Comparative Electrochemical Analysis of Lithium and Lithium-Indium Alloy in All-Solid-State Battery
Authors: Park Se-Jin , Joo Soyoung , Shin Heon-Cheol 
Published: December 2024

Lithium-ion batteries (LIBs) are widely used in a variety of applications due to their high energy and power densities, and long cycle life. With the expanding use of LIBs in electric vehicles and energy storage systems, there is very active research into all-solid-state batteries (ASSBs), which offer greater energy density than traditional LIBs and eliminate the inherent fire hazards. Since most of the detailed reactions involved in the performance and degradation of a battery are temperature-sensitive, so-called thermal activation processes, it is very important to accurately assess whether a battery can have the high performance and low degradation characteristics required under different climatic conditions. To evaluate the electrochemical properties of electrode materials in LIBs, a half-cell is typically constructed with the electrode of interest as the working electrode (WE) and lithium metal as auxiliary electrode (AE). Here, lithium metal is close to an ideal non-polarizable material, has a large capacity, and maintains a constant potential during charge/discharge, so it is widely used as AE material in LIB research. However, several issues arise when lithium is used as AE in ASSBs: Lithium metal undergoes mechanical deformation due to the relatively high internal pressure required to ensure good contact between lithium and solid electrolyte; When in contact with sulfide-based solid electrolytes, which are currently of interest due to their high ionic conductivity, side reaction products can lead to an increase in interfacial resistance; the growth of lithium dendrites, often observed in conventional LIBs, is still unavoidable. These issues all affect the half-cell signal, potentially causing a distorted evaluation of the WE’s characteristics.
Lithium-indium alloy is being utilized as AE for ASSB half-cells to replace lithium metal. It exhibits excellent mechanical ductility and maintains a constant reduction potential over a wide stoichiometric range, ensuring excellent contact property and voltage stability. Moreover, it is very easy to fabricate through simple compression at room temperature. Nevertheless, the limited study on its electrochemical properties leaves uncertainty regarding its full functionality as AE for accurate evaluation of WE, particularly in extreme operational conditions. For instance, lithium-indium alloy are primarily based on alloying/dealloying reactions involving solid-state diffusion of lithium, which is generally considered to be a relatively slow process kinetically, while lithium only involves a kinetically favorable plating/stripping process on the surface. Therefore, a comparative analysis of these different reaction mechanisms in terms of kinetics is necessary. This presentation presents a comparative analysis of the electrochemical properties of lithium metal and lithium-indium alloys used as AEs in ASSB half-cells. In particular, the electrochemical properties of lithium-indium alloys with different reaction mechanisms with lithium are investigated over a range of temperatures and current densities, and these differences are discussed from a kinetic point of view. For this purpose, first, using a three-electrode half-cell with lithium or lithium-indium alloy as AE, we compared the electrochemical properties of these two AEs during half-cell operation by interpreting their potential and over-potential changes, and quantifying their detailed resistances. Then, through dc experiments on lithium and lithium-indium symmetrical cells, we identified differences in overvoltage behavior due to differences in their reaction mechanism. In particular, we noted distinct differences in the overpotential behavior of these two electrodes at low temperatures and high current densities. Furthermore, based on the results of a combined dc/ac electrochemical analysis, we derived the overvoltage that dominates the overall overvoltage at each of the two electrodes. Based on these results, we analyzed how the kinetic differences between the two electrodes affect the cathode half-cell signal, in order to derive key considerations for reliable ASSB half-cell evaluation. In this presentation, the advantages and disadvantages of lithium-indium alloy compared to lithium metal as AE will be discussed from a kinetic perspective, focusing on interfacial and bulk resistance (overpotential). Furthermore, methods for utilizing AE to conduct accurate and reliable half-cell tests will be proposed.