December 1 - 6, 2024
Boston, Massachusetts
Symposium Supporters
2024 MRS Fall Meeting & Exhibit
CH04.15.02

Unraveling the Structure and Electrochemical Mechanism in TiNb2O7 via Operando Studies and Theoretical Calculations

When and Where

Dec 5, 2024
2:00pm - 2:15pm
Sheraton, Third Floor, Commonwealth

Presenter(s)

Co-Author(s)

Siddhartha Nanda1,Doosoo Kim1,Hadi Khani1

The University of Texas at Austin1

Abstract

Siddhartha Nanda1,Doosoo Kim1,Hadi Khani1

The University of Texas at Austin1
Understanding the fundamental charge storage and conversion mechanism is of utmost important for developing and designing energy storage devices with exceptional electrochemical performances. In the quest for anodes, graphite and silicon are favored in the high-energy density application. However, they face challenges like overpotentials and lithium plating at high current densities. Recently, Nb-based oxides with a Wadsley–Roth crystallographic shear structure have been proposed as new anode materials for high-energy and high-power lithium-ion batteries (LIBs). The insertion of Li ions into Nb-based oxides mainly occurs at a voltage of about 1.6–1.7 V vs Li<sup>+</sup>/Li, preventing the electrolyte decomposition and lithium-dendrite formation. Among this class of materials, TiNb<sub>2</sub>O<sub>7</sub> (TNO) is the most promising. Its theoretical capacity is 387.6 mAh g<sup>–1</sup> due to multielectron redox reactions involving several redox couples (Ti<sup>4+</sup>/Ti<sup>3+</sup>, Nb<sup>5+</sup>/Nb<sup>4+</sup>, Nb<sup>4+</sup>/Nb<sup>3+</sup>).<br/>Unraveling the charge storage mechanism in the TNO is a challenging task because of complex crystal structure and the similar potentials for redox reactions of the transition metals. To investigate this a combined approach of experimental and theoretical analysis has been conducted.<br/>Reversible charge–discharge capacity of the as-prepared TNO measured in a galvanostatic mode in the 1.0–3.0 V range at the 0.1C rate was 250 mAh g<sup>–1</sup>. Cyclic Voltammetry during lithiation shows one large broad peak between 1.2V to 1.8V (vs Li<sup>+</sup>/Li) which corresponds to multiple reduction reactions of Nb<sup>5+ </sup>and Ti<sup>4+</sup>, because Ti 3d and Nb 4d states overlap in energy.<br/>Operando Raman experiment reveals the order of redox reactions happening between Ti<sup>4+</sup> and Nb<sup>5+</sup>. In the uncycled state, the Raman peaks at 998 cm<sup>-1</sup> and 884 cm<sup>-1</sup> are assigned to edge shared and corner shared NbO<sub>6</sub> octahedra. Similarly in the mid frequency region, the strong peaks at 647 cm<sup>-1</sup> and 538 cm<sup>-1</sup> are assigned to edge shared and corner shared TiO<sub>6</sub> octahedra. As soon as the discharge starts, the peak corresponds to corner shared NbO<sub>6</sub> disappears and the peak corresponding to edge shared NbO<sub>6</sub> undergoes red shift indicating the reduction of Nb<sup>5+</sup>/Nb<sup>4+</sup> in the edge sharing octahedra site. At the same time both the peaks for TiO<sub>6</sub> undergo red shift confirming the reduction of Ti<sup>4+</sup>/Ti<sup>3+</sup>. At around 1.5V (vs Li<sup>+</sup>/Li), the peak position for edge sharing NbO<sub>6</sub> remain the unchanged, while the peak correspond to corner sharing NbO<sub>6</sub> keeps undergoing red shift revealing the further reduction of Nb<sup>4+/3+</sup> at the corner shared octahedra site. On the other hand, almost all the peaks corresponding to TiO<sub>6 </sub>disappear starting at 1.7V and remain the same till the end of discharge. Quantum computational calculation has been performed to study electronic structure and to calculate the Raman modes with DFT using PBE functional.<br/>To understand the Raman behavior and structural changes, in situ X-Ray diffraction has been performed. From Rietveld refinement, 5 distinct transitional metal sites (M1-M5) were identified. It has been observed that with the lithiation of TiNb<sub>2</sub>O<sub>7</sub>, the M5 site which has lowest Nb<sup>5+ </sup>occupancy and hence predominantly occupied by Ti<sup>4+</sup>, undergoes severe distortion. It can be comprehended that, due to this large distortion, the Raman peaks have disappeared once Ti<sup>4+ </sup>reduces to Ti<sup>3+</sup>. The refinement reveals the phase changes which supports our operando Raman analysis.

Keywords

Raman spectroscopy | x-ray diffraction (XRD)

Symposium Organizers

Rachel Carter, U.S. Naval Research Laboratory
David Halat, Lawrence Berkeley National Laboratory
Mengya Li, Oak Ridge National Laboratory
Duhan Zhang, Massachusetts Institute of Technology

Symposium Support

Bronze
Nextron Corporation

Session Chairs

Mengya Li
Duhan Zhang

In this Session