Vacancy Ordering Research Articles

A W/Al Co-doped Na0.44MnO2 Cathode Material for Enhanced Sodium-Ion Storage.

The Na0.44MnO2 cathode has attracted enormous interest owing to its low cost, low toxicity, and stable structure, but its practical application is still hindered by the limited sodium storage sites. Element doping is widely used to improve its capacity. However, cation and anion substitution could barely reach a satisfactory compromise between the structural stability and reversible capacity. Herein, we show that the above issue could be overcome via the synergetic effect of W and Al substitution. Combining the electrochemical and in situ X-ray powder diffraction (XRD) measurements, we reveal that the substitution of W effectively facilitates the tunnel-to-layered phase transformation, while the further substitution of Al eliminates the Na+/vacancy ordering during the extraction/insertion of Na+ ions, resulting in a layered Na0.44Mn0.94W0.01Al0.05O2 (NMO-1W5Al) with negligible Na+/vacancy ordering upon cycling. In addition, NMO-1W5Al represents a wider Na+ interlayer spacing to accelerate the diffusion of Na+, which improves the rate performance. The high specific capacity, remarkable rate performance, and high cycling stability of NMO-1W5Al are promising for large-scale energy storage systems.

Structural Regulation of P2‐Type Layered Oxide with Anion/Cation Codoping Strategy for Sodium‐Ion Batteries

AbstractP2‐type layered transition metal oxides are potential cathodes for sodium‐ion batteries (SIBs), but they commonly suffer from severe capacity degradation owing to multiple phase transitions and Na+/vacancy ordering during the extraction/insertion process. An anionic/cationic co‐doping strategy at high sodium contents is proposed to effectively achieve high‐rate and long‐term stability of P2‐Na0.67Ni0.33Mn0.67O2. The resulting Na0.75Mg0.1Ni0.23Mn0.67O1.95F0.05 (NMNMOF) cathode delivers a reversible capacity of 116 mAh g−1 at 75 mA g−1 and maintains an initial capacity of 73% at 1500 mA g−1 after 1000 cycles. The Mg/F anionic/cationic co‐doping strategy impacts the local environment of the surrounding transition metal and oxygen, regulates the electron distribution, and modifies the initial diffusion state of Na sites, enhancing the diffusion ability of Na+. Moreover, the phase transition of P2‐O2 is well suppressed and the decrease in Mn3+ content greatly alleviates the Jahn–Teller effect to enhance structural stability. The full‐cell devices with NMNMOF cathode and hard carbon anode demonstrate a high capacity of 80 mAh g−1 at 10 C and an excellent cycle life of over 500 cycles for applications. The anionic/cationic co‐doping strategy will inspire the rational design of P2‐type layered oxides and provide a new perspective for advanced SIBs.

Unveiling nodeless unconventional superconductivity proximate to honeycomb-vacancy ordering in the Ir-Sb binary system

Vacancies in solid-state physics are underexplored in materials with strong electron-electron correlations. Recent research on the Ir-Sb binary system revealed an extended buckled-honeycomb vacancy (BHV) order. Superconductivity arises by suppressing BHV ordering through high-pressure growth with excess Ir atoms or Rh substitution, yet the superconducting pairing nature remains unknown. To explore this, we conducted muon spin rotation experiments on Ir1−δSb (synthesized at 5.5 GPa, Tc = 4.2 K) and ambient pressure synthesized optimally Rh-doped Ir1−xRhxSb (x=0.3, Tc = 2.7 K). The exponential temperature dependence of the superfluid density suggests a fully gapped superconducting state exists in both samples. The ratio of Tc to the superfluid density resembles that of unconventional superconductors. A significant increase in the superfluid density in the high-pressure synthesized sample correlates with Tc, indicating that unconventional superconductivity is intrinsic to the Ir-Sb binary system. These findings, along with the dome-shaped phase diagram, highlight IrSb as the first unconventional superconducting parent phase with ordered vacancies, requiring further theoretical investigations.

Achieving complete solid-solution reaction in layered cathodes with reversible oxygen redox for high-stable sodium-ion batteries

P2-type layered Mn-based oxides are promising cathode materials for sodium-ion batteries (SIBs), but it is still challenging to achieve both high capacity and stability because of complex phase transitions and irreversible oxygen release at high voltage. To address these challenges, an optimal P2-type Na0.67Mn0.8Cu0.15Ti0.05O2 (NMCT) cathode with a complete solid-solution reaction and reversible oxygen redox reaction over a wide voltage range was developed. The introduction of the Na–O–Ti configuration leads to fewer delocalized electrons on oxygen and thus enhances oxygen redox activity, while the high energetic overlap between O 2p and Cu 3d states and the increased Mn–O hybridization strengthen the rigidity of oxygen framework to achieve reversible and stable oxygen redox reaction. In addition, the reinforced TM–O interaction, combined with the ameliorated Mn3+ Jahn-Teller distortion and disrupted Na+/vacancy ordering, synergistically eliminate the undesired P2–OP4 phase transition and lead to a complete solid-solution reaction, which greatly facilitates Na+ transport kinetics and stabilizes structural integrity. As a consequence, improved rate performance and cycling stability are achieved for NMCT. Our present study provides a promising avenue for simultaneously utilizing the reversible oxygen redox activity and maintaining the structural integrity to accomplish the capacity-stability trade-off of Mn-based oxide cathodes for constructing practical SIBs.

Microstructure Morphology of Chemical and Structural Phase Separation in Thermally treated KxFe2-ySe2Superconductor.

The iron-based KxFe2-ySe2 superconductor displays phase separation, leading to the coexisting metallic phase embedded in an antiferromagnetic matrix. The metallic character of the system is believed to arise from a percolative granular network affecting normal as well as superconducting state properties. This network can be manipulated and controlled through thermal treatments. In this study, we have used scanning X-ray micro-fluorescence to visualize morphology of the phase separation and the percolation in KxFe2-ySe2, manipulated by distinct thermal treatments, i.e., fast quenching and slow cooling. We find a differing spatial correlation between Fe and K in differently treated samples, ascribed to different Fe vacancy ordering. We have identified an intermediate phase that acts as an interface between the two phases. The high temperature quenching produces oriented clustered microstructure in which the percolation threshold is lower and hence a more effective network for the transport pathways. Instead, the slow cooling results in larger interfaces around the percolation threshold affecting the superconducting properties of the system. The results provide a quantitative characterization of microstructural morphology of differently grown KxFe2-ySe2 showing potential for the design of electronic devices based on sub-micron scale chemical phase separation, thus opening avenues for further studies of complex heterogeneous structures.

Tuning Na Occupation and Annealing Temperature on Na Diffusion Pathways in P2-Type NaxNi0.25Mn0.75O2 for Sodium-Ion Batteries by Ab Initio Calculations.

The NaxNi0.25Mn0.75O2 cathode material draws ongoing interest owing to its considerable specific capacity along with its elevated average operating voltage. However, its application is limited by weak rate performance and quick capacity fading. In this study, a series of NaxNi0.25Mn0.75O2 (x = 0.65, 0.70, 0.75, 0.80) cathode materials are prepared by the solid-phase method based on an orthogonal experiment. The optimum preparation process is investigated by optimizing factors such as Na content, calcination temperature, calcination time, and heating rate. The Nae/Naf ratio is adjusted, and the Na+ at different sites are rearranged to reduce the Na+/vacancy ordering by changing the Na content on the basis of process optimization. Owing to the fast migration kinetics of Nae sites, experimental results indicate that the P2-Na0.75Ni0.25Mn0.75O2 cathode material, which has Na+ occupying more thermodynamically stable Nae sites, demonstrates superior battery performance. High initial discharge specific capacity (157.2 mAh g-1) along with favorable cycle performance of the Na0.75Ni0.25Mn0.75O2 cathode material can be achieved by modifying the Nae site occupancy and optimizing the experimental conditions. Together with the microscopic control of Na+ occupancy, this novel orthogonal experiment design offers a fresh perspective and approach to a thorough comprehension of cathode materials for sodium-ion batteries.

Oxygen vacancy order–disorder transition process during topotactic filament formation in a perovskite oxide tracked by Raman microscopy and transmission electron microscopy

Vacancy-ordered perovskite oxides are attracting attention due to their diverse functions such as resistive switching, electrocatalytic activity, oxygen diffusivity, and ferroelectricity. It is important to clarify the chemical lattice strains arising from compositional changes and the associated vacancy order–disorder phase transitions at the atomic scale. Here, we elucidate the intermediate process of a topotactic phase transition in Ca-doped bismuth ferrite films consisting of alternating stacks of oxygen perovskite layers and a brownmillerite-type oxygen vacancy layer. We use Raman spectroscopy and transmission electron microscopy to closely examine the evolution of local strains exerted on the constituent sub-layers by electrochemical oxidation. A negative Raman chemical shift is observed during oxidation, which is linearly correlated with the local negative chemical expansivity of the oxygen layer. It seemingly contradicts with the general trend that oxides undergo lattice contraction upon oxidation. Oxygen vacancies initially confined in the vacancy layers can be understood to diffuse into the oxygen layers during melting of the ordered structure. The finding deepens our understanding of the electro-chemo-mechanical coupling of vacancy-ordered oxides.

Unexpected Elevated Working Voltage by Na+/Vacancy Ordering and Stabilized Sodium‐Ion Storage by Transition‐Metal Honeycomb Ordering

AbstractNa+/vacancy ordering in sodium‐ion layered oxide cathodes is widely believed to deteriorate the structural stability and retard the Na+ diffusion kinetics, but its unexplored potential advantages remain elusive. Herein, we prepared a P2‐Na0.8Cu0.22Li0.08Mn0.67O2 (NCLMO‐12 h) material featuring moderate Na+/vacancy and transition‐metal (TM) honeycomb orderings. The appropriate Na+/vacancy ordering significantly enhances the operating voltage and the TM honeycomb ordering effectively strengthens the layered framework. Compared with the disordered material, the well‐balanced dual‐ordering NCLMO‐12 h cathode affords a boosted working voltage from 2.85 to 3.51 V, a remarkable ~20 % enhancement in energy density, and a superior cycling stability (capacity retention of 86.5 % after 500 cycles). The solid‐solution reaction with a nearly “zero‐strain” character, the charge compensation mechanisms, and the reversible inter‐layer Li migration upon sodiation/desodiation are unraveled by systematic in situ/ex situ characterizations. This study breaks the stereotype surrounding Na+/vacancy ordering and provides a new avenue for developing high‐energy and long‐durability sodium layered oxide cathodes.

A high-entropy cathode for sodium-ion batteries: Cu/Zn-doping O3-Type Ni/Fe/Mn layer oxides

The O3 layered oxides have been extensively investigated as cathode materials for sodium-ion batteries due to their remarkable theoretical capacity. However, the large radius of Na+ lead to complex phase transitions and tortuous diffusion channels during extraction/insertion, which ultimately restricts the Na+ diffusion kinetics and cyclic stability. In this study, we report a Zn and Cu co-doping strategy to the high entropy layer oxide Na [Ni0·2Fe0·2Mn0·4Cu0·15Zn0.05]O2 (HEO-CuZn) using the sol-gel method to prepare the oxides. Here, Zn is used to stabilize the structure of layer between the transition metal and O atoms, which slows down the adverse phase transition. In the fabricated sample, the element Cu provides additional capacity and inhibits excessive oxidation. The prepared HEO-CuZn used as cathode for Na+ ion battery exhibits better electrochemical performance, delivering a high specific capacity of 148 mA h g−1, and 84 % capacity retention after 100 cycles, which is attributed to the expanded Na+ transfer channels, reduced activation energy and interface side reactions, thus enhancing the Na+ diffusion kinetics. Meanwhile, the high entropy strategy stabilizes the overall structure by reducing the John-Teller distortion and suppressing the Na+/vacancy order, and effectively avoids adverse phase transitions such as O′3 and P′3. This study provides a new insight for the advance of the next generation high specific energy sodium-ion battery.

Structural Complexities in Sodium Ion Conductive Antiperovskite Revealed by Cryogenic Transmission Electron Microscopy.

We use low-dose cryogenic transmission electron microscopy (cryo-TEM) to investigate the atomic-scale structure of antiperovskite Na2NH2BH4 crystals by preserving the room-temperature cubic phase and carefully monitoring the electron dose. Via quantitative analysis of electron beam damage using selected area electron diffraction, we find cryogenic imaging provides 6-fold improvement in beam stability for this solid electrolyte. Cryo-TEM images obtained from flat crystals revealed the presence of a new, long-range-ordered supercell with a cubic phase. The supercell exhibits doubled unit cell dimensions of 9.4 Å × 9.4 Å as compared to the cubic lattice structure revealed by X-ray crystallography of 4.7 Å × 4.7 Å. The comparison between the experimental image and simulated potential map indicates the origin of the supercell is a vacancy ordering of sodium atoms. This work demonstrates the potential of using cryo-TEM imaging to study the atomic-scale structure of air- and electron-beam-sensitive antiperovskite-type solid electrolytes.

3D oxygen vacancy distribution and defect-property relations in an oxide heterostructure

Oxide heterostructures exhibit a vast variety of unique physical properties. Examples are unconventional superconductivity in layered nickelates and topological polar order in (PbTiO3)n/(SrTiO3)n superlattices. Although it is clear that variations in oxygen content are crucial for the electronic correlation phenomena in oxides, it remains a major challenge to quantify their impact. Here, we measure the chemical composition in multiferroic (LuFeO3)9/(LuFe2O4)1 superlattices, mapping correlations between the distribution of oxygen vacancies and the electric and magnetic properties. Using atom probe tomography, we observe oxygen vacancies arranging in a layered three-dimensional structure with a local density on the order of 1014 cm−2, congruent with the formula-unit-thick ferrimagnetic LuFe2O4 layers. The vacancy order is promoted by the locally reduced formation energy and plays a key role in stabilizing the ferroelectric domains and ferrimagnetism in the LuFeO3 and LuFe2O4 layers, respectively. The results demonstrate pronounced interactions between oxygen vacancies and the multiferroic order in this system and establish an approach for quantifying the oxygen defects with atomic-scale precision in 3D, giving new opportunities for deterministic defect-enabled property control in oxide heterostructures.

Unexpected Elevated Working Voltage by Na+/Vacancy Ordering and Stabilized Sodium-Ion Storage by Transition-Metal Honeycomb Ordering.

Na+/vacancy ordering in sodium-ion layered oxide cathodes is widely believed to deteriorate the structural stability and retard the Na+ diffusion kinetics, but its unexplored potential advantages remain elusive. Herein, we prepared a P2-Na0.8Cu0.22Li0.08Mn0.67O2 (NCLMO-12 h) material featuring moderate Na+/vacancy and transition-metal (TM) honeycomb orderings. The appropriate Na+/vacancy ordering significantly enhances the operating voltage and the TM honeycomb ordering effectively strengthens the layered framework. Compared with the disordered material, the well-balanced dual-ordering NCLMO-12 h cathode affords a boosted working voltage from 2.85 to 3.51 V, a remarkable ~20 % enhancement in energy density, and a superior cycling stability (capacity retention of 86.5 % after 500 cycles). The solid-solution reaction with a nearly "zero-strain" character, the charge compensation mechanisms, and the reversible inter-layer Li migration upon sodiation/desodiation are unraveled by systematic in situ/ex situ characterizations. This study breaks the stereotype surrounding Na+/vacancy ordering and provides a new avenue for developing high-energy and long-durability sodium layered oxide cathodes.

Ordering of oxygen vacancies in hydroxyapatite under electron irradiation

Understanding the mechanisms of radiation induced defect generation is essential for assessment of materials to be used in nuclear environments. In the current work, we investigate the effect of 10 MeV electron irradiation on the generation and possible ordering of defects/oxygen vacancies in hydroxyapatite (HAP) powders. Comprehensive analyses of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Electron Paramagnetic Resonance (EPR) and Raman spectra establish that (a) HAP has a high level of structural stability even after exposure to electron irradiation; (b) irradiation leads to the generation of surface defects/oxygen vacancy predominantly in the PO43− polyanion site, particularly in part of asymmetric bonding within the P–O bonds and (c) there is noticeable evidence for an ordered arrangement of oxygen vacancies within the HAP irradiated at 1 MGy dose. These radiation-induced defects, such as oxygen vacancies, can migrate within the HAP lattice, leading to formation of defect/oxygen vacancies clusters which ultimately results in the ordering tendency of oxygen vacancies within the lattice. The observed ordering, as evidenced by the photoluminescence intensities, aligns with the sequence HAP-1MGy > HAP-20MGy > HAP, providing further support for the presence of ordered oxygen vacancies.

Atomically Resolved Transition Pathways of Iron Redox.

The redox transition between iron and its oxides is of the utmost importance in heterogeneous catalysis, biological metabolism, and geological evolution. The structural characteristics of this reaction may vary based on surrounding environmental conditions, giving rise to diverse physical scenarios. In this study, we explore the atomic-scale transformation of nanosized Fe3O4 under ambient-pressure H2 gas using in-situ environmental transmission electron microscopy. Our results reveal that the internal solid-state reactions dominated by iron diffusion are coupled with the surface reactions involving gaseous O or H species. During reduction, we observe two competitive reduction pathways, namely Fe3O4 → FeO → Fe and Fe3O4 → Fe. An intermediate phase with vacancy ordering is observed during the disproportionation reaction of Fe2+ → Fe0 + Fe3+, which potentially alleviates stress and facilitates ion migration. As the temperature decreases, an oxidation process occurs in the presence of environmental H2O and trace amounts of O2. A direct oxidation of Fe to Fe3O4 occurs in the absence of the FeO phase, likely corresponding to a change in the water vapor content in the atmosphere. This work elucidates a full dynamical scenario of iron redox under realistic conditions, which is critical for unraveling the intricate mechanisms governing the solid-solid and solid-gas reactions.

Vacancy Ordering in Ultrathin Copper Oxide Films on Cu(111).

Oxide thin films grown on metal surfaces have wide applications in catalysis and beyond owing to their unique surface structures compared to their bulk counterparts. Despite extensive studies, the atomic structures of copper surface oxides on Cu(111), commonly referred to as "44" and "29", have remained elusive. In this work, we demonstrated an approach for the structural determination of oxide surfaces using element-specific scanning tunneling microscopy (STM) imaging enhanced by functionalized tips. This approach enabled us to resolve the atomic structures of "44" and "29" surface oxides, which were further corroborated by noncontact atomic force microscopy (nc-AFM) measurements and Monte Carlo (MC) simulations. The stoichiometry of the "44" and "29" frameworks was identified as Cu23O16 and Cu16O11, respectively. Contrary to the conventional hypothesis, we observed ordered Cu vacancies within the "44" structure manifesting as peanut-shaped cavities in the hexagonal lattice. Similarly, a combination of Cu and O vacancies within the "29" structure leads to bean-shaped cavities within the pentagonal lattice. Our study has thus resolved the decades-long controversy on the atomic structures of "44" and "29" surface oxides, advancing our understanding of copper oxidation processes and introducing a robust framework for the analysis of complex oxide surfaces.

Percolation-Induced Ferrimagnetism from Vacancy Order in [Gua]Mn1-xFe2x/3(HCOO)3 Hybrid Perovskites.

We report the magnetic behavior of the hybrid perovskites [Gua]Mn1-xFe2x/3□x/3(HCOO)3 (0 ≤ x ≤ 0.88), showing that vacancy ordering drives bulk ferrimagnetism for x > 0.6. The behavior is rationalized in terms of a simple microscopic model of percolation-induced ferrimagnetism. Monte Carlo simulations driven by this model reproduce the experimental dependence of magnetic susceptibility on x and show that, at intermediate compositions, domains of short-range vacancy order lead to the emergence of local magnetization. Our results open up a new avenue for the design of multiferroic hybrid perovskites.

Influence of Interlayer Cation Ordering on Na Transport in P2-Type Na0.67-xLiy Ni0.33-zMn0.67+zO2 for Sodium-Ion Batteries.

P2-type Na2/3Ni1/3Mn2/3O2 (PNNMO) has been extensively studied because of its desirable electrochemical properties as a positive electrode for sodium-ion batteries. PNNMO exhibits intralayer transition-metal ordering of Ni and Mn and intralayer Na+/vacancy ordering. The Na+/vacancy ordering is often considered a major impediment to fast Na+ transport and can be affected by transition-metal ordering. We show by neutron/X-ray diffraction and density functional theory (DFT) calculations that Li doping (Na2/3Li0.05Ni1/3Mn2/3O2, LFN5) promotes ABC-type interplanar Ni/Mn ordering without disrupting the Na+/vacancy ordering and creates low-energy Li-Mn-coordinated diffusion pathways. A structure model is developed to quantitatively identify both the intralayer cation mixing and interlayer cationic stacking fault densities. Quasielastic neutron scattering reveals that the Na+ diffusivity in LFN5 is enhanced by an order of magnitude over PNNMO, increasing its capacity at a high current. Na2/3Ni1/4Mn3/4O2 (NM13) lacks Na+/vacancy ordering but has diffusivity comparable to that of LFN5. However, NM13 has the smallest capacity at a high current. The high site energy of Mn-Mn-coordinated Na compared to that of Ni-Mn and higher density of Mn-Mn-coordinated Na+ sites in NM13 disrupts the connectivity of low-energy Ni-Mn-coordinated diffusion pathways. These results suggest that the interlayer ordering can be tuned through the control of composition, which has an equal or greater impact on Na+ diffusion than the Na+/vacancy ordering.

Epitaxial oxide ionotronics: Interfaces and oxygen vacancies

Epitaxial oxide ionotronics: Interfaces and oxygen vacancies

Ti-doped O3-NaNi0.5Mn0.5O2 as high-performance cathode materials for sodium-ion batteries

With favorable electrochemical activity, NaNi0.5Mn0.5O2(NNMO) has been a key cathode material in sodium-ion batteries. However, the phase-transition irreversible and kinetics sluggish issues in NaNi0.5Mn0.5O2 greatly limit its application in sodium-ion batteries. Here, various Ti-doped O3-NaNi0.5Mn0.5-xTixO2 cathode materials were fabricated via solid-phase method. The extra Ti-doping treatment effectively stabilized the transition layer of metal and enlarged the Na layer spacing, as well as suppressed the Na+/vacancy ordering. In particular, the obtained O3-NaNi0.5Mn0.46Ti0.04O2 (NNMOTi-4) exhibits initial reversible capacity of 108.6 mAh g−1 at 0.1C and remarkable 65.2% capacity retention after 100 cycles at 1C. Accordingly, this work provides a facile Ti-doping strategy to regulate the structure and electrochemical performance of layered NaxTMO2 for sodium-ion batteries.

A water-stable high-voltage P3-type cathode for sodium-ion batteries

The Na-deficient P3-type layered oxide cathode material usually experience complex in-plane Na+/vacancy ordering rearrangement and undesirable P3-O3 phase transitions in the high-voltage region, leading to inferior cycling performance. Additionally, they exhibit unsatisfactory stability when exposed to water for extended periods. To address these challenges, we propose a Cu/Ti co-doped P3-type cathode material (Na0.67Ni0.3Cu0.03Mn0.6Ti0.07O2), which effectively mitigates Na+/vacancy ordering and suppresses P3-O3 phase transitions at high voltages. As a result, the as-prepared sample exhibited outstanding cyclic performance, with 81.9% retention after 500 cycles within 2.5–4.15 V, and 75.7% retention after 300 cycles within 2.5–4.25 V. Meanwhile, it demonstrates enhanced Na+ transport kinetics during desodiation/sodiation and reduced growth of charge transfer impedance (Rct) after various cycles. Furthermore, the sample showed superb stability against water, exhibiting no discernible degradation in structure, morphology, or electrochemical performance. This co-doping strategy provides new insights for innovative and prospective cathode materials.