Lattice oxygen loss during cathode charging significantly limits the charge storage capacity of lithium-ion batteries (LiBs). Therefore, elucidating the oxygen loss and subsequent surface reconstruction phenomena remains an ongoing pursuit with practical implications. We report an in situ oxygen detection strategy using scanning electrochemical microscopy (SECM) that reveals an unprecedented two-stage oxygen evolution behavior from commercial cathodes. This highly sensitive SECM method captured an unreported transient oxygen release at less than 3.3 V vs Li+/Li during the first charge cycle of LiCoO2, LiNi0.33Mn0.33Co0.33O2 and LiNi0.8Mn0.1Co0.1O2. At the main oxygen loss process above 3.3 V vs Li+/Li, SECM mapping highlighted spatial and temporal heterogeneities. Finite element simulations were used to quantify the rate of instantaneous oxygen release, with rates of ~30 pmol/cm2s for the steady-state oxygen evolution. This SECM approach revealed incipient degradation processes and created new quantitative and spatially resolved opportunities for investigating degradation in operating LiB cathodes.
Na-ion batteries (NIBs) are proposed as a promising candidate for beyond Li-ion chemistries, however, a key challenge associated with NIBs is the inability to achieve intercalation in graphite anodes. This phenomenon has been investigated and is believed to arise due to the thermodynamic instability of Na-intercalated graphite. We have recently demonstrated theoretical calculations showing it is possible to achieve thermodynamically stable Na-intercalated graphene structures with a fluorine surface modifier. Here, we present experimental evidence that Na+ intercalation is indeed possible in fluorinated few-layer graphene (F-FLG) structures using cyclic voltammetry (CV), ion-sensitive scanning electrochemical microscopy (SECM), and in situ Raman spectroscopy. SECM and Raman spectroscopy confirmed Na+ intercalation in F-FLG, while CV measurements allowed us to quantify Na-intercalated F-FLG stoichiometries around NaC14-18. These stoichiometries are higher than previously reported values for NaC186 in graphite. Our experiments revealed that reversible Na+ ion intercalation also requires a pre-formed Li-based SEI in addition to the surface fluorination, thereby highlighting the critical role of SEI in controlling ion-transfer kinetics in alkali-ion batteries. In summary, our findings highlight the use of surface modification and careful study of electrode-electrolyte interfaces and interphases as an enabling strategy for NIBs.
Choosing reference electrodes for nonaqueous electrochemical measurements, especially in energy storage research, is challenging due to lengthy experiments (>1 day), the lack of alternatives to the commonly used Ag/Ag + reference electrode (RE), the introduction of junction potentials, and the possibility of sample contamination. Often, quasi-reference electrodes (QREs) such as Ag wires and Li metal strips are used. However, small changes in electrolyte composition can cause large potential drifts, and their surfaces may be reactive to the solution. Here, we propose an alternative QRE based on polypyrrole electrodeposited on Pt wire (PPyQRE) encased in a glass tube with the open end sealed with commercial frits. While freestanding PPyQRE wires have been reported in the literature, simple encasing of the PPyQRE overcomes the above-mentioned drawbacks of QREs while providing a reliable reference potential that is closer to the performance of an RE. During cyclic voltammetric and bulk electrolysis testing of a redox mediator in solution, the encased PPyQRE exhibited stable reference potentials over multiple charge/discharge cycles with minimal drift (∼5 mV) after ∼2.25 days of operation. We also tested the reliability of our reference during the testing of multilayer graphene Li-ion anodes, which often involve cycling samples at highly reducing potentials (<−3 V vs Fc/Fc + ) over long durations (>1 day). In the same testing conditions, the Ag/Ag + electrode led to observable Ag deposits on the graphene and large potential drifts (∼50 mV), while the PPyQRE exhibited no measurable drift and revealed changes in voltammetric features that were obscured by reference drift when using Ag/Ag + . Minor reference drifts of ∼30 mV over long usage of the PPyQRE (∼2 months) can be addressed by calibration with a ferrocene couple at the end of experiments. These results highlight the advantages of using an encased PPyQRE as a simple and practical reference electrode for electrochemical measurements in the field of nonaqueous energy storage research.
Developing a deeper understanding of dynamic chemical, electronic, and morphological changes at interfaces is key to solving practical issues in electrochemical energy storage systems (EESSs). To unravel this complexity, an assortment of tools with distinct capabilities and spatiotemporal resolutions have been used to creatively visualize interfacial processes as they occur. This review highlights how electrochemical scanning probe techniques (ESPTs) such as electrochemical atomic force microscopy, scanning electrochemical microscopy, scanning ion conductance microscopy, and scanning electrochemical cell microscopy are uniquely positioned to address these challenges in EESSs. We describe the operating principles of ESPTs, focusing on the inspection of interfacial structure and chemical processes involved in Li-ion batteries and beyond. We discuss current examples, performance limitations, and complementary ESPTs. Finally, we discuss prospects for imaging improvements and deep learning for automation. We foresee that ESPTs will play an enabling role in advancing EESSs as we transition to renewable energies. Expected final online publication date for the Annual Review of Analytical Chemistry, Volume 16 is June 2023. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.