Operando XRD studies on Bi2MoO6as anode material for Na-ion batteries.

Based on the same rocking-chair principle as rechargeable Li-ion batteries, Na-ion batteries are promising solutions for energy storage benefiting from low-cost materials comprised of abundant elements. However, despite the mechanistic similarities, Na-ion batteries require a different set of active materials than Li-ion batteries. Bismuth molybdate (Bi2MoO6) is a promising NIB anode material operating through a combined conversion/alloying mechanism. We report anoperandox-ray diffraction (XRD) investigation of Bi2MoO6-based anodes over 34 (de)sodiation cycles revealing both basic operating mechanisms and potential pathways for capacity degradation. Irreversible conversion of Bi2MoO6to Bi nanoparticles occurs through the first sodiation, allowing Bi to reversibly alloy with Na forming the cubic Na3Bi phase. Preliminary electrochemical evaluation in half-cellsversusNa metal demonstrated specific capacities for Bi2MoO6to be close to 300 mAh g-1during the initial 10 cycles, followed by a rapid capacity decay.OperandoXRD characterisation revealed that the increased irreversibility of the sodiation reactions and the formation of hexagonal Na3Bi are the main causes of the capacity loss. This is initiated by an increase in crystallite sizes of the Bi particles accompanied by structural changes in the electronically insulating Na-Mo-O matrix leading to poor conductivity in the electrode. The poor electronic conductivity of the matrix deactivates the NaxBi particles and prevents the formation of the solid electrolyte interface layer as shown by post-mortem scanning electron microscopy studies.

Caesium for Perovskite Solar Cells: An Overview.

Perovskite solar cells have the potential to revolutionize the world of photovoltaics, and their efficiency close to 23 % on a lab-scale recently certified this novel technology as the one with the most rapidly raising performance per year in the whole story of solar cells. With the aim of improving stability, reproducibility and spectral properties of the devices, in the last three years the scientific community strongly focused on Cs-doping for hybrid (typically, organolead) perovskites. In parallel, to further contrast hygroscopicity and reach thermal stability, research has also been carried out to achieve the development of all-inorganic perovskites based on caesium, the performances of which are rapidly increasing. The potential of caesium is further strengthened when it is used as a modifying agent of charge-carrier layers in solar cells, but also for the preparation of perovskites with peculiar optoelectronic properties for unconventional applications (e.g., in LEDs, photodetectors, sensors, etc.). This Review offers a 360-degree overview on how caesium can strongly tune the properties and performance of perovskites and relative perovskite-based devices.

Unraveling the (De)sodiation Mechanisms of BiFeO3 at a High Rate with Operando XRD.

Development of new anode materials for Na-ion batteries strongly depends on a detailed understanding of their cycling mechanism. Due to instrumental limitations, the majority of mechanistic studies focus on operando materials' characterization at low cycling rates. In this work, we evaluate and compare the (de)sodiation mechanisms of BiFeO3 in Na-ion batteries at different current densities using operando X-ray diffraction (XRD) and ex situ X-ray absorption spectroscopy (XAS). BiFeO3 is a conversion-alloying anode material with a high initial sodiation capacity of ∼600 mAh g-1, when cycled at 0.1 A g-1. It does not change its performance or cycling mechanism, except for minor losses in capacity, when the current density is increased to 1 A g-1. In addition, operando XRD characterization carried out over multiple cycles shows that the Bi ⇋ NaBi (de)alloying reaction and the oxidation of Bi at the interface with the Na-Fe-O matrix are detrimental for cycling stability. The isolated NaBi ⇋ Na3Bi reaction is less damaging to the cycling stability of the material.

(De)sodiation Mechanism of Bi2MoO6 in Na-Ion Batteries Probed by Quasi-Simultaneous Operando PDF and XAS.

Operando characterization can reveal degradation processes in battery materials and are essential for the development of battery chemistries. This study reports the first use of quasi-simultaneous operando pair distribution function (PDF) and X-ray absorption spectroscopy (XAS) of a battery cell, providing a detailed, atomic-level understanding of the cycling mechanism of Bi2MoO6 as an anode material for Na-ion batteries. This material cycles via a combined conversion-alloying reaction, where electrochemically active, nanocrystalline Na x Bi particles embedded in an amorphous Na-Mo-O matrix are formed during the first sodiation. The combination of operando PDF and XAS revealed that Bi obtains a positive oxidation state at the end of desodiation, due to formation of Bi-O bonds at the interface between the Bi particles and the Na-Mo-O matrix. In addition, XAS confirmed that Mo has an average oxidation state of +6 throughout the (de)sodiation process and, thus, does not contribute to the capacity. However, the local environment of Mo6+ changes from tetrahedral coordination in the desodiated state to distorted octahedral in the sodiated state. These structural changes are linked to the poor cycling stability of Bi2MoO6, as flexibility of this matrix allows movement and coalescence of the Na x Bi particles, which is detrimental to the electrochemical stability.

Designing a Safe Electrolyte Enabling Long-Life Li/S Batteries.

Lithium-sulfur (Li/S) batteries suffer from "shuttle" reactions in which soluble polysulfide species continuously migrate to and from the Li metal anode. As a consequence, the loss of active material and reactions at the surface of Li limit the practical applications of Li/S batteries. LiNO3 has been proposed as an electrolyte additive to reduce the shuttle reactions by aiding the formation of a stable solid electrolyte interphase (SEI) at the Li metal, limiting polysulfide shuttling. However, LiNO3 is continuously consumed during cycling, especially at low current rates. Therefore, the Li/S battery cycle life is limited by the LiNO3 concentration in the electrolyte. In this work, an ionic liquid (IL) [N-methyl-(n-butyl)pyrrolidinium bis(trifluoromethylsulfonyl)imide] was used as an additive to enable longer cycle life of Li/S batteries. By tuning the IL concentration, an enhanced stability of the SEI and lower flammability of the solutions were demonstrated, that is, higher safety of the battery. The Li/S cell built with a high sulfur mass loading (4 mg cm-2 ) and containing the IL-based electrolyte demonstrated a stable capacity of 600 mAh g-1 for more than double the number of cycles of a cell containing LiNO3 additive.

Corrigendum: On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites.

This corrects the article DOI: 10.1038/srep31896.

On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites.

The interest of the scientific community on methylammonium lead halide perovskites (MAPbX3, X = Cl, Br, I) for hybrid organic-inorganic solar cells has grown exponentially since the first report in 2009. This fact is clearly justified by the very high efficiencies attainable (reaching 20% in lab scale devices) at a fraction of the cost of conventional photovoltaics. However, many problems must be solved before a market introduction of these devices can be envisaged. Perhaps the most important to be addressed is the lack of information regarding the thermal and thermodynamic stability of the materials towards decomposition, which are intrinsic properties of them and which can seriously limit or even exclude their use in real devices. In this work we present and discuss the results we obtained using non-ambient X-ray diffraction, Knudsen effusion-mass spectrometry (KEMS) and Knudsen effusion mass loss (KEML) techniques on MAPbCl3, MAPbBr3 and MAPbI3. The measurements demonstrate that all the materials decompose to the corresponding solid lead (II) halide and gaseous methylamine and hydrogen halide, and the decomposition is well detectable even at moderate temperatures (~60 °C). Our results suggest that these materials may be problematic for long term operation of solar devices.

Solid Solutions of Rare Earth Cations in Mesoporous Anatase Beads and Their Performances in Dye-Sensitized Solar Cells.

Solid solutions of the rare earth (RE) cations Pr(3+), Nd(3+), Sm(3+), Gd(3+), Er(3+) and Yb(3+) in anatase TiO2 have been synthesized as mesoporous beads in the concentration range 0.1-0.3% of metal atoms. The solid solutions were have been characterized by XRD, SEM, diffuse reflectance UV-Vis spectroscopy, BET and BJH surface analysis. All the solid solutions possess high specific surface areas, up to more than 100 m(2)/g. The amount of adsorbed dye in each photoanode has been determined spectrophotometrically. All the samples were tested as photoanodes in dye-sensitized solar cells (DSSCs) using N719 as dye and a nonvolatile, benzonitrile based electrolyte. All the cells were have been tested by conversion efficiency (J-V), quantum efficiency (IPCE), electrochemical impedance spectroscopy (EIS) and dark current measurements. While lighter RE cations (Pr(3+), Nd(3+)) limit the performance of DSSCs compared to pure anatase mesoporous beads, cations from Sm(3+) onwards enhance the performance of the devices. A maximum conversion efficiency of 8.7% for Er(3+) at a concentration of 0.2% has been achieved. This is a remarkable efficiency value for a DSSC employing N719 dye without co-adsorbents and a nonvolatile electrolyte. For each RE cation the maximum performances are obtained for a concentration of 0.2% metal atoms.