Unveiling the Dynamics of Solid Electrolyte Interphase Evolution in Li-Ion Batteries Via Operando X-Ray Reflectivity: Experimental Insights for Advanced Energy Storage

Abstract

The Solid-Electrolyte-Interphase (SEI) is a crucial component of Li-ion batteries (LIBs), as it passivates the highly reactive electrode from the electrolyte and helps to stabilize the electrode/electrolyte interface. However, the SEI formation and evolution can also limit the cycling performance and the capacity retention of the battery. Accurate electrochemical models must therefore account for the SEI and properly simulate it. In order to investigate experimentally the SEI, various techniques have been deployed, including electron microscopy1, X-ray photoelectron spectroscopy (XPS)2,3 and Nuclear magnetic resonance (NMR)4.Providing reliable information on the SEI evolution during cycling, and thus benchmarking models, is challenging with these ex-situ or destructive techniques, as they hardly allow in situ observation. On the other hand, synchrotron X-ray reflectivity (XRR) can be used for the operando investigation of interfacial phenomena. It provides information on the thickness, density, and roughness of the SEI, as well as their changes upon (de)lithiation or in out-of-equilibrium conditions. Moreover, operando XRR can be performed under controlled battery operating conditions, providing relevant information on the SEI. Recently, several works reported that operando XRR experiment can provide in situ structural information of the formation and the growth of SEI with sub-nanometer resolution during the cycling5–7.Herein, we report the results of operando XRR experiments performed at the beamline BM32 of the European Synchrotron Radiation Facility (ESRF) to investigate the SEI on Si anode using novel, sustainable fluorine-free electrolytes. Indeed, in the quest for environmentally friendly and safe LIBs, removing the fluorinated electrolytes that are toxic and release corrosive compounds is a necessary step. One way to enhance the safety and sustainability of LIBs is to replace the conventional fluorinated electrolytes by fluorine-free alternatives. A F-free composition based on the lithium bis(oxalato) borate (LiBOB) salt recently showed promising performance in commercially relevant cell configurations8. As with conventional electrolytes, the F-free electrolyte reacts at the surface of the electrodes during the first charge, thus forming the SEI. Characterizing the F-free SEI growth and stability is thus key to understand its behavior and to improve the cell performance for this promising green electrolyte.In this work, operando XRR experiments were performed in electrochemical cells with different electrolyte compositions: 1 M LiPF6 in ethylene carbonate (EC):ethyl methyl carbonate (EMC) = 3:7 vol % (LP57), 0.7 M LiBOB in EC:EMC = 3:7 vol % (LiBOB), and 0.7 M LiBOB in EC:EMC = 3:7 vol % with 2 wt% vinylene carbonate (LiBOB-VC) during at least three cycles. XRR data show that the formations of SEI layers and their evolutions during the cycling for these two types of electrolytes are different. Furthermore, a layer with low electron density (ED) is still present after total delithiation in the LiBOB-cells, while the ED evolutions are generally reversible for LP57 cell. This suggests that the F-free SEI has different properties during cycling than the SEI formed with conventional salt LiPF6.In summary, operando XRR is a powerful technique for investigating the impact of new electrolyte chemistry and formulation on the SEI properties, which significally influence batteries performances. Moreover, the in situ and in real-time experimental insights with sub-nanometer resolution from this technique provides valuable information for the development of more accurate and predictive models for the SEI evolution. Its unique capabilities make it an essential tool for advancing the understanding of SEI behavior and designing more efficient and stable energy storage systems.Figure 1: (a) Principle of operando X-ray reflectometry. (b) XRR data and fit-derived EDP of LiBOB cell upon lithiation. Figure 1