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Md Abdullah Al Muhit

Publications and source records attributed to Md Abdullah Al Muhit.

2 recordsLinked to original sources

Battery Material Comparisons Should Refocus on Diffusivity with Best Practices

The continuous demand for improved batteries motivates the discovery and advancement of materials with improved transport. Ionic diffusivity is the relevant material property where its measurement depends on accurate assessment of the active material length-scale, generally from the mass-specific surface area. In this perspective, we argue for renewed focus on diffusivity comparisons. A procedural review of 303 recent open-access publications about battery material development revealed two aspects: (1) 49% of publications support structure-property transport claims using diffusivity values and (2) of those reporting diffusivity values, 15% clearly stated that the length scale was measured after grinding-alone or stated that grinding was not used at all. Diffusivity assessment rationally requires length scale measurement after grinding (grind-measure), rather than the reverse. A range of measurement methods are compared, including SEM, BET, and SAXS as well as the resulting apparent diffusivities. Common errors and pitfalls of each of these approaches are described. As an example, datasets are presented for TiNb2O7 (TNO1) and Ti2Nb10O29 (TNO2) made from sol-gel (SOL) and solid state (SS) techniques using rigorous quantitative measurements to separately compare material diffusivities and galvanostatic performance. Here, the SOL samples had shorter length-scales and lower diffusion coefficients. Galvanostatic cell measurements, however, revealed that the shorter length-scales more than compensated for the lower diffusivities with better overall high-rate capacity retention. This example shows how cell level metrics often differ from underlying diffusivities. We argue that materials development needs renewed focus on property measurements like diffusivity where best-practices are important to derive meaningful insights towards structure-property relationships.

cond-mat.mtrl-sci↗

Combined Experimental and Computational Analysis of Lithium Diffusion in Isostructural Pair VNb9O25 and VTa9O25

Wadsley-Roth crystal structures are an attractive class of materials for batteries because lithium diffusion is facilitated by the ReO3-like block structure with electron transport enabled by edge-sharing along shear planes. However, clear structure-property relationships remain limited, making it challenging to develop improved materials. Here, the first lithiation of VTa9O25 is reported, enabling a direct isostructural comparison with the better-known VNb9O25. These materials have similar unit cell volumes and atomic radii yet exhibit different voltage windows, C-rate dependent capacities, and transport metrics. Time-dependent overpotential analysis reveals ionic diffusion as the primary bottleneck to high rate-performance in both cases, however, the lithium diffusivity for VNb9O25 was an order of magnitude faster than that for VTa9O25. These experimental trends aligned well with density functional theory calculations combined with molecular dynamics that show a factor of six faster diffusion in VNb9O25. Nudged elastic band calculations of the probable hopping pathways indicate that VNb9O25 consistently exhibits a lower activation barrier for lithium diffusion. Bader charge analysis reveals a larger net charge on Li in VNb9O25 due to the higher electronegativity of Nb which stabilizes the transition state and lowers the barrier. This stabilization arises from the stronger Coulombic interaction between Li and its coordinated O-environment. These materials behave similarly upon lithiation wherein the lattice vectors (corresponding to the block plane) increase until about 50% lithiation and then decrease. However, the electronic structure differs, indicating that VNb9O25 undergoes a insulator to metal transition at a lower state of charge compared with VTa9O25. Overall, this work establishes the role of the cation (Nb or Ta) on the electronic and transport properties during lithiation.

cond-mat.mtrl-sci↗