Disordered Rock-Salt Structures in Next-Generation Lithium–Ion Batteries: An Outlook from Cation Disorder to Electrochemical Design

Abstract

The growing demand for high-energy-density, cost-effective, and cobalt-free cathode materials has led to the development of other promising materials, such as disordered rock-salt (DRX) structures, for next-generation LIBs. Apart from other conventional layered and spinel frameworks, DRX materials exhibit cation disorder and percolating lithium diffusion networks that, in turn, enable high lithium mobility and compositional flexibility. In this overview, the fundamental principles of DRX structures are examined, primarily focusing on how cation disorder, anionic redox activity, and short-range order (SRO) can be tailored to modify or enhance their electrochemical behavior. Here, we further discuss the main synthetic strategies and tuning methodology. Additionally, we highlight recent advances in understanding charge-compensation mechanisms, voltage hysteresis, and capacity retention through experimental and computational methods, including machine learning and Monte Carlo simulations. In addition, it discusses integrating DRX materials with advanced electrolytes and conductive frameworks to overcome kinetic limitations. Finally, we present emerging challenges and design perspectives, and, last, a SWOT analysis, all of which are needed to bridge the gap from the lab to commercial implementation, underlining the key role of DRX chemistry in shaping the future of sustainable, high-performance LIBs.