Atomistic Insights into Solid-State Phase Transition Mechanisms of P2-Type Layered Mn Oxides for High-Energy Na-Ion Battery Cathodes DOI Creative Commons
Aniello Langella, Arianna Massaro, Ana B. Muñoz‐García

et al.

ACS Energy Letters, Journal Year: 2025, Volume and Issue: 10(3), P. 1089 - 1098

Published: Feb. 6, 2025

Mn-based layered oxides hold great promise as high-energy, cost-effective cathodes for sodium-ion batteries (NIBs), but repetitive Na+ cycling induces harmful phase transitions. Understanding these mechanisms is essential designing better performing NIB cathodes. Applying density functional theory (DFT) and variable cell-nudged elastic band (VC-NEB) calculations, we provide atomistic insights into transformation pathways energy barriers in P2-Na x MnO2 material its Ni-doped variant. We reveal the key P2-to-OP4/O2 P2-to-P2' transitions that occur across various sodiation levels, involving substantial rearrangements around transition metal sites, with tetrahedral states accountable barriers. Our analysis of bond length angle distortions highlights shear deformations are pivotal triggering P-to-O gliding at low sodium levels. Based on insights, our structural distortion metrics offer a straightforward computationally efficient descriptor to evaluate integrity oxides, enabling design NIBs improved stability extended lifespan.

Language: Английский

Atomistic Insights into Solid-State Phase Transition Mechanisms of P2-Type Layered Mn Oxides for High-Energy Na-Ion Battery Cathodes DOI Creative Commons
Aniello Langella, Arianna Massaro, Ana B. Muñoz‐García

et al.

ACS Energy Letters, Journal Year: 2025, Volume and Issue: 10(3), P. 1089 - 1098

Published: Feb. 6, 2025

Mn-based layered oxides hold great promise as high-energy, cost-effective cathodes for sodium-ion batteries (NIBs), but repetitive Na+ cycling induces harmful phase transitions. Understanding these mechanisms is essential designing better performing NIB cathodes. Applying density functional theory (DFT) and variable cell-nudged elastic band (VC-NEB) calculations, we provide atomistic insights into transformation pathways energy barriers in P2-Na x MnO2 material its Ni-doped variant. We reveal the key P2-to-OP4/O2 P2-to-P2' transitions that occur across various sodiation levels, involving substantial rearrangements around transition metal sites, with tetrahedral states accountable barriers. Our analysis of bond length angle distortions highlights shear deformations are pivotal triggering P-to-O gliding at low sodium levels. Based on insights, our structural distortion metrics offer a straightforward computationally efficient descriptor to evaluate integrity oxides, enabling design NIBs improved stability extended lifespan.

Language: Английский

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