Porosity Development at Li-Rich Layered Cathodes in All-Solid-State Battery during In Situ Delithiation

Structural evolutions are crucial for determining the performance of high-voltage lithium, manganese-rich layered cathodes. Moreover, interface between electrode and electrolyte plays a critical role in governing ionic transfer in all-solid-state batteries. Here, we unveil two different types of porous structure in Li_1.2Ni_0.2Mn_0.6O₂ cathode with LiPON solid-state electrolyte. Nanopores are found near the cathode/electrolyte interface at pristine state, where cation mixing, phase transformation, oxygen loss, and Mn reduction are also found. In situ Li⁺ extraction induces the evolution of nanovoids, initially formed near the interface then propagated into the bulk. Despite the development of nanovoids, layered structure is conserved, suggesting the nature of nanopores and nanovoids are different and their impact would be divergent. This work demonstrates the intrinsic interfacial layer, as well as the dynamic scenario of nanovoid formation inside high-capacity layered cathode, which helps to understand the performance fading in cathodes and offers insight into the all-solid-state battery design.