Electrolyte‐Salts Regulated Hydrogen‐Bonding Configuration and Interphase Formation Achieving Highly Stable Anode for Rechargeable Aqueous Sodium‐Ion Batteries

Abstract Hydrogen evolution reactions that cause the alkalization of aqueous electrolytes generally frustrate the structural stability and cycling performance of NaTi 2 (PO 4 ) 3 /C anode material for rechargeable aqueous sodium‐ion batteries (ASIBs). Herein, a novel highly concentrated electrolyte with a large hydrogen‐evolution overpotential and hydroxide‐capture ability is rationally established by incorporating a bifunctional Mg(Ac) 2 additive into a concentrated NaAc aqueous solution. The highly concentrated electrolyte salts (4 m NaAc+3 m Mg(Ac) 2 ) favor regulation on hydrogen‐bonding configurations and kinetically shift the hydrogen evolution potential to a lower value of −1.37 V (vs Ag/AgCl). The Mg(Ac) 2 additive plays particular roles in spontaneously capturing hydroxide ions generated during hydrogen evolution reactions on anode surfaces and simultaneously forming a protective Mg(OH) 2 ‐like interphase. As a result, the unique electrolyte significantly improves the structural stability and cycling performance of NaTi 2 (PO 4 ) 3 /C anode (94.8% capacity retention after 100 cycles at 100 mA·g −1 ). The effect of salt concentration on hydrogen bonding configurations of aqueous electrolytes is investigated with Raman spectroscopy and FTIR spectroscopy. The interphase is identified by coupling EDS mapping, X‐ray photoelectron spectroscopy, and X‐ray diffraction. This work provides a new strategy for improving the cycling stability of aqueous sodium‐ion batteries.