Revealing Nanoscale Chemical Heterogeneities in Polycrystalline Mo-BiVO4 Thin Films.

The activity of polycrystalline thin film photoelectrodes is impacted by local variations of the material properties due to the exposure of different crystal facets and the presence of grain/domain boundaries. Here a multi-modal approach is applied to correlate nanoscale heterogeneities in chemical composition and electronic structure with nanoscale morphology in polycrystalline Mo-BiVO4 . By using scanning transmission X-ray microscopy, the characteristic structure of polycrystalline film is used to disentangle the different X-ray absorption spectra corresponding to grain centers and grain boundaries. Comparing both spectra reveals phase segregation of V2 O5 at grain boundaries of Mo-BiVO4 thin films, which is further supported by X-ray photoelectron spectroscopy and many-body density functional theory calculations. Theoretical calculations also enable to predict the X-ray absorption spectral fingerprint of polarons in Mo-BiVO4 . After photo-electrochemical operation, the degraded Mo-BiVO4 films show similar grain center and grain boundary spectra indicating V2 O5 dissolution in the course of the reaction. Overall, these findings provide valuable insights into the degradation mechanism and the impact of material heterogeneities on the material performance and stability of polycrystalline photoelectrodes.

Disparate Exciton-Phonon Couplings for Zone-Center and Boundary Phonons in Solid-State Graphite.

The exciton-phonon coupling in highly oriented pyrolytic graphite is studied using resonant inelastic x-ray scattering (RIXS) spectroscopy. With ∼70 meV energy resolution, multiple low energy excitations associated with coupling to phonons can be clearly resolved in the RIXS spectra. Using resonance dependence and the closed form for RIXS cross section without considering the intermediate state mixing of phonon modes, the dimensionless coupling constant g is determined to be 5 and 0.35, corresponding to the coupling strength of 0.42 eV+/-20 meV and 0.20 eV+/-20 meV, for zone center and boundary phonons, respectively. The reduced g value for the zone-boundary phonon may be related to its double resonance nature.

Simultaneous Structural and Electronic Transitions in Epitaxial VO_{2}/TiO_{2}(001).

Recent reports have identified new metaphases of VO_{2} with strain and/or doping, suggesting the structural phase transition and the metal-to-insulator transition might be decoupled. Using epitaxially strained VO_{2}/TiO_{2} (001) thin films, which display a bulklike abrupt metal-to-insulator transition and rutile to monoclinic transition structural phase transition, we employ x-ray standing waves combined with hard x-ray photoelectron spectroscopy to simultaneously measure the structural and electronic transitions. This x-ray standing waves study elegantly demonstrates the structural and electronic transitions occur concurrently within experimental limits (±1 K).

Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi0.8Co0.15Al0.05O2.

Enabling practical utilization of layered R3̅m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode-electrolyte interactions that often induce failure. Using Li[Ni0.8Co0.15Al0.05]O2 (NCA) as a model layered compound, the chemical and structural stability in a strenuous thermal and electrochemical environment was explored. Operando microcalorimetry and electrochemical impedance spectroscopy identified a fingerprint for a structural decomposition and transition-metal dissolution reaction that occurs on the positive electrode at full delithiation. Surface-sensitive characterization techniques, including X-ray absorption spectroscopy and high-resolution transmission electron microscopy, measured a structural and morphological transformation of the surface and subsurface regions of NCA. Despite the bulk structural integrity being maintained, NCA surface degradation at a high state of charge induces excessive transition-metal dissolution and significant positive electrode impedance development, resulting in a rapid decrease in electrochemical performance. Additionally, the impact of electrolyte salt, positive electrode surface area, and surface Li2CO3 content on the magnitude and character of the dissolution reaction was studied.

Three-dimensional ruthenium-doped TiO2 sea urchins for enhanced visible-light-responsive H2 production.

Three-dimensional (3D) monodispersed sea urchin-like Ru-doped rutile TiO2 hierarchical architectures composed of radially aligned, densely-packed TiO2 nanorods have been successfully synthesized via an acid-hydrothermal method at low temperature without the assistance of any structure-directing agent and post annealing treatment. The addition of a minuscule concentration of ruthenium dopants remarkably catalyzes the formation of the 3D urchin structure and drives the enhanced photocatalytic H2 production under visible light irradiation, not possible on undoped and bulk rutile TiO2. Increasing ruthenium doping dosage not only increases the surface area up to 166 m(2) g(-1) but also induces enhanced photoresponse in the regime of visible and near infrared light. The doping introduces defect impurity levels, i.e. oxygen vacancy and under-coordinated Ti(3+), significantly below the conduction band of TiO2, and ruthenium species act as electron donors/acceptors that accelerate the photogenerated hole and electron transfer and efficiently suppress the rapid charge recombination, therefore improving the visible-light-driven activity.

Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes.

The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na0.6[Li0.2Mn0.8]O2 and compare it with Na2/3[Mg1/3Mn2/3]O2. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na0.6[Li0.2Mn0.8]O2 stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na2/3[Mg1/3Mn2/3]O2. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes.

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering.

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques.

Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials.

Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. We demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and rate performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.The performance of lithium-excess cation-disordered oxides as cathode materials relies on the extent to which the oxygen loss during cycling is mitigated. Here, the authors show that incorporating fluorine is an effective strategy which substantially improves the cycling stability of such a material.

High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source.

An endstation with two high-efficiency soft x-ray spectrographs was developed at Beamline 8.0.1 of the Advanced Light Source, Lawrence Berkeley National Laboratory. The endstation is capable of performing soft x-ray absorption spectroscopy, emission spectroscopy, and, in particular, resonant inelastic soft x-ray scattering (RIXS). Two slit-less variable line-spacing grating spectrographs are installed at different detection geometries. The endstation covers the photon energy range from 80 to 1500 eV. For studying transition-metal oxides, the large detection energy window allows a simultaneous collection of x-ray emission spectra with energies ranging from the O K-edge to the Ni L-edge without moving any mechanical components. The record-high efficiency enables the recording of comprehensive two-dimensional RIXS maps with good statistics within a short acquisition time. By virtue of the large energy window and high throughput of the spectrographs, partial fluorescence yield and inverse partial fluorescence yield signals could be obtained for all transition metal L-edges including Mn. Moreover, the different geometries of these two spectrographs (parallel and perpendicular to the horizontal polarization of the beamline) provide contrasts in RIXS features with two different momentum transfers.

The Anode Challenge for Lithium-Ion Batteries: A Mechanochemically Synthesized Sn-Fe-C Composite Anode Surpasses Graphitic Carbon.

Carbon-based anodes are the key limiting factor in increasing the volumetric capacity of lithium-ion batteries. Tin-based composites are one alternative approach. Nanosized Sn-Fe-C anode materials are mechanochemically synthesized by reducing SnO with Ti in the presence of carbon. The optimum synthesis conditions are found to be 1:0.25:10 for initial ratio of SnO, Ti, and graphite with a total grinding time of 8 h. This optimized composite shows excellent extended cycling at the C/10 rate, delivering a first charge capacity as high as 740 mAh g-1 and 60% of which still remained after 170 cycles. The calculated volumetric capacity significantly exceeds that of carbon. It also exhibits excellent rate capability, delivering volumetric capacity higher than 1.6 Ah cc-1 over 140 cycles at the 1 C rate.

Perovskite Sr-Doped LaCrO3 as a New p-Type Transparent Conducting Oxide.

Epitaxial La1-x Srx CrO3 deposited on SrTiO3 (001) is shown to be a p-type transparent conducting oxide with competitive figures of merit and a cubic perovskite structure, facilitating integration into oxide electronics. Holes in the Cr 3d t2g bands play a critical role in enhancing p-type conductivity, while transparency to visible light is maintained because low-lying d-d transitions arising from hole doping are dipole forbidden.