P1-2764Unveiling Superionic Lithium Transport and Defect Tolerance in LiNbOCl4 from First-Principles Molecular DynamicsSolid-State Battery Group, GREEN Halimah HarfahE-mail：：HARFAH.Halimah@nims.go.jpKey Words: LiNbOCl4, Solid electrolytes, All-solid-state batteries•All-solid-state batteries (ASSBs) demand electrolytes that are both highly conductive and mechanically resilient for safe, high-energy applications.•This study introduces defect-tolerant oxyhalide electrolytes that merge the stability of oxides with the fast-ion transport of halides for next-generation sustainable batteries⚫LiNbOCl₄shows superionic Li-ion conductivity with low Eₐ ≈ 0.24 eV⚫LiCl Schottky defects keep the structure soft but slightly raise the migration barrier by disturbing anion motion.⚫Overall, LiNbOCl₄remains a robust and defect-tolerant solid electrolyte.ConclusionStructural, Thermodynamic Properties, Mechanical and Thermal BehaviorLi-ion Dynamics and Microscopic Insights⚫Deepen understanding of structure–dynamics relationships governing Li-ion transport in oxyhalides.⚫Broaden simulations to related compounds and explore pathways to further improve conductivity.⚫Combine theoretical insights with experimental collaboration for practical solid-electrolyte design.Future Plan•Activation energy Eₐ = 0.236 eV (pristine), 0.241 eV (Schottky).•Room-temperature conductivity: 9.57 ×10⁻³ and 8.20 ×10⁻³ S cm⁻¹.•Slight conductivity drop despite larger bottleneck (1.9 Å vs 1.5 Å).•Dynamic gatingvia coherent anion rotation enables bottleneck breathing.•Schottky defects cause rotational incoherence → suppressed high-frequency O-phonon (~80 meV) → higher migration barrier.•Van HoveandBACFanalyses show weakened temporal correlation and transport cooperativity.Introduction•LiNbOCl₄ unites oxide-like stability with halide-level ionic conductivity (~10 mS cm⁻¹).•DFT-MD simulations reveal how LiCl Schottky defects influence Li-ion transport and lattice dynamics.•The study uncovers adynamic gating mechanismenabling superionic conduction and defect toleranceTheme underDiscussion•DFT-D3(BJ) vdW functional reproduces experiment with < 1.5 % error.•Both pristine (–2.101 eV atom⁻¹) and defected (–2.104 eV atom⁻¹) phases are metastable yet synthesizable (ΔEₕᵤₗₗ < 0.02 eV atom⁻¹).•Bulk modulus ≈ 16 GPa→ mechanical softness comparable to Li₃PS₄.•Thermal expansion αV= 1.03 ×10⁻⁴ K⁻¹ (pristine) and 8.4 ×10⁻⁵ K⁻¹ (defected) → good structural flexibility.𝐷𝐷=12𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑟𝑟2(𝑑𝑑)σ =𝑐𝑐𝑧𝑧𝑧𝑧2𝐷𝐷𝑘𝑘𝐵𝐵𝑇𝑇LiCl SchottkyPristineLiCl SchottkyPristine(a)(b)(a)(b)PristineLiCl SchottkyLi Nb O Cl
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