Structural Distortion in the Wadsley-Roth Niobium Molybdenum Oxide Phase Triggering Extraordinarily Stable Battery Performance.

Wadsley-Roth niobium oxide phases have attracted extensive research interest recently as promising battery anodes. We have synthesized the niobium-molybdenum oxide shear phase (Nb, Mo)13 O33 with superior electrochemical Li-ion storage performance, including an ultralong cycling lifespan of at least 15000 cycles. During electrochemical cycling, a reversible single-phase solid-solution reaction with lithiated intermediate solid solutions is demonstrated using in situ X-ray diffraction, with the valence and short-range structural changes of the electrode probed by in situ Nb and Mo K-edge X-ray absorption spectroscopy. This work reveals that the superior stability of niobium molybdenum oxides is underpinned by changes in octahedral distortion during electrochemical reactions, and we report an in-depth understanding of how this stabilizes the oxide structure during cycling with implications for future long-life battery material design.

Designing a hybrid electrode toward high energy density with a staged Li+ and PF6 - deintercalation/intercalation mechanism.

Existing lithium-ion battery technology is struggling to meet our increasing requirements for high energy density, long lifetime, and low-cost energy storage. Here, a hybrid electrode design is developed by a straightforward reengineering of commercial electrode materials, which has revolutionized the "rocking chair" mechanism by unlocking the role of anions in the electrolyte. Our proof-of-concept hybrid LiFePO4 (LFP)/graphite electrode works with a staged deintercalation/intercalation mechanism of Li+ cations and PF6 - anions in a broadened voltage range, which was thoroughly studied by ex situ X-ray diffraction, ex situ Raman spectroscopy, and operando neutron powder diffraction. Introducing graphite into the hybrid electrode accelerates its conductivity, facilitating the rapid extraction/insertion of Li+ from/into the LFP phase in 2.5 to 4.0 V. This charge/discharge process, in turn, triggers the in situ formation of the cathode/electrolyte interphase (CEI) layer, reinforcing the structural integrity of the whole electrode at high voltage. Consequently, this hybrid LFP/graphite-20% electrode displays a high capacity and long-term cycling stability over 3,500 cycles at 10 C, superior to LFP and graphite cathodes. Importantly, the broadened voltage range and high capacity of the hybrid electrode enhance its energy density, which is leveraged further in a full-cell configuration.

A Long Cycle-Life High-Voltage Spinel Lithium-Ion Battery Electrode Achieved by Site-Selective Doping.

Spinel LiNi0.5 Mn1.5 O4 (LNMO) is a promising cathode candidate for the next-generation high energy-density lithium-ion batteries (LIBs). Unfortunately, the application of LNMO is hindered by its poor cycle stability. Now, site-selectively doped LNMO electrode is prepared with exceptional durability. In this work, Mg is selectively doped onto both tetrahedral (8a) and octahedral (16c) sites in the Fd 3 ‾ m structure. This site-selective doping not only suppresses unfavorable two-phase reactions and stabilizes the LNMO structure against structural deformation, but also mitigates the dissolution of Mn during cycling. Mg-doped LNMOs exhibit extraordinarily stable electrochemical performance in both half-cells and prototype full-batteries with novel TiNb2 O7 counter-electrodes. This work pioneers an atomic-doping engineering strategy for electrode materials that could be extended to other energy materials to create high-performance devices.

P2-Na(x)VO2 system as electrodes for batteries and electron-correlated materials.

Layered oxides are the subject of intense studies either for their properties as electrode materials for high-energy batteries or for their original physical properties due to the strong electronic correlations resulting from their unique structure. Here we present the detailed phase diagram of the layered P2-Na(x)VO(2) system determined from electrochemical intercalation/deintercalation in sodium batteries and in situ X-ray diffraction experiments. It shows that four main single-phase domains exist within the 0.5≤x≤0.9 range. During the sodium deintercalation (intercalation), they differ from one another in the sodium/vacancy ordering between the VO(2) slabs, which leads to commensurable or incommensurable superstructures. The electrochemical curve reveals that three peculiar compositions exhibit special structures for x = 1/2, 5/8 and 2/3. The detailed structural characterization of the P2-Na(1/2)VO(2) phase shows that the Na(+) ions are perfectly ordered to minimize Na(+)/Na(+) electrostatic repulsions. Within the VO(2) layers, the vanadium ions form pseudo-trimers with very short V-V distances (two at 2.581 Å and one at 2.687 Å). This original distribution leads to a peculiar magnetic behaviour with a low magnetic susceptibility and an unexpected low Curie constant. This phase also presents a first-order structural transition above room temperature accompanied by magnetic and electronic transitions. This work opens up a new research domain in the field of strongly electron-correlated materials. From the electrochemical point of view this system may be at the origin of an entire material family optimized by cationic substitutions.

Photocatalytic water oxidation by a pyrochlore oxide upon irradiation with visible light: rhodium substitution into yttrium titanate.

A stable visible-light-driven photocatalyst (λ≥450 nm) for water oxidation is reported. Rhodium substitution into the pyrochlore Y2 Ti2 O7 is demonstrated by monitoring Vegard's law evolution of the unit-cell parameters with changing rhodium content, to a maximum content of 3 % dopant. Substitution renders the solid solutions visible-light active. The overall rate of oxygen evolution is comparable to WO3 but with superior light-harvesting and surface-area-normalized turnover rates, making Y2 Ti1.94 Rh0.06 O7 an excellent candidate for use in a Z-scheme water-splitting system.

O'3-Na(x)VO2 system: a superstructure for Na(1/2)VO2.

The electrochemical cycling in a sodium battery of the lamellar oxide NaVO(2) is reversible in the Na(x)VO(2) composition range 1/2 ≤ x ≤ 1. The complex electrochemical curve reveals the presence of several transitions taking place during deintercalation. With the help of in situ X-ray diffraction, we observed the structural transitions taking place between Na(2/3)VO(2) and Na(1/2)VO(2). The diffractograms show the presence of several monophasic domains separated by biphasic domains. All phases present a monoclinic distortion of the α-NaFeO(2) structure in the composition range 1/2 ≤ x ≤ 2/3. Moreover the presence of a superstructure is evidenced for Na(1/2)VO(2). It is the first time that an ordered structure is reported at the Na(1/2)MO(2) composition with an O'3 oxygen stacking. A thorough investigation of electrochemically obtained O'3-Na(1/2)VO(2) was performed. The structure refinement reveals the existence of a sodium/vacancy ordering, with a peculiar arrangement of the V-V distances hinting at a pairing of vanadium atoms. Our first measurements of the physical properties of O'3-Na(1/2)VO(2) show a semiconductor behavior and a complex thermal dependence of the magnetic susceptibility related to the pairing of the vanadium atoms.

Preparation of pyrite concentrate powder from the Thackaringa mine for quantitative phase analysis using X-ray diffraction.

The quantitative phase analysis using X-ray diffraction of pyrite ore concentrate samples extracted from the Thackaringa mine is problematic due to poor particle statistics, microabsorption and preferred orientation. The influence of sample preparation on these issues has been evaluated, with ball milling of the powder found most suitable for accurate and precise quantitative phase analysis. The milling duration and other aspects of sample preparation have been explored, resulting in accurate phase reflection intensities when particle sizes are below 5 µm. Quantitative phase analysis on those samples yielded precise phase fractions with standard deviations below 0.3 wt%. Some discrepancy between the elemental composition obtained using X-ray powder diffraction data and that determined using wavelength-dispersive X-ray fluorescence was found, and is thought to arise from unaccounted for crystalline phase substitution and the possible presence of an amorphous phase. This study provides a methodology for the precise and accurate quantitative phase analysis of X-ray powder diffraction data of pyrite ore concentrate from the Thackaringa mine and a discussion of the limitations of the method. The optimization process reveals the importance of confirming reproducibility on new samples, with as much prior knowledge as possible.

Understanding Rechargeable Battery Function Using In Operando Neutron Powder Diffraction.

The performance of rechargeable batteries is influenced by the structural and phase changes of components during cycling. Neutron powder diffraction (NPD) provides unique and useful information concerning the structure-function relation of battery components and can be used to study the changes to component phase and structure during battery cycling, known as in operando measurement studies. The development and use of NPD for in operando measurements of batteries is summarized along with detailed experimental approaches that impact the insights gained by these. A summary of the information gained concerning battery function using in operando NPD measurements is provided, including the structural and phase evolution of electrode materials and charge-carrying ion diffusion pathways through these, which are critical to the development of battery technology.

Postmining management in france: situation and perspectives.

Even if most French mines are definitively closed, potential risks remain above the abandoned sites. In addition to surface instability, some mining sites may be affected by dangerous gas emissions, flooding events, or environmental impacts. Those kinds of disorders strongly influence the land-use management of the concerned areas. The present article presents the French mining historical context and identifies the major kinds of residual risks and harmful effects that may affect abandoned mine sites. The prevention policy applied on the national territory is then discussed and prospects for further developments are proposed.