INTERFACES IN THIN-FILM SOLID-STATE BATTERIES

Abstract

The lack of a diagnostics approach to monitor interface kinetics in solid-state batteries (SSBs) results in an incomplete knowledge of the mechanisms affecting device performance. In this study, a new protocol for process control of SSB interface formation and their evolution during operation is presented. Thin-film SSBs and diagnostic test devices that are composed by a permutation of isolated layers were simultaneously fabricated using sequential sputtering deposition and in-situ patterning using shadow masks. Physics-based electric circuit models were designed for deconvolution of impedance profiles, which enabled an evaluation of bulk properties and space-charge layers at interfaces individually and during operation under different states-of-charge. Relative permittivity values of fundamental battery components (cathode, electrolyte and anode) were calculated as a function of the frequency and the applied voltage. Interfacial impedances, as well as space-charge layers formed at heterojunctions during charge and discharge processes, were successfully deconvoluted using the diagnostic test devices and electric circuit modeling. The cathode-electrolyte interphase was kinetically stable under a voltage window of 0 – 3.6 V vs Cu, and it had an estimated ionic conductivity of the order of 10-9 S/cm, hence it is a localized limiting factor for Li+ transfer. The anode-electrolyte interphase was thermodynamically stable upon completion of the fabrication process, but it became kinetically unstable during charge and discharge cycles. Hence, the proposed diagnostics protocol enlightened the necessity of implementing interfacial engineering on these interphases in the future for improvement of cyclability and stability of SSBs and ionic devices.