Boosting the sodium storage behaviors of carbon materials in ether-based electrolyte through the artificial manipulation of microstructure

Highlights: • The porosity and microstructure of carbon are tailored by a NH₃ thermal etching route. • A stable reversible capacity of 352 mAh g^-1 at 50 mA g^-1 and a high rate capability of 101 mAh g^-1 at 16 A g^-1 are achieved. • The solvent co-intercalation, pseudocapacitive behaviors, and robust SEI formation both contribute to a superior sodium storage in ether-based electrolyte. -- Abstract: The porous carbon blacks rationally designed by a facile yet efficient NH₃ thermal etching route have been investigated as anode materials in an ether-based electrolyte for sodium-ion batteries. The as-synthesized CBN35 carbon black with a 35% weight loss after NH₃ thermal etching exhibited a large specific charge capacity of 352 mAh g⁻¹ at 50 mA g⁻¹ and a superior rate capability of 101 mAh g⁻¹ at 16000 mA g⁻¹, due to its highest microporosity, an appropriate surface area, a desirable microstructure, and a promising hybrid intercalation mechanism. Impressively, even cycled at 1600 mA g⁻¹ over 3200 cycles, an outstanding reversible capacity of 103 mAh g⁻¹ with a negligible 0.0162% capacity loss per cycle can still be achieved. Based on the multimodal characterizations including the structural probes of phase evolution for carbon materials, the electrochemical techniques, and the surface-sensitive XAS measurements, the exceptional electrochemical properties should stem from several merits of modified carbon black system. While the particular microporous structure provides relatively more accessible sodium storage sites, a novel hybrid intercalation mechanism in ether-based electrolyte would incorporate the sodium ion insertion into the disordered structure with the solvated sodium ion species co-intercalation into the graphitic phase. In addition to the diffusion-controlled redox reactions, the noticeable surface-induced pseudocapacitive reactions also significantly contribute to the charge storage upon sodiation and guarantee the rapid migrations of sodium ions/solvated compounds. This system further features a controlled emergence of a robust but thin solid electrolyte interphase layer, which could suppress the side reactions of active electrode with reactive electrolyte, maintain the fragile porous structure upon cycling, and facilitate the migrations of sodium ions and solvated sodium ion compounds.