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

What is a fuel cell?

An electro-chemical energy conversion device
! Similar to a battery Difference is mostly a matter of strict definitions Uses fluid fuels Energy storage vs energy conversion ! Converts chemical energy ! electricity without intermediate heat step ! There is heat release that is required but for a different reasons Can be a low temperature device ! All chemical reactions involve electrons so its a more precise form of energy conversion than burning a fuel to liberate the energy as heat (lower quality energy) and then
trying to scavenge as much of the heat energy back to high quality energy (mechanical)

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

Fuel Cells for Transportation

Proton Exchange Membrane Fuel Cells (PEMFC)
! High Power Density ! High part load efficiency ! Good Efficiency ! Low Temperature (80C) for quick startup ! Very thin membranes are possible (25 m) to minimize system size ! Low impurity tolerance ! Durability ! High materials cost ! Freeze protection

Introduction to Fuel Cells

Electrochemical Energy Conversion Device

_
Anode

electrons (e-)

+
Cathode

H2
Anodic Reaction H2 " 2 H+ + 2 e6

proton transport (H+)

O2
Electrolyte Electrodes and Catalyst

Cathodic Reaction 1/ O + 2 H+ + 2 e- " H O 2 2 2

Fuel Cell Reactions

+ ions move from anode to cathode - ions move from cathode to anode
Fuel Cell Anode Reaction Cathode Reaction Conducting Ion* (OH)H+ H+ H+ (CO3)2O2-

Alkaline Fuel Cell (AFC) Proton Exchange Membrane Fuel Cell (PEMFC) Direct Methanol Fuel Cell (DMFC) Phosphoric Acid Fuel Cells Molten Carbonate Fuel Cells Solid Oxide Fuel Cells

H2 + 2(OH)- " 2 H2O + 2eH2 " 2H+ +2eCH3OH + H2O " CO2 + 6H+ + 6eH2 " 2H+ +2eH2 + CO32- " H2O + CO2 + 2eH2 + O2- " H2O + 2e-

1/2 O2 + H2O + 2e- " 2(OH)1/2 O2 + 2H+ +2e- " H2O 1/2 O2 + 2H+ + 2e- " H2O 1/2 O2 + 2H+ +2e- " H2O 1/2 O2 + CO2 + 2e- " CO321/2 O2 + 2e- " O2-

Fuel Cell Efficiency

1.4 1.2
cell potential [V]

Enthalpy

1 0.9

Free Energy Mixed Potential Activation

0.8
thermal efficiency

1 0.8 0.6 0.4 0.2 Mass Transport 0 0 400 800 1200

0.7 0.6 0.5 0.4 0.3 Resistance 0.2 0.1 0 2000

1600

current density [mA/cm2]

Fuel Cell Power and Efficiency

E = E0 b ln i Ri me(ni)
1.2 0.45 0.4 1 0.35 0.8
cell potential [V]

0.3 0.25
power [W/cm2]

0.6 0.2 0.4 0.15 0.1 0.2 0.05 0 0 200 400 600 800 1000 1200 1400 current density [mA/cm2] 0

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 = #nFErev #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

!
10

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

11

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

Temp 25C 80C 130C 200C 600C 1000C

12

H2 + 1/2O2 ! H2O 1 bar reactant pressure (standard conditions) product H2O ! Hrxn ! Grxn " theoretical Etn (V) Erev (V) phase (kJ/mol) (kJ/mol) LHV (vapor) -241.8 -228.6 94.5% 1.253 1.185 HHV (liquid) -286 - 237.3 83% 1.482 1.229 LHV -242.3 -226.2 93.3% 1.256 1.172 HHV -283.8 -233.7 82.3% 1.471 1.212 LHV -242.8 -223.9 92.2% 1.258 1.160 HHV -282.1 -230.4 81.7% 1.462 1.195 LHV -243.8 -219.1 89.8% 1.259 1.131 LHV -247.2 -198.1 80.1% 1.277 1.023 LHV -249.4 -175.8 70.5% 1.288 0.908

Voltage and energy

The Nernst equation
! ! ! #G = #G0+RTlnQ ! Chemical reaction: aA + bB " cC + dD #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

Q=

[C ]c [ D] d
[ A]a [ B]b

#G=-nF#E - an analogous equation can be used to convert #H into a potential

! #H=-nF#Etn
maximum work output #G E rev = = total energy input #H E tn

"theoretical =
"real =
!
13

actual work output E = total energy input E tn

Fuel cell efficiency (2)

Components of cell efficiency Reversible efficiency - theoretical efficiency
E rev "rev = #G = #H E thermal Voltage efficiency- efficiency based upon operating voltage "v = E !
! E rev

Faradaic efficiency
"f = i if

Utilization efficiency - reactant utilization

"u =
n reacted n total

!
!

Auxiliary loads - parasitic power consumption

"a = 1 #

Total Efficiency is multiplicative

"total = "rev "v " f "u "a

PPL Ptotal

!
14

Electrode reactions
Anode reactions
! Oxidation - electron loss from reactant ! Electron enters electrode ! H2 $ H+ + eAnode (-) e-

Galvanic Cell
Ammeter e-

NO3-

Na+
Salt bridge

NO3-

Cathode (+) Silver

Na+

Cathode reactions
! Reduction - electron gain for reactants ! Electron leaves electrode ! O2 + 4H+ + 4e-

Copper

NO3

Cu2 + NO3Cu2 NO3+ NO3-

Porous Plugs

NO3NO3 Overall: E = 0.459 V therefore is spontaneous

-

NO3 Ag + Ag NO3+

Ag
+

Ag
+

$ 2H2O

Oxidation: Cu(s) " Cu2+(aq) + 2 eEa0 = -0.3402 V

Reduction: Ag+(aq) + e- " Ag(s) Eco = 0.7996 V

Find better figure!

15

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

+ Distance from electrode

VF

16

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 - Faradays 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 )

17

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.

&

&

18

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 2 2

+ H+ + e- " H2O

Reactions occur on one electrode and lead to reduced potential

V

! 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
1

0.8
cell voltage [V]

0.6

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

0 0
20

250

500

750

1000
2

1250

1500

current density [mA/cm ]

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
! Ionic migration in presence of electric field ! Grotthus Mechanism
real fuel cell _ _ _ _ _ _ _ _ anode + + + + + + + + cathode electrolyte _ + _ + _ + _ + _ + _ + _ + _ + double layers anode _ _ _ _ _ _ _ _ + + + + + + + + cathode electrolyte _ _ _ _ _ _ _ _ + + + + + + + +

Positive ion conduction

! Acid electrolyte fuel cells ! PAFC, PEMFC, DMFC

Negative ion conduction

! basic/salt electrolyte ! AFC, MCFC

Solid Electrolyte
! defect conduction ! Solid Oxide Fuel Cell
ideal fuel cell

Ohms Law
! #V = IR
22

double 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 ! Conduct e- to current collector
Substrate Active layer Diffusion layer

Polymer electrolyte

24

Electrocatalyst particle on carbon support

Catalyst layer impregnated with 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

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 ! series - multiple single cells, higher voltage
Gas Flow Bipolar Plate Electrode/Catalyst Electrolyte Electrode/Catalyst Gas Flow Bipolar Plate Single Cell Components Multi-Cell Stack

H2 26

O2

Proton Exchange Membrane Fuel Cells (PEMFCs)

Low temperature - 80C
! 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
! Hydrophobic ! Hydrophillic
F C F F C F F C F F C O F C F F C F F C F C F F CF2 - CF2 SO3SO3SO3SO3
-

F C F F C F

F C F F C F

O S O OH+

SO3- SO3SO3-

CF2 - CF2 SO3SO3SO3SO3-

SO3SO3CF2 - CF2
28

SO3SO3-

SO3SO3- SO3
-

SO3CF2 - CF2

Polymer membranes
Water is key
! Membrane reorganization ! Conductivity
Nafion 115
1

0.1

" [S/cm]
0.01

Nafion 115
0.001 0
29

6 ! [H2O/SO3H]

10

12

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

CO Fractional Coverage !CO .

1.00 0.80 0.60 0.40 1 ppm CO 0.20 0.00 50 100 150 Temperature [ C]
o

100 ppm CO

10 ppm CO

200

250

30

Direct Methanol Fuel Cell (DMFC)

Electrolyte
! ! ! ! Same as PEMFC, Perfluorosulfonic Acid Membrane - (i.e. Nafion) Anode: CH3OH + H2O " CO2 + 6H+ + 6eCathode: 1/2 O2 + 2H+ + 2e- " H2O Overall: CH3OH + 3/2 O2 " CO2 + 2H2O 60C to 100C

Electrode reactions

Operating Temperature and Pressure

!

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 Low electro-activity for methanol Reduced efficiency and power Develop electrocatalysts for electro-oxidation of methanol to improve kinetics and current density Minimize crossover of methanol, which is very soluble in polymer membrane Reduce poisoning of catalysts by reaction intermediates

Disadvantages
! !

Issues/Challenges
!

31

! !

Solid oxide fuel cells (SOFC)

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

Electrode Reactions
! ! Anode Reaction: H2 + O2- " H2O + 2eCathode 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 and air leave in exhaust stream ! low utilization " high H2 concentration in cell and exhaust ! high utilization " low H2 concentration in cell and exhaust
Efficiency
60

Fuel utilization

Optimization
! Efficiency, operating cost, reliability, fuel cell life, operating flexibility

70

80

90

H2 Utilization factor

Tradeoffs:
! efficiency vs power density
Higher Efficiency

Operating Parameters:
! Load ! Temperature ! Pressurization ! Gas concentration ! Reactant utilization
Lower Efficiency voltage V

Integration of secondary systems

! fuel processing ! cogeneration/bottoming cycle
34

current density mA/cm2