Fast single metal cation conduction in ion-water aggregated aqueous battery electrolytes

Abstract Metal ion transport in solution is closely linked to its interactions with counter anions and solvent molecules. This interplay creates a longstanding trade-off between transference number (tM n ⁺), ionic conductivity (δ), and solvation process. Advanced aqueous batteries with metal negativ...

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Main Authors: Chen Xu, Huijian Wang, Chengjun Lei, Jinye Li, Wenjiao Ma, Xiao Liang
Format: Article
Language:English
Published: Nature Portfolio 2025-05-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-59958-x
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author Chen Xu
Huijian Wang
Chengjun Lei
Jinye Li
Wenjiao Ma
Xiao Liang
author_facet Chen Xu
Huijian Wang
Chengjun Lei
Jinye Li
Wenjiao Ma
Xiao Liang
author_sort Chen Xu
collection DOAJ
description Abstract Metal ion transport in solution is closely linked to its interactions with counter anions and solvent molecules. This interplay creates a longstanding trade-off between transference number (tM n ⁺), ionic conductivity (δ), and solvation process. Advanced aqueous batteries with metal negative electrode require electrolytes with unity tM n ⁺, high δ and low solvation energy. Here we introduce guanidinium sulfate (Gdm2SO4) into metal sulfate aqueous solutions to construct the ion-water aggregated electrolytes. These electrolytes exhibit fast single ion conduction, approaching unity tM n ⁺ and high δ over 50 mS cm−1 for various metal cations (M= Zn, Cu, Fe, Sn and Li). The ion-water aggregates, dynamically formed by strong hydrogen bonding between sulfate anions, guanidinium cations and water, featuring an unfrustrated topological structure to suppress both anion mobility and water activity. This general configuration decouples the metal charge carrier from its coordination sheath, resulting in decreased solvation energy. These merits lead to homogeneous metal plating/stripping behavior with high coulombic efficiency of 99.9%. Moreover, the ion-water aggregates with reinforced kosmotropic characteristics significantly decrease the freezing point of the sulfate-based electrolytes to –28 oC, making them widely applicable in aqueous metal batteries for both intercalation and conversion positive electrodes.
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spelling doaj-art-2554347a0f5347bfb74d3b98bd99f5362025-08-20T03:07:56ZengNature PortfolioNature Communications2041-17232025-05-0116111010.1038/s41467-025-59958-xFast single metal cation conduction in ion-water aggregated aqueous battery electrolytesChen Xu0Huijian Wang1Chengjun Lei2Jinye Li3Wenjiao Ma4Xiao Liang5State Key Laboratory of Chem/Bio-Sensing and Chemometrics, Joint International Research Laboratory of Energy Electrochemistry, College of Chemistry and Chemical Engineering, Hunan UniversityState Key Laboratory of Chem/Bio-Sensing and Chemometrics, Joint International Research Laboratory of Energy Electrochemistry, College of Chemistry and Chemical Engineering, Hunan UniversityState Key Laboratory of Chem/Bio-Sensing and Chemometrics, Joint International Research Laboratory of Energy Electrochemistry, College of Chemistry and Chemical Engineering, Hunan UniversityState Key Laboratory of Chem/Bio-Sensing and Chemometrics, Joint International Research Laboratory of Energy Electrochemistry, College of Chemistry and Chemical Engineering, Hunan UniversityState Key Laboratory of Chem/Bio-Sensing and Chemometrics, Joint International Research Laboratory of Energy Electrochemistry, College of Chemistry and Chemical Engineering, Hunan UniversityState Key Laboratory of Chem/Bio-Sensing and Chemometrics, Joint International Research Laboratory of Energy Electrochemistry, College of Chemistry and Chemical Engineering, Hunan UniversityAbstract Metal ion transport in solution is closely linked to its interactions with counter anions and solvent molecules. This interplay creates a longstanding trade-off between transference number (tM n ⁺), ionic conductivity (δ), and solvation process. Advanced aqueous batteries with metal negative electrode require electrolytes with unity tM n ⁺, high δ and low solvation energy. Here we introduce guanidinium sulfate (Gdm2SO4) into metal sulfate aqueous solutions to construct the ion-water aggregated electrolytes. These electrolytes exhibit fast single ion conduction, approaching unity tM n ⁺ and high δ over 50 mS cm−1 for various metal cations (M= Zn, Cu, Fe, Sn and Li). The ion-water aggregates, dynamically formed by strong hydrogen bonding between sulfate anions, guanidinium cations and water, featuring an unfrustrated topological structure to suppress both anion mobility and water activity. This general configuration decouples the metal charge carrier from its coordination sheath, resulting in decreased solvation energy. These merits lead to homogeneous metal plating/stripping behavior with high coulombic efficiency of 99.9%. Moreover, the ion-water aggregates with reinforced kosmotropic characteristics significantly decrease the freezing point of the sulfate-based electrolytes to –28 oC, making them widely applicable in aqueous metal batteries for both intercalation and conversion positive electrodes.https://doi.org/10.1038/s41467-025-59958-x
spellingShingle Chen Xu
Huijian Wang
Chengjun Lei
Jinye Li
Wenjiao Ma
Xiao Liang
Fast single metal cation conduction in ion-water aggregated aqueous battery electrolytes
Nature Communications
title Fast single metal cation conduction in ion-water aggregated aqueous battery electrolytes
title_full Fast single metal cation conduction in ion-water aggregated aqueous battery electrolytes
title_fullStr Fast single metal cation conduction in ion-water aggregated aqueous battery electrolytes
title_full_unstemmed Fast single metal cation conduction in ion-water aggregated aqueous battery electrolytes
title_short Fast single metal cation conduction in ion-water aggregated aqueous battery electrolytes
title_sort fast single metal cation conduction in ion water aggregated aqueous battery electrolytes
url https://doi.org/10.1038/s41467-025-59958-x
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AT chengjunlei fastsinglemetalcationconductioninionwateraggregatedaqueousbatteryelectrolytes
AT jinyeli fastsinglemetalcationconductioninionwateraggregatedaqueousbatteryelectrolytes
AT wenjiaoma fastsinglemetalcationconductioninionwateraggregatedaqueousbatteryelectrolytes
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