Defect Engineering and Anisotropic Modulation of Ionic Transport in Perovskite Solid Electrolyte LixLa(1-x)/3NbO3.

Solid electrolytes, such as perovskite Li3xLa2/1-xTiO3, LixLa(1-x)/3NbO3 and garnet Li7La3Zr2O12 ceramic oxides, have attracted extensive attention in lithium-ion battery research due to their good chemical stability and the improvability of their ionic conductivity with great potential in solid electrolyte battery applications. These solid oxides eliminate safety issues and cycling instability, which are common challenges in the current commercial lithium-ion batteries based on organic liquid electrolytes. However, in practical applications, structural disorders such as point defects and grain boundaries play a dominating role in the ionic transport of these solid electrolytes, where defect engineering to tailor or improve the ionic conductive property is still seldom reported. Here, we demonstrate a defect engineering approach to alter the ionic conductive channels in LixLa(1-x)/3NbO3 (x = 0.1~0.13) electrolytes based on the rearrangements of La sites through a quenching process. The changes in the occupancy and interstitial defects of La ions lead to anisotropic modulation of ionic conductivity with the increase in quenching temperatures. Our trial in this work on the defect engineering of quenched electrolytes will offer opportunities to optimize ionic conductivity and benefit the solid electrolyte battery applications.

Systematic analysis of electron energy-loss near-edge structures in Li-ion battery materials.

Electrical conductivity, state of charge and chemical stability of Li-ion battery materials all depend on the electronic states of their component atoms, and tools for measuring these reliably are needed for advanced materials analysis and design. Here we report a systematic investigation of electron energy-loss near-edge structures (ELNES) of Li-K and O-K edges for ten representative Li-ion battery electrodes and solid-state electrolytes obtained by performing transmission electron microscopy with a Wien-filter monochromator-equipped microscope. While the peaks of Li-K edges are positioned at about 62 eV for most of the materials examined, the peak positions of O-K edges vary within a range of about 530 to 540 eV, and the peaks can be categorised into three groups based on their characteristic edge shapes: (i) double peaks, (ii) single sharp peaks, and (iii) single broad peaks. The double peaks of group (i) are attributable to the d0 electronic configuration of their transition metal ions bonded to O atoms. The origin of the different peak shapes of groups (ii) and (iii) is more subtle but insights are gained using density functional theory methods to simulate O-K ELNES edges of group (ii) material LiCoO2 and group (iii) material LiFePO4. Comparison of their densities of states reveals that in LiCoO2 the Co-O hybrid orbitals are separated from Li-O hybrid orbitals, resulting in a sharp peak in the O-K edge, while Fe-O, Li-O and P-O hybrid orbitals in LiFePO4 partially overlap each other and produce a broad peak.

One-step synthesis of TiO2 nanorod arrays on Ti foil for supercapacitor application.

Titanium dioxide (TiO2) nanorod arrays grown directly on Ti metal foil were prepared by a facile one-step hydrothermal method, in which the Ti foil serves as both substrate and precursor. The nanorods are tetragonal rutile single crystal with growth orientation along the [001] direction. The electrochemical properties of the TiO2 nanorod arrays were systematically investigated by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy using a three-electrode system. As a result, the TiO2 nanorod arrays exhibit good areal specific capacitance and excellent cyclic stability by retaining more than 98% of the initial specific capacitance after 1000 cycles. In addition, a good flexibility of the Ti foil with TiO2 nanorod arrays was demonstrated by the stable electrochemical performance under different bending angles, which indicates that TiO2 nanorod arrays grown on Ti foil could be a promising electrode material for flexible supercapacitor application.

Atomic-Level Changes during Electrochemical Cycling of Oriented LiMn2O4 Cathodic Thin Films.

Spinel LiMn2O4 is an attractive lithium-ion battery cathode material that undergoes a complex series of structural changes during electrochemical cycling that lead to rapid capacity fading, compromising its long-term performance. To gain insights into this behavior, in this report we analyze changes in epitaxial LiMn2O4 thin films during the first few charge-discharge cycles with atomic resolution and correlate them with changes in the electrochemical properties. Impedance spectroscopy and scanning transmission electron microscopy are used to show that defect-rich LiMn2O4 surfaces contribute greatly to the increased resistivity of the battery after only a single charge. Sequences of {111} stacking faults within the films were also observed upon charging, increasing in number with further cycling. The atomic structures of these stacking faults are reported for the first time, showing that Li deintercalation is accompanied by local oxygen loss and relaxation of Mn atoms onto previously unoccupied sites. The stacking faults have a more compressed structure than the spinel matrix and impede Li-ion migration, which explains the observed increase in thin-film resistivity as the number of cycles increases. These results are used to identify key factors contributing to conductivity degradation and capacity fading in LiMn2O4 cathodes, highlighting the need to develop techniques that minimize defect formation in spinel cathodes to improve cycle performance.

The three-dimensional morphology of nickel nanodots in amorphous silica and their role in high-temperature permselectivity for hydrogen separation.

We report the development of technologically important nickel (Ni) nanodots (nanoparticles) dispersed in amorphous silica (SiO2) for high-temperature permselectivity for hydrogen separation membranes, crucial in hydrocarbon reactions and H(2) production, and present the systematic reconstruction of the three-dimensional (3D) structures of the nanodots using electron nano-tomography. 3D structures using cryogenic high-angle annular dark field scanning transmission electron microscopy (Cryo-HAADF-STEM), which is a more accurate method for nanoparticle morphology than conventional chemisorption, are correlated with experimental reversible hydrogen adsorption properties. The correlations provide the first direct evidence of very high activity on the nanoparticle surface and the nature of adsorption sites. The results have important implications in general for the use of electron nano-tomography in the design of supported metallic nanoparticles for hydrogen separation membranes.

PEDOT coated iron phosphide nanorod arrays as high-performance supercapacitor negative electrodes.

PEDOT coated iron phosphide nanorod arrays are synthesized and demonstrated as high-performance negative electrodes for supercapacitors with high areal specific capacitance and significantly improved cycling stability. A MnO2//FeP/PEDOT aqueous asymmetric supercapacitor is fabricated with a high volumetric capacitance of 4.53 F cm-3 and an energy density of 1.61 mW h cm-3.

Three-Dimensional Cobalt Phosphide Nanowire Arrays as Negative Electrode Material for Flexible Solid-State Asymmetric Supercapacitors.

Despite the great progress that has been accomplished in supercapacitors, the imbalance of the development of positive and negative electrode materials still remains a critical issue to achieve high energy density; therefore, exploring high-performance negative electrode materials is highly desirable. In this article, three-dimensional cobalt phosphide (CoP) nanowire arrays were synthesized on a carbon cloth and were utilized as a binder-free supercapacitor negative electrode. The as-synthesized CoP nanowire arrays presented a high capacitance of 571.3 mF/cm2 at a current density of 1 mA/cm2. By using CoP nanowire arrays as the negative electrode and MnO2 nanowire arrays as the positive electrode, a flexible solid-state asymmetric supercapacitor has been fabricated and has exhibited excellent electrochemical performance, such as a high energy density of 0.69 mWh/cm3 and a high power density of 114.2 mW/cm3. In addition, the solid-state asymmetric supercapacitor shows high cycle stability with 82% capacitance retention after 5000 charge/discharge cycles. This work demonstrates that CoP is a promising negative electrode material for high-performance supercapacitor applications.

Amine/Hydrido Bifunctional Nanoporous Silica with Small Metal Nanoparticles Made Onsite: Efficient Dehydrogenation Catalyst.

Multifunctional catalysts are of great interest in catalysis because their multiple types of catalytic or functional groups can cooperatively promote catalytic transformations better than their constituents do individually. Herein we report a new synthetic route involving the surface functionalization of nanoporous silica with a rationally designed and synthesized dihydrosilane (3-aminopropylmethylsilane) that leads to the introduction of catalytically active grafted organoamine as well as single metal atoms and ultrasmall Pd or Ag-doped Pd nanoparticles via on-site reduction of metal ions. The resulting nanomaterials serve as highly effective bifunctional dehydrogenative catalysts for generation of H2 from formic acid.

Atomic sites and stability of Cs+ captured within zeolitic nanocavities.

Zeolites have potential application as ion-exchangers, catalysts and molecular sieves. Zeolites are once again drawing attention in Japan as stable adsorbents and solidification materials of fission products, such as (137)Cs(+) from damaged nuclear-power plants. Although there is a long history of scientific studies on the crystal structures and ion-exchange properties of zeolites for practical application, there are still open questions, at the atomic-level, on the physical and chemical origins of selective ion-exchange abilities of different cations and detailed atomic structures of exchanged cations inside the nanoscale cavities of zeolites. Here, the precise locations of Cs(+) ions captured within A-type zeolite were analyzed using high-resolution electron microscopy. Together with theoretical calculations, the stable positions of absorbed Cs(+) ions in the nanocavities are identified, and the bonding environment within the zeolitic framework is revealed to be a key factor that influences the locations of absorbed cations.

First-principles calculations of lithium-ion migration at a coherent grain boundary in a cathode material, LiCoO(2).

Results of theoretical calculations are reported, examining the effect of a coherent twin boundary on the electrical properties of LiCoO(2) . This study suggests that internal interfaces in LiCoO(2) strongly affect the battery voltage, battery capacity, and power density of this material, which is of particular concern if it is used in all-solid-state Li-ion batteries.