Modified Metallic Lithium for Anodes in Lithium Batteries

ANDREA C. CALDERÓN; VICTORIA BRACAMONTE; GUILLERMINA LUQUE; SERGIO ALEXIS PAZ; MANUEL OTERO; FERNANDO COMETTO; GUADUALUPE PEÑARANDA; PAULA VALENTINA SARAVIA; J. BRIZUELA; F. EROLES; MURIEL ZAMPIERI; DANIEL BARRACO; EZEQUIEL PEDRO MARCOS LEIVA

Mar del Plata

Congreso; 34th Topical Meeting (TM) de la Sociedad Internacional de Electroquímica (ISE); 2023

Sociedad Internacional de Electroquímica

Lithium metal anode represents the “holy grail” of battery research for its extremely high theoretical specific capacity (3860 mA h g−1), its lowest redox potential (−3.04 V vs. the standard hydrogen electrode), and its low gravimetric density (0.534 g cm−3). The main issue associated with this material is the uncontrollable deposition/dissolution of Li causing the formation and growth of high surface area lithium (HSAL) during repeated charge/discharge processes that induce a series of thorny problems, such as possible battery short circuits and low Coulombic Efficiency resulting from the high reactivity of Li metal towards the electrolyte solvents and the salt anions. Metallic lithium is thermodynamically unstable, and immediately forms a solid-electrolyte interphase (SEI) when immersed into an electrolyte. An ideal SEI should inhibit the further reaction between Li and electrolytes and suppress the HSAL. However, spontaneously formed SEI in conventional liquid electrolytes is fragile and heterogeneous with variable spatial resistance, which induces uneven Li-ions flow, random Li deposition underneath, and the formation of HSAL [1]. To try to solve the problems inherent in the use of metallic lithium as an anode, different strategies have emerged, including that of using an artificial SEI on metallic Li to have a controlled interface between the anode and the electrolyte. Recently, polymer electrolytes [1,2] and 2D nanomaterials [3], among others, have been studied extensively for applications in LMBs. In this presentation, we will discuss the results obtained using hexagonal boron nitride (hBN) to modify the surface of the metallic lithium anode and its effect on the regulation of HSAL formation. We will also present the result of ab initio studies to analyze the system in an atomic scale, and dynamic molecular simulations to understand the formation of HSAL during the deposition/dissolution of lithium. We present an experimental and theoretical approach to studying and improving the properties of metallic lithium anodes. [1] C.A. Calderón, A. Vizintin, J. Bobnar, D.E. Barraco, E. Leiva, A. Visintin, S. Fantini, F. Fischer, R. Dominko, Lithium Metal Protection by a Cross-Linked Polymer Ionic Liquid and Its Application in Lithium Battery, ACS Appl. Energy Mater. 3 (2020) 2020-2027, doi: 10.1021/acsaem.9b02309.[2] J. Amici, C.A. Calderón, D. Versaci, G. Luque, D. Barraco, E. Leiva, C. Francia, S. Bodoardo, Composite polymer electrolyte with high inorganic additive contents to enable metallic lithium anode, Electrochimica Acta 404 (2022) 139772 - 139781, doi: 10.1016/j.electacta.2021.139772.[3] Wu, X. Li, Z. Rao, X. Xu, Z. Cheng, Y. Liao, L. Yuan, X. Xie, Z. Li, Y. Huang, Electrolyte with boron nitride nanosheets as leveling agent towards dendrite-free lithium metal anodes, Nano Energy 72 (2020) 104725-104733, doi: 10.1016/j.nanoen.2020.104725[4] Mayers, M. Z., Kaminski, J. W., & Miller, T. F. (2012). Suppression of Dendrite Formation via Pulse Charging in Rechargeable Lithium Metal Batteries. The Journal of Physical Chemistry C, 116(50), 26214–26221. https://doi.org/10.1021/jp309321w