Carbon Layer Orientation and Closed-Pore Construction Achieving Ultra-Low Specific Surface Area Hard Carbon for High-Performance Na-ion Storage

Abstract

Addressing the critical trade-off between initial Coulombic efficiency (ICE) and reversible capacity in hard carbon anodes for Na-ion batteries (NIBs), we introduce a novel coupling strategy that combines carbon layer orientation reconstruction with closed-pore construction to produce hard carbon with an ultra-low specific surface area. We demonstrate that the nanographite domains within the hard carbon precursor undergo entropy-driven orientation reconstruction through the synergistic regulation of heteroatom doping and medium-temperature carbonization. This process not only increases interlayer spacing and promotes structural disorder but also enables the formation of dense, closed pores and ultramicropores at domain boundaries via confined atomic migration, while simultaneously encapsulating surface open pores within internal closed ones. Due to this unique pore architecture, our hard carbon exhibits an ultra-low specific surface area of 1.89 m2 g-1 with a markedly higher proportion of closed pores. As a result, our hard carbon achieves a remarkable reversible capacity of 342.3 mAh g-1 at 20 mA g-1, with an exceptional ICE of 90.4% and a dominant plateau capacity of 262.3 mAh g-1 (76.6%) for NIBs. We believe this coupling strategy provides a new paradigm for the structural engineering of high-ICE anode materials in advanced NIBs.