In Situ Plasma Polymerization of Self-Stabilized Polythiophene Enables Dendrite-Free Lithium Metal Anodes with Ultra-Long Cycle Life.

Abstract

Constructing a flexible and chemically stable multifunctional layer for the lithium (Li) metal anodes is a highly effective approach to improve the uneven deposition of Li+ and suppress the dendrite growth. Herein, an organic protecting layer of polythiophene is in situ polymerized on the Li metal via plasma polymerization. Compared with the chemically polymerized thiophene (C-PTh), the plasma polymerized thiophene layer (P-PTh), with a higher Young's modulus of 8.1GPa, shows strong structural stability due to the chemical binding of the polythiophene and Li. Moreover, the nucleophilic C─S bond of polythiophene facilitates the decomposition of Li salts in the electrolytes, promoting the formation of LiF-rich solid electrolyte interface (SEI) layers. The synergetic effect of the rigid LiF as well as the flexible PTh-Li can effectively regulate the uniform Li deposition and suppress the growth of Li dendrites during the repeated stripping-plating, enabling the Li anodes with long-cycling lifespan over 8000h (1mAcm-2 , 1 mAhcm-2) and 2500h (10mAcm-2 , 10 mAhcm-2 ). Since the plasma polymerization is facile (5-20min) and environmentally friendly (solvent-free), this work offers a novel and promising strategy for the construction of the forthcoming generation of high-energy-density batteries.