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Sodium transition metal oxides with a layered structure are one of the most widely studied cathode materials for Na+-ion batteries. Since the mobility of Na+ in such cathode materials is a key factor that governs the performance of material, electrochemical and muon spin rotation and relaxation techniques are here used to reveal the Na+-ion mobility in a P2-type Na0.5MgxNi0.17-xMn0.83O2 (x = 0, 0.02, 0.05 and 0.07) cathode material. Combining electrochemical techniques such as galvanostatic cycling, cyclic voltammetry, and the galvanostatic intermittent titration technique with mu+SR, we have successfully extracted both self-diffusion and chemical-diffusion under a potential gradient, which are essential to understand the electrode material from an atomic-scale viewpoint. The results indicate that a small amount of Mg substitution has strong effects on the cycling performance and the Na+ mobility. Amongst the tested cathode systems, it was found that the composition with a Mg content of x = 0.02 resulted in the best cycling stability and highest Na+ mobility based on electrochemical and mu+SR results. The current study clearly shows that for developing a new generation of sustainable energy-storage devices, it is crucial to study and understand both the structure as well as dynamics of ions in the material on an atomic level. Title in dissertation list of papers: Na-mobility in P2-type Na0.5MgxNi0.17−xMn0.83O2 (0 ≤ x ≤ 0.07) from electrochemical and muon-spin relaxation studies

The crystal structure and magnetic properties of the cubic spinel MgFeMnO4 were studied by using a series of in-house techniques along with large-scale neutron diffraction and muon spin rotation spectroscopy in the temperature range between 1.5 and 500 K. The detailed crystal structure is successfully refined by using a cubic spinel structure described by the space group Fd3̅m. Cations within tetrahedral A and octahedral B sites of the spinel were found to be in a disordered state. The extracted fractional site occupancies confirm the presence of antisite defects, which are of importance for the electrochemical performance of MgFeMnO4 and related battery materials. Neutron diffraction and muon spin spectroscopy reveal a ferrimagnetic order below TC = 394.2 K, having a collinear spin arrangement with antiparallel spins at the A and B sites, respectively. Our findings provide new and improved understanding of the fundamental properties of the ferrispinel materials and of their potential applications within future spintronics and battery devices., MgFeMnO4 crystallizes in the typical cubic spinel with cation disordering between the tetrahedra A and the octahedra B sites. Combining the in-house experiments with neutron (n0) and muon (μ+) techniques, we reveal (i) the accurate crystal structure and site occupancy of MgFeMnO4 at 300 and 500 K, (ii) clear presence of antisite defects that have importance for the compound’s electrochemical performance, and (iii) MgFeMnO4 enters into a collinear ferrimagnetic ordering below TC = 394.2 K.

The magnetic ground states in highly ordered double perovskites LaSr1−xCaxNiReO6 (x = 0.0, 0.5, 1.0) are studied in view of the Goodenough-Kanamori rules of superexchange interactions in this paper. In LaSrNiReO6, Ni and Re sublattices are found to exhibit curious magnetic states separately, but no long range magnetic ordering is achieved. The magnetic transition at ~255 K is identified with the independent Re sublattice magnetic ordering. Interestingly, the sublattice interactions are tuned by modifying the Ni-O-Re bond angles through Ca doping. Upon Ca doping, the Ni and Re sublattices start to display a ferrimagnetically ordered state at low temperature. The neutron powder diffraction data reveals long range ferrimagnetic ordering of the Ni and Re magnetic sublattices along the crystallographic b-axis. The transition temperature of the ferrimagnetic phase increases monotonically with increasing Ca concentration.

Electron-phonon and electron-electron interactions are found to cooperatively drive the long-range charge order in cuprates., Charge order is universal to all hole-doped cuprates. Yet, the driving interactions remain an unsolved problem. Electron-electron interaction is widely believed to be essential, whereas the role of electron-phonon interaction is unclear. We report an ultrahigh-resolution resonant inelastic x-ray scattering (RIXS) study of the in-plane bond-stretching phonon mode in stripe-ordered cuprate La1.675Eu0.2Sr0.125CuO4. Phonon softening and lifetime shortening are found around the charge ordering wave vector. In addition to these self-energy effects, the electron-phonon coupling is probed by its proportionality to the RIXS cross section. We find an enhancement of the electron-phonon coupling around the charge-stripe ordering wave vector upon cooling into the low-temperature tetragonal structure phase. These results suggest that, in addition to electronic correlations, electron-phonon coupling contributes substantially to the emergence of long-range charge-stripe order in cuprates.

The underlying mechanism behind the metal-to-insulator transition in ${\mathrm{VO}}_{2}$ is still a topic of intense debate. The two leading theoretical interpretations associate the transition with either electron-lattice or electron-electron correlations. Novel experimental results are required to converge towards one of the two scenarios. Here we report on a temperature-dependent angle-resolved photoelectron study of ${\mathrm{VO}}_{2}$ thin films across the metal-to-insulator transition. The obtained experimental results are compared to density functional theory calculations. We find an overall energy shift and compression of the electronic band structure across the transition while the overall band topology is conserved. The results demonstrate the importance of electron-electron correlations in establishing the insulating state.

Since the discovery of graphene, intensive efforts have been made in search of novel two-dimensional (2D) materials. Decreasing the materials dimensionality to their ultimate thinness is a promising route to unveil new physical phenomena, and potentially improve the performance of devices. Among recent 2D materials, analogs of graphene, the group IV elements have attracted much attention for their unexpected and tunable physical properties. Depending on the growth conditions and substrates, several structures of silicene, germanene, and stanene can be formed. Here, we report the synthesis of a Kagome lattice of silicene on aluminum (111) substrates. We provide evidence of such an exotic 2D Si allotrope through scanning tunneling microscopy (STM) observations, high-resolution core-level (CL) and angle-resolved photoelectron spectroscopy (ARPES) measurements, along with Density Functional Theory calculations., 13 pages, 6 figures

The authors study a charge-orbital-spin correlation of high-pressure synthesized quasi-one-dimensional NaMn${}_{2}$O${}_{4}$ and Li${}_{0.92}$Mn${}_{2}$O${}_{4}$ using a low-temperature neutron powder diffraction.

In the quest for developing novel and efficient batteries, a great interest has been raised for sustainable K-based honeycomb layer oxide materials, both for their application in energy devices as well as for their fundamental material properties. A key issue in the realization of efficient batteries based on such compounds, is to understand the K-ion diffusion mechanism. However, investigation of potassium-ion (K$$^+$$ + ) dynamics in materials using e.g. NMR and related techniques has so far been very challenging, due to its inherently weak nuclear magnetic moment, in contrast to other alkali ions such as lithium and sodium. Spin-polarised muons, having a high gyromagnetic ratio, make the muon spin rotation and relaxation ($$\mu ^+$$ μ + SR) technique ideal for probing ions dynamics in these types of energy materials. Here we present a study of the low-temperature magnetic properties as well as K$$^+$$ + dynamics in honeycomb layered oxide material $${\hbox {K}_2\hbox {Ni}_2\hbox {TeO}_6}$$ K 2 Ni 2 TeO 6 using mainly the $$\mu ^+$$ μ + SR technique. Our low-temperature $$\mu ^+$$ μ + SR results together with complementary magnetic susceptibility measurements find an antiferromagnetic transition at $$T_{\mathrm{N}}\approx 27$$ T N ≈ 27 K. Further $${\mu}^{+}$$ μ + SR studies performed at higher temperatures reveal that potassium ions (K$$^+$$ + ) become mobile above 200 K and the activation energy for the diffusion process is obtained as $$E_{\mathrm{a}}=121 (13)$$ E a = 121 ( 13 ) meV. This is the first time that K$$^+$$ + dynamics in potassium-based battery materials has been measured using $$\mu ^+$$ μ + SR. Assisted by high-resolution neutron diffraction, the temperature dependence of the K-ion self diffusion constant is also extracted. Finally our results also reveal that K-ion diffusion occurs predominantly at the surface of the powder particles. This opens future possibilities for potentially improving ion diffusion as well as K-ion battery device performance using nano-structuring and surface coatings of the particles.

The authors use a combination of positive and negative muon spin rotation and relaxation to investigate fluctuations of nuclear magnetic fields in an olivinetype Li-ion battery material.

Phase transitions have been surmised as underlying factors behind the exceptional electrochemical, ionic and magnetic functionalities that have catapulted honeycomb layered oxides as superb functional materials. As such, in this study (short communication), we explore temperature elevation as an avenue for inducing phase transitions in honeycomb layered oxides adopting the composition A2M2TeO6 (A = Li, Na, K; M = (transition) metal). X-ray diffraction analyses indicate structural changes occurring in Na2Ni2TeO6 hexagonal lattice (centrosymmetric P63/mcm → accentric P63(22) space group) with increase in temperature, whilst in the potassium homologue (K2Ni2TeO6), the phase transitions entail multiple changes in the lattice (from the initial hexagonal → monoclinic (pseudo-orthorhombic) lattice at intermediate temperatures) which reverts back to its initial hexagonal lattice with further increase in temperatures. This study opens an alternative channel for generating phase transition beside electrochemical alkali (re)insertion.

Natural abundance, impressive chemical characteristics and economic feasibility have rekindled the appeal for rechargeable sodium (Na) batteries as a practical solution for the growing energy demand, environmental sustainability and energy independence. However, the scarcity of viable positive electrode materials remains a huge impediment to the actualization of this technology. In this paper, we explore honeycomb layered oxides adopting the composition Na$_2$Ni$_{2-x}$Co$_x$TeO$_6$ ($x = 0, 0.25$ and $0.50$) as feasible positive electrode (cathode) materials for rechargeable sodium batteries at both room- and elevated temperatures using ionic liquids. Through standard galvanostatic assessments and analyses we demonstrate that substitution of nickel with cobalt in Na$_2$Ni$_2$TeO$_6$ leads to an increase in the discharge voltage to nearly $4$ V (versus Na$^+$ / Na) for the Na$_2$Ni$_{2-x}$Co$_x$TeO$_6$ family of honeycomb layered oxide materials, which surpasses the attained average voltages for most layered oxide positive electrode materials that facilitate Na-ion desertion. We also verify the increased kinetics within the Na$_2$Ni$_{2-x}$Co$_x$TeO$_6$ honeycomb layered oxides during operations at elevated temperatures which lead to an increase in reversible capacity of the rechargeable Na battery. This study underpins the doping of congener transition metal atoms to the honeycomb structure of Na$_2$Ni$_2$TeO$_6$ in addition to elevated-temperature operation as a judicious route to enhance the electrochemical performance of analogous layered oxides., 16 pages, 4 figures, 1 cover art (Electronic Supplementary Information: 10 pages, 5 figures, 3 tables)

In the quest for developing novel and efficient batteries, a great interest has been raised for sustainable K-based honeycomb layer oxide materials, both for their application in energy devices as well as for their fundamental material properties. A key issue in the realization of efficient batteries based on such compounds, is to understand the K-ion diffusion mechanism. However, investigation of potassium-ion (K\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^+$$\end{document}+) dynamics in materials using e.g. NMR and related techniques has so far been very challenging, due to its inherently weak nuclear magnetic moment, in contrast to other alkali ions such as lithium and sodium. Spin-polarised muons, having a high gyromagnetic ratio, make the muon spin rotation and relaxation (\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\mu ^+$$\end{document}μ+SR) technique ideal for probing ions dynamics in these types of energy materials. Here we present a study of the low-temperature magnetic properties as well as K\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^+$$\end{document}+ dynamics in honeycomb layered oxide material \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\hbox {K}_2\hbox {Ni}_2\hbox {TeO}_6}$$\end{document}K2Ni2TeO6 using mainly the \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\mu ^+$$\end{document}μ+SR technique. Our low-temperature \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\mu ^+$$\end{document}μ+SR results together with complementary magnetic susceptibility measurements find an antiferromagnetic transition at \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$T_{\mathrm{N}}\approx 27$$\end{document}TN≈27 K. Further \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\mu}^{+}$$\end{document}μ+SR studies performed at higher temperatures reveal that potassium ions (K\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^+$$\end{document}+) become mobile above 200 K and the activation energy for the diffusion process is obtained as \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$E_{\mathrm{a}}=121 (13)$$\end{document}Ea=121(13) meV. This is the first time that K\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^+$$\end{document}+ dynamics in potassium-based battery materials has been measured using \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\mu ^+$$\end{document}μ+SR. Assisted by high-resolution neutron diffraction, the temperature dependence of the K-ion self diffusion constant is also extracted. Finally our results also reveal that K-ion diffusion occurs predominantly at the surface of the powder particles. This opens future possibilities for potentially improving ion diffusion as well as K-ion battery device performance using nano-structuring and surface coatings of the particles.

Proper characterisation of investigated samples is vital when studying superconductivity as impurities and doping inhomogeneities can affect the physical properties of the measured system. We present a method where a polarised neutron imaging setup utilises the precession of spin-polarised neutrons in the presence of a trapped field in the superconducting sample to spatially map out the critical temperature for the phase transition between superconducting and non-superconducting states. We demonstrate this method on a superconducting crystal of the prototypical high-temperature superconductor (La,Sr)$_2$CuO$_4$. The results, which are backed up by complementary magnetic susceptibility measurements, show that the method is able to resolve minor variations in the transition temperature across the length of the LSCO crystal, caused by inhomogeneities in strontium doping., 11 pages, 7 figures

Detailed understanding of charge diffusion processes in a lithium-ion battery is crucial to enable its systematic improvement. Experimental investigation of diffusion at the interface between active particles and the electrolyte is challenging but warrants investigation as it can introduce resistances that, for example, limit the charge and discharge rates. Here, we show an approach to study diffusion at interfaces using muon spin spectroscopy. By performing measurements on LiFePO4 platelets with different sizes, we determine how diffusion through the LiFePO4 (010) interface differs from that in the center of the particle (i.e., bulk diffusion). We perform ab initio calculations to aid the understanding of the results and show the relevance of our interfacial diffusion measurement to electrochemical performance through cyclic voltammetry measurements. These results indicate that surface engineering can be used to improve the performance of lithium-ion batteries.

The temperature dependent dehydrogenation of naphthalene on Ni(111) has been investigated using vibrational sum-frequency generation spectroscopy, X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory with the aim of discerning the reaction mechanism and the intermediates on the surface. At 110 K, multiple layers of naphthalene adsorb on Ni(111); the first layer is a flat lying chemisorbed monolayer, whereas the next layer(s) consist of physisorbed naphthalene. The aromaticity of the carbon rings in the first layer is reduced due to bonding to the surface Ni-atoms. Heating at 200 K causes desorption of the multilayers. At 360 K, the chemisorbed naphthalene monolayer starts dehydrogenating and the geometry of the molecules changes as the dehydrogenated carbon atoms coordinate to the nickel surface; thus, the molecule tilts with respect to the surface, recovering some of its original aromaticity. This effect peaks at 400 K and coincides with hydrogen desorption. Increasing the temperature leads to further dehydrogenation and production of H-2 gas, as well as the formation of carbidic and graphitic surface carbon. Published under license by AIP Publishing.

The K2Cr8O16 compound belongs to a series of quasi-1D compounds with intriguing magnetic properties that are stabilized through a high-pressure synthesis technique. In this study, a muon spin rotation, relaxation and resonance (μ+SR) technique is used to investigate the pressure dependent magnetic properties up to 25 kbar. μ+SR allows for measurements in true zero applied field and hereby access the true intrinsic material properties. As a result, a refined temperature/pressure phase diagram is presented revealing a novel low temperature/high pressure (pC1 = 21 kbar) transition from a ferromagnetic insulating to a high-pressure antiferromagnetic insulator. Finally, the current study also indicates the possible presence of a quantum critical point at pC2 ~ 33 kbar where the magnetic order in K2Cr8O16 is expected to be fully suppressed even at T = 0 K.

QC 20211215

QC 20211215

We report a muon spin rotation and relaxation (μ+SR) study on Na0.7CoO2 powder samples, where the sodium (Na) has been intercalated via an electrochemical reaction inside a Na-ion battery. The zero field μ+SR measurement at T = 2 K shows a paramagnetic state for the as-grown sample whereas an antiferromagnetic (AF) ordered state is seen for the electrochemically cycled one. Furthermore, the temperature dependence of the muon-spin precession frequencies reveals a Néel transition temperature of TN = 22 K. The results demonstrate the importance of having high-quality homogenous samples, and put the existing NaxCoO2 magnetic phase diagram under debate. QC 20211124

QC 20211215

In this study, the magnetic ground state of the hollandite type material K2Cr8O16 was tuned by externally applied pressure and investigated using µ+SR method in Zero-field (ZF) and weak-transversefield (wTF) configurations. As a result, the obtained magnetic transition temperature for the measuredpressures differs notably from magnetization measurements. Moreover, both wTF and ZF data reveala transition between two different magnetically ordered states at low temperatures for higher pressures. Further theoretical and experimental studies are currently being planned in order to elucidatethe detailed nature of the magnetically ordered phase. QC 20211130

QC 20211124

electronic band structure of MgB2 involves a unique combination of two-and three-dimensional (3D) electrons derived from the boron sigma and pi states, respectively. We have mapped out the sigma and pi bands over the complete Brillouin zone, including the full disconnected Fermi surface, using high-resolution soft x-ray angle-resolved photoelectron spectroscopy. The measured band structure, which is closely related to that of graphene, is in overall good agreement with the density functional theory-general gradient approximation (DFT-GGA), though differences in Fermi surface volume are seen. Surprisingly, the measured bands are wider than calculated, by similar to 8% for the s and similar to 10-15% for the p bands. This solves the long-standing challenge of establishing the full 3D electronic structure of the model compound MgB2, and it demonstrates the tendency of DFT-GGA to overestimate the band narrowing due to exchange correlations effects.

Motivated by the search for design principles of rare-earth-free strong magnets, we present a study of electronic structure and magnetic properties of the ferromagnetic metal Fe3GeTe2 within local density approximation (LDA) of the density functional theory, and its combination with dynamical mean-field theory (DMFT). For comparison to these calculations, we have measured magnetic and thermodynamic properties as well as X-ray magnetic circular dichroism and the photoemission spectrum of single crystal Fe3GeTe2. We find that the experimentally determined Sommerfeld coefficient is enhanced by an order of magnitude with respect to the LDA value. This enhancement can be partially explained by LDA+DMFT. In addition, the inclusion of dynamical electronic correlation effects provides the experimentally observed magnetic moments, and the spectral density is in better agreement with photoemission data. These results establish the importance of electronic correlations in this ferromagnet., Comment: 6 pages, 5 eps embedded eps figures. Physical Review B, accepted version

We present an angle-resolved photoelectron spectroscopy study of YBa2Cu3O7-delta films in situ grown by pulsed laser deposition. We have successfully produced underdoped surfaces with ordered oxygen vacancies within the CuO chains resulting in a clear ortho-II band folding of the Fermi surface. This indicates that order within the CuO chains affects the electronic properties of the CuO2 planes. Our results highlight the importance of having not only the correct surface carrier concentration, but also a very well ordered and clean surface in order that photoemission data on this compound be representative of the bulk.

We present angle-resolved photoelectron spectroscopy data probing the electronic structure of the Nd-substituted high-T-c cuprate La1.48Nd0.4Sr0.12CuO4. Data have been acquired at low and high p ...

An angle-resolved photoemission study of the scattering rate in the superconducting phase of the high-temperature superconductor La2-xSrxCuO4 with x=0.145 and x=0.17, as a function of binding ene ...

We have studied low-temperature magnetic properties as well as high-temperature lithium ion diffusion in the battery cathode materials LixNi1/3Co1/3Mn1/3O2 by the use of muon spin rotation/relaxation. Our data reveal that the samples enter into a 2D spin-glass state below TSG=12 K. We further show that lithium diffusion channels become active for T>Tdiff=125 K where the Li-ion hopping-rate [nu(T)] starts to increase exponentially. Further, nu(T) is found to fit very well to an Arrhenius type equation and the activation energy for the diffusion process is extracted as Ea=100 meV., Submitted to Journal of Physics: Conference Series (2014)