Functional Composite Dual-Phase In Situ Self-Reconstruction Design for High-Energy-Density Li-Rich Cathodes

The unique anionic redox mechanism provides, high-capacity, irreversible oxygen release and voltage/capacity degradation to Li-rich cathode materials (LRO, Li1.2Mn0.54Co0.13Ni0.13O2). In this study, an integrated stabilized carbon-rock salt/spinel composite heterostructured layers (C@spinel/MO) is constructed by in situ self-reconstruction, and the generation mechanism of the in situ reconstructed surface is elucidated. The formation of atomic-level connections between the surface-protected phase and bulk-layered phase contributes to electrochemical performance. The best-performing sample shows a high increase (63%) of capacity retention compared to that of the pristine sample after 100 cycles at 1C, with an 86.7% reduction in surface oxygen release shown by differential electrochemical mass spectrometry. Soft X-ray results show that Co3+ and Mn4+ are mainly reduce in the carbothermal reduction reaction and participate in the formation of the spinel/MO rock-salt phase. The results of oxygen release characterized by Differential electrochemical mass spectrometry (DEMS) strongly prove the effectiveness of surface reconstruction. In this work, an integrated carbon-spinel/rock salt functional composite structure (C@spinel/MO) is generated by a simple carbothermal reduction process inducing in situ self-reconstruction on the lithium-rich cathode (LRO) surface. This unique multi-layer composite structure effectively enhances the structural stability of LRO, inhibits the precipitation of oxygen, and enhances the cycle stability of LRO.image