(Energy Technology Division Graduate Student Award sponsored by BioLogic) Probing and Engineering Electrode-Electrolyte Interfaces in Electrochemical Energy Storage and Conversion
Authors: Zhang Yirui , Wang Tao , Giordano Livia , Fraggedakis Dimitrios , Huang Botao , Stephens Ryan , Bazant Martin Z. , Shao-Horn Yang 
Published: September 2023

Climate change demands the development of clean energy technologies, where rechargeable batteries and fuel cells promise a bright future by integrating with solar or wind energy. Li-ion batteries and fuel cells also play essential roles in electrifying transportation in replacement of internal combustion engines. Central to these electrochemical systems is the electrode-electrolyte interface, where (electro)chemical surface reactions or intercalation reactions occur, and its thermodynamic and kinetic properties determine the energy density, power density, and lifetime of the electrochemical devices. However, the molecular structures at the interface and how they promote or suppress the desired reactions remain unclear, hindering the rational design of electrode-electrolyte interfaces to improve the performance of electrochemical devices.

This talk focuses on the fundamental understanding of the interfacial (electro)chemical reaction mechanisms at the molecular level and charges transfer kinetics at the electrified interfaces. First, an in situ Fourier-transform infrared spectroscopy (FTIR) method was developed to examine the parasitic reactions between carbonate electrolytes and lithium nickel, manganese and cobalt oxides (NMC) in Li-ion batteries, and unique evidence for dehydrogenation reactions on Ni-rich NMC was revealed, which accounted for interface impedance build-up and battery capacity fading. Based on the proposed mechanism, strategies based on electrolyte non-covalent interactions were demonstrated to improve battery lifetime. In the second part of the talk, the research extended in situ FTIR characterization and electrolyte engineering to electrocatalytic reactions central to fuel cell technologies. An interfacial layer of protic ionic liquids with different acid dissociation constants were found to enhance the oxygen-reduction reaction (ORR), attributed to strengthened hydrogen bonding between ORR products and ionic liquids, revealed by in situ surface-enhanced infrared absorption spectroscopy and density functional theory (DFT) calculations. For the hydrogen evolution reaction (HER), similarly, promoting hydrogen bonding between interfacial water molecules also facilitated proton-coupled electron transfer kinetics, resulting in favorable HER in controllable organic confinements. Finally, this talk will introduce fundamental, theoretical aspects of charge transfer processes at the electrode-electrolyte interface - the kinetic mechanism for ion intercalation. Experimental evidence from a charge-adjusted electrochemical method showed that Li-ion intercalation occurs by coupled ion-electron transfer (CIET), which governs the current-dependent maximum capacity and power density of intercalation batteries. these research efforts have laid a solid foundation for the rational design of electrochemical interfaces employing the physical chemistry of electrodes and electrolytes, for next-generation electrochemical storage devices with improved energy and power density and cycle life.