•Platinum Metals Rev.

, 2013, 57, (2), 137–142•

“Polymer Electrolyte Membrane and

Direct Methanol Fuel Cell Technology”
Edited by Christoph Hartnig (Chemetall GmbH, Germany) and Christina Roth
(Institute for Applied Materials – Energy Storage Systems, Karlsruhe Institute of
Technology, Germany), Woodhead Publishing Series in Energy, Woodhead Publishing Ltd,
Cambridge, UK, 2012; Volume 1: Fundamentals and Performance of Low Temperature Fuel
Cells, 436 pages, ISBN: 978-1-84569-773-0, £150.00, €180.00, US$255.00; Volume 2: In
Situ Characterization Techniques for Low Temperature Fuel Cells, 524 pages, ISBN: 978-1-
84569-774-7, £165.00, €200.00, US$280.00

http://dx.doi.org/10.1595/147106713X664824 http://www.platinummetalsreview.com/

Reviewed by Bruno G. Pollet Introduction

HySA Systems Competence Centre, SAIAMC, University of This book set covers polymer electrolyte membrane
the Western Cape, Modderdam Road, Private Bag X17, fuel cells (PEMFCs) and direct methanol fuel cells
Bellville 7535, Cape Town, South Africa (DMFCs). It is aimed at novice readers as well as
Email: [email protected] experienced fuel cell scientists and engineers in this
area. There are 34 contributors in Volume 1 and 30 in
Volume 2, predominantly from Germany, with some
contributions from the UK, France, Denmark, Italy,
Switzerland, the USA and Canada. The editors are well
known for their research, work and contributions in
the fields of low-temperature fuel cell technology and
materials components characterisation. Dr Christoph
Hartnig is based at Chemetall GmbH and was formerly
Head of Research at both BASF Fuel Cell GmbH and
the Centre for Solar Energy and Hydrogen Research
(Zentrum für Sonnenenergie- und Wasserstoff-
Forschung Baden-Württemberg (ZSW)), Germany.
Professor Dr Christina Roth is Professor for Renewable
Energies at the Technische Universität Darmstadt and
Head of a Research Group at the Institute for Applied
Materials – Energy Storage Systems, Karlsruhe Institute
of Technology (KIT) in Germany.

Volume 1: “Fundamentals and Performance

of Low Temperature Fuel Cells”
Volume 1 consists of two parts. Part I is entitled
‘Fundamentals of Polymer Electrolyte Membrane and
Direct Methanol Fuel Cell Technology’, and Part II is
entitled ‘Performance Issues in Polymer Electrolyte
Membrane and Direct Methanol Fuel Cells’.

Fuels and Materials

Part I consists of five chapters.Chapter 1: ‘Fuels and Fuel
Processing for Low Temperature Fuel Cells’ deals with
the effects of fuel type and quality on low-temperature
fuel cell performance and degradation. The chapter

137 © 2013 Johnson Matthey

http://dx.doi.org/10.1595/147106713X664824 •Platinum Metals Rev., 2013, 57, (2)•

gives short overviews of fuel processing, fuel storage Electrocatalysts

methods and alternative sources of hydrogen. An Chapter 3:‘Catalyst and Membrane for Low Temperature
excellent diagram overview of fuel processing for Fuel Cells’ focuses on fuel cell electrocatalysis and
fuel cell systems (Figure 1) by Iain Staffell (Imperial the importance of the type and loading of the
College, London,UK) (1) is given. Chapter 2: ‘Membrane cathode catalyst. The current anode and cathode
Materials and Technology for Low Temperature Fuel catalyst loadings for low-temperature PEMFCs are ca.
Cells’ gives a very good overview of the most recent 0.2 mgPt cm–2 and 0.4 mgPt cm–2, respectively, with a
investigations in PEM materials for low-temperature target for automotive applications of a total catalyst
PEMFCs with a section on PEM materials for high- loading of 0.2 mgPt cm–2 (with anode catalyst loading of
temperature applications. It reviews perfluorosulfonic 0.05 mgPt cm–2 and cathode catalyst loading of
acid PEMs and non-perfluorinated PEMs including 0.15 mgPt cm–2) for a cell voltage of 0.85 V, assuming a
sulfonic acid, phosphonic, heterocycle functionalised CO-free hydrogen supply. Figure 2 shows the evolution of
and acid doped membrane materials. A short section Pt loading and estimated fuel cell balance of plant from
is specifically dedicated to the morphology and 2006 (2). Both carbonaceous and non-carbonaceous
microstructure of ionomer membranes. electrocatalyst support materials are mentioned

Natural gas
Function Methods Output gas
composition
Remove the sulfur based
Hydro-
odorants added to natural gas 95
desulfurisation,
for safety reasons: Desulfuriser C2 % C
selective H H
Al 6, 1 4, 4
ZnO + H2S ZnS + H2O adsorption % %
CO
25ºC 2

Catalytically process methane 10% CO,

into hydrogen with steam and Steam reforming,
partial oxidation, 10% CO2, 0.5–1% CH4
an absence of oxygen: Reformer SOFC
Ni-Al/Pt-Pd autothermal
CH4 + H2O CO + 3H2 reforming
650–850ºC
Improve the hydrogen yield and
reduce concentration of the High-temperature 0.5–1% CO, 15% CO2
waste carbon monoxide: (HT) and low- Shift reactor PAFC
Cu-Zn/Fe-Cr temperature (LT)
CO + H2O CO2 + H2
350–450ºC (HT) shift
175–300ºC (LT)
Reduce CO concentration to Preferential
ppm levels: oxidation, pressure 10 ppm CO, 15% CO2
Pt-Ru/Rh-Al swing adsorption, CO removal PEMFC
CO + ½O2 CO2
150–200ºC methanisation

Reduce CO2 concentration to 10 ppm CO,

Soda lime
ppm levels: 100 ppm CO2
adsorption, CO2 scrubber AFC
CO2 + Ca(OH)2 CaCO3+ regenerative
25ºC H2O amines, electrical
swing adsorption

Fig. 1. An overview of fuel processing for fuel cell systems (1) (Courtesy of Iain Staffell, University of
Birmingham, UK, and Woodhead Publishing)

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http://dx.doi.org/10.1595/147106713X664824 •Platinum Metals Rev., 2013, 57, (2)•

Fig. 2.
–1 Key Evolution
US$30 kW (US DOE target) of platinum
2015
1 W cm–2 Power density (W cm–2) loadings and
Estimated balance of plant estimated
2010 US$51 kW–1 fuel cell
833 mW cm–2 (US$ kW–1) (including assembly
balance
and testing) of plant
US$61 kW–1 Platinum loading (mgPt cm–2) used (Reproduced
2009
833 mW cm–2 in automotive PEMFC stacks at a from (2) by
Year

cell voltage of 0.676 V permission of

US$73 kW–1 Elsevier)
2008 Platinum loading (gPt kW–1) used in
715 mW cm–2
automotive PEMFC stacks
2007 US$94 kW–1
583 mW cm–2

2006 US$108 kW–1

700 mW cm–2
0 0.2 0.4 0.6 0.8 1.0 1.2
–1 –2
Platinum loadings, gPt kW or mgPt cm

(including, for example, metal oxides (3)) for both highlight other ex situ characterisation methods for
PEMFCs and direct methanol fuel cells (DMFCs). bulk or contact resistance, surface morphology or fibre
The chapter also highlights some of the most structure and mechanical strength measurements (7).
recent developments in anode and cathode catalysts There is also little information on the possible thermal
(including ultra-low Pt) used in low-temperature fuel conductivity effect of the microporous layer on cell
cells. These include core-shell and binary and ternary performance.
alloy electrocatalysts – platinum alloyed with cobalt, The chapter then broadly discusses the role of flow
copper, iron, molybdenum, nickel and/or ruthenium. field design for both low-temperature PEMFC and DMFC
The chapter also discusses new approaches in fuel with some brief discussions around the importance
cell electrocatalysis research and development, for of flow field plate material, especially its interaction
example the reduction of the Pt content and the with the gas diffusion layer material under various
investigation of Pt-free compounds (for example operating conditions and applications (7, 8). Perhaps
Co and Fe incorporated in nitrogen macrocycle for completeness the authors could have added a short
structures) based upon either non-precious metals section on ex situ characterisation and accelerated
or alloyed transition metals. However, the chapter ageing/accelerated stress tests for flow field plate
does not touch on advanced cathode catalysts such materials. This chapter also discusses the importance
as the famous 3M platinum nano-structured thin film of the system layouts of the two low-temperature fuel
(NSTF) (4), which is a bit of a disappointment. For cells, i.e. balance of plant, including reactant supplies
those who are interested in learning further about fuel and thermal management. For Chapter 4, perhaps
cell electrocatalysis, there are a number of additional the section on system aspects of low-temperature
books which I would strongly recommend (4–6). fuel cells could have been a separate chapter in the
book emphasising the correlation between the flow
Gas Diffusion Media field plate design and material, the gas diffusion layer
Chapter 4: ‘Gas Diffusion Media, Flow Fields and material and the overall system design and layout.
System Aspects in Low Temperature Fuel Cells’ covers
the role and importance of gas diffusion media Environmental Aspects
(teflonated/unteflonated woven and non-woven), flow Chapter 5: ‘Recycling and Life Cycle Assessment of
field plate designs on performance and degradation Fuel Cell Materials’ focuses on the environmental
and system design criteria for low-temperature aspects of fuel, fuel cell components and fuel cell
applications.The chapter briefly states characterisation stacks as well as recycling. The chapter highlights the
methods for gas diffusion layers, although it does not fact that pgms such as Pt, Pd and Rh are successfully

139 © 2013 Johnson Matthey

http://dx.doi.org/10.1595/147106713X664824 •Platinum Metals Rev., 2013, 57, (2)•

recycled from today’s vehicles (principally from all operating conditions and briefly describes how
catalytic converters – modern vehicles may contain that degradation can be minimised, in turn increasing
around 1 g of Pt for petrol and around 8 g of Pt for performance and durability, by improving the overall
diesel (2)) and the technologies can be adopted to stack design at component material and operational
recycle Pt from fuel cell systems. This chapter is very levels.
interesting and well-written as recycling of fuel cell Chapter 7: ‘Catalyst Ageing and Degradation in
components and systems and their impact on the Polymer Electrolyte Membrane Fuel Cells’ focuses on
environment is often neglected, and a ‘zero-to-landfill’ performance degradation of electrocatalysts affected
approach is required in order to lead to long-term by the relatively harsh operating conditions within
cost savings. It also highlights that recycling in the fuel low-temperature fuel cells and discusses catalyst
cell manufacturing industry will become paramount ageing mechanisms. For example, it explains the
for mass-produced systems in which environmental three principal mechanisms attributed to the loss
considerations will have to be taken into account of electrochemical surface area for pure Pt and Pt
(for example, collection/separation systems, recycling alloys supported on carbon, i.e. dissolution (leading
processes, component reuse, remanufacturability and to Pt redeposition or Pt precipitation), migration
energy recovery). Life cycle assessment models of with concomitant coalescence and detachment of
fuels and fuel cell components are discussed in detail Pt nanoparticles from the carbonaceous support as
and the standardised life cycle assessment protocol well as complete or incomplete carbon corrosion
(International Organization for Standardisation – ISO of the support material. The discussion then focuses
14040 series) is briefly mentioned. on the main effects causing such mechanisms:
temperature, pH, anion types, water partial pressure,
Operation and Ageing Pt particle size and electrode potential variations
Part II in Volume 1 consists of seven chapters: and for Pt alloy electrocatalysts, dealloying of the
Chapter 6: ‘Operation and Durability of Low non-precious metal (mainly transition metals as they
Temperature Fuel Cells’ gives an excellent overview are not stable in acidic environments – for example
of the effects of low-temperature PEMFC operating Pt-Co catalysts are known to exhibit poor performance
conditions (thermal, water and reactant management, under intense cycling conditions). The chapter also
contamination types and levels and duty cycling) on briefly reviews ex situ and in situ catalyst degradation
performance and durability (which is also correlated characterisation methods with an emphasis on a very
to component material properties, their designs and useful, powerful and newly developed technique –
cycling abilities). The chapter highlights the major identical location transmission electron microscopy
degradation processes occurring in the pgm-based (IL-TEM) – that was originally developed by the
cathode catalyst layer and PEM regions present for chapter’s authors (Figure 3). The technique provides

(a) (b) (c)

100 nm

50 nm

50 nm

Fig. 3. Series of IL-TEM micrographs of platinum particles on a carbon support, showing: (a) Particle
detachment; (b) Particle movement and agglomeration; and (c) Displacement of the carbon support under
various harsh potential cycling conditions (Reproduced by permission of Woodhead Publishing)

140 © 2013 Johnson Matthey

http://dx.doi.org/10.1595/147106713X664824 •Platinum Metals Rev., 2013, 57, (2)•

insights into electrocatalyst stability on the nanoscale to elucidate ageing mechanisms and their possible
level under various regimes and thus allows a direct predictions. The author also discusses the newly
(visual) observation of the effect of electrochemical developed transient, multi-scale and multi-physics
treatments on carbon-supported high surface area single cell model MEMEPhys® (13) and emphasises
electrocatalysts (9). the need to generate representative accelerated testing
methods in the field.
Durability Tests Finally, Volume 1 ends with Chapter 12 entitled
Chapter 8: ‘Degradation and Durability Testing of ‘Experimental Monitoring Techniques for Polymer
Low Temperature Fuel Cell Components’ is well- Electrolyte Membrane Fuel Cells’. This chapter
written and well-structured. It discusses accelerated describes the various techniques and methods
durability test protocols (ex situ and in situ) mainly employed for on-line and off-line logging, monitoring
for the critical low-temperature PEMFC components and diagnosis of important fuel cell parameters (for
which are the PEM, the electrocatalyst and the example, temperature, humidity, current distribution,
electrocatalyst carbonaceous support materials. local pressure distribution and pressure drop) during
The chapter also briefly covers the effect of fuel operation.
contaminants on durability. Chapter 8 nicely
highlights the main publications dealing with Volume 2: “In Situ Characterization
degradation and durability studies and protocols for Techniques for Low Temperature Fuel Cells”
the membrane electrode assembly (MEA) and its Volume 2 consists of three parts: Part I entitled
subcomponents. ‘Advanced Characterization Techniques for Polymer
Chapter 9 is a very good and systematic discussion Electrolyte Membrane and Direct Methanol Fuel
of the stochastic microstructure techniques for the Cells’, Part II entitled ‘Characterization of Water
determination of transport property parameters as well and Fuel Management in Polymer Electrolyte
as the study of the effect of porous structure materials Membrane and Direct Methanol Fuel Cells’ and Part
upon transport behaviours within the critical PEMFC III entitled ‘Locally Resolved Methods for Polymer
catalyst layer, gas diffusion layer and microporous Electrolyte Membrane and Direct Methanol Fuel
layer regions. Cell Characterization’. I thoroughly enjoyed reading
Volume 2 as it covers comprehensively the important
Modelling and main (in situ) techniques and methods currently
Chapter 10: ‘Multi-scale Modelling of Two-Phase employed in characterising in detail MEA and MEA
Transport in Polymer Electrolyte Membrane Fuel subcomponents (fuel cell electrocatalyst, catalyst
Cells’ discusses in detail the pore network model and layer, membrane and gas diffusion medium) as
the lattice Boltzmann model for the modelling of well as water and fuel management. It would have
two-phase flow in porous PEMFC materials such as been very useful to have included a summary table
gas diffusion layers and catalyst layers. The chapter showing the in situ and ex situ characterisation
describes how pore-scale information (for example, techniques which help to elucidate the degradation
microstructure, transport and performance) can be mechanisms for all MEA components and water
useful for more predictive macroscopic scale-up. and fuel management (including extended X-ray
Chapter 11, entitled ‘Modelling and Analysis of absorption fine structure (EXAFS), IL-TEM, three-
Degradation Phenomena in Polymer Electrolyte dimensional (3D)-TEM, in situ X-ray tomography
Membrane Fuel Cells’, is an excellent review of (XRT), small angle X-ray scattering (SAXS), X-ray
the various available models describing PEMFC adsorption near edge structure (Δμ XANES),
degradation phenomena and mechanisms. The neutron radiography, neutron tomography, magnetic
chapter highlights the most important work on resonance imaging, synchrotron radiography,
the subject in the last 20 years and also briefly Raman spectroscopy, scanning electron microscopy
introduces pioneering work by, for example, Springer (SEM) and laser optical methods).
et al. (Los Alamos National Laboratory, New Mexico,
USA) (10), Bernardi and Verbrugge (General Motors Conclusions
Research and Environmental Staff, USA) (11) and This two-volume set presents a fairly comprehensive
Antoine (Université de Genève, Switzerland) et al. and detailed review of low-temperature PEMFCs and
(12). This chapter also describes systematically and DMFCs and their in situ characterisation methods
comprehensively the various modelling approaches by reviewing in detail their fundamentals and

141 © 2013 Johnson Matthey

http://dx.doi.org/10.1595/147106713X664824 •Platinum Metals Rev., 2013, 57, (2)•

performance as well as advanced in situ spectroscopic 10 T. E. Springer, T. A. Zawodzinski and S. Gottesfeld,

techniques for their characterisation. I was impressed J. Electrochem. Soc., 1991, 138, (8), 2334
by the content and breadth of this detailed work. There 11 D. M. Bernardi and M. W. Verbrugge, J. Electrochem.
are of course already books available covering similar Soc., 1992, 139, (9), 2477
areas and there is some duplication between chapters 12 O. Antoine, Y. Bultel and R. Durand, J. Electroanal.
(for example, fuel cell descriptions), but this does not Chem., 2001, 499, (1), 85
detract from the overall experience. The book set also 13 A. A. Franco, ‘A Physical Multiscale Model of the
Electrochemical Dynamics in a Polymer Electrolyte Fuel
highlights the key challenges for the commercialisation
Cell – An Infinite Dimensional Bond Graph Approach’,
of PEMFC-based systems, mainly related to life cycle PhD Thesis, Université Claude Bernard Lyon-1,
analysis of the overall systems and global research France, 2005
and development efforts on materials development for
durability and long term operation.
This is a very informative work, especially with
regard to current progress on in situ characterisation
techniques (Volume 2). Although I was a little
disappointed at the lack of high-temperature PEMFC
information, I would definitely recommend this book
set for readers who are either experienced or new in
this exciting field.

References
1 I. Staffell, ‘Fuel Cells for Domestic Heat and Power:
Are They Worth It?’, PhD Thesis, School of Chemical
Engineering, University of Birmingham, UK, September
2009
2 B. G. Pollet, I. Staffell and J. L. Shang, Electrochim. Acta,
2012, 84, 235 and references therein
3 S. Sharma and B. G. Pollet, J. Power Sources, 2012,
208, 96
4 M. K. Debe, Nature, 2012, 486, (7401), 43
5 “Catalysis in Electrochemistry: From Fundamentals to
Strategies for Fuel Cell Development”, eds. E. Santos and
W. Schmickler, John Wiley & Sons, Inc, Hoboken, New
Jersey, USA, 2011 “Polymer Electrolyte Membrane and Direct Methanol
6 “PEM Fuel Cell Electrocatalysts and Catalyst Layers: Fuel Cell Technology”, Volumes 1 & 2
Fundamentals and Applications”, ed. J. Zhang, Springer-
Verlag London Ltd, Guildford, Surrey, UK, 2008 The Reviewer
7 A. El-kharouf and B. G. Pollet, ‘Gas Diffusion Media
Bruno G. Pollet FRSC recently joined
and Their Degradation’, in “Polymer Electrolyte Fuel Cell Hydrogen South Africa (HySA) Systems
Degradation”, eds. M. M. Mench, E. C. Kumbur and T. Competence Centre at the University
N. Veziroglu, Elsevier Inc, Waltham, Massachusetts, USA, of the Western Cape as Director and
2012, pp. 215-247 Professor of Hydrogen and Fuel Cell
Technologies. Pollet has extensive
8 P. J. Hamilton and B. G. Pollet, Fuel Cells, 2010, 10, expertise in the research fields of
(4), 489 PEMFC, fuel cell electrocatalysis and
electrochemical engineering. Website:
9 K. J. J. Mayrhofer, S. J. Ashton, J. C. Meier, G. K. H. http://www.hysasystems.org/
Wiberg, M. Hanzlik and M. Arenz, J. Power Sources,
2008, 185, (2), 734

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