NOx Sensor Development

Abstract

NO{sub x} compounds, specifically NO and NO{sub 2}, are pollutants and potent greenhouse gases. Compact and inexpensive NO{sub x} sensors are necessary in the next generation of diesel (CIDI) automobiles to meet government emission requirements and enable the more rapid introduction of more efficient, higher fuel economy CIDI vehicles. Because the need for a NO{sub x} sensor is recent and the performance requirements are extremely challenging, most are still in the development phase. Currently, there is only one type of NO{sub x} sensor that is sold commercially, and it seems unlikely to meet more stringent future emission requirements. Automotive exhaust sensor development has focused on solid-state electrochemical technology, which has proven to be robust for in-situ operation in harsh, high-temperature environments (e.g., the oxygen stoichiometric sensor). Solid-state sensors typically rely on yttria-stabilized zirconia (YSZ) as the oxygen-ion conducting electrolyte and then target different types of metal or metal-oxide electrodes to optimize the response. Electrochemical sensors can be operated in different modes, including amperometric (a current is measured) and potentiometric (a voltage is measured), both of which employ direct current (dc) measurements. Amperometric operation is costly due to the electronics necessary to measure the small sensor signal (nanoampere current at ppm NO{sub x} levels), and cannot be easily improved to meet the future technical performance requirements. Potentiometric operation has not demonstrated enough promise in meeting long-term stability requirements, where the voltage signal drift is thought to be due to aging effects associated with electrically driven changes, both morphological and compositional, in the sensor. Our approach involves impedancemetric operation, which uses alternating current (ac) measurements at a specified frequency. The approach is described in detail in previous reports and several publications. Briefly, impedancemetric operation has shown the potential to overcome the drawbacks of other approaches, including higher sensitivity towards NO{sub x}, better long-term stability, potential for subtracting out background interferences, total NO{sub x} measurement, and lower cost materials and operation. Past LLNL research and development efforts have focused on characterizing different sensor materials and understanding complex sensing mechanisms. Continued effort has led to improved prototypes with better performance, including increased sensitivity (to less than 5 ppm) and long-term stability, with more appropriate designs for mass fabrication, including incorporation of an alumina substrate with an imbedded heater. Efforts in the last year to further improve sensor robustness have led to successful engine dynamometer testing with prototypes mounted directly in the engine manifold. Previous attempts had required exhaust gases to be routed into a separate furnace for testing due to mechanical failure of the sensor from engine vibrations. A more extensive cross-sensitivity study was also undertaken this last year to examine major noise factors including fluctuations in water, oxygen, and temperature. The quantitative data were then used to develop a strategy using numerical algorithms to improve sensor accuracy. The ultimate goal is the transfer of this technology to a supplier for commercialization. Due to the recent economic downturn, suppliers are demanding more comprehensive data and increased performance analysis before committing their resources to take the technology to market. Therefore, our NO{sub x} sensor work requires a level of technology development more thorough and extensive than ever before. The objectives are: (1) Develop an inexpensive, rapid-response, high-sensitivity and selective electrochemical sensor for oxides of nitrogen (NO{sub x}) for compression-ignition, direct-injection (CIDI) exhaust gas monitoring; (2) Explore and characterize novel, effective sensing methodologies based on impedance measurements and designs and manufacturing methods that could be compatible with mass fabrication; and (3) Collaborate with industry in order to (ultimately) transfer the technology to a supplier for commercialization.