Sodium superionic conductor sputter-deposited coatings

Thin sodium superionic conductor (Nasicon) coatings are deposited on rotating substrates by co-sputtering in the reactive mode of a Zr-Si and a Na₃PO₄ target. The influence of the discharge current and of the target-to-substrate distance is investigated owing to the targeted Na₃Zr₂Si₂PO₁₂ stoichiometry. A thermo-structural analysis shows that the amorphous as-deposited coating of convenient composition crystallises around 700 °C in the monoclinic structure. Electrical measurements performed at room temperature after various annealing treatments indicate a ionic conductivity of about 2·10⁻³ S·cm⁻¹, consistent with that of bulk Nasicon. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

The luminescence properties of Eu2+ doped Na2CaMg(PO4)2 phosphor

The blue-emitting phosphors of Eu²⁺-doped Na₂CaMg(PO₄)₂ were prepared by high-temperature solid-state reaction. The crystal phase formation was confirmed by X-ray powder diffraction measurement. The luminescence properties were investigated by photoluminescence excitation and emission spectra. The phosphor exhibited the blue luminescence due to the 4f⁶5d¹→4f⁷ transition of Eu²⁺ ions under the excitation of near UV light. The influence of temperature on the luminescence intensities and decay lifetimes of Eu²⁺ was investigated. An unusual increase of the decay lifetimes of the 4f⁶5d emission of Eu²⁺ ion is observed in Na₂CaMg(PO₄)₂ from 10 K to room temperature. The thermal stability of the luminescence of Eu²⁺-doped Na₂CaMg(PO₄)₂ was discussed.     

Towards a thin films electrochromic device using NASICON electrolyte

The optimisation of the morphology of WO₃ thin films allowed a more efficient electrochromic colouring using Na⁺ ions than H⁺ ones. Therefore, sodium superionic conductor (Na₃Zr₂Si₂PO₁₂, NASICON) films may be used as electrolyte in inorganic electrochromic devices. In this paper, the structure, chemical composition, morphology and electrochromic properties of WO₃, ZnO:Al and Na₃Zr₂Si₂PO₁₂ thin films were studied to develop a novel type of electrochromic device. WO₃, ZnO:Al and Na₃Zr₂Si₂PO₁₂ thin films were deposited using reactive magnetron sputtering of tungsten, zinc and aluminium and Zr–Si and Na₃PO₄ targets, respectively. For transparent conductive oxide coatings, a correlation was established between the deposition parametres and the film’s structure, transmittance and electrical resistivity. Classical sputtering methods were not suitable for the deposition of NASICON films on large surface with homogenous composition. On the other hand, the use of high-frequency pulsed direct current generators allowed the deposition of amorphous films that crystallised after thermal annealing upon 700 °C in the Na₃Zr₂Si₂PO₁₂ structure. Amorphous films exhibited ionic conductivity close to 2 × 10⁻³ S cm⁻¹. Finally, preliminary results related to the electrochromic performance of NASICON, WO₃ and indium tin oxide devices were given. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, France, Sept. 9–15, 2007.     

Dielectric and conduction mechanism studies of PVA-orthophosphoric acid polymer electrolyte

Polyvinyl alcohol (PVA)-based proton conducting polymer electrolytes have been prepared by the solution cast technique. The conductivity is observed to increase from 10⁻⁹ to 10⁻⁴ S cm⁻¹ as a result of orthophosphoric acid (H₃PO₄) addition. The plot of conductivity vs temperature shows that a phase transition occurred at 343 K in the sample PVA-33 wt% H₃PO₄. The β-relaxation peak is observed at 313 K. The glass transition temperature of PVA-33 wt% H₃PO₄ is 343 K. Orthophosphoric acid seems to play a dual role, i.e., as a proton source and as a plasticizer. The ac conductivity σ _ac = Aω ^s was also calculated in the temperature range from 303 to 353 K. The conduction mechanism was inferred by plotting the graph of s vs T from which the conduction mechanism for sample PVA-17 wt% H₃PO₄ was inferred to occur by way of the overlapping large polaron tunneling (OLPT) model and the conduction mechanism for the sample PVA-33 wt% H₃PO₄ by way of the correlated barrier height (CBH) model.     

Dynamics in molecular crystals: An application of proton NMR to selectively protonated biphenyl. Do the rings flip together or independently?

The synthesis of a specific isotopomer, C₆D₄H(ortho)-H(ortho)D₄C₆ of biphenyl is reported. The intramolecular dipolar coupling of the protons leads to a well-resolved single-crystal proton nuclear magnetic resonance (NMR) spectrum and allows one to study the dynamics of the phenyl rings in a unique way. At room temperature and above, the most conspicuous dynamical mode consists of 180° ring flips. The present data together with previous measurements of the total flip rate allow us to conclude that the rings flip almost exclusively independently of each other. Between the incommensurate (IC) phase transition of biphenyl at 38 K andT=250 K, the prominent namical mode consists of oscillatory twists ϕ(t) of the two rings. The data allow us to infer the mean square, (φ²), of these twists. (φ²) is found to grow linearly withT for 50<T<200 K. From the slope of (φ²) vs.T the frequency (the wave number[(v)\tilde]\tilde v) is derived. The result is[(v)\tilde] = 20\tilde v = 20 cm⁻¹. ForT<38 K, the spectra give direct evidence of the IC phase transition and its nature (stripelike rather than quiltlike). The temperature dependence of the magnitude of the order parameter of the IC phase is obtained.     

Phase transitions in the Na3PO4-BiPO4 system

Abstract

The Na₃PO₄-BiPO₄ system has been investigated by X-ray diffraction and D.T.A. It features two definite compounds: Na₃Bi(PO₄)₂ and Na₃Bi₅(PO₄)₆, the first one being polymorphic. It crystallizes in two orthorhombic and two hexagonal forms below melting at 1025°C. The H.T. phase has the glaserite structure, and the other ones are related. Na₃Bi₅(PO₄)₆ is stable only at 680 ? t ? 820°C, but can easily be quenched. It has a non-centrosymmetric cubic structure (S.H.G.) of the eulytite type, and so potential piezoelectric applications can be expected. Na₃PO₄ and Na₃Bi(PO₄)₂ display two extensive ranges of solid solutions with the replacement mechanism 3Na⁺ → Bi³⁺ in the formula Na_3-3x Bi _x PO₄, respectively with 0 ? x ? 0.29 and 0.5 ? x ? 0.62 over 950°C.     

Vibrational study of H3OUO2PO4 · 3 H2O (HUP) and related compounds. phase transitions and conductivity mechanisms: part I,KUO2PO4 · 3 H2O (KUP)

Infrared and Raman spectra of polycrystalline KUO₂PO₄ · 3 H₂O (KUP) and its isotopic derivatives KUO₂P¹⁸O₄ · 3 H₂O and KUO₂PO₄ · 3 D₂O have been investigated in the 4000-10-cm^?1 range at different temperatures. An assignment of the bands in terms of UO₂, PO₄ and H₂O vibrations has been proposed. Combined differential scanning calorimetry and spectroscopic data show two diffuse phase transitions near 130 and 230 K. Comparison of the vibrational spectra of phase I at 300 K and phase IV at 100 K indicates that ordering of the water molecules with subsequent ordering of PO₄ tetrahedra on a site with lower symmetry appears to be the main mechanism responsible for the phase transformation. All the six O-H distances of water molecules in phase IV are found to be crystallographically nonequivalent. Conducting ion frequencies and the corresponding force constants have been determined for the analogous compounds MUP with M = K⁺, Na⁺, Ag⁺, NH⁺₄, Tl⁺ and H₃O⁺ and compared with other properties of these ionic conductors. Conductivity mechanisms in these materials are discussed.     

Conductivity studies and ion transport mechanism in LiI–Li3PO4 solid electrolyte

Mixtures of LiI–Li₃PO₄ were sintered at low temperature. It was observed that the conductivity improved up to 10⁻³ S cm⁻¹ with the addition of LiI. Infrared technique (Fourier transform infrared spectroscopy [FTIR]) was employed to detect the presence of polyhedral structures. From the FTIR spectra of the binary samples with various weight percents of LiI, the PO₄ ³⁻ bands and the PO bending experienced small shifting which indicates that interaction has occurred. Alternating current conductivity versus frequency shows a linear variation suggesting that the behavior follows Jonsher power law. The conduction mechanism of LiI–Li₃PO₄ solid electrolyte follows the quantum mechanical tunneling model.     

Hydrothermal synthesis, controlled microstructure, and photoluminescence of hydrated Zn3(PO4)2: Eu3+ nanorods and nanoparticles

In this article, Zn₃(PO₄)₂: Eu³⁺ nanorods and nanoparticles have been prepared by the hydrothermal method. The optimum pH value has been found at the range of 3–8 for the preparation of orthorhombic Zn₃(PO₄)₂: Eu³⁺, whose morphologies are affected by the pH value. At the same temperature for hydrothermal reaction, the product presents nanorods at pH 4, while it shows nanoparticles at pH 6. Furthermore, the influences of the hydrothermal reaction temperature on the morphology and microstructure have also been investigated, suggesting that the morphology and microstructure cannot be changed with the hydrothermal temperature at the same pH value. Finally, the photoluminescence of Eu³⁺ on Zn₃(PO₄) nanorod/nanoparticle have been studied, both of which present the characteristic emission lines of Eu³⁺ and the ⁵D₀–⁷F₁ transition corresponds the strongest emission. This indicates that Eu³⁺ occupied the inversion center in Zn₃(PO₄) host.     

The vibrational spectra and structural properties of Me7Eu2UO2(PO4)5 crystals

We investigate the vibrational spectra of crystals of ternary orthophosphates Me₇Eu₂UO₂·(PO₄)₅ (Me–Na, Rb, Cs) obtained by solid-phase synthesis. We show that in these materials the effect of coordination distorts the geometry of the PO ₄ ³⁻ tetrahedron and decreases its symmetry. We conclude that the PO ₄ ³⁻ tetrahedrons in Me₇Eu₂UO₂(PO₄)₅ occupy two nonequivalent positions in the lattice. The character of manifestation and the number of oscillation frequencies observed allow the assumption that they have the C_3v- and C₂-symmetry. This symmetry of two crystallographically nonequivalent groups of PO ₄ ³⁻ ensures a complete set of bands in the IR absorption spectra of the crystals investigated. We show that these crystals exhibit chain structural motifs. Translated from Zhurnal Prikladnoi Spektroskopii, Vol, 64, No. 4, pp. 467–470, July–August, 1997.     

Na+-ion conductivity of double phosphate Na3Sc2(PO4)3 in the region of the β-γ transition

The Na⁺-ion conductivity σ of double phosphate Na₃Sc₂(PO₄)₃ in the region of the β-γ transition has been studied using impedance spectroscopy (1–10⁶ Hz). The polycrystalline sample of Na₃Sc₂(PO₄)₃ has been prepared by solid-phase synthesis and ceramic technology. It has been found that, upon the β-γ transition, the conductivity σ of Na₃Sc₂(PO₄)₃ suffers a ～1.5-fold jump at 470 ± 2 K upon heating and a ～2.5-fold jump at 430 ± 4 K upon cooling (the temperature hysteresis of the jump in σ is 40 K). For double sodium-scandium phosphate γ-Na₃Sc₂(PO₄)₃ in the superionic state, σ attains 0.07 S/cm at 700 K and the ion transport activation enthalpy is 0.42 ± 0.02 eV.     

Kinetics of accumulation and decay of paramagnetic centers in γ-irradiated doped phosphate glasses

The dose dependences and decay kinetics of PO ₄ ^2? and PO ₃ ^2? paramagnetic centers and radiation-reduced europium Eu^(3+)? in γ-irradiated phosphate glasses of composition 4Na₂O · La₂O₃ · 7P₂O₅ doped with europium are studied. The data obtained are discussed within the trapping volume model in the approximation of short irradiation duration. It is shown that the trapping volume parameter v decreases with increasing irradiation dose. A physical interpretation of the parameter v is proposed.     

Far-infrared reflectivity spectrum of potassium dihydrogen phosphate,polarized along the c axis,reinvestigated in the ferroelectric phase

The infrared (IR) reflectivity spectrum of KH₂PO₄, polarized along the c axis, has been carefully reinvestigated in the vicinity of the phase transition temperature and in the ferroelectric phase, between 10 and 600 cm⁻¹. Two new results are displayed by the present study of the A₁, spectrum in the ferroelectric phase of KH₂PO₄: first, the activity of the expected A¹ librational lattice mode is evidenced, the lattice mode parameters of this mode were never previously determined by IR spectroscopy in KH₂PO₄; and second, the peculiar behaviour of the broad reflection band corresponding to the A₁ translational lattice mode is observed for the first time in KH₂PO₄, and discussed.     

Synthesis of high performance Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C cathode material by ultrasonic-assisted sol–gel method

A novel ultrasonic-assisted sol–gel method is proposed to prepare Li₃V₂(PO₄)₃/C cathode material. X-ray diffraction analyses show that both Li₃V₂(PO₄)₃/C(A) synthesized by the ultrasonic-assisted sol–gel method and Li₃V₂(PO₄)₃/C(B) synthesized by a traditional sol–gel method have monoclinic structure. Scanning electron microscopy images indicate that the Li₃V₂(PO₄)₃/C(A) composite has a more uniform morphology than that of the Li₃V₂(PO₄)₃/C(B) composite. In the voltage range of 3.0–4.3 V (vs. Li/Li⁺), the initial specific discharge capacities of the Li₃V₂(PO₄)₃/C(A) and Li₃V₂(PO₄)₃/C(B) samples are 129.8 and 125.9 mAh g⁻¹ at 1C rate (1C = 133 mA g⁻¹), respectively. Furthermore, at 2-C charge/10-C discharge rate, the specific discharge capacity of the Li₃V₂(PO₄)₃/C(A) composite retains 113.2 mAh g⁻¹ after 50 cycles, but the Li₃V₂(PO₄)₃/C(B) composite only presents a capacity of 94.8 mAh g⁻¹.     

Structural phase transitions evidenced by Mössbauer spectrometry in a ferric fluorophosphate: Na3Fe2(PO4)2F3

⁵⁷Fe Mössbauer spectrometry was carefully applied to Na₃Fe₂(PO₄)₂F₃, a fluorophosphate crystalline ferric compound. Two structural phase transitions involving very slight motions of Na⁺ cations were evidenced from the temperature dependence of the quadrupolar splitting, in agreement with those observed in isotypic compounds, either by diffraction technique or by calorimetric measurement. Consequently, it is important to emphasise the extremely high neighbouring sensitivity of ⁵⁷Fe Mössbauer spectrometry.     

Preparation and characterization of sodium binary system (NaI–Na3PO4) inorganic solid electrolyte

New binary inorganic salt such as sodium iodide (NaI)–sodium phosphate (Na₃PO₄) has a great potential to be used as a solid electrolyte, and this solid electrolyte system exhibits high ionic conductivity up to 10^?4 S cm^?1. The solid electrolyte compounds were prepared by mechanical milling followed by pelletizing and sintering at low temperature. The electrical conductivity study was carried out as a function of NaI concentration by impedance spectroscopy technique and the maximum conductivity of (1.02?±?0.19)?×?10^?4 S cm^?1 at room temperature was obtained for the composition 0.50 NaI:0.50 Na₃PO₄. The increase in conductivity is probably due to the increase in number of mobile charge carriers through the conducting pathway provided by tetrahedral structures of Na₃PO₄. The presence of P–O and PO₄ ^3? bands was detected by the infrared technique Fourier transform infrared spectroscopy had been shifted indicating changes in polyhedral structure which in turn led to the formation of conducting channel by corner sharing or through edges. The mobility of the charge carriers in the various compositions of the binary system was investigated by using ²³Na magic angle spinning solid-state nuclear magnetic resonance. The narrowing of the line width ²³Na spectra in the optimum composition of the binary NaI–Na₃PO₄ system can be assigned to Na population with higher ion mobility. X-ray diffraction technique revealed that the addition of NaI resulted in reducing the crystallinity of the samples. Field emission scanning electron microscopy micrographs revealed finer microstructure of the milling samples with grains growth formation and densification upon sintering.     

Optimised NASICON ceramics for Na+ sensing

NASICON dense ceramics were obtained from solid state reaction between SiO₂, Na₃PO₄·12H₂O and two different types of zirconia: monoclinic ZrO₂ and the yttria-doped tetragonal phase (ZrO₂)_0.97(Y₂O₃)_0.03. Higher temperatures were needed to obtain dense samples of the yttrium free composition (1265 °C). The electrical conductivity, at room temperature, of the yttria-doped samples sintered at 1230 °C (0.20 S/m) is significantly higher than the value obtained with the material prepared from pure ZrO₂. The impedance spectra show that the differences in conductivity are predominantly due to the higher grain boundary resistance of the undoped ceramics, probably due to formation of monoclinic zirconia and glassy phases along the grain boundary. Further improvement of the electrical conductivity could be achieved after optimization of the grain size and density of grain boundaries. A maximum conductivity value of about 0.27 S/m at room temperature was obtained with the yttria-doped samples sintered at 1220 °C for 40 h. Yttria-doped and undoped ceramics were tested as Na⁺ potentiometric sensors. The detection limit of the yttria-doped sample (10⁻⁴ mol/l) was one order of magnitude lower than the obtained with the undoped material. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16 – 22, 2001.     

New phase transition in LiKSO4

A subtle first order phase transition in LiKSO₄ has been discovered with the help of a temperature dependent study of the Raman intensity measurements of certain polar modes in different polarization configurations. The room temperature hexagonal C⁶₆ (P6₃) phase transforms to trigonal C⁴_3v (P31c) phase at 201°K while cooling; the reverse transformation (on heating) takes place at 242°K. The phase transition appears to be primarily associated with a cooperative reorientation of SO₄ tetrahedra in the crystal.     

Solvothermal synthesis of LiCo<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript>/C cathode materials for lithium-ion batteries

LiCo_1−x Mn _x PO₄/C cathode materials are selectively synthesized by a solvothermal method in ethylene glycol solvent using glucose, LiCl, H₃PO₄, MnCl₂·4H₂O, and Co(NO₃)₂·6H₂O as precursors. The obtained samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) and the electrochemical performances are also evaluated using a LAND CT2001A battery test system at room temperature. XRD result demonstrates the formation of LiCo_1−x Mn _x PO₄ solid solution and the enlarged channels are benefit for Li⁺ migration. SEM graph indicates that the particle size of LiCo_0.5Mn_0.5PO₄/C is about several hundred nanometers and aggregates to large particles located in the range of 2–3 μm. TEM image illustrates that the core/shell-structured LiCo_0.5Mn_0.5PO₄/C solid solution is indeed obtained by this method. The high specific surface area (35 m²/g) of LiCo_0.5Mn_0.5PO₄/C could make this solid solution contact with the electrolyte more sufficiently and benefit for Li⁺ transportation. The capacity, flat voltage, and cyclical stability of LiCo_1−x Mn _x PO₄/C are improved compared to LiMnPO₄ and LiCoPO₄ due to the improved electronic conductivity and lithium-ion conductivity which resulted from carbon coating and foreign element incorporation.     

CW one-micron (4F3/2-4I11/2) laser oscillation of Nd3+ ions in the melilite-type crystal Ca2MgSi2O7:Nd3+(Na+) at its incommensurate–commensurate phase transition

The spectroscopic and stimulated-emission (⁴F_3/2→⁴I_11/2) properties of the novel melilite-type laser crystal Ca₂MgSi₂O₇:Nd³⁺(Na⁺) were studied in a temperature range that covers its incommensurate–commensurate (IC↔N) phase transition. The phase transition temperatures of both undoped Ca₂MgSi₂O₇ and the doped crystal were ascertained at 346.6 K (undoped) and 341.3 K (doped) by means of differential scanning calorimetry (DSC). The temperature-dependent spectroscopic and laser experiments showed a significant decrease in CW output power and a strong distortion of the generated lasing beam in the region of the phase transition. The observed crystal field disorder of Nd³⁺ lasants in Ca₂MgSi₂O₇:Nd³⁺(Na⁺) is dominantly due to occupation of the position of Ca²⁺ by cations of different valency, while the influence of incommensurability is of minor importance.