Gas Evolution from Sulfide-Based All-Solid-State Batteries

The demand for high-performance batteries for electrical vehicles (EV) and large-scale energy storage systems have accelerated the development of all-solid-state batteries. Switching from organic liquid electrolyte to solid electrolyte (SE) ensures, not only the high energy density (Wh/L), but also an intrinsic improvement to safety from the removal of flammable solvent in the liquid electrolyte. However, for the development of all-solid-state batteries, still many problems exist toward commercialisation. One challenge is their chemical/electrochemical stability. In case of Li6PS5Cl argyrodite, their electrochemical decomposition was proposed as following reaction. [1] Li6PS5Cl → Li4PS5Cl + 2Li+ + 2e → Li3PS4 + Sx + LiCl → P2Sx + Sx + LiCl + 3Li+ + 3e (1) However, this proposed reaction is bulk electrochemical decomposition of argyrodite. To understand the decomposition in actual cell, layered oxide cathode/argyrodite composite were analysed by in situ Raman microscopy, X-ray photoelectron spectroscopy and Time-of-flight secondary ion mass spectrometry. [2, 3] This research reports actual solid decomposition product formed by active material and solid electrolyte such as POx or (S2)2- compound. Not only for solid decomposition product, but also gaseous decomposition product can be generated from the interface between cathode materials and SE. Previously, much work has demonstrated that O2 and CO2 gases are released from the positive electrode material within the lithium-ion cell. [4] These exothermic surface reactions are important not only for cell swelling in the long-term usage, but also for cell combustion. However, the gas releasing behaviour of positive electrode mixture in all-solid-state batteries are still not well recognised. In this research, we focused on the gas releasing behaviour of all-solid-state batteries. LiNi0.6Mn0.2Co0.2O2 was selected for cathode materials in this research. For the solid electrolyte itself and LiNi0.6Mn0.2Co0.2O2/SE mixture were analysed by Differential Electrochemical Mass Spectroscopy (DEMS). Furthermore, to understand the importance of surface chemistry, air stored LiNi0.6Mn0.2Co0.2O2 and Al2O3 coated LiNi0.6Mn0.2Co0.2O2were prepared. Since air contamination (H2O and CO2) is detrimental for Ni-rich cathode and battery [5], we propose role of surface chemistry in all-solid-state batteries by comparing different LiNi0.6Mn0.2Co0.2O2 composites. As shown in Figure 1, CO2 and O2 gas evolution is observed within an all-solid-state cell as it is charged up to 5 V, with evolution beginning at ca. 4 V highlighting the requirement of stabilising interfaces even when a solid-state electrolyte is used. Figure 1. Comparison of O2 and CO2 gas evolution from (a) Li6PS5Cl and (b) LiNi0.6Mn0.2Co0.2O2/ Li6PS5Cl composite when charged to 5 V vs. Li/Li+. [1] L. Zhou, N. Minafara, W. G. Zeier, L. F. Nazar, Innovative Approaches to Li-Argyrodite Solid Electrolytes for All-Solid-State Lithium Batteries, Acc. Chem. Res., 54, (2021) 2717–2728 [2] Y. Zhou, C. Doerrer, J. Kasemchainan, P. G. Bruce, M. Pasta, L. J. Hardwick, Observation of Interfacial Degradation of Li6PS5Cl against Lithium Metal and LiCoO2 via In Situ Electrochemical Raman Microscopy, Batter. & Supercaps, 3, (2020) 647 –652 [3] F. Walther, R. Koerver, T. Fuchs, S. Ohno, J. Sann, M. Rohnke, W. G. Zeier, J. Janek, Visualization of the Interfacial Decomposition of Composite Cathodes in Argyrodite-Based All-Solid-State Batteries Using Time-of-Flight Secondary-Ion Mass Spectrometry, Chem. Mater, 31, (2019), 3745-3755 [4]S. Sharifi-Asl, J. Lu, K. Amine, R. Shahbazian-Yassar, Oxygen Release Degradation in Li-Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches, Adv. Energy Mater., 9, (2019) 1900551 [5] H. Kim, A. Choi, S. W. Doo, J. Lim, Y. Kim, K. T. Lee, Role of Na+ in the cation disorder of [Li1-xNax] NiO2 as a cathode for lithium-ion batteries, J. Electrochem. Soc., 165, (2018), A201 Figure 1