Vous êtes sur la page 1sur 35

Fuel Cells: Fundamentals,

Types, and Fuel Storage


Carly Reed
History
 1839
 Sir William Grove – “Gas Voltaic Battery”
 Two Pt strips surrounded by closed tubes containing H2 and O2 in
dilute H2SO4
 Produced H2O and electricity, but very inconsistent
 1889
 Term “fuel cell” coined by Ludwig Mond
 1902
 J.H. Reid – first to use NaOH in place of acid electrolyte
 1952
 Alkaline fuel cell developed by Francis Bacon - later used in
Apollo space missions
 1960-1965
 First successful application achieved with space technology
during NASA Apollo space program
Interest in Fuel Cells
 Development of fuel cells has lagged behind:
 Higher cost
 Materials problems
 Operational inadequacies
 During the 20th century as need for electricity increased,
primary fuel sources were still so abundant
 Currently, with a desire to decrease:
 Dependence on fossil fuels and foreign oil supplies
 Emissions of NO2, NO3, SO2, CO2 and their effects on
ozone levels, acid rain, and global warming
 Fuel cells with renewable energy sources
 High electrical efficiency
Fuel Cells: Components and Functions
 MEA = membrane
electrode assembly
(electrolyte and
electrodes)
 Anode = fuel
electrode; electronic
conductor and
catalyst
 Cathode = air
electrode; electronic
conductor and
catalyst
 Electrolyte =
oxygen-ion
conductor, electron
inhibitor
Fuel Cells: Types
 Fuel cell types can be divided in two ways:
 Low v. High Temperature
 Electrolyte Types
 Alkaline

 Polymer Electrolyte Membrane (Proton


Exchange Membrane)
 Direct Methanol

 Phosphoric Acid

 Molten Carbonate

 Solid Oxide
Alkaline Fuel Cell
 First AFC developed by Francis Bacon (1930s)
 In the Apollo missions
 85% KOH
 200-230oC
 Ni anode and NiO cathode
 Acidic fuel cells had been used, but alkaline had
faster oxygen reduction kinetics
 Fuel cells were used to provide electricity, cool the
ship, and provide potable water
Alkaline Fuel Cell

Anode: C/Pt or Cathode: C/Pt


C/Raney Ni/Pt r.t.-80oC

H2 O2

H2O
1 A/cm2 at 0.7 V
OH-
35%
KOH

O2 + H2O + 2e-  HO2- + OH-


H2 + 2OH-  H2O + 2e- HO2- + H2O + 2e- 3OH-
Alkaline Fuel Cell
 Advantages:
 Low cost electrolyte solution (KOH 30-35%)
 Non-noble catalyst withstand basic conditions
 O2 kinetics faster in alkaline solution
 OH- v. H2O
Alkaline Fuel Cell
 Problem Areas and Solutions:
 Catalysts
 Pt – expensive
 Raney Ni – wettability; chemical composition
- Y. Kiros, Pt/Co alloys; similar ability to reduce O2
- E.D. Geeter et. al testing Ag and Co to replace Pt
 Pure gases only
 CO32- builds up in electrolyte and clogs pores
 CO2 + 2OH-  CO32- + H2O
 Fe sponges can be inserted to absorb CO2
 Circling electrolyte can slow build up of CO32-
Polymer Electrolyte Membrane Fuel Cell
 Used by NASA in Gemini mission
 employed polystyrene sulfonate (PSS) polymer (unstable)
 Nafion – developed by Dupont (1960s)
 Currently used in most PEMs
 Polytetrafluoroethylene (PTFE) backbone with a
perfluorinated side chain that is terminated with a sulfonic
acid group
 More stable, higher conductivity
 The Dow Chemical Company
 Developed a polymer similar to Nafion
 Shorter side chain and only one ether oxygen

 No longer available
Polymer Electrolyte Membrane Fuel Cell
 Chemical structure of Nafion

 Hydration of membrane dissociates proton of


acid group
 Solvated protons are mobile in polymer and
provide conductivity
Polymer Electrolyte Membrane Fuel Cell

Anode: C/Pt 85-105oC Cathode: C/Pt

H2 O2
H+

H2O
NAFION

H2  2H+ + 2e- O2 + 2H+ + 2e-  H2O2


H2O2 + 2H+ + 2e-  H2O
1 A/cm2 at 0.7 V
Polymer Electrolyte Membrane Fuel Cell
 Advantages:
 Nonvolatile membrane
 CO2 rejecting electrolyte
 few material problems
 Problems:
 Slow O2 kinetics
 Hydration of membrane is difficult (30-60%)
 Formed at cathode, but difficult to keep in
membrane
 Too little = dehydration and loss of ion transport

 Solutions

- Humidify gases
- Impregnate Nafion with SiO2 or TiO2
Direct Methanol Fuel Cell

Anode: Pt/Ru/C 85-105oC Cathode: Pt/C

N
A
400 mA/cm2 at 0.5V F
at 60oC I
O
N

O2 + 2H+ + 2e-  H2O2


CH3OH + H2O CO2 + 6H+ + 6e- H2O2 + 2H+ + 2e-  H2O
Direct Methanol Fuel Cell
 Pt catalyst have highest activity for MeOH
oxidation thus far
 Ru enhances MeOH catalytic activity
OH- forms at lower voltage
 CO blocks sites on Pt surface, Ru helps oxidize
to CO2
Direct Methanol Membrane Fuel Cell
 Advantages:
 Direct fuel conversion – no reformer needed, all positive
aspects of PEMFC
 CH3OH – natural gas or biomass
 Existing infastructure for transporting petrol can be
converted to MeOH

 Problems:
 High catalyst loading (1-3mg/cm2 v. 0.1-0.3 mg/cm2)
 CH3OH hazardous
 Low efficiency (MeOH crossover – lowers potential)
Direct Methanol Membrane Fuel Cell
 Solving the Crossover Dilemma
 Alter thickness of polymer membrane
 Thinner = decreases ion flow resistance
 Thicker = decreases MeOH crossover
 Cs+ doped membranes
 Tricolli, University of Pisa, 1998
 Lower affinity for H2O
 MeOH tolerant cathodes
 Mo2Ru5S5 – N. Alonso-Vante, O. Solorza-Feria
 Higher oxygen reduction activity in presence of
MeOH
 (Fe-TMPP)2O – S. Gupta, Case Western, 1997
 High oxygen reduction, insensitive to MeOH
Phosphoric Acid Fuel Cell
 Most commercially developed fuel cell
 Mainly used in stationary power plants
 More than 500 PAFC have been installed and tested
around the world
 Most influential developers of PAFC
 UTC Fuel Cells, Toshiba, and Fuji Electric
Phosphoric Acid Fuel Cell
Anode: Pt/C 200oC Cathode: Pt/C

CH4 or H2 O2

H+
Si matrix
PTFE binding
separator

100% H2O
H2PO4

H2 – 2e- = 2H+ O2 + 4H+ + 4e-  2H2O


Phosphoric Acid Fuel Cell

 Advantages:
 H2O rejecting electrolyte
 high temps favor H2O2 decomposition
 O2 + H2O +2e-  H2O2
 Stable H2O2 lowers cell voltage and corrodes electrode
 Problems:
 O2 kinetic hindered
 CO catalyst poison at anode
 H2 only suitable fuel
 low conducting electrolyte
Molten Carbonate Fuel Carbonate
 Developed in the mid-20th century
 Developed because all carbonaceous fuel
produce CO2
 Using CO32- electrolyte eliminates need to
regulate CO32- build up
Molten Carbonate Fuel Carbonate

Anode: Ni/Al or Ni/Cr 580-700oC Cathode: NiO

H2, CxH2x+2 O2, CO2

CO32-
LiAlO3 used to
150 mA/cm2 at
0.8 V at 600oC support
electrolyte
Li2CO3
and
Na2CO3

CH4 + 2H2O  4H2 + CO2 + 4e-


O2 + 2CO2 + 4e-  2CO32-
H2 +CO32-  H2O + CO2 + 2e-
Molten Carbonate Fuel Cell
 Advantages:
 Higher efficiency (v. PEMFC and PAFC) (50-70%)
 Internal reforming (H2 or CH4)
 No noble metal catalyst (High T increases O2 kinetics)
 No negative effects from CO or CO2

 Problems:
 Materials resistant to degradation at high T
 Ni, Fe, Co steel alloys better than SS
 NiO at cathode leeches into CO32- reducing efficiency
or crossing over causing short circuiting
 Dope electrode and electrolyte with Mg
 Kucera and Myles (LiFeO2 or Li2MnO3 stabilize)
Solid Oxide Fuel Cell
 1899 Nernst observed conduction in
various types of stabilized zirconia at T >
600oC
 1937 Baur and Preis demonstrated a fuel
cell based on zirconium oxide
Solid Oxide Fuel Cell
Anode = NiO-YSZ cermet 800-1000oC Cathode = La1-xSrxMnO3

H2, CxH2x+2 O2

O2- Interconnector
1mA at 0.7V material = Mg
or Sr doped
lanthanum
Y doped chromate
ZrO2

H2 + O2-  H2O + 2e- OR O2 + 2e-  2O2-


CH4 + 4O2-  2H2O + CO2 + 8e-
Solid Oxide Fuel Cell
 Advantages:
 Solid electrolyte eliminates leaks
 H2O management, catalyst flooding, slow O2
kinetic are not problematic
 CO and CO2 are not problematic
 Internal reforming - almost any hydrocarbon or
hydrogen fuel
 Problems:
 Severe material constraints due to high T
 Stainless steal at lower temperatures
 Alloyed metal or Lanthanum Chromite material
Fuel Cell Stacks
 Individual Cell
0.5-1.0V
 Increase system voltage
by stacking cells
 Cells’ voltages are added
in series; current constant
over all cells
 Interconnects act as flow
channels for gases and
connects anode of one cell
to cathode of the next.
Must be gas tight and
made from conducting
material.
Applications
Fuel cells are being developed for
application in:
 Stationary power plants
 Automobiles
 Portable electronics

To enable mobile power source, fuel must


also be portable
Hydrogen Storage: Gas and Liquid
 Pure H2 gas
 eliminates reformer
 eliminates risk of catalyst degradation from
impure fuel
 space limitations
 explosive
 Liquid H2
 highest energy density of any H2 storage
method
 limited by boiling point (-253oC)
 1-2% evaporation each day
Hydrogen Storage: Metal Hydrides
 A metal alloy exposed to H2  MH
 Upon heating H2 released
 150-700 cm3/g
 “Powerballs” (Powerball Technology Inc)
 NaH pellets coated in waterproof skin
Hydrogen Storage: Ammonia Borane

 S. Shore (1955)
 Ammonia Borane H3NBH3
 Advantages over MH
 Air and Water Stable
 Heat to release H2

 19% wt. storage of H2

 Developed by Millennium Cell


Hydrogen Storage

 Carbon Nanotubes, Glass Microspheres, Zeolites


 H2 can permeate at elevated P and T
 At ambient T and P, H2 is trapped in structure
 Heating releases H2
Hydrogen Storage: Zeolites
 D. Fraenkel (1977)
 Tested by Fritz and Ernst (1995)
 Cs3Na9(AlO2SiO2)12
 Loaded at 2.5-10.0 MPa at 573oC
 9.2cm3/g
Fuel Reformation
 Catalytic steam reformation
 Light hydrocarbons and alcohols (highest yield reforming
process)
 Endothermic
 Partial oxidation
 Heavier hydrocarbons
 Exothermic (Combustion)
 Autothermal reforming
 Reformed fuel must be treated to remove CO
References
 Carrette, Linds. Friedrich, K. Stimming, Ulrich. Fuel Cells: Principles, Types,
Fuels, and Applications. Chemphyschem 2000, 1, 162-193
 Winter, Martin. Brodd, Ralph. What Are Batteries, Fuel Cells, and
Supercapacitors? Chem. Rev. 2004, 104, 4245-42969
 Kee, Robert J. Zhu, Huayang. Goodwin, David G. Solid-oxide fuel cells with
hydrocarbon fuels. Proceedings of the Combustion Institute 2005, 2379-2404
 Groves, W.G. Philos Mag (14) 1939 127-130
 E.D. Geeter, M.Mangan, S.Spaepen, W. Stinissen, G. Vennekens. J. Power
Sources 1999, 80, 207
 Y. Kiros. J. Electrochem. Soc. 1996, 41, 2595
 Mauritz, Kenneth. Moore, Robert B. The State of Understanding Nafion Chem.
Rev. 2004, 104, 4535-3585
 Tricoli, V. Journal of the Electrochemical Society 1998, 145 (11), 3798-3801
 Alonso-Vante, N. Tributsch, H. Solorza-Feria, O. Electrochim. Acta 1995, 40,
567.
 Gupta, S. Tryk, D. Zecevic, S.K. Aldred, W. Guo, D. Savinelli, R.F. J.Appl.
Electrochem. 1998, 28,673
 Status of Carbonate Fuel Cells J. Power Sources 56 (1995) 1-10
 Fraenkel, D. Shabtai, J. Encapsulation of hydrogen in molecular sieve zeolites
JACS 1977 7074-7076
 Fritz, M. Ernst,S. Int. J. Hydrogen Energy 1995, 20 (12) 967
 Shore, Sheldon JACS 1956 78 (2) 502-503