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Silicon and Germanium Nanowires Anode Materials for Lithium and Sodium-ion Batteries Open Access


Other title
Sodium ion batteries
Lithium ion batteries
Type of item
Degree grantor
University of Alberta
Author or creator
Kohandehghan, Alireza
Supervisor and department
Mitlin, David (Department of Chemical and Materials Engineering)
Examining committee member and department
Zhang, Hao (Department of Chemical and Materials Engineering)
Semagina, Natalia (Department of Chemical and Materials Engineering)
Shahbazian-Yassar, Reza (Department of Materials Science and Engineering, Michigan Technological University)
Secanell Gallart, Marc (Department of Mechanical Engineering)
Zeng, Hongbo (Department of Chemical and Materials Engineering)
Department of Chemical and Materials Engineering
Materials Engineering
Date accepted
Graduation date
Doctor of Philosophy
Degree level
This thesis is focused on the silicon-based anode materials for lithium-ion batteries (LIBs) as well as germanium-based electrode materials for sodium-ion batteries (NIBs). In our first attempt we studied electrochemical cycling stability and degradation mechanisms of silicon nanowires (SiNWs) coated with Mg and Mg2Si for LIB anodes. Compared to SiNWs, both Mg-and Mg2Si-coated materials show significant improvement in coulombic efficiency (CE) during cycling, with pure Mg coating being slightly superior by ~ 1% in each cycle. XPS measurements on cycled nanowire forests showed lower Li2CO3 and higher polyethylene oxide content for coated nanowires, thus revealing a passivating effect towards electrolyte decomposition. The formation of large voids between the nanowire assembly and the substrate during cycling, causing the nanowires to lose electrical contact with the substrate, is identified as an important degradation mechanism. In our second attempt we demonstrated that nanometer-scale TiN coatings deposited by atomic layer deposition (ALD), and to a lesser extent by magnetron sputtering, will significantly improve the electrochemical cycling performance of SiNWs LIB anodes. A 5 nm thick ALD coating resulted in optimum cycling capacity retention (55% vs. 30% for SiNWs, after 100 cycles) and CE (98% vs. 95%, at 50 cycles), also more than doubling the high rate capacity retention (e.g. 740 vs. 330 mAh/g at 5C). The conformal 5 nm TiN remains sufficiently intact to limit the growth of the solid electrolyte interphase (SEI), which in turn both improves the overall CE and reduces the life-ending delamination of the nanowire assemblies from the underlying current collector. Our third attempt was demonstrating cycling performance improvement for SiNWs LIB anodes by a thin partially dewetted coating of Sn. The optimum architecture 3Sn/SiNWs (i.e. a Sn layer with an average film thickness of a 3 nm covering the nanowire) maintained a reversible capacity of 1865 mAh/g after 100 cycles at a rate of 0.1C. This is almost double of the SiNWs, where the reversible capacity after 100 cycles was 1046 mAh/g (~ 78% improvement). The 1Sn/SiNWs and 3Sn/SiNWs electrodes demonstrated much improved cycling CE, with > 99% vs. 94 - 98% for SiNWs. At a high current density of 5C, these nanocomposite offered 2X the capacity retention of bare SiNWs (~ 20 vs. ~ 10% of 0.1C capacity). It is demonstrated that the Sn coating both lithiates and delithiates at a higher voltage than Si and thus imparts a compressive stress around the nanowires. This confines their radial expansion in favor of longitudinal, and reduces the well-known failure mode by lithiation-induced nanowire stranding and fracture. TOF-SIMS analysis on the post-cycled delithiated specimens shows enhanced Li signal near the current collector due to accelerated SEI formation at the interface. FIB demonstrates concurrent en-masse delamination of SEI agglomerated sections of the nanowires from the current collector. Both of these deleterious effects are lessened by the presence of the Sn coatings. Germanium is a promising sodium ion battery (NIB, NAB, SIB) anode material that is held back by its extremely sluggish kinetics and poor cyclability. In our last attempt we demonstrated for the first time that activation by a single lithiation - delithiation cycle leads to a dramatic improvement in practically achievable capacity, in rate capability and in cycling stability of Ge nanowires (GeNWs) and Ge thin films (GeTF). TEM and TOF-SIMS analysis shows that without activation, the initially single crystal GeNWs are effectively Na inactive, while the 100 nm amorphous GeTF sodiate to only less than half their thickness. Activation with Li induces amorphization (in GeNWs) reducing the barrier for nucleation of the NaxGe phase(s), while introducing a dense distribution of nanopores that reduce the Na solid-state diffusion distances and buffer the sodiation stresses. The resultant sodiation kinetics are promising: Tested at 0.15C (1C = 369 mA/g, i.e. Na:Ge 1:1) for 50 cycles the GeNWs and GeTFs maintain a reversible (desodiation) capacity of 346 mAh/g and 418 mAh/g. The nanowires and films demonstrate a capacity of 355 and 360 mAh/g at 1C and 284 and 310 mAh/g at 4C, respectively. Even at a very high rate of 10C the GeTF delivers over 169 mAh/g.
This thesis is made available by the University of Alberta Libraries with permission of the copyright owner solely for the purpose of private, scholarly or scientific research. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.
Citation for previous publication
Kohandehghan, Alireza, Peter Kalisvaart, Martin Kupsta, Beniamin Zahiri, Babak Shalchi Amirkhiz, Zhipeng Li, Elmira L. Memarzadeh, Leonid A. Bendersky, and David Mitlin. “Magnesium and magnesium-silicide coated silicon nanowire composite anodes for lithium-ion batteries.” J. Mater. Chem. A 1, (2013): 1600-1612Kohandehghan, Alireza, Peter Kalisvaart, Kai Cui, Martin Kupsta, Elmira Memarzadeh, and David Mitlin. “Silicon nanowire lithium-ion battery anodes with ALD deposited TiN coatings demonstrate a major improvement in cycling performance.” J. Mater. Chem. A 1, (2013): 12850-12861.Kohandehghan, Alireza, Kai Cui, Martin Kupsta, Elmira Memarzadeh, Peter Kalisvaart, and David Mitlin. “Nanometer-scale Sn Coatings Improve the Performance of Silicon Nanowire LIB Anodes.” J. Mater. Chem. A 2, (2014): 11261-11279.Kohandehghan, Alireza, Kai Cui, Martin Kupsta, Jia Ding, Elmira Memarzadeh, Peter Kalisvaart, and David Mitlin. “Activation with Li Enables Facile Sodium Storage in Germanium.” Nano Lett., 2014, 14 (10), pp 5873–5882.

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