Applicability of sodium sulfate as a solid electrolyte for a sulfur oxides sensor

The electromotive force (EMF) has been measured on SO₂O₂SO₃ concentration cells using undoped and 4 at.% yttrium-doped Na₂SO₄ as solid electrolytes at temperatures between 920 and 1120 K. Two types of electrolytes prepared by sintering and infiltration have proven to work basically well above 973 K. The observed EMF's are consistent with the values calculated from the Nernst equation in the wide concentration range of SO_x, showing that the ionic transference number is unity both in the undoped and yttrium-doped Na₂SO₄. A large difference in SO_x pressures between the anode and the cathode leads to the lowering of the EMF because of the permeation of gases through the macroscopic defects such as pores and cracks in the electrolyte. The experimental results suggest that improvement of the sinterability and the stabilization of the high temperature phase are the indispensable problems to solve for the practical application of Na₂SO₄ as a solid electrolyte to an SO_x sensor.     

Rietveld refinement results on three nonstoichiometric monoclinic NASICONs

The results of three powder Rietveld refinements of monoclinic NASICONs, prepared by different methods, are examined. Neutron TOF data were collected on two samples: a sol-gel prepared NASICON was found to have the formula Na₃Zr_1.93Si₂PO_11.86 and a reheated commercially available NASICON a formula of Na_3.17Zr_1.93Si_1.9P_1.1O₁₂. Following our neutron study on a nonstoichiometric hydrothermally prepared NASICON we prepared the same nonstoichiometric phase by sol-gel methods and X-ray Rietveld analysis yielded the formula Na_3.2Zr_1.68Si_1.84P_1.16O_11.54. These stoichiometries can be represented by the general formula Na_1+4y+xZr_2−y−zSi_xO_12−2z where z represents the ZrO₂ mole deficiency and y the amount of Zr⁴⁺ vacancies compensated by 4Na⁺. These differences in stoichiometry are accompanied by structural differences such as Si/P segregation and variations in cavity occupancy by Na⁺. It is proposed that the method of preparation is largely responsible for the observed differences.     

Charge storage performance of lithiated iron phosphate/activated carbon composite as symmetrical electrode for electrochemical capacitor

In this study, a symmetric electrochemical capacitor was fabricated by adopting a lithium iron phosphate (LiFePO₄)-activated carbon (AC) composite as the core electrode material in 1.0 M Na₂SO₃ and 1.0 M Li₂SO₄ aqueous electrolyte solutions. The composite electrodes were prepared via a facile mechanical mixing process. The structural properties of the nanocomposite electrodes were characterised by scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) analysis. The electrochemical performances of the prepared composite electrode were studied using cyclic voltammetry (CV), galvanostatic charge–discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that a maximum specific capacitance of 112.41 F/g was obtained a 40 wt% LiFePO₄ loading on an AC electrode compared with that of a pure AC electrode (76.24 F/g) in 1 M Na₂SO₃. The improvement in the capacitive performance of the 40 wt% LiFePO₄–AC composite electrode is believed to be attributed to the contribution of the synergistic effect of the electric double layer capacitance (EDLC) of the AC electrode and pseudocapacitance via the intercalation/extraction of H⁺, OH⁻, Na⁺ and SO₃²⁻ and Li⁺ ions in LiFePO₄ lattices. In contrast, it appears that the incorporation of LiFePO₄ into AC electrodes does not increase the charge storage capability when Li₂SO₄ is used as the electrolyte. This behaviour can be explained by the fact that the electrolyte system containing SO₄²⁻ only exhibits EDLC in the Fe-based electrodes. Additionally, Li⁺ ions that have lower conductivity and mobility may lead to poorer charge storage capability compared to Na⁺ ions. Overall, the results reveal that the AC composite electrodes with 40 wt% LiFePO₄ loading on a Na₂SO₃ neutral electrolyte exhibit high cycling stability and reversibility and thus display great potential for electrochemical capacitor applications.     

Ionic transport in the Na2SO4Na2WO4 and Na2SO4M2(SO4)3 (M=La,Dy, Sm,In) systems

Premelted, predried Na₂SO₄, premelted Na₂WO₄, Na₂SO₄Na₂WO₄ composites and Na₂SO₄M₂(SO₄)₃ (M = La, Dy, Sm, In) have been studied by means of X-ray diffraction, DTA and electrical conductivity measurements. The high temperature, highly conducting Na₂SO₄ phase I has been successfully stabilised at room temperature; the Na₂SO₄ containing 4 mole% La₂(SO₄)₃ exhibits the highest conductivity (σ) and lowest activation energy (E_a) (σ=1.08 × 10⁻³ω⁻¹ cm⁻¹ at 290°C and E_a=0.50 eV) and therefore this system appears promising for further development.     

Orientational disorder,glass/crystal transition and superionic conductivity in nasicon

The relations between the orientational disorder of SiO₄(PO₄) tetrahedra and fast sodium diffusion in superionic NASICON have been studied by conductivity (complex impedance method), DSC, X-ray powder difraction and vibrational spectroscopy (IR and Raman). Sol-gel routes allow to obtain pure glassy NASICON (Na_1+xZr₂Si_xP_3-xO₁₂x≅2) in the 500−700°C temperature range. Tetragonal zirconia nucleates above 700°C and disappears at about 900°C when the isolated tetrahedra framework is formed: a high orientational static disorder of tetrahedra exists and the symmetry is rhombohedral at all studied temperatures (20−600 K). Thermal treatment above 1100°C induces a drastic decrease of the static orientational disorder and nucleation of monoclinic zirconia. The resulting compound exhibits a monoclinic symmetry at R.T. and three phase transitions, two diffuse at about 60 K and 520 K and the 423 K monoclinic-rhombohedral transition associated with the superionic conducting state. An increase in dynamic disorder (broad Rayleigh wing up to 500 cm^-1 is simultaneously observed. The lower the static disorder at low temperature, the higher the dynamic orientational disorder and the phase transitions, and the lower the activation energy of conductivity at high temperature.     

Performance evaluation of polyacrylamide/silver composite as electrode material in electrochemical capacitor

In this research, polyacrylamide/Ag composite is synthesized and used as an electrode in an electrochemical capacitor (EC). The characterization of the composite is performed by X-ray diffraction, scanning electron microscopy, and cyclic voltammetry methods. The electrochemical characterization is conducted in an electrolytic solution of KOH and an electrolytic solution of Na₂SO₄. The capacitance of the polyacrylamide/Ag composite is associated mainly with the reduction/oxidation of Ag. The specific capacitance of the EC using the KOH electrolyte is 950 Fg^?1, which is better than the capacitance in the Na₂SO₄ electrolyte. This behavior is explained by the respective physical characteristics of the two electrolytes.     

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.     

Luminescence investigations on sulfate apatite Na6(SO4)2FCl:RE (RE=Dy, Ce or Eu) phosphors

A new phosphor in the Cl-F system doped with Dy, Ce and Eu has been reported. Characterization of this phosphor using XRD, PL and TL techniques is described. Polycrystalline Na₆(SO₄)₂FCl:Dy; Na₆(SO₄)₂FCl:Ce and Na₆(SO₄)₂FCl:Eu phosphors prepared by a solid state diffusion method have been studied for their X-ray diffraction, photoluminescence (PL) and thermoluminescence (TL)characteristics. The PL excitation and emission spectra of phosphors were obtained. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, respectively, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows the Ce³⁺ emission at 322 nm due to 5d→4f transition of Ce³⁺ ion. In Na₆(SO₄)₂FCl:Eu lattice, Eu²⁺ as well as Eu³⁺ emissions are observed. The emission of europium ion in this compound exhibits the blue as well as red emission. The TL glow curves of the same compounds have the simple structure with a prominent peak at 150, 175 and 200 °C. TL response, fading, reusability and trapping parameters of the phosphors are also studied. The TL glow curves of γ-irradiated Na₆(SO₄)₂FCl sample show one glow peak indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak are calculated using Chen’s half width method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. The intensity of the TL glow peaks increases with increase of the added γ-ray dose to the samples.     

Photoluminescence spectra of thenardite Na2SO4 activated with rare-earth ions, Ce, Sm, Tb, Dy and Tm

Five Na₂SO₄:RE³⁺ phosphors activated with rare-earth (RE) ions (RE³⁺=Ce³⁺, Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) were synthesized by heating natural thenardite Na₂SO₄ from Ai-Ding Salt Lake, Xinjiang, China with small amounts of rare-earth fluorides, CeF₃, SmF₃, TbF₃, DyF₃ and TmF₃, at 920 °C in air. The photoluminescence (PL) and optical excitation spectra of the obtained phosphors were measured at 300 and 10 K. In the PL spectrum of Na₂SO₄:Ce³⁺ at 300 K, two overlapping bands with peaks at 335 and 356 nm due to Ce³⁺ were first observed. Narrow bands observed in PL and excitation spectra of Na₂SO₄:RE³⁺ (RE³⁺=Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) phosphors were well identified with the electronic transitions within the 4fⁿ (n=5, 8, 9 and 12) configurations of RE³⁺. The existence of excitation bands with high luminescence efficiency at wavelengths shorter than 230 nm is characteristic of Na₂SO₄:RE³⁺ (RE³⁺=Sm³⁺, Tb³⁺, Dy³⁺ and Tm³⁺) phosphors. The obtained results suggest that these phosphors are unfavorable as the phosphor for usual fluorescence tubes, i.e., mercury discharge tubes, but may be favorable as the phosphor for UV-LED fluorescent tubes and as cathodoluminescence, X-ray luminescence and thermoluminescence phosphors.     

Electrical conductivity of binary sulphates of lithium sulphate

To engineer lithium sulphate based material with high ionic conductivity at lowest possible temperature, the electrical conductivity of binary sulphates of Li₂SO₄ with Na₂SO₄, K₂SO₄, MgSO₄, ZnSO₄ and Ag₂SO₄ has been measured in the temperature range from 513 K to 773 K. The results are interpreted on the basis of different phases present therein. Li₂SO₄:Ag₂SO₄(40:60) mol % has high ionic conductivity = 2.17×10^-3(ohm cm)^-1 at 606 K which could be utilized in power sources.     

Characterization of oxide layers formed on electrochemically treated Ti by using soft X-ray absorption measurements

The oxide layers of electrolytic oxidized titanium (Ti) were characterized using Ti L_2,3 and O K edge X-ray absorption. The spectra show that the structure of the oxide layers that are formed during a 1 min treatment are dependent on the concentration of the electrolyte (H₂SO₄ or Na₂SO₄) with which the Ti surface was treated, and also on the magnitude of the potential that was applied during the anodic oxidation process (100 V or 150 V). It is found that a potential of 150 V and an electrolyte concentration of 0.5 M or 1.0 M produces a layer of TiO₂ having rutile crystal structure.     

SILAR deposited Bi2S3 thin film towards electrochemical supercapacitor

Bi₂S₃ thin film electrode has been synthesized by simple and low cost successive ionic layer adsorption and reaction (SILAR) method on stainless steel (SS) substrate at room temperature. The formation of interconnected nanoparticles with nanoporous surface morphology has been achieved and which is favourable to the supercapacitor applications. Electrochemical supercapacitive performance of Bi₂S₃ thin film electrode has been performed through cyclic voltammetry, charge-discharge and stability studies in aqueous Na₂SO₄ electrolyte. The Bi₂S₃ thin film electrode exhibits the specific capacitance of 289 Fg⁻¹ at 5 mVs⁻¹ scan rate in 1 M Na₂SO₄ electrolyte.     

Two new low-temperature phase transitions in the Li(NH4)1 − x Na x SO4 system

Dielectric measurements, X-ray diffraction and Raman scattering techniques have been used to investigate Li(NH₄)_0.99Na_0.01SO₄ (LASS1%) and Li(NH₄)_0.80Na_0.20SO₄ (LASS20%) crystals in the temperature range from 200 to 10?K. These are interesting systems because of the presence of hydrogen bonds and structural defects and because the mother crystal, LiNH₄SO₄, is ferroelectric at room temperature. From the analysis of the results we can conclude that the substitution of Na⁺ ions in the structure of LiNH₄SO₄, even at quantities as low as 1%, is sufficient to induce additional phase transitions to the LiNH₄SO₄ system. The new phase transitions are observed at 181 and 115?K for LASS1% and at 208 and 133?K for LASS20% and both are reversible.     

The adsorption of SO2 on iron surfaces studied by x-ray photoelectron spectroscopy

The interaction of SO₂ with evaporated iron surfaces in the temperature range 80–450 K was investigated by using X-ray photoelectron spectroscopy. At 300 K, SO₂ decomposed at the initial stage of the interaction and gave adsorbed S with the S2p peak at 161.9 eV and adsorbed O with the O1s at 530.0 eV. Further exposure of SO₂ gave adsorbed SO₄ with S2p at 166.8 eV O1s at 531.3 eV, being different in binding energies from ionic SO₄^2?. This indicates the two stage reaction Of SO₂ with iron surface; SO₂(gas) → S(ads) + 20(ads), SO₂(gas) + 2O(ads) → SO₄(ads). The first reaction did not occur at low temperature or in the presence of adsorbed O. The adsorbed SO₄ formed at 80 K showed a quantitative decomposition reaction into S(ads) and O(ads) in the temperature range 200–350 K.     

Electrical conductivity and phase diagram of the Na2SO4CaSO4 system

Very high vacancy concentrations may be obtained in solid solutions of the high temperature phase of Na₂SO₄. In this paper the Na₂SO₄CaSO₄ system has been studied using differential scanning calorimetry (DSC), impedance spectroscopy and X-ray powder diffraction. The phase diagram, especially the stability range of the solid solution of the high temperature Na₂SO₄ phase, has been redetermined. The electrical conductivity of this solid solution increases rapidly with increasing CaSO₄ content and reaches a maximum for about 5 mol% CaSO₄; the conductivity at e.g. 300°C, 3.5×10⁻³ (μ cm)⁻¹, is almost three orders of magnitude higher than that of pure Na₂SO₄.     

硫酸(氢)根吸附层对Pd(111)电极上甲酸氧化反应的影响研究

本文使用循环伏安法和电势阶跃法分别研究了添加和不添加Na₂SO₄的0.1 mol/LH₂SO₄+0.1 mol/LHCOOH溶液中Pd(111)电极上甲酸氧化反应(FAO)的动力学行为,并与同样条件下0.1 mol/LHClO₄中的动力学行为进行比较. 加入0.05 mol/L或者0.1 mol/LNa₂O₄后,在相同的电位下负向扫描的FAO电流比正向扫描的显著减小. 本文推测在(SO₄^*_ad)_m+[(H₂O)_n-H₃O⁺]或(SO₄^*_ad)_m+[Na⁺(H₂O)_n-H₃O⁺]吸附层相转变电势以正的电位, 这个吸附层的结构可能随着电位的增加或Na₂SO₄的加入变得更加致密和稳定. 因此,破坏或者脱附致密的硫酸(氢)根吸附层变得更加困难,使得FAO 动力学在较高电位和随后的负扫电位受到明显的抑制.     

Electrical conductivity of superionic solid solutions of Na2SO4 with Mx (XO4)y -[M=Na,K, Rb,Cd, GdandX=W,Mo, S,Si;x=1, 2, 4 andy=1, 3]

Electrical conductivity data are reported for solid solutions of Na₂SO₄, K₂WO₄, Na₂WO₄, Na₂MoO₄, Rb₂SO₄, Na₄SiO₄ and Gd₂ (SO₄)₃. In all cases, except K₂SO₄, we observed an increase in Na⁺ conductivity effected by lattice expansion and/or incorporation of ion vacancies in addition to a structural transformation. Boundary conditions were shown to exist for these factors to yield a limiting Na⁺ conductivity with a constant fraction of Na⁺ based on a percolation model of transport. The higher conductivity data observed for the larger radius isovalent WO^2-₄ and aliovalent SiO^4-₄ doped Na₂SO₄ show conclusively that the anion-rotation ”cogwheel” mechanism does not contribute to the cationic conductivity in Na₂SO₄.     

Photoelectrochemical properties of FTO/m-BiVO4 electrode in different electrolytes solutions under visible light irradiation

Photoelectrochemical properties of FTO/BiVO₄ electrode were investigated in different electrolytic solutions, potassium chloride (KCl) and sodium sulphate (Na₂SO₄), and under visible light irradiation condition. In order to accomplish that, an FTO/BiVO₄ electrode was built by combining the solution combustion synthesis technique with the dip-coating deposition process. The morphology and structure of the BiVO₄ electrode were investigated through X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. Photoelectrochemical properties were analyzed through chronoamperometry measurements. Results have shown that the FTO/BiVO₄ electrode presents higher electroactivity in the electrolyte Na₂SO₄, leading to better current stabilization, response time, and photoinduced current density, when compared to KCl electrolyte. Besides, this electrode shows excellent performance for methylene blue degradation under visible light irradiation condition. In Na₂SO₄, the electrode has shown higher degradation rate, 51 %, in contrast to 44 % in KCl, plus higher rate constant, 174?×?10^?4 min^?1 compared to 150?×?10^?4 min^?1 in KCl. Results presented in this communication leads to the indication of BiVO₄ thin films as alternate materials to use in heterogeneous photoelectrocatalysis, more specifically in decontamination of surface water.     

Electrical properties of the Ag2SO4-Na2SO4 binary system

A systematic investigation of the Ag₂SO₄-Na₂SO₄ binary system which forms a complete solid solution in the entire compositional range reveals the mobility of Ag⁺ as well as Na⁺. This is concluded on the basis of the appearance of two overlapping semicircles in the complex impedance plane. Transport number measurements using Tubandt and dc polarisation methods support the mobility of both ions. Further, the maximum conductivity for 30 Ag₂SO₄-70 Na₂SO₄ is due to optimum percolating paths resulting from lattice expansion. The decrease in conductivity beyond this, is caused by the increased interaction of Ag⁺ and Na⁺.     

Phase transition in an occupationally disordered sulfate system

We have investigated the behavior of the Li_1.43Cs_0.57SO₄ single-crystal Raman spectra and dielectric permittivity as a function of temperature. It was observed that the crystal, which is an occupationally disordered system, with orthorhombic C_2v² structure at room temperature, undergoes a phase transition at 230 K. In the new phase the SO₄ tetrahedra remain in two non-equivalent sites and there is no evidence of the doubling of the unit cell.