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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Topotactic Reduction‐Driven Crystal Field Excitations in Brownmillerite Manganite Thin Films

Topotactic reduction of perovskite oxides offers a powerful approach for discovering novel phenomena, such as superconducting infinite-layer nickelates and polar metallicity, and is commonly accompanied by the emergence of multiple valence states and/or complex crystal fields of transition metals. However, understanding the complex interplay between crystal chemistry, electronic structure, and physical properties at the spin- and orbital-resolved levels in these reduced systems remains elusive. Here, in this study, x-ray absorption spectroscopy, resonant inelastic x-ray scattering (RIXS), and density functional theory calculations are used to uncover topotactic metal-insulator transition and orbital-specific crystal field excitations in brownmillerite La 0.67 Ca 0.33 MnO 2.5 thin films. The Mn valence states are found to be Mn 2+ /Mn 3+ , along with their corresponding populations at octahedral and tetrahedral sites, which effectively weaken the Mn-O hybridization compared to the parent perovskite phase. As a result, La 0.67 Ca 0.33 MnO 2.5 films exhibit an antiferromagnetic insulating ground state. Moreover, by combining the RIXS measurements on selected single-valence manganites, specifically MnO, LaMnO 3 , and CaMnO 3 , with orbital- and spin-resolved density-of-states calculations, the study identifies the dd excitations of octahedrally and tetrahedrally coordinated Mn 2+ /Mn 3+ ions, directly linking the microscopic electronic structure to the macroscopic magnetic/electrical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Promoting reversibility of layered potassium cathode through interstitial doping

With the increasing needs for large-scale and low-cost energy storage devices, Mn-based layered oxide cathodes have achieved considerable researching interests for potassium-ion batteries owing to their high energy density, abundant resource and low toxicity. However, their developments are challenged by the absence of suitable cathode materials to tolerate large-sized K-ion insertion/extraction and the presence of Jahn-Teller distortion of Mn 3+ . To address this issue, here we present a strategy of embedding boron into interstitial tetrahedral sites to obtain a P3-K 0.5 Mn 0.8 Co 0.2 B 0.1 O 2 cathode. Strong B-O covalent bonds facilitate the construction of robust orthorhombic framework and alleviate the undesired elongation of Mn-O bonds, contributing to excellent electrochemical performance. In addition, boron ions are verified to promote the formation of a homogeneous cathode electrolyte interphase layer, improving interfacial stability and realizing highly reversible cycling in a wide voltage range (1.4-4.3 V). This strategy provides a new pathway towards the development of high-performance cathode materials for potassium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification

Regardless of the prevailing capacity and energy density of lithium, manganese-rich layered oxide (LMR-NMC) cathodes, continuous decay of voltage and overall energy density during cycling hinders this material from commercialization in Li-ion batteries. Although significant work focuses on single doping of Na and F, analysis in portraying the benefit of these ions in diminishing the structural distortion during activation cycle is in doubt. In this study, the effects of co-doping Na and F into the LMR-NMC structure in stabilizing the structure and mitigating oxygen loss during the first cycle are closely examined via in situ x-ray measurements. Na and F co-doping shows a 30% lower degree of Li + /Ni 2+ mixing in the Li layer (C2/m structure), 50% reduced Debye-Waller factor of Mn-O bonding, increase reversible TM migration, and faster Li diffusion relative to the pristine material. Due to the utilization of Ni redox chemistry below 4.4 V, less oxygen redox is required for charge compensation at high voltage. This study offers the first instance to quantitatively evaluate the effects of co-doping Na and F in LMR-NMC cathode in order to minimize voltage degradation by altering the local ordering of O3-type structure, which may rationalize strategies to overcome the issues of the material.

25 ENERGY STORAGE↗
DOE OSTI2021

Tunning the linkage of structure units to enable stable spinel-based cathode in the wide potential window

The low practical capacity (<140 mA h g –1 ) of spinel phase LiMn 2–x Ni x O 4 (0 < x < 1) excludes it from high energy density lithium ion batteries (LIBs) for powering electric vehicles. Extending the operating potential window from 3.0 to 4.8 V to 2.0–4.8 V can double the capacity, but result in fast capacity decay due to the drastic cubic-tetragonal phase transition below 3.0 V, induced by serious Jahn-Teller (J-T) distortion of structure units (Mn 3+ )O 6 octahedra. Herein, we propose a novel strategy to suppress J-T distortion by tuning the linkage of structure units MnO 6 octahedra. The original full-vertex-sharing LiO 4 tetrahedra around MnO 6 octahedra in spinel phase are partially replaced by edge-sharing LiO 6 octahedra, which relate Mn-O bonds along the dz 2 direction with those along the d xy plane, thus significantly mitigating J-T distortion and suppressing the phase transition when discharged to 2.0 V. Following this strategy, the prepared spinel-based cathode achieves a high reversible capacity of about 290 mA h g –1 and an energy density up to 957 W h kg –1 with improved cycling stability. Furthermore, this work finds a new opportunity for the traditional spinel cathode towards applications in high energy density LIBs in a low cost and sustainable manner.

25 ENERGY STORAGE↗
DOE OSTI2023

Activity of Metal-Fluorine States upon Delithiation of Disordered Rocksalt Oxyfluorides

The capacity of transition-metal oxides as Li-ion battery cathodes is limited by instabilities that arise when high states of charge are achieved. Oxyfluorides with a disordered rocksalt structure have emerged as attractive alternatives, but the role of F in their electrochemical function, particularly when cationic redox produces high formal oxidation states, remains to be ascertained. Here, using X-ray absorption spectroscopy, we confirm the existence of Mn-F covalent interactions in Li 2 MnO 2 F and Li 2 Mn 2/3 Nb 1/3 O 2 F. New unoccupied states evolve from hybrid 3d-2p states of both Mn-F and Mn-O bonds when the phases are delithiated, particularly in the presence of Mn(IV). The results challenge the assumption of F as anion whose covalent states with the metal are tapped at very high potentials, providing instead a nuanced picture of redox compensation in oxyfluorides. They suggest the existence of unique knobs of design of battery cathodes by manipulating the covalent interactions between transition metals and two different anions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Origins of Irreversibility in Layered NaNi x Fe y Mn z O 2 Cathode Materials for Sodium Ion Batteries

Layered NaNi x Fe y Mn z O 2 cathode (NFM) is of great interest in sodium ion batteries due to its high theoretical capacity and utilization of abundant, low-cost, environmentally-friendly raw materials. Nevertheless, there remains insufficient understanding on the concurrent local environment evolution in each transition metal (TM) that largely influences the reversibility of the cathode materials upon cycling. In this work, we investigate the reversibility of TM ions in layered NFMs with varying Fe contents and potential windows. Utilizing ex situ synchrotron X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) of pre-cycled samples the valence and bonding evolution of the TMs are elucidated. It is found that Mn is electrochemically inactive as indicated by the insignificant change of Mn valence and Mn-O bonding distance. Fe is electrochemically inactive after the first five cycles. The Ni redox couple contributes most of the charge compensation for NFMs. Ni redox is quite reversible in the cathodes with less Fe contents. Furthermore, the Ni redox couple shows significant irreversibility with high Fe content of 0.8. The electrochemical reversibility of the NFM cathode becomes increasingly enhanced with the decrease of either Fe content or with lower upper charge cutoff potential.

25 ENERGY STORAGE↗
DOE OSTI2022

Li 8 MnO 6 : A Novel Cathode Material with Only Anionic Redox

In Li-excess transition-metal-oxide cathode materials, anionic oxygen redox can offer high capacity and high voltages, although peroxo and superoxo species may cause oxygen loss, poor cycling performance, and capacity fading. Previous work showed that undesirable formation of peroxide and superoxide bonds is controlled to some extent by Mn substitution, and the present work uses density functional calculations to examine the reasons for this by studying the anionic redox mechanism Li 8 MnO 6 . This material is obtained by substituting Mn for Sn in Li 8 SnO 6 or for Zr in Li 8 ZrO 6 , and we also compare to previous work on those materials. The calculations predict that Li 8 MnO 6 is stable at room temperature (with a band gap of 3.19 eV as calculated HSE06 and 1.82 eV as calculated with the less reliable with PBE+U), and they elucidate the chemical and structural effects involved in the inhibition of oxygen release in this cathode. Throughout the whole delithiation process, only O 2- ions are oxidized. The directional Mn-O bonds formed from unfilled 3d orbitals effectively inhibit the formation of O-O bonds, and the layered structure is maintained even after removing 3 Li per Li 8 MnO 6 formula unit. The calculated average voltage for removal of 3 Li is 3.69 V by HSE06, and the corresponding capacity is 389 mAh/g. The high voltage of oxygen anionic redox and the high capacity result in a high energy density of 1436 Wh/kg. The Li-ion diffusion barrier for the dominant interlayer diffusion path along the c-axis is 0.57 eV by PBE+U. Finally, these results help us to understand the oxygen redox mechanism in a new lithium-rich Li 8 MnO 6 cathode material and contribute to the design of high-energy-density lithium-ion-battery cathode materials with favorable electrochemical properties based on anionic oxygen redox.

Li8MnO6↗
DOE OSTI2021

Tuning local chemistry of P2 layered-oxide cathode for high energy and long cycles of sodium-ion battery

Layered transition-metal oxides have attracted intensive interest for cathode materials of sodium-ion batteries. However, they are hindered by the limited capacity and inferior phase transition due to the gliding of transition-metal layers upon Na + extraction and insertion in the cathode materials. Here, we report that the large-sized K + is riveted in the prismatic Na + sites of P2-Na 0.612 K 0.056 MnO 2 to enable more thermodynamically favorable Na + vacancies. The Mn-O bonds are reinforced to reduce phase transition during charge and discharge. 0.901 Na + per formula are reversibly extracted and inserted, in which only the two-phase transition of P2 ↔ P’2 occurs at low voltages. It exhibits the highest specific capacity of 240.5 mAh g -1 and energy density of 654 Wh kg -1 based on the redox of Mn 3+ /Mn 4+ , and a capacity retention of 98.2% after 100 cycles. This investigation will shed lights on the tuneable chemical environments of transition-metal oxides for advanced cathode materials and promote the development of sodium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Electronic and structural properties of single-crystal Jahn–Teller active Co 1+x Mn 2–x O 4 thin films

Recent investigations on spinel CoMn 2 O 4 have shown its potential for applications in water splitting and fuel cell technologies as it exhibits strong catalytic behavior through oxygen reduction reactivity. To further understand this material, we report for the first time the synthesis of single-crystalline Co 1+x Mn 2-x O 4 thin films using molecular beam epitaxy. By varying sample composition, we establish links between cation stoichiometry and material properties using in-situ x-ray photoelectron spectroscopy, x-ray diffraction, scanning transmission electron microscopy, x-ray absorption spectroscopy, and spectroscopic ellipsometry. Our results indicate that excess Co ions occupy interstitial tetrahedral sites up to a certain stoichiometry, then are substitutional for octahedrally-coordinated Mn beyond this threshold. Here, we compare these results with density functional theory models of stoichiometric CoMn 2 O 4 to understand how the Jahn-Teller distortion and hybridization in Mn-O bonds impact the ability to hole dope the material with excess Co. The findings provide important insights into CoMn 2 O 4 and related spinel oxides for future application as inexpensive oxygen reduction reaction catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Interplay between electron localization, magnetic order, and Jahn-Teller distortion dictates LiMnO2 phase stability

The development of manganese (Mn)-rich cathodes for Li-ion batteries promises to alleviate potential supply chain bottlenecks in battery manufacturing. Fundamental challenges in Mn-rich cathodes arise from phenomena such as structural changes due to cooperative Jahn-Teller (JT) distortions of in octahedral environments, Mn migration, and phase transformations to spinel-like order, all of which affect the electrochemical performance. These physically complex phenomena motivate an re-examination of the Li-Mn-O rock-salt space, with a focus on the thermodynamics of the prototypical, polymorphs. It is found that the generalized gradient approximation (GGA-PBEsol) and meta-GGA ( ) density functionals with empirically fitted on-site Hubbard corrections yield spurious stable phases for , such as predicting a phase with -like order ( ) to be the ground state instead of the orthorhombic (Pmmn) phase, which is the experimentally known ground state. Accounting for antiferromagnetic order in each structure is shown to have a substantial effect on the total energies and resulting phase stability. By using hybrid-GGA (HSE06) and GGA with self-consistent Hubbard parameters (on-site and inter-site ) calculated from linear response theory, the experimentally observed phase stability trends are recovered. The calculated on-site between Mn- states in the experimentally observed orthorhombic, layered, and spinel phases are significantly smaller than in and disordered layered structures, by within GGA. The smaller values of are shown to be correlated with a collinear ordering of JT distortions, in which all orbitals are oriented in the same direction. This cooperative JT effect can lead to greater electron delocalization from Mn along the states due to increased Mn-O covalency, which contributes to the greater electronic stability compared to the phases with noncollinear JT arrangements. The structures with collinear ordering of JT distortions also generate greater vibrational entropy, which helps stabilize these phases at high temperature. These phases are shown to be strongly insulating with large calculated band gaps , which are computed using HSE06 and .

Kam, Ronald L↗
DOE OSTI2023

Effect of off-diagonal elements in the Wannier Hamiltonian on DFT + DMFT for low-symmetry materials: Study of Li 2 MnO 3

Here, we study the effect of the off-diagonal elements of the Wannier Hamiltonian on the electronic structure of the low-symmetry material Li 2 MnO 3 ( C2/m ), using dynamical mean field theory calculations with a continuous-time quantum Monte Carlo impurity solver. The presence of significant off-diagonal elements leads to a pronounced suppression of the energy gap. The off-diagonal elements are largest when the Wannier projection is used based on the global coordinate, and they remain substantial even with the projection using the local coordinate close to the direction of Mn-O bonds. We show that the energy gap is enhanced by the diagonalization of the Mn d block in the full p-d Hamiltonian with the application of a unitary rotation matrix. Additionally, the inclusion of small double counting energy is crucial for achieving the experimental gap by reducing p-d hybridization. Furthermore, we establish the efficiency of a low-energy (d-only basis) model for studying the electronic structure of Li 2 MnO 3 , as the Wannier basis represents a hybridized state of Mn d and O p orbitals. These findings suggest an appropriate approach for investigating low-symmetry materials using the density functional theory plus dynamical mean field theory (DFT + DMFT) method. We also find that the antiferromagnetic ground state $\Gamma$ 2u is stable with U ≤ 2 eV within density functional theory+$U$ calculations, which is much smaller than the widely used U = 5 eV.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Structural, vibrational, thermal, and magnetic properties of mullite-type NdMnTiO 5 ceramic

Mullite-type $R$Mn 2 O 5 ($R$ = Y, rare-earth element) ceramics are of ongoing research attention because of their interesting crystal-chemical and magnetic properties. We report nuclear and magnetic structures of NdMnTiO 5 together with its spectroscopic, thermogravimetric, and magnetic properties. The polycrystalline sample is prepared by solid-state synthesis and characterized from neutron and X-ray powder diffraction data Rietveld refinements. NdMnTiO 5 crystallizes in the orthorhombic space group $Pbam$ with metric parameter $a$ = 755.20(1) pm, $b$ = 869.91(1) pm, $c$ = 582.42(1) pm, and $V$ = 382.62(1) 10 6 pm 3 . The Mn 3+ and Ti 4+ cations are observed to be located in the octahedral and pyramidal sites, respectively. The vibrational features in these polyhedral sites are characterized by Raman and Fourier transform infrared spectroscopes. The higher decomposition temperature of NdMnTiO 5 , compared to other $R$Mn 2 O 5 phases, is explained in terms of the higher bond strength of Ti-O bonds than those of Mn-O bonds. Temperature-dependent DC magnetic susceptibility suggests a paramagnetic to antiferromagnetic phase transition at 43(1) K. Inverse susceptibility in the paramagnetic region above 120 K follows the Curie-Weiss law, resulting in a magnetic moment of 6.33(1) μ B per formula unit. Neutron diffraction data collected at 7.5 K reveal that the magnetic moments of Nd 3+ and Mn 3+ in NdMnTiO 5 are incommensurately ordered with a propagation vector $k$ = (0, 0.238, 0.117).

36 MATERIALS SCIENCE↗
DOE OSTI2023

The crystal structure of feitknechtite (β-MnOOH) and a new MnOOH polymorph

Studies suggest that feitknechtite (β-MnOOH) is a prevalent, and perhaps necessary, intermediate phase during the synthesis of birnessite-like phases, the abiotic oxidation of Mn2+, and the transformation of biogenic hexagonal phyllomanganates to more complex Mn oxides in laboratory and natural systems. Researchers have generally described feitknechtite as consisting of pyrochroite-like (or cadmium iodide-like) Mn-O octahedral layers, but a detailed crystal structure has not been reported. For this work, we used TEM/SAED and powder XRD and Rietveld refinements to derive the unit cell and, for the first time, report a complete structure description for feitknechtite (β-MnOOH). Rietveld refinements were also completed for three natural feitknechtite/hausmannite samples, and time-resolved synchrotron XRD experiments were used to follow the thermal transformation of feitknechtite to hausmannite. Additionally, we identified and report the structure for a second, and perhaps novel, MnOOH polymorph (proposed designation ε-MnOOH), mixed with the synthetic feitknechtite, that is similar to β-MnOOH but with a different layer stacking.

58 GEOSCIENCES↗
NASA NTRS1977

The design of an Fe-12Mn-O.2Ti alloy steel for low temperature use

An investigation was made to improve the low temperature mechanical properties of Fe-8 approximately 12% Mn-O 2Ti alloy steels. A two-phase(alpha + gamma) tempering in combination with cold working or hot working was identified as an effective treatment. A potential application as a Ni-free cryogenic steel was shown for this alloy. It was also shown that an Fe-8Mn steel could be grain-refined by a purely thermal treatment because of its dislocated martensitic structure and absence of epsilon phase. A significant reduction of the ductile-brittle transition temperature was obtained in this alloy. The nature and origin of brittle fracture in Fe-Mn alloys were also investigated. Two embrittling regions were found in a cooling curve of an Fe-12Mn-O 2Ti steel which was shown to be responsible for intergranular fracture. Auger electron spectroscopy identified no segregation during solution-annealing treatment. Avoiding the embrittling zones by controlled cooling led to a high cryogenic toughness in a solution-annealed condition.

Hwang, S. K.↗
DOE OSTI2020

Materials Data on Mn2O3 by Materials Project

Mn2O3 is Hausmannite-like structured and crystallizes in the orthorhombic Pbca space group. The structure is three-dimensional. there are five inequivalent Mn3+ sites. In the first Mn3+ site, Mn3+ is bonded to six O2- atoms to form a mixture of distorted edge and corner-sharing MnO6 octahedra. The corner-sharing octahedra tilt angles range from 48–61°. There are a spread of Mn–O bond distances ranging from 1.92–2.28 Å. In the second Mn3+ site, Mn3+ is bonded to six O2- atoms to form a mixture of distorted edge and corner-sharing MnO6 octahedra. The corner-sharing octahedra tilt angles range from 48–60°. There are a spread of Mn–O bond distances ranging from 1.94–2.29 Å. In the third Mn3+ site, Mn3+ is bonded to six O2- atoms to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedra tilt angles range from 48–50°. There are a spread of Mn–O bond distances ranging from 1.99–2.12 Å. In the fourth Mn3+ site, Mn3+ is bonded to six O2- atoms to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedra tilt angles range from 48–50°. There are a spread of Mn–O bond distances ranging from 1.99–2.12 Å. In the fifth Mn3+ site, Mn3+ is bonded to six O2- atoms to form a mixture of distorted edge and corner-sharing MnO6 octahedra. The corner-sharing octahedra tilt angles range from 48–61°. There are a spread of Mn–O bond distances ranging from 1.95–2.32 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Mn3+ atoms. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Mn3+ atoms. In the third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Mn3+ atoms. In the fourth O2- site, O2- is bonded to four Mn3+ atoms to form distorted corner-sharing OMn4 tetrahedra. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Mn3+ atoms. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Mn3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Mn2O3 by Materials Project

Mn2O3 is Corundum structured and crystallizes in the trigonal R-3c space group. The structure is three-dimensional. Mn3+ is bonded to six equivalent O2- atoms to form a mixture of corner, edge, and face-sharing MnO6 octahedra. The corner-sharing octahedra tilt angles range from 47–60°. There are three shorter (2.03 Å) and three longer (2.11 Å) Mn–O bond lengths. O2- is bonded to four equivalent Mn3+ atoms to form a mixture of distorted corner and edge-sharing OMn4 trigonal pyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on MnO2 by Materials Project

MnO2 crystallizes in the trigonal R3m space group. The structure is three-dimensional. there are two inequivalent Mn4+ sites. In the first Mn4+ site, Mn4+ is bonded to four O2- atoms to form corner-sharing MnO4 tetrahedra. The corner-sharing octahedra tilt angles range from 57–59°. There are three shorter (1.95 Å) and one longer (2.08 Å) Mn–O bond lengths. In the second Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three equivalent MnO4 tetrahedra and edges with four equivalent MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.87–2.02 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to three Mn4+ atoms. In the second O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to four Mn4+ atoms. In the third O2- site, O2- is bonded in a distorted T-shaped geometry to three equivalent Mn4+ atoms. In the fourth O2- site, O2- is bonded in a water-like geometry to two equivalent Mn4+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on MnO2 by Materials Project

MnO2 crystallizes in the orthorhombic Pbcm space group. The structure is three-dimensional. Mn4+ is bonded to six O2- atoms to form a mixture of edge and corner-sharing MnO6 octahedra. The corner-sharing octahedra tilt angles range from 0–50°. There are a spread of Mn–O bond distances ranging from 1.84–2.06 Å. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to three equivalent Mn4+ atoms. In the second O2- site, O2- is bonded in a square co-planar geometry to four equivalent Mn4+ atoms. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to two equivalent Mn4+ atoms.

36 MATERIALS SCIENCE↗