Superior Sodium Storage Properties in the Anode Material NiCr₂S₄ for Sodium‐Ion Batteries: An X‐ray Diffraction, Pair Distribution Function, and X‐ray Absorption Study Reveals a Conversion Mechanism via Nickel Extrusion

Abstract The pseudo‐layered sulfide NiCr₂S₄ exhibits outstanding electrochemical performance as anode material in sodium‐ion batteries (SIBs). The Na storage mechanism is investigated by synchrotron‐based X‐ray scattering and absorption techniques as well as by electrochemical measurements. A very high reversible capacity in the 500th cycle of 489 mAh g⁻¹ is observed at 2.0 A g⁻¹ in the potential window 3.0–0.1 V. Full discharge includes irreversible generation of Ni⁰ and Cr⁰ nanoparticles embedded in nanocrystalline Na₂S yielding shortened diffusion lengths and predominantly surface‐controlled charge storage. During charge, Ni⁰ and Cr⁰ are oxidized, Na₂S is consumed, and amorphous Ni and Cr sulfides are formed. Limiting the potential window to 3.0–0.3 V an unusual nickel extrusion sodium insertion mechanism occurs: Ni²⁺ is reduced to nanosized Ni⁰ domains, expelled from the host lattice, and is replaced by Na⁺ cations to form O3‐type like NaCrS₂. Surprisingly, the discharge and charge processes comprise Na⁺ shuttling between highly crystalline NiCr₂S₄ and NaCrS₂ enabling a superior long‐term stability for 3000 cycles. The results not only provide valuable insights for the electrochemistry of conversion materials but also extend the scope of layered electrode materials considering the reversible nickel extrusion sodium insertion reaction as new concept for SIBs.