Surface Gradient Desodiation Chemistry in Layered Oxide Cathode Materials

Abstract Sodium‐ion batteries (SIBs) as a promising technology for large‐scale energy storage have received unprecedented attention. However, the cathodes in SIBs generally suffer from detrimental cathode‐electrolyte interfacial side reactions and structural degradation during cycling, which leads to severe capacity fade and voltage decay. Here, we have developed an ultra‐stable Na 0.72 Ni 0.20 Co 0.21 Mn 0.55 Mg 0.036 O 2 (NCM‐CS‐GMg) cathode material in which a Mg‐free core is encapsulated by a shell with gradient distribution of Mg using coprecipitation method with Mg‐hysteretic cascade feedstock followed by calcination. From the interior to outer surface of the shell, as the content of electrochemically inactive Mg gradually increases, the Na + deintercalation amount gradually decreases after charged. Benefiting from this surface gradient desodiation, the surface transition metal (TM) ion migration from TM layers to Na layers is effectively inhibited, thus suppressing the layered‐to‐rock‐salt phase transition and the resultant microcracks. Besides, the less formation of high‐valence TM ions on the surface contributes to a stable cathode‐electrolyte interface. The as‐prepared NCM‐CS‐GMg exhibits remarkable cycling life over 3000 cycles with a negligible voltage drop (0.127 mV per cycle). Our findings highlight an effective way to developing sustainable cathode materials without compromising on the initial specific capacity for SIBs.