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Fuel Cell Technology
Topics
         1. A Very Brief History
         2. Electrolysis
         3. Fuel Cell Basics
               - Electrolysis in
         Reverse
               - Thermodynamics
               - Components
               - Putting It
         Together
         4. Types of Fuel Cells
               - Alkali
               - Molten Carbonate
               - Phosphoric Acid
               - Proton Exchange
         Membrane
               - Solid Oxide
         5. Benefits
         6. Current Initiatives
               - Automotive
         Industry
               - Stationary Power
         Supply Units
               - Residential Power
         Units
         7. Future
A Very Brief History



     Considered a curiosity in the
     1800’s. The first fuel cell was
     built in 1839 by Sir William
     Grove, a lawyer and gentleman
     scientist. Serious interest in
     the fuel cell as a practical
     generator did not begin until
     the 1960's, when the U.S. space
     program chose fuel cells over
     riskier nuclear power and more
     expensive solar energy. Fuel
     cells furnished power for the
     Gemini and Apollo spacecraft,
     and still provide electricity
     and water for the space
     shuttle.(1)
s this have to do with fuel cells?”




                            By providing
                            energy from a
                            battery, water
                            (H2O) can be
                            dissociated into
                            the diatomic
                            molecules of
                            hydrogen (H2)
                            and oxygen (O2).
             Figure 1
Basics
lectrolysis in reverse.”



         The familiar process of electrolysis
         requires work to proceed, if the
         process is put in reverse, it should
         be able to do work for us
         spontaneously.

         The most basic    “black box”
         representation     of a fuel cell in
         action is shown   work
                            below:

            Figure 2




            O2
                       fuel                H2O
            H2
                       cell


                       heat
uel Cell Basics
hermodynamics

             H2(g)    +       ½O2(g)     H2O(l)

  Other gases in the fuel and air inputs
  (such as N2 and CO2) may be present,
  but as they are not involved in the
  electrochemical reaction, they do not
  need to be considered in the energy
 1 Thermodynamic properties at 1Atm and 29
  calculations.
                          H2             O2       H2O (l)
     Enthalpy             0               0       -285.83
     (H)                                           kJ/mol
     Entropy         130.68            205.14      69.91
     (S)              J/mol·K           J/mol·K    J/mol·K


    Enthalpy is defined as the energy of a
    system plus the work needed to make
    room for it in an environment with
    constant pressure.

    Entropy can be considered as the
    measure of disorganization of a
uel Cell Basics
hermodynamics


f the chemical reaction using Hess’ Law:
 ΔHreaction = ΣHproducts     –   ΣHreactants
   = (1mol)(-285.83   kJ/mol)   –             (0)
   = -285.83 kJ



py of chemical reaction:
  ΣSproducts –     ΣSreactants
mol)(69.91   J/mol·K)] – [(1mol)(130.68   /mol·K) + (½mol)(2
                                          J


63.34   /K
        J




 gained by the system:
  = TΔS
  = (298K)(-163.34 J/K)
  = -48.7 kJ
uel Cell Basics
hermodynamics


free energy is then calculated by:
      ΔH     –    TΔS
  = (-285.83 kJ) – (-48.7 kJ)
  = -237 kJ
done on the reaction, assuming reversibility a
   W = ΔG

one on the reaction by the environment is:
 W = ΔG = -237 kJ


sferred to the reaction by the environment
 ΔQ = TΔS = -48.7 kJ


   More simply stated:
   The chemical reaction can do 237 kJ of
   work and produces 48.7 kJ of heat to
   the environment.
Fuel Cell Basics
Components


      Anode: Where the fuel reacts or
      "oxidizes", and releases electrons.
      Cathode: Where oxygen (usually from
      the air) "reduction" occurs.
      Electrolyte: A chemical compound that
      conducts ions from one electrode
      to the other inside a fuel cell.
      Catalyst: A substance that causes or
      speeds a chemical reaction
      without itself being affected.
      Cogeneration: The use of waste heat to
      generate electricity. Harnessing
      otherwise wasted heat boosts the
      efficiency of power-generating
      systems.
      Reformer: A device that extracts
      pure hydrogen from
l Cell Basics
tting it together.




                     Figure 3
Types of Fuel Cells



       The five most common types:


       •Alkali
       •Molten Carbonate
       •Phosphoric Acid
       •Proton Exchange Membrane
       •Solid Oxide
Types of Fuel Cells




                                                      SOFC




 Vorteil: Keine aufwendige Brenngas-Aufbereitung
 Nachteil: Hohe Betriebstemperaturen = Hohe System-Kosten
  Starke Material-Beanspruchung
Alkali Fuel Cell



                    compressed
                    hydrogen and
                    oxygen fuel
                    potassium
                    hydroxide (KOH)
                    electrolyte
                    ~70% efficiency

         Figure 4   150˚C - 200˚C
                    operating temp.
                      300W to 5kW
        requires pure hydrogen
                      output
        fuel and platinum
        catylist → ($$)
        liquid filled container →
        corrosive leaks
Molten Carbonate Fuel Cell (MCFC)

                       carbonate salt
                       electrolyte
                       60 – 80%
                       efficiency
                       ~650˚C operating
                       temp.
                       cheap nickel
                       electrode
           Figure 5    catylist
                    up to 2 MW
   The operating temperature is up
                    constructed,
   too hot for manyto 100 MW designs
                     applications.
                    exist
   carbonate ions are consumed in
   the reaction → inject CO2 to
   compensate
hosphoric Acid Fuel Cell (PAFC)



                        phosphoric acid
                        electrolyte
                        40 – 80% efficiency
                        150˚C - 200˚C
                        operating temp
                        11 MW units have
                        been tested
         Figure 6     sulphur free
                      gasoline can be
             The electrolyte a fuel
                      used as
             is very corrosive
             Platinum
             catalyst is very
Proton Exchange Membrane (PEM)



                     thin permeable
                     polymer sheet
                     electrolyte
                     40 – 50%
                     efficiency
                     50 – 250 kW
                     80˚C operating
        Figure 7
                     temperature

        electrolyte will not
        leak or crack
        temperature good for
        home or vehicle use
Solid Oxide Fuel Cell (SOFC)



                           hard ceramic
                           oxide
                           electrolyte
                           ~60% efficient
                           ~1000˚C
                           operating
                           temperature
          Figure 8
                     cells output
   high temp / catalyst can 100 kW
                     up to extract
   the hydrogen from the fuel at the
   electrode
   high temp allows for power
   generation using the heat, but
   limits use
Benefits

 Efficient:   in theory and in practice


 Portable:    modular units


 Reliable: few moving parts to wear out
 or break


 Fuel Flexible: With a fuel reformer,
 fuels such as natural gas, ethanol,
               methanol, propane,
 gasoline, diesel, landfill
 gas,wastewater,        treatment
 digester gas, or even ammonia can be
 used


 Environmental:   produces heat and
 water (less than combustion in both
terial‘s challenges of the PEM Fuel Cel
Review of Membrane
           (Nafion) Properties




• Chemical Structure
• Proton Conduction
Process
• Water Transport and
 Interface Reactions




11/25/12         Fuel Cell Fundamentals   20
cal structures of some membrane mater

 PSSA            PESA
 poly(sty        (Polyepoxy-
 rene-co-        succinic Acid)
 styrenes
 ulfonic
 acid)
 (PSSA)
                 α,β,β-
                 Trifluorosty
 Nafion,TM       rene grafted
 Membrane C      onto
                 poly(tetrafl
                 uoro-
                 ethylene)
                 with post-
                  Poly –
                 sulfonation)
                  AMPS
                  Poly(2-acrylamido-
 Dow
                  2-methylpropane
                  sulfonate)
Nafion Membrane
Chemical Structure
Nafion Membrane
on Conduction Process
The water transport
        through Nafion
          Membrane
Water flux due to electroosmotic drag (mol/cm2 s) is: Nw, drag = Iξ(λ)/F.
Where: I is the cell current, ξ(λ) is the electroosmotic drag coefficient at a
given state of membrane hydration λ(=N(H2O)/N(SO3H) and F is the Faraday
constant. This flux acts to dehyddrate the anode side of a cell and to
introduce additional water at the cathode side.
          The buildup of water at the cathode (including the product water
from the cathode reaction) is reduced, in turn, by diffusion back down the
resulting water concentration gradient (and by hydraulic permeation of water
in differentially pressurized cells where the cathode is held at higher overall
pressure). The fluxes (mol/cm2 s) brought about by the latter two
mechanisms within the membrane are:
          Nw,diff = -D(λ)∆c/ ∆z,       Nw,hyd = -khyd(λ)∆P/ ∆z
where D is the diffusion coefficient in the ionomer at water content λ, ∆c/ ∆z
is a water concentration gradient along the z-direction of membrane
thickness, khyd is the hydraulic permeability of the membrane, and ∆P/ ∆z is a
pressure gradient along z.
The water transport
     through Nafion
       Membrane
Many techniques have been
introduced to prevent the
dehydration of the anode
(including the introduction of
liquid water into the anode
and/or cathode, etc. – which,
however, can lead to “flooding”
problems that inhibit mass
transfer).
However, the overall question of
“water management,” including the
issue of drag as a central
component, has been solved to a
very significant extent by the
application of sufficiently thin
PFSA membranes (<100 µm thick) in
PEFCs, combined with humidification
of the anode fuel gas stream.
Water Transport (& Interface
            Reactions)
in Nafion Membrane of the PEM Fuel
               Cell
Material‘s challenges of the SOFC
Solid Oxide Fuel Cell
                                                    SOFC

                Air side = cathode: High oxygen partial pressure

                     O2
                                 H2 + 1/2O2  H2O



                                                  1
                                conductance = σ µ
H2                                                d


     H2O

       Fuel side= anode: H2 + H2O= low oxygen partial pressure
Electromotive Force (EMF)
                                                         SOFC

        Chemical Reactions in 2 separated compartements:
              - Cathode (Oxidation): ½O2 + 2e-  O2-
              - Anode (Reduction): H2 + O  H2O + 2e
                                           2-         -

                                                          ∆G = Free Enthalpie
                                                          z = number of charge carriers
                                                          F = Faraday Constant
                    EMF of a galvanic Cell:               ∆G0= Free Enthalpie in

                      (1) EMF = ∆Gr /-z F                               standart state
                                                          R = Gas Constant




                                                         a ( H 2O )
SOFC:     ½O2 + H2  H2O         (2) ∆G = ∆G0 + RT ln
                                                      a( H 2 )a (O2 ) 0.5

             difference of ∆G between anode und cathode 

                                       RT p ( O2 )
                                                     K
             Nernst Equation:
                                 EMK =    ln
                                       4 F p ( O2 )
                                                    A
Elektrochemische Potential
                                                        SOFC

     Oxygen ions migrate due to an electrical
     and chemical gradient


               ∆µ (O 2− ) = ∆µ (O 2− ) − 2 F ∆ϕ
                %
          Electrochemichal   Chemical      Electrical
              Potential      Potential     Potential

Driving force for the O2- Diffusion through the electrolyte are the
different oxygen partial pressures at the anode and the cathode
side:         ∆µ (O 2− )
                %
                                σi
                                   ∆µ (O 2− )
                                                        ji = ionic current

                         ji = −     %                   σi= ionic conductivity

                                2F
engl. Open Circuit Voltage (OCV)
                                                  SOFC

                                                  σi
∆µ (O ) = ∆µ (O ) − 2 F ∆ϕ
 %    2−            2−
                                           ji = −    ∆µ (O 2− )
                                                      %
                                                  2F

                 What happems in case :

                         ∆µ
                          % (O 2− ) = 0

                             ji = 0
           No current
OCV        Electrical potential difference = chemical potetial
Leistungs-Verluste
                                                                       SOFC



                        Under load decrease of cell voltage
                                   and internal losses

                                 U(I) = OCV - I(RE+ RC+RA) - ηC - ηA

OCV
                                                  (RE+ RC+RA)    Ohmic resistances
cell voltage U(I) [V]




                                                  ηC
                                                       Non ohmic resistances=
                                                  ηA        over voltages

                        cell current I [mA/cm2]
Überspannungen
                                                SOFC

 Over voltages exist at interfaces of
 •     Elektrolyte - Cathode
 •     Elektrolyte - Anode

   Reasons:


   •Kinetic hindrance of the electrochemical reactions
   •Bad adheasion of electrode and electrolyte
   •Diffusion limitations at high current densities
Ohm‘s losses
                                        SOFC

            Past                        Future
                                800nm




                               Kathode           Anode




Reduce electrolyte thickness
Leistungs-Verluste
                                                                                                              SOFC

                                                   OCV                        1
                                                                                                   (RE+ RC+RA)




                                                   cell voltage U(I) [V]
                                                                                                  ηC
                                                                                                  ηA

                                                                                                   2
                                                                                   cell current I [mA/cm2]
                                                                                                                   3


                     (1) Open circuit voltage (OCV), I = 0
                     (2) SOFC under Load  U-I curve
                     (3) Short circuit, Vcell = 0

                                                                                           (2)                          0.5

                                             1.0
                          Zellspannung [V]                                                                              0.4

                                             0.8




                                                                                                                          Leistung [W/cm
                                                                                                                        0.3
                                             0.6

                                                                                                                        0.2
                                             0.4




                                                                                                                                   2
                                                                                                                                        ]
                                                                                                                        0.1
                                             0.2

                         (1)                 0.0
                                                                           900°C
                                                                           in Luft/Wasserstoff                    (3) 0.0
                                               0.0                                0.5          1.0          1.5     2.0
                                                                                                         2
                                                                                        Stromdichte [A/cm ]
How to determine the electrical conductance
                                                                 SOFC




                                              Iinput Umeasured
 Electrical resistance:
             U     ∆L
 R = f (T ) = =
              I A *σ

 Electrical conductivity:          U :    voltage [V]
                                   I :    current [A]
       σ0    Ea                    R :    resistivity [ohm]
 σ=   log( −    )                  ∆L :   distance between both
    T        kT                           inner wires [cm]
                                   A    : sample surface [cm2]
          1                        σ    : conductivity [S/m]
  σ T vs.   ⇒ Ea                   Ea   : activation energy [eV]
          T                        T    : temperature [K]
                                   K    : Boltzmann constant
SOFC




SOFC-Designs
SOFC Design
                                   SOFC


                        Tubular design
              i.e. Siemens-Westinghouse design




                  Segment-type tubular design




                           Planar design
                  i.e. Sulzer Hexis, BMW design
Tubular Design – Siemens-Westinghouse
                                                        SOFC
                                         Why was tubular design
                                         developed in 1960s by
                   cathode               Westinghouse?
               interconnection           • Planar cell: Thermal
                                         expansion mismatch
          cathode                        between ceramic and
            (air)                        support structures leads to
                                         problems with the gas
                                         sealing  tubular design
            air flow      anode (fuel)   was invented

                                         Advantages of tubular
                                         design:
                                         • At cell plenum: depleted air
                                         and fuel react  heat is
                                         generated  incoming
                                         oxidant can be pre-heated.
                                         • No leak-free gas
                                         manifolding needed in this
Tubular Design – Siemens-Westinghouse
                                                     SOFC
                              To overcome problems new
cathode                       Siemens-Westinghouse „HPD-
  (air)
                              SOFC“ design:

                              New: Flat cathode tube with
                              ligaments

 anode (fuel)   electrolyte    Advantages of HPD-SOFC:
                               • Ligaments within cathode  short
                               current pathways  decrease of
                               ohmic resistance
                               • High packaging density of cells
                              Siemens-Westinghouse shifted from
                               compared to tubular design
                              basic technology to cost reduction and
                              scale up.

                              Power output: Some 100 kW can be
                              produced.
Planar Design – Sulzer Hexis
                                                   SOFC

                   interconnect      Advantages of planar
                     cathode (air)
                                     design:
                                     • Planer cell design of bipolar
                    electrolyte
                                     plates  easy stacking  no
                    anode (fuel)
                                     long current pathways
                                     • Low-cost fabrication
                                     methods, i.e. Screen printing
                                     and tape casting can be
                                     used.

                                     Drawback of tubular
                                     design:
                                     • Life time of the cells 3000-
                                     7000h  needs to be
                                     improved by optimization of
                                     mechanical and
                                     electrochemical stability of
                                     used materials.
Planar Design – BMW
                                                         SOFC
     Air channel


                                 bipolar plate
                        Cathode current collector
                               cathode
                              electrolyte
                                 anode
                           porous metallic substrate
                        Fe-26Cr-(Mo, Ti, Mn, Y2O3) alloy
                               bipolar plate


    Fuel channel                             Application
                                             Batterie replacement in the
                   20-50 µm   Plasma spray   BMW cars of the 7-series.
                   5-20 µm    Plasma spray

                   15-50 µm   Plasma spray   Power output: 135 kW is
                                             aimed.
Current Initiatives
Automotive Industry

   Most of the major auto manufacturers have
   fuel cell vehicle (FCV) projects currently
   under way, which involve all sorts of fuel
   cells and hybrid combinations of
   conventional combustion, fuel reformers and
   battery power.

   Considered to be the first gasoline powered
   fuel cell vehicle is the H20 by GM:
                             GMC S-10 (2001)
                             fuel cell battery hybr
                             low sulfur gasoline fue
                             25 kW PEM
                             40 mpg
                             112 km/h top speed




                  Figure 9
Current Initiatives
Automotive Industry


                          Fords Adavanced
                          Focus FCV (2002)
                          fuel cell battery
                          hybrid
                          85 kW PEM
                          ~50 mpg
                          (equivalent)
                          4 kg of
                          compressed H2 @
              Figure 10
                          5000 psi


    Approximately 40
    fleet vehicles
    are planned as a
    market
    introduction for
    Germany,                 Figure 11
    Vancouver and
    California for
Current Initiatives
 Automotive Industry

Chrysler NECAR 5 (introduced in 2000)




                              85 kW PEM
                              fuel cell
                              methanol fuel
                              reformer
                              required
                              150 km/h top
                              speed


                  Figure 12

this model completed a California to Washing
permit for Japanese roads
Current Initiatives
Automotive Industry

Mitsubishi Grandis FCV minivan




                                 fuel cell /
                                 battery
                                 hybrid
                                 68 kW PEM
                                 compressed
                                 hydrogen
                                 fuel
                                 140 km/h top
                 Figure 13
                                 speed
         Plans are to launch as a
         production vehicle for Europe in
         2004.
Current Initiatives
Stationary Power Supply Units
   More than 2500 stationary fuel cell
   systems have been installed all over
   the world - in hospitals, nursing homes,
   hotels, office buildings, schools,
   utility power plants, and an airport
   terminal, providing primary power or
   backup. In large-scale building
   systems, fuel cells can reduce
   facility energy service costs by 20%
   to 40% over conventional energy
   service.




                          Figure 14

   A fuel cell installed at McDonald’s
   restaurant, Long Island Power
   Authority to install 45 more fuel
Current Initiatives
Residential Power Units

   There are few residential fuel cell
   power units on the market but many
   designs are undergoing testing and
   should be available within the next
   few years. The major technical
   difficulty in producing residential fuel
   cells is that they must be safe to
                            Residential
   install in a home, and be easily
                            fuel cells
   maintained by the average homeowner.
                            are typically
                            the size of a
                            large deep
                            freezer or
                            furnace, such
                            as the Plug
                            Power 7000
              Figure 15     unit shown
   If a power company was here, and cost
                             to install a
                            $5000 - $10
   residential fuel cell power unit in a
                            000.
   home, it would have to charge the
   homeowner at least 40 ¢/kWh to be
Future

 “...projections made by car companies
 themselves and energy and automotive
 experts concur that around 2010, and
 perhaps earlier, car manufacturers
 will have mass production capabilities
 for fuel cell vehicles, signifying the
 time they would be economically
 available to the average consumer.”
 Auto Companies on Fuel Cells, Brian Walsh and Peter
 A commercially available fuel cell
 Moores, posted on www.fuelcells.org
 power plant would cost about
 $3000/kW, but would have to drop
 below $1500/kW to achieve widespread
 market penetration.
 http://www.fuelcells.org/fcfaqs.htm
 Technical and engineering innovations
 are continually lowering the capital
 cost of a fuel cell unit as well as
 the operating costs, but it is expected
 that mass production will be of the
 greatest impact to affordability.
Future



         internal
         combustion
         obsolete?
         solve pollution
         problems?
         common in homes?
         better designs?
         higher
         efficiencies?
         cheaper
         electricity?
         reduced
         petroleum
         dependency?
References

 (1) FAQ section, fuelcells.org
 (2) Long Island Power Authority press release: Plug Power
 Fuel Cell Installed at McDonald’s Restaurant, LIPA to
     Install 45 More Fuel Cells Across Long Island, Including Homes,

 http://www.lipower.org/newscenter/pr/2003/feb26.fuelce
 ll.html
 (3) Proceedings of the 2000 DOE Hydrogen Program Review:
 Analysis of Residential Fuel Cell Systems & PNGV
     Fuel Cell Vehicles,
 http://www.eere.energy.gov/hydrogenandfuelcells/pdfs/2
 8890mm.pdf

 Figures
 1, 3   http://hyperphysics.phy-
 astr.gsu.edu/hbase/thermo/electrol.html
 4 – 8 http://fuelcells.si.edu/basics.htm
 10
 http://www.moteurnature.com/zvisu/2003/focus_fcv/focus
 _fcv.jpg
 11
 http://www.granitestatecleancities.org/images/Hydrogen_F
 uel_Cell_Engine.jpg
 12
 http://www.in.gr/auto/parousiaseis/foto_big/Necar07_2883.
 jpg
 13
 http://www3.caradisiac.com/media/images/le_mag/mag138/o
 eil_mitsubishi_grandis_big.jpg
 14
 http://www.lipower.org/newscenter/pr/2003/feb26.fuelce

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Fuel cell

  • 2. Topics 1. A Very Brief History 2. Electrolysis 3. Fuel Cell Basics - Electrolysis in Reverse - Thermodynamics - Components - Putting It Together 4. Types of Fuel Cells - Alkali - Molten Carbonate - Phosphoric Acid - Proton Exchange Membrane - Solid Oxide 5. Benefits 6. Current Initiatives - Automotive Industry - Stationary Power Supply Units - Residential Power Units 7. Future
  • 3. A Very Brief History Considered a curiosity in the 1800’s. The first fuel cell was built in 1839 by Sir William Grove, a lawyer and gentleman scientist. Serious interest in the fuel cell as a practical generator did not begin until the 1960's, when the U.S. space program chose fuel cells over riskier nuclear power and more expensive solar energy. Fuel cells furnished power for the Gemini and Apollo spacecraft, and still provide electricity and water for the space shuttle.(1)
  • 4. s this have to do with fuel cells?” By providing energy from a battery, water (H2O) can be dissociated into the diatomic molecules of hydrogen (H2) and oxygen (O2). Figure 1
  • 5. Basics lectrolysis in reverse.” The familiar process of electrolysis requires work to proceed, if the process is put in reverse, it should be able to do work for us spontaneously. The most basic “black box” representation of a fuel cell in action is shown work below: Figure 2 O2 fuel H2O H2 cell heat
  • 6. uel Cell Basics hermodynamics H2(g) + ½O2(g) H2O(l) Other gases in the fuel and air inputs (such as N2 and CO2) may be present, but as they are not involved in the electrochemical reaction, they do not need to be considered in the energy 1 Thermodynamic properties at 1Atm and 29 calculations. H2 O2 H2O (l) Enthalpy 0 0 -285.83 (H) kJ/mol Entropy 130.68 205.14 69.91 (S) J/mol·K J/mol·K J/mol·K Enthalpy is defined as the energy of a system plus the work needed to make room for it in an environment with constant pressure. Entropy can be considered as the measure of disorganization of a
  • 7. uel Cell Basics hermodynamics f the chemical reaction using Hess’ Law: ΔHreaction = ΣHproducts – ΣHreactants = (1mol)(-285.83 kJ/mol) – (0) = -285.83 kJ py of chemical reaction: ΣSproducts – ΣSreactants mol)(69.91 J/mol·K)] – [(1mol)(130.68 /mol·K) + (½mol)(2 J 63.34 /K J gained by the system: = TΔS = (298K)(-163.34 J/K) = -48.7 kJ
  • 8. uel Cell Basics hermodynamics free energy is then calculated by: ΔH – TΔS = (-285.83 kJ) – (-48.7 kJ) = -237 kJ done on the reaction, assuming reversibility a W = ΔG one on the reaction by the environment is: W = ΔG = -237 kJ sferred to the reaction by the environment ΔQ = TΔS = -48.7 kJ More simply stated: The chemical reaction can do 237 kJ of work and produces 48.7 kJ of heat to the environment.
  • 9. Fuel Cell Basics Components Anode: Where the fuel reacts or "oxidizes", and releases electrons. Cathode: Where oxygen (usually from the air) "reduction" occurs. Electrolyte: A chemical compound that conducts ions from one electrode to the other inside a fuel cell. Catalyst: A substance that causes or speeds a chemical reaction without itself being affected. Cogeneration: The use of waste heat to generate electricity. Harnessing otherwise wasted heat boosts the efficiency of power-generating systems. Reformer: A device that extracts pure hydrogen from
  • 10. l Cell Basics tting it together. Figure 3
  • 11. Types of Fuel Cells The five most common types: •Alkali •Molten Carbonate •Phosphoric Acid •Proton Exchange Membrane •Solid Oxide
  • 12. Types of Fuel Cells SOFC Vorteil: Keine aufwendige Brenngas-Aufbereitung Nachteil: Hohe Betriebstemperaturen = Hohe System-Kosten  Starke Material-Beanspruchung
  • 13. Alkali Fuel Cell compressed hydrogen and oxygen fuel potassium hydroxide (KOH) electrolyte ~70% efficiency Figure 4 150˚C - 200˚C operating temp. 300W to 5kW requires pure hydrogen output fuel and platinum catylist → ($$) liquid filled container → corrosive leaks
  • 14. Molten Carbonate Fuel Cell (MCFC) carbonate salt electrolyte 60 – 80% efficiency ~650˚C operating temp. cheap nickel electrode Figure 5 catylist up to 2 MW The operating temperature is up constructed, too hot for manyto 100 MW designs applications. exist carbonate ions are consumed in the reaction → inject CO2 to compensate
  • 15. hosphoric Acid Fuel Cell (PAFC) phosphoric acid electrolyte 40 – 80% efficiency 150˚C - 200˚C operating temp 11 MW units have been tested Figure 6 sulphur free gasoline can be The electrolyte a fuel used as is very corrosive Platinum catalyst is very
  • 16. Proton Exchange Membrane (PEM) thin permeable polymer sheet electrolyte 40 – 50% efficiency 50 – 250 kW 80˚C operating Figure 7 temperature electrolyte will not leak or crack temperature good for home or vehicle use
  • 17. Solid Oxide Fuel Cell (SOFC) hard ceramic oxide electrolyte ~60% efficient ~1000˚C operating temperature Figure 8 cells output high temp / catalyst can 100 kW up to extract the hydrogen from the fuel at the electrode high temp allows for power generation using the heat, but limits use
  • 18. Benefits Efficient: in theory and in practice Portable: modular units Reliable: few moving parts to wear out or break Fuel Flexible: With a fuel reformer, fuels such as natural gas, ethanol, methanol, propane, gasoline, diesel, landfill gas,wastewater, treatment digester gas, or even ammonia can be used Environmental: produces heat and water (less than combustion in both
  • 19. terial‘s challenges of the PEM Fuel Cel
  • 20. Review of Membrane (Nafion) Properties • Chemical Structure • Proton Conduction Process • Water Transport and Interface Reactions 11/25/12 Fuel Cell Fundamentals 20
  • 21. cal structures of some membrane mater PSSA PESA poly(sty (Polyepoxy- rene-co- succinic Acid) styrenes ulfonic acid) (PSSA) α,β,β- Trifluorosty Nafion,TM rene grafted Membrane C onto poly(tetrafl uoro- ethylene) with post- Poly – sulfonation) AMPS Poly(2-acrylamido- Dow 2-methylpropane sulfonate)
  • 24. The water transport through Nafion Membrane Water flux due to electroosmotic drag (mol/cm2 s) is: Nw, drag = Iξ(λ)/F. Where: I is the cell current, ξ(λ) is the electroosmotic drag coefficient at a given state of membrane hydration λ(=N(H2O)/N(SO3H) and F is the Faraday constant. This flux acts to dehyddrate the anode side of a cell and to introduce additional water at the cathode side. The buildup of water at the cathode (including the product water from the cathode reaction) is reduced, in turn, by diffusion back down the resulting water concentration gradient (and by hydraulic permeation of water in differentially pressurized cells where the cathode is held at higher overall pressure). The fluxes (mol/cm2 s) brought about by the latter two mechanisms within the membrane are: Nw,diff = -D(λ)∆c/ ∆z, Nw,hyd = -khyd(λ)∆P/ ∆z where D is the diffusion coefficient in the ionomer at water content λ, ∆c/ ∆z is a water concentration gradient along the z-direction of membrane thickness, khyd is the hydraulic permeability of the membrane, and ∆P/ ∆z is a pressure gradient along z.
  • 25. The water transport through Nafion Membrane Many techniques have been introduced to prevent the dehydration of the anode (including the introduction of liquid water into the anode and/or cathode, etc. – which, however, can lead to “flooding” problems that inhibit mass transfer). However, the overall question of “water management,” including the issue of drag as a central component, has been solved to a very significant extent by the application of sufficiently thin PFSA membranes (<100 µm thick) in PEFCs, combined with humidification of the anode fuel gas stream.
  • 26. Water Transport (& Interface Reactions) in Nafion Membrane of the PEM Fuel Cell
  • 28. Solid Oxide Fuel Cell SOFC Air side = cathode: High oxygen partial pressure O2 H2 + 1/2O2  H2O 1 conductance = σ µ H2 d H2O Fuel side= anode: H2 + H2O= low oxygen partial pressure
  • 29. Electromotive Force (EMF) SOFC Chemical Reactions in 2 separated compartements: - Cathode (Oxidation): ½O2 + 2e-  O2- - Anode (Reduction): H2 + O  H2O + 2e 2- - ∆G = Free Enthalpie z = number of charge carriers F = Faraday Constant EMF of a galvanic Cell: ∆G0= Free Enthalpie in (1) EMF = ∆Gr /-z F standart state R = Gas Constant a ( H 2O ) SOFC: ½O2 + H2  H2O (2) ∆G = ∆G0 + RT ln a( H 2 )a (O2 ) 0.5 difference of ∆G between anode und cathode  RT p ( O2 ) K Nernst Equation: EMK = ln 4 F p ( O2 ) A
  • 30. Elektrochemische Potential SOFC Oxygen ions migrate due to an electrical and chemical gradient ∆µ (O 2− ) = ∆µ (O 2− ) − 2 F ∆ϕ % Electrochemichal Chemical Electrical Potential Potential Potential Driving force for the O2- Diffusion through the electrolyte are the different oxygen partial pressures at the anode and the cathode side: ∆µ (O 2− ) % σi ∆µ (O 2− ) ji = ionic current ji = − % σi= ionic conductivity 2F
  • 31. engl. Open Circuit Voltage (OCV) SOFC σi ∆µ (O ) = ∆µ (O ) − 2 F ∆ϕ % 2− 2− ji = − ∆µ (O 2− ) % 2F What happems in case : ∆µ % (O 2− ) = 0 ji = 0 No current OCV Electrical potential difference = chemical potetial
  • 32. Leistungs-Verluste SOFC Under load decrease of cell voltage and internal losses U(I) = OCV - I(RE+ RC+RA) - ηC - ηA OCV (RE+ RC+RA) Ohmic resistances cell voltage U(I) [V] ηC Non ohmic resistances= ηA over voltages cell current I [mA/cm2]
  • 33. Überspannungen SOFC Over voltages exist at interfaces of • Elektrolyte - Cathode • Elektrolyte - Anode Reasons: •Kinetic hindrance of the electrochemical reactions •Bad adheasion of electrode and electrolyte •Diffusion limitations at high current densities
  • 34. Ohm‘s losses SOFC Past Future 800nm Kathode Anode Reduce electrolyte thickness
  • 35. Leistungs-Verluste SOFC OCV 1 (RE+ RC+RA) cell voltage U(I) [V] ηC ηA 2 cell current I [mA/cm2] 3 (1) Open circuit voltage (OCV), I = 0 (2) SOFC under Load  U-I curve (3) Short circuit, Vcell = 0 (2) 0.5 1.0 Zellspannung [V] 0.4 0.8 Leistung [W/cm 0.3 0.6 0.2 0.4 2 ] 0.1 0.2 (1) 0.0 900°C in Luft/Wasserstoff (3) 0.0 0.0 0.5 1.0 1.5 2.0 2 Stromdichte [A/cm ]
  • 36. How to determine the electrical conductance SOFC Iinput Umeasured Electrical resistance: U ∆L R = f (T ) = = I A *σ Electrical conductivity: U : voltage [V] I : current [A] σ0 Ea R : resistivity [ohm] σ= log( − ) ∆L : distance between both T kT inner wires [cm] A : sample surface [cm2] 1 σ : conductivity [S/m] σ T vs. ⇒ Ea Ea : activation energy [eV] T T : temperature [K] K : Boltzmann constant
  • 38. SOFC Design SOFC Tubular design i.e. Siemens-Westinghouse design Segment-type tubular design Planar design i.e. Sulzer Hexis, BMW design
  • 39. Tubular Design – Siemens-Westinghouse SOFC Why was tubular design developed in 1960s by cathode Westinghouse? interconnection • Planar cell: Thermal expansion mismatch cathode between ceramic and (air) support structures leads to problems with the gas sealing  tubular design air flow anode (fuel) was invented Advantages of tubular design: • At cell plenum: depleted air and fuel react  heat is generated  incoming oxidant can be pre-heated. • No leak-free gas manifolding needed in this
  • 40. Tubular Design – Siemens-Westinghouse SOFC To overcome problems new cathode Siemens-Westinghouse „HPD- (air) SOFC“ design: New: Flat cathode tube with ligaments anode (fuel) electrolyte Advantages of HPD-SOFC: • Ligaments within cathode  short current pathways  decrease of ohmic resistance • High packaging density of cells Siemens-Westinghouse shifted from compared to tubular design basic technology to cost reduction and scale up. Power output: Some 100 kW can be produced.
  • 41. Planar Design – Sulzer Hexis SOFC interconnect Advantages of planar cathode (air) design: • Planer cell design of bipolar electrolyte plates  easy stacking  no anode (fuel) long current pathways • Low-cost fabrication methods, i.e. Screen printing and tape casting can be used. Drawback of tubular design: • Life time of the cells 3000- 7000h  needs to be improved by optimization of mechanical and electrochemical stability of used materials.
  • 42. Planar Design – BMW SOFC Air channel bipolar plate Cathode current collector cathode electrolyte anode porous metallic substrate Fe-26Cr-(Mo, Ti, Mn, Y2O3) alloy bipolar plate Fuel channel Application Batterie replacement in the 20-50 µm Plasma spray BMW cars of the 7-series. 5-20 µm Plasma spray 15-50 µm Plasma spray Power output: 135 kW is aimed.
  • 43. Current Initiatives Automotive Industry Most of the major auto manufacturers have fuel cell vehicle (FCV) projects currently under way, which involve all sorts of fuel cells and hybrid combinations of conventional combustion, fuel reformers and battery power. Considered to be the first gasoline powered fuel cell vehicle is the H20 by GM: GMC S-10 (2001) fuel cell battery hybr low sulfur gasoline fue 25 kW PEM 40 mpg 112 km/h top speed Figure 9
  • 44. Current Initiatives Automotive Industry Fords Adavanced Focus FCV (2002) fuel cell battery hybrid 85 kW PEM ~50 mpg (equivalent) 4 kg of compressed H2 @ Figure 10 5000 psi Approximately 40 fleet vehicles are planned as a market introduction for Germany, Figure 11 Vancouver and California for
  • 45. Current Initiatives Automotive Industry Chrysler NECAR 5 (introduced in 2000) 85 kW PEM fuel cell methanol fuel reformer required 150 km/h top speed Figure 12 this model completed a California to Washing permit for Japanese roads
  • 46. Current Initiatives Automotive Industry Mitsubishi Grandis FCV minivan fuel cell / battery hybrid 68 kW PEM compressed hydrogen fuel 140 km/h top Figure 13 speed Plans are to launch as a production vehicle for Europe in 2004.
  • 47. Current Initiatives Stationary Power Supply Units More than 2500 stationary fuel cell systems have been installed all over the world - in hospitals, nursing homes, hotels, office buildings, schools, utility power plants, and an airport terminal, providing primary power or backup. In large-scale building systems, fuel cells can reduce facility energy service costs by 20% to 40% over conventional energy service. Figure 14 A fuel cell installed at McDonald’s restaurant, Long Island Power Authority to install 45 more fuel
  • 48. Current Initiatives Residential Power Units There are few residential fuel cell power units on the market but many designs are undergoing testing and should be available within the next few years. The major technical difficulty in producing residential fuel cells is that they must be safe to Residential install in a home, and be easily fuel cells maintained by the average homeowner. are typically the size of a large deep freezer or furnace, such as the Plug Power 7000 Figure 15 unit shown If a power company was here, and cost to install a $5000 - $10 residential fuel cell power unit in a 000. home, it would have to charge the homeowner at least 40 ¢/kWh to be
  • 49. Future “...projections made by car companies themselves and energy and automotive experts concur that around 2010, and perhaps earlier, car manufacturers will have mass production capabilities for fuel cell vehicles, signifying the time they would be economically available to the average consumer.” Auto Companies on Fuel Cells, Brian Walsh and Peter A commercially available fuel cell Moores, posted on www.fuelcells.org power plant would cost about $3000/kW, but would have to drop below $1500/kW to achieve widespread market penetration. http://www.fuelcells.org/fcfaqs.htm Technical and engineering innovations are continually lowering the capital cost of a fuel cell unit as well as the operating costs, but it is expected that mass production will be of the greatest impact to affordability.
  • 50. Future internal combustion obsolete? solve pollution problems? common in homes? better designs? higher efficiencies? cheaper electricity? reduced petroleum dependency?
  • 51. References (1) FAQ section, fuelcells.org (2) Long Island Power Authority press release: Plug Power Fuel Cell Installed at McDonald’s Restaurant, LIPA to Install 45 More Fuel Cells Across Long Island, Including Homes, http://www.lipower.org/newscenter/pr/2003/feb26.fuelce ll.html (3) Proceedings of the 2000 DOE Hydrogen Program Review: Analysis of Residential Fuel Cell Systems & PNGV Fuel Cell Vehicles, http://www.eere.energy.gov/hydrogenandfuelcells/pdfs/2 8890mm.pdf Figures 1, 3 http://hyperphysics.phy- astr.gsu.edu/hbase/thermo/electrol.html 4 – 8 http://fuelcells.si.edu/basics.htm 10 http://www.moteurnature.com/zvisu/2003/focus_fcv/focus _fcv.jpg 11 http://www.granitestatecleancities.org/images/Hydrogen_F uel_Cell_Engine.jpg 12 http://www.in.gr/auto/parousiaseis/foto_big/Necar07_2883. jpg 13 http://www3.caradisiac.com/media/images/le_mag/mag138/o eil_mitsubishi_grandis_big.jpg 14 http://www.lipower.org/newscenter/pr/2003/feb26.fuelce

Notas do Editor

  1. PE (polymer electrolyte) FCs utilize a polymeric electrolyte. Nafion TM , a perfluorinated polymer with sidechains terminating in sulfonic acid moieties, and its close perfluorosulfonic acid (PFSA) relatives, are currently the state-of-the-art in membranes for PEFCs, satisfying an array of requirements for effective, long-term use in fuel cells. They combine well the important requirements for a membrane in a PEFC, namely: high protonic conductivity, high chemical stability under typical operating conditions, and low gas permeabilities. Typically, thickness of PFSA membranes for PEFCs range between 50 and 175  m. The main source of PFSA membranes is DuPont (USA), where these membranes were invented in the 1960’s and made into a commercial product for the chlor-alkali industry. Other sources of developmental PFSA membranes have been Dow Chemical (USA), Asahi Glass (Japan), and Asahi Chemicals (Japan).
  2. The most important property of ionomeric membranes employed in polymer electrolyte fuel cells is the high protonic conductivity they provide at the current densities typically required in PEFCs. The specific conductivity of fully hydrated PFSA (immersed) membranes is about 0.1 S/cm at room temperature, and about 0.15 S/cm at the typical cell operation temperature of 80 ºC. These high protonic conductivities provide the basis for the high power densities achievable in PEFCs. The dependence of proton mobility in PFSA membranes on water content is, however, quite critical, and demands effective cell and stack design to maintain a high level of water through the thickness of the membrane for the complete range of dynamic operation.
  3. The number of water molecules carried through the membrane per proton is a central factor in determinating the water profiles in the membrane of an operating PEFC. There is an important difference between the electroosmotic drag coefficient,  (  ), a characteristic of an ionomeric membrane with fixed water content and flat water profile, and the net water flux through an operating fuel cell. The latter is the resultant of several water transport modes in the cell. For fully hydrated and (immersed) Nafion 1100 membranes, a drag coefficient of 2.5 H 2 O/SO 3 H is measured, whereas for a membrane equilibrated with vapor-phase water the drag coefficient is close to 1.0 H 2 O/H + over a wide range of water contents. The lack of dependence of the drag coefficient on membrane nanostructure suggests that the drag coefficient is determined by the basic elements of the proton transport process; I.e.; via the hydronium ion or complex..