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The performance of many technologies, such as Li- and Na-ion batteries as well as some two-dimensional (2D) electronics, is dependent upon the reversibility of stacking-sequence-change phase transformations. However, the mechanisms by which such transformations lead to degradation are not well understood. This study explores lattice-invariant shear as a source of irreversibility in stacking-sequence changes, and through an analysis of crystal symmetry shows that common electrode materials (graphitic carbon, layered oxides, and layered sulfides) are generally susceptible to lattice-invariant shear. The resulting irreversible changes to microstructure upon cycling ("electrochemical creep") could contribute to the degradation of the electrode and capacity fade.

Although layered lithium oxides have become the cathode of choice for state-of-the-art Li-ion batteries, substantial gaps remain between the practical and theoretical energy densities. With the aim of supporting efforts to close this gap, this work reviews the fundamental operating mechanisms and challenges of Li intercalation in layered oxides, contrasts how these challenges play out differently for different materials (with emphasis on Ni–Co–Al (NCA) and Ni–Mn–Co (NMC) alloys), and summarizes the extensive corpus of modifications and extensions to the layered lithium oxides. Particular emphasis is given to the fundamental mechanisms behind the operation and degradation of layered intercalation electrode materials as well as novel modifications and extensions, including Na-ion and cation-disordered materials.

A mesoscopic chemical reaction kinetics model to predict the formation of zirconium oxide and hydride accumulation light-water reactor (LWR) fuel clad is presented. The model is designed to include thermodynamic information from ab initio electronic structure methods as well as parametric information in terms of diffusion coefficients, thermal conductivities and reaction constants. In contrast to approaches where the experimentally observed time exponents are captured by the models by design, our approach is designed to be predictive and to provide an improved understanding of the corrosion process. We calculate the time evolution of the oxide/metal interface and evaluate the order of the chemical reactions that are conducive to a t 1/3 dependence. We also show calculations of hydrogen cluster accumulation as a function of temperature and depth using spatially dependent cluster dynamics. Strategies to further cohesively integrate the different elements of the model are provided.

Graphitic carbon is currently considered the state-of-the-art material for the negative electrode in lithium-ion cells, mainly due to its high reversibility and low operating potential. However, carbon anodes exhibit mediocre charge/discharge rate performance, which contributes to severe transport-induced surface-structural damage upon prolonged cycling, and limits the lifetime of the cell. Lithium bulk diffusion in graphitic carbon is not yet completely understood, partly due to the complexity of measuring bulk transport properties in finite-sized, non-isotropic particles. To solve this problem for graphite, we use the Devanathan-Stachurski electrochemical methodology combined with ab-initio computations to deconvolute, and quantify the mechanism of lithium-ion diffusion in highly oriented pyrolytic graphite (HOPG). The results reveal inherent high lithium-ion diffusivity in the direction parallel to the graphene plane (ca. 10^-7 - 10^-6 cm2 s-1), as compared to sluggish lithium-ion transport along grain boundaries (ca. 10^-11 cm^2 s^-1), indicating the possibility of rational design of carbonaceous materials and composite electrodes with very high rate capability., 9 pages, 3 figures