Boosting Interfacial Ion Transfer in Potassium-Ion Batteries via Synergy Between Nanostructured Bi@NC Bulk Anode and Electrolyte

Abstract

Using high-capacity alloy-type anodes can greatly advance potassium-ion batteries (PIBs). However, the primary limits are unstable solid electrolyte interphase (SEI) and tough interfacial ion transfer associated with large-size K⁺ during electrochemical (de)alloy reactions. Here, we achieve excellent energy storage performance of PIBs via the synergy between a nanostructured Bi@N-doped carbon (Bi@NC) bulk anode and a KPF₆-dimethoxyethane (DME) electrolyte. The Bi@NC material with a high tap density of 3.81 g cm^-3 is prepared by simply pyrolyzing a commercial Bi salt yet affords a favorable nano/microstructure consisting of Bi nanograins confined in 3D ultrathin N-doped carbon shells, facilitating electron/ion transport and structural integrity. Detailed impedance spectroscopy investigation unveils that K⁺ transport through SEI at the Bi@NC anode, rather than the desolvation of K⁺, dominates the interfacial K⁺ transfer. More importantly, spectroscopic and microscopic characterizations provide clear evidence that the interplay between Bi@NC anode and optimized KPF₆-DME electrolyte can produce a unique SEI layer containing Bi³⁺-solvent complex that enables the activation energy of interfacial K⁺ transfer as low as 25.9 kJ mol^-1, thereby ultrafast charge transfer at Bi@NC. Consequently, the Bi@NC anode in half cells achieves exceptional rate capability (206 mAh g^-1 or 784 mAh cm^-3 at 120C) accompanied by high specific capacity (331 mAh g^-1 or 1261 mAh cm^-3) and long cycle life (running 1400 cycles at 15C with a tiny capacity fading rate of 0.013% per cycle). Moreover, the Bi@NC anode and KPF₆-DME electrolyte are also compatible with a potassium Prussian blue cathode and assembled full PIBs achieve stable cyclability (87.3% capacity retention after 100 cycles at 2.5C) and excellent rate performance (65.1% capacity retention upon increasing rates from 1 to 20C).