Mixed potential gas sensors with layered Au,Pt-YSZ electrode comprising a thick-film Pt-YSZ electrode and a covering thin-film Au layer deposited in two different thicknesses, respectively, were studied in this work It was shown by GD-OES analysis that the Au layer is not uniformly admixed with the Pt-YSZ bulk after firing treatment at 850 °C, but results in a gradient of Au from top over the thickness of the electrode Surprisingly, also this kind of layered electrode exhibits a mixed-potential characteristic, which was confirmed by open circuit potential measurement Better sensitivity to CO was found for the electrode with thicker Au layer, and was attributed to the reduced catalytic activity for the oxygen reduction reaction by addition of Au This aspect was investigated by cyclic voltammetry, and the dependence of electrochemical behaviors of the electrodes on temperature was studied as well Over all, the experiments have clearly shown, that mixed potential formation at the Au,Pt-YSZ MPE can be dominated by a relatively thin Au,Pt-layer in the top part of the porous electrode material

Mixed-potential gas sensor with layered Au,Pt-YSZ electrode: Investigating the sensing mechanism with steady state and dynamic electrochemical methods

Electrodes for solid electrolyte sensors for the measurement of CO and H2 content in air

Morphological and structural properties of layered Au,Pt-YSZ mixed-potential gas sensing electrodes (APE) prepared under different temperature treatments were studied by environmental scanning electron microscopy (ESEM), X-ray crystallography (XRD) and glow-discharge optical emission spectroscopy (GD-OES), and correlated with open-circuit potential (OCP) and cyclic voltammetry (CV) measurements under gas exposures at elevated temperatures. The electrode sintered at 1050 °C for 4 h provides a more uniform Au distribution both on the surface and in the inner part of the electrode. Correspondingly, the OCP response of this electrode to CO is clearly higher than that of the electrode sintered at 850 °C for 10 min. This can be well correlated with a smaller oxygen reduction reaction (ORR) observed in the related CV diagrams. Moreover, a transition from the diffusional transport to the charge transfer reaction kinetics controlled mixed-potential formation was observed between 20 and 5 vol.% O2 at the APE sintered at 1050 °C for 4 h.

Layered Au,Pt-YSZ mixed potential gas sensing electrode: Correlation among sensing response, dynamic electrochemical behavior and structural properties

Composite solid-state electrolytes (CSEs) have been developed rapidly in recent years owing to their high electrochemical stability, low cost, and easy processing characteristics. Most CSEs, however, require high temperatures or flammable liquid solvents to exhibit their acceptable electrochemical performance. Room-temperature all-solid-state batteries without liquid electrolytes are still unsatisfactory and under development. Herein, we have prepared a composite solid electrolyte with excellent performance using a polymer electrolyte poly(vinylidene fluoride-hexafluoropropylene) and an inorganic electrolyte Li6.4La3Zr1.4Ta0.6O12. With the assistance of lithium salts and plasticizers, the prepared CSE achieves a high ionic conductivity of 4.05 × 10–4 S·cm–1 at room temperature. The Li/CSE/Li symmetric cell can be stably cycled for more than 1000 h at 0.1 mA/cm2 without short circuits. The all-solid-state lithium metal battery using a LiFePO4 cathode displays a high discharge capacity of 148.1 mAh·g–1 and a capacity retention of 90.21% after 100 cycles. Moreover, the high electrochemical window up to 4.7 V of the CSE makes it suitable for high-voltage service environments. The all-solid-state battery using a lithium nickel-manganate cathode shows a high discharge specific capacity of 197.85 mAh·g–1 with good cycle performance. This work might guide the improvement of future CSEs and the exploration of flexible all-solid-state lithium metal batteries.

High-Performance Poly(vinylidene fluoride-hexafluoropropylene)-Based Composite Electrolytes with Excellent Interfacial Compatibility for Room-Temperature All-Solid-State Lithium Metal Batteries

Electrochemical characteristics of a layered Au,Pt-YSZ mixed-potential (APE) gas sensing electrode were studied by open circuit potential (OCP) and electrochemical impedance measurements (EIS), especially in relation to effects of aging under ambient air conditions and cathodic polarization. Mixed-potential response of the APE to CO was found to be drastically reduced after 100 days of operation in ambient air, which is correlated with a clear change in the shape of the EIS characteristics and a considerably increased polarization resistance (Rp). By applying a cathodic polarization, the reduced sensitivity can be almost fully restored. Also the EIS characteristics tend to show a similar behavior as observed in the initial state. The influence of cathodic polarization treatment on the regeneration of the electrochemical (OCP and EIS) behaviors is found to be clearly enhanced at elevated temperatures (700 °C), while oxygen concentration seems to play no role on this regeneration effect. This polarization treatment will highly improve stability of the APE and is expected to enable applications like flue gas analysis.

Stability improvement of layered Au,Pt-YSZ mixed-potential gas sensing electrodes by cathodic polarization: Studies by steady state and dynamic electrochemical methods

A model of conductivity of nanocomposite ceramics consisting of solid-electrolyte and dielectric phases is proposed based on the assumption that the conductivity of grain boundaries between the solid-electrolyte and dielectric phases is higher than the conductivity of the volume of particles in the solid-electrolyte phase and its grain boundaries. Taking into account the size of particles, the thickness of grain boundaries, and the bulk and grain-boundary conductivities, the grain size of composite ceramics for which the conductivity may exceed the conductivity of single-phase solid-electrolyte ceramics is assessed. For testing this model, the composite samples are synthesized based on dielectric magnesium oxide and solid-electrolyte cerium oxide doped with samarium oxide. It is shown that introduction of 50 mol % magnesium oxide into composite ceramics has virtually no effect on its conductivity as compared with single-phase solid-electrolyte ceramics. This result can be explained by assuming the appearance of accelerated transport routes for oxygen ions in grain boundaries between dielectric and solid-electrolyte phases. Further dispersion, optimization of the ratio, and increase in distribution homogeneity of components can confirm the validity of the proposed conductivity model and open up the possibility of preparation of oxide solid-electrolyte materials with higher conductivity.

Nanocomposite Ceramics on the Basis of Magnesium, Cerium, and Samarium Oxides

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6.5.3 Recent developments in materials for potentiometric sensors

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Nanocomposite Ceramics on the Basis of Magnesium, Cerium, and Samarium Oxides

6.5.3 Recent developments in materials for potentiometric sensors