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For reasons of cost and supply security issues, there is growing interest in the development of rechargeable sodium ion batteries, particularly for large-scale grid storage applications. Like the much better known and technologically important lithium ion analogs, the devices operate by shuttling alkali metal cations between two host materials, which undergo insertion processes at different electrochemical potentials. A particular challenge for the sodium systems is identification of a suitable anode material due to the fact that sodium does not intercalate into graphite. Although several alternatives, including disordered carbons and alloys are being investigated, the most promising options at present lie with titanates, not in the least because of attractive characteristics such as low toxicity, ease of synthesis, wide availability, and low cost. A large variety of sodium titanate compounds can be prepared, many of which have tunnel or layered structures that can readily undergo reversible reductive intercalation reactions. A brief overview of the physical, structural, and electrochemical characteristics of several of the most promising materials for sodium-ion battery applications is given in this paper, and a comparison is made between the sodium and the lithium insertion behaviors. For some of these compounds, insertion of sodium occurs at unusually low potentials, a feature that has important implications for the design of high-energy sodium-ion systems.

The complexity of layered-spinelyLi2MnO3·(1 –y)Li1+xMn2–xO4(Li:Mn = 1.2:1; 0 ≤x≤ 0.33;y≥ 0.45) composites synthesized at different temperatures has been investigated by a combination of x-ray diffraction (XRD), x-ray absorption spectroscopy (XAS), and nuclear magnetic resonance (NMR). While the layered component does not change substantially between samples, an evolution of the spinel component from a high to a low lithium excess phase has been traced with temperature by comparing with data for pure Li1+xMn2–xO4. The changes that occur to the structure of the spinel component and to the average oxidation state of the manganese ions within the composite structure as lithium is electrochemically removed in a battery have been monitored using these techniques, in some cases in situ. Our6Li NMR results constitute the first direct observation of lithium removal from Li2MnO3and the formation of LiMnO2upon lithium reinsertion.

In situ techniques with high temporal, spatial and chemical resolution are key to understand ubiquitous solid-state phase transformations, which are crucial to many technological applications. Hard X-ray spectro-imaging can visualize electrochemically driven phase transformations but demands considerably large samples with strong absorption signal so far. Here we show a conceptually new data analysis method to enable operando visualization of mechanistically relevant weakly absorbing samples at the nanoscale and study electrochemical reaction dynamics of iron fluoride, a promising high-capacity conversion cathode material. In two specially designed samples with distinctive microstructure and porosity, we observe homogeneous phase transformations during both discharge and charge, faster and more complete Li-storage occurring in porous polycrystalline iron fluoride, and further, incomplete charge reaction following a pathway different from conventional belief. These mechanistic insights provide guidelines for designing better conversion cathode materials to realize the promise of high-capacity lithium-ion batteries., Hard X-ray spectro-imaging using synchrotron radiation can be used to monitor electrochemical reactions. Here, the authors present X-ray absorption data and resolve phase evolution for the conversion of iron fluoride, a high-capacity Li-ion battery conversion cathode, with nanoscale resolution.

The magnetic properties of layered LiNi0.5Mn0.5O2 and NaNi0.5Mn0.5O2 cathode materials are studied using AC susceptibility and DC magnetization techniques in order to elucidate magnetic interactions within transition metal (TM) layers and between them in samples with various TM distributions. In NaNi0.5Mn0.5O2 antiferromagnetic (AF) ordering transition is found at 60 K and a spin-flop transition at high magnetic field. In LiNi0.5Mn0.5O2 obtained by ion exchange from NaNi0.5Mn0.5O2 ferrimagnetic ordering is found at around 100 K. The saturation magnetization and the hysteresis loop size of ion-exchanged compounds vary from sample to sample, which implies that the Ni2+ ions migrate upon ion exchange process. Magnetic properties of high-temperature and ion-exchanged LiNi0.5Mn0.5O2 are compared; magnetic ordering models for all compounds are proposed based on experimental results and Goodenough-Kanamori rules.