Publication date: 15th December 2025
Magnetic resonance methods, including nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR), are non-invasive, atom-specific, quantitative, and are applicable for liquid and solid-state materials. These features make magnetic resonance ideal tools for operando measurement of an electrochemical device, and for establishing structure-function relationships under device-operating conditions.
For the first part of my talk, I will present how we develop and apply coupled NMR and EPR methods to unravel molecular-level physical and chemical processes in redox flow batteries. I will present case studies on viologen-based RFBs and demonstrate how we monitor the state of charge, unravel degradation reaction mechanisms as well as ion transport through membranes. For the second part, I will present new in situ NMR methods for studying Li-mediated ammonia synthesis, and the direct observation of lithium plating and its concurrent corrosion, nitrogen splitting on lithium metal and protonolysis of lithium nitride. Built upon these insights, we have developed a new alkaline electrochemical ammonia synthetic method. By the end of this talk, I hope to show that operando magnetic resonance is powerful and general, and can be applied for understanding various energy storage and conversion chemistries.
References
1. Zhao E W, Liu T, Jónsson E, Lee J, Temprano I, Jethwa B J, Wang A, Smith H, Carretero-González J, Song Q, Grey C P “In situ NMR metrology reveals reaction mechanisms in redox flow batteries” Nature 2020, 579, 224-228.
2. Zhao E W, Jónsson E, Jethwa B J, Hey D, Lyu D, Brookfield A, Klusener P A A, Collison D, Grey C P “Coupled in situ NMR and EPR studies reveal the electron transfer rate and electrolyte decomposition in redox flow batteries” J. Am. Chem. Soc. 2021, 143, 1885-1895.
3. Luo R, Janssen H J W G, Kentgens A P M, Zhao E W “A parallel line probe for spatially selective electrochemical NMR spectroscopy” J. Magn. Reson. 2024, 361, 107666 (Front cover; Special Issue: New Voices in Magnetic Resonance; Invited).
4. Silva Testa A G, Damhuis M A, Elemans J A A W, Zhao E W “Coupled benchtop NMR and EPR spectroscopy reveals the electronic structure of viologen radicals in a redox flow battery” ACS Electrochemistry, 2025, 1, 1977-1982 (Front cover).
5. Luo R, Gunnarsdóttir A B, Aspers R. L. E. G., Zhao E W “In situ NMR guided design of alkaline electrochemical ammonia synthesis” Science Advances, Accepted. Preprint 10.26434/chemrxiv-2024-cpf4j
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