The performance and durability of Ni-rich cathode materials are controlled in no small part by their mechanical durability, as chemomechanical breakdown at the nano-scale leads to increased internal resistance and decreased storage capacity. The mechanical degradation is caused by the transient lithium diffusion processes during charge and discharge of layered oxide spherical cathode micro-particles, leading to highly anisotropic incompatible strain fields. Experimental characterisation of the transient mechanisms underlying crack and void formation requires the combination of very high resolution in space (sub-micron) and time (sub-second) domains without charge interruption. The present study is focused on sub-micron focused operando synchrotron X-ray diffraction and in situ Ptycho-Tomographic nano-scale imaging of a single nano-structured LiNi_0.8Co_0.1Mn_0.1O₂ core–shell particle during charge to obtain a thorough understanding of the anisotropic deformation and damage phenomena at a particle level. Preferential grain orientation within the shell of a spherical secondary cathode particle provides improved lithium transport but is also associated with spatially varying anisotropic expansion of the hexagonal unit cell in the c-axis and contraction in the a-axis. These effects were resolved in relation to the grain orientation, and the link established with the nucleation and growth of intergranular cracks and voids that causes electrical isolation of active cathode material. Coupled multi-physics Finite Element Modelling of diffusion and deformation inside a single cathode particle during charge and discharge was validated by comparison with experimental evidence and allowed unequivocal identification of key mechanical drivers underlying Li-ion battery degradation.

To explore an effective route of customizing the superelasticity (SE) of NiTi shape memory alloys via modifying the grain structure, binary Ni₅₅Ti₄₅ (wt) alloys were fabricated in as-cast, hot swaged, and hot-rolled conditions, presenting contrasting grain sizes and grain boundary types. In situ synchrotron X-ray Laue microdiffraction and in situ synchrotron X-ray powder diffraction techniques were employed to unravel the underlying grain structure mechanisms that cause the diversity of SE performance among the three materials. The evolution of lattice rotation, strain field, and phase transformation has been revealed at the micro- and mesoscale, and the effect of grain structure on SE performance has been quantified. It was found that (i) the Ni₄Ti₃ and NiTi₂ precipitates are similar among the three materials in terms of morphology, size, and orientation distribution; (ii) phase transformation happens preferentially near high-angle grain boundary (HAGB) yet randomly in low-angle grain boundary (LAGB) structures; (iii) the smaller the grain size, the higher the phase transformation nucleation kinetics, and the lower the propagation kinetics; (iv) stress concentration happens near HAGBs, while no obvious stress concentration can be observed in the LAGB grain structure during loading; (v) the statistical distribution of strain in the three materials becomes asymmetric during loading; (vi) three grain lattice rotation modes are identified and termed for the first time, namely, multi-extension rotation, rigid rotation, and nondispersive rotation; and (vii) the texture evolution of B2 austenite and B19' martensite is not strongly dependent on the grain structure.

The mechanical response of rubbers has been ubiquitously assumed to be only a function of the imposed strain. Using innovative X-ray measurements capturing the three-dimensional spatial volumetric strain fields, we demonstrate that rubbers and indeed many common engineering polymers undergo significant local volume changes. But remarkably, the overall specimen volume remains constant regardless of the imposed loading. This strange behavior which also leads to apparent negative local bulk moduli is due to the presence of a mobile phase within these materials. Combining X-ray tomographic observations with high-speed radiography to track the motion of the mobile phase, we have revised classical thermodynamic frameworks of rubber elasticity. The work opens broad avenues to understand not only the mechanical behavior of rubbers but a large class of widely used engineering polymers.