Synthesis of MgCl+ and Mg2+ Cation Based Novel Electrolytes: Impact of Polydentate Ethers

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 [Mg2(μ‐Cl)3 ⋅ 6THF]+ [Ph4Al]−, A, and [Mg2(μ‐Cl)3 ⋅ 6THF]+ [Ph3AlCl]−, B, have been studied, but their...

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Main Authors: Yogendra Kumar, Ben Dlugatch, Ananya Maddegalla, Yuri Glagovsky, Natalia Fridman, Sri Harsha Akella, Nicole Leifer, Doron Aurbach, Dmitry Bravo‐Zhivotovskii, Malachi Noked
Format: Article
Language:English
Published: Wiley-VCH 2025-05-01
Series:ChemElectroChem
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Online Access:https://doi.org/10.1002/celc.202400678
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author Yogendra Kumar
Ben Dlugatch
Ananya Maddegalla
Yuri Glagovsky
Natalia Fridman
Sri Harsha Akella
Nicole Leifer
Doron Aurbach
Dmitry Bravo‐Zhivotovskii
Malachi Noked
author_facet Yogendra Kumar
Ben Dlugatch
Ananya Maddegalla
Yuri Glagovsky
Natalia Fridman
Sri Harsha Akella
Nicole Leifer
Doron Aurbach
Dmitry Bravo‐Zhivotovskii
Malachi Noked
author_sort Yogendra Kumar
collection DOAJ
description 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 [Mg2(μ‐Cl)3 ⋅ 6THF]+ [Ph4Al]−, A, and [Mg2(μ‐Cl)3 ⋅ 6THF]+ [Ph3AlCl]−, 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]+ [Ph4Al]− 1 and [DG ⋅ MgCl ⋅ 2THF]+ [Ph4Al]− 2, [Mg ⋅ 3DME]2+ 2[Ph3AlCl−] 3 and [Mg ⋅ 2DG]2+ 2[Ph3AlCl−] 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 [Mg2(μ‐Cl)3 ⋅ 6THF]+ cation upon the addition of polydentate ligands. Specifically, with the [Ph4Al]− counter anion (precursor A), the dissociation results in a [MgCl]+ mono‐cation, while with the [Ph3AlCl]− counter anion (precursor B), a [Mg]2+ divalent cation is formed. The resultant MgCl2 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.
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spelling doaj-art-664f6e74f9d64aedbcbc599988ecd1f52025-08-20T03:08:21ZengWiley-VCHChemElectroChem2196-02162025-05-011210n/an/a10.1002/celc.202400678Synthesis of MgCl+ and Mg2+ Cation Based Novel Electrolytes: Impact of Polydentate EthersYogendra Kumar0Ben Dlugatch1Ananya Maddegalla2Yuri Glagovsky3Natalia Fridman4Sri Harsha Akella5Nicole Leifer6Doron Aurbach7Dmitry Bravo‐Zhivotovskii8Malachi Noked9Department of Chemistry Institute of Nanotechnology and Advanced Materials Bar-Ilan University INIES – Israel National Institute for Energy Storage, supported by Israel Ministry of Energy and Infrastructures. Ramat Gan 5290002 IsraelDepartment of Chemistry Institute of Nanotechnology and Advanced Materials Bar-Ilan University INIES – Israel National Institute for Energy Storage, supported by Israel Ministry of Energy and Infrastructures. Ramat Gan 5290002 IsraelDepartment of Chemistry Institute of Nanotechnology and Advanced Materials Bar-Ilan University INIES – Israel National Institute for Energy Storage, supported by Israel Ministry of Energy and Infrastructures. Ramat Gan 5290002 IsraelSchulich faculty of Chemistry Technion-Israel Institute of Technology Haifa 3200003Schulich faculty of Chemistry Technion-Israel Institute of Technology Haifa 3200003Department of Chemistry Institute of Nanotechnology and Advanced Materials Bar-Ilan University INIES – Israel National Institute for Energy Storage, supported by Israel Ministry of Energy and Infrastructures. Ramat Gan 5290002 IsraelDepartment of Chemistry Institute of Nanotechnology and Advanced Materials Bar-Ilan University INIES – Israel National Institute for Energy Storage, supported by Israel Ministry of Energy and Infrastructures. Ramat Gan 5290002 IsraelDepartment of Chemistry Institute of Nanotechnology and Advanced Materials Bar-Ilan University INIES – Israel National Institute for Energy Storage, supported by Israel Ministry of Energy and Infrastructures. Ramat Gan 5290002 IsraelDepartment of Chemistry Institute of Nanotechnology and Advanced Materials Bar-Ilan University INIES – Israel National Institute for Energy Storage, supported by Israel Ministry of Energy and Infrastructures. Ramat Gan 5290002 IsraelDepartment of Chemistry Institute of Nanotechnology and Advanced Materials Bar-Ilan University INIES – Israel National Institute for Energy Storage, supported by Israel Ministry of Energy and Infrastructures. Ramat Gan 5290002 IsraelAbstract 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 [Mg2(μ‐Cl)3 ⋅ 6THF]+ [Ph4Al]−, A, and [Mg2(μ‐Cl)3 ⋅ 6THF]+ [Ph3AlCl]−, 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]+ [Ph4Al]− 1 and [DG ⋅ MgCl ⋅ 2THF]+ [Ph4Al]− 2, [Mg ⋅ 3DME]2+ 2[Ph3AlCl−] 3 and [Mg ⋅ 2DG]2+ 2[Ph3AlCl−] 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 [Mg2(μ‐Cl)3 ⋅ 6THF]+ cation upon the addition of polydentate ligands. Specifically, with the [Ph4Al]− counter anion (precursor A), the dissociation results in a [MgCl]+ mono‐cation, while with the [Ph3AlCl]− counter anion (precursor B), a [Mg]2+ divalent cation is formed. The resultant MgCl2 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.https://doi.org/10.1002/celc.202400678Rechargeable Mg batteriesMg saltsethereal Mg2+ salts solutionsMgCl+
spellingShingle Yogendra Kumar
Ben Dlugatch
Ananya Maddegalla
Yuri Glagovsky
Natalia Fridman
Sri Harsha Akella
Nicole Leifer
Doron Aurbach
Dmitry Bravo‐Zhivotovskii
Malachi Noked
Synthesis of MgCl+ and Mg2+ Cation Based Novel Electrolytes: Impact of Polydentate Ethers
ChemElectroChem
Rechargeable Mg batteries
Mg salts
ethereal Mg2+ salts solutions
MgCl+
title Synthesis of MgCl+ and Mg2+ Cation Based Novel Electrolytes: Impact of Polydentate Ethers
title_full Synthesis of MgCl+ and Mg2+ Cation Based Novel Electrolytes: Impact of Polydentate Ethers
title_fullStr Synthesis of MgCl+ and Mg2+ Cation Based Novel Electrolytes: Impact of Polydentate Ethers
title_full_unstemmed Synthesis of MgCl+ and Mg2+ Cation Based Novel Electrolytes: Impact of Polydentate Ethers
title_short Synthesis of MgCl+ and Mg2+ Cation Based Novel Electrolytes: Impact of Polydentate Ethers
title_sort synthesis of mgcl and mg2 cation based novel electrolytes impact of polydentate ethers
topic Rechargeable Mg batteries
Mg salts
ethereal Mg2+ salts solutions
MgCl+
url https://doi.org/10.1002/celc.202400678
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