Reversible Solid-Liquid Conversion Enabled by Self-Capture Effect for Stable Non-Flow Zinc-Bromine Batteries

Abstract

Non-flow aqueous zinc-bromine batteries without auxiliary components (e.g., pumps, pipes, storage tanks) and ion-selective membranes represent a cost-effective and promising technology for large-scale energy storage. Unfortunately, they generally suffer from serious diffusion and shuttle of polybromide (Br-, Br3-) due to the weak physical adsorption between soluble polybromide and host carbon materials, which results in low energy efficiency and poor cycling stability. Here, we develop a novel self-capture organic bromine material (1,1′-bis[3-(trimethylammonio)propyl]-4,4′-bipyridinium bromine, NVBr4) to successfully realize reversible solid complexation of bromide components for stable non-flow zinc-bromine battery applications. The quaternary ammonium groups (NV4+ ions) can effectively capture the soluble polybromide species based on strong chemical interaction and realize reversible solid complexation confined within the porous electrodes, which transforms the conventional "liquid-liquid" conversion of soluble bromide components into "liquid-solid" model and effectively suppresses the shuttle effect. Thereby, the developed non-flow zinc-bromide battery provides an outstanding voltage platform at 1.7 V with a notable specific capacity of 325 mAh g-1NVBr4 (1 A g-1), excellent rate capability (200 mAh g-1NVBr4 at 20 A g-1), outstanding energy density of 469.6 Wh kg-1 and super-stable cycle life (20000 cycles with 100% Coulombic efficiency), which outperforms most of reported zinc-halogen batteries. Further mechanism analysis and DFT calculations demonstrate that the chemical interaction of quaternary ammonium groups and bromide species is the main reason for suppressing the shuttle effect. The developed strategy can be extended to other halogen batteries to obtain stable charge storage.

Keywords: Solid-liquid conversion, Self-capture, Non-flow zinc-bromine batteries, Quaternary ammonium