Fundamentals,

Types, and Fuel

Storage
Carly Reed

History

1839

1889

J.H. Reid first to use NaOH in place of acid electrolyte

1952

Term fuel cell coined by Ludwig Mond

1902

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

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
90 80 C
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
C/Raney Ni/Pt

Cathode: C/Pt
r.t.-80oC

H2
1 A/cm2 at 0.7 V

O2
H2 O
OH35%
KOH

O2 + H2O + 2e- HO2- + OHH2 + 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

Nafion developed by Dupont (1960s)

employed polystyrene sulfonate (PSS) polymer (unstable)

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

H2

Cathode: C/Pt

O2
H+

H2O
NAF I O N

O2 + 2H+ + 2e- H2O2

H2 2H+ + 2e1 A/cm2 at 0.7 V

H2O2 + 2H+ + 2e- H2O

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

400 mA/cm2 at 0.5V

at 60oC

85-105oC

Cathode: Pt/C

N
A
F
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 CO 2

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

CH4 or H2

O2
H+

PTFE binding
100%
H2PO4

H2 2e- = 2H+

Cathode: Pt/C

Si matrix
separator
H2 O

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

H2, CxH2x+2

O2, CO2
CO32-

150 mA/cm2 at
0.8 V at 600oC

Li2CO3
and
Na2CO3

CH4 + 2H2O 4H2 + CO2 + 4eH2 +CO32- H2O + CO2 + 2e-

Cathode: NiO

LiAlO3 used to
support
electrolyte

O2 + 2CO2 + 4e- 2CO32-

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

H2, CxH2x+2

O2
O2-

1mA at 0.7V

Y doped
ZrO2

H2 + O2- H2O + 2e- OR

CH4 + 4O2- 2H2O + CO2 + 8e-

Cathode = La1-xSrxMnO3

Interconnector
material = Mg
or Sr doped
lanthanum
chromate

O2 + 2e- 2O2-

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 573 oC
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