The lithium manganese oxide spinel Li$_x$Mn$_2$O$_4$, with $0\leq x\leq 2$, is an important example for cathode materials in lithium ion batteries. However, an accurate description of Li$_x$Mn$_2$O$_4$ by first-principles methods like density functional theory is far from trivial due to its complex electronic structure, with a variety of energetically close electronic and magnetic states. It was found that the local density approximation as well as the generalized gradient approximation (GGA) are unable to describe Li$_x$Mn$_2$O$_4$ correctly. Here, we report an extensive benchmark for different Li$_x$Mn$_y$O$_z$ systems using the hybrid functionals PBE0 and HSE06, as well as the recently introduced local hybrid functional PBE0r. We find that all of these functionals yield energetic, structural, electronic, and magnetic properties in good agreement with experimental data. The notable benefit of the PBE0r functional, which relies on on-site Hartree-Fock exchange only, is a much reduced computational effort that is comparable to GGA functionals. Furthermore, the Hartree-Fock mixing factors in PBE0r are smaller than in PBE0, which improves the results for (lithium) manganese oxides. The investigation of Li$_x$Mn$_2$O$_4$ shows that two Mn oxidation states, +III and +IV, coexist. The Mn$^\text{III}$ ions are in the high-spin state and the corresponding MnO$_6$ octahedra are Jahn-Teller distorted. The ratio between Mn$^\text{III}$ and Mn$^\text{IV}$ and thus the electronic structure changes with the Li content while no major structural changes occur in the range from $x=0$ to $1$. This work demonstrates that the PBE0r functional provides an equally accurate and efficient description of the investigated Li$_x$Mn$_y$O$_z$ systems.
X-ray amorphous manganese oxides were prepared by reduction of sodium permanganate by lithium iodide in aqueous medium (MnOx-I) and by decomposition of manganese carbonate at moderate temperature (MnOx-C). TEM showed that these materials are not amorphous, but nanostructured, with a prominent spinel substructure in MnOx-C. These materials intercalate lithium with capacities up to 200 mAh/g at first cycle (potential window 1.8-4.3 V) and 175 mAh/g at 100th cycle. Best performances for MnOx-C are obtained with cobalt doping. Potential electrochemical spectroscopy shows that the initial discharge…
Manganese oxide nanosheets were synthesized using liquid phase exfoliation that achieved suspensions in isopropanol with concentrations of up to 0.45 mg/ml. A study of solubility parameters showed that the exfoliation was optimum in DMF followed by isopropanol and diethylene glycol. Isopropanol was the solvent of choice due to its environmentally friendly nature and ease of use for further processing. The 2D hybrid was synthesized in isopropanol suspensions with concentrations of up to 0.5 mg/ml and demonstrated stability against reaggregation for up to six months. The coexfoliation was found …
Atom probe tomography is routinely used for the characterisation of materials microstructures usually assuming that the microstructure is unaltered by the analysis. When analysing ionic conductors, however, gradients in the chemical potential and the electric field penetrating dielectric atom probe specimens can cause significant ionic mobility. While ionic mobility is undesired when aiming for materials characterisation it offers a strategy to manipulate materials directly in-situ in the atom probe. Here, we present experimental results on the analysis of the ionic conductor Lithium-Manganese…
Unraveling the atomistic and the electronic structure of solid-liquid interfaces is the key to the design of new materials for many important applications, from heterogeneous catalysis to battery technology. Density functional theory (DFT) calculations can in principle provide a reliable description of such interfaces, but the high computational costs severely restrict the accessible time and length scales. Here, we report machine learning-driven simulations of various interfaces between water and lithium manganese oxide (Li$_x$Mn$_2$O$_4$), an important electrode material in lithium ion batte…
Layered LiMnO$_2$ and Li$_2$MnO$_3$ are of great interest for lithium-ion battery cathodes because of their high theoretical capacities. The practical application of these materials is, however, limited due to poor electrochemical performance. We herein report a comprehensive first-principles study of defect physics in LiMnO$_2$ and Li$_2$MnO$_3$ using hybrid-density functional calculations. We find that manganese antisites have low formation energies in LiMnO$_2$ and may act as nucleation sites for the formation of impurity phases. The antisites can also occur with high concentrations in Li$_…
Many positive electrode materials in lithium ion batteries include transition metals which are difficult to describe by electronic structure methods like density functional theory (DFT) due to the presence of multiple oxidation states. A prominent example is the lithium manganese oxide spinel Li$_x$Mn$_2$O$_4$ with $0\leq x\leq2$. While DFT, employing the local hybrid functional PBE0r, provides a reliable description, the need for extended computer simulations of large structural models remains a significant challenge. Here, we close this gap by constructing a DFT-based high-dimensional neural…
We present an analysis of the polymorphic energy ordering and properties of the rock salt and zincblende structures of manganese oxide using fixed node diffusion Monte Carlo (DMC). Manganese oxide is a correlated, antiferromagnetic material that has proven to be challenging to model from first principles across a variety of approaches. Unlike conventional density functional theory and some hybrid functionals, fixed node diffusion Monte Carlo finds the rock salt structure to be more stable than the zincblende structure, and thus recovers the correct energy ordering. Analysis of the site-resolve…
We report a first-principles study of defect thermodynamics and transport in spinel-type lithium manganese oxide LiMn$_2$O$_4$, an important lithium-ion battery electrode material, using density-functional theory and the Heyd-Scuseria-Ernzerhof screened hybrid functional. We find that intrinsic point defects in LiMn$_2$O$_4$ have low formation energies and hence can occur with high concentrations. The electronic conduction proceeds via hopping of small polarons and the ionic conduction occurs via lithium vacancy and/or interstitialcy migration mechanisms. The total conductivity is dominated by…
Two-dimensional manganese oxide layers have been grown on Pd(100) and have been characterized by scanning tunnelling microscopy (STM), low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). The complex surface phase diagram of MnOx on Pd(100) is reported, where nine different novel Mn oxide phases have been detected as a function of the chemical potential of oxygen mO. Three regions of the chemical potential of oxygen can be identified, in which structurally related oxide phases are formed, often in coexistence at the surface. The different regions of mO are reflect…
The structure and magnetic properties of oligonuclear manganese complex [Mn(hfa)2cpo]2 (where hfa is hexafluoroacetylacetonate dehydrate and cpo is 4-cyanopyridine-N-oxide) are presented. In the unit cell, the dinuclear molecules are well isolated from each other. The non-monotonous dependence of magnetic susceptibility is explained in terms of the hierarchy of exchange parameters by using exact diagonalization. The thermodynamic behavior of pure cpo and [Mn(hfa)2(cpo)]2 is simulated numerically in a dimer approximation by an extrapolation to spin S = 5/2. The Mn-Mn exchange integral is evalua…
Structural and Optical properties of the (Na0.5 K0.5)y Li 1-y NbO3 (y = 0.934 & 0.936) ceramics have been explored in terms of the X-Ray diffraction patters, Rietveld analysis, UV-Vis spectroscopy, and Kubelka-Munk functions. Rietveld analysis of both these structures reveals them to be tetragonal with space group P4mm. It is found that increase in Li doping increases the optical band gap. Presence of additional hardening dopant MnO2 is found to have a uniform behavior for both these composition. With increasing MnO2 concentration, the band gap decreases indicative of increase in B-site cation…
The electronic structure is found to be understandable in terms of free-atom term values and universal interorbital coupling parameters, since self-consistent tight-binding calculations indicate that Coulomb shifts of the d-state energies are small. Special-point averages over the bands are seen to be equivalent to treatment of local octahedral clusters. The cohesive energy per manganese for MnO, Mn2O3, and MnO2, in which manganese exists in valence states Mn2+, Mn3+, and Mn4+, is very nearly the same and dominated by the transfer of manganese s electrons to oxygen p states. There are small co…
We performed a systematic study of soft X-ray absorption spectroscopy in various manganese oxides and fluorides. Both Mn L-edges and ligand (O and F) K-edges are presented and compared with each other. Despite the distinct crystal structure and covalent/ionic nature in different systems, the Mn-L spectra fingerprint the Mn valence and spin states through spectral lineshape and energy position consistently and evidently. The clear O- and F- K pre-edge features in our high resolution spectra enable a quantitative definition of the molecular orbital diagram with different Mn valence. In addition,…
Effectiveness of galaxite (Al2O3MnO) and manganese oxide (MnO2) in nucleating acicular ferrite was demonstrated in a steel with composition of Fe-13.92Mn-4.53Al-1.28Si-0.11C. The hot rolled and quenched steel had a duplex microstructure of delta-ferrite and partially transformed austenite. Thermal treatments were used to manipulate the concentration and type of oxides and the ferrite plate density was found to correlate with inclusions of low misfit. Both bainitic and acicular ferrite were observed and the prior austenite had a grain diameter of 16.5 micrometers. Upon tensile testing the retai…
Through direct nanoparticle nucleation and growth on nitrogen doped, reduced graphene oxide sheets and cation substitution of spinel Co3O4 nanoparticles, a manganese-cobalt spinel MnCo2O4/graphene hybrid was developed as a highly efficient electrocatalyst for oxygen reduction reaction (ORR) in alkaline conditions. Electrochemical and X-ray near edge structure (XANES) investigations revealed that the nucleation and growth method for forming inorganic-nanocarbon hybrid results in covalent coupling between spinel oxide nanoparticles and N-doped reduced graphene oxide (N-rmGO) sheets. Carbon K-edg…
Ferroelectric oxides have attracted much attention due to their wide range of applications, especially in electronic devices such as nonvolatile memories and tunnel junctions. As a result, the monolithic integration of these materials into silicon technology and its nanostructuration to develop alternative cost-effective processes are among the central points in current technology. In this work, we used a chemical route to obtain nanowire thin films of a novel Sr1+δMn8O16 (SMO) hollandite-type manganese oxide on silicon. Scanning transmission electron microscopy combined with crystallographic …
A new minimal model is constructed for the doped manganese oxides which exhibit colossal magnetoresistance (CMR), involving broad spin-majority conduction band as well as nearly localised spin-minority electron states. A simple mean field analysis yields a temperature-dependent hybridised band structure with suppressed carrier weight at the Fermi level. Spin stiffness is complex, indicating unusually strong spin wave damping. Experimental and theoretical investigations are needed to further verify the relevance of the proposed model.
We present results of an approach to incorporate redox-active manganese oxide into the 3-dimensional porous structure of carbon xerogels under self-limiting electroless conditions. By varying the structure of the carbon backbone, we found that deposition of manganese oxide preferably takes place on the external surface area of the carbon xerogels. From our detailed analysis we conclude that 3-dimensional carbon xerogels with particle and pore sizes ranging from 10 to 20 nm and low manganese oxide precursor concentration combined with long deposition times are beneficial for fast operating pseu…
We report a novel synthesis route of homogeneously manganese-doped titanium dioxide nanotubes in a broad concentration range. The scroll-type trititanate (H(2)Ti(3)O(7)) nanotubes prepared by hydrothermal synthesis were used as precursors. Mn2+ ions were introduced by an ion exchange method resulting Mn(x)H(2-x)Ti(3)O(7). In a subsequent heat-treatment they were transformed into Mn(y)Ti(1-y)O(2) where y=x/(3+x). The state and the local environment of the Mn2+ ions in the precursor and final products were studied by Electron Spin Resonance (ESR) technique. It was found that the Mn2+ ions occupy…
A new mechanism is proposed to explain the colossal magnetoresistance and related phenomena. Moving electrons accompanied by Jahn-Teller phonon and spin-wave clouds may form composite polarons in ferromagnetic narrow-band manganites. The ground-state and finite-temperature properties of such composite polarons are studied in the present paper. By using a variational method, it is shown that the energy of the system at zero temperature decreases with the formation of composite polaron; the energy spectrum and effective mass of the composite polaron at finite temperature is found to be strongly …
Ruderman-Kittel-Kasuya-Yosida interaction even if their wave functions lack direct overlap. Theory predicts that spin-orbit scattering leads to a Dzyaloshinskii-Moriya type enhancement of this indirect exchange interaction, giving rise to chiral exchange terms. Here we present a combined spin-polarized scanning tunneling microscopy, angle-resolved photoemission, and density functional theory study of MnO$_2$ chains on Ir(100). Whereas we find antiferromagnetic Mn--Mn coupling along the chain, the inter-chain coupling across the non-magnetic Ir substrate turns out to be chiral with a $120^{\cir…
Rational combination holds the key for non-precious metal oxides and economic carbon materials to the creation of high performance air electrode materials. Carbon nanotubes (CNTs)-supported manganese oxides composite catalysts (CMnCs) were obtained by reacting commercial CNTs with MnO$_4^-$ in diluted H$_2$SO$_4$ with cancelling conventional hydrothermal processing or adding surfantant templates. CMnCs were then assembled into commercial air cathodes equipped in metal air fuel cells. CNTs demonstrated structurally much defective. Outer CNT walls were cracked into graphene nano pieces yet remai…
Field-induced magnetization jumps with similar characteristics are observed at low temperature for the intermetallic germanide Gd5Ge4and the mixed-valent manganite Pr0.6Ca0.4Mn0.96Ga0.04O3. We report that the field location -and even the existence- of these jumps depends critically on the magnetic field sweep rate used to record the data. It is proposed that, for both compounds, the martensitic character of their antiferromagnetic-to-ferromagnetic transitions is at the origin of the magnetization steps.
Manganese oxide-coated TiO2 nanotube array (NTA) was synthesized and applied for the (electro)catalytic oxidation of sulfide. By setting the electrodeposition parameters and calcination temperature, the coating obtained was MnO2 or Mn2O3, with rod or needle like morphology. Excellent catalytic activity of the Ti/TiO2 NTA/MnxOy anodes resulted in robust and selective oxidation of sulfide to elemental sulfur via an inner sphere complex between the sulfide ion and Mn-oxide. The penetration of the MnxOy inside the NTA improved adhesion and enhanced the electron transfer, thus enabling complete and…
Lithium ion batteries often contain transition metal oxides like Li$_{x}$Mn$_2$O$_4$ ($0\leq x\leq2$). Depending on the Li content different ratios of Mn$^\text{III}$ to Mn$^\text{IV}$ ions are present. In combination with electron hopping the Jahn-Teller distortions of the Mn$^\text{III}$O$_6$ octahedra can give rise to complex phenomena like structural transitions and conductance. While for small model systems oxidation and spin states can be determined using density functional theory (DFT), the investigation of dynamical phenomena by DFT is too demanding. Previously, we have shown that a hi…
Structural analysis of a layered manganese tungstate diaminoalkane hybrid series suggests that this compound forms a spin-5/2 spin-ladder structure. We use X-ray diffraction, electron microscopy and x-ray absorption spectroscopy results to infer the structure. DC magnetization of the manganese compound and a possible copper analogue appear to show that the manganese system behaves like 1-dimensional antiferromagnetic Heisenberg chains (i.e. $J_{\parallel} \gg J_{\perp})$ while the copper system is fitted well by a $S = {1/2}$ spin ladder model, giving the parameters $g = 1.920 \pm 0.008$, $J_{…
We point out that the existing experimental data of most manganese oxides show the {\sl frustrated} p-wave superconducting condensation in the ferromagnetic phase in the sense that the superconducting coherence is not long enough to cover the whole system. The superconducting state is similar to the $A_{1}$ state in superfluid He-3. The sharp drop of resistivity, the steep jump of specific heat, and the gap opening in tunneling are well understood in terms of the p-wave pairing. In addition, colossal magnetoresistance (CMR) is naturally explained by the superconducting fluctuations with increa…
Hollow carbon spheres (HCS) covered with metal oxide nanoparticles (SnO2 and MnO2, respectively) were successfully synthesized and investigated regarding their potential as anode materials for lithium-ion batteries. Raman spectroscopy shows a high degree of graphitization for the HCS host structure. The mesoporous nature of the nanocomposites is confirmed by Brunauer-Emmett-Teller analysis. For both metal oxides under study, the metal oxide functionalization of HCS yields a significant increase of electrochemical performance. The charge capacity of HCS/SnO2 is 370 mAh/g after 45 cycles (266 mA…
Lithium-rich complex transition-metal oxides Li$_2$MoO$_3$, Li$_2$RuO$_3$, Li$_3$RuO$_4$, Li$_3$NbO$_4$, Li$_5$FeO$_4$, Li$_5$MnO$_4$ and their derivatives are of interest for high-capacity battery electrodes. Here, we report a first-principles density-functional theory study of the atomic and electronic structure of these materials using the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid functional which treats all orbitals in the materials on equal footing. Dimerization of the transition-metal ions is found to occur in layered Li$_2$MoO$_3$, in both fully lithiated and partially delithiated c…
We report studies on the vibrational and elastic behavior of lithium oxide, Li2O around its superionic transition temperature. Phonon frequencies calculated using the ab-initio and empirical potential model are in excellent agreement with the reported experimental data. Further, volume dependence of phonon dispersion relation has been calculated, which indicates softening of zone boundary transverse acoustic phonon mode along [110] at volume corresponding to the superionic transition in Li2O. The instability of phonon mode could be a precursor leading to the dynamical disorder of the lithium s…
We describe the ground- and excited-state electronic structure of bulk MnO and NiO, two prototypical correlated electron materials, using coupled cluster theory with single and double excitations (CCSD). As a corollary, this work also reports the first implementation of unrestricted periodic ab initio equation-of motion CCSD. Starting from a Hartree-Fock reference, we find fundamental gaps of 3.46 eV and 4.83 eV for MnO and NiO respectively for the 16 unit supercell, slightly overestimated compared to experiment, although finite-size scaling suggests that the gap is more severely overestimated…
Mn is used as a dopant to improve the electromechanical properties of perovskite oxides. We elucidate the role of Mn defects and associated vacancies on the electronic, atomic and ferroelectric properties of BaTiO$_3$. Using density functional theory (DFT) and DFT+U we investigate the equilibrium geometry and electronic properties of Mn ion on A or B sites and with compensating oxygen vacancies. We study the change in the oxidation state of Mn in response to local environment changes, such as the presence of oxygen vacancies.
In the present work, the structural, magnetic, and electronic properties of the two- and one-dimensional honeycomb structures of recently synthesized MnO [Zhang et al. Nat. Commun., 20, 1073-1078 (2021)] are investigated by using first principles calculations. Our calculations show that the single layer 2D MnO crystal has a degenerate antiferromagnetic (AFM) ground state and a relatively less favorable ferromagnetic (FM) state. In addition, magnetic anisotropy calculations unveil that the easy-axis direction for magnetism originating from unpaired electron states in manganese atoms is normal t…
Defects and their interactions in crystalline solids often underpin material properties and functionality as they are decisive for stability, result in enhanced diffusion, and act as a reservoir of vacancies. Recently, lithium-rich layered oxides have emerged among the leading candidates for the next-generation energy storage cathode material, delivering 50 % excess capacity over commercially used compounds. Oxygen-redox reactions are believed to be responsible for the excess capacity, however, voltage fading has prevented commercialization of these new materials. Despite extensive research th…
Lithium titanium oxide Li$_4$Ti$_5$O$_{12}$ (LTO) is an intriguing anode material promising particularly long lived batteries, due to its remarkable phase stability during (dis)charging of the cell. However, its usage is limited by its low intrinsic electronic conductivity. Introducing oxygen vacancies can be one method to overcome this drawback, possibly by altering the charge carrier transport mechanism. We use Hubbard corrected density-functional theory (DFT+U) to show that polaronic states in combination with a possible hopping mechanism can play a crucial role in the experimentally observ…
This article reviews the development of cathode materials for secondary lithium ion batteries since its inception with the introduction of lithium cobalt oxide in early 1980s. The time has passed and numerous cathode materials are designed and developed to realize not only the enhanced capacity but also the power density simultaneously. However, there are numerous challenges such as the cyclic stability of cathode materials, their structural and thermal stability, higher operating voltage together with high ionic and electronic conductivity for efficient ion and charge transport during chargin…
In sharp contrast to molecular synthesis, materials synthesis is generally presumed to lack selectivity. The few known methods of designing selectivity in solid-state reactions have limited scope, such as topotactic reactions or strain stabilization. This contribution describes a general approach for searching large chemical spaces to identify selective reactions. This novel approach explains the ability of a nominally "innocent" Na$_2$CO$_3$ precursor to enable the metathesis synthesis of single-phase Y$_2$Mn$_2$O$_7$ -- an outcome that was previously only accomplished at extreme pressures an…
Composite cathode coatings made of a high energy density layered oxide (Li1.2Ni0.15Mn0.55Co0.1O2, theoretical capacity ~377 mAh/g), polyvinylidene fluoride (PVdF) binder, and electron-conduction additives, were bonded to an elastic substrate. An electrochemical cell, built by pairing the cathode with a capacity-matched graphite anode, was electrochemically cycled and the real-time average stress evolution in the cathode coating was measured using a substrate-curvature technique. Features in the stress evolution profile showed correlations with phase changes in the oxide, thus yielding data com…
We review recent ab initio molecular dynamics studies of electrode/electrolyte interfaces in lithium ion batteries. Our goals are to introduce experimentalists to simulation techniques applicable to models which are arguably most faithful to experimental conditions so far, and to emphasize to theorists that the inherently interdisciplinary nature of this subject requires bridging the gap between solid and liquid state perspectives. We consider liquid ethylene carbonate (EC) decomposition on lithium intercalated graphite, lithium metal, oxide-coated graphite, and spinel manganese oxide surfaces…
Manganese oxides have received much attention over the years among the wide range of electrocatalysts for the oxygen evolution reaction (OER) due to their low toxicity, high abundance and rich redox chemistry. While many previous studies focused on the activity of these materials, a better understanding of the material transformations relating to activation or degradation is highly desirable, both from a scientific perspective and for applications. We electrodeposited Na-containing MnOx without long-range order from an alkaline solution to investigate these aspects by cyclic voltammetry, scann…
Electron energy-loss spectrometry was employed to measure the white lines at the L23 absorption edges of the 3d transition-metal oxides and lithium transition-metal oxides. The white-line ratio (L3/L2) was found to increase between d^0 and d^5 and decrease between d^5 and d^10, consistent with previous results for the transition metals and their oxides. The intensities of the white lines, normalized to the post-edge background, are linear for the 3d transition-metal oxides and lithium transition-metal oxides. An empirical correlation between normalized white-line intensity and 3d occupancy is …
We study the stability of Li-O compounds as a function of pressure, with Li ion battery applications and fundamental chemical interest in mind. Using the ab initio evolutionary algorithm, we predict stability of novel compounds LiO4, Li5O3 and Li6O under pressure. LiO4, formed at the pressure of just 6 GPa, can be seen as ε-O8 accepting two electrons from two Li atoms. This phase is superconducting, with Tc up to 12.2 K at 10 GPa. This is remarkable, because elemental oxygen becomes superconducting at much higher pressure (96 GPa) and has much lower Tc (<0.6 K), and suggests that chemical allo…
Transition metal (TM) oxides play an increasingly important role in technology today including applications such as catalysis, solar energy harvesting, and energy storage. In many of these applications, the details of their electronic structure near the Fermi level are critically important for their properties. We propose a first-principles based computational methodology for the accurate prediction of oxygen charge transfer in TM oxides and lithium TM (Li-TM) oxides. To obtain accurate electronic structures, the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional is adopted and the amount of ex…
We report a comprehensive first-principles study of the thermodynamics and transport of intrinsic point defects in layered oxide cathode materials LiMO$_2$ (M=Co, Ni), using density-functional theory and the Heyd-Scuseria-Ernzerhof screened hybrid functional. We find that LiCoO$_2$ has a complex defect chemistry; different electronic and ionic defects can exist under different synthesis conditions, and LiCoO$_2$ samples free of cobalt antisite defects can be made under Li-excess (Co-deficient) environments. A defect model for lithium over-stoichiometric LiCoO$_2$ is also proposed, which involv…
Crystal structures play a vital role in determining materials properties. In Li-ion cathodes, the crystal structure defines the dimensionality and connectivity of interstitial sites, thus determining Li-ion diffusion kinetics. While a perfect crystal has infinite structural coherence, a class of recently discovered high-capacity cathodes, Li-excess cation-disordered rocksalts, falls on the other end of the spectrum: Their cation sublattices are assumed to be randomly populated by Li and transition metal ions with zero configurational coherence based on conventional X-ray diffraction, such that…
Wadsley--Roth crystallographic shear phases form a family of compounds that have attracted attention due to their excellent performance as lithium-ion battery electrodes. The complex crystallographic structure of these materials poses a challenge for first-principles computational modelling and hinders the understanding of their structural, electronic and dynamic properties. In this article, we study three different niobium-tungsten oxide crystallographic shear phases (Nb$_{12}$WO$_{33}$, Nb$_{14}$W$_{3}$O$_{44}$, Nb$_{16}$W$_5$O$_{55}$) using an enumeration-based approach and first-principles…
The results of dc and ac magnetization, heat-capacity, 57Fe Moessbauer spectroscopy, dielectric, pyroelectric current and isothermal magneto-capacitance measurements on a recently reported lithium-based oxide, Li3FeRuO6, related to LiCoO2-type rhombohedral structure (space group, R-3m) are presented. The results reveal that the compound undergoes spin-glass freezing below 15 K. There is a peak around 34 K in pyroelectric data, which can not be attributed to ferroelectricity, but to the phenomenon of thermally stimulated depolarization current. As revealed by magnetocapacitance data above and b…
Using a combination of experimental techniques and density functional theory (DFT) calculations, the influence of lithium insertion on the electronic and electrochemical properties of fluourine-doped SnO$_2$ (FTO) is assessed. For this purpose, we investigate the electrochromic behavior of commercial FTO electrode embedded in a solution of lithium perclorate (LiClO$_4$). The electrochromic properties are evaluated by UV-VIS spectroscopy, cyclic voltammetry, and chronoamperometry. These tests show that FTO exhibits electrochromism with a respectable coloration efficiency ($η=47.9$ cm$^2$/C @ 63…
The role of stoichiometry and growth temperature in the preferential nucleation of material phases in the Li-Nb-O family are explored yielding an empirical growth phase diagram. It is shown that while single parameter variation often produces multi-phase films, combining substrate temperature control with the previously published lithium flux limited growth allows the repeatable growth of high quality single crystalline films of many different oxide phases. Higher temperatures (800-1050 °C) than normally used in MBE were necessary to achieve high quality materials. At these temperatures the de…
Lithium-ion batteries (LIBs) are ubiquitous in everyday applications. However, Lithium (Li) is a limited resource on the planet and is therefore not sustainable. As an alternative to lithium, earth-abundant and cheaper multivalent metals such as aluminum (Al) and calcium (Ca) have been actively researched in battery systems. However, finding suitable intercalation hosts for multivalent-ion batteries is urgently needed. Open-tunneled oxides are a particular category of microparticles distinguished by the presence of integrated one-dimensional channels or nanopores. This work focuses on two prom…
Composite materials achieved by including transition-metal oxides with different structures and morphologies in sulfur are suggested as scalable cathodes for high-energy lithium-sulfur (Li-S) batteries. The composites contain 80 wt.% sulfur and 20 wt.% of either MnO2 or TiO2, leading to a sulfur content in the electrode of 64 wt.% and revealing a reversible, fast, and lowly polarized conversion process in the cell with limited interphase resistance. The S-TiO2 composite exhibits an excellent rate capability between C/10 and 2C, and a cycle life extended over 400 cycles at 2C, owing to the effe…
