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

Published in Chemistry and Materials

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

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.

As renewable energy storage demand grows, the limitations of aqueous zinc metal batteries (AZMBs) in subzero environments become more pronounced. Now, researchers from Harbin University of Science and Technology and Fudan University, led by Professor Xin Liu and Professor Dongliang Chao, have presented a breakthrough solution using trace Na2SO4 as an electrolyte additive. This work offers valuable insights into developing next-generation energy storage technologies that can overcome low-temperature challenges.

Why Na2SO4 Matters

  • Cost-Effective: Na2SO4 is an abundant, low-cost inorganic salt that avoids the flammability and conductivity issues of organic antifreeze agents
  • Electrostatic Regulation: Na+ preferentially adsorbs at the zinc anode surface, repelling Zn2+ and promoting uniform deposition
  • Suppressed Side Reactions: Fewer water molecules coordinate with Na+, reducing hydrogen evolution and harmful byproducts
  • Ultra-Stable Cycling: Zn||Zn cells achieve over 2500 hours at −40°C, and Zn||PANI full cells retain >90% capacity after 8000 cycles

Innovative Design and Features

  • Electrolyte Formulation: The optimized 5ZClO/0.2Na electrolyte (5m Zn(ClO4)2+ 0.2m Na2SO4) maintains high ionic conductivity down to −60°C
  • Hydrogen Bond Disruption: Spectroscopic analyses reveal Na2SO4 further breaks water-water hydrogen bonds, enhancing antifreeze capability
  • Interfacial Engineering: DFT calculations show Na+ adsorption energy (−7.32 eV) exceeds Zn2+(−2.49 eV), enabling preferential interface regulation
  • Nucleation Control: Na+ increases nucleation overpotential, promoting denser, more uniform zinc deposition

Applications and Future Outlook

  • Low-Temperature Energy Storage: Enables reliable battery operation in extreme cold environments for EVs and grid systems
  • Long-Life Power Supplies: Zn||Cu cells maintain 99.5% Coulombic efficiency for >1000 cycles at −40°C
  • Safe and Scalable: Organic-free design maintains aqueous battery safety while improving performance
  • Challenges and Opportunities: Future work will focus on optimizing additive concentrations and exploring other cost-effective inorganic salts

This breakthrough provides a roadmap for developing high-performance, low-temperature AZMBs using simple electrolyte modifications. It highlights the importance of interfacial engineering and cost-effective materials design in advancing energy storage technologies. Stay tuned for more groundbreaking work from Professor Xin Liu and Professor Dongliang Chao's teams!

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Batteries
Physical Sciences > Materials Science > Materials for Energy and Catalysis > Batteries
Electrochemistry
Physical Sciences > Chemistry > Physical Chemistry > Electrochemistry
Surfaces, Interfaces and Thin Film
Physical Sciences > Materials Science > Surfaces, Interfaces and Thin Film
Density Functional Theory
Physical Sciences > Chemistry > Theoretical Chemistry > Computational Chemistry > Density Functional Theory
  • Nano-Micro Letters Nano-Micro Letters

    Nano-Micro Letters is a peer-reviewed, international, interdisciplinary and open-access journal that focus on science, experiments, engineering, technologies and applications of nano- or microscale structure and system in physics, chemistry, biology, material science, and pharmacy.