Final Year Project Interim Report

Title: Design of Redox Flow Lithium-ion Battery (RFLB)

Prepared by: Daniel A0115052X

Introduction
Source of electrical energy can be divided into two categories: Renewable and Non-renewable energy.
Renewable energy includes wind, hydro, solar and geothermal while non-renewable energy includes
fossil fuel such as crude oil, coal and natural gas, nuclear and biomass. The issue pertaining nonrenewable energy such as fossil fuel and natural gas is that they are depleting and would most likely be
not replenished in our lifetimes. Therefore, there is a shift towards the utilization of renewable energy to
meet the world energy demand. However, these sources are intermittent in nature, and storage system
needs to be put in place to ensure reliable supply of energy.

Flow Battery
Flow battery is used for storage instead of solid state processes battery because it offers long cycle life as
well as the greatest flexibility in power to energy rating. On the other hand, batteries that rely on solid
state processes often lead to mechanical breakdown of the active material and hence shorter life cycle.
This is because the active material in a flow battery is in the form of two redox couple solutions that are
stored in the tank and pumped into the electrochemical cells. These solutions are separated by an ion
exchange membrane that serves to prevent mixing between the two solutions.
The basis of flow battery involves electrochemistry concept. During charging, cation is being reduced on
the anodic side whereas cation is being oxidized on the cathodic side. When the battery is discharging, the
opposite occurs. In this manner, energy can be generated through the redox reactions that occur in the
electrochemical cell. Out of a number of redox flow design, only Vanadium Redox Battery (VRB) design
is widely used and commercialized.

Extracted from: http://large.stanford.edu/courses/2011/ph240/xie2/images/f1big.png

Figure 1. Schematic of VRB system

Referring to figure 1, the electrochemical process and working principle of this system follows the
general flow battery system. Since design of the tank is the main focus of this project, it is worth noting
that the tank in this system acts as the storage for both electrolytes, and there is no chemical reaction
occurring in this tank.

Redox Flow Lithium-Ion Battery (RFLB)

Brief Description of the System
RFLB system has been proposed to utilize the high density of lithium ion battery and flexibility of redox
flow system. The performance of the battery has shown a promising result, 10 times that of VRB in terms
of energy density. The performance of the cell is determined by the rates of reactions in both electrode
and tank. In my project, I will be focusing my studies on the tank and its mathematical model. First, it is
important to discuss the reactions between the redox shuttle molecules in the tank.

Given the assumption that these two reactions are irreversible and of first order with respect to the
corresponding reactant shuttle molecule, the kinetics of the reactions and hence the selection of reactor
model can be determined. The rate equations of the reactions can be described as follows:
+

tank
M1

=k

tank
M1

cM 1 ;

M2
tank
R M 2 =k tank
M2 c

The current mathematical model that has been developed employ a continuous stirred tank reactor
(CSTR) model to simplify the simulation process. Figure below shows the graphical representation of
CSTR performance equations.

CSTR for First Order Reaction

0
0
0

-1/rA

0
0
0
0
0.25

0.35

0.45

0.55

0.65

0.75

0.85

XA

Figure 2. Graphical representation of CSTR Performance Equations

In the above diagram, the value of shaded area is used to calculate the space-time of the reactor. The
smaller the space-time indicates a better performance of reactor because it shows that the time required to
process one reactor volume of feed is shorter. Space time will be used in this report to evaluate choices of
reactor design.

Limitations of this model

First limitation would be the assumption that the tank is well mixed and modelled using CSTR model.
Based on the experimental setup, it showed a setup of a typical batch reactor tank without a stirrer.
Therefore, this mathematical model may not capture an accurate representation of the system.
Secondly, TiO2 exist in the reactor in the form of solid. The reaction happening in the tank will involve
reactants that are not in homogenous phase. Hence, the kinetics aspect in the model should be that of
heterogeneous reaction of fluid-solid system.

Areas of Research
Using the knowledge on chemical kinetics and reactor designs taught in CN2116, the aim of my project is
to develop the mathematical model that could provide a better representation of the system. The kinetics
of fluid-particle reactions follows two simple idealized models, the progressive-conversion model and the
shrinking unreacted-core model. Based on the models, I plan to develop the rate equations of the reactions
in the tank using the information.
Furthermore, after the kinetics of the reactions have been determined, I plan to propose the reactor design
that would give the most optimum reactor performance. There are three factors that control the design of a

fluid-solid reactor: 1. The reaction kinetics for single particles, 2. The size of distribution of solids being
treated, 3. The flow patterns of solids and fluids in the reactor.

Work Plan
In the first half of the research period, I focused my studies on understanding the flow battery system in
general and RFLB itself. For the next half of the research period, I would be focusing my research on
studying the kinetics of the redox targeting of anatase TiO 2 for RFLB. From the studies, I plan to include
detailed modeling of the reactive flow in the tank. Determining the rate of reaction in the tank is crucial
because it determines the performance of the cell as well. As mentioned above, once the kinetic models
have been developed, reactor design can be determined as well.
Furthermore, in preparation for the oral presentation next year, I will work closely with my supervisor
through series of video-taped presentations. This is to ensure that I can communicate my research ideas
effectively.