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The success of high capacity energy storage systems based on lithium (Li) batteries relies on the realization of the promise of Li-metal anodes. Li metal has many advantageous properties, including an extremely high theoretical specific capacity (3860 mAh g–1), the lowest electrochemical potential (–3.040 V versus standard hydrogen electrode), and low density (0.59 g cm–3), which, all together, make it a very desirable electrode for energy storage devices. However, while primary Li batteries are used for numerous commercial applications, rechargeable Li-metal batteries that utilize Li-metal anodes have not been as successful. This article discusses the properties of Li metal in the absence of surface stabilization, as well as three different approaches currently under investigation for stabilizing the surface of Li metal to control its reactivity within the electrochemical environment of a Li-based battery.
Lithium-air batteries have received extraordinary attention recently owing to their theoretical gravimetric energies being considerably higher than those of Li-ion batteries. There are, however, significant challenges to practical implementation, including low energy efficiency, cycle life, and power capability. These are due primarily to the lack of fundamental understanding of oxygen reduction and evolution reaction kinetics and parasitic reactions between oxygen redox intermediate species and nominally inactive battery components such as carbon in the oxygen electrode and electrolytes. In this article, we discuss recent advances in the mechanistic understanding of oxygen redox reactions in nonaqueous electrolytes and the search for electrolytes and electrode materials that are chemically stable in the oxygen electrode. In addition, methods to protect lithium metal against corrosion by water and dendrite formation in aqueous lithium-air batteries are discussed. Further materials innovations lie at the heart of research and development efforts that are needed to enable the development of lithium-oxygen batteries with enhanced round-trip efficiency and cycle life.
Markets for energy storage that go beyond portable electronics have emerged rapidly this decade, including powering electric vehicles and “leveling the grid” fed by renewable sources such as solar energy, which are intermittent in supply. These new demands require a significant step-up in energy density that will probably not be met by Li-ion batteries; estimates suggest they are starting to approach their theoretical limits. But in the world of “beyond Li-ion,” the options are limited. One of the most hopeful is the Li-S battery, for which greater energy storage can potentially be realized through phase-transformation chemistry using elemental sulfur as a positive electrode material, which converts to lithium sulfide. These future generation systems offer up to a five-fold increased specific energy and greatly reduced cost factors, but commercialization has been hindered owing to key challenges. Efforts over the last two years to better manipulate the cell chemistry and overcome these challenges are presented.
This issue contains assessments of battery performance involving complex, interrelated physical and chemical processes between electrode materials and electrolytes. Transformational changes in battery technologies are critically needed to enable the effective use of renewable energy sources such as solar and wind to allow for the expansion of hybrid electric vehicles (HEVs) to plug-in HEVs and pure-electric vehicles. For these applications, batteries must store more energy per unit volume and weight, and they must be capable of undergoing many thousands of charge-discharge cycles. The articles in this theme issue present details of several growing interest areas, including high-energy cathode and anode materials for rechargeable Li-ion batteries and challenges of Li metal as an anode material for Li batteries. They also address the recent progress in systems beyond Li ion, including Li-S and Li-air batteries, which represent possible next-generation batteries for electrical vehicles. One article reviews the recent understanding and new strategies and materials for rechargeable Mg batteries. The knowledge presented in these articles is anticipated to catalyze the design of new multifunctional materials that can be tailored to provide the optimal performance required for future electrical energy storage applications.
“Abundance” is an important keyword in materials development. This is particularly the case for the energy storage sector, where materials themselves function as a storage host. The amount of materials is directly linked to the amount of energy stored in the device. In lithium (Li)-ion batteries, transition metal elements are necessary to accommodate a large number of electrons/holes in a reversible redox reaction. Iron, as the fourth most abundant element in the earth’s crust, is an ideal redox center, but practical storage electrodes with Fe redox have long been the “holy grail” of the Li-ion battery since its commercialization in 1991. In this article, the history of replacing Co with Fe in Li-battery electrodes is briefly reviewed followed by recent technical achievements toward more sustainable batteries using Na+ as a guest ion, where the goal would be to discover a high voltage electrode material composed of Na and Fe without compromising the energy density.
This work presents experimental data on the surface and grain boundary energies of tin dioxide nanoparticles at room temperature and high temperature conditions (quenched from 1300 °C), and a discussion of impacts on the fundamental understanding of the nondensification mechanism of SnO2 during sintering. The results were obtained using a combination of water adsorption microcalorimetry, high-temperature oxide melt drop solution calorimetry, and scanning electron transmission microscopy. At room temperature, the average surface and grain boundary energies of anhydrous SnO2 were 1.20 ± 0.02 and 0.71 ± 0.08 J m−2, respectively. At high temperature, SnO2 showed a surface energy of 0.94 ± 0.03 J m−2. This remarkable decrease was attributed to the lower oxygen pressure and was associated with a decrease in contact angle during sintering. This observation indicates a moderate but significant thermodynamic reason behind nondensification behavior of SnO2 in addition to common kinetic descriptions: high sintering temperatures and atmospheres cause smaller dihedral angles that decrease sintering stresses.
We describe an improved experimental approach for characterizing the elastic modulus and hardness of single microfibers through instrumented indentation. A sample mounting technique on a curved surface is presented that ensures contact between an unmodified fiber and substrate. The indentation analysis considers three separate corrections to the well-known Oliver and Pharr method: (i) overestimation of the projected contact area due to sample curvature, (ii) overestimation of projected contact area due to substrate curvature, and (iii) underestimation of fiber stiffness due to the structural compliance of the sample. The method is applied to four types of high performance ballistic fibers: KM2 Plus, Twaron, AuTx, and Dyneema; the results are presented according to both the modified analyses as well as the standard Oliver and Pharr analysis. The modified analyses resulted in an increase in the elastic modulus and hardness of up to 35 and 60%, respectively, compared to the Oliver–Pharr method. The technique has the potential to be applied to single microfilaments under various environmental conditions that may otherwise be compromised by traditional fiber mounting methods.
The crystal structure of a morimotoite garnet, ideally Ca3(Ti4+Fe2+)Si3O12, from the Ice River alkaline complex, British Columbia, Canada was refined by the Rietveld method, space group $Ia\overline 3 d$, and monochromatic synchrotron high-resolution powder X-ray diffraction (HRPXRD) data. Electron-microprobe analysis indicates a homogeneous sample with a formula {Ca2.91Mg0.05Mn2+0.03}Σ3[Ti1.09Fe3+0.46Fe2+0.37Mg0.08]Σ2(Si2.36Fe3+0.51Al0.14)Σ3O12. The HRPXRD data show a two-phase intergrowth. The reduced χ2 and overall R(F2) Rietveld refinement values are 1.572 and 0.0544, respectively. The weight percentage, unit-cell parameter (Å), distances (Å), and site occupancy factors (sofs) for phase-1 are as follows: 76.5(1)%, a = 12.156 98(1) Å, average <Ca–O> = 2.4383, Ti–O = 2.011(1), Si–O = 1.693(1) Å, Ca(sof) = 0.943(2), Ti(sof) = 0.966(2), and Si(sof) = 1.095(3). The corresponding values for phase-2 are 23.5(1)%, a = 12.160 67(2) Å, average <Ca–O> = 2.452, Ti–O = 1.988(3), Si–O = 1.704(3) Å, Ca(sof) = 1.063(7), Ti(sof) = 1.187(7), and Si(sof) = 1.220(8). The two phases cause strain that arises from structural mismatch and gives rise to low optical anisotropy. Because the two phases are structurally quite similar, a refinement using a single-phase model with anisotropic displacement parameters shows no unusual displacement ellipsoid for the O atom that requires a “split O-atom position”, as was done in previous studies.
In the conventional X-ray reflectivity (XRR) analysis, the reflectivity is calculated based on the Parratt formalism, incorporating the effect of the interface roughness according to Nevot and Croce. However, the results of calculations of the XRR have shown strange outcomes, where interference effects increase at a rough surface because of a lack of consideration of diffuse scattering within the Parratt formalism. Therefore, we have developed a new improved formalism in which the effects of the surface and interface roughness are included correctly. In this study, for deriving a more accurate formalism of XRR, we tried to compare the measurements of surface roughness of the same sample by atomic force microscopy (AFM) and XRR. It is found that the AFM result could not be completely reproduced even with the improved XRR formalism. By careful study of the AFM results, we determined the need for an additional effective roughness term within the XRR simulation that depends on the angle of incidence of the beam.
A very efficient analytical method using an automated fusion machine as sample preparation tool and a wavelength-dispersive X-ray fluorescence (WDXRF) spectrometer for the determination of all the elements of interest for the iron ore industry has been optimized from the ISO 9516-1 standard method. This updated method allows for the simplification of both laboratory and spectrometry processes and so, in comparison with the original International Organization for Standardization (ISO) method, becomes less restrictive in practice. This method was used to prepare a large variety of iron ores and exploration samples from all over the world. Results of the prevailing XRF application based on pure oxide standards as described in the ISO standard method are compared to the results of a unique XRF calibration application based on certified reference materials (CRMs) for iron ores and iron ores exploration materials. The universal sample preparation fusion method for iron ores and exploration samples developed during the first phase of this project was used to select and evaluate a set of CRMs. Selected throughout the world from well-recognized sources, the chosen set of CRMs allows a wide coverage for all the elements of interest of the iron ore industry, excluding tin oxide. This fusion method allows a matrix match for materials from different origins. A critical evaluation of precision and accuracy has been performed against the ISO standard method. Reference materials not included in the calibration (control samples) was also investigated for accuracy evaluation. Furthermore, comparisons will be made between the data collected from this fusion method implemented in combination with a Bruker S4 Explorer WDXRF Spectrometer, and the analytical requirements of ISO. All deviations from the prevailing standard method parameters (calibration, standards, flux, Fluxer, etc.) will also be pointed out and discussed.
A confocal micro-X-ray fluorescence (XRF) method with a vacuum chamber was used for investigation of underfilm corrosion that occurs on a painted steel sheet used for automotive applications. A painted steel sheet was prepared by applying electrodeposition coating onto an electro-galvanized steel sheet with a zinc phosphate conversion coating. The spatial resolution of the confocal micro-XRF was about 10.9 ?m at an energy of 17.4 keV. The phosphorus signal from the zinc phosphate layer was able to be observed nondestructively by measuring under the vacuum condition. Each layer of the painted steel sheet was observed from the depth profile analysis of the characteristic elements of each layer. The painted steel sheet was scratched to expose the substrate surface, and then the sheet was then immersed in a NaCl solution for 10 days. The in-depth elemental map of Ti of the corroded steel sheet revealed blister-type corrosion around the scratch. The in-depth elemental maps of Zn and P suggested that the zinc phosphate layer dissolved from the scratched part into the NaCl solution.