The maximum power output and minimum charging time of a lithium-ion battery depend on both ionic and electronic transport. Ionic diffusion within the electrochemically active particles generally represents a fundamental limitation to the rate at which a battery can be charged and discharged. To compensate for the relatively slow solid-state ionic diffusion and to enable high power and rapid charging, the active particles are frequently reduced to nanometre dimensions, to the detriment of volumetric packing density, cost, stability and sustainability. As an alternative to nanoscaling, here we show that two complex niobium tungsten oxides-NbWO and NbWO, which adopt crystallographic shear and bronze-like structures, respectively-can intercalate large quantities of lithium at high rates, even when the sizes of the niobium tungsten oxide particles are of the order of micrometres. Measurements of lithium-ion diffusion coefficients in both structures reveal room-temperature values that are several orders of magnitude higher than those in typical electrode materials such as LiTiO and LiMnO. Multielectron redox, buffered volume expansion, topologically frustrated niobium/tungsten polyhedral arrangements and rapid solid-state lithium transport lead to extremely high volumetric capacities and rate performance. Unconventional materials and mechanisms that enable lithiation of micrometre-sized particles in minutes have implications for high-power applications, fast-charging devices, all-solid-state energy storage systems, electrode design and material discovery.
(1)H and (19)F NMR experiments have identified and quantified the internal surface terminations of Ti3C2Tx MXene. -F and -OH terminations are shown to be intimately mixed and there are found to be significantly fewer -OH terminations than -F and -O, with the proportions highly dependent on the synthesis method.
The nickel-rich layered oxide LiNi0.8Mn0.1Co0.1O2 (NMC811) is a promising future cathode material for lithium-ion batteries in electric vehicles due to its high specific energy density. However, it exhibits fast voltage and capacity fading. In this article, we combine electrochemistry, operando synchrotron X-ray diffraction (XRD), and ex situ solid-state NMR spectroscopy to provide new insights into the structural changes and lithium dynamics of NMC811 during electrochemical charge and discharge, which are essential for a better understanding of its fast degradation. The evolution of the interlayer spacing is tracked by XRD, showing that it gradually increases upon delithiation before collapsing at high state-of-charge (SOC). Importantly, no two-phase O3→O1 transition is observed at high SOC, demonstrating that this cannot be a major cause of degradation. A strong increase of Li dynamics accompanies the increase of the interlayer spacing, which is shown by 7 Li NMR and electrochemical characterization. At high SOC, Li mobility drops considerably, and Li/vacancy ordering can be observed by NMR. A detailed analysis of 7 Li NMR spectra at different SOC is provided, demonstrating how Li NMR can be used to extract information on the dynamics of such challenging paramagnetic samples with several hundred different local Li environments. The insights on the evolution of structure and dynamics of NMC811 will further the understanding of its cycling behavior and contribute to the efforts of mitigating its performance fade.
Nanostructuring and nanosizing have been widely employed to increase the rate capability in a variety of energy storage materials. While nanoprocessing is required for many materials, we show here that both the capacity and rate performance of low-temperature bronze-phase TT- and T-polymorphs of Nb2O5 are inherent properties of the bulk crystal structure. Their unique "room-and-pillar" NbO6/NbO7 framework structure provides a stable host for lithium intercalation; bond valence sum mapping exposes the degenerate diffusion pathways in the sites (rooms) surrounding the oxygen pillars of this complex structure. Electrochemical analysis of thick films of micrometer-sized, insulating niobia particles indicates that the capacity of the T-phase, measured over a fixed potential window, is limited only by the Ohmic drop up to at least 60C (12.1 A·g(-1)), while the higher temperature (Wadsley-Roth, crystallographic shear structure) H-phase shows high intercalation capacity (>200 mA·h·g(-1)) but only at moderate rates. High-resolution (6/7)Li solid-state nuclear magnetic resonance (NMR) spectroscopy of T-Nb2O5 revealed two distinct spin reservoirs, a small initial rigid population and a majority-component mobile distribution of lithium. Variable-temperature NMR showed lithium dynamics for the majority lithium characterized by very low activation energies of 58(2)-98(1) meV. The fast rate, high density, good gravimetric capacity, excellent capacity retention, and safety features of bulk, insulating Nb2O5 synthesized in a single step at relatively low temperatures suggest that this material not only is structurally and electronically exceptional but merits consideration for a range of further applications. In addition, the realization of high rate performance without nanostructuring in a complex insulating oxide expands the field for battery material exploration beyond conventional strategies and structural motifs.
Improving electrochemical energy storage is one of the major issues of our time. The search for new battery materials together with the drive to improve performance and lower cost of existing and new batteries is not without its challenges. Success in these matters is undoubtedly based on first understanding the underlying chemistries of the materials and the relations between the components involved. A combined application of experimental and theoretical techniques has proven to be a powerful strategy to gain insights into many of the questions that arise from the "how do batteries work and why do they fail" challenge. In this Review, we highlight the application of solid-state nuclear magnetic resonance (NMR) spectroscopy in battery research: a technique that can be extremely powerful in characterizing local structures in battery materials, even in highly disordered systems. An introduction on electrochemical energy storage illustrates the research aims and prospective approaches to reach these. We particularly address "NMR in battery research" by giving a brief introduction to electrochemical techniques and applications as well as background information on both in and ex situ solid-state NMR spectroscopy. We will try to answer the question "Is NMR suitable and how can it help me to solve my problem?" by shortly reviewing some of our recent research on electrodes, microstructure formation, electrolytes and interfaces, in which the application of NMR was helpful. Finally, we share hands-on experience directly from the lab bench to answer the fundamental question "Where and how should I start?" to help guide a researcher's way through the manifold possible approaches.
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