Author's personal copy

Applied Energy 105 (2013) 4756

Contents lists available at SciVerse ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Numerical investigations of ow eld designs for vanadium redox ow

batteries
Q. Xu, T.S. Zhao , P.K. Leung
Department of Mechanical Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China

h i g h l i g h t s
" The performance of VRFBs with different ow elds is numerically simulated.
" A power-based efciency is dened and calculated for different ow elds.
" An optimal ow rate exists for each type of ow eld.
" The serpentine ow eld appears to be more suitable for VRFBs.

a r t i c l e

i n f o

Article history:
Received 16 October 2012
Received in revised form 5 December 2012
Accepted 13 December 2012

Keywords:
Flow battery
Vanadium redox ow battery (VRFB)
Numerical modeling
Flow eld
System efciency

a b s t r a c t
As a key component of ow batteries, the ow eld is to distribute electrolytes and to apply/collect electric current to/from cells. The critical issue of the ow eld design is how to minimize the mass transport
polarization at a minimum pressure drop. In this work a three-dimensional numerical model is proposed
and applied to the study of ow eld designs for a vanadium redox ow battery (VRFB). The performance
of three VRFBs with no ow eld and with serpentine and parallel ow elds is numerically tested.
Results show that when a ow eld is included a reduction in overpotentials depends not only on
whether a ow eld can ensure a more even distribution of electrolytes over the electrode surface, but
also on whether the ow eld can facilitate the transport of electrolytes from the ow eld towards
the membrane, improving the distribution uniformity in the through-plane direction. It is also shown
that the pumping power varies with the selection of ow elds at a given ow rate. To assess the suitability of ow elds, a power-based efciency, which takes account of both the cell performance and
pumping power, is dened and calculated for different ow elds at different electrolyte ow rates.
Results indicate that there is an optimal ow rate for each type of ow eld at which the maximum efciency can be achieved. As the cell with the serpentine ow eld at the optimal ow rate shows the highest energy-based efciency and round-trip efciency (RTE), this type of ow eld appears to be more
suitable for VRFBs than the parallel ow eld does.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Renewable energies like solar and wind are among a few of the
central topics of our time. However, the random and intermittent
nature of renewable energy affects the nal quality of power output. Energy storage is the key technology to solve this problem [1].
Among various existing energy-storage techniques, the all-vanadium redox ow battery (VRFB) offers the promise for large scale
energy storage due to its unique features: tolerance to deep discharge without any risk of damage, long cycle life, active thermal
management and independence of energy and power ratings [26].

Corresponding author. Tel.: +852 2358 8647; fax: +852 2358 1543.
E-mail address: metzhao@ust.hk (T.S. Zhao).
0306-2619/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2012.12.041

Although progress has been made over the past decades, significant technical challenges, including slow electrochemical kinetics
in the positive electrode, low solubility of active species in electrolytes and ions crossover through the polymer membrane, are the
barriers that prevent VRFBs from widespread commercialization.
To address these issues, previous efforts include decorating electrodes with metal or inorganic elements [79] or nd alternative
electrode materials [1012], adding additives to electrolyte to improve its solubility [1315], as well as modifying existing membranes and searching for alternatives [1620], have been widely
reported. The design of ow eld of VRFBs is also closely related
to the above mentioned technical issues. However, the studies on
the ow eld design for VRFBs remain limited.
The ow eld serves four functions [2124]: to distribute electrolytes on the electrode surface, to apply/collect electric current

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48

Q. Xu et al. / Applied Energy 105 (2013) 4756

Nomenclature
AV
c
D
df
E1
E2
Ecell
E0
F
I
~im
~is
j1
j2
K
KCK
k1
k2
km
lmem
!
N
~
n
P
p
Q
R
R_
Rcell
S
T
U
W
~
u
x
y
z

specic surface area of the porous electrode (m2 m3)

concentration (mol m3)
diffusivity (m2 s1)
mean bre diameter (m)
negative open circuit potential (V)
positive open circuit potential (V)
cell voltage (V)
equilibrium potential (V)
Faraday constant (C mol1)
current density (A m2)
current density in the solid matrix (A m2)
current density in the electrolyte solution (A m2)
negative electrode current density (A m3)
positive electrode current density (A m3)
permeability of porous material (m2)
CarmanKozeny constant
standard reaction rate constant for negative reaction
(m s1)
standard reaction rate constants for positive reaction
(m s1)
local mass transfer coefcient (m s1)
membrane thickness (m)
molar ux (mol m2 s1)
unit normal vector at a domain boundary
power (W)
pressure (Pa)
volumetric ow rate (ml s1)
gas constant, 8.314 (J mol1 K1)
source term in species conservation
(mol m3 s1)
cell resistance (X m2)
surface area of the electrode
temperature (K)
uniformity factor
work (J)
supercial velocity (m s1)
coordinate (m)
coordinate (m)
valence of ion

equation

to/from the cells, to provide a structural support for the electrode

material and to facilitate heat management. Among these functions, the requirements for the latter three are relatively readily
met. However, to design a ow eld that meets the requirement
for the rst function is much more challenging. To make a VRFB
efcient, it is essential to minimize the mass transfer polarization
over the entire electrode. To this end, a uniform distribution of
electrolytes on the electrode surface is required. However, the uniformity of electrolytes on the electrode surface is usually achieved
at the cost of high ow rates, requiring a higher pumping power,
which will reduce the overall efciency of ow batteries. Hence,
the key issue associated with the ow eld design is how to minimize the mass transport polarization at a minimum pressure drop
through the ow eld.
A few experimental investigations into ow elds of VRFBs have
been reported [2527]. Zhu et al. [25] investigated the effects of
two different ow elds, one with a ow-pass pattern while the
other with a ow-through pattern, on the performance of a VRFB.
The experimental results suggested that the ow-through pattern
tended to increase the electrode effective active area and to enhance the uniformity of liquid electrolyte, resulting in an improvement in the energy efciency by up to 5%. Recently, Zawodzinski

Greek

a+
a
e

w
g
l
m
q
rm
rmem
/m
/mem
/s

anodic transfer coefcients

cathodic transfer coefcients
porosity of porous electrode
efciency
over-potential (V)
ionic mobility (m2 V1 s1)
kinematic viscosity (m2 s1)
density (kg m3)
conductivity of the solid matrix (S m1)
conductivity of polymer electrolyte membrane (S m1)
potential in the solid matrix (V)
potential in the membrane (V)
potential in the electrolyte solution (V)

Superscripts
0
initial value
e
ending value
eff
effective value
s
value at the pore surface of porous electrode
Subscripts
1
negative electrode
2
positive electrode
char
charge
disch
discharge
H+
proton
water
H2O
in
inlet
m
solid matrix
mem
membrane
out
outlet
s
solution
HSO
bisulfate ion
4
V(II)
V2+ ion
V(III)
V3+ ion
V(IV)
VO2+ ion
V(V)
VO
2 ion

et al. [2628] introduced a so-called zero-gap cell architecture with

a serpentine ow eld, enabling the peak power density to be
767 mW cm2, which is signicantly higher than the conventional
cell conguration; the enhancement of the cell performance was
attributed to the enhanced mass transport and reduced internal
resistance.
Numerical modeling and simulation can provide insight to the
ow eld design. To the best of our knowledge, no numerical
investigations into the effect of ow elds on the performance of
VRFBs have been reported. In this work, a three-dimensional model
based on computational uid dynamics and electrochemical reactions is developed. With this model, the effects of ow eld design
(ow-through with no ow eld, with serpentine and parallel ow
elds, as shown in Fig. 1) on the distributions of ion concentrations,
local overpotential and local current density at various ow rates,
as well as on the system efciency are investigated and the ow
eld design that is more suitable for VRFBs is identied.
2. Mathematical model
Consider a typical single VRFB consisting of a Naon membrane,
two graphite electrodes separated by the membrane and two

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Q. Xu et al. / Applied Energy 105 (2013) 4756

49

Fig. 1. Schematic of the three types of ow elds in the VRFB.

current collectors outside the electrodes. Positive and negative

electrolytes are stored in respective reservoirs and circulated
through respective half-cell compartments by pumps. The electrolytes are made of sulfuric acid solution containing vanadium ions.
Chemical and electrical energy can be interchanged by reversible
electrochemical reactions that take place in the electrodes when
the battery is charged or discharged. The reactions that occur in
the electrodes of the VRFB can be expressed as:

At negative electrode :
At positive electrode :

Charge

Discharge

VO2 H2 O  e

Charge

Discharge

1
VO2 2H

During operation, protons transfer through the membrane while

electrons transfer through an external load to form an electrical circuit. In the electrochemical processes, the concentration of each
vanadium ion with specic valence keeps changing, while the total
vanadium ions concentration is constant in both the positive and
negative electrodes. To describe the relative amount of vanadium
ions with different valences, we dene the SOC as:


SOC

cVII

cVtotal


1

cVV

cVtotal


3
2

where cV(II) and cV(V) are the molar concentrations of V2 ; VO

2;
cv total is the total vanadium ions concentration in a certain electrolyte, and the subscripts 1 and 2 represent the negative and positive
electrode, respectively. Alternatively, SOC can also be dened as:





cVIII
cVIV
SOC 1 
1
cVtotal 1
cVtotal 2

where cV(III) and cV(IV) are the molar concentrations of V3+ and VO2+.
2.1. Simplications and assumptions
We consider a three-dimension system with the xy face located in the membrane middle face and the z-axis located at the
normal line through the middle point of the membrane surface.
The simplications and assumptions used in the present work
are as follows:
(1) As indicated in Eqs. (3) and (4), SOC varies with time. However, when the reservoir is sufciently big, the change in SOC
is relatively small. As a result, the transient charging and discharging processes can be simplied as a steady-state
process.
(2) An isothermal condition is assumed in the entire domain.
(3) The membrane is impermeable to all ions and species,
except for protons.
(4) Possible side reactions, such as hydrogen and oxygen evolutions, are not considered.

2.2. Governing equations

2.2.1. Transport in the ow channel
Several ow eld designs are considered: ow-through with no
ow eld, a serpentine ow eld, and a parallel ow eld. For the
VRFB with the serpentine and parallel ow elds, the ow of electrolyte in the channel can be expressed as:

q~
u rp qmr2~
u  r~
u

where q is the electrolyte density, ~

u is the electrolyte velocity, p is
the pressure and m is the kinematic viscosity.
2.2.2. Transport through the porous electrode
In the ow through the porous electrode, the molar ux of each
!


species, N i (with i representing V2 ; V3 ; VO2 ; VO

2 ; H ; HSO4 ),
can be expressed in terms of the modied NernstPlanck equation
as:

!
~
N i Deff
i rc i  Fzi ci li r/s uc i

where ci represents the concentration of each species, F is the Faradaic constant, zi and li are the valence and ionic mobility of each
species, /s is the ionic potential in the electrolyte solution, and
1:5
Deff
Di
i e

is the effective diffusion coefcient of each species, with e and Di

representing, respectively, the porosity of the electrode and the
free-space diffusivity of each species. The supercial electrolyte
velocity ~
u can be expressed using Darcys law as:

m
q ~
u rp
K

where K is the permeability coefcient. The permeability of a porous medium can be described by the KozenyCarman equation as
[29]:
2

df e3
K CK 1  e2

where df is the ber diameter, KCK is the CarmanKozeny constant,

which characterizes the shape and orientation of the brous material.
The ow of charged species results in the current in electrolyte
solution as:

~ii zi F !
Ni

10

The electrolyte is considered to be electrically neutral:

X
zi c i 0

11

Combining Eqs. (6), (10), and (11), we can express the total current
density in the electrolyte as:

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Q. Xu et al. / Applied Energy 105 (2013) 4756

X
X
X
~i ~ii F zi Deff rci  F 2 z2 ci l r/
s
i
i
i
i

12

The conservation of species can be written as:

r  N i R_ i

13

where R_ i is the generation rate for species i [30].

Combining Eqs. (6) and (13) gives:

_
r  ~
uci r  Deff
i rci r  Fzi c i li r/s Ri

14

Due to the conservation of charge, the charge entering the electrolyte solution is balanced by the charge leaving the solid phase:

r ~i r ~is r ~im

15

where ~
is is the current density in the electrolyte solution and ~im is
the current density in the solid matrix.
The electronic potential in the solid matrix is given by Ohms
law:
2
~
reff
m r /m r  im

16

where reff
m and /m are the effective conductivity and electronic potential of the solid matrix.

the porous region, a+ and a are the anodic and cathodic transfer
coefcients, g1 and g2 are the overpotentials in the negative and positive electrodes, respectively.
The interface concentrations csi can be related to the bulk concentrations ci by balancing the electrochemical reaction rate with
the rate of mass transfer of the vanadium ions to (or from) the electrode surface. For the negative electrode during discharge, the balance is:





a;1 F g1
a;1 F g1
km1 cVII  csVII ek1 csVII exp
 csVIII exp 
RT
RT

and





a;1 F g1
a;1 F g1
km1 cVIII  csVIII ek1 csVIII exp
 csVII exp 
RT
RT

km 1:6  104~
u0:4

22

Combining Eqs. (20) and (21), we can express the concentrations of

V(II) and V(III) at the liquidsolid interface as:

csVII

and

!
rmem
N H 
r/mem
F

csVIII

where rmem and /mem are the conductivity and electronic potential
of the ion-exchange membrane. The values of the constants related
to mass and charge transport can be found in Table 1.

21

where km is the mass transfer coefcient and can be approximated

by [31]:

2.2.3. Transport through the membrane

As proton is the only mobile ion, the current conservation equation is:

17

20



a Fg
km cVII ek1 km cVIII exp  ;1RT 1 =A1

23

B1  C 1 =A1


a Fg
km cVIII ek1 km cVII exp  ;1RT 1 =B1

24

A1  C 1 =B1

where

A1 km ek1 exp

a;1 F g1


25

RT


2.2.4. Reaction kinetics

The electrochemical reactions taking place on the solid surfaces
of the porous electrode can be expressed using the ButlerVolmer
Equation as:

and






a;1 F g1
a;1 F g1
j1 eAV Fk1 csVIII a;1 csVII a;1 exp
 exp 
RT
RT

18

C 1 ek1 2 exp

19

A similar approach can be used to solve the concentrations of V(IV)

and V(V) at the liquid/solid interface of positive electrode.
The overpotentials in Eqs. (18) and (19) are dened as follows:

and





a;2 F g2
a;2 F g2
j2 eAV Fk2 csVV a;2 csVIV a;2 exp
 exp 
RT
RT

Eqs. (18) and (19) are for the negative and positive electrodes,
respectively, where AV is specic surface area of the porous electrode, k1 and k2 are the standard rate constants for negative and positive electrochemical reactions, csi ; i 2 fV2 ; V3 ; VO2 ; VO
2 g are
the vanadium-ion concentrations at the liquidsolid interfaces of

Table 1
Transport properties.
Symbols

Value

Unit

Ref.

V2+ ion diffusivity in electrolyte

V3+ ion diffusivity in electrolyte
VO2+ ion diffusivity in electrolyte
VO
2 ion diffusivity in electrolyte
HSO
4 ion diffusivity in electrolyte
Proton diffusivity in membrane

DV(II)
DV(III)
DV(IV)
DV(V)

2.4  1010
2.4  1010
3.9  1010
3.9  1010

m2 s1
m2 s1
m2 s1
m2 s1

[38]
[38]
[38]
[38]

DHSO4

1.33  109
3.5  1010

m2 s1
m2 s1

[39]
[40]

5.55
1.07  106
1500
1000
10

m2 s1
kg m3
S m1
S m1

Deff
H
KCK

m
q
rm
rmem

[29]

a;1 F g1

26

RT

a  a

;1
;1
F g1
RT

27

g1 /m;1  /s;1  E1

28

and

g2 /m;2  /s;2  E2

29

where E1 and E2 are open circuit potentials for reactions (1) and (2),
respectively, and can be approximated using the relevant Nernst
equation as:

E1 E01

Parameters

CarmanKozeny constant
Electrolyte kinematic viscosity
Electrolyte density
Conductivity of the solid phase
Conductivity of the membrane

B1 km ek1 exp

RT cVIII
ln
F
cVII

30

and

E2 E02

RT cVV c2H
ln
F
cVIV

31
E01

where the equilibrium potentials

and
Then the cell voltage can be written as:

Ecell E02  E01

E02

are given in Table 2.

RT cVV cVII c2H

ln
 g1 g2  IRcell
F
cVIV cVIII

discharging
32

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Q. Xu et al. / Applied Energy 105 (2013) 4756

and

Ecell E02  E01 

IRcell

RT cVV cVII c2H

ln
g1  g2
F
cVIV cVIII

charging

33

where I is the current density and Rcell is the cell electrical

resistance.
2.3. Boundary conditions
The boundary conditions can be specied by referring to Fig. 2
as follows:
At z = z1 (the positive electrolyte/endplate interface),

@ci
0;
@z

i VO2 ; VO2 ; H ; HSO4 :

34
Fig. 2. Computational domain.

At z = z2 (the electrolyte/electrode interface),

ci j ci j ; i VO2 ; VO2 ; H ; HSO4 ;

@/s;2
0;
@z
pj pj :

35
At z = z5 (the rib/electrode interface),

36
37

At z = z2 (the rib/electrode interface),

@/s;2
0; /m;2 Ecell;
@z
!
n 0; i VO2 ; VO2 ; H ; HSO4 :
Ni ~

38
39

40
41
42

At z = z4 (the negative electrolyte/membrane interface),

/s;1 /mem ;
!
Ni ~
n 0; i V2 ; V3 ; HSO4 ;
~imem  ~
n ~is  ~
n for proton:

43
44

50

At z = z6 (the negative electrolyte/endplate interface),

@ci
0;
@z

i V2 ; V3 ; H ; HSO4 :

51

@/s
0;
@x

@/m
0;
@x

52

@ci
0; i V2 ; V3 ; H and HSO4 for negative side;
@x

i VO2 ; VO2 ; H and HSO4 for positive side:

45

@/m
0;
@y

46

@ci
0;
@y

i V2 ; V3 ; H and HSO4 for negative side;

47

i VO2 ; VO2 ; H and HSO4 for positive side:

54

48

53

At y = 0 and y = H,

@/s
0;
@y

At z = z5 (the electrolyte/electrode interface),

ci j ci j; i V2 ; V3 ; H ; HSO4 ;
@/s;1
0
@z
pj pj :

49

At x = 0 and x = L,

At z = z3 (the positive electrolyte/membrane interface),

/s;2 /mem ;
!
n 0; i VO2 ; VO2 ; HSO4 ;
Ni ~
~imem  ~
n ~is  ~
n for proton:

@/s;1
0; /m;1 0;
@z
!
n 0; i V2 ; V3 ; H ; HSO4 :
Ni ~

55

At the inlet,

~
u ~
u0

56

At the outlet,

Table 2
Geometric and operating parameters.

p pout
Unit

Ref.

57

Parameters

Symbols

Value

Cathodic transfer coefcient for

reaction (1)
Anodic transfer coefcient for
reaction (1)
Cathodic transfer coefcient for
reaction (2)
Anodic transfer coefcient for
reaction (2)
Standard rate constant for
reaction (1)
Standard rate constant for
reaction (2)
Equilibrium potential for
reaction (1)
Equilibrium potential for
reaction (2)

a-,1

0.5

Assumed

a+,1

0.5

Assumed

rp  ~
n 0 except inlet=outlet

a-,2

0.5

Assumed

a+,2

0.5

Assumed

The internal interfacial conditions (42) and (45) are based on the
current balance to associate the variables in both electrodes for iterative solution.

k1

1.75  107

m s1

[30]

k2

3.0  109

m s1

[30]

E01

0.26

[42]

E02

1.004

[42]

At all the boundaries except the inlet/outlet, the pressure satises

the Neumann condition:

58

3. Results and discussion

The variables in the conservation equations were iteratively
solved using the ANSYS 13.0 package with a combination of the
self-written source terms. The package is based on the nitevolume method. The relative error tolerance was set to 1.0E6.

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Q. Xu et al. / Applied Energy 105 (2013) 4756

3.1. Model validation

The electrode area used here is 100 mm  100 mm, with a thickness of 3 mm. For the serpentine and parallel ow elds, both the
height and width of the channel are 3 mm, and the rib width is
3 mm. The detailed geometric and operating parameters are shown
in Table 3. The numerically predicted performance of the VRFB
with no ow eld is validated against the experimental data
[32]. The operating condition was set to be the same as that in
the experiment. Since the cell voltage was measured as a function
of time, the time-dependant experimental data need to be transformed to the SOC-dependant data for the purpose of comparison.
The transformation method can be found elsewhere [12]. The comparison between the numerical and experimental data is shown in
Fig. 3. It is seen that the three-dimensional model well captures the
trend. The slight discrepancies in the cell voltage between the results may be caused by ions crossover through the membrane
and the side reactions that occurred in the experiment but are
not taken account in numerical simulation.

Fig. 3. Comparison between the numerical solutions and experimental data.

1.00

3.2. Species concentration distribution

0.95

In order to quantify the uniformity of species concentration in

the in-plane surface, we introduce a uniformity factor as [33]:

59

where S is the in-plane surface area of the electrode, ci,m is the mean
species concentration in that surface.
Taking the concentration of VO
2 ion as an example, Fig. 4 shows
the concentration uniformity factors at the outer surface of the
electrode (at the interface between the current collector and the
electrode) for the VRFB with no ow eld and with two types of
ow eld at the current density of 40 mA/cm2. The ion concentration at the inlet was set to 1200 mol/m3. When the ow rate is
5 ml/s, it can be seen that the differences in concentration uniformity between three cases are large: the porous electrode with no
ow eld results in a uniformity factor of 0.684, but the parallel
ow eld exhibits a uniformity factor of 0.836. This result implies
that adding a ow eld can signicantly improve the uniformity,
which tends to improve the cell performance. When the ow rate
increases, the uniformity factors associated with all the three cases
are improved and the difference in the uniformity factor between
different ow elds becomes smaller. For instance, at 20 ml/s,

0.90

Uniformity

s
ZZ
1
1
U 1
ci  ci;m 2 ds
ci;m S

0.85
0.80

Serpentine
Porous
Parallel

0.75
0.70
0.65
5

10

15

Fig. 4. Variations in the VO

2 concentration uniformity at the outer surface of
electrode with electrolyte ow rates.

the uniformity factors for that with no ow eld, with the

serpentine and parallel ow elds become 0.929, 0.962 and
0.978, respectively. It should be noted that although increasing
the ow rate can effectively improve the in-plane distribution,

Table 3
Electrochemistry properties.
Parameters

Symbols

Value

Unit

Ref.

Specic surface area

Electrode thickness
Polymer electrolyte membrane
Electrode height
Electrode width
Operating temperature
Electrode porosity
Electrode ber diameter
Initial V2+ ion concentration

AV
de
dmem
h
w
T
e0
df
c0VII

2  105
3  103
1.8  104
1  101
1  101
300
0.7
17.6
1200

m1
m
m
m
m
K
1
lm
mol m3

[41]

Initial V3+ ion concentration

c0VIII

300

mol m3

Initial VO2+ ion concentration

c0VIV
c0VV
c0HSO
4

300

mol m3

1200

mol m3

3000

mol m3

Initial VO
2 ion concentration
HSO
4 ion concentration
+

Initial H ion concentration

c0H

3000

mol m3

Current density
Electrolyte volumetric ow rate
Pump efciency

I
Q

400
5
0.9

A m2
ml s1
1

wpump

20

Flow rate (ml/s)

[41]

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Q. Xu et al. / Applied Energy 105 (2013) 4756

the reduction in concentration overpotential is achieved at the cost

of the increased pumping power in the VRFB system.
3.3. Overpotential distribution
The average values of overpotentials in both positive and negative electrodes of the VRFBs with no ow eld and with two types
of ow eld are listed in Table 4. As can be seen, the parallel ow
eld shows the largest overpotential, while the serpentine ow
eld and the porous electrode with no ow eld exhibit almost
the same overpotentials. It is worth noting that the overpotential
depends on the distribution uniformity of electrolyte in both the
in-plane and through-plane directions. For the porous electrode
with no ow eld, the in-plane distribution of electrolyte is more
uneven than that in the through-plane direction. With the serpentine and parallel ow elds, the electrolyte is distributed onto the
outer surface of the porous electrode (the interface of the ow
channel and the electrode), and transported through the electrode
towards the membrane by diffusion and convection. For a given
ow rate, as the ow velocity in the parallel channel is smaller
than that in the serpentine channel, the weaker convective effect
in the parallel ow eld leads to a more uneven distribution of
the electrolyte in the through-plane direction and low concentrations adjacent to the membrane, which result in the high overpotential. On the other hand, the stronger convective effect with
the serpentine ow eld enables a more even distribution of electrolyte in the through-plane direction, lowering the overpotential.
When the ow rate increases from 5 ml/s to 20 ml/s, the distribution of electrolyte becomes more uniform and the overpotential
(absolute value) of the positive electrode signicantly reduces
from 0.249 V to 0.205 V for the VRFB with the serpentine ow eld,
as shown in Tables 4 and 5. However, the reduction in overpotential is achieved at the cost of the increased pumping power in the
VRFB system, as can also be seen in Table 5. The variations in overpotential in the positive electrode with electrolyte ow rate for the
VRFBs with no ow eld and with two types of ow eld are
shown in Fig. 5. The change trends are similar: The overpotential
decreases with increasing the ow rate, and the decrease rate of
overpotential slows down at higher ow rates. At the same time
the differences are also distinct: The decrease rates of overpotential for the serpentine and parallel ow elds are more rapid than
that for the porous type; and the parallel ow eld exhibits the
highest overpotential at all ow rates. These phenomena can be explained as follows. As discussed in preceding sections, for the VRFB
with the serpentine and parallel ow elds, the vanadium ions in
the electrolyte are supplied to the active sites of electrode not only
by diffusion but also by convection. On one hand, the increased
ow rate can increase the average electrolyte concentration along
the ow direction, which enlarges the concentration difference be-

tween ow channel and the active sites such that enhances the diffusion effect. On the other hand, the convection effect inside the
porous electrode is improved with the increased ow rate and even
distribution of electrolyte in the through-plane direction can be
achieved. That is the reason why the decrease rate of overpotential
with the ow rate for the VRFBs with serpentine and parallel types
is faster than that with the porous type. In addition, Eq. (19) indicates that an exponential relationship exists between the inverse
of ion concentration and the overpotential for a given current,
explaining why the decrease rate of overpotential becomes smaller
at higher ow rates.
3.4. Pressure drop and corresponding pumping power
The pressure drop is an important parameter for selecting
pumps in the VRFB system. Table 4 shows the pressure drops for
porous electrode and two types of ow eld at the ow rate of
5 ml/s. As can be seen, the porous electrode has the highest pressure drop (957 Pa), whereas the parallel ow eld shows the lowest (83 Pa). This result indicates that at small ow rates, including a
ow eld can signicantly reduce the pressure drop, especially
with the parallel type. Table 4 also shows the corresponding pumping powers for the porous electrode with no ow eld and with
two types of ow eld. When the ow rate becomes higher, e.g.
20 ml/s, the pressure drops for porous electrode and two types of
ow eld increase, as listed in Table 5. Furthermore, the increase
percentage of the pressure drop for the parallel and serpentine
ow elds is much larger than that for the porous electrode with
no ow eld. For the rst two ow elds, the pressure drops increase from 83 to 1170 Pa and from 330 to 4768 Pa, respectively,
while for the porous electrode, from 957 to 4210 Pa as the ow rate
increases from 5 to 20 ml/s. These phenomena can be explained as
follows. For the ow in porous media, Eq. (8) indicates that the
pressure drop increases linearly with the velocity, while for the
fully developed ow in the square channel without a porous sidewall, the frictional factor is proportional to the square of velocity
[34,35]. In the practical operation of VRFBs with the parallel and
serpentine ow elds, a porous sidewall (the interface between
the ow channel and the electrode) exists in the ow channel. Under this condition, part of the electrolyte will be pushed into the
porous electrode; the shear stress at the surface of the porous sidewall becomes smaller than the shear stress at the impermeable
walls. The development of fRe is similar to that without a porous
sidewall, and the ratio of fRe/fRe0 (fRe0 is the fully developed value
for the channel without porous sidewall) depends on the ratio of
the thickness of porous layer to the width of ow channel [36].
Therefore for the parallel and serpentine ow elds, the pressure
drop increases faster than that for the porous electrode as the
velocity increases.

Table 4
Calculated pressure drop, pumping power, overpotential and efciency at the positive and negative electrodes at the ow rate of 5 ml/s.

Parallel
Serpentine
Porous

Dp (Pa)

Ppump (W)

Np (V)

Nn (V)

Qact (W)

Qohm (W)

Ptotal (W)

wpower

83
330
957

4.15e4
1.65e3
4.8e3

0.279
0.249
0.244

0.046
0.039
0.039

1.30
1.152
1.132

0.014
0.014
0.014

6.054
6.056
6.065

0.783
0.807
0.810

Table 5
Calculated pressure drop, pumping power, overpotential and efciency at the positive and negative electrodes at the ow rate of 20 ml/s.

Parallel
Serpentine
Porous

Dp (Pa)

Ppump (W)

Np (V)

Nn (V)

Qact (W)

Qohm (W)

Ptotal (W)

wpower

1170
4768
4210

2.34e2
9.54e2
8.42e2

0.229
0.205
0.212

0.038
0.032
0.033

1.068
0.936
0.972

0.014
0.014
0.014

6.101
6.244
6.222

0.815
0.827
0.819

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Q. Xu et al. / Applied Energy 105 (2013) 4756

0.85
0.28

0.26

0.24

0.22

0.83
0.82
0.81
0.80
0.79

0.20
5

10

15

20

25

0.78

30

Flow rate (ml/s)

3.5. Power and energy-based system efciencies

In this work, power and energy-based system efciencies are
dened by taking account of the consumed pumping power/energy. At a specic operating point (here we use SOC of 0.8 and discharging current density of 400 A/m2, which is a common current
density in practical operations), the power-based system efciency
can be dened as [37]:

Pnet
Ppump Ploss
1
P total
Ptotal

60

where Pnet is the system net output power, Ppump is the pumping
power and Ploss is the lost power. The pumping power depends on
the ow rate Q, the pump efciency wpump and the pressure drop
across the hydraulic circuit. The pumping power is expressed as:

Ppump Q  Dp=wpump

61

where Dp represents the total pressure drop through the piping and
the battery. However, as the pressure drop through piping is typically much smaller than that through the battery, the total pressure
drop can be approximated by that through the battery. It should be
noted that the Ppump includes the total pumping power of two
pumps at both the positive and negative sides.
The lost power can be expressed as:

Ploss IAg1 g2 DU mem 2 

Armem
lmem

10

15

20

25

30

Flow rate (ml/s)

Fig. 5. Variations in the positive electrode overpotential with the electrolyte ow

rates.

wpower

Serpentine
Porous
Parallel

0.84

Serpentine
Porous
Parallel

Power-based efficiency

|Positive electrode overpotential (V)|

54

62

where the rst term in the right hand represents the polarization
loss, while the second term represents the Ohmic loss, with I is
the current density, A is the electrode surface area, DUmem is the
voltage drop through the membrane and lmem is the thickness of
the membrane.
The variations in the power-based system efciency with ow
rate for the VRFBs with no ow eld and with two types of ow
eld are shown in Fig. 6. With the serpentine and porous ow
elds, the power-based system efciency initially increases with
the ow rate, followed by a rapid decrease. The maximum efciency with the serpentine ow eld is 0.833 at 15 ml/s, while
the maximum efciency with the porous electrode is 0.824 at
20 ml/s. However, with the parallel ow eld, the power-based
efciency increases monotonically with the ow rate. The variation
in the power-based efciency with increasing the ow rate is the
consequence of the competition between the reduced lost power
and the increased pumping power. When the ow rate is low,
the reduction of lost power with the ow rate is fast (see Fig. 5),

Fig. 6. Power-based efciency for the VRFB with different ow elds operating at
various ow rates.

which overcomes the increase of the pumping power. However,

when the ow rate becomes larger, the reduction of the lost power
slows down, whereas the increase of the pumping power becomes
prominent. Once the increase in the pumping power surpasses the
reduction in the lost power, the efciency begins to decline. It
turns out that there exists an optimal ow rate at which the
maximum power-based efciency is achieved. As the increase in
the pumping power with the ow rate with the serpentine ow
eld is faster than that with the porous electrode, the efciency
decreases much faster with the serpentine ow eld once the
ow rate exceeds the optimal value. For the VRFB with the parallel
ow eld, as the pumping power is far smaller than that with the
other two, the optimal ow rate is beyond the region discussed
here.
Consider the energy balance during a chargedischarge cycling,
the energy-based system efciency can be dened as:

wenergy

W disch  W pump;disch
W char W pump;char

63

where Wdisch is the output work during discharging and Wchar is the
input work during the charging process. To quantify Wdisch and
Wchar, the cell voltages at various SOCs are needed. Fig. 7a shows
the variation in the positive and negative overpotentials for the
VRFBs with no ow eld and with two ow elds operating at their
respective optimal ow rates. Since the local electrochemical reaction rate is highly inuenced by the concentrations of two ions (See
Eqs. (18) and (19)), the minimum value of overpotential appears
around the SOC of 0.5, while the maximum value is at the lowest
or highest SOC. The corresponding cell voltages are shown in
Fig. 7b. It can be found that the VRFB with the serpentine ow eld
exhibits the lowest charging voltage and the highest discharging
voltage for all SOCs. Moreover, Fig. 8 shows the energy-based efciencies for the VRFBs with no ow eld and with two types of ow
eld: 0.831 with the serpentine ow eld, 0.801 with no ow eld
and 0.789 with the parallel type.
For comparison, the widely-used round trip efciency (RTE) is
dened as:

R t0;disch
Idisch tEdisch tdt
RTE R0 t0;char
Ichar tEchar tdt
0

64

where t0 represents the total charge (or discharge) time.

As shown in Fig. 8, the value of the energy-based efciency is
lower than that of the RTE, as the energy-based efciency elucidates the energy production and consumption in a VRFB system

Author's personal copy

Q. Xu et al. / Applied Energy 105 (2013) 4756

(a) 0.06

4. Conclusions
Serpentine, 15 ml/s
Porous, 20 ml/s
Parallel, 30 ml/s

0.05

Overpotential (V)

0.04

In this work a three-dimensional numerical model is proposed

and applied to the study of ow eld designs for a vanadium redox
ow battery (VRFB). VRFBs with no ow eld and with serpentine
and parallel ow elds are numerically tested. The salient ndings
are summarized as follows:

0.03
0.02
-0.18
-0.21
-0.24
-0.27
0.0

0.2

0.4

0.6

0.8

1.0

SOC

(b)

1.6

1.5

Cell voltage (V)

I = 40 mA/cm

1.4

1.3

1.2

Serpentine, 15 ml/s
Porous, 20 ml/s
Parallel, 30 ml/s

1.1
0

0.5

1.0

0.5

Fig. 7. Variations of overpotential and cell voltage with SOC for the VRFB with the
ow elds operating at their respective optimal ow rates. (a) Overpotential vs. SOC
and (b) cell voltage vs. SOC.

0.90
System efficiency
Round-trip efficiency

0.846

0.85
0.831

0.816
0.801
0.80

0.789 0.791

0.75

0.70
Serpentine

1. Compared with the conventional battery conguration with the

porous ow-through electrode, including a ow eld can
improve the distribution uniformity of electrolytes through
the electrode, particularly at smaller ow rates.
2. The overpotential in the VRFB depends on the distribution uniformity of electrolytes in both the in-plane and through-plane
directions. The VRFB with the serpentine ow eld shows the
lowest overpotential due to the more even electrolyte distribution over the electrode surface and the enhanced convective
mass transport towards the membrane.
3. The power-based efciency varies with the electrolyte ow
rate. With an increase in the ow rate, the increased pumping
power is offset by the lowered overpotential, indicating that
there is an optimal ow rate for each of the ow elds at which
the maximum efciency can be achieved. Operating at the optimal ow rate, both the energy-based efciency and RTE for the
VRFB with the serpentine ow eld are found to be the highest.
Therefore, the serpentine type appears to be a more suitable
ow eld design for VRFBs than the parallel ow eld.

Acknowledgement

soc

Energy based efficiency

55

Porous

Parallel

Fig. 8. Energy-based efciencies and RTEs for the VRFBs with different ow elds.

more comprehensively. In addition, the differences between the

two efciencies for the VRFB with no ow eld, with serpentine
and parallel ow elds are 0.015, 0.015 and 0.002, respectively,
owing to the fact that the pumping work during a charge
discharge cycling for the VRFB with parallel ow eld is far less
than that with the other two.

The work described in this paper was fully supported by a grant

from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. 622712).

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