PAN–PEO solid polymer electrolytes with high ionic conductivity

The transparent and flexible solid polymer electrolytes (SPEs) are fabricated from polyacrylonitrile–polyethylene oxide (PAN–PEO) copolymer. The formation of the copolymer is confirmed by Fourier-transform infrared spectroscopy (FTIR) and Gel permeation chromatography (GPC) measurements. The effects of acrylonitrile (AN) wt% content and M_n(PEO) on ionic conductivity are investigated by alternating current (ac) impedance spectroscopy. By controlling and adjusting the AN wt% content and doping PEO with high molecular weight, the ionic conductivity of SPEs is optimized. The ionic conductivity of PAN–PEO solid polymer electrolytes is found to be high 6.79 × 10⁻⁴ S cm⁻¹ at 25 °C with an [EO]/[Li] ratio of about 10, and are electrochemically stable up to about 4.8 V versus Li/Li⁺. The conductivity and interfacial resistance remain almost constant even at 80 °C.     

Polymer electrolyte based dye-sensitized solar cell with rice starch and 1-methyl-3-propylimidazolium iodide ionic liquid

Biodegradable rice starch was used to prepare solid polymer electrolytes (SPEs) using sodium iodide salt. The polymer electrolytes are prepared using solution cast technique. 1-methyl-3-propylimidazolium iodide (MPII) ionic liquid was incorporated in the polymer electrolyte. The ionic conductivity of SPEs are measured and temperature-dependent behavior of SPEs studied. All the solid polymer electrolytes follow Arrhenius type of thermal activated model. The ionic conductivity increased after addition of MPII ionic liquid. The highest ionic conductivity of 1.20 × 10^− 3 S cm^− 1 is achieved upon addition of 20 wt.% of MPII ionic liquid. Structural properties of polymer electrolytes are studied with FTIR and XRD which confirmed complexation between polymer and ionic liquid. The polymer electrolytes are analyzed for thermal study using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Dye-sensitized solar cells (DSSC) are fabricated using polymer electrolytes and studied under Sun simulator. The highest energy conversion efficiency of 2.09% is attained after addition of 20 wt.% of MPII ionic liquid.     

Investigation of La3 + Doped Yb2Sn2O7 as new thermal barrier materials

Low thermal conductivity is one of the key requirements for thermal barrier coating materials. From the consideration of crystal structure and ion radius, La^3 + Doped Yb₂Sn₂O₇ ceramics with pyrochlore crystal structures were synthesized by sol–gel method as candidates of thermal barrier materials in aero-engines. As La^3 + and Yb^3 + ions have the largest radius difference in lanthanoid group, La^3 + ions were expected to produce significant disorders by replacing Yb^3 + ions in cation layers of Yb₂Sn₂O₇. Both experimental and computational phase analyses were carried out, and good agreement had been obtained. The lattice constants of solid solution (La_xYb_1 − x)₂Sn₂O₇ (x = 0.3, 0.5, 0.7) increased linearly when the content of La^3 + was increased. The thermal properties (thermal conductivity and coefficients of thermal expansion) of the synthesized materials had been compared with traditional 8 wt.% yttria stabilized zirconia (8YSZ) and La₂Zr₂O₇ (LZ). It was found that La^3 + Doped Yb₂Sn₂O₇ exhibited lower thermal conductivities than un-doped stannates. Amongst all compositions studied, (La_0.5Yb_0.5)₂Sn₂O₇ exhibited the lowest thermal conductivity (0.851 W·m^− 1·K^− 1 at room temperature), which was much lower than that of 8YSZ (1.353 W·m^− 1·K^− 1), and possessed a high coefficient of thermal expansion (CTE), 13.530 × 10^− 6 K^− 1 at 950 °C.     

Synthesis and properties of Ce1−xGdxO2−x/2 solid solution prepared by flame spray pyrolysis

Flame spray pyrolysis, which produces ultrafine particles, was applied to the synthesis of Ce_1−xGd_xO_2−x/2 solid solutions by substituting Gd from a mole fraction of 0–0.40. The solubility limit of Gd in the Ce_1−xGd_xO_2−x/2 solid solution produced by flame spray pyrolysis was between 0.25 and 0.30, which is consistent with the reported value. The as-prepared Ce_1−xGd_xO_2−x/2 particles had a square morphology and a nanometer range in the equivalent diameter. The small particle size made it possible to reduce the sintering temperature of the Ce_1−xGd_xO_2−x/2 solid solution from 1650 °C to 1400 °C for the ceria-based solid electrolytes produced by the solid state preparation. The maximum ionic conductivity was achieved when the mole fraction of Gd was 0.25. The mole fraction for the highest ionic conductivity was the same as the particles produced by hydrothermal synthesis. However, the ionic conductivity of the Ce_1−xGd_xO_2−x/2 prepared by the flame spray pyrolysis (1.01 × 10⁻² S/cm at 600 °C) was higher than that prepared by the hydrothermal synthesis (7.53 × 10⁻³ S/cm at 600 °C).     

Effects of interstitial Li+ ions on the properties of novel Li4.08Zn0.04Si0.96O4 ceramic electrolyte

The aim of this work was to investigate the effects of interstitial ions in the novel Li_4 + 2xZn_xSi_1 − xO₄ (x = 0.04) compound prepared via sol gel method. The compound was indexed to the monoclinic unit cell in the space group P2_1/m and the chemical composition of the compound was very close to the designed composition. The introduction of two interstitial Li⁺ ions increased charge carrier concentration in the doped system resulting in an enhancement of conductivity by an order of magnitude as compared to that of the parent compound, Li₄SiO₄. The compound of Li_4.08Zn_0.04Si_0.96O₄ exhibited total conductivity values of 2.51 × 10^− 5 S cm^− 1 at ambient temperature and 3.01 × 10^− 3 S cm^− 1 at 500 °C. Ionic transference number corresponding to Li⁺ ion transport was also found to be higher than the value obtained for the parent compound. This proved that interstitial Li⁺ ions contributed to the total conductivity in the sample. Linear sweep voltammetry result showed that the Li_4.08Zn_0.04Si_0.96O₄ ceramic electrolyte was electrochemically stable up to 5.80 V versus a Li/Li⁺ reference electrode.     

Effect of polymer modifier chain length on thermal conductive property of polyamide 6/graphene nanocomposites

The influence of polymer modifier chain length on the thermal conductivity of polyamide 6/graphene (GA) nanocomposites, including through-plane (λ_z) and in-plane (λ_x) directions were investigated. Here, three chain lengths of double amino-terminated polyethylene glycol (NH₂–PEG–NH₂) were used to covalently functionalize graphene with graphene content of 5.0 wt%. Results showed that λ_z was enhanced with the chain length of NH₂–PEG–NH₂ increased, but λ_x reached a maximum value at a certain chain length of NH₂–PEG–NH₂. The maximum λ_z and λ_x of GA are 0.406 W m⁻¹ K⁻¹ and 9.710 W m⁻¹ K⁻¹, respectively. This study serves as a foundation for further research on the thermal conductive property of graphene nanocomposites using different chain lengths of polymer modifier to improve the λ_z and λ_x of the thermal conductive materials.     

Influence of Ga3+ ions on spectroscopic and dielectric features of multi component lithium lead boro bismuth silicate glasses doped with manganese ions

Multi-component glasses of the chemical composition 19.5Li₂O–20PbO–20B₂O₃–30SiO–(10 − x)Bi₂O₃–0.5MnO:xGa₂O₃ with 0 ≤ x ≤ 5.0 have been synthesized. Spectroscopic (optical absorption, IR, Raman and ESR) and dielectric properties were investigated. Optical absorption and ESR spectral studies have indicated that managanese ions do exist in Mn³⁺ state in addition to Mn²⁺ state in the samples containing low concentration of Ga₂O₃. The IR and Raman studies indicated increasing degree of disorder in the glass network with the concentration of Ga₂O₃ up to 3.0 mol%. The dielectric constant, loss and ac conductivity are observed to increase with the concentration of Ga₂O₃ up to 3.0 mol%. The quantitative analysis of the results of dielectric properties has indicated an increase in the insulating strength of the glasses as the concentration of Ga₂O₃ is raised beyond 3.0 mol%. This has been attributed to adaption of gallium ions from octahedral to tetrahedral coordination.     

Synthesis and dc conductivity of Nd2/3TiO2.988

The A-site deficient perovskite Nd_2/3TiO_3 − δ was synthesized under an H₂–CO₂ gas mixture. The sample was found to have slight oxygen deficiency of δ∼0.012. The crystal structure was assigned to a double perovskite structure with orthorhombic space group Pmmm, as in the case of La_2/3TiO_3 − δ. Electrical conductivity measurement has also been performed. The temperature dependence of conductivity shows that electronic transport in Nd_2/3TiO_2.988 is well described by Emin–Holstein adiabatic small polaron model. The polaron density extracted from the conductivity measurement is ∼1.96 × 10²⁰ cm^− 3. This result agrees well with nominal polaron density for Nd_2/3TiO_2.988, ∼2.1 × 10²⁰cm^− 3. We have also derived important quantities for transport in Nd_2/3TiO_2.988.     

Effect of solvent ratio on the properties of highly oriented sprayed fluorine-doped tin oxide thin films

Transparent conducting thin films of F:SnO₂ have been deposited onto preheated glass substrates by a spray pyrolysis technique using pentahydrate stannic chloride (SnCl₄·5H₂O) and ammonium fluoride (NH₄F) as precursors and mixture of water and propane-2-ol as solvent. The concentration of SnCl₄·5H₂O and NH₄F is kept fixed and the ratio of water and propane-2-ol solvent in the spraying solution is varied. A fine spray of the source solution using air as a carrier gas has grown films of thickness up to 995 nm. Optical absorption, X-ray diffraction, Van der Pauw technique for measurement of a sheet resistance and Hall effect measurements at room temperature for determination of carrier density and conductivity have been used. The as-deposited films are of polycrystalline SnO₂ with a tetragonal crystal structure and are preferentially having orientation along the (200) direction with texture coefficient as high as 6.16. The average grain size for the as-deposited sample is found to be of the order of 44 nm. The films have moderate optical transmission (up to 70–85% at 550 nm). The figure of merit (ϕ) values vary from 1.95 · 10^− 3 to 35.68 · 10^− 3 Ω^− 1. The films are heavily doped, degenerate and exhibit n-type electrical conductivity. The lowest sheet resistance (R_s) for the optimized sample is 5.1 Ω. The films have a resistivity of 5.43 · 10^− 4 Ω cm and mobility around 7.38 cm² V^− 1 s^− 1.     

Synthesis of conducting ferromagnetic nanocomposite with improved microwave absorption properties

The present paper reports the synthesis of polyaromatic amine–ferromagnetic composite with nanosize TiO₂ (～70–90 nm) and γ-Fe₂O₃ (～10–15 nm) particles via in situ emulsion polymerization. Magnetic and conductivity studies demonstrate that the conducting ferromagnetic composite possesses saturation magnetization (M_S) value of 26.9 emu g^?1 and conductivity of the order of 0.46 S cm^?1, which are measured by vibrating sample magnetometer and four-probe technique, respectively. It is observed that the presence of the nanosized γ-Fe₂O₃ in the polyaniline–TiO₂ matrix affects the electromagnetic shielding property of the composite. Polyaniline–TiO₂–γ-Fe₂O₃ nanocomposite has shown better shielding effectiveness due to absorption (SE_A ～ 45 dB) than the polyaniline-γ-Fe₂O₃ (SE_A ～ 8.8 dB) and polyaniline–TiO₂ (SE_A ～ 22.4 dB) nanocomposite. The polymer composites were further characterized by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) technique.     

The AMWCNTs supported porous nanocarbon composites for high-performance supercapacitor

The porous nanocarbons supported by acid-treated multiwall carbon nanotubes (PC@ACNTs) were prepared by the combination of the hydrothermal polymerization of glucose on ACNTs, carbonization under N₂ protection and final activation with ZnCl₂. The materials were characterized by transmission electron microscopy, X-ray powder diffraction and Raman spectra. The results indicated that the ACNTs distributed uniformly into the framework of the porous carbon. The composites showed the high BET specific surface area up to 1712 m² g⁻¹ and good conductivity. The electrochemical measurements indicated that the composites processed good performances for electrochemical energy storage (210 F g⁻¹ at 0.5 A g⁻¹), and high stability (>99.9%), much higher than the corresponding ACNTs, porous carbons and the samples prepared by using raw MWCNTs as source. The good performance of PC@ACNTs composites was relative with the synergy of good conductivity of ACNTs and large specific surface areas of PC.     

Crystal growth and spectral properties of pure and Co2+-doped Mg3B2O6 crystal

Novel pure and cobalt-doped magnesium borate crystals (Mg₃B₂O₆) have been grown successfully by the Czochralski technique for the first time. Crystal growth, X-ray powder diffraction (XRD) analysis, absorption spectrum, fluorescence spectrum as well as fluorescence decay curve of Co²⁺:Mg₃B₂O₆ (MBO) were described. From the absorption peaks for the octahedral Co²⁺ ions, the crystal-field parameter Dq and the Racah parameter B were estimated to be 943.3 cm⁻¹ and 821.6 cm⁻¹, respectively. The fluorescence lifetime of the transition ⁴T₁(⁴P) → ⁴T₂ centered at 717 nm was measured to be 9.68 ms.     

Synthesis,crystal structure refinement,electrical and magnetic properties of BaV13O18 and SrV13O18

Polycrystalline samples of BaV₁₃O₁₈ and SrV₁₃O₁₈ were prepared by solid-state reaction of BaCO₃, SrCO₃, V₂O₅ and V at 1773–2073 K in flowing Ar. The crystal structures of BaV₁₃O₁₈ (R-3, a_h=12.6293(10) Å, c_h=7.0121(4) Å) and SrV₁₃O₁₈ (a_h=12.5491(7) Å, c_h=6.9878(3) Å) were refined by the Rietveld method using X-ray diffraction data. BaV₁₃O₁₈ exhibited semiconducting behavior with electrical resistivity from 5.8×10⁻³ to 2.7×10⁻³ Ω cm at 100–300 K. Electrical resistivity of SrV₁₃O₁₈ ranged from 1.5×10⁻³ to 1.8×10⁻³ Ω cm, and it increased slightly up to around 250 K and decreased above 250 K with increasing temperature. Negative Seebeck coefficients of both compounds at 100–300 K indicated that electron was the dominant carrier. BaV₁₃O₁₈ and SrV₁₃O₁₈ showed paramagnetism with the effective magnetic moment of 0.11μ_B and 0.15μ_B, respectively, at 10–100 K.     

Microstructures and electrical properties of calcium substituted LaFeO3 as SOFC cathode

Mixed ionic and electronic conductors of La_1−xCa_xFeO_3−δ (LCF, x =0.0–0.5) have been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), dilatometry, and four-probe electrical conductivity measurements. Ca substitution on La site reduces the LaFeO₃ sinterability and the cell volume of this orthorhombic crystal. Dense samples for property studies can be sintered at 1320 °C. Nevertheless, the sintering temperature is near the decomposition temperature of LCF for those solid solutions of x ≥ 0.3. The LCF decomposition is evident when a La-poor secondary phase, not detected in XRD, was revealed in SEM micrographs of 1270 °C thermally etched samples of x ≥ 0.3. Dilatometric studies demonstrate linear increments in thermal expansion with increasing temperature in samples of x ≤ 0.2, while show strange bendings in thermal expansion curves of x = 0.4 and 0.5. The bending in thermal expansion indicates influences of the secondary phase. The TEC value of compositions of x ≤ 0.2 is between 10.8 and 11.7 × 10⁻⁶ °C⁻¹. The LCF electrical conductivity increases with the Ca content and its temperature dependence can be described by the small polaron hopping mechanism. The composition around x = 0.15 promises to be a superior cathode for SOFC since it thermally matches with 8 mol% YSZ and 10 mol% Dy, Er substituted LAMOX electrolytes and possesses electrical conductivity near 90 S cm⁻¹ at 800 °C.     

Spectroscopic properties of Tm3+/Al3+ co-doped sol–gel silica glass

Tm³⁺/Al³⁺ co-doped silica glass was prepared by sol–gel method combined with high temperature sintering. Glasses with compositions of xTm₂O₃–15xAl₂O₃–(100 − 16x) SiO₂ (in mol%, x = 0.1, 0.3, 0.5, 0.8 and 1.0) were prepared. The high thulium doped silica glass was realized. Their spectroscopic parameters were calculated and analyzed by Judd–Ofelt theory. Large absorption cross section (4.65 × 10⁻²¹ cm² at 1668 nm) and stimulated emission cross section (6.00 × 10⁻²¹ cm² at 1812 nm), as well as low hydroxyl content (0.180 cm⁻¹), long fluorescence lifetime (834 μs at 1800 nm), large σ_em × τ_rad (30.05 × 10⁻²¹ cm² ms) and large relative intensity ratio of the 1.8 μm (³F₄ → ³H₆) to 1.46 (³H₄ → ³F₄) emissions (90.33) are achieved in this Tm³⁺/Al³⁺ co-doped silica glasses. According to emission characteristics, the optimum thulium doping concentration is around 0.8 mol%. The cross relaxation (CR) between ground and excited states of Tm³⁺ ions was used to explain the optimum thulium doping concentration. These results suggest that the sol–gel method is an effective way to prepare Tm³⁺ doped silica glass with high Tm³⁺ doping and prospective spectroscopic properties.     

Ionic conductivity of high-purity Gd-doped ceria solid solutions

The Ce_1−xGd_xO_2−δ (0.02 ≤ x ≤ 0.3) solid solutions with ∼30 ppm SiO₂ were prepared through the conventional mixed-oxide method from high-purity CeO₂ and Gd₂O₃ powders. The ionic conductivity (especially the grain boundary (GB) conduction) in this system was studied as a function of dopant content, over the temperature range of 250–750 °C in air, using an impedance spectroscopy. The GB impedance played an important role in the total conduction in the samples with low Gd content (usually x ≤ 0.1), but decreased sharply with increasing Gd content. Both the total and GB conductivities maximized at the composition x = 0.15, and this composition also had the lowest activation energies for the total and GB conduction. The maximum total conductivity at 700 °C, σ_t = 4.07 (Ω m)⁻¹ with the activation energy, E_t = 0.77 eV, was found for the composition x = 0.15.     

A2−αAα′BO4-type oxides as cathode materials for IT-SOFCs (A = Pr,Sm; A′ = Sr; B = Fe,Co)

Preparation, thermal expansion, electrical conductivity and polarization of A_2−αA _α′BO₄-type oxides (A = Pr, Sm, A′ = Sr, B = Fe, Co) were investigated systematically to evaluate their potential as cathode materials for IT-SOFCs. Within 0.8 ≤ α ≤ 1.5, A_2−αSr_αBO_4−δ (A = Pr, Sm, B = Fe, Co) could be obtained as a single K₂NiF₄-structural phase. Thermal expansion coefficients (TECs) of the specimens increase with increasing Sr²⁺ content, TECs of cobaltites are much higher than that of ferrites. The electrical conductivity of cobaltites is in the order of 10² S cm^− 1 near 800 °C, which is acceptable for the cathode of IT-SOFC. Polarization measurements showed that Sm_0.5Sr_1.5CoO_4−δ exhibited the lowest cathodic overpotential at 700–900 °C (72 mV at 500 mA/cm² at 800 °C), being a high potential candidate of cathode material for IT-SOFCs.     

The cation inversion and magnetization in nanopowder zinc ferrite obtained by soft mechanochemical processing

Two zinc ferrite nanoparticle materials were prepared by the same method – soft mechanochemical synthesis, but starting from different powder mixtures: (1) Zn(OH)₂/α-Fe₂O₃ and (2) Zn(OH)₂/Fe(OH)₃. In both cases a single phase system was obtained after 18 h of milling. The progress of the synthesis was controlled by X-ray diffractometry (XRD), Raman spectroscopy, TEM and magnetic measurements. Analysis of the XRD patterns by Rietveld refinement allowed determination of the cation inversion degree for both obtained single phase ZnFe₂O₄ samples. The sample obtained from mixture (1) has the cation inversion degree 0.3482 and the sample obtained from mixture (2) 0.400. Magnetization measurements were confirmed that the degrees of the inversion were well estimated. Comparison with published data shows that used method of synthesis gives nano powder samples with extremely high values of saturation magnetizations: sample (1) 78.3 emu g⁻¹ and sample (2) 91.5 emu g⁻¹ at T = 4.5 K.     

(TiZrHf)P2O7: An equimolar multicomponent or high entropy ceramic with good thermal stability and low thermal conductivity

ZrP₂O₇ is a promising material for high temperature insulating applications. However, decomposition above 1400 °C is the bottleneck that limiting its application at high temperatures. To improve the thermal stability, a novel multicomponent equimolar solid solution (TiZrHf)P₂O₇ was designed and successfully synthesized in this work inspired by high-entropy ceramic (HEC) concept. The as-synthesized (TiZrHf)P₂O₇ exhibits good thermal stability, which is not decomposed after heating at 1550 °C for 3 h. It also shows lower thermal conductivity (0.78 W m⁻¹ K⁻¹) compared to the constituting metal pyrophosphates TiP₂O₇, ZrP₂O₇ and HfP₂O₇. The combination of high thermal stability and low thermal conductivity renders (TiZrHf)P₂O₇ promising for high temperature thermal insulating applications.     

Electrical properties and thermal expansion of cobalt doped apatite-type lanthanum silicates based electrolytes for IT-SOFC

The thermal expansion and conductivities have been investigated for Co³⁺ doped lanthanum silicates. The apatite-type lanthanum silicates with formula La₁₀Si_6?xCo_xO_27?x/2 (x = 0.2, 0.4, 0.6, 0.8, 1.0, 1.5) were synthesized by sol–gel process. The thermal expansion coefficient (TEC) of La₁₀Si_6?xCo_xO_27?x/2 was improved with increasing cobalt content because of the lower valence and larger radius of Co³⁺ ion compared to Si⁴⁺. Analysis of AC impedance spectroscopy showed that conductivity increased first and then decreased with increasing cobalt content. There is an optimum doping amount of cobalt and La₁₀Si_5.2Co_0.8O_26.6 exhibits the highest conductivity of 3.33 × 10^?2 S/cm at 800 °C. When x ≤ 0.8, the local distortion caused by doping with Co³⁺ can significantly affect the oxygen channels and assist the migration of the interstitial oxide ions, resulting in the improvement of ionic conductivity. However, excess Co³⁺ dopant (0.8 < x ≤ 1.5) reduced the number of interstitial oxide ions and decreased the conductivity.