Molecular Coordination Engineering Enables Aminoethyl Phosphonic Acid as a Multifunctional Additive for High-Performance Zinc-Iodine Flow Batteries

Han Shi; Jing Cui; Zhikun Liu; Peng Kang

doi:10.1007/s12209-026-00488-y

Transactions of Tianjin University ›› :1 -10. DOI: 10.1007/s12209-026-00488-y

Research Article

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Molecular Coordination Engineering Enables Aminoethyl Phosphonic Acid as a Multifunctional Additive for High-Performance Zinc-Iodine Flow Batteries

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¹School of Chemical Engineering and Technology, Tianjin University, 300350, Tianjin, China

^a kang.peng@tju.edu.cn

Han Shi

Han Shi is a PhD student at Tianjin University, supervised by Prof. Peng Kang. Her postgraduate research focused on electrochemistry, including redox flow batteries and electrocatalytic CO₂.

Jing Cui

Jing Cui is a PhD student at Tianjin University, supervised by Prof. Peng Kang. Her postgraduate research has focused on electrolytes for flow batteries.

Zhikun Liu

Zhikun Liu is a PhD student at Tianjin University, supervised by Prof. Peng Kang. His postgraduate research focused on electrochemistry, including all-iron redox flow batteries and electrocatalytic CO₂ reduction under flue gas or acidic conditions.

Peng Kang

Peng Kang is a doctoral supervisor and a national-level young talent. A graduate of the University of Science and Technology of China (B.S.) and Stanford University (Ph.D.), he completed his postdoctoral training at the University of North Carolina at Chapel Hill under the guidance of renowned scholars Maurice Brookhart and Thomas J. Meyer. His current research interests lie in advanced electrochemical systems, including CO₂ electrochemical capture and utilization, flow battery energy storage, and water electrolysis catalysts and separators

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Abstract

The practical application of aqueous zinc-ion batteries is critically hindered by the instability of the zinc metal anode, which suffers from uncontrollable dendrite growth and detrimental side reactions. Conventional electrolyte additives often focus solely on homogenizing the zinc-ion flux, while neglecting the pivotal role of crystallographic regulation. Herein, we propose a fundamental strategy to manipulate zinc deposition behavior through selective molecular adsorption. We introduce 2-aminoethylphosphonic acid (AEP) as a novel electrolyte additive that preferentially adsorbs onto the (100) and (101) crystal planes of zinc, as confirmed by experimental evidence from electric double-layer capacitance measurements, and theoretical DFT calculations, which reveal a lower adsorption energy on the (002) facet. Consequently, the AEP-modified electrolyte enables a densely packed zinc morphology and a significantly optimized interface, which collectively contribute to markedly enhanced electrode kinetics and cycling stability. The improved negative electrolyte enables the zinc-iodine flow battery (ZIFB) to operate for 600 h (1500 cycles) with a high energy efficiency (> 83%) at 80 mA/cm². This work underscores the critical importance of crystallographic engineering via selective molecular adsorption. The mechanistic insights gained into the dual regulation of solvation structure and interfacial growth provide a new design principle for advanced electrolytes targeting highly reversible metal anodes.

Keywords

Aqueous zinc batteries / Electrolyte additive / Molecular design / Interface engineering / Phosphonate

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Han Shi, Jing Cui, Zhikun Liu, Peng Kang. Molecular Coordination Engineering Enables Aminoethyl Phosphonic Acid as a Multifunctional Additive for High-Performance Zinc-Iodine Flow Batteries. Transactions of Tianjin University 1-10 DOI:10.1007/s12209-026-00488-y

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