FUEL CELL REACTION KINETICS

M. OLIVIER
marjorie.olivier@fpms.ac.be

19/05/2008 19/05/2008

INTRODUCTION Each electrochemical reaction event results in the transfer of one or more electrons, the current produced by a fuel cell (number of electrons per time) depends on the rate of the electrochemical reaction (number of reactions per time). Increasing the rate of the electrochemical reaction is therefore crucial to improve fuel cell performance. - Catalysis; - Electrode design.

2 2

INTRODUCTION Electrochemical processes are heterogeneous. Electrochemical reactions, like the HOR:

H 2 2 H + + 2 e
take place at the interface between an electrode and an electrolyte.

3 3

INTRODUCTION Current expressed the rate of charge transfer

dQ dN i= = nF dt dt
dN dt

[A]

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

Charge is the total amount of electricity produced

t

i dt = Q = nFN
0

4 4

INTRODUCTION 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.

i j= A

[A cm ]
2

The rate of the electrochemical reaction per unit area:

v=

i j 1 dN = = A dt nF A nF

[mol s

cm 2

5 5

INTRODUCTION ACTIVATION ENERGY In order for reactants to be converted into products, they must first make it over the activation energy. The probability that reactant species can make over this barrier determines the rate at which the reaction occurs.

6 6

ACTIVATION ENERGY

H 2 2 H + + 2 e
1) Mass transport of H2 gas to the electrode:

(H

2 ( bulk )

H 2( near electrode) )

2) Adsorption of H2 onto the electrode surface:

(H

2 ( near electrode )

+ M M KH2 )

3) Separation of the H2 molecule into two individually bound (chemisorbed) hydrogen atoms on the electrode surface:

(M K H 2 + M 2 M K H )
7 7

ACTIVATION ENERGY

4) Transfer of electrons from the chemisorbed hydrogen atoms to the electrode, releasing H+ ions into the electrolyte

2 M K H M + e + H (+ near electrode )

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

+ 2 H (+ H near electrode ) (bulk electrolyte )

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. 8 8

ACTIVATION ENERGY

9 9

ACTIVATION ENERGY

The slowest step can be represented as:

M KH M + e + H

10 10

ACTIVATION ENERGY 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 [MH] to [(M + e-) + H+] a = the activated state

11 11

ACTIVATION ENERGY Only species in the activated state can undergo the transition from reactant to product. The probability of finding species in the activated state is exponentially dependent on the size of the activation barrier.

Pact = e
* R

* G1 RT

The reaction rate in the forward direction (reactants products)

v1 = c f1 e
f1 = the decay rate to products

* G1 ( RT )

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

12 12

ACTIVATION ENERGY NET RATE OF A REACTION The net rate is given by the difference in rates between the forward and reverse reactions. Forward reaction Reverse reaction

( ) M K H (M + e )+ H

M K H M + e + H +
+

The net reaction rate v is defined as:

v = v1 v2 v = c f1 e
* R
* G1 RT

c f2 e
* 1 * 2

* P

* G2 RT

Grxn = G G
13 13

ACTIVATION ENERGY NET RATE OF A REACTION

v = c f1 e

* R

* G1 RT

( c f2 e
* P

* G1 Grxn

) RT

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*.

14 14

ACTIVATION ENERGY EXCHANGE CURRENT DENSITY

j1 = n F c f1 e

* R

* G1 RT

( j2 = n F c f 2 e
* P

* G1 Grxn

) RT

At thermodynamic equilibrium, the forward and reverse current density must balance, there is no net current density (j=0).

j1 = j2 = j0
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. 15 15

ACTIVATION ENERGY GALVANI POTENTIAL Before the build-up of the interfacial potential (), 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*.

16 16

ACTIVATION ENERGY BUTLER-VOLMER EQUATION Electrochemical reactions = ability to manipulate the size of the activation barrier by varying the cell potential If the Galvani potential across a reaction interface is reduced, the free energy of the forward reaction will be favoured over the reverse reaction. While the chemical energy system is the same as before, changing the electrical potential (b) upsets the balance between the forward and reverse activation barriers. Reducing the Galvani potential by reduces the forward activation barrier (G1*<G*) and increases the reverse activation barrier (G2*>G*).

17 17

ACTIVATION ENERGY BUTLER-VOLMER EQUATION The forward activation barrier is decreased by nF while the reverse activation barrier is increased by (1-)nF. The value of depends on the symmetry of the activation barrier called the transfer coefficient. For most electrochemical reactions, ranges from about 0,2 to 0,5.

18 18

ACTIVATION ENERGY BUTLER-VOLMER EQUATION

j1 = j0 enF ( RT ) j2 = j0 e (1 )nF ( RT ) j = j0 enF ( RT ) e (1 )nF ( RT )

Butler-Volmer Equation
The current produced by an electrochemical reaction increases exponentially with activation overvoltage. 19 19

ACTIVATION ENERGY BUTLER-VOLMER EQUATION Activation overvoltage act = voltage which is sacrificed (lost) to overcome the activation barrier associated with electrochemical reaction The Butler-Volmer equation tells us that if you want more electricity (current) from our fuel cell, we must pay a price in terms of lost voltage.

20 20

ACTIVATION ENERGY BUTLER-VOLMER EQUATION

Having a high j0 is absolutely critical to good fuel cell performance. They are several ways to increase j0. 21 21

HOW TO IMPROVE KINETIC PERFORMANCE

j0 = n F c f1 e
We have four ways to increase j0:

* R

* G1 RT

- Increase the reactant concentration CR* - Decrease the activation barrier G1* - Increase the temperature T - Increase the number of possible reaction sites (increase the reaction interface roughness)

22 22

HOW TO IMPROVE KINETIC PERFORMANCE INCREASE REACTANT CONCENTRATION The thermodynamic benefit is minor, due to the logarithmic form of the Nernst Equation. In contrast, the kinetic benefit is significant, with a linear impact. Kinetic reactant concentration effects generally work against us for several reasons: -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

23 23

HOW TO IMPROVE KINETIC PERFORMANCE DECREASE ACTIVATION BARRIER Highly catalytic electrode dramatically increases j0. A catalytic electrode lowers the activation barrier. The freeenergy curves depend on the nature of the electrode metal. For the case of the hydrogen charge transfer: -If the [MH] 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 [MH] bond is too strong, the hydrogen bonds too well to the electrode surface and it is difficult to liberate H+. The optimal compromise between bonding and reactivity occurs for intermediate-strengh [MH] bonds: Pt, Pd, Ir and Rh. 24 24

HOW TO IMPROVE KINETIC PERFORMANCE DECREASE ACTIVATION BARRIER

Catalyst electrode Hydrogen Oxygen Platinum Platinum

Medium

j0 (A cm-2)

Acid Alkaline Acid

10-3 10-4 10-9

25 25

HOW TO IMPROVE KINETIC PERFORMANCE INCREASE TEMPERATURE Like changing the activation barrier, changing temperature has an exponential effect on j0.

26 26

HOW TO IMPROVE KINETIC PERFORMANCE INCREASE REACTION SITES 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.

A j0 = j ' A
' 0

j0

= the intrinsic exchange current density of a perfectly smooth electrode surface = an intrinsic property of an electrode for a specific electrochemical reaction

27 27

SIMPLIFIED ACTIVATION KINETICS POLARISATION RESISTANCE

j = j0 e
act<15mV

nF ( RT )

(1 )nF ( RT )

When act Is Very Small

j = j0

nF act RT

A Taylor series expansion of the exponential terms can be performed with powers higher than 1 neglected. The current and overvoltage are linearly related for small deviations from equilibrium and are independent of .

RT act = j = Rt j nFj0
Rt = Polarisation resistance 28 28

SIMPLIFIED ACTIVATION KINETICS TAFEL EQUATION When act Is Very Large act> 50-100 mV The second exponential term in the Butler-Volmer equation becomes negligible. On other words, the forward-reaction direction dominates, corresponding to a completely irreversible reaction process.

j = j0 e

nF act ( RT )

RT RT ln j0 + ln j act = nF nF act = a + b log j

29 29

SIMPLIFIED ACTIVATION KINETICS TAFEL EQUATION

30 30

DIFFERENT FUEL CELL REACTIONS PRODUCE DIFFERENT KINETICS

The HOR kinetics are extremely fast, while the ORR kinetics are extremely slow. Completion of the ORR requires many individual steps and significant molecular reorganization. 31 31

DIFFERENT FUEL CELL REACTIONS PRODUCE DIFFERENT KINETICS

32 32

DIFFERENT FUEL CELL REACTIONS PRODUCE DIFFERENT KINETICS HOR

33 33

DIFFERENT FUEL CELL REACTIONS PRODUCE DIFFERENT KINETICS ORR

34 34

CATALYST-ELECTRODE DESIGN - Maximize reaction surface area, area highly porous, nanostructured electrodes to achieve intimate contact between gas phases pores, the electrically conductive electrode, and the ionconductive 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.

35 35

CATALYST-ELECTRODE DESIGN - Optimal catalyst material: - High mechanical strength - High electrical conductivity - Low corrosion - High porosity - Ease of manufacturability - High catalytic activity (high j0) For PEMFC: platinum is currently the best known catalyst For higher temperature fuel cells, nickel- or ceramic-based catalysts are often used.

36 36

CATALYST-ELECTRODE DESIGN

Gas diffusion layer

37 37