| AVS 65th International Symposium & Exhibition | |
| Surface Science Division | Thursday Sessions |
| Session SS+AS+BI+MI+NS-ThA |
| Session: | Organic/Inorganic Surfaces, Interfaces and Nanostructures |
| Presenter: | Venkateshkumar Prabhakaran, Physical Sciences Division, Pacific Northwest National Laboratory |
| Authors: | V. Prabhakaran, Physical Sciences Division, Pacific Northwest National Laboratory M.H. Engelhard, Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory A. Martinez, Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory G.E. Johnson, Physical Sciences Division, Pacific Northwest National Laboratory S. Thevuthasan, Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory V. Murugesan, Physical Sciences Division, Pacific Northwest National Laboratory |
| Correspondent: | Click to Email |
A molecular-level understanding of structural and chemical transformations of electrolyte at solid-electrolyte interfaces (SEI) is critical for rational design of electrochemical materials. Despite numerous studies, evolution of the transient and metastable species which dictates the cascade of interfacial reactions are still not clear. The challenge is to establish the chemical homogeneity within interface to clearly delineate the origin of various decomposition reaction products and their energetic pathways. Soft landing of mass-selected ions is ideally suited for building the interface with selected constituent which can alleviate the complexity associated with diverse and correlated processes within SEI layer.1-4 Herein, we report the development and first demonstration of new capabilities that combine ion soft landing with operando infrared reflection-absorption spectroscopy (IRRAS) to study the decomposition of counter anions and solvent molecules on bare lithium metal surfaces. Specifically, we discreetly deposited sulfonyl imide based electrolyte anion (TFSI-) and solvated Lithium cations without corresponding counter ions onto bare lithium metal using soft landing approach and monitored their decomposition using in-situ IRRAS and ex-situ x-ray photoelectron spectroscopy (XPS). Operando IRRAS and XPS measurements captured the signatures of transient species arising from decomposition of electrolyte anions and solvent molecules in real time. We will discuss, our unique approach of building interface with precise control over the constituents and subsequently detect the spectroscopic signatures of transient species during decomposition processes.
References:
1. Johnson, G. E.; Hu, Q.; Laskin, J., Soft landing of complex molecules on surfaces. Annual Review of Analytical Chemistry 2011,4, 83-104.
2. Prabhakaran, V.; Mehdi, B. L.; Ditto, J. J.; Engelhard, M. H.; Wang, B.; Gunaratne, K. D. D.; Johnson, D. C.; Browning, N. D.; Johnson, G. E.; Laskin, J., Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing. Nature Communications2016,7, 11399.
3. Prabhakaran, V.; Johnson, G. E.; Wang, B.; Laskin, J., In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces. Proceedings of the National Academy of Sciences 2016,113, 13324-13329.
4. Gunaratne, K. D. D.; Johnson, G. E.; Andersen, A.; Du, D.; Zhang, W.; Prabhakaran, V.; Lin, Y.; Laskin, J., Controlling the Charge State and Redox Properties of Supported Polyoxometalates via Soft Landing of Mass-Selected Ions. Journal of Physical Chemistry C 2014,118, 27611-27622.