CN104897761A - YSZ-based mixed potential NO2 sensor based on graded In2O3 sensitive electrodes and its preparation method - Google Patents

YSZ-based mixed potential NO2 sensor based on graded In2O3 sensitive electrodes and its preparation method Download PDF

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CN104897761A
CN104897761A CN201510320454.1A CN201510320454A CN104897761A CN 104897761 A CN104897761 A CN 104897761A CN 201510320454 A CN201510320454 A CN 201510320454A CN 104897761 A CN104897761 A CN 104897761A
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卢革宇
刘方猛
梁喜双
孙鹏
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Jilin University
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Abstract

本发明属于气体传感器技术领域,具体涉及一种基于分等级In2O3敏感电极的YSZ基混成电位型NO2传感器及其制备方法,该传感器主要可用于汽车尾气的检测。传感器依次由带有Pt加热电极的Al2O3陶瓷板、YSZ基板、参考电极和敏感电极组成;参考电极为条状Pt,敏感电极为条状In2O3,两电极彼此分立且对称地制备在YSZ基板上表面的两端,YSZ基板的下表面与带有Pt加热电极的Al2O3陶瓷板粘结在一起。本发明以YSZ基板作为离子导电层,利用具有高电化学催化活性的In2O3为敏感电极,通过不同煅烧温度(800℃~1200℃)来改变敏感电极材料的微观形貌,达到提高敏感特性的目的。

The invention belongs to the technical field of gas sensors, and in particular relates to a YSZ-based mixed potential NO 2 sensor based on graded In 2 O 3 sensitive electrodes and a preparation method thereof. The sensor can be mainly used for detecting automobile exhaust. The sensor consists of an Al 2 O 3 ceramic plate with a Pt heating electrode, a YSZ substrate, a reference electrode and a sensitive electrode in sequence; the reference electrode is a strip-shaped Pt, and the sensitive electrode is a strip-shaped In 2 O 3 , and the two electrodes are separated from each other and symmetrically Both ends of the upper surface of the YSZ substrate were prepared, and the lower surface of the YSZ substrate was bonded with an Al2O3 ceramic plate with a Pt heating electrode. In the present invention, the YSZ substrate is used as the ion-conducting layer, In 2 O 3 with high electrochemical catalytic activity is used as the sensitive electrode, and the microscopic morphology of the sensitive electrode material is changed through different calcination temperatures (800°C-1200°C), so as to improve the sensitivity purpose of the feature.

Description

基于分等级In2O3敏感电极的YSZ基混成电位型NO2传感器及制备方法YSZ-based mixed potential NO2 sensor based on graded In2O3 sensitive electrodes and its preparation method

技术领域technical field

本发明属于气体传感器技术领域,具体涉及一种基于分等级In2O3敏感电极的YSZ基混成电位型NO2传感器及其制备方法,该传感器主要可用于汽车尾气的检测。The invention belongs to the technical field of gas sensors, and in particular relates to a YSZ-based mixed potential NO 2 sensor based on graded In 2 O 3 sensitive electrodes and a preparation method thereof. The sensor can be mainly used for detecting automobile exhaust.

背景技术Background technique

NO2作为一群高活性反应气体(NOx)的一种,主要来源于燃烧排放过程,尤其是公路机动车辆尾气排放。大量排放出来的NO2不但会引起诸如酸雨、温室效应、臭氧层破坏等严重的大气污染问题,而且对人类的呼吸系统造成重度损伤。为了从源头上有效解决相关的污染问题,保护人类的身体健康,开发廉价、微型、敏感、可靠的气体传感器用于监测和控制NOx是迫切的需要。由于汽车发动机尾气排放处于典型的长期高温、高湿和多种气体共存环境,要求在这种环境下正常工作的传感器必须具有良好敏感特性。在过去的十几年里,基于固体电解质(YSZ)和氧化物敏感电极的混成电位型气体传感器满足以上要求,对于在汽车尾气检测方面的应用来说,已经被证明是一种非常可靠的设备,而成为备受瞩目的一类新型气体传感器。NO 2 , as one of a group of highly active reactive gases (NO x ), mainly comes from the combustion emission process, especially the exhaust emission of road motor vehicles. A large amount of NO 2 emitted will not only cause serious air pollution problems such as acid rain, greenhouse effect, and ozone layer destruction, but also cause serious damage to human respiratory system. In order to effectively solve the related pollution problems from the source and protect human health, it is urgent to develop cheap, miniature, sensitive and reliable gas sensors for monitoring and controlling NOx . Since the exhaust emissions of automobile engines are in a typical environment of long-term high temperature, high humidity and the coexistence of various gases, the sensors required to work normally in this environment must have good sensitivity characteristics. Over the past ten years, hybrid potentiometric gas sensors based on solid electrolyte (YSZ) and oxide sensitive electrodes have met the above requirements and have proven to be very reliable devices for applications in automotive exhaust detection. , and become a new type of gas sensor that has attracted much attention.

稳定氧化锆基混成电位型NO2传感器的敏感机理是:气氛中NO2通过敏感电极层向三相反应界面扩散,在扩散过程中由于发生反应(1),NO2的浓度会逐渐降低,氧化物敏感电极的多孔性会决定NO2浓度的降低程度。在气体/敏感电极/YSZ的三相界面处,同时发生NO2的电化学还原反应和氧的电化学氧化反应,反应(2)和(3)构成一个局部电池,当两者反应速率相等时,反应达到平衡,在敏感电极上形成混成电位,它与参考电极的电位差作为传感器的检测信号。检测信号大小由电化学反应(2)和(3)的速率来决定,而反应速率取决于敏感电极材料的电化学和化学催化活性、电极材料微观结构(比如材料的多孔性、粒度、形貌等)。The sensitive mechanism of the stable zirconia - based mixed potential NO2 sensor is: NO2 in the atmosphere diffuses to the three - phase reaction interface through the sensitive electrode layer. During the diffusion process, the concentration of NO2 will gradually decrease due to the reaction ( 1 ), and the oxidation The porosity of the material sensitive electrode will determine the reduction degree of NO2 concentration. At the three-phase interface of gas/sensing electrode/YSZ, the electrochemical reduction reaction of NO and the electrochemical oxidation reaction of oxygen occur simultaneously, and the reactions ( 2 ) and (3) constitute a local battery, when both reaction rates are equal , the reaction reaches equilibrium, and a mixed potential is formed on the sensitive electrode, and the potential difference between it and the reference electrode is used as the detection signal of the sensor. The magnitude of the detection signal is determined by the rate of electrochemical reactions (2) and (3), and the reaction rate depends on the electrochemical and chemical catalytic activity of the sensitive electrode material, the microstructure of the electrode material (such as the porosity, particle size, and morphology of the material). wait).

反应式如下:The reaction formula is as follows:

NO2→NO+1/2O2   (1)NO 2 →NO+1/2O 2 (1)

NO2+2e-→NO+O2-   (2)NO 2 +2e- NO+O 2- (2)

O2-→1/2O2+2e-   (3)O 2- → 1/2O 2 +2e - (3)

目前,为了制备更高敏感特性的传感器,国内外大多数研究者致力于敏感电极材料的研究。例如,本课题组制作的以Cr2O3-WO3为敏感电极材料的YSZ基混成电位型NO2传感器对100ppm NO2的混成电位值为52mV(Quan Diao,Chengguo Yin,Yingwei Liu,Jianguo Li,Xun Gong,Xishuang Liang,Shiqi Yang,Hong Chen,Geyu Lu,Mixed-potential-type NO2sensor using stabilizedzirconia and Cr2O3-WO3nanocomposites,Sensor and Actuators B 180(2013)90-95)。此类NO2传感器的缺点在于响应值低、灵敏度不够高,达不到实用的要求。另外,由于电极材料的形貌会影响NO2在电极层的扩散过程,从而影响气体在三相界面处的电化学反应,因此开发具有特殊形貌的多孔性敏感电极材料进一步提高传感器的敏感特性(灵敏度、响应值、选择性、稳定性等)具有重要的意义。At present, in order to prepare sensors with higher sensitivity characteristics, most researchers at home and abroad are devoted to the research of sensitive electrode materials. For example, the YSZ-based mixed potential NO 2 sensor made by our research group with Cr 2 O 3 -WO 3 as the sensitive electrode material has a mixed potential value of 52mV for 100ppm NO 2 (Quan Diao, Chengguo Yin, Yingwei Liu, Jianguo Li , Xun Gong, Xishuang Liang, Shiqi Yang, Hong Chen, Geyu Lu, Mixed-potential-type NO 2 sensor using stabilized zirconia and Cr 2 O 3 -WO 3 nanocomposites, Sensor and Actuators B 180(2013) 90-95). The shortcoming of this kind of NO 2 sensor is that the response value is low, the sensitivity is not high enough, and it cannot meet the practical requirements. In addition, since the morphology of the electrode material will affect the diffusion process of NO2 in the electrode layer, thereby affecting the electrochemical reaction of the gas at the three - phase interface, the development of a porous sensitive electrode material with a special morphology will further improve the sensitivity of the sensor. (Sensitivity, response value, selectivity, stability, etc.) are of great significance.

发明内容Contents of the invention

本发明的目的是提供一种基于分等级In2O3敏感电极的YSZ基混成电位型NO2传感器及制备方法,以提高NO2传感器敏感性能,促进这种传感器在汽车尾气检测领域的实用化。本发明所得到的传感器除了具有高灵敏度外,还具有很好的选择性、重复性、稳定性。The purpose of the present invention is to provide a YSZ - based mixed potential NO sensor based on graded In 2 O 3 sensitive electrodes and its preparation method, so as to improve the sensitive performance of the NO sensor and promote the practical application of this sensor in the field of automobile exhaust detection . In addition to high sensitivity, the sensor obtained by the invention also has good selectivity, repeatability and stability.

本发明所涉及的NO2传感器是基于固体电解质YSZ和高电化学催化性能分等级In2O3为敏感电极所构筑的新型NO2传感器,YSZ(Y2O3的物质的量掺杂比例为8%的ZrO2)作为离子导电层。 The NO2 sensor involved in the present invention is based on solid electrolyte YSZ and high electrochemical catalytic performance graded In2O3 is a novel NO2 sensor built as a sensitive electrode, and the doping ratio of the substance amount of YSZ ( Y2O3 is 8% ZrO 2 ) as the ion-conducting layer.

本发明所述的一种基于分等级In2O3敏感电极的YSZ基混成电位型NO2传感器,如图1所示,其特征在于:依次由带有Pt加热电极的Al2O3陶瓷板、YSZ基板、参考电极和敏感电极组成;参考电极为条状Pt,敏感电极为条状In2O3,两电极彼此分立且对称地制备在YSZ基板上表面的两端,YSZ基板的下表面与带有细条状Pt加热电极的Al2O3陶瓷板粘结在一起;敏感电极材料是将1~2mmol的In(NO3)3·4.5H2O溶于30~60mL去离子水中,搅拌使其溶解;然后将4~6mmol蔗糖和2.5~5mmol尿素加入到In(NO3)3溶液中,搅拌使其溶解;将得到的混合溶液转移到聚四氟乙烯反应釜中,密闭后于160~180℃下反应12~18h,反应结束后自然冷却到室温;反应釜中产物经离心、洗涤、干燥后得到预聚物沉淀,再在800~1200℃下烧结2~4小时制备得到。其中,如图3a所示,分等级In2O3是由带孔的纳米片构建而成的具有一定星状结构,而纳米片是由纳米颗粒组成。A YSZ - based mixed potentiometric NO sensor based on graded In 2 O 3 sensitive electrodes according to the present invention, as shown in Figure 1, is characterized in that it consists of Al 2 O 3 ceramic plates with Pt heating electrodes in sequence , YSZ substrate, reference electrode and sensitive electrode; the reference electrode is strip-shaped Pt, the sensitive electrode is strip-shaped In 2 O 3 , the two electrodes are separated from each other and symmetrically prepared at both ends of the upper surface of the YSZ substrate, and the lower surface of the YSZ substrate It is bonded with Al 2 O 3 ceramic plates with thin strip-shaped Pt heating electrodes; the sensitive electrode material is to dissolve 1~2mmol In(NO 3 ) 3 ·4.5H 2 O in 30~60mL deionized water, stir Make it dissolve; then add 4-6mmol sucrose and 2.5-5mmol urea into the In(NO 3 ) 3 solution, stir to dissolve it; React at ~180°C for 12-18 hours, and cool naturally to room temperature after the reaction; the product in the reactor is centrifuged, washed, and dried to obtain a prepolymer precipitate, and then sintered at 800-1200°C for 2-4 hours. Among them, as shown in Figure 3a, the graded In 2 O 3 is constructed from nanosheets with holes and has a certain star-like structure, and the nanosheets are composed of nanoparticles.

本发明以YSZ基板作为离子导电层,利用具有高电化学催化活性的In2O3为敏感电极,通过不同煅烧温度(800℃~1200℃)来改变敏感电极材料的微观形貌,达到提高敏感特性的目的。In the present invention, the YSZ substrate is used as the ion-conducting layer, In 2 O 3 with high electrochemical catalytic activity is used as the sensitive electrode, and the microscopic morphology of the sensitive electrode material is changed through different calcination temperatures (800°C-1200°C), so as to improve the sensitivity purpose of the feature.

本发明所述的一种基于分等级In2O3敏感电极的YSZ基混成电位型NO2传感器的制备方法,其步骤如下:A kind of YSZ based mixed potential type NO sensor based on graded In 2 O 3 sensitive electrodes according to the present invention, its steps are as follows:

(1)制作Pt参考电极:在YSZ基板上表面的一端使用Pt浆制作15~20μm厚的Pt参考电极,同时将一根Pt丝对折后用Pt浆粘在参考电极中间位置上作为电极引线,然后将YSZ基板在90~120℃条件下烘烤1~2小时,再将YSZ基板在1000~1200℃下烧结1~2小时,排除Pt浆中的松油醇,最后降至室温;(1) Making a Pt reference electrode: Use Pt paste on one end of the upper surface of the YSZ substrate to make a 15-20 μm thick Pt reference electrode, and at the same time fold a Pt wire in half and stick it to the middle of the reference electrode with Pt paste as the electrode lead Then bake the YSZ substrate at 90-120°C for 1-2 hours, then sinter the YSZ substrate at 1000-1200°C for 1-2 hours, remove the terpineol in the Pt slurry, and finally cool down to room temperature;

(2)制作敏感电极:将前述所得到的敏感电极材料用去离子水调成浆料,质量浓度为2~20%;用敏感电极材料的浆料在与参考电极对称的YSZ基板上表面的另一端制备20~30μm厚的敏感电极,同样将一根Pt丝对折后用Pt浆粘在敏感电极上作为电极引线;(2) Make sensitive electrodes: adjust the sensitive electrode materials obtained above into slurry with deionized water, and the mass concentration is 2 to 20%; use the slurry of sensitive electrode materials on the YSZ substrate upper surface symmetrical to the reference electrode Prepare a sensitive electrode with a thickness of 20-30 μm at the other end, and also fold a Pt wire in half and stick it on the sensitive electrode with Pt paste as the electrode lead;

(3)将上述制备有参考电极和敏感电极的YSZ基板在800~1000℃下烧结1~3小时;优选的高温烧结时的升温速率为1~2℃/min;(3) Sintering the above-mentioned YSZ substrate prepared with the reference electrode and the sensitive electrode at 800-1000°C for 1-3 hours; the preferred heating rate during high-temperature sintering is 1-2°C/min;

(4)制备无机粘合剂:量取水玻璃(Na2SiO3·9H2O)2~4mL,并称取Al2O3粉体0.7~1.0g,将得到的水玻璃与Al2O3粉体混合并搅拌均匀,制得无机粘合剂;(4) Preparation of inorganic binder: Measure 2-4 mL of water glass (Na 2 SiO 3 ·9H 2 O), weigh 0.7-1.0 g of Al 2 O 3 powder, and mix the obtained water glass with Al 2 O 3 The powders are mixed and stirred evenly to obtain an inorganic binder;

(5)使用无机粘合剂将YSZ基板的下表面和带有Pt加热电极的Al2O3陶瓷板粘结在一起;( 5 ) The lower surface of the YSZ substrate and the Al2O3 ceramic plate with Pt heating electrodes were bonded together using an inorganic adhesive;

其中,带有Pt加热电极的Al2O3陶瓷板是在Al2O3陶瓷板上通过丝网印刷Pt得到,带有Pt加热电极的Al2O3陶瓷板一同作为器件的加热板使用;Among them, the Al 2 O 3 ceramic plate with Pt heating electrode is obtained by screen printing Pt on the Al 2 O 3 ceramic plate, and the Al 2 O 3 ceramic plate with Pt heating electrode is used together as the heating plate of the device;

(6)将粘合好的器件进行焊接、封装,从而制作得到本发明所述的以In2O3为敏感电极的YSZ基混成电位型传感器。(6) Welding and packaging the bonded devices, so as to produce the YSZ-based hybrid potential sensor with In 2 O 3 as the sensitive electrode of the present invention.

本发明的优点:Advantages of the present invention:

(1)传感器利用典型的固体电解质——稳定氧化锆(YSZ),具有良好的热稳定性和化学稳定性,可在高温下(汽车尾气中)检测NO2(1) The sensor uses a typical solid electrolyte—stabilized zirconia (YSZ), which has good thermal and chemical stability and can detect NO 2 at high temperatures (in automobile exhaust).

(2)采用水热法制备分等级In2O3作为传感器敏感电极材料,制备方法简单,利于批量化的工业化生产。(2) The hydrothermal method is used to prepare graded In 2 O 3 as the sensitive electrode material of the sensor, the preparation method is simple, and it is beneficial to batch industrial production.

(3)通过改变不同的煅烧温度(800℃~1200℃)优化敏感电极材料的微观结构,利于待测气体快速到达三相界面参与电化学反应,减少在扩散过程中的消耗,从而使传感器有很高的灵敏度。(3) Optimizing the microstructure of the sensitive electrode material by changing different calcination temperatures (800°C to 1200°C) facilitates the gas to be measured to quickly reach the three-phase interface to participate in the electrochemical reaction and reduce the consumption in the diffusion process, so that the sensor is effective Very high sensitivity.

附图说明Description of drawings

图1:本发明所述的YSZ基混成电位型NO2传感器的结构示意图。Figure 1: Schematic diagram of the structure of the YSZ - based hybrid potentiometric NO sensor of the present invention.

各部分名称:In2O3敏感电极1、YSZ基板2、Pt参考电极3、Pt丝4、Pt点5、Al2O3陶瓷板6、Pt加热电极7、无机粘合剂8。Names of each part: In 2 O 3 sensitive electrode 1, YSZ substrate 2, Pt reference electrode 3, Pt wire 4, Pt point 5, Al 2 O 3 ceramic plate 6, Pt heating electrode 7, inorganic binder 8.

图2:本发明所制备的In2O3敏感电极材料的XRD图。Figure 2: XRD pattern of the In 2 O 3 sensitive electrode material prepared in the present invention.

如图2所示,为In2O3敏感电极材料的XRD图,通过与标准谱图对比,本发明制备的In2O3与标准卡片JCPDS#65-3170一致,为立方晶系In2O3。表明本发明制备的敏感电极材料为In2O3材料。As shown in Figure 2, it is the XRD pattern of the In 2 O 3 sensitive electrode material. By comparing with the standard spectrum, the In 2 O 3 prepared by the present invention is consistent with the standard card JCPDS#65-3170, and is cubic In 2 O 3 . It shows that the sensitive electrode material prepared by the present invention is In 2 O 3 material.

图3:本发明所制备的不同煅烧温度下的敏感电极材料的SEM图。Figure 3: SEM images of sensitive electrode materials prepared by the present invention at different calcination temperatures.

如图3所示,a:800℃,b:1000℃,c:1200℃煅烧的In2O3敏感电极材料的SEM图,插图为局部区域的放大图。从图中可以看出,随着煅烧温度的升高,材料所具有的特殊形貌逐渐消失,颗粒大小和孔道大小逐渐增大,由此可以看出,改变敏感材料的烧结温度能够改变敏感电极的微观形貌,电极的多孔性利于气体的扩散。As shown in Figure 3 , a: 800 °C, b: 1000 °C, c: 1200 °C SEM images of In2O3 sensitive electrode materials calcined, the inset is the enlarged image of the local area. It can be seen from the figure that as the calcination temperature increases, the special morphology of the material gradually disappears, and the particle size and pore size gradually increase. It can be seen that changing the sintering temperature of the sensitive material can change the sensitivity of the sensitive electrode. The microscopic morphology of the electrode is conducive to the diffusion of gas.

图4:传感器S800、S1000和S1200对不同浓度NO2的响应浓度对数曲线。Figure 4 : Concentration logarithmic curves of sensors S800, S1000 and S1200 in response to different concentrations of NO2.

如图4所示,为实施例1、实施例2和实施例3所制作的器件的电动势差ΔV随NO2浓度的变化,从图中可以看出,三种器件的ΔV和NO2浓度的对数都成很好的线性关系,将其斜率定义为传感器的灵敏度,实施例1、2和实施例3的灵敏度分别为61、68和33mV/decade。由此可见,以1000℃下烧结的In2O3作为敏感电极材料的YSZ基混成电位型NO2传感器S1000具有最高的灵敏度。As shown in Figure 4, the electromotive force difference ΔV of the devices made in Example 1, Example 2 and Example 3 varies with the concentration of NO 2 . The logarithm has a good linear relationship, and its slope is defined as the sensitivity of the sensor. The sensitivities of Examples 1, 2, and 3 are 61, 68, and 33 mV/decade, respectively. It can be seen that the YSZ-based hybrid potentiometric NO 2 sensor S1000, which uses In 2 O 3 sintered at 1000°C as the sensitive electrode material, has the highest sensitivity.

图5:以1000℃下烧结的In2O3作为敏感电极材料的传感器S1000的选择性。Figure 5 : Selectivity of the sensor S1000 with In2O3 sintered at 1000°C as the sensitive electrode material.

如图5所示,为传感器S1000的选择性,从图中可以看出,器件对NO2与其他气体的的共存气体灵敏度改变较小,由此可见,器件对NO2具有很好的选择性。As shown in Figure 5, it is the selectivity of the sensor S1000. It can be seen from the figure that the sensitivity of the device to the coexistence of NO 2 and other gases has a small change. It can be seen that the device has a good selectivity to NO 2 .

图6:传感器S1000对NO2的长期稳定性。Figure 6: Long - term stability of sensor S1000 against NO2.

如图6所示,为传感器S1000在30天的测试期间对100ppm和200ppmNO2的稳定性,从图中可以看出,器件对NO2表现出了良好的长期稳定性。As shown in Figure 6 , the stability of the sensor S1000 to 100ppm and 200ppm NO2 during the 30-day test period, it can be seen from the figure that the device exhibits good long - term stability to NO2.

具体实施方式Detailed ways

实施例1:Example 1:

用水热法制备In2O3材料,将In2O3作为敏感电极材料制作YSZ基混成电位型NO2传感器,并测试传感器气敏性能,具体过程如下:In 2 O 3 material was prepared by hydrothermal method, and In 2 O 3 was used as a sensitive electrode material to make a YSZ-based hybrid potentiometric NO 2 sensor, and the gas-sensing performance of the sensor was tested. The specific process is as follows:

1.制作Pt参考电极:在长宽2×2mm、厚度0.2mm的YSZ基板上表面的一端使用Pt浆制作一层0.5mm×2mm大小、15μm厚的Pt参考电极,同时用一根Pt丝对折后用Pt浆粘在参考电极中间位置上引出电极引线;然后将YSZ基板在100℃条件下烘烤1.5小时,再将YSZ基板在1000℃下烧结1.5小时,从而排除铂浆中的松油醇,最后降至室温。1. Make a Pt reference electrode: use Pt slurry to make a Pt reference electrode with a size of 0.5mm×2mm and a thickness of 15μm on one end of the upper surface of the YSZ substrate with a length and width of 2×2mm and a thickness of 0.2mm, and fold it in half with a Pt wire Finally, stick the Pt paste on the middle position of the reference electrode to lead out the electrode lead; then bake the YSZ substrate at 100°C for 1.5 hours, and then sinter the YSZ substrate at 1000°C for 1.5 hours to eliminate the terpineol in the platinum paste , and finally down to room temperature.

2.制作In2O3敏感电极:首先用水热法制备In2O3材料。将1mmol的In(NO3)3·4.5H2O溶于30mL去离子水中,搅拌使其溶解;然后将4mmol蔗糖和2.5mmol尿素加入到In(NO3)3溶液中,搅拌使其溶解;将得到的混合溶液转移到聚四氟乙烯反应釜中,密封紧密置于160℃烘箱中反应12h,反应结束后自然冷却到室温。经过离心、洗涤干燥得到预聚物沉淀。最后将得到的沉淀在800℃下烧结2小时,升温速率2℃/min,从而得到In2O3敏感电极材料。2. Fabrication of In 2 O 3 sensitive electrodes: firstly prepare In 2 O 3 material by hydrothermal method. Dissolve 1 mmol of In(NO 3 ) 3 ·4.5H 2 O in 30 mL of deionized water, stir to dissolve; then add 4 mmol of sucrose and 2.5 mmol of urea to the In(NO 3 ) 3 solution, stir to dissolve; The obtained mixed solution was transferred to a polytetrafluoroethylene reactor, sealed tightly and placed in an oven at 160° C. for 12 hours. After the reaction, it was naturally cooled to room temperature. After centrifugation, washing and drying, the prepolymer precipitate was obtained. Finally, the obtained precipitate was sintered at 800° C. for 2 hours with a heating rate of 2° C./min to obtain In 2 O 3 sensitive electrode materials.

取5mg In2O3粉末用去离子水100mg调成浆料,将In2O3浆料在与参考电极对称的YSZ基板上表面的另一端涂覆一层0.5mm×2mm大小、20μm厚的敏感电极,同样用一根铂丝对折后用Pt浆粘在敏感电极上引出电极引线。Take 5mg of In 2 O 3 powder and make a slurry with 100 mg of deionized water, and coat the In 2 O 3 slurry with a layer of 0.5mm×2mm and 20μm thick on the other end of the upper surface of the YSZ substrate symmetrical to the reference electrode. The sensitive electrode is also folded in half with a platinum wire and glued to the sensitive electrode with Pt paste to lead out the electrode lead.

将制作好的带有参考电极和敏感电极的YSZ基板以2℃/min的升温速率升温至800℃并保持2h后降至室温。The prepared YSZ substrate with the reference electrode and the sensitive electrode was heated to 800°C at a heating rate of 2°C/min and kept for 2h before cooling down to room temperature.

3.粘结具有加热电极的陶瓷板。使用无机粘合剂(Al2O3和水玻璃Na2SiO3·9H2O,质量约比5:1配制)将YSZ基板的下表面(未涂覆电极的一侧)与同样尺寸的带有Pt加热电极的Al2O3陶瓷板(长宽2×2mm、厚度0.2mm)进行粘结;3. Bonding ceramic plates with heating electrodes. Use an inorganic binder (Al 2 O 3 and water glass Na 2 SiO 3 9H 2 O, prepared in a mass ratio of about 5:1) to bond the lower surface of the YSZ substrate (the side that is not coated with electrodes) with a tape of the same size Al 2 O 3 ceramic plates (length and width 2×2mm, thickness 0.2mm) with Pt heating electrodes are bonded;

4.器件焊接、封装。将器件焊接在六角管座上,套上防护罩,制作完成混成电位型NO2传感器,标记为传感器S800。4. Device welding and packaging. Weld the device on the hexagonal socket, put on the protective cover, and complete the hybrid potential NO 2 sensor, which is marked as sensor S800.

实施例2:Example 2:

以1200℃烧结的In2O3材料作为敏感电极材料,制作NO2传感器,其制作过程为:The In 2 O 3 material sintered at 1200°C is used as the sensitive electrode material to make the NO 2 sensor. The manufacturing process is as follows:

将前述方法所制备的In2O3在马弗炉里1200℃烧结得到敏感电极材料In2O3(1200℃),器件制作过程与实施例1相同,标记为传感器S1200。The In 2 O 3 prepared by the aforementioned method was sintered in a muffle furnace at 1200° C. to obtain the sensitive electrode material In 2 O 3 (1200° C.). The device manufacturing process is the same as that of Example 1, marked as sensor S1200.

实施例3:Example 3:

以1000℃烧结的In2O3材料作为敏感电极材料,制作NO2传感器,其制作过程为:The In 2 O 3 material sintered at 1000°C is used as the sensitive electrode material to make the NO 2 sensor. The manufacturing process is as follows:

将前述方法所制备的In2O3在马弗炉里1000℃烧结得到敏感电极材料In2O3(1000℃),器件制作过程与实施例1相同,标记为传感器S1000。The In 2 O 3 prepared by the aforementioned method was sintered in a muffle furnace at 1000°C to obtain the sensitive electrode material In 2 O 3 (1000°C). The fabrication process of the device was the same as in Example 1, marked as sensor S1000.

将传感器连接在Rigol信号测试仪上,分别将传感器置于空气、5ppm NO2、10ppm NO2、20ppm NO2、50ppm NO2、100ppm NO2、200ppm NO2、300ppmNO2的气氛中进行电压信号测试。Connect the sensor to the Rigol signal tester, place the sensor in the atmosphere of air, 5ppm NO 2 , 10ppm NO 2 , 20ppm NO 2 , 50ppm NO 2 , 100ppm NO 2 , 200ppm NO 2 , 300ppm NO 2 for voltage signal test .

表1中列出了分别以In2O3(800℃)、In2O3(1000℃)和In2O3(1200℃)为敏感电极材料制作的YSZ基混成电位型传感器在不同浓度NO2气氛中的电动势和在空气重的电动势的差值随NO2浓度的变化值。从表中可以看到,三种器件均对NO2具有良好的响应特性,其中器件S1000的灵敏度(斜率)最高,为68mV/decade,大于器件S800的61mV/decade和器件S1200的33mV/decade。且器件S1000对各个浓度NO2的响应值都最大,表现出最高的灵敏度。由此可见,具有特殊形貌的分等级In2O3敏感电极材料构筑的器件对NO2具有良好的敏感特性,通过改变敏感电极材料的烧结温度改变敏感材料的电化学催化活性和多孔性,从而提高传感器的电极反应效率得到了具有高灵敏度的YSZ基混成电位型NO2传感器。Table 1 lists the YSZ-based hybrid potentiometric sensors made of In 2 O 3 (800°C) , In 2 O 3 (1000°C) and In 2 O 3 (1200°C) as sensitive electrode materials respectively at different concentrations of NO 2 The difference between the electromotive force in the atmosphere and the electromotive force in the air varies with the NO 2 concentration. It can be seen from the table that all three devices have good response characteristics to NO2, and the sensitivity (slope) of device S1000 is the highest, which is 68mV/decade, which is greater than 61mV/decade of device S800 and 33mV/decade of device S1200. And the device S1000 has the largest response value to each concentration of NO 2 , showing the highest sensitivity. It can be seen that the device constructed by the graded In 2 O 3 sensitive electrode material with special morphology has good sensitivity to NO 2 , and the electrochemical catalytic activity and porosity of the sensitive material can be changed by changing the sintering temperature of the sensitive electrode material. Thus improving the electrode reaction efficiency of the sensor, a YSZ-based hybrid potentiometric NO 2 sensor with high sensitivity was obtained.

表1分别以In2O3(800℃)、In2O3(1000℃)和In2O3(1200℃)为敏感电极材料的传感器S800、S1000和S1200的ΔV随NO2浓度的变化Table 1 Variation of ΔV with NO 2 concentration for sensors S800, S1000 and S1200 using In 2 O 3 (800°C), In 2 O 3 (1000°C) and In 2 O 3 (1200°C) as sensitive electrode materials respectively

Claims (4)

1. one kind based on graduation In 2o 3the YSZ base of sensitive electrode blendes together electric potential type NO 2sensor, is characterized in that: successively by the Al with Pt heating electrode 2o 3ceramic wafer, YSZ substrate, reference electrode and sensitive electrode form; Reference electrode is strip Pt, and sensitive electrode is strip In 2o 3, two electrodes are separate and be prepared in the two ends of YSZ upper surface of base plate symmetrically, lower surface and the Al with fine strip shape Pt heating electrode of YSZ substrate 2o 3ceramic wafer is bonded together; Sensitive electrode material is by the In (NO of 1 ~ 2mmol 3) 34.5H 2o is dissolved in 30 ~ 60mL deionized water, stirs and makes it dissolve; Then 4 ~ 6mmol sucrose and 2.5 ~ 5mmol urea are joined In (NO 3) 3in solution, stir and make it dissolve; The mixed solution obtained is transferred in teflon reactor, after airtight, at 160 ~ 180 DEG C, react 12 ~ 18h, after reaction terminates, naturally cool to room temperature; In reactor product through centrifugal, washing, obtain prepolymer precipitation after drying, then sinter at 800 ~ 1200 DEG C and prepare for 2 ~ 4 hours.
2. one according to claim 1 is based on graduation In 2o 3the YSZ base of sensitive electrode blendes together electric potential type NO 2the preparation method of sensor, its step is as follows:
(1) Pt reference electrode is made: use Pt to starch the thick Pt reference electrode of making 15 ~ 20 μm in one end of YSZ upper surface of base plate, be bonded at after the doubling of a Pt silk on reference electrode centre position as contact conductor with Pt slurry simultaneously, then YSZ substrate is toasted 1 ~ 2 hour under 90 ~ 120 DEG C of conditions, again YSZ substrate is sintered 1 ~ 2 hour at 1000 ~ 1200 DEG C, get rid of the terpinol in Pt slurry, be finally down to room temperature;
(2) sensitive electrode is made: by aforementioned obtained sensitive electrode material deionized water furnishing slurry, mass concentration is 2 ~ 20%; Prepare 20 ~ 30 μm of thick sensitive electrodes with the slurry of sensitive electrode material at the other end of the YSZ upper surface of base plate with reference electrode symmetry, be also bonded at after the doubling of a Pt silk on sensitive electrode as contact conductor with Pt slurry equally;
(3) the YSZ substrate of reference electrode and sensitive electrode above-mentioned preparation is had to sinter 1 ~ 3 hour at 800 ~ 1000 DEG C;
(4) use inorganic bond by the lower surface of YSZ substrate and the Al with Pt heating electrode 2o 3ceramic wafer is bonded together;
(5) device bonded is carried out welding, encapsulating, thus prepare based on graduation In 2o 3the YSZ base of sensitive electrode blendes together electric potential type NO 2sensor.
3. as claimed in claim 2 a kind of based on graduation In 2o 3the YSZ base of sensitive electrode blendes together electric potential type NO 2the preparation method of sensor, is characterized in that: measure water glass Na 2siO 39H 2o 2 ~ 4mL, and take Al 2o 3powder 0.7 ~ 1.0g, by the water glass that obtains and Al 2o 3powder mixes and stirs, and namely prepares inorganic bond.
4. as claimed in claim 2 a kind of based on graduation In 2o 3the YSZ base of sensitive electrode blendes together electric potential type NO 2the preparation method of sensor, is characterized in that: with the Al of Pt heating electrode 2o 3ceramic wafer is at Al 2o 3ceramic wafer is obtained by serigraphy Pt.
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