Properties Of Transition Metal Oxides Research Articles

Achieving excellent mechanical and electrical properties in transition metal oxides and rare earth oxide‐doped KNN‐based piezoceramics

AbstractPotassium sodium niobate (KNN)‐based piezoelectric ceramics have emerged as a promising alternative to lead‐based systems due to their exceptional properties. While extensive research has focused on improving the electrical properties of KNN‐based ceramics through doping and processing optimization, the concurrent investigation of their mechanical properties has been lacking. This study presents a comprehensive analysis of the mechanical and electrical properties of KNN‐based lead‐free piezoceramics doped with various transition metal oxides and rare earth oxides, based on substantial experimental data. Our findings reveal that the as‐sintered KNN‐based ceramics exhibit not only outstanding electrical properties but also remarkable mechanical robustness compared to conventional toughened lead zirconate titanate (PZT)‐based ceramics. These exceptional electrical and mechanical properties are attributed to the micro‐scale and atomic‐scale structure of the modified KNN‐based ceramics, characterized by a highly condensed structure, an inhomogeneous distribution of nano‐domain structure, and the presence of amorphous intergranular films at grain boundaries.

Highly efficient and fast modulation of magnetic coupling interaction in the SrCoO2.5/La0.7Ca0.3MnO3 heterostructure.

Effective manipulation of magnetic properties in transition-metal oxides is one of the crucial issues for the application of materials. Up to now, most investigations have focused on electrolyte-based ionic control, which is limited by the slow speed. In this work, the interfacial coupling of the SrCoO2.5/La0.7Ca0.3MnO3 (LCMO) bilayer is effectively modulated with fast response time. After being treated with diluted acetic acid, the bilayer changes from antiferromagnetic/ferromagnetic (AFM/FM) coupling to FM/FM coupling and the Curie temperature is also effectively increased. Meanwhile, the corresponding electric transport properties are modulated within a very short time. Combined with the structure characterization and X-ray absorption measurements, we find that the top SrCoO2.5 layer is changed from the antiferromagnetic insulator to the ferromagnetic metal phase, which is attributed to the formation of the active oxygen species due to the reaction between the protons in the acid and the SrCoO2.5 layer. The bottom LCMO layer remains unchanged during this process. The response time of the bilayer with the acid treatment method is more than an order of magnitude faster than other methods. It is expected that this acid treatment method may open more possibilities for manipulating the magnetic and electric properties in oxide-based devices.

Physical and Electrochemical Properties of Transition Metal Oxides with Hollow Structure As Sulfur Host Material for Lithium-Sulfur Batteries

INTRODUCTION Because of its high theoretical energy density, possibly low cost, and environmental friendliness, lithium-sulfur (Li-S) batteries have received a lot of interest. However, the principal disadvantage impeding the success of Li–S batteries lies in the severe leakage and migration of soluble lithium polysulfide intermediates out of cathodes upon cycling caused “shuttle effect”. The loss of active sulfur species incurs significant capacity decay and poor battery lifespans which has prevented it from commercial realization.Several researches have been conducted with an attempt to improve capacity of batteries while maintaining life of the Li-S cellใ including an introduction of nanostructured cathode host materials. Two main approaches have currently been explored a. chemical confinement and b. physical confinement to anchor the lithium poly-sulfide (LiPSs) reaction products durin the charging process. Transition metal oxides such as TiO2 and SnO2 has been studied with a potential material to anchor polysulfides via Lewis acid–base interactions and thus maybe able to chemically confine LiPSs within or on the transition metal oxide. Physical confinement may also be possible by trapping LiPSs within a transition metal oxide host structure e.g. hollow structure and thus help impedes polysulfide dissolution into the electrolyte. In this study, TiO2 and SnO2 are focused to understand the physical and electrochemical properties of sulfur host material with hollow structures. The in situ XAS is also conducted to understand the behavior of the dissolution and migration of long-chain LiPSs intermediates (Li2S x , 4 ≤ x ≤ 8) in the sulfur cathode upon discharge. EXPERIMENTAL The transition metal oxide, TiO2 and SnO2, were successfully synthesized by a templated method. The synthesis process involved four steps, preparation of SiO2 spheres, synthesis of SiO2@transition metal oxide core-shell structure by coating transition metal oxide shell on SiO2 and crystallization by calcination and etching the SiO2@transition metal oxide to form hollow transition metal oxide spheres. Structural properties of the synthesized samples were studied by X-ray diffraction (XRD) using Cu-Kα (λ=1.5418 Å) radiation. Particle morphologies and size of the resulting compounds were observed using a field emission scanning electron microscope. Composite electrodes for electrochemical studies were prepared by doctor blade coating of a slurry compound onto carbon-coated aluminium foil current-collectors. The transition metal oxide and sulfur composite, conductive carbon and PVDF binder were mixed in the ratio of 80:10:10 by weight. Electrochemical characterizations were performed by in 2032 coin cells and Galvanostatic charge-discharge cycling was done between 1.8-3.0 V at 0.1C using a MACCOR Series 4000 at room temperature. RESULTS AND DISCUSSIONS Based on the XRD results, single phase anatase TiO2 and tetragonal SnO2 were both successfully synthesized by the templated method. SEM images (Fig. 1a and 1b) demonstrate that TiO2 and SnO2 are generally spherical structures with nanometer scale dimensions ranging from 250-350 nm and 450-500 nm, respectively. The interior hollow region can be seen clearly in the images of broken spheres. The shelled surface of the synthesized powders is hierarchically made up of interconnected nanocrystals providing a possibly porous structure. Hence, the hierarchically porous and hollow structure has a large surface area for adsorbing the LiPSs distributed in the electrolyte.Fig. 1c shows the charge and discharge voltage profiles of SnO2 and sulfur composite electrode cathode in the first five cycles. Two discharge plateaus were clearly observed, which might be attributed to the two-step sulfur-lithium reaction process. The initial plateau, centered about 2.30 V, was commonly attributed to the reduction of the S8 ring and the formation of S8 2−. The second discharge plateau at 2.10 V was attributed to further reduction of the higher polysulfides (Li2S n , 4 ≤ n ≤ 8) to the lower polysulfides (Li2S n , n ≤ 3). There exhibited two plateaus in the charge process at about 2.25 and 2.35 V, respectively. Electrochemical performance in relations to capacity retention and the in situ XAS to understand the behavior of the dissolution and migration of LiPSs will be discussed in the meeting. Figure 1

Self-assembled microflower-like NiCo2X4 (X = O, S, Se) as electrodes for asymmetric supercapacitors

The substitution of chalcogen elements has a notable influence on the microstructure and electrochemical properties of transition metal oxides. However, the underlying mechanism necessitates clarification. In this investigation, self-assembled microflower-like NiCo2X4 (X = O, S, Se) structures were successfully synthesized, and their microstructures and electrochemical performance were systematically examined using both theoretical and experimental approaches. Theoretical analysis demonstrated that the replacement of chalcogen elements significantly enhances the energy band structure of the material, thus effectively improving its electrochemical performance. Experimental results revealed that, in comparison to NiCo2O4 and NiCo2S4, NiCo2Se4 displayed remarkable electrochemical performance, with a specific capacitance of 1899 F g–1 at a current density of 1 A g–1 and a promising rate capability (with a capacitance retention increase of up to 71.9% when the current density was elevated from 1 A g–1 to 10 A g–1). Additionally, the asymmetric device (NiCo2Se4//AC), composed of NiCo2Se4 as the positive electrode and activated carbon (AC) as the negative electrode, exhibited an energy density of 42.44 Wh kg–1 at a power density of 1600 W kg–1. As a result, this study offers novel insights into the fabrication of transition metal compounds for energy storage applications.

Improving charge transport in integrated MoO3/C electrode materials for water-in-salt energy storage systems by incorporating oxygen vacancies

Improvements in the charge storage properties of ⍺-MoO3 used as an electrode with a 30 m ZnCl2 water-in-salt electrolyte have been achieved by enhancements in electron and ion transport enabled by an inventive synthesis route. Electron transport was improved through the integration of MoO3 with dopamine-derived carbon via a chemical preintercalation route, and enhanced ion transport was achieved by incorporating oxygen vacancies in MoO3 structure through ethanol reduction under hydrothermal conditions. The presence of carbon was confirmed by corresponding D and G bands observed in Raman spectroscopy measurements. The presence of oxygen vacancies was proven through correlated XPS, TGA, Raman spectroscopy and XRD analyses, with the introduction of oxygen vacancies leading to an expanded interlayer region. Four-point probe measurements provided evidence of increased electronic conductivity due to the incorporation of carbon, and cyclic voltammetry-based charge storage mechanism analyses revealed increases in ion transport kinetics due to oxygen vacancy formation. Tuning the oxygen vacancy concentration is critical, as excessive concentrations of these point defects leads to structural instability and poor capacity retention. This work demonstrates the combined potential of carbon and oxygen vacancies in moderate concentrations to enhance the charge storage properties of transition metal oxides. The strategies developed in this study offer a path to the development of promising materials for high-rate, high-capacity, and long-duration electrochemical energy storage technologies.

Synergistic Effect between Fe<sup>4+</sup> and Co<sup>4+</sup> on Oxygen Evolution Reaction Catalysis for CaFe<sub>1−</sub><i><sub>x</sub></i>Co<i><sub>x</sub></i>O<sub>3</sub>

Chemical substitution is an effective way to improve electrocatalytic properties in transition metal oxides. We investigate the synergistic effect between Fe4+ and Co4+ ions on the catalytic activity for oxygen evolution reaction (OER) in the Fe-Co-mixed perovskite oxide CaFe1–xCoxO3. The OER activity of CaFe1–xCoxO3 is substantially increased by small amounts of Co (Fe) doping into CaFeO3 (CaCoO3), leading to the superiority compared to the pure Fe and Co perovskite oxides. The x dependences of the OER overpotential and specific activity for CaFe1–xCoxO3 (0.05 ≦ x ≦ 0.95) are expressed by constant offset from the weighted average between CaFeO3 and CaCoO3, which can be interpreted to be the synergistic effect between Fe4+ and Co4+ ions on OER activity. The absence of the optimum x for the highest activity for CaFe1–xCoxO3 contrasts with the volcano-like plots reported in various mixed-metal oxides. First-principle calculations using the special quasirandom structure models on CaFe1–xCoxO3 (x = 0.03–0.5) demonstrate that about half the amount of Fe4+ is electronically activated to possess smaller charge-transfer energies, corroborating the enhancement of catalytic activity in CaFe1–xCoxO3. These findings provide new insight into the synergistic effects in complex transition metal oxide catalysts.

Multi-state structural modulation of hydrogenated VO2 revealed by in situ x-ray diffraction

The generation and control of multiple phases via hydrogen insertion open up avenues for tuning the properties of transition metal oxides. Here, by employing both in situ x-ray diffractions and in situ electrical measurements, we accurately probed the full structural phase transitions during the reversible process of hydrogen insertion into and extraction from the vanadium dioxide lattice. Repeatable switches between the hydrogenated VO2 phases and the pristine VO2 phase were demonstrated, implying potential applications for hydrogen detection/storage and multi-state information memorizers. Moreover, different phases were further discussed by synchrotron x-ray absorption spectroscopy and theoretical first-principles calculations, which reveal that hydrogen insertion greatly affects the filling of the d-band as well as the electrical properties. This work will provide fundamental insight into the comprehensive understanding of hydrogen-induced phase transition in metal oxides and may guide the development of proton-based sensors and devices.

(Invited) Effect of Polaron Formation on Optical and Carrier Transport Properties of Transition Metal Oxides As Photoelectrodes from First-Principles Calculations

Transition metal oxides are promising photoelectrode materials for solar-to-fuel conversion applications. However, their performance is limited by the low carrier mobility (especially electron mobility) due to the formation of small polarons. Recent experimental studies have shown improved carrier mobility and conductivity by atomic doping; however the underlying mechanism is not understood. A fundamental atomistic-level understanding of the effects on small polaron transport is critical to future material design with high conductivity. In this talk, we will discuss the effect of small polaron formation on optical and carrier transport properties of transition metal oxides from first-principles calculations.First, we resolve the conflicting findings that have been reported on the optical gap of a well-known catalysis Co3O4 as an example[1]. We confirm that the formation of small hole polarons significantly influences the optical absorption spectra and introduces extra spectroscopic signature below the intrinsic band gap, leading to a 0.8 eV transition that is often misinterpreted as the band edge that defines the fundamental gap.Then we discuss the formation of small polarons' effect on carrier concentration, by resolving the controversy of nature of "shallow" or "deep" impurities of intrinsic oxygen vacancies in BiVO4 as an example[2], i.e. how to unify different experiments with the correct definition of ionization energy in polaronic oxides. We further discuss why certain dopants can have very low optimal concentrations (or very early doping bottleneck) in polaronic oxides such as Fe2O3, through a novel "electric-multipole" clustering between dopants and polarons[3]. These multipoles can be very stable at room temperature and are difficult to fully ionize compared to separate dopants, and thus they are detrimental to carrier concentration improvement. This allows us to uncover mysteries of the doping bottleneck in hematite and provide guidance for optimizing doping and carrier conductivity in polaronic oxides toward highly efficient energy conversion applications. In addition, we show the importance of synthesis condition such as synthesis temperature and oxygen partial pressure on dopant and polaron concentrations, and how to optimize the synthesis condition based on theoretical predictions[4].At the end, we show different theoretical models for polaron mobility calculations from a macroscopic dielectric continuum picture with an example of spin polarons in CuO[5] and a microscopic polaron hopping picture by combining generalized Landau-Zener theory and kinetic Monte-Carlo samplings for doped oxides[6].Our first-principles calculations provide important insights and suggest design principles for optimal optical and transport properties of polaronic oxides.

Synthesis, structure and electrical properties of Ti4+ and Zr4+ doped MoO3 transition metal oxide

Hereby, we report synthesis, structural and electrical properties of transition metal oxides of the type Mo0.99Ti0.01-xZrxO3 [x = 0.0, 0.01]. The materials synthesized by solid state route were double calcined before characterizations. We employed a reliable X-ray diffraction characterization technique to confirm the crystal structure acquired by these samples. We used room temperature frequency dependent dielectric measurements to investigate the electric behaviour of these transition oxide materials. Both transition metal ion substituted molybdenum oxides on analysis of XRD data reveals their crystallization into the orthorhombic phase with space group Pbnm. The analysis of frequency dependent room temperature dielectric characteristics of these samples inferred these samples to be better dielectric materials. These transition metal oxides were found to have lower values of dielectric permittivity and dielectric dissipation thereby makes them ideal for high-frequency applications. Comparatively, the dielectric constant and the dielectric loss for Zr-doping are rather low. However, the Ti doped MoO3 displays more smooth behaviour. Furthermore, this piece of work throws light on electrical properties viz. ac conductivity, electric impedance and electric modulus of the as synthesized transition metal oxides.

Photoinduced small electron polarons generation and recombination in hematite

Polarons generally affect adversely the photochemical and photophysical properties of transition metal oxides. However, the excited-state dynamics of polarons are not fully established to date and thus require an atomistic understanding. We focus on α-Fe2O3 with photoexcitation, electron injection, and heterovalent doping as the small polaron models, and conduct simulations of ab initio adiabatic molecular dynamics (AIMD) and nonadiabatic molecular dynamics (NA-MD). The elaborately designed AIMD simulations show that localization of electron at a single Fe site is an adiabatic and ultrafast process within sub-15 fs. Fe2O3 doping with an electron or a Si and Ti dopant forms a localized electron polaron while photoexcitation forms localized electron and hole polarons simultaneously, leading to diverse electron–hole recombination dynamics. NA-MD simulations demonstrate that recombination of an electron polaron created by doping with a delocalized hole at the valence band maximum of α-Fe2O3 takes place around 5 ps, while recombination between a pair of small electron and hole polarons in photoexcited Fe2O3 delays to about 110 ps owing to weak NA coupling and fast decoherence process. The ultrafast formation of small electron polarons in α-Fe2O3 impedes the accumulation of delocalized holes in the valence band that directly participate in water oxidation at photoanodes. The detrimental effect can be partially circumvented in photoexcited Fe2O3 for slowing electron–hole recombination despite polarons may retain low charge mobility. These findings provide a fundamental understanding of the excited-state dynamics of small electron polaron in α-Fe2O3 and may help design efficient transition metal oxides photoanodes.

Coupling structural evolution and oxygen-redox electrochemistry in layered transition metal oxides.

Lattice oxygen redox offers an unexplored way to access superior electrochemical properties of transition metal oxides (TMOs) for rechargeable batteries. However, the reaction is often accompanied by unfavourable structural transformations and persistent electrochemical degradation, thereby precluding the practical application of this strategy. Here we explore the close interplay between the local structural change and oxygen electrochemistry during short- and long-term battery operation for layered TMOs. The substantially distinct evolution of the oxygen-redox activity and reversibility are demonstrated to stem from the different cation-migration mechanisms during the dynamic de/intercalation process. We show that the π stabilization on the oxygen oxidation initially aids in the reversibility of the oxygen redox and is predominant in the absence of cation migrations; however, the π-interacting oxygen is gradually replaced by σ-interacting oxygen that triggers the formation of O-O dimers and structural destabilization as cycling progresses. More importantly, it is revealed that the distinct cation-migration paths available in the layered TMOs govern the conversion kinetics from π to σ interactions. These findings constitute a step forward in unravelling the correlation between the local structural evolution and the reversibility of oxygen electrochemistry and provide guidance for further development of oxygen-redox layered electrode materials.

Correlating Orbital Composition and Activity of LaMnxNi1-xO3 Nanostructures toward Oxygen Electrocatalysis.

The atomistic rationalization of the activity of transition metal oxides toward oxygen electrocatalysis is one of the most complex challenges in the field of electrochemical energy conversion. Transition metal oxides exhibit a wide range of structural and electronic properties, which are acutely dependent on composition and crystal structure. So far, identifying one or several properties of transition metal oxides as descriptors for oxygen electrocatalysis remains elusive. In this work, we performed a detailed experimental and computational study of LaMnxNi1–xO3 perovskite nanostructures, establishing an unprecedented correlation between electrocatalytic activity and orbital composition. The composition and structure of the single-phase rhombohedral oxide nanostructures are characterized by a variety of techniques, including X-ray diffraction, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and electron microscopy. Systematic electrochemical analysis of pseudocapacitive responses in the potential region relevant to oxygen electrocatalysis shows the evolution of Mn and Ni d-orbitals as a function of the perovskite composition. We rationalize these observations on the basis of electronic structure calculations employing DFT with HSE06 hybrid functional. Our analysis clearly shows a linear correlation between the OER kinetics and the integrated density of states (DOS) associated with Ni and Mn 3d states in the energy range relevant to operational conditions. In contrast, the ORR kinetics exhibits a second-order reaction with respect to the electron density in Mn and Ni 3d states. For the first time, our study identifies the relevant DOS dominating both reactions and the importance of understanding orbital occupancy under operational conditions.

Interplay between polarization, strain, and defect pairs in Fe-doped SrMnO3−δ

Defect chemistry, strain, and structural, magnetic and electronic degrees of freedom constitute a rich space for the design of functional properties in transition metal oxides. Here, we show that it is possible to engineer polarity and ferroelectricity in non-polar perovskite oxides via polar defect pairs formed by anion vacancies coupled to substitutional cations. We use a self-consistent site-dependent DFT+$U$ approach that accounts for local structural and chemical changes upon defect creation and which is crucial to reconcile predictions with the available experimental data. Our results for Fe-doped oxygen-deficient SrMnO$_3$ show that substitutional Fe and oxygen vacancies can promote polarity due to an off-center displacement of the defect charge resulting in a net electric dipole moment, which polarizes the lattice in the defect neighborhood. The formation of these defects and the resulting polarization can be tuned by epitaxial strain, resulting in enhanced polarization also for strain values lower than the ones necessary to induce a polar phase transition in undoped SrMnO$_3$. For high enough defect concentrations, these defect dipoles couple in a parallel fashion, thus enabling defect- and strain-based engineering of ferroelectricity in SrMnO$_3$.

Modified cobalt-manganese oxide-coated carbon felt anodes: an available method to improve the performance of microbial fuel cells.

The novel MnCo2O4 (MCO/CF), CNTs-MnCo2O4 (CNTs-MCO/CF) and MnFe2O4-MnCo2O4 (MFO-MCO/CF) electrodes were prepared on carbon felt (CF) by simple hydrothermal and coating method as anodes for MFC. The modified anodes combine the electrocatalytic properties of transition metal oxides (TMOs), the high electrical conductivity of CNTs and the good biocompatibility of CF. These anodes play a synergistically role in the synthesis of structural, to realize high-efficiency electron transfer, low resistance and sufficient space for microbial colonization, while also ensuring high power density. The maximum power density of the composite electrodes CNTs-MCO/CF and MFO-MCO/CF were 4268mW/m3 and 3660mW/m3, respectively. The synergistic effect of multi-component effectively improves the performance of MFC. This work not only offers a good design and preparation concept for functional TMOs composite electrodes, but also provides an important guide for the fabrication of CNTs-doped MFC anodes.

Probing the effect of Mg doping on triclinic Na2Mn3O7 transition metal oxide as cathode material for sodium-ion batteries

Triclinic Na2Mn3O7 has been identified as a promising material for high-capacity sodium-ion batteries. However, the knowledge on the effect of doping of metal ions and structural transformations of Na2Mn3O7 during dis(charge) is limited. Integration of alkali metal-ions, specially Mg2+ can enhance the electrochemical properties in transition metal oxides. Herein, a series of Mg2+ doped triclinic Na2Mn3O7 cathode materials was explored for the first time. Electrochemical analysis revealed that Mg2+ improves specific capacities, and rate capabilities. Ex situ X-ray diffraction (XRD) and Galvanostatic charge discharge cycling (GCD) showed that the triclinic phase reversibly converts into two monoclinic phases at high Na+ insertion levels. Na+ extraction at high potentials is supported by another biphasic region which converts to a major triclinic phase at the end of the charge. GCD, cyclic voltammetry (CV) and ex situ X-ray absorption spectroscopy (XAS) documented that the capacity mainly evolved through a Mn4+/3+ redox couple and a reversible O2-/n− redox reaction. CV and Galvanostatic intermittent titration techniques (GITT) showed that Mg2+ reduces the Na+-vacancy ordering and improves the Na+ diffusion. The 2 mol.% Mg-doped material exhibited a high specific capacity of 143 mAh/g after 30 cycles and a rate capability of 93 mAh/g (at 500 mA/g). GCD analysis demonstrated that O2-/n− redox is remarkably stable up to at least 90 cycles. Full cells made using the 0.5 mol.% Mg-doped material displayed a promising discharge specific capacity of 80 mAh/g. The effects of cation doping into the complex crystal structures, phase transformations during Na+ de(intercalation) and the importance of O2-/n− redox for achieving high capacities were uncovered. The findings of this work will guide the design of novel cathode materials for sodium-ion batteries.

Hydrogen in nonstoichiometric cubic titanium monoxides: X-ray and neutron diffraction, neutron vibrational spectroscopy and NMR studies

Hydrogen-induced changes in the properties of transition-metal oxides have attracted much recent attention due to numerous applications of these materials including catalysis, H2 production, low-temperature H2 sensing, solar cells, and air purification. However, basic properties of hydrogenated titanium monoxides have not been investigated so far. In the present work, we report the results of the first studies of the crystal structure, vibrational spectra, and mobility of H atoms in TiO0.72H0.30 and TiO0.96H0.14 using X-ray diffraction (XRD), neutron powder diffraction, neutron vibrational spectroscopy, and nuclear magnetic resonance (NMR). The hydrogenated compound TiO0.72H0.30 is found to retain the disordered cubic B1-type structure of the initial titanium monoxide, where H atoms exclusively occupy vacancies in the oxygen sublattice. It has been revealed that hydrogenation of the disordered cubic TiO0.96 leads to the formation of the two-phase compound TiO0.96H0.14, where the disordered B1-type phase coexists with the monoclinic phase of Ti5O5 type with an ordered arrangement of vacancies. In both phases, H atoms are found to occupy only vacancies in the oxygen sublattice. The low-temperature inelastic neutron scattering spectra of TiO0.72H0.30 and TiO0.96H0.14 in the energy transfer range of 40–180 meV exhibit a single peak due to optical oxygen vibrations (centered on about 60 meV) and a broad structure at 90–170 meV due to optical H vibrations. The unusual width of this structure can be attributed to the broken symmetry of hydrogen sites in the titanium monoxides: because of the presence of vacancies in the titanium sublattice, the actual point symmetry of these sites appears to be lower than octahedral. Proton NMR measurements have revealed that both hydrogenated compounds are metallic; no signs of hydrogen diffusive motion in TiO0.72H0.30 and TiO0.96H0.14 at the frequency scale of about 105 s-1 have been found up to 370 K.

Adjusting the Coordination Environment of Mn Enhances Supercapacitor Performance of MnO2

AbstractThe electrochemical properties of transition metal oxides strongly depend on the coordination environment of metal atoms. Nevertheless, the relationship between the coordination environment of metal atoms and electrochemical performance of metal oxides is unclear, while the strategy of adjusting the coordination environment of metal atoms is rare. Herein, the engineering of the coordination environment of Mn atoms in manganese dioxides (MnO2) by using a triethanolamine (TEA) complex‐induced method is reported. The detailed experimental characterizations and density functional theory calculations show that the optimized Mn coordination environment with oxygen deficiency and more corner‐shared Mn–Mn shells results in apparent electron dislocation and forms an effective built‐in electrical field. As a result, the obtained MnO2‐TEA sample exhibits a high conductivity and an excellent ion diffusion capacity, with a remarkable specific capacitance of 417.5 F g−1 at 1 A g−1. At the power density of 450.0 W kg−1, the fabricated asymmetric supercapacitor delivers the maximal energy density (57.4 Wh kg−1). This work not only provides an effective strategy of adjusting the coordination environment of metal atoms in metal oxides, but also presents a deeper understanding of the electronic structure dependent electrochemical performance of electrode materials.

Reversible Rapid Hydrogen Doping of WO3 in Non-Acid Solution.

Hydrogenation, an effective way to tune the properties of transition metal oxide (TMO) thin films, has been long awaited to be performed safely and without an external energy input. Recently, metal-acid-TMO has been reported to be an effective approach for hydrogenation, but the requirement of acid limits its application. In this work, the reversible and rapid hydrogen doping of WO3 in NaOH(aq) | Al(s) | WO3(s) is revealed by structural and electrical measurements. Accompanied by the structural phase transition identified by in situ X-ray diffraction, the electric resistance of the WO3 film is found to be able to change by 5 orders of magnitude. A significant electrical response of touching, 8-fold in amplitude and 3 s in a cycle, can be achieved in the low-resistance state. These reactions are reversible at room temperature. This study unambiguously proves that the hydrogenation-driven dynamic phase transition of WO3 in metal-solution-WO3 systems could occur not only in acid solutions but also in some non-acid environments. Unlike the monotonic increase of resistance revealed during HδWO3 to WO3 transition, an intriguing non-monotonic evolution was found for crystal lattice parameter c, indicating that the mechanism of WO3 hydrogenation involves a series of metastable states, more comprehensive and reasonable. This work sheds light on the potential applications of metal-solution-TMO hydrogenation in touching sensors, circuits survey, and information storage.

Origin of the orbital polarization of Co2+ in La2CoTiO6 and ( LaCoO3)1+(LaTiO3)1 : A DFT+U and DFMT study

The unequal electronic occupation of localized orbitals (orbital polarization), and associated lowering of symmetry and degeneracy, play an important role in the properties of transition metal oxides. Here, we examine systematically the underlying origin of orbital polarization, taking as exemplar the 3$d$ manifold of Co$^{2+}$ in a variety of spin, orbital and structural phases in the double perovskite La$_2$CoTiO$_6$ and the (001) superlattice (LaCoO$_3$)$_1$+(LaTiO$_3$)$_1$ systems. Superlattices are of specific interest due to the large experimentally observed orbital polarization of their Co cations. Based on first principles calculations, we find that robust and observable orbital polarization requires symmetry reduction through the lattice structure; the role of local electronic interactions is to greatly enhance the orbital polarization.

Constrained density functional theory plus the Hubbard U correction approach for the electronic polaron mobility: A case study of TiO2

The formation and migration of polarons have important influences on physical and chemical properties of transition metal oxides. Density functional theory plus the Hubbard U correction (DFT+U) and constrained density functional theory (cDFT) are often used to obtain the transfer properties for small polarons. In this work we have implemented the cDFT plus the Hubbard U correction method in the projector augmented wave (PAW) framework, and applied it to study polaron transfer in the bulk phases of TiO2. We have confirmed that the parameter U can have significant impact on theoretical prediction of polaronic properties. It was found that using the Hubbard U calculated by the cDFT method with the same orbital projection as used in DFT+U, one can obtain theoretical prediction of polaronic properties of rutile and anatase phases of TiO2 in good agreement with experiment. This work indicates that the cDFT+U method with consistently evaluated U is a promising first-principles approach to polaronic properties of transition metal oxides without empirical input.