摘要
固体电解质基气体传感器具有结构简单、选择性好及灵敏度高等优点，尤其是优异的高温稳定性，使其具有广泛的应用前景。敏感材料是提高固体电解质基气体传感器性能的关键。本论文以固体电解质基NO_2和H_2传感器为研究对象，采用湿化学浸渍技术，在固体电解质多孔骨架层中制备纳米结构的敏感材料。采用XRD、SEM、EDX等分析方法和动电位扫描、恒电位、电化学阻抗谱及脉冲电位等电化学测试技术，系统研究了传感器的微观结构、气敏性能及响应机理等。
以硝酸盐溶液为敏感材料前驱液，采用湿化学浸渍技术，在Ce_(0.9)Gd_(0.1)O_(1.9)（5CGO）多孔骨架层中成功制备了纳米结构的钙钛矿型敏感材料La_(0.75)Sr_(0.25)Mn_(0.5)Cr_(0.5)O_(3-δ)（LSCM）。LSCM颗粒均匀地分布在多孔骨架层中，粒径50~150nm之间。随着煅烧温度的升高，LSCM颗粒逐渐长大。分别以LSCM和CGO为敏感电极和固体电解质，组装成电流型NO_2传感器，在400~600℃之间，对NO_2表现出优异的敏感性。响应电流与NO_2浓度呈线性关系。传感器响应、恢复迅速，具有较好的稳定性。同时，对O_2和CO_2表现出良好的抗干扰能力。
采用交流阻抗技术，研究了以LSCM为敏感电极的NO_2传感器的气敏性能和响应机理。结果表明：该传感器在交流阻抗的工作方式下，对NO_2表现出良好的响应性能。随着NO_2浓度增大，总阻抗值|Z|线性减小。通过对不同NO_2浓度下的阻抗谱拟合和等效电路分析表明，传感器对NO_2的响应是由于NO_2在气体|LSCM|CGO三相界面处的电化学催化分解。
研究了基于复合敏感材料（LSCM/Ag和LSCM/CGO）电流型NO_2传感器的性能。与单相LSCM敏感材料相比，电子导电相Ag或离子导电相CGO的引入可明显提高传感器的响应电流、灵敏度和响应速度。在500~700℃之间，传感器的响应信号与NO_2浓度呈线性关系。该传感器表现出良好的重现性、稳定性及抗干扰能力。
采用湿化学浸渍技术，在钇稳定的氧化锆（YSZ）多孔骨架层中成功制备了纳米结构的尖晶石型敏感材料MCr_2O_4(M=Cu, Ni, Zn)，并组装成NO_2传感器。研究了其在不同工作方式下（阻抗、电流及脉冲电位）的气敏性能。结果表明：传感器对NO_2表现出良好的敏感性能。响应、恢复迅速，传感器的响应信号与NO_2浓度呈良好的线性关系。与恒电位法相比，在脉冲电位的工作方式下，传感器的响应电流和灵敏度均明显提高。响应电流达到1×10-3A级，灵敏度达到1.5μA/ppm。该传感器表现出优异的响应能力，响应时间仅为0.1s。对O_2具有良好的抗干扰能力。
研究了基于纳米敏感材料的固体电解质基电流型H_2传感器。采用固相反应法制备了质子导体CaZr_(0.9)In_(0.1)O_(3-δ)。利用ZnO作为烧结助剂，有效降低了CaZr_(0.9)In_(0.1)O_(3-δ)电解质的烧结温度。经1350℃烧结5h，得到具有良好致密性、较高电导率和优异稳定性的CaZr_(0.9)In_(0.1)O_(3-δ)电解质。采用湿化学浸渍技术在CaZr_(0.9)In_(0.1)O_(3-δ)多孔骨架层中成功地制备了纳米结构的敏感材料ZnO和SnO_2。在500~700℃之间，组装成的电流型H_2传感器表现出较高的灵敏度、优异的响应和恢复能力及良好的稳定性。
The solid electrolyte type gas sensors with simple structure, good selectivity and highsensitivity, especially excellent chemical and physical durability at elevated temperatures,have the widespread prospect of application. It is important to study the design andsynthesis of sensing materials which were the key factors for improving the performanceof the sensors. In the present work, the solid electrolyte type NO_2and H_2sensors werefabricated using nano-structured sensing materials which were prepared in the poroussolid electrolyte layers by impregnating method. The composition and microstructure ofthe sensors were characterized by XRD, SEM and EDX. The sensing performances andmechanisms were investigated by potentiodynamic method, potentiostatic method, ACimpedance spectroscopy and pulse potential method.
Nano-structured perovskite-type oxide La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3-δ)（LSCM）as sensingelectrode was prepared in the porous Ce_(0.9)Gd_(0.1)O_(1.9)（5CGO）layer by impregnating methodusing nitrate salts precursor solution. The LSCM particles in the range of50–150nm werehomogeneously dispersed in the porous CGO layer. With calcining temperature increasing,LSCM particles gradually grew up. An amperometric NO_2sensor using nano-structuredLSCM sensing electrode with CGO electrolyte was fabricated. The sensor showed goodsensitivity to NO_2at400~600℃. The response current was linearly related to theconcentration of NO_2. The sensor showed good response–recovery characteristics,reproducibility and stability. Negligible effects of O_2and CO_2on the sensor response wereobserved.
The sensing performance and mechanism of the NO_2sensor using nano-structuredLSCM sensing electrode were investigated by AC impedance spectroscopy. The resultsshowed that the impedancemetric NO_2sensor was sensitive to NO_2.With the increase inthe NO_2concentration, the total impedance values (|Z|) linearly decreased. Anequivalent-circuit model analysis for the impedance spectra showed that sensor responseto NO_2was attributed to the processes occurring at the triple-phase boundary.
Amperometric NO_2sensors using nano-structured composite sensing electrodes（LSCM/Ag and LSCM/CGO）with CGO electrolyte were fabricated. Compared withsingle LSCM sensing electrode, the sensors with composite sensing electrodes showedextraordinarily higher response currents, sensitivities and response rates. The responsecurrent was linearly related to the concentration of NO_2at500~700℃. The sensorsshowed good response–recovery characteristics, stability and anti-interference ability tothe coexistence gases.
Novel NO_2sensors were fabricated using nano-structured spinel-type oxides MCr2O4(M=Cu, Ni, Zn) as sensing electrodes prepared in the porous yttria-stabilized zirconia(YSZ) layer by impregnating method. The sensing performances of the NO_2sensors wereinvestigated using different working modes, including amperometric, impedancemetricand pulse potential mode. The sensor showed good sensitivity and response–recoverycharacteristics to NO_2. The response current was linearly related to the concentration ofNO_2. Compared with the potentiostatic mode, the sensors using pulse potential modeshowed extraordinarily higher response current and sensitivity which could reach1×10-3Aand1.5μA ppm-1, respectively. The response time of the sensors was0.1s. A negligibleeffect on the sensor response was observed when O_2concentration varying from0to20vol.%.
Amperometric hydrogen sensors using nano-structured sensing electrodes and aproton conductor CaZr_(0.9)In_(0.1)O_(3-δ)as electrolyte were fabricated. A bilayer CaZr_(0.9)In_(0.1)O_(3-δ)electrolyte including both a dense layer and a porous layer was prepared by conventionalsolid state reaction method. During the preparation of electrolyte, sintering aid (ZnO) wasintroduced into CaZr_(0.9)In_(0.1)O_(3-δ)for promoting its sintering. CaZr_(0.9)In_(0.1)O_(3-δ)with highdensified structure, good conductivity and excellent chemical stability was prepared aftersintered at1350℃for5h. The nano-structured ZnO and SnO_2particles were in-situprepared in the porous CaZr_(0.9)In_(0.1)O_(3-δ)backbone by impregnating method. The sensorshowed good sensitivities, response–recovery characteristics, reproducibility and stability.
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