Tailoring Co‐Free LiNi_0.5Mn_1.5O₄ Material for High‐Voltage Lithium‐Ion Batteries: Particle Design & Grain Boundary Engineering

Abstract Cobalt‐free LiNi_0.5Mn_1.5O₄ (LNMO) is a promising cathode material for high‐energy and power‐density lithium‐ion batteries (LIBs). However, its commercial adoption is hindered by rapid capacity degradation due to the unstable LNMO/electrolyte interface caused by LNMO's high operating voltage. Structural degradation from Jahn–Teller distortion and metal‐ion dissolution also contributes to poor cycling stability. Additionally, producing industrial‐grade LNMO with high tap density, low surface area and reduced metal‐ion dissolution is challenging. This study addresses these challenges through a rational material design approach, synthesizing LNMO with large spherical secondary particles (>14.0 µm) and high tap density (>2.0 g cm⁻³). The primary particles (1.5–6.0 µm) exhibit a truncated‐octahedral shaped morphology that predominantly exposes (111) surface facets, with fewer (100) surfaces, stabilizing the LNMO/electrolyte interface, reducing metal dissolution, and enhancing lithium‐ion kinetics. Silicon infusion into grain boundaries further improves structural integrity by forming a silicon‐rich phase. The tailored LNMO demonstrates exceptional rate capability, cycling stability, and improved interfacial kinetics, significantly advancing the potential for cobalt‐free LNMO in high‐voltage LIBs. This work highlights the importance of tailored cathode material design for achieving the performance and stability required for emerging high‐voltage LIBs applications.