Electric cycling is one of the major damage sources in lithium-ion batteries and extensive work has been produced to understand and to slow down this phenomenon. The damage is related to the insertion and extraction of lithium ions in the active material. These processes cause mechanical stresses which in turn generate crack propagation, material loss and pulverization of the active material. In this work, the principles of diffusion induced stress theory are applied to predict concentration and stress field in the active material particles. Coupled and uncoupled models are derived, depending on whether the effect of hydrostatic stress on concentration is considered or neglected. The analytical solution of the coupled model is proposed in this work, in addition to the analytical solution of the uncoupled model already described in the literature. The analytical solution is a faster and simpler way to deal with the problem which otherwise should be solved in a numerical way with finite difference method or a finite element model. The results of the coupled and uncoupled models for three different state of charge levels are compared assuming the physical parameters of anode and cathode active material. Finally, the effects of tensile and compressive stress are analysed.

Nowadays, lithium-ion batteries are one of the most widespread energy storage systems, being extensively employed in a large variety of applications. A significant effort has been made to develop advanced materials and manufacturing processes with the aim of increasing batteries performance and preserving nominal properties with cycling. Nevertheless, mechanical degradation is still a significant damaging mechanism and the main cause of capacity fade and power loss. Lithium ions are inserted and extracted into the lattice structure of active materials during battery operation, causing the deformation of the crystalline lattice itself. Strain mismatches within the different areas of the active material caused by the inhomogeneous lithium-ions concentration induce mechanical stresses, leading ultimately to fracture, fatigue issues, and performance decay. Therefore, a deep understanding of the fracture mechanics in active materials is needed to meet the rapidly growing demand for next-generation batteries with long-term stability, high safety, excellent performance, and long life cycle. This review aims to analyze the fracture mechanics in the active material microstructure of electrodes due to battery operations from an experimental point of view. The main fracture mechanisms occurring in the common cathode and anode active materials are described, as well as the factors triggering and enhancing fracture. At first, the results obtained by performing microscopy and diffraction analysis in different materials are discussed to provides visual evidence of cracks and their relation with lattice structure. Then, fatigue phenomena due to crack growth as a function of the number of cycles are evaluated to assess the evolution of damage during the life cycle, and the effects of fracture on the battery performance are described. Finally, the literature gaps in the characterization of the fracture behavior of electrode active materials are highlighted to enhance the development of next-generation lithium-ion batteries.

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Electrochemical-mechanical modelling is a key issue to estimate the damage of active material, as direct measurements cannot be performed due to the particles nanoscale. The aim of this paper is to overcome the common assumptions of spherical and standalone particle, proposing a general approach that considers a parametrized particle shape and studying its influence on the mechanical stresses which arise in active material particles during battery operation. The shape considered is a set of ellipsoids with variable aspect ratio (elongation), which aims to approximate real active material particles. Active material particle is divided in two domains: non-contact domain and contact domain, whether contact with neighbouring particles affects stress distribution or not. Non-contact areas are affected by diffusion stress, caused by lithium concentration gradient inside particles. Contact areas are affected simultaneously by diffusion stress and contact stress, caused by contact with neighbouring particles as a result of particle expansion due to lithium insertion. A finite element model is developed in Ansys™APDL to perform the multi-physics computation in non-spherical domain. The finite element model is validated in the spherical case by analytical models of diffusion and contact available for simple geometry. Then, the shape factor is derived to describe how particle shape affects mechanical stress in non-contact and contact domains.

Good energy density, long lifetime, high capacity and high voltage make Lithium-ion batteries the most widespread energy storage systems, suitable for several fields of application. Nevertheless, usage leads to cell degradation which mainly results in capacity and power fade. Degradation phenomena are the result of the interaction between mechanical and electro-chemical mechanisms, which are reviewed in this paper. Lithium-ion batteries store and deliver electric energy by means of ions transport between anode and cathode through the electrolyte. The active material of the electrodes consists of micrometer particles which can host lithium ions through insertion/extraction processes. These processes are modelled as diffusion-mechanical problem, since the lithium concentration gradient within the particle due to ions diffusion generates internal stresses in analogy with a temperature gradient. The model in this work, usually referred as diffusion induced stress (DIS), can predict the stresses in the active material particles which are the driving force for damage, pulverization, exfoliation and crack propagation. Indeed, the damage induced by the insertion/extraction processes explains the capacity reduction over charge/discharge cycles: a critical issue for batteries lifetime.