Losses in Fuel Cells

Fuel Cell Reaction Kinetics

 Electrode Kinetic

Current = Charge/Time
dQ nFdN
i= =
dt dt
t
⇔ ∫ idt = Q = nFN
0i
j = [ A / cm 2 ] Heterogeneous
H t process
A
H2 ⇔ 2H++2e-

H2 + M → M ⋅⋅⋅ H2
M ⋅ ⋅ ⋅ H 2 + M → 2( M ⋅ ⋅ ⋅ H )
M ⋅ ⋅ ⋅ H → M + e− + H +
 Electrode Kinetic

⎛ −Δ
ΔG
G1 ⎞
⎜ ⎟
Probability of P = Ke ⎝ RT ⎠
act
activation
⎛ − ΔG1 ⎞
⎜ ⎟
F
Forwardd
v = KcR f1 Pact = KcR f1e
* * ⎝ RT ⎠
reaction rate 1
⎛ − ΔG2 ⎞
Backward ⎜ ⎟
reaction rate v2 = KcP f 2 Pact = KcP f 2 e
* * ⎝ RT ⎠

⎛ − ΔG1 ⎞ ⎛ − ΔG2 ⎞
⎜ ⎟ ⎜ ⎟
v = v1 − v2 = KcR* f1e ⎝ RT ⎠
− KcP* f 2 e ⎝ RT ⎠

Rate of reaction ⎛ − ΔG1 ⎞ ⎛ − ΔG1 − ΔGrxn ⎞

⎜ ⎟ ⎜ ⎟
= KcR* f1e ⎝ RT ⎠
− KcP* f 2 e ⎝ RT ⎠
 Equilibrium Potential: Galvani Potential
Conversion to current density
⎛ − ΔG1 ⎞ ⎛ − ΔG1 − ΔGrxn ⎞
⎜ ⎟ ⎜ ⎟
j = nFv = nFc f e *
R 1
⎝ RT ⎠
− nFc f 2 e*
P
⎝ RT ⎠

= j1 − j2

At equilibrium
j = j1 − j2 = 0
j1 = j2 = j0 :E
:Exchange
h C
Currentt D
Density
it
⎛ − ΔG1 ⎞ ⎛ − ΔG + + ⎞
⎜ +αnFΔφ ⎟ ⎜ ⎟
⎜ RT ⎟
j1 = nFcR* f1e ⎝ RT ⎠
= nFcR* fe ⎝ ⎠

⎛ − ΔG1 − ΔGrxn ⎞ ⎛ − ΔG + + ⎞
⎜ + nFΔφ ⎟ ⎜ ⎟
⎜ RT ⎟
j2 = nFcP* f 2 e ⎝ RT ⎠
= nFcP* fe ⎝ ⎠
Bultler-Volmer Equation: Non-Equilibrium

⎛ αnFη ⎞
⎜ ⎟
j1 = j0 e ⎝ RT ⎠

⎛ (1−α ) nFη ⎞
−⎜ ⎟
j 2 = j0 e ⎝ RT ⎠

⎛ ⎛⎜ αRT
nFη ⎞
⎟ ⎟⎞
⎛ (1−α ) nFη ⎞
−⎜
j = j0 ⎜ e ⎝ ⎠
−e ⎝ RT ⎠⎟
⎜ ⎟
⎝ ⎠
⎛ C ⎛⎜ αRT nFη ⎞
⎟ C ⎟⎞
⎛ (1−α ) nFη ⎞
−⎜
⎜
j = j0 0 e R ⎝ ⎠
− 0e P ⎝ RT ⎠⎟
⎜ CR C ⎟
⎝ P ⎠

Bulter-Volmer Equation
Bultler-Volmer Equation: Non-Equilibrium
⎛ C ⎛⎜ αRT
nFη ⎞
⎟ C − ⎜ ⎟⎞
⎛ (1−α ) nFη ⎞

j = j0 ⎜ 0 e
R ⎝ ⎠
− 0e
P ⎝ RT ⎠⎟
⎜ CR C ⎟
⎝ P ⎠
Exchange Current Density Effect
⎛ C ⎛⎜ αRT
nFη ⎞
⎟ C − ⎜ ⎟⎞
⎛ (1−α ) nFη ⎞

j = j0 ⎜ 0 e ⎝
R ⎠
− 0e⎝
P RT ⎠⎟
⎜ CR C ⎟
⎝ P ⎠
 Improving Kinetic

⎛ C ⎜⎛ αRT
nFη ⎞
⎟ C ⎟⎞
⎛ (1−α ) nFη ⎞
−⎜
⎜
j = j0 0 e
R ⎝ ⎠
− 0e
P ⎝ RT ⎠⎟
⎜ CR C ⎟
⎝ P ⎠
1. CR: Increase
1 I reactant concentration
i
2. Increase j0
⎛ − ΔG + + ⎞
⎜ ⎟
⎜ RT ⎟
j0 = nFC * fe ⎝ ⎠

• Decrease the activation energy (G++)

• Increase T
• Increase reaction site (equivalent to C*)
 Simplified B-V Equation
1. When ηact is very small

nFη act
j = j0
RT

1. When ηact is large

αnFη act
RT RT
j = j0 e RT
or η act = − ln j0 + ln j
αnF αnF
= a + b log j
Tafel Equation
B-V Equation: Practical Consideration
Hydrogen

Oxygen

Triple Phase Boundary

Understanding Catalyst via DFT

Hydrogen dissociation

Oxygen dissociation
O2 Dissociation & Incorporation

by Prof. F. B. Prinz, Stanford University