Effect of Co and Pr doping on the properties of solar-reflective ZnFe2O4 dark pigment

NASA Astrophysics Data System (ADS)

Suwan, M.; Sangwong, N.; Supothina, S.

2017-03-01

High NIR-reflective Co-doped ZnFe2O4 black pigments were synthesized by a simple solid-state reaction of ZnO and Fe2O3 in the presence of 3 to 30 wt.% Co3O4 at 1000 and 1100 °C. A series of black pigments with low L* values in a range of 25.5-26.5 and NIR reflectance of 39.5-48.7% were obtained at 1000 °C while the pigments with comparable L* values and slightly lower NIR reflectance were obtained at 1100 °C. A change of the pigment property could be attributed to substitution of Co2+ for Zn2+ as revealed by XRD analysis as well as reflectance spectra. Calcination of ZnO and Fe2O3 in the presence of 3 to 30 wt.% Pr6O11 at 1100 °C resulted in dark brown composite pigments consisting of ZnFe2O4, PrFe2O3 and unreacted Fe2O3 with L* value around 40 ±1 and NIR reflectance in a range of 48-50%.

In-situ synthesized ZnFe2O4 firmly anchored to the surface of MWCNTs as a long-life anode material with high lithium storage performance

NASA Astrophysics Data System (ADS)

Yang, Tianbo; Zhang, Wanxi; Li, Linlin; Jin, Bo; Jin, Enmei; Jeong, Sangmoon; Jiang, Qing

2017-12-01

Because of two different metal cations in the crystal structures, binary transition metal oxides possess a lot of unique properties. ZnFe2O4 emerges from these transition metal oxides on account of its high theoretical capacity (1072 mAh g-1). One-dimensional multi-walled carbon nanotubes (MWCNTs) would be a desirable conductive additive for ZnFe2O4, thereby improving the electrochemical performance of ZnFe2O4. In this work, we prepare ZnFe2O4/MWCNTs by solvothermal method with further heat-treatment. ZnFe2O4 nanoparticles are firmly anchored to the surface of MWCNTs. ZnFe2O4/MWCNTs nanocomposite displays high specific capacity (1278 mAh g-1 at a current density of 200 mA g-1 after 200 cycles, and 565 mAh g-1 at a current density of 1500 mA g-1 after 500 cycles), and good rate performance (367 mAh g-1 even at a current density of 6000 mAh g-1 after 80 cycles). The superior electrochemical performance may promote ZnFe2O4 to be a promising alternative anode in lithium-ion batteries.

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

DOE PAGES

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2017-04-24

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

Rietveld refinement and electrical properties of Ni-Zn spinel ferrites

NASA Astrophysics Data System (ADS)

Hooda, Ashima; Sanghi, Sujata; Agarwal, Ashish; Khasa, Satish; Hooda, Bhawana

2017-05-01

NiFe2O4, ZnFe2O4, Ni0.5Zn0.5Fe2O4 spinel samples have been synthesized by conventional solid state reaction technique. Powder X-ray diffraction and Rietveld refinement revealed that the samples were single Spinel phase with space group fd3m. The average crystalline size (D), lattice constant (a), X-ray density (ρx), measured density (ρm) and Porosity (P) of prepared samples were determined from XRD data. The dc electrical resistivity (p) was measured as a function of temperature. The variations of ρ were explained on the basis of Verwey and de Bohr mechanism. The value of DC resistivity found to increase with increase Zn concentration.

Enhanced photocatalytic performances and magnetic recovery capacity of visible-light-driven Z-scheme ZnFe2O4/AgBr/Ag photocatalyst

NASA Astrophysics Data System (ADS)

He, Jie; Cheng, Yahui; Wang, Tianzhao; Feng, Deqiang; Zheng, Lingcheng; Shao, Dawei; Wang, Weichao; Wang, Weihua; Lu, Feng; Dong, Hong; Zheng, Rongkun; Liu, Hui

2018-05-01

High efficiency, high stability and easy recovery are three key factors for practical photocatalysts. Z-scheme heterostructure is one of the most promising photocatalytic systems to meet all above requirements. However, efficient Z-scheme photocatalysts which could absorb visible light are still few and difficult to implement at present. In this work, the composite photocatalysts ZnFe2O4/AgBr/Ag were prepared through a two-step method. A ∼92% photodegradation rate on methyl orange was observed within 30 min under visible light, which is much better than that of individual ZnFe2O4 or AgBr/Ag. The stability was also greatly improved compared with AgBr/Ag. The increased performance is resulted from the suitable band alignment of ZnFe2O4 and AgBr, and it is defined as Z-scheme mechanism which was demonstrated by detecting active species and electrochemical impedance spectroscopy. Besides, ZnFe2O4/AgBr/Ag is ferromagnetic and can be recycled by magnet. These results show that ZnFe2O4/AgBr/Ag is a potential magnetically recyclable photocatalyst which can be driven by visible light.

Study on the Electrochemical Reaction Mechanism of ZnFe2O4 by In Situ Transmission Electron Microscopy

PubMed Central

Su, Qingmei; Wang, Shixin; Yao, Libing; Li, Haojie; Du, Gaohui; Ye, Huiqun; Fang, Yunzhang

2016-01-01

A family of mixed transition–metal oxides (MTMOs) has great potential for applications as anodes for lithium ion batteries (LIBs). However, the reaction mechanism of MTMOs anodes during lithiation/delithiation is remain unclear. Here, the lithiation/delithiation processes of ZnFe2O4 nanoparticles are observed dynamically using in situ transmission electron microscopy (TEM). Our results suggest that during the first lithiation process the ZnFe2O4 nanoparticles undergo a conversion process and generate a composite structure of 1–3 nm Fe and Zn nanograins within Li2O matrix. During the delithiation process, volume contraction and the conversion of Zn and Fe take place with the disappearance of Li2O, followed by the complete conversion to Fe2O3 and ZnO not the original phase ZnFe2O4. The following cycles are dominated by the full reversible phase conversion between Zn, Fe and ZnO, Fe2O3. The Fe valence evolution during cycles evidenced by electron energy–loss spectroscopy (EELS) techniques also exhibit the reversible conversion between Fe and Fe2O3 after the first lithiation, agreeing well with the in situ TEM results. Such in situ TEM observations provide valuable phenomenological insights into electrochemical reaction of MTMOs, which may help to optimize the composition of anode materials for further improved electrochemical performance. PMID:27306189

Operando identification of the point of [Mn- 2]O- 4 spinel formation during gamma-MnO 2 discharge within batteries

DOE PAGES

Gallaway, Joshua W.; Hertzberg, Benjamin J.; Zhong, Zhong; ...

2016-05-07

The rechargeability of γ-MnO 2 cathodes in alkaline batteries is limited by the formation of the [Mn 2]O 4 spinels ZnMn 2O 4 (hetaerolite) and Mn 3O 4 (hausmannite). However, the time and formation mechanisms of these spinels are not well understood. Here we directly observe γ-MnO 2 discharge at a range of reaction extents distributed across a thick porous electrode. Coupled with a battery model, this reveals that spinel formation occurs at a precise and predictable point in the reaction, regardless of reaction rate. Observation is accomplished by energy dispersive X-ray diffraction (EDXRD) using photons of high energy andmore » high flux, which penetrate the cell and provide diffraction data as a function of location and time. After insertion of 0.79 protons per γ-MnO 2 the α-MnOOH phase forms rapidly. α-MnOOH is the precursor to spinel, which closely follows. ZnMn 2O 4 and Mn 3O 4 form at the same discharge depth, by the same mechanism. The results show the final discharge product, Mn 3O 4 or Mn(OH) 2, is not an intrinsic property of γ-MnO 2. While several studies have identified Mn(OH) 2 as the final γ-MnO 2 discharge product, we observe direct conversion to Mn 3O 4 with no Mn(OH) 2.« less

Spinel and post-spinel phase assemblages in Zn 2TiO 4: an experimental and theoretical study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yanyao; Liu, Xi; Shieh, Sean R.

Zn2TiO4 spinel (Zn2TiO4-Sp) was synthesized by a solid-state reaction method (1573 K, room P and 72 h) and quasi-hydrostatically compressed to ~24 GPa using a DAC coupled with a synchrotron X-ray radiation (ambient T). We found that the Zn2TiO4-Sp was stable up to ~21 GPa and transformed to another phase at higher P. With some theoretical simulations, we revealed that this high-P phase adopted the CaTi2O4-type structure (Zn2TiO4-CT). Additionally, the isothermal bulk modulus (KT) of the Zn2TiO4-Sp was experimentally obtained as 156.0(44) GPa and theoretically obtained as 159.1(4) GPa, with its first pressure derivative K'TKT' as 3.8(6) and 4.37(4), respectively.more » The volumetric and axial isothermal bulk moduli of the Zn2TiO4-CT were theoretically obtained as KT = 150(2) GPa (K'TKT' = 5.4(2); for the volume), KT-a = 173(2) GPa (K'T-aKT-a' = 3.9(1); for the a-axis), KT-b = 74(2) GPa (K'T-bKT-b' = 7.0(2); for the b-axis), and KT-c = 365(8) GPa (K'T-cKT-c' = 1.5(4); for the c-axis), indicating a strong elastic anisotropy. The Zn2TiO4-CT was found as ~10.0 % denser than the Zn2TiO4-Sp at ambient conditions. The spinel and post-spinel phase assemblages for the Zn2TiO4 composition at high T have been deduced as Zn2TiO4-Sp, ZnTiO3-ilmenite + ZnO-wurtzite, ZnTiO3-ilmenite + ZnO-rock salt, ZnTiO3-perovskite + ZnO-rock salt, and Zn2TiO4-CT as P increases, which presumably implies a potential stability field for a CT-type Mg2SiO4 at very high P.« less

Spinel NixZn1-xFe2O4 (0.0 ≤ x ≤ 1.0) nano-photocatalysts: Synthesis, characterization and photocatalytic degradation of methylene blue dye

NASA Astrophysics Data System (ADS)

Padmapriya, G.; Manikandan, A.; Krishnasamy, V.; Jaganathan, Saravana Kumar; Antony, S. Arul

2016-09-01

Spinel NixZn1-xFe2O4 (x = 0.0 to 1.0) nanoparticles were successfully synthesized by a simple microwave combustion method (MCM) using metal nitrates as raw materials and glycine as the fuel. The structural, morphological and opto-magnetic properties of the spinel NixZn1-xFe2O4 ferrites were determined by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), high resolution scanning electron microscopy (HR-SEM), energy dispersive X-ray (EDX) spectroscopy, high resolution transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED) pattern, UV-Visible diffuse reflectance spectroscopy (DRS), photoluminescence (PL) spectroscopy and vibrating sample magnetometer (VSM). Powder XRD, and EDX analysis was confirmed the formation of pure phase of spinel ferrites. HR-SEM and HR-TEM analysis was confirmed the formation of sphere like-particle morphology of the samples with smaller agglomeration. VSM analysis clearly showed the superparamagnetic and ferromagnetic nature of the samples. The Ms value is 3.851 emu/g for undoped ZnFe2O4 sample and it increased with increase in Ni content. Photo-catalytic degradation (PCD) of methylene blue (MB) dye using the samples were carried out and observed good PCD results.

Nanostructure ZnFe2O4 with Bacillus subtilis for Detection of LPG at Low Temperature

NASA Astrophysics Data System (ADS)

Goutham, Solleti; Kumar, Devarai Santhosh; Sadasivuni, Kishor Kumar; Cabibihan, John-John; Rao, Kalagadda Venkateswara

2017-04-01

The present study deals with the development of a chemical sensor for the detection of liquefied petroleum gas (LPG) at a low operating temperature using Zinc ferrite (ZnFe2O4)/ Bacillus subtilis ( B. subtilis) hybrid nanostructures. The nanostructure ZnFe2O4 and B. subtilis powder, taken in equal proportion was made into films using the spin coating technique. X-ray diffraction, thermal analysis, scanning electron microscopy, and transmission electron microscopy were used to study morphology, structure and crystallite size. The sensing properties of the hybrid structure were studied and excellent response was observed in the temperature range of 50-55°C for 400 ppm LPG, when compared to the individual components of the hybrid. The signal output of the proposed sensor were extremely stable for more than 30 days. This method proposes the usage of the biomolecule/metal oxide composites in electronics and helps to reduce the metal oxide usage.

Folic acid-functionalized magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell composite particles: synthesis and application in drug release.

PubMed

Yang, Dandan; Wei, Kaiwei; Liu, Qi; Yang, Yong; Guo, Xue; Rong, Hongren; Cheng, Mei-Ling; Wang, Guoxiu

2013-07-01

A drug delivery system was designed by deliberately combining the useful functions into one entity, which was composed of magnetic ZnFe2O4 hollow microsphere as the core, and mesoporous silica with folic acid molecules as the outer shell. Amine groups coated magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell (MZHM-MSS-NH2) composite particles were first synthesized by a one-pot direct co-condensation method. Subsequently a novel kind of folic acid-functionalized magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell (MZHM-MSS-NHFA) composite particles were synthesized by conjugating folic acid as targeted molecule to MZHM-MSS-NH2. Ibuprofen, a well-known antiphlogistic drug, was used as a model drug to assess the loading and releasing behavior of the composite microspheres. The results show that the MZHM-MSS-NHFA system has the higher capacity of drug storage and good sustained drug-release property. Copyright © 2013 Elsevier B.V. All rights reserved.

Facial synthesis of carbon-coated ZnFe2O4/graphene and their enhanced lithium storage properties

NASA Astrophysics Data System (ADS)

Yao, Libing; Su, Qingmei; Xiao, Yanling; Huang, Min; Li, Haojie; Deng, Huihui; Du, Gaohui

2017-07-01

Carbon-coated ZnFe2O4 spheres with sizes of 110-180 nm anchored on graphene nanosheets (ZF@C/G) are successfully prepared and applied as anode materials for lithium ion batteries (LIBs). The obtained ZF@C/G presents an initial discharge capacity of 1235 mAh g-1 and maintains a reversible capacity of 775 mAh g-1 after 150 cycles at a current density of 500 mA g-1. After being tested at 2 A g-1 for 700 cycles, the capacity still retains 617 mAh g-1. The enhanced electrochemical performances can be attributed to the synergetic role of graphene and uniform carbon coating ( 3-6 nm), which can inhibit the volume expansion, prevent the pulverization/aggregation upon prolonged cycling, and facilitate the electron transfer between carbon-coated ZnFe2O4 spheres. The electrochemical results suggest that the synthesized ZF@C/G nanostructures are promising electrode materials for high-performance lithium ion batteries. [Figure not available: see fulltext.

Synthesis, characterization and photocatalytic properties of Mg1-xZnxAl2O4 spinel nanoparticles

NASA Astrophysics Data System (ADS)

Li, Hui; Liu, Yuqin; Tang, Junkai; Deng, Yanxi

2016-08-01

Mg1-xZnxAl2O4 spinel nanoparticles with x = 0, 0.05, 0.10, 0.15 and 0.20 were prepared via the chemical coprecipitation method. The obtained samples were characterised by thermal gravimetric and differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectroscopy, UV-Vis diffuse reflection spectrum, transmission electron microscopy and 27Al MAS-NMR spectroscopy. Mg1-xZnxAl2O4 spinel powders with the mean crystallite size of around 11 nm-14 nm were obtained. The crystallinity of the MgAl2O4 samples increases with the increase in the calcination temperature. At the same calcination temperature, higher amount of Zn2+ substitution leads to the higher level of crystallinity, but has no apparent influence on the mean crystallite size of the samples. The photocatalytic activity of the obtained Mg1-xZnxAl2O4 spinel nanoparticles was evaluated by monitoring the degradation of methylene blue under UV light. The degradation rates of methylene blue using the MgAl2O4 nanoparticles prepared at the calcination temperatures of 700 °C and 800 °C are much higher than those prepared at 900 °C and 1000 °C. The photocatalytic activities of the spinel powders with lower level of Zn2+ substitution such as Mg0.95Zn0.05Al2O4 are inferior to that of MgAl2O4. Results of 27Al MAS-NMR spectroscopy analysis and the first principle total density of state calculations reveal that this is probably due to the substitutions of Zn2+ decreasing the degree of Al3+ ions inversion over the sites of tetrahedral and octahedral coordination. With the increase in the amounts of Zn2+ substitution, the effects of Zn2+ additions on the photocatalytic activities become gradually predominant, leading to the increases in the degradation rates. The methylene blue degraded by 99% within 4 h using the Mg0.8Zn0.2Al2O4 spinel powders.

Olivine-modified spinel-spinel transitions in the system Mg2SiO4-Fe2SiO4: Calorimetric measurements, thermochemical calculation, and geophysical application

NASA Astrophysics Data System (ADS)

Akaogi, Masaki; Ito, Eiji; Navrotsky, Alexandra

1989-11-01

The olivine(α)-modified spinel(β)-spinel (γ) transitions in the system Mg2SiO4-Fe2SiO4 were studied by high-temperature solution calorimetry. Enthalpies of the β-γ and a α-γ transitions in Mg2SiO4 at 975 K and of the α-γ transition in Fe2SiO4 at 298 K were measured. The γ solid solution showed a positive enthalpy of mixing. Phase relations at high pressures and high temperatures were calculated from these thermochemical data including correction for the effect of nonideality of α, β, and γ solid solutions. The calculated phase diagrams agree well with those determined experimentally by Katsura and Ito very recently. The α - (Mg0.89, Fe0.11)2SiO4 transforms to β through a region of α+β without passing through the α+γ phase field at around 400 km depth in the mantle with an interval of about 18(±5) km. Temperatures at 390 and 650 km depths are estimated to be about 1673 and 1873 K, respectively, assuming an adiabatic geotherm.

Effect of metal cation ratio on chemical properties of ZnFe2O4/AC composite and adsorption of organic contaminant

NASA Astrophysics Data System (ADS)

Meilia, Demara; Misbah Khunur, Mochamad; Setianingsih, Tutik

2018-01-01

Porous woody char is biochar prepared through pyrolisis. The biochar can be used as adsorbent. In this research, ZnFe2O4/AC composite was synthesized through imregnation of the woody biochar with ZnFe2O4 to study effect of mol ratio of Fe(III) and Zn(II) toward their physicochemistry and adsorption of drug wastewater. Paracetamol was used as adsorbate model. This research was conducted in several steps, including activation of the woody biochar using KOH activator at temperatur 500 °C for 15 min to produce the activated carbon, fungsionalization of the carbon using H2SO4 oxidator (6M) at temperature of 80 °C for 3 h, impregnation of the oxidized activated carbon with Zn-Fe-LDH (Layered Double Hydroxide) at various mol ratio of Fe(III) and Zn(III), including 1:2, 1:3 and 1:4 using NaOH solution (5M) for coprecipitation, and calcination of Zn-Fe-LDH/AC at 950 °C for 5 min to produce ZnFe2O4/AC. FTIR diffraction characterization indicated existence of M-O (M = Zn(II), Fe(III)) and OH functional groups. FTIR spectra showed increasing of bands connected to -OH by increasing of the ratio till the ratio was achieved at 1:4, then decreased again. The ratio mol showed effect on the adsorption of paracetamol. Profile of adsorption value was fit with changing of functional groups. The highest adsorption was achieved at the ratio of 1:4. After calcination it gave the adsorption value of 17,66 mg/g.

Mesoporous Silica Matrix as a Tool for Minimizing Dipolar Interactions in NiFe2O4 and ZnFe2O4 Nanoparticles

PubMed Central

Virumbrales, Maider; Saez-Puche, Regino; Torralvo, María José; Blanco-Gutierrez, Veronica

2017-01-01

NiFe2O4 and ZnFe2O4 nanoparticles have been prepared encased in the MCM (Mobile Composition of Matter) type matrix. Their magnetic behavior has been studied and compared with that corresponding to particles of the same composition and of a similar size (prepared and embedded in amorphous silica or as bare particles). This study has allowed elucidation of the role exerted by the matrix and interparticle interactions in the magnetic behavior of each ferrite system. Thus, very different superparamagnetic behavior has been found in ferrite particles of similar size depending on the surrounding media. Also, the obtained results clearly provide evidence of the vastly different magnetic behavior for each ferrite system. PMID:28640197

Determination of the spinel group end-members based on electron microprobe analyses

NASA Astrophysics Data System (ADS)

Ferracutti, Gabriela R.; Gargiulo, M. Florencia; Ganuza, M. Luján; Bjerg, Ernesto A.; Castro, Silvia M.

2015-04-01

The spinel group minerals have been the focus of many studies, not only because of their economic interest, but also due to the fact that they are very useful as petrogenetic indicators. The application End-Members Generator (EMG) allows to establish, based on electron microprobe analyses (EMPA), the 19 end-members of the spinel group: MgAl2O4 (Spinel sensu stricto, s.s.), FeAl2O4 (Hercynite), MnAl2O4 (Galaxite), ZnAl2O4 (Gahnite), MgFe2O4 (Magnesioferrite), Fe3O4 (Magnetite), MnFe2O4 (Jacobsite), ZnFe2O4 (Franklinite), NiFe2O4 (Trevorite), MgCr2O4 (Magnesiochromite), FeCr2O4 (Chromite), MnCr2O4 (Manganochromite), ZnCr2O4 (Zincochromite), NiCr2O4 (Nichromite), MgV2O4 (Magnesiocoulsonite), FeV2O4 (Coulsonite), MnV2O4 (Vuorelainenite), Mg2TiO4 (Qandilite) and Fe2TiO4 (Ulvöspinel). EMG is an application that does not require an installation process and was created with the purpose of performing calculations to obtain: cation proportions (per formula unit, p.f.u.), end-members of the spinel group, redistribution proportions for the corresponding end-members in the Magnetite prism or Ulvöspinel prism and a data validation section to check the results. EMG accepts .csv data files and the results obtained can be used to represent a given dataset with the SpinelViz program or any other 2D and/or 3D graph plotting software.

Dipole defects in MgAl2O4 spinel crystals

NASA Astrophysics Data System (ADS)

Ayres, F.; de Souza, S. S.; Blak, A. R.

In order to study defects of dipole origin in normal and inverse spinel structures, Thermally Stimulated Depolarisation Current (TSDC) measurements have been carried out in MgAl2O4 spinel crystals doped with Fe, Cr, Mn and Co. The TSDC spectrum of the as-received sample labelled R shows two bands at 160K and 290K. Temperatures above 700K destroy the 290K band and γ-irradiation up to 1,500kGy restores the peak. In another sample labelled UC, the 290K band, of dipole origin, is only detected after γ-irradiation. The dipole origin of the 160K band has already been verified. This band is affected neither by γ-irradiation nor by thermal treatment. The reduction of the 290K band is observed when heating the samples between 350K and 480K for three minutes at each temperature. The correlation between the thermal reduction of the 290K band and the study of V-centres in MgAl2O4 spinels indicates the possible attribution of the band to V-type centres.

Superparamagnetic nanocrystalline ZnFe2O4 with a very high Curie temperature.

PubMed

Deka, Sasanka; Joy, P A

2008-08-01

Studies on the magnetic properties of nanocrystalline ZnFe2O4 synthesized by an autocombustion method are reported. Superparamagnetic behavior is observed for the nanocrystalline materials with particle sizes of 8 nm and 17 nm, with superparamagnetic blocking temperatures of 65 K and 75 K, respectively. Magnetic hysteresis with very large coercivities of 533 Oe and 325 Oe, respectively, are observed at 12 K. Studies on the temperature variation of the magnetization above room temperature indicate that the Curie temperature is as high as approximately 800 K when compared to the paramagnetic nature of bulk zinc ferrite at room temperature.

MgAl2O4 spinel refractory as containment liner for high-temperature alkali salt containing environments

DOEpatents

Peascoe-Meisner, Roberta A [Knoxville, TN; Keiser, James R [Oak Ridge, TN; Hemric, James G [Knoxville, TN; Hubbard, Camden R [Oak Ridge, TN; Gorog, J Peter [Kent, WA; Gupta, Amul [Jamestown, NY

2008-10-21

A method includes containing a high-temperature alkali salt containing environment using a refractory containment liner containing MgAl.sub.2O.sub.4 spinel. A method, includes forming a refractory brick containing MgAl.sub.2O.sub.4 spinel having an exterior chill zone defined by substantially columnar crystallization and an interior zone defined by substantially equiaxed crystallization; and removing at least a portion of the exterior chill zone from the refractory brick containing MgAl.sub.2O.sub.4 spinel by scalping the refractory brick containing MgAl.sub.2O.sub.4 spinel to define at least one outer surface having an area of substantially equiaxed crystallization. A product of manufacture includes a refractory brick containing MgAl.sub.2O.sub.4 spinel including an interior zone defined by substantially equiaxed crystallization; and at least one outer surface having an area of substantially equiaxed crystallization.

Novel ternary composites: Preparation, performance and application of ZnFe2O4/TiO2/polyaniline

NASA Astrophysics Data System (ADS)

Li, Juanbi; Xiao, Qiushi; Li, Liangchao; Shen, Junhai; Hu, Diqiong

2015-03-01

A series of ZnFe2O4/TiO2/polyaniline ternary composites with excellent photocatalytic activity were successfully synthesized by chemical method. The phase composition, morphology, conductivity, electrical and magnetic performances of the as-samples were characterized by means of modern measurement technology. And the photocatalytic degradation activity tests for the samples were estimated using rhodamine B (RhB) and methyl orange (MO) as targeted pollutants. The results indicated that there existed some interactions between each component in the ternary composites, and the electrical conductivities and photocatalytic degradation activities of the ternary composites were improved due to the coating of polyaniline. Moreover, when the mass fraction of aniline was up to 50%, the ternary composite exhibited a great decontaminating (including photocatalytic degradation and adsorption) activity of on both MO and RhB and displayed an excellent reusability.

Cr diffusion in MgAl2O4 synthetic spinels: preliminary results

NASA Astrophysics Data System (ADS)

Freda, C.; Celata, B.; Andreozzi, G.; Perinelli, C.; Misiti, V.

2012-04-01

Chromian spinel is an accessory phase common in crustal and mantle rocks, including peridotites, gabbros and basalts. Spinel, it has been identified as one of the most effective, sensible, and versatile petrogenetic indicator in mafic and ultramafic rock systems due to the strict interdependence between its physico-chemical properties (chemical composition, cation configuration etc.) and genetic conditions (temperature, pressure, and chemical characteristics of the system). In particular, studies on intra- and inter-crystalline Mg-Fe2+, Cr-Al exchange demonstrated the close relationship between spinel composition and both degree of partial melting and equilibrium temperature of spinel-peridotites. Moreover, studies focused on the chemical zoning of Mg-Fe2+ and/or Cr-Al components in spinel have been used, combined with a diffusion model, to provide quantitative information on peridotites and gabbros pressure-temperature paths and on deformation mechanisms. Although these potentials, most of the experimental studies have been performed on spinels hosting a limited content of divalent iron (sensu stricto, MgAl2O4), whereas the scarce studies on Cr-Al inter-diffusion coefficient have been performed at 3-7 GPa as pressure boundary condition. In order to contribute to the understanding of processes occurring in the lithospheric mantle, we have initiated an experimental research project aiming at determining the Cr-Al inter-diffusion in spinel at 2 GPa pressure and temperature ranging from 1100 to 1250 °C. The experiments were performed in a end-loaded piston cylinder by using a 19 mm assembly and graphite-Pt double capsules. As starting materials we used synthetic Mg-Al spinel (200-300 μm in size) and Cr2O3 powder. Microanalyses of experimental charge were performed on polished carbon-coated mounts by electronic microprobe. Line elemental analyses were made perpendicular to the contact surface between Cr2O3 powder and spinel, at interval of 2 μm. By processing these

Sulfidation behavior of ZnFe2O4 roasted with pyrite: Sulfur inducing and sulfur-oxygen interface exchange mechanism

NASA Astrophysics Data System (ADS)

Min, Xiaobo; Zhou, Bosheng; Ke, Yong; Chai, Liyuan; Xue, Ke; Zhang, Chun; Zhao, Zongwen; Shen, Chen

2016-05-01

The sulfidation roasting behavior was analyzed in detail to reveal the reaction mechanism. Information about the sulfidation reaction, including phase transformation, ionic migration behavior and morphological change, were obtained by XRD, 57Fe Mossbauer spectroscopy, XPS and SEM analysis. The results showed that the sulfidation of zinc ferrite is a process of sulfur inducing and sulfur-oxygen interface exchange. This process can be divided into six stages: decomposition of FeS2, formation of the oxygen-deficient environment, migration of O2- induced by S2(g), formation of ZnFe2O4-δ, migration of Fe2+ accompanied by the precipitation of ZnO, and the sulfur-oxygen interface exchange reaction. The sulfidation products were zinc blende, wurtzite, magnetite and a fraction of zinc-bearing magnetite. These findings can provide theoretical support for controlling the process during which the recovery of Zn and Fe is achieved through the combined flotation-magnetic separation process.

Mixed Metal Oxides of the Type CoxZn1-xFe2O4 as Photocatalysts for Malachite Green Degradation Under UV Light Irradiation.

PubMed

Tzvetkov, Martin; Milanova, Maria; Cherkezova-Zheleva, Zara; Spassova, Ivanka; Valcheva, Evgenia; Zaharieva, Joana; Ivan, Mitov

2017-06-01

A combination of thermal and mechanical (high energy ball milling) treatment was applied in an attempt to obtain polycrystalline mixed metal binary and ternary oxides of the type CoxZn1-xFe2O4 (x = 0; 0.25; 0.5; 0.75; 1). The synthetic procedure used successfully produced single-phased, homogeneous ZnFe2O4, CoFe2O4, and Co0.75Zn0.25Fe2O4, as well as mixed oxides, whose composition depended both on the duration of the high energy ball milling and the ratio Zn(II)/Co(II). The formation of spinel-like structures was proved by XRD, Mössbauer spectroscopy and Raman spectroscopy. For the characterization of the samples low-temperature N2 adsorption, UV/Vis spectroscopy and transmission electron microscopy were applied. The energy band gap of the samples was calculated, suggesting they are promising photocatalysts. The decomposition of the Malachite Green in model water solutions under UV-light irradiation was successfully achieved in the presence of the samples as photocatalysts. The highest rate constant was obtained for the sample synthesized at longer milling time in combination with higher Zn(II)/Co(II) ratio. The photocatalytic activity of the ternary mixed oxides was compared with the pure hematite, α-Fe2O3, and the binary ZnFe2O4 and CoFe2O4 ferrites with spinel structure that were treated in the same way. A synergetic effect of α-Fe2O3 and the spinel-like structure on the photocatalytic properties of ternary mixed metal oxides was detected.

Ion irradiation-induced crystal structure changes in inverse spinel MgIn 2O 4

DOE PAGES

Tang, Ming; Valdez, James A.; Wang, Yongqiang; ...

2016-07-29

We performed 400 keV Ne and 200 keV He ion irradiations on fully inverse MgIn 2O 4 samples at cryogenic temperature (~ 77 K), in order to examine the influence of radiation-induced cation disordering on crystal structure. In the case of MgIn 2O 4 samples irradiated with Ne ions to a peak displacement damage dose of 4 displacements per atom (dpa), a spinel-to-rocksalt phase transformation was observed. Conversely, for MgIn 2O 4 samples irradiated with He ions to a peak displacement damage dose of 5 dpa, the only observed structural effect involved cation rearrangements from an inverse to a “random”more » spinel structure.« less

NiFe2O4 Spinel Protection Coating for High-Temperature Solid Oxide Fuel Cell Interconnect Application

NASA Astrophysics Data System (ADS)

Irankhah, Reza; Raissi, Babak; Maghsoudipour, Amir; Irankhah, Abdullah; Ghashghai, Sasan

2016-04-01

In the present study, Ni-Fe spinel powder was synthesized via a solid state reaction. In the next step, the electrophoretic deposition (EPD) method was used to apply the NiFe2O4 spinel, as an oxidation-resistant layer, on a commercially available stainless steel (SUS 430) in a potential range of 100 to 300 V. Microscopic studies of the deposited layers showed that crack-free NiFe2O4 films were obtained at 100 V. The coated and uncoated samples were then pre-sintered in air and 5% H2 bal Ar atmospheres at 900 °C for 3 h followed by cyclic oxidation at 800 °C for 500 h. The investigation of the oxidation resistance of the samples using Energy Dispersive Spectroscopy (EDS) revealed that the NiFe2O4 coating acted as an effective barrier against chromium migration into the coating. The oxidation resistance of 5% H2 bal Ar pre-sintered sample was enhanced with an oxidation rate constant ( K P) of 8.9 × 10-15 g2 cm-4 s-1.

Compositional dependence of elastic moduli for transition-metal oxide spinels

NASA Astrophysics Data System (ADS)

Reichmann, H. J.; Jacobsen, S. D.; Boffa Ballaran, T.

2012-12-01

Spinel phases (AB2O4) are common non-silicate oxides in the Earth's crust and upper mantle. A characteristic of this mineral group is the ability to host a wide range of transition metals. Here we summarize the influence of transition metals (Fe, Zn, and Mn) on the pressure dependence of elastic moduli of related spinels (magnetite, gahnite, and franklinite) using GHz-ultrasonic interferometry. Measurements were carried out up to 10 GPa in diamond-anvil cells using hydrostatic pressure media. Transition metals with unfilled 3d orbitals strongly influence the elastic properties of spinels. Franklinite (Zn,Mn)Fe2O4 and magnetite Fe3O4 with transition metals on both A and B cation sites exhibit pressure-induced mode softening of C44, whereas C44 of gahnite(ZnAl2O4) and spinel (MgAl2O4) exhibit positive pressure derivatives of the shear moduli. Spinels with two transition elements tend to undergo phase changes at a lower pressure than those with none or only one transition metal. Along the Mn-Zn solid solution, the variation of moduli with composition is non-linear, and a mid-range franklinite composition studied here shows a minimum in C44 compared with either end-member: MnFe2O 4 or ZnFe2O4. In general, the linear variation of sound velocity with density (Birch's Law) is followed by spinels, however spinels containing only one or no transition metals follow a distinct slope from those containing transition metals on both A and B sites. The Cauchy relation, 0.5(C12 - C44) = P is fulfilled by spinels with only one or no transition metals, suggesting that that Coulomb interactions dominate. Spinels with two transition metals fail to meet the Cauchy relation, indicating strong directional dependence and covalent character of bonding. The bonding character of transition metals is crucial to understanding the elastic behavior of natural and synthetic spinel solid solutions containing transition metals.

Structural, dielectric and magnetic properties of ZnFe2O4-Na0.5Bi0.5TiO3 multiferroic composites

NASA Astrophysics Data System (ADS)

Bhasin, Tanvi; Agarwal, Ashish; Sanghi, Sujata; Yadav, Manisha; Tuteja, Muskaan; Singh, Jogender; Rani, Sonia

2018-04-01

Multiferroic xNa0.5Bi0.5TiO3-(1-x)ZnFe2O4 (x=0.10, 0.20) composites were prepared by conventional solid state reaction method. Rietveld analysis of XRD data shows that samples exhibit both cubic (Fd-3m) and rhombohedral (R3c) crystal structure. Structural parameters and unit cell volume of samples vary with composition. The dielectric constant and dielectric loss (tanδ) display dispersion at low frequency due to space charge polarization and inhomogeneity in the composites. Magnetic analysis depicts the antiferromagnetic behavior of composites and magnetization is enhanced with the introduction of ferrite (ZnFe2O4) phase.

Persistent three- and four-atom orbital molecules in the spinel Al V2O4

NASA Astrophysics Data System (ADS)

Browne, Alexander J.; Kimber, Simon A. J.; Attfield, J. Paul

2017-10-01

Electronic instabilities in transition-metal compounds may lead to ground states containing orbital molecules when direct metal-metal orbital interactions occur. The spinel Al V2O4 was reported to contain V717 + orbital heptamers that emerge below a 700 K charge ordering transition. Our x-ray total scattering analysis of Al V2O4 between 300 and 1100 K reveals a very different picture as the postulated heptamers are found to be pairs of spin-singlet V39 + trimers and V48 + tetramers, and these orbital molecules persist to at least 1100 K in a disordered high-temperature cubic phase.

The effect of calcination temperature on the formation and magnetic properties of ZnMn2O4 spinel

NASA Astrophysics Data System (ADS)

Hermanto, B.; Ciswandi; Afriani, F.; Aryanto, D.; Sudiro, T.

2018-03-01

The spinel based on transition-metal oxides has a typical composition of AB2O4. In this study, the ZnMn2O4 spinel was synthesized using a powder metallurgy technique. The Zn and Mn metallic powders with an atomic ratio of 1:2 were mechanically alloyed for 3 hours in aqueous solution. The mixed powder was then calcined in a muffle furnace at elevated temperature of 400, 500 and 600 °C. The X-ray Diffractometer (XRD) was used to evaluate the formation of a ZnMn2O4 spinel structure. The magnetic properties of the sample at varying calcination temperatures were characterized by a Vibrating Sample Magnetometer (VSM). The results show that the fraction of ZnMn2O4 spinel formation increases with the increase of calcination temperature. The calcination temperature also affects the magnetic properties of the samples.

Photoelectrochemical enhancement of ZnO/BiVO4/ZnFe2O4/rare earth oxide hetero-nanostructures

NASA Astrophysics Data System (ADS)

She, Xuefeng; Zhang, Zhuo; Baek, Minki; Yong, Kijung

2018-01-01

Over the decades, researchers have made great efforts to turn the world into a cleaner place through efficient recycling of industrial waste and developing of green energy. Here we demonstrate a prototype heterostructure photoelectrochemical (PEC) cell fabricated using recycled industrial waste. ZnFe2O4 (ZFO) nanorod (NR) clusters were synthesized on the BiVO4@ZnO hetero-nanostructures using recycled rare earth oxide (REO) slags as Fe source. The NR-based PEC cell exhibited a significantly enhanced photon to hydrogen conversion efficiency over the entire UV and visible spectrum. Further study demonstrates that the photo-carrier separation and migration processes can be facilitated by the cascade band alignment of the heterostructure and the clustered nanostructure network. In addition, the life-time of the photo-carriers can be enhanced by the REO passivation layer, leading to a further increased PEC performance. Our results present a novel approach for high efficiency PEC cells, and offer great promises to the efficient recycling of industrial waste for clean renewable energy applications.

In situ studies of ion irradiated inverse spinel compound magnesium stannate (Mg 2SnO 4)

NASA Astrophysics Data System (ADS)

Xu, P.; Tang, M.; Nino, J. C.

2009-06-01

Magnesium stannate spinel (Mg 2SnO 4) was synthesized through conventional solid state processing and then irradiated with 1.0 MeV Kr 2+ ions at low temperatures 50 and 150 K. Structural evolutions during irradiation were monitored and recorded through bright field images and selected-area electron diffraction patterns using in situ transmission electron microscopy. The amorphization of Mg 2SnO 4 was achieved at an ion dose of 5 × 10 19 Kr ions/m 2 at 50 K and 10 20 Kr ions/m 2 at 150 K, which is equivalent to an atomic displacement damage of 5.5 and 11.0 dpa, respectively. The spinel crystal structure was thermally recovered at room temperature from the amorphous phase caused by irradiation at 50 K. The calculated electronic and nuclear stopping powers suggest that the radiation damage caused by 1 MeV Kr 2+ ions in Mg 2SnO 4 is mainly due to atomic displacement induced defect accumulation. The radiation tolerance of Mg 2SnO 4 was finally compared with normal spinel MgAl 2O 4.

Polyethylene glycol coated CoFe{sub 2}O{sub 4} nanoparticles: A potential spinel ferrite for biomedical applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Humbe, Ashok V.; Birajdar, Shankar D.; Jadhav, K. M., E-mail: drjadhavkm@gmail.com

2015-06-24

The structural and magnetic properties of the polyethylene glycol (PEG) coated cobalt spinel ferrite (CoFe{sub 2}O{sub 4}) nanoparticles have been reported in the present study. CoFe{sub 2}O{sub 4} nanoparticles were prepared by sol-gel auto-combustion method using citric acid + ethylene glycol as a fuel. The prepared powder of cobalt ferrite nanoparticles was annealed at 600°C for 6h and used for further study. The structural characterization of CoFe{sub 2}O{sub 4} nanoparticles were carried out by X-ray diffraction technique. The X-ray analysis confirmed the formation of single phase cubic spinel structure. The crystallite size, Lattice constant and X-ray density of the PEGmore » coated CoFe{sub 2}O{sub 4} nanoparticles were calculated by using XRD data. The presence of PEG on CoFe{sub 2}O{sub 4} nanoparticles and reduced agglomeration in the CoFe{sub 2}O{sub 4} nanoparticles were revealed by SEM studies. The magnetic properties were studied by pulse field hysteresis loop tracer technique at a room temperature. The magnetic parameters such as saturation magnetization, remanence magnetization, coercivity etc have been obtained. These magnetic parameters were get decreased by PEG coating.« less

Structural, optical and dielectric properties of transition metal (MFe2O4; M = Co, Ni and Zn) nanoferrites

NASA Astrophysics Data System (ADS)

Chand, Prakash; Vaish, Swapnil; Kumar, Praveen

2017-11-01

In the present work, transition metal spinel ferrite (MFe2O4; M = Co, Ni, Zn) nanostructures synthesized by chemical co-precipitation method. XRD analysis confirms the formation of cubic spinel-type structure with space group Fd3m and the average crystallite size calculated by Scherrer's formula found to be in 9-14 nm range. Scanning electron microscopy was used to study surface morphology of the samples. Moreover, Raman and PL spectra also confirm the formation of the cubic structure. The Raman spectra measured on cobalt, nickel and zinc ferrite revealed a larger number of phonon bands than expected for the cubic spinel structure. The calculated optical energy band gaps, obtained by Tauc's relation from UV-Vis absorption spectra are found to be as 2.44, 3.54 and 3.25 eV for CoFe2O4, NiFe2O4&ZnFe2O, respectively. The analysis of the complex impedance spectra of all ferrites samples shows the presence of one semicircular arc at all selected temperatures, signifying a key role of the grain boundary contribution. The dielectric constants (ε ‧) were measured in the frequency range from 10 Hz to 5 MHz at different temperatures and is found to be decreased suddenly with an increase in frequency and maintain a steady state or constant at higher frequencies for all the three samples. The AC conductivity is found to be increased with frequency and temperature of all the three samples which is explained on the basis of Koop's phenomenological theory.

Effect of cutting edge radius on surface roughness in diamond tool turning of transparent MgAl2O4 spinel ceramic

NASA Astrophysics Data System (ADS)

Yue, Xiaobin; Xu, Min; Du, Wenhao; Chu, Chong

2017-09-01

Transparent magnesium aluminate spinel (MgAl2O4) ceramic is one of an important optical materials. However, due to its pronounced hardness and brittleness, the optical machining of this material is very difficult. Diamond turning has advantages over the grinding process in flexibility and material removal rate. However, there is a lack of research that could support the use of diamond turning technology in the machining of MgAl2O4 spinel ceramic. Using brittle-ductile transition theory of brittle material machining, this work provides critical information that may help to realize ductile-regime turning of MgAl2O4 spinel ceramic. A characterization method of determination the cutting edge radius is introduced here. Suitable diamond tools were measured for sharpness and then chosen from a large number of candidate tools. The influence of rounded cutting edges on surface roughness of the MgAl2O4 spinel ceramic is also investigated. These results indicate that surface quality of MgAl2O4 spinel is relate to the radius of diamond tool's cutting edge, cutting speed, and feed rate. Sharp diamond tools (small radius of cutting edge) facilitated ductile-regime turning of MgAl2O4 spinel and shows great potential to reduce surface roughness and produce smoother final surface.

Temperature and field dependent magnetization studies on nano-crystalline ZnFe2O4 thin films

NASA Astrophysics Data System (ADS)

Sahu, B. N.; Suresh, K. G.; Venkataramani, N.; Prasad, Shiva; Krishnan, R.

2018-05-01

Single phase nano-crystalline zinc ferrite (ZnFe2O4) thin films were deposited on fused quartz substrate using the pulsed laser deposition technique. The films were deposited at different substrate temperatures. The field dependence of magnetization at 10 K shows hysteresis loops for all the samples. Temperature dependence of the field cooled (FC) and zero field cooled (ZFC) magnetization indicated irreversible behavior between the FC and ZFC data, and the irreversibility depends on the measuring magnetic field. The thermo-magnetic irreversibility in the magnetization data is correlated with the magnitude of the applied field and the coercivity (HC) obtained from the M-H loops.

Molecular dynamics simulations of spinels: LiMn2O4 and Li4Mn5O12 at high temperatures

NASA Astrophysics Data System (ADS)

Ledwaba, R. S.; Matshaba, M. G.; Ngoepe, P. E.

2015-04-01

Energy storage technologies are critical in addressing the global challenge of clean sustainable energy. Spinel lithium manganates have attracted attention due to their electrochemical properties and also as promising cathode materials for lithium-ion batteries. The current study focused on the effects of high temperatures on the materials, in order to understand the sustainability in cases where the battery heats up to high temperature and analysis of lithium diffusion aids in terms of intercalation host compatibility. It is also essential to understand the high temperature behaviour and lithium ion host capability of these materials in order to perform the armorphization and recrystalization of spinel nano-architectures. Molecular dynamics simulations carried out to predict high temperature behaviour of the spinel systems. The NVE ensemble was employed, in the range 300 - 3000K. The melting temperature, lithium-ion diffusion and structural behaviour were monitored in both supercell systems. LiMn2O4 indicated a diffusion rate that increased rapidly above 1500K, just before melting (˜1700K) and reached its maximum diffusion at 2.756 × 10-7 cm2s-1 before it decreased. Li4Mn5O12 indicated an exponential increase above 700K reaching 8.303 × 10-7 cm2s-1 at 2000K and allowing lithium intercalation even above its melting point of around 1300K. This indicated better structural stability of Li4Mn5O12 and capability to host lithium ions at very high temperatures (up to 3000 K) compared to LiMn2O4.

Structural, dielectric and gas sensing behavior of Mn substituted spinel MFe2O4 (M=Zn, Cu, Ni, and Co) ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Ranjith Kumar, E.; Siva Prasada Reddy, P.; Sarala Devi, G.; Sathiyaraj, S.

2016-01-01

Spinel ferrite (MnZnFe2O4, MnCuFe2O4, MnNiFe2O4 and MnCoFe2O4) nanoparticles have been prepared by evaporation method. The annealing temperature plays an important role on changing particle size of the spinel ferrite nanoparticles was found out by X-ray diffraction and transmission electron microscopy. The role of manganese substitution in the spinel ferrite nanoparticles were also analyzed for different annealing temperature. The substitution of Mn also creates a vital change in dielectric properties have been measured in the frequency range of 100 kHz to 5 MHz. These spinel ferrites are decomposed to α-Fe2O3 after annealing above 550 °C in air. Through the characterization of the prepared powder, the effect of annealing temperature, chemical composition and preparation technique on the microstructure, particle size and dielectric properties of the Mn substituted spinel ferrite nanoparticles are discussed. Furthermore, Conductance response of Mn substituted MFe2O4 ferrite nanoparticles were measured by exposing the materials to reducing gas like liquefied petroleum gas (LPG).

Reduced grain boundary energies in rare-earth doped MgAl 2O 4 spinel and consequent grain growth inhibition

DOE PAGES

Hasan, Md M.; Dholabhai, Pratik P.; Dey, Sanchita; ...

2017-05-15

In this paper, grain growth inhibition in MgAl 2O 4 spinel nanostructure was achieved by grain boundary (GB) segregation of rare-earth dopants. Microcalorimetric measurements showed that dense spinel compacts doped with 3 mol% of R 2O 3 (R = Y, Gd, and La) had decreased GB energies as compared to the undoped spinel, representing reduction in the driving force for grain growth. Segregation energies of the three dopants to the Σ3 (111) GB were calculated by atomistic simulation. The dopants with higher ionic radius tend to segregate more strongly to GBs. The GB energies were calculated from atomistic simulation and,more » consistent with experiments, a systematic reduction in GB energy with dopant ionic size was found. Finally, high temperature grain growth experiments revealed a significant reduction of grain growth in the doped nanostructures as compared to the undoped one, which was attributed to increased metastability or possibly also a GB dragging originated from the dopant segregation.« less

Synthesis of Carbon-Based Spinel NiCo2O4 Nanocomposite and Its Application as an Electrochemical Capacitor

NASA Astrophysics Data System (ADS)

Shahraki, Mohammad; Elyasi, Saeed; Heydari, Hamid; Dalir, Nima

2017-08-01

In this study, a thermal method was used to synthesize spinel NiCo2O4 and carbon nanotubes (CNTs)@NiCo2O4 with an average size 50 nm and 20 nm, respectively. Addition of CNTs into NiCo2O4 noticeably increases the active surface area compared to pure spinel NiCo2O4. SEM analyses showed that the morphologies are spherical in both pure and composite samples. Uniform CNTs@NiCo2O4 nanoparticles exhibit high specific capacitance of 210 F g-1 at 2 A g-1 and a good retention capacity of 92.70% after 2500 cycles, which shows a considerable improvement compared to NiCo2O4. Additionally, an exceptional rate capability of about 73.2% was obtained at 50 A g-1. Such remarkable electrochemical performance of the CNTs@NiCo2O4 can be attributed to high specific surface area and also uniform structure which increase the exposure of active sites available for reaction on the surface shortened transport pathways for both electrons and ion. Also, volume change during the charge-discharge process is mainly alleviated compared to pure spinel NiCo2O4. A carbonaceous material such as the CNT facilitates the charge transfer and improves the stability of frame against volume change.

Investigation of Synthetic Mg(1.3)V(1.7)O4 Spinel with MgO Inclusions: Case Study of a Spinel with an Apparently occupied Interstitial Site

NASA Technical Reports Server (NTRS)

Uchida, Hinako; Righter, Kevin; Lavina, Barbara; Nowell, Matthew M.; Wright, Stuart I.; Downs, Robert T.; Yang, Hexiong

2007-01-01

A magnesium vanadate spinel crystal, ideally MgV2O4, synthesized at 1 bar, 1200 C and equilibrated under FMQ + 1.3 log f(sub o2) condition, was investigated using single-crystal X-ray diffraction, electron microprobe, and electron backscatter (EBSD). The initial X-ray structure refinements gave tetrahedral and octahedral site occupancies, along with the presence of 0.053 apfu Mg at an interstitial octahedral site . Back-scattered electron (BSE) images and electron microprobe analyses revealed the existence of an Mg-rich phase in the spinel matrix, which was too small (less than or equal to 3microns) for an accurate chemical determination. The EBSD analysis combined with X-ray energy dispersive spectroscop[y (XEDS) suggested that the Mg-rich inclusions are periclase oriented coherently with the spinel matrix. The final structure refinements were optimized by subtracting the X-ray intensity contributions (approx. 9%) of periclase reflections, which eliminated the interstitial Mg. This study provides insight into possible origins of refined interstitial cations reported in the the literature for spinel, and points to the difficulty of using only X-ray diffraction data to distinguish a spinel with interstitial cations from one with coherently oriented MgO inclusions.

Synthesis and characterization of spinel type high-power cathode materials Li MxMn2-x O4 (M=Ni, Co, Cr)

NASA Astrophysics Data System (ADS)

Yoon, Y. K.; Park, C. W.; Ahn, H. Y.; Kim, D. H.; Lee, Y. S.; Kim, J.

2007-05-01

The transition metal-doped spinel cathode materials, LiM0.5Mn1.5O4 (M=Ni. Co, Cr) were prepared by solid-state reaction. The structure and morphology of the samples were investigated by X-ray diffraction, Rietveld refinement and scanning electron microscopy (SEM). The diffraction peaks of all the samples corresponded to a single phase of cubic spinel structure with a space group Fd3m. Field-emission SEM shows octahedron like shapes and the primary particles size was between 500 nm and 2 μm. Oxidation states of Ni, Co and Cr were found to be 2+, 2+ and 3+ as revealed by X-ray photoelectron spectroscopy. During discharging, LiNi0.5Mn1.5O4 and LiCo0.5Mn1.5O4 sample shows more than 130 mAh/g between 3.5 and 5.2 V at a current density of 0.65 mA/cm2 and well developed plateau around 5 V, respectively.

Effects of calcination temperature for rate capability of triple-shelled ZnFe2O4 hollow microspheres for lithium ion battery anodes

NASA Astrophysics Data System (ADS)

Hwang, Hojin; Shin, Haeun; Lee, Wan-Jin

2017-04-01

Triple-shelled ZnFe2O4 hollow microspheres (ZFO) as anode materials for lithium ion battery are prepared through a one-pot hydrothermal reaction using the composite solution consisting of sucrose in water and metal ions in ethylene glycol (EG), followed by different calcination processes. The architectures of ZFO micro spheres are differently synthesized through a mutual cooperation of inward and outward ripening with three different calcination temperatures. Thin triple-shelled ZnFe2O4 hollow microspheres calcined at 450 °C (ZFO-450) delivers a high reversible capacity of 932 mA h g-1 at a current density of 2 A g-1 even at the 200th cycle without obvious decay. Furthermore, ZFO-450 delivers 1235, 1005, 865, 834, and 845 mA h g-1 at high current densities of 0.5, 2, 5, 10, and 20 A g-1 after 100 cycles. Thin triple-shelled hollow microsphere prepared at an optimum calcination temperature provides exceptional rate capability and outstanding rate retention due to (i) the formation of nanoparticles leading to thin shell with morphological integrity, (ii) the facile mass transfer by thin shell with mesoporous structure, and (iii) the void space with macroporous structure alleviating volume change occurring during cycling.

Effects of calcination temperature for rate capability of triple-shelled ZnFe2O4 hollow microspheres for lithium ion battery anodes

PubMed Central

Hwang, Hojin; Shin, Haeun; Lee, Wan-Jin

2017-01-01

Triple-shelled ZnFe2O4 hollow microspheres (ZFO) as anode materials for lithium ion battery are prepared through a one-pot hydrothermal reaction using the composite solution consisting of sucrose in water and metal ions in ethylene glycol (EG), followed by different calcination processes. The architectures of ZFO micro spheres are differently synthesized through a mutual cooperation of inward and outward ripening with three different calcination temperatures. Thin triple-shelled ZnFe2O4 hollow microspheres calcined at 450 °C (ZFO-450) delivers a high reversible capacity of 932 mA h g−1 at a current density of 2 A g−1 even at the 200th cycle without obvious decay. Furthermore, ZFO-450 delivers 1235, 1005, 865, 834, and 845 mA h g−1 at high current densities of 0.5, 2, 5, 10, and 20 A g−1 after 100 cycles. Thin triple-shelled hollow microsphere prepared at an optimum calcination temperature provides exceptional rate capability and outstanding rate retention due to (i) the formation of nanoparticles leading to thin shell with morphological integrity, (ii) the facile mass transfer by thin shell with mesoporous structure, and (iii) the void space with macroporous structure alleviating volume change occurring during cycling. PMID:28418001

Magnetic properties of mixed spinel BaTiO{sub 3}-NiFe{sub 2}O{sub 4} composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarkar, Babusona; Dalal, Biswajit; Dev Ashok, Vishal

2014-03-28

Solid solution of nickel ferrite (NiFe{sub 2}O{sub 4}) and barium titanate (BaTiO{sub 3}), (100-x)BaTiO{sub 3}–(x) NiFe{sub 2}O{sub 4} has been prepared by solid state reaction. Compressive strain is developed in NiFe{sub 2}O{sub 4} due to mutual structural interaction across the interface of NiFe{sub 2}O{sub 4} and BaTiO{sub 3} phases. Quantitative analysis of X-ray diffraction and X-ray photo electron spectrum suggest mixed spinel structure of NiFe{sub 2}O{sub 4}. A systematic study of composition dependence of composite indicates BaTiO{sub 3} causes a random distribution of Fe and Ni cations among octahedral and tetrahedral sites during non-equilibrium growth of NiFe{sub 2}O{sub 4}. Themore » degree of inversion decreases monotonically from 0.97 to 0.75 with increase of BaTiO{sub 3} content. Temperature dependence of magnetization has been analyzed by four sublattice model to describe complex magnetic exchange interactions in mixed spinel phase. Curie temperature and saturation magnetization decrease with increase of BaTiO{sub 3} concentration. Enhancement of strain and larger occupancy of Ni{sup 2+} at tetrahedral site increase coercivity up to 200 Oe. Magnetostructual coupling induced by BaTiO{sub 3} improves coercivity in NiFe{sub 2}O{sub 4}. An increase in the demagnetization and homogeneity in magnetization process in NiFe{sub 2}O{sub 4} is observed due to the interaction with diamagnetic BaTiO{sub 3}.« less

Magneto-structural correlation in Co0.8Cu0.2Cr2O4 cubic spinel

NASA Astrophysics Data System (ADS)

Kumar, Ram; Rayaprol, S.; Siruguri, V.; Xiao, Y.; Ji, W.; Pal, D.

2018-05-01

Neutron and X-ray diffraction, magnetic susceptibility, and specific heat measurements have been used to investigate the magneto-structural phase transitions in 20% Cu substituted multiferroic CoCr2O4 spinel. The Jahn-Teller active Cu2+ ion in the tetrahedral A-site of the spinel configuration induces the Jahn-Teller distortion slightly above the Néel temperature. In this compound, we observe a Jahn-Teller distortion of the crystal structure at 90 K. It was further observed that the high temperature cubic (Fd 3 ‾ m) structure coexists with the low temperature orthorhombic (Fddd) structure till the lowest temperature of measurement.

Enhancement of Electrochemical Performance of LiMn2O4 Spinel Cathode Material by Synergetic Substitution with Ni and S

PubMed Central

Bakierska, Monika; Świętosławski, Michał; Gajewska, Marta; Kowalczyk, Andrzej; Piwowarska, Zofia; Chmielarz, Lucjan; Dziembaj, Roman; Molenda, Marcin

2016-01-01

Nickel and sulfur doped lithium manganese spinels with a nominal composition of LiMn2−xNixO4–ySy (0.1 ≤ x ≤ 0.5 and y = 0.01) were synthesized by a xerogel-type sol-gel method followed by subsequent calcinations at 300 and 650 °C in air. The samples were investigated in terms of physicochemical properties using X-ray powder diffraction (XRD), transmission electron microscopy (EDS-TEM), N2 adsorption-desorption measurements (N2-BET), differential scanning calorimetry (DSC), and electrical conductivity studies (EC). Electrochemical characteristics of Li/Li+/LiMn2−xNixO4–ySy cells were examined by galvanostatic charge/discharge tests (CELL TEST), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). The XRD showed that for samples calcined at 650 °C containing 0.1 and 0.2 mole of Ni single phase materials of Fd-3m group symmetry and nanoparticles size of around 50 nm were obtained. The energy dispersive X-ray spectroscopy (EDS) mapping confirmed homogenous distribution of nickel and sulfur in the obtained spinel materials. Moreover, it was revealed that the adverse phase transition at around room temperature typical for the stoichiometric spinel was successfully suppressed by Ni and S substitution. Electrochemical results indicated that slight substitution of nickel (x = 0.1) and sulfur (y = 0.01) in the LiMn2O4 enhances the electrochemical performance along with the rate capability and capacity retention. PMID:28773491

Thermodynamic Stability of Transition Metal Substituted LiMn 2-xMxO 4 (M=Cr, Fe, Co, and Ni) Spinels

NASA Astrophysics Data System (ADS)

Lai, Chenying

The formation enthalpies from binary oxides of LiMn2O 4, LiMn2-xCrxO4 (x = 0.25, 0.5, 0.75 and 1), LiMn2-xFexO4 (x = 0.25 and 0.5), LiMn2-xCoxO4 (x = 0.25, 0.5, and 0.75) and LiMn1.75Ni 0.25O4 at 25 °C have been measured by high-temperature oxide-melt-solution calorimetry and were found to be strongly exothermic. Increasing Cr, Co and Ni content leads to more thermodynamically stable spinels, but increasing Fe content does not significantly affect the stability. The formation enthalpies from oxides of the fully substituted spinels, LiMnMO 4 (M = Cr, Fe and Co) become more exothermic (implying increasing stability) with decreasing ionic radius of the metal and lattice parameters of the spinel. The trend in enthalpy versus metal content is roughly linear, suggesting a close-to-zero heat of mixing in LiMn2O4 - LiMnMO 4 solid solutions. These data confirm that transition metal doping is beneficial for stabilizing these potential cathode materials for lithium-ion batteries.

Growth and optical waveguide fabrication in spinel MgGa2O4 crystal

NASA Astrophysics Data System (ADS)

Wang, Liang-Ling; Cui, Xiao-Jun; Rensberg, Jura; Wu, Kui; Wesch, Werner; Wendler, Elke

2017-10-01

We report on optical waveguide fabrication in a spinel MgGa2O4 crystal by 6.0 MeV carbon ion implantation at a fluence of 2 × 1015 ions/cm2 for the first time to our knowledge. The MgGa2O4 crystal was grown by the floating zone method. The refractive index profile reconstructed by reflectivity calculation method showed that the MgGa2O4 waveguide is a typical barrier waveguide. The typical barrier-shaped refractive index profile is attributed mainly to the nuclear energy deposition of the incident carbon ions into the MgGa2O4 crystal. By performing end-coupling measurements and using the beam propagation method (BPM) for the analysis of the observed modes, it can be concluded that the modes can be confined inside the waveguide.

Expansion during the formation of the magnesium aluminate spinel (MgAl(2)O(4)) from its basic oxide (MgO and Al(2)O(3)) powders

NASA Astrophysics Data System (ADS)

Duncan, Flavia Cunha

The extraordinary expansion during the reaction sintering of the magnesium aluminate spinel (MgAl2O4) from its basic oxide (MgO and Al2O3) powders was studied. Experimental series of different size fractions of the reacting materials were formulated to produce the Mg-Al spinel. After batches were prepared, specimens were compacted and fired in air from 1200° to 1700°C for a fixed firing time. A separate set of specimens was fired as a function of time to determine the reaction kinetic parameters. Dimensional changes confirmed that extraordinary expansions of three to four times greater than the prediction from the reaction of solids occur. The solid-state reactions were monitored by X-ray diffraction. The activation energy of the spinel reaction formation was determined to be 280 +/- 20 kJ/mol. It is believed to be associated with the diffusivity of Mg 2+ in either magnesia or spinel during the development of the final spinel structure. New porosity developed in the compacts during the reaction formation of spinel. Scanning electron microscopy confirmed that the magnesia evaporated leaving behind porous magnesia grains, condensed on the alumina particles and reacted to form a shell of spinel. Hollow spinel particles resulted from the original particles of alumina. These porosities generated within the reacting materials influenced the expansions. Final volumetric expansion could potentially reach 56% as a result of the reaction of solids and the porosity generation within MgO and Al2O3. Models of a single alumina particle with and without development of internal porosity were developed. 3-D arrangements of particles showed additional porosity, influencing on the expansions. The decrease in porosity of some specimens fired at higher temperatures indicated that sintering and densification occur simultaneously with the reaction formation of spinel. The decrease in the interparticle porosity limits the full expansion of the particulates to levels lower than the

Mechanism of γ-irradiation induced phase transformations in nanocrystalline Mn0.5Zn0.5Fe2O4 ceramics

NASA Astrophysics Data System (ADS)

Jagadeesha Angadi, V.; Anupama, A. V.; Choudhary, Harish K.; Kumar, R.; Somashekarappa, H. M.; Mallappa, M.; Rudraswamy, B.; Sahoo, B.

2017-02-01

The structural, infrared absorption and magnetic property transformations in nanocrystalline Mn0.5Zn0.5Fe2O4 samples irradiated with different doses (0, 15, 25 and 50 kGy) of γ-irradiation were investigated in this work and a mechanism of phase transformation/decomposition is provided based on the metastable nature of the Mn-atoms in the spinel lattice. The nano-powder sample was prepared by solution combustion route and the pellets of the sample were exposed to γ-radiation. Up to a dose of 25 kGy of γ-radiation, the sample retained the single phase cubic spinel (Fd-3m) structure, but the disorder in the sample increased. On irradiating the sample with 50 kGy γ-radiation, the spinel phase decomposed into new stable phases such as α-Fe2O3 and ZnFe2O4 phases along with amorphous MnO phase, leading to a change in the surface morphology of the sample. Along with the structural transformations the magnetic properties deteriorated due to breakage of the ferrimagnetic order with higher doses of γ-irradiation. Our results are important for the understanding of the stability, durability and performance of the Mn-Zn ferrite based devices used in space applications.

Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

NASA Technical Reports Server (NTRS)

Fielder, William L.; Singer, Joseph

1988-01-01

A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

Interfacial strain effects on lithium diffusion pathways in the spinel solid electrolyte Li-doped MgAl2O4

NASA Astrophysics Data System (ADS)

O'Rourke, Conn; Morgan, Benjamin J.

2018-04-01

The (Li,Al)-codoped magnesium spinel (LixMg1 -2 xAl2 +xO4 ) is a solid lithium-ion electrolyte with potential use in all-solid-state lithium-ion batteries. The spinel structure means that interfaces with spinel electrodes, such as LiyMn2O4 and Li4 +3 zTi5O12 , may be lattice matched, with potentially low interfacial resistances. Small lattice parameter differences across a lattice-matched interface are unavoidable, causing residual epitaxial strain. This strain potentially modifies lithium diffusion near the electrolyte-electrode interface, contributing to interfacial resistance. Here, we report a density functional theory study of strain effects on lithium diffusion pathways for (Li,Al)-codoped magnesium spinel, for xLi=0.25 and xLi=0.5 . We have calculated diffusion profiles for the unstrained materials, and for isotropic and biaxial tensile strains of up to 6 % , corresponding to {100 } epitaxial interfaces with LiyMn2O4 and Li4 +3 zTi5O12 . We find that isotropic tensile strain reduces lithium diffusion barriers by as much as 0.32 eV , with typical barriers reduced by ˜0.1 eV. This effect is associated with increased volumes of transitional octahedral sites, and broadly follows qualitative changes in local electrostatic potentials. For biaxial (epitaxial) strain, which more closely approximates strain at a lattice-matched electrolyte-electrode interface, changes in octahedral site volumes and in lithium diffusion barriers are much smaller than under isotropic strain. Typical barriers are reduced by only ˜0.05 eV. Individual effects, however, depend on the pathway considered and the relative strain orientation. These results predict that isotropic strain strongly affects ionic conductivities in (Li,Al)-codoped magnesium spinel electrolytes, and that tensile strain is a potential route to enhanced lithium transport. For a lattice-matched interface with candidate spinel-structured electrodes, however, epitaxial strain has a small, but complex, effect on lithium

IR spectroscopic determination of OH defects in spinel group minerals

NASA Astrophysics Data System (ADS)

Halmer, M. M.; Libowitzky, E.; Beran, A.

2003-04-01

Previous experimental studies showed that spinel phases, likely to occur in the transition zone of the Earth's mantle, contain essential amounts of water in form of OH groups. The g-Mg_2SiO_4 phase is reported to contain 27000 wt.ppm H_2O. The corresponding IR spectrum shows very broad absorption bands centered at 3645 and 3345cm-1 with a shoulder at 3120cm-1 (Kohlstedt et al., 1996). Thus, it is evident that under high-pressure conditions the spinel structure is capable to incorporate OH groups. Up to present, hydrogen contents of spinels from upper Earth's mantle and from crustal occurrences have not been reported in the literature. It is the aim of this study to prove the presence of OH defects in spinels of naturally occurring paragenesis and to develop some ideas on the structural incorporation mode based on promising results obtained from synthetic phases. Highly disordered non-stoichiometric Verneuil-grown MgAl spinels are characterized by two significant bands centered at 3355cm-1 and 3510cm-1, which show variations in band intensities. Synthetic H_ high-temperature treated intermediate compounds in the spinel-magnesioferrite (MgFe_2O_4), spinel-hercynite (FeAl2O4) and spinel-franklinite (ZnFe2O4) system from Andreozzi et al. (2001) indicate variable behavior. Whereas some of the spectra, which may be also correlated to d-d transitions of IVFe2+ (Skogby and Halenius, 2003) show broad absorptions in the 3500-3100cm-1 range, a pure MgAl2O4 end member sample is characterized by a rather sharp mode at 3450cm-1. Naturally occurring gahnite crystals (ZnAl2O_4) show significantly broad absorption band at 3400cm-1, which resembles some of the bands of the former synthetic samples. Based on the calibration of Libowitzky and Rossman (1997) the analytical H_2O content of the natural gahnite sample was determined to 580 wt.ppm. The position of the absorption bands implies weak hydrogen bonding of the OH defects in the spinel structure. This work was partly supported by

Enhanced magneto-optical and photo-catalytic properties of transition metal cobalt (Co2+ ions) doped spinel MgFe2O4 ferrite nanocomposites

NASA Astrophysics Data System (ADS)

Abraham, A. Godlyn; Manikandan, A.; Manikandan, E.; Vadivel, S.; Jaganathan, S. K.; Baykal, A.; Renganathan, P. Sri

2018-04-01

In this study, spinel magnesium cobalt ferrite (CoxMg1-xFe2O4: x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) nanocomposites were synthesized successfully by modified sol-gel combustion method. Magnesium nitrate, cobalt nitrate and iron nitrate were used as the source of divalent (Mg2+ and Co2+) and trivalent (Fe3+) cations, respectively and urea were used as the reducing (fuel) agent. The effects of cobalt ions on morphology, structural, optical, magnetic and photo-catalytic properties of spinel CoxMg1-xFe2O4 nanocomposites were investigated. Various characterization methods, including X-ray powder diffraction (XRD), high resolution scanning electron microscope (HR-SEM), transmission electron microscopy (HR-TEM), energy-dispersive X-ray spectroscopy (EDX), Fourier transforms infrared (FT-IR) spectroscopy, vibrating sample magnetometer (VSM) and photo-catalytic degradation (PCD) activity were used to study the phase purity, microstructure, particle size, elemental composition, functional group determination, band gap calculation, magnetic properties and degradation efficiency of nanoparticles, respectively. The observed results showed that the final products consists cubic spinel phase with sphere-like nanoparticles morphologies. Furthermore, spinel Co0.6Mg0.4Fe2O4 nanocomposite showed highest PCD efficiency (98.55%) than other composition of ferrite nanoparticles.

MgAl{sub 2}O{sub 4}(001) based magnetic tunnel junctions made by direct sputtering of a sintered spinel target

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belmoubarik, Mohamed; Sukegawa, Hiroaki, E-mail: sukegawa.hiroaki@nims.go.jp; Ohkubo, Tadakatsu

We developed a fabrication process of an epitaxial MgAl{sub 2}O{sub 4} barrier for magnetic tunnel junctions (MTJs) using a direct sputtering method from an MgAl{sub 2}O{sub 4} spinel sintered target. Annealing the sputter-deposited MgAl{sub 2}O{sub 4} layer sandwiched between Fe electrodes led to the formation of a (001)-oriented cation-disorder spinel with atomically sharp interfaces and lattice-matching with the Fe electrodes. A large tunnel magnetoresistance ratio up to 245% at 297 K (436% at 3 K) was achieved in the Fe/MgAl{sub 2}O{sub 4}/Fe(001) MTJ as well as an excellent bias voltage dependence. These results indicate that the direct sputtering is an alternative methodmore » for the realization of high performance MTJs with a spinel-based tunnel barrier.« less

Low‐Temperature Combustion Synthesis of a Spinel NiCo2O4 Hole Transport Layer for Perovskite Photovoltaics

PubMed Central

Papadas, Ioannis T.; Ioakeimidis, Apostolos; Armatas, Gerasimos S.

2018-01-01

Abstract The synthesis and characterization of low‐temperature solution‐processable monodispersed nickel cobaltite (NiCo2O4) nanoparticles (NPs) via a combustion synthesis is reported using tartaric acid as fuel and the performance as a hole transport layer (HTL) for perovskite solar cells (PVSCs) is demonstrated. NiCo2O4 is a p‐type semiconductor consisting of environmentally friendly, abundant elements and higher conductivity compared to NiO. It is shown that the combustion synthesis of spinel NiCo2O4 using tartaric acid as fuel can be used to control the NPs size and provide smooth, compact, and homogeneous functional HTLs processed by blade coating. Study of PVSCs with different NiCo2O4 thickness as HTL reveals a difference on hole extraction efficiency, and for 15 nm, optimized thickness enhanced hole carrier collection is achieved. As a result, p‐i‐n structure of PVSCs with 15 nm NiCo2O4 HTLs shows reliable performance and power conversion efficiency values in the range of 15.5% with negligible hysteresis. PMID:29876223

Band diagram and rate analysis of thin film spinel LiMn 2O 4 formed by electrochemical conversion of ALD-grown MnO

DOE PAGES

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.; ...

2016-09-22

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2O 4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2O 4 thin films in electrolytes containing Li +, Na +, K +, and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2O 4 informed by screened hybrid density functional theory calculationsmore » is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2O 4. It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2O 4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.« less

Synthesis and characterization of lithium aluminum-doped spinel (LiAl xMn 2- xO 4) for lithium secondary battery

NASA Astrophysics Data System (ADS)

Lee, Yun-Sung; Kumada, Naoki; Yoshio, Masaki

LiAl xMn 2- xO 4 has been synthesized using various aluminum starting materials, such as Al(NO 3) 3, Al(OH) 3, AlF 3 and Al 2O 3 at 600-800°C for 20 h in air or oxygen atmosphere. A melt-impregnation method was used to synthesize Al-doped spinel with good battery performance in this research. The Al-doped content and the intensity ratio of (3 1 1)/(4 0 0) peaks can be important parameters in synthesizing Al-doped spinel which satisfies the requirements of high discharge capacity and good cycleability at the same time. The decrease in Mn 3+ ion by Al substitution induces a high average oxidation state of Mn ion in the LiAl xMn 2- xO 4 material. The electrochemical behavior of all samples was studied in Li/LiPF 6-EC/DMC (1:2 by volume)/LiAl xMn 2- xO 4 cells. Especially, the initial and last discharge capacity of LiAl 0.09Mn 1.97O 4 using LiOH, Mn 3O 4 and Al(OH) 3 complex were 128.7 and 115.5 mAh/g after 100 cycles. The Al substitution in LiMn 2O 4 was an excellent method of enhancing the cycleability of stoichiometric spinel during electrochemical cycling.

MOF-5(Zn)-Fe2O4 nanocomposite based magnetic solid-phase microextraction followed by HPLC-UV for efficient enrichment of colchicine in root of colchicium extracts and plasma samples.

PubMed

Bahrani, Sonia; Ghaedi, Mehrorang; Dashtian, Kheibar; Ostovan, Abbas; Mansoorkhani, Mohammad Javad Khoshnood; Salehi, Amin

2017-11-01

In present work, facile method is developed for determination of colchicine in human plasma sample, autumn and spring root of colchicium extracts by ultrasound assisted dispersive magnetic solid phase microextraction followed by HPLC-UV method (UAD-MSPME-HPLC-UV). Magnetic (Fe 2 O 4 -nanoparticles) metal organic framework-5, (MOF-5(Zn)-Fe 2 O 4 NPs) was synthesized by dispersing MOF-5 and Fe(NO 3 ) 3 .9H 2 O in ethylene glycol (as capping agent) and NaOH (pH adjustment agent) by hydrothermal method. The prepared sorbent was characterized via XRD and SEM analysis and applied as magnetic solid phase in UAD-MSPME-HPLC-UV method. In this method, colchicine molecules were sorbed on MOF-5(Zn)-Fe 2 O 4 NPs sorbent by various mechanisms like ion exchange, hydrogen bonding and electrostatic, ᴨ-ᴨ, hard-hard and dipole-ion interaction followed by exposing sonication waves as incremental mass transfer agent and then the sorbent was separated from the sample matrix by an external magnetic fields. Subsequently, accumulated colchicine were eluted by small volume of desorption organic solvent. Influence of operational variables such as MOF-5(Zn)-Fe 2 O 4 NPs mass, volume of extracting solvent and sonication time on response property (recovery) were studied and optimized by central composite design (CCD) combined with desirability function (DF) approach. Under optimum condition, the method has wide linear calibration rang (0.5-1700ngmL -1 ) with reasonable detection limit (0.13ngmL -1 ) and R 2 =0.9971. Finally, the UAD-MSPME-HPLC-UV method was successfully applied for determination of colchicine autumn and spring root of colchicium extracts and plasma samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Stabilization of MgAl2O4 spinel surfaces via doping

NASA Astrophysics Data System (ADS)

Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.; Uberuaga, Blas P.

2016-07-01

Surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. Here, we report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl2O4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y3+, Gd3+, La3+) and one tetravalent dopant (Zr4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.

Mn1.4Co1.4Cu0.2O4 spinel protective coating on ferritic stainless steels for solid oxide fuel cell interconnect applications

NASA Astrophysics Data System (ADS)

Chen, Guoyi; Xin, Xianshuang; Luo, Ting; Liu, Leimin; Zhou, Yuchun; Yuan, Chun; Lin, Chucheng; Zhan, Zhongliang; Wang, Shaorong

2015-03-01

In an attempt to reduce the oxidation and Cr evaporation rates of solid oxide fuel cells (SOFCs), Mn1.4Co1.4Cu0.2O4 spinel coating is developed on the Crofer22 APU ferritic stainless steel substrate by a powder reduction technique. Doping of Cu into Mn-Co spinels improves electrical conductivity as well as thermal expansion match with the Crofer22 APU interconnect. Good adhesion between the coating and the alloy substrate is achieved by the reactive sintering process using the reduced powders. Long-term isothermal oxidation experiment and area specific resistance (ASR) measurement are investigated. The ASR is less than 4 mΩ cm2 even though the coated alloy undergoes oxidation at 800 °C for 530 h and four thermal cycles from 800 °C to room temperature. The Mn1.4Co1.4Cu0.2O4 spinel coatings demonstrate excellent anti-oxidation performance and long-term stability. It exhibits a promising prospect for the practical application of SOFC alloy interconnect.

Heterostructured ZnFe2O4/Fe2TiO5/TiO2 Composite Nanotube Arrays with an Improved Photocatalysis Degradation Efficiency Under Simulated Sunlight Irradiation

NASA Astrophysics Data System (ADS)

Xiong, Kun; Wang, Kunzhou; Chen, Lin; Wang, Xinqing; Fan, Qingbo; Courtois, Jérémie; Liu, Yuliang; Tuo, Xianguo; Yan, Minhao

2018-03-01

To improve the visible light absorption and photocatalytic activity of titanium dioxide nanotube arrays (TONTAs), ZnFe2O4 (ZFO) nanocrystals were perfused into pristine TONTA pipelines using a novel bias voltage-assisted perfusion method. ZFO nanocrystals were well anchored on the inner walls of the pristine TONTAs when the ZFO suspensions (0.025 mg mL-1) were kept under a 60 V bias voltage for 1 h. After annealing at 750 °C for 2 h, the heterostructured ZFO/Fe2TiO5 (FTO)/TiO2 composite nanotube arrays were successfully obtained. Furthermore, Fe3+ was reduced to Fe2+ when solid solution reactions occurred at the interface of ZFO and the pristine TONTAs. Introducing ZFO significantly enhanced the visible light absorption of the ZFO/FTO/TONTAs relative to that of the annealed TONTAs. The coexistence of type I and staggered type II band alignment in the ZFO/FTO/TONTAs facilitated the separation of photogenerated electrons and holes, thereby improving the efficiency of the ZFO/FTO/TONTAs for photocatalytic degradation of methylene blue when irradiated with simulated sunlight. [Figure not available: see fulltext.

Physical and photoelectrochemical properties of the spinel LiMn2O4 and its application in photocatalysis

NASA Astrophysics Data System (ADS)

Douafer, S.; Lahmar, H.; Benamira, M.; Rekhila, G.; Trari, M.

2018-07-01

Nanocrystalline lithium manganese oxide (LiMn2O4), synthesized by the sol-gel method, crystallizes in the spinel structure. The physical, electrical, and photoelectrochemical properties were studied for the photocatalytic degradation of methyl orange, a toxic compound, under solar irradiation. The diffuse reflectance spectrum allowed the direct band gap (1.99 eV) to be calculated. The Fourier transform IR spectrum contained all the characteristic peaks of the spinel LiMn2O4, which exhibited n-type behavior. The thermal evolution of the electrical conductivity exhibited an Arrhenius-type behavior with an activation energy of 0.27 eV. The Mott-Schottky curve allowed the determination of the flat band potential (-0.24 V vs. the saturated calomel electrode) as well as the carrier density (1.78 × 1021 cm-3). The detoxification of water containing methyl orange with LiMn2O4 as a photocatalyst was successfully completed. Total degradation for an initial concentration of 10-4 M methyl orange at pH ∼3 and 25 °C was obtained in less than 5 h under solar irradiation. No adsorption was obtained in the dark in the presence of LiMn2O4.

Synthesis and characterization of mesoporous spinel NiCo2O4 using surfactant-assembled dispersion for asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Hsu, Chun-Tsung; Hu, Chi-Chang

2013-11-01

A simple and scalable process has been developed for synthesizing spinel NiCo2O4 nanocrystals through a thermal decomposition method. The introduction of hexadecyltrimethylammonium bromide (CTAB, (C16H33)N(CH3)3Br) into precursor solutions significantly enhances the homogeneity and porosity of spinel NiCo2O4. The porosity and high specific surface area of NiCo2O4 preserves the brilliant pseudo-capacitive performances due to providing smooth paths for electrolyte penetration and ion diffusion into inner active sites. Morphologies and microstructures of the active materials are examined by transmission electron microscopic (TEM) and X-ray diffraction (XRD) analyses. Thermogravimetric analysis (TGA) is used to evaluate the thermal properties of precursor solutions. The electrochemical performances of NiCo2O4 are systematically characterized by cyclic voltammetry and charge-discharge tests. Asymmetric supercapacitors are assembled with these brilliant binary oxides as the positive electrode and activated carbon as the negative electrode. The highly porous NiCo2O4 exhibits superior capacitive performances, i.e., high specific capacitance (764 F g-1 at 2 mV s-1) and long cycle life.

Stabilization of MgAl 2O 4 spinel surfaces via doping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.

Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl 2O 4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y 3+, Gd 3+,more » La 3+) and one tetravalent dopant (Zr 4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.« less

Stabilization of MgAl 2O 4 spinel surfaces via doping

DOE PAGES

Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.; ...

2016-02-06

Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl 2O 4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y 3+, Gd 3+,more » La 3+) and one tetravalent dopant (Zr 4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.« less

Studies on the efficient dual performance of Mn1-xNixFe2O4 spinel nanoparticles in photodegradation and antibacterial activity.

PubMed

Jesudoss, S K; Vijaya, J Judith; Kennedy, L John; Rajan, P Iyyappa; Al-Lohedan, Hamad A; Ramalingam, R Jothi; Kaviyarasu, K; Bououdina, M

2016-12-01

The present work describes the successful synthesize of spinel magnetic ferrite Mn 1-x Ni x Fe 2 O 4 (x=0.0, 0.1, 0.2, 0.3, 0.4 & 0.5) nanoparticles via a simple microwave combustion method which was then evaluated for its photocatalytic activity in the degradation of indigo carmine (IC) synthetic dye, a major water pollutant. Our results reveal that the synthesized of Ni 2+ doped MnFe 2 O 4 nanoparticles possess well-crystalline pure cubic spinel phase, exhibit excellent optical and magnetic properties. Further, the photocatalytic performance of the synthesized nanoparticles at different concentration ratios of Ni 2+ ions was monitored by photocatalytic degradation of indigo carmine synthetic dye under UV (λ=365nm) light irradiation. In order to get maximum photocatalytic degradation (PCD) efficiency, we have optimized various parameters, which include catalyst dosage, initial dye concentration, pH and Ni 2+ dopant content. It was found that the reaction was facilitated with optimum catalyst dose of 50mg/100mL, high dye concentrations of 150mg/L and acidic pH and among all the synthesized samples, Mn 0·5 Ni 0.5 Fe 2 O 4 exhibit superior performance of photocatalytic activity on the degradation of indigo carmine synthetic dye. These results highlighted the potential use of effective, low-cost and easily available photocatalysts for the promotion of wastewater treatment and environmental remediation. In addition, the antibacterial activity of spinel magnetic Mn 1-x Ni x Fe 2 O 4 nanoparticles against two Gram positive bacteria (Staphylococcus aureus and Bacillus subtilis) and two Gram negative bacteria (Pseudomonas aeruginosa and Escherichia coli) was also examined. Our antibacterial activity results are comparable with the results obtained using the antibiotic, streptomycin. Copyright © 2016 Elsevier B.V. All rights reserved.

Magnetically induced phonon splitting in A Cr 2 O 4 spinels from first principles

DOE PAGES

Wysocki, Aleksander L.; Birol, Turan

2016-04-22

We study the magnetically-induced phonon splitting in cubic ACr 2O 4 (A=Mg, Zn, Cd) spinels from first principles and demonstrate that the sign of the splitting, which is experimentally observed to be opposite in CdCr 2O 4 compared to ZnCr 2O 4 and MgCr 2O 4, is determined solely by the particular magnetic ordering pattern observed in these compounds. We further show that this interaction between magnetism and phonon frequencies can be fully described by the previously proposed spin-phonon coupling model [C. J. Fennie and K. M. Rabe, Phys. Rev. Lett. 96, 205505 (2006)] that includes only the nearest neighbormore » exchange. In conclusion, using this model with materials specific parameters calculated from first principles, we provide additional insights into the physics of spin-phonon coupling in this intriguing family of compounds.« less

Electronic and Optical Properties of a Semiconducting Spinel (Fe 2 CrO 4 )

DOE PAGES

Chambers, Scott A.; Droubay, Timothy C.; Kaspar, Tiffany C.; ...

2017-01-13

Epitaxial chromium ferrite (Fe 2CrO 4), prepared by state-of-the-art oxygen plasma assisted molecular beam epitaxy, is shown to exhibit unusual electronic transport properties driven by the crystallographic structure and composition of the material. By replacing 1/3 of the Fe cations with Cr converts the host ferrimagnet from a metal into a semiconductor by virtue of its fixed valence (3+); Cr substitutes for Fe at B sites in the spinel lattice. Conversely, replacing 2/3 of the Fe cations with Cr results in an insulator. Three candidate conductive paths, all involving electron hopping between Fe 2+ and Fe 3+, are identified inmore » Fe 2CrO 4. Moreover, Fe 2CrO 4 is shown to be photoconductive across the visible portion of the electromagnetic spectrum. As a result, this material is of potential interest for important photo-electrochemical processes such as water splitting.« less

[Catalytic stability in wet air oxidation of carboxylic acids over ZnFe0.25Al1.75 O4 catalyst].

PubMed

Xu, Ai-hua; Yang, Min; Du, Hong-zhang; Peng, Fu-yong; Sun, Cheng-lin

2007-07-01

Oxalic, formic and acetic acid are main intermediate products in catalytic wet air oxidation process (CWAO). The catalytic activity and stability in CWAO of the three short-chain organic acids over ZnFe0.25Al1.75O4 catalyst were studied. Oxalic acid is the only oxidizable intermediate and the largest amount of Fe leaching is 9.5 mg L(-1) at 160 degrees C during CWAO process. Formic and acetic acid have little influence on Fe leaching. Due to the strong reducible ability of oxalic acid, the amount of Fe leaching is larger in nitrogen atmosphere than that in oxygen atmosphere. Salicylic acid can be also degraded by ZnFe0.25Al1.75O4 catalyst with a high catalytic activity and stability.

A Green Protocol for Synthesis of MAl2O4, [M=Cu and Co] Spinels Under Microwave Irradiation Method

NASA Astrophysics Data System (ADS)

Yuvasravana, R.; George, P. P.

Nanosized metal aluminates MAl2O4, [M=Cu and Co] are synthesized from their nitrates solution by using pomegranate peel extract as fuel in microwave combustion. MAl2O4 [M=Cu and Co] nanoparticles are grown in microwave assisted synthesis followed by annealing at 700∘C. The nanoparticles have been characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), UV-VIS spectroscopy and photoluminescence (PL) spectroscopy. The PXRD analysis has confirmed their spinel composition. The green protocol and microwave combustion route for spinel synthesis are rapid, simple, without any hazardous chemicals as reducing or stabilizing agents and economical.

Existence of Fe{sup 4+} ions in Co{sub 2.25}Fe{sub 0.75}O{sub 4} spinel ferrite confirmed from SXRD and XANES spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Panda, Manas Ranjan, E-mail: manasranjan056@gmail.com; Bhowmik, R. N.; Sinha, A. K.

2015-06-24

The Co{sub 2.25}Fe{sub 0.75}O{sub 4} ferrite composition has been prepared by chemical co-precipitation route. The as-prepared sample after annealing at 900°C in air formed single phase cubic spinel structure. Synchrotron X-ray diffraction and X-ray absorption near edge structure (XANES) measurements were used to study charge states of the cations in octahedral and tetrahedral sites of the cubic spinel structure. Raman spectra indicated normal cubic spinel structure. XANES data suggested the existence of Fe{sup 4+} ions in the spinel structure.

The effect of cation doping on spinel LiMn 2O 4: a first-principles investigation

NASA Astrophysics Data System (ADS)

Shi, Siqi; Ouyang, Chuying; Wang, Ding-sheng; Chen, Liquan; Huang, Xuejie

2003-05-01

The effect of the cation doping on the electronic structure of spinel LiM yMn 2- yO 4 (M=Cr, Mn, Fe, Co and Ni) has been calculated by first-principles. Our calculation shows that new M-3d bands emerge in the density of states compared with that in LiMn 2O 4. Simultaneously, the new O-2p bands appear accordingly in almost the same energy range around the Fermi energy owing to the M-3d/O-2p interaction. It is found that the appearance of new O-2p bands in the lower energy position results in a higher intercalation voltage. Consequently, the origin of higher intercalation voltage in LiM yMn 2- yO 4 can be ascribed to the lower O-2p level introduced by the doping cation M.

Fe2SiO4-rich spinel as mineral in a shocked meteorite - constraints on P-T conditions during shock

NASA Astrophysics Data System (ADS)

Tschauner, O.; Ma, C.; Asimow, P. D.; Kostandova, N.

2008-12-01

We report the occurrence of a spinel phase (Fe0.8, Mg0.2)2(Si0.9, Fe0.1)O4 in veins of the L4 chondrite Laundry West, Nullarbor, Australia. While Fe2SiO4-rich spinel has been reported from the Umbarger meteorite earlier (Xie et al. Am .Min. 87, 1257, 2002), the present study is the first to present complete structural and chemical information. We collected powder diffraction, EBSD, and EMP data, all confirming structure and chemistry of this new mineral, the Fe-endmember analog of Mg2SiO4 ringwoodite. The observation of this spinel phase, which forms at pressures of a few GPa under static conditions, in a shocked meteorite is a contribution to a finer shock metamorphic scale. The vicinity of these FeSi-spinel grains to melted (Fe,Ni)S in combination with modeling of shock reverberation in a FeS-silicate system allows for estimating a lower limit of the peak shock pressure and temperature: The fayalite-spinel P-T phase boundary and the melting curve of (Fe,Ni)S determine a fixed point in P-T space of 5-6 GPa and 1500 - 1600 K. However, the bulk shock pressure (and temperature) was lower and can be calculated by impedance match. Acknowledgements: We dedicate this work to our friend and collaborator Thomas J. Ahrens. We are particularly grateful to Dr. Zhongwu Wang, CHESS, for providing beamtime and support at station B2. This work was supported by NNSA Cooperative Agreement DOE-FC88-01NV14049 and NASA/Goddard grants under awards NNG04GP57G and NNG04GI07G. Participation by NK was supported by the Caltech SURF program and in particular by Mr. and Mrs. Robert E. Anderson.

Nature of the Electrochemical Properties of Sulphur Substituted LiMn2O4 Spinel Cathode Material Studied by Electrochemical Impedance Spectroscopy

PubMed Central

Bakierska, Monika; Świętosławski, Michał; Dziembaj, Roman; Molenda, Marcin

2016-01-01

In this work, nanostructured LiMn2O4 (LMO) and LiMn2O3.99S0.01 (LMOS1) spinel cathode materials were comprehensively investigated in terms of electrochemical properties. For this purpose, electrochemical impedance spectroscopy (EIS) measurements as a function of state of charge (SOC) were conducted on a representative charge and discharge cycle. The changes in the electrochemical performance of the stoichiometric and sulphur-substituted lithium manganese oxide spinels were examined, and suggested explanations for the observed dependencies were given. A strong influence of sulphur introduction into the spinel structure on the chemical stability and electrochemical characteristic was observed. It was demonstrated that the significant improvement in coulombic efficiency and capacity retention of lithium cell with LMOS1 active material arises from a more stable solid electrolyte interphase (SEI) layer. Based on EIS studies, the Li ion diffusion coefficients in the cathodes were estimated, and the influence of sulphur on Li+ diffusivity in the spinel structure was established. The obtained results support the assumption that sulphur substitution is an effective way to promote chemical stability and the electrochemical performance of LiMn2O4 cathode material. PMID:28773819

Spontaneous electric polarization in the B-site magnetic spinel GeCu2O4

NASA Astrophysics Data System (ADS)

Yanda, Premakumar; Ghara, Somnath; Sundaresan, A.

2018-04-01

We report the observation of a spontaneous electric polarization at the antiferromagnetic ordering temperature (TN ∼ 33 K) of Cu2+ ions in the B-site magnetic spinel GeCu2O4, synthesized at high pressure and high temperature. This compound is known to crystallize in a tetragonal structure (space group I41/amd) due to Jahn-Teller distortion of Cu2+ ions and exhibit a collinear up-up-down-down (↑↑↓↓) antiferromagnetic spin configuration below TN. We found a clear dielectric anomaly at TN, where an electric polarization appears in the absence of applied magnetic field. The electric polarization is suppressed by applied magnetic fields, which demonstrates that the compound GeCu2O4 is a type-II multiferroic.

CoFe 2O 4 spinel protection coating thermally converted from the electroplated Co-Fe alloy for solid oxide fuel cell interconnect application

NASA Astrophysics Data System (ADS)

Bi, Z. H.; Zhu, J. H.; Batey, J. L.

CoFe 2O 4 has been demonstrated as a potential spinel coating for protecting the Cr-containing ferritic interconnects. This spinel had an electrical conductivity of 0.85 S cm -1 at 800 °C in air and an average coefficient of thermal expansion (CTE) of 11.80 × 10 -6 K -1 from room temperature to 800 °C. A series of Co-Fe alloys were co-deposited onto the Crofer 22 APU ferritic steel via electroplating with an acidic chloride solution. After thermal oxidation in air at 800 °C, a CoFe 2O 4 spinel layer was attained from the plated Co 0.40Fe 0.60 film. Furthermore, a channeled Crofer 22 APU interconnect electrodeposited with a 40-μm Co 0.40Fe 0.60 alloy film as a protective coating was evaluated in a single-cell configuration. The presence of the dense, Cr-free CoFe 2O 4 spinel layer was effective in blocking the Cr migration/transport and thus contributed to the improvement in cell performance stability.

Ab initio investigation of the thermodynamics of cation distribution and of the electronic and magnetic structures in the LiMn2O4 spinel

NASA Astrophysics Data System (ADS)

Santos-Carballal, David; Ngoepe, Phuti E.; de Leeuw, Nora H.

2018-02-01

The spinel-structured lithium manganese oxide (LiMn2O4 ) is a material currently used as cathode for secondary lithium-ion batteries, but whose properties are not yet fully understood. Here, we report a computational investigation of the inversion thermodynamics and electronic behavior of LiMn2O4 derived from spin-polarized density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections (DFT+U-D3). Based on the analysis of the configurational free energy, we have elucidated a partially inverse equilibrium cation distribution for the LiMn2O4 spinel. This equilibrium degree of inversion is rationalized in terms of the crystal field stabilization effects and the difference between the size of the cations. We compare the atomic charges with the oxidation numbers for each degree of inversion. We found segregation of the Mn charge once these ions occupy the tetrahedral and octahedral sites of the spinel. We have obtained the atomic projections of the electronic band structure and density of states, showing that the normal LiMn2O4 has half-metallic properties, while the fully inverse spinel is an insulator. This material is in the ferrimagnetic state for the inverse and partially inverse cation arrangement. The optimized lattice and oxygen parameters, as well as the equilibrium degree of inversion, are in agreement with the available experimental data. The partial equilibrium degree of inversion is important in the interpretation of the lithium ion migration and surface properties of the LiMn2O4 spinel.

Cation disorder in MgX2O4 (X = Al, Ga, In) spinels from first principles

NASA Astrophysics Data System (ADS)

Jiang, Chao; Sickafus, Kurt E.; Stanek, Christopher R.; Rudin, Sven P.; Uberuaga, Blas P.

2012-07-01

We have performed first-principles density functional theory calculations to investigate the possible physical origins of the discrepancies between the existing theoretical and experimental studies on cation distribution in MgX2O4 (X = Al, Ga, In) spinel oxides. We show that for MgGa2O4 and MgIn2O4, it is crucial to consider the effects of lattice vibrations to achieve agreement between theory and experiment. For MgAl2O4, we find that neglecting short-range order effects in thermodynamic modeling can lead to significant underestimation of the degree of inversion. Furthermore, we demonstrate that the common practice of representing disordered structures by randomly exchanging atoms within a small periodic supercell can incur large computational error due to either insufficient statistical sampling or finite supercell size effects.

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–y Mn y O 4 (0.4 ≤ y ≤ 1)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

The thermal conversion of chemically delithiated layered Li 0.5Ni 1-yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2-yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied in lithium-ion cells. Amore » bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. The study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1)

DOE PAGES

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

2015-10-28

The thermal conversion of chemically delithiated layered Li 0.5Ni 1–yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated in this paper. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied inmore » lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. Finally, the study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

The thermal conversion of chemically delithiated layered Li 0.5Ni 1–yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated in this paper. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied inmore » lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. Finally, the study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less

ZnFe2O4-C/LiFePO4-CNT: A Novel High-Power Lithium-Ion Battery with Excellent Cycling Performance.

PubMed

Varzi, Alberto; Bresser, Dominic; von Zamory, Jan; Müller, Franziska; Passerini, Stefano

2014-07-15

An innovative and environmentally friendly battery chemistry is proposed for high power applications. A carbon-coated ZnFe 2 O 4 nanoparticle-based anode and a LiFePO 4 -multiwalled carbon nanotube-based cathode, both aqueous processed with Na-carboxymethyl cellulose, are combined, for the first time, in a Li-ion full cell with exceptional electrochemical performance. Such novel battery shows remarkable rate capabilities, delivering 50% of its nominal capacity at currents corresponding to ≈20C (with respect to the limiting cathode). Furthermore, the pre-lithiation of the negative electrode offers the possibility of tuning the cell potential and, therefore, achieving remarkable gravimetric energy and power density values of 202 Wh kg -1 and 3.72 W kg -1 , respectively, in addition to grant a lithium reservoir. The high reversibility of the system enables sustaining more than 10 000 cycles at elevated C-rates (≈10C with respect to the LiFePO 4 cathode), while retaining up to 85% of its initial capacity.

Structural study of Ti-doped CoFe{sub 2}O{sub 4} mixed spinel ferrite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, P., E-mail: pankaj.7007@rediffmail.com; Sharma, P.; Dar, M. A.

2016-05-06

We present the results on atomic and lattice structure of the polycrystalline spinel ferrites system Co{sub 1-x} Ti{sub x}Fe{sub 2}O{sub 4} (x = 0.0, 0.25, 0.50) synthesized by following the conventional solid-state reaction route. The observed X-ray diffraction (XRD) data confirms that all the prepared samples are indexed in cubic crystal structure (space group Fd3m). Diffraction pattern showed TiO{sub 2} phase due to presence of Ti{sup +4} ions. Four Raman active phonon modes are observed for CoFe{sub 2}O{sub 4} sample existing around 295, 462, 585, 689, cm{sup −1} as Eg, T{sub 2g}(2), T{sub 2g}(3), and A{sub 1g}, respectively. With 25more » % Ti ion doping, the peak T{sub 2g}(3) disappears, while to that T{sub 2g}(1) emerges. This is an indication of presence of TiO{sub 2} phase in Co{sub 0.75}Ti{sub 0.25}Fe{sub 2}O{sub 4} and Co{sub 0.5}Ti{sub 0.5}Fe{sub 2}O{sub 4} ceramics.« less

Structural behavior of ZnCr 2S 4 spinel under pressure

DOE PAGES

Efthimiopoulos, I.; Lochbiler, T.; Tsurkan, V.; ...

2016-12-15

Here, the series of Cr-chalcogenide spinels ACr 2X 4 (A = Zn, Cd, Hg; X = S, Se) exhibits a rich phase diagram upon compression, as revealed by our recent investigations. There exist, however, some open questions regarding the role of cations in the observed structural transitions. In order to address these queries, we have performed X-ray diffraction and Raman spectroscopic studies on the ZnCr 2S 4 spinel up to 42 GPa, chosen mainly due to the similarity of the Zn 2+ and Cr 3+ cationic radii. Two reversible structural transitions were identified at 22 and 33 GPa, into a I4 1/ amd and an orthorhombic phase, respectively. Close comparison with the behavior of relevant Cr-spinels revealed that the structural transitions are mainly governed by the competition of the magnetic exchange interactions present in these systems, and not by steric effects. In addition, careful inspection of the starting Fdmore » $$\\bar{3}$$m phase revealed a previously unnoticed isostructural transition. The latter is intimately related to changes in the electronic properties of these systems, as evidenced by our Raman studies. Our results provide insights for tuning the physical and chemical properties of these materials, even under moderate compression, as well as promoting the understanding of similar pressure-induced effects in relevant systems.« less

The performance of spinel bulk-like oxygen-deficient CoGa2O4 as an air-cathode catalyst in microbial fuel cell

NASA Astrophysics Data System (ADS)

Liu, Di; Mo, Xiaoping; Li, Kexun; Liu, Yi; Wang, Junjie; Yang, Tingting

2017-08-01

Nano spinel bulk-like CoGa2O4 prepared via a facile hydrothermal method is used as a high efficient electrochemical catalyst in activated carbon (AC) air-cathode microbial fuel cell (MFC). The maximum power density of the modified MFC is 1911 ± 49 mW m-2, 147% higher than the MFC of untreated AC cathode. Transmission electron microscope (TEM) and X-ray diffraction (XRD) exhibit the morphology and crystal structure of CoGa2O4. Rotating disk electrode (RDE) confirms the four-electron pathway at the cathode during the oxygen reduction reaction (ORR). Thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) illustrate that the high rate oxygen vacancy exist in the CoGa2O4. The oxygen vacancy of CoGa2O4 plays an important role in catalytic activity. In a word, the prepared nano spinel bulk-like CoGa2O4 provides an alternative to the costly Pt in air-cathode for power output.

Hybrid supercapacitor devices based on MnCo2O4 as the positive electrode and FeMn2O4 as the negative electrode

NASA Astrophysics Data System (ADS)

Nagamuthu, Sadayappan; Vijayakumar, Subbukalai; Lee, Seong-Hun; Ryu, Kwang-Sun

2016-12-01

MnCo2O4 nanosheets and FeMn2O4 nanospheres were synthesized using a hydrothermal method. Choline chloride was used as the capping agent during the preparation of the nanoparticles. XRD patterns confirmed the spinel structure of MnCo2O4 and FeMn2O4. XPS measurements were used to determine the oxidation state of the prepared spinel metal oxides. HRTEM images revealed the formation of hexagonal nanosheets of MnCo2O4 and nanospheres of FeMn2O4. Electrochemical measurements were made for both positive and negative electrodes using three electrode systems. MnCo2O4 Exhibits 282C g-1 and FeMn2O4 yields 110C g-1 at a specific current of 1 A g-1. Hybrid supercapacitor device was fabricated using MnCo2O4 as the positive and FeMn2O4 as the negative electrode material. The hybrid supercapacitor device was delivered a maximum power of 37.57 kW kg-1.

Lithium Storage Performance of Zinc Ferrite Nanoparticle Synthesized with the Assistance of Triblock Copolymer P123.

PubMed

Yao, J H; Li, Y W; Song, X B; Zhang, Y F; Yan, J

2018-05-01

The ZnFe2O4 samples with the triblock copolymer P123 (P123) additive quantity of 0 wt.%, 2 wt.%, 5 wt.%, 8 wt.% and 10 wt.% were prepared by a very facile homogeneous precipitation method followed by high temperature sintering. The microstructures of the prepared samples were analyzed by X-ray diffraction (XRD) and Field emission scanning electron microscopy (FESEM). The results revealed that the five prepared samples are all normal spinel zinc ferrite (ZnFe2O4); the sample with the P123 additive quantity of 8 wt.% has the smallest particle size among the five samples. The lithium storage performances of the prepared samples are characterized by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge tests. The results demonstrated that adding proper amount of P123 can obviously improve the lithium storage performances of zinc ferrite spinel powder. But excessive P123 can induce the particle agglomerates so that the lithium storage performance of sample decays significantly. The ZnFe2O4 sample with the P123 additive quantity of 8 wt.% exhibited the highest electrochemical activity, the best rate performance, and superior cycling stability. For example, after 50 charge/discharge cycles under a current density of 120 mA g-1, the ZnFe2O4 sample with the P123 additive quantity of 8 wt.% can retain a specific discharge capacity of 468 mAh g-1, much higher than that of for the ZnFe2O4 sample with the P123 additive quantity of 0 wt.% (224 mAh g-1).

Flexure Strength and Optical Transparency of Magnesium-Aluminate Spinel (MgAlO4): Influence of Polishing and Glass Coating

DTIC Science & Technology

2016-12-01

resulting from the addition of a sodium aluminosilicate ( SiO2 -BaO- Na2O-B2O3-Al2O3) glass coating on coarse-grained transparent spinel having 3...MgAlO4): Influence of Polishing and Glass Coating by Steve M Kilczewski, Robert J Pavlacka, Jeffrey J Swab, Jane W Adams, and Jared C Wright...Magnesium–Aluminate Spinel (MgAlO4): Influence of Polishing and Glass Coating by Steve M Kilczewski and Jared C Wright TKC Global, Herndon, VA

On stoichiometry and intermixing at the spinel/perovskite interface in CoFe2O4/BaTiO3 thin films.

PubMed

Tileli, Vasiliki; Duchamp, Martial; Axelsson, Anna-Karin; Valant, Matjaz; Dunin-Borkowski, Rafal E; Alford, Neil McN

2015-01-07

The performance of complex oxide heterostructures depends primarily on the interfacial coupling of the two component structures. This interface character inherently varies with the synthesis method and conditions used since even small composition variations can alter the electronic, ferroelectric, or magnetic functional properties of the system. The focus of this article is placed on the interface character of a pulsed laser deposited CoFe2O4/BaTiO3 thin film. Using a range of state-of-the-art transmission electron microscopy methodologies, the roles of substrate morphology, interface stoichiometry, and cation intermixing are determined on the atomic level. The results reveal a surprisingly uneven BaTiO3 substrate surface formed after the film deposition and Fe atom incorporation in the top few monolayers inside the unit cell of the BaTiO3 crystal. Towards the CoFe2O4 side, a disordered region extending several nanometers from the interface was revealed and both Ba and Ti from the substrate were found to diffuse into the spinel layer. The analysis also shows that within this somehow incompatible composite interface, a different phase is formed corresponding to the compound Ba2Fe3Ti5O15, which belongs to the ilmenite crystal structure of FeTiO3 type. The results suggest a chemical activity between these two oxides, which could lead to the synthesis of complex engineered interfaces.

Doping effect on charge ordering in the spinel compound AlV_2-xCr_xO_4

NASA Astrophysics Data System (ADS)

Horibe, Yoichi; Kurushima, Kosuke; Mori, Shigeo; Shingu, Masao; Katsufuji, Takuro

2004-03-01

It is reported that AlV_2O4 with the spinel-type structure shows the charge-ordering (CO) behavior below 700K.[1] Because the average valence of V is V^2.5+ in this compound, the CO structure is characterized by the unique CO pattern with V^2+:V^4+=3:1. In this talk, we will report doping effect on the CO structure in AlV_2O_4. In particular, we will focus on changes of microstructure related to the CO structure by Cr doping by transmission electron microscopy. Firstly we confirmed that AlV_2O4 has a long-ranged CO structure characterized by a single wave vector q=(1/2)[111]. On the other hand, we found the presence of diffuse scatterings at the (1/2)[111] and (1/2)[1-11]-type positions in AlV_1.875Cr_0.125O4 at room temperature. This means that the CO structure in AlV_1.875Cr_0.125O4 has two wave vectors of q=(1/2)[111] and q=the (1/2)[1-11]. Furthermore, the long-ranged CO structure in AlV_2O4 changes into the short-ranged one by substituting Cr ions into the V ones. The correlation length of CO in x=0.125 can be estimated to be about 5 nm. Our results suggest that the Cr doping destroyed the CO correlation effectively. It is revealed that by substituting Cr ions to V ones, the CO state is suppressed drastically and disappeared with x > 0.125. [1] K. Matsuno et al., J. Phys. Soc. Jpn 70, 1456 (2001)

Structural, magnetic, dielectric, and electrical properties of NiFe2O4 spinel ferrite nanoparticles prepared by honey-mediated sol-gel combustion

NASA Astrophysics Data System (ADS)

Yadav, Raghvendra Singh; Kuřitka, Ivo; Vilcakova, Jarmila; Havlica, Jaromir; Masilko, Jiri; Kalina, Lukas; Tkacz, Jakub; Enev, Vojtěch; Hajdúchová, Miroslava

2017-08-01

In this study, NiFe2O4 nanoparticles were synthesized using a honey-mediated sol-gel combustion method. The synthesized nanoparticles and samples annealed at 800 °C and 1100 °C were characterized by X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and vibrating sample magnetometry (VSM). XRD and Raman spectroscopy confirmed the formation of a cubic spinel ferrite structure. FE-SEM demonstrated the octahedral morphology of the NiFe2O4 spinel ferrite nanoparticles with sizes ranging from 10 to 70 nm. Quantitative analysis based on XPS suggested a mixed spinel structure comprising NiFe2O4 nanoparticles. XPS analysis determined occupation formulae of (Ni0.212+ Fe0.443+)[Ni0.792+ Fe1.563+]O4 and (Ni0.232+ Fe0.503+)[Ni0.772+ Fe1.503+]O4, for the as-prepared NiFe2O4 nanoparticles and those annealed at 1100 °C, respectively. Magnetic measurements showed that the saturation magnetization increased with the crystallite size from 32.3 emu/g (20 nm) to 49.9 emu/g (163 nm), whereas the coercivity decreased with the crystallite size from 162 Oe (20 nm) to 47 Oe (163 nm). Furthermore, the dielectric constant, dielectric loss tangent, and AC conductivity of the NiFe2O4 nanoparticles were dependent on the frequency (1-107 Hz) and grain size. The influence of the grain size was also observed by modulus spectroscopy based on the Cole-Cole plot.

DFT studies on H 2O adsorption and its effect on CO oxidation over spinel Co 3O 4 (110) surface

NASA Astrophysics Data System (ADS)

Xu, Xiang Lan; Li, Jun Qian

2011-12-01

Adsorption of H2O and its effect on CO oxidation over spinel Co3O4 (110) surface were studied by density functional theory calculations. H2O is adsorbed favorably at the octahedral cobalt (Cooct) site through O atom on the surface. Hydrogen bonding interaction between 1s orbitals of H atoms in H2O and the 2p orbitals of surface active oxygen sites plays a key role for H2O adsorption. The inhibition effect of H2O adsorption on the CO oxidation over the surfaces is attributed to the competition between H2O and CO molecules for the surface twofold coordinated oxygen site.

Synthesis and characterization of magnesium aluminate (MgAl2O4) spinel (MAS) thin films

NASA Astrophysics Data System (ADS)

Ahmad, Syed Muhammad; Hussain, Tousif; Ahmad, Riaz; Siddiqui, Jamil; Ali, Dilawar

2018-01-01

In a quest to identify more economic routes for synthesis of magnesium aluminate (MgAl2O4) spinel (MAS) thin films, dense plasma focus device was used with multiple plasma focus shots. Structural, bonding between composite films, surface morphological, compositional and hardness properties of MAS thin films were investigated by using x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive x-rays (EDX) analysis and Vickers micro hardness test respectively. In XRD graph, the presence of MgAl2O4 diffraction peaks in crystallographic orientations (222), (400) and (622) pointed out the successful formation of polycrystalline thin films of MgAl2O4 with face centered cubic structure. The FTIR spectrums showed a major common transmittance band at 697.95 cm-1 which belongs to MgAl2O4. SEM micrographs illustrated a mesh type, granular and multi layers microstructures with significant melting effects. EDX spectrum confirmed the existence of magnesium, oxygen and aluminum in MAS films. A common increasing behavior in micro-hardness of composite MgAl2O4 films by increasing number of plasma focus shots was found.

Copper-promoted circumneutral activation of H2O2 by magnetic CuFe2O4 spinel nanoparticles: Mechanism, stoichiometric efficiency, and pathway of degrading sulfanilamide.

PubMed

Feng, Yong; Liao, Changzhong; Shih, Kaimin

2016-07-01

To evaluate the heterogeneous degradation of sulfanilamide by external energy-free Fenton-like reactions, magnetic CuFe2O4 spinel nanoparticles (NPs) were synthesized and used as catalysts for activation of hydrogen peroxide (H2O2). The physicochemical properties of the CuFe2O4 NPs were characterized with several techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and magnetometry. In the catalytic experiments, CuFe2O4 NPs/H2O2 oxidation showed the best degradation performance in the circumneutral conditions that resulted from the presence of Cu(II) on the surface of the CuFe2O4 NPs. The surface area-normalized pseudo-first-order rate constants were calculated as 2.60 × 10(-2) L m(-1) min(-1), 2.58 × 10(-3) L m(-1) min(-1), 1.92 × 10(-3) L m(-1) min(-1), and 7.30 × 10(-4) L m(-1) min(-1) for CuO, CuFe2O4 NPs, Fe3O4, and α-Fe2O3 catalysts, respectively. Thus, solid state Cu(II) was more reactive and efficient than Fe(III) in the circumneutral activation of H2O2; this finding was further supported by the results regarding the stoichiometric efficiency of H2O2. The effects of experimental parameters such as the oxidant dosage and catalyst loading were investigated. The mechanism for H2O2 activation on the spinel surface was explored and could be explained by the solid redox cycles of Fe(II)/Fe(III) and Cu(II)/Cu(I). Based on the products detected, a degradation pathway via the CS bond cleavage is proposed for the degradation of sulfanilamide. The findings of this study suggest that copper can be used as a doping metal to improve the reactivity and expand the effective pH range of iron oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

TEM Studies: The Key for Understanding the Origin of the 3.3 V and 4.5 V Steps Observed in LiMn 2O 4-based Spinels

NASA Astrophysics Data System (ADS)

Dupont, L.; Hervieu, M.; Rousse, G.; Masquelier, C.; Palacín, M. R.; Chabre, Y.; Tarascon, J. M.

2000-12-01

Transmission electron microscopy (TEM) measurements were performed on electrochemically partially delithiated prepared spinel Li1-xMn2O4 samples. The potential-composition profile of LiMn2O4 exhibits (besides the two plateaus at 4.05 and 4.1 V) two additional redox steps of identical capacity at 4.5 and 3.3/3.95 V. We found by TEM studies that these extra steps are the signature of a reversible phase transition between LiMn2O4 spinel type structure and a new Li1-xMn2O4 double hexagonal (DH) type structure (a≈5.8 Å, c≈8.9 Å, P63mc). The latter is isotypic with DH LiFeSnO4. Selected area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM) made it possible to identify the mechanism by which this cubic-DH phase transition occurs within a particle. Based on the structural findings the origin as well as the similar electrochemical capacity of the 3.3/3.95 and 4.5 V anomalies are explained.

The role of reduced graphene oxide on the electrochemical activity of MFe2O4 (M = Fe, Co, Ni and Zn) nanohybrids

NASA Astrophysics Data System (ADS)

Suresh, Shravan; Prakash, Anand; Bahadur, D.

2018-02-01

In this work, a comparative study of electrochemical performance of reduced graphene oxide-ferrites (RGO-MFe2O4, M = Fe, Co, Ni, and Zn) nanohybrids synthesized by hydrothermal method was done. The structural morphology and investigation of other physical properties of nanohybrids confirm the cubic spinel phase of the MFe2O4, reduction of graphene oxide and the distribution of ferrite nanoparticles (NPs) on RGO nanosheets. The role of RGO on the electrochemical behavior of nanohybrids was understood by quantifying the charge storage capacitance and charging-discharging behavior in a 0.1 M Na2SO4 electrolyte. The specific capacitance values of pristine Fe3O4, CoFe2O4, NiFe2O4, and ZnFe2O4 are 128, 117, 15.2 and 9.1 F g-1 respectively whereas specific capacitance of RGO-Fe3O4, RGO-CoFe2O4, RGO-NiFe2O4 and RGO-ZnFe2O4 are 233, 200, 25 and 66.8 F g-1 respectively. Our investigation suggests that apart from specific surface area of nanohybrids other factors such as structural morphology determine interaction between nanohybrids and electrolyte ions which play critical role in elevating the performance of electrodes.

ZnFe2O4-C/LiFePO4-CNT: A Novel High-Power Lithium-Ion Battery with Excellent Cycling Performance

PubMed Central

Varzi, Alberto; Bresser, Dominic; von Zamory, Jan; Müller, Franziska; Passerini, Stefano

2014-01-01

An innovative and environmentally friendly battery chemistry is proposed for high power applications. A carbon-coated ZnFe2O4 nanoparticle-based anode and a LiFePO4-multiwalled carbon nanotube-based cathode, both aqueous processed with Na-carboxymethyl cellulose, are combined, for the first time, in a Li-ion full cell with exceptional electrochemical performance. Such novel battery shows remarkable rate capabilities, delivering 50% of its nominal capacity at currents corresponding to ≈20C (with respect to the limiting cathode). Furthermore, the pre-lithiation of the negative electrode offers the possibility of tuning the cell potential and, therefore, achieving remarkable gravimetric energy and power density values of 202 Wh kg−1 and 3.72 W kg−1, respectively, in addition to grant a lithium reservoir. The high reversibility of the system enables sustaining more than 10 000 cycles at elevated C-rates (≈10C with respect to the LiFePO4 cathode), while retaining up to 85% of its initial capacity. PMID:26190956

Unique atom hyper-kagome order in Na4Ir3O8 and in low-symmetry spinel modifications.

PubMed

Talanov, V M; Shirokov, V B; Talanov, M V

2015-05-01

Group-theoretical and thermodynamic methods of the Landau theory of phase transitions are used to investigate the hyper-kagome atomic order in structures of ordered spinels and a spinel-like Na4Ir3O8 crystal. The formation of an atom hyper-kagome sublattice in Na4Ir3O8 is described theoretically on the basis of the archetype (hypothetical parent structure/phase) concept. The archetype structure of Na4Ir3O8 has a spinel-like structure (space group Fd\\bar 3m) and composition [Na1/2Ir3/2](16d)[Na3/2](16c)O(32e)4. The critical order parameter which induces hypothetical phase transition has been stated. It is shown that the derived structure of Na4Ir3O8 is formed as a result of the displacements of Na, Ir and O atoms, and ordering of Na, Ir and O atoms, ordering dxy, dxz, dyz orbitals as well. Ordering of all atoms takes place according to the type 1:3. Ir and Na atoms form an intriguing atom order: a network of corner-shared Ir triangles called a hyper-kagome lattice. The Ir atoms form nanoclusters which are named decagons. The existence of hyper-kagome lattices in six types of ordered spinel structures is predicted theoretically. The structure mechanisms of the formation of the predicted hyper-kagome atom order in some ordered spinel phases are established. For a number of cases typical diagrams of possible crystal phase states are built in the framework of the Landau theory of phase transitions. Thermodynamical conditions of hyper-kagome order formation are discussed by means of these diagrams. The proposed theory is in accordance with experimental data.

The role of annealing temperature and bio template (egg white) on the structural, morphological and magnetic properties of manganese substituted MFe2O4 (M=Zn, Cu, Ni, Co) nanoparticles

NASA Astrophysics Data System (ADS)

Ranjith Kumar, E.; Jayaprakash, R.; Kumar, Sanjay

2014-02-01

Manganese substituted ferrites (ZnFe2O4, CuFe2O4, NiFe2O4 and CoFe2O4) have been prepared in the bio template medium by using a simple evaporation method. The annealing temperature plays an important position on changing particle size and morphology of the mixed ferrite nanoparticles were found out by X-ray diffraction, transmission electron microscopy and scanning electron microscopy methods. The role of manganese substitution in the mixed ferrite nanoparticles were also analyzed for different annealing temperature. The substitution of Mn also creates a vital change in magnetic properties which is studied by using vibrating sample magnetometer (VSM). These spinel ferrites are decomposed to α-Fe2O3 after annealing above 550 °C in air. However, α-Fe2O3 phase was slowly vanished after ferrites annealing above 900 °C. The effect of this secondary phase on the structural change and magnetic properties of the mixed ferrite nanoparticles is discussed.

Green Synthesis of NiFe2O4 Spinel-Structured Nanoparticles Using Hydrangea paniculata Flower Extract with Excellent Magnetic Property

NASA Astrophysics Data System (ADS)

Karunakaran, Gopalu; Jagathambal, Matheswaran; Van Minh, Nguyen; Kolesnikov, Evgeny; Kuznetsov, Denis

2018-05-01

Nickel ferrite (NiFe2O4) spinel-structured nanoparticles (NPs) were synthesized by a green synthesis approach using Hydrangea paniculata flower extract. Green synthesis of NPs was preliminary monitored by a color change. Further confirmation was carried out using different techniques. X-ray diffraction analysis confirmed the cubic crystalline system (fcc) of NiFe2O4. Energy-dispersive spectrum analysis showed the presence of iron, nickel, oxygen, and carbon. Scanning electron microscopy revealed the agglomerating nature of the NPs (30-50 nm). The specific surface area was found to be 46.73 m2/g, revealing the average size D of NPs to be 24 nm. Transmission electron microscopy confirmed the spherical, oval, and irregular shapes of the NPs with a size range between 10 nm and 45 nm, and an average size of 28 nm. The magnetization of the obtained NiFe2O4 NPs in a high magnetic field of 20 kOe was found to be 20 emu/g. The values of remanent magnetization (M r) and coercive field (H c) were found to be 1.1 emu/g and 28 Oe, respectively. In the process of magnetization reversal (with a small value of M r/M s, 0.055), NiFe2O4 NPs had a loop with low energy loss, showing that the obtained NiFe2O4 NPs were soft magnetic materials. The magnetization curve with a sigmoidal shape indicated that the obtained NiFe2O4 NPs are super-paramagnetic material. In addition, the comparison of green synthesis with the methods available in the literature proved that the green synthesis is the best method. Thus, it is clear that green synthesis is a novel eco-friendly approach for the synthesis of magnetic NiFe2O4 NPs.

Natural Occurrence of Fe2SiO4 - in Shocked Umbarger l6 Chondrite

NASA Astrophysics Data System (ADS)

Xie, Z.; Sharp, T. G.

2001-12-01

Fe2SiO4 with the spinel structure was synthesized by Ringwood [1] and inferred to be important in Earth's upper mantle [1,2], but it has not previously been found in nature. Umbarger is an L6 chondrite, which contains a series of high-pressure phases: ring-woodite, akimotoite, augite and hollandite-structured plagioclase [3-6]. Transmission electron microscopy also revealed a Fe2SiO4-spinel and stishovite assem-blage in a Fe-rich zone of a melt pocket. Phyllosili-cates and glass are also associated with the Fe2SiO4-spinel, indicating post-shock aqueous glass alteration. The Fe2SiO4-spinel grains are equant to irregular, with sizes from 100 to 400 nm. Diffraction patterns can only be indexed as a spinel structure, but the unit cell is a little large (a= 8.46 Å) relative to synthetic Fe2SiO4-spinel (a=8.234 Å [1]). EDS analyses show that the spinel has a fayalite compositon with Fe/(Fe+Mg) ratio ranging from 62% to 97%. Stishovite occurs as elongated prismatic crystals up to 1 mm long and up to 100 mm wide. The alteration products in Umbarger are phyllosilicates rich in Fe and Si, with a basal layer spacing of about 9.7 Å. Crystallization of melt veins began with akimotoite and ringwoodite at pressures up to 25 GPa and ended with augite at pressure less than 18 GPa [3, 4]. Mg2SiO4-spinel and stishovite are stable in the pres-sure range from 15 GPa to 25 GPa in the enstatite-forsterite system [7], while Fe2SiO4-spinel and stishovite is stable at lower pressure. Fe2SiO4-spinel and stishovite assemblage, like that of Akimotoite plus ringwoodite, is a sub-solidus assemblage, indicating crystallization of a supercooled liquid during rapid cooling and decompression associated with shock pres-sure release. Reference: [1] Ringwood A.E. (1958) GCA,15, 18-29. [2] Irifune T. (1993) The Island Arc, 2, 55-71. [3] Xie Z. and Sharp T. G. (2000a) LPS XXXI, 2065.pdf. [4] Xie Z. and Sharp T. G. (2000b) MAPS, 35 A172. [5] Xie Z. et al.(2001) LPS XXXII, 1805.pdf. [6] Sharp T.G. (2001

In-situ high-pressure x-ray diffraction study of zinc ferrite nanoparticles

DOE PAGES

Ferrari, S.; Kumar, R. S.; Grinblat, F.; ...

2016-04-23

We have studied the high-pressure structural behavior of zinc ferrite (ZnFe 2O 4) nanoparticles by powder X-ray diffraction measurements up to 47 GPa. We found that the cubic spinel structure of ZnFe 2O 4 remains up to 33 GPa and a phase transition is induced beyond this pressure. The high-pressure phase is indexed to an orthorhombic CaMn 2O 4-type structure. Upon decompression the low- and high-pressure phases coexist. The compressibility of both structures was also investigated. We have observed that the lattice parameters of the high-pressure phase behave anisotropically upon compression. Further, we predict possible phase transition around 55 GPa.more » For comparison, we also studied the compression behavior of magnetite (Fe 3O 4) nanoparticles by X-ray diffraction up to 23 GPa. Spinel-type ZnFe 2O 4 and Fe 3O 4 nanoparticles have a bulk modulus of 172 (20) GPa and 152 (9) GPa, respectively. Lastly, this indicates that in both cases the nanoparticles do not undergo a Hall-Petch strengthening.« less

In-situ high-pressure x-ray diffraction study of zinc ferrite nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferrari, S.; Kumar, R. S.; Grinblat, F.

We have studied the high-pressure structural behavior of zinc ferrite (ZnFe 2O 4) nanoparticles by powder X-ray diffraction measurements up to 47 GPa. We found that the cubic spinel structure of ZnFe 2O 4 remains up to 33 GPa and a phase transition is induced beyond this pressure. The high-pressure phase is indexed to an orthorhombic CaMn 2O 4-type structure. Upon decompression the low- and high-pressure phases coexist. The compressibility of both structures was also investigated. We have observed that the lattice parameters of the high-pressure phase behave anisotropically upon compression. Further, we predict possible phase transition around 55 GPa.more » For comparison, we also studied the compression behavior of magnetite (Fe 3O 4) nanoparticles by X-ray diffraction up to 23 GPa. Spinel-type ZnFe 2O 4 and Fe 3O 4 nanoparticles have a bulk modulus of 172 (20) GPa and 152 (9) GPa, respectively. Lastly, this indicates that in both cases the nanoparticles do not undergo a Hall-Petch strengthening.« less

Crystal growth and magnetic properties of spinel (Co,Mn)3O4

NASA Astrophysics Data System (ADS)

Kang, Sun Hee; Kim, Ill Won; Jeong, Yoon Hee; Koo, Tae Yeong

2012-04-01

Single crystals of cubic and tetragonal spinel Co3-xMnxO4 (x=1.0 and 1.5) were successfully grown using a solvent evaporation method with PbF2 flux. Single crystals in octahedral shape with a size of about 4 mm on edge were obtained from 100 cm3 Pt crucibles. Ferrimagnetic transitions were detected at 170 K and 160 K from the measurements of temperature dependent magnetization and specific heat of Co2MnO4 and Co1.5Mn1.5O4, respectively. Low temperature field-dependent magnetization curves give a strong indication of the non-collinear spin structure, offering an insulating Co3-xMnxO4 system as a possible candidate for examining the multiferroicity.

Study on the energy band structure and photoelectrochemical performances of spinel Li{sub 4}Ti{sub 5}O{sub 12}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ge, Hao; Tian, Hui; Song, Hua

2015-01-15

Highlights: • Spinel Li{sub 4}Ti{sub 5}O{sub 12} possesses more positive potential of valence band and wider band gap than TiO{sub 2}. • Spinel Li{sub 4}Ti{sub 5}O{sub 12} displays typical n-type semiconductor characteristic and excellent UV-excitateded photocatalysis activity. • Our preliminary study will open new perspectives in investigation of other lithium-based compounds for new photocatalysts. - Abstract: Energy band structure, photoelectrochemical performances and photocatalysis activity of spinel Li{sub 4}Ti{sub 5}O{sub 12} are investigated for the first time in this paper. Li{sub 4}Ti{sub 5}O{sub 12} possesses more positive valence band potential and wider band gap than TiO{sub 2} due to its valencemore » band consisting of Li{sub 1s} and Ti{sub 3d} orbitals mixed with O{sub 2p}. Li{sub 4}Ti{sub 5}O{sub 12} shows typical photocatalysis material characteristics and excellent photocatlytic activity under UV irradiation.« less

Nanofibrillated Cellulose-Assisted Synthesis of Fiber-Like ZnO-ZnFe2O4 Composites with Enhanced Visible-Light-Driven Photocatalytic Activity

NASA Astrophysics Data System (ADS)

Cai, Aijun; Guo, Aiying; Du, Liqiang; Chang, Yongfang; Wang, Xiuping

2018-05-01

In this article, fiber-like ZnO-ZnFe2O4 composites are obtained by using nanofibrillated cellulose as a biotemplate. The as-prepared composites exhibit strong absorbance in the visible-light region. The ZnO-ZnFe2O4 composites exhibit a similar bandgap (1.88 eV) compared with the ZnFe2O4 (1.85 eV). The ZnO-ZnFe2O4 composites can be easily collected by an external magnet, which contributes to improving the utilization efficiency of the photocatalysts. The photocatalytic activity of the ZnO-ZnFe2O4 catalysts was evaluated by photodegrading rhodamine B (RhB) under visible-light irradiation. Compared with ZnO and ZnFe2O4, the ZnO-ZnFe2O4 catalysts show higher photocatalytic activity due to the efficient electron-hole separation.

Low temperature magnetization and anomalous high temperature dielectric behaviour of (1-x) YMnO3/xZnFe2O4 composites

NASA Astrophysics Data System (ADS)

Kumar, Virendra; Gaur, Anurag

2018-04-01

We synthesized YMnO3 and ZnFe2O4 composites, (1-x)YMnO3/x(ZnFe2O4) with x = 0, 0.05, 0.10, and 0.15 by high temperature sintering. X-ray diffraction (XRD) patterns indicate the successful formation of composites. Weak ferromagnetism is manifested below Néel temperature (TN) for pristine YMnO3, according to (M-H) study performed at 10 K. For (1-x)YMnO3/xZnFe2O4 (x = 0.05, 0.10, 0.15) a thin coercivity is observed in all compositions, due to short range magnetic ordering at low temperature after the insertion of ZnFe2O4. For pristine YMnO3 explicit divarication between FC-ZFC curves is observed, with crimps observed in both FC and ZFC curves at 75 K, which is the TN of YMnO3. For 1-x(YMnO3)/x ZnFe2O4 composites (x = 0.05, 0.10, 0.15) crimps are perceived only in ZFC curves at slightly varying values of 39.8, 42.32 and 45.63 K respectively. Anomalous peaks are observed in high temperature dielectric curves above 400 K for 1-x(YMnO3)/xZnFe2O4 (x = 0, 0.05, 0.10, 0.15) composites due to Maxwell-Wagner relaxation effect.

Vibrational and elastic properties of silicate spinels A2SiO4 (A = Mg, Fe, Ni, and Co)

NASA Astrophysics Data System (ADS)

Kushwaha, A. K.; Ma, C.-G.; Brik, M. G.; Akbudak, S.

2018-06-01

A six-parameter bond-bending force constant model is used to calculate the zone-center (Γ = 0) Raman and infrared phonon mode frequencies, elastic constants and related properties, the Debye temperatures, and sound velocities along high-symmetry directions for A2SiO4 (A = Mg, Fe, Ni, and Co) spinels. The main outcomes of the calculations are that the interactions between Si and O atoms (first-neighbor interaction) are stronger than those between A and Oatoms (A = Mg, Fe, Ni, and Co) (second-neighbor interaction). The elastic constants C11, C12, and C44 decrease in the order Mg > Fe > Ni > Co. The calculated bulk modulus, Poisson's ratio, and anisotropy decrease in the sequence Fe2SiO4 → Ni2SiO4 → Co2SiO4 → Mg2SiO4. On comparison, we find overall good agreement with the available experimental and previously calculated data.

Comparison effects and electron spin resonance studies of α-Fe2O4 spinel type ferrite nanoparticles.

PubMed

Bayrakdar, H; Yalçın, O; Cengiz, U; Özüm, S; Anigi, E; Topel, O

2014-11-11

α-Fe2O4 spinel type ferrite nanoparticles have been synthesized by cetyltrimethylammonium bromide (CTAB) and ethylenediaminetetraacetic acid (EDTA) assisted hydrothermal route by using NaOH solution. Electron spin resonance (ESR/EPR) measurements of α-Fe2O4 nanoparticles have been performed by a conventional x-band spectrometer at room temperature. The comparison effect of nanoparticles prepared by using CTAB and EDTA in different α-doping on the structural and morphological properties have been investigated in detail. The effect of EDTA-assisted synthesis for α-Fe2O4 nanoparticles are refined, and thus the spectroscopic g-factor are detected by using ESR signals. These samples can be considered as great benefits for magnetic recording media, electromagnetic and drug delivery applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Nanoporous LiMn2O4 spinel prepared at low temperature as cathode material for aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Wang, F. X.; Xiao, S. Y.; Gao, X. W.; Zhu, Y. S.; Zhang, H. P.; Wu, Y. P.; Holze, R.

2013-11-01

LiMn2O4 spinel was prepared by a hydrothermal method using α-MnO2 nanotubes as precursor at 180 °C, a temperature much lower than that in previously reported methods. It is nanoporous with a pore size of about 40-50 nm and a BET surface area of 9.76 m2 g-1. It exhibits a high specific capacitance of 189 F g-1 at 0.3 A g-1 as a cathode for an aqueous supercapacitor. Even at 12 A g-1, it still has a capacitance of 166 F g-1. After 1500 cycles, there is no evident capacity fading. The LiMn2O4 cathode can deliver an energy density of 31.9 Wh kg-1 at 3480 W kg-1 and even maintain 19.4 Wh kg-1 at about 5100 W kg-1 based on the mass of LiMn2O4.

Spinel, YbFe2O4, and Yb2Fe3O7 types of structure for compounds in the In2O3 and Sc2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, Cu, or Zn) at temperatures over 1000C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kimizuka, N.; Mohri, T.

In the Sc2O3-Ga2O3-CuO, Sc2O3-Ga2O3-ZnO, and Sc2O3-Al2O3-CuO systems, ScGaCuO4, ScGaZnO4, and ScAlCuO4 with the YbFe2O4-type structure and Sc2Ga2CuO7 with the Yb2Fe3O7-type structure were obtained. In the In2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, or Zn), InGaFeO4, InGaNiO4, and InFeT MgO4 with the spinel structure, InGaZnO4, InGaMgO4, and InAl-CuO4 with the YbFe2O4-type structure, and In2Ga2MnO7 and In2Ga2ZnO7 with the Yb2Fe3O7-type structure were obtained. InGaMnO4 and InFe2O4 had both the YbFe2O4-type and spinel-type structures. The revised classification for the crystal structures of AB2O4 compounds is presented, based upon the coordination numbers of constituent A and B cations. 5more » references, 2 tables.« less

Structure and Electrical Properties of Mn-Cu-O Spinels

NASA Astrophysics Data System (ADS)

Bobruk, M.; Durczak, K.; Dąbek, J.; Brylewski, T.

2017-04-01

The study presents the results of structural and electrical conductivity investigations of a Cu1.3Mn1.7O4 spinel obtained using EDTA gel processes. An amorphous gel was synthesized and calcinated for 5 h in air at temperatures of 673, 773, 873, and 973 K. When calcinating the gel at temperatures below 973 K, the obtained powders consisted of two phases—the regular Cu1.5Mn1.5O4 spinel and manganese(III) oxide. At 973 K, Mn2O3 was no longer observed, but a new Mn3O4 phase appeared in addition to the Cu1.5Mn1.5O4 spinel. Green bodies prepared from these powders were sintered for 2 h in air at 1393 K. The obtained sinters had a porosity of around 12% and were composed predominantly of the spinel phase, with minor amounts of Mn3O4 and, in the case of three of four sinters—CuO. Electrical conductivity measurements were taken over the temperature range of 300-1073 K. A change in the character of conductivity of the studied sinters was observed in the range of 400-430 K, and it was associated with an increase in activation energy from 0.20 to 0.56 eV. The electrical conductivity of the studied sinters ranged from 74.8 to 88.4 S cm-1, which makes the Cu1.3Mn1.7O4 material suitable for application as a protective-conducting coating in IT-SOFC ferritic stainless steel interconnects.

Cerium and zinc: Dual-doped LiMn 2O 4 spinels as cathode material for use in lithium rechargeable batteries

NASA Astrophysics Data System (ADS)

Thirunakaran, R.; Sivashanmugam, A.; Gopukumar, S.; Rajalakshmi, R.

Pristine spinel lithium manganese oxide (LiMn 2O 4) and zinc- and cerium-doped lithium manganese oxide [LiZn xCe yMn 2- x- yO 4 (x = 0.01-0.10; y = 0.10-0.01)] are synthesized for the first time via the sol-gel route using p-amino benzoic acid as a chelating agent to obtain micron-sized particles and enhanced electrochemical performance. The sol-gel route offers shorter heating time, better homogeneity and control over stoichiometry. The resulting spinel product is characterized through various methods such as thermogravimetic and differential thermal analysis (TG/DTA), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrochemical galvanostatic cycling studies. Charge-discharge studies of LiMn 2O 4 samples heated at 850 °C exhibit a discharge capacity of 122 mAh g -1 and a corresponding 99% coulombic efficiency in the 1st cycle. The discharge capacity and cycling performance of LiZn 0.01Ce 0.01Mn 1.98O 4 is found to be superior (124 mAh g -1), with a low capacity fade (0.1 mAh g -1 cycle -1) over the investigated 10 cycles.

Mössbauer study and magnetic properties of MgFe2O4 crystallized from the glass system B2O3/K2O/P2O5/MgO/Fe2O3

NASA Astrophysics Data System (ADS)

Shabrawy, S. El; Bocker, C.; Miglierini, M.; Schaaf, P.; Tzankov, D.; Georgieva, M.; Harizanova, R.; Rüssel, C.

2017-01-01

An iron containing magnesium borate glass with the mol% composition 51.7 B2O3/9.3 K2O /1 P2O5/27.6MgO/10.4Fe2O3was prepared by the conventional melts quenching method followed by a thermal treatment process at temperatures in the range from 530 to 604 °C.The thermally treated samples were characterized by X-ray diffraction, scanning and transmission electron microscopy. It was shown that superparamagnetic MgFe2O4 nanoparticles were formed during thermal treatment. The size of the spinel type crystals was in the range from 6 to 15 nm. Mössbauer spectra of the powdered glass ceramic samples and the extracted nanoparticles after dissolving the glass matrix in diluted acid were recorded at room temperature. The deconvolution of the spectra revealed the crystallization of two spinel phases MgFe2O4 (as a dominant phase) and superparamagnetic maghemite, γ-Fe2O3 (as a secondary phase). Room temperature magnetic measurements showed that, increasing the crystallization temperature changed the superparamagnetic behavior of the samples to ferrimagnetic behavior. The Curie temperatures of the samples were measured and showed a higher value than that of the pure bulk MgFe2O4.

Orbital ordering in FeV2O4: Spinel with two orbitally active sites

NASA Astrophysics Data System (ADS)

Sarkar, Soumyajit; Saha-Dasgupta, T.

2011-12-01

By employing first-principles electronic structure calculations, we investigate orbital ordering in FeV2O4, a spinel with orbital degrees of freedom both at Fe and V sites that exhibits two tetragonal phases, one compressed at high temperature and another elongated at low temperature. Our first-principles study shows the ferro-orbital ordering of dx2-y2 and d3z2-r2 types at Fe sites at the high- and low-temperature phases, respectively. The orbital ordering at V sites is found to consist of orbital chains running along different directions with orbitals rotated alternatively within each chain, similar to that found for MnV2O4 [S. Sarkar , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.102.216405 102, 216405 (2009)]. Further, we find that the single-ion anisotropy effect with hard and easy c axis favors the compressed and elongated tetrahedral shapes. This gives rise to magnetocrystalline anisotropy-dependent shapes, similar to that reported in the context of rare-earth-based magnetic shape memory alloys.

First-Principles Thermodynamics Study of Spinel MgAl 2 O 4 Surface Stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Qiuxia; Wang, Jian-guo; Wang, Yong

The surface stability of all possible terminations for three low-index (111, 110, 100) structures of the spinel MgAl2O4 has been studied using first-principles based thermodynamic approach. The surface Gibbs free energy results indicate that the 100_AlO2 termination is the most stable surface structure under ultra-high vacuum at T=1100 K regardless of Al-poor or Al-rich environment. With increasing oxygen pressure, the 111_O2(Al) termination becomes the most stable surface in the Al-rich environment. The oxygen vacancy formation is thermodynamically favorable over the 100_AlO2, 111_O2(Al) and the (111) structure with Mg/O connected terminations. On the basis of surface Gibbs free energies for bothmore » perfect and defective surface terminations, the 100_AlO2 and 111_O2(Al) are the most dominant surfaces in Al-rich environment under atmospheric condition. This is also consistent with our previously reported experimental observation. This work was supported by a Laboratory Directed Research and Development (LDRD) project of the Pacific Northwest National Laboratory (PNNL). The computing time was granted by the National Energy Research Scientific Computing Center (NERSC). Part of computing time was also granted by a scientific theme user proposal in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at PNNL in Richland, Washington.« less

Zincoberaunite, ZnFe3+ 5(PO4)4(OH)5ṡ6H2O, a new mineral from the Hagendorf South pegmatite, Germany

NASA Astrophysics Data System (ADS)

Chukanov, Nikita V.; Pekov, Igor V.; Grey, Ian E.; Price, Jason R.; Britvin, Sergey N.; Krzhizhanovskaya, Maria G.; Kampf, Anthony R.; Dünkel, Bernhard; Keck, Erich; Belakovskiy, Dmitry I.; MacRae, Colin M.

2017-06-01

The new mineral zincoberaunite, ideally ZnFe3+ 5(PO4)4(OH)5·6H2O, the Zn analogue of beraunite, is found in the Hagendorf South granitic pegmatite, Hagendorf, Bavaria, Germany, in two associations: (1) with potassium feldspar, quartz, jungite, phosphophyllite and mitridatite (the holotype) and (2) with flurlite, plimerite, Zn-bearing beraunite, schoonerite, parascholzite/scholzite, robertsite and altered phosphophyllite (the cotype). Zincoberaunite occurs as radial or randomly oriented aggregates of flexible fibers up to 1.5 mm long and up to 3 μm thick. D calc is 2.92 g/cm3 for the holotype and 2.94 g/cm3 for the cotype. Zincoberaunite is optically biaxial (-), α = 1.745(5), β = 1.760(5), γ = 1.770(5), 2 V meas = 80(5)°. Chemical composition of the holotype (electron probe microanalyser; H2O by gas chromatography of ignition products) is: MgO 0.28 wt%, CaO 0.47 wt%, ZnO 7.36 wt%, Al2O3 0.88 wt%, Fe2O3 42.42 wt%, P2O5 31.63 wt%, H2O 16.2 wt%, total 101.1 wt%. The empirical formula calculated on the basis of 27 oxygen atoms per formula unit is (Zn0.83Ca0.08Mg0.06)∑0.97(Fe3+ 4.88Al0.16)∑5.04(PO4)4.09(OH)4.78 · 5.86H2O. Zincoberaunite is monoclinic, space group C2 /c; refined unit cell parameters (for the holotype at room temperature and the cotype at 100 K, respectively) are: a 20.837(2) and 20.836(4), b 5.1624(4) and 5.148(1), c 19.250(1) and 19.228(4) Å, β 93.252(5) and 93.21(3)°, V 2067.3(3) and 2059.2(7) Å3, Z = 4. The crystal structure of the holotype specimen has been refined by the Rietveld method ( R p = 0.30 %; R B = 0.18 %) whereas the structure of the cotype has been solved from the single crystal data and refined to R 1 = 0.056 based on 1900 unique reflections with I > 2σ( I). The strongest reflections of the powder X-ray diffraction pattern of the holotype specimen [( d, Å) ( I, %) ( hkl)] are: 10.37 (100) (200), 9.58 (32) (002), 7.24 (26) (20-2), 4.817 (22) (111), 4.409 (13) (112), 3.483 (14) (11-4, 600), 3.431 (14) (404), 3.194 (15

Mitigation of chromium poisoning of cathodes in solid oxide fuel cells employing CuMn1.8O4 spinel coating on metallic interconnect

NASA Astrophysics Data System (ADS)

Wang, Ruofan; Sun, Zhihao; Pal, Uday B.; Gopalan, Srikanth; Basu, Soumendra N.

2018-02-01

Chromium poisoning is one of the major reasons for cathode performance degradation in solid oxide fuel cells (SOFCs). To mitigate the effect of Cr-poisoning, a protective coating on the surface of interconnect for suppressing Cr vaporization is necessary. Among the various coating materials, Cu-Mn spinel coating is considered to be a potential candidate due to their good thermal compatibility, high stability and good electronic conductivity at high temperature. In this study, Crofer 22 H meshes with no protective coating, those with commercial CuMn2O4 spinel coating and the ones with lab-developed CuMn1.8O4 spinel coating were investigated. The lab-developed CuMn1.8O4 spinel coating were deposited on Crofer 22 H mesh by electrophoretic deposition and densified by a reduction and re-oxidation process. With these different Crofer 22 H meshes (bare, CuMn2O4-coated, and CuMn1.8O4-coated), anode-supported SOFCs with Sr-doped LaMnO3-based cathode were electrochemically tested at 800 °C for total durations of up to 288 h. Comparing the mitigating effects of the two types of Cu-Mn spinel coatings on Cr-poisoning, it was found that the performance of the denser lab-developed CuMn1.8O4 spinel coating was distinctly better, showing no degradation in the cell electrochemical performance and significantly less Cr deposition near the cathode/electrolyte interface after the test.

Efficacy of heat generation in CTAB coated Mn doped ZnFe2O4 nanoparticles for magnetic hyperthermia

NASA Astrophysics Data System (ADS)

Raland, R. D.; Borah, J. P.

2017-01-01

Manganese doped Zinc ferrite (Mn-ZnFe2O4, where Mn  =  0%, 3%, 5% and 7%) nanoparticles were synthesized by a simple co-precipitation method. CTAB (cetyltrimethylammonium bromide) was used as a surfactant to inhibitgrowth and agglomeration. In this work, we have discussed on the influence of CTAB and Mn doping in tailoring the structural and magnetic properties of Mn-ZnFe2O4 nanoparticles for the effective application of magnetic hyperthermia. X-ray diffraction (XRD) pattern confirmed the formation of cubic spinel structure of Mn-ZnFe2O4 nanoparticles. Lattice parameter and x-ray densities were obtained from the Rietveld refinement of the XRD pattern. The presence of CTAB as a stabilizing layer adsorbed on the surface of the nanoparticles were confirmed by transmission electron microscope (TEM) and Raman vibrational spectrum. The saturation magnetization showsan increasing trend with Mn addition owing to cationic re-distribution and an increase super-exchange interaction between the two sub-lattices. Superparamagnetic behaviorof Mn-ZnFe2O4 nanoparticles were confirmed by temperature-dependent zero-field-cooling (ZFC) and field-cooling (FC) magnetization curves. The efficiency of induction heating measured by its specific absorption rate (SAR) and intrinsic loss power (ILP) value varies as a function of saturation magnetization. It has been hypothesized that the maximum generation of heat arises from Neel relaxation mechanism. The optimum generation of heat of Mn-ZnFe2O4 nanoparticle is determined by the higher frequency (f  =  337 kHz) range and maximum concentration of Mn doping.

Coexisting nanoscale inverse spinel and rock salt crystallographic phases in NiCo2O4 epitaxial thin films grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Sharona, H.; Loukya, B.; Bhat, U.; Sahu, R.; Vishal, B.; Silwal, P.; Gupta, A.; Datta, R.

2017-12-01

The origin of alternating wavy dark-bright stripe-like contrast in strain contrast transmission electron microscopy images of NiCo2O4 (NCO) epitaxial thin films grown by pulsed laser deposition has been investigated. The nanoscale stripe-like pattern is determined to be associated with coexisting rock salt (RS) and inverse spinel crystal phases. The presence of two different phases, not addressed in previous reports, is experimentally confirmed by both electron diffraction and high resolution transmission electron microscopy imaging. First principles based calculations, together with compressive strain present in the films, support the formation of such coexisting crystallographic phases in NCO. Similar microstructural patterns and RS structure are not observed in epitaxial films of two other oxides of the spinel family, namely, NiFe2O4 and CoFe2O4. A correlation between the coexisting structures and the macroscopic physical properties of NCO is discussed.

Characterization of dipole defects in MgAl2O4 spinel

NASA Astrophysics Data System (ADS)

Carvalhaes, R. P. M.; da Rocha, M. S. F.; de Souza, S. S.; Blak, A. R.

2005-01-01

Dipole defects in gamma-irradiated and thermal treated MgAl2O4 samples have been studied through thermally stimulated depolarisation currents(TSDC) technique and computer modelling methods. The presence of TSDC bands varies from sample to sample and some crystals do not present any band. The origin of these bands has been investigated in several different samples. In the spectra of spinels showing TSDC peaks, three bands at 130K, 160K and 320K are observed. The peaks at 130K and 160K have been attributed to dipole defects. After 1200kGy of gamma irradiation the broad band at 320K dislocates to 290K and increases ten times. Pulsed thermal treatments between 350K and 470K produce a progressive reduction of the peak area and a shift in the peak position back to 320K. A detailed analysis of the curve indicates the possibility of a superposition of peaks. Gamma irradiation restores the 320K TSDC peak. Taking into account optical absorption(OA) and electron paramagnetic resonance(EPR) results, the thermal reduction of the 320K TSDC band was attributed to V-type centres as a result of hole trapping at tetrahedral and octahedral cation vacancies. Computer modelling methods, based on lattice energy and defect minimisation, were applied to identify dipole defects that occur in these crystals. The calculations were made in normal and inverse spinel structures, doped with Cr, Co, Mn and Fe in order to justify the presence of dipole bands.

Nanostructural origin of semiconductivity and large magnetoresistance in epitaxial NiCo2O4/Al2O3 thin films

NASA Astrophysics Data System (ADS)

Zhen, Congmian; Zhang, XiaoZhe; Wei, Wengang; Guo, Wenzhe; Pant, Ankit; Xu, Xiaoshan; Shen, Jian; Ma, Li; Hou, Denglu

2018-04-01

Despite low resistivity (~1 mΩ cm), metallic electrical transport has not been commonly observed in inverse spinel NiCo2O4, except in certain epitaxial thin films. Previous studies have stressed the effect of valence mixing and the degree of spinel inversion on the electrical conduction of NiCo2O4 films. In this work, we studied the effect of nanostructural disorder by comparing the NiCo2O4 epitaxial films grown on MgAl2O4 (1 1 1) and on Al2O3 (0 0 1) substrates. Although the optimal growth conditions are similar for the NiCo2O4 (1 1 1)/MgAl2O4 (1 1 1) and the NiCo2O4 (1 1 1)/Al2O3 (0 0 1) films, they show metallic and semiconducting electrical transport, respectively. Post-growth annealing decreases the resistivity of NiCo2O4 (1 1 1)/Al2O3 (0 0 1) films, but the annealed films are still semiconducting. While the semiconductivity and the large magnetoresistance in NiCo2O4 (1 1 1)/Al2O3 (0 0 1) films cannot be accounted for in terms of non-optimal valence mixing and spinel inversion, the presence of anti-phase boundaries between nano-sized crystallites, generated by the structural mismatch between NiCo2O4 and Al2O3, may explain all the experimental observations in this work. These results reveal nanostructural disorder as being another key factor for controlling the electrical transport of NiCo2O4, with potentially large magnetoresistance for spintronics applications.

Synthesis and electrochemical characterization of Li 1.05RE xCr yMn 2- x- yO 4 spinel as cathode material for rechargeable Li-battery

NASA Astrophysics Data System (ADS)

Xie, Yanting; Yang, Rudong; Yan, Lan; Qi, Lu; Dai, Kehua; He, Ping

The spinel phases of Li 1.05RE xCr yMn 2- x- yO 4 (RE = Sc, Ce, Pr, Tb; 0 ≤ x ≤ 0.05; 0 ≤ y ≤ 0.1) were prepared by a soft chemical method. The structural and electrochemical properties of Li 1.05RE xCr yMn 2- x- yO 4 were investigated by X-ray diffraction (XRD), Transmission electron microscopy (TEM) and charge-discharge experiments. Rare earth element-Sc and transition metal-Cr as co-substituents stabilize the spinel framework and improve charge-discharge performance. For Li 1.05Sc 0.01Cr 0.03Mn 1.96O 4, the capacity of the cell maintained 95% of the initial capacity at the 80th cycle. The rare earth elements of the variable valent metals such as Ce 3+/4+, Pr 3+/4+, Tb 3+/4+ with transition metal Cr 3+ as co-substituent do not stable framework of spinel or improve the cycling performance. Cyclic voltammetry (CV) were measured to provide clues for the improved cycling performance of cathode electrodes.

Effect of zinc-borate glass addition on the thermal properties of the cordierite/Al2O3 composites containing nano-sized spinel crystal.

PubMed

Jo, Sinae; Kang, Seunggu

2013-11-01

Low-melting zinc-borate glass was added to the cordierite/Al2O3 composite in order to improve the sintering facility of Al2O3 and formation of nano-sized spinel crystal of high thermal conductivity. Increasing the ZnO/B2O3 ratio in the zinc-borate glass increased the ZnAl2O4 spinel and decreased the Al4B2O9 crystal peak intensities in X-ray diffraction pattern. The XRD peak intensities of the ZnAl2O4 spinel and Al4B2O9 crystals in the specimen containing 10 wt% zinc-borate glass (10G series) are higher than that of the specimen containing 5 wt% zinc-borate glass (5G series). The microstructures of most 10G series specimens had the flower-shaped crystal which was composed of 50 nm wide and 250 nm long needle-like crystals and identified as ZnAl2O4 spinel phase. The thermal conductivity of the 10G series specimen was higher than that of the 5G series in any ZnO/B2O3 ratio due to the formation of plenty of nano-sized ZnAl2O4 spinel of high thermal conductivity. Particularly, the thermal conductivity of the cordierite/Al2O3 composite containing 10 wt% zinc-borate glass of ZnO/B2O3 weight ratio = 1.5 was 3.8 W/Km which is much higher than that of the published value (3.0 W/Km).

Superexchange Effects on Oxygen Reduction Activity of Edge-Sharing [Cox Mn1-x O6 ] Octahedra in Spinel Oxide.

PubMed

Zhou, Ye; Sun, Shengnan; Xi, Shibo; Duan, Yan; Sritharan, Thirumany; Du, Yonghua; Xu, Zhichuan J

2018-03-01

Mn-Co containing spinel oxides are promising, low-cost electrocatalysts for the oxygen reduction reaction (ORR). Most studies are devoted to the design of porous Mn-Co spinels or to strongly coupled hybrids (e.g., MnCo 2 O 4 /N-doped-rmGO) to maximize the mass efficiency. The lack of analyses by metal oxide intrinsic activity (activity normalized to catalysts' surface area) hinders the development of fundamental understanding of the physicochemical principles behind the catalytic activities. A systematic study on the composition dependence of ORR in ZnCo x Mn 2- x O 4 (x = 0.0-2.0) spinel is presented here with special attention to the role of edge sharing [Co x Mn 1- x O 6 ] octahedra in the spinel structure. The ORR specific activity of ZnCo x Mn 2- x O 4 spans across a potential window of 200 mV, indicating an activity difference of ≈3 orders of magnitude. The curve of composition-dependent ORR specific activity as a function of Co substitution exhibits a volcano shape with an optimum Mn/Co ratio of 0.43. It is revealed that the modulated e g occupancy of active Mn cations (0.3-0.9), as a consequence of the superexchange effect between edge sharing [CoO 6 ] and [MnO 6 ], reflects the ORR activity of edge sharing [Co x Mn 1- x O 6 ] octahedra in the ZnCo x Mn 2- x O 4 spinel oxide. These findings offer crucial insights in designing spinel oxide catalysts with fine-tuned e g occupancy for efficient catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A general approach for MFe2O4 (M = Zn, Co, Ni) nanorods and their high performance as anode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Nana; Xu, Huayun; Chen, Liang; Gu, Xin; Yang, Jian; Qian, Yitai

2014-02-01

MFe2O4 (M = Zn, Co, Ni) nanorods are synthesized by a template-engaged reaction, with β-FeOOH nanorods as precursors which are prepared by a hydrothermal method. The final products are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). The electrochemical properties of the MFe2O4 (M = Zn, Co, Ni) nanorods are tested as the anode materials for lithium ion batteries. The reversible capacities of 800, 625 and 520 mAh g-1 are obtained for CoFe2O4, ZnFe2O4 and NiFe2O4, respectively, at the high current density of 1000 mA g-1 even after 300 cycles. The superior lithium-storage performances of MFe2O4 (M = Zn, Co, Ni) nanorods can be attributed to the one-dimensional (1D) nanostructure, which can shorten the diffusion paths of lithium ions and relax the strain generated during electrochemical cycling. These results indicate that this method is an effective, simple and general way to prepare good electrochemical properties of 1D spinel Fe-based binary transition metal oxides. In addition, the impact of different reaction temperatures on the electrochemical properties of MFe2O4 nanorods is also investigated.

Experimental evidence for the magnetic moment directions of Cr2+ and Cr3+ cations in the spinel ferrites Cux1Crx2Fe3-x1-x2O4

NASA Astrophysics Data System (ADS)

Zhang, X. Y.; Xu, J.; Li, Z. Z.; Qi, W. H.; Tang, G. D.; Shang, Z. F.; Ji, D. H.; Lang, L. L.

2014-08-01

(A)[B]2O4 spinel ferrite samples with the composition Cux1Crx2Fe3-x1-x2O4 (0.0≤x1≤0.284 and 1.04≥x2≥0.656) were prepared by a chemical co-precipitation method. X-ray diffraction patterns indicated that the samples had a single-phase cubic spinel structure. It is interesting that the saturation magnetization of the samples increased when Cu2+ or Cu3+ (with 1 or 2μB of magnetic moment) substituted for Cr2+ or Cr3+ (with 4 or 3μB), which cannot be obviously explained if the magnetic moments of Cr2+ and Cr3+ cations are assumed to be parallel to those of the Fe and Cu cations. However, with the assumption that the magnetic moments of Cr2+ and Cr3+ cations are antiparallel to the Fe and Cu cation moments in spinel ferrites, the dependence on the Cu doping level of the sample magnetic moments at 10 K was fitted successfully, using the quantum-mechanical potential barrier model earlier proposed by our group. Using the cation distributions obtained in the fitting process, the experimental observation that the magnetic moment of the samples increased with increasing Cu doping level was explained. This work therefore provides experimental evidence that the magnetic moments of the Cr2+ and Cr3+ cations are antiparallel to those of the Fe and Cu cations in spinel ferrites.

Magnetic moment directions and distributions of cations in Cr (Co) substituted spinel ferrites Ni0.7Fe2.3O4

NASA Astrophysics Data System (ADS)

Xue, L. C.; Lang, L. L.; Xu, J.; Li, Z. Z.; Qi, W. H.; Tang, G. D.; Wu, L. Q.

2015-09-01

Powder samples of the spinel ferrites MxNi0.7-xFe2.3O4 (M = Cr, Co and 0.0 ≤ x ≤ 0.3) and CrxNi0.7Fe2.3-xO4 (0.0 ≤ x ≤ 0.3) were synthesized using the chemical co-precipitation method. The XRD spectra confirmed that the samples had a single-phase cubic spinel structure. Magnetic measurements showed that the magnetic moments (μexp) per formula both at 10 K and 300 K increased with Co substitution, while the values of μexp decreased with Cr substitution. Applying the assumption that the magnetic moments of Cr2+ and Cr3+ lie antiparallel to those of the divalent and trivalent Fe, Co, and Ni cations in the same sublattice of spinel ferrites, these interesting behaviors could be easily interpreted. The cation distributions of the three series of samples were estimated successfully by fitting the dependences of μexp, measured at 10 K, on the doping level x, using a quantum-mechanical potential barrier model earlier proposed by our group. The results obtained for the Cr cation distributions at the (A) and [B] sites are very close to those obtained elsewhere using neutron diffraction.

Facile and cost effective synthesis of mesoporous spinel NiCo2O4 as an anode for high lithium storage capacity

NASA Astrophysics Data System (ADS)

Jadhav, Harsharaj S.; Kalubarme, Ramchandra S.; Park, Choong-Nyeon; Kim, Jaekook; Park, Chan-Jin

2014-08-01

To fulfill the high power and high energy density demands for Li-ion batteries (LIBs) new anode materials need to be explored to replace conventional graphite. Herein, we report the urea assisted facile co-precipitation synthesis of spinel NiCo2O4 and its application as an anode material for LIBs. The synthesized NiCo2O4 exhibited an urchin-like microstructure and polycrystalline and mesoporous nature. In addition, the mesoporous NiCo2O4 electrode exhibited an initial discharge capacity of 1095 mA h g-1 and maintained a reversible capacity of 1000 mA h g-1 for 400 cycles at 0.5 C-rate. The reversible capacity of NiCo2O4 could still be maintained at 718 mA h g-1, even at 10 C. The mesoporous NiCo2O4 exhibits great potential as an anode material for LIBs with the advantages of unique performance and facile preparation.To fulfill the high power and high energy density demands for Li-ion batteries (LIBs) new anode materials need to be explored to replace conventional graphite. Herein, we report the urea assisted facile co-precipitation synthesis of spinel NiCo2O4 and its application as an anode material for LIBs. The synthesized NiCo2O4 exhibited an urchin-like microstructure and polycrystalline and mesoporous nature. In addition, the mesoporous NiCo2O4 electrode exhibited an initial discharge capacity of 1095 mA h g-1 and maintained a reversible capacity of 1000 mA h g-1 for 400 cycles at 0.5 C-rate. The reversible capacity of NiCo2O4 could still be maintained at 718 mA h g-1, even at 10 C. The mesoporous NiCo2O4 exhibits great potential as an anode material for LIBs with the advantages of unique performance and facile preparation. Electronic supplementary information (ESI) available: Experimental details and additional experimental results. See DOI: 10.1039/c4nr02183e

3D CNT macrostructure synthesis catalyzed by MgFe2O4 nanoparticles-A study of surface area and spinel inversion influence

NASA Astrophysics Data System (ADS)

Zampiva, Rúbia Young Sun; Kaufmann Junior, Claudir Gabriel; Pinto, Juliano Schorne; Panta, Priscila Chaves; Alves, Annelise Kopp; Bergmann, Carlos Pérez

2017-11-01

The MgFe2O4 spinel exhibits remarkable magnetic properties that open up numerous applications in biomedicine, the environment and catalysis. MgFe2O4 nanoparticles are excellent catalyst for carbon nanotube (CNT) production. In this work, we proposed to use MgFe2O4 nanopowder as a catalyst in the production of 3D macroscopic structures based on CNTs. The creation of these nanoengineered 3D architectures remains one of the most important challenges in nanotechnology. These systems have high potential as supercapacitors, catalytic electrodes, artificial muscles and in environmental applications. 3D macrostructures are formed due to an elevated density of CNTs. The quantity and quality of the CNTs are directly related to the catalyst properties. A heat treatment study was performed to produce the most effective catalyst. Factors such as superficial area, spinel inversion, crystallite size, degree of agglomeration and its correlation with van der Waals forces were examined. As result, the ideal catalyst properties for CNT production were determined and high-density 3D CNT macrostructures were produced successfully.

Magnetocaloric effect in cubic spinel Co(Cr0.95Fe0.05)2O4

NASA Astrophysics Data System (ADS)

Kumar, Ram; Rayaprol, S.; Xiao, Y.; Ji, W.; Siruguri, V.; Pal, D.

2018-04-01

The crystal structure, magnetic properties and magnetocaloric effect (MCE) of Co(Cr0.95Fe0.05)2O4 have been studied. Co(Cr0.95Fe0.05)2O4 synthesized by solid-state reaction method, crystallizes in normal cubic spinel structure with Fd-3m space group. Neutron powder diffraction (NPD) and magnetic measurements when compared to the undoped CoCr2O4, show that the compound is ferrimagnetic (FIM) and transition temperature (TC) is enhanced due to Fe substitution. Analysis of structural and magnetic properties shows the existence of two different sites of magnetic clusters due to Fe/Cr cation disorder. The competition between the moments of the two different sub-lattices gives rise to the temperature induced magnetization reversal at compensation tempearature (Tcomp) = 44 K. The magnetocaloric effect (simply the change in magnetic entropy i.e, -ΔSM) has been observed in Co(Cr0.95Fe0.05)2O4 with different applied magnetic fields (max. H = 90 kOe). We found maximum change of magnetic entropy ˜1.2 J/kg K, for a field change of 90 kOe at FIM transition temperature (TC˜110 K) with relative cooling power (RCP) of ˜13 J/kg. Moreover, the sign change of -ΔSM across the compensation temperature (Tcomp˜ 44 K) shows another phase transition across Tcomp in Co(Cr0.95Fe0.05)2O4. The values of MCE and RCP are also appreciable so as to consider Co(Cr0.95Fe0.05)2O4 as a magnetic refrigerant above liquid nitrogen temperature.

Stabilization of scandium rich spinel ferrite CoFe{sub 2−x}Sc{sub x}O{sub 4} (x≤1) in thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lefevre, Christophe, E-mail: christophe.lefevre@ipcms.unistra.fr; Roulland, François; Thomasson, Alexandre

2015-12-15

Scandium rich cobalt ferrites Co{sub y}Fe{sub 3−x−y}Sc{sub x}O{sub 4} with y~1 never obtained in bulk could be stabilized in pulsed laser deposited thin films. Scandium contents of up to x=1 are reached. The cell parameter increases versus x as awaited when considering the size of scandium. It is equal to 0.8620 nm for x=1, significantly higher than that of CoFe{sub 2}O{sub 4} (0.8396 nm). The lattice mismatch between the MgO (100) substrate and the scandium-containing spinel leads to an increased roughness. Cobalt is displaced from the octahedral site by Sc and mainly occupies the tetrahedral sites for high x values.more » - Graphical abstract: Magnification of the XRD patterns recorded on thin films of CoFe{sub 2-x}Sc{sub x}O{sub 4} for x=0, 0.45, 1 and 1.2, the arrows denote the (004) and (008) diffraction lines of the spinel phase.« less

FC and ZFC magnetic properties of ferro-spinels (MFe2O4) prepared by solution-combustion method

NASA Astrophysics Data System (ADS)

Aravind, G.; Kumar, R. Vijaya; Nathaniyal, V.; Rambabu, T.; Ravinder, D.

2017-07-01

Magnetic ferro-spinels MFe2O4 (M= Co and Ni) prepared by citrate-gel solution combustion method using metal nitrates with low sintering temperature (500°C). From the XRD and TEM studies confirm that a nano crystalline nature of the prepared samples. Field Cooled (FC) and Zero Field Cooled (ZFC) magnetic studies of the prepared ferro-spinels are measured by using vibrating sample magnetometer (VSM). The resultant magnetization of the prepared samples as a function of an applied magnetic field 10 T was measured at two different temperatures 5 K and 310 K. Field Cooled (FC) and Zero Field Cooled (ZFC) magnetization measurements under an applied field of 100 Oe and 1000 Oe in the temperature range of 5-375 K were carried out, which shows the blocking temperature of these two samples at around 350 K.

Atomic-deficient nanostructurization in water-sorption alumomagnesium spinel ceramics MgAl2O4

NASA Astrophysics Data System (ADS)

Ingram, A.

2018-02-01

Atomic-deficient nanostructurization in alumomagnesium MgAl2O4 ceramics sintered at 1100-1400 °C caused by water sorption are studied employing positron annihilation lifetime spectroscopy. Detected PAL spectra are reconstructed from unconstrained x4-term decomposition, and further transformed to x3-term form to be applicable for analysis with x3-x2-CDA (coupling decomposition algorithm). It is proved that water-immersion processes reduce positronium (Ps) decaying in large-size holes of ceramics (1.70-1.84 nm in radius) at the expense of enhanced trapping in tiny ( 0.2 nm in radius) Ps-traps. The water sorption is shown to be more pronounced in structurally imperfect ceramics sintered at T s = 1100-1200 °C due to irreversible transformations between constituting phases, while reversible physical-sorption processes are dominated in structurally uniform ceramics composed of main spinel phase.

Thermodynamic Stability of Low- and High-Index Spinel LiMn 2 O 4 Surface Terminations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Warburton, Robert E.; Iddir, Hakim; Curtiss, Larry A.

2016-05-04

Density functional theory calculations are performed within the generalized gradient approximation (GGA+U) to determine stable terminations of both low- and high-index spinel LiMn2O4 (LMO) surfaces. A grand canonical thermodynamic approach is employed, permitting a direct comparison of offstoichiometric surfaces with previously reported stoichiometric surface terminations at various environmental conditions. Within this formalism, we have identified trends in the structure of the low-index surfaces as a function of the Li and O chemical potentials. The results suggest that, under a range of chemical potentials for which bulk LMO is stable, Li/O and Li-rich (111) surface terminations are favored, neither of whichmore » adopts an inverse spinel structure in the subsurface region. This thermodynamic analysis is extended to identify stable structures for certain high-index surfaces, including (311), (331), (511), and (531), which constitute simple models for steps or defects that may be present on real LMO particles. The low- and high-index results are combined to determine the relative stability of each surface facet under a range of environmental conditions. The relative surface energies are further employed to predict LMO particle shapes through a Wulff construction approach, which suggests that LMO particles will adopt either an octahedron or a truncated octahedron shape at conditions in which LMO is thermodynamically stable. These results are in agreement with the experimental observations of LMO particle shapes.« less

Structural and magnetic transitions in spinel FeM n 2 O 4 single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nepal, Roshan; Zhang, Qiang; Dai, Samuel

Materials that form the spinel structure are known to exhibit geometric frustration, which can lead to magnetic frustration as well. Through magnetization and neutron diffraction measurements, we find that FeMn 2O 4 undergoes one structural and two magnetic transitions. The structural transition occurs at T s ~595K from cubic at high temperatures to tetragonal at low temperatures. Here, two magnetic transitions are ferrimagnetic at T FI–1 ~373K and T FI–2 ~50K, respectively. Further investigation of the specific heat, thermal conductivity, and Seebeck coefficient confirms both magnetic transitions. Of particular interest is that there is a significant magnetic contribution to themore » low-temperature specific heat and thermal conductivity, providing a unique system to study heat transport by magnetic excitations.« less

Structural and magnetic transitions in spinel FeM n 2 O 4 single crystals

DOE PAGES

Nepal, Roshan; Zhang, Qiang; Dai, Samuel; ...

2018-01-11

Materials that form the spinel structure are known to exhibit geometric frustration, which can lead to magnetic frustration as well. Through magnetization and neutron diffraction measurements, we find that FeMn 2O 4 undergoes one structural and two magnetic transitions. The structural transition occurs at T s ~595K from cubic at high temperatures to tetragonal at low temperatures. Here, two magnetic transitions are ferrimagnetic at T FI–1 ~373K and T FI–2 ~50K, respectively. Further investigation of the specific heat, thermal conductivity, and Seebeck coefficient confirms both magnetic transitions. Of particular interest is that there is a significant magnetic contribution to themore » low-temperature specific heat and thermal conductivity, providing a unique system to study heat transport by magnetic excitations.« less

Nitrogen-doped graphene aerogel-supported spinel CoMn2O4 nanoparticles as an efficient catalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Liu, Yisi; Li, Jie; Li, Wenzhang; Li, Yaomin; Chen, Qiyuan; Zhan, Faqi

2015-12-01

Spinel CoMn2O4 (CMO) nanoparticles grown on three-dimensional (3D) nitrogen-doped graphene areogel (NGA) is prepared by a facile two-step hydrothermal method. The NGA not only possesses the intrinsic property of graphene, but also has abundant pore conformations for supporting spinel metal oxide nanoparticles, thus would be suitable as a good electrocatalysts' support for oxygen reduction reaction (ORR). The structure, morphology, porous properties, and chemical composition of CMO/NGA are investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption measurements, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of catalysts is discussed by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and rotating disk electrode (RDE) measurements in O2-saturated 0.1 M KOH electrolyte. The CMO/NGA hybrid exhibits more positive onset potential and half-wave potential, faster charge transfer than that of CMO and NGA, and its electrocatalytic performance is comparable with the commercial 20 wt.% Pt/C. Furthermore, it mainly favors a direct 4e- reaction pathway, and has excellent ethanol tolerance and high durability, which is attributed to the unique 3D crumpled porous nanostructure of NGA with large specific area and fast electron transport, and the synergic covalent coupling between the CoMn2O4 nanoparticles and NGA.

The influence of Ga doping on structural magnetic and dielectric properties of NiCr0.2Fe1.8O4 spinel ferrite

NASA Astrophysics Data System (ADS)

Ajmal, Muhammad; Islam, M. U.; Ashraf, Ghulam Abbas; Nazir, Muhammad Aamir; Ghouri, M. I.

2017-12-01

A series of spinel ferrites NiCr0.2GaxFe1.8-xO4 (x=0.00, 0.002, 0.04, 0.06, 0.08) was prepared by co precipitation technique. The influence of rare earth element Ga ions the structural dielectric and magnetic properties of NiCr0.2Fe1.8O4 ferrites was investigated. The X-ray diffraction confirmed the phase precipitated out was pure spinel phase with few traces of secondary phases. The crystallite size decreases and density increases with the increases of Ga contents. The magnetic moment, saturation magnetization and remanent magnetization increased with addition of Ga ions in spinel ferrite. The dielectric constant is described that it decreases more suddenly at low frequencies as compare at higher frequencies. The decrease in dielectric loss with frequency follows Deby's relaxation phenomena. Both the variation in tan loss and dielectric loss with frequency shows a similar. AC conductivity increases with the increases of frequency which inversely proportional to concentration of Ga3+ ions follows Jonscher law. These Gallium Chromium doped nickel ferrites are very helpful for high frequency switching devices.

High performance cobalt-free Cu1.4Mn1.6O4 spinel oxide as an intermediate temperature solid oxide fuel cell cathode

NASA Astrophysics Data System (ADS)

Zhen, Shuying; Sun, Wang; Li, Peiqian; Tang, Guangze; Rooney, David; Sun, Kening; Ma, Xinxin

2016-05-01

In this work Cu1.4Mn1.6O4 (CMO) spinel oxide is prepared and evaluated as a novel cobalt-free cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Single phase CMO powder with cubic structure is identified using XRD. XPS results confirm that mixed Cu+/Cu2+ and Mn3+/Mn4+ couples exist in the CMO sample, and a maximum conductivity of 78 S cm-1 is achieved at 800 °C. Meanwhile, CMO oxide shows good thermal and chemical compatibility with a 10 mol% Sc2O3 stabilized ZrO2 (ScSZ) electrolyte material. Impedance spectroscopy measurements reveals that CMO exhibits a low polarization resistance of 0.143 Ω cm2 at 800 °C. Furthermore, a Ni-ScSZ/ScSZ/CMO single cell demonstrates a maximum power density of 1076 mW cm-2 at 800 °C under H2 (3% H2O) as the fuel and ambient air as the oxidant. These results indicate that Cu1.4Mn1.6O4 is a superior and promising cathode material for IT-SOFCs.

Micro-XANES Measurements on Experimental Spinels and the Oxidation State of Vanadium in Spinel-Melt Pairs

NASA Technical Reports Server (NTRS)

Righter, K.; Sutton, S.R.; Newville, M.

2004-01-01

Spinel can be a significant host phase for V as well as other transition metals such as Ni and Co. However, vanadium has multiple oxidation states V(2+), V(3+), V(4+) or V(5+) at oxygen fugacities relevant to natural systems. We do know that D(V) spinel/melt is correlated with V and TiO2 content and fO2, but the uncertainty of the oxidation state under the range of natural conditions has made elusive a thorough understanding of D(V) spinel/melt. For example, V(3+) is likely to be stable in spinels, based on exchange with Al in experiments in the CaO-MgO-Al2O3-SiO2 system. On the other hand, it has been argued that V(4+) will be stable across the range of natural oxygen fugacities in nature. In order to gain a better understanding of D(V) spinel/melt we have equilibrated spinel-melt pairs at controlled oxygen fugacities, between HM to NNO, where V is present in the spinel at natural levels (approx. 300 ppm V). These spinel-melt pairs were analyzed using micro-XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with spinel compositional data (Ti, V content) and oxygen fugacity, to unravel the effects of these variables on D(V) spinel/melt.

Microwave hydrothermal-assisted preparation of novel spinel-NiFe2O4/natural mineral composites as microwave catalysts for degradation of aquatic organic pollutants.

PubMed

Shen, Manli; Fu, Lu; Tang, Jianhua; Liu, Mingyu; Song, Youtao; Tian, Fangyuan; Zhao, Zhigang; Zhang, Zhaohong; Dionysiou, Dionysios D

2018-05-15

In this study, novel spinel-NiFe 2 O 4 /natural mineral (sepiolite, diatomite and kaolinite) composites were developed using microwave (MW) hydrothermal method, and applied in MW-induced catalytic degradation (NiFe 2 O 4 /natural mineral/MW) of organic pollutants such as sodium dodecyl benzene sulfonate (SDBS), azo fuchsine (AF), methyl parathion (MP), and crystal violet (CVL) in solution. Catalytic activities of three NiFe 2 O 4 /natural mineral composites were compared. The effects of material synthesis process parameters such as molar ratios of NiFe 2 O 4 and natural mineral, and pH of precursor solutions for synthesizing catalysts, and degradation parameters such as MW irradiation time and catalyst reuse cycles were also investigated. The principle on NiFe 2 O 4 /natural mineral/MW degradation was provided. The results reveal that organic pollutants in wastewater can be removed completely using NiFe 2 O 4 /natural mineral/MW within minutes. NiFe 2 O 4 /sepiolite shows higher catalytic activity than the others. The calculated degradation rate constants are 1.865, 0.672, 0.472, and 0.329 min -1 for SDBS, AF, MP, and CVL, respectively, using NiFe 2 O 4 /sepiolite/MW system. The performance of NiFe 2 O 4 /natural mineral can be maintained for three reuse cycles. Active species OH, O 2 - , and h + play main roles in NiFe 2 O 4 /sepiolite/MW degradation. Hence, NiFe 2 O 4 /sepiolite/MW technology with rapid and cost-effective degradation, magnetic separation, and no secondary pollution, demonstrates to be promising in treating organic contaminants in wastewater. Copyright © 2018 Elsevier B.V. All rights reserved.

(Mn,Co)(3)O-4 Spinel Coatings on Ferritic Stainless Steels for SOFC Interconnect Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Z Gary; Xia, Gordon; Li, Xiaohong S.

(Mn,Co)3O4 spinel with a nominal composition of Mn1.5Co1.5O4 demonstrates excellent electrical conductivity, satisfactory thermal and structural stability, as well as good thermal expansion match to ferritic stainless steel interconnects. A slurry-coating technique was developed for fabricating the spinel coatings onto the steel interconnects. Thermally grown layers of Mn1.5Co1.5O4 not only significantly decreased the contact resistance between a LSF cathode and stainless steel interconnect, but also acted as a mass barrier to inhibit scale growth on the stainless steel and to prevent Cr outward migration through the coating. The level of improvement in electrical performance and oxidation resistance (i.e. the scalemore » growth rate) was dependent on the ferritic substrate composition. For E-brite and Crofer22 APU, with a relatively high Cr concentration (27wt% and 23%, respectively) and negligible Si, the reduction of contact ASR and scale growth on the ferritic substrates was significant. In comparison, limited improvement was achieved by application of the Mn1.5Co1.5O4 spinel coating on AISI430, which contains only 17% Cr and a higher amount of residual Si.« less

Spinel Co3O4 nanomaterials for efficient and stable large area carbon-based printed perovskite solar cells.

PubMed

Bashir, Amna; Shukla, Sudhanshu; Lew, Jia Haur; Shukla, Shashwat; Bruno, Annalisa; Gupta, Disha; Baikie, Tom; Patidar, Rahul; Akhter, Zareen; Priyadarshi, Anish; Mathews, Nripan; Mhaisalkar, Subodh G

2018-02-01

Carbon based perovskite solar cells (PSCs) are fabricated through easily scalable screen printing techniques, using abundant and cheap carbon to replace the hole transport material (HTM) and the gold electrode further reduces costs, and carbon acts as a moisture repellent that helps in maintaining the stability of the underlying perovskite active layer. An inorganic interlayer of spinel cobaltite oxides (Co 3 O 4 ) can greatly enhance the carbon based PSC performance by suppressing charge recombination and extracting holes efficiently. The main focus of this research work is to investigate the effectiveness of Co 3 O 4 spinel oxide as the hole transporting interlayer for carbon based perovskite solar cells (PSCs). In these types of PSCs, the power conversion efficiency (PCE) is restricted by the charge carrier transport and recombination processes at the carbon-perovskite interface. The spinel Co 3 O 4 nanoparticles are synthesized using the chemical precipitation method, and characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and UV-Vis spectroscopy. A screen printed thin layer of p-type inorganic spinel Co 3 O 4 in carbon PSCs provides a better-energy level matching, superior efficiency, and stability. Compared to standard carbon PSCs (PCE of 11.25%) an improved PCE of 13.27% with long-term stability, up to 2500 hours under ambient conditions, is achieved. Finally, the fabrication of a monolithic perovskite module is demonstrated, having an active area of 70 cm 2 and showing a power conversion efficiency of >11% with virtually no hysteresis. This indicates that Co 3 O 4 is a promising interlayer for efficient and stable large area carbon PSCs.

Nanosized LiM YMn 2- YO 4 (M = Cr, Co and Ni) spinels synthesized by a sucrose-aided combustion method . Structural characterization and electrochemical properties

NASA Astrophysics Data System (ADS)

Amarilla, J. M.; Rojas, R. M.; Pico, F.; Pascual, L.; Petrov, K.; Kovacheva, D.; Lazarraga, M. G.; Lejona, I.; Rojo, J. M.

Spinels of composition LiM YMn 2- YO 4, M = Cr 3+, Co 3+, or Ni 2+, Y = 0.1 and 1 for the Cr and Co dopants, Y = 0.05 and 0.5 for the Ni sample, have been synthesized by a sucrose-aided combustion method. The samples as prepared require of an additional thermal treatment at 700 °C, 1 h to get stoichiometric single-phase spinels. The samples consist of aggregated particles of small size (45-50 nm) as deduced from transmission electron microscopy and X-ray powder diffraction. The electrochemical behaviour of the six spinels as cathodes in lithium cells has been analysed at 5 and 4 V under high current, 1 C rate. At 5 V the discharge capacity of LiNi 0.5Mn 1.5O 4 is higher than the one shown by LiCrMnO 4 and LiCoMnO 4, and it shows an elevated cyclability, i.e. capacity retention of 85.3% after 100 cycles. At 4 V the discharge capacity is similar for LiNi 0.05Mn 1.95O 4, LiCr 0.1Mn 1.9O 4 and LiCo 0.1Mn 1.9O 4, and all the three spinels show similar and very high cyclability, i.e. capacity retention >90% after 100 cycles. The spinels preserve their starting capacity up to currents as high as 2 C rate. The nanometric size of the samples explains the high rate capability of the synthesized spinels.

Graphene-Supported Spinel CuFe2O4 Composites: Novel Adsorbents for Arsenic Removal in Aqueous Media

PubMed Central

La, Duong Duc; Nguyen, Tuan Anh; Jones, Lathe A.; Bhosale, Sheshanath V.

2017-01-01

A graphene nanoplate-supported spinel CuFe2O4 composite (GNPs/CuFe2O4) was successfully synthesized by using a facile thermal decomposition route. Scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), Electron Dispersive Spectroscopy (EDS), X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) were employed to characterize the prepared composite. The arsenic adsorption behavior of the GNPs/CuFe2O4 composite was investigated by carrying out batch experiments. Both the Langmuir and Freundlich models were employed to describe the adsorption isotherm, where the sorption kinetics of arsenic adsorption by the composite were found to be pseudo-second order. The selectivity of the adsorbent toward arsenic over common metal ions in water was also demonstrated. Furthermore, the reusability and regeneration of the adsorbent were investigated by an assembled column filter test. The GNPs/CuFe2O4 composite exhibited significant, fast adsorption of arsenic over a wide range of solution pHs with exceptional durability, selectivity, and recyclability, which could make this composite a very promising candidate for effective removal of arsenic from aqueous solution. The highly sensitive adsorption of the material toward arsenic could be potentially employed for arsenic sensing. PMID:28587257

Thermal and composition driven phase transition in the co-operative Jahn-Teller distorted Zn1-xCuxCr2O4 spinel

NASA Astrophysics Data System (ADS)

Saraswathy, S.; Kalavathi, S.; Rajamadhavan, R.; Asuvathraman, R.

2018-04-01

Phase pure poly crystalline powder samples of spinel compounds with formula Zn1-xCuxCr2O4 have been synthesized. It is found that for a critical concentration of Cu with x=0.58 cubic structure of the parent ZnCr2O4 transforms into a tetragonal structure. The well-known co-operative Jahn-Teller effect induces the structural transition and the observed variation of lattice parameters as a function of Cu substitution displays the role of strain. Thermally driven destruction of the co-operative Jahn-Teller effect and the resultant reverting back to cubic structure is observed to complete at 850 K and 373 K in pristine CuCr2O4 and Zn0.4Cu0.6Cr2O4. A first order transition observed for Zn0.4Cu0.6Cr2O4 is at variance with the continuous transition observed in the literature for Mg0.46Cu0.54Cr2O4.

Spin canting and magnetic transition in NixZn1-xFe2O4 (x=0.0, 0.5 and 1.0) nanoparticles

NASA Astrophysics Data System (ADS)

Rani, Stuti; Raghav, Dharmendra Singh; Yadav, Prashant; Varma, G. D.

2018-04-01

Nanoparticles of NixZn1-xFe2O4(x=0.0, 0.5 and 1.0) have been synthesized via co-precipitation method and studied thestructural and magnetic properties. Rietveld refinement of X ray diffraction data of as synthesized samples revealthat the samples have mixed spinel structure with space group Fd-3m. The lattice parameter of the samples decreases as doping concentration of Ni ions increases. Magnetic measurements show paramagnetic to ferrimagnetic transition at room temperature on Ni doping in ZnFe2O4 nanoparticles. The magnetic measurements also show spin canting in samples possibly due to their nanocrystalline nature. The spin canting angles have been calculated with the help of Yafet-Kittel (Y-K) model. Furthermore, the Law of approach (LA) fitting of M-H curves indicates that the samples are highly anisotropicin nature. The Arrot plots of as synthesized samples also indicate the paramagnetic to ferrimagnetic transition. The correlation between the structural and observed magnetic properties of NixZn1-xFe2O4(x=0.0, 0.5 and 1.0) nanocrystals will be described and discussed in this paper.

Cation-Deficient Spinel ZnMn2O4 Cathode in Zn(CF3SO3)2 Electrolyte for Rechargeable Aqueous Zn-Ion Battery.

PubMed

Zhang, Ning; Cheng, Fangyi; Liu, Yongchang; Zhao, Qing; Lei, Kaixiang; Chen, Chengcheng; Liu, Xiaosong; Chen, Jun

2016-10-05

Rechargeable aqueous Zn-ion batteries are attractive cheap, safe and green energy storage technologies but are bottlenecked by limitation in high-capacity cathode and compatible electrolyte to achieve satisfactory cyclability. Here we report the application of nonstoichiometric ZnMn 2 O 4 /carbon composite as a new Zn-insertion cathode material in aqueous Zn(CF 3 SO 3 ) 2 electrolyte. In 3 M Zn(CF 3 SO 3 ) 2 solution that enables ∼100% Zn plating/stripping efficiency with long-term stability and suppresses Mn dissolution, the spinel/carbon hybrid exhibits a reversible capacity of 150 mAh g -1 and a capacity retention of 94% over 500 cycles at a high rate of 500 mA g -1 . The remarkable electrode performance results from the facile charge transfer and Zn insertion in the structurally robust spinel featuring small particle size and abundant cation vacancies, as evidenced by combined electrochemical measurements, XRD, Raman, synchrotron X-ray absorption spectroscopy, FTIR, and NMR analysis. The results would enlighten and promote the use of cation-defective spinel compounds and trifluoromethanesulfonic electrolyte to develop high-performance rechargeable zinc batteries.

Topotactic Reactions, Structural Studies, and Lithium Intercalation in Cation-Deficient Spinels with Formula Close to Li 2Mn 4O 9

NASA Astrophysics Data System (ADS)

Palos, A. Ibarra; Anne, M.; Strobel, P.

2001-08-01

The composition Li2Mn4O9, reported as a spinel oxide containing vacancies on both tetrahedral and octahedral sites [A. de Kock et al., Mater. Res. Bull. 25, 657 (1990)], was approached using three different preparation routes: low-temperature solid state reaction (A), chemical delithiation (B), and electrochemical delithiation (C). Rietveld refinements from neutron diffraction data confirmed the double-vacancy scheme proposed previously for product A, but with more tetrahedral and fewer octahedral vacancies than in the ideal Li2Mn4O9 formula. Low-temperature solid state reactions systematically result in broad reflections. Sample B, which was obtained topotactically, exhibits much narrower reflections. But chemical analyses, thermogravimetry, and neutron diffraction show that the acid treatment introduces significant amounts of protons, resulting in a formula close to Li0.92HMn4O9. Samples A and B were cycled electrochemically in lithium cells at 3 V with better stability than LiMn2O4, probably due to their higher initial manganese oxidation state. No separate electrochemical step linked to the filling of vacancies is observed in A, whereas B gives an additional redox step ca. 200 mV above the main plateau. This feature is not observed on compounds A or C; it is reversible, and seems to be a specific property of this spinel with a low initial cell parameter (8.09 Å). Sample A2 with double cation vacancies is especially stable on cycling at 3 V, and shows a very small volume variation on lithium intercalation.

Spinel CuCo2O4 nanoparticles supported on N-doped reduced graphene oxide: a highly active and stable hybrid electrocatalyst for the oxygen reduction reaction.

PubMed

Ning, Rui; Tian, Jingqi; Asiri, Abdullah M; Qusti, Abdullah H; Al-Youbi, Abdulrahman O; Sun, Xuping

2013-10-29

In this Letter, for the first time, we demonstrated the preparation of a highly efficient electrocatalyst, spinel CuCo2O4 nanoparticles supported on N-doped reduced graphene oxide (CuCo2O4/N-rGO), for an oxygen reduction reaction (ORR) under alkaline media. The hybrid exhibits higher ORR catalytic activity than CuCo2O4 or N-rGO alone, the physical mixture of CuCo2O4 nanoparticles and N-rGO, and Co3O4/N-rGO. Moreover, such a hybrid affords superior durability to the commercial Pt/C catalyst.

New structure of high-pressure body-centered orthorhombic Fe 2SiO 4

DOE PAGES

Yamanaka, Takamitsu; Kyono, Atsushi; Nakamoto, Yuki; ...

2015-08-01

Here, a structural change in Fe 2SiO 4 spinel and the structure of a new high pressure phase are determined by Rietveld 26 profile fitting of x-ray diffraction data up to 64 GPa at ambient temperature. The compression curve of the spinel is discontinuous at approximately 20 GPa. Fe Kβ x-ray emission measurements at high pressure show that the transition from a high spin (HS) to an intermediate spin (IS) state begins at 17 GPa in the spinel phase. The IS electronic state is gradually enhanced with pressure, which results in an isostructural phase transition. A transition from the cubic spinel structure to a body centered orthorhombic phase (I-Fe 2SiO 4) with space group Imma and Z=4 was observed at approximately 34 GPa. The structure of I-Fe 2SiO 4 has two crystallographically distinct FeO 6 octahedra, which are arranged in layers parallel to (101) and (011) and are very similar to the layers of FeO 6 octahedra that constitute the spinel structure. Silicon also exists in six-fold coordination in I-Fe 2SiO 4. The transformation to the new high-pressure phase is reversible under decompression at ambient temperature. A Martensitic transformation of each slab of the spinel structure with translation vector [more » $$\\vec{1/8}$$ $$\\vec{1/8}$$ $$\\vec{1/8}$$] generates the I-Fe 2SiO 4 structure. Laser heating of I-Fe 2SiO 4 at 1500 K results in a decomposition of the material to rhombohedral FeO and SiO 2 stishovite.« less

Morphology and structure features of ZnAl{sub 2}O{sub 4} spinel nanoparticles prepared by matrix-isolation-assisted calcination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Xuelian, E-mail: xueliandu@126.com; Li, Liqiang; Zhang, Wenxing

2015-01-15

Graphical abstract: The substrate ZnO as the isolation medium is effective in preventing the sintering and agglomeration of ZnAl{sub 2}O{sub 4} nanoparticles, and it also prevents their contamination. High purity, well-dispersed, and single-crystal ZnAl{sub 2}O{sub 4} nanoparticles with 3.72 eV band gap were obtained. - Abstract: Well-dispersed ZnAl{sub 2}O{sub 4} spinel nanoparticles with an average crystalline size of 25.7 nm were synthesized successfully and easily by polymer-network and matrix-isolation-assisted calcination. The product microstructure and features were investigated by X-ray diffractometry, thermogravimetric and differential thermal analysis, Fourier transform-infrared spectroscopy, N{sub 2} adsorption–desorption isotherms, and energy dispersive X-ray spectra. The morphology andmore » optical performance of the as-prepared ZnAl{sub 2}O{sub 4} nanoparticles were characterized by scanning electron microscope, transmission electron microscopy, and photoluminescence spectrometer. Experimental results indicate that excess ZnO acted as the isolation medium is effective in preventing the sintering and agglomeration of ZnAl{sub 2}O{sub 4} nanoparticles, and it also prevents their contamination. Then, high purity and well-dispersed ZnAl{sub 2}O{sub 4} nanoparticles with single-crystal structure were obtained.« less

Evaluation of IKTS Transparent Polycrystalline Magnesium Aluminate Spinel (MgAl2O4) for Armor and Infrared Dome/Window Applications

DTIC Science & Technology

2013-03-01

interacted with (15). 4.3.3 Experimental Procedure Two MgAl2O4 spinel samples with nominal 0.6- and 1.6-μm mean grain sizes were tested using advanced...unable to make specific quantitative predictions at this time. Due to the nature of the experimental process, this technique is suitable only for...Information From Spherical Indentation; ARL-TR-4229; U.S. Army Research Laboratory: Aberdeen Proving Ground, MD, 2007. 24. ASTM E112. Standard Test

Evolution of magnetization in epitaxial Zn1‑x Fe x O z thin films (0  ⩽  x  ⩽  0.66) grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Brachwitz, Kerstin; Böntgen, Tammo; Lenzner, Jörg; Ghosh, Kartik; Lorenz, Michael; Grundmann, Marius

2018-06-01

We demonstrate the development of phases in Zn1‑xFexOz thin films with 0  ⩽  x  ⩽  0.66, i.e. the end point phases are semiconducting ZnO for x  =  0, and ferrimagnetic zinc ferrite (ZnFe2O4) for x  =  0.66. With increasing x, the x-ray scattering intensity of the structural ZnO wurtzite phase decreases while that of the (1 1 1)-oriented ZnFe2O4 spinel phase increases. For x  >  0.4, single phase spinel layers are obtained. The enhanced formation of the spinel phase is supported by deviations from the usually expected stoichiometric transfer of chemical composition from target to thin film in pulsed laser deposition. We find that all mixed film samples show an excess of iron in relation to the target composition, independent of the growth pressure. The saturation magnetization of the samples increases with x for 0  ⩽  x  ⩽  0.66 and shows a ferrimagnetic behavior. The temperature dependence of magnetization points to Curie temperatures well above 400 K for x  ⩾  0.4. With that, the precise tuning of magnetic performance of the thin layers is possible, yielding a design degree of freedom for application-related requirements.

New structure of high-pressure body-centered orthorhombic Fe 2 SiO 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamanaka, Takamitsu; Kyono, Atsushi; Nakamoto, Yuki

2015-08-01

A structural change in Fe2SiO4 spinel (ringwoodite) has been found by synchrotron powder diffraction study and the structure of a new high-pressure phase was determined by Monte-Carlo simulation method and Rietveld profile fitting of X-ray diffraction data up to 64 GPa at ambient temperature. A transition from the cubic spinel structure to a body centered orthorhombic phase (I-Fe2SiO4) with space group Imma and Z = 4 was observed at approximately 34 GPa. The structure of I-Fe2SiO4 has two crystallographically independent FeO6 octahedra. Iron resides in two different sites of sixfold coordination: Fe1 and Fe2, which are arranged in layers parallelmore » to (101) and (011) and are very similar to the layers of FeO6 octahedra in the spinel structure. Silicon is located in the sixfold coordination in I-Fe2SiO4. The transformation to the new high-pressure phase is reversible under decompression at ambient temperature. A martensitic transformation of each slab of the spinel structure with translation vector Embedded Image generates the I-Fe2SiO4 structure. Laser heating of I-Fe2SiO4 at 1500 K results in a decomposition of the material to rhombohedral FeO and SiO2 stishovite. FeKβ X-ray emission measurements at high pressure up to 65 GPa show that the transition from a high spin (HS) to an intermediate spin (IS) state begins at 17 GPa in the spinel phase. The IS electron spin state is gradually enhanced with pressure. The Fe2+ ion at the octahedral site changes the ion radius under compression at the low spin, which results in the changes of the lattice parameter and the deformation of the octahedra of the spinel structure. The compression curve of the lattice parameter of the spinel is discontinuous at ~20 GPa. The spin transition induces an isostructural change.« less

The effect of bismuth on the structure, magnetic and electric properties of Co2MnO4 spinel multiferroic

NASA Astrophysics Data System (ADS)

Chouaya, H.; Smari, M.; Walha, I.; Dhahri, E.; Graça, M. P. F.; Valente, M. A.

2018-04-01

Mixed Co2Mn1-xBixO4 (x = 0, x = 0.05 and x = 0.1) samples were prepared by the sol-gel method using the citric acid route and characterized by various techniques. The X-ray diffraction (XRD) and Raman spectroscopic analyses confirmed the formation of inverse spinel cubic structure with Fd 3 ‾ m space group. The introduction of Bismuth (Bi) into Co2MnO4 did not modify the ferrimagnetic character of the parent compound Co2MnO4, whereas the field-cooled magnetizations MFC and the Curie temperature Tc decreased when increasing the Bi content. The electrical properties showed an activation energy (Ea) increase caused by the decrease of the double-exchange interaction following the substitution of Mn3+ by Bi3+. Eventually, the temperature coefficient of resistance (TCR) shows significant values for all samples can be investigated also as good candidates for bolometer applications.

Liquid-solid equilibria involving spinel, ilmenite, and ferropseudobrookite in the system 'FeO'-Al2O3-TiO2 in contact with metallic iron

NASA Technical Reports Server (NTRS)

Schreifels, W. A.; Muan, A.

1975-01-01

Phase relations in the liquidus temperature region of the system 'FeO'-Al2O3-TiO2 in contact with metallic iron, at a total pressure below 1 atm, have been determined by the quenching technique. Four invariant points have been located, with phase assemblages and temperatures as follows; wuestite, ulvoespinel, nercynite and liquid, 1306 C; ulvoespinel, ilmenite, ferropseudobrookite and liquid, 1340 C; ulvoespinel, hercynite, ferropseudobrookite and liquid, 1367 C; hercynite, ferropseudobrookite, corundum and liquid, 1465 C. The data obtained confirm the presence of a miscibility gap between titanate and aluminate spinels, and provide quantitative data for the effect of Al2O3 on mutual stability relations among spinel, ilmenite, and ferropseudobrookite phases in the presence of liquid at high temperatures and strongly reducing conditions. It is shown that Al2O3 has a strong stabilizing effect on the phase assemblage ferropseudobrookite and spinel relative to ilmenite.

Fabrication of spinel Li4-xTi5O12 via ion exchange for high-rate lithium-ion batteries

NASA Astrophysics Data System (ADS)

Cheng, Chongling; Liu, Hongjiang; Li, Jun; Xue, Xin; Cao, Hui; Wang, Dayang; Shi, Liyi

2015-06-01

The present work demonstrates that lithium ions can be stepwise substituted by protons from spinel Li4Ti5O12 crystalline particles though simple ion-exchange in aqueous HCl solution with the aid of heat treatment. This enables us to continuously tune the Li-to-Ti stoichiometric ratios from 0.80 to 0.59, 0.41, 0.21, 0.15, and 0.09, thus transforming Li4Ti5O12 to Li4-xTi5O12 nanocrystals. The resulting nanocrystals maintain the spinel crystal structure when x becomes smaller than 3. Among as-prepared the Li4-xTi5O12 crystalline particles, Li1Ti5O12 shows the highest capacity of 193 mAh g-1 at 1C and 148 mAh g-1 at 20C, lower current impedance (47 Ω), significantly improved rate capability and fairly long cycle life. This excellent electrochemical performance makes spinel Li4-xTi5O12 particles as a promising anode candidate for lithium ion batteries superior.

Pressure-induced amorphization of charge ordered spinel AlV{sub 2}O{sub 4} at low temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malavi, Pallavi S., E-mail: malavips@barc.gov.in; Karmakar, S., E-mail: malavips@barc.gov.in; Sharma, S. M.

2014-04-24

Structural properties of charge ordered spinel AlV{sub 2}O{sub 4} have been investigated under high pressure at low temperature (80K) by synchrotron based x-ray diffraction measurements. It is observed that upon increasing pressure the structure becomes progressively disordered due to the distortion of the AlO{sub 4} tetrahedral unit and undergoes amorphization above ∼12 GPa. While releasing pressure, the rhombohedral phase is only partially recovered at a much lower pressure (below 5 GPa). Within the stability of the rhombohedral phase, the distortion in the vanadium heptamer increases monotonically with pressure, suggesting enhanced charge ordering. This result is in sharp contrast with themore » recent observation of pressure-induced frustration in the charge ordered state leading to structural transition to the cubic phase at room temperature [JPCM 25, 292201, 2013].« less

Spin Glass Order by Antisite Disorder in the Highly Frustrated Spinel Oxide CoAl2O4

NASA Astrophysics Data System (ADS)

Hanashima, Kentaro; Kodama, Yuta; Akahoshi, Daisuke; Kanadani, Chikahide; Saito, Toshiaki

2013-02-01

We experimentally studied the effects of the intersite mixing disorder between the A-site and B-site on the magnetic properties of the highly frustrated spinel oxide CoAl2O4 by measuring DC and AC susceptibilities. We controlled the inversion parameter η systematically from 0.0467 to 0.153 for (Co1-η Alη)[Al2-ηCoη]O4 by changing the heat treatment condition of the sample preparation. For η≤ 0.0643, no magnetic transition is observed down to 2 K, indicating a spin liquid (SL) regime for η≤ 0.0643, whereas for η≥ 0.101, a spin glass (SG) transition emerges at about Tg = 4.5 K, which is almost independent of η. In addition, the coefficient of the H--Tg relation is fairly large compared with that of a conventional SG. Our results suggest that some degrees of additional exchange randomness and local distortion by the quenched antisite disorder lead to degeneracy breaking in the SL state and induce SG order.

Mg1-xZnxFe2O4 nanoparticles: Interplay between cation distribution and magnetic properties

NASA Astrophysics Data System (ADS)

Raghuvanshi, S.; Mazaleyrat, F.; Kane, S. N.

2018-04-01

Correlation between cationic distribution, magnetic properties of Mg1-xZnxFe2O4 (0.0 ≤ x ≤ 1.0) ferrite is demonstrated, hardly shown in literature. X-ray diffraction (XRD) confirms the formation of cubic spinel nano ferrites with grain diameter between 40.8 to 55.4 nm. Energy dispersive spectroscopy (EDS) confirms close agreement of Mg/Fe, Zn/Fe molar ratio, presence of all elements (Mg, Zn, Fe, O), formation of estimated ferrite composition. Zn addition (for Mg) shows: i) linear increase of lattice parameter aexp, accounted for replacement of an ion with higher ionic radius (Zn > Mg); ii) presence of higher population of Fe3+ ions on B site, and unusual occurrence of Zn, Mg on A and B site leads to non-equilibrium cation distribution where we observe inverse to mixed structure, and is in contrast to reported literature where inverse to normal transition is reported; iii) effect on A-A, A-B, B-B exchange interactions, affecting coercivity Hc, Ms. A new empirical relation is also obtained showing linear relation between saturation magnetization Ms - inversion parameter δ, oxygen parameter u4 ¯ 3 m. Non-zero Y-K angle (αYK) values implies Y-K type magnetic ordering in the studied samples.

High-pressure transformation in the cobalt spinel ferrites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blasco, J., E-mail: jbc@posta.unizar.es; Subías, G.; García, J.

2015-01-15

We report high pressure angle-dispersive x-ray diffraction measurements on Co{sub x}Fe{sub 3−x}O{sub 4} (x=1, 1.5, 1.75) spinels at room temperature up to 34 GPa. The three samples show a similar structural phase transformation from the cubic spinel structure to an analogous post-spinel phase at around 20 GPa. Spinel and post-spinel phases coexist in a wide pressure range (∼20–25 GPa) and the transformation is irreversible. The equation of state of the three cubic spinel ferrites was determined and our results agree with the data obtained in related oxide spinels showing the role of the pressure-transmitting medium for the accurate determination ofmore » the equation of state. Measurements releasing pressure revealed that the post-spinel phase is stable down to 4 GPa when it decomposes yielding a new phase with poor crystallinity. Later compression does not recover either the spinel or the post-spinel phases. This phase transformation induced by pressure explains the irreversible lost of the ferrimagnetic behavior reported in these spinels. - Graphical abstract: Pressure dependence of the unit cell volume per formula unit for Co{sub 1.5}Fe{sub 1.5}O{sub 4} spinel. Circles and squares stand for spinel and postspinel phases, respectively. Dark (open) symbols: determination upon compression (decompression). - Highlights: • The pressure induces similar phase transformation in Co{sub 3−x}Fe{sub x}O{sub 4} spinels (1≤x≤2). • The postspinel phases decompose after releasing pressure. • The irreversibility of this phase transformation explains the disappearance of magnetism in these spinels after applying pressure. • Accurate equation of state can be obtained up to 10 GPa using an alcohol mixture as pressure transmitting medium. • The equation of state suggests similar elastic properties for these spinels in this composition range.« less

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2 O 4 spinel in oxidizing atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Wei-Zhen; Nie, Lei; Cheng, Yingwen

With the capability of MgAl2O4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement in Pt exposure was achieved when themore » sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. A dynamic stabilization mechanism involving wetting\

Facile synthesis of mesoporous spinel NiCo2O4 nanostructures as highly efficient electrocatalysts for urea electro-oxidation

NASA Astrophysics Data System (ADS)

Ding, Rui; Qi, Li; Jia, Mingjun; Wang, Hongyu

2014-01-01

Mesoporous spinel nickel cobaltite (NiCo2O4) nanostructures were synthesized via a facile chemical deposition method coupled with a simple post-annealing process. The physicochemical properties were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and nitrogen sorption measurements. The electrocatalytic performances were investigated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) tests. The obtained NiCo2O4 materials exhibit typical agglomerate mesoporous nanostructures with a large surface area (190.1 m2 g-1) and high mesopore volume (0.943 cm3 g-1). Remarkably, the NiCo2O4 shows much higher catalytic activity, lower overpotential, better stability and greater tolerance towards urea electro-oxidation compared to those of cobalt oxide (Co3O4) synthesized by the same procedure. The NiCo2O4 electrode delivers a current density of 136 mA cm-2 mg-1 at 0.7 V (vs. Hg/HgO) in 1 M KOH and 0.33 M urea electrolytes accompanied with a desirable stability. The impressive electrocatalytic activity is largely ascribed to the high intrinsic electronic conductivity, superior mesoporous nanostructures and rich surface Ni active species of the NiCo2O4 materials, which can largely boost the interfacial electroactive sites and charge transfer rates for urea electro-oxidation, indicating promising applications in future wastewater remediation, hydrogen production and fuel cells.Mesoporous spinel nickel cobaltite (NiCo2O4) nanostructures were synthesized via a facile chemical deposition method coupled with a simple post-annealing process. The physicochemical properties were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and nitrogen sorption measurements. The electrocatalytic performances were investigated by cyclic voltammetry

Superparamagnetic MFe2O 4 (M = Ni, Co, Zn, Mn) nanoparticles: synthesis, characterization, induction heating and cell viability studies for cancer hyperthermia applications.

PubMed

Sabale, Sandip; Jadhav, Vidhya; Khot, Vishwajeet; Zhu, Xiaoli; Xin, Meiling; Chen, Hongxia

2015-03-01

Superparamagnetic nanoferrites are prepared by simple and one step refluxing in polyol synthesis. The ferrite nanoparticles prepared by this method exhibit particle sizes below 10 nm and high degree of crystallinity. These ferrite nanoparticles are compared by means of their magnetic properties, induction heating and cell viability studies for its application in magnetic fluid hyperthermia. Out of all studied nanoparticles in present work, only ZnFe2O4 and CoFe2O4 MNPs are able to produce threshold hyperthermia temperature. This rise in temperature is discussed in detail in view of their magneto-structural properties. Therefore ZnFe2O4 and CoFe2O4 MNPs with improved stability, magnetic induction heating and cell viability are suitable candidates for magnetic hyperthermia.

Structural, magnetic, elastic, dielectric and electrical properties of hot-press sintered Co1-xZnxFe2O4 (x = 0.0, 0.5) spinel ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Singh Yadav, Raghvendra; Kuřitka, Ivo; Havlica, Jaromir; Hnatko, Miroslav; Alexander, Cigáň; Masilko, Jiri; Kalina, Lukas; Hajdúchová, Miroslava; Rusnak, Jaroslav; Enev, Vojtěch

2018-02-01

In this article, Co1-xZnxFe2O4 (x = 0.0 and 0.5) disc-shaped pellets were formed by hot-press sintering of nanoparticles at temperature 925 °C for 10 min in vacuum atmosphere under 30 MPa mechanical pressure. X-ray diffraction study confirmed the formation of spinel cubic ferrite structure of hot-press sintered spinel ferrite Co1-xZnxFe2O4 (x = 0.0 and 0.5) samples. The scanning electron microscopy image indicated that the growth and densification of smaller ferrite nanoparticles were higher than larger ferrite nanoparticles. Magnetic properties of sintered samples were investigated by the superconducting quantum interface device (SQUID) magnetometer at room temperature. The hot press sintered Co1-xZnxFe2O4 (x = 0.0 and 0.5) pellet samples exhibited magnetic properties dependent on the grain size of spinel ferrite particles. The maximum saturation magnetization 82.47 emu/g was obtained for Co0.5Zn0.5Fe2O4 hot press sintered sample of ball-milled ferrite particles. Further, the impact of grain size and density of sample on hardness, dielectric property and ac conductivity of hot-press sintered samples was investigated. In addition, the longitudinal wave velocity (Vl), transverse wave velocity (Vt), mean elastic wave velocity (Vm), bulk modulus (B), rigidity modulus (G), Young's modulus (E), Poisson ratio (σ) and Debye temperature (θD) were calculated. The elastic moduli of hot press sintered ferrite samples were corrected to zero porosity using Hosselman and Fulrath model.

Magnetic moment directions and distributions of cations in Cr (Co) substituted spinel ferrites Ni{sub 0.7}Fe{sub 2.3}O{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, L. C.; Lang, L. L.; Li, Z. Z.

2015-09-15

Powder samples of the spinel ferrites M{sub x}Ni{sub 0.7−x}Fe{sub 2.3}O{sub 4} (M = Cr, Co and 0.0 ≤ x ≤ 0.3) and Cr{sub x}Ni{sub 0.7}Fe{sub 2.3−x}O{sub 4} (0.0 ≤ x ≤ 0.3) were synthesized using the chemical co-precipitation method. The XRD spectra confirmed that the samples had a single-phase cubic spinel structure. Magnetic measurements showed that the magnetic moments (μ{sub exp}) per formula both at 10 K and 300 K increased with Co substitution, while the values of μ{sub exp} decreased with Cr substitution. Applying the assumption that the magnetic moments of Cr{sup 2+} and Cr{sup 3+} lie antiparallel tomore » those of the divalent and trivalent Fe, Co, and Ni cations in the same sublattice of spinel ferrites, these interesting behaviors could be easily interpreted. The cation distributions of the three series of samples were estimated successfully by fitting the dependences of μ{sub exp}, measured at 10 K, on the doping level x, using a quantum-mechanical potential barrier model earlier proposed by our group. The results obtained for the Cr cation distributions at the (A) and [B] sites are very close to those obtained elsewhere using neutron diffraction.« less

Strong magneto-optical effects in A Cr2O4 (A =Fe,Co ) spinel oxides generated by tetrahedrally coordinated transition metal ions

NASA Astrophysics Data System (ADS)

Kocsis, V.; Bordács, S.; Deisenhofer, J.; Kiss, L. F.; Ohgushi, K.; Kaneko, Y.; Tokura, Y.; Kézsmárki, I.

2018-03-01

Magneto-optical effects have been investigated over the infrared visible spectral range in A Cr2O4 (A =Fe,Co ) spinel oxides with noncollinear spin orders in their ground states. We found large magneto-optical Kerr rotation and ellipticity at the on-site d -d transitions of the A2 + ions located within the charge gap. The magneto-optical Kerr rotation of ϑKerr≈12∘ observed in CoCr2O4 is unprecedentedly large among magnetic semiconductors and points toward the uniqueness of tetrahedrally coordinated Co2 + ions in generating strong magneto-optical response. Criteria of strong magneto-optical effects emerging at on-site d -d transitions of transition metal ions are discussed.

Synthesis and property of spinel porous ZnMn2O4 microspheres

NASA Astrophysics Data System (ADS)

Guo, N.; Wei, X. Q.; Deng, X. L.; Xu, X. J.

2015-11-01

Mesoporous ternary zinc manganese oxides on the Ti sheet substrate are prepared by easy and fast hydrothermal method for the first time. The obtained ZnMn2O4 materials with homogenously distributed pores have been characterized by XRD, SEM and Raman spectra, which show the good crystal phase and particles for improving supercapacitive performance. XRD and SEM images show that the as-prepared samples have good crystallinity, and ZnMn2O4 microsphere has an average diameter of 10 μm. In addition, ZnMn2O4 are also characterized in 2 M KOH solution using three-electrode system. In the work, we study that different substrates (Ti, carbon and nickel foam) have an important effect on the electrochemical performance of the samples. The research of cyclic voltammogram (CV) indicates that the obtained specific capacitance (155 F g-1) values on nickel foam substrate for the ZnMn2O4 microspheres are higher than the values reported for some inexpensive oxides. However, the specific capacitance of all ZnMn2O4 samples has almost no change at two different scan rates which shows good long-term cycling stability. The electrochemical impedance spectroscopy with a small resistance reveals that the as-synthesized samples have good frequency response characteristics. These results indicate that the unique ZnMn2O4 electrode would be a promising electrode for high-performance supercapacitor applications.

The phases and magnetic properties of (Ti, Co), and Cr doped Zn 2Y-type hexagonal ferrite

NASA Astrophysics Data System (ADS)

Chang, Y. H.; Wang, C. C.; Chin, T. S.; Yen, F. S.

1988-04-01

The phases and magnetic properties of Y-type hexagonal ferrite, Ba 2Zn 2 (Ti, Co) yFe 12-2 yO 22 doped with two sets of ions, (Ti, Co) and Cr were studied. In (Ti, Co) - doped ferrites the second phase appears at y ⩾ 0.6, which is a spinel type with the formula of (Zn 1-ηCo η)(Fe 2-δCo δ)O 4. Two resonant peaks are observed in ESR studies at the fields of 1020 and 2430 Oe, respectively, at a frequency of 9.684 GHz. The linewidth increases with the addition of the dopants. In chromium doped ferrite, two phases are identified as the amount of chromium is up to 0.2: spinel type of Zn(Fe 2-ɛCr ɛ)O 4 and orthorhombic BaCr 2O 4. Although the amount of Cr used does not influence the resonant field of the unique peak of the derivative curves from ESR, it eventually enlarges the linewidth.

NiCo2O4-Based Supercapacitor Nanomaterials

PubMed Central

Wang, Chenggang; Zhou, E; He, Weidong; Deng, Xiaolong; Huang, Jinzhao; Ding, Meng; Wei, Xianqi; Liu, Xiaojing; Xu, Xijin

2017-01-01

In recent years, the research on supercapacitors has ushered in an explosive growth, which mainly focuses on seeking nano-/micro-materials with high energy and power densities. Herein, this review will be arranged from three aspects. We will summarize the controllable architectures of spinel NiCo2O4 fabricated by various approaches. Then, we introduce their performances as supercapacitors due to their excellent electrochemical performance, including superior electronic conductivity and electrochemical activity, together with the low cost and environmental friendliness. Finally, the review will be concluded with the perspectives on the future development of spinel NiCo2O4 utilized as the supercapacitor electrodes. PMID:28336875

Morphology and composition of spinel in Pu'u 'O'o lava (1996-1998), Kilauea volcano, Hawaii

USGS Publications Warehouse

Roeder, P.L.; Thornber, C.; Poustovetov, Alexei; Grant, A.

2003-01-01

The morphology and composition of spinel in rapidly quenched Pu'u 'O'o vent and lava tube samples are described. These samples contain glass, olivine phenocrysts (3-5 vol.%) and microphenocrysts of spinel (~0.05 vol.%). The spinel surrounded by glass occurs as idiomorphic octahedra 5-50 μm in diameter and as chains of octahedra that are oriented with respect to each other. Spinel enclosed by olivine phenocrysts is sometimes rounded and does not generally form chains. The temperature before quenching was calculated from the MgO content of the glass and ranges from 1150oC to 1180oC. The oxygen fugacity before quenching was calculated by two independent methods and the log f O2 ranged from -9.2 to -9.9 (delta QFM=-1). The spinel in the Pu'u'O'o samples has a narrow range in composition with Cr/(Cr+Al)=0.61 to 0.73 and Fe2+/(Fe2++Mg) =0.46 to 0.56. The lower the calculated temperature for the samples, the higher the average Fe2+/(Fe2++Mg), Fe3+ and Ti in the spinel. Most zoned spinel crystals decrease in Cr/(Cr+Al) from core to rim and, in the chains, the Cr/(Cr+Al) is greater in the core of larger crystals than in the core of smaller crystals. The occurrence of chains and hopper crystals and the presence of Cr/(Cr+Al) zoning from core to rim of the spinel suggest diffusion-controlled growth of the crystals. Some of the spinel crystals may have grown rapidly under the turbulent conditions of the summit reservoir and in the flowing lava, and the crystals may have remained in suspension for a considerable period. The rapid growth may have caused very local (μm) gradients of Cr in the melt ahead of the spinel crystal faces. The crystals seem to have retained the Cr/(Cr+Al) ratio that developed during the original growth of the crystal, but the Fe2+/(Fe2++Mg) ratio may have equilibrated fairly rapidly with the changing melt composition due to olivine crystallization. Six of the samples were collected on the same day at various locations along a 10-km lava tube and the

Computational Investigation of Technetium(IV) Incorporation into Inverse Spinels: Magnetite (Fe 3 O 4 ) and Trevorite (NiFe 2 O 4 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Frances N.; Um, Wooyong; Taylor, Christopher D.

2016-05-17

Iron oxides and oxyhydroxides play an important role in minimizing the mobility of redox-sensitive elements in engineered and natural environments. For the radionuclide technetium-99 (Tc), these phases hold promise as primary hosts for increasing Tc loading into glass waste form matrices, or as secondary sinks during the long-term storage of nuclear materials. Recent experiments show that the inverse spinel, magnetite [Fe(II)Fe(III)2O4], can incorporate Tc(IV) into its octahedral sub-lattice, and in that same class of materials, trevorite [Ni(II)Fe(III)2O4] is also being investigated for its ability to host Tc(IV). However, questions remain regarding the most energetically favorable charge-compensation mechanism for Tc(IV) incorporationmore » in each structure, which will affect Tc behavior under changing waste processing or storage conditions. Here, quantum-mechanical methods were used to evaluate incorporation energies and optimized lattice bonding environments for three different, charge-balanced Tc(IV) incorporation mechanisms in magnetite and trevorite. In both cases, the removal of two octahedral Fe(II) or Ni(II) ions upon the addition of Tc(IV) to an octahedral site is the most stable mechanism, relative to the creation of octahedral Fe(III) defects or increasing octahedral Fe(II) content. Following hydration-energy corrections, Tc(IV) incorporation into magnetite is energetically favorable while an energy barrier exists for trevorite.« less

Thermoelectric Properties of Variants of Cu4Mn2Te4 with Spinel-Related Structure.

PubMed

Guo, Quansheng; Vaney, Jean-Baptiste; Virtudazo, Raymond; Minami, Ryunosuke; Michiue, Yuichi; Yamabe-Mitarai, Yoko; Mori, Takao

2018-05-07

Thermoelectric properties of Cu 4 Mn 2 Te 4 , which is antiferromagnetic with a Néel temperature T N = 50 K and crystallizes in a spinel-related structure, have been investigated comprehensively here. The phase transition occurring at temperatures 463 and 723 K is studied by high-temperature X-ray diffraction (XRD) and differential scanning calorimetry (DSC), and its effect on thermoelectric properties is examined. Hypothetically Cu 4 Mn 2 Te 4 is semiconducting according to the formula (Cu + ) 4 (Mn 2+ ) 2 (Te 2- ) 4 , while experimentally it shows p-type metallic conduction behavior, exhibiting electrical conductivity σ = 2500 Ω -1 cm -1 and Seebeck coefficient α = 20 μV K -1 at 325 K. Herein, we show that the carrier concentration and thus the thermoelectric transport properties could be further optimized through adding electron donors such as excess Mn. Discussions are made on the physical parameters contributing to the low thermal conductivity, including Debye temperature, speed of sound, and the Grüneisen parameter. As a result of simultaneously boosted power factor and reduced thermal conductivity, a moderately high zT = 0.65 at 680 K is obtained in an excess Mn\\In co-added sample, amounting to 5 times that of the pristine Cu 4 Mn 2 Te 4 . This value ( zT = 0.65) is the best result ever reported for spinel and spinel-related chalcogenides.

Crystallographic origin of cycle decay of the high-voltage LiNi0.5Mn1.5O4 spinel lithium-ion battery electrode.

PubMed

Pang, Wei Kong; Lu, Cheng-Zhang; Liu, Chia-Erh; Peterson, Vanessa K; Lin, Hsiu-Fen; Liao, Shih-Chieh; Chen, Jin-Ming

2016-06-29

High-voltage spinel LiNi0.5Mn1.5O4 (LNMO) is considered a potential high-power-density positive electrode for lithium-ion batteries, however, it suffers from capacity decay after extended charge-discharge cycling, severely hindering commercial application. Capacity fade is thought to occur through the significant volume change of the LNMO electrode occurring on cycling, and in this work we use operando neutron powder diffraction to compare the structural evolution of the LNMO electrode in an as-assembled 18650-type battery containing a Li4Ti5O12 negative electrode with that in an identical battery following 1000 cycles at high-current. We reveal that the capacity reduction in the battery post cycling is directly proportional to the reduction in the maximum change of the LNMO lattice parameter during its evolution. This is correlated to a corresponding reduction in the MnO6 octahedral distortion in the spinel structure in the cycled battery. Further, we find that the rate of lattice evolution, which reflects the rate of lithium insertion and removal, is ∼9 and ∼10% slower in the cycled than in the as-assembled battery during the Ni(2+)/Ni(3+) and Ni(3+)/Ni(4+) transitions, respectively.

Synthetic and natural chromium-bearing spinels: an optical spectroscopy study

NASA Astrophysics Data System (ADS)

Taran, M. N.; Parisi, F.; Lenaz, D.; Vishnevskyy, A. A.

2014-09-01

Four samples of synthetic chromium-bearing spinels of (Mg, Fe2+)(Cr, Fe3+)2O4 composition and four samples of natural spinels of predominantly (Mg, Fe2+)(Al, Cr)2O4 composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr2O4 spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr3+ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed 4 A 2 g → 4 T 2 g and 4 A 2 g → 4 T 1 g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spinels is related to trigonal distortion of the octahedral site in the spinel structure. A small, if any, splitting of the U-band can only be resolved at curve-fitting analysis. In all synthetic high-chromium spinels, a couple of relatively narrow and weak bands of the spin-allowed transitions 4 A 2 g → 2 E g and 4 A 2 g → 2 T 1 g of Cr3+, intensified by exchange-coupled interaction between Cr3+ and Fe3+ at neighboring octahedral sites of the structure, appear at ~14,400 and ~15,100 cm-1. A vague broad band in the range from ca. 15,000 to 12,000 cm-1 in synthetic spinels is tentatively attributed to IVCr2+ + VICr3+ → IVCr3+ + VICr2+ intervalence charge-transfer transition. Iron, mainly as octahedral Fe3+, causes intense high-energy absorption edge in near UV-range (ligand-metal charge-transfer O2- → Fe3+, Fe2+ transitions). As tetrahedral Fe2+, it appears as a strong infrared absorption band at around 4,850 cm-1 caused by electronic spin-allowed 5 E → 5 T 2 transitions of IVFe2+. From the composition shift of the U-band in natural and synthetic MgCr2O4 spinels, the coefficient of local structural relaxation around Cr3+ in spinel MgAl2O4-MgCr2O4 system was evaluated as ~0.56(4), one of the lowest among (Al, Cr)O6 polyhedra known so far. The octahedral modulus

Stress Induced Charge-Ordering Process in LiMn 2O 4

DOE PAGES

Chen, Yan; Yu, Dunji; An, Ke

2016-07-25

In this letter we report the stress-induced Mn charge-ordering process in the LiMn 2O 4 spinel, evidenced by the lattice strain evolutions due to the Jahn–Teller effects. In situ neutron diffraction reveals the initial stage of this process at low stress, indicating the eg electron localization at the preferential Mn sites during the early phase transition as an underlying charge-ordering mechanism in the charge-frustrated LiMn 2O 4. The initial stage of this transition exhibits as a progressive lattice and charge evolution, without showing a first-order behavior.

Facile Synthesis of Carbon-Coated Spinel Li4Ti5O12/Rutile-TiO2 Composites as an Improved Anode Material in Full Lithium-Ion Batteries with LiFePO4@N-Doped Carbon Cathode.

PubMed

Wang, Ping; Zhang, Geng; Cheng, Jian; You, Ya; Li, Yong-Ke; Ding, Cong; Gu, Jiang-Jiang; Zheng, Xin-Sheng; Zhang, Chao-Feng; Cao, Fei-Fei

2017-02-22

The spinel Li 4 Ti 5 O 12 /rutile-TiO 2 @carbon (LTO-RTO@C) composites were fabricated via a hydrothermal method combined with calcination treatment employing glucose as carbon source. The carbon coating layer and the in situ formed rutile-TiO 2 can effectively enhance the electric conductivity and provide quick Li + diffusion pathways for Li 4 Ti 5 O 12 . When used as an anode material for lithium-ion batteries, the rate capability and cycling stability of LTO-RTO@C composites were improved in comparison with those of pure Li 4 Ti 5 O 12 or Li 4 Ti 5 O 12 /rutile-TiO 2 . Moreover, the potential of approximately 1.8 V rechargeable full lithium-ion batteries has been achieved by utilizing an LTO-RTO@C anode and a LiFePO 4 @N-doped carbon cathode.

AC conductivity and dielectric properties of Ti-doped CoCr 1.2Fe 0.8O 4 spinel ferrite

NASA Astrophysics Data System (ADS)

Elkestawy, M. A.; Abdel kader, S.; Amer, M. A.

2010-01-01

Dielectric properties of spinel ferrite samples Co 1+xTi xCr 1.2-2xFe 0.8O 4 (0≤ x≤0.5) were investigated as a function of frequency at different temperatures using a complex impedance technique. Also Cole-Cole diagrams of both permittivity and electric modulus were investigated at different temperatures to have an insight into the electric nature of the studied solids. It has been found that the electric modulus M* is the dominating property clarifying the intrinsic picture of these polycrystalline ferrites. The low conductivity and loss factor values indicate that the studied compositions may be good candidates for practical applications.

Structural and optical properties of NiFe2O4 synthesized via green technology

NASA Astrophysics Data System (ADS)

Patel, S.; Saleem, M.; Varshney, Dinesh

2018-05-01

The nanoparticles of NiFe2O4 were successfully synthesized via green technology using banana peel extract as the catalyst as well as the medium for reaction technique is reported. Analysis of X-ray diffraction spectrum revealed the cubic structure for the prepared spinel ferrite samples crystallized into cubic spinel structure with the space group Fd3m. The Retvield refinement was carried out which obeyed the results obtained from the XRD spectrum analysis of the sample. Raman spectrum provided confirmation for the spinel structure formation and five active Raman modes were observed. Since the optical band-gap value shows inverse response to the crystallite size, The UV-Vis spectrum study confirmed dual but reduced band-gap value.

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

DOE PAGES

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros; ...

2017-12-06

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co

In situ synthesis of water-soluble magnetic graphitic carbon nitride photocatalyst and its synergistic catalytic performance.

PubMed

Zhang, Shouwei; Li, Jiaxing; Zeng, Meiyi; Zhao, Guixia; Xu, Jinzhang; Hu, Wenping; Wang, Xiangke

2013-12-11

Water-soluble magnetic-functionalized graphitic carbon nitride (g-C3N4) composites were synthesized successfully by in situ decorating spinel ZnFe2O4 nanoparticles on g-C3N4 sheets (CN-ZnFe) through a one-step solvothermal method. The magnetic properties of CN-ZnFe can be effectively controlled via tuning the coverage density and the size of ZnFe2O4 nanoparticles. The results indicate that the CN-ZnFe exhibits excellent photocatalytic efficiency for methyl orange (MO) and fast separation from aqueous solution by magnet. Interestingly, the catalytic performance of the CN-ZnFe is strongly dependent on the loading of ZnFe2O4. The optimum activity of 160CN-ZnFe photocatalyst is almost 6.4 and 5.6 times higher than those of individual g-C3N4 and ZnFe2O4 toward MO degradation, respectively. By carefully investigating the influence factors, a possible mechanism is proposed and it is believed that the synergistic effect of g-C3N4 and ZnFe2O4, the smaller particle size, and the high solubility in water contribute to the effective electron-hole pairs separation and excellent photocatalytic efficiency. This work could provide new insights that g-C3N4 sheets function as good support to develop highly efficient g-C3N4-based magnetic photocatalysts in environmental pollution cleanup.

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2O 4 spinel in oxidizing atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Wei -Zhen; Nie, Lei; Cheng, Yingwen

With the capability of MgAl 2O 4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated in this paper, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2 nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement inmore » Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H 2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. Finally, a dynamic stabilization mechanism involving wetting/nucleation seems to be responsible for the evolution of surface compositions upon cyclic oxidizing and reducing thermal treatments.« less

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2O 4 spinel in oxidizing atmosphere

DOE PAGES

Li, Wei -Zhen; Nie, Lei; Cheng, Yingwen; ...

2017-01-13

With the capability of MgAl 2O 4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated in this paper, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2 nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement inmore » Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H 2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. Finally, a dynamic stabilization mechanism involving wetting/nucleation seems to be responsible for the evolution of surface compositions upon cyclic oxidizing and reducing thermal treatments.« less

The structural and Raman spectral studies on Ni0.5Cu0.5Fe2O4 ferrite

NASA Astrophysics Data System (ADS)

Somani, M.; Saleem, M.

2018-05-01

Spinel ferrite Ni0.5Cu0.5Fe2O4 has been successfully prepared via solid state reaction. The crystal structure studies using XRD technique revealed cubic structure of the sample. The XRD spectra was further refined via Retvield Refinement and all the parameters regarding structure were obtained which confirmed cubic structure. The assigned space group was found to be Fd-3m. Particle size was calculated to be 56 nm. The Raman Spectra revealed five active Raman modes which confirmed spinel structure.

Electronic and Electrochemical Properties of Li 1–x Mn 1.5 Ni 0.5 O 4 Spinel Cathodes As a Function of Lithium Content and Cation Ordering

DOE PAGES

Moorhead-Rosenberg, Zach; Huq, Ashfia; Goodenough, John B.; ...

2015-10-05

The electronic and electrochemical properties of the high-voltage spinel LiMn 1.5Ni 0.5O 4 as a function of cation ordering and lithium content have been investigated. Conductivity and activation energy measurements confirm that charge transfer occurs by small polaron hopping and the charge carrier conduction is easier in the Ni:3d band than in the in Mn:3d band. Seebeck coefficient data reveal that the Ni 2+/ 3+. and Ni 3+/ 4+ redox couples are combined in a single,3d band, and that maximum charge carrier concentration occurs where the average Ni oxidation state is close to 3+, corresponding to x = 0.5 inmore » Li Li 1-xMn 1.5Ni 0.5O 4. Furthermore, maximum electronic conductivity is found at x = 0.5, regardless of cation ordering. The thermodynamically stable phases formed during cycling were investigated by recording the X-ray diffraction (XRD) of chemically delithiated powders. The more ordered spinels maintained two separate two-phase regions upon lithium extraction, while the more disordered samples exhibited a solid-solubility region from LiMn 1.5Ni 0.5O 4 to Li 0.5Mn 1.5Ni 0.5O 4. The conductivity and phase-transformation data of four samples with varying degrees of cation ordering were compared to the electrochemical data collected with lithium cells. Only the most ordered spinel showed inferior rate performance, while the sample annealed for a shorter time performed comparable to the unannealed or disordered samples. Our results challenge the most common beliefs about high-voltage spinel: (i) low Mn 3+ content is responsible for poor rate performance and (ii) thermodynamically stable solid-solubility is critical for fast kinetics.« less

Slow dynamics in the geometrically frustrated magnet ZnFe2O4: Universal features of aging phenomena in spin glasses

NASA Astrophysics Data System (ADS)

Mamiya, H.; Tsujii, N.; Terada, N.; Nimori, S.; Kitazawa, H.; Hoshikawa, A.; Ishigaki, T.

2014-07-01

To clarify the universal features of spin glasses, we carefully studied slow dynamics in a geometrically frustrated magnet ZnFe2O4 with slight disorders, regarded as an "unconventional" Heisenberg spin glass, using time-resolved neutron diffractometry and magnetometry. The results indicate that "aging" can be attributed not to growth of the short-range order detected by a diffuse scattering but to aging of a hidden aperiodic correlation, as expected from theories for spin glasses. Concerning aging, peculiar behavior was found; the decay of thermoremanent magnetization is extremely accelerated if the sample is heated/cooled briefly midway through the isothermal slow relaxation. Conversely, magnetization surprisingly increases despite the absence of a magnetic field when the temperature returns after the brief heating/cooling. The behavior can be explained as a destabilization of the aged spin configuration due to the thermal perturbations and subsequent spontaneous restoration of the original spin configuration after the destabilization. Whereas such destabilization and restoration do not occur during freezing into numerous metastable states in a fixed energy landscape, these are possible in an energy landscape with a temperature-sensitive funnel-like structure. These features, consistent with the ghost domain scenario of the droplet picture, are the same as for conventional Heisenberg spin glasses such as dilute magnetic alloys and dilute magnetic semiconductors. In other words, they are universal features in Heisenberg spin glasses including unconventional ones.

A photochemical proposal for the preparation of ZnAl{sub 2}O{sub 4} and MgAl{sub 2}O{sub 4} thin films from β-diketonate complex precursors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cabello, G., E-mail: gerardocabelloguzman@hotmail.com; Lillo, L.; Caro, C.

2016-05-15

Highlights: • ZnAl{sub 2}O{sub 4} and MgAl{sub 2}O{sub 4} thin films were prepared by photo-chemical method. • The Zn(II), Mg(II) and Al(III) β-diketonate complexes were used as precursors. • The photochemical reaction was monitored by UV–vis and FT-IR spectroscopy. • The results reveal spinel oxide formation and the generation of intermediate products. - Abstract: ZnAl{sub 2}O{sub 4} and MgAl{sub 2}O{sub 4} thin films were grown on Si(100) and quartz plate substrates using a photochemical method in the solid phase with thin films of β-diketonate complexes as the precursors. The films were deposited by spin-coating and subsequently photolyzed at room temperaturemore » using 254 nm UV light. The photolysis of these films results in the deposition of metal oxide thin films and fragmentation of the ligands from the coordination sphere of the complexes. The obtained samples were post-annealed at different temperatures (350–1100 °C) for 2 h and characterized by FT-Infrared spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force miscroscopy (AFM), and UV–vis spectroscopy. The results indicate the formation of spinel-type structures and other phases. These characteristics determined the quality of the films, which were obtained from the photodeposition of ternary metal oxides.« less

Structural, optical and dielectric studies of Er substituted zinc ferrite nanospheres

NASA Astrophysics Data System (ADS)

Shoba, M.; Kaleemulla, S.

2017-12-01

The cationic distributions among tetrahedral and octahedral sites in spinel ferrites have a profound influence on their properties. Many studies were reported with various transition metal (TM) and rare earth (RE) cations distribution. We report the synthesis, structural, morphology, lattice vibrational, optical and dielectric properties of heavy RE cation (Er) substituted ZnFe2O4 as a function of different experimental parameters. The coprecipitated and calcined ZnFe2-xErxO4 (x = 0, 0.2, 0.4, 0.6 & 0.8) compounds crystallizes in cubic spinel structure and show narrow particle size distribution due to surfactant PEG. Particle size reduces (27-16 nm) with enhance of Er concentration (x = 0 to 0.8) in the compounds. The EDAX spectra of the samples incorporation Er3+ ions into the lattice and the cubic lattice parameter enhances with Er3+ concentration. The lattice vibrational spectra reveal that the particles surface were free from surfactant PEG. Optical excitation studies show that energy band gap (Eg) of compounds reduces (1.85-2.00 eV) with enhance of Er concentration. The temperature, as well as frequency dependent dielectric constant (εrʹ) of ZnFe2-xErxO4, shows enhanced εrʹ with Er concentration up to x = 0.4 and then reduces with further enhancing of Er concentration. The dielectric loss factor (εrʹʹ) show similar variation with Er concentration. Further, both εrʹ and εrʹʹ were reduced with enhancing of field frequency. In addition, both εrʹ and εrʹʹ were enhanced with temperature and showed exponential change at low frequencies and high temperature and is attributed magnetic transition at around 525 K. The interface polarization mechanism is the predominant one in the present samples. The ac impedance spectra show two semicircles and each semicircle results from dielectric relaxation due to either particle (grain) or particles interface (grain boundary) polarization. The ac impedance reduces with enhancing of temperature. From the above

Depolarization currents in Al 2O 3 and MgAl 2O 4 oxides

NASA Astrophysics Data System (ADS)

Carvalhaes, R. P. M.; Rocha, M. S.; de Souza, S. S.; Blak, A. R.

2004-06-01

In the present work, dipole defects in γ-irradiated and thermally treated samples of Al 2O 3 and MgAl 2O 4 oxides are investigated, applying the thermally stimulated depolarisation currents technique (TSDC). The TSDC spectra of MgAl 2O 4 doped with Fe 2+, Fe 3+, Co 2+, Cr 3+ and Mn 2+ show four bands at 130 K, 160 K, 250 K and 320 K, and the spectra of Al 2O 3 doped with Mg 2+, Cr 3+ and Fe 3+ show bands between 230 K and 260 K. It has been observed that the bands at 130 K, 160 K and 250 K in MgAl 2O 4 spinel and that the 230 K and 240 K bands in Al 2O 3 are related to dipole defects. The other bands are possibly related to different types of charge storage mechanisms (space-charge and interfacial polarisation) or deal with distributions in activation energies and/or in relaxation times. A thermal decrease of the TSDC bands for heat treatments above 1000 K has been observed. In MgAl 2O 4 spinel, the 250 K band could be recovered after γ-irradiation and the two dipole peaks in Al 2O 3 were partially recovered. Thermal treatments affect the dipole aggregation processes in both oxides. Optical absorption (AO) results indicate that the presence of bands of water molecules in the infrared region obstructs the appearance of the TSDC bands in both Al 2O 3 and MgAl 2O 4. The 250 K peak in MgAl 2O 4 was correlated to V-type centres and the 250 K peak in Al 2O 3 to a substitutional Mg 2+ ion near a trapped hole localised on an adjacent oxygen ion.

One Dimensional(1D)-to-2D Crossover of Spin Correlations in the 3D Magnet ZnMn 2O 4

DOE PAGES

Disseler, S. M.; Chen, Y.; Yeo, S.; ...

2015-12-08

In this paper we report on the intriguing evolution of the dynamical spin correlations of the frustrated spinel ZnMn 2O 4. Inelastic neutron scattering and magnetization studies reveal that the dynamical correlations at high temperatures are 1D. At lower temperature, these dynamical correlations become 2D. Surprisingly, the dynamical correlations condense into a quasi 2D Ising-like ordered state, making this a rare observation of two dimensional order on the spinel lattice. Remarkably, 3D ordering is not observed down to temperatures as low as 300 mK. This unprecedented dimensional crossover stems from frustrated exchange couplings due to the huge Jahn-Teller distortions aroundmore » Mn 3+ ions on the spinel lattice.« less

Composition and structure of acid leached LiMn 2-yTi yO 4 (0.2≤ y≤1.5) spinels

NASA Astrophysics Data System (ADS)

Avdeev, Georgi; Amarilla, José Manuel; Rojo, José María; Petrov, Kostadin; Rojas, Rosa María

2009-12-01

Lithium manganese titanium spinels, LiMn 2-yTi yO 4, (0.2≤ y≤1.5) have been synthesized by solid-state reaction between TiO 2 (anatase), Li 2CO 3 and MnCO 3. Li + was leached from the powdered reaction products by treatment in excess of 0.2 N HCl at 85 °C for 6 h, under reflux. The elemental composition of the acidic solution and solid residues of leaching has been determined by complexometric titration, atomic absorption spectroscopy and X-ray fluorescence analysis. Powder X-ray diffraction was used for structural characterization of the crystalline fraction of the solid residues. It has been found that the amount of Li + leached from LiMn 2-yTi yO 4 decreases monotonically with increasing y in the interval 0.2≤ y≤1.0 and abruptly drops to negligibly small values for y>1.0. The content of Mn and Li in the liquid phase and of Mn and Ti in the solid (amorphous plus crystalline) residue, were related to the composition and cation distribution in the pristine compounds. A new formal chemical equation describing the process of leaching and a mechanism of the structural transformation undergone by the initial solids as a result of Li + removal has been proposed.

Evolution of magnetic and orbital properties in the magnetically diluted A -site spinel Cu1 -xZnxRh2O4

NASA Astrophysics Data System (ADS)

Zakrzewski, A. V.; Gangopadhyay, S.; MacDougall, G. J.; Aczel, A. A.; Calder, S.; Williams, T. J.

2018-06-01

In frustrated spinel antiferromagnets, dilution with nonmagnetic ions can be a powerful strategy for probing unconventional spin states or uncovering interesting phenomena. Here, we present x-ray, neutron scattering, and thermodynamic studies of the effects of magnetic dilution of the tetragonally distorted A -site spinel antiferromagnet, CuRh2O4 , with nonmagnetic Zn2 + ions. Our data confirm the helical spin order recently identified at low temperatures in this material, and further demonstrate a systematic suppression of the associated Néel temperature with increasing site dilution towards a continuous transition with critical doping of xspin˜0.44 . Interestingly, this critical doping is demonstrably distinct from a second structural critical point at xJ T˜0.6 , which is consistent with the suppression of orbital order on the A site through a classical percolative mechanism. This anomalously low value for xspin is confirmed via multiple measurements, and is inconsistent with predictions of classical percolation theory, suggesting that the spin transition in this material is driven by an enhancement of preexisting spin fluctuations with weak dilution.

Role of SiO2 coating in multiferroic CoCr2O4 nanoparticles

NASA Astrophysics Data System (ADS)

Kamran, M.; Ullah, Asmat; Mehmood, Y.; Nadeem, K.; Krenn, H.

2017-02-01

Effect of silica (SiO2) coating concentration on structural and magnetic properties of multiferroic cobalt chromite (CoCr2O4) nanoparticles have been studied. The nanoparticles with average crystallite size in the range 19 to 28 nm were synthesised by sol-gel method. X-ray diffraction (XRD) analysis has verified the composition of single-phase cubic normal spinel structure of CoCr2O4 nanoparticles. The average crystallite size and cell parameter decreased with increasing SiO2 concentration. TEM image revealed that the shape of nanoparticles was non-spherical. Zero field cooled/field cooled (ZFC/FC) curves revealed that nanoparticles underwent a transition from paramagnetic (PM) state to collinear short-range ferrimagnetic (FiM) state, and this PM-FiM transition temperature decreased from 101 to 95 K with increasing SiO2 concentration or decreasing crystallite size. A conical spin state at Ts = 27 K was also observed for all the samples which decreased with decreasing average crystallite size. Low temperature lock-in transition was also observed in these nanoparticles at 12 K for uncoated nanoparticles which slightly shifted towards low temperature with decreasing average crystallite size. Saturation magnetization (Ms) showed decreasing trend with increasing SiO2 concentration, which was due to decrease in average crystallite size of nanoparticles and enhanced surface disorder in smaller nanoparticles. The temperature dependent AC-susceptibility also showed the decrease in the transition temperature (Tc), broadening of the Tc peak and decrease in magnetization with increasing SiO2 concentration or decreasing average crystallite size. In summary, the concentration of SiO2 has significantly affected the structural and magnetic properties of CoCr2O4 nanoparticles.

Coupled ferroelectric polarization and magnetization in spinel FeCr2S4

PubMed Central

Lin, L.; Zhu, H. X.; Jiang, X. M.; Wang, K. F.; Dong, S.; Yan, Z. B.; Yang, Z. R.; Wan, J. G.; Liu, J.-M.

2014-01-01

One of the core issues for multiferroicity is the strongly coupled ferroelectric polarization and magnetization, while so far most multiferroics have antiferromagnetic order with nearly zero magnetization. Magnetic spinel compounds with ferrimagnetic order may be alternative candidates offering large magnetization when ferroelectricity can be activated simultaneously. In this work, we investigate the ferroelectricity and magnetism of spinel FeCr2S4 in which the Fe2+ sublattice and Cr3+ sublattice are coupled in antiparallel alignment. Well defined ferroelectric transitions below the Fe2+ orbital ordering termperature Too = 8.5 K are demonstrated. The ferroelectric polarization has two components. One component arises mainly from the noncollinear conical spin order associated with the spin-orbit coupling, which is thus magnetic field sensitive. The other is probably attributed to the Jahn-Teller distortion induced lattice symmetry breaking, occuring below the orbital ordering of Fe2+. Furthermore, the coupled ferroelectric polarization and magnetization in response to magnetic field are observed. The present work suggests that spinel FeCr2S4 is a multiferroic offering both ferroelectricity and ferrimagnetism with large net magnetization. PMID:25284432

Exploration of spin state and exchange integral of cobalt ions in stoichiometric ZnCo{sub 2}O{sub 4} spinel oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Che, Xiangli; Li, Liping; Li, Guangshe, E-mail: guangshe@fjirsm.ac.cn

2016-04-04

This work reports on spin state and exchange integral of cobalt ions in stoichiometric ZnCo{sub 2}O{sub 4} nanoparticles with varying particle size from about 24 to 105 nm. Cobalt ions in ZnCo{sub 2}O{sub 4} nanoparticles are present as trivalence in mixed spin state. The effective magnetic moment is distributed in the range of 2.1 ∼ 1.31 μ{sub B} at room temperature with coarsening of nanoparticles. Further, it is demonstrated that stoichiometric ZnCo{sub 2}O{sub 4} undergoes a magnetic transition from paramagnetism to antiferromagnetism with decrease of temperature, showing a transition temperature of about 5 K. The standard molar entropy and enthalpy for 24 nm ZnCo{sub 2}O{sub 4}more » are 170.6 ± 1.7 J K{sup −1} mol{sup −1} and 28.2 ± 0.3 kJ mol{sup −1} at 298.15 K, respectively. Based on the heat capacity data, the exchange integral is determined to be 4.16 × 10{sup −22} J. The results report here are really important for further understanding the magnetic and electronic properties of spinel oxides.« less

Exceptionally Active and Stable Spinel Nickel Manganese Oxide Electrocatalysts for Urea Oxidation Reaction.

PubMed

Periyasamy, Sivakumar; Subramanian, Palaniappan; Levi, Elena; Aurbach, Doron; Gedanken, Aharon; Schechter, Alex

2016-05-18

Spinel nickel manganese oxides, widely used materials in the lithium ion battery high voltage cathode, were studied in urea oxidation catalysis. NiMn2O4, Ni1.5Mn1.5O4, and MnNi2O4 were synthesized by a simple template-free hydrothermal route followed by a thermal treatment in air at 800 °C. Rietveld analysis performed on nonstoichiometric nickel manganese oxide-Ni1.5Mn1.5O4 revealed the presence of three mixed phases: two spinel phases with different lattice parameters and NiO unlike the other two spinels NiMn2O4 and MnNi2O4. The electroactivity of nickel manganese oxide materials toward the oxidation of urea in alkaline solution is evaluated using cyclic voltammetric measurements. Ni1.5Mn1.5O4 exhibits excellent redox characteristics and lower charge transfer resistances in comparison with other compositions of nickel manganese oxides and nickel oxide prepared under similar conditions.The Ni1.5Mn1.5O4modified electrode oxidizes urea at 0.29 V versus Ag/AgCl with a corresponding current density of 6.9 mA cm(-2). At a low catalyst loading of 50 μg cm(-2), the urea oxidation current density of Ni1.5Mn1.5O4 in alkaline solution is 7 times higher than that of nickel oxide and 4 times higher than that of NiMn2O4 and MnNi2O4, respectively.

Li-Diffusion in Spinel Li[Ni1/2Mn3/2]O4 Powder and Film Studied with μ+SR

NASA Astrophysics Data System (ADS)

Sugiyama, Jun; Nozaki, Hiroshi; Umegaki, Izumi; Mukai, Kazuhiko; Cottrell, Stephen P.; Shiraki, Susumu; Hitosugi, Taro; Sassa, Yasmine; Suter, Andreas; Salman, Zaher; Prokscha, Thomas; Månsson, Martin

A dynamic behavior in spinel Li[Ni1/2Mn3/2]O4 has been studied with μ+SR measurements in film and powder samples in the temperature range between 5 and 500 K. Both samples exhibited a broad ferromagnetic transition below 120 K, indicating the random distribution of Ni and Mn ions at the octahedral 16d site. Above 150 K, the ZF-μ+SR spectrum showed a dynamic behavior well explained by a dynamic Kubo-Toyabe function. Assuming a jump diffusion of Li+ at the tetrahedral 8a site to the vacant octahedral 16c site, a diffusion coefficient of Li+ is estimated as ˜5 × 10-11 cm2/s at 300 K and ˜8 × 10-11 cm2/s at 350 K and ˜14 × 10-11 cm2/s at 400 K, with thermal activation energy Ea ˜ 0.1 eV.

Large exchange bias effect in NiFe2O4/CoO nanocomposites

NASA Astrophysics Data System (ADS)

Mohan, Rajendra; Prasad Ghosh, Mritunjoy; Mukherjee, Samrat

2018-03-01

In this work, we report the exchange bias effect of NiFe2O4/CoO nanocomposites, synthesized via chemical co-precipitation method. Four samples of different particle size ranging from 4 nm to 31 nm were prepared with the annealing temperature varying from 200 °C to 800 °C. X-ray diffraction analysis of all the samples confirmed the presence of cubic spinel phase of Nickel ferrite along with CoO phase without trace of any impurity. Sizes of the particles were studied from transmission electron micrographs and were found to be in agreement with those estimated from x-ray diffraction. Field cooled (FC) hysteresis loops at 5 K revealed an exchange bias (HE) of 2.2 kOe for the sample heated at 200 °C which decreased with the increase of particle size. Exchange bias expectedly vanished at 300 K due to high thermal energy (kBT) and low effective surface anisotropy. M-T curves revealed a blocking temperature of 135 K for the sample with smaller particle size.

Dielectric and impedance study of praseodymium substituted Mg-based spinel ferrites

NASA Astrophysics Data System (ADS)

Farid, Hafiz Muhammad Tahir; Ahmad, Ishtiaq; Ali, Irshad; Ramay, Shahid M.; Mahmood, Asif; Murtaza, G.

2017-07-01

Spinel ferrites with nominal composition MgPryFe2-yO4 (y = 0.00, 0.025, 0.05, 0.075, 0.10) were prepared by sol-gel method. Temperature dependent DC electrical conductivity and drift mobility were found in good agreement with each other, reflecting semiconducting behavior. The dielectric properties of all the samples as a function of frequency (1 MHz-3 GHz) were measured at room temperature. The dielectric constant and complex dielectric constant of these samples decreased with the increase of praseodymium concentration. In the present spinel ferrite, Cole-Cole plots were used to separate the grain and grain boundary's effects. The substitution of praseodymium ions in Mg-based spinel ferrites leads to a remarkable rise of grain boundary's resistance as compared to the grain's resistance. As both AC conductivity and Cole-Cole plots are the functions of concentration, they reveal the dominant contribution of grain boundaries in the conduction mechanism. AC activation energy was lower than dc activation energy. Temperature dependence normalized AC susceptibility of spinel ferrites reveals that MgFe2O4 exhibits multi domain (MD) structure with high Curie temperature while on substitution of praseodymium, MD to SD transitions occurs. The low values of conductivity and low dielectric loss make these materials best candidate for high frequency application.

Improved electrochemical performance of spinel LiMn(1.5)Ni(0.5)O4 through MgF2 nano-coating.

PubMed

Wu, Qing; Zhang, Xiaoping; Sun, Shuwei; Wan, Ning; Pan, Du; Bai, Ying; Zhu, Huiyuan; Hu, Yong-Sheng; Dai, Sheng

2015-10-14

A spinel LiMn1.5Ni0.5O4 (LMNO) cathode material synthesized by a sol-gel method is modified by MgF2 nano-coating via a wet coating strategy. The results of X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM) showed that the MgF2 nano-coating layers do not physically change the bulk structure of the pristine material. Compared with the pristine compound, the MgF2-coated LMNO electrodes display enhanced cycling stabilities. Particularly, the 5 wt% MgF2-coated LMNO demonstrates the best reversibility, with a capacity retention of 89.9% after 100 cycles, much higher than that of the pristine material, 69.3%. The dQ/dV analysis and apparent Li(+) diffusion coefficient calculation prove that the kinetic properties are enhanced after MgF2 surface modification, which partly explains the improved electrochemical performances. Electrochemical impedance spectroscopy (EIS) and Fourier transform infrared spectroscopy (FTIR) data confirm that the MgF2 coating layer helps in suppressing the fast growth of the solid electrolyte interface (SEI) film in repeated cycling, which effectively stabilizes the spinel structure. Additionally, differential scanning calorimetry (DSC) tests show that the MgF2 nano-coating layer also helps in enhancing the thermal stability of the LMNO cathode.

Electrochemically synthesized nanocrystalline spinel thin film for high performance supercapacitor

NASA Astrophysics Data System (ADS)

Gupta, Vinay; Gupta, Shubhra; Miura, Norio

Spinels are not known for their supercapacitive nature. Here, we have explored electrochemically synthesized nanostructured NiCo 2O 4 spinel thin-film electrode for electrochemical supercapacitors. The nanostructured NiCo 2O 4 spinel thin film exhibited a high specific capacitance value of 580 F g -1 and an energy density of 32 Wh kg -1 at the power density of 4 kW kg -1, accompanying with good cyclic stability.

An in situ X ray diffraction study of the kinetics of the Ni2SiO4 olivine-spinel transformation

NASA Technical Reports Server (NTRS)

Rubie, D. C.; Tsuchida, Y.; Yagi, T.; Utsumi, W.; Kikegawa, T.

1990-01-01

The kinetics of the olivine-spinel transformation in Ni2SiO4 were investigated in an in situ X-ray diffraction experiments in which synchrotron radiation was used as an X-ray source. The starting material was Ni2SO4 olivine which was hot-pressed in situ at 980 C and 2.5 GPa; during the transformation, X-ray diffraction patterns were collected at intervals of 30 or 120 sec. The kinetic data were analyzed using Cahn's (1956) model. The activation energy for growth at 3.6-3.7 GPa was estimated as 438 + or - 199 kJ/mol. It is shown that, in order to make significant extrapolations of the kinetic data to a geological scale, the dependence of the rates of both nucleation and growth on temperature and pressure must be evaluated separately.

Structural transition in Mg-doped LiMn 2O 4: a comparison with other M-doped Li-Mn spinels

NASA Astrophysics Data System (ADS)

Capsoni, Doretta; Bini, Marcella; Chiodelli, Gaetano; Massarotti, Vincenzo; Mozzati, Maria Cristina; Azzoni, Carlo B.

2003-01-01

The charge distribution in the Mg-doped lithium manganese spinel Li 1.02Mg xMn 1.98- xO 4 with 0.00< x≤0.20 is discussed and compared to those pertinent to other M-doped samples (M=Ni 2+, Co 3+, Cr 3+, Al 3+ and Ga 3+). EPR spectra, low temperature X-ray diffraction and conductivity data are related to the cooperative Jahn-Teller (J-T) transition occurring at about 280 K in the undoped sample. The sensitivity of the cationic sublattice in displaying electronic and magnetic changes after substitution is remarked. The inhibition of the J-T transition is related to the ratio r=|Mn 4+|/|Mn 3+| as deduced from the charge distribution model [Li 1- xt+Mg xt2+] tetr[Li y+ xt+Mg xo2+Mn 1-3 y-2 x3+Mn 1+2 y+ x4+] octa where x= xo+ xt. For y=0.02 and x=0.02, a value r=1.177 is obtained, very close to rlim=1.18, the limit value beyond which the transition is inhibited.

Investigation of electrical studies of spinel FeCo2O4 synthesized by sol-gel method

NASA Astrophysics Data System (ADS)

Lobo, Laurel Simon; Kalainathan, S.; Kumar, A. Ruban

2015-12-01

In this work, spinel FeCo2O4 is synthesized by sol-gel method using succinic acid as a chelating agent at 900 °C. The structural, spectroscopic and morphological characterization was carried out by using X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscopy equipped with Energy Dispersive X-ray spectrometer (SEM-EDX). The M-H loop at room temperature confirms the ferromagnetic property of the sample. The frequency and temperature dependence of dielectric constant (εʹ) and dielectric loss (tan δ) shows the presence of Maxwell-Wagner relaxation in the sample due to the presence of oxygen vacancy. Nyquist plot for frequency and temperature domain signifies the presence of grain effect, grain boundary effect and electrode interface in the conduction process. Electric modulus under suppression of electrode polarization shows the grain and grain boundary effects. The electrode polarization is observed in the lower frequency range of the conductivity graph.

The Role of Spinel Minerals in Lunar Magma Evolution

NASA Astrophysics Data System (ADS)

Taylor, L. A.; Head, J. W.; Pieters, C. M.; Sunshine, J. M.; Staid, M.; Isaacson, P.; Petro, N. E.

2009-12-01

The Moon Mineralogy Mapper (M3), a NASA guest instrument on Chandrayaan-1, India’s first mission to the Moon, was designed to map the surface mineralogy of the Moon using reflected solar radiation at visible and near-infrared wavelengths, which contain highly diagnostic absorptions due to minerals. The M3 spectrometer has discovered several new and unexpected aspects of the geology and petrology of the Moon, some involving specific oxide phases. Spinel minerals, with the general formula, AB2O4, present clues as to the oxygen fugacity, the nature of magmatic systems, and their evolution, particularly during the early stages of crystallization. On the Moon, with its total lack of Fe3+ and minerals such as magnetite, observed spinels range between spinel, MgAl2O4; hercynite, FeAl2O4; Chromite, FeCr2O4; and ulvöspinel, Fe(FeTi)2O4. They manifest themselves in three distinctly different igneous rock types: highlands rocks of anorthosites/troctolites, gabbro-norites; mare basalts with various TiO2 contents; and basaltic pyroclastic volcanic glasses. Although spinels occur as minor minerals in the Apollo collection, unique rock types dominated by Mg-spinel (with olivine and pyroxene abundances below detection limits, assumed to be ~5%) have been identified by M3 on the Moon. Because the spinel-bearing rocks detected by M3 have no signature of a significant olivine component, they must be dominated by plagioclase and spinel. Pink Mg-spinels typically occur as a minor phase in troctolites (plagioclase + olivine), a highland rock formed after the initial Ferroan Anorthosite (FAN) crust, presumably by serial magmatism deep within the crust, with intrusion upward. FANs were formed by floatation of plagioclase in the lunar magma ocean (LMO), whereas spinels would sink due to their much higher density. Thus, a plagioclase-rich rock type with a strong Mg-spinel spectral signature would have to be part of later highland intrusives. The excess Mg-spinel could be the product of

Neutron diffraction study of the inverse spinels Co2TiO4 and Co2SnO4

NASA Astrophysics Data System (ADS)

Thota, S.; Reehuis, M.; Maljuk, A.; Hoser, A.; Hoffmann, J.-U.; Weise, B.; Waske, A.; Krautz, M.; Joshi, D. C.; Nayak, S.; Ghosh, S.; Suresh, P.; Dasari, K.; Wurmehl, S.; Prokhnenko, O.; Büchner, B.

2017-10-01

We report a detailed single-crystal and powder neutron diffraction study of Co2TiO4 and Co2SnO4 between the temperature 1.6 and 80 K to probe the spin structure in the ground state. For both compounds the strongest magnetic intensity was observed for the (111)M reflection due to ferrimagnetic ordering, which sets in below TN=48.6 and 41 K for Co2TiO4 and Co2SnO4 , respectively. An additional low intensity magnetic reflection (200)M was noticed in Co2TiO4 due to the presence of an additional weak antiferromagnetic component. Interestingly, from both the powder and single-crystal neutron data of Co2TiO4 , we noticed a significant broadening of the magnetic (111)M reflection, which possibly results from the disordered character of the Ti and Co atoms on the B site. Practically, the same peak broadening was found for the neutron powder data of Co2SnO4 . On the other hand, from our single-crystal neutron diffraction data of Co2TiO4 , we found a spontaneous increase of particular nuclear Bragg reflections below the magnetic ordering temperature. Our data analysis showed that this unusual effect can be ascribed to the presence of anisotropic extinction, which is associated to a change of the mosaicity of the crystal. In this case, it can be expected that competing Jahn-Teller effects acting along different crystallographic axes can induce anisotropic local strain. In fact, for both ions Ti3 + and Co3 +, the 2 tg levels split into a lower dx y level yielding a higher twofold degenerate dx z/dy z level. As a consequence, one can expect a tetragonal distortion in Co2TiO4 with c /a <1 , which we could not significantly detect in the present work.

Profound Interfacial Effects in CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4 Core/Shell Nanoparticles

NASA Astrophysics Data System (ADS)

Polishchuk, Dmytro; Nedelko, Natalia; Solopan, Sergii; Ślawska-Waniewska, Anna; Zamorskyi, Vladyslav; Tovstolytkin, Alexandr; Belous, Anatolii

2018-03-01

Two sets of core/shell magnetic nanoparticles, CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4, with a fixed diameter of the core ( 4.1 and 6.3 nm for the former and latter sets, respectively) and thickness of shells up to 2.5 nm were synthesized from metal chlorides in a diethylene glycol solution. The nanoparticles were characterized by X-ray diffraction, transmission electron microscopy, and magnetic measurements. The analysis of the results of magnetic measurements shows that coating of magnetic nanoparticles with the shells results in two simultaneous effects: first, it modifies the parameters of the core-shell interface, and second, it makes the particles acquire combined features of the core and the shell. The first effect becomes especially prominent when the parameters of core and shell strongly differ from each other. The results obtained are useful for optimizing and tailoring the parameters of core/shell spinel ferrite magnetic nanoparticles for their use in various technological and biomedical applications.

Surface characterization of ZnO/ZnMn{sub 2}O{sub 4} and Cu/Mn{sub 3}O{sub 4} powders obtained by thermal degradation of heterobimetallic complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barrault, Joeel, E-mail: joel.barrault@univ-poitiers.fr; Makhankova, Valeriya G., E-mail: leram@univ.kiev.ua; Khavryuchenko, Oleksiy V.

2012-03-15

From the selective transformation of the heterometallic (Zn-Mn or Cu-Mn) carboxylate complexes with 2,2 Prime -bipyridyl by thermal degradation at relatively low (350 Degree-Sign C) temperature, it was possible to get either well defined spinel ZnMn{sub 2}O{sub 4} over zinc oxide or well dispersed copper particles surrounded by a manganese oxide (Mn{sub 3}O{sub 4}) in a core-shell like structure. Morphology of the powder surface was examined by scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX). Surface composition was determined by X-ray photoelectron spectroscopy (XPS). Specific surface of the powders by nitrogen adsorption was found to be 33{+-}0.2 and 9{+-}0.06more » m{sup 2} g{sup -1} for Zn-Mn and Cu-Mn samples, respectively, which is comparable to those of commercial products. - Graphical abstract: From the selective transformation of heterometallic (Zn-Mn or Cu-Mn) carboxylate complexes, it was possible to get either well defined spinel ZnMn{sub 2}O{sub 4} over zinc oxide or well dispersed copper particles surrounded by a manganese oxide (Mn{sub 3}O{sub 4}) in a core-shell like structure. Highlights: Black-Right-Pointing-Pointer Thermal degradation of heterometallic complexes results in fine disperse particles. Black-Right-Pointing-Pointer Core-shell Cu/Mn{sub 3}O{sub 4} particles are obtained. Black-Right-Pointing-Pointer ZnMn{sub 2}O{sub 4} spinel layer covers ZnO particles.« less

Photoelectrochemical and theoretical investigations of spinel type ferrites (MxFe3-xO4) for water splitting: a mini-review

NASA Astrophysics Data System (ADS)

Taffa, Dereje H.; Dillert, Ralf; Ulpe, Anna C.; Bauerfeind, Katharina C. L.; Bredow, Thomas; Bahnemann, Detlef W.; Wark, Michael

2017-01-01

Solar-assisted water splitting using photoelectrochemical cells (PECs) is one of the promising pathways for the production of hydrogen for renewable energy storage. The nature of the semiconductor material is the primary factor that controls the overall energy conversion efficiency. Finding semiconductor materials with appropriate semiconducting properties (stability, efficient charge separation and transport, abundant, visible light absorption) is still a challenge for developing materials for solar water splitting. Owing to the suitable bandgap for visible light harvesting and the abundance of iron-based oxide semiconductors, they are promising candidates for PECs and have received much research attention. Spinel ferrites are subclasses of iron oxides derived from the classical magnetite (FeIIFe2IIIO4) in which the FeII is replaced by one (some cases two) additional divalent metals. They are generally denoted as MxFe3-xO4 (M=Ca, Mg, Zn, Co, Ni, Mn, and so on) and mostly crystallize in spinel or inverse spinel structures. In this mini review, we present the current state of research in spinel ferrites as photoelectrode materials for PECs application. Strategies to improve energy conversion efficiency (nanostructuring, surface modification, and heterostructuring) will be presented. Furthermore, theoretical findings related to the electronic structure, bandgap, and magnetic properties will be presented and compared with experimental results.

Improved electrochemical performance of spinel LiMn 1.5Ni 0.5O 4 through MgF 2 nano-coating

DOE PAGES

Wu, Qing; Zhang, Xiaoping; Sun, Shuwei; ...

2015-07-08

In this paper, a spinel LiMn 1.5Ni 0.5O 4 (LMNO) cathode material synthesized by a sol–gel method is modified by MgF 2 nano-coating via a wet coating strategy. The results of X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM) showed that the MgF 2 nano-coating layers do not physically change the bulk structure of the pristine material. Compared with the pristine compound, the MgF 2-coated LMNO electrodes display enhanced cycling stabilities. Particularly, the 5 wt% MgF 2-coated LMNO demonstrates the best reversibility, with a capacity retention of 89.9% after 100more » cycles, much higher than that of the pristine material, 69.3%. The dQ/dV analysis and apparent Li + diffusion coefficient calculation prove that the kinetic properties are enhanced after MgF 2 surface modification, which partly explains the improved electrochemical performances. Electrochemical impedance spectroscopy (EIS) and Fourier transform infrared spectroscopy (FTIR) data confirm that the MgF 2 coating layer helps in suppressing the fast growth of the solid electrolyte interface (SEI) film in repeated cycling, which effectively stabilizes the spinel structure. Finally and additionally, differential scanning calorimetry (DSC) tests show that the MgF 2 nano-coating layer also helps in enhancing the thermal stability of the LMNO cathode.« less

Cation Distribution and Magnetism in Quenched ZnFe2O4

NASA Astrophysics Data System (ADS)

Yuan, Qiao; Pan, Linlin; Liu, Run; Wang, Jingming; Liao, Zuzhen; Qin, Lili; Bi, Jian; Gao, Daojiang; Wu, Jiangtao

2018-03-01

Spinel ferrites constitute one of the most important families of magnets; their properties are believed to be highly dependent on cation occupancy. Zinc ferrite materials synthesized by various methods are usually reported to exhibit enhanced magnetism, but the mechanism underlying such enhancement remains poorly understood, with at least three effects being considered, namely cation distribution, oxygen vacancies, and surface spin disorder. We report herein the individual influence of cation distribution on the magnetic properties of zinc ferrite microparticles, synthesized by solid-state reaction with a fast (200 K/s) quench process. Based on structure analyses including x-ray powder diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy, Mössbauer spectroscopy, and magnetic measurements, it is concluded that the as-prepared samples exhibited different cation distribution with inversion degree increasing from approximately 0.18 to 0.28 with increasing calcination temperature from 800°C to 1200°C. The magnetism measured at 2 K was found to be enhanced with increase of the inversion degree, while that measured at 300 K was found to be independent of inversion degree. The mechanism of the enhanced magnetization is that the indirect interaction between A and B site at low temperature is stronger than that between two nearest B sites.

Cation Distribution and Magnetism in Quenched ZnFe2O4

NASA Astrophysics Data System (ADS)

Yuan, Qiao; Pan, Linlin; Liu, Run; Wang, Jingming; Liao, Zuzhen; Qin, Lili; Bi, Jian; Gao, Daojiang; Wu, Jiangtao

2018-07-01

Spinel ferrites constitute one of the most important families of magnets; their properties are believed to be highly dependent on cation occupancy. Zinc ferrite materials synthesized by various methods are usually reported to exhibit enhanced magnetism, but the mechanism underlying such enhancement remains poorly understood, with at least three effects being considered, namely cation distribution, oxygen vacancies, and surface spin disorder. We report herein the individual influence of cation distribution on the magnetic properties of zinc ferrite microparticles, synthesized by solid-state reaction with a fast (200 K/s) quench process. Based on structure analyses including x-ray powder diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy, Mössbauer spectroscopy, and magnetic measurements, it is concluded that the as-prepared samples exhibited different cation distribution with inversion degree increasing from approximately 0.18 to 0.28 with increasing calcination temperature from 800°C to 1200°C. The magnetism measured at 2 K was found to be enhanced with increase of the inversion degree, while that measured at 300 K was found to be independent of inversion degree. The mechanism of the enhanced magnetization is that the indirect interaction between A and B site at low temperature is stronger than that between two nearest B sites.

Experimental heat capacities, excess entropies, and magnetic properties of bulk and nano Fe3O4-Co3O4 and Fe3O4-Mn3O4 spinel solid solutions

NASA Astrophysics Data System (ADS)

Schliesser, Jacob M.; Huang, Baiyu; Sahu, Sulata K.; Asplund, Megan; Navrotsky, Alexandra; Woodfield, Brian F.

2018-03-01

We have measured the heat capacities of several well-characterized bulk and nanophase Fe3O4-Co3O4 and Fe3O4-Mn3O4 spinel solid solution samples from which magnetic properties of transitions and third-law entropies have been determined. The magnetic transitions show several features common to effects of particle and magnetic domain sizes. From the standard molar entropies, excess entropies of mixing have been generated for these solid solutions and compared with configurational entropies determined previously by assuming appropriate cation and valence distributions. The vibrational and magnetic excess entropies for bulk materials are comparable in magnitude to the respective configurational entropies indicating that excess entropies of mixing must be included when analyzing entropies of mixing. The excess entropies for nanophase materials are even larger than the configurational entropies. Changes in valence, cation distribution, bonding and microstructure between the mixing ions are the likely sources of the positive excess entropies of mixing.

Nickel removal by biosorption onto medlar male flowers coupled with photocatalysis on the spinel ZnMn2O4

PubMed Central

2014-01-01

Ni2+ is a highly toxic above 0.07 mg/L and its removal is of high significance. The biosorption of Ni2+ onto medlar male flowers (MMF) was studied in relation with the physical parameters like pH, contact time, biosorbent dosage, Ni2+ concentration and temperature. The interaction biosorbent-Ni2+ was examined by the FTIR technique. The equilibrium was achieved within 40 min and the data were well fitted by the Langmuir and Redlich-Peterson (R-P) models. The maximum Ni2+ uptake capacity was 17.073 mg/g at 25°C and the Ni2+ removal follows a pseudo-second order kinetic with activation energy of 13.3 kJ/mol. The thermodynamic parameters: ΔS°, ΔH° and ΔG° showed that the biosorption was spontaneous and endothermic. MMF was used as a post treatment technique and the biosorption was coupled with the visible light driven Ni2+ reduction over the spinel ZnMn2O4. The effect of the pH, ZnMn2O4 loading and light intensity on the photoactivity was investigated. 77.5% of Ni2+ was reduced after ~140 min under optimal conditions. The Ni2+ removal reached a rate conversion of 96% of with the coupled system biosorption/photocatalysis is very promising for the water treatment. PMID:24401700

A New CuO-Fe2 O3 -Mesocarbon Microbeads Conversion Anode in a High-Performance Lithium-Ion Battery with a Li1.35 Ni0.48 Fe0.1 Mn1.72 O4 Spinel Cathode.

PubMed

Di Lecce, Daniele; Verrelli, Roberta; Campanella, Daniele; Marangon, Vittorio; Hassoun, Jusef

2017-04-10

A ternary CuO-Fe 2 O 3 -mesocarbon microbeads (MCMB) conversion anode was characterized and combined with a high-voltage Li 1.35 Ni 0.48 Fe 0.1 Mn 1.72 O 4 spinel cathode in a lithium-ion battery of relevant performance in terms of cycling stability and rate capability. The CuO-Fe 2 O 3 -MCMB composite was prepared by using high-energy milling, a low-cost pathway that leads to a crystalline structure and homogeneous submicrometrical morphology as revealed by XRD and electron microscopy. The anode reversibly exchanges lithium ions through the conversion reactions of CuO and Fe 2 O 3 and by insertion into the MCMB carbon. Electrochemical tests, including impedance spectroscopy, revealed a conductive electrode/electrolyte interface that enabled the anode to achieve a reversible capacity value higher than 500 mAh g -1 when cycled at a current of 120 mA g -1 . The remarkable stability of the CuO-Fe 2 O 3 -MCMB electrode and the suitable characteristics in terms of delivered capacity and voltage-profile retention allowed its use in an efficient full lithium-ion cell with a high-voltage Li 1.35 Ni 0.48 Fe 0.1 Mn 1.72 O 4 cathode. The cell had a working voltage of 3.6 V and delivered a capacity of 110 mAh g cathode -1 with a Coulombic efficiency above 99 % after 100 cycles at 148 mA g cathode -1 . This relevant performances, rarely achieved by lithium-ion systems that use the conversion reaction, are the result of an excellent cell balance in terms of negative-to-positive ratio, favored by the anode composition and electrochemical features. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile synthesis of electrospun MFe2O4 (M = Co, Ni, Cu, Mn) spinel nanofibers with excellent electrocatalytic properties for oxygen evolution and hydrogen peroxide reduction

NASA Astrophysics Data System (ADS)

Li, Mian; Xiong, Yueping; Liu, Xiaotian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

2015-05-01

Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m2 g-1) than those of the CoFe2O4 NPs (5.93 m2 g-1)) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media.Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment