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 % % #
5 5→ 6 6 45 6 6 6 →5 54

3 4 6 →345 6 6 6 7545 6 6 6 → 54
5
Anode : H2 2H+ + 2e-
Cathode: 1/2O2+ 2H+ + 2e- H2O
Overall : H2 + 1/2O2 H2O Courtesy from Rina Lum (IHPC)
 !
% && '#∆%$( ' " # $
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H2 + 1/2O2 H2O (l); ∆H = -286 kJ/mol - HHV

H2 + 1/2O2 H2O (g); ∆H = -242 kJ/mol - LHV H2 + 1/2O2 H2O

Parameter Higher Heating Value (HHV) Lower Heating Value (LHV) + ',
Enthalpy ∆H -286 kJ/mol -242 kJ/mol (- ) & '
Gibbs Free Energy ∆G -237 kJ/mol -229 kJ/mol
(
Reversible Voltage, Er 1.229 V 1.185 V
(. ,
Theoretical Efficiency, εr 83% 94.5%
 /

Transportation Portable Power Generation

Stationary Power Generation Space and Defense

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Q = −(T∆S )i / nF + i(η + η )
.

act ohmic
+η conc

E (i ) = Eo − b ln i − iR
Eo = Er + b ln io ! B ' . ' # ? *<+ - +
 ,

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- #* *<+ 1 @
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Garcia, et al, 2004, JFSCT

Accounts for concentration variations

of methanol across the anode backing
layer (ABL), anode catalyst layer
(ACL), and membrane
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 Mass transport equations are combined
with kinetic equations to calculate the
cell voltage
Anode and cathode
over-potential

δ I
Vcell = U oO2 − U oMeOH − η a + η c − m cell
κ
Thermodynamic
equilibrium potentials of Ohmic drop
oxygen reduction and across the
methanol oxidation membrane

ηa, ηc and Icell are dependent on

concentration profile of methanol
 1 & '

Anode Backing Layer (ABL)

B
dN MeOH ,z
Differential mass balance =0
dz

Methanol flux B
B dc MeOH ,z
(Fick’s Law of Diffusion) N MeOH , z = − DB
dz

Governing Equation d 2 c: MeOH

B
,z
=0
2
dz
B
Boundary Conditions: z=
: 0 cMeOH = cb
B
z = zI cMeOH = c IB = K I c IA

Analytical solution B K I c IA − cb
cMeOH = z + cb
δB
 1 & '

Membrane Layer (M)

M
dN MeOH ,z
Differential mass balance =0
dz

M
Methanol flux (diffusion and M dc MeOH ,z I
electro-osmotic drag )
N MeOH , z = − DM + ξ MeOH cell
dz F
Governing Equation
M
d 2: cMeOH ,z
Electro-osmosis drag
=0 coefficient, number of
2 methanol molecules
dz
dragged by hydrogen
ion in the membrane
Boundary Conditions: z = z II c M = c M
= K c A
MeOH II II II
z = z III c M
MeOH ≈ 0

M δB + δA − z
Analytical solution c MeOH = K II c IIA +1
δM
 1 & '

Anode Catalyst Layer (ACL)

A
Differential dN MeOH ,z r j
mass balance = MeOH = −
dz M MeOH 6F
Homogenous reaction

A
kcMeOH
Volumetric current
j = aI 0MeOH
, ref eα Aη A F / RT
+ λeα Aη A F / RT
density (A/cm3) A
cMeOH
:
A
Methanol flux A dc MeOH ,z
(Fick’s Law of Diffusion) N MeOH , z = −DA
dz
d 2 c MeOH
M
,z j
Governing Equation DA =
dz 2 6F
A
z = zI cMeOH = c IA
Boundary Conditions
A
z = z II cMeOH = c IIA
 1 & '

Anode Catalyst Layer (ACL)

A I cell
Analytical solution cMeOH = z 2 + C1z + C2
12 Fδ A D A

c IIA − c IA I cell (2δ B + δ A )

A A
A (c II − c I )δ B I cell δ B (δ B + δ A )
C1 = − C2 = c I − +
δA 12 Fδ A D A δA 12 Fδ A D A
z = z: I A B
Jump mass balance at N MeOH ,z = N MeOH , z
interface of ACL A M
z = z II N MeOH ,z = N MeOH , z

I cell δ B : I δ
δ A DM K II ( DB cb − ) + δ M D A DB cb − (1 + 6ξ MeOH ) cell B
12 F 6F
c IA =
DB K I (δ A DM K II + δ M D A ) + δ B D A DM K II
I I
δM D A DB cb − δ A DB K I (1 + 12ξ MeOH ) cell − δ B D A (1 + 6ξ MeOH ) cell
2F 6F
c IIA =
DB K I (δ A DM K II + δ M D A ) + δ B D A DM K II
 '
Cell current density

δ B +δ A δ B +δ A A
kcMeOH
I cell = j dz = aI 0MeOH
, ref eα Aη A F / RT dz
δB δB
A
cMeOH + λeα Aη A F / RT
Obtain ηa for given value of Icell

Cathode
co 2
Oxygen reduction I cell + I leakage = I 0O, 2ref eα cη c F / RT I leakage = 6 FN MeOH
M
,z
co 2 , ref

Obtain ηc for given value of Icell

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