From Micropores to Ultra-micropores inside Hard Carbon: Toward Enhanced Capacity in Room-/Low-Temperature Sodium-Ion Storage

HIGHLIGHTS: Hard-carbon anode dominated with ultra-micropores (< 0.5 nm) was synthesized for sodium-ion batteries via a molten diffusion–carbonization method. The ultra-micropores dominated carbon anode displays an enhanced capacity, which originates from the extra sodium-ion storage sites of the designed ultra-micropores. The thick electrode (~ 19 mg cm(−2)) with a high areal capacity of 6.14 mAh cm(−2) displays an ultrahigh cycling stability and an outstanding low-temperature performance. ABSTRACT: Pore structure of hard carbon has a fundamental influence on the electrochemical properties in sodium-ion batteries (SIBs). Ultra-micropores (< 0.5 nm) of hard carbon can function as ionic sieves to reduce the diffusion of slovated Na(+) but allow the entrance of naked Na(+) into the pores, which can reduce the interficial contact between the electrolyte and the inner pores without sacrificing the fast diffusion kinetics. Herein, a molten diffusion–carbonization method is proposed to transform the micropores (> 1 nm) inside carbon into ultra-micropores (< 0.5 nm). Consequently, the designed carbon anode displays an enhanced capacity of 346 mAh g(−1) at 30 mA g(−1) with a high ICE value of ~ 80.6% and most of the capacity (~ 90%) is below 1 V. Moreover, the high-loading electrode (~ 19 mg cm(−2)) exhibits a good temperature endurance with a high areal capacity of 6.14 mAh cm(−2) at 25 °C and 5.32 mAh cm(−2) at − 20 °C. Based on the in situ X-ray diffraction and ex situ solid-state nuclear magnetic resonance results, the designed ultra-micropores provide the extra Na(+) storage sites, which mainly contributes to the enhanced capacity. This proposed strategy shows a good potential for the development of high-performance SIBs. [Image: see text] SUPPLEMENTARY INFORMATION: The online version of this article (10.1007/s40820-020-00587-y) contains supplementary material, which is available to authorized users.