Understanding the impact of surface catalysis on the interfacial evolution of battery electrodes during energy storage is key to developing reliable, efficient, and safe high-energy density technologies. The formation of interphases is essential for the operation at anodes, where the solid-electrolyte interphase (SEI) kinetically stabilizes the electrode; recently, the formation of interfacial structures at high-energy density cathodes has also garnered great interest due to the kinetic and Coulombic limitations it places on the performance of various promising materials. [1] Elucidating how electrode surface structure, composition, and potential-dependent behavior impact the degradation reactions of the electrolyte and solvent is a fundamental pursuit with significant practical implications, as it may be key to engineering safe devices and to improve the efficiency of growing and aging stable interfaces at an industrial scale. Thus, understanding how surface reactions prompt the evolution of interfaces is a pressing challenge. While X-ray and mass-spectrometric methods [2,3] have been used to characterize these chemistries, probing the surface chemistry of these electrodes with higher versatility, in situ and with high spatiotemporal and chemical resolution represents a formidable analytical challenge.Here, we present an analytical methodology based on the use of scanning electrochemical microscopy in various modes for quantitatively detecting the formation, in real time and with high spatial resolution, of gaseous by-products such as O2 and CO2 from the catalytic decomposition of the electrolyte/solvent at battery electrodes. Using the generation/collection mode we developed an analytical platform capable of resolving these two species in order to quantify material degradation processes as a function of state of charge, and by using the feedback mode we can simultaneously monitor their impact on the interfacial kinetics of the electrode. By insightfully using ultramicroelectrode methods, and principles of CO2 electroreduction, we evaluated the nonaqueous reaction mechanisms involved in the detection to provide quantitative guidance on the relationship between the detected signal and the quantification of the processes undergoing at the battery electrode. We tested the response of our probes on a model NMC cathode, confirming O2 and CO2 evolution processes under conditions reported to exhibit bulk decomposition and surface passivation, respectively. This work creates a foundation not only for the high spatiotemporal evolution of interfacial processes at battery electrodes, but also for the understanding of CO2-related mechanisms in nonaqueous solvents.[1] Li, W. et al. Nature Comm. 2017, 8, 14589[2] Li, Q. et al. ACS Appl. Mater. Interfaces 2020, 12, 2, 2319–2326[3] McCloskey, B.D. et al. J. Phys. Chem. Lett. 2012, 3, 997-1001
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