One stone two birds: Pitch assisted microcrystalline regulation and defect engineering in coal-based carbon anodes for sodium-ion batteries

Coal-based carbons with abundant resources and low cost are regarded as promising anode materials for sodium‐ion batteries (SIBs). However, their ordered carbon microstructure and abundant surface defects often result in low Na-storage capacity and poor initial coulombic efficiency (ICE). Herein, we propose a simple vapor deposition strategy to synthesize coal-based carbons coated with pitch-based soft carbon layer (PCLC) for potential use as anodes for SIBs. The deposition of pitch-based volatile species allows for an efficient cross-linking reaction between hydroxyl‑containing volatile species and oxygen-rich functional groups of coal, thus generating a disordered inner-phase microcrystalline structure with dominant pseudo-graphitic phase in coal-derived carbon. Meanwhile, the exterior soft carbon coating layer substantially reduces surface defects and increases the electrical conductivity of coal-based carbon. Unlike the pristine lignite coal pyrolytic carbon which exhibited a Na-storage capacity of 290.2 mAh g−1 and ICE of 59.9%, the optimal PCLC (PCLC-1) delivered a higher reversible capacity of 312.2 mAh g−1 and a much-improved ICE of 85.3%. In addition, the PCLC-1 electrode also demonstrated excellent cycle stability with 93.4% retention after 1,000 cycles. When coupled with O3-NaNi1/3Fe1/3Mn1/3O2 cathode, PCLC-1 as an anode in a full cell configuration achieved a high energy density of 220.9 Wh kg−1 with excellent cycling and rate performance. The proposed work offers a unique insight into modulating the microcrystalline structure and surface chemistry of high-performance coal-based carbon anode materials for commercial SIBs.