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  1. Here, nanosized electrodes for Li-ion batteries typically display improved electrochemical properties, which are generally attributed to the reduced dimensionality for lithiation. However, the intriguing roles of surface defects and disorder associated with the nanosized materials are often overlooked. Here, combining atomically resolved structural analysis with density functional theory calculations, we reveal that the formation of intrinsic oxygen vacancies near surface in silver hollandite nanorods modifies the local atomic structure and valence state. These surface reconstructions resulted from oxygen vacancies can significantly affect the diffusion pathways in what are otherwise one-dimensional (1D) tunneled structures. On the basis of energy barrier calculations,more » we demonstrate that the oxygen vacancies boost ionic transport through the edge sharing MnO 6 polyhedra in the a–b plane. Thus, within a single rod different from the inherent 1D tunnel diffusion in the interior, the ionic transport at oxygen vacancy decorated surfaces likely adopts a three-dimensional diffusion pathway including both tunnel and planar diffusion.« less
  2. Conversion electrodes, such as magnetite (Fe 3O 4), offer high theoretical capacities (>900 mAh/g) because of multiple electron transfer per metal center. Capacity retention for conversion electrodes has been a challenge in part because of the formation of an insulating surface electrolyte interphase (SEI). This paper provides the first detailed analysis of the lithiation of Fe 3O 4 using isothermal microcalorimetry (IMC). The measured heat flow was compared with heat contributions predicted from heats of formation for the Faradaic reaction, cell polarization, and entropic contributions. The total measured energy output of the cell (7260 J/g Fe 3O 4) exceeded themore » heat of reaction predicted for full lithiation of Fe 3O 4 (5508 J/g). During initial lithiation (3.0–0.86 V), the heat flow was successfully modeled using polarization and entropic contributions. Heat flow at lower voltage (0.86–0.03 V) exceeded the predicted values for iron oxide reduction, consistent with heat generation attributable to electrolyte decomposition and surface electrolyte interphase (SEI). Operando X-ray absorption spectroscopy (XAS) indicated that the oxidation state of the Fe centers deviated from predicted values beginning at ~0.86 V, supportive of SEI onset in this voltage range. Finally and thus, these combined results from electrochemistry, IMC, and XAS indicate parasitic reactions consistent with SEI formation at a moderate voltage and illustrate an approach for deconvoluting Faradaic and non-Faradaic contributions to heat, which should be broadly applicable to the study of energy-storage materials and systems.« less
  3. Here, we report on the synthesis of submicron Li 1+xV 3O 8 fibers through a facile mixed ethanol/water solution-mediated solvothermal route in the absence of surfactants. All the raw materials used are commercially available, relatively inexpensive, and low-toxic, and these can be handled in an ambient atmosphere, rendering this synthetic route as reasonably facile and efficient. To ensure a desirable and acceptable sample crystallinity and purity, we introduced a postannealing treatment at 500°C. The monoclinic phase formation of the fiber sample was probed in detail using a series of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, infrared spectroscopy, X-raymore » photoelectron spectroscopy, high resolution transmission electron microscopy, and selected area electron diffraction measurements. Both morphology and chemical composition could be carefully and systematically tuned in terms of generating a class of novel, pure, and well-defined motifs of Li 1+xV 3O 8. A plausible mechanism for the formation of submicron-diameter fibers has been discussed in addition to the expected phase transformation within our Li-V-O materials. Our comprehensive study should provide for needed fundamental insights into putting forth a viable synthesis strategy for the generation of well-defined morphological variants of layered oxide materials for battery applications.« less
  4. Here, a series of one-dimensional CuFe 2O 4 nano/sub-micron wires possessing different diameters, crystal phases, and crystal sizes have been successfully generated using a facile template-assisted co precipitation reaction at room temperature, followed by a short post-annealing process. The diameter and the crystal structure of the resulting CuFe 2O4 (CFO) wires were judiciously tuned by varying the pore size of the template and the post-annealing temperature, respectively. Carbon nanotubes (CNTs) were incorporated to generate CFO-CNT binder-free anodes, and multiple characterization techniques were employed with the goal of delineating the relationships between electrochemical behavior and the properties of both the CFOmore » wires (crystal phase, wire diameter, crystal size) and the electrode architecture (binder-free vs. conventionally prepared approaches). The study reveals several notable findings. First, the crystal phase (cubic or tetragonal) did not influence the electrochemical behavior in this CFO system. Second, regarding crystallite size and wire diameter, CFO wires with larger crystallite sizes exhibit improved cycling stability, while wires possessing smaller diameters exhibiting higher capacities. Finally, the electrochemical behavior is strongly influenced by the electrode architecture, with CFO-CNT binder-free electrodes demonstrating significantly higher capacities and cycling stability compared to conventionally prepared coatings. The mechanism(s) associated with the high capacities under low current density but limited electrochemical reversibility of CFO electrodes under high current density were probed via x-ray absorption spectroscopy (XAS) mapping with sub-micron spatial resolution for the first time. Results suggest that the capacity of the binder-free electrodes under high rate is limited by the irreversible formation of Cu 0, as well as limited reduction of Fe 3+, to Fe 2+ not Fe 0. The results (1) shed fundamental insight into the reversibility of CuFe 2O 4 materials cycled at high current density and (2) demonstrate that a synergistic effort to control both active material morphology and electrode architecture is an effective strategy for optimizing electrochemical behavior.« less
  5. Future advances in energy storage systems rely on identification of appropriate target materials and deliberate synthesis of the target materials with control of their physiochemical properties in order to disentangling the contributions of distinct properties to the functional electrochemistry. Furthermore, this goal demands systematic inquiry using model materials that provide the opportunity for significant synthetic versatility and control. Ideally, a material family that enables direct manipulation of characteristics including composition, defects and crystallite size while remaining within the defined structural framework would be necessary. Accomplishing this through direct synthetic methods is desirable to minimize the complicating effects of secondary processing.
  6. Doped motifs offer an intriguing structural pathway toward improving conductivity for battery applications. Specifically, Ca-doped, three-dimensional “flower-like” Li 4–xCa xTi 5O 12 (“x” = 0, 0.1, 0.15, and 0.2) micrometer-scale spheres have been successfully prepared for the first time using a simple and reproducible hydrothermal reaction followed by a short calcination process. The products were experimentally characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) mapping, inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge testing. Calcium dopantmore » ions were shown to be uniformly distributed within the LTO structure without altering the underlying “flower-like” morphology. The largest lattice expansion and the highest Ti 3+ ratios were noted with XRD and XPS, respectively, whereas increased charge transfer conductivity and decreased Li +-ion diffusion coefficients were displayed in EIS for the Li 4–xCa xTi 5O 12 (“x” = 0.2) sample. The “x” = 0.2 sample yielded a higher rate capability, an excellent reversibility, and a superior cycling stability, delivering 151 and 143 mAh/g under discharge rates of 20C and 40C at cycles 60 and 70, respectively. In addition, a high cycling stability was demonstrated with a capacity retention of 92% after 300 cycles at a very high discharge rate of 20C. In addition, first-principles calculations based on density functional theory (DFT) were conducted with the goal of further elucidating and understanding the nature of the doping mechanism in this study. The DFT calculations not only determined the structure of the Ca-doped Li 4Ti 5O 12, which was found to be in accordance with the experimentally measured XPD pattern, but also yielded valuable insights into the doping-induced effect on both the atomic and electronic structures of Li 4Ti 5O 12.« less
  7. We present that the oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating “high aspect ratio” LaNiO 3 and LaMnO 3more » nanostructures. As the main focus of our demonstration of principle, we prepared as-synthesized LaNiO 3 rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. In addition, we observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO 3 rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO 2.« less

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