Revealing the Calcium Assisted Partial Catalytic Graphitization of Lignin-Derived Hard Carbon Anode and Its Electrochemical Behaviors in Sodium Ion Batteries

Among the various contenders for next-generation sodium-ion battery anodes, hard carbons stand out for their notable reversible capacity, extended cycle life, and cost-effectiveness. Their economic advantage can be further enhanced by using inexpensive precursors, such as biomass waste. Lignin, one of the most abundant natural biopolymers on Earth, which can be readily obtained from wood, possesses a three-dimensional amorphous polymeric structure, making it a suitable candidate for producing carbonaceous materials through appropriate carbonization processes for energy storage applications. In this work, we synthesized hard carbon using lignin containing CaSO4 to facilitate partial catalytic graphitization to improve the microstructural features, such as interlayer spacing, degree of disorder, and surface defects. Partial catalytic graphitization enables hard carbon to develop an ordered structure compared with hard carbon carbonized without CaSO4 as analyzed by X-ray diffraction, Raman spectroscopy, scanning/transmission electron microscopy, and X-ray photoelectron spectroscopy. The CaSO4-aided partially catalytic graphitized hard carbon (CCG-HC) exhibited improved electrochemical performance, showing a larger portion of the low-voltage plateau—an indicator typically associated with a highly ordered structure—compared to simply carbonized hard carbon (HC). Notably, CCG-HC delivered a reversible capacity of 237 mAh g−1, retained 95.6% of its capacity over 100 cycles at 50 mA g−1, and exhibited 127 mAh g−1 at 1.0 A g−1.