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Solid‐state electrolytes (SSEs) with high ionic conductivities are crucial for safer and high‐capacity batteries. Interface effects in nanocomposites of SSEs and insulators can lead to profound increases in conductivity. Understanding the composition of the interface is crucial for tuning the conductivity of composite solid electrolytes. Herein, X‐ray Raman Scattering (XRS) spectroscopy is used for the first time to unravel the nature of the interface effects responsible for conductivity enhancements in nanocomposites of complex hydride‐based electrolytes (LiBH4, NaBH4, and NaNH2) and oxides. XRS probe of the Li, Na, and B local environments reveals that the interface consists of highly distorted/defected and structurally distinct phase(s) compared to the original compounds. Interestingly, nanocomposites with higher concentrations of the interface compounds exhibit higher conductivities. Clear differences are observed in the interface composition of SiO2‐ and Al2O3‐based nanocomposites, attributed to differences in the reactivity of their surface groups. These results demonstrate that interfacial reactions play a dominant role in conductivity enhancement in composite solid electrolytes. This work showcases the potential of XRS in investigating interface interactions, providing valuable insights into the often complex ion conductor/insulator interfaces, especially for systems containing light elements such as Li, B, and Na present in most SSEs and batteries. [ABSTRACT FROM AUTHOR]

Solid‐state sodium ion conductors are crucial for the next generation of all‐solid‐state sodium batteries with high capacity, low cost, and improved safety. Sodium closo‐carbadodecaborate (NaCB11H12) is an attractive Na‐ion conductor owing to its high thermal, electrochemical, and interfacial stability. Mechanical milling has recently been shown to increase conductivity by five orders of magnitude at room temperature, making it appealing for application in all‐solid‐state sodium batteries. Intriguingly, milling longer than 2 h led to a significant decrease in conductivity. In this study, X‐ray Raman scattering (XRS) spectroscopy is used to probe the origin of the anomalous impact of mechanical treatment on the ionic conductivity of NaCB11H12. The B, C, and Na K‐edge XRS spectra are successfully measured for the first time, and ab initio calculations are employed to interpret the results. The experimental and computational results reveal that the decrease in ionic conductivity upon prolonged milling is due to the increased proximity of Na to the CB11H12 cage, caused by severe distortion of the long‐range structure. Overall, this work demonstrates how the XRS technique, allowing investigation of low Z elements such as C and B in the bulk, can be used to acquire valuable information on the electronic structure of solid electrolytes and battery materials in general. [ABSTRACT FROM AUTHOR]

X-ray spectroscopy of iron-bearing compounds under high pressure and high temperature is an important tool to understand geological processes in the deep Earth. However, the sample environment using a diamond anvil cell complicates spectroscopic measurements and leads to long data acquisition times. We present a setup for resonant and non-resonant X-ray emission spectroscopy and showcase its capabilities for in situ studies at high pressure and high temperature. Spin-state imaging of laser-heated FeCO3 at 75 GPa via Kβ1,3 emission spectroscopy demonstrates the great potential of this setup with measurement times within seconds for robust spin-state analysis results. The results of Kβ1,3 emission spectroscopy of cold-compressed Fe2O3 reveal a two-step spin transition with the ζ-phase between 57 GPa and 64 GPa, having iron in different spin states at the different iron sites. The phase transition via ζ- to Θ-phase causes a delocalization of the electronic states, which is supported by 1s2p resonant X-ray emission spectroscopy. [ABSTRACT FROM AUTHOR]

Knowledge of the microscopic structure of fluids and changes thereof with pressure and temperature is important for the understanding of chemistry and geochemical processes. In this work we investigate the influence of sodium chloride on the hydrogen-bond network in aqueous solution up to supercritical conditions. A combination of in situ X-ray Raman scattering and ab initio molecular dynamics simulations is used to probe the oxygen K-edge of the alkali halide aqueous solution in order to obtain unique information about the oxygen's local coordination around the ions, e.g. solvation-shell structure and the influence of ion pairing. The measured spectra exhibit systematic temperature dependent changes, which are entirely reproduced by calculations on the basis of structural snapshots obtained via ab initio molecular dynamics simulations. Analysis of the simulated trajectories allowed us to extract detailed structural information. This combined analysis reveals a net destabilizing effect of the dissolved ions which is reduced with rising temperature. The observed increased formation of contact ion pairs and occurrence of larger polyatomic clusters at higher temperatures can be identified as a driving force behind the increasing structural similarity between the salt solution and pure water at elevated temperatures and pressures with drawback on the role of hydrogen bonding in the hot fluid. We discuss our findings in view of recent results on hot NaOH and HCl aqueous fluids and emphasize the importance of ion pairing in the interpretation of the microscopic structure of water. [ABSTRACT FROM AUTHOR]

We describe the use of a silver-coated 90 ∘ parabolic mirror of 33 mm focal length as objective for imaging, on-axis laser heating and radiospectrometric temperature measurements of a sample compressed in a diamond anvil cell in a laser heating system. There, spatial resolution and imaging quality of the parabolic mirror are similar to the one of a 10× objective. The temperature measurements between 500 and 900 nm are essentially free from chromatic aberration. The parabolic mirror was also perforated with a 220-μm hole, allowing for on-axis imaging, laser heating and incidence of X-rays simultaneously at synchrotron facilities. The parabolic mirror is thus a well-suited alternative to existing refractive and reflective objectives in laboratory and synchrotron laser heating systems. [ABSTRACT FROM AUTHOR]

Using inelastic X-ray scattering beyond the dipole limit and hard X-ray photoelectron spectroscopy we establish the dual nature of the U 5f electrons in UM2Si2 (M = Pd, Ni, Ru, Fe), regardless of their degree of delocalization. We have observed that the compounds have in common a local atomic-like state that is well described by the U 5f² configuration with the (1) 1 and -2 quasi-doublet symmetry. The amount of the U 5f3 configuration, however, varies considerably across the UM2Si2 series, indicating an increase of U 5f itineracy in going from M = Pd to Ni to Ru and to the Fe compound. The identified electronic states explain the formation of the very large ordered magnetic moments in UPd2Si2 and UNi2Si2, the availability of orbital degrees of freedom needed for the hidden order in URu2Si2 to occur, as well as the appearance of Pauli paramagnetism in UFe2Si2. A unified and systematic picture of the UM2Si2 compounds may now be drawn, thereby providing suggestions for additional experiments to induce hidden order and/or superconductivity in U compounds with the tetragonal body-centered ThCr2Si2 structure. [ABSTRACT FROM AUTHOR]

The second-order phase transition into a hidden order phase in URu2Si2 goes along with an order parameter that is still a mystery, despite 30 years of research. However, it is understood that the symmetry of the order parameter must be related to the symmetry of the low-lying local electronic f-states. Here, we present results of a spectroscopic technique, namely core-level nonresonant inelastic X-ray scattering (NIXS). This method allows for the measurement of local high-multipole excitations and is bulk-sensitive. The observed anisotropy of the scattering function unambiguously shows that the 5f ground-state wave function is composed mainly of the Γ1 with majority Jz = |4〉 + |-4〉 and/or Γ2 singlet states. The incomplete dichroism indicates the possibility that quantum states of other irreducible representation are mixed into the ground state. [ABSTRACT FROM AUTHOR]

The one-dimensional cobaltate Ca 3 Co 2 O 6 is an intriguing material having an unconventional magnetic structure, displaying quantum tunneling phenomena in its magnetization. Using a newly developed experimental method, s -core-level non-resonant inelastic x-ray scattering (s -NIXS), we were able to image the atomic Co 3 d orbital that is responsible for the Ising magnetism in this system. We can directly observe that corrections to the commonly accepted ideal prismatic trigonal crystal field scheme occur in Ca 3 Co 2 O 6 , and it is the complex d 2 orbital occupied by the sixth electron at the high-spin Co trig 3 + ( d 6 ) sites that generates the Ising-like behavior. The ability to directly relate the orbital occupation with the local crystal structure is essential to model the magnetic properties of this system. Ca 3 Co 2 O 6 has an unconventional magnetic structure displaying quantum tunnelling phenomena in its magnetization. Here, the authors use s-core-level non-resonant inelastic X-ray scattering to image the atomic Co 3d orbital that is responsible for the Ising magnetism in this system. [ABSTRACT FROM AUTHOR]