Metal Glycerolate‐Based Synthesis and Structure–Property Relationships of LiNi _{1− x − y}

Lithium‐ion batteries are currently the dominant energy storage systems, with cathode materials playing a significant role in electrochemical performance, safety, and cost. Among these materials, layered LiNi _{1− x − y} Co _x Mn _y O ₂ (NCM)‐based cathodes stand out due to their competitive cost, compositional versatility, high capacity and energy density. Controlling the Ni/Co/Mn ratio is a key strategy for optimizing the balance between capacity, structural stability, and electrochemical performance. In this work, metal glycerolates synthesized via a solvothermal route were employed as hybrid organic–inorganic precursors to prepare NCM materials. The compositional variation, spanning from low‐ to high‐Ni content, enabled a direct correlation between Ni content, structural disorder, and electrochemical performance. Increasing the Ni content promoted Li ⁺ /Ni ²⁺ cation mixing and structural disorder, resulting in reduced discharge capacity of Ni‐rich NCM cathodes. In contrast, low‐Ni NCM compositions exhibited improved structural ordering and electrochemical behavior, with Mg ²⁺ doping effectively improving the stabilization of the LiNi _0.33 Co _0.33 Mn _0.33 O ₂ (NCM 333) structure and enhancing its rate capability and cycling stability. These findings provide important insights into the relationship between composition, structural ordering, and electrochemical behavior, while highlighting both the potential and current limitations of metal glycerolate‐based synthesis for NCM cathodes. Thus, metal glycerolates offer a basis for the rational design of cost‐effective and more sustainable energy storage materials.