Response Characteristics of a Stable Mixed Potential Ammonia Sensor in Simulated Diesel Exhaust
Meeting the EPA Tier 3 emissions reduction requirements while simultaneously increasing fuel economy to meet new CAFE standards will require optimization of advanced combustion strategies and emissions control technologies as well their state of operation under transient vehicle operation. NOx sensors are needed to reduce variations in emissions control, lower the cost of closed loop DEF dosing control, improve consumption of both fuel and DEF. NH3 sensors are needed to monitor DEF injection and prevent NH3 slip—a condition under which unreacted ammonia from the SCR is emitted in the tailpipe exhaust. The ammonia slip is treated as a more harmful pollutant than the NOx emissions. Ideally, both NH3 and NOx sensors would be incorporated into a closed-loop system to maintain ammonia close to stoichiometry in the SCR system, and could also serve to monitor engine out and tailpipe out emissions in order to ensure regulatory compliance.
Mixed-potential sensors are electrochemical devices that develop a non-Nernstian potential due to differences in the redox kinetics of various gas species at each electrode/electrolyte gas interface1,2. The difference in the steady-state redox reaction rates between the “fast” and “slow” electrodes gives rise to the measured mixed potential response. A patented LANL sensor design incorporates dense electrodes and a porous electrolyte and reproducible and stable sensors are prepared using a simple ceramic tape cast approach3. The use of dense electrodes minimizes deleterious heterogeneous catalysis, and the increased morphological stability of dense electrodes yields a robust electrochemical interface, increasing lifetime durability4. The use of a dense gold wire-working electrode (e.g. the slow electrode), imparts preferential selectivity to NH3, and avoids the stability problems one finds when using thin film, porous Au electrodes5.
In this work, we present recent results from testing a Au/YSZ/Pt tape cast sensor in ORNL’s high flow reactor at the NRTC that was especially constructed to simulate the exhaust gas constituents produced by lean burn vehicles powered by CIDI diesel engines with, and without emissions controls. The sensor was characterized at 525 and 625°C for NH3, CO, C3H6, C3H8, and NOx in a pre-heated base gas composition of 1%O2, 5%H2O, 5%CO2 flowing at 15 slpm. The sensor exhibited fast response time equal to the response time of the system’s switching valve (T90<0.6s). Moreover, in simulations of ammonia slip resulting from overdosing an SCR, the sensor was able to easily measure 20ppm injections of NH3 in the presence of the interferent gas species at combined concentrations ten times higher than the NH3. These data provide experimental confirmation of the concept of using a mixed-potential electrochemical NH3 sensor for tail pipe out applications. New data from recent engine out testing of pre-commercial prototype sensors that utilize design principles of tape sensors but are based on High Temperature Ceramic Co-Fire (HTCC) construction6 will be presented and discussed.
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The authors would like to thank Roland Gravel and the DOE Vehicle Technology Office for providing funding for this work.