Covalency competition induced selective bond breakage and surface reconstruction in manganese cobaltite towards enhanced electrochemical charge storage

Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn are prone to react with the hydroxyl ions in alkaline electrolyte upon electrochemical cycling and separates on the surface of spinel to reconstruct into d-MnO_(2) nanosheets irreversibly,thus results in a change of the reaction mechanism with Kþion intercalation.However,the low capacity has greatly limited its practical application.Herein,we found that the tetrahedrally-coordinated Co_(2) þions were leached when MnCo_(2)_(4) was equilibrated in 1 mol L^(-1) HCl solution,leading to the formation of layered CoOOH on MnCo_(2)_(4) surface which is originated from the covalency competition induced selective breakage of the CoT–O bond in CoT–O–CoO and subsequent rearrangement of free Co_(6) octahedra.The as-formed CoOOH is stable upon cycling in alkaline electrolyte,exhibits conversion reaction mechanism with facile proton diffusion and is free of massive structural evolution,thus enables utilization of the bulk electrode material and realizes enhanced specific capacity as well as facilitated charge transfer and ion diffusion.In general,our work not only offers a feasible approach to deliberate modification of MnCo_(2)_(4)'s surface structure,but also provides an in-depth understanding of its charge storage mechanism,which enables rational design of the spinel oxides with promising charge storage properties.

Magnetocaloric properties and Griffiths phase of ferrimagnetic cobaltite CaBaCo_(4)O_(7)

We present a study on the magnetocaloric properties of a CaBaCo_(4)O_(7) polycrystalline cobaltite along with research on the nature of magnetic phase transition.The magnetization as a function of temperature identifies the ferrimagnetic to paramagnetic transition at a Curie temperature of 60 K.Moreover,a Griffiths-like phase is confirmed in a temperature range above T_(C).The compound undergoes a crossover from the first to second-order ferrimagnetic transformation,as evidenced by the Arrott plots,scaling of the universal entropy curve,and field-dependent magnetic entropy change.The maximum of entropy change is 3 J/kg⋅K for ΔH=7 T at T_(C),and a broadening of the entropy peak with increasing magnetic field indicates a field-induced transition above T_(C).The analysis of the magnetic entropy change using the Landau theory reveals the second-order phase transition and indicates that the magnetocaloric properties of CaBaCo_(4)O_(7) are dominated by the magnetoelastic coupling and electron interaction.The corresponding values of refrigerant capacity and relative cooling power are estimated to be 33 J/kg and 42 J/kg,respectively.

Highly efficient mixed-metal spinel cobaltite electrocatalysts for the oxygen evolution reaction

Cation substitution in spinel cobaltites(e.g.,ACo2O4,in which A=Mn,Fe,Co,Ni,Cu,or Zn)is a promising strategy to precisely modulate their electronic structure/properties and thus improve the corresponding electrochemical performance for water splitting.However,the fundamental principles and mechanisms are not fully understood.This research aims to systematically investigate the effects of cation substitution in spinel cobaltites derived from mixed-metal-organic frameworks on the oxygen evolution reaction(OER).Among the obtained ACo2O4 catalysts,FeCo2O4 showed excellent OER performance with a current density of 10 mA·cm^-2 at an overpotential of 164 mV in alkaline media.Both theoretical calculations and experimental results demonstrate that the Fe substitution in the crystal lattice of ACo2O4 can significantly accelerate charge transfer,thereby achieving enhanced electrochemical properties.The crystal field of spinel ACo2O4,which determines the valence states of cations A,is identified as the key factor to dictate the OER performance of these spinel cobaltites.

Electronic Structures and Chemical Bonds of Cobaltite and Ni-Doped

The relation among electronic structure, chemical bond and thermoelectric property of Ca3 Co2 O6 and Ni-doped was studied by density function theory and discrete variation method（DFT-DVM）. The results indicate that the highest valence band（ HVB ）attd the lowest conduction band（ LCB ） are mainly attribuled to Co3d, Ni3d and O2p atomic orbitals. The property of a semiconductor is shown from the gap between HVB and LCB. The gap of Ni-doped one is less than that of Ca3 Co2 O6. The non-metal bond or ceramic characteristic of Ni-doped one is weaker than that of Ca3 Co2 O6, but the metal characteristics of Ni-doped one are stronger than those of Ca3 Co2 O6. The thermoelectric property should be improved by adding Ni element into the system of Ca3 Co2 O6 .

Effect of Substitution Degree and the Calcination Temperature on the N₂O Decomposition over Zinc Cobaltite Catalysts

In this paper, a series of zinc cobaltite catalysts with the general formula Znx-Co1-xCo2O4 (x = 0.25, 0.50, 0.75 and 1.0) has been prepared using the co-precipitation method. Thermal analyzes (TGA and DTA) were used to follow up the thermal events accompanying the heat treatment of the parent mixture. Based on these results, the various parent mixtures were calcined at 500℃. The obtained solid catalysts were characterized by using XRD, FT-IR and N2-adsorption. The catalytic decomposition of N2O to N2 and O2 was carried out on the zinc-cobaltite catalysts. It was found that partial replacement of Co2+ by Zn2+ in Co3O4 spinel oxide led to a significant improvement in their N2O decomposition activity. Moreover, the catalytic activity was found to be depended on the calcination temperature utilized.

Transition Metal-Nonmetal in Conductivity of Ceramic Hole-Doped Cobaltites

In bulk granulated cobaltite La1–xSrxCoO3 with the size of granules of order of 1 micron at strontium hole doping with replacement factor x = 0.35, a transition “metal-nonmetal” in the conductivity was revealed, presumably connected with AFM ordering of the moments of granules. The assumption is proved by the agreement between the experiment and results of calculation within the limits of a model offered for electron transport based on the account of in-granule double exchange Zener mechanism and intergranule mechanism of spin-polarized tunneling on the nearest neighbours with AFM exchange interaction. The calculation differs in that conductivities within granules are summarized, while total resistance of the system is represented as a sum of resistances of the granules. In addition, the existence of AFM interaction between granules is supported by the observed insensitivity of conductivity to a low external magnetic field (up to 5 kOe).

Facile synthesis of samarium and cerium doped double perovskite cobaltite with enhanced dielectric response

The investigation of Sm-Ce doping on structure,conduction,and dielectric response of Bi_(2)Ca_(2-2x)Sm_(x)CexCoO_(6)(x=0.000,0.025,0.050,0.075)(BCSCCO)are presented.All the specimens were synthesized by a facile synthesis technique named the co-precipitation route.X-ray diffraction(XRD)reveals that BCSCCO crystallizes into one phase with space group P21/m.The crystallite size,dislocation density,lattice parameters,lattice strain,unit cell volume,and bulk density were determined using XRD data.The structural properties of Bi_(2)Ca_(2)CoO_(6)were examined using calculations based on the density functional theory.Theoretical and experimental values discrepancy is less than 1%.A scanning electron microscope was used for performing a microstructural analysis.The SEM images demonstrate the homogeneous distribution of grains with a range of sizes(0.054-0.090μm).The alternating current(ac)conductivity,dielectric permittivity,and tangent loss were also studied as a function of frequency(20 Hz-3 MHz)at different temperatures(100-500℃).All synthesized samples were examined using non-linear Debye's function to determine their spreading factor and relaxation time.The specimen with the lowest crystallite size(∼23 nm)exhibits a high dielectric permittivity(∼3.80×10^(6)).The conduction mechanism was examined in the studied samples with the use of Jonscher's power law.The power law indicates that the BCSCCO(x=0.000,0.025)follows correlated barrier hopping,whereas the x=0.050 and 0.075 compositions follow non-overlapping polaron tunneling.The studied specimen Bi_(2)Ca_(1.9)0Sm_(0.05)0Ce_(0.05)_(0)CoO_(6)with the highest density(∼5.65 g/cm^(3))displays a high electrical conductivity(∼46.1 S/cm).These findings correspond to those published for ceramics made from calcium cobaltite using solid-state reactions(5.0-26.0 S/cm).

Effect of the addition of rare earths on the activity of alumina supported copper cobaltite in CO oxidation, CH_4 oxidationand NO decomposition

The effect of the addition of small amounts of rare earths （Ln=La, Ce, Nd and Gd） to alumina supported copper-cobalt spinel oxide on the catalysts efficiency in CO and CH4 oxidation and in NO decomposition was investigated. Samples of Ln/CuCo/AI catalyst were prepared and characterized by X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, atomic absorption spectroscopy （AAS）, scanning electron mieroscopy-energy dispersive spectroscopy （SEM-EDS）, H2-temperature-programmed reduc- tion （H2-TPR）, electron paramagnetic resonanee （EPR） spectroscopy and low temperature nitrogen adsorption, The results showed that the addition of rare earths changed the surface state of the alumina supported copper-cobalt spinel catalyst. As a result, partial re- duction of copper species was observed as well as migration of these species between the surface and the bulk. The Ln/CuCo/A1 catalysts behaved differently in oxidation and reduction processes. In oxidation processes where oxide structure was important, Ce/CuCo/A1 and Nd/CuCo/A1 were the most active catalysts. The catalyst Ce/CuCo/AI was the most active in the oxidation reactions because of the availability and favorable surface distribution of the redox couples Cu＋/Cu2＋ and Ce3＋/Ce4＋. In NO decompostion, Ln-modified catalysts significantly improved the selectivity of the process to N2.

Multilevel resistive switching and synaptic plasticity of nanoparticulated cobaltite oxide memristive device

Multilevel resistive switching(RS)is a key property to embrace the full potential of memristive devices for non-volatile memory and neuromorphic computing applications.In this study,we employed nanoparticulated cobaltite oxide(Co_(3)O_(4))as a model material to demonstrate the multilevel RS and synaptic learning capabilities because of its multiple and stable redox state properties.The Pt/Co_(3)O_(4)/Pt memristive device exhibited tunable RS properties with respect to different voltages and compliance currents(CC)without the electroforming process.That is,the device showed voltage-dependent RS at a higher CC whereas CC-dependent RS was observed at lower CC.The device showed four different resistance states during endurance and retention measurements and non-volatile memory results indicated that the CC-based measurement had less variation.Besides,we investigated the basic and complex synaptic plasticity properties using the analog current-voltage characteristics of the Pt/Co_(3)O_(4)/Pt device.In particular,we mimicked the potentiation–depression and four-spike time-dependent plasticity(STDP)rules such as asymmetric Hebbian,asymmetric anti-Hebbian,symmetric Hebbian,and symmetric antiHebbian learning rules.The results of the present work indicate that the cobaltite oxide is an excellent nanomaterial for both multilevel RS and neuromorphic computing applications.

Characterization of Polycrystalline Nickel Cobaltite Nanostructures Prepared by DC Plasma Magnetron Co-Sputtering for Gas Sensing Applications

In this work, a gas sensor is fabricated from polycrystalline nickel cobaltite nano films deposited on transparent substrates by closed-field unbalanced dual-magnetrons （CFUBDM） co-sputtering technique. Two targets of nickel and cobalt are mounted on the cathode of discharge system and co-sputtered by direct current （DC） argon discharge plasma in presence of oxygen as a reactive gas. The total gas pressure is 0.5 mbar and the mixing ratio of Ar：O2 gases is 5：1. The characterization measurements performed on the prepared films show that their transmittance increases with the incident wavelength, the polycrystalline structure includes 5 crystallographic planes, the average particle size is about 35nm, the electrical conductivity is linearly increasing with increasing temperature, and the activation energy is about 0.41 eV. These films show high sensitivity to ethanol vapor.

碱促进的钴酸镁催化剂上的氧化亚氮分解(英文)

The direct decomposition of N2O was investigated over a series of magnesium cobaltite catalysts,MgxCo1-xCo2O4(0.0 ≤ x ≤ 1.0) ,which were prepared by the thermal decomposition of stoichiometric amounts of magnesium hydroxide and cobalt acetate. The thermal genesis of the different catalysts from their precursors was explored using thermogravimetric analysis,differential thermal analysis,and X-ray diffraction. Texture analysis was carried out using N2 adsorption at -196 °C. We found that all the catalysts that were calcined at 500 °C have a spinel structure. N2O decomposition activity was found to increase with an increase in the spinel structure's magnesium content. The influence of alkali cation promoters(Li,Na,K,and Cs) on the activity of the most active catalyst in the MgxCo1-xCo2O4 series,i.e. MgCo2O4,was also investigated. The sequence of the promotional effect was found to be: un-promoted < Li < Na < Cs < K-promoted catalyst. The reason for the increase in activity for the added alkali cations was electronic in nature. Additionally,the dependence of the activity on the K/Co ratio was also determined. The highest activity was obtained for the catalyst with a K/Co ratio of 0.05. A continuous decrease in activity was obtained for higher K/Co ratios. This decrease in activity was attributed to the elimination of mesoporosity in the catalysts with K/Co ratios > 0.05,based on N2 adsorption and scanning electron microscopy results.

Structural engineering of cathodes for improved Zn-ion batteries

Aqueous zinc-ion batteries(ZIBs) are attracting considerable attention because of their low cost,high safety and abundant anode material resources.However,the major challenge faced by aqueous ZIBs is the lack of stable and high capacity cathode materials due to their complicated reaction mechanism and slow Zn-ion transport kinetics.This study reports a unique 3 D ’flower-like’ zinc cobaltite(ZnCo_(2)O_(4-x)) with enriched oxygen vacancies as a new cathode material for aqueous ZIBs.Computational calculations reveal that the presence of oxygen vacancies significantly enhances the electronic conductivity and accelerates Zn^(2+) diffusion by providing enlarged channels.The as-fabricated batteries present an impressive specific capacity of 148.3 mAh g^(-1) at the current density of 0.05 A g^(-1),high energy(2.8 Wh kg^(-1)) and power densities(27.2 W kg^(-1)) based on the whole device,which outperform most of the reported aqueous ZIBs.Moreover,a flexible solid-state pouch cell was demonstrated,which delivers an extremely stable capacity under bending states.This work demonstrates that the performance of Zn-ion storage can be effectively enhanced by tailoring the atomic structure of cathode materials,guiding the development of low-cost and eco-friendly energy storage materials.

Electronic Structure and Thermoelectric Properties of Ca_3Co_4O_9

The relation among electronic structure, chemical bond and thermoelectric property of Ca3 Co4 O9 was studied using density function and discrete variation method （DFT-DVM）. The gap between the highest valence band （HVB） and the lowest conduction band （LCB） shows a semiconducting property. Ca3 Co4 O9 consists of CoO2 and Ca2 CoO3 two layers. The HVB and LCB near Fermi level are only mainly from O（ 2 ） 2p and Co （2） 3d in Ca2 CoO3 layer. Therefore, the semiconducting or thermoelectric property of Ca3 Co4 O9 should be mainly from Ca2 CoO3 layer, but it seems to have no direct relation to the CoO2 layer, which is consistent with that binary oxides hardly have a thermoelectric property, but trinary oxide compounds have quite a good thermoelectric property. The covalent and ionic bonds of Ca2 CoO3 layer are both weaker than those of CoO2 layer. Ca plays the role of connections between CoO2 and Ca2 CoO3 layers in Ca3 Co4 O9, decrease the ionic and covalent bond strength, and improve the thermoelectric property.

Fe-doping induced Griffiths-like phase in La_(0.7)Ba_(0.3)CoO_3

The effect of Fe-doping on the magnetic properties of the ABO3-type perovskite cobaltites La0.7Ba0.3CoO3（0≤ y≤0.80） is reported. With no apparent structural change in any doped sample, the Curie temperature （Tc） and the magnetization （M） are greatly suppressed for y ≤0.30 samples, while a distinct increase in Tc for the y=0.40 sample is observed. With the further increase of Fe concentration, Tc increases monotonically. Griffiths-like phases in 0.40≤y ≤0.60 samples are confirmed. The formation of the Griffiths-like phase is ascribed to B-site disordering induced isolation of ferromagnetic （FM） clusters above Tc.

NiCo2O4 decorated PANI–CNTs composites as supercapacitive electrode materials

Hierarchical Ni CoO/PANI/CNTs hybrid composites were designed and fabricated having a layer of Ni CoOon the surface of PANI encapsulated CNTs with different morphologies. Physicochemical attributes of the synthesized composites were examined by FTIR, UV–visible and X-ray diffraction（XRD）techniques. Morphological aspects were evaluated by field-emission scanning microscopy（FESEM）,electron diffraction spectroscopy（EDS）, high resolution transmission electron microscopy（HRTEM） and selected area electron diffraction（SAED） studies. Electrochemical measurements revealed an improved specific capacitance of 2250 F/g at a scan rate of 5 m V/s and 2000 F/g at a current density of 1 A/g with good rate capability using a three-electrode system. These enhanced features are achieved from the well designed nanostructure and the synergistic contributions of individual components in the electrode material.

Electric properties of La_(0.8)Sr_(0.2)CoO_3 nanoceramics

The electric measurements were carried out for La0.8Sr0.2CoO3 nanoceramics by using impedance spectroscopy methods. The resistance of sample was practically independent of frequency in measurement range. Its dependence on reciprocal temperature showed quite complicated mechanism of conduction. The most striking property of investigated sample was its resistance decreasing with increasing applied polarization.

Synthesis and Thermoelectric Properties of Ca_(2.6)Nd_ ( 0.4)Co_4O_9 Compound

The layered cobaltite Ca 2.6Nd 0.4Co 4O 9 was synthesized by the solid-state reaction. Their crystal structure was determined by the X-ray powder diffraction and CELL program. The prepared Ca 2.6Nd 0.4Co 4O 9 compound has the monoclinic symmetry. The electrical conductivity and Seebeck coefficient were measured from room temperature to 700 ℃ in air. Both the properties increase while rising temperature. The thermoelectric power of Ca 2.6Nd 0.4Co 4O 9 is about 242 4 μV·K -1. The results imply a promising way to enhance the thermoelectric properties of the layered cobaltite oxides by optimizing their composition and microstructure.

Thermoelectric Properties of Ca_3Co_4O_9 Ceramics

Ca3Co4O9 ceramics were prepared using the sol-gel process with ordinary pressing sintering and their thermoelectric properties were measured from room temperature to 673 K. The experimental results show that single phase Ca3Co4O9 can be fabricated at 750-900 ℃ in different citrate acid molar proportions for 0.2-1.0. For all the oxides, both the Seebeck coefficients S and the electrical conductivitiesκincrease with the increasing temperature. The Seebeck coefficients S are all positive. The thermal conductivities κ increase with the increasing temperature also and the lattice thermal conductivityκl plays an important role to the thermal conductivity κ. The citrate acid molar proportions have a large influence on the particle sizes, which influences the thermoelectric properties of the ceramics. The figure of merit increases with the increasing temperature and reaches 4.5×10^-5 K^-1 at 573 K for the sample in the citrate acid molar proportion of 0.46.

CaCo_1-xRu_xO_y: Role of Ru/Co Ratio on Its Transport Properties

Calcium cobaltites, especially Ca3Co4O9 with a misfit layered structure, are promising thermoelectric materials due to their suitability for high temperature applications and low densities. The existence of low spin-state electronic configurations for both and species is one of the key parameter to explain the large thermopower values. Ruthenium oxide, with a layered structure, exhibits strong electron-electron correlation and the extended nature of their 4d electrons enhances orbital overlapping which is expected to influence the transport characteristics of CaCo1-xRuxOy (CCR) samples, by affecting the spin state of the 3d Co ions. The effect on thermopower and electrical resistivity due to partial substitution of Co by Ru ions, up to 0.33 moles, from 300 to 600 K was investigated. A sharp decline in resistivity and in thermopower was observed until a transition ion ratio (TIR), (Ru/(Ru + Co)), of 0.5 is reached, beyond which both the properties became less sensitive to TIR. These variations in the transport properties are explained by the presence of 4d Ru in close proximity to the Co, which could influence the spin and oxidation state of Co ions. The Co rich and Ru rich samples exhibit very distinct microstructures and phase assemblages.

Nickel foam supported Cr-doped NiCo2O4/FeOOH nanoneedle arrays as a high-performance bifunctional electrocatalyst for overall water splitting

Efficient and robust noble-metal-free bifunctional electrocatalysts for overall water splitting(OWS)is of great importance to realize the large-scale hydrogen production.Herein,we report the growth of undoped and Cr-doped NiCo2O4(Cr-NiCo2O4)nanoneedles(NNs)on nickel foam(NF)as bifunctional electrocatalysts for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).We demonstrate that Cr-doping significantly improves activity for HER and OER by increasing the conductivity of NNs and allowing more active sites on NNs electrochemically accessible.When amorphous FeOOH is electrodeposited on the surface of Cr-NiCo2O4 NNs,the resulting FeOOH/Cr-NiCo2O4/NF exhibits itself as an excellent bifunctional catalyst for OWS.In the two-electrode cell where FeOOH/Cr-NiCo2O4/NF is used both as cathode and anode for OWS,a cell voltage of only 1.65 V is required to achieve an electrolysis current density of 100 mA·cm^−2.In addition,the catalyst shows a very high stability for OWS,the two-electrode cell can operate at a consist current density of 20 mA·cm^−2 for 10 h OWS with the cell voltage being stable at ca.1.60 V.These results demonstrate that FeOOH/Cr-NiCo2O4/NF possesses an OWS performance superior to most of transition-metal based bifunctional electrocatalysts working in alkaline medium.The excellent bifunctional activity and stability of FeOOH/Cr-NiCo2O4/NF are attributed to the following reasons:(i)The NN structure provides a large specific surface area;(ii)the high conductivity of Cr-NiCo2O4 enables more active centers on the far-end part of NNs to be electrochemically reached;(iii)the deposition of FeOOH supplies additional active sites for OWS.