Numerical simulation of bromine crossover

behavior in flow battery

Cite as: AIP Conference Proceedings 1820, 040015 (2017); https://doi.org/10.1063/1.4977287
Published Online: 13 March 2017

Yaobin Jia, Shijian Cheng, Dandan Chu, et al.

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AIP Conference Proceedings 1820, 040015 (2017); https://doi.org/10.1063/1.4977287 1820, 040015

© 2017 Author(s).
 Numerical Simulation of Bromine Crossover Behavior in
Flow Battery
Yaobin Jia1, a), Shijian Cheng2, b), Dandan Chu1, c) and Xin Li1, d)
1
School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, China.
2
Xinjiang Oilfield Company gas production plant, Xinjiang, China.
a)
727969777@qq.com
b)
1825856834@qq.com
c)
1277324664@qq.com
d)
Corresponding author: klkxlx@163.com

Abstract. Br2 and HBr has its own series of advantages as the positive electrolyte solution, so some batteries select the
Br2/Br- as the positive electrolyte solution, such as sodium polysulfide/bromine flow battery, zinc/bromine flow battery,
vanadium/ bromine flow batteries and hydrogen/bromine flow batteries. But the crossover benavior of bromine occurs in
these batteries too, resulting in cross-contamination, capacity loss and affecting battery’s performance. In this work, we
build numerical models to study the influence of bromine crossover phenomenon on the three forms of bromine crossover,
the concentration of electrolyte on the cathode side and the flow rate of the negative side in the quinone bromine flow
battery, to find the main models affecting the bromine crossover and the impact of bromine crossover on battery
performance. It was found that the three ways of crossover through the membranes was mainly by diffusion. By reducing
the concentration of positive electrolyte solution, the bromine crossover can be reduced and Coulomb Efficiency can be
improved. Rising the flow rate of the electrolyte solution on the negative side and reducing the differential between positive
side’s pressure and negative side’s pressure can also reduce the amount of bromine crossover to improve Coulomb
efficiency in the battery.

Key words: Quinone bromine flow battery; the Crossover of bromine; Numerical simulation; Process parameters;
Coulomb Efficiency.

INTRODUCTION

In recent years, with the non-renewable energy crisis intensified, the study of large-scale energy storage batteries
have also attracted more and more attention [1]. Common electrochemical energy storage methods include: secondary
batteries, redox flow batteries, renewable fuel batteries [2]. Secondary batteries and renewable fuel batteries are costly,
while the cost of redox flow battery is relatively low. It avoids using a variety of heavy metals, which is
environmentally friendly. The redox flow battery is an important large-scale efficient storage technology, which is an
important way to solve the renewable energy power generation’s problem such as uncontinuous, unstable and
uncontrollable [3]. In 1974, Thaller proposed a new electrochemical energy storage technology, which is the redox
flow battery [4]. All-vanadium redox flow battery is a typical double-flow battery, which is a kind of liquid battery
that is technically mature and closest to commercialization [5]. However, its electrolyte has a narrow reaction
temperature range, and energy density is relatively low [6]. With Br2 and HBr as positive electrolyte solution, it has
its own advantages: Br2 is in the form of liquid at room temperature, Br2/Br- is more prone to electrochemical reaction
and the potential is relatively high, while the redox potential Br2/Br- is not strongly dependent on the electrode material
in the dynamic aspects . Therefore, some of the flow battery select Br 2/Br- as positive electrolyte solution such as
sodium polysulfide / bromine flow battery [7], zinc bromine flow battery [8] and hydrogen bromine flow battery [9].
However, Br2/Br-electrolyte solution has many shortcomings, bromine solution is toxic in health, safety and

Advances in Materials, Machinery, Electronics I

AIP Conf. Proc. 1820, 040015-1–040015-8; doi: 10.1063/1.4977287
Published by AIP Publishing. 978-0-7354-1488-4/$30.00

040015-1
environmental problems. Bromine is a small molecule that can easily pass through the Nafion membrane, resulting in
cross-contamination and capacity loss, which affects the battery performance. In 2014, Huskinson used anthraquinone
disulfonic acid as the negative active material in the aqueous solution, bromine as positive active substances in the
flow battery, and the cross-contamination phenomenon occurred in positive and negative active substances [10]. And
this phenomenon also occurs in the flow batteries which use bromine as electrolyte, such as sodium polysulfide /
bromine flow battery [11], zinc bromine flow battery [12] and hydrogen bromine flow battery [13-14], so the research
of bromine through phenomenon is very important.
In order to further study quinone bromine flow battery, the effects of three forms of bromine permeable membrane,
positive electrolyte concentration and negative side flow rate on the bromine permeation phenomenon were simulated
and analyzed. Through the establishment of a mathematical model we studied the main ways to influence the amount
of bromine and bromine in the battery performance.

MATHEMATICAL MODEL ESTABLISHMENT

Geometric Model
Because this model focuses on the transmission of bromide ions in the membrane, the battery is simplified to a
two-dimensional model, as shown in Fig 1. The model mainly consists of four layers of porous electrode and
membrane on both sides positive and negative electrodes, the electrolyte solution in the positive and negative reservoir
were delivered to the corresponding porous electrode through the pump and react:
Positive reaction equation:

ʹ‫ݎܤ ֖ ି ݎܤ‬ଶ ൅ ʹ݁ ି (1)

Negative reaction equation:

 ൅ ʹ݁ ି ൅ ʹ‫ ܪ‬ା ֖ ‫ܪ‬ଶ‫ܵܳܣ‬ (2)

FIGURE 1. Geometric model

Control Equation
The two-dimensional dynamic model is based on the following assumptions:
(1)The solution is an incompressible dilute solution.
(2)The material involved in the battery calculation is homogeneous.
(3)Electrolyte flow is considered laminar and does not account for the effect of gravity.
(4)Because the quinone molecule of the negative side is larger, so ignore the quinone molecules through the
membrane.
(5)The battery is operated under constant temperature conditions.

040015-2
 The two-dimensional model is considered from the viewpoints of mass conservation, conservation of momentum,
conservation of charge and kinetics of electrochemical reaction, because the two-dimensional model is simpler than
the three-dimensional model with flow channel, so when the Nernst-Planck equation is used to calculate the flux, in
addition to considering diffusion and convection, the effect of electromigration is also considered.
There are convective, diffusive and electromigration modes in the membrane, and it is assumed that the quinone
molecules are too large to pass through the membrane. Therefore, only the flow of bromine from the positive electrode
side to the negative electrode electrolyte solution is considered here. The flux of Br 2 and Br- in the film is:

ࡺ࢏ǡ‫ ܕ‬ൌ ࢛࢓ ή ܿ௜ െ ‫ܦ‬௜ǡ௠ ‫ܿ׏‬௜ െ ‫ݖ‬௜ ‫ܿܨ‬௜ ‫ݑ‬௜௠ ‫߶׏‬௟ǡ௠ (3)

The flow of the electrolyte in the membrane is represented by the Schlogl equation in the membrane [15]:
఑೛ǡ೘ ఑ഝǡ೘
࢛࢓ ൌ െ ‫ ࢖׏‬െ ܿ௙ ‫߶׏ܨ‬௟ǡ௠ (4)
ఓ ఓ

Where ߢ௣ǡ௠ and ߢథǡ௠ are the membrane osmotic pressure and electrodynamic osmotic pressure, c f is the charge
concentration of the membrane, ߶௟ǡ௠ is the membrane potential. Membrane involves the control equation [16], the
membrane charge conservation can be expressed as:

σ௜ ‫ݖ‬௜ ߝ௠ ܿ௜ ൅ ‫ݖ‬௙ ܿ௙ ൌ Ͳ (5)

ߝ௠ is the porosity of the membrane, ‫ݖ‬௙ is charged by a charged ion.

Boundary Conditions
As shown in Fig 1, the electrolyte solution flows into the inlet and out of the outlet from both sides of the positive
and negative electrodes. There is no matter passing through the porous electrode and the contact surface of the
membrane. That is, the flux is zero, the electron can only be transmitted in the conductor. The flux of the electrons is
zero at the interface between the membrane and the electrode.
When the Br2 pass through the membrane to the negative electrolyte solution, the chemical reaction occurs
immediately after H2AQS is encountered, the speed is much greater than the electrochemical reaction, so the model is
considered with no Br2 on the negative side. The reaction happens quickly at the interface of negative electrode and
the membrane:

‫ݎܤ‬ଶ ൅ ‫ܪ‬ଶ‫ ܵܳܣ ֖ ܵܳܣ‬൅ ʹ‫ ܪ‬ା ൅ ʹ‫ି ݎܤ‬ (6)

Therefore, the fluxes of Br2 , Br- and H+ at the interface between the positive electrode and the film are:

ࡺ࢏ǡ࢓ ൌ ࢛࢓ ή ܿ௜ െ ‫ܦ‬௜ǡ௠ ‫ܿ׏‬௜ െ ‫ݖ‬௜ ‫ܿܨ‬௜ ‫ݑ‬௜௠ ‫߶׏‬௟ǡ௠ (7)

ࡺࡴశ ǡ࢓ ൌ െ࢏࢙ǡ‫ܠ‬Ȁ‫ ܨ‬െ ࡺ࡮࢘ష ǡ࢓ (8)

The flux of the material at the interface between the negative electrode and the membrane is:

௠ ష ‫߶׏‬
ࡺ࡮࢘ష ǡ࢓ ൌ ࢛࢓ ή ܿ஻௥ ష െ ‫ܦ‬௜ǡ௠ ‫ܿ׏‬஻௥ష െ ‫ݖ‬஻௥ ష ‫ܿܨ‬஻௥ష ‫ݑ‬஻௥ ௟ǡ௠ ൅ ʹࡺ࡮࢘૛ ǡ࢓ (9)

ࡺࡴ૛ ࡭ࡽࡿǡ࢓ ൌ െ૛ࡺ࡮࢘૛ ǡ࢓ (10)

ࡺ࡭ࡽࡿǡ࢓ ൌ ૛ࡺ࡮࢘૛ǡ࢓ (11)

ࡺࡴశ ǡ࢓ ൌ െ࢏࢙ǡ‫ܠ‬Ȁ‫ ܨ‬െ ࡺ࡮࢘ష ǡ࢓ ൅ ʹࡺ࡮࢘૛ ǡ࢓ (12)

040015-3
 Meshing
The two-dimensional model is based on the finite element method and is meshed with Comsol Multiphysics
software. The membrane and the porous electrode are divided into 6803 meshes (3306 internal free Degrees of
freedom.

RESULTS AND DISCUSSION

Model Validation

FIGURE 2. Bromine permeation experiment and simulation comparison chart

In order to show that the bromine permeation through the two-dimensional dynamic model can reflect the bromine
permeation during the operation of the battery, Fig. 2 presents a comparison of experimental and simulated bromine
permeabilities at 180 mL min -1 and 210 mL min-1. From the figure we can see that the experimental data and simulation
results can be a good fit, indicating that the model can be used to simulate the operation of the battery during the
bromine permeation.

Bromine through Mass Transfer Mode

In the operation of the battery, the bromine in the positive electrolyte solution flows through the membrane into
the negative electrode electrolyte solution in the form of diffusion, electromigration and convection. According to the
foregoing, there is no Br2 on the negative side, Br2 reacts fast at the contact surface of the negative electrode and the
membrane and two Br- were generated. Fig. 3 shows the Br-flux at the interface between the negative electrode and
the membrane when charging and discharging for 10 min. (a) and (b), respectively, show the charge and discharge of
Br-flux at the flow rate of 180 mL min -1 and 210 mL min-1. It can be seen from the figure, in the experimental operating
conditions, the three transmission modes, diffusion is the most important mass transfer mode. Since the main factors
influencing the diffusion are the concentration gradient and the diffusion coefficient, the main effect of convection is
the flow rate, so we change the concentration and flow rate of the electrolyte solution to explore the change of bromine
in the battery. (Positive and negative values of all the histogram fluxes in this chapter indicate the direction, in which
the positive flux indicates the transfer of bromine from the positive electrode to the negative electrode, whereas the
negative flux indicates that the bromine is transferred from the negative electrode to the positive electrode)

040015-4
 a b
FIGURE 3. Br- flux in the mass transfer mode at the interface between the negative electrode and the membrane at
10 min of charge and discharge (a charge b discharge)

Concentration

In order to make the organic quinone compound (0.02 mol L-1AQS + 2 mol L-1) fully react, the excess of bromine
electrolyte solution (2 mol L-1HBr + 0.5 mol L-1) was used on the positive electrode. The concentration of bromine
electrolyte solution was adjusted to 1 mol L-1HBr + 0.25 mol L-1, 2 mol L-1HBr + 0.5 mol L-1 and 3 mol L-1HBr + 0.75
mol L-1, while the concentration of negative electrode remains 210 mL min -1. The bromine permeate flux is shown in
Figure 4 (a) (the Br- initial concentration in the figure is taken as an example), it is clear that the bromine permeate
flux decreases with the decrease of the electrolyte concentration. (b) shows the comparison of the Coulomb efficiency
and the simulated value under the experimental operating conditions, and the effect of the Coulomb efficiency at the
three concentrations. We can see that with low cross-contamination, Coulomb efficiency will be greatly improved.

a b
FIGURE 4. Bromide permeation and battery Coulomb Efficiency at three different concentrations of positive
electrolyte (a Brome permeation b Coulomb Efficiency)

In Figure, 5 (a) and (b) shows the three kinds of mass transfer method due to changes in the concentration of
electrolyte solution after charging and discharging 10mins. As can be seen from the figure, regardless of which mass
transfer mode is, with the decrease of the concentration, the flux of the mass transfer was also reduced. The change of
the three mass transfer modes completely accorded with the Nernst-Planck equation, the decrease of the bromine
concentration on the positive side greatly reduced the bromine permeation.

040015-5
 a b
FIGURE 5. Br-flux in the mass transfer mode at the interface between the negative electrode and the membrane at
10 min of charge and discharge (a charge b discharge)

Flow Rate

The positive and negative sides of the concentration of the two sides are set as the same flow rate, because both
sides of the electrolyte solution is different, so the viscosity and density will be different. According to the Brinkman
equation, when two sides are of the same flow rate, there must be pressure difference between positive and negative
sides, so the electrolyte convection occurs through the membrane on both sides of the membrane. So by adjusting the
the flow rate of negative side, the bromide permeability excess can be ajusted. Fig. 6 (a) shows the bromine
breakthrough when the flow rate of the negative electrolyte was set to 0.9 times (189 mL min -1) and 1.1 times (231
mL min-1) of the experimental value (210 mL min -1) It can be seen from the figure that increasing the flow rate of the
electrolyte on the negative electrode side is advantageous in reducing the bromine permeation amount. Figure (b) is
the corresponding three kinds of flow rate of the Coulomb efficiency, we can see that increasing the negative side of
the flow rate can significantly improve the Coulomb efficiency.

a b
FIGURE 6. Bromide permeation and battery Coulomb Efficiency at three different concentrations of negative
electrolyte (a Brome permeation b Coulomb Efficiency)

Figure 7 (a) and (b) show the three mass transfer mode with the three flow rate changes when charging and
discharging patterns are 10 min. As can be seen from the figure, with the negative electrode electrolyte flow rate
increases , the fluxes of the three mass transfer modes are decreasing, and when the flow rate of the negative electrolyte
is 231 mL min-1, the effects of electromigration and convection are very small, the main influencing factor is diffusion.

040015-6
 a b
FIGURE 7. Br-flux in the mass transfer mode at the interface between the negative electrode and the membrane at
10 min of charge and discharge (a charge b discharge)

CONCLUSION

Based on the research of bromine permeation experiment of the quinone bromine flow battery, the numerical
model was established, and the following conclusions were drawn:
(1) Bromide diffusion, electromigration and convection are three mass transfer ways through the membrane, the
diffusion is the most important mass transfer mode.
(2) Through the Nernst-Planck equation, the flux of three kinds of mass transfer modes can be reduced by reducing
the excess positive electrolyte solution concentration. We can reduce the bromine permeation and improve the
Coulomb efficiency of the battery. .
(3) If the electrolyte solution on the positive and negative sides are different, the viscosity and density will be
different, so the pressure of two sides will be different. When adjusting the flow rate of negative side to achieve
bilateral pressure balance, the amount of bromine permeate can affected. So by increasing the flow rate of the
electrolyte solution of the negative side, the amount of bromine permeate can be effectively reduced, and the battery
Coulomb efficiency can be improved.

ACKNOWLEDGEMENTS
The project was supported by the National Natural Science Foundation of China (21111120074).

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