Understanding the Effect of Mechanical Degradation on the Performance of Solid-State Batteries through Particle Simulations

Abstract

All-solid-state batteries (ASSBs) have garnered significant interest as a promising alternative to conventional lithium-ion batteries, offering improved safety, higher energy density, longer lifespan, faster charging and wider operating temperature range. A key advantage of ASSBs is the use of solid electrolytes (SE), which eliminate the risks associated with flammable liquid electrolytes. However, the complex electrochemical behavior and multi-scale nature of ASSBs pose challenges in designing and optimizing their performance. This study employs Discrete Element Method (DEM) particle-based models to better understand degradation behavior of ASSBs by considering electrochemical reaction, mass and charge transfer, intercalation expansion and material deformationOur simulations were developed in MATLAB and were performed on a half-cell configuration comprising a SE-layer and an anode electrode. The anode electrode was composed of a particle mixture containing active material (AM) and SE. In our simulations, Si was employed as AM, which experiences substantial intercalation expansion during charge cycling 1. Our previously developed DEM model2,3 resolved elastic and plastic deformation of both AM and SE particles which become compressed due to the intercalation expansion. The simulation of intercalation was achieved by integrating the Newman electrochemical model,4 into the DEM mechanical model. Building on our earlier study5, where the Li concentration was resolved within each AM particle, this study is also accounting for the Li-ion potential within each SE particle. Interparticle conduction and diffusion were computed by determining the contact area of AM-AM and SE-SE contacts, which were affected by the compression of the electrode. The electrochemical reaction was calculated at the AM-SE interface using the Butler-Volmer equation, and in addition the influence of compressive stress on the reaction6 was included.Figure 1(a) depicts the Li concentration and Li-ion potential distribution within the half-cell during charging at different states of charge (SOC), while Figure 1(b) provides a 3D view of the distributions at a SOC of 50%. A considerable expansion of the Si anode is evident. The gradients of Li concentration and Li-ion potential signify significant mass and charge transfer resistance during the charging process. Comparing the distribution of the particles, the anode becomes more porous after the first cycle for the same value of SOC. This effect is attributed to the extensive expansion of the Si anode, leading to plastic compression of the SE layer, which becomes more compact after each cycle. The growing porosity diminishes the contact area between particles, ultimately resulting in the degradation of the half-cell's capacity. In addition to SE-layer compaction, this study aims to investigate several degradation mechanisms and their impact on the performance of ASSBs, including the development of shell voids resulting from AM-SE delamination, crack propagation through SE, and fragmentation of AM.The results of this study provide valuable insights into understanding the effect of mechanical degradation on the performance of ASSBs. By improving our understanding of these mechanisms, we can work towards enhancing the durability and lifespan of ASSBs, ultimately contributing to the development of next-generation energy storage systems. Acknowledgment This work was supported by JSPS KAKENHI Grant-in-Aid for Scientific Research on Innovative Areas, “Science on Interfacial Ion Dynamics for Solid State Ionics Devices, Computational & Data Science” (Gp-A03, grant number 19H05815); and MEXT “Program for Promoting Researches on the Supercomputer Fugaku” (Fugaku battery & Fuel Cell Project), grant number JPMXP1020200301. References M. N. Obrovac and L. Christensen, Electrochem. Solid-State Lett., 7, A93 (2004).M. So, G. Inoue, R. Hirate, K. Nunoshita, S. Ishikawa, and Y. Tsuge, J. Electrochem. Soc., 168, 030538 (2021).M. So, G. Inoue, R. Hirate, K. Nunoshita, S. Ishikawa, and Y. Tsuge, Journal of Power Sources, 508, 230344 (2021).J. Newman and K. E. Thomas-Alyea, Electrochemical Systems, 3rd edition., p. 672, Wiley-Interscience, Hoboken, N.J, (2004).M. So, S. Yano, A. Permatasari, T. D. Pham, K. Park, and G. Inoue, Journal of Power Sources, 546, 231956 (2022).G. Bucci, T. Swamy, S. Bishop, B. W. Sheldon, Y.-M. Chiang, and W. C. Carter, J. Electrochem. Soc., 164, A645 (2017). Figure 1