Microcrystalline Nanofiber Electrode with Adaptive Intrinsic Structure and Microscopic Interface

Abstract A strategy of microcrystalline aggregation is proposed to fabricate energy storage electrode with outstanding capacity and stability. Carbon‐rich electrode (BDTG) functionalized with benzo[1,2‐b:4,5‐b′]dithiophene units and butadiyne segments are prepared. The linear conjugate chains pack as microcrystalline nanofibers on nanoscale, which further aggregates to form a porous interpenetrating network. The microcrystalline aggregation feature of BDTG exhibit stable structure during long cycling test, revealing the following advantage in structure and property. The stretchable butadiyne linker facilitates reversible adsorption and desorption of Li with the aid of adjacent sulfur heteroatom. The alkyne‐alkene transition exhibits intrinsic structural stability of microcrystalline region in BDTG electrodes. Meanwhile, alkynyl groups and sulfur heteroatoms on the surface of BDTG nanofibers participate in the formation of microscopic interface, providing a stable interfacial contact between BDTG electrodes and adjacent electrolyte. As a proof‐of‐concept, BDTG‐based electrode shows high capacity (1430 mAh g⁻¹ at 50 mA g⁻¹) and excellent cycle performance (8000 cycles under 5 A g⁻¹) in half‐cell of lithium‐ion batteries, and a reversible capacity of 120 mAh g⁻¹ is obtained under the current density of 2 C in full‐cell. This work shows microcrystalline aggregation is beneficial to realize adaptive intrinsic structure and interface contact during the charge‐discharge process.