Mechanical Failure of Core-Shell Cathode Particles: The Effects of Concentration-Dependent Material Properties and Phase Field Fracture Modelling
Authors: Tu Yang , Wu Billy , Ai Weilong , Martinez-Paneda Emilio 
Published: August 2024

The use of core-shell cathode particles in lithium-ion batteries is an attractive approach to enhancing energy density whilst retaining lifetime, through reducing undesired reactions at the electrode-electrolyte interface and limiting the volume change of the electrode particles. However, mechanical failure through the fracture and debonding of the core-shell interface is a major challenge. In this work, we employ a coupled finite-element model to predict and mitigate the mechanical failure of core-shell cathode structures, taking as example a particle of NMC811 (core) coated with NMC111 (shell). In particular, we focus on two aspects:
The first one involves the assumptions of material properties as inputs of the model. The material properties are often considered constant by battery modelling researchers, yet these parameters can vary significantly during charge/discharge. For example, experiments have unveiled a three-orders-of-magnitude drop in the diffusion coefficient of NMC materials during discharge [1]. Here, we incorporate material properties obtained from experimental data, including concentration-dependent diffusion coefficient obtained from GITT measurement and partial molar volume derived from in situ X-ray diffraction data. Our results indicate that when assuming a concentration-dependent partial molar volume, the maximum values of tensile hoop stress in the shell are nearly three times lower than those predicted with constant average properties, diminishing the likelihood of fracture.
When accounting for concentration-dependent diffusion coefficient, large concentration gradient is observed near the outer surface of the core due to reduced lithium mobility at high states of lithiation, hindering full electrode capacity utilisation. The significant concentration gradient and capacity underutilisation align with direct observations from experiments [2]. Notably, these phenomena cannot be captured in modelling if assuming constant diffusion coefficient. These findings offer new perspectives on the performance and design of core-shell electrode particles. Safe design maps in terms of core size and shell thickness to mitigate fracture and debonding are obtained.
The second focus of this work is the utilisation of phase field fracture model in predicting cracking behaviours within the core-shell particle. Phase field modelling provides a continuous representation of cracks, enabling the tracking of complex cracking patterns [3]. We predict cracking behaviors caused by volume changes during charge/discharge, as well as inaccessible capacity and newly created active surface area caused by cracking. Our multiphyics model can hopefully act as a catalyst, accelerating the development process of the core-shell structured cathode particles and shortening the time to market of advanced batteries with extended lifetime.
References
[1] Chen, C.H., Planella, F.B., O’regan, K., Gastol, D., Widanage, W.D. and Kendrick, E., 2020. Development of experimental techniques for parameterization of multi-scale lithium-ion battery models. Journal of The Electrochemical Society, 167(8), p.080534.
[2] Xu, C., Merryweather, A.J., Pandurangi, S.S., Lun, Z., Hall, D.S., Deshpande, V.S., Fleck, N.A., Schnedermann, C., Rao, A. and Grey, C.P., 2022. Operando visualization of kinetically induced lithium heterogeneities in single-particle layered Ni-rich cathodes. Joule, 6(11), pp.2535-2546.
[3] Ai, W., Wu, B. and Martínez-Pañeda, E., 2022. A coupled phase field formulation for modelling fatigue cracking in lithium-ion battery electrode particles. Journal of Power Sources, 544, p.231805.

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