New insight into structural transformation in Li-rich layered oxide during the initial charging

2015 ◽  
Vol 3 (23) ◽  
pp. 12220-12229 ◽  
Author(s):  
Chong-Heng Shen ◽  
Shou-Yu Shen ◽  
Fang Fu ◽  
Chen-Guang Shi ◽  
Hui-Yi Zhang ◽  
...  

In Li1.2Ni0.12Co0.15Mn0.53O2 oxide, four lines of lattice fringe from O3 rhombohedral phase are squeezed into two lines from spinel cubic phase at 4.70 V charged state under the effect of microstress.

2021 ◽  
pp. 2010095
Author(s):  
Chul‐Ho Jung ◽  
Do‐Hoon Kim ◽  
Donggun Eum ◽  
Kyeong‐Ho Kim ◽  
Jonghyun Choi ◽  
...  

2007 ◽  
Vol 1056 ◽  
Author(s):  
Luiz G. Jacobsohn ◽  
Bryan L. Bennett ◽  
Stephanie C. Sitarz ◽  
Ozan Ugurlu ◽  
Ana L. Lima Sharma ◽  
...  

ABSTRACTIn this work we explore the uniqueness of solution combustion synthesis (SCS) technique to produce luminescent nanostructured materials with metastable phases. We synthesized Gd2O3:Eu with the high-temperature phase and induced phase transformation toward the room temperature phase to investigate the effects of structural transformation on the luminescent properties. SCS is based on exothermic redox reactions that undergo self-sustaining combustion, yielding powders composed of agglomerates of nanocrystals with typical dimensions of tens of nanometers. Synthesis of materials through SCS occurs in conditions far from thermodynamic equilibrium and, due to the high temperatures achieved during combustion, metastable crystallographic phases can be formed. Eu-doped Gd2O3 was obtained with base-centered monoclinic structure and average nanocrystal size of 35 nm as determined by Debye-Scherre analysis. Phase transformation to the cubic structure was induced by isothermal annealing at 1000 oC for up to 152 hrs and followed by x-ray diffraction (XRD). Luminescence excitation and emission spectra were obtained as a function of annealing time. The transformation from monoclinic to cubic structure was followed by the behavior of the (111) monoclinic/(222) cubic intensity ratio. The ratio value for the as-prepared material is 6, decreasing fast to 3 after 5 hrs. annealing, and reaching a value of 0.1 after 152 hrs. Concomitant to the structural transformation, nanocrystal size was followed for both crystalline phases. The average nanocrystal size for the cubic phase increases from 27 to 47 nm from 1 to 152 hrs., respectively. On the other hand, nanocrystals with the monoclinic phase remained with a constant size around 38 nm. Overall, variation in size is small due to the low connectivity among nanocrystals resulting from the low isostatic pressure employed to prepare the pellets, together with the non-uniform shape of the agglomerates. Photoluminescence excitation spectra are dominated by a broad centered near 278 nm and assigned to the O2-Eu3+ charge transfer band. Photoluminescence emission results present the 5D0-7FJ (with J = 0-4) transitions of Eu3+ ions. The behavior of these bands was investigated as a function of annealing time and subsequently related to the structural changes.


Author(s):  
J. B. Wright ◽  
J. F. Lovering

SummaryThe electron probe was used to analyse for Fe, Ti, Mg, Al, and Mn. Vanadium could not be determined because of interference from Ti. Calcium was shown to be present only in inclusions of apatite and silicate; it does not oceur in the titanomagnetite structure.Homogeneous grains (magnetite-ulvöspinel solid solutions) do not vary greatly in bulk composition, averaging close to 61% Fe and 8 % TiO2. Inhomogeneous grains contain variable amounts of hematite-ilmenite lamellae produced by progressive oxidation of the homogeneous grains. In the early stages there is rapid build-up of titanium in the rhombohedral lamellae, which are initially relatively poor in iron. As oxidation proceeds the almost titanium-free cubic phase becomes strongly enriched in magnesium, aluminium, and manganese, while the iron: titanium ratio in the rhombohedral phase increases. The end-product may be a homogeneous titanhematite, if initial concentrations of Mg, Al, and Mn are low. Otherwise residuals of a relatively iron-poor almost titanium-free (Mg, Al, Mn)-enriched cubic phase remain in the titanhematite. The behaviour of iron and titanium agrees with recent synthetic work in the system. Some of the oxidized grains contain transparent spinel lamellae exsolved from the cubic phase. Exsolution may commence at different stages in the oxidation process, but the reason is not clear—there are no significant differences in the composition of phases with and without spinel lamellae.Analyses and normative compositions are presented for the different phases in each grain, where possible. The compositional changes accompanying oxidation satisfactorily explain the slope of the thermomagnetic curves : there is no need to invoke bulk compositional variations within a given ironsand sample.Samples from an ilmenite and a non-titaniferous magnetite concentrate were also briefly examined.


2014 ◽  
Vol 975 ◽  
pp. 86-91
Author(s):  
Emanuelle Z. Santos ◽  
Reginaldo Muccillo

Zirconia stabilized with 8-12 mol% scandia shows the highest value of oxide ion conductivity among zirconia-based oxides. However, the cubic-rhombohedral phase transition at approximately 600 °C prevents its use as high temperature solid electrolyte. To circumvent this problem, additives have been proposed. In this work, ZrO2:10 mol% Sc2O3 was mixed to MnO2 and sintered at 1200 oC/2 h + 1450 °C/2 h with addition of 1, 1.5, 2 and 2.5 mol% MnO2. All specimens were analyzed by X-ray diffraction for structural phase evaluation and dilatometry for densification. Polished and thermally etched surfaces were observed in scanning electron microscope and scanning probe microscope. Impedance spectroscopy measurements were carried out in the frequency range 5 Hz-13 MHz in the 300-500 oC temperature range. The main results show that the manganese dioxide addition prior to sintering leads to the formation of single cubic phase, to the reduction of the maximum shrinkage temperature, and to an increase in the value of the total oxide ion conductivity.


Author(s):  
Sergey Yarmolenko ◽  
Jag Sankar ◽  
Nicholas Bernier ◽  
Michael Klimov ◽  
Jay Kapat ◽  
...  

The phase composition and sintering behavior of two commercially available 10mol%Sc2O3–1mol%CeO2–ZrO2 ceramics produced by Daiichi Kigenso Kagaku Kogyo (DKKK) and Praxair have been studied. DKKK powders have been manufactured using a wet coprecipitation chemical route, and Praxair powders have been produced by spray pyrolysis. The morphology of the powders, as studied by scanning electron microscopy, has been very different. DKKK powders were presented as soft (∼100μm) spherical agglomerates containing 60–100nm crystalline particles, whereas the Praxair powders were presented as sintered platelet agglomerates, up to 30μm long and 3–4μm thick, which consisted of smaller 100–200nm crystalline particles. X-ray diffraction analysis has shown that both DKKK and Praxair powders contained a mixture of cubic (c) and rhombohedral (r) phases: 79% cubic +21% rhombohedral for DKKK powders and 88% cubic +12% rhombohedral for Praxair powders. Higher quantities of the Si impurity level have been detected in Praxair powder as compared to DKKK powder by secondary ion mass spectroscopy. The morphological features, along with differences in composition and the impurity level of both powders, resulted in significantly different sintering behaviors. The DKKK powders showed a more active sintering behavior than of Praxair powders, reaching 93–95% of theoretical density when sintered at 1300°C for 2h. Comparatively, the Praxair powders required high sintering temperatures at 1500–1600°C. However, even at such high sintering temperatures, a significant amount of porosity was observed. Both DKKK and Praxair ceramics sintered at 1300°C or above exist in a cubic phase at room temperature. However, if sintered at 1100°C and 1200°C, the DKKK ceramics exist in a rhombohedral phase at room temperature. The DKKK ceramics sintered at 1300°C or above exhibit cubic to rhombohedral and back to cubic phase transitions upon heating at a 300–500°C temperature range, while Praxair ceramics exist in a pure cubic phase upon heating from room temperature to 900°C. However, if heated rather fast, the cubic to rhombohedral phase transformation could be avoided. Thus it is not expected that the observed phase transitions play a significant role in developing transformation stresses in ScCeZrO2 electrolyte upon heating and cooling down from the operation temperatures.


2018 ◽  
Vol 60 (10) ◽  
pp. 2022
Author(s):  
Ю.Э. Китаев ◽  
С.А. Кукушкин ◽  
А.В. Осипов ◽  
А.В. Редьков

AbstractA new trigonal (rhombohedral) SiC phase, existence of which was previously theoretically predicted by a symmetry analysis, is studied. It is shown that the phase can be formed during the growth of SiC films by the method of substitution of atoms on the surface of a Si substrate. Ab initio calculations of the crystal structure of a new phase and its Raman spectra are performed by the quantum chemistry method. The difference of the selection rules for the Raman active vibrations for this rhombohedral phase from the selection rules for a cubic phase in the coordinate system aligned with the translation vectors of the rhombohedral phase is established. Series of thin SiC/Si films by annealing time are synthesized by the method of the topochemical substitution of atoms, and their Raman spectra are analyzed. The presence of the spectral line (258 cm^–1), that is close to the line of a new trigonal (rhombohedral) phase calculated by the ab initio method, has been found in the Raman spectra of the samples at the initial stage of the growth of a SiC film, which indirectly confirms its existence.


2020 ◽  
Vol 8 (47) ◽  
pp. 24833-24867
Author(s):  
Jennifer H. Stansby ◽  
Neeraj Sharma ◽  
Damian Goonetilleke

The complex behaviour of layered oxide cathode materials at high voltages currently limits the energy densities which can be achieved by sodium-ion batteries.


2014 ◽  
Vol 70 (a1) ◽  
pp. C43-C43
Author(s):  
Nan Zhang ◽  
Hiroko Yokota ◽  
A. Glazer ◽  
Zuo-Guang Ye

The crystal structure and its relationship with the high piezoelectric performance of PbZr1-xTixO3 (PZT) have been studied for years, especially near the morphotropic phase boundary (MPB). Now the bridging monoclinic Cm phase in the MPB separating the not-group-subgroup-related R3c and P4mm has been widely accepted. However, in recent high-resolution powder diffraction experiments and Rietveld refinement analyses, the presence of the monoclinic Cm phase was found across the whole composition from the MPB to the rhombohedral region. Around the MPB, the structure seems to become more complicated, with a mixture of three phases[1]. It was also found that the local structure of PZT can be different from its average structure by examining the anisotropic displacement ellipsoids of both Pb and O: 1) the Pb atoms in the rhombohedral phase are displaced away from the threefold symmetry axes to create locally monoclinic symmetry that averages out to form an overall rhombohedral symmetry[2]; 2) at high temperature, the local effect of the low-temperature oxygen octahedra tilts remained even in the cubic phase[3]. In order to better study the local structures of PZT, we have carried out a series of high-resolution neutron diffraction experiments on both powder samples using Pair Distribution Function (PDF) analysis and single crystal samples using Diffuse Scattering (DS) analysis. The difference between the average and local structures is confirmed. The local distribution of the Pb displacements directions are plotted out for different compositions in PZT (x = 0.20, 0.30 and 0.40), which reveals on approaching MPB, the Pb atoms are tend to displace on one monoclinic mirror plane forming a macroscopic monoclinic phase. This is the first time that the local monoclinic short range order in Zr-rich PZT has been observed.


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