Unveiling the Structural Evolution of Ag_1.2Mn₈O₁₆ 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 Å × 4.6 Å) in its structural framework, which provide facile diffusion pathways for guest ions. In this work, a silver-ion-containing α-MnO₂ (Ag_1.2Mn₈O₁₆) is examined as a candidate cathode material for Li based batteries. Electrochemical stability of Ag_1.2Mn₈O₁₆ 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 Li_xAg_1.2Mn₈O₁₆ is >4. Ag metal forms at this level of lithiation concomitant with a large structural distortion to the Mn-O framework. In contrast, lattice a only expands by 2.2% and Mn-O/Mn-Mn distances show minor changes (∼1.4%) at x < 2. The structural deformation (tunnel breakage) at x > 4 inhibits the recovery of the original structure, leading to poor cycle stability at high lithiation levels. This report establishes the correlation among local structure changes, amorphization processes, formation of Ag⁰, and long-term cycle stability for this silver-containing α-MnO₂ type material at both low and high lithiation levels.