A Practical and Sustainable Ni/Co-Free High-Energy Electrode Material: Nanostructured LiMnO₂

Ni/Co-free high-energy positive electrode materials are of great importance to ensure the sustainability of Li-ion battery production and its supply chain in addition to minimizing environmental impact. Here, nanostructured LiMnO₂ with both orthorhombic/monoclinic layered domains is synthesized, and its lithium storage properties and mechanism are examined. High-energy mechanical milling is used to convert the metastable and nanosized LiMnO₂ adopting the cation-disordered rocksalt structure to an optimal domain-segregated layered LiMnO₂. This positive electrode produces an energy density of 820 W h kg^-1, achieved by harnessing a large reversible capacity with relatively small voltage hysteresis on electrochemical cycles. Moreover, voltage decay for cycling, as observed for Li-excess Mn-based electrode materials, is effectively mitigated. Furthermore, by determining the structure-property relationships of different LiMnO₂ polymorphs, LiMnO₂ with similar domain structure and surface area is successfully synthesized with an alternative and simpler method, without the metastable precursor and high-energy mechanical milling. The cyclability of domain-containing LiMnO₂ is also improved with the use of a highly concentrated electrolyte coupled with a lithium phosphate coating due to the suppression of Mn dissolution. These findings maximize the possibility of the development of high-energy, low-cost, and practical rechargeable batteries made from sustainable and abundant Mn sources without Ni/Co.