Elucidating the Influence of Electrolyte Additives on Iron Electroplating Performance Towards Application in Iron-Based Batteries

09 August 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


All-iron redox flow batteries are a promising alternative for grid-scale energy storage; however, their efficiency and lifetime are hampered by the poorly understood plating process, the limited reversibility of the negative half-cell, and the presence of competitive reactions. In this work, we propose a methodology to deconvolute the nucleation parameters of iron via a suite of electrochemical techniques, spectroscopy, and analytical models, coupled with microscopic and crystallographic techniques. We perform a systematic analysis with iron-based electrolytes to deconvolute the simultaneous plating and hydrogen evolution reactions, and investigate an array of additives to tune electroplating descriptors. We find that all additives studied are able to regulate the plating process and find that highly stable iron-complexes based on buffers, such as iron-borates or -citrates deliver greater battery performance in symmetric configuration, with nearly 50% higher cyclability than the baseline electrolyte. These additives show superior selectivity, with improvements in faradaic efficiencies from 60% to ~90% due to the balanced effects of enhanced nucleation and side reaction suppression. Herewith, the aim of this study is to bridge the knowledge gap between the role of additives, kinetics and efficiency of the electrodeposition reaction, and their interplay defining battery cycling performance.


electrolyte engineering
electrochemical engineering
all iron redox flow batteries
cycling stability

Supplementary materials

Supporting Information - Elucidating the Influence of Electrolyte Composition on Iron Electroplating Performance for High-Power Iron-Based Flow Batteries
The content included in the SI file comprises: S1. Raw data for chronoamperometric nucleation analysis S2. Modeling fitting results for the deconvolution of plating currents and nucleation parameter S3. Electrode stability and self-discharge behavior S4. Symmetric SwagelokTM cell cycling performance S5. References


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