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Qingfeng Li · David Aili
Hans Aage Hjuler · Jens Oluf Jensen
Editors

High Temperature
Polymer Electrolyte
Membrane Fuel Cells
Approaches, Status, and Perspectives
High Temperature Polymer Electrolyte
Membrane Fuel Cells
Qingfeng Li • David Aili •
Hans Aage Hjuler •
Jens Oluf Jensen
Editors

High Temperature
Polymer Electrolyte
Membrane Fuel Cells
Approaches, Status,
and Perspectives
Editors
Qingfeng Li David Aili
Department of Energy Conversion Department of Energy Conversion
and Storage and Storage
Technical University of Denmark Technical University of Denmark
Lyngby, Denmark Lyngby, Denmark

Hans Aage Hjuler Jens Oluf Jensen

Danish Power Systems Department of Energy Conversion
Kvistgård, Denmark and Storage
Technical University of Denmark
Lyngby, Denmark

ISBN 978-3-319-17081-7 ISBN 978-3-319-17082-4 (eBook)

DOI 10.1007/978-3-319-17082-4
Springer Cham Heidelberg New York Dordrecht London

Library of Congress Control Number: 2015948948

# Springer International Publishing Switzerland 2016

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or
part of the material is concerned, specifically the rights of translation, reprinting, reuse of
illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way,
and transmission or information storage and retrieval, electronic adaptation, computer software,
or by similar or dissimilar methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are
exempt from the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in
this book are believed to be true and accurate at the date of publication. Neither the publisher nor
the authors or the editors give a warranty, express or implied, with respect to the material
contained herein or for any errors or omissions that may have been made.

Printed on acid-free paper

Springer International Publishing AG Switzerland is part of Springer Science+Business Media

(www.springer.com)
Contents

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Jens Oluf Jensen, Hans Aage Hjuler,
David Aili, and Qingfeng Li
2 Modifications of Sulfonic Acid-Based Membranes . . . . . . . . . 5
Antonino S. Aricò, Vincenzo Baglio, Francesco Lufrano,
Alessandro Stassi, Irene Gatto, Vincenzo Antonucci,
and Luca Merlo
3 Acid–Base Chemistry and Proton Conductivity . . . . . . . . . . . 37
Qingfeng Li, David Aili, Robert F. Savinell,
and Jens Oluf Jensen
4 Applications of Acid–Base Blend Concepts
to Intermediate Temperature Membranes . . . . . . . . . . . . . . . 59
Jochen Kerres
5 Pyridine Containing Aromatic Polyether Membranes . . . . . . 91
Joannis K. Kallitsis, Aikaterini K. Andreopoulou,
Maria Daletou, and Stylianos Neophytides
6 Techniques for PBI Membrane Characterization . . . . . . . . . 127
Dirk Henkensmeier and David Aili
7 Synthesis of Polybenzimidazoles . . . . . . . . . . . . . . . . . . . . . . 151
Jingshuai Yang, Ronghuan He, and David Aili
8 Phosphoric Acid and its Interactions
with Polybenzimidazole-Type Polymers . . . . . . . . . . . . . . . . . 169
Carsten Korte, Fosca Conti, Jürgen Wackerl,
and Werner Lehnert
9 Polybenzimidazole Membranes by Post Acid Doping . . . . . . . 195
David Aili, Jens Oluf Jensen, and Qingfeng Li
10 PBI Membranes Via the PPA Process . . . . . . . . . . . . . . . . . . 217
Kayley Fishel, Guoqing Qian, and Brian C. Benicewicz

v
vi Contents

11 Polybenzimidazoles with Enhanced Basicity:

A Chemical Approach for Durable Membranes . . . . . . . . . . 239
Simone Angioni, Davide Carlo Villa,
Piercarlo Mustarelli, and Eliana Quartarone
12 Polybenzimidazole/Porous Poly(tetrafluoro ethylene)
Composite Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
T. Leon Yu
13 PBI-Based Composite Membranes . . . . . . . . . . . . . . . . . . . . . 275
José J. Linares, Liliane C. Battirola, and Justo Lobato
14 Catalysts and Catalyst-Layers in HT-PEMFCs . . . . . . . . . . . 297
Tom Engl, Lorenz Gubler, and Thomas J. Schmidt
15 Catalyst Support Material and Electrode Fabrication . . . . . . 315
Marina Welsch and Markus Perchthaler
16 Design and Optimization of HT-PEMFC MEAs . . . . . . . . . . 331
Jung Ock Park and Suk-Gi Hong
17 Characterization of HT-PEM
Membrane-Electrode-Assemblies . . . . . . . . . . . . . . . . . . . . . . 353
F. Javier Pinar, Maren Rastedt, Nadine Pilinski,
and Peter Wagner
18 Approaches for the Modeling of PBI/H3PO4
Based HT-PEM Fuel Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
Christian Siegel, Sebastian Lang, Ed Fontes,
and Peter Beckhaus
19 Bipolar Plates and Gaskets: Different Materials
and Processing Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
Isabel Kundler and Thorsten Hickmann
20 Stack Concepts for High Temperature Polymer
Electrolyte Membrane Fuel Cells . . . . . . . . . . . . . . . . . . . . . . 441
Holger Janßen, Jen Supra, and Werner Lehnert
21 High Temperature PEM Fuel Cell Systems, Control
and Diagnostics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
Søren Juhl Andreasen, Søren Knudsen Kær,
Kristian Kjær Justesen, and Simon Lennart Sahlin
22 Durability Issues and Status of PBI-Based Fuel Cells . . . . . . 487
Mark Tonny Dalsgaard Jakobsen, Jens Oluf Jensen,
Lars Nilausen Cleemann, and Qingfeng Li
23 High Temperature Polymer Electrolyte Fuel Cell
Systems for Aircraft Applications . . . . . . . . . . . . . . . . . . . . . 511
Wendelin Waiblinger, Josef Kallo, Johannes Schirmer,
and K. Andreas Friedrich
Contents vii

24 Electrochemical Hydrogen Pumping . . . . . . . . . . . . . . . . . . . 527

Kayley Fishel, Guoqing Qian, Glenn Eisman,
and Brian C. Benicewicz

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
Preface

Since the concept of high temperature polymer electrolyte membrane fuel

cells (HT-PEMFC) was proposed in early 1990s, it has attracted a large
interest in the fuel cell community and over time spread around the world.
Hundreds of patents have been filed and thousands of research papers have
been published on the subject. Both research and development activities are
flourishing at research institutions as well as in industrial companies. Many
new scientists and engineers have been educated in the field and more are
coming. Multiple products including polymer membranes, electrodes, cells,
stacks, and systems are today available on the market, though a real com-
mercial breakthrough is yet to be seen.
Thus, we decided that it was time to review and update the knowledge
about the materials and technology in a book dedicated to the HT-PEMFC.
Our aim is that it will be used as a reference for the fuel cell communities in
universities and companies as well as for students around the world.
Going forward, the main challenges for HT-PEMFC—as for other fuel
cell technologies—are the cost, performance, and the durability issues. The
use of platinum and other noble metals as well as other expensive materials is
a significant barrier for the technology to enter the market on a large scale.
Also the durability or the lifetime of materials, components, and systems
must be enhanced. Further, there might be even more barriers for an
emerging technology that need to be overcome which can be customer
adaptation, concerns about pressurized hydrogen, toxic fuels, and other
hazards. We hope that this book can be helpful to overcome at least some
of these challenges.
We are very pleased to have received so many well-written chapters from
researchers and workers of expertise in the field. We would like to thank all
the authors for the many hours they have spent. We are also grateful for the
good discussions we have had with the authors. The authors of the individual
chapters were granted a high degree of freedom to follow their own
preferences with regard to use of abbreviations and to their choice of English
orthography, though attempts are made to keep technical terms consistent.
We would also like to mention that the group of contributors was not put
together with the aim to include all key research groups or companies
involved in the PBI-based HT-PEMFC development, but merely to cover,
as we see it, the most important scientific aspects of the technology without
too much redundancy. This means that several leading groups are not directly
ix
x Preface

represented as authors but well referred to in the chapters. We hope for their
understanding.
A special thanks goes to Kenneth Howell, Abira Sengupta, and other staff
from Springer Publishing in New York. They have been extremely helpful
for all practical aspects of getting this book published.
Finally, on behalf of all the authors, we would like to thank all funding
agencies, universities, and companies that have made it possible to do all the
work in the laboratories around the world.

Lyngby, Denmark Qingfeng Li

Lyngby, Denmark David Aili
Lyngby, Denmark Jens Oluf Jensen
Kvistgård, Denmark Hans Aage Hjuler
Contributors

David Aili Department of Energy Conversion and Storage, Technical

University of Denmark, Kgs. Lyngby, Denmark
Søren Juhl Andreasen Department of Energy Technology, Aalborg
University, Aalborg East, Denmark
Aikaterini K. Andreopoulou Department of Chemistry, University of
Patras, Rio-Patras, Greece
Foundation for Research and Technology Hellas/Institute of Chemical Engi-
neering Sciences (FORTH/ICE-HT), Patras, Greece
Simone Angioni Department of Chemistry and INSTM, University of
Pavia, Pavia, Italy
Vincenzo Antonucci CNR-ITAE, Messina, Italy
Antonino S. Arico CNR-ITAE, Messina, Italy
Vincenzo Baglio CNR-ITAE, Messina, Italy
Liliane C. Battirola Instituto de Quı́mica, Universidade de Campinas,
Campinas, SP, Brazil
Peter Beckhaus ZBT GmbH – Zentrum für BrennstoffzellenTechnik,
Duisburg, Germany
Brian C. Benicewicz Department of Chemistry and Biochemistry,
University of South Carolina, Columbia, SC, USA
Lars Nilausen Cleemann Department of Energy Conversion and Storage,
Technical University of Denmark, Kgs. Lyngby, Denmark
Fosca Conti Department of Chemical Sciences, University of Padova,
Padova, Italy
Maria Daletou Foundation for Research and Technology Hellas/Institute of
Chemical Engineering Sciences (FORTH/ICE-HT), Patras, Greece
Glenn Eisman H2Pump LLC, Latham, NY, USA
Tom Engl Electrochemistry Laboratory, Paul Scherrer Institut, Villigen
PSI, Switzerland
Kayley Fishel Department of Chemistry and Biochemistry, University of
South Carolina, Columbia, SC, USA
xi
xii Contributors

Ed Fontes COMSOL AB, Stockholm, Sweden

K. Andreas Friedrich Institute of Engineering Thermodynamics, German
Aerospace Center, Stuttgart, Germany
Irene Gatto CNR-ITAE, Messina, Italy
Lorenz Gubler Electrochemistry Laboratory, Paul Scherrer Institut,
Villigen PSI, Switzerland
Ronghuan He Department of Chemistry, College of Sciences, Northeastern
University, Shenyang, China
Dirk Henkensmeier Fuel Cell Research Center, Korea Institute of Science
and Technology, Seongbukgu, Seoul, South Korea
Thorsten Hickmann Eisenhuth GmbH & Co. KG, Osterode am Harz,
Germany
Hans Aage Hjuler Danish Power Systems, Kvistgård, Denmark
Suk-Gi Hong Samsung Advanced Institute of Technology, Samsung
Electronics, Co. Ltd, Seoul, South Korea
Mark Tonny Dalsgaard Jakobsen Department of Energy Conversion and
Storage, Technical University of Denmark, Kgs. Lyngby, Denmark
Holger Janßen Forschungszentrum Jülich GmbH, Jülich, Germany
Jens Oluf Jensen Department of Energy Conversion and Storage, Techni-
cal University of Denmark, Kgs. Lyngby, Denmark
Kristian Kjær Justesen Department of Energy Technology, Aalborg
University, Aalborg East, Denmark
Joannis K. Kallitsis Department of Chemistry, University of Patras,
Rio-Patras, Greece
Foundation for Research and Technology Hellas/Institute of Chemical
Engineering Sciences (FORTH/ICE-HT), Patras, Greece
Josef Kallo Institute of Engineering Thermodynamics, German Aerospace
Center, Stuttgart, Germany
Jochen Kerres Institute of Chemical Process Engineering, University of
Stuttgart, Stuttgart, Germany
Carsten Korte Institute for Energy and Climate Research, Electrochemical
Process Engineering (IEK-3), Jülich, Germany
Isabel Kundler Eisenhuth GmbH & Co. KG, Osterode am Harz, Germany
Søren Knudsen Kær Department of Energy Technology, Aalborg Univer-
sity, Aalborg East, Denmark
Sebastian Lang Technische Universität Darmstadt, Fachgebiet Thermische
Verfahrenstechnik, Darmstadt, Germany
Contributors xiii

Werner Lehnert Institute of Energy and Climate Research, Electrochemi-

cal Process Engineering (IEK-3), Forschungszentrum Jülich GmbH, Jülich,
Germany
Qingfeng Li Department of Energy Conversion and Storage, Technical
University of Denmark, Kgs. Lyngby, Denmark
José J. Linares Instituto de Quı́mica, Universidade de Brası́lia, Brası́lia,
DF, Brazil
Justo Lobato Chemical Engineering Department, Universidad de Castilla-
La Mancha, Ciudad Real, Spain
Francesco Lufrano CNR-ITAE, Messina, Italy
Luca Merlo Solvay Specialty Polymers, Bollate (MI), Italy
Piercarlo Mustarelli Department of Chemistry and INSTM, University of
Pavia, Pavia, Italy
Stylianos Neophytides Foundation for Research and Technology Hellas/
Institute of Chemical Engineering Sciences (FORTH/ICE-HT), Patras,
Greece
Jung Ock Park Samsung Advanced Institute of Technology, Samsung
Electronics, Co. Ltd, Seoul, South Korea
Markus Perchthaler Elcomax GmbH, Munich, Germany
Nadine Pilinski NEXT ENERGY, EWE Research Centre for Energy
Technology, Oldenburg, Germany
F. Javier Pinar NEXT ENERGY, EWE Research Centre for Energy
Technology, Oldenburg, Germany
Guoqing Qian Department of Chemistry and Biochemistry, University of
South Carolina, Columbia, SC, USA
Eliana Quartarone Department of Chemistry and INSTM, University of
Pavia, Pavia, Italy
Maren Rastedt NEXT ENERGY, EWE Research Centre for Energy
Technology, Oldenburg, Germany
Simon Lennart Sahlin Department of Energy Technology, Aalborg
University, Aalborg East, Denmark
Robert F. Savinell Department of Chemical Engineering, Case Western
Reserve University, Cleveland, OH, USA
Johannes Schirmer Institute of Engineering Thermodynamics, German
Aerospace Center, Stuttgart, Germany
Thomas J. Schmidt Electrochemistry Laboratory, Paul Scherrer Institut,
Villigen PSI, Switzerland
Laboratory of Physical Chemistry, ETH Zürich, Zürich, Switzerland
xiv Contributors

Christian Siegel Siegel Schleimer Ingénieurs-conseils SARL, Belvaux,

Luxembourg
Alessandro Stassi CNR-ITAE, Messina, Italy
Jen Supra Forschungszentrum Jülich GmbH, Jülich, Germany
Davide Carlo Villa Department of Chemistry and INSTM, University of
Pavia, Pavia, Italy
Jürgen Wackerl Institute for Energy and Climate Research, Electrochemi-
cal Process Engineering (IEK-3), Jülich, Germany
Peter Wagner NEXT ENERGY, EWE Research Centre for Energy
Technology, Oldenburg, Germany
Wendelin Waiblinger Institute of Engineering Thermodynamics, German
Aerospace Center, Stuttgart, Germany
Jesse S. Wainright Case Western Reserve University, Cleveland, OH, USA
Marina Welsch Elcomax GmbH, Munich, Germany
Jingshuai Yang Department of Chemistry, College of Sciences,
Northeastern University, Shenyang, China
T. Leon Yu Department of Chemical Engineering and Materials Science,
Fuel Cell Center, Yuan Ze University, Chung-Li, Taoyuan, Taiwan
About the Editors

David Aili obtained his M.Sc. degree in Organic Chemistry in 2007 from
the Institute of Technology at Linköping University after a diploma project at
the Arrhenius Laboratory, Stockholm University. He subsequently moved to
Technical University of Denmark to pursue a Ph.D. in the field of proton
conducting membranes for electrochemical energy conversion technologies
under the supervision of Professor Niels J. Bjerrum at the Department of
Chemistry. After obtaining his Ph.D. degree in 2011 and after a shorter
period as a development engineer in the phenolic resin business, he joined
the newly formed Department of Energy Conversion and Storage at Techni-
cal University of Denmark in 2012 as a Postdoctoral Research Fellow. His
current research covers fundamental and application-oriented aspects of ion
conducting materials with special emphasis on polymer-based membranes.

Hans Aage Hjuler was educated as M.Sc. (Chemistry) at Technical Univer-

sity of Denmark in 1980. In 1983, he obtained his Ph.D. degree in Advanced
Rechargeable Batteries at Technical University of Denmark. As postdoc, he
formed a significant research group in batteries (from 1983) and fuel cells
R&D (from 1988). He has worked with PAFC, MCFC, SOFC, and
PEM-based fuel cell systems and materials. He worked as laboratory man-
ager with superconducting materials (high Tc) at NKT Research Center from
1991 to 1994. He was director in Novo Nordisk from 1998 to 2009. He was
one of the founders of Danish Power Systems in 1994 and chairman from
xv
xvi About the Editors

1994 to 2010. He was appointed Managing Director, CEO in 2010. H.A.H. is

vice-chair of the Board of Directors of the Danish Partnership for Hydrogen
and Fuel Cells, member of Annex 22, International Energy Agency (IEA)
Implementing Agreement on Advanced Fuel Cells. He is member of the
Scientific Committee of Fuel Cell and Hydrogen Joint Undertaking
(FCH-JU), European Commission, Brussels, Belgium.

Jens Oluf Jensen is a full Professor at Technical University of Denmark,

where he is heading the section named Proton Conductors (ca. 25 people) at
Department of Energy Conversion and Storage. He is the coordinator of the
technology tracks for PEM fuel cells and for low temperature electrolyzers at
the department. In 1997, he received his Ph.D. for a study on metal hydrides
for batteries. Today, his research fields include high temperature PEM fuel
cells and alkaline electrolyzers. The approach is experimental and focused on
materials like electrolytes, catalysts, and electrode structures. He has
initiated and coordinated numerous national and international research
projects, mostly in collaboration with industry, and arranged a number of
symposia/workshops. Lately, he chaired the third International Carisma
Conference in Copenhagen 2012 and the Danish Korean PEM Fuel cell
workshop in Seoul 2013. He is a board member of the Partnership for
About the Editors xvii

Hydrogen and Fuel cells in Denmark. At DTU, he has taught at numerous

courses and is at present involved in teaching hydrogen energy and fuel cells
as well as thermodynamics.

Qingfeng Li is a full professor at Department of Energy Conversion and

Storage, Technical University of Denmark. His research areas include proton
conducting electrolytes, electrocatalysts, and the related technologies partic-
ularly fuel cells and electrolyzers. He received his Ph.D. in electrochemistry
from Northeastern University, China, in 1990 and was awarded Doctor
Degree of Technices at DTU in 2006. As a postdoc, he started in the middle
of 1990s the research on high temperature polymer electrolyte membrane
fuel cells at DTU. He has participated/coordinated more than 20 EU and
Nordic research projects within the fuel cell area and is currently the leader of
4M Centre devoted to fundamental research on mechanisms, materials,
manufacturing, and management of high temperature polymer electrolyte
membrane fuel cells, funded by Innovation Fund Denmark. He is an active
member of, among other, the Electrochemical Society and the International
Society of Electrochemistry (and currently the region representative of
Denmark 2012-now). Prof. Li has been involved in teaching at all DTU
levels including a lecturing and an experimental course on Hydrogen Energy
and Fuel cells.
 Overture: The Early History of
PBI/Phosphoric Acid Membranes
Robert F. Savinell and Jesse S. Wainright

The two of us, Robert F. Savinell (R.F.S.) and Jesse S. Wainright (J.S.W.),
have collaborated on the development of PBI/PA membranes for fuel cells at
CWRU from the very early days, and are pleased to tell this story about the
early history of the PBI/PA high temperature membrane for fuel cells.
It was in the late 1980s time period when R.F.S. was the Associate
Director of the Case Center for Electrochemical Sciences (now the Yeager
Center for Electrochemical Sciences at Case Western Reserve University)
working with Professor Ernest B Yeager (see Fig. 1).

Robert F. Savinell (*) • Jesse S. Wainright

Department of Chemical Engineering, A.W. Smith
Building, Case Western reserve University,
Cleveland, Ohio 44106, USA
e-mail: Robert.savinell@case.edu

xix
xx Overture: The Early History of PBI/Phosphoric Acid Membranes

Fig. 1. Robert F. Savinell on far left and Professor Yeager on right of plaque at the celebration
of the renaming of the Case Center of Electrochemical Sciences to the Yeager Center for
Electrochemical Sciences with CWRU administrators and Dorothy Hummel Hovorka, wife of
Frank Hovorka, Professor Yeager’s Ph.D. advisor

At that time, Professor Yeager’s group was interested in enhancing the

electrokinetics of oxygen reduction reaction in a phosphoric acid electrolyte.
One approach he took was to add perfluorinated surfactants to a phosphoric
acid electrolyte so as to enrich the oxygen activity near the electrocatalyst
surface. Indeed, this worked to some extent and enhanced oxygen reduction
polarization curves were demonstrated. It was this work that stimulated our
thinking about fuel cells and the idea of using a high temperature membrane.
In early 1991, Professor Yeager and R.F.S. met with colleagues on a
weekly basis to discuss research strategies to address the development of a
high performance direct methanol fuel cell. These meetings explored many
different aspects of improving methanol fuel cell performance from
electrocatalysts and membrane materials to cell designs. A number of times
we would go down a strategic path in great detail, but only to throw out the
approach after weeks of deep discussion. After about 6 months of weekly
discussions and as we rapidly drew near a proposal submission deadline, we
concluded that if a proton conducting polymer membrane can be developed
that operates at ~200  C, then there would be “opportunities to overcome the
catalyst’s activity and stability problems.” The thought was that the right
membrane could lead to high performance direct methanol fuel cells.
Overture: The Early History of PBI/Phosphoric Acid Membranes xxi

Fig. 2. Professor Morton Litt examining an early sample

of a cast PBI membrane (from Case Alumnus, Spring
1997)

We then set out to propose a research program with its principle objective
being the development of a high proton conducting solid polymer electrolyte
membrane which is chemically stable under the oxidizing and reducing
conditions existing in a direct methanol fuel cell and operates at temperatures
of 200  C. Two approaches that were proposed involved new polymers with
superacid functional groups such as the perfluorinated sulfonimides and the
perfluorinated phosphonic acid materials, with the thought that they would
retain water even at higher temperatures. Looking for alternative approaches,
Professor Morton Litt of CWRU (see Fig. 2) brought to our attention the 1977
work of Hoel and Grunwald [J. Phys. Chem., 81 2135 (1977)] which reported
evidence of proton conductivity in films of polybenzimidazole, although the
conductivities were quite low (104 S cm1). Professor Litt suggested we
explore poly(benzimidazoles) and poly(quinolones) by doping films with
acid and even trying to functionalize the films with acid groups.
These polymers were known to be stable at elevated temperatures. As the
PI for the research program, R.F.S. decided to include this idea to broaden
our membrane approaches. The proposal was submitted to the US Defense
Advanced Research Projects Agency (DARPA) on July 11, 1991, and
included the three polymer approaches mentioned above, as well as new
electrocatalysts for operating in these polymeric environments, and a variety
of fundamental measurements. We also proposed integrating these new
materials in a laboratory scale “microfuel cell” to demonstrate actual
operating performance. The program was selected for funding and a contract
awarded in 1992. This is when J.S.W., just completing his Ph.D. studies,
joined R.F.S. and the team to pursue this research program (see Fig. 3).
 xxii Overture: The Early History of PBI/Phosphoric Acid Membranes

Fig. 3. Jesse S. Wainright and Robert F. Savinell in the early days of PBI/PA
research (from Case Alumnus, Spring 1997)

CW1 − H3PO4 Conductivity

0.30

CW #1
0.25
85% H3PO4
Conductivity / ohm−1 cm−1

heating
0.20
cooling

0.15

0.10

0.05

Nafion-H3PO4

0.00
0 40 80 120 160 200
Temperature / °C
Fig. 4. Four-point conductivity measurements for Nafion 117 and polybenzi-
midazole films infused with phosphoric acid. Conductivity cell measurements of
phosphoric acid shown for comparison. Figure 3 of the first quarter (ending
September 1992) project report of the CWRU DARPA methanol fuel cell project
Overture: The Early History of PBI/Phosphoric Acid Membranes xxiii

The CWRU DARPA program pursued all three polymer approaches simul-
taneously. Eventually, we learned that the superacid perfluorinated polymer
strategy produced some very intriguing membrane films, but none performed
any better at elevated temperatures than the state-of-the-art Nafion product of
DuPont. Here, we will summarize of our early quarterly progress reports of
the CWRU DARPA program that give some insight on our early thinking and
contain much unpublished data and results. During the first quarter of the
project, sulfuric acid and phosphoric acid sorption in PBI films studies were
initiated. It was demonstrated that with a H2SO4/PBI molar ratio of 0.2,
the PBI unit interacted so strongly with the acid that the acid could not be
extracted from the polymer with water. The first conductivity measurements
were made on acid-doped PBI, and the first quarterly project report for the
period ending September 1992 stated: “The third set of results is for the
CWRU undoped polybenzimidazole sample which has been given the desig-
nation CW1. As received, this material exhibited a very low conductivity,
ca. 104 S cm1. Doped films are expected to have much higher proton
conductivity. We pretreated the undoped film in H3PO4 for 1 h at 150  C and
the conductivity was found to be very high, as shown in Figure 3 (Fig. 4 of
this article). This data was obtained in dry air. The conductivity of the CW1
sample is much greater than that of the hydrated Nafion sample and
approaches the conductivity of the liquid phosphoric acid. It would appear
that the CW1 sample is acting as an acid support.”
During the second quarter, ending December 1992, it was shown that
phosphoric acid-doped PBI was more thermally stable than undoped PBI
films. Studies also measured sulfuric acid and phosphoric acid permeation
through PBI films in order to predict doping times. More controlled
experiments of conductivity as a function of acid doping took place during
this quarter, with phosphoric acid doping levels of 25, 33, and 42 mol%, all
showing relatively low conductivities.
In the third quarter of this program, ending March 1993, we demonstrated
that as phosphoric acid doping levels increased from 40 to 170–190 mol%
(mole acid to PBI repeat unit X100), the conductivity also improved substan-
tially. J.S.W. was the persistent researcher in the lab who recognized the
increasing conductivity trend with acid doping level and continued the
studies to explore the effects on conductivity at even higher acid doping
levels. We also showed that doping with excess sulfuric acid increased
conductivity, and 250 mol% sulfuric acid-doped PBI at 160  C had about a
quarter of the conductivity of Nafion at 80  C fully hydrated. But, high
doping levels with sulfuric acid at temperatures of 350  C for a few minutes
sulfonated PBI, which decreased conductivity. During that quarter, we also
xxiv Overture: The Early History of PBI/Phosphoric Acid Membranes

began to appreciate the importance of phosphoric acid dehydration and

polymerization in low humidity conditions so we initiated experiments
controlling the relative humidity during conductivity measurements. It was
shortly after this quarter we discontinued using sulfuric acid, and focused
attention on phosphoric acid doping of PBI. During the third quarter, we also
started measuring oxygen and methanol permeation rates through a PBI/acid-
doped film and compared the measured permeability with those of Nafion
and acid-doped/Nafion films.
During the fourth quarter, ending June 1993, we started exploring various
PBI-type structures. Also during the first year of the program, we studied the
Nafion/PA system as well and used its conductivity, stability, and permeabil-
ity characteristics as a basis for comparison with PBI/PA or PBI/SA results.
The research performed during the fifth quarter of the program, ending
September 1993, was especially significant. We became fully aware of the
importance of high molecular weight PBI polymers for film strength. We
demonstrated high conductivity with PA doping levels of 350 mol%,
approaching 0.02 S cm1 at 190  C. Doping levels would later be increased
to over 500 mol% in our labs, and even higher by other researchers. We
demonstrated methanol vapor cross over permeation rates an order of mag-
nitude below that of the hydrated Nafion in direct liquid methanol fuel cells.
The polarization curve and the operating stability under constant voltage and
constant current load were demonstrated in a PBI/PA fuel cell. Some of these
original data graphs are shown in Figure 5 (Figs. 6.5.1b, 6.5.1c, 6.5.1d of the
September 1993 Progress Report). The efforts of two of our Ph.D. students,
Jiang-Tao Wang and Dacong Weng, were particularly instrumental in
obtaining these key early results. We learned that a Nafion/PA membrane
in a fuel cell, although having high ac conductivity, could not sustain high dc
current densities. This result bothered us and suggested that there were
fundamental differences in the transport mechanism as compared to a
PBI/PA membrane. It was shortly into the second year of the program that
we stopped much of our work on the Nafion/PA system, with the exception of
using it for evaluating elecrocatalyst performance under elevated tempera-
ture conditions. Recently, we collaborated with the DTU group to investigate
the Nafion/PA system and repeated some of the observations we made earlier
at CWRU. Although not fully understood, there are clearly some significant
differences in proton conduction between the Nafion/PA and PBI/PA
systems. As a colleague recently commented to one of us, “you may have
just been lucky to stumble upon the PBI/PA system.”
Overture: The Early History of PBI/Phosphoric Acid Membranes xxv

Fig. 5. These figures are taken from the fifth quarter progress report of the CWRU DARPA Direct Methanol Fuel Cell
Program, dated September 1993. They show the first results of fuel cell testing with PBI/PA in a fuel cell

The DARPA program continued for another 3 years. During this period,
Professor Litt and his students developed a way to cast doped films in one
step that increased both the doping levels possible and the consistency of the
acid content. We explored operating a PBI/PA membrane fuel cell with
various fuels, fuel purities, and measured temperature effects. We began to
appreciate the relevancy of the technology for fuel cells operating on
reformed fuels. Our studies with PBI/PA evolved to become more thorough
and under better controlled conditions, and our understanding of the conduc-
tivity mechanism became deeper by studying water drag and performing
NMR studies. In addition to the electrolyte work, we developed new oxygen
reduction reaction electrocatalysts, including methanol-tolerant high perfor-
mance non-precious metal C–N ligands.
The CWRU patents were licensed to several companies, and our
publications (>15 papers from 1995 to 1998) on PBI/PA fuel cell membranes
garnered more attention in the USA and worldwide. These licensee
companies as well as other corporate and university researchers from around
the world further explored the PBI/PA approach to improve mechanical and
proton conducting properties and to evaluate the membranes in operating fuel
cells and electrolyzers at elevated temperatures.
xxvi Overture: The Early History of PBI/Phosphoric Acid Membranes

So what will be the long-lasting significance of the PBI/PA system, if any?

Well, the system does not represent the best environment for electrochemical
reactions such as oxygen reduction, and it certainly cannot be used at lower
temperatures with liquid water present. But we are sure PBI/PA and similar
polymers and approaches will continue to find applications in electrochem-
istry. Phosphoric acid is a highly conductive electrolyte rich in fascination
because of its fundamental mechanisms for proton transport. But other
doping acids might also be explored as well. In our view, the most significant
feature of the PBI/PA membrane discovery is that it opened the door to our
thinking about high temperature proton conducting membranes in general,
and stimulated global research to find a better approach. As a result, many
researchers have been cross-trained in electrochemistry and polymer/
materials science through their work on this technology. These cross-trained
scientists and engineers are those who will likely find better solutions in the
future for efficient and cost-effective energy conversion technologies. On a
personal level, our work on this system has led to close collaboration and
friendship with colleagues and students at CWRU, and especially between
the two coauthors of this article. It also led to many fruitful and rewarding
collaborations and friends from around the world. This is what we value
the most.

Robert F. Savinell Jesse S. Wainright

Distinguished University Professor and George Research Professor
S. Dively Professor of Engineering Case Western Reserve University
Case Western Reserve University
 Introduction
Jens Oluf Jensen, Hans Aage Hjuler, David Aili,
and Qingfeng Li
High temperature polymer electrolyte membrane
fuel cells (HT-PEMFC) have been an active field
of research and development over more than two
decades. The term high temperature used in this
book refers to a temperature range from 100 to
200  C, relative to the well-developed PEMFC
technology typically operating at 80  C. It
should be stressed that fuel cells working at
temperatures up to 200  C still belong to the
overall class of low temperature fuel cells, in
contrast to high temperature fuel cells which
are molten carbonate fuel cells (MCFC) and
solid oxide fuel cells (SOFC) all working at
above 600  C.
The temperature range from 100 to 200  C
does not sound very high in any engineering
sense; however, a significant effort is indeed
behind the development of high temperature
polymer electrolyte membranes and their cells,
from both materials science and technological
points of view. Obviously, elevated temperatures
tend to challenge thermal, chemical, and mechan-
ical stability of polymer materials, but besides
that, obtaining sufficient proton conductivity in
J.O. Jensen (*) • D. Aili • Q. Li
Department of Energy Conversion and Storage,
Kemitorvet 207, 2800 Lyngby, Denmark
e-mail: jojen@dtu.dk; larda@dtu.dk; qfli@dtu.dk
H.A. Hjuler
Danish Power Systems ApS, Egeskovvej 6C, 3490
Kvistgård, Denmark
e-mail: hah@daposy.dk
# Springer International Publishing Switzerland 2016
Q. Li et al. (eds.), High Temperature Polymer Electrolyte Membrane Fuel Cells,
DOI 10.1007/978-3-319-17082-4_1
1
a stable and practical way, most preferably under
ambient pressure, is far from trivial. One might
think that a proton, a positive hydrogen ion, being
orders of magnitude smaller than any other ion
will have the ability to travel easily through many
materials simply due to its tiny size. The contrary
is true. The extremely small size makes the
charge density very high, and the protons are
always associated to other species. In a liquid
electrolyte, this is not a problem since other
mobile molecules carry the proton as a charged
species and establish a net movement of the
protons. The first fuel cells were developed
around liquid electrolytes, but from a construc-
tion and handling point of view and in order to
make the electrolyte as thin as possible to mini-
mize internal resistance, solid electrolytes are
very attractive and the electrolyte of interest
here is the proton-conducting polymer. The cells
are referred to as polymer fuel cells, polymer
electrolyte fuel cells (PEFC), or polymer electro-
lyte membrane fuel cells/proton exchange mem-
brane fuel cells (PEMFC).
In traditional PEMFC (based on polyper-
fluorosulfonic acid, PFSA), water is used as
such a proton shuttle and the polymer membrane
must be highly humidified in order to maintain
proton conductivity. An increase in operating
temperature from 80 to 150  C leads to an
increase of the water vapor pressure from 0.47
to 4.8 bar (ten times) and the membrane will dry
out and lose conductivity unless the fuel cell is
1
2 J.O. Jensen et al.
operated under a correspondingly increased pres-
sure, which is impractical in most cases. At
200  C, the water vapor pressure is as high as
15 bar. Additionally, softening of PFSA
membranes is mechanically limiting the opera-
tion at elevated temperatures.
The question is then: why increase the working
temperature of a PEMFC? This fuel cell has been
very successful and one of the key advantages is
the low working temperature. Startup is easy,
the gases need not to be preheated, the selection
of construction materials is wide (including
elastomers for sealing), and degradation
processes are generally slower at lower tem-
peratures. All this is true, but there are yet a
number of advantages of a higher temperature.
Key drivers for the development have been
(1) increased tolerance to fuel impurities
(in particular, carbon monoxide) of the platinum
catalyst, (2) easier water management or even no
water management at all (when conduction is not
depending on water), (3) easier thermal manage-
ment (cooling) due to higher temperature differ-
ence to the surroundings, and (4) a higher quality
of the waste heat.
The fact that the tolerance to carbon monox-
ide increases with increasing temperature is well
known from phosphoric acid fuel cells (PAFC),
which also apply platinum as electrocatalysts.
The carbon monoxide tolerance is critical if the
fuel is hydrogen obtained via reforming (chemi-
cal conversion) of carbon containing fuels. In this
process, the carbonaceous fuel is converted into
hydrogen and carbon dioxide, but traces of car-
bon monoxide are always present as a by- prod-
uct. Carbon monoxide adsorbs strongly to
platinum surfaces and blocks the access of
hydrogen. At 80  C, a carbon monoxide content
as low as 20 ppm (0.002 %) in the fuel stream
results in a significant loss in cell performance,
but at 160  C, even 0.5–1 % carbon monoxide
has only a minor effect. Therefore, very pure
hydrogen or a complicated cleaning system is
mandatory for the low temperature PEMFC, but
not for high temperature PEMFC. Cells can thus
be easily operated on abundant fuels like metha-
nol, natural gas (methane), or liquefied petroleum
gas (LPG) through reforming when a hydrogen
infrastructure is missing.
In a conventional low temperature PEMFC, a
careful management of the water balance (water
management) to maintain a high degree of hydra-
tion of the membrane is a delicate matter. It is
crucial for maintaining high conductivity and is
done by humidification of the gas flows into the
fuel cell. Water is also produced in the cell and if
the net content gets above saturation water
condenses and blocks gas channels and porosities
leading to a severe performance drop. The water
management is further complicated by a high
electroosmotic drag of water, i.e., water transport
along with the protons, in PFSA membranes.
At temperatures above the boiling point of
water at the actual operating pressure, condensa-
tion cannot take place. This is indeed the case in
a high temperature PEMFC. Moreover, if con-
duction is based on another proton carrier than
water, then water management should be much
less intensive or even needless.
Easier cooling of PEMFC is a wish of the
automotive industry because even though fuel
cells produce less heat than small internal com-
bustion engines (ICE), heat removal is more
challenging with a low temperature fuel cell.
While the ICE rejects most of its heat through
the exhaust and a smaller part through the cooler,
the fuel cell does so mostly via the coolant loop
and a radiator. Besides, the temperature differ-
ence between the coolant and the surrounding is
smaller in case of an 80  C fuel cell than of the
ICE. The transfer of more heat by means of a
smaller temperature difference calls for a much
larger radiator, which is not convenient for the
auto developers. A fuel cell working temperature
of 120–130  C should be enough to compensate
for this effect. Similarly, if a high temperature
PEMFC is air cooled, the air flow needed is
much smaller because it carries more heat
per volume and a smaller and less energy-
intensive blower can be applied. Finally, as
about half of the energy of the fuel is converted
into heat in a fuel cell, it would be most desirable
if this heat could be better utilized. The number
of uses for this heat rises with temperature.
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VI.
LAULU ESI-ISISTÄNI,
LAUKUNKANTAJISTA

Sinä hiukan ylpeänä

suorasta nenästäsi ja vaakunasi kahdeksasta kentästä
hyppäät silmilleni
ystäväni,
ja kysyt minulta, ääni väristen,
kuka oli iso-isäni.
Ja minä hyvin ylpeänä:
kuningas.

Hänelle olivat alamaisia kahdeksan kihlakunnan tiet,

hiekkaiset, pitkät tiet, ja sateenkaariset unelmien sotajoukot.
Ja hänen sukupuunsa haarat olivat täynnä tuskan hikihelmiä
ja kuolema istui jokaisen lehvän päässä.

Ja sinä naurahdat minulle.

Mutta minä,
minä käsken sinun itkeä
ja paljastaa pääsi pitkien sarkofaagien edessä,
joissa esi-isäni nukkuvat.
Niistä nousee huokausten höyry.
Ja reunoihin olen upottanut korkokuvia:
kuninkaitten saaton,
synkeän, synkeän saaton,
jossa esi-isäni vaeltavat
selässä haavoja, jalat palaen, silmät niin
totisina,
kuninkaitten saaton,
ylpeän, ylpeän saaton.
DAIDALOS JA IKAROS

1. Ikaros

Olen vanki, tee mulle siivet. Mun rintaani ahdistaa nämä

tylyt ja sumuiset rannat, koko autio Kreetanmaa,

ja katkerat kreetalaiset
ja Minoksen synkeä ies.
Oi, isäni, tee mulle siivet.
Olen vanki, ja vapaa mies

minä voisin olla. Pois mennä

yli meren aallokon.
Toden totta. Ma tiedän: suuri
sen takana elämä on.

Toden totta. Kaupungeissa

olet kertonut asunees
ja pauhun ja jylinän kuullees
joka päivä sun huoneesees.
 Ja kauppiaitten säädyn
sinä rikkaaks kuvailit,
maamiehet rauhallisiks
ja viisaiks filosofit.

Ja jalojen soturien
sinä kerroit elävän näin:
teräs silmissä, tanassa keihäs.
Ja kuolevan pystyin päin.

Sinä naiset kuvailit kauneiks:

he on sisaret, morsiamet
ja vaimot ja nuoret äidit.
Vaan isäni, isäni, et

mua milloinkaan ole vienyt pois sinne. Ja yksin sain joka

päivä vain tuta kaipuun ja ikävän rinnassain.

Hei, kuuntele, meri huutaa

ja lokit kirkuvat,
hei, Neptunuksen kasvot
ovat vihreet ja ilkkuvat.

Hei, kangastus on noussut

meren ylle värisemään:
ma sun kaupunkisi ja maasi
niin hehkuvina nään…

Oi, isäni, tee mulle siivet:

meren yllä vapaus on,
meren yllä nään lentävän tähtein
ja kuun ja auringon
 ylen suurta ja tuntematonta ja kaunista kohti. Ja nään: ne
kaikki sittenkin tietää kuin jonkin määränpään.

2. Daidalos ja Ikaros

Me kohotamme katseemme. Ja siivet kimmeltävät on,

nähkää, meille lahjoittanut suuri Kohtalo: maa, meri vaipuu
allemme. Nyt meidät kauas kantaa yötaivas ja sen värisevä
eetteri.

Te valmistitte käsillänne köyhän ravintonne

ja verhositte vartalonne kehnoin tappuroin.
Oi, katsokaa te jälkeemme ja nähkää ihmetellen:
on kuninkaitten rikkaudet meille annetut.

Te vapisitte pimeässä kauhukuvain eessä

ja itkitte ja pakenitte metsään pimeään.
Me rintahaarniskoissa ja miekat hioittuina
kuin sotauroot käymme yli aavain kenttien.

Te kyynärpuulla mittasitte ajatusten polvet

ja punnitsitte nauloin kaikki pienet sananne.
On meidän mittanauhoinamme kiertotähtein radat
ja punnuksina ovat itse kuu ja aurinko.

Niin raivoisina kuin te joskus luojan kirositte

ja kirositte elämänne vuodet kuluneet,
niin hartaina me kumarramme luojan eteen päämme,
me, joille hän on lahjoittanut suuren huomenen.
 Te ruikuttaen kerjäsitte kuolemattomuutta
ja väsyitte kuin sylilapset haudan povehen.
Me kerran putoamme. Vaan siivin liekehtivin
ja ylpein otsin katoamme niinkuin sankarit.
SUVINEN ILTA VUODEN 1927
PROMOTSIONIKANTAATTI

Laulu esi-isille

Miten kauneina nukkuvat lapses alla koivun vihreän.

He nauravat maailmalle joka näyttää hymyilevän:

näes, taivaalla on pilvi ihan, ihan punainen, ja vihreä

niitty sen alla ja puro keskellä sen —

ja kauneina nukkuvat lapses alla koivun vihreän ja

nauravat maailmalle, joka näyttää hymyilevän.

LAPSI:

Älä säikähdä, rakas äiti, minä juuri heräsin. Minä kuljin

unessa äsken minä unessa vaelsin.

Ihan niinkuin sadussa kerroit

isoisän siellä näin,
 ja isoäidin helmaan
minä aivan hetkeks jäin.

He oli niin köyhät ja nöyrät

ja kovin surulliset.
Et siitä koskaan, äiti,
ole kertonutkaan, et.

He olivat nähneet nälkää,

ja vilua, huomasin sen.
Ja huomasin: kova ja raskas
oli hyväily molempien.

Älä säikähdä, rakas äiti, minä juuri heräsin, minä kuljin

unessa äsken, minä unessa vaelsin.

Työn laulu

Me kohotamme kätemme, ja raskain, tylyin iskuin maan

pintaan vajoo kuokkamme ja multa vapisee. Me tiedämme: on
edessämme aava halla-noro, vaan takanamme kellertää jo
viljavainiot.

Sun isäsi, mun isäni on synkän päivän jälkeen

pois vaeltaneet kaskimaalta otsin vaipunein.
Ja katso, veli, kuokka jäi ja halla-noro meille,
vaan katso, veli, jäi myös nämä kädet väkevät.

Sun isäsi, mun isäni on miekoin vyötettyinä

yön hämäryyteen tehneet työtä käsin palavin.
Ja katso, veli, miekan myös mä sidoin kupeelleni:
sen teräksessä piirtyy jana ruosteenpunainen.

Sun poikasi, mun poikani, kun kerran ehtoo saapuu ja

meidät viedään väsyneinä hautaan kalpeaan, käy ylpeinä ja
onnellisin käsin kuokan varteen ja katso, veli, miekan myös
he sitoo kupeelleen.

Suvivirsi.

Ota, Herra, korviis lastes kiitos.

Väkevänä kohoo ylitsemme keskisuves kaari, jota katsoin

me, kun esikoises, iloitsemme.

Katso, jyvistä ja ytimestä

tiukkuu syksyyn kallistuva maailmas.

Palvelijas, heinämiehet palaa

pitkin kukkaspenkereistä tietä.

Kellastuvan elopellon keskeen syttyy yksinäinen rääkkälintu

raskain äänin valittamaan. Kuule! Kirkonkelloin malmi laulaa
tuolta kaukaa, vehmaan koivukunnaan takaa. Kuule, kuule,
ota lastes kiitos!

Joku soutaa. Tuulen viri rientää kaislikossa solisten. Ja

kuule! Äännähdellen, siivet vettä viistäin kavahtavat sorsat,
lentoon nousten. Sadelintu helein huilunäänin huutaa
leppäsuppaasta. Ja kuule! Kirkonkelloin malmi laulaa tuolta
kaukaa, vehmaan koivukunnaan takaa.
 Esikoises, voimattomin äänin veisaa sulle, Herra,
suvivirren. Kuule, kuule! Harmain, raskain soinnuin,
kirkkaana, kuin hopeainen tiuku taikka värjyin, metsän
huminana suvivirsi saapuu korkeuksiis.

Katso, jyvistä ja ytimestä tiukkuu syksyyn kallistuva

maailmas!

Ota, Herra, korviis lastes kiitos!

Laulu isänmaasta

LAPSI:

Tule, lähde, yö jo saapuu, minä olen jo viluinen. Kai

kehrääjälintu lentää: minä kuulen laulun sen —

kai varjo, en tiedä, mistä on niitylle vierähtänyt, ja

sumu, katso jo hyppii ja haamut näen nyt,

ja huuhkaja kamalin äänin on noussut huutamaan. Oi

kuule, äiti, jouduin keskelle kauhujen maan.

KUORO:

Älä pelkää, rakas lapsi, ole aivan turvallinen. On

lähellä äitis ja isäs ja parvi sisarien,

ja koti on tuossa ja piha ja hevoshaka on tuo, ja

kotilammelta tuuli kaislain huminan tuo,
 ja katso, tuolla on kylä,
ja kylässä ihmiset —
ne on sun kansaas kaikki.
Miks vielä vapiset?

Ne ottavat nuijansa raskaan,

ne tarttuvat keihääseen
sun puolestas taistellakseen
mieheen viimeiseen.

On yhtä verta he kanssas. Ja rakas Isänmaa on

ympärilläs. Ja kaikki he sitä rakastaa.

Kuoleman laulu

Me istuimme rannalla kahden kuin odottaen jotakin

ja silloin se tuli yksinään airoin äänettömin.
Se souti tänne. Tunsin, miten kätesi kangistui.
Se sukelsi hämystä esiin ja ohitsemme ui.

Sinä nousit ja katsoit kauan ja puhkesit nyyhkytyksiin

kun kaikki jo oli ohi. Ja minusta tuntui niin
kuin jotakin olisit löynnyt ja heti hävittänyt.
Vaan mitä se on? Minä istun ja kummastelen
nyt.

Veden kalvoon lehtiä halavain ja lehmusten pudonnut on.

Ne kiitää vaahdossa ohitse. Surusiko on pohjaton?
Sinä venheessä suvisen päivänkö näit soutavan sumuhun?
Vai omanko nuoruutesi, oman nuoruutesi sun?
 Oi katso. Halavat on tummat. Ihan kaikki katoaa:
sinä kuolet kerran itsekin, ja samoin kuolee maa.
Vaan sittenkin, juuri siksi: sinä elät kuitenkin.
Joka aamu aurinko palaa taas purjein liekehtivin.
 *** END OF THE PROJECT GUTENBERG EBOOK LAULU
VAAKALINNUSTA ***

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