<p>Solid electrolytes (SEs) typically consist of a static framework of anions (FA) and a sublattice of mobile cations (M), with non-covalent dispersion interactions (<i>E</i><sub><i>d</i><i>i</i><i>s</i><i>p</i></sub>) playing a key role in structural stability. However, the impact of these interactions on M-ion migration—whether they assist or hinder it—remains unclear. In this study, we investigate the diffusion barriers of M-ions in SE frameworks, focusing on the M<sub>2</sub>B<sub>12</sub>H<sub>12</sub> family (M = Li, Na, K), and clarify the role of non-covalent interactions. Our computational analyses reveal that moving from Li to Na to K analogues in M<sub>2</sub>B<sub>12</sub>H<sub>12</sub> results in significant changes in many-body dispersion (MBD) interactions. The MBD interactions act as springs embedded within the M<sub>2</sub>B<sub>12</sub>H<sub>12</sub> framework, regulating the effective coordination number (ECN) of M-ions and shaping the potential energy landscape for their migration. A linear correlation is observed between ECN and <i>E</i><sub><i>d</i><i>i</i><i>s</i><i>p</i></sub>, consistent across different alkali ions. This correlation&#xa0;reveals a unified mechanism in which dispersion interactions regulate M-ion migration barrier and identifies a critical bottleneck for beyond-Li diffusion in M<sub>2</sub>B<sub>12</sub>H<sub>12</sub> SEs. Intriguingly, MBD interactions further influence the prefactor in the diffusivity equation, driving anomalous diffusion behavior in SEs.</p><p></p>

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Ion coordination and migration mechanisms in alkali metal complex borohydride-based solid electrolytes

  • Shweta Choudhary,
  • Swastika Banerjee

摘要

Solid electrolytes (SEs) typically consist of a static framework of anions (FA) and a sublattice of mobile cations (M), with non-covalent dispersion interactions (Edisp) playing a key role in structural stability. However, the impact of these interactions on M-ion migration—whether they assist or hinder it—remains unclear. In this study, we investigate the diffusion barriers of M-ions in SE frameworks, focusing on the M2B12H12 family (M = Li, Na, K), and clarify the role of non-covalent interactions. Our computational analyses reveal that moving from Li to Na to K analogues in M2B12H12 results in significant changes in many-body dispersion (MBD) interactions. The MBD interactions act as springs embedded within the M2B12H12 framework, regulating the effective coordination number (ECN) of M-ions and shaping the potential energy landscape for their migration. A linear correlation is observed between ECN and Edisp, consistent across different alkali ions. This correlation reveals a unified mechanism in which dispersion interactions regulate M-ion migration barrier and identifies a critical bottleneck for beyond-Li diffusion in M2B12H12 SEs. Intriguingly, MBD interactions further influence the prefactor in the diffusivity equation, driving anomalous diffusion behavior in SEs.