Premium
Synthesis of MgCl + and Mg 2+ Cation Based Novel Electrolytes: Impact of Polydentate Ethers
Author(s) -
Kumar Yogendra,
Dlugatch Ben,
Maddegalla Ananya,
Glagovsky Yuri,
Fridman Natalia,
Akella Sri Harsha,
Leifer Nicole,
Aurbach Doron,
BravoZhivotovskii Dmitry,
Noked Malachi
Publication year - 2025
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.202400678
Subject(s) - denticity , chemistry , electrolyte , nuclear chemistry , inorganic chemistry , medicinal chemistry , radiochemistry , organic chemistry , crystal structure , electrode
Abstract The development of efficient electrolytes is crucial for advancing magnesium (Mg) batteries, which hold promise for next‐generation energy storage systems. Previously, electrolytes such as [Mg 2 (μ‐Cl) 3 ⋅ 6THF] + [Ph 4 Al] − , A, and [Mg 2 (μ‐Cl) 3 ⋅ 6THF] + [Ph 3 AlCl] − , B , have been studied, but their performance has been limited by issues related to ion dissociation and electrochemical stability. In this study, we report the synthesis of novel electrolytes by introducing polydentate ligands to these known systems, leading to the formation of [DME ⋅ MgCl ⋅ 3THF] + [Ph 4 Al] − 1 and [DG ⋅ MgCl ⋅ 2THF] + [Ph 4 Al] − 2 , [Mg ⋅ 3DME] 2+ 2[Ph 3 AlCl − ] 3 and [Mg ⋅ 2DG] 2+ 2[Ph 3 AlCl − ] 4 . These firstly discovered compounds were thoroughly characterized using X‐ray crystallography and NMR spectroscopy. Our findings reveal that the choice of counter anion plays a pivotal role in the products and mechanism of the dissociation of the bridged [Mg 2 (μ‐Cl) 3 ⋅ 6THF] + cation upon the addition of polydentate ligands. Specifically, with the [Ph 4 Al] − counter anion (precursor A ), the dissociation results in a [MgCl] + mono‐cation, while with the [Ph 3 AlCl] − counter anion (precursor B ), a [Mg] 2+ divalent cation is formed. The resultant MgCl 2 byproduct enhances solubility, expands electrochemical windows, and improves cyclic stability, leading to superior electrochemical performance of the new electrolytes ( 1 , 2 , 3 , and 4 ) compared to the original precursors. These insights offer valuable guidelines for the design and synthesis of advanced electrolytes for rechargeable magnesium batteries, potentially paving the way for more efficient and stable energy storage solutions.