Nanoparticle-Based Electrodes with High Charge Transfer Efficiency through Ligand Exchange Layer-by-Layer Assembly

Organic-ligand-based solution processes of metal and transition metal oxide (TMO) nanoparticles (NPs) have been widely studied for the preparation of electrode materials with desired electrical and electrochemical properties for various energy devices. However, the ligands adsorbed on NPs have a significant effect on the intrinsic properties of materials, thus influencing the performance of bulk electrodes assembled by NPs for energy devices. To resolve these critical drawbacks, numerous approaches have focused on developing unique surface chemistry that can exchange bulky ligands with small ligands or remove bulky ligands from NPs after NP deposition. In particular, recent studies have reported that the ligand-exchange-induced layer-by-layer (LE-LbL) assembly of NPs enables controlled assembly of NPs with the desired interparticle distance, and interfaces, dramatically improving the electrical/electrochemical performance of electrodes. This emerging approach also demonstrates that efficient surface ligand engineering can exploit the unique electrochemical properties of individual NPs and maximize the electrochemical performance of the resultant NP-assembled electrodes through improved charge transfer efficiency. This report focuses on how LE-LbL assembly can be effectively applied to NP-based energy storage/conversion electrodes. First, the basic principles of the LE-LbL approach are introduced and then recent progress on NP-based energy electrodes prepared via the LE-LbL approach is reviewed.