Journal Article

Mitigating the Rock-Salt Phase Transformation in Disordered LNMO Through Synergetic Solid-State AlF3/LiF Modifications

Horta, Sharona, Lu, Xuan, Escudero, Carlos, Black, Ashley P, Biendicho, Jordi Jacas, Cabot, Andreu, Martínez, Elías, Chang, Xingqi, Ibáñez, Maria, Llorca, Jordi

2025

Overview

High-voltage disordered spinel LiNi0.5Mn1.5O4 is a promising cathode material for high power density in lithium-ion batteries. However, it suffers from poor cycle life associated with the rock-salt phase transformation. This study presents a straightforward synthesis approach to enhance the electrochemical performance of LiNi0.5Mn1.5O4 through a synergistic solid-state modification with LiF and AlF3. This dual modification promotes rapid Li⁺ diffusion, enables near-complete delithiation/lithiation, approaching the theoretical capacity of disordered LiNi0.5Mn1.5O4, and, more importantly, effectively mitigates the formation of the rock-salt phase, thereby enhancing structural stability, as confirmed by operando X-ray absorption spectroscopy (XAS) and synchrotron X-ray diffraction (SXRD). As a result, the optimized LiNi0.5Mn1.5O4 (10 mg AlF3 + 30 mg LiF) delivers high reversible capacities of 142.1, 139.1, 129.2, 121.6, 110.3, 93.5, and 76.1 mAh∙g-1 at 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, 4.0C, and 5.0C, respectively. Full cells using graphite as the anode and a high-loading cathode exhibit excellent cycling performance. They retain 80% of their capacity after 200 cycles at 0.5C within a voltage window of 3.5-4.9 V with cathode loading of 11 mg∙cm-2. The findings of this study will significantly advance high-power LiNi0.5Mn1.5O4 materials, offering improved battery life and thereby enhancing their potential for practical applications.High-voltage disordered spinel LiNi0.5Mn1.5O4 is a promising cathode material for high power density in lithium-ion batteries. However, it suffers from poor cycle life associated with the rock-salt phase transformation. This study presents a straightforward synthesis approach to enhance the electrochemical performance of LiNi0.5Mn1.5O4 through a synergistic solid-state modification with LiF and AlF3. This dual modification promotes rapid Li⁺ diffusion, enables near-complete delithiation/lithiation, approaching the theoretical capacity of disordered LiNi0.5Mn1.5O4, and, more importantly, effectively mitigates the formation of the rock-salt phase, thereby enhancing structural stability, as confirmed by operando X-ray absorption spectroscopy (XAS) and synchrotron X-ray diffraction (SXRD). As a result, the optimized LiNi0.5Mn1.5O4 (10 mg AlF3 + 30 mg LiF) delivers high reversible capacities of 142.1, 139.1, 129.2, 121.6, 110.3, 93.5, and 76.1 mAh∙g-1 at 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, 4.0C, and 5.0C, respectively. Full cells using graphite as the anode and a high-loading cathode exhibit excellent cycling performance. They retain 80% of their capacity after 200 cycles at 0.5C within a voltage window of 3.5-4.9 V with cathode loading of 11 mg∙cm-2. The findings of this study will significantly advance high-power LiNi0.5Mn1.5O4 materials, offering improved battery life and thereby enhancing their potential for practical applications.