scholarly journals Deep hydration of an Li7–3x La3Zr2 M III x O12 solid-state electrolyte material: a case study on Al- and Ga-stabilized LLZO

2021 ◽  
Vol 78 (1) ◽  
Author(s):  
Günther J. Redhammer ◽  
Gerold Tippelt ◽  
Daniel Rettenwander
Keyword(s):  
Solid State ◽  
Tetrahedral Site ◽  
Charge Balance ◽  
X Ray Diffraction ◽  
Solid State Electrolyte ◽  
X Ray ◽  
Unit Cell Size ◽  
Ceramic Sintering ◽  
Distinct Increase

Single crystals of an Li-stuffed, Al- and Ga-stabilized garnet-type solid-state electrolyte material, Li7La3Zr2O12 (LLZO), have been analysed using single-crystal X-ray diffraction to determine the pristine structural state immediately after synthesis via ceramic sintering techniques. Hydrothermal treatment at 150 °C for 28 d induces a phase transition in the Al-stabilized compound from the commonly observed cubic Ia\overline{3}d structure to the acentric I\overline{4}3d subtype. LiI ions at the interstitial octahedrally (4 + 2-fold) coordinated 48e site are most easily extracted and AlIII ions order onto the tetrahedral 12a site. Deep hydration induces a distinct depletion of LiI at this site, while the second tetrahedral site, 12b, suffers only minor LiI loss. Charge balance is maintained by the incorporation of HI, which is bonded to an O atom. Hydration of Ga-stabilized LLZO induces similar effects, with complete depletion of LiI at the 48e site. The LiI/HI exchange not only leads to a distinct increase in the unit-cell size, but also alters some bonding topology, which is discussed here.

Structural analysis of excess-anion C-type rare earth oxide: a case study with Gd1−xCexO1.5+x/2(x= 0.20 and 0.40)

2003 ◽  
Vol 36 (4) ◽  
pp. 1082-1084 ◽  
Author(s):  
V. Grover ◽  
S. N. Achary ◽  
A. K. Tyagi
Keyword(s):  
Rare Earth ◽  
Structural Analysis ◽  
Metal Ion ◽  
Rare Earth Oxide ◽  
Charge Balance ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cell Parameters ◽  
Lattice Space

Structural analysis of anion-rich C-type Gd2O3was carried by the Rietveld refinement of the powder X-ray diffraction data for compositions Gd0.8Ce0.2O1.60and Gd0.6Ce0.4O1.70. Both compounds have a body-centred cubic lattice (space groupIa\bar{3}, No. 206,Z= 32) with unit-cell parameters of 10.8488 (1) and 10.8542 (1) Å, respectively. Both of these compounds are iso-structural with the C-type rare earth oxides, with excess anions as required for charge balance. The structural analysis reveals that there are two different kinds of metal ion site, namely 8b(M1) and 24d(M2), and two different kinds of anion sites, namely 48e(O1) and 16c(O2). The excess anions occupy the 16c(xxx) sites. The two metal ions each form an approximately eightfold-coordination polyhedron with O1 and O2. The details of these two compositions are explained and compared with both the CeO2structure and the Gd2O3structure,i.e.the end member.

scholarly journals Single-crystal neutron and X-ray diffraction study of garnet-type solid-state electrolyte Li6La3ZrTaO12: an in situ temperature-dependence investigation (2.5 ≤ T ≤ 873 K)

2021 ◽  
Vol 77 (1) ◽  
pp. 123-130
Author(s):  
Günther J. Redhammer ◽  
Martin Meven ◽  
Steffen Ganschow ◽  
Gerold Tippelt ◽  
Daniel Rettenwander
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Czochralski Method ◽  
Atomic Displacement ◽  
X Ray Diffraction ◽  
Solid State Electrolyte ◽  
Cubic Symmetry ◽  
X Ray ◽  
Site Occupation ◽  
Atomic Displacement Parameters

Large single crystals of garnet-type Li6La3ZrTaO12 (LLZTO) were grown by the Czochralski method and analysed using neutron diffraction between 2.5 and 873 K in order to fully characterize the Li atom distribution, and possible Li ion mobility in this class of potential candidates for solid-state electrolyte battery material. LLZTO retains its cubic symmetry (space group Ia 3 d) over the complete temperature range. When compared to other sites, the octahedral sites behave as the most rigid unit and show the smallest increase in atomic displacement parameters and bond length. The La and Li sites show similar thermal expansion in their bond lengths with temperature, and the anisotropic and equivalent atomic displacement parameters exhibit a distinctly larger increase at temperatures above 400 K. Detailed inspection of nuclear densities at the Li1 site reveal a small but significant displacement from the 24d position to the typical 96h position, which cannot, however, be resolved from the single-crystal X-ray diffraction data. The site occupation of LiI ions on Li1 and Li2 sites remains constant, so there is no change in site occupation with temperature.

Schmidite and wildenauerite, two new schoonerite-group minerals from the Hagendorf-Süd pegmatite, Oberpfalz, Bavaria

2018 ◽  
Vol 83 (02) ◽  
pp. 181-190
Author(s):  
Ian E. Grey ◽  
Erich Keck ◽  
Anthony R. Kampf ◽  
John D. Cashion ◽  
Colin M. MacRae ◽  
...  
Keyword(s):  
Thermal Analysis ◽  
Tetrahedral Site ◽  
Orthorhombic Symmetry ◽  
Charge Balance ◽  
X Ray Diffraction ◽  
Unit Cell Parameters ◽  
X Ray ◽  
Cell Parameters ◽  
Symmetry Space ◽  
Symmetry Space Group

AbstractSchmidite, Zn(Fe3+0.5Mn2+0.5)2ZnFe3+(PO4)3(OH)3(H2O)8 and wildenauerite, Zn(Fe3+0.5Mn2+0.5)2Mn2+Fe3+(PO4)3(OH)3(H2O)8 are two new oxidised schoonerite-group minerals from the Hagendorf-Süd pegmatite, Hagendorf, Oberpfalz, Bavaria, Germany. Schmidite occurs as radiating sprays of orange–brown to copper-red laths on and near to altered phosphophyllite in a corroded triphylite nodule, whereas wildenauerite forms dense compacts of red laths, terminating Zn-bearing rockbridgeite. The minerals are biaxial (+) with α = 1.642(2), β = 1.680(1), γ = 1.735(2) and 2Vmeas = 81.4(8)° for schmidite, and with α = 1.659(3), β = 1.687(3), γ = 1.742(3) and 2Vmeas = 73(1)° for wildenauerite. Electron microprobe analyses, with H2O from thermal analysis and FeO/Fe2O3 from Mössbauer spectroscopy, gave FeO 0.4, MgO 0.3, Fe2O3 23.5, MnO 9.0, ZnO 15.5, P2O5 27.6, H2O 23.3, total 99.6 wt.% for schmidite, and FeO 0.7, MgO 0.3, Fe2O3 25.2, MnO 10.7, ZnO 11.5, P2O5 27.2, H2O 24.5, total 100.1 wt.% for wildenauerite. The empirical formulae, scaled to 3 P and with OH– adjusted for charge balance are Zn1.47Mn2+0.98Mg0.05Fe2+0.04Fe3+2.27(PO4)3(OH)2.89(H2O)8.54 for schmidite and Zn1.11Mn2+1.18Mg0.05Fe2+0.08Fe3+2.47(PO4)3(OH)3.25(H2O)9.03 for wildenauerite. The two minerals have orthorhombic symmetry, space group Pmab and Z = 4. The unit-cell parameters from refinement of powder X-ray diffraction data are a = 11.059(1), b = 25.452(1) and c = 6.427(1) Å for schmidite, and a = 11.082(1), b = 25.498(2) and c = 6.436(1) Å for wildenauerite. The crystal structures of schmidite and wildenauerite differ from that of schoonerite in having minor partitioning of Zn from the [5]Zn site to an adjacent vacant tetrahedral site [4]Zn, separated by ~1.0 Å from [5]Zn. The two minerals are distinguished by the cation occupancies in the octahedral M1 to M3 sites. Schmidite has M1 = M2 = (Fe3+0.5Mn2+0.5) and M3 = Zn and wildenauerite has M1 = M2 = (Fe3+0.5Mn2+0.5) and M3 = Mn2+.

Oxyanion Substituted Ettringites: Synthesis and Characterization; and their Potential Role In Immobilization of As, B, Cr, Se and V

1989 ◽  
Vol 178 ◽  
Author(s):  
Premkumari Kumarathasan ◽  
Gregory J. McCarthy ◽  
David J. Hassett ◽  
Debra F. Pflughoeft-Hassett
Keyword(s):  
Room Temperature ◽  
Potential Role ◽  
Charge Balance ◽  
X Ray Diffraction ◽  
X Ray ◽  
Unit Cell Size ◽  
Potentially Hazardous Elements ◽  
Ftir Spectrometry ◽  
Structural Formulae

AbstractLong-term batch leaching studies of composites of lignite combustion and gasification ashes with a calcium-based scrubber waste have shown the prominent formation of an ettringite structure phase, accompanied by reductions in solution concentrations of potentially hazardous elements such as boron and selenium. The possibility that oxyanions such as arsenate, borate, chromate, molybdate, selenate and vanadate might substitute for sulfate in the ettringite structure has been explored. There are literature reports of fully substituted borate, chromate and selenate [ettringites]*, and of two minerals with partial borate for sulfate substitution. X-ray diffraction phase pure products with chromate and selenate, substituted completely for the sulfate in ettringite, and with arsenate, borate and vanadate partially substituted for sulfate, have been synthesized at room temperature by mixing soluble Ca, Al and sulfate sources and maintaining a pH> 12 with NaOH additions. Attempts to substitute substantial amount of molybdate for sulfate were unsuccessful. The resulting phases were characterized chemically by ICAP spectrometry, ion chromatography and thermal analysis, and for phase purity and unit cell size by XRD. The speciation of the oxyanions in the substituted [ettringite] were confirmed by FTIR spectrometry. In solid solutions, the sulfate/oxyanion ratio was greater in the precipitated solid than in the synthesis solution. Chemical analyses of the [ettringites] did not give simple stoichiometries analogous to Ca6Al2(SO4)(OH)12 ·26H2O. Because nonstoichiometry can be attributed to numerous possibilities for charge balance and defects, structural formulae of the oxyanion substituted [ettringites] could not be established.

Palenzonaite, berzeliite, and manganberzeliite: (As5+, V5+, Si4+)O4 tetrahedra in garnet structures

2012 ◽  
Vol 76 (5) ◽  
pp. 1081-1097 ◽  
Author(s):  
M. Nagashima ◽  
T. Armbruster
Keyword(s):  
Microprobe Analysis ◽  
Electron Microprobe Analysis ◽  
Divalent Cations ◽  
Tetrahedral Site ◽  
Site Occupancy ◽  
Charge Balance ◽  
X Ray Diffraction ◽  
Ionic Radii ◽  
X Ray ◽  
The Mean

AbstractSchäferite, NaCa2Mg2(V5+O4)3; palenzonaite, NaCa2Mn22+(V5+O4)3; berzeliite, NaCa2Mg2(As5+O4)3; and manganberzeliite, NaCa2Mn2+2(As5+O4)3, are cubic minerals with garnet structures (space group Iad) in which tetrahedrally coordinated V5+ and/or As5+ at the Z site are charge balanced by disordered Na+ and Ca2+ at the X site, and divalent Mg2+ and Mn2+ cations at the octahedrally coordinated Y site. The crystal chemistry of palenzonaite (from the Molinello and Gambatesa mines, Italy, and the Fianel mine, Switzerland), berzeliite (from Långban, Sweden, and Montaldo, Italy), and manganberzeliite (from Varenche, Italy, and the Gozaisho mine, Japan) were studied by electron microprobe analysis and single-crystal X-ray diffraction methods. Structure refinements converged to R1 values of 1.36–2.42%. The tetrahedral site in these garnet structures is mainly occupied by pentavalent As5+ or V5+ (only up to about 20% randomly distributed Si4+ is present). Charge balance is maintained by variations in the Ca/Na ratio at the X site. Heterovalent substitution (Na+ ↔ Ca2+) at the distorted square antiprism X site in vanadate- and arsenate-bearing garnets allows full occupancy of the octahedral Y site by divalent cations (primarily Mg2+ and Mn2+). There is a positive correlation between the <Z–O> and <Y–O> bond lengths and the mean ionic radii of the substituent elements, but there is no correlation between the <X–O> bond length and the variable Na/Ca site occupancy. The ionic radii of octahedrally coordinated Mg2+ and Mn2+ are such that the shared octahedral–dodecahedral edges are similar in length to the unshared octahedral edges, which is a measure of lattice distortion in garnet structures.

The Collagenic Molecular Structural Unit of Solid State Complexes

1971 ◽  
Vol 29 ◽  
pp. 478-479
Author(s):  
Kenneth M. Richter ◽  
John A. Schilling
Keyword(s):  
Molecular Weight ◽  
Solid State ◽  
Structural Unit ◽  
X Ray Diffraction ◽  
X Ray ◽  
Naoh Treatment

The structural unit of solid state collagen complexes has been reported by Porter and Vanamee via EM and by Cowan, North and Randall via x-ray diffraction to be an ellipsoidal unit of 210-270 A. length by 50-100 A. diameter. It subsequently was independently demonstrated by us in dog tendon, dermis, and induced complexes. Its detailed morphologic, dimensional and molecular weight (MW) aspects have now been determined. It is pear-shaped in long profile with m diameters of 57 and 108 A. and m length of 263 A. (Fig. 1, tendon, KMnO4 fixation, Na-tungstate; Fig. 2a, schematic of unit in long, C, and x-sectional profiles of its thin, xB, and bulbous, xA portions; Fig. 2b, tendon essentially unmodified by ether and 0.4 N NaOH treatment, Na-tungstate). The unit consists of a uniquely coild cable, c, of ṁ 22.9 A. diameter and length of 2580-3316 A. The cable consists of three 2nd-strands, s, each of m 10.6 A.

TEM studies of solid-state reactions in sputter-deposited Nb/Al multilayer thin films

1996 ◽  
Vol 54 ◽  
pp. 1020-1021
Author(s):  
F. Ma ◽  
S. Vivekanand ◽  
K. Barmak ◽  
C. Michaelsen
Keyword(s):  
Thin Films ◽  
Solid State ◽  
Stoichiometric Composition ◽  
Analytical Electron Microscopy ◽  
Grain Structure ◽  
Solid State Reactions ◽  
Multilayer Thin Films ◽  
X Ray Diffraction ◽  
X Ray ◽  
Sputter Deposited

Solid state reactions in sputter-deposited Nb/Al multilayer thin films have been studied by transmission and analytical electron microscopy (TEM/AEM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The Nb/Al multilayer thin films for TEM studies were sputter-deposited on (1102)sapphire substrates. The periodicity of the films is in the range 10-500 nm. The overall composition of the films are 1/3, 2/1, and 3/1 Nb/Al, corresponding to the stoichiometric composition of the three intermetallic phases in this system.Figure 1 is a TEM micrograph of an as-deposited film with periodicity A = dA1 + dNb = 72 nm, where d's are layer thicknesses. The polycrystalline nature of the Al and Nb layers with their columnar grain structure is evident in the figure. Both Nb and Al layers exhibit crystallographic texture, with the electron diffraction pattern for this film showing stronger diffraction spots in the direction normal to the multilayer. The X-ray diffraction patterns of all films are dominated by the Al(l 11) and Nb(l 10) peaks and show a merging of these two peaks with decreasing periodicity.

Fabrication and study the effect of the laser on the properties of the compound Tl2-xHgxBa2-ySryCa2Cu3O10+δ superconductor

2018 ◽  
pp. 168
Author(s):  
A. Kareem Dahash Ali ◽  
Nihad Ali Shafeek
Keyword(s):  
Transition Temperature ◽  
Solid State ◽  
Hydrostatic Pressure ◽  
Electrical Properties ◽  
Co2 Laser ◽  
Temperature Shift ◽  
Unit Cell ◽  
X Ray Diffraction ◽  
X Ray ◽  
Structural And Electrical Properties

This study included the fabrication of    compound (Tl2-xHgxBa2-ySryCa2Cu3O10+δ) in a manner solid state and under hydrostatic pressure ( 8 ton/cm2) and temperature annealing(850°C), and determine the effect of the laser on the structural and electrical properties elements in the compound, and various concentrations of x where (x= 0.1,0.2,0.3 ). Observed by testing the XRD The best ratio of compensation for x is 0.2 as the value of a = b = 5.3899 (A °), c = 36.21 (A °) show that the installation of four-wheel-based type and that the best temperature shift is TC= 142 K  .When you shine a CO2 laser on the models in order to recognize the effect of the laser on these models showed the study of X-ray diffraction of these samples when preparing models with different concentrations of the values ​​of x, the best ratio of compensation is 0.2 which showed an increase in the values ​​of the dimensions of the unit cell a=b = 5.3929 (A °), c = 36.238 (A°). And the best transition temperature after shedding laser is TC=144 K. 

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