Between vibrations and diffusion: the persistence of memory in ion conduction

Andrey Poletayev^a^,^b^,^c, Matthias Hoffmann^c, James Dawson^d, Samuel Teitelbaum^c^,^e, Mariano Trigo^c, Saiful Islam^a, Aaron Lindenberg^b^,^c

^aDepartment of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK

^bDepartment of Materials Science & Engineering, Stanford University

^cSLAC National Accelerator Laboratory, Stanford University, Stanford, CA, USA, United States

^dDepartment of Chemistry, Newcastle University, Newcastle upon Tyne, UK

^eDepartment of Physics, Arizona State University, Tempe, AZ, USA

Proceedings of 24th International Conference on Solid State Ionics (SSI24)

Fundamentals: Experiment and simulation

London, United Kingdom, 2024 July 14th - 19th

Organizers: John Kilner and Stephen Skinner

Oral, Andrey Poletayev, presentation 506
Publication date: 10th April 2024

Predicting practical rates of transport in condensed phases enables the rational design of materials, devices and processes. This is especially critical to developing low-carbon energy technologies such as rechargeable batteries. For ionic conduction, the collective mechanisms, variation of conductivity with timescales and confinement, and ambiguity in the phononic origin of translation, call for a direct probe of the fundamental steps of ionic diffusion: ion hops. However, such hops are rare-event large-amplitude translations, and are challenging to excite and detect. Here we use single-cycle terahertz pumps to impulsively trigger ionic hopping in battery solid electrolytes. This is visualized by an induced transient birefringence, enabling direct probing of anisotropy in ionic hopping on the picosecond timescale. The relaxation of the transient signal measures the decay of orientational memory, and the production of entropy in diffusion [1]. We extend experimental results using in silico transient birefringence to identify vibrational attempt frequencies for ion hopping. Using nonlinear optical methods, we probe ion transport at its fastest limit, distinguish correlated conduction mechanisms from a true random walk at the atomic scale, and demonstrate the connection between activated transport and the thermodynamics of information.

Furthermore, we study the influence of this memory on the correspondence between descriptors extractable from atomistic simulation and macroscopically observable transport rates and activation energies. Using large-scale simulations, we reproduce the frequency dependence of AC ionic conductivity and of activation energies [2]. We show that due to the collective nature of ion transport single ion hops cannot be considered a step of macroscopic-derived random-walk models typically used to understand ion diffusion and conduction in condensed phases.

References:

[1] Poletayev, A.D., et al., The persistence of memory in ionic conduction probed by nonlinear optics. Nature 2024, 625, 691-696.

[2] Poletayev, A.D., et al., Defect-driven anomalous transport in fast-ion conducting solid electrolytes. Nature Materials 2022, 21, 1066-1073.

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