Electro-Chemo-Mechanical Modeling of Composite Cathodes in All-Solid-State Li-Ion Batteries

A model-based understanding can assist and accelerate developing all-solid-state batteries (ASSB). In addition to chemo-mechanical influences within electrode particles (e.g., NMC) 1-2, a solid electrolyte (e.g., argyrodites) introduces additional interfacial interactions between electrode and electrolyte phases 3-5. The present research derives and implements a coupled multi-physics finite-element model that captures electrochemical, transport, and structural behaviors of composite electrode structures. The models incorporate concentration-dependent and anisotropic material properties that are based on previously published combinations of experiment and density functional theory (DFT). These include stiffness and fracture toughness, porosity and crystallographic orientation, and operating conditions such as charge/discharge rates and external pressure. Figure 1 illustrates predicted stresses developed during electrode manufacturing. The relatively complex cathode microstructure is based on replicating scanning electron microscopy (SEM) images 6. The composite electrode consists of electrode, electrolyte, and pore phases (Fig. 1a). As illustrated in Fig. 1b, the ASSB synthesis process involves applying and removing high compressive pressure, which causes plastic deformation and introduces residual stresses. Figure 1c shows residual von Mises stresses near electrode-electrolyte interfaces that can be on the order of a gigapascal. The synthesis-generated residual stresses serve as initial conditions for modeling the chemo-mechanics during battery cycling. During cell operation, spatially varying Li concentrations cause material deformation and associated stresses. Figure 1d shows predicted crack nucleation and growth during operation. Depending on the stress levels, crack nucleation and growth leads to cell degradation and capacity fade. The models predict interfacial fracture and phase separations using phase-field fracture theory. In phase-field formulation, the sharp cracks are approximated as diffuse cracks using a process-zone. High values of the phase parameter ξ (Fig. 1d) represent cracked surfaces. The structural disintegration and loss of active surface areas increase the tortuous path for Li/Li-ion transport, which eventually manifests as capacity-fade. The simulations are validated using published experimental work. The modeling approach, which combines phase-field and finite-element algorithms, is implemented using the COMSOL Multiphysics software. The models are expected to inform microstructure/manufacturing design and optimal operating conditions that improve cycling performance and limit/prevent mechanical damage. 1 K. Taghikhani, P.J. Weddle, J.R. Berger, and R.J. Kee. Modeling coupled chemo-mechanical behavior of randomly oriented NMC811 polycrystalline Li-ion battery cathodes. J. Electrochem. Soc., 168(8):080511, 2021. 2 R. Xu, Y. Yang, F. Yin, P. Liu, P. Cloetens, Y. Liu, F. Lin, and K. Zhao, Heterogeneous damage in Li-ion batteries: experimental analysis and theoretical modeling. J. Mech. Phys. Solids , 129, 160, 2019. 3 K. Taghikhani, P.J. Weddle, R.M. Hoffman, J.R. Berger, and R.J. Kee. Electro-chemo-mechanical finite-element model of single-crystal and polycrystalline NMC cathode particles embedded in an argyrodite solid electrolyte. Electrochim. Acta , 460:142585, 2023. 4 A. Bielefeld, D.A. Weber, R. Rueß, V. Glavas, and J. Janek. Influence of lithium ion kinetics, particle morphology and voids on the electrochemical performance of composite cathodes for all-solid-state batteries. J. Electrochem. Soc ., 169(2):020539, 2022. 5 P. Minnmann, F. Strauss, A. Bielefeld, R. Ruess, P. Adelhelm, S. Burkhardt, S.L. Dreyer, E. Trevisanello, H. Ehrenberg, T. Brezesinski, F.H. Richter, and J. Janek. Designing cathodes and cathode active materials for solid-state batteries. Adv. Energy Mater. , 12(35):2201425, 2022. 6 C. Doerrer, I. Capone, S. Narayanan, J. Liu, C.R.M. Grovenor, M. Pasta, and P.S. Grant. High energy density single-crystal NMC/Li 6 PS 5 Cl cathodes for all-solid-state lithium-metal batteries. ACS Appl. Mater. & interfaces , 13(31):37809–37815, 2021. Figure 1