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

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

Visible light-driven H2 production over highly dispersed Ruthenia on Rutile TiO2 nanorods

The immobilization of miniscule quantities of RuO2 (~0.1%) onto one-dimensional (1D) TiO2 nanorods (NRs) allows H2 evolution from water under visible light irradiation. Rod-like rutile TiO2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO2 to enable photocatalytic activity in the visible region. The superior performance is rationalized on the basis of fundamental experimental studies and theoretical calculations, demonstrating that RuO2(110) grown as 1D nanowires on rutile TiO2(110), which occurs only at extremely low loads of RuO2, leads to the formation of a heterointerface that efficiently adsorbs visible light. The surface defects, band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers.Peer ReviewedPostprint (published version

Visible Light-Driven H2 Production over Highly Dispersed Ruthenia on Rutile TiO2 Nanorods

The immobilization of miniscule quantities of RuO2 (∼0.1%) onto one-dimensional (1D) TiO2 nanorods (NRs) allows H2 evolution from water under visible light irradiation. Rod-like rutile TiO2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO2 to enable photocatalytic activity in the visible region. The superior performance is rationalized on the basis of fundamental experimental studies and theoretical calculations, demonstrating that RuO2(110) grown as 1D nanowires on rutile TiO2(110), which occurs only at extremely low loads of RuO2, leads to the formation of a heterointerface that efficiently adsorbs visible light. The surface defects, band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers.U.S. Department of Energy DE-SC001270

High Reversibility of Lattice Oxygen Redox in Na-ion and Li-ion Batteries Quantified by Direct Bulk Probes of both Anionic and Cationic Redox Reactions

The reversibility and cyclability of anionic redox in battery electrodes hold the key to its practical employments. Here, through mapping of resonant inelastic X-ray scattering (mRIXS), we have independently quantified the evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. The bulk-Mn redox emerges from initial discharge and is quantified by inverse-partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn activities likely lead to the voltage fade. O-K super-partial fluorescence yield (sPFY) analysis of mRIXS shows 79% lattice oxygen-redox reversibility during initial cycle, with 87% capacity sustained after 100 cycles. In Li1.17Ni0.21Co0.08Mn0.54O2, lattice-oxygen redox is 76% initial-cycle reversible but with only 44% capacity retention after 500 cycles. These results unambiguously show the high reversibility of lattice-oxygen redox in both Li-ion and Na-ion systems. The contrast between Na2/3Mg1/3Mn2/3O2 and Li1.17Ni0.21Co0.08Mn0.54O2 systems suggests the importance of distinguishing lattice-oxygen redox from other oxygen activities for clarifying its intrinsic properties.Comment: 33 pages, 8 Figures. Plus 14 pages of Supplementary Materials with 12 Figure

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 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 0.4, corresponding to the coupling strength of 0.42 eV +/- 40 meV and 0.21 eV +/- 30 meV, for zone center and boundary phonons respectively. The reduced g value for zone-boundary phonon may be related to its double resonance nature.Comment: Main text is 20 pages with 4 figures Supplementary information is 10 pages with 3 figure

Adsorption-controlled growth of BiVO4 by molecular-beam epitaxy

Single-phase epitaxial films of the monoclinic polymorph of BiVO4 were synthesized by reactive molecular-beam epitaxy under adsorption-controlled conditions. The BiVO4 films were grown on (001) yttria-stabilized cubic zirconia (YSZ) substrates. Four-circle x-ray diffraction, scanning transmission electron microscopy (STEM), and Raman spectroscopy confirm the epitaxial growth of monoclinic BiVO4 with an atomically abrupt interface and orientation relationship (001)BiVO4 parallel to (001)(YSZ) with [100]BiVO4 parallel to [100](YSZ). Spectroscopic ellipsometry, STEM electron energy loss spectroscopy (STEM-EELS), and x-ray absorption spectroscopy indicate that the films have a direct band gap of 2.5 +/- 0.1 eV

Lone-pair stabilization in transparent amorphous tin oxides:a potential route to p-type conduction pathways

The electronic and atomic structures of amorphous transparent tin oxides have been investigated by a combination of X-ray spectroscopy and atomistic calculations. Crystalline SnO is a promising p-type transparent oxide semiconductor due to a complex lone-pair hybridization that affords both optical transparency despite a small electronic band gap and spherical s-orbital character at the valence band edge. We find that both of these desirable properties (transparency and s-orbital valence band character) are retained upon amorphization despite the disruption of the layered lone-pair states by structural disorder. We explain the anomalously large band gap widening necessary to maintain transparency in terms of lone-pair stabilization via atomic clustering. Our understanding of this mechanism suggests that continuous hole conduction pathways along extended lone pair clusters should be possible under certain stoichiometries. Moreover, these findings should be applicable to other lone-pair active semiconductors

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 spectrographsare 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