The thermal behaviour of the quadrupole hyperfine interaction in (NH4)2HfF6

A TDPAC investigation has been accomplished on (NH₄)₂ HfF₆ between 14 and 620 K. A phase transition was observed below 390 K. The low temperature phase is characterized by two non-equivalent sites for hafnium atoms in a 1∶1 ratio. The high temperature phase, on the other hand, is depicted by a unique quadrupole interaction. Above 400 K, the compound decomposes successively to NH₄ HfF₅, NH₄ Hf₂F₉ and HfF₄. An enthalpy of 76±4 kJ/mol could be determined for the (NH₄)₂ HfF₆→NH₄ HfF₅+NH₄F chemical reaction. The hyperfine interaction and thermal evolution of (NH₄)₂ HfF₆ was found to be quite similar to that of (NH₄)₂ ZrF₆.     

Investigation of ion transport in Li<Subscript>8</Subscript>ZrO<Subscript>6</Subscript> and Li<Subscript>6</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> solid electrolytes

Lithium ionic conductivity and spin-lattice relaxation rates were measured in Li₈ZrO₆ and Li₆Zr₂O₇ solid electrolytes. It was found that the Li₈ZrO₆ solid electrolyte undergoes a transition to the superionic state in the temperature range 673–703 K. It was shown that Li⁺ ions are mobile in particular lattice positions of the Li₆Zr₂O₇ phase, and that ionic conductivity is monotonic at an activation energy of 79.4 kJ/mol.     

Anomalous thermal behaviour of β-(NH4)2HfF6

It has been determined that the thermally activated α→β transition occurring in (NH₄)₂HfF₆ at about 370 K is not always reversible. The β-phase hysteresis was investigated between 14 and 400 K. It was possible to explain previously published results without considering the Goldanskii-Karyagin effect.     

Super-protonic phase transition and fast ionic conductivity of Li+ in [Li0.2(NH4)0.8]2TeCl6

The differential scanning calorimetry diagram of [Li_0.2(NH₄)_0.8]₂TeCl₆ showed one anomaly at 526 K accompanied with a shoulder at 505 K.The conductivity plot exhibits two anomalies at 496 and 526 K, which characterize the beginning and the end of the crossing to superionic conductor state. The low temperature conduction is ensured essentially by Li⁺. A sudden jump confirms the presence of a superionic protonic transition related to the fast motion of Li⁺ and H⁺ ions. Above 526 K, the high temperature phase is characterized by high electrical conductivity (10^− 3 Ω^− 1 m^− 1) and low activation energy (E_a < 0.3 eV).The dielectric constant evolution as a function of frequency and temperature revealed the same anomaly.Transport properties in this material appear to be due to Li⁺ and H⁺ ions' hopping mechanism.     

Phase evolution, Raman spectroscopy and microwave dielectric behavior of (Li1/4Nb3/4) doped ZrO2-TiO2 system

The phase evolution, Raman spectroscopy and microwave dielectric properties of (Li_1/4Nb_3/4) doped ZrO₂-TiO₂ system were investigated. The effects of the Zr/Ti ratio and the (Li_1/4Nb_3/4) substitution were addressed. X-ray diffraction and electron diffraction analysis showed that the crystalline phases of the (Li_1/4Nb_3/4) doped ZrO₂-TiO₂ ceramics depended greatly on the Zr/Ti ratio. The sample with Zr/Ti ratio of 7/9 crystallized as Zr₅Ti₇O₂₄ phase structure, a commensurate structure with a tripled a-axis superstructure and a Z^TTZ_TT sequence. Secondary phase of monoclinic ZrO₂ phase appeared when the Zr/Ti ratio was as high as 9/7. Raman analysis showed that the Raman peaks located at 651 and 624 cm⁻¹ were assigned to the vibration modes of Zr-O octahedron and Ti-O octahedron, respectively. The dielectric constant and quality factor (Qf value) of the (Li_1/4Nb_3/4) doped ZrO₂-TiO₂ ceramics decreased slightly as the Zr/Ti ratio changed from 6/10 to 9/7. The temperature coefficient of resonate frequency (TCF value) was sensitive to the Zr/Ti ratio and it showed a negative value when the Zr/Ti ratio was close to 5:7. Meanwhile, the TCF value of ZrO₂-TiO₂ ceramics could also be tailored by the (Li_1/4Nb_3/4) substitution.     

Electrochemical comparison between SnO2 and Li2SnO3 synthesized at high and low temperatures

Li₂SnO₃ has been synthesized at 1000 °C from Li₂CO₃ and SnO₂ (high temperature form - HT) and it has also been prepared from ball-milled SnO₂ and Li₂CO₃ at 650 °C (low temperature form - LT). The Li₂SnO₃ materials have been tested as a negative electrode for possible use in a Li-ion cell and their electrochemical behaviour has been compared with that of SnO₂. In theory, Li₂SnO₃ and SnO₂ should be able to cycle the same number of lithium atoms per tin atom but on the initial discharge SnO₂ has inserted more lithium than Li₂SnO₃. During the initial discharge of SnO₂ and Li₂SnO₃, a side electrochemical reaction seems to be occurring. The resultant compound apparently inserts lithium reversibly for potentials around 1 V; however, cycling from 0.02–2 V significantly degrades performance compared to 0.02–1 V. Li₂SnO₃ (HT) allows the de-insertion of more lithium than Li₂SnO₃ (LT) and SnO₂ in the first charge. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Calculation of 7Li MAS NMR chemical shift in La4/3−yLi3yTi2O6

The chemical shifts of ⁷Li MAS nuclear magnetic resonance spectra in La_4/3−yLi_3yTi₂O₆ (LLTO) showed negative values and decreased with increasing lithium concentration. The chemical shifts were interpreted by Pople’s theory in which the ⁷Li chemical shifts were due to the local paramagnetic currents of the closest oxygen ions. Lattice parameters and coordination of oxygen were obtained by Rietveld analysis of X-ray diffraction data. The gross population and electron excitation energy were calculated by DV-Xα method.     

Quadrupole hyperfine interaction and thermal stability of ZrF4.3H2O

The quadrupole hyperfine interaction of ZrF₄.3H₂O is reported. This compound is observed to dehydrate to ZrF₄ at 325 K. Spectra taken on cooling were observed to be time dependent, and the rehydration process involved was investigated at 293, 298 and 302 K. Contrary to what had previously been determined in HfF₄.3H₂O, no intermediate compound was observed to participate in the reaction investigated, thus confirming structural differences already reported to exist between these isoformulae compounds.     

Low temperature structural phase transition in hafnium and zirconium tetrafluoride trihydrates

From time-differential perturbed angular correlation (TDPAC) measurements, the monoclinic and triclinic crystal structures in hafnium and zirconium tetrafluoride trihydrates are found to be present simultaneously in both the compounds. From previous TDPAC and XRD investigations, a monoclinic crystal structure for HfF₄·3H₂O but, for its analogues zirconium compound, a triclinic structure was reported. Contrary to earlier reports, the triclinic fraction in HfF₄·3H₂O is found to be maximum (80%) at room temperature. In fact, the triclinic crystal structure of HfF₄·3H₂O is reported here which was not known prior to this report. In ZrF₄·3H₂O, a strong signal (80–90%) for the triclinic structure is found at room temperature while the monoclinic fraction appears as a weak signal (10–15%). Structural phase transitions in these trihydrate compounds have been observed in the temperature range 298–333 K.     

Temperature dependence of the electric field gradient in HfF4.HF.2H2O

The hyperfine quadrupole interaction in HfF₄.HF.2H₂O was studied using the time differential perturbed angular correlation (TDPAC) technique. The electric field gradient (EFG) and the corresponding asymmetry parameter were measured in the temperature range from 9 to 350 K. The EFG is characterized by a rather strong increase with temperature, whereas the asymmetry parameter reaches its maximum value (η≈1) at aboutT=160 K. At 420 K, the complex is dehydrated and looses HF: The quadrupole parameters determined from subsequent TDPAC measurements are charateristic for HfF₄.     

Optical thermometry through green and red upconversion emissions in Er/Yb/Li:ZrO2 nanocrystals

Variations of fluorescence intensity ratio of green (generated from Er^{3+ 2}H_11/2 and ⁴S_3/2 levels) and red (generated from the sublevels of Er^{3+ 4}F_9/2 level) upconversion emissions in Er³⁺/Yb³⁺/Li⁺:ZrO₂ nanocrystals have been studied as a function of temperature under 976 nm laser diode excitation. In the temperature range of 323-673 K, the maximum sensitivities of about 0.0134 K^− 1 and 0.0104 K^− 1 are obtained by using green and red emission, respectively. Er³⁺/Yb³⁺/Li⁺:ZrO₂ nanocrystals show potential application value in nanoscale thermal sensor.     

TDPAC characterization of Ni2HfF8·12H2O and its decomposition products

The hyperfine interaction in Ni₂HfF₈·12H₂O has been determined between 77 K and 1100 K by means of the time-differential perturbed angular correlation technique. From 200 K on, the one-site phase existing at lower temperatures undergoes a gradual phase transition until, at room temperature, the populations of both phases attain a 2:1 ratio. While the quadrupole frequencies characterizing them exhibit aT ^3/2 thermal dependence, their population ratio seems to obey a Boltzmann distribution. At 350 K, when the η-value of the high temperature phase electric field gradient approaches its maximum value, the starting compound decomposes to NiHfF₆·6H₂O. A kinetics study of the Ni₂HfF₈·12H₂O recovery at room temperature seems to indicate that a tri-dimensional diffusion mechanism is responsible for the corresponding reaction process. The first decomposition product of NiHfF₆·6H₂O left to atmospheric pressure is found to be NiHfF₆·4H₂O at 368 K and, between 414 K and 590 K, the high temperature cubic phase of NiHfF₆ and Hf₂OF₆ can be simultaneously observed. Finally, monoclinic HfO₂ appears from 1020 K on, having been preceded by an interaction which can be though of as depicting a preliminary stage in hafnia formation.     

Synthesis and CO2 capture property of high aspect-ratio Li2ZrO3 nanotubes arrays

High aspect-ratio Li₂ZrO₃ nanotubes were prepared by hydrothermal method using ZrO₂ nanotubes layers as templates. Characterizations of SEM, XRD, TEM and CO₂ adsorption were performed. The results showed that tetragonal Li₂ZrO₃ nanotubes arrays containing a little monoclinic ZrO₂ can be obtained using this simple method. The mean diameter of the nanotubes is approximately 150 nm and the corresponding specific surface area is 57.9 m² g⁻¹. Moreover, the obtained Li₂ZrO₃ nanotubes were thermally analyzed under a CO₂ flow to evaluate their CO₂ capture property. It was found that the as-prepared Li₂ZrO₃ nanotubes arrays would be an effective acceptor for CO₂ at high temperature.     

Lithium superionic conductors Li3InBr6 and LiInBr4 studied by 7Li, 115In NMR

Li₃InBr₆ undergoes a phase transition to a superionic phase at 314 K associated with a steep increase of the conductivity (σ = 4 × 10^− 3 Scm^− 1 at 330 K). This superionic phase is isomorphous with Li₃InCl₆ in which a positional disorder at the In³⁺ site is introduced. A pseudo cubic-close-packing of the bromide ions is formed in this phase. On the other hand, a new superionic phase of LiInBr₄ was found above ca 315 K and its structure was confirmed to be a defect spinel. The dynamic properties of the cations in these two superionic phases were investigated by ⁷Li and ¹¹⁵In NMR spectroscopy.     

Conductivity studies on LiX–Li2S–Sb2S3–P2S5 (X = LiI or Li3PO4) glassy system

New sulfide glasses in the Li₂S–Sb₂S₃–P₂S₅ system have been prepared by classical quenching technique where glassy domain remains up to 50% molar addition of Li₂S and electrical conductivities have been determined by impedance spectroscopy. Room temperature DC conductivity vs Li₂S content exhibits two regions implying different conductivity mechanisms. The compositions of low lithium content presented low electronic conductivities close to 0.01 μS/cm at room temperature (due to Sb₂S₃ semiconducting properties). The compositions of medium lithium content could result to mixed ionic–electronic conductors with predominant ionic conductivity with a maximum close to 1 μS/cm; Arrhenius behavior is found between 25 °C and T _g for all glasses, but activation energy is found to be somehow above most similar systems. A comparative study with glasses belonging to the other chalcogenide systems has been undertaken and values of the decoupling index are reported, and in order to validate conductivity data, a circuit equivalent circuit was proposed and fitted parameters were calculated with good agreement.     

Existence of an incommensurate phase in a Li2B4O7 crystal

The x-ray diffraction spectra of Li₂B₄O₇ single crystals are investigated in the temperature range 80–300 K, and the lattice parameter c is determined in the same temperature range in the presence of a periodically varying temperature field. An incommensurate phase is not observed anywhere in the temperature range investigated, regardless of whether the crystals are subjected to a periodic temperature field. Fiz. Tverd. Tela (St. Petersburg) 39, 1461–1463 (August 1997)     

7Li and 51V NMR study on Li+ ionic diffusion in lithium intercalated LixV2O5

Li_xV₂O₅ (0.4 < x < 1.4) prepared by solid-state reaction were studied by ⁷Li and ⁵¹V NMR spectroscopy. ⁷Li NMR spectra showed a narrowing of the line width in relation to Li⁺ionic diffusion. Analysis of Li_xV₂O₅ using a Debye-type relaxation model showed a low activation energy ∼0.07 eV in the sample of x = 0.4 below room temperature, and revealed a Li⁺ionic diffusion with larger activation energy ∼0.5 eV above 450 K in lithium-rich samples. The latter is ascribed to the existence of a multi-phase system comprising stable ɛ- and γ-phases, resulting from complicated phase transitions at high temperature. These shapes and shifts enable the classification of the β-, ɛ-, δ-, and γ-phases. The ionic diffusion of Li⁺ ions is discussed in relation to the complicated phase transitions.     

A lithium salt additive Li<Subscript>2</Subscript>ZrF<Subscript>6</Subscript> for enhancing the electrochemical performance of high-voltage LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode

In this work, Li₂ZrF₆, a lithium salt additive, is reported to improve the interface stability of LiNi_0.5Mn_1.5O₄ (LNMO)/electrolyte interface under high voltage (4.9 V vs Li/Li⁺). Li₂ZrF₆ is an effective additive to serve as an in situ surface coating material for high-voltage LNMO half cells. A protective SEI layer is formed on the electrode surface due to the involvement of Li₂ZrF₆ during the formation of SEI layer. Charge/discharge tests show that 0.15 mol L^?1 Li₂ZrF₆ is the optimal concentration for the LiNi_0.5Mn_1.5O₄ electrode and it can improve the cycling performance and rate property of LNMO/Li half cells. The results obtained by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) demonstrate that Li₂ZrF₆ can facilitate the formation of a thin, uniform, and stable solid electrolyte interface (SEI) layer. This layer inhibits the oxidation decomposition of the electrolyte and suppresses the dissolution of the cathode materials, resulting in improved electrochemical performances.     

Strong reaction channels at barrier energies in the system 6Li + 208Pb

Large cross-section reaction channels were measured in the systems ⁶Li( ⁷Li) + ²⁰⁸Pb with high statistical accuracy at 5(3) energies around the Coulomb barrier from 29 to 39 MeV. These channels were assigned (mainly) to the breakup of ⁶Li, very loosely bound, into α + d and to the breakup of ⁵Li, produced by n-transfer to the target, into α + p and to similar processes with ⁷Li beam. The cross-sections with ⁶Li, S _α = 1.475 MeV, are systematically larger than the ⁷Li ones. This reflects, most likely, the higher binding energy of ⁷Li, S _α = 2.468 MeV. Theoretical predictions for the ⁶Li + ²⁰⁸Pb system which include for ⁶Li breakup to continuum states within a continuum discretized coupled-channels approach (CDCC) and resonant breakup plus n-transfer with DWBA reproduce the angular distribution shapes but still underestimate the cross-sections by a factor ∼ 3. Received: 15 January 2001 / Accepted: 3 March 2001