Aqueous sodium-ion batteries may solve the cost and safety issues associated with the energy storage systems for the fluctuating supply of electricity based on solar and wind power. Compared to their lithium counterparts, aqueous sodium-ion batteries offer multiple advantages including more earth abundant sodium, cheaper electrode materials and electrolyte solutions as well as less costly manufacturing conditions. However, poor overall performance and low electrode utilization (much of the electrode material ends up being electrochemically inactive) are the main barriers implementing them in (micro)grid systems.

Here we characterize the surface reactions on NASICON-type phosphate anode material and rationalize their close associations with capacity fading upon slow cycling of aqueous sodium-ion batteries. The surface reactions result in the formation of an electrically insulating surface layer causing the failure of electrochemical performance and the precipitation of surface particles that blocks the pores thereby leading to poor electrode utilization. These findings provide insight into new possibilities of improving the electrochemical performance of aqueous sodium-ion batteries by the design of protective layers through surface modifications that prevent the formation of insulating surface layers and insoluble precipitates.