Table Of ContentAnalysis of Reaction and Transport
Processes in Zinc Air Batteries
Daniel Schröder
Analysis of Reaction
and Transport Processes
in Zinc Air Batteries
Daniel Schröder
Gießen, Deutschland
Genehmigte Dissertation an der TU Braunschweig, Fakultät für Maschinenbau, 2015
ISBN 978-3-658-12290-4 ISBN 978-3-658-12291-1 (eBook)
DOI 10.1007/978-3-658-12291-1
Library of Congress Control Number: 2015959488
Springer Vieweg
© Springer Fachmedien Wiesbaden 2016
This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or
part of the material is concerned, speci(cid:191) cally the rights of translation, reprinting, reuse of illus-
trations, recitation, broadcasting, reproduction on micro(cid:191) lms 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 speci(cid:191) c 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 Vieweg is a brand of Springer Fachmedien Wiesbaden
Springer Fachmedien Wiesbaden is part of Springer Science+Business Media
(www.springer.com)
Analysis of Reaction and Transport
Processes in Zinc Air Batteries
Von der Fakult¨at fu¨r Maschinenbau
der Technischen Universit¨at Carolo-Wilhelmina zu
Braunschweig
zur Erlangung der Wu¨rde
eines Doktor-Ingenieurs (Dr.-Ing.)
genehmigte Dissertation
von: Dipl.-Ing. Daniel Schr¨oder
aus (Geburtsort): Waren (Mu¨ritz)
eingereicht am: 19.02.2015
mu¨ndliche Pru¨fung am: 17.07.2015
Gutachterinnen / Gutachter:
Prof. Dr.-Ing. Ulrike Krewer
Prof. Dr.-Ing. Thomas Turek
Prof. Dr.-Ing. Arno Kwade
2015
Acknowledgments
The research for this thesis was conducted during the last four years partly
at the Otto-Hahn Research group for Portable Energy Systems at the Otto-
von-Guericke University Magdeburg and at the Max-Planck-Institute for
DynamicsofComplexTechnicalSystemsinMagdeburg,andattheInstitute
ofEnergyandProcessSystemsEngineeringattheTUBraunschweig. During
this period, I had the pleasure to work alongside many people and I want
to express my gratitude to them at this point.
First of all, I thank Prof. Dr.-Ing. Ulrike Krewer who gave me the
opportunity to work on the topic of zinc air batteries, and who guided
and encouraged me throughout the entire time. Her enormous attention to
detailandcriticalthinkinghelpedmetoshapethethesis,withalltheminor
steps within it, to the current state. Furthermore, I thank Prof. Dr.-Ing.
Thomas Turek from the TU Clausthal for the interest in my thesis, the
helpful scientific discussions at various conferences, and for assessing the
thesis. I also thank Prof. Dr.-Ing. Arno Kwade for helpful discussions at
various conferences and project meetings, and for chairing the doctoral
committee.
AgreatamountofgratitudebelongstomyclosestcolleaguesinMagdeburg
(andlaterBraunschweig),namelyQingMao,PrashantKhadke,MaikKraus,
Nebojsa Korica, Youngseung Na and Christine Weinzierl. It was always a
pleasure to discuss with you about the fundamentals of research and life.
I am strongly indebted to you for several discussions that helped me to
shape the experimental and model-based parts of this thesis. Furthermore,
I want to thank Thomas Khadyk, Christian Oettel, Christoph Hertel, Peter
Heidebrecht, Mathias Pfafferodt and Federico Zenith of the Max-Planck-
VIII Acknowledgements
Institute for sharing their thoughts on research and life in general at the
daily lunch breaks.
I appreciate the help of my colleagues Niels Brinkmeier, Paul Alps, An-
dreasHauschkeandSebastianStengerattheinstituteinBraunschweig;each
of you was essential to help me to settle and feel welcome in Braunschweig.
I also thank my colleagues in the battery research group in Braunschweig,
Georg Lenze, Fridolin Ro¨der, Angelica Staeck and Nan Lin. I am indebted
to Horst Mu¨ller for the numerous discussions/lessons about numerical meth-
ods, teaching, and accounting. I also thank Victor Emenike and Georg
Lenze for the fruitful discussions (topical and non-topical) in our office.
Inaddition,attheMax-Planck-InstituteMagdeburgIwouldliketothank
thelibraryteam,themembersofthemechanicalandtheelectricalworkshop,
andthelabassistantsBiankaStein,MarkusIkertandJessicaBunge. Thanks
alsobelongtoInaSchunke,NinaBo¨ge,WilfriedJanßen,SergejMaserowand
Uwe Herrmann, since they provided me with technical and non-technical
advice at all time at the TU Braunschweig. Their contribution is often
under-appreciated but crucial for good research.
I also thank Ingo Manke and especially Tobias Arlt of the Helmholtz-
Zentrum Berlin, who contacted me for the joint research on X-ray tomogra-
phy of zinc air batteries. I appreciate the numerous hours to plan, conduct
and analyze the X-ray measurements together. I thank them for the various
discussionsthatledtoourjointpublications,andtheX-rayimagesprovided
for parts of this thesis.
Moreover, I thank the students/coworkers Ilona Heidenreich, Thomas
Gebken, Markus Pollack, Jan-Robert Schwarz, thereof especially Becca
McClain, Vincent Laue, Michael K¨onig, and Neeraj Nitin Sinai Borker for
the joyful and fruitful research together. I also acknowledge Becca McClain,
Prashant Khadke, Christine Weinzierl, Youngseung Na, Tobias Arlt, and
Victor Emenike for their critical review and proofreading of the manuscript
of this thesis.
Finally, I want thank my family and Carla, who always supported and
encouraged me the most.
Contents
Acknowledgments VII
List of Figures XII
List of Tables XVII
List of Abbreviations XIX
List of Symbols XXI
Abstract XXXIII
Kurzfassung XXXV
1 Introduction 1
1.1 Composition and Working Principle of Zinc Air Batteries 1
1.2 State of the Art: Potentials and Drawbacks 11
2 Motivation and Scope of this Thesis 17
Part 1 – Characterizing Reaction and Transport Pro-
cesses 21
3 Basics of the Experimental Methods Applied 23
3.1 Electrochemical Methods 23
3.2 X-ray Tomography 29
X Contents
4 Experimental Set-Ups and Measurement Details 39
4.1 Set-Ups Applied 39
4.1.1 In-House Zinc Air Batteries 39
4.1.2 Commercial Button Cell Batteries 44
4.2 Measurement Details 45
4.2.1 Electrochemical Characterization of In-House Batter-
ies 45
4.2.2 Electrochemical Characterization of Button Cell Bat-
teries 48
4.2.3 X-ray Tomography Specifications 48
5 Experimental Results and Discussion 51
5.1 Basic Processes 52
5.2 Zinc Electrode Processes 64
5.2.1 Impact of State-of-Discharge 65
5.2.2 Reaction of a Single Particle 68
5.2.3 Volume Expansion 69
5.3 Air Electrode Processes 73
5.3.1 FloodingoftheAirElectrodewithLiquidElectrolyte 73
5.3.2 Catalyst Impact 79
6 Detailed One-Dimensional Air Electrode Model 83
6.1 Model Description 83
6.2 Implementation of Flooding and Pulse-Current Operation 88
6.3 Simulated Overpotential and Oxygen Distribution 89
Part 2 – Identifying Factors for Long-Term Stable Op-
eration 95
7 Theoretical Considerations on Air-Composition Impact 97
7.1 Relative Humidity 97
7.2 Carbon Dioxide 101
Contents XI
7.3 Oxygen 104
7.4 Temperature 105
8 Model Approach to Reveal Air-Composition Impact 109
8.1 State of the Art: Existing Model Approaches 109
8.2 Basic Model 113
8.3 Scenarios to Account for Air-Composition Impact 120
8.4 Design Parameters and Material Properties 130
8.5 Assumptions 132
9 Simulation Results and Discussions for Air-Composition Im-
pact 135
9.1 Ideal Case Operation of Zinc Air Batteries 136
9.2 Impact of Air-Composition on Operation Stability 142
9.3 Validity of the Model-Based Analysis 161
9.3.1 Unaccounted Processes 161
9.3.2 Non-Ideal Solution Chemistry 164
10 Summary and Overall Conclusions 173
10.1 For Part 1 173
10.2 For Part 2 175
Appendices 179
A Modeling 181
A.1 Parameters and Derivations for Air Electrode Model 181
A.2 Parameters and Derivations for Basic Model and Scenarios 188
A.3 Additional Simulation Results 200
B Experimental 201
B.1 Designing the In-House Set-Up for X-ray Tomography 201
B.2 Preparation of the Electrolyte Solutions 209
B.3 Titration of the Solutions 209
