
1
) 3.0585
HSO ;þ
4

which is c0;mem Initial concentrations of all vanadium species in membrane 0

Vanadium
(mol L1)
c0;mem Hþ initial concentrations in membrane (mol L1) 1.99
! Q
 n $!
v ¼ x1 < x < x2 ; x3 < x < x4 (32) Hþ
Electrolyte volume in each half-cell (mL) 25
wcell Lele V0
T Operating temperature (K) 300
At the outlet of the electrode, the pressure boundary condition is Iapp Current (mA cm2) 50
applied, which is u Inlet volumetric flow rate (mL min1) 20
pout Output pressures (Pa) 0
e1860
p ¼ pout (33)
At the electrode/current collector interface and at the upper and
bottom interface of the membrane region, the impermeable-wall
2
condition for mass transfer and fluid flow is specified, i.e.,  a þ  ð1aþ Þ csurfþ

jþ ¼ As Fkþ cele cele 4 VO2 exp aþ F hþ

! VO2þ VOþ
n $Vp ¼ 0 (34)
2 cele
VOþ
RT
2
3
csurf2þ

ð1  aþ ÞF h þ 5
 VO exp (36b)
cele2þ RT
VO
2.2.4. Initial conditions
Initially, SOC is set to be 0.15 at the beginning of the charge- whereAs denotes the specific surface area of the porous electrodes,
discharge cycle and it is defined as follows: and h is the overpotential for the electrode reaction, which is
defined as
cele
2þ
Negative Electrolyte : SOC ¼ V
(35a) h ¼ fele ele
s  fl  E0 (37)
cele þ cele
V2þ 3þ
V
In Eq. (37), E0 is the equilibrium thermodynamic potential,
which can be calculated by using Nernst equation
cele
VOþ
Positive Electrolyte : SOC ¼ 2
(35b) !
cele þ cele2þ 0 RT cele
3þ
VOþ 2 VO E0; ¼ E0; þ In V (38a)
F ce 2þ
V

cele
2þ þ c
ele
VOþ 0  2 1
V
Whole battery : SOC ¼ 2
(35c) c ele $ cele
cele þ cele þ cele
VOþ
þ cele2þ 0 RT B VO2 þ
H þ
C
V2þ V3þ 2 VO E0;þ ¼ E0;þ þ In@ A (38b)
F cele2þ
The initial vanadium ions concentrations in both tanks are set to VO

be 1.04 mol L1. The volumes of electrolyte in both half-cells are

Notice that the surface concentration of each species i is actually
kept at 25 ml. More details can be found in Table 4.
different from the bulk concentration of species i inside the pores of
the electrode due to the local transfer resistance from the pore to
the active reaction surface. The transfer rate of species from bulk
2.3. Electrochemical kinetics solution to active surface is physically balanced by mass con-
sumption or generation rate of species caused by electrode re-
The transfer current densities for negative and positive elec- actions and the description of aforementioned process is presented
trode reactions are formulated by using the Bulter-Volmer ex-
in Table 5. Finally, the species concentration at active surface csurf
2þ ,
pressions, which are as follows: V
csurf
3þ , c
surf , and csurf can be expressed as a function of species
VOþ
"
2þ
V VO
 a   ð1a Þ csurf
2

3þ a F h concentration in bulk solution. The detailed expressions are pre-

j ¼ As Fk cele
V2þ
cele
V3þ
V
exp sented in Table 5.
cele RT
V3þ

#
csurf
2þ ð1  a ÞF h 2.4. Numerical method
V
 exp (36a)
cele RT
V2þ
The mass/species transport in a VRFB during charge-discharge
cycling can be obtained by solving the above governing equations
 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299 289

Table 5
Species balance at active reaction surface and expressions of species surface concentration.

Term Expression
2þ
! " !
! #

V cele surf
2þ  c 2þ a ð1a Þ csurf
2þ ð1  a ÞF h csurf a F h
V V V V3þ
FDV2þ ¼ Fk ðcele
2þ Þ ðcele
3þ Þ  exp  exp
rp V V cele RT c ele RT
V2þ V3þ
! " surf !
!
#
V3þ cele
V
surf
3þ  c 3þ
V a ð1a Þ c 2þ
V ð1  a ÞF h csurf
V3þ a F h
FDV3þ ¼  Fk ðcele
2þ Þ ðcele
3þ Þ  exp  exp
rp V V cele RT cele RT
V2þ V3þ
! 2 0 1
! 3
VO 2þ
cele2þ  csurf2þ
csurf
csurf2þ

aþ ð1  aþ ÞF hþ
ð1aþ Þ VOþ aþ F hþ 5
FDVO2þ VO VO
¼ Fkþ ðcele2þ Þ ðcele
VOþ
Þ 4  @ ele2 Aexp
VO
exp
rp VO 2 RT cele2þ
cVOþ RT
VO 2
0 1 2 ! 0 1 3
VOþ cele  csurf csurf2þ
csurfþ

2
VOþ VOþ aþ ð1aþ Þ ð1  aþ ÞF hþ @ VO2 Aexp aþ F hþ 5
FDVOþ @ 2 2 A
¼  Fkþ ðcele2þ Þ ðcele
VO þÞ  4 VO exp 
2 rp VO 2 cele2þ RT cele
VOþ
RT
VO 2

csurf
2þ cele ele ele
2þ þ A1 ðc 2þ þ c 3þ Þ
V V V V
1 þ A1 þ B1
csurf 3þ þ B1 ðc 2þ þ c 3þ Þ
cele ele ele
3þ
V V V V
1 þ A 1 þ B1
csurf2þ cele2þ þ A2 ðcele2þ þ cele
VOþ
Þ
VO VO VO 2

1 þ A 2 þ B2
csurf
VOþ
cele
VOþ
þ B2 ðcele2þ þ cele
VOþ
Þ
2 2 VO 2

1 þ A2 þ B2

!a
A1 cele
a F h k $rp V2þ
exp
RT DV2þ cele
V3þ
B1
ele
!ð1a Þ
ð1  a ÞF h k $rp cV3þ
exp
RT DV3þ cele
V2þ
0 1aþ
A2
ele
aþ F hþ kþ $rp @cVO2þ A
exp
RT DVO2þ celeþ
VO2
B2 0 1ð1aþ Þ

ele
ð1  aþ ÞF hþ kþ $rp @ cVOþ2 A
exp
RT DVOþ cele2þ
2 VO

associated with the specific boundary and initial conditions. In this

work, all the governing equations were numerically solved by using
COMSOL Multi-physics software with a combination of the built-in
Tertiary Current Distribution, Secondary Current Distribution,
Darcy's Law, Domain ODEs and DAEs, Global ODEs and DAEs, Events
and Laplace Equation interfaces. In the dynamic simulations, all the
variables are iteratively solved until the pre-set convergent crite-
rions are reached for each time-step, and the relative error toler-
ance of each variable is set to be 2:5  106 . In this work, the mesh
independence has been verified through investigating three
different kinds of gridding systems, i.e., Mesh 1: 36(X-direction) 
8(Y-direction), Mesh 2: 38(X-direction)  10 (Y-direction) and
Mesh 3: 40(X-direction)  12(Y-direction). Total elements of Mesh
1, Mesh 2 and Mesh 3 are, respectively, 288, 380 and 480, and all
elements are quadrilateral. It should be noticed that the grids are
non-uniformly arranged along X-direction, and the elements in the
electrode are distributed through decreasing arithmetic sequence
from the current collector to the membrane side. The charge-
discharge voltages of the VRFB are plotted under three meshes
and the operating conditions are the same as that for charge- Fig. 2. Grid independence verification.
discharge voltage validation in section 2.5. As can be seen in
Fig. 2, for three different meshes, the predicted charge-discharge
2.5. Model validation
voltages of the battery for the first charge-discharge cycle are
completely consistent for three different meshes. In the present
The simulated battery charge-discharge voltages are firstly
studies, Mesh 2 (i.e., 38(X-direction)  10 (Y-direction)) is finally in
compared against experimental data found in the literature to
the simulation in consideration of both the calculating accuracy and
validate the model. The conditions for the simulations are the same
the computing cost. Generally, the simulation for each case spends
as that for experimental measurements [40]. For each half-cell, the
approximately 26 hours on an Intel Xeon 2.5 GHz workstation with
electrolyte solution with the volume of 60 mL and initial vanadium
a 56.0 GB RAM.
ions concentration of 1.04 mol L1 was supplied to the electrode at
290 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299

the volumetric flow rate of 30 mL min1. The battery was charged

from the initial SOC of 0.15 to the upper voltage limit of 1.7 V, and
then discharged to SOC of 0.15 at the applied current density of
40 mA cm2. It is worth noting that the SOC herein is the value of
SOC for the total battery as defined in Eq. (35c). Fig. 3 shows the
comparison of the simulated and measured charge-discharge
voltage of the battery with Nafion 117 membrane in a charge-
discharge cycle. Generally, as can be seen, the simulations can
well capture the variation trends of battery voltage with time, and
the simulated battery voltages well match the experimental data
[40] with an average error below 0.4%, which thus validating the
present model.
To further validate the model, we also compare the predicted
discharge capacity ratio during long-time cycling with the experi-
mental data [51]. Herein, the discharge capacity ratio of nth cycle is
defined as the ratio of the discharge capacity of nth cycle to the
discharge capacity of the first cycle, i.e.,

0 1nth Fig. 4. Comparison between the predicted discharge capacity ratio of a VRFB and the
ð end
B C experimental data [51].
@ Idt A
start
Discharge
discharge capacity ratio ¼ 0 11th  100% (39) 3. Results and discussion
ð end
B C
@ Idt A It is well known that the imbalance of electrolyte crossover
start
Discharge
causes the buildup of vanadium ions in one half-cell and a corre-
sponding decrease in the other, leading to the problem of battery
The discharge capacity ratio can clearly illustrate the trend of capacity decay [28,30,31,38e51]. As a matter of fact, the crossover
capacity decay of the battery with Nafion 117 membrane during of vanadium ions through the membrane by diffusion, convection
cycling. Fig. 4 compared the simulated and experimentally deter- and migration cannot be entirely avoided. However, the imbalance
mined discharge capacity ratio during 46 charge-discharge cycles of electrolyte crossover during charge-discharge cycling can be
at the applied current density of 50 mA cm2. In each charge- alleviated by optimizing the operating strategies, thus minimizing
discharge cycle, the VRFB is charged and discharged to cutoff the battery capacity decay. In the following, the influence of
voltages of 1.7 V and 1.1 V. For both half-cells, the electrolyte solu- asymmetric operating strategies on the characteristics of capacity
tion with initial vanadium ions concentration of 1.04 mol L1 and decay, vanadium ions crossover as well as the charge-discharge
the volume of 25 mL was pumped to the electrode at the volumetric performance of a VRFB with Nafion 117 membrane were investi-
flow rate of 20 mL min1. Clearly, as can be seen, the discharge gated in detail. The operating conditions for the asymmetric
capacity ratio is gradually decreased when undergoing long-time operating conditions are the same as those for discharge capacity
cycling. The predicted variation trend of capacity decay well ratio validation.
matches the experimental results [51], and the maximum error
between the simulated results and the experimental data is less
3.1. Effects of asymmetric operating concentrations
than 3.2%.

3.1.1. Capacity decay and vanadium ions crossover

Fig. 3. Comparison between the predicted charge-discharge voltages of a VRFB and the
experimental data [40].
In this section, the influences of asymmetric initial electrolyte
concentrations on the characteristics of battery capacity decay and
vanadium ions crossover were investigated. In the simulations, the
initial vanadium ions concentration of negative electrolyte is fixed
at 1.04 mol L1 while the initial concentration of positive electrolyte
is varied from 1.04 mol L1 to 2.00 mol L1. Four cases were
compared, i.e., Base Case: c0v;tot;þ ¼1.04 mol L1, Case A-1:
c0v;tot;þ ¼1.30 mol L1, Case A-2: c0v;tot;þ ¼1.57 mol L1 and Case A-3:
c0v;tot;þ ¼2.00 mol L1. To maintain the same initial amount of va-
nadium ions in both half-cells, the electrolyte volume in positive
half-cell is correspondingly varied for various asymmetric con-
centration conditions. Details can be found in Table 6.
Fig. 5 shows the variation trend of the predicted discharge ca-
pacity ratio during 46 charge-discharge cycles for four cases stud-
ied. As can be seen, for Base Case, the discharge capacity ratio is
significantly decreased during battery cycling. Totally, the discharge
capacity is lowered by 20.5% after 46 cycles. With asymmetric
concentration strategies (i.e., increasing initial vanadium ions
concentration of positive electrolyte), the discharge capacity decay
can be obviously suppressed. For example, increasing the vanadium
ions concentration of positive electrolyte to 1.30 mol L1 (i.e., Case
 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299 291

Table 6
Details of various asymmetric operating conditions.

Various cases c0v;tot;þ V 0;tank n0v;tot;þ c0;ele c0;ele pout

þ
Hþ ;þ HSO ;þ
4
/mol L1 /mL /mol /mol L1 /mol L1 /Pa

Base Case 1.04 25.0 0.026 5.0975 3.0585 0

Case A-1 1.30 20.0 0.026 6.3719 3.8231 0
Case A-2 1.57 16.5 0.026 6.7386 4.0432 0
Case A-3 2.00 13.0 0.026 9.8029 5.8817 0
Case B-1 1.04 25.0 0.026 5.0975 3.0585 750
Case B-2 1.04 25.0 0.026 5.0975 3.0585 1250
Case B-3 1.04 25.0 0.026 5.0975 3.0585 1860

Fig. 5. Effects of asymmetric electrolyte concentration conditions on the discharge Fig. 6. Variations of the amount of vanadium ions in each half-cell for various asym-
capacity of a VRFB during 46 charge-discharge cycles. metric electrolyte concentration conditions during 46 charge-discharge cycles.

A-1), the total discharge capacity loss is lowered to 13.2%. With
increasing the positive electrolyte concentration to 2.00 mol L1
(i.e., Case A-3), the discharge capacity is almost kept unchanged
during 46 charge-discharge cycles. The above results indicated that
increasing initial concentration of total vanadium ions in positive
half-cell can mitigate discharge capacity decay during battery
cycling.
To explain the reason why the discharge capacity decay can be
reduced by applying asymmetric electrolyte concentration opera-
tion strategies, the variation trends of total vanadium ions in each
half-cell at the end of discharge process in each cycle are clearly
plotted in Fig. 6. Obviously, for Base Case, the total amount of va-
nadium ions in positive half-cell is significantly increased from
0.026 mol to 0.030 mol during 46 charge-discharge cycles whereas
the total amount of vanadium ions in negative half-cell is corre-
spondingly decreased from 0.026 mol to 0.022 mol. This means that
the net crossover of vanadium ions is from the negative half-cell to
the positive half-cell. As a consequence, the decrease of total
amount of vanadium ions in negative half-cell becomes the domi-
nant factor limiting the battery discharge capacity. With increasing
the initial vanadium ions concentration of positive electrolyte, the
imbalance of vanadium ions in two half-cells is greatly suppressed.
Especially, for Case A-3, the total amount of vanadium ions in each
half-cell can be maintained constant during battery cycling, indi-
cating that the crossover of vanadium ions is completely balanced
during battery cycling, which is the right reason that leads to the
constant discharge capacity during battery cycling.
The alleviation of electrolyte imbalance can also be illustrated by
plotting the transient SOC values in both negative and positive
electrodes of the battery during the 45th charge-discharge cycle. As
indicated in Fig. 7, for Base case, the SOC in the positive electrode is
much lower than that in the negative electrode. This can be
explained as follows. In charge process, the amount of V3þ ions
reduced to V2þ ions is equal to the amount of VO2þ ions oxidized to
VOþ2 ions. Because of less amount of vanadium ions in negative half-
cell, almost all the V3þ ions is reduced to V2þ ions and thus the SOC
value can reaches nearly at the end of the charge process whereas
only part of VO2þ ions is converted to VOþ 2 ions, resulting in a
relatively lower value of SOC in the positive electrode. Besides, the
variation rate of SOC in the negative electrode is higher than that in
the positive electrode due to the same reacting amounts for both
electrodes and less vanadium ions in the negative half-cell. With
increasing the initial vanadium ion concentration of positive elec-
trolyte, the difference in SOC values of both electrodes is obviously
decreased and the identical SOC values of both electrodes can be
achieved for Case A-3, also indicating the balance of vanadium ions
in two half-cells. Also, it is clear that the charge-discharge time of a
cycle is greatly improved with increasing the initial concentration
of positive electrolyte.
To illustrate the behavior of vanadium ions crossover through
the membrane, Fig. 8 displays the transfer flux of vanadium ion
couples (i.e.,V2þ =V3þ couple, VO2þ =VOþ2 couple) by diffusion, con-
vection and migration as well as the net crossover flux of vanadium
ions in the 45th charge-discharge cycle for four different cases
studied. In the figure, positive flux value represents the transfer of
vanadium ions from negative to positive side whereas the negative
value means the vanadium ions transfer from positive to negative
side. Clearly, as can be seen, among three different transfer modes,
the diffusion transfer of vanadium ions driven by concentration
292 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299
Fig. 7. Variations of SOCs in negative and positive electrodes in the 45th charge-discharge cycle for various asymmetric electrolyte concentration conditions.
gradient across the membrane is the dominant factor responsible
for vanadium ions crossover in the membrane. As indicated in
Fig. 8a, due to the different diffusion coefficients of various vana-
dium ions, the diffusion flux of V2þ =V3þ couple from the negative to
positive side is obviously not equal to the diffusion flux of
VO2þ =VOþ 2 couple, which is the main reason that causes the
imbalance of vanadium ions crossover. As for the convection and
migration transfer flux vanadium ions, both exhibit relatively little
effects on the total fluxes of vanadium ions couples. Also, it is found
that the direction of convective transfer of vanadium ions couples is
changed during charge and discharge processes. It can be explained
as follows. The convective transfer of vanadium ions is composed of
osmotic convection and electro-osmotic convection. The osmotic
convection driven by pressure gradient across the membrane is
nearly zero because of same operating pressure in both electrodes,
whereas the electro-osmotic convection caused by ionic current
flow contributes to the convective flux of vanadium ions crossover,
which is determined by the applied current direction [41]. As for
the net vanadium ions crossover, as shown in Fig. 8a, a net flux of
vanadium ions is transferred from negative to positive half-cell in a
charge-discharge cycle mainly due to the reason that the diffusion
flux of V2þ =V3þ couple from negative to positive side is higher than
that of VO2þ =VOþ 2 couple from positive to negative side, which thus
causes the accumulation of vanadium ions in the positive half-cell
as indicated in Fig. 6. Increasing the initial concentration of positive
electrolyte, the diffusion flux of VO2þ =VOþ
2 couple from positive to
negative side in a cycle is enhanced due to the increased concen-
tration gradient and the increased charge-discharge time, which
counteracts the diffusion flux of V2þ =V3þ couple from negative to
positive side. As a result, the imbalance of vanadium ions crossover
can be alleviated. As can be seen in Fig. 8, the net transfer flux of
vanadium ions is obviously decreased with applying asymmetric
concentration operating conditions, and a complete balance of
vanadium ion couple crossover can be achieved in Case A-3.
3.1.2. Charge-discharge voltages
The change of initial vanadium ion concentration of positive
electrolyte will definitely influence the charge-discharge voltage of
the battery. In this section, the battery charge-discharge perfor-
mances under various initial concentrations of positive electrolyte
(i.e. Base Case, Case A-1, Case A-2 and Case A-3) were examined in
detail.
Fig. 9 shows the simulated time-dependent battery voltages
during the 45th charge-discharge cycle for four cases studied. It is
 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299
Fig. 8. Transfer flux of vanadium ion couples by diffusion, convection and migration as well as the net flux of vanadium ions crossover in the 45th charge-discharge cycle for various
asymmetric electrolyte concentration condition.
Fig. 9. Effects of asymmetric electrolyte concentration conditions on the charge-
discharge voltages of a VRFB in the 45th charge-discharge cycle.
seen that the charge-discharge time of the battery is greatly
improved with increasing the initial vanadium ions concentration
of positive electrolyte, indicating the improvement of battery
discharge capacity. It is also shown that the charge voltage of the
293
battery is obviously lowered while the discharge voltage of the
battery is greatly increased with increasing the initial vanadium
ions concentration of positive electrolyte. This means that the
battery charge-discharge performance can also be improved with
adopting asymmetric electrolyte concentration operation strategy.
To clearly explain the reason that causes the improvement of bat-
tery charge-discharge performance with asymmetric electrolyte
concentration operation strategy, the variations of potential losses
in both electrodes of the battery during the 45th charge-discharge
cycle for various initial concentrations of positive electrolyte were
displayed in Fig. 10. Herein, the potential loss of electrode reaction,
DEloss , is defined as follows
DEloss ¼ jhj ¼ fele ele 
s  fl  E0  (40)
As can be seen in Fig. 10, generally, for all cases studied, the
battery potential losses are much higher at the beginning and the
end of charge/discharge processes. This can be explained as follows.
At the starting and the end of charge (or discharge) processes, the
concentration of one kind of vanadium ions in each electrode is low
and even approaching zero, which thus lowers the reaction kinetics
and increases the potential loss as indicated in Eq. (40). For various
initial concentrations of positive electrolyte, the potential losses in
both electrodes are obviously different. As can be seen in Fig. 10b,
increasing the initial concentrations of positive electrolyte, the
mean potential loss of positive electrode reaction is greatly
294 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299
Fig. 10. Potential loss of negative electrode reaction and potential loss of positive
electrode reaction in the 45th cycle for asymmetric electrolyte concentrations.
decreased owing to the decreased activation and concentration
polarizations. Nevertheless, the mean potential loss of negative
electrode reaction is also slightly decreased as indicated in Fig. 10a,
which is due to the difference of the total amount of vanadium ions
in negative electrode for different cases studied as indicated in
Fig. 6.
The above results indicated that with asymmetric concentration
operation strategies proposed in this study, the overall battery
charge-discharge performance can also be improved due to the
decreased potential losses of electrode reactions.
3.2. Effects of asymmetric operating pressures
3.2.1. Capacity decay and vanadium ions crossover
In this part, the effects of asymmetric outlet pressures on the
behavior of battery discharge capacity decay and the characteristics
of vanadium ions crossover were detailedly investigated. In the
simulations, the relative value of outlet pressure (i.e., the relative
pressure between the absolute outlet pressure of electrolyte and
the atmospheric pressure) for negative electrode is fixed at 0 Pa,
while the relative value of outlet pressure for positive electrode is
increased. Four cases were studied, i.e., Base Case: pout
þ ¼ 0 Pa, Case
B-1: pout
þ ¼ 750 Pa, Case B-2: pout
þ ¼ 1250 Pa and Case B-3:
pout
þ ¼ 1860 Pa. Details can be found in Table 6.
Fig. 11 shows the variation trends of the discharge capacity ratio
during 46 charge-discharge cycles for four cases studied. As can be
seen, for Base Case, the discharge capacity of the battery is
remarkably decreased by 20.5% during 46 charge-discharge cycles.
With asymmetric operation pressures strategy (i.e., increasing the
relative value of positive outlet pressure), the decay behavior of
battery discharge capacity can be obviously suppressed. For
example, increasing relative value of positive outlet pressure to
750 Pa (i.e., Case B-1), the total discharge capacity loss during 46
cycles is decreased to 10.0%. With increasing the relative value of
positive outlet pressure to 1860 Pa (i.e., Case B-3), the discharge
capacity during 46 charge-discharge cycles is kept almost un-
changed. The above results imply that the asymmetric operating
pressure strategy (i.e., increasing the relative value of positive
outlet pressure) can help to mitigate the problem of discharge ca-
pacity decay during battery cycling.
To clearly explain the reason why the discharge capacity decay
can be suppressed by increasing relative value of the positive outlet
pressure, Fig. 12 displays the variation of total amount of vanadium
ions in each half-cell at the end of discharge process for each cycle.
For Base Case, the vanadium ions is gradually accumulated in
positive half-cell during battery cycling due to the net transfer flux
of vanadium ions from the negative to the positive half-cell.
Improving relative value of the positive outlet pressure, the
imbalance of the amounts of vanadium ions in two half-cells is
greatly mitigated. Especially, for Case B-3 (i.e., increasing relative
value of the positive outlet pressure to 1860 Pa), the amount of
vanadium ions in each half-cell can be maintained constant during
battery cycling, implying that the crossover of vanadium ions is
balanced in each cycle. The above results indicated that the refer-
ence outlet pressure of 1860 Pa for positive electrode is the point
that balancing the vanadium crossover as well as eliminating the
capacity decay of the battery, which is the foundation for the
determination of such pressure constrains.
The impact of asymmetric operating pressure strategy on the
electrolyte imbalance can also be displayed by comparing the
variation curves of SOC for both negative and positive half-cell in
the 45th charge-discharge cycle. As shown in Fig. 13, clearly, there is
great discrepancy between the SOC values and SOC variation rates
for positive and negative half-cells for Base Case. The reason for the
Fig. 11. Effects of asymmetric operation pressures on the discharge capacity of a VRFB
during 46 charge-discharge cycles.
 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299
Fig. 12. Variations of the amount of vanadium ions in each half-cell for various
asymmetric operation pressures during 46 charge-discharge cycles.
phenomena is explained in detail in section 3.1.1. Increasing relative
value of the positive outlet pressure, the difference in SOC values of
Fig. 13. Variations of SOCs in negative and positive electrodes in the 45th charge-discharge cycle for various asymmetric operation pressures conditions.
295
both electrodes can be significantly obviously abated and the
identical SOC values of both electrodes can be realized for Case B-3,
which also means the balance of vanadium ions in two half-cells.
Besides, it is seen that the charge-discharge time of the 45th cycle
is greatly increased with improving relative value of the positive
outlet pressure.
To reveal the impact of asymmetric operating pressure strategy
on the behavior of vanadium ions crossover, the transfer flux of
vanadium ion couples (i.e., V2þ =V3þ couple, VO2þ =VOþ 2 couple) by
diffusion, convection and migration as well as the net crossover flux
of vanadium ions in the 45th charge-discharge cycle for various
cases studied are clearly presented in Fig. 14. It is clear that
increasing relative value of the positive outlet pressure, the
convective flux of vanadium ions is obviously enhanced during the
charge process, whereas the convective flux of vanadium ions is
decreased during the discharge process. Consequently, the imbal-
ance of convection flux of vanadium ions is enhanced, which in turn
offsets the imbalance of diffusion flux of vanadium ions in an entire
charge-discharge cycle and thus resulting in the suppression of net
crossover of vanadium ions. To illustrate the impact of asymmetric
outlet pressure strategy on the imbalance of convective flux of
vanadium ions during the charge and discharge processes, Fig. 15
also displays the superficial velocity of osmotic convection driven
296 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299
Fig. 14. Transfer flux of vanadium ion couples by diffusion, convection and migration as well as net crossover flux of vanadium ions crossover in the 45th charge-discharge cycle for
various asymmetric operation pressures condition.
by pressure gradient across the membrane and the velocity of
electro-osmotic convection due to charge transport in the mem-
brane at the SOC of 0.5 in the 45th cycle. As can be seen, the di-
rection of electro-osmotic convection is changed in the charge and
discharge processes, while its magnitude keeps constant because of
the same value of current density during charge and discharge
processes. As for the osmotic convection from positive to negative
electrode caused by pressure gradient, it is increased when relative
value of the positive outlet pressure is increased. Consequently, the
convection flux of vanadium ions is enhanced during charge pro-
cess while it is lowered during discharge process.
3.2.2. Charge-discharge performance
The influence of asymmetric outlet pressure on battery charge-
discharge performance was explored in this section. Fig. 16 shows
the simulated dynamic battery voltages in the 45th charge-
discharge cycle for cases studied. Generally, the charge-discharge
time of the battery is greatly improved with increasing relative
value of the positive outlet pressure, indicating the improvement of
battery discharge capacity. However, the mean charge/discharge
voltage of the battery is basically unchanged with increasing rela-
tive value of the positive outlet pressure. The phenomena can be
explained by plotting the potential losses of negative and positive
electrode reactions. As shown in Fig. 17, increasing the relative
value of the positive outlet pressure, the potential loss of negative
electrode reaction is slightly decreased whereas the potential loss
of positive electrode reaction is slightly increased, which thus re-
sults in little effect on the overall voltage of the battery.
4. Conclusion
A two-dimensional, isothermal, transient model with consid-
ering vanadium ions crossover through the membrane is presented
for a vanadium redox flow battery. Emphasis is located on exam-
ining the influence of asymmetric electrolyte concentrations and
asymmetric operation pressures on the characteristics of discharge
capacity decay and vanadium ions crossover as well as the charge-
discharge performance of a VRFB during cycling. The main findings
are as follows:
(1) When the battery is operated at same electrolyte concen-
trations and same operation pressures in both half-cells, a
net flux of vanadium ions is transferred from negative to
positive half-cell during battery cycling mainly due to the
reason that diffusion flux of V2þ =V3þ ions couple through the
membrane to positive side is higher than the diffusion flux of
VO2þ =VOþ 2 ions couple to negative side, causing the accu-
mulation of vanadium ions in positive half-cell and the cor-
responding reduction in the negative side. Consequently, the
battery discharge capacity is gradually reduced during bat-
tery cycling.
 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299 297

Fig. 15. Electrolyte velocity in the membrane by osmotic and electro-osmotic convection at SOC of 0.5 during charge and discharge processes of the 45th cycle for various
asymmetric operation pressures.

unchanged (i.e., asymmetric concentration operating strat-

(3) For asymmetric pressure operating strategy (i.e., increasing
Fig. 16. Effects of asymmetric operation pressure conditions on the charge-discharge
voltages of a VRFB in the 45th charge-discharge cycle.
(2) With increasing the initial vanadium ions concentration of
positive electrolyte while keeping the negative side
egy), the discharge capacity decay can be obviously miti-
gated, which is attributed to the fact that the increased
diffusion flux of VO2þ =VOþ 2 couple to negative side can
diminish the imbalance of vanadium crossover. Nevertheless,
with the increase of initial vanadium concentration of posi-
tive electrolyte, the charge voltage of battery is obviously
lowered while the discharge voltage of the battery is obvi-
ously increased due to the reduced activation and concen-
tration polarizations of both electrode reactions, meaning
that the overall charge-discharge performance of the battery
can be improved with this asymmetric concentration oper-
ating strategy.
relative value of the positive outlet pressure), the discharge
capacity decay can also be suppressed during battery cycling
as the result of improved balance of electrolyte in both
electrodes. This can be explained by the fact that the
imbalance of vanadium ions diffusion crossover is compen-
sated by the increased osmotic-convection crossover driven
by pressure gradient. As for the charge-discharge voltages of
battery, it is almost kept unchanged with increasing relative
value of the positive outlet pressure.
298 M.Y. Lu et al. / Electrochimica Acta 309 (2019) 283e299

k reaction rate constant for electrode reaction (m s1)

L component thickness (m)
M molecular weight (g mol1)
!
n outward normal vector
!
N flux (mol m2 s1)
p pressure (Pa)
Q volumetric flow rate (m3s1)
rp pore radius (mm)
R universal gas constant (J mol1K1)
S source or sink (mol m3 s1)
t time (t)
T temperature (K)
!v velocity vector (m s1)
V volume (m3)
w width (m)
z valence

Greek
a transfer coefficient
ε porosity
h overpotential (V)
k permeability (m2)
m dynamic viscosity (Pa s)
r density (kg m3)
s conductivity (Sm1)
f potential (V)

Superscript
0 initial condition
1st the first cycle
avg average value
cc current collector
eff effective value
ele electrode
in inlet of the electrode
mem membrane
Fig. 17. Potential loss of negative electrode reaction and potential loss of positive nth the nth cycle
electrode reaction in the 45th cycle for asymmetric operation pressures. out outlet of the electrode
surf surface of the electrode
tank tank in the battery
Acknowledgements

Subscript
This work was financially sponsored by the National Natural
 negative half cell
Science Foundation of China (No.51876159) and Shaanxi Province
þ positive half cell
Youth Science & Technology New Star Plan (2016KJXX-56).
cell the battery
f fixed membrane structure
Nomenclature species: V2þ ; V3þ ; VO2þ ; VOþ þ  2
i 2 ; H ; HSO4 and SO4
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s solid or electronic
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