Lecture #5 - Fuel Cell Fundamentals

Introduction to Fuel Cell Science

and Engineering

Chris Yang
Hydrogen Economy
TTP 289-002

Topics
• Electrochemistry
• Thermodynamics
• Kinetics
• Single Cells
• Stacks
• Fuel Cell Systems
• Applications

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Apa itu sel bahan bakar?
• Perangkat konversi energi elektro-kimia
! Mirip dengan baterai
• Perbedaan sebagian besar masalah definisi yang ketat
• Menggunakan bahan bakar cairan
• Penyimpanan energi vs konversi energi
! Mengubah energi kimia! listrik tanpa langkah panas menengah
! Ada pelepasan panas yang diperlukan tetapi untuk alasan yang berbeda
• Dapat menjadi perangkat suhu rendah
! Semua reaksi kimia melibatkan elektron sehingga merupakan bentuk konversi energi yang lebih
tepat daripada
• membakar bahan bakar untuk membebaskan energi sebagai panas (energi kualitas lebih rendah)
dan kemudian mencoba untuk mengumpulkan sebanyak-banyaknya energi panas kembali ke energi
berkualitas tinggi (mekanis)

Motivation for Fuel Cells

• Direct Chemical Energy Conversion
! High Efficiency - part load
! Low-to-zero Emissions (depends on fuel)
! Cogeneration / Distributed Generation
! Fuel Flexibility - possibly carbon neutral
• Uncertainties
! Economics
! Fuel Source
• Emissions
• Efficiency

4
Fuel Cells for Transportation
• Proton Exchange Membrane Fuel Cells (PEMFC)
! High Power Density
! High part load efficiency
! Good Efficiency
! Low Temperature (80°C) for quick startup
! Very thin membranes are possible (25 µm) to minimize system size

! Low impurity tolerance

! Durability
! High materials cost
! Freeze protection

Introduction to Fuel Cells

• Electrochemical Energy Conversion Device

_ electrons (e-) +
Anode Cathode

proton
transport
(H+)
H2 O2

Anodic Reaction Electrolyte Cathodic Reaction

H2 " 2 H+ + 2 e- Electrodes and Catalyst
1/ O + 2 H+ + 2 e- " H O
2 2 2
6
 Fuel Cell Reactions
• + ions move from anode to cathode
• - ions move from cathode to anode
Fuel Cell Anode Reaction Cathode Reaction Conducting
Ion*

Alkaline Fuel Cell (AFC) H2 + 2(OH)- " 2 H2O + 2e- 1/2 O2 + H2O + 2e- " 2(OH)- (OH)-

Proton Exchange Membrane Fuel Cell H2 " 2H+ +2e- 1/2 O2 + 2H+ +2e- " H2 O H+
(PEMFC)

Direct Methanol Fuel Cell (DMFC) CH3OH + H2O " CO2 + 6H+ + 6e- 1/2 O2 + 2H+ + 2e- " H2O H+

Phosphoric Acid Fuel Cells H2 " 2H+ +2e- 1/2 O2 + 2H+ +2e- " H2 O H+

Molten Carbonate Fuel Cells H2 + CO32- " H2O + CO2 + 2e- 1/2 O2 + CO2 + 2e- " CO32- (CO3)2-

Solid Oxide Fuel Cells H2 + O2- " H2O + 2e- 1/2 O2 + 2e- " O2- O2-

Fuel Cell Efficiency

1
1.4 Enthalpy
0.9

1.2 Free Energy 0.8

0.7
1
thermal efficiency
cell potential [V]

Mixed Potential
0.6
0.8
Activation 0.5

0.6 0.4

0.3
0.4
0.2
Resistance
0.2
0.1
Mass Transport
0 0
0 400 800 1200 1600 2000
2
8 current density [mA/cm ]
Fuel Cell Power and Efficiency
E = E0 – b ln i –Ri –me(ni)
1.2 0.45

0.4
1
0.35

0.8 0.3
cell potential [V]

power [W/cm2]
0.25
0.6
0.2

0.4 0.15

0.1
0.2
0.05

0 0
0 200 400 600 800 1000 1200 1400
current density [mA/cm2]

Fuel Cell Thermodynamics

• Potential electricity output of a chemical reaction
"G "H # T"S
#G is the the free energy change for the reaction
#H is the enthalpy change for the reaction
#S is the entropy change for the reaction
• H2 + 1/2 O2 " H2O + work + heat
• #G is the maximum useful work associated with a chemical reaction
"G #nFE rev
• #H is the maximum heat associated with a chemical reaction
"H #nFE therm
• Entropy loss for the overall reaction
• 1.5 gas molecules " 0.5 or 0 gas molecules

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 Redox fuel reactions
• Oxidation states - amount of oxygen and hydrogen
! CH4 - #Hf = -74.9 kJ/mol
! CH2O - #Hf = -115.9 kJ/mol
! CO - #Hf = -110.5 kJ/mol
! CH3OH - #Hf = -201.1 kJ/mol
! CH2OOH - #Hf = -387.5 kJ/mol
! CO2 - #Hf = -393.5 kJ/mol

! H - #Hf = 218.0 kJ/mol

! HO - #Hf = 39.0 kJ/mol
! H2 - #Hf = 0 kJ/mol
! H2O - #Hf = -242.8 kJ/mol

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Fuel cell thermodynamics

• #G = #H -T#S
• Entropy reduction (#S <0) for fuel cell reaction
! #G < 0 because #H is very negative, so reaction is spontaneous
! Heat must be liberated to counteract entropy loss

H2 + 1/2 O2 ! H2O
1 bar reactant pressure (standard conditions)
Temp product H2O ! Hrxn ! Grxn " theoretical Etn (V) Erev (V)
phase (kJ/mol) (kJ/mol)
25°C LHV (vapor) -241.8 -228.6 94.5% 1.253 1.185
HHV (liquid) -286 - 237.3 83% 1.482 1.229
80°C LHV -242.3 -226.2 93.3% 1.256 1.172
HHV -283.8 -233.7 82.3% 1.471 1.212
130°C LHV -242.8 -223.9 92.2% 1.258 1.160
HHV -282.1 -230.4 81.7% 1.462 1.195
200°C LHV -243.8 -219.1 89.8% 1.259 1.131
600°C LHV -247.2 -198.1 80.1% 1.277 1.023
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1000°C LHV -249.4 -175.8 70.5% 1.288 0.908
 Voltage and energy
• The Nernst equation
! #G = #G0+RTlnQ
Q 
C c  D d
! Chemical reaction: aA + bB " cC + dD
[ A]a [B]b
! #G0=-nF#Erev
! #E = #Erev - (RT/nF)lnQ
• As Q increases, reaction goes towards completion, voltage drops
• The potential energy associated with less reactants is lower than the potential
energy associated with more reactants
• #G=-nF#E - an analogous equation can be used to convert #H into a
potential
! #H=-nF#Etn
maximum work output #G E rev
"theoretical   
total energy input #H E tn

actual work output E

"real  
total energy input E tn
13

Fuel cell efficiency (2)

• Components of cell efficiency
• Reversible efficiency - theoretical efficiency
E
" rev  #G  E rev
#H thermal
• Voltage efficiency- efficiency based upon operating voltage
"v  E
E rev
• Faradaic efficiency
" f  i
if
• Utilization efficiency - reactant utilization
n reacted
"u 
n total
• Auxiliary loads - parasitic power consumption
PPL
" a 1 #
Ptotal
• Total Efficiency is multiplicative
"total "rev "v " f "u "a

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 Electrode reactions
• Anode reactions Galvanic Cell
Ammeter
! Oxidation - electron loss
from reactant e- e-

! Electron enters
electrode
NO3- Na +
! H2 $ H+ + e- Anode (-) Salt bridge
NO3- Cathode (+)

Na+ Silver
Copper
• Cathode reactions Cu2
Porous Plugs NO3-
Ag
+
NO 3 - +

! Reduction - electron Cu2 NO 3- NO 3-

Ag
+
NO3-
gain for reactants +
NO3-
Ag
+
Ag
NO3-
NO3- +
! Electron leaves
electrode Oxidation: Overall: Reduction:
Cu(s) " Cu2+(aq) + 2 e- E = 0.459 V Ag+(aq) + e- " Ag(s)
! O2 + 4H+ + 4e- $ 2H2O Ea0 = -0.3402 V therefore is E co = 0.7996 V
spontaneous

Find better figure!

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Electrode reaction kinetics

• Reactants interact with the electrodes
• The potential energy of those interactions will depend upon the voltage
applied to the electrodes
• Anode reaction - electron moves to electrode
• Increased voltage (more positive) induces anode reaction
• Increasing forward rate decreases backward rate
Potential Energy

+ VF
-

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Distance from electrode
Electrode kinetics
• Butler-Volmer equation
! Describes the current as a function of electrode potential (voltage)
! O + e- $ R (switch sign for reverse reaction)


i  F k f coe "#VF / RT " kr cr e (1"# )VF / RT  
! i - current, F - Faraday’s constant, kf and kr - rate constants for forward
and reverse reactions, co and cr - concentration of oxidized and reduced
species, % - the symmetry factor for electrode reaction and V - electrode
voltage
io  Fk f coe ( " #VR F / RT )  Fkr cr e ((1" # )VR F / RT )
! io is exchange current density, the equilibrium current developed at an
electrode, VR is the reversible electrode potential
" (V # VR )
! The overpotential & is the difference between the actual voltage and the
reversible voltage.


i  io e (" #$F / RT ) " e ((1" # )$F / RT ) 
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Electrode kinetics (2)

• Anodic reactions require a positive value for the overpotential to
increase the rate of reaction
• Cathodic reactions require a negative value for the overpotential to
increase the rate of reaction
• The sum is a net reduction in the overall voltage to increase reaction
rates.

&
&

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Mixed potential
• Platinum can be oxidized which can be a problem because it
competes with hydrogen oxidation.
! Pt + H2O $ PtOH + H+ + e-
! Pt + H2O $ PtO + 2H+ + 2e-
! 1/ O + H+ + e- " H2O
2 2

• Reactions occur on one electrode and lead to reduced potential

! Hydrogen and methanol crossover is another reason for a mixed or

corrosion potential

19

Oxidation kinetics
• The current potential (iV) curves will depend strongly only the kinetics
of the fuel being oxidized

0.8
cell voltage [V]

0.6

0.4
Pure Hydrogen
2M Methanol
0.2 Hydrogen +
100 ppm CO

0
0 250 500 750 1000 1250 1500
2
current density [mA/cm ]
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Ion conduction
• Electric Field
! ' = #V/d
• Force on Ion
! Felectric = z e ' = [z e #V]/d
• Balance between Forces - electric field and viscous drag
! Fdrag = 6()v& ()-cross sectional area, v-velocity, &-viscosity)
! Velocity = [ze']/[6()&]
• Conduction speed (velocity) is related to current and conductivity
! increased current/conductivity
• greater electric field (thinner electrolyte, larger voltage)
• increased charge on ion
• smaller cross sectional area
• lower electrolyte viscosity (increased temperature)

21

Ion conduction (2)

• Liquid Electrolytes anode cathode
_ electrolyte_
! Ionic migration in presence of electric field + +
_ + _ +
! Grotthus Mechanism _ + _ +
real fuel cell _ _
+ +
• Positive ion conduction _
_ +
_
_ +
_ + _ +
! Acid electrolyte fuel cells _
+
_
+
+ +
! PAFC, PEMFC, DMFC
• Negative ion conduction double
layers
! basic/salt electrolyte
! AFC, MCFC anode cathode

• Solid Electrolyte _
_ +
electrolyte
_
_ +
_ + +
! defect conduction _
ideal fuel cell _ + _ +
+ +
! Solid Oxide Fuel Cell _
+
_ +
_ _
• Ohm’s Law _
_
+
+
_
_
+
+
+ +
! #V = IR
double
22 layers
Mass transport (concentration) overpotential
• If the reaction is proceeding at the electrodes, there will be a
reduction in the concentration of reactants.
• Reactants are supplied to the electrodes via diffusion
• At very high current densities (reaction rate) the rate of diffusion may
be slower than the rate of reactant utilization
• The Nernst equation describes effects of reduction in reactant
concentration
! #E = #Erev - (RT/nF)lnQ

Q 
C c  D d
[ A]a [B]b

23

Gas diffusion electrodes

• 3 phase contact area
! Gas, liquid and solid
• Reaction on platinum catalyst particles (35 nm) on carbon powder
! Reactant diffusion
! Production of H+ and e-
! Need to conduct protons away into membrane
Substrate Active layer
! Conduct e- to current collector Diffusion layer

Polymer
electrolyte

Electrocatalyst Catalyst layer

24 particle on impregnated with
carbon support polymer electrolyte
 Bipolar Plates
• Act as gas separators - gas impermeable
• Flow fields for gases - flow pattern is important
• Current collectors - high conductivity
• Polymer graphite or metallic
• End plates have high current flow
Anode
Inlet

Cathode
Inlet Anode
Exhaust
_ 1 2 3 4 +

Cathode
Exhaust

25

Building high power systems

• Single Cell Power Output
! Power Density = Voltage x Current Density = VCi
• Stack Power Output
! Power Output = Voltage x Current
= Cell Voltage x Number of Cells x Current Density x Area
= VCNCiA
• Net Power = Power Output - Auxiliary Power Requirements
• Cells in series and parallel
! parallel - larger area electrode, more current
Single Cell
Components
! series - multiple single cells, higher voltage Multi-Cell Stack

Gas Flow Bipolar Plate

Electrode/Catalyst

Electrolyte

Electrode/Catalyst

Gas Flow Bipolar Plate

H2 O2

26
 Proton Exchange Membrane Fuel Cells (PEMFCs)
• Low temperature - 80°C
! Immobilized acid polymer membrane
• Fluorinated membrane (Nafion)
• Water content is crucial
• Balance between dehydration and flooding
! High conductivity at low temperature
! Platinum electrocatalyst is required for increased reaction rates
• CO and H2S poisoning at low concentrations
! Heat management issues
• Components
! High surface area Platinum catalyst w/ polymer

27

Fluorinated Ionomer Membranes

• Phase separation
F F F F F F F
! Hydrophobic C C C C C C C
! Hydrophillic F F F F F F
O
F F F
F C C C C F
F F
F C F O S O
F O-
H+
CF2 - CF2 CF2 - CF2
SO3- SO3-
SO3- SO3- SO3-
SO3-
SO3 - SO3 - SO3-

SO3-
SO3- SO3- SO3-
SO3- SO3- SO3-
SO3-
-
SO3 SO3
-
CF2 - CF2
CF2 - CF2

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Polymer membranes
• Water is key
! Membrane reorganization
! Conductivity

Nafion 115

0.1
" [S/cm]

0.01

Nafion 115

0.001
0 2 4 6 8 10 12
! [H2O/SO3H]
29

CO poisoning
• CO poisoning of anode electrocatalyst
! CO + Pt ! Pt-CO
! H2 + 2Pt ! 2 Pt-H

1.00
CO Fractional Coverage CO

0.80
100 ppm CO

0.60

10 ppm CO
0.40
1 ppm CO
0.20

0.00
50 100 150 200 250
o
Temperature [ C]
30
Direct Methanol Fuel Cell (DMFC)
• Electrolyte
! Same as PEMFC, Perfluorosulfonic Acid Membrane - (i.e. Nafion)
• Electrode reactions
! Anode: CH3OH + H2O " CO2 + 6H+ + 6e-
! Cathode: 1/2 O2 + 2H+ + 2e- " H2O
! Overall: CH3OH + 3/2 O2 " CO2 + 2H2O
• Operating Temperature and Pressure
! 60°C to 100°C
• Fuel introduced as liquid feed 1 M methanol (1 mole methanol/liter) on anode side
• Platinum ruthenium catalyst
• Advantages
! Easier transportation/storage of methanol
! water and thermal management issues easier
• Disadvantages
! Low electro-activity for methanol
! Reduced efficiency and power
• Issues/Challenges
! Develop electrocatalysts for electro-oxidation of methanol to improve kinetics and current
density
31 ! Minimize crossover of methanol, which is very soluble in polymer membrane
! Reduce poisoning of catalysts by reaction intermediates

Solid oxide fuel cells (SOFC)

• Solid electrolyte
! Nonporous Y2O3 stabilized ZrO2 (30-40 µm thickness)

• Electrode Reactions
! Anode Reaction: H2 + O2- " H2O + 2e-
! Cathode Reaction: O2 + 2e- " 2O2-

• High Operating Temperature

! Internal reforming
! Rapid kinetics without precious metals
! High quality heat for cogeneration, bottoming cycle
! Materials requirements

• Advantages of solid state system

! 2 phase interface
! reduced corrosion, electrolyte management issues

• Oxide Ion Conduction

• Cell Configurations
! Tubular Seal-less Design
• Siemens Westinghouse Tubular Cell

! Bipolar (Flat Plate) Configuration

• Complexity and Seals
32
Solid Oxide Fuel Cells

33

Operation and system considerations

• Fuel utilization
Efficiency

! fuel and air leave in exhaust stream

! low utilization " high H2 concentration in cell and exhaust
! high utilization " low H2 concentration in cell and exhaust
• Optimization 60 70 80 90

H2 Utilization
! Efficiency, operating cost, reliability, fuel cell life, operating flexibility factor
• Tradeoffs:
! efficiency vs power density Higher Efficiency

• Operating Parameters:
! Load Lower Efficiency
voltage V
! Temperature
! Pressurization
! Gas concentration
! Reactant utilization
• Integration of secondary systems current density mA/cm2
! fuel processing
! cogeneration/bottoming cycle
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