creator Pelliccione, Christopher J. advisor Segre, Carlo U Tin is an attractive alternative to replace traditional carbon based anodes in lithium-ion batteries (LIBs) due to the nearly three-fold increase in theoretical capacity over carbon. However, metallic tin su↵ers from volumetric expansion of the crystal structure during initial lithium insertion that quickly degrades the material and reduces the performance of the battery. Various techniques have been previously investigated with the goal of suppressing this destructive expansion by incorporating oxygen or a lithium-inactive metal into the tin to provide structural support and mitigate volumetric expansion. These materials show increased capacity retention compared to metallic tin, but still su↵er from capacity fading. The nature of these structural degradations must be fully understood to permit engineering of materials that avoid these destructive tendencies and can be considered as viable options for LIBs. In situ X-ray absorption spectroscopy (XAS) measurements were acquired on Sn, SnO2, Sn3 O2(OH)2, Cu6Sn5 and Ni3Sn4 nanoparticle anodes for LIBs. Accompanying the electrochemical characterization conducted on each material, the local atomic structure was modeled as a function of potential during the first charge and also as a function of charged/discharged states for several cycles. The extended X-ray absorption fine structure (EXAFS) theoretical modeling included the first unambiguous observation of Sn-Li coordination numbers and atomic distances in tin-based anode materials. From correlating the electrochemical performance to the EXAFS analysis, the long-term capacity retention of tin-based anodes is dependent on the structural deformations that occur during the first charge. The conversion of oxygen to amorphous Li2O, and the network that it forms, has a dramatic e↵ect on the kinetics of the system and the stability of the local metallic tin structure. Submitted by Erma Thomas (thomase@iit.edu) on 2015-09-18T17:55:25Z No. of bitstreams: 2 Final_Thesis_Manuscript.pdf: 30181718 bytes, checksum: d20fc319ec34210848788d71a5e2dd8e (MD5) Signed_Thesis_Title_Page.pdf: 11820 bytes, checksum: 63ad335eaba675bf20103ac50f51f5b4 (MD5) Made available in DSpace on 2015-09-18T17:55:25Z (GMT). No. of bitstreams: 2 Final_Thesis_Manuscript.pdf: 30181718 bytes, checksum: d20fc319ec34210848788d71a5e2dd8e (MD5) Signed_Thesis_Title_Page.pdf: 11820 bytes, checksum: 63ad335eaba675bf20103ac50f51f5b4 (MD5) Previous issue date: 2015-05 Ph.D. in Physics, May 2015 2015 2015-05 http://hdl.handle.net/10560/3564 en Dissertation born digital application/pdf In Copyright http://rightsstatements.org/page/InC/1.0/ Restricted Access PHYS / Physics Illinois Institute of Technology Affiliated department