In-situ TEM on the coalescence of birnessite manganese dioxides nanosheets during lithiation process

• Evolution of MnO2 nanosheets during lithiation was in situ observed.
• MnO2 was reacted with Li to form Mn and LiO2.
• Nanosheets expanded and aggregated due to lithiation.

Nanostructure is believed to produce great benefits for anode materials in lithium ion batteries (LIBs) by enhancing lithium ion transfer, accommodating large volume change and increasing surface area. Whether the nanostructure (especially the porous nanostructure) could be well held during charging/discharging process is one of the most commonly concerned issues in LIBs research. The dynamic evolution of birnessite manganese dioxides nanosheets during lithiation process is investigated by in-situ transmission electron microscopy (TEM) for the first time. The TiO2@MnO2 core-shell nanowires are used as the anode and Li metal as the counter electrode inside the TEM. Interestingly, the lithiation process is confirmed as MnO2 and Li converting to Li2O and Mn. The original porous structure of the nanosheets is hard to preserve during lithiation process due to lithiation-induced contact flattening.

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