[ppt]slide 1 - department of chemistry & biochemistry...
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Fuel Cells: Fundamentals, Types, and Fuel
StorageCarly Reed
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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
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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
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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
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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
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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
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35% KOH
O2H2
H2O
OH-
Alkaline Fuel Cell
Anode: C/Pt or C/Raney Ni/Pt
Cathode: C/Pt
H2 + 2OH- H2O + 2e-
O2 + H2O + 2e- HO2- + OH-
HO2- + H2O + 2e- 3OH-
1 A/cm2 at 0.7 V
r.t.-80oC
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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
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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 CO3
2-
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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
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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
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Polymer Electrolyte Membrane Fuel Cell
H2 2H+ + 2e- O2 + 2H+ + 2e- H2O2
H2O2 + 2H+ + 2e- H2O
Anode: C/Pt Cathode: C/Pt
N A F I O N
1 A/cm2 at 0.7 V
85-105oC
H2 O2
H+
H2O
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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
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Direct Methanol Fuel Cell
Anode: Pt/Ru/C Cathode: Pt/C
CH3OH + H2O CO2 + 6H+ + 6e-
O2 + 2H+ + 2e- H2O2
H2O2 + 2H+ + 2e- H2O
N A F I O N
85-105oC
400 mA/cm2 at 0.5V at 60oC
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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
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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)
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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
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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
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Phosphoric Acid Fuel Cell
Anode: Pt/C Cathode: Pt/C
H2 – 2e- = 2H+ O2 + 4H+ + 4e- 2H2O
200oC
100%H2PO4
Si matrix separatorPTFE binding
CH4 or H2 O2
H+
H2O
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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
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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
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Molten Carbonate Fuel Carbonate
Anode: Ni/Al or Ni/Cr Cathode: NiO
CH4 + 2H2O 4H2 + CO2 + 4e-
H2 +CO32- H2O + CO2 + 2e-
O2 + 2CO2 + 4e- 2CO32-
Li2CO3
and Na2CO3
LiAlO3 used to support electrolyte
580-700oC
150 mA/cm2 at 0.8 V at 600oC
H2, CxH2x+2 O2, CO2
CO32-
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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 CO3
2- reducing efficiency or crossing over causing short circuiting
Dope electrode and electrolyte with Mg Kucera and Myles (LiFeO2 or Li2MnO3 stabilize)
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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
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Solid Oxide Fuel Cell
Cathode = La1-xSrxMnO3
Y doped ZrO2
Anode = NiO-YSZ cermet 800-1000oC
H2 + O2- H2O + 2e- OR
CH4 + 4O2- 2H2O + CO2 + 8e-
O2 + 2e- 2O2-
Interconnector material = Mg or Sr doped lanthanum chromate
1mA at 0.7V
H2, CxH2x+2 O2
O2-
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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
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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.
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ApplicationsFuel cells are being developed for
application in: Stationary power plants Automobiles Portable electronics
To enable mobile power source, fuel must also be portable
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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
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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
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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
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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
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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
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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
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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