Electrode materials for zirconia sensors working at temperatures lower than 500 K

doi:10.1016/0925-4005(93)85314-Z

Sensors and Actuators B: Chemical

Volume 13, Issues 1–3, May 1993, Pages 27-30

https://doi.org/10.1016/0925-4005(93)85314-Z Get rights and content

Abstract

With Bi₂Ru₂O₇ and Bi₃Ru₃O₁₁ as electrode materials, the zirconia sensor can be used at a temperature as low as 450 K. Chemical gaseous pre-treatments, efficient over several weeks, significantly shorten the response times down to a few seconds.

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HfO<inf>2</inf>-based electrolyte potentiometric oxygen sensors for liquid sodium
2020, Electrochimica Acta
The use of potentiometric sensors for the on-line monitoring of oxygen in molten sodium in fast breeder reactors has been studied since the 1970s. However, their lifetime and the reproducibility of the results are inadequate for commercial development. In this study, the performance of the sensor using yttria-doped hafnia is studied and compared with results obtained with thoria- and zirconia-based electrolytes. The yttria-doped hafnia sensor tested, in the form of a tube, exhibits a very reproducible signal and remarkable stability under very low oxygen levels (ca. 0.02 ppm) and low temperatures (200–300 °C), with a lifetime of ca. two months. Consequently, this electrolyte can be viewed as a promising material for sensing oxygen in molten sodium. The main sources of errors observed in the application of these sensors are reviewed under severe conditions at low temperatures. Discrepancies between the calculated electromotive force (emf) of the cell and the slope of the theoretical Nernst law and the experimental values are analyzed and hypotheses are discussed in order to explain the deviations from the expected values. For the zirconia-based sensor, an original interpretation of the sensor’s response to a change in oxygen concentration, obtained at low temperatures, is proposed, involving peroxide ions.
Limiting current oxygen sensor based on La<inf>0.8</inf>Sr<inf>0.2</inf>Ga<inf>0.8</inf>Mg<inf>0.2</inf>O<inf>3−δ</inf> as both dense diffusion barrier and solid electrolyte
2017, Ceramics International
Citation Excerpt :
Since the plugging and deformation of pore-based diffusion barriers often occur compared with the dense diffusion barrier, attention has been paid to dense diffusion barrier limiting current oxygen sensor. Many mixed oxide-ion/electron conductor (MIEC) materials for dense diffusion barrier have been reported such as La1−xSrxMnO3 (LSM) [3–6], La1−xSrxCoO3 (LSC) [3,7], La0.8Sr0.2Co0.8Fe0.2O3−δ (LSCF) [8], La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) [9], La0.8Sr0.2(Ga1−xNx)0.8Mg0.2O3−δ (N=Fe, Co, LSGFM, LSGCM) [10], Sr0.9Y0.1CoO3−δ (SYC) [2], terbia-yttria stabilized zirconia (Tb-YSZ) [11], platinum-yttria stabilized zirconia (Pt-YSZ) [12], and NiO+alumina/yttria stabilized zirconia (NiO/3Y20A) [13]. However, there is a mismatch of the physical and chemical compatibility between MIEC and solid electrolyte, leading to a degradation of sensing performance.
La_0.8Sr_0.2Ga_0.8Mg_0.2O_3−δ (LSGM) was synthesized by a high temperature solid-state reaction. The crystal structure, relative density and electrical conductivity were measured with XRD, Archimedes method, and Van Der Pauw DC four-probe method. A limiting current oxygen sensor based on LSGM as both solid electrolyte and dense diffusion barrier was prepared by a Pt paste bonding method. The results show that LSGM has pure perovskite structure (cubic symmetry with space group of Pm-3m (No.221)), high density (relative density is 97.6%) and electrical conductivity (0.18 S∙cm⁻¹ at 1073 K). The sensor works optimally over temperature range of 973‒1123 K and oxygen concentration of 1.92%‒21%. The operating voltage ranges from 0.67 to 0.98 V. The limiting current is in proportion to oxygen concentration. The sensor has the highest sensitivity at 1123 K and low measurement error of less than 4%.
A high performance limiting current oxygen sensor with Ce <inf>0.8</inf>Sm<inf>0.2</inf>O<inf>1.9</inf> electrolyte and La <inf>0.8</inf>Sr<inf>0.2</inf>Co<inf>0.8</inf>Fe<inf>0.2</inf>O<inf>3</inf> diffusion barrier
2013, Electrochimica Acta
Citation Excerpt :
The diffusion barrier material used for limiting current type oxygen sensor is required to have high electronic conductivity, adequate oxygen ionic conductivity, matched thermal expansion coefficient with the electrolyte, high catalytic activity in oxygen reduction and good chemical stability. At present, most attention has paid to using La0.84Sr0.16MnO3 (LSM) as the diffusion barrier layer [16–18]. However, the LSM may be not the most ideal material for the oxygen diffusion barrier layer.
A dense diffusion barrier limiting current oxygen sensor with Ce_0.8Sm_0.2O_1.9 (SDC) solid electrolyte and La_0.8Sr_0.2Co_0.8Fe_0.2O₃ (LSCF) dense diffusion barrier was developed. The effects of the oxygen concentration and temperature on the limiting current were investigated and the response time of the oxygen sensor was measured. The limiting current oxygen sensor exhibits a good limiting current platform when the oxygen volume fraction is from 0 to 0.21. The limiting current linearly increases with the oxygen volume fraction. At 973 K, it improves from 40 to 120 mA as the oxygen volume fraction increases from 0.038 to 0.21. In addition, the limiting current oxygen sensor shows a wide voltage platform interval, which is from ∼0.5 to ∼1.7 V. The response time of the sensors is about 15–30 s. The sensor continuously operated at 973 K for 60 h, its limmiting current is almost invariable, which is ∼30 mA. These results suggest that the oxygen sensor with LSCF as a dense diffusion barrier and SDC as a solid electrolyte provides a potential approach to the performance improvement of the limiting current oxygen sensor for practice use.
Design and testing of electrochemical oxygen sensors for service in liquid lead alloys
2011, Journal of Nuclear Materials
Electrochemical oxygen sensors currently used for measuring the chemical potential of oxygen in liquid lead alloys were investigated by five European laboratories, focussing on factors influencing the accuracy of the sensor output, the long-term performance in experimental facilities and methods of testing the sensors before installation and during operation in a plant. The design of different electrochemical oxygen sensors is introduced, along with the experimentally determined sensor reliability and appropriate testing methods. The reported results summarize the results of Task 4.2.4 within Domain 4 (DEMETRA) of the integrated project (IP) EUROTRANS that was funded by the EURATOM 6th Framework Programme.
Subsolidus phase equilibria in the RuO<inf>2</inf>-Bi<inf>2</inf>O <inf>3</inf>-ZrO<inf>2</inf> system
2011, Materials Research Bulletin
Citation Excerpt :
These materials include RuO2 and electrically conducting ruthenates, which are known to be useful electrocatalysts for oxygen reduction. Kleitz et al. reported good results when using bismuth ruthenates as electrodes for the YSZ solid electrolyte [8]. The compatibility of RuO2 and SrRuO3 with YSZ was evaluated by Hrovat et al. [9,10].
Subsolidus equilibria in air in the RuO₂–Bi₂O₃–ZrO₂ system were studied with the aim of obtaining information on possible interactions between a Bi₂Ru₂O₇-based cathode and a ZrO₂-based solid electrolyte in solid-oxide fuel cells (SOFCs). No ternary compound was found in the system. The tie lines are between Bi₂Ru₂O₇ and ZrO₂, and between Bi₂Ru₂O₇ and gamma-Bi₂O₃—the ZrO₂ stabilised Bi₂O₃ phase, stable at temperatures over 710 °C.
Subsolidus phase equilibria in the Al<inf>2</inf>O<inf>3</inf>-CeO <inf>2</inf>-PbO and Al<inf>2</inf>O<inf>3</inf>-CeO<inf>2</inf>-RuO<inf>2</inf> systems
2004, Materials Research Bulletin
The subsolidus phase equilibria in air for the Al₂O₃–CeO₂–PbO and Al₂O₃–CeO₂–RuO₂ systems were studied with the aim of obtaining information on possible interactions between a CeO₂-based solid electrolyte in solid-oxide fuel cells (SOFCs) and other oxides. No ternary compound was found in either of the systems. The tie line in the Al₂O₃–PbO–CeO₂ system is between Al₂Pb₂O₅ and the CeO₂.

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¹: Present address: Shimadzu Corporation, 1 Nishinokyo-Kuwabaracho, Nakagyo-ku, Kyoto 604, Japan.

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Electrode materials for zirconia sensors working at temperatures lower than 500 K

Abstract

Solid State Ionics

Solid State Ionics

Sensor and Actuators

Solid State Ionics