Ion recognition enables fast Mg–Cl bond dissociation kinetics and better Mg plating/stripping reversibility

Rechargeable Mg-metal batteries hold considerable promise for renewable energy storage and utilization. However, the Mg stripping/plating processes suffer from sluggish ion pairs dissociation kinetics, resulting in poor rate and cycle properties. In this work, an efficient skeleton host containing d...

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Main Authors: Jiacheng Yang, Jinlei Zhang, Kun Zhang, Jing Liu, Zhenfang Zhou, Zhenjiang Li, Guicun Li, Guanglei Cui, Zhonghua Zhang
Format: Article
Language:English
Published: KeAi Communications Co., Ltd. 2024-12-01
Series:Journal of Magnesium and Alloys
Online Access:http://www.sciencedirect.com/science/article/pii/S2213956723002141
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author Jiacheng Yang
Jinlei Zhang
Kun Zhang
Jing Liu
Zhenfang Zhou
Zhenjiang Li
Guicun Li
Guanglei Cui
Zhonghua Zhang
author_facet Jiacheng Yang
Jinlei Zhang
Kun Zhang
Jing Liu
Zhenfang Zhou
Zhenjiang Li
Guicun Li
Guanglei Cui
Zhonghua Zhang
author_sort Jiacheng Yang
collection DOAJ
description Rechargeable Mg-metal batteries hold considerable promise for renewable energy storage and utilization. However, the Mg stripping/plating processes suffer from sluggish ion pairs dissociation kinetics, resulting in poor rate and cycle properties. In this work, an efficient skeleton host containing dissimilar coupling elements with varied electronegativity has been designed to promote interfacial reaction kinetics by accelerating the Mg–Cl bond dissociation process. As a proof-of-concept prototype, the N/O-doped cobalt nanoparticles embedded in carbonaceous polyhedrons has been synthesized via facile high temperature annealing of zeolitic imidazolate framework-67 (ZIF-67). The exposed electron-rich N/O sites and electron-deficient Co sites can regulate the adsorbing structure configuration of [Mg-Cl]+ complex ions by selectively bonding with the Mg2+ and Cl– through chemical coordination linkage, respectively. The elongated bond length from 2.596 Å to 2.679 Å and the weakened bond strength are beneficial for the complex ions dissociation, leading to better charge transfer kinetics. In addition, the better magnesiophilic property accompanied by the conductive and porous permeable three-dimensional architecture realizes the homogeneous electrodeposition of Mg and improved electrode kinetics. The decreased overpotential has been verified in both magnesium organohaloaluminates electrolyte (from 290 mV to 189 mV) and conventional Mg(TFSI)2-based electrolyte (from 600 mV to 200 mV). The designed skeleton host also exhibits excellent long cycle lifespan above 2300 h and extra-high average Coulombic efficiency of 99.65 % within 700 cycles. The accelerated bond splitting strategy enables improved metal-anode reversibility, which is also insightful to high concentrated or other electrolyte systems that contain abundant ion pairs or aggregates.
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spelling doaj-art-eab1843b53704b63ba5b15e805f75eee2025-08-20T02:46:47ZengKeAi Communications Co., Ltd.Journal of Magnesium and Alloys2213-95672024-12-0112125205521510.1016/j.jma.2023.09.021Ion recognition enables fast Mg–Cl bond dissociation kinetics and better Mg plating/stripping reversibilityJiacheng Yang0Jinlei Zhang1Kun Zhang2Jing Liu3Zhenfang Zhou4Zhenjiang Li5Guicun Li6Guanglei Cui7Zhonghua Zhang8College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR ChinaCollege of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR ChinaZibo Institute for Product Quality Inspection, Zibo 255063, PR ChinaCollege of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR China; Department of Pharmacy, Jining Medical University, Rizhao 276826, PR ChinaCollege of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR China; Corresponding authors at: College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR China.College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR ChinaCollege of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR ChinaQingdao Industrial Energy Storage Research Institute, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, PR ChinaCollege of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR China; Qingdao Industrial Energy Storage Research Institute, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, PR China; Corresponding authors at: College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR China.Rechargeable Mg-metal batteries hold considerable promise for renewable energy storage and utilization. However, the Mg stripping/plating processes suffer from sluggish ion pairs dissociation kinetics, resulting in poor rate and cycle properties. In this work, an efficient skeleton host containing dissimilar coupling elements with varied electronegativity has been designed to promote interfacial reaction kinetics by accelerating the Mg–Cl bond dissociation process. As a proof-of-concept prototype, the N/O-doped cobalt nanoparticles embedded in carbonaceous polyhedrons has been synthesized via facile high temperature annealing of zeolitic imidazolate framework-67 (ZIF-67). The exposed electron-rich N/O sites and electron-deficient Co sites can regulate the adsorbing structure configuration of [Mg-Cl]+ complex ions by selectively bonding with the Mg2+ and Cl– through chemical coordination linkage, respectively. The elongated bond length from 2.596 Å to 2.679 Å and the weakened bond strength are beneficial for the complex ions dissociation, leading to better charge transfer kinetics. In addition, the better magnesiophilic property accompanied by the conductive and porous permeable three-dimensional architecture realizes the homogeneous electrodeposition of Mg and improved electrode kinetics. The decreased overpotential has been verified in both magnesium organohaloaluminates electrolyte (from 290 mV to 189 mV) and conventional Mg(TFSI)2-based electrolyte (from 600 mV to 200 mV). The designed skeleton host also exhibits excellent long cycle lifespan above 2300 h and extra-high average Coulombic efficiency of 99.65 % within 700 cycles. The accelerated bond splitting strategy enables improved metal-anode reversibility, which is also insightful to high concentrated or other electrolyte systems that contain abundant ion pairs or aggregates.http://www.sciencedirect.com/science/article/pii/S2213956723002141
spellingShingle Jiacheng Yang
Jinlei Zhang
Kun Zhang
Jing Liu
Zhenfang Zhou
Zhenjiang Li
Guicun Li
Guanglei Cui
Zhonghua Zhang
Ion recognition enables fast Mg–Cl bond dissociation kinetics and better Mg plating/stripping reversibility
Journal of Magnesium and Alloys
title Ion recognition enables fast Mg–Cl bond dissociation kinetics and better Mg plating/stripping reversibility
title_full Ion recognition enables fast Mg–Cl bond dissociation kinetics and better Mg plating/stripping reversibility
title_fullStr Ion recognition enables fast Mg–Cl bond dissociation kinetics and better Mg plating/stripping reversibility
title_full_unstemmed Ion recognition enables fast Mg–Cl bond dissociation kinetics and better Mg plating/stripping reversibility
title_short Ion recognition enables fast Mg–Cl bond dissociation kinetics and better Mg plating/stripping reversibility
title_sort ion recognition enables fast mg cl bond dissociation kinetics and better mg plating stripping reversibility
url http://www.sciencedirect.com/science/article/pii/S2213956723002141
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