Dissecting ionic favorable hydrogen bond chemistry in hybrid separators for aqueous zinc-ion batteries

Abstract

Separators, regulating the ion transport channels between electrodes, are crucial for maintaining the properties of electrochemical batteries. However, sluggish ion transport and desolvation kinetics in aqueous zinc-ion batteries (AZIBs) cause uneven ion flux at the separator–electrode interface, accelerating Zn dendrite growth. Herein, we systematically dissect ionic favorable hydrogen bond chemistry in a hybrid separator engineered through rational boron nitride (BN) doping into polyacrylonitrile (PAN) separators. Notably, in situ Fourier transform infrared spectroscopy (FTIR) analyses reveal that the hydrogen bond network in a BN-PAN separator improved the desolvation of Zn²⁺ by immobilizing water molecules through hydrogen bond interactions, thus effectively increasing the transference number of zinc ions. Capitalizing on the ionic favorable properties, uniform electric field distribution and zinc plating/stripping behavior are achieved at the separator–electrode interface, efficiently suppressing the formation of zinc dendrites and by-products. As a result, the BN-PAN separator demonstrates extended cycling stability, exceeding 1100 h at a current density of 1.0 mA cm⁻² and 700 h at a current density of 5.0 mA cm⁻², while exhibiting enhanced rate capability and stability in full cells. This work offers valuable insights into leveraging hydrogen bond chemistry for the design of fast ion-transport separators in aqueous batteries.