Abstract
Semi-solid fluid electrode-based battery (SSFB) and supercapacitor technologies are seen as very promising candidates for grid energy storage. However, unlike for traditional batteries, their performance can quickly get compromised by the formation of a poorly conducting solid-electrolyte interphase (SEI) on the particle surfaces. In this work we examine SEI film formation in relation to typical electrochemical conditions by combining cyclic voltammetry (CV) with quartz crystal microbalance dissipation monitoring (QCM-D). Sputtered layers of typical SSFB materials like titanium dioxide (TiO(2)) and carbon, immersed in alkyl carbonate solvents, are cycled to potentials of relevance to both traditional and flow systems. Mass changes due to lithium intercalation and SEI formation are distinguished by measuring the electrochemical current simultaneously with the damped mechanical oscillation. Both the TiO(2) and amorphous carbon layers show a significant irreversible mass increase on continued exposure to (even mildly) reducing electrochemical conditions. Studying the small changes within individual charge-discharge cycles, TiO(2) shows mass oscillations, indicating a partial reversibility due to lithium intercalation (not found for carbon). Viscoelastic signatures in the megahertz frequency regime confirm the formation and growth of a soft layer, again with oscillations for TiO(2) but not for carbon. All these observations are consistent with irreversible SEI formation for both materials and reversible Li intercalation for TiO(2). Our results highlight the need for careful choices of the materials chemistry and a sensitive electrochemical screening for fluid electrode systems.