Binder‐Induced Ultrathin SEI for Defect‐Passivated Hard Carbon Enables Highly Reversible Sodium‐Ion Storage

Hard carbon is one of the most promosing anodes for resource‐rich sodium‐ion batteries. However, an unsatisfactory solid–electrolyte‐interphase formed by irreversible electrolyte consumption caused by defects or oxygen‐containing functional groups of hard carbon impedes its further application. Herein, a novel composite binder that is composed of polar polymer chondroitin sulfate A (sodium salt) and polyethylene oxide by hydrogen bonding demonstrates defect passivation capability. This composite binder can reduce the exposure of defects by forming hydrogen bonds with oxygen functional groups on the hard carbon surface and inhibit the decomposition of electrolyte confirmed by in situ differential electrochemical mass spectrometry. In situ Raman and theoretical calculations reveal that multiple polar functional groups in chondroitin sulfate A (sodium salt) can accelerate the transport of Na + by adsorbing and facilitate the decomposition of PF 6 − to form NaF. Additionally, polyethylene oxide in the composite binder can increase viscosity and accelerate the transport of Na + . As a result, an ultra‐thin (9 nm, cyro‐TEM) and NaF‐rich solid–electrolyte interphase is obtained, thereby the hard carbon anode achieves improved initial Coulombic efficiency (84%) and high‐capacity retention of 94% after 150 cycles in a NaPF 6 /ethylene carbonate/dimethyl carbonate electrolyte.