Professional Documents
Culture Documents
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
i
dQ i nF
dN
idt Q nFN
dt dt 0
1
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
dN
i nF (2)(96400C / mol )(2.05 104 mol / min)(1 min/ 60s) 0.657 A
dt
3
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
2
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
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.
3
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
4
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
2 M H ( M e ) H near
electrode
a: activation state
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Pact e G1 /( RT )
†
10
5
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
v v1 v2
forward - reverse
v c*R f1e G1 /( RT ) cP* f 2 e G2 /( RT )
Grxn G1 G2
v cR* f1eG1 /( RT ) cP* f 2 e ( G1 Grxn ) /( RT )
12
6
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
j nFv
j1 nFcR f1e G1 /( 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.
13
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
G1†increase to G ,
†
G2†
decrease to G
†
j1 nFc*R f1eG
†
/( RT )
Grxn nF ) /( RT )
j2 nFcP* f 2e ( G
14
7
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
E 0 anode cathode
15
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
8
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
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.
17
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
9
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
19
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
j2 j0 e1 nF / RT
( 0.5 nF ) / RT act
RT
ln10
8.314 298.15 ln10 0.059 V
j0e nF 0.5 2 96, 400
20
10
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
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.
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
22
11
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
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.
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
12
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
25
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
26
13
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
14
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
RT RT
act ln j0 ln j
nF nF
29
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
15
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
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
31
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
32
16
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Requirements:
• High mechanical strength
• High electrical conductivity
• Low corrosion
• High porosity
• Ease of manufacturability
• High catalytic activity (high j0)
34
17
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Thin layer is preferred for better gas diffusion and catalyst utilization.
Thick layer incorporates higher catalyst loading and presents more TPBs.
The GDL protects the often delicate catalyst structure, provides mechanical
strength, allows easy gas access to the catalyst, and enhances electrical
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.
35
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
Finding optimal catalysts by trial and error is too time consuming and
expensive.
They also show the promise that next-generation quantum tools might
provide in exploring alternative catalyst materials and nanostructured
surfaces.
36
18
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
37
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
38
19
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
39
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).
40
20
5/10/2011
Chapter 3: Fuel Cell Reaction Kinetic Copyright © 2007 by Dr. Biao Zhou
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
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
42
21
5/10/2011
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.
44
22