nanostructured materials for high-performance lithium-ion battery anodes based on earth abundant ...

225 Pages·2013·5.69 MB·English

NANOSTRUCTURED MATERIALS FOR
HIGH-PERFORMANCE LITHIUM-ION
BATTERY ANODES BASED ON EARTH
ABUNDANT ELEMENTS

MA YUE

NATIONAL UNIVERSITY OF SINGAPORE

2013
NANOSTRUCTURED MATERIALS FOR
HIGH-PERFORMANCE LITHIUM-ION
BATTERY ANODES BASED ON EARTH
ABUNDANT ELEMENTS

MA YUE
(B.Sc., Nanjing University)

A THESIS SUBMITTED
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
NUS GRADUATE SCHOOL FOR INTEGRATIVE
SCIENCE AND ENNGINEERING
NATIONAL UNIVERSITY OF SINGAPORE

2013
DECLARATION

I hereby declare that this thesis is my original
work and it has been written by me in its
entirety. I have duly acknowledged all the
sources of information which have been used in
the thesis.

This thesis has also not been submitted for any degree in any
university previously.

Ma Yue
3, August, 2013
Acknowledgement

First and foremost, I would like to extend my deepest and sincerest appreciation
to my supervisor Professor Lee Jim Yang. His invaluable and continuous
guidance, unwavering support and strong encouragement have helped me
develop in-depth understanding of my research subject and overcome
considerable difficulties during my Ph.D program. Prof Lee’s meticulous
attitude and endless enthusiasm for scientific research have deeply inspired me
and establish a role model for my life-long learning. I sincerely treasure this
precious experience, which will be extremely valuable for my future
professional career.

I would like to convey my gratitude to all my colleagues in the research group,
in particular, Dr. Qingbo Zhang, Dr. Bo Liu, Dr. Chao Zhang, Dr. Qu Jianglan,
Dr. Yue Yu, Dr. Chunliu Fang, Dr. Ge Ji, Dr. Jie Zeng, Dr. Chaohe Xu, Dr.
Dongyun Chen, Dr. David Julius, Ms. Meihua Lu, Mr. Qiaofeng Yao, Mr. Zhi
Wen Chia, Mr. Chin Hsien Cheng, Mr. Ji Bao, Mr. Bo Ding, Mr. Yi Zhang, Mr.
Baihua Qu and Mr. Liuqing Yang. I thank them for their valuable suggestions
and stimulating discussions.

I would also like to express my thanks to the technical staff in the department
especially Mr. Kok Hong Boey, Mr. Phai Ann Chia, Dr. Zeliang Yuan, Mr. Ning
I
Mao, Ms. Chai Keng Lee, Mr. Zhicheng Liu, and Mr. Evan Tan. Their superb
technical service and wholehearted support are essential for the timely
completion of this study.

The financial supports by the way of Research Scholarship from National
University of Singapore Graduate School for Integrative Science and
Engineering (NGS) are greatly acknowledged.

Finally, I am deeply indebted to my parents and friends for their love, support,
and encouragement during my Ph.D. program.

II
TABLE OF CONTENT

ACKNOWLEDGEMENT .............................................................................................. I
TABLE OF CONTENT ................................................................................................ III
SUMMARY ............................................................................................................ VIII
LIST OF TABLES ....................................................................................................... XI
LIST OF FIGURES .................................................................................................... XII
LIST OF ABBREVIATIONS ................................................................................. XVIII
CHAPTER 1 INTRODUCTION .................................................................................... 1
1.1 Background ........................................................................................................... 1
1.2 Objectives and scope............................................................................................. 5
CHAPTER 2 LITERATURE REVIEW ......................................................................... 9
2.1 Lithium ion batteries ............................................................................................. 9
2.2 Nanomaterials for reversible Li+ storage ............................................................ 15
2.3 Structures assembled by nanoscale building units .............................................. 17
2.3.1 One-dimensional nanostructures ................................................................... 18
2.3.2 Structures with hollow cavities ..................................................................... 20
2.3.3 Porous structure ............................................................................................ 22
2.4 Surface modification ........................................................................................... 26
2.4.1 Surface coating ............................................................................................. 27
2.4.2 Conductive matrix encapsulation .................................................................. 29
III
2.4.3 Mixed-conducting network ........................................................................... 30
2.5 Doping of Li+ storage compounds ...................................................................... 31
2.5.1 Heteroatom doping ....................................................................................... 31
2.5.2 Doping of vacancy or defect ......................................................................... 33
CHAPTER 3 SYNTHESIS OF MIXED-CONDUCTING CARBON COATED
POROUS r-Fe O MICROPARTICLES AND THEIR
2 3
PROPERTIES FOR REVERSIBLE LI STORAGE ............................. 35
3.1 Introduction ......................................................................................................... 35
3.2 Experimental section ........................................................................................... 36
3.2.1 Materials ....................................................................................................... 36
3.2.2 Materials preparation .................................................................................... 37
3.2.3 Materials characterization ............................................................................. 37
3.2.4 Electrochemical measurements ..................................................................... 38
3.3 Results and discussion ........................................................................................ 39
3.4 Conclusions ......................................................................................................... 51
CHAPTER 4 NITROGEN-DOPED CARBON-ENCAPSULATION OF Fe O
3 4
FOR INCREASED REVERSIBILITY IN LI+ STORAGE BY
THE CONVERSION REACTION ....................................................... 53
4.1 Introduction ......................................................................................................... 53
4.2 Experimental section ........................................................................................... 56
4.2.1 Materials ....................................................................................................... 56
4.2.2 Materials preparation .................................................................................... 57
IV
4.2.3 Materials characterization ............................................................................. 58
4.2.4 Electrochemical measurements ..................................................................... 59
4.3 Results and discussion ........................................................................................ 59
4.4 Conclusions ......................................................................................................... 71
CHAPTER 5 NITROGEN-DOPED CARBON ENCAPSULATION OF
ULTRAFINE SILICON NANOCRYSTALITES FOR THE
HIGH PERFORMANCE LITHIUM ION STORAGE ......................... 73
5.1 Introduction ......................................................................................................... 73
5.2 Experimental section ........................................................................................... 77
5.2.1 Materials ....................................................................................................... 77
5.2.2 Materials preparation .................................................................................... 77
5.2.3 Materials characterization ............................................................................. 79
5.2.4 Electrochemical measurements ..................................................................... 80
5.3 Results and discussion ........................................................................................ 81
5.4 Conclusion .......................................................................................................... 95
CHAPTER 6 FACILE SOLVOTHERMAL SYNTHESIS OF ANATASE TiO
2
MICROSPHERES WITH ADJUSTABLE MESOPOROSITY
FOR THE REVERSIBLE STORAGE OF LITHIUM IONS ............... 97
6.1 Introduction ......................................................................................................... 97
6.2 Experimental section ......................................................................................... 100
6.2.1 Materials ..................................................................................................... 100
6.2.2 Materials preparation .................................................................................. 101
V
6.2.3 Materials characterization ........................................................................... 102
6.2.4 Electrochemical measurements ................................................................... 102
6.3 Results and discussion ...................................................................................... 103
6.4 Conclusion ........................................................................................................ 117
CHAPTER 7 CARBON-ENCAPSULATED F-DOPED LI Ti O AS AN
4 5 12
EXTREME HIGH RATE ANODE MATERIAL FOR
REVERSIBLE LI+ STORAGE ........................................................... 119
7.1 Introduction ....................................................................................................... 119
7.2 Experimental section ......................................................................................... 122
7.2.1 Materials ..................................................................................................... 122
7.2.2 Materials preparation .................................................................................. 123
7.2.3 Materials characterization ........................................................................... 125
7.2.4 Electrochemical measurements ................................................................... 125
7.3 Results and discussion ...................................................................................... 126
7.4 Conclusion ........................................................................................................ 144
CHAPTER 8 Fe-DOPED Mn O WITH HIERARCHICAL POROSITY AS A
x y
HIGH-PERFORMANCE LITHIUM ION BATTERY ANODE ........ 146
8.1 Introduction ....................................................................................................... 146
8.2 Experimental section ......................................................................................... 149
8.2.1 Materials ..................................................................................................... 149
8.2.2 Materials preparation .................................................................................. 149
8.2.3 Materials characterization ........................................................................... 150
VI
8.2.4 Electrochemical measurements ................................................................... 151
8.3 Results and discussion ...................................................................................... 151
8.4 Conclusion ........................................................................................................ 169
CHAPTER 9 CONCLUSION AND FUTURE WORK ............................................. 171
9.1 Conclusion ........................................................................................................ 171
9.2 Future work ....................................................................................................... 175
9.2.1 Optimizing the electrode fabrication process and the parameters for
electrochemical testing .............................................................................. 175
9.2.2 Investigation of the SEI layer formed on the metal oxide anodes .............. 176
9.2.3 Optimization of porosity and free volume .................................................. 177
REFERENCES ........................................................................................................... 179
PUBLICATIONS ........................................................................................................ 202

VII