Synergetic Electronic Spin Modulation and Asymmetric Orbital Hybridization at CoSe2/Fe3Se4 Interface Inducing Robust SEI for Enhanced Sodium Ion Storage

Abstract

Transition metal selenides (TMSes) are recognized as promising anode materials for sodium-ion batteries (SIBs) owing to their ideal capacity and low cost, but their practical application suffers from crucial issues of inferior cycling stability and sluggish reaction kinetics. Herein, we design a magnetic CoSe₂/Fe₃Se₄ (CFSE) heterostructure to simultaneously regulate orbitals and spin features, aiming to systematically reveal their synergistic effect on sodium-ion storage. The orbital spin splitting of CFSE heterostructure drives the Co²⁺ spin state transition from low to high, which improves the adsorption energy and lowers the diffusion energy barrier of sodium ions. Meanwhile, Co−Se−Fe asymmetric orbital hybridization promotes a charge transfer pathway at the interface and ensures the directional migration of ions, thereby inhibiting irreversible structural variations, and tailoring an ultrathin and robust SEI film during battery operation. As a result, the as-prepared CFSE electrodes achieve a high reversible capacity of 395.8 mAh g⁻¹ at 2.0 A g⁻¹ over 1200 cycles and deliver an excellent rate stability of 364.4 mAh g⁻¹ at 10.0 A g⁻¹. This work provides an in-depth understanding of the spin-orbit modulation mechanism and inspiration for developing advanced conversion-type anodes.