A macrocyclic amine-based electrolyte for lithium–sulfur batteries: Li ion encapsulation regulates electrode performance

Abstract

The widespread use of lithium–sulfur (Li–S) batteries is hindered by slow cathode kinetics, the shuttle effect, and dendrite growth on the anode. We show that these challenges can be overcome by replacing a linear ether (i.e., 1,2-dimethoxyethane) in commonly used electrolytes with a macrocyclic amine, 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (TMTAC). Theoretical studies and experimental data indicate that the cavity of TMTAC matches a Li ion to form a robust solvation structure. Such a solvation structure not only leads to 3D deposition of Li2S on the cathode, which is responsible to the reduced overpotentials of Li2S nucleation and decomposition, but also suppresses Li dendrite growth on the anode. Moreover, the shuttle effect of polysulfides is effectively suppressed as the quantity of free TMTAC in the TMTAC-based electrolyte is substantially reduced. As a result, coin-type cells prepared with TMTAC-based electrolytes exhibit outstanding performance metrics for all key device parameters. Furthermore, pouch-type cells can be prepared with high sulfur loadings (e.g., 3.43 mg cm−2) and a low electrolyte to sulfur ratio (e.g., 6.16 μl mg−1) while maintaining a high areal specific capacity (3.38 mA h cm−2). This work demonstrates that the effective solvation of critical ions in energy storage devices is paramount to achieving peak performance.