Single Crystalline Na 0.67 Ni 0.33 Mn 0.67 O 2 Positive Electrode Material via Molten Salt Synthesis for Sodium Ion Batteries
P2-layered Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) has emerged as a promising positive electrode material for sodium ion batteries due to its appealing electrochemical properties. Synthesis of polycrystalline NNMO (PC-NNMO) materials through conventional calcination of solid precursors remains the prevailing method, where heating occurs in a dry environment with air or O 2 . On the other hand, the molten salt method, where precursors are submerged in molten salt medium during calcination, emerged in recent years to be a scalable technique for more controlled crystal growth and uniform morphology in a variety of materials. Here, we utilize the molten salt method to synthesize single crystalline NNMO (SC-NNMO) materials with enhanced electrochemical properties. The SC-NNMO material exhibits an initial specific discharge capacity of 95 mAh g –1 at a 0.1C rate, retaining approximately 88.5% of its capacity after 100 cycles over a wide voltage range of 2.0–4.2 V. Furthermore, SC-NNMO maintains a capacity retention of 83.9% after 300 cycles at a 1C rate compared to 66.6% for PC-NNMO, indicating excellent long-term cycling stability. This stability is further confirmed by the performance of an SC-NNMO//hard carbon full cell, which retains 90.3% of its capacity after 200 cycles at 1C within a voltage window of 1.9–4.1 V. The enhancement in stability of the SC-NNMO sample is attributed to the single crystalline structure suppressing the undesired P2–O2 phase transition at high voltage. This study also presents an easy, efficient, and straightforward molten salt process for SC-NNMO material synthesis, offering valuable insights into the potential application of such methodology for the large-scale, cost-effective production of various sodium-layered transition metal oxide positive electrode materials for SIBs.