Ion Conducting Polymer Interfaces for Lithium Metal Anodes: Impact on the Electrodeposition Kinetics

Abstract Electrochemical cells that utilize metals (e.g., lithium, sodium, zinc) as anodes are under intense investigation as they are projected to replace the current lithium‐ion batteries to serve as a more energy‐dense option for commercial applications. In addition, metal electrodes provide opportunities for fundamental research of different phenomena, such as ion transport and electrochemical kinetics, in the complex environment of reactive metal‐electrodeposition. In this work, computationally and experimentally the competing effects related to transport and kinetics during the metal electrodeposition process are examined. Using Brownian dynamics simulations, it is shown that slower deposition kinetics results in a more compact and uniform Li morphology. This finding is experimentally implemented by designing ion‐containing polymeric coatings on the electrodes that simultaneously provide pathways for lithium‐ion transport, while impeding the charge transfer (Li + + e − → Li) at heterogeneous surfaces. It is further shown that these ionic polymer interfaces can significantly extend the cell‐lifetime of a lithium metal battery in both ether‐based and carbonate‐based electrolytes. Through theoretical and experimental investigations, it is found that a low kinetic to transport rate ratio is a major factor in influencing the Li plating morphology. The plating morphology can be further fine‐tuned by increasing ionic conductivity.