Influence of Chloride and Electrolyte Stability on Passivation Layer Evolution at the Negative Electrode of Mg Batteries Revealed by operando EQCM‐D

• Published in: Angewandte Chemie International Edition 2024-12, Vol.63 (52), p.e202413058-n/a
• Main Authors: Schick, Benjamin W., Vanoppen, Viktor, Uhl, Matthias, Kruck, Matthias, Riedel, Sibylle, Zhao‐Karger, Zhirong, Berg, Erik J., Hou, Xu, Jacob, Timo
• Format: Article
• Language: English
• Subjects: Contaminants; Cycles; Electrochemistry; Electrodes; Electrolytes; Energy storage; EQCM−D; Hydrodynamic Spectroscopy; Interphase; Magnesium; Magnesium chloride; Mg Battery Electrolyte; Passivity; Plating; Quartz crystal microbalance; Quartz crystals; Spectroscopy; Stability
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202413058

Rechargeable magnesium batteries are promising for future energy storage. However, among other challenges, their practical application is hindered by low coulombic efficiencies of magnesium plating and stripping. Fundamental processes such as the formation, structure, and stability of passivation layers and the influence of different electrolyte components on them are still not fully understood. In this work, we gain unique insights into the initial Mg plating and stripping cycles by comparing magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2)‐ and magnesium tetrakis(hexafluoroisopropyloxy)borate (Mg[B(hfip)4]2)‐based electrolytes, each with and without MgCl2, on gold electrodes by highly sensitive operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCM−D) applying hydrodynamic spectroscopy. With the stable Mg[B(hfip)4]2‐based electrolytes, highly efficient and interphase‐free cycling is possible and passivation layers are attributed to electrolyte contaminants. These are forming and degrading during the so‐called initial conditioning process. With the more reactive Mg(TFSI)2‐based electrolyte, thick passivation layers with small pores are growing during cycling. We demonstrate that the addition of chloride lowers the amount of passivated Mg deposits in these electrolytes and accelerates the currentless dissolution of the passivation layer. This has a positive effect since we observe the most efficient cycling and uniform deposition when no interphase is present on the electrode. Understanding passivation layer formation, its morphology and dissolution is essential to systematically develop electrolytes which enable highly reversible Mg deposition. By applying operando electrochemical quartz crystal microbalance with dissipation monitoring, the impact of chloride and differences between more and less stable electrolytes are revealed, showing that highly efficient interphase‐free cycling is possible.