ENGINEERING DESING AND INNOVATION

Engg1000
Chem.Eng.: Batteries for electric cars
 Books

On batteries
Handbook of batteries

Electrochemistry and general descriptions on batteries

Chemistry: The molecular nature of matter and
change / Silberberg

Chemistry for Scientist and Engineers / Fine

Foundations of Chemistry / Garnett

Electrochemistry
basic theory
What is a battery?
 How electricity is produced from a battery?

Electricity is produced
by chemical reactions:
Electrochemical reactions

Resulting from the chemical

energy stored
within the galvanic cell

• Many chemical substances

can accept and donate e-.
• Electrochemical reaction: electron
transfer between an electronic
conductor and some species.
You will

• Be introduced to some basic electrochemistry: redox reactions, half cell

potential

• Learn how a cell works

• Be introduced to standard potential, Nernst equation and be able to predict

battery voltage, determine current and power output

• Learn about the factors affecting batteries performances: internal resistance,

polarisation, ohmic resistance, geometry, electrode surface

• The importance of current/voltage/ power in delivering power

• History of battery development and common batteries

You will be able

• To design a battery
Redox reactions
Half cell reactions
Redox reaction - Terminology
Many chemical substances can accept and donate e- oxidation -reduction

A redox (oxidation-reduction) reaction

involves the transfer electron(s) from one chemical species to another

Mg Mg2+ + 2e- Oxidation : loss of electrons

1/2O2 + 2e- O2- Reduction : gain of electrons

e-

Transfer of
X electron Y
X loses electrons Y gains electrons
X is oxidized Y is reduced
X is the reducing agent Y is the oxidizing agent
Redox reaction – Half reaction
It is useful in studying redox processes to break reactions into pairs :

Half reactions

One representing the oxidation - One representing the reduction

Zn(s) Zn(aq)2+ + 2e- Oxidation – Half reaction

Cu(aq)2+ + 2e- Cu Reduction – Half reaction

Zn(s) + Cu(aq)2+ Zn(aq)2+ + Cu Overall reaction (Galvanic cell)

By using an oxidizing and reducing agent e- can be transferred and
thus electricity produced

No electricity is produced
 How a battery works?
How to generate electricity?
Operation of a galvanic cell
The half reaction are physically separated and connected by an external circuit through
which the electrons are travelling

CuSO4
ZnSO4

Zn(s) Zn(aq)2+ + 2e- Cu2+ + 2e- Cu

• A charge imbalance arise and stop the cell operating

The salt bridge allows ions to flow to reestablish neutrality in both half cells.
The salt bridge is made of inert ions that cannot react.

• Notation for a galvanic cell:

Zn(s) Zn(aq)2+ Cu(aq)2+ Cu(s)

Anode on left Cathode on right

•Why a galvanic cell works? Why electrons flow in the direction shown?

Zn(s) Zn(aq)2+ + 2e- this reaction shifts to the right

Cu(s) Cu(aq)2+ + 2e- this reaction shifts to the left

Zn gives electron more easily than Cu does

Zn is a stronger reducing agent
•The purpose of a galvanic cell is to convert the free energy change of
a spontaneous chemical reaction into the kinetic energy of electrons moving
through an external circuit (electrical energy).

•The ability of producing electrical energy is related to the difference

in electrical potential between the two electrodes
Active vs. inactive electrode

For many reaction they are no reactants /

products able to serve as electrode

Use of inactive electrodes: e.g. platinum,

graphite conduct e- but do not take part of the
electrochemical reactions
 Standard potential
Predicting battery voltage and current
 Basic principles – Predicting cell potential
The ability of producing electrical energy is related to the difference in
electrical potential between the two electrodes

This difference is the cell potential (Ecell) also called the voltage or the
electromotive force (emf)

• For a current to flow spontaneously, Ecell > 0

• The more positive Ecell is the more work the cell can do

• if Ecell = 0, the reaction stops (equilibrium state)

•If Ecell < 0, there is no reaction

The unit for Ecell , the electrical potential, is the volt (V)
The unit for Ecell , the electrical potential, is the volt (V)

The unit of the electrical charge is the coulomb (C)

1V = 1 J/C

For 1 volt of electrical potential, 1 joule of energy is released for each

coulomb of charge that moves between the electrodes
Standard Cell potential
The potential of a galvanic cell is affected by changes in concentration,
energy losses (heat of the cell and external circuit).
To compare the output of different cells, a standard cell potential (E0) is
introduced

E0 is the potential measured at 298 K, and in standard conditions of 1 atm

for gases, 1 M for solutions, pure solid for electrodes, with no current flowing

Zn(s) + Cu2+(aq, 1M) Zn2+ (aq, 1M) + Cu

E0 = 1.10 V
Standard Half-Cell potential
To predict cell potential, standard half-cell potential are introduced

Is the potential associated with a given half-reaction (one cell

compartment)

By convention, the standard potential always refers to the half-reaction

written as a reduction.

Zn(aq)2+ + 2e- Zn(s) E0 zinc

reduction
Cu(aq)2+ + 2e- Cu(s) E0 copper
The overall reaction involves the oxidation of zinc and reduction of copper.

Zn(s) Zn(aq)2+ + 2e- - E0 zinc (anode) oxidation

Cu(aq)2+ + 2e- Cu(s) E0 copper (cathode) reduction

Zn(s) + Cu(aq)2+ Zn(aq)2+ + Cu

By inversing the zinc half reaction, the overall cell potential (E0 cell) is the sum
of the two half-cell potential

E0 cell = E0 copper - E0 zinc

E0 cell = E0 cathode (reduction) - E0 anode (oxidation)

 Practically E0(half-cell) is determined against a standard electrode:

The hydrogen electrode H+(aq, 1M) + 2e- H2 (g, 1 atm) E0H/ref = 0.00 V
Stronger oxidizing Stronger reducing
agent agent
Potential of a cell operating:
concentration effects
The evolution of the potential with concentration (non standard conditions) is given by
the Nernst equation:

0 RT 0 0.0591
Ecell E ln Q E log Q
nF n

R = 8.314 472(15) J K−1 mol−1, gas constant

T = 298 K, absolute temperature
F = 9.65  ×104 C mol−1, Faraday constant, the number of coulombs per mole of
electrons – the charge of 1 mole of electrons

products Cd 2
Q Cd(s) + 2Ag(aq)+ Cd(aq)2+ + 2Ag(s) Q 2
reactants Ag
 0 0.0591 product
Ecell E ln
n reactants

Changes in Ecell and Concentration

Stages in cell Q Relative [Products] and [Reactants]

operation

1. Ecell > E0 <1 [P] < [R] cell begins to operate

2. Ecell = E0 =1 [P] = [R] concentrations equal
3. Ecell < E0 >1 [P] > [R] cell still running
4. Ecell = 0 equilibrium [P] >> [R] no more free energy released
 Batteries
Voltage, Current, Power delivered
Batteries – Voltage delivered
A battery is a combination of galvanic cells arranged in series
- + - + - +
Ebat = 3Ecell

- +

VA – VB = Ebat = V
A B
V= R Ohm’s law
Ebat = R
R

- +
With the internal resistance: ri
ri
A B VA – VB = R = Ebat - ri

R
Batteries -Maximum discharge current
The electric current is the flow of electric charge per second

The unit of the electrical charge is the coulomb (C)

Current ( ) - unit is the ampere (A), 1A = 1C/1s

max for R = 0

VA – VB = R = Ebat - ri max = Ebat/ri

Battery 9 V, ri = 2 max = 4.5A

Car battery 12V, ri = 1/50 max = 600 A

Batteries – Power delivered
Amount of electrical energy transferred per unit of time / rate at which electricity
is consumed

P= V unit is the watt (W), 1W = 1V.1A = (J/C).(J.s) = J/s

V = R Ohm’s law gives P= 2R = V2/R

P (W) V (V) I (A) R ( )

Light bulb 100 240 0.4 600
Heater 2000 240 8 30
Body 100 IR radiation
Electrical blanket 50

P = IEbat = I2 (R + ri) R 0, max = Ebat/ri , P max = E2bat/ri = 2

max ri

Battery 9 V, ri = 2 max = 4.5A, P max = 40 W

Car battery 12V, ri = 1/50 max = 600 A, P max = 7 kW

Factors affecting batteries performances
 The thermodynamic says that the reaction will proceed if E0 > 0

However, it does not say how fast? What is the kinetic of the reaction?

The reaction rate is proportional to the current.

The current can vary bewteen 0 and max
Relationship between current and reaction rate
Electron flow in electronic conductors

The rate transfer

in any part of the cell
may become the limiting
Ion flow in electrolyte
rate.

Electron transfer at electrode/electrolyte interface

Maximize reaction rate

• Increase electrode surface area – porous electrode

• Reduce distance between electrodes – optimize cell geometry

• Use electrolyte of high ionic conductivity

• Use inert auxiliary materials

• Use materials having good electrical conductivity

Factors affecting current-voltage
Activation polarization
Activation + ‘Ohmic’ or ‘IR’ drop
concentration overvoltage
e-
Counter - ions
Oxidized
Reduced
Anode

Diffusion

Charge transfer/
crystallization
Concentration profile

Electrode-solution Bulk
interface
During discharge Ecell / dis E0 E pol E0 Iri

• ri includes the internal ohmic resistance, and polarization terms

• ri is not constant especially when the current-voltage curve has an S-shape

 Degree of voltage fall-off differs between cell types.

Higher polarization and/or increase in ohmic resistance cause higher voltage drop.
Discharge current and discharge power

Ecell / dis E0
The discharge current is: I dis
R R ri

0 2
2 E R
The discharge power is: P Ecell / dis I dis P 2
R ri

The maximum admissible discharge current, adm, and associated discharge

power, Padm, constitute important characteristics of the cell.

They will determine a critical value, Ecrit , of cell voltage

The maximum admissible discharge current, adm, and associated discharge
power, Padm, constitute important characteristics of the cell.

They will determine a critical value, Ecrit , of cell voltage

Limitations to current and voltage delivered

• Equilibrium voltage changes with electrolyte concentration

• With current flow there are resistive drops

• With current flow, there is an electrolyte concentration gradient near the electrode.
Hence, the lower concentration near the electrode, Nernst equation predicts
a lower voltage

• Physical resistance to movement of ions through electrolyte

•Additional surface chemistry issues: activation energies of electrodes surface –

energy needed for the adsorption of reactive species, release of electrons.

Cells designed for low discharge loads contain maximum quantities of active material

Cells designed for high-rate performance contain large surface electrodes to

minimize internal resistance and enhance current density
Effect of temperature
• If T is too low : kinetics are slow, discharge voltage is low

• If T is too high : side reaction/corrosion takes place thus reduce efficiency