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# 5/10/2011

Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## Chapter 3: Fuel Cell Reaction Kinetic

3.1 Introduction to electrode kinetics
3.2 Why charge transfer reactions have an activation energy
3.3 Activation energy determines reaction rate
3.4 Calculating net rate of a reaction
3.5 Rate of reaction at equilibrium: exchange current density
3.6 Potential of a reaction at equilibrium: Galvani potential
3.7 Potential and rate: Butler-Volmer equation
3.8 Exchange currents and eletrocatalysis: how to improve kinetic
performance
3.9 Simplified activation kinetics: Tafel equation
3.10 Different fuel cell reactions produce different kinetics
3.11 Catalyst-electrode design
3.12 Quantum mechanics: Framework for understanding catalysis
in fuel cells
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.1 Introduction to electrode kinetics

3.1.1 Electrochemical reactions are different from chemical
reactions
All electrochemical reactions involve the transfer of charge
(electrons) between an electrode and a chemical species. This
distinguishes electrochemical reactions from chemical reactions. In
chemical reactions, charge transfer occurs directly between two
chemical species without the liberation of free electrons.
3.1.2 The electrochemical reactions are heterogeneous
Only occur at the interface between and electrode and an
electrolyte. H 2  2 H   2e 
3.1.3 Current is a rate, 3.1.4 Charge is an amount
The unit of current is the ampere; an ampere is a coulomb (charge)
per second (C/s)
t

i
dQ i  nF
dN
 idt  Q  nFN
dt dt 0

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.1 Introduction to electrode kinetics

Example 3.1. Assuming 100% fuel utilization, how much current
can a fuel cell produce if provisioned with 5 sccm H2 gas at STP?
(1 sccm = 1 standard cubic centimeter per minute.) Assume
sufficient oxidant is also supplied.

## Solution: In this problem, we are provided with a volumetric flow

rate of H2 gas. To get current, we need to convert volumetric flow
rate into molar flow rate and then convert molar flow rate into
current. Treating H2 as an ideal gas, the molar flow rate is related to
the volumetric flow rate via the ideal gas law:
dN P  dV / dt  dN (1atm)(0.005L / min)
   2.05 104 molH 2 / min
dt RT dt  0.082 L.atm /( mol.K  (298.15K )

dN
i  nF  (2)(96400C / mol )(2.05 104 mol / min)(1 min/ 60s)  0.657 A
dt
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.1 Introduction to electrode kinetics

Example 3.2. A fuel cell operates for 1 h at 2 A current load and
then operates for 2 more h at 5 A current load. Calculate the total
number of moles of H2 consumed by the fuel cell over the course
of this operation. To what mass of H2 does this correspond?
Assume 100% fuel utilization.

## Solution: From the time-current profile that we are given, we can

calculate the total amount of electricity produced by this fuel cell
(as measured by the accumulated charge). Then, we can calculate
the total number of moles of H2 processed by the reaction.
Qtot  i1t1  i2t2  (2 A)(3600s )  (5 A)(7200s )  43, 200C
Qtot 43, 200C
N H2    0.224molH 2
nF (2)(96, 400C / mol )
Since the molar mass of H2 is approximately 2 g/mol, this
corresponds to about 0.448 g of H2.
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.1 Introduction to electrode kinetics

3.1.5 Current density (current per unit area) is more
fundamental than current
It allows the reactivity of different surfaces to be compared on a
per-unit area basis. Current density j is usually expressed in units
of amperes per square centimeter (A/cm2):
i
j
A
where A is the area. In a similar fashion to current density,
electrochemical reaction rates can also be expressed on a per unit-
area basis. We give per unit-area reaction rates the symbol v:
1 dN i j
v  
A dt nFA nF

Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.1 Introduction to electrode kinetics

3.1.6 Potential controls electron energy
Potential (voltage) is a measure of electron energy. The electron
energy in a metal is measured by the Fermi level. By controlling
the electrode potential, we control the electron energy in an
electrochemical system (Fermi level), thereby influencing the
direction of a reaction.

Electrode potential can be manipulated to trigger reduction (left) or oxidation (right). The
thermodynamic equilibrium electrode potential (middle) corresponds to the situation where the
oxidation and reduction processes are balanced.

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.1 Introduction to electrode kinetics

3.1.7 Reaction rates are finite
Even if a reaction is energetically favorable, because an
energy barrier (called an activation energy) impedes the
conversion of reactants into products.

Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## Basic steps for H 2  2 H   2 e

1. Mass transport of H2 gas to the electrode:
( H 2( bulk )  H 2( near electrode ) )
2. Absorption of H2 onto the electrode surface:
( H 2( near electrode ) )  M  MH 2 )
3. Separation of the H2 molecule into two individually bound
(chemisorbed) hydrogen atoms on the electrode surface:
M  H 2  M  2 M  H
4. Transfer of electrons from the chemisorbed hydrogen atoms to
the electrode, releasing H+ ions into the electrolyte:
2   M  H  ( M  e  )  H near

electrode 

## 5. Mass transport of the H+ ions away from the electrode:

2   H near
 

electrode  H bulk electrolyte 

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.2 Why charge transfer reactions have an activation energy

2   M  H  ( M  e  )  H near

electrode 

a: activation state

Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.3 Activation energy determines reaction rate

Pact is the probability of finding a reactant species in the
activated state, G1† is the size of the energy barrier between
the reactant and activated states, R is the gas constant, and T is
the temperature (K).

Pact  e G1 /( RT )

## v1 is the reaction rate in the forward direction (reactants 

products), c*R is the reactant surface concentration (mol/cm2),
and f1 is the decay rate to products.

## v1  cR  f1  Pact  cR f1e G1 /( RT )

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.3 Activation energy determines reaction rate

The decay rate f1 to products is given by the lifetime of the
activated species and the likelihood that it will convert to a
product instead of back to a reactant. (A species in the
activated state can "fall" either way.)
Pa  p
f1 
a
Pa  p is the probability that the activated state will decay to the
product state and  a is the lifetime of the activated state. Both
decay rates to products (f1) and decay rates to reactants (f2) can
be computed.

1

## k is Boltzmann's constant and h is Planck's constant

kT kT G1† /( RT )
f1  f 2  v1  cR e
h h
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.4 Calculating net rate of a reaction

Forward reaction: M  H  ( M  e )  H 
Reverse reaction: M  H  ( M  e  )  H 

v  v1  v2
 

forward - reverse
 v  c*R f1e G1 /( RT )  cP* f 2 e G2 /( RT )
   
Grxn G1 G2
  v  cR* f1eG1 /( RT )  cP* f 2 e  ( G1 Grxn ) /( RT )

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.5 Rate of reaction at equilibrium: exchange current density

j  nFv
j1  nFcR f1e G1 /( RT )

## j2  nFcP f 2e  ( G1 Grxn /( RT )

j1  j2  j0
j0 is the exchange current density for the reaction. Although at
equilibrium the net reaction rate is zero, both forward and
reverse reactions are taking place at a rate which is
characterized by j0 - this is called dynamic equilibrium.

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

chemical energy.

##  across the reaction interface

exactly counterbalances the
chemical free energy difference
between the reactant and product
states.

G1†increase to G ,

G2†
decrease to G

j1  nFc*R f1eG

/( RT )

 Grxn  nF ) /( RT )
j2  nFcP* f 2e  ( G
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## The anode anode and cathode cathode interfacial potentials are

called Galvani potentials, the exact magnitude of these Galvani
potentials are as-yet unknowable.

E 0  anode  cathode

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.7 Potential and rate: Butler-Volmer Equation

Decreasing the Galvani potential by  reduces
the forward activation barrier and increases
the reverse activation barrier.
G1  G G2  G
The forward activation barrier is decreased by
nF while the reverse activation barrier is
increased by (1-)nF.

##  depends on the symmetry of the activation

barrier. Called the transfer coefficient, 
expresses how the change in the electrical
potential across the reaction interface changes
the sizes of the forward versus reverse
activation barrier.  is always between 0 and
1. For "symmetric" reactions,  = 0.5. For
most electrochemical reactions,  ranges from
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## At equilibrium, the current densities for the forward and reverse

reactions are both given by j0. Away from equilibrium, we can write
the new forward and reverse current densities by starting from j0
and taking into account the changes in the forward and reverse
activation barriers:
j1  j0e
 nF  /  RT  1  nF /  RT 
j0  nFc*R f1e G , j2  j0e

/( RT )

Grxn  nF  ) /( RT )
 nFc*P f 2 e  ( G
j  j0 e     j0e
j  j1  j2  nF / RT 1  nF /  RT 

The local concentration also effects the current density:

 c* c* 
j  j00  0*R e nF  /  RT   0*P e 1 nF /  RT  
 cR cP 
The equations are called Bulter-Volmer equations.
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## The Butler-Volmer equation basically states that the current

produced by an electrochemical reaction increases exponentially
with activation overvoltage.

## Activation overvoltage is the label given to , recognizing that 

represents voltage which is sacrificed (lost) to overcome the
activation barrier associated with the electrochemical reaction.

## Butler-Volmer equation tells us that if we want more electricity

(current) from our fuel cell, we must pay a price in terms of lost
voltage.

## act represents the activation loss appearing in the Butler-Volmer

equation, the activation overvoltage.
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.7 Potential and rate: Butler-Volmer Equation

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## Example 3.3. If a fuel cell reaction exhibits  = 0.5 and n = 2 at

room temperature, what activation overvoltage is required to
increase the forward current density by one order of magnitude and
decrease the reverse current density by one order of magnitude?

## Solution: Since  = 0.5, the reaction is symmetric. We can look at

either the forward or reverse term in the Butler-Volmer equation to
calculate the overvoltage necessary to cause an order-of-magnitude
change in current density. Using the forward term
j1  j0 e
 nF  /  RT 
10 j1 j0e act 2   
 nF / RT
 10  e nF   /  RT 
 j0e(0.5 nF ) /  RT  j1 j0e act1   
 nF / RT

j2  j0 e1 nF /  RT 
( 0.5 nF ) /  RT   act 
RT
ln10 
 8.314  298.15 ln10  0.059 V
 j0e  nF  0.5 2  96, 400 
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## For simple electrochemical systems, variations between reactions

can be treated in terms of variations in kinetic parameters such as 
and j0 using the Butler-Volmer equation.

The magnitude of the activation loss (in other words, the size of
act) depends on the reaction kinetic parameters. The loss especially
depends on the size of j0.

##  cR*  nF  /  RT  cP* 1 nF /  RT  

j  j00  0* e  0* e 
 cR cP 
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.8 Exchange currents and electrocatalysis: how to

improve kinetic performance
Improving kinetic performance from increasing j0.

## F, n , R are constants, f1 is not easy to be significantly improved.

*
1. Increase the reactant concentration cR
2. Decrease the activation barrier G1

## 3. Increase the temperature T.

4. Increase the number of possible reaction sites (i.e., increase the
reaction interface roughness).

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.8 Exchange currents and electrocatalysis: how to

improve kinetic performance
3.8.1 Increase the reactant concentration

## The kinetic benefit to increasing reactant concentration is

significant (comparing to the reversible voltage), with a linear
rather than logarithmic impact.
j0  nFcR f1e G1 /( RT )

Problems:
1. Most fuel cells use air instead of pure oxygen at the cathode.
This leads to an approximate 5 x reduction in the oxygen kinetics
compared to pure oxygen operation.

## 2. Will be discussed in Chapter 5, reactant concentrations tend to

decrease at fuel cell electrodes during high-current-density
operation (due to mass transport limitations).
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.8 Exchange currents and electrocatalysis: how to

improve kinetic performance
3.8.2 Decrease the activation barrier

## A catalytic electrode is one which

significantly lowers the activation barrier
for the reaction (exponential effect).

## Not too strong, not too weak,

intermediate-strength bond (Pt, Pd)

## is also affected by the choice of catalyst.

 is based on the symmetry of the free-
energy curve in the vicinity of the
activated state.
j0  nFcR f1e G1 /( RT )

##  changes only slightly with choice of

 cR*  nF  /  RT  cP* 1 nF /  RT  
catalyst, so it is often overlooked j  j00  0* e  0* e 
compared to other catalytic effects.  cR cP 
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.8 Exchange currents and electrocatalysis: how to

improve kinetic performance
3.8.3 Increase the temperature

## The higher level of thermal activity (at higher temperature)

increases the likelihood that a given reactant will possess sufficient
energy to reach the activated state.

## At high overvoltage levels, increasing the temperature can actually

decrease' the current density (explained in 3.9)

## j0  nFcR f1e G1 /( RT )

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.8 Exchange currents and electrocatalysis: how to

improve kinetic performance
3.8.4 Increase the number of possible reaction sites (i.e.,
increase the reaction interface roughness).

## Current densities are generally based on the plane, or projected

geometric area of an electrode. If an electrode surface is extremely
rough, the true electrode surface area can be orders of magnitude
larger than the geometric electrode area.
A'
j0  j '0
A
A platinum catalyst electrode with an effective surface area is 1000
times greater than smooth platinum.

## j0  nFcR f1e G1 /( RT )

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## When dealing with fuel cell reaction kinetics, the Butler-Volmer

equation often proves unnecessarily complicated.

## When act is very Small (less than about 15 mV at room

temperature), a Taylor series expansion of the exponential terms
can be performed with powers higher than 1 neglected (ex  1 + x
for small x).
nFact
j  j0
j  j0 e
 nF  /  RT  1  nF /  RT 
 j0e RT
j0 values can therefore be obtained from measurements of j versus
act at low values of act (i.e., low current densities).

## But due to impurity currents, ohmic losses, mass transport effects,

j0 values are usually extracted from high overvoltage measurements
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## When act is large (greater than 50-100 mV at room temperature),

the second exponential term in the Butler-Volmer equation becomes
negligible. In other words, the forward-reaction direction
dominates, corresponding to a completely irreversible reaction
process.
j  j0 e     j0e    
 nF / RT  1 nF / RT j  j0enF act /( RT )
RT RT
 act   ln j0  ln j  act  a  b log j
 nF  nF
It is known as the Tafel equation, and b is called the Tafel slope.
Tafel equation even predates the Butler-Volmer equation.

## Large amounts of net current are more interested in fuel cell

operations. Therefore, the second simplification of the Butler-
Volmer equation (the Tafel equation) proves more useful in most
discussions.
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.9 Simplified activation kinetics: Tafel equation

RT RT
 act   ln j0  ln j
 nF  nF

## Example 3.4. Calculate j0 and  for the hypothetical reaction in the

figure. Assume the kinetic response depicted in the figure is for an
electrochemical reaction at room temperature with n = 2.
j0  e 10  4.54  105 A/cm 2

RT

 8.314  298.15  0.257
0.25  0.10 slope  nF  0.05  2  96, 400 
slope   0.05
5  (8)

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## More on temperature effects

At high overvoltage levels, increasing the temperature can actually
decrease the current density.
  G1† /( RT )
j  j0 e nFact /( RT ) 
j0  nFcR f1e
j  Ae G1 /( RT ) e nFact /( RT )  Ae ( G1  nFact ) /( RT )
† †

## When  nF act  G1† , j increases with temperature increases

When  nF act  G1† , j decreases with temperature increases

## When activation overvoltage levels greater than G1† /  nF , increasing

the temperature is no longer helpful.

## This effect is seldom seen experimentally. Other positive effects of

increasing the temperature (such as improvements in ion
conductivity and mass transport) usually outweigh this reaction
kinetics effect.
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## 3.10 Different fuel cell reactions produce different kinetics

The more sluggish the reaction is, the less kinetic parameters (α, j0),
depends on the complication of the reactions.
2H2  4H   4e O2  4e  4H   2H2O

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## The results showed why the hydrogen is much better than

hydrocarbons --- fast reaction, no carbon.

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## However reactions are not only depending on fuels, also depending

on types of electrolyte used.

## The differences in reaction chemistry and temperature for these fuel

cell types means that different catalysts are used. For low-
temperature acidic fuel cells (PEMFCs and PAFCs) a Pt-based
catalyst is used. For AFCs, nickel-based catalysts are used. For
SOFCs, nickel-based or ceramic-based catalysts are used.
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.11 Catalyst-electrode design

triple phase zones or triple phase boundaries (TPBs)

Requirements:
• High mechanical strength
• High electrical conductivity
• Low corrosion
• High porosity
• Ease of manufacturability
• High catalytic activity (high j0)

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## 3.11 Catalyst-electrode design

Thickness of most fuel cell catalyst layers is between ~ 10 and 50 m.

Thin layer is preferred for better gas diffusion and catalyst utilization.

## Usually, the catalyst layer is reinforced by a thicker porous electrode support

layer. In a PEMFC, this electrode support layer is called the gas diffusion layer
(GDL).

The GDL protects the often delicate catalyst structure, provides mechanical
conductivity.

Thickness from 100 to 400 m. a thinner electrode support generally provides
better gas access but may also present increased electrical resistance or decreased
mechanical strength. Details in Chapter 8.
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.12 Quantum mechanics: framework for understanding

catalysis in fuel cells
Catalyst in a fuel cell is crucial for designing next-generation fuel cell
systems.

## PEMFC today rely on the availability of platinum or platinum alloys as

catalytic materials, but platinum is scarce and expensive.

Finding optimal catalysts by trial and error is too time consuming and
expensive.

## Quantum-mechanics-based simulation tools became available, they

provide good qualitative insight into how a catalyst works.

They also show the promise that next-generation quantum tools might
provide in exploring alternative catalyst materials and nanostructured
surfaces.
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## 3.12 Quantum mechanics: framework for understanding

catalysis in fuel cells

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

## 3.12 Quantum mechanics: framework for understanding

catalysis in fuel cells

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## 3.12 Quantum mechanics: framework for understanding

catalysis in fuel cells

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

Summary
• Electrochemical reactions involve the transfer of electrons and
occur at surfaces.
• Because electrochemical reactions involve electron transfer, the
current generated is a measure of the reaction rate.
• Because electrochemical reactions occur at surfaces, the rate
(current) is proportional to the reaction surface area.
• Current density is more fundamental than current. We use current
density (current per unit area) to normalize the effects of system
size.
• An activation barrier impedes the conversion of reactants to
products (and vice versa).

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Summary
• A portion of the fuel cell voltage is sacrificed to lower the
activation barrier, thus increasing the rate at which reactants are
converted into products and the current density generated by the
reaction.
• The sacrificed (lost) voltage is known as activation overvoltage
act.
• The relationship between the current density output and the
activation overvoltage is exponential. It is described by the Butler-
Volmer equation j  j0  e nF /( RT )   j0  e  (1 ) nF /( RT ) 
act act

## • The exchange current density j0 measures the equilibrium rate at

which reactant and product species are exchanged in the absence of
an activation overvoltage. A high j0 indicates a facile reaction, while
a low j0 indicates a sluggish reaction.
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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

Summary
• Activation overvoltage losses are minimized by maximizing j0.
There are four major ways to increase: (1) increase reactant
concentration, (2) increase reaction temperature, (3) decrease the
activation barrier (by employing a catalyst), and (4) increase the
number of reaction sites (by fabricating high-surface-area
electrodes and 3D structured reaction interfaces).
• Fuel cells are usually operated at relatively high current densities
(high activation overvoltages). At high activation overvoltage, fuel
cell kinetics can be approximated by a simplified version of the
Butler-Volmer equation, j  j0  e nF /( RT ) . In a generalized
act

## logarithmic form, this is known as the Tafel equation act  a  b log j

,where b is the Tafel slope.

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Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

Summary
• For a H2-O2 fuel cell, the hydrogen (anode) kinetics are generally
facile and produce only a small activation loss. In contrast, the
oxygen kinetics are sluggish and lead to significant activation loss
(at low temperature).
• The details of fuel cell reaction kinetics are dependent on the
fuel, electrolyte chemistry, and operation temperature. For low-T
fuel cells, Pt is commonly used as a catalyst. High-T fuel cells
employ nickel- or ceramic-based catalysts.
• The main requirements for an effective fuel cell catalyst are (1)
activity, (2) conductivity, and (3) stability (specifically thermal,
mechanical, and chemical stability in the fuel cell environment).

43

Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou

Summary
• To increase j0, fuel cell catalyst-electrodes are designed to
maximize the number of reaction sites per unit area. Increasing the
number of reaction sites means maximizing triple-phase boundary
regions, where the electrolyte, reactant, and catalytically active
electrode phases meet. The best catalyst-electrodes are carefully
optimized, porous high-surface area structures.

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