Electrochemical NOx Sensor for Monitoring Diesel Emissions

Woo, L Y ; Glass, R S

关键词: AUTOMOBILES;    CALIBRATION;    CATALYSTS;    COMMERCIALIZATION;    DETECTION;    DYNAMOMETERS;    ELECTROLYTES;    FREQUENCY MEASUREMENT;    GASES;    HYDROCARBONS;    IMPEDANCE;    MONITORING;    OXYGEN;    POLLUTANTS;    SAMPLING;    SENSITIVITY;    THERMODYNAMICS;    WATER VAPOR;   

DOI  :  10.2172/945730
RP-ID  :  LLNL-TR-408750
PID  :  OSTI ID: 945730
Others  :  TRN: US200904%%133

学科分类：材料科学（综合）

美国|英语

来源: SciTech Connect

【 摘 要 】

Increasingly stringent emissions regulations will require the development of advanced gas sensors for a variety of applications. For example, compact, inexpensive sensors are needed for detection of regulated pollutants, including hydrocarbons (HCs), CO, and NO{sub x}, in automotive exhaust. Of particular importance will be a sensor for NO{sub x} to ensure the proper operation of the catalyst system in the next generation of diesel (CIDI) automobiles. Because many emerging applications, particularly monitoring of automotive exhaust, involve operation in harsh, high-temperature environments, robust ceramic-oxide-based electrochemical sensors are a promising technology. Sensors using yttria-stabilized zirconia (YSZ) as an oxygen-ion-conducting electrolyte have been widely reported for both amperometric and potentiometric modes of operation. These include the well-known exhaust gas oxygen (EGO) sensor. More recently, ac impedance-based (i.e., impedance-metric) sensing techniques using YSZ have been reported for sensing water vapor, hydrocarbons, CO, and NO{sub x}. Typically small-amplitude alternating signal is applied, and the sensor response is measured at a specified frequency. Most impedance-metric techniques have used the modulus (or magnitude) at low frequencies (< 1 Hz) as the sensing signal and attribute the measured response to interfacial phenomena. Work by our group has also investigated using phase angle as the sensing signal at somewhat higher frequencies (10 Hz). The higher frequency measurements would potentially allow for reduced sampling times during sensor operation. Another potential advantage of impedance-metric NO{sub x} sensing is the similarity in response to NO and NO{sub 2} (i.e., total-NO{sub x} sensing). Potentiometric NO{sub x} sensors typically show higher sensitivity to NO2 than NO, and responses that are opposite in sign. However, NO is more stable than NO{sub 2} at temperatures > 600 C, and thermodynamic calculations predict {approx}90% NO, balance NO{sub 2}. Since automotive exhaust sensors will probably be required to operate at temperatures > 600 C, NO is the dominant component in thermodynamic equilibrium and the target NOx species. Also, the use of upstream catalysts could further promote the conversion of NO{sub x} species to NO. Therefore, the focus of current work is to investigate the response to NO. Nevertheless, minimizing the sensitivity to a variety of competing species is important in order to obtain the accuracy necessary for achieving the emission limits. Mitigating the effect of interfering gases (e.g., O{sub 2}, water vapor, HCs, etc.) is an area of current study. For impedance metric NO{sub x} sensors, our previous work has demonstrated that the cross-sensitivity to O{sub 2} may be accounted for by comparing measurements at multiple frequencies. Other strategies for compensation are also being explored, including calibration using data from existing sensors located nearby. Our current work has made significant advances in terms of developing prototype sensors more suitable for commercialization. Also, dynamometer testing has provided real-world sensor performance data that will be useful in approaching potential suppliers to whom we can transfer the technology for commercialization. The advances are a direct result of understanding the sensing mechanisms responsible for impedance-based NO{sub x} sensing and the effect of materials choice and sensor design/geometry.