Pierfrancesco Ombrini

arXiv2025

Crossover Dynamics of Non-Fickian Ionic Diffusion in Solids

Ionic diffusion in solids is central to energy storage, electronics, and catalysis, yet its chemical origins are difficult to resolve because conventional diffusion models struggle with effects of confinement, crystallographic disorder, lattice distortions, and coupling to electronic or phononic carriers. These challenges are especially pronounced in battery materials, where ionic and electronic motion occur together, complicating interpretation of electrochemical measurements. Here we use tracer exchange as a direct, non-electrochemical probe to reveal distinct ion-transport regimes in the one-dimensional conductor olivine Li_xFePO4 (0 <= x <= 1). Lithium isotope exchange validates single-file diffusion governed by strong ion-ion correlations, where 1D confinement suppresses bypassing and preserves spatial order. Kinetic Monte Carlo simulations and chronoamperometry quantify both Faradaic and non-Faradaic surface exchange, identifying electron transport, rather than Li+ mobility, as the rate-limiting step for electrochemical reaction. In addition, Li-Na exchange exhibits apparent superdiffusion, with rates that increase with Na content. Simulations attribute this behavior to surface-exchange limitations and Na-induced lattice strain that enhances cross-channel Li+ hopping and drives a crossover from 1D to quasi-2D transport. Four-dimensional STEM, in situ synchrotron XRD, X-ray absorption spectroscopy, and Mossbauer spectroscopy confirm that lattice softening and concerted polaron motion contribute to the observed dynamics. These results establish tracer exchange as a powerful tool for probing coupled ion-electron transport and provide chemical insight into how lattice mechanics and multicomponent exchange shape ionic diffusion in solids.

cond-mat.mtrl-sci↗

arXiv2025

Reinforcement Learning for Robust Ageing-Aware Control of Li-ion Battery Systems with Data-Driven Formal Verification

Rechargeable lithium-ion (Li-ion) batteries are a ubiquitous element of modern technology. In the last decades, the production and design of such batteries and their adjacent embedded charging and safety protocols, denoted by Battery Management Systems (BMS), has taken central stage. A fundamental challenge to be addressed is the trade-off between the speed of charging and the ageing behavior, resulting in the loss of capacity in the battery cell. We rely on a high-fidelity physics-based battery model and propose an approach to data-driven charging and safety protocol design. Following a Counterexample-Guided Inductive Synthesis scheme, we combine Reinforcement Learning (RL) with recent developments in data-driven formal methods to obtain a hybrid control strategy: RL is used to synthesise the individual controllers, and a data-driven abstraction guides their partitioning into a switched structure, depending on the initial output measurements of the battery. The resulting discrete selection among RL-based controllers, coupled with the continuous battery dynamics, realises a hybrid system. When a design meets the desired criteria, the abstraction provides probabilistic guarantees on the closed-loop performance of the cell.

eess.SY↗