Effect of Electrolyte Additives on the Cycling Performance of Li Metal and the Kinetic Mechanism Analysis

Lithium metal secondary batteries (LMBs) have extremely high energy densities and are considered the most promising energy storage and conversion systems in the future. We start with the formation and growth process of the Li metal deposited layer to reveal and clarify the reasons for the apparent comprehensive performance of the Li metal anode. Specifically, under the conditions of ether electrolyte and typical additives, the apparent Coulombic efficiency, micromorphology of the deposition layer, SEI information, and the kinetic mechanism of the Li plating/stripping process under a series of current density conditions are studied. The results show that in the electrolyte containing LiNO₃, Li metal exhibits excellent cycling performance, the Li plating layer is denser, and the particles in the plating layer are smooth and uniform. In the electrolyte containing FEC, the performance of Li metal is also improved to some extent. Then, we use microelectrode technology to obtain the kinetic parameters of elementary steps in the deposition process of Li metal and find that the stability of the kinetic parameters of mass transfer, interface, and surface steps and their good matching degree are conducive to the good cycling stability of the Li metal anode. This study reveals the kinetic relationship among the apparent comprehensive performances of Li metal, the electrolyte composition, and operating conditions, which provides a reliable dynamic reference for screening and optimizing electrolytes.