ABSTRACT
Modifying the surfaces of zinc and other metallic substrates is considered an effective strategy to enhance the reversibility of the zinc deposition and stripping processes. While a variety of surface modification strategies have been explored, their ability to be practically implemented is not always trivial due to the associated high costs and complexity of the proposed techniques. In this study, we showcase a straightforward method for preparing ultrathin polyelectrolyte coatings using polydiallyldimethylammonium chloride (PDDA) and polyethylenimine (PEI). The coatings, characterized by their electrostatic charge and hydrophobicity, suppress side reactions and even out the electrodeposition process across the substrate surface. The PDDA-coated anodes demonstrate significantly reduced voltage hysteresis, uniform zinc morphology, improved self-discharge rates, and an impressive Coulombic efficiency exceeding 99% over prolonged cycling. Our findings highlight the potential that such cost-effective and straightforward surface treatments could be widely applied in Zn metal-based batteries.
ABSTRACT
The design of electrolyte solutions that permit reversible and efficient Mg metal electrodeposition is one of the most important tasks in the development of rechargeable Mg batteries. Several types of electrolyte solutions for Mg metal anodes have been developed and explored over the last two decades. These investigations have contributed to a better understanding of the Mg deposition and stripping processes. However, the Coulombic efficiency (CE) for reversible electrodeposition reported for these various systems and their performance in comparison to one another remained unclear. We used rigorous electrochemical methods to accurately quantify the average CE of the major electrolyte solutions considered for secondary Mg metal batteries. We demonstrated how changes in the experiential protocols influence CE measurements, resulting in inconsistent reports. Even though exceptional efficiency has been reported for a variety of systems, we discovered that the only candidate that currently meets the 99% CE benchmark during a prolonged cycling procedure is the dichloro-complex, which is a first-generation Grignard-based electrolyte solution. Second- and third-generation Grignard-free and chloride-free solutions showed reasonable CE only when the deposition currents densities were lowered. This comprehensive and systematic investigation will help to create a more accurate treasure map for potential electrolyte solutions for rechargeable Mg metal anodes.
