Gold-composite electrodes for hydrocarbon sensors based on YSZ solid electrolyte

In potentiometric zirconia based sensors gold electrodes show a high sensitivity for hydrocarbons (HC's) when the measurements are carried out in non equilibrated oxygen containing gas mixtures at temperatures <700 °C. This behaviour explained by mixed potential theory is not stable and depends strongly on preparation and particularly on measuring conditions. To modify the electrode behaviour composites consisting of gold and gallium oxide were investigated. Gold pastes with different amount of Ga₂O₃ were prepared and screen printed on YSZ pellets. After sintering at defined temperatures between 900 and 950 °C the cells were tested regarding the electrode behaviour in a C₃H₆, O₂ gas mixture using a platinum air reference electrode. These composite electrodes show as compared with pure gold an enhanced sensitivity at low propylene concentrations and a time-independent characteristic at high concentrations of C₃H₆. The optimal composition is found to be at 20 mass-% Ga₂O₃. This electrode can be treated in reducing gases at temperatures 850 °C without changing its characteristics. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Fabrication and electrochemical performance of La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> impregnated porous YSZ cathode

La_0.5Sr_0.5CoO₃-yttria-stabilized zirconia (LSCO-YSZ) composite cathode for solid oxide fuel cell (SOFC) has been fabricated by wet impregnation method. Nitrate precursors of La, Sr, and Co have been impregnated into the pre-sintered porous YSZ matrix, which is converted into LSCO phase after calcination at 850 °C in the presence of glycine as confirmed from X-ray diffraction. LSCO of 5, 7, and 10 wt% impregnated porous YSZ have been electrochemically characterized using 2-probe AC conductivity method. Maximum ionic conductivity of 0.27 S/cm at 800 °C and activation energy of 0.15 eV between 600 and 800 °C have been observed for 10 wt% LSCO-YSZ cathode. Area-specific resistance of 1.01 Ω cm² at 800 °C is estimated for the electrolyte-supported half-cell (10 wt% LSCO-YSZ/YSZ). After testing the LSCO-YSZ cathode matrix, the electrolyte-supported full cell (10 wt% LSCO-YSZ/YSZ/NiO-YSZ) has been tested and produced maximum power density 51.12 mW/cm² (109.38 mA/cm²) at 800 °C. The electrolyte-supported full cell exhibited 6 Ω cm² electrode polarization at 800 °C in H₂, which is in higher side leading to low performance. LSCO-YSZ/YSZ/NiO-YSZ SOFC found to give stable performance up to 2 h and scanning electron microscopy analysis has been carried out before and after cell testing to assess the morphological changes.     

Synthesis and characterization of Li4Ti5O12/graphene composite as anode material with enhanced electrochemical performance

The use of graphene as a conductive additive to enhance the rate capability and cycle stability of Li₄Ti₅O₁₂ electrode material has been demonstrated. Li₄Ti₅O₁₂ and its composite with graphene (1.86 wt%) are prepared by ball milling and simple chemical method, respectively. Among the as-synthesized composites, Li₄Ti₅O₁₂ particles uniformly clung to the graphene sheets. When used as an electrode material for lithium ion battery, the composite presents excellent rate performance and high cyclic stability. It is found that the composite displayed high-rate capacity of 118.7 mAh?g^?1 at 20 C. Furthermore, the composite exhibits good cycle stability, retaining over 96 % of its initial capacity after 50 cycles at 10 C. The excellent electrochemical performance is attributed to a decrease in the charge-transfer resistance.     

Effect of sintering temperature on the elemental diffusion and electrical conductivity of SrTiO<Subscript>3</Subscript>/YSZ composite ceramic

The 50 vol% SrTiO₃/yttria-stabilized zirconia (YSZ) composite ceramic was prepared through powder sintering route in 1400～1500 °C. Only the cubic YSZ and SrTiO₃ phases are detected in all the sintered ceramics, and the typical XRD peak positions of both phases have varied dramatically. The grain sizes and relative densities of all specimens increase evidently with the sintering temperature. The width of the SrTiO₃/YSZ interfacial region increases from 100.4 to 468.8 nm as the sintering temperature rises from 1400 to 1500 °C. The total electrical conductivities of the sample sintered at 1500 °C are remarkably higher than those at 1400 and 1450 °C, while the ion transference numbers drop from 0.837 to 0.731 with sintering temperature from 1400 to 1500 °C. The variations in the electrical properties above can be interpreted based on the effects of sintering temperature on the elemental diffusions during the sintering process.     

Effects of atomization conditions on morphology and SOFC anode performance of spray pyrolyzed NiO–Sm0.2Ce0.8O1.9 composite particles

NiO–Sm_0.2Ce_0.8O_1.9 (NiO–SDC) composite particles were synthesized by spray pyrolysis (SP). SP resulted in composite particles of NiO enveloped with SDC and these capsule-type composite particles would reduce aggregation of Ni during the reduction from NiO to Ni metals. SOFC anode microstructures and morphologies of NiO–SDC composite precursor particles much affects on SOFC power densities or anode polarization. Therefore, we focused on atomizing conditions of SP process. Relationship between ultrasonic atomization conditions and morphologies of NiO–SDC composites were investigated by controlling temperatures of atomization vessels. The atomizing temperature changed concentration of mists in the vessel, and mean particle size and particle size distribution were increased with an increase in temperature of the atomization vessels. Some extremely large particles were observed by synthesizing at higher atomization temperatures. Large particles contained voids in the particles. The voids in the composite particles would play a role of pore-formers. SOFC measurement showed the synthesis at the atomizing temperature of 30 °C resulted in the high-performance anode. The atomizing process of SP much affected morphology of anode precursor particles, and the atomizing conditions were important to improve anode performance.     

Influence of graphene nanoplatelet content on the electromagnetic and microwave absorbing properties of BiFeO<Subscript>3</Subscript>/GNP/epoxy composites

Ternary composites of BiFeO₃/graphene nanoplatelet (GNP)/epoxy composites were synthesized and its electromagnetic and microwave absorbing properties were studied; the main absorbing mechanism was illustrated. The phase, microstructure, and microwave absorbing properties were characterized by X-ray diffraction, scanning electron microscope, and vector network analyzer. The results indicated that the BiFeO₃ was successfully synthesized and the GNP was uniformly distributed in the composites, and the complex permittivity of BiFeO₃/GNP/epoxy composites increased with increasing the GNP content due to the interface polarization and conductance loss. The minimum reflection loss value was reached to ??45 dB at 9.25 GHz with the thickness of 1.4 mm when the GNP content was 2 wt%, and also the absorbing properties of (BiFeO₃+GNP)/epoxy composites can be tailored by the GNP content and composite thickness, which may be used as a kind of absorbing materials with good absorbing performance and low density.

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Graphical abstract The reflection loss curves and the simulated matching thickness of GNP-BiFeO₃-epoxy composites with 2 wt% GNP content. As can be seen, the minimum reflection loss value was reached to ??45 dB at 9.25 GHz with the thickness of 1.4 mm, and also the quarter-wavelength matching theory can be used to illustrate the good absorbing properties of GNP-BiFeO₃-epoxy composites.

     

Synthesis and performance of Sm0.9Sr0.1Cr0.5Fe0.5O3 as anode material for SOFCs running on H2S-containing fuel

Sm_0.9Sr_0.1Cr_0.5Fe_0.5O₃ (SSCF) was successfully synthesized by gel combustion method. The structure and physicochemical properties of SSCF were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR). The results showed that SSCF had orthorhombic perovskite-type structure and a homogeneous distribution of pores and particles with grain size in the range 200–300 nm. Meanwhile, SSCF exhibited good chemical compatibility with electrolyte Ce_0.8Sm_0.2O_1.9 (SDC), and no additional diffraction peaks associated with impurities were observed after exposure to 10 %?v/v H₂/N₂ and 1 %?v/v H₂S/N₂. The conductivities of SSCF were evaluated with DC four-probe method in various atmospheres at 400–800 °C. The highest conductivities of SSCF were 0.56, 0.26 and 0.12 S?cm^?1 in air, 10 %?v/v H₂/N₂ and 1 %?v/v H₂S/N₂, respectively. The electrochemical properties were measured for the cell with configuration of SSCF-SDC/SDC/Ag at different temperatures. Electrochemical impedance spectroscopy (EIS) revealed that with the increase in temperature, the ohmic and total interfacial resistances of the cell decreased and the ohmic resistance gradually became the main factor affecting the performance of the cell.     

Microstructure and electrochemical properties of porous La2NiO4+δ electrodes spin-coated on Ce0.8Sm0.2O1.9 electrolyte

Porous La₂NiO_4+?? electrodes were prepared from superfine starting powder on dense substrates of Ce_0.8Sm_0.2O_1.9 electrolyte by a spin coating technique. The microstructure and electrochemical properties of the electrodes were investigated within the sintering temperature range of 1,000?C1,100?°C. An obvious effect of sintering temperature on the microstructure and electrochemical properties was detected. The variation of the electrochemical properties with sintering temperature was explained in relation to the microstructural evolution of the porous electrodes. It was detected that the electrode processes greatly depended on the microstructure of the electrodes. The polarization of surface oxygen exchange process was found to be the major contribution to the total electrode polarization. The electrode sintered at 1,050?°C showed the optimum electrocatalytic activity among the investigated electrodes. At 800?°C, the electrode exhibited a polarization resistance of 0.42????cm², an overpotential of 48?mV at a current density of 200?mA?cm^?2 and an exchange current density of 121?mA?cm^?2.     

Development and characterisation of glass and glass ceramic sealants for solid oxide electrolyser cells

Glass and glass ceramic are now well known for their high performances as sealants operating around 800 °C in solid oxide electrolyser cell. Several new formulations have been prepared and investigated: silica alkali borosilicate glass formulations that will create a glass sealant and calcium aluminosilicate formulations that will create a glass ceramic sealant. Thermal and physicochemical properties of several glasses and glass ceramics along with the crystallisation behaviour were investigated. The glass transition temperatures (T _g) of the prepared glasses were found to be within the range of 600–730 °C. Shrinkage, sintering, softening, deformation and crystallisation temperatures of the parent glasses have been measured by hot stage microscopy. Microstructure and chemical composition of crystalline phases have been investigated using microprobe analysis. Bonding characteristics as well as chemical interactions of the parent glasses with yttria-stabilised zirconia (YSZ®) electrolyte and high chromium steel-based interconnect (Crofer®) have also been studied.     

Synthesis,characterization, and thermal stability of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript>/CR-Ag multilayered nanostructures

The controllable synthesis and characterization of novel thermally stable silver-based particles are described. The experimental approach involves the design of thermally stable nanostructures by the deposition of an interfacial thick, active titania layer between the primary substrate (SiO₂ particles) and the metal nanoparticles (Ag NPs), as well as the doping of Ag nanoparticles with an organic molecule (Congo Red, CR). The nanostructured particles were composed of a 330-nm silica core capped by a granular titania layer (10 to 13 nm in thickness), along with monodisperse 5 to 30 nm CR-Ag NPs deposited on top. The titania-coated support (SiO₂/TiO₂ particles) was shown to be chemically and thermally stable and promoted the nucleation and anchoring of CR-Ag NPs, which prevented the sintering of CR-Ag NPs when the structure was exposed to high temperatures. The thermal stability of the silver composites was examined by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). Larger than 10 nm CR-Ag NPs were thermally stable up to 300 °C. Such temperature was high enough to destabilize the CR-Ag NPs due to the melting point of the CR. On the other hand, smaller than 10 nm Ag NPs were stable at temperatures up to 500 °C because of the strong metal-metal oxide binding energy. Energy dispersion X-ray spectroscopy (EDS) was carried out to qualitatively analyze the chemical stability of the structure at different temperatures which confirmed the stability of the structure and the existence of silver NPs at temperatures up to 500 °C.     

New insight on nanostructure assembling of high-performance electrode materials: synthesis of surface-modified hexagonal β-Ni(OH)<Subscript>2</Subscript> nanosheets as an example

Hexagonal β-Ni(OH)₂ nanosheets with thickness of ～12 nm were synthesized by a hydrothermal method at 150 °C using nickel chloride as nickel source and morpholine as alkaline. Electrodes for application in pseudocapacitor were assembled through a traditional technique: pressing a mixture of β-Ni(OH)₂ nanosheets and acetylene black onto nickel foam. Due to the hexagonal shape of rigid β-Ni(OH)₂ nanosheet and the mediation of surface-modified glycerol during electrochemical charge–discharge cycles, a nanostructure of electrode material with facile interior pathway for the transfer of electrolyte was formed. As a result, the as-formed electrodes presented high specific capacitance of 1,917 F g^?1 at current density of 1.6 A g^?1 in 3 mol L^?1 KOH solution. At high charge and discharge current density of 31.3 A g^?1, the electrodes still remained a high specific capacitance of 1,289 F g^?1. The interesting results obtained from this investigation may provide a new insight for the synthesis of electrode materials with high electrochemical performance.     

PFM characterization of (K0.5Na0.5)0.95La0.05(Nb0.9Ti0.05)O2.9 ceramics lead free

The results of ferroelectric properties studies of KNN doped with La and Ti and sintered at temperatures in the interval of 1100 °C–1190 °C are presented in this work. The doping was achieved by the substitution of La for ions in A sites and Ti for ions in the B sites. Values of 94 % of the theoretical density were accomplished. The effect of the sintering temperature and the inclusion of the La and Ti cations in the KNN structure is evident through the shift in the ferroelectric-paraelectric transition temperature of ～110 °C with respect to that of pure KNN (420 °C). Microstructure and ferroelectric analyses were carried out using Piezoresponse Force Microscopy (PFM) and hysteresis loops with interesting results, ΔP _r=9 (μC/cm²) and P _r/P _max=0.41, even when the saturation of the materials is not reached.     

Influences of interfacial adhesion on gas barrier property of functionalized graphene oxide/ultra-high-molecular-weight polyethylene composites with segregated structure

The segregated graphene oxide(GO)/ultra-high-molecular-weight polyethylene (UHMWPE) composite films with various interfacial adhesion property were prepared by mechanical blending method from UHMWPE, GO, dodecyl amine (DA) functionalized graphene oxide(DA–GO) or uniform DA–GO/high density polyethylene (DA–GO/HDPE) powder. The results of XRD and XPS indicated that DA chain was successfully grafted onto GO sheets via a chemical method, which enhanced the interfacial adhesion between UHMWPE particles and GO sheets. The characterizations of POM and SEM proved that good segregated structure was only obtained in DA–GO/UHMWPE or DA–GO/HDPE/UHMWPE composite. Strong interfacial adhesion between fillers and matrix exhibits positive effect on gas barrier property. Compared to the GO/UHMWPE composite film, dramatic decrease in O₂ permeability coefficient by 42.2 and 48.1%, from 15.4 × 10^?14 to 8.9 × 10^?14 and 8.0 × 10^?14 cm³ cm cm^?2 s^?1 Pa^?1, is achieved upon the addition of only 0.5 wt% fillers, respectively. The DSC results demonstrated that the enhanced gas barrier performance was ascribed to the strong interfacial adhesion between DA–GO/HDPE and UHWMPE matrix, rather than the crystallinity of UHWMPE matrix. Additionally, the decrease in UHMWPE particle size might be conducive to improving the gas barrier property of composite films due to the formation of more isolation layers perpendicular to the film plane.     

MgAl2SiO6-incorporated poly(ethylene oxide)-based electrolytes for all-solid-state lithium batteries

Poly(ethylene oxide) (PEO)-based composite polymer electrolytes (CPEs), comprising various concentrations of lithium hexafluorophosphate and magnesium aluminium silicate, were prepared by hot-press technique. The membranes were characterised by scanning electron microscopy, tensile and thermal analyses. It has been demonstrated that the incorporation of the ceramic filler in the polymeric matrix has significantly enhanced the ionic conductivity, thermal stability and mechanical integrity of the membrane. It also improved the interfacial properties with lithium electrode. Finally, an all-solid-state lithium cell composed of Li/CPE/LiFePO₄ has been assembled and its cycling performance was analysed at 70 °C. The cell delivered a discharge capacity of 115 mAh g^?1 at 1 °C rate and is found to be higher than previous reports.     

Roles of Al-doped ZnO (AZO) modification layer on improving electrochemical performance of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> thin film cathode

Al-doped ZnO (AZO) was sputtered on the surface of LiNi_1/3Co_1/3Mn_1/3O₂ (NCM) thin film electrode via radio frequency magnetron sputtering, which was demonstrated to be a useful approach to enhance electrochemical performance of thin film electrode. The structure and morphology of the prepared electrodes were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectrometer, and transmission electron microscopy techniques. The results clearly demonstrated that NCM thin film showed a strong (104) preferred orientation and AZO was uniformly covered on the surface of NCM electrode. After 200 cycles at 50 μA μm^?1 cm^?2, the NCM/AZO-60s electrode delivered highest discharge capacity (78.1 μAh μm^?1 cm^?2) compared with that of the NCM/AZO-120s electrode (62.4 μAh μm^?1 cm^?2) and the bare NCM electrode (22.3 μAh μm^?1 cm^?2). In addition, the rate capability of the NCM/AZO-60s electrode was superior to the NCM/AZO-120s and bare NCM electrodes. The improved electrochemical performance can be ascribed to the appropriate thickness of the AZO coating layer, which not only acted as HF scavenger to keep a stable electrode/electrolyte interface but also reduced the charge transfer resistance during cycling.     

Evaluation of a cobalt-free Ba0.5Sr0.5Fe0.9Nb0.1O3?δ cathode material for intermediate-temperature solid oxide fuel cells

A cobalt-free Ba_0.5Sr_0.5Fe_0.9Nb_0.1O_3??? (BSFNb) perovskite-type oxide was investigated as the cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs) with Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte. XRD results showed that BSFNb cathode was chemically compatible with the electrolyte SDC up to 1,000?°C. The maximum output of anode-supported thin-film SOFC reached 503?mW?cm^?2 at 650?°C when employing humidified H₂ as fuel and static air as oxidizer. The electrode polarization resistance was low as 0.078????cm² at 650?°C, and the activation energy of the electrode polarization resistance was 129.72?kJ?mol^?1. The experimental results indicated that the cobalt-free BSFNb was a promising cathode candidate for IT-SOFCs.     

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.     

Electrochromic properties of WO3 thin film onto gold nanoparticles modified indium tin oxide electrodes

Gold nanoparticles (GNPs) thin films, electrochemically deposited from hydrogen tetrachloroaurate onto transparent indium tin oxide (ITO) thin film coated glass, have different color prepared by variation of the deposition condition. The color of GNP film can vary from pale red to blue due to different particle size and their interaction. The characteristic of GNPs modified ITO electrodes was studied by UV-vis spectroscopy, scanning electron microscope (SEM) images and cyclic voltammetry. WO₃ thin films were fabricated by sol-gel method onto the surface of GNPs modified electrode to form the WO₃/GNPs composite films. The electrochromic properties of WO₃/GNPs composite modified ITO electrode were investigated by UV-vis spectroscopy and cyclic voltammetry. It was found that the electrochromic performance of WO₃/GNPs composite films was improved in comparison with a single component system of WO₃.     

Development of monodispersed MnCO<Subscript>3</Subscript>/graphene nanosheet composite as anode for lithium-ion battery by hydrothermal synthesis

A unique monodispersed MnCO₃/graphene nanosheet composite is synthesized by a simple one-step hydrothermal method and used as anode of lithium-ion battery. X-ray diffraction patterns show the typical rhombohedral structure of MnCO₃. A transmission electron micrograph reveals that MnCO₃ is evenly distributed on the graphene nanosheet surface with a uniform diameter of 100 nm. Electrochemical performance results show that the specific discharge capacities of MnCO₃/graphene nanosheet composite remain above 1015.9 mAh g^?1 at a rate of 0.2 C after 85 cycles in the potential window of 0.01–2.0 V and even at a high rate of 1.0 C this parameter remains at 683.5 mAh g^?1 after 100 cycles. Thus, the composite also exhibits favorable rate performance. The excellent reversible capacities are attributed to the highly dispersed and large nanosheet structure of the composite, which may not only facilitate the fast transport of Li⁺ ions between the electrode and electrolyte but also provide enough surfaces to accommodate extra Li⁺ ions that contribute to partial interfacial storage capacities. Additionally, graphene nanosheet can effectively improve electrical conductivity of the composite. Therefore, MnCO₃/graphene nanosheet composite can be a great potential anode material for lithium-ion batteries.     

Impedance studies on bismuth-ruthenate-based electrodes

Doped bismuth ruthenates and bismuth ruthenate-stabilized bismuth oxide composites were studied as prospective cathode material for solid oxide fuel cells. Symmetric cells were fabricated on gadolinium-doped ceria electrolytes and studied by electrochemical impedance spectroscopy. Ca- and Ag-doped bismuth ruthenate electrodes (5–10 mol%) showed the same characteristic frequency as undoped bismuth ruthenate but with higher activation energy and slightly better performance above ∼550 °C. At 700 °C, area-specific resistance (ASR) of undoped, 5 mol% Ca and 5 mol% Sr-doped bismuth ruthenate electrode was 1.45, 1.24, and 1.41  Ωcm², respectively. The change in ASR as a function of oxygen partial pressure and current bias suggests that the rate-limiting steps for oxygen reduction in bismuth ruthenate systems are charge transfer and surface diffusion of dissociatively adsorbed oxygen to triple phase boundaries. Introduction of the erbia-stabilized bismuth oxide (ESB) phase reduced both the rate-limiting steps resulting in much improved electrode performance. At 700 °C, composite electrodes containing 31.25–43.75 wt% ESB exhibited an ASR of 0.08–0.11 Ωcm².