Temperature Dependent EXAFS to Address Functional Mechanisms in Battery Materials
ECS Meeting Abstracts(2023)
Abstract
Increasing the contribution of renewable energy sources is necessary to meet the fast increase of global energy needs and match the CO2 reduction targets. In order to address these challenges, intensive research efforts are ongoing both in energy harvesting and storage technologies such as solar panels, fuel cells, supercapacitors and batteries. The latter are required to match the energy demand and supply; in fact, batteries are by far the most ubiquitous energy storage technology currently employed. Synchrotron x-ray spectroscopies have played a key role in the continuous development and breakthroughs in battery science, thanks to their capability to provide accurate information on electronic structure of the redox active element, local structure, and morphological information. In particular, X-ray absorption spectroscopy (XAS) is more and more employed for addressing battery materials [1]. Generally, XAS studies on battery materials are performed at a single temperature as a function of charge, to access information on the electrochemical behavior and charge transfer mechanism during the intercalation or deintercalation process. However, the fact that the charging/discharging process is expected to have direct influence on the bond length characteristics, strength and disorder, it is important to perform temperature dependence measurements to find a realistic correlation between the local structure and the battery characteristics. Indeed, temperature-dependent studies quantitatively allow to discriminate in between static and dynamic disorder, and to have direct access to the local force constant between the atom pairs. Here the interest of performing temperature dependent extended X-ray absorption fine structure (EXAFS) studies is highlighted by exploiting several examples. In Li and Mn-rich NMC cathodes temperature-dependent EXAFS investigation revealed the evolution of the lattice rigidity which directly affects the reversible anionic redox contribution [2-3]. Similar studies on Ti based MXene-type [4], NaxCoO2 [5], and V2O5 [6] electrode materials underline the importance of the local atomic correlations as limiting factor in the ion diffusion in battery materials. References [1] Marcus Fehse, Antonella Iadecola, Laura Simonelli, Alessandro Longo and Lorenzo Stievano, Phys. Chem. Chem. Phys., 2021, 23, 23445–23465 [2] Shehab Ali, Wojciech Olszewski, Carlo Marini, Arefeh Kazzazi, Hyeongseon Choi, Matthias Kuenzel, Dominic Bresser, Stefano Passerini, DinoTonti, Laura Simonelli, Materials Today Physics 24(2022) 100687 [3] Y. Yu et. al, Energy Environ. Sci. 14 (2021) 2322–2334. [4] Wojciech Olszewski, Carlo Marini, Satoshi Kajiyama, Masashi Okubo, Atsuo Yamada, Takashi Mizokawa, Naurang Lal Saini, Laura Simonelli, Phys. Chem. Chem. Phys., 2023 (in press), doi : https://doi.org/10.1039/D2CP04759D [5] W. Olszewski, Marta Ávila Pérez, Carlo Marini, Eugenio Paris, Xianfen Wang, Tatsumi Iwao, Masashi Okubo, Atsuo Yamada, Takashi Mizokawa, Naurang Lal Saini, and Laura Simonelli , J. Phys. Chem. C 120 (2016) 4227–4232. [6] W. Olszewski, Irene Isturiz, Carlo Marini, Marta Avila, Masashi Okubo, Huiqiao Li, Haoshen Zhou, Takashi Mizokawa, Naurang Lal Saini and Laura Simonelli, Phys. Chem. Chem. Phys. 20 (2018) 15288–15292.
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