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Soluble Lead-Acid Redox Flow
Battery
Introduction
In a redox flow battery electrochemical energy is stored as redox couples in the
electrolyte, which is stored in tanks outside the electrochemical cell. During operation,
electrolyte is pumped through the cell and, due to the electrochemical reactions, the
individual concentrations of the active species in the electrolyte are changed.

The state of charge of the flow battery is determined by the electrolyte species
concentrations, the total flowing electrolyte volume in the system
(tank + pump + hoses + cell), and possibly also by the concentration of solid species on
the electrodes. Depending on the cell chemistry the cell can have separated or
combined anode and cathode compartments and electrolyte tanks.

Pump

Pb2+

HSO4− Negative Positive
Electrode Cell Electrode
Tank (Pb) (PbO2/PbO)
+
2+ H
Pb +
H
HSO4−

Figure 1: Working principle of the soluble lead acid flow battery.

1 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY

Solved with COMSOL Multiphysics 5.2

In the soluble lead acid flow battery one electrolyte solution is used. The active
component in the electrolyte is the lead ion that reacts on the electrodes to form solid
lead (negative electrode) or lead oxide (positive electrode). The electrode chemistry is
similar to a traditional lead-acid battery, with the difference that solid lead sulfonate is
not formed in the electrodes.

This example simulates a soluble lead-acid flow battery during an applied
charge-discharge load cycle. The surface chemistry of the positive electrode is modeled
by using two different lead oxides and two different positive electrode reactions in the
model.

Model Definition

CELL GEOMETRY AND MESH
The electrochemical cell consist of two flat 10 cm square electrodes, placed in parallel
with a 12 mm gap in between. The aspect ratio of the cell motivates modeling the cell
in 2D. The cell geometry and mesh is shown in Figure 2.

Outlet

Negative electrode Positive electrode

Inlet

Figure 2: Geometry and mesh of the electrochemical cell.

2 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY

Solved with COMSOL Multiphysics 5.2

Due to the very high electrical conductivity of the electrodes, the potential gradients
in the electrodes are neglected, and the electrodes are not included in the geometry.

To handle possible edge effects in the electrolyte, 1 mm regions are added at the inlet
and outlet, outside the active electrode region.

A mapped rectangular mesh is used, and boundary meshing is used to resolve the steep
gradients in the electrolyte close to the electrode surfaces.

ELECTROLYTE MASS AND CURRENT TRANSPORT EQUATIONS
The electrolyte is based on a mixture of lead methane sulfonate, methane sulfonic acid
and water, which in this model is assumed to dissociate into an electrolyte consisting
of Pb2+, H+, HSO4--ions dissolved in a bulk solution of zero-charged species (mainly
water). Electroneutrality is assumed locally in the electrolyte. The combination of
these assumptions allow for the use of Tertiary Current Distribution, Nernst-Planck
interface for modeling the electrolyte transport.

The electric potential in the electrodes is assumed to be space independent. The
negative electrode is grounded. On the positive electrode, an electrode potential is
calculated in order to fulfill a current density condition defined by the load cycle (using
the Electrode Surface boundary node).

A load cycle of 1 h charge, 20 s rest, 1 h discharge, 20 s is applied twice to the cell.
During charge or discharge a constant current density corresponding to a mean
current density in the cell 200 A/m2 is applied.

The species fluxes are defined on the electrode surfaces according to the electrode
reactions below. An Inflow condition is used at the inlet with the inlet concentrations
( c in, Pb 2+ and c in, H + ) taken from the tank model described below. An Outflow
condition is set at the outlet. All other boundaries are isolated.

Negative Electrode Reaction
On the negative electrode the following electrode reaction occurs:

2+ -
Pb + 2e ⇔ Pb ( s )

with the kinetics being described by a Butler-Volmer expression:

i Pb = Fk 0 c Pb2+  exp  -------- – exp  – -------- 
Pb Fη Fη
  RT  RT 

Pb
Where k 0 + is a rate constant and c Pb 2+ is the concentration of lead ions in the
electrolyte.

3 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY

neg = 0V + -------. (The deviation of the equilibrium potential of the side reaction versus the positive main reaction equilibrium potential is controlled by the rate parameters. c H + is the electrolyte proton concentration and c H + is the proton reference concentration in the electrolyte at equilibrium. Solved with COMSOL Multiphysics 5. The positive main reaction has the following equilibrium potential. exp  -------- PbO 2 Fη   -------- Fη   i PbO 2 = Fk 0 c Pb 2+ ------- 0   RT – exp  – RT  cH+ PbO 0 where k 0 2 is a rate constant.8V – -------. pos = 1. 2+ PbO 2 ( s ) + 4H + 2e ⇔ Pb + 2H 2 O with the kinetics being described by a Butler-Volmer expression: cH+ . is the same as for the positive electrode main reaction (Equation 1). described by the Nernst Equation: RT  c Pb2+ E 0. The equilibrium potential for the negative electrode is assumed to follow the Nernst equation according to: RT E 0.) 4 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . In this model the following side reaction is investigated: + - PbO 2 ( s ) + 2H + 2e ⇔ PbO ( s ) + H 2 O where the electrode is kinetics is described by PbO 2  K 0 c PbO exp  -------- – K 0 c H + c PbO 2 exp  – --------  f 2 Fη b Fη i PbO = Fk 0 (2)   RT  RT  where the overpotential. η.ln ( c Pb 2+ ) nF Positive Electrode Main Reaction The positive electrode main reaction is: + .2 As reference electrode we use the negative electrode at reference conditions.ln  ----------- (1) nF  c H +  Positive Electrode Side Reaction Multiple types of lead oxides may form on the positive electrode.

Pb 2+) =  ( N Pb 2+ ⋅ n ) dS –  ( N Pb 2+ ⋅ n ) dS outlet inlet V ---. Assuming good mixing in the tank the inlet concentrations. 1000 kg/m3. and viscosity μ. and c PbO and c PbO 2 are the surface concentration of the lead oxides (mol/m2). H + . H +) =  ( N H + ⋅ n ) dS –  ( N H + ⋅ n ) dS outlet inlet Where V is the total volume of flowing electrolyte in the tank. Solved with COMSOL Multiphysics 5. ( N Pb2+ ⋅ n and N H + ⋅ n denote the molar fluxes of the respective electrolyte species in the normal direction to the boundary). The convective flow is used as a model input to the Tertiary Current Distribution. 10-3 Pa·s. Nernst-Planck interface.d (c L d t in.≈ 300 μ where the parameter values for water are used for the density ρ. are governed by the following ODEs: V ---. Vin is applied at the inlet. The two ODEs are modeled using an ODEs and DAEs interface. and L is the height of the electrodes. c in. In this way the flow model is stationary and only solved for once. 5 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . and is then led into the cell again on the inlet side. a pressure condition is applied to the outlet.2 f b In Equation 2 K 0 and K 0 are rate constants. The induced convection at the electrode surfaces due to the electrochemical reactions is assumed to be negligible. The relevant Reynolds number for the flow between the plates is: ρV in h Re = ---------------. We can assume that the flow is in the laminar regime (Re<2000). FLUID FLOW EQUATIONS The fluid is led into the cell at a velocity Vin of 2.d (c L d t in. Pb 2+ and c in. and hence the Laminar Flow interface is used to model the fluid flow.3 cm/s. TA N K M O D E L The electrolyte flowing out from the cell flows into the tank. and no slip conditions are applied to the electrode surfaces and channel walls. undergoes mixing.

c PbO and c PbO 2 (SI unit: mol/m2). Nernst-Planck interface by the electrochemical currents. creating molar sources according to Faraday’s law (using a Electrolyte-Electrode Interface Coupling node). Figure 4 shows the cell voltage during the load cycling.2 SURFACE CONCENTRATIONS ON THE POSITIVE ELECTRODE Two different lead oxides. The surface concentrations of these two species. are modeled using a Surface Reactions interface. 6 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . Results and Discussion Figure 3 shows the flow field and pressure drop for the cell. The parabolic velocity profile is expected for this rectangular geometry (Poiseuille flow). Figure 3: Velocity field and pressure. The surface reaction model is coupled to the electrochemical reactions in the Tertiary Current Distribution. Solved with COMSOL Multiphysics 5. The first charge cycle voltages differs from the second. may be formed on the positive electrodes due to the electrochemical reactions. PbO and PbO2.

The build-up of PbO2 starts during the first charge cycle. 7 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . which in turn explains the difference in cell voltages during the first and second charge cycles in Figure 4.2 Figure 4: Cell potential versus time. The modified kinetics on the positive electrode impacts the overpotentials. Figure 5 shows the average surface concentrations of PbO and PbO2 at the positive electrode during the load cycle. Solved with COMSOL Multiphysics 5. The presence of PbO alters the kinetics of the positive electrode during the second charge cycle. Figure 7 shows the difference in local current densities between the different parts of the load cycle. whereas there is only small amounts of PbO formed until the beginning of the discharge cycle.

The reasons for these variations are due to the lead ion consumption to form the lead oxide layer. Figure 6 shows the inlet concentrations of lead ions and protons from the tank model during the load cycling. 8 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . The lead ion concentrations is lower and the proton concentration is higher at the beginning of the second charge cycle. compared to the initial values. Solved with COMSOL Multiphysics 5.2 Figure 5: Average surface concentrations of the two different lead oxides on the positive electrode. and the proton release from water molecules in the same process.

9 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . Solved with COMSOL Multiphysics 5.2 Figure 6: Inlet lead ion and proton concentrations versus time.

Figure 8 and Figure 9 depict the Pb2+ concentration distribution in the electrolyte at the end of the first charge and discharge step. The PbO2 and PbO reactions occurring on the positive electrode. Pb on the negative. Solved with COMSOL Multiphysics 5. Large gradients are present in the boundary layer close to the electrode surfaces.2 Figure 7: Local current densities of the electrode reactions. 10 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . respectively.

2 Figure 8: Lead ion concentration in the electrolyte at the end of the first charging cycle. 11 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . Solved with COMSOL Multiphysics 5.

Figure 10 and Figure 11 plot the proton concentration distributions in the electrolyte at the end of the first charge and discharge step. 12 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY .2 Figure 9: Lead ion concentration in the electrolyte at the end of the discharge cycle. Solved with COMSOL Multiphysics 5. Also for this species large gradients are present in the boundary layer close to the electrode surfaces.

13 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . Solved with COMSOL Multiphysics 5.2 Figure 10: Hydrogen ion concentration in the electrolyte at the end of the first charging cycle.

p. Electrochemical Systems. A589–A599. vol. R. Thomas-Alyea. Table 11. Collins. Application Library path: Batteries_and_Fuel_Cells_Module/ Flow_Batteries/pb_flow_battery 14 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . 955–965.2 Figure 11: Hydrogen ion concentration at the end of the discharge cycle. 2004. Newman and K. and F. References 1. “Developments in the Soluble Lead-acid Flow Battery. 2. D.1. John Wiley & Sons. 2010. Willis. 2010. Low. Electrochem. Shah. vol. Electrochemical Society. R. Walsh. A. J. Walsh. D. 40. “A Mathematical Model for the Soluble Lead-Acid Flow Battery.” J. Solved with COMSOL Multiphysics 5. J. Appl. Wills. 157. 3. C. Pletcher. pp. Stratton-Campbell.” J. pp. 284. and F.

select Preset Studies>Stationary. 3 In the Width text field. locate the Parameters section. GLOBAL DEFINITIONS Parameters 1 On the Home toolbar. select Fluid Flow>Single-Phase Flow>Laminar Flow (spf). Solved with COMSOL Multiphysics 5. 3 Click Add. 6 Click Done. 2 In the Settings window for Explicit. 2 In the Select physics tree.2 Modeling Instructions From the File menu. locate the Size and Shape section. DEFINITIONS Explicit 1 1 On the Definitions toolbar. NEW 1 In the New window. 4 Click Study. click Explicit. 15 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . MODEL WIZARD 1 In the Model Wizard window. 2 In the Settings window for Parameters. choose New. 3 Click Load from File. 4 In the Height text field. click Model Wizard. click 2D. 2 In the Settings window for Rectangle. 4 Browse to the application’s Application Library folder and double-click the file pb_flow_battery_parameters. 5 In the Select study tree. type 12[mm]. GEOMETRY 1 Rectangle 1 (r1) 1 On the Geometry toolbar. 5 Click the Build All Objects button. click Parameters.txt. locate the Input Entities section. click Primitives and choose Rectangle. type 10[cm].

choose Boundary. locate the Input Entities section. 2 In the Settings window for Explicit. 3 From the Geometric entity level list. choose Boundary. 5 Right-click Explicit 3 and choose Rename. 7 Click OK. click Explicit. 4 Select Boundary 1 only. 3 From the Geometric entity level list. type Positive electrode in the New label text field. 7 Click OK.2 3 From the Geometric entity level list. 4 Select Boundary 4 only. type Inlet in the New label text field. Explicit 3 1 On the Definitions toolbar. Explicit 4 1 On the Definitions toolbar. 7 Click OK. 6 In the Rename Explicit dialog box. type Negative electrode in the New label text field. 4 Select Boundary 3 only. Explicit 2 1 On the Definitions toolbar. choose Boundary. type Outlet in the New label text field. choose Boundary. 6 In the Rename Explicit dialog box. 4 Select Boundary 2 only. click Explicit. Solved with COMSOL Multiphysics 5. 3 From the Geometric entity level list. 16 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . locate the Input Entities section. 2 In the Settings window for Explicit. 5 Right-click Explicit 4 and choose Rename. 6 In the Rename Explicit dialog box. click Explicit. locate the Input Entities section. 5 Right-click Explicit 1 and choose Rename. 2 In the Settings window for Explicit. 7 Click OK. 6 In the Rename Explicit dialog box. 5 Right-click Explicit 2 and choose Rename.

LAMINAR FLOW (SPF) Fluid Properties 1 1 In the Model Builder window. 5 Locate the Laminar Inflow section. ADD MATERIAL 1 On the Home toolbar. liquid (mat1) On the Home toolbar. 3 In the tree. choose Laminar inflow. choose Outlet.01. type U_in. click Boundaries and choose Inlet. 4 Locate the Pressure Conditions section. locate the Boundary Selection section. select Built-In>Water. click Add Material to close the Add Material window.2 MATERIALS Use the material parameter values for water from the model library. locate the Boundary Selection section. 2 Go to the Add Material window. locate the Model Inputs section. Outlet 1 1 On the Physics toolbar. In the Uav text field. 7 In the Lentr text field. 4 Click Add to Component in the window toolbar. liquid. 3 In the T text field. 6 Select the Constrain outer edges to zero check box. Inlet 1 1 On the Physics toolbar. MATERIALS Water. click Boundaries and choose Outlet. 4 Locate the Boundary Condition section. 2 In the Settings window for Fluid Properties. 2 In the Settings window for Inlet. 17 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . expand the Component 1 (comp1)>Laminar Flow (spf) node. Select the Normal flow check box. From the list. type 0. 3 From the Selection list. choose Inlet. click Add Material to open the Add Material window. Solved with COMSOL Multiphysics 5. 3 From the Selection list. 2 In the Settings window for Outlet. then click Fluid Properties 1. type T.

under Component 1 (comp1)>Mesh 1>Boundary Layers 1 click Boundary Layer Properties. 2 In the Settings window for Distribution. 2 Select Boundaries 2 and 3 only. choose Predefined distribution type. 2 Select Boundaries 1 and 4 only. 2 In the Settings window for Boundary Layers. 4 From the Thickness of first layer list. right-click Mesh 1 and choose More Operations>Edge. locate the Distribution section. 2 Select Boundaries 1 and 4 only. right-click Mesh 1 and choose Build All. 5 In the Element ratio text field. Solved with COMSOL Multiphysics 5. under Component 1 (comp1) right-click Mesh 1 and choose More Operations>Edge. Boundary Layer Properties 1 In the Model Builder window. type 30. 4 In the Number of elements text field. 3 Right-click Component 1 (comp1)>Mesh 1>Edge 2 and choose Distribution. 3 Clear the Smooth transition to interior mesh check box. click to expand the Transition section. Edge 1 1 In the Model Builder window. locate the Boundary Layer Properties section. 4 Right-click Mesh 1 and choose Mapped. type 5e-5. choose Manual. 3 In the Settings window for Boundary Layer Properties. 3 From the Distribution properties list.2 MESH 1 The rectangular geometry makes a mapped mesh suitable for this problem. Distribution 1 1 Right-click Component 1 (comp1)>Mesh 1>Edge 1 and choose Distribution. 18 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . 5 In the Thickness text field. 6 In the Model Builder window. Edge 2 1 In the Model Builder window. Boundary Layers 1 1 Right-click Mesh 1 and choose Boundary Layers. type 5.

2 7 Click the Build All button. type Flow in the New label text field. 2 In the Settings window for Arrow Surface. click Compute. STUDY 1 On the Home toolbar. click Plot. right-click Pressure (spf) and choose Rename. From the Color list. 8 Click OK. 7 In the Rename 2D Plot Group dialog box. Solved with COMSOL Multiphysics 5. 4 Locate the Coloring and Style section. 3 Find the x grid points subsection. under Results right-click Pressure (spf) and choose Arrow Surface. 19 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . type 5. RESULTS Pressure (spf) 1 In the Model Builder window. In the Points text field. 5 On the Pressure (spf) toolbar. 6 In the Model Builder window. choose Black. locate the Arrow Positioning section.

1 On the Home toolbar. In the table. select Electrochemistry>Tertiary Current Distribution. Nernst-Planck (tcdee). 2 Go to the Add Physics window. Solved with COMSOL Multiphysics 5. 5 In the Concentrations table. Locate the Dependent Variables section. select Chemical Species Transport>Surface Reactions (sr). 4 Click to expand the Dependent variables section. enter the following settings: cs_PbO cs_PbO2 5 Find the Physics interfaces in study subsection. enter the following settings: Studies Solve Study 1 7 Click Add to Component in the window toolbar. Click Add Concentration.2 ADD PHYSICS Now add the electrochemistry to the model. In the table. Locate the Dependent Variables section. start by adding the appropriate physics interface. enter the following settings: Studies Solve Study 1 20 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . 2 In the Add physics tree. Click Add Surface Concentration. 3 In the Add physics tree. 4 In the Surface (adsorbed) species concentrations table. ADD PHYSICS 1 Go to the Add Physics window. enter the following settings: cPbII cH cHSO4 6 Find the Physics interfaces in study subsection. click Add Physics to open the Add Physics window. 3 Click to expand the Dependent variables section.

click Add Study to open the Add Study window. 3 Find the Physics interfaces in study subsection. 3 Locate the Definition section. The max(eps^2. select Preset Studies>Time Dependent. Solved with COMSOL Multiphysics 5. 6 In the Function text field. 5 On the Home toolbar. 4 Click Add Study in the window toolbar.. click Add Study to close the Add Study window. type E_neg_nernst in the Function name text field. 5 Locate the Units section. a very small number). ADD STUDY 1 On the Home toolbar. In the Select study tree. select Mathematics>ODE and DAE Interfaces>Global ODEs and DAEs (ge). 3 Find the Studies subsection. type 0+8. 21 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY .. (eps is the machine epsilon. 2 In the Add physics tree. In the Expression text field.31*Temp/ (2*96485)*log(max(eps^2. type Temp. In the Arguments text field.) expressions are used here to avoid evaluating logarithms of negative numbers. DEFINITIONS Define the electrode potentials from Nernst Equation by using analytic functions. Analytic 1 (an1) 1 On the Home toolbar. click Functions and choose Local>Analytic. type K. ADD PHYSICS 1 Go to the Add Physics window. 2 Go to the Add Study window.concPbII/(1000[mol/m^3]))). In the table.2 6 Click Add to Component in the window toolbar. 5 On the Home toolbar. type V. 2 In the Settings window for Analytic. enter the following settings: Studies Solve Study 1 4 Click Add to Component in the window toolbar. mol/m^3.. click Add Physics to close the Add Physics window. 4 In the Arguments text field. concPbII.

mol/m^3. click Functions and choose Local>Rectangle. type t_charge.2 Analytic 2 (an2) 1 On the Home toolbar. 5 Locate the Smoothing section. type 1. type 1. In the Size of transition zone text field. type 1. type 1. 2 In the Settings window for Analytic. 2 In the Settings window for Rectangle. type Temp. 4 In the Upper limit text field. In the Arguments text field. In the Lower limit text field. 2 In the Settings window for Rectangle. 6 In the Function text field. 4 In the Upper limit text field. type 2*t_charge+t_rest+t_discharge+t_rest. Solved with COMSOL Multiphysics 5. In the Lower limit text field. concPbII. In the Expression text field. 4 In the Upper limit text field.8-8. mol/m^3. Rectangle 1 (rect1) 1 On the Home toolbar. Rectangle 2 (rect2) 1 On the Home toolbar. click Functions and choose Local>Rectangle. 3 Locate the Definition section. type charge2 in the Function name text field. 3 Locate the Parameters section. Rectangle 3 (rect3) 1 On the Home toolbar. 4 In the Arguments text field. In the Size of transition zone text field. 3 Locate the Parameters section. 22 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . 2 In the Settings window for Rectangle. type discharge1 in the Function name text field. concH.31*Temp/ (2*96485)*(log(max(eps^2. click Functions and choose Local>Rectangle. Use a number of rectangle functions to set up the charge/discharge cycle that will be a function of time. 5 Locate the Units section. type E_pos_nernst in the Function name text field. type t_charge+t_rest+t_discharge. In the Size of transition zone text field. 5 Locate the Smoothing section. type t_charge+t_rest+t_discharge+t_rest. click Functions and choose Local>Analytic.concPbII/(1000[mol/ m^3])))-4*log(max(eps^2. type K.concH/(1000[mol/m^3])))). 5 Click to expand the Smoothing section. 3 Locate the Parameters section. type 0. type t_charge+t_rest. type V. type charge1 in the Function name text field. In the Lower limit text field.

type 2. 11 In the Model Builder window. 3 From the From electroneutrality list. type 1. 4 Browse to the application’s Application Library folder and double-click the file pb_flow_battery_variables. 6 In the DcH text field. 3 Click Load from File. 4 In the T text field. click Tertiary Current Distribution. 3 From the u list.txt. Inflow 1 1 On the Physics toolbar. Load the variables from a text file. 5 Locate the Diffusion section. 2 In the Settings window for Inflow. Solved with COMSOL Multiphysics 5. type D_PbII. 1 On the Home toolbar. then click Electrolyte 1. 23 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY .) TE R T I A R Y C U R R E N T D I S T R I B U T I O N . 8 Locate the Migration in Electric Field section. Nernst-Planck (tcdee). (The tcdee. locate the Variables section. choose Velocity field (spf). type D_H. locate the Model Inputs section. Nernst-Planck. N E R N S T . locate the Species section. Nernst-Planck (tcdee). 7 In the DcHSO4 text field. click Variables and choose Local Variables.phisext-variable is the electric potential on the boundary. 10 In the zcHSO4 text field. Electrolyte 1 1 In the Model Builder window. choose cHSO4. click Boundaries and choose Inflow. type T. type D_HSO4.2 Variables 1 Now the defined analytical functions can be used to set up variables on the negative and positive electrodes. 2 In the Settings window for Tertiary Current Distribution. expand the Tertiary Current Distribution.P L A N C K ( T C D E E ) 1 In the Model Builder window. locate the Boundary Selection section. 9 In the zcH text field. In the DcPbII text field. type -1. In the zcPbII text field. under Component 1 (comp1) click Tertiary Current Distribution. 2 In the Settings window for Variables. Nernst-Planck (tcdee) node. 2 In the Settings window for Electrolyte.

In the Eeq text field. click Boundaries and choose Outflow. 6 Locate the Boundary Condition Type section. Outflow 1 1 On the Physics toolbar. type cH_in. click Boundaries and choose Electrode Surface. 3 From the Selection list. 7 In the αa text field. choose Outlet. type E_neg. type i_cycle. then click Electrode Reaction 1. 3 In the T text field. Solved with COMSOL Multiphysics 5. choose Flux (Danckwerts). type 1. 2 In the Settings window for Electrode Surface. type cPbII_in. 6 In the i0 text field. In the nm text field. 2 In the Settings window for Electrode Reaction. choose Negative electrode. 3 From the Selection list. choose Average current density. Electrode Surface 1 1 On the Physics toolbar. 5 Locate the Electrode Kinetics section. From the list. 5 In the il.2 3 From the Selection list. expand the Electrode Surface 1 node. From the Kinetics expression type list. locate the Boundary Selection section. Electrode Reaction 1 1 In the Model Builder window. locate the Boundary Selection section. type F_const*k0_Pb*cPbII. type -1. type 2. 2 In the Settings window for Outflow. 24 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . choose Positive electrode.average text field. 4 Locate the Equilibrium Potential section. type T. choose Inlet. 3 From the Selection list. In the c0.cPbII text field. locate the Model Inputs section.cH text field. 8 In the αc text field. choose Butler-Volmer. 4 Locate the Boundary Condition section. click Boundaries and choose Electrode Surface. 4 Locate the Concentration section. type 1. 9 Locate the Stoichiometric Coefficients section. locate the Boundary Selection section. 10 In the νcPbII text field. 5 In the c0. 2 In the Settings window for Electrode Surface. Electrode Surface 2 1 On the Physics toolbar. From the Boundary condition list.

3 In the cPbII text field. type T. then click Electrode Reaction 1. Nernst-Planck (tcdee) click Initial Values 1. 4 Locate the Equilibrium Potential section. type -4.c0_PbII). type F_const*k0_PbO2*cPbII*(cH/c0_H). 6 In the i0 text field. 7 Locate the Stoichiometric Coefficients section. type c0_H. under Component 1 (comp1)>Tertiary Current Distribution. 3 In the T text field.c0_H)-E_neg_nernst(T. type i_PbO. 9 In the νcH text field. Initial Values 1 1 In the Model Builder window. 2 In the Settings window for Electrode Reaction. In the nm text field. 2 In the Settings window for Initial Values. 2 In the Settings window for Electrode Reaction.2 6 In the φs. type E_pos. In the nm text field. type -E_neg_nernst(T. expand the Electrode Surface 2 node. under Component 1 (comp1)>Tertiary Current Distribution. type 1. 4 In the cH text field.c0_PbII. Electrode Surface 2 In the Model Builder window. From the Kinetics expression type list. choose Butler-Volmer. 8 In the νcPbII text field. In the Eeq text field. 3 From the Kinetics expression type list. Solved with COMSOL Multiphysics 5. Nernst-Planck (tcdee) click Electrode Surface 2. locate the Model Inputs section. locate the Initial Values section. 25 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . 5 In the νcH text field. choose User defined.c0_PbII).ext text field. 4 Locate the Stoichiometric Coefficients section. type 2. Electrode Reaction 2 1 On the Physics toolbar. Electrode Reaction 1 1 In the Model Builder window. 5 Locate the Electrode Kinetics section. type -2. locate the Electrode Kinetics section. In the iloc text field. 5 In the phil text field. type E_pos_nernst(T. type 2. type c0_PbII. click Attributes and choose Electrode Reaction.

DEFINITIONS The tank model is based on two ODE's and the integrals of the ion fluxes over the electrode boundaries. 4 Locate the Stoichiometric Coefficients section. 3 From the Selection list. Reaction Coefficients 1 1 In the Model Builder window. Solved with COMSOL Multiphysics 5. type -1. type -1. locate the Boundary Selection section. type 1. click Tertiary Current Distribution. choose Local current density (tcdee/eebii2/er1). under Component 1 (comp1)>Surface Reactions (sr) click Electrode-Electrolyte Interface Coupling 1. locate the Model Inputs section. 2 In the Settings window for Surface Reactions. 3 From the iloc list. expand the Electrode-Electrolyte Interface Coupling 1 node. 2 In the Settings window for Reaction Coefficients. 3 From the iloc list. 4 Locate the Stoichiometric Coefficients section. type 2. 3 From the Selection list. then click Reaction Coefficients 1. click Boundaries and choose Electrode-Electrolyte Interface Coupling. Nernst-Planck (tcdee) and choose Surface Reactions (sr). 6 In the νcsPbO2 text field. Electrode-Electrolyte Interface Coupling 1 In the Model Builder window. 5 In the νcsPbO text field. locate the Boundary Selection section. Reaction Coefficients 2 1 On the Physics toolbar. type 2. choose Positive electrode.2 SURFACE REACTIONS (SR) On the Physics toolbar. Electrode-Electrolyte Interface Coupling 1 1 On the Physics toolbar. 2 In the Settings window for Electrode-Electrolyte Interface Coupling. click Attributes and choose Reaction Coefficients. locate the Model Inputs section. under Component 1 (comp1) click Surface Reactions (sr). 5 In the νcsPbO2 text field. 2 In the Settings window for Reaction Coefficients. choose Local current density (tcdee/eebii2/er2). choose All boundaries. In the nm text field. 26 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . 1 In the Model Builder window. In the nm text field.

tcde e. 4 From the Selection list. click Component Couplings and choose Integration. 3 Locate the Source Selection section.t) (1) Initial value Initial value Description (u_0) (1) (u_t0) (1/s) cPbII_ cPbII_int-L/ c0_PbII 0 Pb ion inlet in V*(comp1.t fluxy_cPbII)) cH_in cH_int-L/ c0_H 0 Proton inlet V*(comp1. choose Boundary.int_ou concentration tlet(comp1. choose Boundary. 2 In the Settings window for Global Equations. From the Geometric entity level list.int_ou concentration tlet(comp1.int_inlet(c omp1.tcdee. 4 From the Selection list.tcde e.tcdee. Solved with COMSOL Multiphysics 5.tflu xy_cH)) 27 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . choose Outlet. type int_outlet in the Operator name text field. choose Inlet. under Component 1 (comp1)>Global ODEs and DAEs (ge) click Global Equations 1. 3 Locate the Source Selection section.int_inle t(comp1. enter the following settings: Name f(u. type int_inlet in the Operator name text field.2 Integration 1 (intop1) 1 On the Definitions toolbar. locate the Global Equations section.utt. click Component Couplings and choose Integration. 2 In the Settings window for Integration. Integration 2 (intop2) 1 On the Definitions toolbar. From the Geometric entity level list. GLOBAL ODES AND DAES (GE) Global Equations 1 1 In the Model Builder window.tfluxy_cPbII) -comp1.tfluxy_cH)-co mp1. 2 In the Settings window for Integration. 3 In the table.ut.

choose Negative electrode.2 4 Locate the Units section. type tcdee. type tcdee. This creates a probe for the electric potential at the positive electrode. 3 From the Selection list. From the list. In the Expression text field. 2 In the Settings window for Boundary Probe. 4 Locate the Expression section. 28 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . locate the Source Selection section. click Probes and choose Boundary Probe. Boundary Probe 3 (bnd3) 1 On the Definitions toolbar. 3 From the Selection list. Find the Dependent variable quantity subsection. choose Positive electrode. 4 Locate the Expression section. Boundary Probe 1 (bnd1) 1 On the Definitions toolbar. 2 In the Settings window for Boundary Probe. This creates a probe for the PbO2-current density at the positive electrode. In the Expression text field. locate the Source Selection section. Solved with COMSOL Multiphysics 5. click Probes and choose Boundary Probe.iloc_er1. 3 From the Selection list. 5 Find the Source term quantity subsection. click Probes and choose Boundary Probe. 4 Locate the Expression section. 3 From the Selection list. This creates a probe for the local current density at the negative electrode. locate the Source Selection section. 2 In the Settings window for Boundary Probe. choose Positive electrode. DEFINITIONS Use Boundary Probes to store certain variables for all time steps during the solver sequence. choose Concentration (mol/m^3). locate the Source Selection section. From the list.iloc_er2. This creates a probe for the PbO-current density at the positive electrode. choose Positive electrode. 2 In the Settings window for Boundary Probe. In the Expression text field. type tcdee.phisext. Boundary Probe 4 (bnd4) 1 On the Definitions toolbar. choose Reaction rate (mol/ (m^3*s)). and to be able to plot these results during while solving. Boundary Probe 2 (bnd2) 1 On the Definitions toolbar. click Probes and choose Boundary Probe.

From the menu. Click cs_PbO2 . 29 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . From the Settings list.600. locate the Source Selection section.Surface concentration. click Probes and choose Boundary Probe. enter the following settings: Physics interface Solve for Discretization Laminar Flow physics 5 Click to expand the Values of dependent variables section. 3 From the Selection list.10900). This creates probes for the average surface concentrations at the positive electrode. choose Positive electrode. instead.Surface concentration in the upper-right corner of the section. Find the Values of variables not solved for subsection. 2 In the Settings window for Boundary Probe. Solved with COMSOL Multiphysics 5.7260) range(7320. 6 From the Method list. Boundary Probe 5 (bnd5) 1 On the Definitions toolbar. Step 1: Time Dependent 1 In the Model Builder window.600. use the velocity field from the first study. then click Step 1: Time Dependent. Boundary Probe 6 (bnd6) 1 On the Definitions toolbar. locate the Study Settings section.600. 2 In the Settings window for Boundary Probe. type range(0. choose Solution. choose Component 1 (comp1)>Surface Reactions>cs_PbO . 3 In the Times text field. 3 From the Selection list. locate the Source Selection section. choose Positive electrode. 4 Locate the Expression section. 2 In the Settings window for Time Dependent. click Probes and choose Boundary Probe.iloc_er1. 4 Click Replace Expression in the upper-right corner of the Expression section. type tcdee. expand the Study 2 node. STUDY 2 Now set up the solver. In the Expression text field. Do not solve for the velocity field. 4 Locate the Physics and Variables Selection section. Locate the Values of Dependent Variables section.2 4 Locate the Expression section.3600) range(3660. choose User controlled. In the table.

2 In the Settings window for 1D Plot Group.2 7 From the Study list. choose Manual. type Cell Potential vs Time. choose Manual. 1D Plot Group 8 1 In the Settings window for Table Graph. locate the Data section. click Plot. 9 Click OK. 7 Right-click 1D Plot Group 8 and choose Rename. Stationary. 3 In the Columns list. RESULTS 1D Plot Group 8 1 On the Home toolbar. select External electric potential (V). click Add Plot Group and choose 1D Plot Group. click 1D Plot Group 8. 5 On the 1D Plot Group 8 toolbar. choose 1. choose Study 1. Select the x-axis label check box. 4 In the Model Builder window. 30 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . 7 Select the y-axis label check box. type Time (s). 4 In the Title text area. Solved with COMSOL Multiphysics 5. 2 From the Plot columns list. 1D Plot Group 9 1 On the Home toolbar. 6 In the associated text field. 6 Click the Zoom Extents button on the Graphics toolbar. click Table Graph. Boundary Probe 1. 8 From the Selection list. type Cell Potential in the New label text field. Table Graph 1 On the 1D Plot Group 8 toolbar. 8 In the Rename 1D Plot Group dialog box. 5 Locate the Plot Settings section. click to expand the Title section. click Add Plot Group and choose 1D Plot Group. click Compute. 3 From the Title type list. 8 In the associated text field. type Voltage (V). TABLE Go to the Table window. 9 On the Home toolbar.

1D Plot Group 9 1 In the Settings window for Table Graph. Select the Show legends check box. click Add Plot Group and choose 1D Plot Group. 5 Locate the Plot Settings section. choose Manual. 3 In the Columns list. Boundary Probe 2. 3 From the Title type list. Solved with COMSOL Multiphysics 5. right-click 1D Plot Group 9 and choose Rename. enter the following settings: Legends PbO2 formation PbO formation Pb formation 7 On the 1D Plot Group 9 toolbar. 7 Select the y-axis label check box.2 2 In the Settings window for 1D Plot Group. Local current density (A/m^2). 9 Click to expand the Legend section. 2 From the Plot columns list. 4 Click to expand the Legends section. and Local current density (A/m^2). Boundary Probe 3. 9 In the Model Builder window. From the Position list. click Plot. type Current density (A/m<sup>2</sup>). 6 In the table. 1D Plot Group 10 1 On the Home toolbar. choose Manual. 8 In the associated text field. Boundary Probe 4. locate the Title section. 5 From the Legends list. choose Manual. 4 In the Title text area. Select the x-axis label check box. choose Local current density (A/m^2). type Time (s). 6 In the associated text field. Table Graph 1 On the 1D Plot Group 9 toolbar. click Table Graph. locate the Data section. 8 Click the Zoom Extents button on the Graphics toolbar. type Average local reaction current densities. 11 Click OK. 10 In the Rename 1D Plot Group dialog box. choose Lower right. type Local current densities in the New label text field. 31 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY .

enter the following settings: Legends PbO2 PbO 7 On the 1D Plot Group 10 toolbar. 11 Click OK. 1D Plot Group 10 1 In the Settings window for Table Graph. Boundary Probe 5 and Surface concentration (mol/m^2). 4 In the Title text area. choose Manual. 5 From the Legends list. 32 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . right-click 1D Plot Group 10 and choose Rename. type Surface concentrations in the New label text field. 2 In the Settings window for 1D Plot Group. click Plot. choose Manual. choose Manual. 3 From the Title type list. 4 Locate the Legends section. 8 In the associated text field. locate the Data section. 9 In the Model Builder window. 8 Click the Zoom Extents button on the Graphics toolbar. Select the x-axis label check box. choose Surface concentration (mol/m^2). locate the Title section. locate the Title section. Solved with COMSOL Multiphysics 5. 3 From the Title type list. 6 In the table. 2 From the Plot columns list. Boundary Probe 6. type Electrode surface concentration (mol/ m<sup>2</sup>). 1D Plot Group 6 1 In the Model Builder window. Select the Show legends check box. type Time (s). type Average surface concentrations.2 2 In the Settings window for 1D Plot Group. 7 Select the y-axis label check box. 5 Locate the Plot Settings section. Table Graph 1 On the 1D Plot Group 10 toolbar. choose Manual. click Table Graph. 10 In the Rename 1D Plot Group dialog box. 6 In the associated text field. 3 In the Columns list. under Results click 1D Plot Group 6.

type Cell inlet concentrations. click Plot. locate the Data section. 10 In the Rename 1D Plot Group dialog box. choose 3600. From the menu.2 4 In the Title text area. 16 Click OK. Concentration (tcdee) 1 In the Settings window for 2D Plot Group. 14 Right-click 2D Plot Group 11 and choose Rename. 11 In the Settings window for 2D Plot Group. choose Study 2/Solution 2 (sol2). 2 In the Settings window for 2D Plot Group. 10 In the Model Builder window. 9 Click the Zoom Extents button on the Graphics toolbar. click 2D Plot Group 11. 17 Click the Zoom Extents button on the Graphics toolbar. 6 In the associated text field. locate the Data section. 2D Plot Group 11 1 On the Home toolbar. 7 Right-click Results>2D Plot Group 11>Surface 1 and choose Height Expression. click Add Plot Group and choose 2D Plot Group. 6 In the Settings window for Surface. choose 7260. 8 On the 2D Plot Group 11 toolbar. Solved with COMSOL Multiphysics 5. type Concentration (mol/m<sup>3</sup>). type Electrolyte concentrations in the New label text field. locate the Data section. Select the x-axis label check box. 3 From the Data set list. 9 Right-click Results>1D Plot Group 6 and choose Rename. 5 Right-click 2D Plot Group 11 and choose Surface.Concentration. 7 Select the y-axis label check box. 33 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . 11 Click OK. choose Component 1>Tertiary Current Distribution. Nernst-Planck>cH . type Time (s). 12 From the Time (s) list. click Plot. click Replace Expression in the upper-right corner of the Expression section. 8 In the associated text field. 15 In the Rename 2D Plot Group dialog box. 4 From the Time (s) list. 13 On the 2D Plot Group 11 toolbar. 5 Locate the Plot Settings section. type Electrolyte concentration distribution in the New label text field.

expand the Concentration (tcdee) node. 10 In the Settings window for 2D Plot Group. right-click Concentration (tcdee) and choose Rename. click Plot. click Plot. 4 Right-click Surface 1 and choose Height Expression. 11 From the Time (s) list. 6 Click the Zoom Extents button on the Graphics toolbar. 9 Click OK. 13 Click the Zoom Extents button on the Graphics toolbar. locate the Data section. Solved with COMSOL Multiphysics 5.2 2 From the Time (s) list. 5 On the Concentration (tcdee) toolbar. 34 | SOLUBLE LEAD-ACID REDOX FLOW BATTERY . 8 In the Rename 2D Plot Group dialog box. choose 3600. type PbII Concentration distribution in the New label text field. 3 In the Model Builder window. 12 On the PbII Concentration distribution toolbar. 7 In the Model Builder window. choose 7260.