Three-Dimensional Monolithically Self-Grown Metal Oxide Highly Dense Nanonetworks as Free-Standing High-Capacity Anodes for Lithium-Ion Batteries

Transition metal oxides (TMOs) have been widely studied as potential next-generation anode materials, owing to their high theoretical gravimetric capacity. However, to date, these anodes syntheses are plagued with time-consuming preparation processes, two-dimensional electrode fabrication, binder requirements, and short operational cycling lives. Here, we present a scalable single-step reagentless process for the synthesis of highly dense Mn₃O₄-based nanonetwork anodes based on a simple thermal treatment transformation of low-grade steel substrates. The monolithic solid-state chemical self-transformation of the steel substrate results in a highly dense forest of Mn₃O₄ nanowires, which transforms the electrochemically inactive steel substrate into an electrochemically highly active anode. The proposed method, beyond greatly improving the current TMO performance, surpasses state-of-the-art commercial silicon anodes in terms of capacity and stability. The three-dimensional self-standing anode exhibits remarkably high capacities (>1500 mA h/g), a stable cycle life (>650 cycles), high Coulombic efficiencies (>99.5%), fast rate performance (>1.5 C), and high areal capacities (>2.5 mA h/cm²). This novel experimental paradigm acts as a milestone for next-generation anode materials in lithium-ion batteries, and pioneers a universal method to transform different kinds of widely available, low-cost, steel substrates into electrochemically active, free-standing anodes and allows for the massive reduction of anode production complexity and costs.