Correction: 5D total scattering computed tomography reveals the full reaction mechanism of a bismuth vanadate lithium ion battery anode.

Correction for '5D total scattering computed tomography reveals the full reaction mechanism of a bismuth vanadate lithium ion battery anode' by Jonas Sottmann et al., Phys. Chem. Chem. Phys., 2022, 24, 27075-27085, https://doi.org/10.1039/D2CP03892G.

5D total scattering computed tomography reveals the full reaction mechanism of a bismuth vanadate lithium ion battery anode.

We have used operando 5D synchrotron total scattering computed tomography (TSCT) to understand the cycling and possible long term deactivation mechanisms of the lithium-ion battery anode bismuth vanadate. This anode material functions via a combined conversion/alloying mechanism in which nanocrystals of lithium-bismuth alloy are protected by an amorphous matrix of lithium vanadate. This composite is formed in situ during the first lithiation of the anode. The operando TSCT data were analyzed and mapped using both pair distribution function and Rietveld methods. We can follow the lithium-bismuth alloying reaction at all stages, gaining real structural insight including variations in nanoparticle sizes, lattice parameters and bond lengths, even when the material is completely amorphous. We also observe for the first time structural changes related to the cycling of lithium ions in the lithium vanadate matrix, which displays no interactions beyond the first shell of V-O bonds. The first 3D operando mapping of the distribution of different materials in an amorphous anode reveals a decline in coverage caused by either agglomeration or partial dissolution of the active material, hinting at the mechanism of long term deactivation. The observations from the operando experiment are backed up by post mortem transmission electron microscope (TEM) studies and theoretical calculations to provide a complete picture of an exceptionally complex cycling mechanism across a range of length scales.

Sr2Fe1+xRe1-xO6 double perovskites: magnetoresistance and (magneto)thermopower.

Polycrystalline Sr2Fe1+xRe1-xO6 samples have been synthesized and structurally characterized by X-ray powder diffraction, transmission electron microscopy and X-ray absorption spectroscopy. Resistivity strongly increases with x, but a large and negative magnetoresistance persists up to x = 0.33. This is discussed considering the charge delocalization in iron and rhenium t2g orbitals.

Operando investigations of lithiation and delithiation processes in a BiVO4 anode material.

BiVO4 undergoes a series of conversion and alloying reactions as an anode material in lithium ion batteries. The current work demonstrates a charge capacity of 485 mA h g-1 after 50 cycles in a voltage range of 0-2.00 V (graphite has a capacity of 372 mA h g-1 theoretically). An exceptionally high volumetric capacity makes BiVO4 suitable for compact applications (volumetric capacity of 3984 mA h cm-3 for BiVO4 in comparison to 756 mA h cm-3 for graphite theoretically). Reaction steps and electronic transformations have been identified by operando quasi simultaneous synchrotron X-ray diffraction and absorption spectroscopy studies. An irreversible reaction step occurs for the Bi3+/Bi0 redox pair, whereas reversible mechanisms are found for the V5+/V3+ and Bi0/Bi3- redox pairs. The proposed mechanisms are supported by density functional theory (DFT) calculations.

Chemical Structures of Specific Sodium Ion Battery Components Determined by Operando Pair Distribution Function and X-ray Diffraction Computed Tomography.

To improve lithium and sodium ion battery technology, it is imperative to understand how the properties of the different components are controlled by their chemical structures. Operando structural studies give us some of the most useful information for understanding how batteries work, but it remains difficult to separate out the contributions of the various components of a battery stack (e.g., electrodes, current collectors, electrolyte, and binders) and examine specific materials. We have used operando X-ray diffraction computed tomography (XRD-CT) to study specific components of an essentially unmodified working cell and extract detailed, space-resolved structural information on both crystalline and amorphous phases that are present during cycling by Rietveld and pair distribution function (PDF) methods. We illustrate this method with the first detailed structural examination of the cycling of sodium in a phosphorus anode, revealing surprisingly different mechanisms for sodiation and desodiation in this promising, high-capacity anode system.

Perovskite to postperovskite transition in NaFeF3.

The GdFeO3-type perovskite NaFeF3 transforms to CaIrO3-type postperovskite at pressures as low as 9 GPa at room temperature. The details of such a transition were investigated by in situ synchrotron powder diffraction in a multianvil press. Fit of the p-V data showed that the perovskite phase is more compressible than related chemistries with a strongly anisotropic response of the lattice metrics to increasing pressure. The reduction in volume is accommodated by a rapid increase of the octahedral tilting angle, which reaches a critical value of 26° at the transition boundary. The postperovskite form, which is fully recoverable at ambient conditions, shows a regular geometry of the edge-sharing octahedra and its structural properties are comparable to those found in CaIrO3-type MgSiO3 at high pressure and temperature. Theoretical studies using density functional theory at the GGA + U level were also performed and describe a scenario where both perovskite and postperovskite phases can be considered Mott-Hubbard insulators with collinear magnetic G- and C-type antiferromagnetic structures, respectively. Magnetic measurements are in line with the theoretical predictions with both forms showing the typical behavior of canted antiferromagnets.