Unveiling the Structural Evolution of Ag1.2Mn8O16 under Coulombically Controlled (De)Lithiation

MnO2 materials are considered promising cathode materials for rechargeable lithium, sodium, and magnesium batteries due to their earth abundance and environmental friendliness. One polymorph of MnO2, α-MnO2, has 2 × 2 tunnels (4.6 A × 4.6 A) in its structural framework, which provide facile diffusion pathways for guest ions. In this work, a silver-ion-containing α-MnO2 (Ag1.2Mn8O16) is examined as a candidate cathode material for Li based batteries. Electrochemical stability of Ag1.2Mn8O16 is investigated through Coulombically controlled reduction under 2 or 4 molar electron equivalents (e.e.). Terminal discharge voltage remains almost constant under 2 e.e. of cycling, whereas it continuously decreases under repetitive reduction by 4 e.e. Thus, detailed structural analyses were utilized to investigate the structural evolution upon lithiation. Significant increases in lattice a (17.7%) and atomic distances (∼4.8%) are observed when x in LixAg1.2Mn8O16 is >4. Ag metal forms at this level of lithiation conco...