Fuel Cell:

A fuel cell is a electrochemical device that converts chemical

energy of fuels into electrical energy

Fuels: Hydrogen, methane, butane and gasoline

Construction of the fuel

cell:
•Porous electrodes
•Electrolyte
•Catalyst

The general representation:

Fuel/electrode/electrolyte/electrode/
oxidant
 Fuel Cell
an electrochemical energy
conversion device
Ø To convert the chemicals hydrogen and oxygen
into water, and in the process it produces
electricity.

Ø Battery: the other electrochemical device that we

are all familiar.
Ø A battery has all of its chemicals stored inside, and
it converts those chemicals into electricity too.
Ø This means that a battery eventually "goes dead"
and you either throw it away or recharge it.
 For a fuel cell

ØChemicals constantly flow into the cell so it

never goes dead.
ØAs long as there is a flow of chemicals into
the cell, the electricity flows out of the cell.
ØMost fuel cells in use today use hydrogen
and oxygen as the chemicals.
 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: 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
 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
 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- ½ O2 + 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
 Direct Methanol Fuel Cell

Ø Pt catalyst have highest activity for MeOH oxidation

thus far
Ø Ru enhances MeOH catalytic activity
OH- forms at lower voltage
Ø 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 infrastructure 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(Not
in course)
• 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(Not in
course)
Anode: Pt/C 200oC Cathode: Pt/C

CH4 or H2 O2

H+
Si matrix
PTFE binding
separator

100% H2O
H3PO4
 Phosphoric Acid Fuel Cell(Not in
course)
• 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
 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
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
 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