In Situ Solid-State NMR Spectroscopy of Electrochemical Cells: Batteries, Supercapacitors, and Fuel Cells

Electrochemical cells, in the form of batteries (or supercapacitors) and fuel cells, are efficient devices for energy storage and conversion. These devices show considerable promise for use in portable and static devices to power electronics and various modes of transport and to produce and store electricity both locally and on the grid. For example, high power and energy density lithium-ion batteries are being developed for use in hybrid electric vehicles where they improve the efficiency of fuel use and help to reduce greenhouse gas emissions. To gain insight into the chemical reactions involving the multiple components (electrodes, electrolytes, interfaces) in the electrochemical cells and to determine how cells operate and how they fail, researchers ideally should employ techniques that allow real-time characterization of the behavior of the cells under operating conditions. This Account reviews the recent use of in situ solid-state NMR spectroscopy, a technique that probes local structure and dynamics, to study these devices. In situ NMR studies of lithium-ion batteries are performed on the entire battery, by using a coin cell design, a flat sealed plastic bag, or a cylindrical cell. The battery is placed inside the NMR coil, leads are connected to a potentiostat, and the NMR spectra are recorded as a function of state of charge. (7)Li is used for many of these experiments because of its high sensitivity, straightforward spectral interpretation, and relevance to these devices. For example, (7)Li spectroscopy was used to detect intermediates formed during electrochemical cycling such as LixC and LiySiz species in batteries with carbon and silicon anodes, respectively. It was also used to observe and quantify the formation and growth of metallic lithium microstructures, which can cause short circuits and battery failure. This approach can be utilized to identify conditions that promote dendrite formation and whether different electrolytes and additives can help prevent dendrite formation. The in situ method was also applied to monitor (by (11)B NMR) electrochemical double-layer formation in supercapacitors in real time. Though this method is useful, it comes with challenges. The separation of the contributions from the different cell components in the NMR spectra is not trivial because of overlapping resonances. In addition, orientation-dependent NMR interactions, including the spatial- and orientation-dependent bulk magnetic susceptibility (BMS) effects, can lead to resonance broadening. Efforts to understand and mitigate these BMS effects are discussed in this Account. The in situ NMR investigation of fuel cells initially focused on the surface electrochemistry at the electrodes and the electrochemical oxidation of methanol and CO to CO2 on the Pt cathode. On the basis of the (13)C and (195)Pt NMR spectra of the adsorbates and electrodes, CO adsorbed on Pt and other reaction intermediates and complete oxidation products were detected and their mode of binding to the electrodes investigated. Appropriate design and engineering of the NMR hardware has allowed researchers to integrate intact direct methanol fuel cells into NMR probes. Chemical transformations of the circulating methanol could be followed and reaction intermediates could be detected in real time by either (2)H or (13)C NMR spectroscopy. By use of the in situ NMR approach, factors that control fuel cell performance, such as methanol cross over and catalyst performance, were identified.