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Engg1000
Chem.Eng.: Batteries for electric cars
Books
On batteries
Handbook of batteries
Electricity is produced
by chemical reactions:
Electrochemical reactions
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
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
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.
•Why a galvanic cell works? Why electrons flow in the direction shown?
This difference is the cell potential (Ecell) also called the voltage or the
electromotive force (emf)
• The more positive Ecell is the more work the cell can do
The unit for Ecell , the electrical potential, is the volt (V)
The unit for Ecell , the electrical potential, is the volt (V)
1V = 1 J/C
E0 = 1.10 V
Standard Half-Cell potential
To predict cell potential, standard half-cell potential are introduced
By inversing the zinc half reaction, the overall cell potential (E0 cell) is the sum
of the two half-cell potential
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
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
- +
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
max for R = 0
However, it does not say how fast? What is the kinetic of the reaction?
Diffusion
Charge transfer/
crystallization
Concentration profile
Electrode-solution Bulk
interface
During discharge Ecell / dis E0 E pol E0 Iri
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
• 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
Cells designed for low discharge loads contain maximum quantities of active material