Alkoxide hydrolysis in-situ constructing robust trimanganese tetraoxide/graphene composite for high-performance lithium storage

Herein we develop a novel and effective alkoxide hydrolysis approach to in-situ construct the trimanganese tetraoxide (Mn₃O₄)/graphene nanostructured composite as high-performance anode material for lithium-ion batteries (LIBs). This is the first report on the synthesis of Mn₃O₄/graphene composite via a facile hydrolysis of the manganese alkoxide (Mn-alkoxide)/graphene precursor. Before hydrolysis, two dimensional (2D) Mn-alkoxide nanoplates are closely adhered to 2D graphene nanosheets via Mn-O chemical bonding. After hydrolysis, the Mn-alkoxide in-situ converts to Mn₃O₄, while the Mn-O bond is preserved. This leads to a robust Mn₃O₄/graphene hybrid architecture with 15 nm Mn₃O₄ nanocrystals homogeneously anchoring on graphene nanosheets. This not only prevents the Mn₃O₄ nanocrystals agglomeration but also inversely mitigates the graphene nanosheets restacking. Moreover, the flexible and conductive graphene nanosheets can accommodate the volume change. This maintains the structural and electrical integrity of the Mn₃O₄/graphene electrode during the cycling process. As a result, the Mn₃O₄/graphene composite displays superior lithium storage performance with high reversible capacity (741 mAh g⁻¹ at 100 mA g⁻¹), excellent rate capability (403 mAh g⁻¹ at 1000 mA g⁻¹) and long cycle life (527 mAg g⁻¹ after 300 cycles at 500 mA g⁻¹). The electrochemical performance highlights the importance of rational design nanocrystals anchoring on graphene nanosheets for high-performance LIBs application.