Chapter01 Introduction 2020-03-02

1.
Introduction to Fuel Cells
Literature:
[1] K. Kordesch and G. Simader, Fuel Cells and their Applications, Wiley-VCH,
Weinheim, 1996.
[2] J. Larminie and A. Dicks, Fuel Cell Systems Explained, Wiley, Chichester, 2003
[3] W. Vielstich et al., Handbook of Fuel Cells, Wiley, Chichester, 2003
Lecture Fuel Cell Technology, Chair for Process Systems Engineering (Prof. K. Sundmacher) Winter Term 2019/20 1
Contents
1. Introduction to Fuel Cells

1.1 Energy Conversion in Fuel Cells
1.2 Working principle
1.3 Fuel Cells types
1.4 Application of Fuel Cells
1.5 Historical Aspects
Energy Conversion Principle of a Fuel Cell Compared
with Conventional Power Plant
Electrochemical Conversion
(so called „Cold Combustion“)
Chemical Electrical
Energy Energy
Fuel Cell
Generator
Combustion Conventional
Power Plant
Thermal Engine
Thermal (e.g. Steam Turbine) Mechanical
Energy Energy
Sankey Diagram of a Fuel Cell Compared with
Conventional Plant
Fuel Cell
Electrical
Chemical Energy
Energy
Combustion Steam Generator

Thermal
Energy Turbine
Electrical
Chemical Energy
Energy
Thermal Energy
Cycle Processes: Conversion of Thermal Energy into
Mechanical Work
Overall system
Energy storage
T
Moving Weights
receive heat Qin Piston (Area A)
W 5g
5g
5g 5g
5g
5g 5g
Wärme- 5g 5g 5g 5g 5g 5g5g 5g
Kraftmaschine
do work
reject heat Qout

Working gas
Cylinder
Enviroment
Te
Idealized Heat-engine
First Law of Thermodynamics
Energy is conserved; it can be neither created nor destroyed.

The change of internal energy of a closed system is equal to
the sum of the change in the heat and the change in work.
dU = dQ + dW
If the system performs mechanical work it follows:
dU = dQ + PdV
The sign conventions for heat, work, and internal energy are as follows: the internal energy and temperature of a system
decrease when the system either loses heat or does work on its surroundings. Conversely, the internal energy and temperature
increase when the system gains heat from its surroundings or when the surroundings do work on the system.
Carnot cycle
The Carnot cycle (upper limit in efficiency of any classical

thermodynamic engine) when acting as a heat engine
consists of the following steps:
Win
• 1→2: Reversible isothermal expansion of the gas at
the "hot" temperature, T of energy storage Wout
(isothermal heat addition or absorption).

Carnot cycle
on a PV diagram
• 2→3: Isentropic (reversible adiabatic) expansion of
the gas (isentropic work output). W TE
  1
• 3→4: Reversible isothermal compression of the gas Qin T
at the "cold" temperature, Te . (isothermal heat 25 (298 K)
rejection) (temperature of environment). 200 (473 K)
• 4→1: Isentropic compression of the gas (isentropic

work input).
Energy Conversion in a Heat Engine
Example: Gas Turbine
Fuel T p3=p2
T3
Combustor Qin 3
Com- work output

pressor 2 3 p4=p1
2
~ qH
4
Turbine work input

Gene-
Air 1 4 rator T1
Qout
Flue gas 1
qL
s
 Brayton-Cycle (p=const) s1=s2 s3=s4
s3
 1→2: Isentropic compression (W in) qH   T ( s) ds
s2
 2→3: Isobaric (open system) s1
qL    T ( s) ds
heat supply (combustion) s4
 3→4: Isentropic expansion (Wout , Turbine) W q

  1 L
 4→1: Isobaric heat removal Qin qH
Contents

Working Principle of a Continuous Stirred
Tank Reactor
B
A A A AB Oxidation: A  A+ + e-
(A,B) Reduction: B + e- + A+  AB
e-
e- Overall: A + B  AB
A A
B B
B
Working Principle of a Fuel Cell
Separation layer layer

- not permeable for A, B, AB
- ion-conductive
- electrically isolating
A
A (A) Oxidation: A  A+ + e-
A+ Reduction: B + e- + A+  AB
AB Overall: A + B  AB
B e- (B)
B AB
Thermodynamic Efficiency
Gibbs free energy change = maximum electrical energy produced

R g f

Rhf
Enthalpy of formation =
chemical energy of H2O
- Fuel & O2
H2 + 1/2O2  H2O
∆hf = −241.83 kJ mol−1 (steam) LHV
∆hf = −285.84 kJ mol−1 (liquid) HHV
 R g f
E R g f  0  E  0 Spontaneous reaction
zF
Technical Implementation of the Fuel Cell Principle
Fuel Gas Entry

Electrolyte
Single Cell
Pore
e-
Oxidant Exit
Current
e- A A+
Collector -
+
A
AB, B Porous
A+
Oxidant Entry Anode
A
B
Porous Porous
Fuel Gas Exit Anode Electrolyte Cathode
Layer
Single Cells form a Cell Stack
Monopolar Cell Construction (In series)
+
- _
- + +
Anode Monopolar Cell
Electrolyte
Cathode Construction
Series connection
+
_ _ _
+ +
_
+ - + +
_
Single Cell
Anodic Gas
Cathodic Gas Cell Stack _ _
+ + +
_
I  I1  I 2  I 3
R  R1  R2  R3
Monopolar Cell Construction (Parallel)
+
- - - - -
Anode
Monopolar Cell
Electrolyte Construction
Cathode
Parallel
connection
+
- - - - -
+ + + + +
_
Single Cell
Anodic Gas
Cathodic Gas Cell Stack
+ + + + +
_
I  I1  I 2  I 3
1 / R  1 / R1  1 / R2  1 / R3
Bipolar Cell Construction
+
_ _ _
+ +
Anode Bipolar Cell
Electrolyte
Cathode Construction
_ _
+ + +
_
Bipolar Plate End Plate
Single Cell _ + _ + _ + _ + _
+
_ +
Anodic Gas
Cathodic Gas Cell Stack
Real Fuel Cell Stacks
Contents

Classification of Fuel Cells by their Electrolyte
Temperature
range
State of
Abr. Fuel Cell Type Electrolyte
Aggregation
AFC Alkaline Fuel Cell KOH Liquid
PEMFC Polymer-Electrolyte Membrane Fuel Cell Polymer Membrane Solid
Concentrated
PAFC Phosphoric Acid Fuel Cell Liquid
Phosphoric Acid
Molten
MCFC Molten Carbonate Fuel Cell Liquid
Carbonate Melts
SOFC Solid Oxide Fuel Cell Stabilized Metal Oxide Solid
The „old“ fuel cell types
Alkaline Fuel Cell (AFC)

&
Phosphoric Acid Fuel Cell (PAFC)
Alkaline Fuel Cell (AFC)
KOH (static electrolyte fixed in a porous inert

membrane, or circulating electrolyte) Alkaline Fuel Cell (AFC)
Electrolyte 35-50% KOH

Separation of
Diaphragms, porous membranes
reaction volumes
Anodic/ cathodic feed Pure hydrogen/ pure oxygen
Charge Carrier Hydroxide-ion
H2 + 2 OH-  2 H2O + 2 e-
H2 Catalysts Platinum, palladium, ruthenium, nickel, silver
(H2), H2O
Temperature range* 60 - 90°C
Efficiency* 50 - 60 %
OH-
Raney-silver, raney-nickel, graphite, stainless
Materials
steel
O2, H2O (O2, H2O)
1/
2 O2 + H2O + 2 e-  2 OH- Advantages
Reliable system, fastest oxygen reduction
kinetics, cheap!
Clean hydrogen is needed, carbon dioxide-
Disadvantages
sensitive (<10ppm) => air operation difficult
Application areas Space applications, submarines
*K. Kordesch, G. Simader, Fuel Cells and their Applications; VCH Verlagsgesellschaft, Weinheim, 1996, S. 52
First Applications of AFC
Pratt & Whitney technicians

assemble alkaline fuel cells for
Apollo service modules (1964)
Karl Kordesch of Union Carbide on his

alkaline fuel cell motorcycle (1967)
Images from http://fuelcells.si.edu (09-27-2002)
Current AFC Programs & Developers
Companies developing AFCs:

Apollo Energy Systems Inc. (USA)
Zevco (USA)
Astris (Canada)
UTC Fuel cells (USA)
and some others….
Zevco hybrid truck (2001) with 5 kW AFC
Astris E5-B AFC for portable power supply
Concentrated Phosphoric Acid

(fixed in a porous inert matrix)
Electrolyte Concentrated phosporic acid

Separation of Diaphragms/ pouros membranes
reaction volumes (e.g. SiC-PTFE matrix)
Anodic/ cathodic feed hydrogen (also from reformer)/ air
H2  2 H+ + 2 e- Charge Carrier Hydrogen-ion
H2, (H2O) (H2, H2O) Catalysts Platinum, platinum alloys
Temperature range* 160 - 220°C
H+ Efficiency* 55%
Materials Graphite
O2, (H2O) (O2), H2O Carbon dioxide tolerant, carbon monoxide

1/
2 O2 + 2 H+ + 2 e-  H2O tolerant (1-3%), ready for market, utilization of
Advantages
natural gas and air, combined heat and power
production possible
Disadvantages Lowest efficiency, corrosion problems

Application areas Dispersed power applications
Reformer: CH4 + H2O  3H2 + CO
First Applications of PAFC
Project team for 5 kW-PAFC system for a

Allis Chalmers farm tractor (1965)
Image from http://fuelcells.si.edu (09-27-2002)
40 kW PAFC system (1979)

Image #325,002,001 from the ETV Collection, U.S. Department of Energy
Current PAFC Programs & Developers
UTC Power‘s PureCell (former ONSI)

• 200 kW PAFC
• More than 260 system operational (65MW worldwide)
• Transport, stationary systems, space
• Police stations, hospitals, libraries,
hotels, shopping centers
• Life time > 50.000h
• Efficiency ~37%
• Price target: 2000$ / kW
Other companies
•Toshiba (Japan)
•Sanyo (Japan)
•Fuji Electric (Japan)
The classic:
The Proton Exchange Membrane
Fuel Cell (PEMFC)
Polymer-Electrolyte Membrane Fuel Cell (PEMFC)
Polymer-Electrolyte Membrane
Polymer-Electrolyte Membrane Fuel Cell (PEMFC)
(e.g. NafionTM, DowTM Membrane,
Fumatech, Solvay)
Polymer membrane (ion-exchange-polymers
Electrolyte
with sulfonic acid groups)
Separation of
Polymer membrane
reaction volumes
Anodic/ cathodic feed Hydrogen, reforming gas/ oxygen, air
Charge Carrier Hydrogen-ion
H2  2 H+ + 2 e- Catalysts Platinum, platinum alloys
H2, (H2O) (H2, H2O) Temperature range* 15 - 100°C
H+ Materials Graphite, gold-plated stainless steel
Highest specific performance, flexible
Advantages
dynamics, solid electrolyte
O2, (H2O) (O2), H2O
1/
2 O2 + 2 H+ + 2 e-  H2O
Clean hydrogen is needed, CO-sensitive (< 2-
20 ppm), frost-sensitive, membranes and
Disadvantages
catalysts very expensive, membrane has to be
humidified (water management)
Space application, cars, substitute for

Application areas rechargeable batteries, local power supply,
portable power supply, submarines
PEMFC – Membranes
Available membranes (NAFION or Ideal membrane properties:

other fluorosulphonate ionomers):
a) Chemical and thermal stability
[CF2]n [CF2] n b) Mechanical strength while very thin

[CF2] n
[CF2] n
- c) High ionic conductivity (high proton concentration)
SO3- SO3
[CF2]n SO3-
SO3- H 2O d) Impermeable for all other species
H+
H 2O H O H 2O
SO3- 2 H2O
+
H HO
H+ H2O H+ 2 New developments:
+
H H O
2
H 2O a) Proton-conductive without water (less/no swelling):
H2O H2O
H2O 1 nm
Blends of acidic and basic polymers with aromatic
Inhomogeneous, swollen material with regions backbones (also no fluor content)
containing only the polymer backbones, and
b) Higher operating temperatures (CO tolerance !):
water-filled channel structures in which
solvated protons and water are mobile e.g. Polybenzimidazole (PBI, up to 200°C)
=> Water is transported through the material c) Radiation-grafted classical membranes:
=> Humidification necessary (for proton
solvation) “Trap” water inside membrane (nearly closed outer
nanopores when membrane is swollen)
=> Maximum operating temperature (80)120°C
Three-Phase Interface and other Mass Transport
Components of a PEM fuel cell stack
Single Cell Assembly
PEMFC Programs & Developers
Companies developing PEMFCs:

Ballard Power Systems, Plug Power,
NUVERA fuel cells and nearly all car
manufacturers…
Ballard mark 1030, Residential
power supply system; 1.2kW
Demonstration PEMFC, 20 W
Stationary power supply system; 250 kW
Using liquid fuel:
The Direct Methanol Fuel Cell (DMFC)
and other Direct Fuel Cells (DFC)
Recommended literature:
1. Schultz, T.; Zhou, S.; Sundmacher, K.: Current status of and recent developments in the
direct methanol fuel cell, Chem.Eng.Technol. 24 No.12 (2001) 1223-1233
2. Arico, A.S.; Srinivasan, S.; Antonucci, V.: DMFCs: From fundamental aspects to
technology development, Fuel Cells 1 No.2 (2001) 133-161
Advancement of PEMFC –
Direct Methanol Fuel Cell (DMFC)
PEM = Polymer Electrolyte Membrane
(e.g. NafionTM, DowTMMembrane ,
Fumatech, Solvay)
Direct Methanol Fuel Cell (DMFC)
Polymer membrane (ion-exchange-polymers

Electrolyte
with sulfonic acid groups)
Separation of
Polymer membrane
reaction volumes
Anodic/ cathodic feed Methanol-water-mixture/ oxygen, air
CH3OH, H2O CH3OH + H2O  6 H+ + 6 e- + CO2 (CH OH), H O, CO
3 2 2 Charge Carrier Hydrogen-ion
Catalysts Platinum, platinum alloys (e.g. Pt-Ru)
H+ Temperature range 20 - 90°C
Efficiency 50 - 60 %
Materials Graphite, stainless steel
O2, (H2O) (O2), H2O
3/
2 O2 + 6 H+ +6 e-  3 H2O Advantages no reforming step needed, solid electrolyte
methanol cross-over, frost-sensitive,

Disadvantages
membranes and catalysts very expensive
substitute for rechargeable batteries, local

Application areas
power supply, cars
DMFC – Major Problems
a) Slow anode methanol oxidation kinetics and catalyst activity degradation:
Large amounts of expensive PtRu catalyst needed
=> better catalysts, higher temperatures (>> 100°C), oxidants
(oxygen, peroxides etc.) added to methanol-water solution in
small quantities (to overcome catalyst activity degradation)
b) Methanol permeation through membrane:
Severe loss of performance and fuel
=> better membranes
c) Carbon dioxide bubble formation in anode liquid (figure):
Carbon dioxide gas has to be removed from fuel system
=> intelligent integration into DMFC system necessary
d) Water permeation through membrane:
CO2 bubbles in DMFC
Flooding of cathode (air) channels anode channels
=> better membranes, high air flow velocities in cathode channels
e) Cell can freeze below –10..-20°C:
Fuel is liquid methanol-water solution (cCH3OH = 1-3 mol/dm³)
=> higher methanol concentration => better membranes !
DMFC – Better Membranes
Available membranes (NAFION etc.): New membranes:

Methanol is transported through a) Proton-conductive without water (less/no swelling):
water-filled nanopores
Blends of acidic and basic polymers with aromatic
[CF2]n [CF2]n backbones (no fluor content)
[CF2]n
[CF2]n
SO3- SO3- b) Higher operating temperatures (much faster
[CF2]n SO3- H2O SO3- anode methanol oxidation kinetics):
H+
H O H2O H2O
SO3- 2
CH OH + 1-2 nm e.g. Polybenzimidazole (PBI, up to 200°C)
H+ CH3OH H+ 3 H HO
2
+
H HO
2
c) Radiation-grafted classical membranes:
H2O
CH3OH “trap” water inside membrane (nearly close outer
H2O 1 nm
nanopores when membrane is swollen)
4 nm
d) Polymer-zeolite composite membranes (figure left):
Protons can pass through zeolite particles, but
methanol can not
NONE OF THESE AVAILABLE ON THE MARKET !
ALL OF THESE ALSO INTERESTING FOR PEMFC !
Current DMFC Programs & Developers
Companies developing DMFCs:

Smart Fuel Cell (SFC) GmbH (Germany, photos)
also Toshiba, Motorola, NEC, Giner
and (very few) others….
SFC/Medion DMFC laptop docking station (35 W), SFC portable DMFC power supply (50 W)
release planned end of 2004 for hobby, outdoor, caravans, commercial, …
SFC DMFC system for Beta-Camcorders (25 W)
Other Direct Fuel Cells (DFC)
DFCs are typically based on DMFC principle !
Possible fuels for DFCs (most promising candidates):
a) Dimethylether (DME, CH3-O-CH3):
- First tests done, full oxidation seems possible
- DME is cheap and not toxic
- Small quantities of methanol formed as reaction intermediate
- DME is very volatile (boiling point –23°C, saturation pressure 5.1 bar at 20°C !)
b) Ethanol (CH3-CH2OH):
- Only partial oxidation achieved on classical metal catalysts
- Ethanol is cheap and not toxic
c) Dimethoxymethan (CH3O-CH2-OCH3):
- Forms methanol as intermediate
- Liquid at ambient conditions (not as volatile as DME)
d) Dimethoxyethan (CH3O-CH2- CH2- OCH3):
- Full oxidation not yet proven
e) Formic Acid (H-COOH):
- good performance proven, full oxidation proven
- Formic Acid is corrosive and toxic
Ref.: Kurzweil, P.: Brennstoffzellentechnik, Vieweg, Wiesbaden (2003)
Anything is fuel:
Molten Carbonate Fuel Cell (MCFC)
MCFC Working principle
Molten Carbonate Fuel Cell (MCFC)
Molten carbonate salts (62% Li2CO3 / 38%

Electrolyte
K2CO3) in LiOAlO2
H2 +CO32-  H2O+ CO2+2e- Anodic/ cathodic feed

Natural gas, reformate gas, hydrogen,
hydrocarbons, coal gas/ air, carbon dioxide
H2, CO CO +CO32-  2CO2+2e- (H2, CO) Charge Carrier Carbonate ions
CO2, H2O
Catalysts Nickel (An.), nickel oxide (Cath.)
CO32- Temperature range 570 - 700°C
Efficiency 45 - 55 %
Materials Nickel, steel
O2, CO2 ½O2 + CO2 + 2e-  CO32- (O2, CO2)
combined heat and power production possible,
Advantages use of fossil fuels and air, internal reforming
possible, CO-tolerant
Disadvantages Slow system dynamics, sulfur-sensitive
Distributed power generation, combined
Application areas
heat/power production
Reformer: CxHy + xH2O  (x+y/2)H2 + xCO

WGS: CO + H2O  H2 + CO2
Direct Internal Reforming and
catalytic combustion in MCFC
CH4 + H2O  CO + 3H2 Air
H2O, CO2
CO + H2O  CO2 + H2
Fuel gas (CH4, CO, H2)
(CH4, H2O)
H2 + CO32-  H2O + CO2 + 2e -
CO + CO32-  2CO2 + 2e - e-
Anode electrode
Catalytic
Electrolyte 2-
Ucell
(Li2CO3/K2CO3)
CO 3
Combustion
Chamber
Cathode electrode
½O2+ CO2 + 2e -  CO32-
Exhaust
gas O2, CO2
T600°C (N2, CO2)
Direct Internal Reforming (DIR) Catalytic combustion chamber

• Production of hydrogen from hydrocarbons • Provides the required carbon dioxide for
inside the anode channel the cathode channel.
• Continuous removal of reforming products • Internal carbon cycle (but still CO2-
by oxidation emissions!)
• Heat integration of endothermic reforming
process and exothermic oxidation process
The Hotmodule MCFC by MTU CFC Solutions
Open Hotmodule Hotmodule plant in Magdeburg

- 280 kWel
- 342 cell stack
- 48% electric system efficiency
MCFCs are not truly commercial
- Field trial phase
(>20 plants operational in 2004)
Images courtesy of MTU CFC Solutions, Germany
The Hotmodule MCFC by MTU CFC Solutions
Ventilation
Mixing chamber
Exhaust cathode
Air inlet
Air outlet
Electrical control
Connection to the grid
Air outlet
Air circulation
Fuel feed
Heating for start up H2O inlet
Cleaned fuel
Sketch of the Hotmodule Air inlet

Image courtesy of MTU CFC Solutions, Germany
Ion conducting ceramics:
Solid Oxide Fuel Cell (SOFC)
SOFC Working principle
Solid Oxide Fuel Cell (SOFC)
Stabilized metal oxide (e.g. yttria-stabilized

Electrolyte
zirconia)
H2 +O2-  H2O+2e-
Anodic/ cathodic feed Natural gas, coal gas, reformate gas/ air
H2, CO CO +O2-  CO2+2e- (H2, CO) Charge Carrier Oxygen-ion
CO2, H2O Catalysts Perovskites (cathode), nickel, nickel cermet
O2- Temperature range* 800 - 1100°C
Materials Nickel, ceramics
O2 ½O2 + 2e-  O2- (O2)
combined heat and power production possible,
Advantages
use of fossil fuels and air, sulfur tolerant
Dissatisfying electrode lifetime, material
Disadvantages
problems
Application areas Power generation, APU
Tubular SOFC by Siemens-Westinghaus
Tubular construction
Tube Length 1,5 m

Diameter 22 mm
Sources: Power journal (Siemens), 1/2001

www.pg.siemens.com/en/fuelcells
Planar SOFC by Sulzer-Hexis
Current collector Sulzer Hexis HXS 1000 Premiere

- 1 kWel / 2,5 kW th
- Fuelled with natural gas
Cathode - Test phase 2002-06 in NRW
Electrolyte
Anode
Air
Current collector www.hexis.ch (10-10-2002)
To exhaust gas
burner CO, H2
H. Knappstein, Einsatz einer 1 kW Hochtemperatur-
Brennstoffzelle,Thyssengas, 2001
Anode supported planar geometry

Low electrolyte thickness (break-through)
FC EXPO 2015, Tokyo, Japan G. DiGiuseppe et al., J. Fuel Cell Sci. Technol. 9 (2011) 011016
Thyssengas spezial report, Thyssengas GmbH, 2002
Inspired by nature:
Bio Fuel Cell (BioFC)
BioFC working principle
Working principle
Bacteria or Enzymes • Bacteria or Enzymes promote electrochemical
reactions on both electrodes
Materials
„Food“ F F' • Anode: bacteria (e.g. Rhodoferax, Geobacter) or
enzymes (e.g. Glucose-Oxidase) to consume bio
e- fuel (e.g. Glucose)
• Cathode: Noble metal, bacteria or enzymes
A+ Hearing
Devices Pacemakers
Possible Neuro-
O2 e- applications Stimulators LVAD
ICD/CHF
A • Environmental Devices
Artificial
Hearts
sensors Insulin Pumps Drug
• Waste water Pumps
Incontinence
treatment Devices
Bone Growth
Stimulators
BioFC : Microbial
Waste water treatment

Microbial Electrolyser for
H2 production (Appl Microbiol Biotechnol
(2011) 89:2053–2063)
https://en.wikipedia.org/wiki/Sewage_treatment
Different designs of microbial electrochemical
reactors (Env. Science and Technology
40 (2006) 5181-5192)
• Performance: μW cm-2 – mW cm-2

• Low cost
• High stability
• Electricity and/or products
BioFC : Enzymatic
Hearing Pacemaker Adam Heller:

Devices Potentially implantable
LVAD
Neuro-
miniature batteries,
Artificial
Stimulators Heart Anal. Bioanal. Chem. 385
ICD/CHF (2006) 469-473:
Drug Pumps
Devices “The sizes of electronic
Insulin Pumps systems are defined by their
Bone Growth
displays and by their
Incontinence Stimulators
batteries. The battery and
Devices
the display are also the
largest components of the
most widely used analytical
systems.”
• Performance: μW cm-2 – mW cm-2

• Implantable fuel cell
Miniature power source for
glucose sensing contact lenses
• High stability
(Analytical Chemistry, 85 (2013) 6342−6348)
Different types of BioFC
Free enzymes Fixed enzymes
e- e- e- e-
Membrane
e- “Food” e- “Food” e.g. blood FC:
Pure enzymes e- Glucose serves as fuel,
e-
(“dead” System) e- dissolved oxygen as
e-
Mediator H2 O e- H2 O e- oxidant
Enzyme
e- ox. “Food” H+ e- ox. “Food” H+
e- e.g. in ocean sediments:

e- O2 O2
“Living” Cell Biomass in sediments
e-
serves as fuel, dissolved
Bacteria oxygen in the water as
“Food” “Food” oxidant.
+ Simple construction + Membrane not required

- Mediators often times toxic + Higher power density
- Mediators need to be + Compact design (electrode distance)
replaced regularly - Enzymes difficult to immobilise
- Separating membrane
required
Contents

NECAR – New Electric Car of Mercedes Benz
NECAR 1 (1994)
Lab Van, H2-operation
800kg FC system
2 seats
NECAR 4 (1999)
Zero Emission Vehicle
Liquid H2-operation
145 km/h, 70 kW, 450 km
5 seats
NECAR 5 (2000) F-Cell (2003)

on-board Kompr. H2
methanol reformer 140 km/h, 65 kW,
150 km, 4,2 l/100km
Images from http://www.mercedes-benz.com (10-10-2002)

www.daimlerchrysler.com (5.1.2007)
Examples for Fuel Cell Driven Vehicles (FCVs)
Opel HydroGen 3 (2001)

Liquid or compr. H2-operation,
150 km/h, 90 kW, 400 km
Opel/GM petrol reformer +

fuel cell drive train
(size approx. like standard Otto engine)
Examples for Fuel Cell Driven Vehicles
MB Citaro Citybus (2002) MB Sprinter (2001)

Compr. H2-operation Compr. H2-operation
200 kW, 200 km 120 km/h, 55 kW, 150 km
30 busses in 10 cities 16000 km Total
Military use in special ships and submarines

First submarine ready for service (build by HDW,
Kiel, Germany in 2002), PEMFC/SOFC/MCFC
Examples of Fuel Cell Driven Vehicles
FCX Clarity - Honda
Fuel Cell
power train
Li-ion
HP H2 tank
Battery
HYMotion (VW) and H-Tron (Audi)
http://world.honda.com/automobile-technology/CLARITY/five_seater.html
Focus on HTFC
Toyota Mirai (2016)

ca. 60000$
Battery with regenerative

breaking, used for
acceleration
H2 storage in tanks
Images from https://ssl.toyota.com/mirai/fcv.html
Fuel Cells as Auxiliary Power Units (APU)
In cars, trucks, buses,

cooling containers:
- low kW-range
- using same fuel as vehicle
- SOFC (BMW, Acumetrics etc.)
In ships:
- high kW up to MW-range
- using same fuel as ship
- SOFC, MCFC
In airplanes:
- ~400-500 kW
- kerosine as fuel
- SOFC (e.g. Boeing)
Examples for Single-Home
Power Generation
Hexis
Galileo 1000 N
based on a SOFC
1 kWel / 2,5 kW th
fuelled with natural gas
Vaillant Fuel Cell Space-Heater

based on a PEMFC
1-4,6 kWel / 1,5-7 kW th
fuelled with natural gas
Image from
http://www.vaillant.de
(10-10-2002)
ECS Transactions, 25 (2) 3-10 (2009)
Examples for Multi-Home Power Generation
250 kW PEMFC combined power

heat unit P2B of Alstom Ballard
(fuelled with natural gas)
Image from http://www.ballard.com (11-10-2002)
220 kW PAFC combined power

heat unit PureCell 200
of UTC Power
(fuelled with natural gas)
Image from http://www.UTCpower.com (5.1.2007)
Examples for Stationary Power Generation Systems
SOFC plant
by ZTEK
Image from MTU Friedrichshafen
MCFC plant HotModule

by MTU Friedrichshafen
Fuel Cell Power Plants
Fuel Cell Energy
• Conceptual study for a 40 MW MCFC plant
• Parallel assembly of 250 kW modules
• Coupling with single turbine
• Efficiency: 62% elec.
Other companies:
• Mitsubishi: SOFC, >100MW
• GE: IGFC, SOFC, >400MW
• Siemens: SOFC, >100MW
Small-scale and Portable Applications
Fraunhofer ISE
(Germany): 35W PEMFC
Micro Cell (1W/cm³)

Ballard Power Systems
(Canada & Germany):
1 kW PEMFC-System
Examples for Fuel Cells for Portable Devices
Casio PEMFC system with a

integrated micro-reformer Image from (11-10-2002)
http://www.avistalabs.com
(fuelled with methanol)
Image from http://www.casio.com (11-10-2002)
100 W portable PEMFC Independence 100

by Avista Labs (fuelled with hydrogen)
Small-scale and Portable DMFC Applications
Portable Systems
(20-100 W)
25 W Camcorder
Fuel Cell
Notebook Dockingstation
Images from SmartFuelCell GmbH (Munich, Germany)
Contents

Important Facts of Fuel Cell History
1990‘s: Development of new membrane materials for PEM-FC‘s (DOW, DuPont, Gore)
1980‘s/1990‘s: Development of high temperature fuel cells (MCFC,SOFC)
1970‘s: Substitution of AFC systems by PAFC systems
1960‘s: Use of fuel cells in space programs

1960‘s: Gemini (PEM) and Apollo (AFC)
1920: Gas diffusion electrode was invented
1866: Invention of the Generator by Siemens
1837/39: Schönbein / Grove invented the fuel cell

1832: Faraday discovered important interrelationships of electrolysis
Grove´s Battery Driving an Electrolytic Cell
Christian Friedrich Schönbein
Chemist, 1799-1868
Sir William Robert Grove

Lawyer and Scientist, 1811-1896
Electrolyser
Platinum Hydrogen
Electrode
Sulphurous
Acid
"Water will be the coal of the future"
„The energy of tomorrow is water

being decomposed
by electrical current.
The decomposed elements of water,
hydrogen and oxygen,
will save the energy supply on earth for
an incalculable time period.“
Jules Verne, 1870
Jules Verne was a French writer. He became famous for his novels like “Around the
World in 80 Days” (1873). He is considered as one of the founders of science fiction
literature.
Application of a PEMFC System
in the Gemini Space Program
Demonstration of toughness of a
polymer electrolyte membrane
developed by General Electric (1965)
Technicians inspect a PEM fuel cell

in the Gemini 7 spacecraft (1965)
Use of a Fuel Cell in the Apollo Space Program
1.5-kW alkaline fuel cell from the

Apollo spacecraft. Two of these
units were used, each weighing
113 kg. These fuel cells provided
the electrical power, and much of
the potable water, for the craft that
took man to the Moon.
Image from http://fuelcells.si.edu (09-27-2002)
Examples of Prototypes built during the 60´s
Project team for 5 kW-PAFC system for a

Allis Chalmers farm tractor (1965)
Karl Kordesch of Union Carbide on his

alkali fuel cell motorcycle (1967)
Literature and Links
1. Larminie, J.: Fuel Cell Systems Explained, Wiley, Chichester (2000)

2. Vielstich, W. (ed.): Handbook of fuel cells, Wiley, Chichester (2003)
3. Kurzweil, P.: Brennstoffzellentechnik, Vieweg, Wiesbaden (2003)
4. Ledjeff-Hey, K.: Brennstoffzellen: Entwicklung, Technologie, Anwendung, C.F. Müller,
Heidelberg (2001)
5. Carette, L., Friedrich, K.A., Stimming, U.: Fuel Cells – Fundamentals and Applications,
Fuel Cells 1, No. 1, 2001, 5-39
• Fuel Cell and Hydrogen Joint Undertaking

https://www.fch-ju.eu/
• European Commission, Energy Research
http://ec.europa.eu/research/energy/
• Initiative Brennstoffzelle
http://www.initiative-brennstoffzelle.de

Chapter01 Introduction 2020-03-02

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter01 Introduction 2020-03-02

Uploaded by

Copyright:

Available Formats

1.

Introduction to Fuel Cells

1. Introduction to Fuel Cells

Combustion Steam Generator

reject heat Qout

Energy is conserved; it can be neither created nor destroyed.

The Carnot cycle (upper limit in efficiency of any classical

(isothermal heat addition or absorption).

• 4→1: Isentropic compression of the gas (isentropic

Com- work output

Turbine work input

 3→4: Isentropic expansion (Wout , Turbine) W q

1. Introduction to Fuel Cells

Separation layer layer

Gibbs free energy change = maximum electrical energy produced

Fuel Gas Entry

1. Introduction to Fuel Cells

AFC Alkaline Fuel Cell KOH Liquid

PEMFC Polymer-Electrolyte Membrane Fuel Cell Polymer Membrane Solid

SOFC Solid Oxide Fuel Cell Stabilized Metal Oxide Solid

Alkaline Fuel Cell (AFC)

KOH (static electrolyte fixed in a porous inert

Electrolyte 35-50% KOH

Pratt & Whitney technicians

Karl Kordesch of Union Carbide on his

Companies developing AFCs:

Zevco hybrid truck (2001) with 5 kW AFC

Astris E5-B AFC for portable power supply

Concentrated Phosphoric Acid

Electrolyte Concentrated phosporic acid

O2, (H2O) (O2), H2O Carbon dioxide tolerant, carbon monoxide

Disadvantages Lowest efficiency, corrosion problems

Reformer: CH4 + H2O  3H2 + CO

Project team for 5 kW-PAFC system for a

Image from http://fuelcells.si.edu (09-27-2002)

40 kW PAFC system (1979)

UTC Power‘s PureCell (former ONSI)

Space application, cars, substitute for

Available membranes (NAFION or Ideal membrane properties:

[CF2]n [CF2] n b) Mechanical strength while very thin

Single Cell Assembly

Companies developing PEMFCs:

Stationary power supply system; 250 kW

Polymer membrane (ion-exchange-polymers

methanol cross-over, frost-sensitive,

substitute for rechargeable batteries, local

Available membranes (NAFION etc.): New membranes:

Companies developing DMFCs:

SFC DMFC system for Beta-Camcorders (25 W)

Molten Carbonate Fuel Cell (MCFC)

Molten carbonate salts (62% Li2CO3 / 38%

H2 +CO32-  H2O+ CO2+2e- Anodic/ cathodic feed

Reformer: CxHy + xH2O  (x+y/2)H2 + xCO

Direct Internal Reforming (DIR) Catalytic combustion chamber

Open Hotmodule Hotmodule plant in Magdeburg

Images courtesy of MTU CFC Solutions, Germany

Sketch of the Hotmodule Air inlet

Solid Oxide Fuel Cell (SOFC)

Stabilized metal oxide (e.g. yttria-stabilized

Tube Length 1,5 m

Sources: Power journal (Siemens), 1/2001

Current collector Sulzer Hexis HXS 1000 Premiere

Anode supported planar geometry

Waste water treatment