Molecule and Microstructure Modulations of Cyano-Containing Electrodes for High-Performance Fully Organic Batteries.

Cyano-containing electrodes usually promise high theoretical potentials while suffering from uncontrollable self-dissolution and sluggish reaction kinetics. Herein, to remedy their limitations, an unprecedented core-shell heterostructured electrode of carbon nanotubes encapsulated in poly(1,4-dicyanoperfluorobenzene sulfide) (CNT@PFDCB) is rationally crafted via molecule and microstructure modulations. Specifically, the linkage of sulfide bridges of PFDCB prevents the active cyano groups from dissolving, resulting in a robust structure. The fluorinations modulate the electronic configurations in frontier orbitals, allowing higher electrical conductivity and elevated output voltage. Combined with the core-shell architecture to unlock the sluggish diffusion kinetics for both electrons and guest ions, the CNT@PFDCB exhibits an impressive capacity (203.5 mAh g-1), remarkable rate ability (127.6 mAh g-1 at 3.0 A g-1), and exceptional cycling stability (retaining 81.1% capacity after 3000 cycles at 1.0 A g-1). Additionally, the Li-storage mechanisms regarding PFDCB are thoroughly revealed by in-situ attenuated total reflection infrared spectroscopy, in-situ Raman spectroscopy, and theoretical simulations, which involve the coordination interaction between Li ions and cyano groups and the electron delocalization along the conjugated skeleton. More importantly, a practical fully organic cell based on the CNT@PFDCB is well-validated that demonstrates a tremendous potential of cyanopolymer as the cathode to replace its inorganic counterparts.