Table Of ContentIn Situ Investigations of Solid Electrolyte
Interphase Formation and Properties in Lithium
Ion Batteries
by
Anton V. Tokranov
B.S. Materials Science and Engineering, Johns Hopkins University, 2009
A dissertation submitted in partial fulfillment of the
requirements for the Degree of Doctor of Philosophy
in the School of Engineering at Brown University
Providence, Rhode Island
May, 2015
© Copyright 2015 by Anton V. Tokranov
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This dissertation by Anton V. Tokranov is accepted in its present form
by the School of Engineering as satisfying the
dissertation requirement for the degree of Doctor of Philosophy
Date ______________ ______________________________________
(Professor Brian W. Sheldon), Advisor
Recommended to the Graduate Council
Date ______________ ______________________________________
(Professor Eric Chason), Reader
Date ______________ ______________________________________
(Professor Huajian Gao), Reader
Approved by the Graduate Council
Date ______________ ______________________________________
(Professor Peter M. Weber)
Dean of the Graduate School
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Curriculum Vitae
Anton V. Tokranov was born on December 19th 1988 in Leningrad, USSR (which
became St. Petersburg, Russian Federation shortly after birth). After 6th grade Anton
moved with his parents to United States, and in 2006 he graduate from Shaker High
School, in New York state. He was accepted to Johns Hopkins University (Baltimore,
MD) where Anton majored in Materials Science. At the end of his sophomore year
(2008) he was able to do a summer REU at Carnegie Mellon University. During junior
year Anton started doing research on Nanoporous metals, and was able to graduate with
honors in 3 years.
In 2009, he was awarded a fellowship to pursue Ph.D. degree in Engineering at
Brown University, Providence, RI. Anton accepted the position and started his research
on July 2009. During his time he has had a productive collaboration with General Motors
Corporation which resulting in several publications, and the first 1st author paper
published in 2013, titled: “The Origin of Stress in the Solid Electrolyte Interphase on
Carbon Electrodes for Li Ion Batteries”. The subsequent work also included Burker
Corporation and resulted in the work titled: “In Situ Atomic Force Microscopy Study of
Initial Solid Electrolyte Interphase Formation on Silicon Electrodes for Li-Ion Batteries”.
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Acknowledgements
Firstly, I would like to acknowledge my advisor Professor Brian W. Sheldon who
guided me through this dissertation. With his help and direction I was able to organize
my thoughts in a coherent manner. This was imperative since I have a tendency to get
distracted with experiments: the size of the appendices is evidence of this. It was a great
honor and a pleasure to conduct work under his supervision. I would also like to express
my gratitude to my thesis readers, Professor Eric Chason and Professor Huajian Gao, for
their time, patience and instructive suggestions that have contributed substantially to this
thesis.
I would also like to acknowledge my collaborators. First, I would like to thank Dr.
Xingcheng Xiao at General Motors for his advice and suggestions: it was with his support
that this project got started. I would also like to thank Dr. Chunzeng Li and Dr. Stephen
Minne from Bruker for allowing me to test their in situ AFM setup. This hugely advanced
my work. Additionally I want to express my gratitude to Dr. Amartya Mukhopadhyay,
who worked with me when he was a post-doc at Brown and continued our collaboration
when he became a professor.
I am also grateful to the administrative assistants and technical staff within the
School of Engineering at Brown University for their invaluable assistance. Most notably:
Anthony McCormick for keeping FIB and TEMs working, Michael Jibitsky for keeping
the cleanroom running well, Charles Vickers for making all the parts I drew up, Brian
Corkum and Paul Waltz for helping me whenever I decide to break something in lab, and
Diane Felber and Peggy Mercurio for all the administrative work I made them do.
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I want to thank members of Professor Sheldon’s lab. They were always there to
help me out whether I needed to run my idea’s by them, or help with something in lab, as
long as it wasn’t cleaning the lab. This includes Aaron Kessman, Amartya
Mukhopadhya, Dawei Lui, Yang Lei, Xin Su, Sumit Kumar Soni, Jay Sheth, Ravi
Kumar, Leah Nation, Sugeetha Vasudevan, Susan Herringer, Will Ellis, and Kevin Sena.
Additionally I would like to thank Professor Robert Hurt and Fei Guo for their help and
collaboration on the carbon work.
I also want to thank all my friends for helping me through this and still being my
friend when I disappeared for a bit. Special thanks goes to Don Ho for being a great
roommate, and Aruna Sigdel for being a great replacement roommate. Dan Corbi and
Sarah Schrier who still managed to stay in touch after college. To the climbing group
that kept changing members, but never died out, including Ravi Kumar, Naubahar Agha,
Daniel Gerbig, Sebastjan Glinsek, Melissa Holzhauer, Chris Geggie, and the previously
mentioned Don Ho. And to all my friends I tortured with long bike rides and hikes,
including the ones listed above with the addition of Jay Sheth, whom I could never get
into climbing. Lastly Brown cycling for getting me started in racing. Thanks Guys!
Finally, I thank my parents for setting me on this path, and giving me advice,
including some technical (I guess there are upsides to having two parents with PhDs.).
Lastly I want to thank my loving and supportive girlfriend Andrea Weber, who has now
put up with me for almost 4 years. More importantly is that she is still putting up with
me as I am writing this at a completely reasonable hour, love you! Thank you everyone!
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This work is dedicated to my parents
Dr. Vadim Tokranov & Dr. Natalya Tokranova
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Table of Contents
Signature Page iii
Curriculum Vitae iv
Acknowledgments v
Table of Content viii
List of Tables xii
List of Figures xiii
Abstract xix
1. INTRODUCTION…………………………………………….………….. 1
1.1. Lithium Ion Battery Background...…..………………………………... 1
1.2. Lithium Ion Battery Operation.……………………………………….. 2
1.3. Solid Electrolyte Interphase...…………………………………………. 4
1.4. SEI Formation…...…………………………………………………….. 5
1.5. Thesis Organization…...………………………………………………. 6
1.6. References……………………………………………………………... 7
2. INITIAL EXPERIMENTS ON STRESS IN GRAPHITIC CARBON
DURING CYCLING……………………………………………………... 10
2.1. Introduction…………………………………………………………… 10
2.2. Experimental Details...………………………………………………... 11
2.3. Results………………………………………………………………….13
2.3.1. Development of well-ordered graphitic thin films……....................13
viii
2.3.2. Electrochemical behavior of the CVD C films ……….................... 14
2.3.3. In-situ stress determination during galvanostatic cycling…………. 16
2.4. Discussion……………………………………………………………... 17
2.5. Conclusion…………………………………………………………….. 19
2.6. References……………………………………………………………... 20
3. THE ORIGIN OF STRESS IN THE SOLID ELECTROLYTE
INTERPHASE ON CARBON ELECTRODES FOR LI ION
BATTERIES……………………………………….……………………… 23
3.1. Introduction …………………………………………………………… 23
3.2. Experimental Methods ………………………………………………... 25
3.3. Near-Surface Processes During the First Cycle……………………….. 27
3.3.1. Irreversible stress evolution………..………………………………. 27
3.3.2. Near surface characterization……………………………………… 29
3.3.3. Impact of ALD aluminum oxide coatings ………………………… 31
3.3.4. Interpretation ………………………………………………………. 32
3.4. Impact of Cycling Conditions ………………………………………… 35
3.4.1. First cycle variations……………………………………………….. 35
3.4.2. Later cycles and passivation of the surface………………………… 39
3.5. Discussion and Conclusions …………………………………………. 42
3.6. References……………………………………………………………... 47
4. IN SITU ATOMIC FORCE MICROSCOPY STUDY OF INITIAL
SOLID ELECTROLYTE INTERPHASE FORMATION ON
SILICON ELECTRODES FOR LI-ION BATTERIES………………... 52
4.1. Introduction …………………………………………………………… 52
4.2. Experimental Approach..……………………………………………… 54
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4.3. Results………………………………………………………………… 56
4.3.1. Expansion and contraction of Si Islands…………………………… 56
4.3.2. SEI on copper……………………………………………………….60
4.3.3. Simultaneous SEI formation and silicon expansion.………………. 62
4.3.4. Silicon coated with aluminum oxide ……………………………….67
4.3.5. Surface roughness …………………………………………………. 70
4.3.6. Impact of initial cycling conditions ……………………………...... 72
4.4. Analysis and Discussion ……………………………………………... 74
4.4.1. SEI formation ……………………………………………………… 74
4.4.2. SEI thickness and stability ………………………………………… 82
4.5. Conclusions …………….……………………………………………...91
4.6. References …………………………………………………………….. 93
5. Evolution of Solid Electrolyte Interphase on Silicon in the
Intermediate Time Range………………………………………………… 100
5.1. Introduction ……………………………………………………………100
5.2. Experimental Setup …………………………………………………… 101
5.3. Results………………………………………………………………….105
5.3.1. SEI growth, structure and deformation…………………………….. 105
5.3.2. Interfacial phenomena ……………………………………………... 108
5.4. Analysis and Discussion ……………………………………………... 113
5.4.1. Mathematical model of SEI formation ……………………………. 113
5.4.2. Comparisons with EIS data ………………………………………... 123
5.4.3. Implications for the mechanical response of the SEI ……………… 130
5.5. Conclusions ……………………………………………………………137
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Description:Additionally I want to express my gratitude to Dr. Amartya Mukhopadhyay, who worked with This includes Aaron Kessman, Amartya This assembly is done inside a glove box and the seal is maintained using a. Kalrez o-ring.
