International Journal of Heat and Mass Transfer 148 (2020) 119040

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International Journal of Heat and Mass Transfer

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

Transport phenomena associated with capacity loss of all-vanadium

redox flow battery
Dong Kyu Kim a, Sang Jun Yoon c,d, Sangwon Kim b,d,∗
a
School of Mechanical Engineering, Chung-Ang University, Seoul 06974, Korea
b
KIST Europe, Korea Institute of Science and Technology, Campus E71, Saarbrücken 66123, Germany
c
Center for membranes, Korea Research Institute of Chemical Technology, Daejeon 34114, Korea
d
Transfercenter Sustainable Electrochemistry, Saarland University, Saarbrücken 66125, Germany

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

Article history: This study investigates transport of different species through the Nafion® 115 membrane in an all vana-
Received 5 April 2019 dium redox flow battery to understand transport phenomena associate with capacity loss. We consider
Revised 7 November 2019
several driving forces related to transport of vanadium ions, proton, and water molecules and examine
Accepted 10 November 2019
the variations in ion concentration during charge-discharge, and long-term operation. First, variations in
ion concentration are analyzed during the 3rd and the 300th charge-discharge cycles to compare the ion
Keywords: transport process at between early stage and late stage. The capacity loss is closely related to the self-
All-vanadium flow battery discharge reaction caused by diffusion through the membrane, and proton transport is another important
Capacity loss factor of capacity loss since the imbalance in proton concentration can accelerate water transport through
Species transport
the membrane. Furthermore, variations in solution volume and ion concentration are examined during
Osmosis
long-term charge-discharge cycles. Since ions accumulate on the positive electrode due to self-discharge
Prediction of state of charge
reaction and repeated electrochemical reaction, water molecules transport to the positive electrode side.
Finally, the relationship between the changes in solution volume and capacity loss is examined, and an
empirical equation is suggested for the prediction of capacity loss from changes in the solution volume
during long-term operation. Through the results, we can predict the lifetime of VFB system by simple
measurement.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction their understanding of the transport phenomena associated with

Over the last few decades, large-scale energy-storage systems
(ESSs) have gained much attention as an alternative energy source
of power grids. Since the power generation from renewable en-
ergy sources such as wind turbines can be intermittent, many re-
searchers and manufacturers started to develop large-scale ESSs to
supplement power supply [1,2]. Among the large-scale ESSs, all-
vanadium redox flow batteries (VFBs) have garnered most interest
because of their high energy efficiency, long cycle life, low main-
tenance cost, and flexibility for scale-up [3,4]. The VFB system was
first proposed by the Skyllas-Kazacos group in 1985. Since then,
many companies have succeeded in developing megawatt (MW)-
class VFB systems [5,6], and some companies even tried to develop
large-scale commercial VFB systems to supply power to the grid
[7,8]. Although there is much competition among these companies,
∗
Corresponding author at: KIST Europe, Korea Institute of Science and Technol-
ogy, Campus E71, Saarbrücken 66123, Germany.
E-mail address: sangwon.kim@kist-europe.de (S. Kim).
capacity loss of VFBs remains unsatisfactory.
Many experimental and numerical studies have been conducted
to study the transport phenomena that are related to capacity loss
of the VFB system. Some experimental studies investigated the
variations in vanadium ions concentration and changes in solution
volume during operation [9–11]; the results showed that the vana-
dium ion concentration and volume of the electrolyte vary during
self-discharge and long-term charge-discharge cycling. Other stud-
ies developed three-dimensional transient models to show the dis-
tribution of vanadium ions in a VFB by considering the crossover
of vanadium ions during change and discharge [12,13]; the results
showed that the distribution of vanadium ions and the capacity
loss of a VFB are affected by the crossover of vanadium ions. Other
researchers developed dynamic models to understand the effect of
side reactions on the capacity loss during repetitive cycling [14–
16]. Although most previous studies offer a basic understanding of
the mechanism of capacity loss and help us to predict the amount
of capacity loss during long-term operation of a VFB, they did not
consider the effect of transport of protons and water molecules on

https://doi.org/10.1016/j.ijheatmasstransfer.2019.119040
0017-9310/© 2019 Elsevier Ltd. All rights reserved.
2 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040

vanadium ions, protons, and water molecules through the mem-

Nomenclature brane. Specially, we considered self-discharge reaction, charge im-
balance, osmotic drag force, and hydraulic pressure difference be-
ɛ Porosity tween electrodes to explain transport of proton and water accu-
Ve Volume of electrode (m3 ) rately. Furthermore, we conducted experiments to obtain the cell
C Concentration (mol/m3 ) voltages and changes in solution volume to validate the model. In
Q Flow rate (m3 /s) addition, to ensure the reliability of the developed model, some
j Current density (A/m2 ) of electrolytes were collected, and the concentration changes of
A Area (m2 ) vanadium ions were measured using UV–VIS spectroscopy during
w Thickness (m) charge-discharge cycles.
D Diffusion coefficient (m2 /s)
nd Electro-osmotic drag coefficient 2.1. Modeling
η Overpotential (V)
P Pressure (bar) The assumptions of the developed model follow that of previ-
ρ Density (kg/m3 ) ous studies [6-9]. The assumptions are listed below:
μ Viscosity (Pa•s)
κ Permeability (cm2 ) (1) The flow is regarded as incompressible and laminar.
(2) Since the model is developed based on the lumped model,
Subscripts membrane and electrode have isotropic and homogeneous
i Ions physical properties.
m Membrane (3) The cell is operated in moderate temperature range. Therefore,
e Electrode the effect of temperature changes on the performance is ne-
s Surface glected.
d Drag (4) The cell is operated in stable voltage range and the electrolyte
pore Pore of the membrane is perfectly sealed. Therefore, hydrogen evolution, oxygen reac-
res Reservoir tion, and oxidation of V2+ ions are also neglected.

When modeling the VFB, we focused on explanation of the

capacity loss. Therefore, it is still necessary to understand relation- transport of ions in the VFB as a result of different driving forces
ship between the various ions transport and their associated reac- that are shown in Fig. 1(a).
tions to explain the capacity loss. First, we calculated the variations in vanadium ion concentra-
The objective of this study is to examine the transport phe- tion by considering the electrochemical reaction, side reaction, dif-
nomena associated with capacity loss of an all-vanadium redox fusion, and convection at each electrode. The variations in the
flow battery. The study began with the development of a tran- vanadium ion concentration are expressed using species conserva-
sient model to understand the transport phenomena through the tion shown as follows [17].
membrane during long-term charge-discharge cycling. Since capac-
dCi
ity loss is closely related to the transport of ions through the mem- εVe = n˙ i, f low ± n˙ i,electrochem − n˙ i,di f f (3)
brane, the model described the transport of vanadium ions, pro- dt
tons, and water molecules affected by electrochemical reaction, dif- where ɛ is the porosity, Ve is the volume of the electrode, Ci is the
fusion, osmosis, hydraulic pressure difference, and self-discharge concentration of each ion, and n is number of moles.
reaction. The investigation began with an examination of the varia-
tions in ion concentration and solution volume during the 3rd and
n˙ i, f low = Q (Cires − Ci ) (4)
the 300th charge–discharge cycles, respectively. Next, the changes Q is the flow rate, and Cires is concentration of ion in the tank.
in the capacity loss of the VFB was analyzed by examining the re-
lationship between the variations in ion concentration and solu- j
n˙ i,electrochem = Ae (5)
tion volume during long-term charge-discharge cycling. Finally, an F
empirical equation is suggested to predict the change in state of Ae is surface area of electrode, j is the current density, and F is
charge (SOC) using change in electrolyte volume. Faraday’s number. The plus sign is used for V2+ , and VO2 + ions,
and minus sign is used for V3+ , and VO2+ ions. The third term in
2. Methods
Eq. (3) is expressed as below.

The all-vanadium redox flow battery is a type of flow battery Am

n˙ V (II ),di f f = (D C + 2DV (V )CV (V ) + DV (IV )CV (IV ) ) (6)
that uses vanadium as the electroactive material at the negative wm V ( I I ) V ( I I )
electrode and positive electrode, and the electrolyte circulates be- A
tween the cell and the reservoir. The redox reaction takes place at n˙ V (III ),di f f = m (DV (III )CV (III ) − 3DV (V )CV (V ) − 2DV (IV )CV (IV ) ) (7)
wm
electrodes in the cell, while the energy is stored chemically in the A
external reservoir; therefore, the power and capacity are indepen- n˙ V (IV ),di f f = m (DV (IV )CV (IV ) − 3DV (II )CV (II ) − 2DV (III )CV (III ) ) (8)
wm
dently determined by the cell size and electrolyte volume, respec-
A
tively. The main reactions at the positive electrode and negative n˙ V (V ),di f f = m (DV (V )CV (V ) + 2DV (II )CV (II ) + DV (III )CV (III ) ) (9)
electrode of the VFB are shown as follows: wm
charge Here, Am is the area of the membrane, wm is the thick-
VO2+ + H2 O−e−  VO2 + + 2H+ E0 = 1.00Vvs.SHE (1) ness of the membrane, and Di is the diffusion coefficient of
discharge
each ion. The diffusion coefficient is 5.261 × 10−6 cm2 /min for V2+ ,
charge
V3+ + e−  V2+ E0 = −1.00Vvs.SHE (2) 1.933 × 10−6 cm2 /min for V3+ , 4.095 × 10−6 cm2 /min for VO2+ , and
discharge
3.538 × 10−6 cm2 /min for VO2 + [18]. In Eq. (3), the first term on
The following section describes the VFB model that we devel- the right-hand side is the change in vanadium concentration re-
oped; it includes several driving forces to explain the transport of sulting from the flow rate, and the second term is that resulting
 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040 3

at the positive electrode is represented by the equation

dCH + (+)
εVe = n˙ i, f low + n˙ i,H + ,(+) + n˙ H + ,di f f
dt
−n˙ H + ,sel f (+) − n˙ H + ,balance (16)
while the transport of protons at the negative electrode is repre-
sented by the equation
dCH + (−)
εVe = n˙ i, f low + n˙ i,H + ,(−) − n˙ H + ,di f f
dt
−n˙ H + ,sel f (−) + n˙ H + ,balance (17)
The first and the second terms represent the changes in pro-
ton concentration due to convection and the electrochemical re-
action, respectively. Since the electrochemical reactions at positive
and negative electrodes involve one electron and 2 mol of hydro-
gen are generated at positive electrode during charge process, vari-
ation in proton is expressed as follow [11].
j
n˙ i,H+ ,(+) = −(Am − 2Ae ) (18)
F
j
n˙ i,H+ ,(−) = Am (19)
F
The third term in Eqs. (16) and (17), n˙ H + ,di f f , is the pro-
ton transport due to diffusion induced by the difference between
the concentration of the negative electrode and positive electrode
given by
Am DH +  
n˙ H+ ,di f f = CH + (−) − CH + (+) (20)
wm
The fourth term in Eqs. (16) and (17), n˙ H + ,sel f , on the right-hand
side shows the consumption of protons due to self-discharge reac-
tion described by Eqs. (10) to (15):

n˙ H+ ,sel f (+) = 2 wAmm DV (II )CV (II )  (+ )electrode

n˙ H+ ,sel f (−) = wAmm 2DV (IV )CV (IV ) + 4DV (V )CV (V ) (− )electrode
(21)
The last term in Eqs. (16) and (17), n˙ H + ,balance , shows the trans-
port of protons due to charge imbalance. The transport of vana-
dium ions with different charge numbers causes the charge imbal-
ance between the negative electrode and positive electrode. There-
fore, the proton transports through the membrane to match the
Fig. 1. Schematic diagram of species transports in all-vanadium redox flow battery: charge balance that is shown as follows:
(a) transport of vanadium ions and protons; (b) transport of water molecules.
Am
n˙ H+ ,balance = (2DV (II )CV (II ) + 3DV (III )CV (III )
wm
from the electrochemical reaction. The third term represents the −2DV (IV )CV (IV ) − DV (V )CV (V ) ) (22)
variation in ion concentration resulting from diffusion and self-
discharge reactions. This study also examined the water transport through the
The self-discharge reaction at the positive electrode is repre- membrane as a result of several driving forces that are shown in
sented by the equations Fig. 1(b). The variations in water concentration on the side of the
positive electrode and the side of the negative electrode are ex-
V2+ + 2VO2 + + 2H+ → 3VO2+ + H2 O (10) pressed as follows:
V3+ + VO2 + → 2VO2+ (11) dCH2 O(+)
2+ 2+ + 3+ εVe = n˙ i, f low + n˙ water,(+) + n˙ water,di f f
V + VO + 2H → 2V + H2 O (12) dt
+n˙ water,sel f (+) + n˙ water,osmos + n˙ water,press (23)
while the self-discharge reaction at the negative electrode is rep-
resented by the equations
dCH2 O(−)
VO2+ + V2+ + 2H+ → 2V3+ + H2 O (13) εVe = n˙ i, f low + n˙ water,(−) − n˙ water,di f f
+ 2+ + 3+ dt
VO2 + 2V + 4H → 3V + 2H2 O (14)
+n˙ water,sel f (−) − n˙ water,osmos − n˙ water,press (24)
+ 3+ 2+
VO2 + V → 2VO (15)
The first and the second terms on the right-hand side of
These self-discharge reactions are induced by the crossover of Eqs. (23) and (24) show the changes in water concentration due
vanadium ions that are calculated at the third term in Eq. (3). In to convection and the electro-osmotic drag force, respectively.
the case of proton transport, we considered several driving forces j
associated with the transport of protons. The transport of protons Cwater,(+) = −(Ae nd,H+ + Am ) (25)
F
4 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040

j E(+ ) and E(− ) are open circuit potential for positive and negative
Cwater,(−) = Ae nd,H+ (26)
electrode that are expressed as follow. Em is a Donnan potential
F
The third term, n˙ water,di f f , expresses the water trans- across the membrane due to the differences in proton activities
port through the membrane as a result of water molecules
 
RT CH + ,ca
being dragged along by the diffused vanadium ions and Em = ln (37)
F CH + ,an
protons:
Am  
n˙ water,di f f = n D C + nd,V (III ) DV (III )CV (III ) − nd,V (IV ) DV (IV )CV (IV ) − nd,V (V ) DV (V )CV (V )
wm d,V (II ) V (II ) V (II )
Am DH +  
−nd,H + CH + (−) − CH + (+) (27)
wm

where nd, i is the osmotic drag coefficient, which is equal to 6 for 

V2+ and V3+ , 5 for VO2+ , 3 for VO2 + , and 2.5 for H+ [19–22]. Be-
cause VFB cell is filled with liquid, inherent interfacial resistance
of the individual membrane can be negligible [23]. Therefore, we
used intrinsic drag coefficient for each vanadium ion as an osmotic
(IR )k is total ohmic loss containing the resistance of the
k
membrane, electrode, and current collector; and η is the overpo-
tential as expressed by the Butler–Volmer equation.


drag coefficient regardless of types of membrane. Water generation 2RT j

η (+ ) = a sinh (38)
due to the self-discharge reaction, n˙ water,sel f , is considered in the F 2F kca CV (IV )CV (V )
fourth term, and the water generations at the positive electrode 

and negative electrode are expressed as follows: 2RT j

η (− ) = − a sinh (39)
Am D2CV (II ) F 2F kan CV (III )CV (II )
n˙ water,sel f (+) = (28)
wm
Am   Here, k(+ ) and k(− ) are the reaction rate constant for each elec-
n˙ water,sel f (−) = D4CV (IV ) + 2D5CV (V ) (29) trode that are shown follow.
wm    

0
In addition, we considered the water transport by osmosis, F Eca Tre f 1 1
k(+) = k(+),re f exp − (40)
n˙ water,osmos , i.e., the force to equalize the ion concentration on both R Tre f T
sides. The variation in water concentration by osmosis is expressed    

as 0
F Ean Tre f 1 1
k(−) = k(−),re f exp − − (41)
n˙ water,osmos = κ Am RT (CCa,total − CAn,total ) (30) R Tre f T
Here, κ is permeability of water through Nafion® 115 that is SOC is determined by the portion of VO2 + ions in the catholyte
4 × 10−16 cm2 [22]. Ci, total is the total sum of ion concentration at 1.6 V because the VO2 + ions limit the use of the VFB.
at each electrode. Lastly, we included water transport due to the
difference of hydraulic pressure, n˙ water,press , between negative elec- CV (V )
SOC = (42)
trode and positive electrode that is expressed by Darcy’s law de- CV (V ) + CV (IV )
rived from Navier-Stokes equation shown as below [24].
Using the above expressions, we developed a lumped transient
κπ r pore 2 ρ P model for VFB using the program Simulink (MathWorks, USA) to
n˙ water,press = · (31)
μ wm express the detailed physicochemical processes inside a unit cell
[11]. The operating conditions and physical properties for model
where ρ is the density of electrolyte, rpore is the radius of pores in
are the same with the values used in the experiment that are
the membrane (2.07 nm) [25], and μ is the viscosity of the elec-
shown in next section.
trolyte (20.1 × 10−3 Pa•s) [26]. The pressure difference, P, that is
resulted from difference of the electrolyte volume in the external
2.2. Experiment
tank is calculated shown as follow.
P = ρ gh (32) Experimental setups which is shown in Fig. 2(a) were pre-
his difference of electrolyte height in negative and positive side pared to examine the variations in capacity loss by measuring the
external tank. changes in solution volume and voltage during charge and dis-
The concentration of each ion at the external tank is expressed charge, and long-term charge and discharge cycling. The VFB sin-
as follow. gle cell was assembled by sandwiching the membrane (Nafion®
115, Sigma-Aldrich, USA) between two graphite bipolar plates. The
dCires Q
=ε (C res − Ci ) (33) active area of the single cell was 49 cm2 , and the electrochemi-
dt Vres i cal reaction took place in the carbon felt (GFD4.6 EA, SGL Group,
The obtained water concentration is used to calculate volume Germany) that was prepared by acid and thermal treatments for
of electrolyte in reservoir which is expressed as follow. 30 h at 400 °C under the atmosphere. Electrons transported to the
res
dVwater Q Mwater ρwater potentiostat (SP-150, BioLogic, France) through the current collec-
= res
(34) tor. 1.6 M V3+ in 3 M H2 SO4 solution (80 mL) was prepared as the
dt Cwater
negative electrolyte and 1.6 M VO2+ in 3 M H2 SO4 solution (80 mL)
Cell voltage is then calculated as: was prepared as the positive electrolyte, and the electrolyte was
 
rev
Ecell = Ecell − (IR )k − |η| (35) stored in a mass cylinder to measure the changes in solution vol-
k k
ume. The electrolyte was circulated through the mass cylinder and
rev is the reversible open circuit voltage that is shown as
the cell by a pump (labV1, Shenchen, China). Physical properties
where Ecell
of cell components are listed in Table 1. Using this experimental
follow.
setup, the charge and discharge reaction continued until the 300th
rev
Ecell = E ( + ) − E ( − ) + Em (36) cycle at a current density of 80 mA/cm2 .
 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040 5

The measurement of SOC during charge-discharge cycle is con-

ducted using UV–VIS spectroscopy (Agilent Technologies, Cary
8454 UV–vis). We selected VO2+ ions in catholyte to analyze the
concentration of ions because V2+ ions in anolyte is easily oxi-
dized in the air. During the cell operation, catholyte of 0.125 ml
is collected to measure the concentration of VO2+ ions concentra-
tion. We also collected anolyte of the same amount with catholyte
to match the balance of electrolyte. Using the collected catholyte,
0.02 M VO2+ in 3 M H2 SO4 solution is prepared to analyze changes
in concentration of vanadium ions. The prepared samples are
shown in Fig. 2(b). Here, absorbance of UV–VIS spectroscopy was
measured at 760 nm.

3. Results and discussion

In this section, we will validate the VFB model by comparing

the output of the model with experimental results obtained dur-
ing a charge–discharge reaction. Using this model, we analyzed the
variations in ion concentration of the VFB for long-term operation.

3.1. Model validation

The model was validated by comparisons of the voltage and

changes in solution volume in the 3rd and the 300th cycle that is
shown in Fig. 3(a), and (b). Moreover, the adequacy of the consid-
ered driving forces was convinced by comparing the experimen-
tal results of the relationship between SOC and voltage with the
model results that is shown in Fig. 3(c).
The calculated results are represented by lines, and the exper-
imental results are represented by symbols in Fig. 3. The model
shows good agreement (within 8% of the average error) with the
experimental data. Even though there are small deviations be-
Fig. 2. Images of experimental setup for examination of changes in vanadium ion
concentration: (a) Experimental setup of the VFB; (b) Samples of catholyte at dif-
tween the experimental and numerical results at the beginning of
ferent SOC. the discharge process, this model is reasonably accurate for analy-
sis of the species transport in the VFB.
Table 1
Physical properties of cell components. 3.2. Species transport during charge-discharge reaction in the 3rd
Parameters Value and the 300th cycles

Thickness of membrane 127 μm [27]

In this section, we will compare the transport of various species
Conductivity of membrane 0.1 S/cm [27]
Water uptake of membrane 38% water [27] in the VFB during the charge and discharge reaction in the 3rd
Nominal thickness of electrode 4.6 mm [28] and the 300th cycles. Different from previous studies that exam-
Open porosity of electrode 94 [28] ined only the transport of vanadium ions, this study includes an
Area-specific resistance of electrode <0.15  · cm2 [28]
examination of the transport of vanadium ions, protons, and wa-
Density of electrolyte 1.35 kg/l [29]
Molecular weight of electrolyte 163.01 g/mol [29]
ter molecules. The variations in voltage and solution volume are
shown in Fig. 3. It can be seen that the charge and discharge
time of the 300th cycle (2799 s) is lower than that at the 3rd cy-
Table 2 cle (4400 s), indicating capacity loss of the VFB; the energy effi-
Operating conditions of the experiment. ciency reduced by 1.75%. Meanwhile, the solution volume at nega-
Parameters Value tive electrode increases during charging and decreases during dis-
Area of membrane 49 cm2
charging. The variation in solution volume at positive electrode
Upper / lower voltage limit 1.6 V/1.0 V varied in opposite direction compared with negative electrode. Af-
Current density 80 mA/cm ter the 300th cycle, the trend is the same as that at the 3rd cycle,
Volume of electrolyte 80 mL but total volume of electrolyte at positive electrode increases, and
Flow rate 65 mlpm
that at negative electrode decreases. The variations in solution vol-
Maximum number of cycles 300
ume and capacity loss can be explained by examining the transport
of ions in the VFB.
The variations in the concentration of vanadium ions at the
The upper and lower limits of the voltage were 1.6 V for charg- positive electrode are shown in Fig. 4(a); it can be seen that the
ing and 1.0 V for discharging to avoid hydrogen evolution, respec- VO2 + ion concentration increases and the VO2+ ion concentra-
tively, and the mass cylinder was covered by rubber cap to prevent tion decreases during the charging process at the 3rd and the
air contact. Temperature of laboratory was maintained at 20 °C, and 300th cycles, as explained in a previous study [16]. The varia-
the operating voltage was in moderate condition, so we assume tions in vanadium concentration are the result of the self-discharge
that the operating temperature of the cell is in reasonable range. reaction and diffusion as shown in Fig 4(b) and (c). Here, the
We measured the solution volume at intervals of five cycles. The loss of ion concentration due to diffusion is described by neg-
experimental conditions are listed in Table 2. ative value. When charge process starts, the amount of VO2 +
6 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040
Fig. 3. Model validation by comparing the numerical (lines) and experimental
(symbols) data for the 3rd and 300th charge–discharge cycles: (a) variations in volt-
age; (b) changes in solution volume; (c) variations in SOC with respect to voltage.
transported across the membrane is small, 0.01 mol/m. At the end
of charge, however, the amount of VO2 + transported to negative
electrode become large 0.03 mol/ m. Since the number of VO2 +
ions is large at the end of charge process, the amount of diffu-
sion is also large. The diffused ions result in the self-discharge
reaction; VO2 + ions are consumed and VO2+ ions are generated
at the positive electrode, which lead to changes in ion concentra-
tion and reduces the capacity. The variations in ion concentration
by self-discharge reaction are similar to that by diffusion, but the
amount of concentration variation by self-discharge is larger than
Fig. 4. Changes in vanadium ion concentration at positive electrode as a result of
different driving forces during the charge and discharge reaction: (a) variations in
vanadium ion concentration during the charge and discharge reaction; (b) changes
in VO2+ ion concentration due to self-discharge reaction and diffusion; (c) changes
in VO2 + ion concentration due to self-discharge reaction and diffusion.
that by diffusion. Therefore, we can expect that VO2+ ion increases
and VO2 + ion decreases as cycle proceed.
Changes in vanadium ion concentration at negative electrode
are shown in Fig. 5. The trend is similar to the phenomena oc-
curred in positive electrode, except direction of reaction is reverse.
During the self-discharge reaction, V2+ ions are consumed, and V3+
ions are generated. Therefore, the concentration changes of V2+ ion
have negative values, and that of V3+ ion have positive values. The
same as positive electrode, changes due to diffusion shows ion loss.
In addition, this model describes the transport of protons in
the VFB in response to the driving forces. Fig 6(a) shows varia-
tion of proton concentration considering all of driving forces. The
total amount of proton ion increases during charge and decreases
during discharge, and the maximum value of proton ions increases
as the reaction progress. Since the charge time is longer than dis-
charge time, the proton ions are continuously accumulated. The
dominant driving forces to determine the proton concentration are
 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040
Fig. 5. Changes in vanadium ion concentration at negative electrode as a result of
different driving forces during the charge and discharge reaction: (a) variations in
vanadium ion concentration during the charge and discharge reaction; (b) changes
in V2+ ion concentration due to self-discharge reaction and diffusion; (c) changes
in V3+ ion concentration due to self-discharge reaction and diffusion.
flow rate and the main reaction, because the amount of changes
in proton concentration by flow rate and the main reaction is
100 times larger than that by other driving forces. Fig 6(b) shows
changes in proton ion concentration during the 3rd charge and
discharge reaction. During charge process, about 8 mol/m3 of hy-
drogen are continuously generated, and about 7 mol/m3 of hydro-
gen are emitted by circulated flow between reservoir and the cell
(right side axis in Fig 6(b)). Therefore, we can expect that the
proton concentration increases during the charging process. The
same phenomena occur in opposite direction during discharge re-
action, so the amount of proton ions decreases. Furthermore, pro-
tons are consumed continuously because of the self-discharge re-
action. The amount of self-discharge reaction, however, is changed
during charge and discharge reaction. The amount of proton con-
sumption is 0.018 mol/m3 at the end of charge process, however,
that at the end of discharge process is 0.002 mol/m3 . Since the
amount of required vanadium ions for self-discharge reaction are
changed during the reaction, the amount of proton consumption
due to self-discharge reaction is varied. Diffusion is another impor-
7
Fig. 6. Changes in proton concentration at positive electrode as a result of differ-
ent driving forces during the charge and discharge reaction: (a) variations in pro-
ton concentration during charge and discharge reaction; (b) comparison of driving
forces acting during the 3rd cycle; (c) comparison of driving forces acting during
the 300th cycle.
tant driving force of the transport of protons during the charge and
discharge cycles. The amount of proton transport across the mem-
brane is negligible during the 3rd cycle. Because proton ion con-
centration at positive and negative electrode is almost the same
at early stage. Next, charge imbalance should be considered as an-
other cause of the proton transport. Since the transported vana-
dium ions have different charge numbers, protons are transported
to match the charge balance between the two electrodes; the pro-
tons move from the positive electrode to the negative electrode
because the charge number of vanadium ions on the positive elec-
trode side is higher than that on the negative electrode side. How-
ever, the amount of proton transport across the membrane due to
charge imbalance is negligible compared with other driving forces.
It only affects proton transport of 0.001 mol/m3 . In Fig. 6(c), varia-
tion of proton concentration during the 300th cycle is presented.
One noticeable change compared with early stage is the proton
transport due to diffusion. As the reaction progressed, the proton
8 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040
Fig. 7. Changes in proton concentration at negative electrode as a result of differ-
ent driving forces during the charge and discharge reaction: (a) variations in pro-
ton concentration during charge and discharge reaction; (b) comparison of driving
forces acting during the 3rd cycle; (c) comparison of driving forces acting during
the 300th cycle.
concentration at positive electrode is largely accumulated, so con-
centration difference between two electrodes become large. There-
fore, proton transport due to diffusion increases significantly. The
amount of proton transport is 0.0 0 02 mol m−3 during the 3rd cycle,
but 0.018 mol/m3 during the 300th cycle.
Changes in proton concentration at negative electrode are
shown in Fig. 7(a). The trend is similar to the phenomena occurred
in positive electrode. During the 3rd cycle, proton concentration in-
creases during charge and decreases during discharge process. The
proton concentration at the end of charge at negative electrode is
relatively small compared with that at positive electrode. Since the
number of protons associated with self-discharge reaction at neg-
ative electrode is large shown in Fig. 7(b), total amount of proton
concentration at negative electrode is smaller than that at positive
electrode. In addition, during the 300th cycles, the maximum value
Fig. 8. Changes in solution volume at positive electrode resulting from different
driving forces during the charge and discharge reaction: (a) comparison of driving
forces acting during the 3rd cycle; (b) comparison of driving forces acting during
the 300th cycle.
of the concentration of protons increased significantly at the posi-
tive electrode, but slightly at the negative electrode: 1550 mol/m3
increase at positive electrode, and 400 mol/m3 increase at negative
electrode. This is resulted from the proton transfer due to diffusion
that is shown in Fig. 7(c). With charge-discharge cycles proceed,
the difference of proton concentration become large. It is resulted
in large amount of proton transfer across the membrane and com-
plement the loss of proton due to self-discharge reaction. There-
fore, the amount of proton increase is relatively small at negative
electrode.
Finally, we analyze the amount of water transported through
the membrane in response to different driving forces at the posi-
tive electrode; the results are shown in Fig. 8. First, we know that
the dominant driving force for water transport is osmosis in both
the 3rd and 300th cycles. About 70% of the total volume of water is
transported through the membrane. Furthermore, water molecules
can be dragged by the diffusion of vanadium ions and protons.
During the 3rd cycle, the amount of water transported by diffusion
of vanadium ions is larger than that transported by the diffusion
of proton. During the 300th cycle, however, the effect of proton
transport is more significant than that of the transport of vana-
dium ions. Since the drag coefficient of vanadium ions is larger
than that of protons, vanadium ions can carry a large amount of
water at the beginning. However, during the 300th cycle, the dif-
ference between the concentration of protons at the negative elec-
trode and positive electrode is higher than that the difference in
 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040
Fig. 9. Changes in solution volume at negative electrode resulting from different
driving forces during the charge and discharge reaction: (a) comparison of driving
forces acting during the 3rd cycle; (b) comparison of driving forces acting during
the 300th cycle.
vanadium ion concentration. Therefore, a larger volume of water is
transported by the protons than vanadium ions, which is the rea-
son why the proton transport should be considered as a driving
force of water transport. On the other hand, the amount of water
generated by the self-discharge reaction is similar during the 3rd
and the 300th cycle. Because the variations in ion concentration
due to the self-discharge reaction are similar during the processes.
Meanwhile, the amount of water transported due to the difference
between the hydraulic pressure difference at the negative electrode
and positive electrode is negligible.
Changes in solution volume resulting from different driving
forces at negative electrode are shown in Fig. 9. The effect of driv-
ing forces on the water transport at negative electrode is similar
to that at positive electrode. At the 3rd cycle, the dominant driving
forces of the water transport is osmosis and diffusion of vanadium
ions, while at the 300th cycle, the dominant driving forces are the
osmosis and diffusion of proton. The direction of water transport
is determined by the difference of ions concentration accumulated
in each electrode that is explained in the next section.
3.3. Species transport during long-term cycles of charge and
discharge reaction
Capacity loss is an important issue for long-term operation of
the VFB. In this section, we present the results of analysis of the
changes in solution volume and ion concentration during the long-
term operation.
9
Fig. 10. Changes in solution volume during long-term cycles of charge and dis-
charge; the symbols represent the experimental results, and the lines represent the
numerical results.
Fig. 11. Changes in ion concentration during the long-term cycles of charge and
discharge at 1.0 V; the symbols represent the experimental results, and the lines
represent the numerical results.
The changes in the solution volume at the negative electrode
and the positive electrode during long-term operation are shown
in Fig. 10, where the symbols represent the experimental results
and the lines represent the numerical results. The solution volume
at the positive electrode increases from 46 to 51.4 mL, and that at
the negative electrode decreases from 46 to 38.2 mL, i.e., the de-
crease in solution volume at the negative electrode is larger than
the increase in solution volume at the positive electrode. These re-
sults can be understood by examining the variation in ion concen-
tration that are shown in Figs. 11 and 12. The Fig. 11 shows the
variations in ion concentration at 1.0 V during long-term operation
of the VFB. As the VFB continues to operate, the VO2+ concentra-
tion increases, but the V3+ concentration decreases. Since a large
amount of V2+ ions are transported to the positive electrode due
to crossover, the self-discharge reaction on the positive electrode
side actively proceeds, and a large amount of VO2+ ions is pro-
duced and accumulated at the positive electrode. The consumption
of V2+ ions at negative electrode leads to decrease of the max-
imum concentration of V3+ ions. Moreover, the amount of VO2 +
ions decreases because reduced V2+ ion concentration limits the
conversion of VO2 + ions during charging. These variations in vana-
10 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040
Fig. 12. Changes in solution volume in response to different driving forces during
the long-term cycles of the charge and discharge reaction: (a) changes in solution
volume at the positive electrode; (b) changes in solution volume at the negative
electrode.
dium ions result in capacity loss during long-term operation of the
VFB. On the other hand, we already know that the concentration of
protons increases as VFB continues to operate due to proton gener-
ation during charging process, as explained in the previous section.
Therefore, the total amount of ions in the positive electrode half-
cell increases with cycles.
The changes in ion concentration lead to water transport in the
long-term operation of the VFB shown in Fig. 12. Since the total ion
concentration at the positive electrode side increases more than
that at the negative electrode side, the water transport by osmosis
is headed toward the positive electrode side. Water molecules that
are dragged by diffused ions move towards the opposite direction
as that caused by osmosis.
On the other hand, the amount of water generated by the self-
discharge reaction (see Eqs. (10) to (15)) is higher at negative elec-
trode than that at the positive electrode and the effect of the dif-
ference in hydraulic pressure is negligible.
Except for the self-discharge reaction, the amount of water
transport due to each reaction occurs symmetrically. Nevertheless,
the imbalance between volume increase of the solution at the pos-
itive electrode and volume decrease of the solution at the nega-
tive electrode is due to the water decomposition reaction occurring
during the charging process at the positive electrode. Once wa-
ter is transported from negative electrode to positive electrode due
to osmosis, some of water transported to the positive electrode is
consumed during charge process. Thus, the volume increase of the
solution at the positive electrode is smaller than the volume de-
Fig. 13. Relationship between volume change at negative electrode, capacity loss,
and SOC in the long-term cycles of charge and discharge reaction.
creases of the solution at the negative electrode, and an imbalance
in the volume of the solution between the two electrodes occurs.
3.4. Prediction of capacity loss from the change in solution volume
In the previous section, we discussed the changes in solution
volume caused by ion transport. In this section, we will show
how the SOC and capacity loss can be predicted by measuring the
changes in solution volume at the negative electrode. The relation-
ship between the ratio of volume change at the negative electrode,
capacity loss, and SOC are shown in Fig. 13. We used the anolyte to
measure the changes in solution volume because the changes are
large at the negative electrode.
The measurement showed that the variations in capacity and
SOC were inversely proportional to the change in solution volume.
While the solution volume was changed by 4%, the capacity de-
creased by 30%, and the SOC dropped from 84% to 76%. More-
over, the SOC and capacity loss decreased continuously as the so-
lution volume changed. Using the relationship between change in
solution volume and SOC, we suggested the following empirical
equations to predict the variation in SOC when the temperature
is about 20 °C:
SOC = −3 ln(rvol,an ) + 80.4 (43)
V
rvol,an = nth (44)
Vinitial
where, rvol, an is the volume ratio during the initial cycle, Vinitial is
the volume during the initial cycle and Vnth is the volume dur-
ing the nth cycle. Using these equations, we can easily predict the
changes in SOC of the VFB during long-term operation.
4. Conclusions
The transport phenomena in an all vanadium redox flow battery
were analyzed to understand the relationship between changes in
solution volume and capacity loss. We first examined the driving
forces associated with the transport of vanadium ions, protons, and
water molecules. To explain the water transport through the mem-
brane, we developed model considering diffusion, self-discharge
reaction, osmosis, and the difference in hydraulic pressure at the
negative electrode and positive electrode. Using this model, we
examined the variation in ion concentration during the 3rd and
300th cycles. As the reaction progresses, the charge and discharge
 D.K. Kim, S.J. Yoon and S. Kim / International Journal of Heat and Mass Transfer 148 (2020) 119040
time decreases owing to the imbalance in vanadium ion concen-
tration. The concentration of VO2+ ions and protons at the pos-
itive electrode increase with continued operation, but the respec-
tive concentration of the other ions decreases. Furthermore, we ex-
amined the changes in solution volume in the long-term cycles of
charge and discharge. The solution volume increases on the posi-
tive electrode side. Since large number of protons accumulated on
the positive electrode side during a charge-discharge reaction, wa-
ter molecules head toward the positive electrode side. Finally, we
examined the relationship between capacity loss and changes in
the solution volume. As the solution volume decreases, the charge
capacity decrease; the capacity and SOC decrease drastically until
the volume decrease reaches 4%. Using this relationship, an empir-
ical equation is suggested for predicting the changes in SOC during
long-term operation of the VFB by simple measurement. These re-
sults can contribute to accelerate commercialization of VFB system.
Declaration of Competing Interest
None.
Acknowledgments
This research was supported by the Basic Science Research Pro-
gram through the National Research Foundation of Korea funded
by the Ministry of Science and ICT (NRF-2019R1F1A1058036). Ad-
ditional support was provided by basic research project funded by
Korea Institute of Science and Technology Europe and ‘GO-KRICT’
project funded by Korea Research Institute of Chemical Technology.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.ijheatmasstransfer.
2019.119040.
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