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Contents
Contents
1 Fundamentals
1.1 H2 /O2 electrochemical device . . . .
1.2 Reactant consumption and feed . . .
1.3 Hydrogen energy and power . . . .
1.4 Fuel cell stack power . . . . . . . . .
1.5 Fuel cell efficiencies . . . . . . . . .
1.5.1 Different efficiencies . . . . .
1.5.2 Electric efficiency calculation
1.6 Polarization curve . . . . . . . . . .
2 Fuel cell system (FCS)
2.1 Anode subsystem . . . . . . . . . .
2.2 Cathode subsystem . . . . . . . . .
2.2.1 Cathode water management
2.2.2 Stack pressure drop . . . . .
2.2.3 Cathode air compression . .
2.3 Coolant subsystem . . . . . . . . . .
2.4 Fuel cell system efficiency . . . . . .
2.4.1 FCS electric efficiency . . . .
2.4.2 Auxiliary components . . . .
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21
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23
24
27
27
29
30
30
31
3 Example calculations
32
3.1 Stack operating parameters . . . . . . . . . . . . . . . . 36
4 Appendix 1: Fundamentals
37
4.1 Thermodynamic fundamentals . . . . . . . . . . . . . . 37
c Alexander Kabza
Contents
4.2
4.3
4.4
4.5
4.6
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39
40
41
43
43
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49
49
60
61
61
62
67
68
69
c Alexander Kabza
1 Fundamentals
This is a collection of relevant formulas, calculations and equations
for designing a fuel cell system (FCS).
1
O2 H2 O(g)
2
r H < 0
The reaction enthalpy r H is equal to the enthalpy of water formation f H. The (chemical) energy content of any fuel is called heating
value (for more information on thermodynamics see chapter 4.1). The
heating value of hydrogen is equal to the absolute value of the reaction enthalpy. Because product water is produced either as gaseous
or liquid phase, we distinguish between the lower heating value (LHV)
and the higher heating value (HHV) of hydrogen:
H2 +
1
O2 H2 O(g)
2
kJ
mol
H2 +
1
O2 H2 O(l)
2
kJ
mol
c Alexander Kabza
Please note that LHV and HHV have positive signs whereas H is
negative. All thermodynamic potentials are dependent on temperature and pressure, but are defined at thermodynamic standard conditions (25 C and 100 kPa, standard ambient temperature and pressure
SATP, see also section 4.4).
The difference between LHV and HHV of 44.01 kJ/mol is equal to the
molar latent heat of water vaporization at 25 C.
The (thermodynamic) electromotive force (EMF) or reversible open
cell voltage (OCV) E 0 of any electrochemical device is defined as:
E0 =
G
nF
f GH2 O(g)
= 1.184 V
2F
El0 =
f GH2 O(l)
= 1.229 V (1.1)
2F
c Alexander Kabza
0
ELHV
=
LHV
= 1.253 V
2F
0
EHHV
=
HHV
= 1.481 V
2F
(1.2)
Those two values are the voltage equivalent to the enthalpy H, also
called thermal cell voltage (see [1], page 27) or thermoneutral voltage.
H and G are dependent on temperature; therefore also the corresponding voltage equivalents are functions of temperature. The temperature dependency (of absolute values) is as follows:
T [C]
LHV [kJ/mol]
HHV [kJ/mol]
G H2O(g) [kJ/mol]
G H2O(l) [kJ/mol]
-25
241.3
287.4
230.8
245.4
0
241.6
286.6
229.7
241.3
25
241.8
285.8
228.6
237.1
50
242.1
285.0
227.5
233.1
100
242.6
283.4
225.2
225.2
200
243.5
280.0
220.4
210.0
400
245.3
265.8
210.3
199.0
600
246.9
242.3
199.7
230.4
800
248.2
218.8
188.7
267.1
1000
249.3
195.3
177.5
308.3
300
290
Enthalpy [kJ/mol]
280
HHV
LHV
DG H2O(l)
DG H2O(g)
270
260
250
240
230
220
210
200
0
20
40
60
80
100
120
140
160
180
200
T [C]
Calculated with HSC Chemistry 6.21
c Alexander Kabza
n O2 =
I N
2F
[n H2 ] =
I N
1
= n H2
4F
2
mol
sec
[n O2 ] =
(1.3)
mol
sec
I is the stack load (electric current, [I] = A), and N is the amount of
single cells (cell count, [N ] = ). 2 is again the amount of exchanged
electrons per mole H2 for the hydrogen oxidation; respectively 4 eper mole O2 for the oxygen reduction. F is the Faraday constant.
The stoichiometry defines the ratio between reactant feed (into the
fuel cell) and reactant consumption (inside the fuel cell). Due to fuel
cell design and water management issues etc. the stoichiometry must
always be more than one:
=
n feed
n consumed
>1
[] =
The reactant feed for H2 and air into the fuel cell stack are now defined
by an anode and cathode stoichiometry :
n H2 , feed = n H2 anode =
n air, feed =
c Alexander Kabza
I N
anode
2F
(1.4)
n O2
I N
cathode =
cathode
xO2
4F xO2
I N
(anode 1)
2F
!
I N
cathode
1
=
4F
xO2
[m]
=
g
sec
The mass flow for stack anode and cathode inlet are therefore:
IN
anode MH2
2F
(1.5)
IN
cathode Mair
4F xO2
(1.6)
m
H2 , feed =
m
air, feed =
The dry mass gas flow at stack cathode outlet contains less oxygen
than air and is calculated as:
m
cathode, out = m
air, feed m
O2 , consumed
c Alexander Kabza
IN
cathode
Mair MO2
=
4F
xO 2
(1.7)
The volume flow V is calculated by the gas density or the molar gas
volume V0, mol :
m
= V0, mol n
V =
[V ] =
l
min
Both the gas density and the molar gas volume V0, mol are temperature and pressure dependent! Therefor the referring temperature and
pressure need to be defined. N or n indicates that the volume flow
is normalized to a specific reference temperature and pressure (e.g.
[V ] = Nl/min or ln /min). Physical standard temperature and pressure
(STP) is defined as 0 C and 101.325 kPa (for more information see
Nl
.
section 4.4). The molar gas volume at STP is V0, mol = 22.414 mol
The amount of product water is equal to hydrogen consumption (equation 1.3) and given by:
n H2 O, prod = n H2 =
I N
2F
[n H2 O ] =
mol
sec
I N
MH2 0
2F
[m
H2 O ] =
g
sec
(1.8)
c Alexander Kabza
kJ
285.83 mol
HHV
kJ
kWh
=
= 141.79
39.39
g
M
2.02 mol
g
kg
WH2 , LHV =
10
kJ
241.82 mol
kJ
kWh
= 119.96
33.32
g
2.02 mol
g
kg
WH2 , HHV
kJ
285.83 mol
kWh
J
HHV
=
= 3.54 3
=
ln = 12.75
V0, mol
mln
mn
22.414 mol
WH2 , LHV
kJ
241.82 mol
kWh
J
= 3.00 3
=
ln = 10.79
mln
mn
22.414 mol
[PH2 , HHV ] =
J
=W
sec
(1.9)
(1.10)
c Alexander Kabza
(1.11)
11
(1.12)
1.481 V
1
AveCell
(1.13)
The voltage equivalent 1.481 V is defined by equation 1.2. To calculate the thermal power based on LHV this voltage equivalent needs
to be replaced by 1.253 V.
Recovered heat The recovered heat is that part of the thermal stack
power that is actually converted into usable heat. This is e.g. the heat
transferred into the (liquid) coolant and can be calculated as follows:
Precovered heat = V cp T
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12
Coolant parameters are: Volume flow V , heat capacity cp , temperature increase T and density .
Due to technical issues not all thermal power can be transferred to
coolant; therefore:
Precovered heat < Ptherm, HHV
The unusable or waste heat:
Pwaste heat = Ptherm, HHV Precovered heat
This waste heat consists of two parts:
1. Heat rejected to ambient via stack surface (radiant heat).
2. Heat loss by cathode exhaust enthalpy; or more precise by the
difference between air outlet and air inlet enthalpy.
c Alexander Kabza
13
G
H
f GH2 O(g)
E0
1.184 V
= 0g =
= 94.5%
LHV
ELHV
1.253 V
f GH2 O(l)
El0
1.229 V
=
= 0
=
= 83.1%
HHV
EHHV
1.481 V
The Handbook of Fuel Cells [1] calls this simply ideal efficiency.
The Fuel Cell Handbook [2] calls this efficiency the thermal efficiency
of an ideal fuel cell operating reversibly on pure hydrogen and oxygen
at standard conditions.
Fuel Cell Systems Explained [3] calls this efficiency the maximum efficiency possible or maximum efficiency limit which explains it also
very well.
c Alexander Kabza
14
Electric efficiency
defined as:
el =
Pel
Pfuel, consumed
Pel is the stack electric (gross) power and Pfuel, consumed is the consumed fuel power (see equations 1.12 and 1.10).
The electric efficiency can easily expressed as (more details see section 1.5.2):
el, LHV =
AveCell
1.253 V
or el, HHV =
AveCell
1.481 V
(1.14)
c Alexander Kabza
Pel
Pfuel, feed
15
Pel is the stack electric gross power and Pfuel, feed is the fuel feed power
(see equations 1.12 and 1.11).
According to equation 1.14 it is:
fuel, el, LHV =
AveCell
1.253 V anode
AveCell
1.481 V anode
el
anode
AveCell
E0
AveCell
AveCell
=
0
El
1.229 V
c Alexander Kabza
AveCell
83.1%
1.481 V
16
Ptherm
Pfuel, consumed
1.481 V AveCell
1.481 V
Recovered heat efficiency Due to the fact that not all thermal power
Ptherm is transferred into the coolant the recovery heat efficiency can
be calculated:
recovered heat =
Precovered heat
Ptherm
Precovered heat
V cp T
=
Ptherm, HHV
(1.481 V AveCell) N I
Pel + Ptherm
=1
Pfuel, consumed
c Alexander Kabza
17
Obviously total < 1, because Precovered heat < Ptherm and Pfuel, feed >
Pfuel, consumed !
Pel
Pfuel, consumed
to
AveCell
?
1.253 V
c Alexander Kabza
Pel
Pfuel, consumed
AveCellN I
= AveCell2F
n H2 LHV
LHV
AveCell
AveCell
=
0
1.253 V
ELHV
18
thermalpower(HHV)
cellvoltage
thermalpower(LHV)
0.9
U[V]/P[W/cm]/efficiency[%]
800mV
0.8
electricpower
700mV
0.7
64%
600mV
56%
0.6
electricefficiency
(LHV)
0.5
500mV
48%
40%
0.4
0.3
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
currentdensity[A/cm]
1.4
1.6
1.8
2.0
For simulation and modeling it is helpful to have a mathematical expression for the PolCurves. The following empirical equation with
physical background describes the voltage current dependency quite
well (see [5], [6]):
E = E0 b (log j + 3) Rj m expnj
(1.15)
c Alexander Kabza
19
c Alexander Kabza
20
0.8
0.8
0.6
0.6
0.4
0.4
0.2
0.2
0.5
1.5
0.8
0.8
0.6
0.6
0.4
0.4
0.2
0.2
0.5
1.5
2
c Alexander Kabza
1.5
2
Variation m: 1e-4 - 3e-4 - 5e-4 cm /A
0.5
0.5
1.5
21
Fuel
Air
Recovered
heat
Fuel
Processing
System
Air
Processing
System
Ventilation
Inertgas
Water
EMD,
vibration,
wind,rain,
temperature,etc.
Ventilation
System
Thermal
Management
System
Wasteheat
FuelCell
Module(Stack)
Power
Conditioning
System
Waterand/or
Byproduct
Management
Internalpower
needs
Automatic
Control
System
Onboard
Energy
storage
Usablepower
Electrical(net)
Discharge
water
Exhaustgases,
ventilation
EMI,noise,
vibration
Source:IEC622821:2005 Fuelcelltechnologies,Part1:Terminology
The main components are the fuel cell stack, an air processing system (e. g. a compressor and humidifier), the fuel gas supply, thermal
management system etc. Other peripheral components are valves,
pumps, electrical devices etc. Fuel like hydrogen (from a tank system) and air (ambient) are feed into the FCS.
c Alexander Kabza
22
Main FCS inputs are fuel (e.g. hydrogen), air and water, but also
electric and thermal power. Main FCS outputs are the electric net
and thermal power, the reactant exhaust gases and product water.
The (electric) gross power is the stack electric power. The difference
between gross and net is the electric power consumed by the peripheral electric components inside the FCS:
Pnet = Pgross Pparipheral
Fuel
The anodeAirflow shall
on one hand
be high enough to remove product
Compressor
cell
stack be low to increase efficiency. This
Coolant on the other
water, but shall
hand
T
T
Periphery
dilemma is often solved by an anode recirculation loop.
in
out
Recirculation pump
Purge valve
H2
Fuel Cell
Stack
anode
Water trap
p2
p1
c Alexander Kabza
23
stack anode off gas is finally purged either into the cathode exhaust
or directly out of the FCS. This purged hydrogen is obviously lost for
the electrochemical conversion, therefore the amout of anode purge
losses shall be minimized.
The relation between hydrogen feed versus consumed hydrogen is
called FCS fuel stoichiometry:
net = fuel,FCS =
H2 feed
fuel feed
=
1
fuel consumed
H2 consumed
c Alexander Kabza
24
Yout =
Yin + 2
Mwater
Mair
MO2
Mair
(2.1)
c Alexander Kabza
25
1.4
0.224
66.6
1.5
0.206
65.2
1.6
0.191
63.9
1.7
0.178
62.7
1.8
0.167
61.6
1.9
0.157
60.6
2.0
0.148
59.5
2.1
0.140
58.6
2.2
0.133
57.8
2.3
0.126
56.8
2.4
0.120
56.0
2.5
0.115
55.2
This table now defines the lowest stack cathode exhaust temperature
T.So.C under which (theoretically) all product water can be fully removed as a function of cathode stoichiometry . If this temperature
gets lower, the cathode stoichiometry must be increased to remove
product water.
What happens if this temperature increases? One one hand the cathode stoichiometry may be decreased; but this is of course not doable
for temperatures above 65 C corresponding to cathode stoichiometry
below < 1.5. On the other hand either the inlet air may be humidified, or the cathode exhaust pressure may be increased, or both.
c Alexander Kabza
26
x 10
3.5
pout [Pa]
2.5
1.5
0.5
70
75
80
85
Tout [C]
90
95
100
c Alexander Kabza
27
p2 p0
+
p =
2
(A 0 )2 (p0 + p2 )2 + 2 m
2 p0 0
2 A 0
p1
p m
x
(2.2)
Here p2 is the gauge pressure at the stack exhaust, and p0 and 0 are
pressure and air density at STP.
wcomp = cp, m T1
c Alexander Kabza
p2
p1
28
W
kJ
=
kg
g/sec
For dry air at room temperature (25 C) this compression work wcomp
as a function of pressure ratio looks as follows:
160
Isentropicwork[kJ/kg]
Powerpermassflow[W/g/sec]
143
140
127
120
109
100
88
80
65
60
36
40
19
20
0
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Pressureratio []
c Alexander Kabza
W
= 8.1 kW
g/sec
29
[V ] = l/min
0C
cp
kJ/kg K
4.218
4.09
3.68
3.28
20C
g/cm
0.9998
1.018
1053
1.086
cp
kJ/kg K
4.182
4.10
3.72
3.34
40C
g/cm
0.9982
1.011
1044
1.075
cp
kJ/kg K
4.179
4.12
3.76
3.40
60C
g/cm
0.9922
1.002
1034
1.063
cp
kJ/kg K
4.184
4.13
3.80
3.46
80C
g/cm
0.9832
0.993
1023
1.050
cp
kJ/kg K
4.196
4.15
3.84
3.53
g/cm
0.9718
0.983
1010
1.036
c Alexander Kabza
30
When the thermal output is used in the vehicle and the electric and
thermal inputs are negligible, this equation simplifies to:
FCS, el =
Pnet output
Pfuel input
Fuel power input Pfuel input is the fuel (chemical) energy content fed
into the FCS (see equation 1.9). It can be expressed based on LHV
or HHV; both [1] and [8] refer to LHV.
The electric net power output Pnet output is the stack gross power minus
the total electric power consumption of all auxiliary FCS components
(e.g. compressor or blower, pumps, valves, etc.):
Pnet = Pgross Paux
Paux =
Pcomponent i
FCS efficiency can also be expressed as the product of different (system related) efficiencies (see also [1], page 718):
FCS el = stack fuel peripheral
c Alexander Kabza
31
with
stack =
AveCell
,
1.253 V
fuel =
1
fuel
and peripheral =
Pnet
Pgross
I N
cathode (I) Mair
4F xO2
Pcompressor = m
cp, m T1 (I)
1
compressor (, m)
Under the assumption that the power consumption of all other auxiliary components is constant, the total aux power consumption can be
estimated.
c Alexander Kabza
32
3 Example calculations
Hydrogen flow power: A hydrogen flow transports (chemical) power.
According to equation 1.9 the hydrogen flow of e.g. 1 g/sec is equivalent to:
1
ln
m3
g
667.1
40.0 n 48.1 kWLHV 68.0 kWHHV
sec
min
h
Stack efficiency calculation: A fuel cell stack produces 10 kW electric power, the hydrogen feed is 150 ln /min, and the stack runs at
600 mV average cell voltage. Calculate the electric efficiency, the fuel
efficiency and the anode stoichiometry (based on LHV).
el, LHV =
n H2 feed
c Alexander Kabza
AveCell
0.6 V
=
= 47.9%
0
ELHV
1.253 V
ln
150 min
mol
=
ln
sec = 0.1115
sec
22.414 mol 60 min
kJ
10 sec
Pel
=
n H2 feed LHV
0.1115 mol
241.82
sec
kJ
mol
= 37.1%
33
anode =
el, LHV
fuel, el, LHV
47.9%
= 1.29
37.1%
Fuel cell system efficiency Here is an example for a FCS efficiency estimation. The auxiliary power consumption is calculated as
follows:
Paux = Pcompressor +
Pcomponent i
In this example the compressor power Pcompressor is a function of cathode stoichiometry, cathode inlet pressure (pressure ratio ), and compressor efficiency. The cathode stoic cathode is 5.0 to 2.0 for low load
c Alexander Kabza
34
and 1.8 above 0.15 A/cm2 . The cathode inlet pressure is linear between 130 kP a at low and 200 kP a at high load. The compressor efficiency is linear between 70% at low and 80% at high air mass flow.
Based on the polarization curve shown in chapter 1.6, and using the
above parameter to calculate Paux , we get the following electric power
chart:
100
90
gross
net
aux
80
Electricpower[kW]
70
60
50
40
30
20
10
0
0
50
100
150
200
250
Stackload[A]
300
350
400
450
c Alexander Kabza
35
70%
stackel.eff.(gross)[%]
stackfuelel.eff.(net)[%]
FCS_net
60%
Efficiency[%]
50%
40%
30%
20%
10%
0%
0
10
20
30
40
50
FCSnetpower[kW]
60
70
80
90
The FCS peak efficiency is 55% for this example. The zero power
level is called idle point; here the FCS net power is zero, but the FCS
is still operating and consumes fuel.
c Alexander Kabza
36
A/cm2
mV
A
V
kW el
0.05
839
15
168
3
Stack electric
0.10
797
30
159
5
0.20
756
60
151
9
0.40
703
120
141
17
0.60
661
180
132
24
1.00
588
300
118
35
Stoichiometry *
Hydrogen flow
Hydrogen flow
Nl/min
g/sec
3.0
62.7
0.09
Stack anode
2.0
83.6
0.13
1.3
108.7
0.16
1.3
217.4
0.33
1.3
326.2
0.49
1.3
543.6
0.81
Stoichiometry *
Air flow
Air flow
Air flow
Nl/min
g/sec
kg/h
2.2
109.5
2.4
8.5
Stack cathode in
2.0
1.8
199.1
358.4
4.3
7.7
15.4
27.8
1.8
716.8
15.4
55.6
1.8
1075.2
23.2
83.4
1.8
1792.1
38.6
138.9
P therm LHV
P therm HHV
delta HHV - LHV
Coolant inlet temp *
Coolant outlet temp *
Coolant delta T
Coolant flow LHV 2
Coolant flow HHV 2
kW
kW
kW
C
C
K
l/min
l/min
1.2
1.9
0.7
60
61
1
17.9
27.7
13.2
18.7
5.5
60
67
7
27.1
38.3
21.3
29.5
8.2
60
68
8
38.3
53.1
39.9
53.6
13.7
60
70
10
57.4
77.0
RH *
pws at coolant outlet temp
Pressure out
Product water out
Consumed oxygen
Dry cathode out
Wet cathode out
Enthalpy out
P enthalpy out
%
kPa abs
kPa abs
g/sec
g/sec
g/sec
g/sec
kJ/kg
kW
100%
20.84
120
0.3
0.2
2
2
405
1
100%
27.30
131
2.2
2.0
13
16
499
7
100%
28.52
137
3.4
3.0
20
24
500
10
100%
31.12
149
5.6
5.0
34
39
503
17
Hydrogen feed
P chem H2 LHV
P chem H2 HHV
mol/sec
kW
kW
0.16
39
46
0.24
59
69
0.40
98
116
Electric efficiency
Fuel efficiency
%
%
56%
43%
53%
41%
47%
36%
67%
22%
Stack thermal
2.7
4.1
1.4
60
63
3
13.1
19.7
6.0
8.7
2.7
60
66
6
14.3
20.8
* given values
20C and 50% compressor efficiency
2
WEG 50vol% at 60C
1
c Alexander Kabza
37
4 Appendix 1: Fundamentals
4.1 Thermodynamic fundamentals
The four thermodynamic potentials are:
Internal energy U is the total energy of an thermodynamic system
and the sum of all forms of energies. In an isolated system the
internal energy is constant and can not change. As one result of
the first law or thermodynamics the change in the inner energy
can be expressed as the heat dq supplied to the system and the
work dw performed by the system: dU = dq + dw
Free or Helmholtz energy F (or A): is the useful work obtainable
from a thermodynamic system at isothermal and isobaric conditions.
Enthalpy H: The enthalpy is a measure for the energy of a thermodynamic system and the sum of internal energy and the work
for changing the volume: H = U + pV . For each chemical reaction the entropy change defines the reaction to be endothermic
(H < 0) or exothermic (H > 0).
Free or Gibbs enthalpy G: The Gibbs or thermodynamic free enthalpy is the work that a thermodynamic system can perform:
G = H T S. For each chemical reaction G defines the reaction to be exergonic (G < 0) or endergonic (G > 0).
c Alexander Kabza
38
V
A
G T
dH = V dp + T dS
dA = SdT pdV
dG = V dp SdT
c Alexander Kabza
39
and
(U/V )S = p
(H/S)p = T
and
(H/p)S = V
(A/V )T = p
(G/p)T = V
and (A/T )V = S
and (G/T )p = S
c Alexander Kabza
40
0
29.06
1003.4
25
29.10
1004.6
50
29.13
1005.9
100
29.25
1009.9
200
29.67
1024.4
300
30.25
1044.5
400
30.93
1067.9
500
31.64
1092.3
600
32.29
1114.8
Calculated with HSC Chemistry 6.21, air with 78 Vol% N2 , 21% O2 and 1% Ar
Species
N2(g)
O2(g)
H2(g)
CO2(g)
H2O(g)
0
29.12
29.26
28.47
36.04
33.56
25
29.13
29.38
29.05
37.12
33.60
400
30.57
32.76
29.29
48.97
37.25
500
31.26
33.56
29.64
50.97
38.48
600
31.92
34.21
30.00
52.62
39.74
Species
N2(g)
O2(g)
H2(g)
CO2(g)
H2O(g)
0
1039.3
914.4
14124
818.9
1863.1
25
1039.7
918.2
14409
843.5
1865.3
400
1091
1024
14531
1113
2068
500
1116
1049
14703
1158
2136
600
1140
1069
14884
1196
2206
c Alexander Kabza
50
45
cp [JJ/mol K]
41
40
35
30
25
20
0
50
100
150
200
T [C]
Calculated with HSC Chemistry 6.21
c Alexander Kabza
pabs [kPa]
100.000
101.325
101.325
101.325
101.325
100.000
42
Thermodynamic values are defined at 25 C and 100.000 kPa. Therefore SATP (standard ambient temperature and pressure) is used to
express that within this document.
do use the following temperature and pressure as reference for standard volume flows:
T0 = 273.15 K and p0 = 101.325 kPa
Using such types of MFCs require using this reference temperature
and pressure to ensure correct calculations like described above!
By the way The well known molar volume of an ideal gas is given
at this temperature and pressure:
V0, mol = R
c Alexander Kabza
T0
= 22.414 ln /mol
p0
43
j() = j0
!#
(1 )nF
nF
exp
exp
RT
RT
RT
(1 )nF
jc () = j0 exp
RT
c Alexander Kabza
44
j()
1 nF
= 2 sinh
j0
2 RT
The following chart shows the anodic current (green line), the cathodic current (blue) and the Butler-Volmer equation itself (red):
current de
ensity j [mA/cm] / j / j0
8
6
4
2
0
-100
-50
50
100
-2
-4
-6
-8
overpotential [mV]
j0
RT
The following chart shows this linear relation between current density
j and overpotential , with the slope m = nF/RT :
c Alexander Kabza
45
0.5
0.4
0.3
0.2
j / j0
0.1
0.0
-0.1
-10
-5
10
-0.2
-0.3
-0.4
-0.5
overpotential [mV]
In case of high overpotentials (|| > 100mV , = 1/2) the ButlerVolmer equation simplifies to:
ln
j()
1 nF
=
j0
2 RT
ln ( j / j0)
3
2
1
0
-1
50
100
150
200
250
300
-2
-3
-4
overpotential [mV]
The slope of the blue dotted line m = 1/2 nF/RT is the Tafel slope in
the Tafel equation = m j/j0 .
c Alexander Kabza
46
5 Appendix 2: Constant
values and abbreviations
Constant values
sec
Faradays constant F = 96 485.3399 Amol
[11]
J
Molar gas constant R = 8.314472 K mol
[11]
Magnus equation const C1 = 610.780 Pa
C2 = 17.08085
C3 = 234.175 C
Thermodynamics
Standard temp. and pressure
(STP, see section 4.4)
Molar volume of ideal gases
(at STP)
Standard ambient T and p
(SATP)
LHV of H2 (at SATP)
T0 = 273.15 K [12]
p0 = 101.325 kPa [12]
kJ/g [15]
kJ
HHV of H2 (at SATP) HH2 O(l) = 285.83 mol
[13], [14]
=141.79
kJ/g [15]
kJ
[13]
Gibbs free enthalpy of H2 O(g) GH2 O(g) = 228.57 mol
kJ
and H2 O(l) (at SATP) GH2 O(l) = 237.13 mol [13]
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47
Molar weights
Molar weight water
hydrogen
oxygen
nitrogen
CO2
air
Molar fraction of O2 in air
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48
non SI units
N/m2
Nm, Pa m3
J/s
W/A, J/C
V/A
c Alexander Kabza
49
6 Appendix 3: Air
6.1 Moist air
Water vapor and saturation pressure in moist air The water vapor partial pressure at saturation pws (t) is a function of temperature t
[ C]. Its values are documented in tables (e.g. in [16], see also table
on page 59), but also a couple of equations allow its calculation. The
most popular one is the Magnus equation, but others fit with a higher
accuracy to the table values (e.g. equation with ten parameters in the
documentation of Vaisalla products).
Magnus equation:
pws (t) = C1 exp
C2 t
C3 + t
t=
c Alexander Kabza
(t)
C3 ln pws
C1
(t)
C2 ln pws
C1
50
Watervaporsaturationpressure[kPa]
100
101.32
80
70.04
60
47.29
40
31.12
19.90
20
12.33
0.61 1.23 2.34
10
20
4.25
30
7.38
40
50
60
Temperaturet[C]
70
80
Watervaporsaturationpressure[kPa]
1600
90
100
1596
1400
1284
1200
1023
1000
805
800
627
600
481
364
400
200
0
143
199
272
101
100
110
120
130
140
150
160
Temperaturet[C]
170
180
190
200
c Alexander Kabza
Y (p, t) =
51
mw
Rair
pw (t)
Mw
pw (t)
=
mdry air
Rw pair pw (t)
Mair pair pw (t)
[Y ] = kg/kg
(6.1)
With Rw /Rair = 0.622 and pw (t) = pws (t) (see below) we get:
Y (p, t, ) = 0.622
pws (t)
pair pws (t)
(6.2)
2.0
1.8
101.3 kPa
1.6
120 kPa
1.4
150 kPa
1.2
200 kPa
1.0
0.8
RH is 100% (saturation)
0.6
0.4
0.2
0.0
0
c Alexander Kabza
20
40
60
Temperature t [C]
80
100
52
2.0
1.8
Specific hum
midity Y [kg/kg]
1.6
100% RH
75% RH
1.4
50% RH
1.2
25% RH
1.0
0.8
0.6
0.4
0.2
0.0
0
20
40
60
Temperature t [C]
80
100
pw (t)
aw (t)
mw
=
=
pws (t)
aws (t)
mws
= 0.0 1.0
Y (t)
p
Y (t)
p
=
Mw
Mair
(6.3)
Mw pw (t)
1
pw
g K pw (t)
= 2.167
R T0 + t
Rw (t) T0 + t
J T0 + t
c Alexander Kabza
53
600
500
RH is 100% (saturation)
400
300
200
100
0
0
20
40
60
Temperature [C]
80
100
pw (t)
pa
y = 0.0 1.0
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54
1.0
1E-2
Mol fraction y
0.9
0.8
1E-4
0.7
1E-6
0.6
1E-8
0.5
-100
-80
-60
-40
-20
0.4
0.3
101.325 kPa
120 kPa
150 kPa
200 kPa
0.2
0.1
0.0
0
20
40
60
80
Dew point temperature Tdp [C]
100
120
Tdp =
C2 ln
C2 t
C3 +t
t
CC32+t
C3 ln +
c Alexander Kabza
55
C T
exp C32+Tdpdp
pw (t)
=
=
t
pws (t)
exp CC32+t
100
100% RH
80% RH
60% RH
40% RH
20% RH
80
60
40
20
0
-20
0
20
40
60
Temperature t [C]
80
100
100%
90%
relative hum
midity RH [%]
80%
70%
60%
50%
40%
30%
DPT = t - 2K
DPT = t - 5K
DPT = t - 10K
DPT = t - 20K
20%
10%
0%
0
20
40
60
Temperature t [C]
80
100
c Alexander Kabza
56
heat. Since moist air is a mixture of dry air and water vapor, the enthalpy includes the enthalpy of the dry air (the sensible heat hair ) and
the enthalpy of the evaporated water (the latent heat hwater ).
Specific enthalpy h [kJ/kg] of moist air is defined as the total enthalpy
of the dry air and the water vapor mixture per kg of moist air.
The enthalpy consists of three parts: a) warming up dry air from the
reference temperature to the air temperature t, b) evaporating water
inside the moist air and c) warming up water vapor from the reference
temperature to the air temperature t:
h = hair + Y hwater
(6.4)
with
hair = cp, air t
and
[h] = J/g
where Y is the specific humidity of moist air, cp, air is the specific heat
capacity of dry air, cp, water is the specific heat capacity of water vapor
and hwe is the specific enthalpy of water vaporization. In case of dry
air (Y = 0), the enthalpy is a linear function of temperature (with slope
cp, air ). Heat capacities are dependent on temperature (see chapter
4.3), but between 0 and 100 C this may be neglected.
Because the enthalpy is not an absolute value; only the enthalpy difference to a reference temperature can be calculated. Depending on
the unit of temperature, the reference temperature is 0 C if [t] = C;
kJ
or 0 K if [t] = K. If the temperature is given in C, the enthalpy is 0 kg
kJ
at 0 C. If temperature is given in K, the enthalpy is 0 kg
at 0 K.
c Alexander Kabza
57
Due to the fact that only the enthalpy difference is used, it doesnt
matter if temperature is given in K or C! Its just important not to
switch between both units.
The following chart show the enthalpy based on 0 C reference:
500
450
400
350
300
100% RH
75% RH
50% RH
25% RH
dry (0%)
250
200
150
100
50
0
0
10
20
30
40
50
60
Temperature t [C]
70
80
90
100
70
80
90
100
2000
1800
101.325 kPa
120 kPa
150 kPa
200 kPa
Specific enth
halpy h [kJ/kg]
1600
1400
1200
1000
800
600
400
200
0
0
10
20
30
40
50
60
Temperature t [C]
For dry air there is another empirical fit to calculate the enthalpy. This
equation is used in DIN IEC 62282-3-2 [10]:
c Alexander Kabza
h(t) = (A t + B t2 + C t3 )/Mair
58
c Alexander Kabza
59
The following table lists the water vapor saturation pressure over liquid water (below 100 C) according to [16]. Pressure units are converted from pressure unit Torr into Pascal using the following formula:
1 Torr = 1 mmHg =
1Torr=
T[C]
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
133.322 Pa=101325Pa/760Torr
p[mmHg]
4.579
4.926
5.294
5.685
6.101
6.543
7.013
7.513
8.045
8.609
9.209
9.844
10.518
11.231
11.987
12.788
13.634
14.53
15.477
16.477
17.535
18.65
19.827
21.068
22.377
23.756
25.209
26.739
28.349
30.043
31.824
33.695
35.663
37.729
39.898
p[Pa]
610.48
656.75
705.81
757.94
813.40
872.33
934.99
1001.7
1072.6
1147.8
1227.8
1312.4
1402.3
1497.3
1598.1
1704.9
1817.7
1937.2
2063.4
2196.8
2337.8
2486.5
2643.4
2808.8
2983.4
3167.2
3360.9
3564.9
3779.6
4005.4
4242.9
4492.3
4754.7
5030.1
5319.3
c Alexander Kabza
T[C]
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
101325
Source:
Pa 133.322 Pa
760HandbookofChemistryandPhysics,66thedition(1985198
Vaporpressureofwaterbelow100C(pageD189f)
p[mmHg]
42.175
44.563
47.067
49.692
52.442
55.324
58.34
61.5
64.8
68.26
71.88
75.65
79.6
83.71
88.02
92.51
97.2
102.09
107.2
112.51
118.04
123.8
129.82
136.08
142.6
149.38
156.43
163.77
171.38
179.3
187.54
196.09
204.96
214.17
223.73
p[Pa]
5622.9
5941.2
6275.1
6625.1
6991.7
7375.9
7778.0
8199.3
8639.3
9100.6
9583.2
10085.8
10612.5
11160.4
11735.0
12333.7
12958.9
13610.9
14292.2
15000.1
15737.4
16505.3
17307.9
18142.5
19011.8
19915.7
20855.6
21834.2
22848.8
23904.7
25003.3
26143.2
27325.8
28553.7
29828.2
T[C]
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
p[mmHg]
233.7
243.9
254.6
265.7
277.2
289.1
301.4
314.1
327.3
341
355.1
369.7
384.9
400.6
416.8
433.6
450.9
468.7
487.1
506.1
525.76
546.05
566.99
588.6
610.9
633.9
657.62
682.07
707.27
733.24
760
p[Pa]
31157.4
32517.3
33943.9
35423.8
36957.0
38543.5
40183.4
41876.6
43636.4
45462.9
47342.8
49289.3
51315.8
53408.9
55568.8
57808.6
60115.1
62488.2
64941.3
67474.5
70095.6
72800.7
75592.4
78473.5
81446.6
84513.0
87675.5
90935.2
94294.9
97757.3
101325
60
[Eair ] = kJ/kg
[Pair ] = kW
p
p0
T0 and p0 are the reference temperature and pressure, see section 4.4.
Example 1: How much power is required to heat dry air from 20 to
60 C with a mass flow of 30 kg/hr?
h = h60 C/0% h20 C/0% = 40.218 kJ/kg
P = h m
air = 40.218 kJ/kg 30 kg/hr
c Alexander Kabza
1
hr/sec = 335 W
3600
61
P = h m
air = 326.61 kJ/kg 30 kg/hr
1
hr/sec = 2722 W
3600
Isentropic
c Alexander Kabza
62
6.3.2 Thermodynamics
Compression and expansion
Gas in
Compressor
Gas out
Wloss
Wel
Thermodynamic of gases
Internal energy U The first law of thermodynamics [13] defines infinitesimal changes in internal energy dU of an ideal gas as changes
in added heat dq and provided work dw:
dU = dq + dw
c Alexander Kabza
63
Heat capacities C describe the temperature dependencies of internal energy U and enthalpy H:
CV = (U/T )V
Cp = (H/T )p
dU = CV dT
(6.5)
dH = Cp dT
5
cV = R
2
7
= 1.40
5
The specific heat capacities cp, m and cV, m are given as:
cp, m = cp /M
and
cV, m = cV /M
c Alexander Kabza
64
Z 2
dT /T = nR
Z 2
dV /V
cp
>1
cV
c Alexander Kabza
CV
nR
cV
cp cV
1
1
it is:
1
65
1
T1
=
T2
p1
p2
! 1
p1
V2
=
p2
V1
Z V2
p dV =
V1
Z 2
1
dU = CV
Z T2
T1
dT = CV T
The technical work wt,12 is the work that is transferred from or mass
flow via a technical system (for instance a mechanical axle). The
technical work is equal to the enthalpy of the kinetic and potential
energy of a stationary mass flow. The technical work wt,12 for compression is the work given to the drive shaft of the compressor; it
contains the displacement work, but not the friction [18]!
The technical work for an adiabatic process (dq = 0) is defined as:
wt, 12 = +
Z p2
p1
V dp =
Z 2
1
dH = Cp T
p
p2
p1
c Alexander Kabza
Cell Formulary
VFuel
V1 V
2
66
point. Adding the different process areas shown in the pV chart gives:
p2 V 2 +
Z V1
V2
p dV = p1 V1 +
Z p2
V dp
p1
Therefore:
wt, 12 = wV, 12 + p2 V2 p1 V1
Comment: For liquids V 0 and therefore wV, 12 0; then it is:
wt, 12 (p2 p1 ) V
The thermodynamic derivation (see above) defines the following ratios for the isentropic compression or expansion:
V1
=
V2
T1
V2
=
T2
V1
and
1
wt, 12 = h2 h1
wt, 12 = wV, 12
with h = cp, m T
with = cp /cV
The technical work is always more than the volume work, because
> 1.
c Alexander Kabza
67
Real Due to friction the gas compression in a real compressor always dissipates energy to the surroundings or to the cooling system.
This compression process is polytropic. After a polytropic compression the actual end temperature T2, act is always higher compared to
an ideal isentropic compression T2, s :
T2, act > T2, s
The isentropic efficiency s of a compressor is the ratio between isentropic technical work ws, 12 and actual technical work wact, 12 :
s =
T2, s T1
h2, s h1
ws, 12
=
=
wact, 12
T2, act T1
h2, act h1
c Alexander Kabza
68
6.3.4 Examples
Example 1: Isentropic efficiency
Air is compressed from 1 bara at 30 C (303.15 K) to 3 bara at 150 C
(423.15 K). In the compressor there is no energy or air mass flow loss
to the surroundings.
The actual technical work that is done at the air is:
wact = cp, m (T2, act T1 ) = 1005
kJ
J
120 K = 120.6
kg K
kg
Isentropic temperature:
T2, s = T1
3 bara
= 303.15 K
1 bara
!0.285
= 414.6 K
kJ
kg
Isentropic efficiency:
s =
ws
112.4 kJ/kg
=
= 0.932 or 93.2%
wact
120.6 kJ/kg
c Alexander Kabza
69
m
= 27 kg/h, p1 = 2.4 barabs and T1 = 18 = 291K
p2 = 6 barabs and Pel = 1305 W
Air mass flow losses due to gaps and other heat losses to the surroundings are neglected! But of course heat is transferred to the
cooling!
The isentropic technical work given to the air is:
ws = cp, m T1
= 1005
J
kgK
291 K
6 bar
2.4 bar
0.285
kJ
1 = 87.6 kg
kJ
27 kg/h = 2365.2 kJ/h = 657.0 W
kg
Ps
657.0 W
= 0.50 or 50%
=
Pel
1305 W
6.3.5 Comment
The technical work equation is often given in literature with different
indices. The next two equations show the relation between , R, cp
and cV :
cp /cV
cp
R=
(cp cV ) =
(cp cV ) = cp
1
cp /cV 1
cp cV
1
1
cV
R=
(cp cV ) =
(cp cV ) = cV
1
cp /cV 1
cp cV
c Alexander Kabza
70
7.2 Derivation
Stack inlet: Humidified air with specific humidity Y (calculated by
equation 6.2)
c Alexander Kabza
7.2 Derivation
71
NI
Mair
4F
x
m
water in = m
air in Yin
m
air in =
Stack outlet: Water inet and product water exit the cathode
m
cathode, out
IN
cathode
=
Mair MO2
4F
xO2
m
water, out = m
water, in + m
water, prod
The specific humidity at cathode outlet is:
Yout
mwater, out
=
=
m
cathode, out
m
water, in + m
water, prod
IN
4F
cathode
xO2
Mair MO2
Yin + 2
Mwater
Mair
MO2
Mair
c Alexander Kabza
72
p
So.C
pD
S.C
T
Si.C
T
So.C
F
F.Air.C (MFC)
V1
Stack = orifice
V2
p.PC.C
2 1 p
(8.1)
0
1 = 0 p1p+p
is the gas density at pressure p1 (temperature is not con0
sidered here!), and p = p1 p2 is the pressure drop at the orifice. A
c Alexander Kabza
73
p2 p0
+
p =
2
(A 0 )2 (p0 + p2 )2 + 2 m
2 p0 0
2 A 0
p2
p m
x
(8.2)
20
2.60e-04
2.80e-04
3.00e-04
15
10
5
0
c Alexander Kabza
20
40
60
80
Air flow [g/sec]
100
74
p
So.C
pD
S.C
T
Si.C
T
So.C
p
So.C
RStack
m in
m Stack
m C
m out
CVol
In case of steady state conditions the air mass flow into the system is
equal to the air mass flow out of the system:
during steady state: m
in m
out
But during air mass flow transients the volume V between the air feed
and the fuel cell stack needs to be considered, as described here
[19]. The reason therefore is that each individual air flow corresponds
to a specific pressure drop (see equation 8.2), and therefore also the
pressure p1 before the stack is a function of air flow. An increasing air
flow m
in also increases the pressure in the volume V , and therefore
m
C > 0:
during transients: m
in = m
C+m
out
The volume V can be describes as a pneumatic capacity CVol . During air flow up (or down) transients additional air flow m
C goes into (or
comes out of) this capacity. Corresponding to an electric RC-circuit
c Alexander Kabza
75
= RStack CVol
RStack =
p(m)
m
Stack
(non-linear)
V
Rair T
and therefore
V p
m
(8.3)
c Alexander Kabza
Bibliography
76
Bibliography
[1] Arnold Lamm Wolf Vielstich and Hubert A. Gasteiger. Handbook
of Fuel Cells Vol. 1. John Wiley & Sons Ltd, 1 edition, 2003.
[2] U.S. Department of Energy. Fuel Cell Handbook. National Technical Information Service, U.S. Department of Commerce, 7 edition, 2004.
[3] James Larminie and Andrew Dicks. Fuel Cell Systems Explained. John Wiley & Sons Ltd, 2 edition, 2004.
[4] Performance Working Group within the SAE Fuel Cell Standards Committee. SAE J2617: Recommended Practice for testing Performance of PEM Fuel Cell Stack Sub-system for Automotive Applications. SAE International, Nov2007.
[5] S. Srinivasan et al. Advances in solid polymer electrolyte fuel
cell technology with low platinum loading electrodes. J. of Power
Sources, 22:359 375, 1988.
[6] J. Kim et al. Modeling of pemfc performance with an empirical
equation. J. Electrochem. Soc., 142(8):2670 2674, 1995.
[7] Fuel Cell Technologies BSI Technical Committee GEL/105. DD
IEC TS 62282-1:2005 Fuel cell technologies - Part 1: Terminology. BSI British Standards, 18 April 2005.
[8] Performance Working Group within the SAE Fuel Cell Standards Committee. SAE J2615: Testing Performance of Fuel
c Alexander Kabza
Bibliography
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NIST Funda-
[12] DIN. DIN 1343 Reference conditions, normal conditions, normal volume; concepts and values. DIN Deutsches Institut fuer
Normung e. V., 1990.
[13] Peter W. Atkins. Physikalische Chemie, volume 2. VCH Verlagsgesellschaft GmbH, 1990.
[14] DIN. DIN 51857 Gaseous fuels and other gases - Calculation of
calorific value, density, relative density and Wobbe index of pure
gases and gas mixtures. DIN Deutsches Institut fuer Normung
e. V., 1990.
[15] SAE. SAE J2572: Recommended Practice for Measuring Fuel
Consumption and Range of Fuel Cell and Hybrid Fuel Cell Vehicles Fuelled by Compressed Gaseous Hydrogen. SAE International, 2008-10.
[16] David R. Lide. CRC Handbook of Chemistry and Physics. CRC
Press, 1990.
[17] A. J. Leo (Chair). ASME PTC 50-2002 Fuel Cell Power Systems
Performance. The American Society of Mechanical Engineers,
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c Alexander Kabza
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c Alexander Kabza