article · ACS Applied Materials & Interfaces
Lithium manganese oxide is an inexpensive, abundant, and environmentally benign cathode material for lithium-ion batteries, but widespread commercial adoption is limited by capacity loss, low energy density, and fast self-discharge. To address these limitations, a surface modification was developed using high-valence tungsten oxide. Evaluating various compositions identified a 0.5 weight percent tungsten oxide mixture as the most effective formulation. Electrochemical evaluation showed that this modified material achieved superior rate capability, retaining 51 percent of its initial capacity at a 20C discharge rate, compared to 34 percent for the unmodified cathode. Cyclic voltammetry confirmed significantly faster ion diffusion kinetics. Additionally, in situ Raman spectroscopy tracked underlying reaction mechanisms, while operando accelerating rate calorimetry visualised enhanced thermal stability during battery cycling.
Lithium manganese oxide offers substantial cost and environmental advantages for energy storage, but poor durability and heat generation hinder deployment. Demonstrating that a minor addition of tungsten oxide enhances charge rates, ion movement, and thermal resilience helps unlock a cleaner and more affordable cathode chemistry for power-intensive applications.
The findings are directed towards safe, high-voltage lithium-ion batteries for automotive applications, making electric vehicle and battery cell manufacturers the primary target users. The technology appears to be at an applied, laboratory-tested stage, with performance proven across rate capability and thermal stability tests, but it remains short of pilot-scale demonstration or full battery pack integration.
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Lithium manganese oxide (LiMn2O4) is a prevalent cathode material for lithium-ion batteries due to its low cost, abundant material sources, and ecofriendliness. However, its capacity fade, low energy density, and fast auto-discharge hinders its large-scale commercialization. Consequently, scientists are urged to achieve high-performance LMO cathodes through material doping and surface modification using a wide range of transition metals, polymers, and carbon precursors. Few studies have considered the potential of high-valence transition metal oxides in stabilizing the LMO’s cycling process and enhancing the overall battery performance. In this work, we report the synthesis of surface-modified lithium manganese oxide using high-valence tungsten oxide (WVIO3). Different WO3 wt % were investigated before settling for 0.5%WO3-LMO as the synergic surface-modified LMO. Using galvanostatic charge–discharge, 0.50 WO3-LMO exhibited better rate capability by retaining 51% of its initial capacity at a 20C rate, compared to 34% for the pristine LMO. Furthermore, cyclic voltammetry at different scan rates showed that 0.50 WO3-LMO possesses better ion diffusion than pristine LMO, around 10–11 and 10–13 cm2·s–1 respectively. Finally, using in situ Raman spectroscopy, reaction mechanisms during cycling were investigated, and operando accelerating rate calorimetry (ARC) visualized the surface-modified LMO’s cycling thermal stability and highlighted its potential use for safe high-voltage lithium-ion batteries in automotive applications.
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DOI: 10.1021/acsami.3c05708
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