Feng Yan, Chunliu Xu, Junmei Zhao
ABSTRACT Sodium‐ion batteries (SIBs) have garnered significant attention in the field of large‐scale energy storage due to their abundant sodium resources, low cost, and similar working principles to lithium‐ion batteries. The cathode material is a pivotal component that governs the overall energy density and cost structure of SIBs. NASICON‐type Na 3 MnTi(PO 4 ) 3 (NMTP) only contains high abundance elements and allows large capacity with high working voltage based on multi‐electron redox reactions, which makes NMTP become a great potential cathode material for SIBs. However, NMTP suffers from serious voltage hysteresis mainly caused by electronic‐conductivity limits and intrinsic structural defects, deteriorating its available electrochemical performance. In this review, we overview recent insights into mechanisms of voltage hysteresis and modification strategies of NMTP cathodes. Surface carbon coating can only improve apparent electronic conductivity, but metal ion doping is the most effective strategy to suppress intrinsic Mn/Na anti‐site defects (IASD) thus alleviating voltage hysteresis. By comprehensive consideration of solid solubility, valence state, and electronegativity of dopants, we propose a guiding rule for future doping strategies to reduce IASD and suppress voltage hysteresis of NMTP. We hope that this review can provide some insights into the development of NMTP and other NASICON‐type phosphate cathode materials.