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Vol. 18 (2026)

Prioritized Na+ Adsorption-Driven Cationic Electrostatic Repulsion Enables Highly Reversible Zinc Anodes at Low Temperatures

https://doi.org/10.1007/s40820-025-01889-9
Guanchong Mao
Key Laboratory of Engineering Dielectric and Applications (Ministry of Education), School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150080, People’s Republic of China
Pan Xu
Key Laboratory of Engineering Dielectric and Applications (Ministry of Education), School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150080, People’s Republic of China
Xin Liu
Key Laboratory of Engineering Dielectric and Applications (Ministry of Education), School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150080, People’s Republic of China
Xingyu Zhao
Key Laboratory of Engineering Dielectric and Applications (Ministry of Education), School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150080, People’s Republic of China
Zexiang Shen
Key Laboratory of Engineering Dielectric and Applications (Ministry of Education), School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150080, People’s Republic of China
Dongliang Chao
Laboratory of Advanced Materials, Aqueous Battery Center, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Electron Microscope Center of Fudan University, Shanghai Wusong Laboratory of Materials Science, and Faculty of Chemistry and Materials, Fudan University, Shanghai 200433, People’s Republic of China
Minghua Chen
Key Laboratory of Engineering Dielectric and Applications (Ministry of Education), School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150080, People’s Republic of China

Corresponding Author: Minghua Chen

mhchen@hrbust.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 47

Abstract

Aqueous zinc metal batteries (AZMBs) are promising candidates for renewable energy storage, yet their practical deployment in subzero environments remains challenging due to electrolyte freezing and dendritic growth. Although organic additives can enhance the antifreeze properties of electrolytes, their weak polarity diminishes ionic conductivity, and their flammability poses safety concerns, undermining the inherent advantages of aqueous systems. Herein, we present a cost-effective and highly stable Na2SO4 additive introduced into a Zn(ClO4)2-based electrolyte to create an organic-free antifreeze electrolyte. Through Raman spectroscopy, in situ optical microscopy, density functional theory computations, and molecular dynamics simulations, we demonstrate that Na+ ions improve low-temperature electrolyte performance and mitigate dendrite formation by regulating uniform Zn2+ deposition through preferential adsorption and electrostatic interactions. As a result, the Zn||Zn cells using this electrolyte achieve a remarkable cycling life of 360 h at − 40 °C with 61% depth of discharge, and the Zn||PANI cells retained an ultrahigh capacity retention of 91% even after 8000 charge/discharge cycles at − 40 °C. This work proposes a cost-effective and practical approach for enhancing the long-term operational stability of AZMBs in low-temperature environments.


Highlights:
1 The introduction of low-cost, low-reduction-potential Na+ into aqueous Zn-based battery electrolytes suppresses Zn2+ aggregation at the anode interface through preferential Na+ adsorption and inter-cationic electrostatic repulsion, thereby enabling homogeneous Zn deposition and significantly enhanced low-temperature reversibility of Zn anodes.
2 Na+ with low ionic potential spontaneously adsorbs at the anode–electrolyte interface, effectively reducing solvated water molecules and suppressing parasitic reactions, thus significantly improving the Coulombic efficiency of aqueous zinc metal batteries under low temperatures.
3 At a low temperature of − 40 °C, the Zn||Zn cells maintained stable plating/stripping cycles for over 2500 h, and the Zn||PANI full cell exhibited excellent low-temperature performance with over 8000 charge–discharge cycles and a high capacity retention of more than 90%.

Keywords

Low-temperature resistant Organic-free additive Aqueous batteries High stability
Mao, Guanchong, Pan Xu, Xin Liu, Xingyu Zhao, Zexiang Shen, Dongliang Chao, and Minghua Chen. 2025. “Prioritized Na+ Adsorption-Driven Cationic Electrostatic Repulsion Enables Highly Reversible Zinc Anodes at Low Temperatures”. Nano-Micro Letters 18 (September):47. https://doi.org/10.1007/s40820-025-01889-9.
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