Programming Closed Pores in Hard Carbon Anodes via Alcohol‐Regulated Interfacial Assembly for High‐Rate and Durable Sodium‐Ion Storage

ABSTRACT Closed pores are widely recognized as the primary structural domains responsible for the low‐voltage plateau capacity of hard carbon anodes for sodium‐ion batteries (SIBs). However, current strategies for constructing closed pores predominantly rely on post‐carbonization reconstruction, offering limited control over pore accessibility and interfacial chemistry. Here we demonstrate that closed pores can instead be programmed during the precursor assembly process via an alcohol‐regulated interfacial assembly strategy. By systematically modulating the alcohol/water solvent environment, hydrogen‐bond interactions, micelle swelling behavior, and pyrrole polymerization kinetics are cooperatively regulated, enabling programmable precursor confinement and the subsequent transformation of micelle‐pyrrole assemblies into closed‐pore‐rich hard carbons during carbonization. The optimized hard carbon exhibits abundant closed ultramicropores that not only facilitate the quasi‐metallic sodium cluster filling but also promote the formation of a thin inorganic‐rich solid electrolyte interphase (SEI) layer, thereby accelerating sodium‐storage kinetics. As a result, it delivers an outstanding rate capability of 119 mAh g −1 at 10 A g −1 and robust cycling stability over 6000 cycles at 5 A g −1 , as well as excellent low‐temperature performance at −20°C. This work establishes precursor organization programming as a general strategy for constructing closed pores in hard carbon materials toward fast‐charging and long‐life SIBs.