Na(3)Zr(2)Si(2)PO(12) Solid Electrolyte Membrane for High‐Performance Seawater Battery

Seawater batteries (SWBs) have gained tremendous interest in the electrochemical energy storage research field because of their low cost, natural abundance, and potential use for long‐duration energy storage. Advancing a SWB to demonstration projects is plagued by the poor electrochemical performance stemming from the poor interfaces of the solid electrolyte (SE), as well as the structural and chemical instabilities and sluggish ionic transport properties. In this study, the anode compartment of a surrogate SWB is constructed with a Na | SE | hard carbon configuration, and tailored dopants are introduced into the Nasicon‐type Na(3)Zr(2)Si(2)PO(12)(NZSP) SE membrane. After doping with TiO(2), a much more densely packed pellet with uniformly distributed porous structure is obtained. Changes in surface chemistry and local structure in the bulk are observed, which are believed to contribute to the improved ionic conductivity and higher critical current density of the TiO(2)‐doped NZSP. Stable cycling performance with reversible capacities based on different Na storage mechanisms are also demonstrated.