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In this work we analyse the local nonlinear electrochemical impedance spectroscopy (NLEIS) response of a lithium-ion battery and estimate model parameters from measured NLEIS data. The analysis assumes a single-particle model including nonlinear diffusion of lithium within the electrode particles and asymmetric charge transfer kinetics at their surface. Based on this model and assuming a moderately-small excitation amplitude, we systematically derive analytical formulae for the impedances up to the second harmonic response, allowing the meaningful interpretation of each contribution in terms of physical processes and nonlinearities in the model. The implications of this for parameterization are explored, including structural identifiability analysis and parameter estimation using maximum likelihood, with both synthetic and experimentally measured impedance data. Accurate fits to impedance data are possible, however inconsistencies in the fitted diffusion timescales suggest that a nonlinear diffusion model may not be appropriate for the cells considered. Model validation is also demonstrated by predicting time-domain voltage response using the parameterized model and this is shown to have excellent agreement with measured voltage time-series data (11.1 mV RMSE)., Comment: 40 pages (excluding supplementary material). Submitted to the Journal of the Electrochemical Society

Tissue engineering aims to grow artificial tissues \emph{in vitro} to replace those in the body that have been damaged through age, trauma or disease. A recent approach to engineer artificial cartilage involves seeding cells within a scaffold consisting of an interconnected 3D-printed lattice of polymer fibres combined with a cast or printed hydrogel, and subjecting the construct (cell-seeded scaffold) to an applied load in a bioreactor. A key question is to understand how the applied load is distributed throughout the construct. To address this, we employ homogenisation theory to derive equations governing the effective macroscale material properties of a periodic, elastic-poroelastic composite. We treat the fibres as a linear elastic material and the hydrogel as a poroelastic material, and exploit the disparate length scales (small inter-fibre spacing compared with construct dimensions) to derive macroscale equations governing the response of the composite to an applied load. This homogenised description reflects the orthotropic nature of the composite. To validate the model, solutions from finite element simulations of the macroscale, homogenised equations are compared to experimental data describing the unconfined compression of the fibre-reinforced hydrogels. The model is used to derive the bulk mechanical properties of a cylindrical construct of the composite material for a range of fibre spacings, and to determine the local mechanical environment experienced by cells embedded within the construct.

In this article the Butler-Volmer equation used in describing Lithium-ion (Li-ion) batteries is discussed. First, a complete mathematical model based on a macro-homogeneous approach developed by Neuman is presented. Two common mistakes found in the literature regarding a sign in a boundary conditions and the use of the transfer coefficient are mentioned. The paper focuses on the form of the Butler-Volmer equation in the model. It is shown how practical problems can be avoided by taking care in the form used, particularly to avoid difficulties when the solid particle in the electrodes approaches a fully charged or discharged state or the electrolyte gets depleted. This shows that the open circuit voltage and the exchange current density must depend on the lithium concentration in both the solid and the electrolyte in a particular way at the extremes of the concentration ranges.