In situ PDF and solid-state NMR studies of antimony anodes for Na-ion batteries

Sodium-ion batteries have attracted attention in recent years because of the natural abundance of sodium compared to lithium, making them particularly attractive in applications such as large-scale grid storage where low cost and sustainability, rather than light weight is the key issue [1]. Several materials have been suggested as cathodes but far fewer studies have been done on anode materials and, because of the reluctance of sodium to intercalate into graphite, the anode material of choice in commercial lithium-ion batteries, the anode represents a significant challenge to this technology. Materials which form alloys with sodium, particularly tin and antimony, have been suggested as anode materials; their ability to react with multiple sodium ions per metal-atom give potential for high gravimetric capacities[2]. However, relatively little is known about the reaction mechanism in the battery, primarily due to drastic reduction in crystallinity during (dis)charging conditions, but also because the structures formed on electrochemical cycling may not be alloys known to exist under ambient conditions. In this study, we present a study of antimony as an anode in sodium-ion batteries, using in situ pair distribution function (PDF) analysis combined with ex situ solid-state nuclear magnetic resonance studies. PDF experiments were performed at 11-ID-B, APS using the AMPIX electrochemical cell [3], cycling against sodium metal. Inclusion of diffuse scattering in analysis is able to circumvent some of the issues of crystallinity loss, and gain information about the local structure in all regions, independent of the presence of long-range order in the material. This approach has been used to probe local correlations in previously uncharacterised regions of the electrochemical profile and analyse phase progression over the full charge cycle. This analysis has been linked with ex situ 23Na solid-state NMR experiments to examine the local environment of the sodium; these show evidence of known NaxSb phases but indicate additional metastable phases may be present at partial discharge.

Phase transition of nanoparticulate LiFePO₄ during high rate cycling

A fundamental understanding of an electrode material requires the elucidation of its phase transformation mechanism during charge and discharge. Ex situ methods, which are carried out under equilibrium condition, have been widely used in charactering the thermodynamic phases at different states of charge, from which a thermodynamic phase transformation pathway can be constructed. However, ex situ measurements do not always reflect the process occurred in an operating battery as the non-equilibrium operating condition might result in deviations from the thermodynamic process, especially for high-rate materials, such as LiFePO4, which is predicted to exhibit a fundamentally different phase transformation process at high rates [1,2]. To probe the process at high rate, an in situ method with reasonable temporal resolution must be employed. In this work, the high rate galvanostatic cycling process of LiFePO4 nanoparticle electrode in a customised AMPIX cell [3] was investigated in situ by time-resolved synchrotron X-ray powder diffraction. Formation of continuous non-equilibrium solid solution phases between LiFePO4 and FePO4 was observed at 10 C rate. The in situ diffraction patterns were analysed by a refinement strategy that accounts for the asymmetrical diffraction peak profiles due to Li composition variations.

Electrochemical Conversion: Beyond the First Cycle

Conversion based electrode materials offer increased energy storage compared to conventional intercalation materials due to the multiple electrons that reacts per metal ion. However, loss in capacities upon repeated cycling has limited the development of this technology for commercial application. Most structural studies focus on the first discharge-charge cycle [1,2,3]. To understand the loss in capacities with repeated cycling, studies must be extended beyond the first cycle. In conversion reactions, large structural transformations occur such that the electrode is reduced to the nanoscale. Pair distribution function (PDF) analysis is well suited to characterize the structural changes occurring in such nanomaterials. Conversion based iron fluorides (FeF3, FeF2, and FeOF) have been a focus of both structural and mechanistic studies [1,2,3]. An in-depth PDF analysis of what happens beyond the first cycle will be presented for these.

From atoms to electrodes: Mesoscale effects in electrochemical conversion

Batteries are complex multicomponent devices wherein mesoscale phenomena-the nanoscale structure and chemistry of different components, and interactions thereof-drive functionality and performance. For example, electron/ion transport within the composite electrodes relies on bi-continuous nanostructuring to form electrically and ionicly conductive paths. Electrochemical conversion of different salts of a given metal yields a common and ostensibly identical product: the zero valent metal. For example, maximal lithiation of iron-based electrodes produces metallic iron nanoparticles for oxide, fluoride, and oxyfluoride electrodes alike. Accordingly, these provide an opportunity to explore the coupling of nanostructure development and anion chemistry, and correlate these with electrochemical performance. We combine synchrotron-based small angle X-ray scattering (SAXS) and pair distribution function (PDF) measurements to probe metallic iron formed by electrochemical conversion of different iron compounds across multiple length-scales and decouple the influence of anion chemistry and reaction temperature on the atomic structure and nanoscale morphology.