Handout - 2 - Fuel Cell - CHE 231 - PPT

New Energy Technology
Fuel Cell Fundamentals
Presented By: Prof. Hiralal Pramanik
Department of Chemical Engineering & Technology,

Indian Institute of Technology
(Banaras Hindu University)
Varanasi -221005,
Prof. Hiralal Pramanik, IIT-BHU, U.P.,
Dept of India
Chemical Engg & Tech.
Types of Electrochemical Cell
• Electrolytic cell : External electricity is supplied to perform chemical/
electrochemical reaction
Examples: i. Water electrolysis gives H2 and O2
(ii) Electro winning, metal extraction, electroplating, chlor-alkali plant
ii. Charging of cell using external power is electrolytic mode
• Galvanic cell : Electrochemical reaction Gives electricity
Any cell when Gives Electricity
(i) Primary – Non rechargeable battery
(ii) Secondary –Rechargeable Battery
(iii) Fuel Cell is another class of Galvanic cell
Specialty: No charging is required, only fuel like hydrogen and oxidant oxygen are required
Advantages: 1. Efficiency
2. Simplicity
3. Silence
4. No emission or Low emission
Prof. Hiralal Pramanik, IIT-BHU, Dept of
INTRODUCTION TO FUEL CELL
Fuel cells are galvanic cells, in
which free energy of a reaction is
converted into electrical energy .
ΔG = - nFE0.
The overall performance of a

PEMFC is governed by four
parameters:
1.Catalytic activity for the reaction of

interest.
2. Electronic conductivity for transport
of electrons.
3. Ionic conductivity for the transport of
H+ .
4. Porosity allowing for diffusion of
reactants (hydrogen) and oxidant
oxygen.
Electrical Power and Polarization in Fuel cells
E  Ec  Ea  ( E  )  (E  )
cell Cathode Cathode Anode Anode
Where, and  are the losses in fuel cell
Cathode Anode
Note : Loss reduction is the primary aim
Electrical Power /Power Density= Current Density X Cell

Voltage
Three Major Losses in Fuel Cell :
1st : Activation loss- Electrode kinetics
 2nd : Ohmic loss
 3rd Concentration or Mass transport loss
Losses Controlled by :
1. Design Parameters
2. Operating Parameters
Fuel cell catalysis and kinetics
Fuel Cell Reaction Kinetics…………
 Each electrochemical reaction event results

in the transfer of one or more electrons
which results in current from the fuel cell.
 Increasing the rate of the

electrochemical reaction is therefore
crucial to improve fuel cell performance:
-Catalysis (it is important to get electrical

energy from cell at low temperature )
-Electrode Design & Fabrication …. (for better Fig. Internal detail of an Electrode
reaction kinetics and mass transfer )

INTRODUCTION TO REACTION KINETICS
• Electrochemical processes are
heterogeneous.
• Electrochemical reactions, like
the HOR (Hydrogen Oxidation
Reaction) and ORR(Oxygen
Reduction Reaction) take
place at the interface between
an electrode and an
electrolyte.
• Anode
Oxidation/Electrooxidation:
H2 2H+ + 2e-
• Cathode Reduction: Fig. MEA Detail of a PEMFC

½ O2+ 2H+ + 2e- H2O

INTRODUCTION TO REACTION KINETICS
Current expressed the rate of charge transfer
= The rate of the electrochemical reaction (mol/s)
Charge is the total amount of electricity produced:
Because electrochemical reactions only occur at interfaces, the current produced is

usually directly proportional to the area at the interface.
Therefore, current density (current per unit area) is more fundamental than current
The rate of the electrochemical reaction per unit area:

ACTIVATION ENERGY
Take an example of Simple H2 Combustion process……
• For reactants to be converted into products, they must first make it over the
activation energy barrier or Energy hill.
• The probability that reactant species can make over this barrier determines
the rate at which the reaction occurs.
Fig: Free Energy Profile

ACTIVATION ENERGY
Consider an electrochemical
Reaction of a Fuel Cell anode……
• The following Reaction takes place
at fuel cell anode :
Steps involved in the entire process :

(1) Mass transport of H2 gas to the
electrode:
(2) Adsorption of H2 onto the electrode

surface:
(3) Separation of the H2 molecule into

two individually bound (chemisorbed)
hydrogen atoms on the electrode
surface: Chemical Engg & Tech.
ACTIVATION ENERGY
(4) Transfer of electrons from the chemisorbed hydrogen atoms to the electrode,
releasing H+ ions into the electrolyte
(5) & (6) Desorption and mass transport of H+ ions away from the electrode:
The overall reaction rate will be limited by the slowest step in the series.
Suppose that the overall reaction is limited by the electron transfer step between
chemisorbed hydrogen and the metal electrode surface (STEP-4).
The slowest step can be represented as:

ACTIVATION ENERGY
Free Energy and Reaction State for the

above reaction……
• Curve 1: free energy of the reactant state
as a function of the distance separation
between the H atom and the metal surface.
• Curve 2: free energy of the product state as

a function of the distance the H+ ion and the
metal surface.
• Dark line: the minimum energy path for the

conversion of [M…H] to [(M + e-) + H+]
a = the activated state
Only species in the activated state can
undergo the transition from reactant to
product.
. Prof. Hiralal Pramanik, IIT-BHU, Dept of

ACTIVATION ENERGY
• The probability of finding species in the activated state is exponentially
dependent on the size of the activation barrier
• The reaction rate in the forward direction (reactants products)
cR * = the reactant surface concentration (mol/cm2)

f1 = the decay rate to products
Net Rate of Reaction:

The net rate is given by the difference in rates between the forward and
reverse reactions.
Forward reaction:
Reverse reaction:
ACTIVATION ENERGY
• The net reaction rate ν is defined as:
Net Reaction Rate in the form of ∆G1*:
The net rate of a reaction is given by the difference in rates between the
forward and reverse reactions, both of which are exponentially dependent
on an activation barrier, ∆G1*.

EXCHANGE CURRENT DENSITY
• Current density for forward and backward reaction can be derived as
following:
As we know, ν1=j1/nF and
Therefore…
At thermodynamic equilibrium, the forward and reverse current density must

balance, there is no net current density (j=0).
j0 = exchange current density

Although at equilibrium the net reaction is zero, both
forward and reverse reactions are taking place at a rate which is characterized
by j0. Prof. Hiralal Pramanik, IIT-BHU, Dept of
GALVANI POTENTIAL
• In general the reaction would not

be at equilibrium at the instant of
immersion of the electrode to
electrolyte.
• Before the build-up of the

interfacial potential (∆ᶲ), the
forward rate was much faster than
the reverse rate.
• The build-up of an interfacial

potential equalises the situation by
increasing the forward activation
barrier from ∆G1* to ∆G* while
decreasing the reverse reaction
barrier from ∆G2 *to ∆G*.

BUTLER VOLMER EQUATION
• The forward activation barrier is decreased by αnFη while the reverse activation
barrier is increased by (1-α)nFη.
• The value of α depends on the symmetry of the activation barrier called the charge
transfer coefficient.
• It represent the fraction of the polarization which aids the current in the direction
considered.
α value must be in the range of 0 to 1.

For most electrochemical reactions, α ranges from about 0.2 to 0.5.
Butler-Volmer Equation:
j1=f(∆G1*) and jo=f(∆G*)
j= Net current Density ηact =f(j) is called Tafel Equation

HOW TO IMPROVE KINETIC PERFORMANCE
• Having a high j0 is absolutely significant to good fuel cell performance.

There are several ways to increase j0.
• We have four ways to increase j0:
(i) Increase the reactant concentration CR*
(i) Decrease the activation barrier ∆G1*
(iii) Increase the temperature T
(iv)Increase the number of possible reaction sites (increase the reaction

interface roughness)

INCREASE THE REACTANT CONCENTRATION:
The kinetic benefit is significant, with a linear impact.
-most fuel cells use air instead of pure oxygen at the cathode
-reactant concentrations tend to decrease at fuel cell electrodes during high-

current-density operation (mass transport) : further kinetic penalties

• DECREASE ACTIVATION BARRIER:

-Highly catalytic electrode dramatically
increases j0.
-A catalytic electrode allow reactions to
proceed by a pathway involving a lower-
energy transition state or lower activation
barrier. The free energy curves depend on
the nature of the electrode metal.
Fig. Free energy profile for catalysed and uncatalyed
• For the case of the hydrogen charge reaction **
transfer:
-If the [M…H] bond is too weak, it is difficult
for hydrogen to bond to electrode surface
and to transfer charge from the hydrogen to
the electrode;
-If the [M…H] bond is too strong, the
hydrogen bonds too well to the electrode
surface and it is difficult to liberate H+.
** Prof. Hiralal Pramanik, IIT-BHU, Dept of
-The optimal compromise between bonding and reactivity occurs for
intermediate-strength [M…H] bonds: Pt, Pd, Ir and Rh.
Reactant

CATALYST-ELECTRODE DESIGN

• INCREASE TEMPERATURE:
-Like changing the activation barrier, changing temperature has an exponential effect on jo.
-As the temperature of the system increases, the number of molecules that carry enough energy to
react when they collide also increases. The rate of reaction therefore increases with temperature.
• INCREASE REACTION SITES:

-This can be achieved by increasing the roughness of the electrode.
• Increasing the number of available reaction sites per unit area
• If an electrode surface is extremely rough, the true electrode surface area can be orders of
magnitude larger than the geometric (smooth) electrode area and provides many more sites for
reaction.
Note: It is an assumption that reaction only takes place at the electrode surface. In real
case, reactions occur at every location of electrode wherever the catalysts are present.
• There are several techniques to prepare rough electrode. It is a part of electrode fabrication.
1. Rolling
2. Printing
3. Spraying
ELECTRODE DESIGN
• Electrode Design:
- Maximize reaction surface area,
highly porous, nano-structured
electrodes to achieve intimate contact
between gas phases pores, the
electrically conductive electrode, and
the ion-conductive
electrolyte.
• Reaction sites : triple phase zones

or triple phase boundaries (TPBs)
Reaction can only occur where the
three important phases :electrolyte,
gas, and electrically connected
catalyst regions are in contact.
Catalyst layer

Preparation of Anode , Cathode and Membrane Electrode
Assembly (MEA)
Pt-Ru/C electrode-catalysts + Pt-black electrode-catalysts +
Nafion ionomer + Activated carbon Nafion ionomer + Activated
powder + PTFE dispersion carbon+ PTFE dispersion
Mix by ultrasonic agitation Mix by ultrasonic agitation
Paint on carbon paper Paint on carbon paper
Dry carbon paper Dry carbon paper

with electrode with electrode
catalysts and sintered catalysts and sintered
at 300OC at 300OC
Cathode
Anode H2O
CO2 , H+, e-
C2H5OH , H2O
Prof.view
Sectional Hiralal Pramanik, IIT-BHU,
of MEA O2 , H+, Dept
e- of Photograph of MEA
Schematic of Direct Methanol/Ethanol Fuel Cell Setup
Serpentine flow field

Experimental Results Based on Some Important Parameters
Types of Catalysts and Reactant Concentration:
Theoretical OCV for Ethanol=1.145V (Standard)

Experimental OCV=0.815 V
Performance of Electrocatalyst:
Pt-Ru/C>Pt-Black HSA> Pt/C
Reference: Pramanik, H., Warrg, A.A., Basu, S., Journal of Applied Electrochemistry, “Studies Some Operating Parameters and cyclic
voltammetry for a direct ethanol fuel cell, 38(2008)1321-1328
Catalysts loading:
Temperature:
CONCLUSIONS
1. Fuel cell has potential to provide electrical energy in sustainable way
2. To improve the fuel cell performance in terms of voltage and current

needs the following: Active catalyst material with high surface area,
highly porous and electronic conducting GDL, ionic conducting
membrane.
3. Although, the production cost per kW of energy from fuel cell is very
high due to cost of catalysts and other cell components.
This can be reduced with the development of (i) catalyst alloying
noble metal with non noble metal based binary and ternary
catalyst, non-noble metal catalyst (ii) GDL (iii) current collector
and (iv) membrane development.


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New Energy Technology

Fuel Cell Fundamentals

Presented By: Prof. Hiralal Pramanik

Department of Chemical Engineering & Technology,

The overall performance of a

1.Catalytic activity for the reaction of

Electrical Power /Power Density= Current Density X Cell

Three Major Losses in Fuel Cell :

1st : Activation loss- Electrode kinetics

 2nd : Ohmic loss

 3rd Concentration or Mass transport loss

 Each electrochemical reaction event results

 Increasing the rate of the

-Catalysis (it is important to get electrical

Prof. Hiralal Pramanik, IIT-BHU, Dept of

• Cathode Reduction: Fig. MEA Detail of a PEMFC

Prof. Hiralal Pramanik, IIT-BHU, Dept of

= The rate of the electrochemical reaction (mol/s)

Charge is the total amount of electricity produced:

Because electrochemical reactions only occur at interfaces, the current produced is

The rate of the electrochemical reaction per unit area:

Prof. Hiralal Pramanik, IIT-BHU, Dept of

Fig: Free Energy Profile

Steps involved in the entire process :

(2) Adsorption of H2 onto the electrode

(3) Separation of the H2 molecule into

The slowest step can be represented as:

Prof. Hiralal Pramanik, IIT-BHU, Dept of

Free Energy and Reaction State for the

• Curve 2: free energy of the product state as

• Dark line: the minimum energy path for the

. Prof. Hiralal Pramanik, IIT-BHU, Dept of

• The reaction rate in the forward direction (reactants products)

cR * = the reactant surface concentration (mol/cm2)

Net Rate of Reaction:

Net Reaction Rate in the form of ∆G1*:

Prof. Hiralal Pramanik, IIT-BHU, Dept of

At thermodynamic equilibrium, the forward and reverse current density must

j0 = exchange current density

• In general the reaction would not

• Before the build-up of the

• The build-up of an interfacial

Prof. Hiralal Pramanik, IIT-BHU, Dept of

α value must be in the range of 0 to 1.

j= Net current Density ηact =f(j) is called Tafel Equation

• Having a high j0 is absolutely significant to good fuel cell performance.

• We have four ways to increase j0:

(i) Increase the reactant concentration CR*

(i) Decrease the activation barrier ∆G1*

(iii) Increase the temperature T

(iv)Increase the number of possible reaction sites (increase the reaction

Prof. Hiralal Pramanik, IIT-BHU, Dept of

INCREASE THE REACTANT CONCENTRATION:

The kinetic benefit is significant, with a linear impact.

-reactant concentrations tend to decrease at fuel cell electrodes during high-

Prof. Hiralal Pramanik, IIT-BHU, Dept of

• DECREASE ACTIVATION BARRIER:

Prof. Hiralal Pramanik, IIT-BHU, Dept of

Prof. Hiralal Pramanik, IIT-BHU, Dept of

• INCREASE REACTION SITES:

• Increasing the number of available reaction sites per unit area

• Reaction sites : triple phase zones

Prof. Hiralal Pramanik, IIT-BHU, Dept of