CN1053738C - 氧浓度探测器 - Google Patents
氧浓度探测器 Download PDFInfo
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Abstract
本发明提供了一种带有电极的氧浓度探测器,它具有良好的耐热性和耐用性并保持在较高的灵敏度。排气侧的电极形成在固体电解质的一个侧面上,进气侧的电极形成在固体电解质的另一侧面上。排气侧电极包括骨架电极和反应电极。骨架电极具有5至20μm的薄膜厚度和小于10%的孔隙率,它是厚的耐热薄膜,主要用于形成骨架部分。反应电极则具有0.5至2μm的薄膜厚度和10%至50%的孔隙率,它是薄的高灵敏度薄膜,主要用于形成反应部分。
Description
本发明涉及到一种氧浓度探测器。具体地说,本发明涉及到适于探测诸如内燃机废气中氧浓度的氧浓度探测器。
为了制做用于探测从诸如汽车内燃机中排出的废气中氧浓度的氧浓度探测器,已知过去有用非电解镀敷、真空镀膜、网板印刷等手段形成电极的方法。
在上述方法中,带有用非电解镀敷、真空镀膜等手段所形成的电极的氧浓度探测器具有下列优点:由于电极的厚度较薄,所以探测器能很快适应所要探测气体中氧浓度的变化并能探测出该氧浓度。
另一方面,在带有用网板印刷等手段所形成的电极的氧浓度探测器中,网板印刷会对使用铂涂料或类似物质的未烧结的板片产生影响,并且要同时烧结多个未经烧结的板片。因此,电极的厚度会相对变大。换句话说,用网板印刷形成的电极的厚度要比用非电解镀敷、真空镀膜等手段形成的电极的厚度大5至20倍,所以,带有用网板印刷所形成的电极的氧浓度探测器具有较高的耐热性。
但是,在带有用网板印刷所形成的电极的氧浓度探测器中,由于电极具有较大的厚度,所以从电极表面至三相分界点(三态点)的气体扩散距离会变大。因此,会产生这样的问题,即电极上所要探测的气体扩散性降低且探测器的响应速度下降,这在低温状态下尤为显著。
为了解决上述问题,已知在该技术中存在有一种方法,在这种方法中,将陶瓷粉末混和进铂涂料中以防止铂颗粒在烧结过程中烧结成块,从而获得较高的电极孔隙率。但是,依照这种方法,电极高厚度的效应仍然很大,而提高灵敏度的效果却不大。
实施本发明是为了解决上述先有技术中的问题,本发明的目的是提供一种氧浓度探测器,这种探测器不仅有良好的耐热性及耐用性,而且保持有较高的灵敏度。
为实现上述目的,依照本发明之第一实施例的结构,用两种电极即第一电极与第二电极来构成探测电极。在本发明的第一实施例中,在把第一电极具体形成为骨架部分且把第二电极具体形成为反应部分时,第一电极的厚度应小于第二电极的厚度,且前者的孔隙率要低于后者的孔隙率。
因此,由于第一电极具有大于第二极的厚度,所以,第一电极具有高于第二电极的耐热性。但是,由于第二电极除具有大于第一电极的孔隙率以外还具有相对较小的薄膜厚度,所以第二电极具有高于第一电极的灵敏度。
依照本发明之第二实施例的结构,第二电极具有小于第一电极的薄膜厚度,但具有高于第一电极的灵敏度。尽管第二电极具有低于第一电极的耐热性,但由于第二电极的厚度小于第一电极的厚度,所以能获得较高的灵敏度。
在本发明之第一和第二实施例的结构中,第一电极与第二电极的配合可以同时实现高耐热性和高灵敏度,而这两者一般认为是彼此矛盾的。
如上所述,在本发明的氧浓度探测器中,形成在固体电解质主体表面之一上的探测电极在组成结构上包括:具有耐热性的第一厚电极,此电极基本上用于构成骨架部分;以及高灵敏度的第二薄电极,此电极基本上用于构成反应部件。因此,所说的氧浓度探测器在下述方面具有良好的效果,即在配合过程中可以完全利用第一电极的良好的耐热性以及第二电极的良好的灵敏度。
本发明的上述和其它目的以及新颖特征将在以下参照附图的说明中表现得更加明显,在附图中:
图1是依照本发明之第一实例的探测器装置组件的概略分解透视图;
图2是显示使用了本发明之上述第一实施例的氧探测器的剖面图;
图3是沿图1中III—III线的剖面图;
图4是显示第一电极的孔隙率变化时厚度与耐热性之间关系的特性曲线图;
图5是显示第二电极的孔隙率变化时厚度与耐热性之间关系的特性曲线图;
图6是显示与先有技术对照实例相比本发明之第一实例中装置温度与响应时间之间关系的特性曲线图;
图7是显示与先有技术对照实例相比本发明之第一实例中高温状态下停留时间与电阻之间关系的特性曲线图;
图8是依照本发明第二实例之探测器装置的探测电极的概略透视图;
图9是依照本发明第三实例之探测器装置的探测电极的概略透视图;
图10是依照本发明第四实例之探测器装置的探测电极的概略透视图;
图11是显示本发明另一实例的说明图。
以下将参照附图详细说明本发明的最佳实例。
本发明的第一实例说明了本发明在图2所示之由氧化锆制成的氧浓度探测器中的应用。
图1是图2所示之探测器装置6的分解图,图3是沿图1III—III线作为图1之放大剖面图的概略图。
在图2中,通过将陶瓷粉末装进由氧化铝制成的容器2的端部内从而形成配备有云母3的氧探测器1。由氧化铝构成的绝缘体4沿轴向方向放置在云母3上,用嵌塞的方式固定住外罩5以便从以上所说的部件的外表面来盖住这些部件。用具有开孔及底部的圆柱形罩盖8经由空间9罩住插在空器2中央部分内的探测器装置6的末梢端部分6a以及云母3和绝缘体4。
图1之概略分解图显示了探测器装置6的分解结构。在图1中,通过顺序地层压陶瓷涂层片11、电极部分12、衬层13以及陶瓷片14以形成陶瓷探测器6。在实践中,当同时烧结探测器装置6组成部分的原始材料时,就会形成该探测器装置。在下文中,将逐一说明上述探测器装置的每个组成部分。
衬层13由诸如Al2O3、Si3N4等绝缘材料制成。这是为了确保下文中出现的铂加热件22与电极部分12之间的电绝缘性。衬层13上包括一沿轴向延伸的气体入口21。此气体入口21的一端21a与衬层13的端面13a相通,而另一端21b则与扁平侧面13c相通。开口21b形成于朝向进气侧电极24的位置处,电极24被用作参考电极,下文将对它予以说明。
电极部分12包括:薄的片状固体电解质25,此电解质具有彼此相反的主表面;位于进气侧的电极24,此电极作为参考电极形成在固体电解质25的一个主表面上;以及位于排气侧的电极26,此电极作为探测电极形成在固体电解质25的另一个表面上。固体电解质25包括由掺有Y2O3、Yb2O3或类似物质的ZrO2所构成的氧离子传导体。
位于排气侧的电极26起探测电极的作用,它包括:用作第一电极的骨架电极26a,此电极呈格栅状;以及用作第二电极的反应电极,此电极装在所述格栅的空隙内。如图3所示,骨架电极26a和反应电极26b均形成在衬层25的表面上。骨架电极26a和反应电极26b两者都具有预定水平的耐热性和气体扩散率并具有较高的灵敏度。此外,骨架电极26a相对较厚且比反应电极26b更结实(密实),并具有高于反应电极26b的耐热性,而反应电极26b则相对较薄且比滑架电极26a更多孔,并具有高于骨架电极26a的气体扩散率和灵敏度。
骨架电极26a具有5μm至20μm的厚度并具有小于10%最好为从2%至低于10%的孔隙率。由于上述薄膜厚度至少为5μm,所以能够保证有较高的耐热性和较好的耐用性,如果上述薄膜厚度超过20μm,则气体扩散率会明显降低。
由于以下原因,所说的孔隙率最好至少为2%。如果该孔隙率小于2%,透气性会显著降低,而且,特别是在反应电极经长期使用而损坏时,上述孔隙率的范围是为了确保由骨架电极来承担探测器的功能。所述的孔隙率必须小于10%,这是因为,如果该孔隙率大于10%,那么,骨架电极26a会存在有过多的孔隙,因而耐热性会下降。
图4是改变骨架电极厚度时测定具有2%、6%和10%孔隙率的骨架电极的耐热性所得到的结果。在这种情况下,图4中具有2%、6%和10%孔隙率的骨架电极分别称之为“A”、“B”和“C”。
如图4所示,例如,在将骨架电极放置1000℃下50小时时,厚度为5μm、孔隙率为10%的骨架电极的电阻百分率的变化超过了10%。这意味着在高温下使用所述氧探测器会产生耐热性方面的问题。因而,可作这样的理解,当所述孔隙率小于10%,最好在2%至小于10%范围内时,才能够获得良好的效果。
反应电极26b最好具有在0.5μm至5μm范围内的薄膜厚度以及在10%至50%范围内的孔隙率。如果所述的薄膜厚度小于5μm,就可能妨碍反应电极的功能,而当该薄膜厚度超过5μm时,就不能保证有足够的灵敏度。所说的孔隙率必须至少为10%,这是因为,如果该孔隙率不小于10%,透气性则会变差。所说的孔隙率最多为50%,这是因为,如果该孔隙率超过50%,则耐热性会显著降低。
图5显示了在孔隙率分别为10%、25%和48%的情况下反应电极的厚度变化时的灵敏度。在该图中具有10%、25%和48%孔隙率的电极分别称之为“D”、“E”和“F”。
如图5所示,厚度为2μm、孔隙率为10%时的响应时间约为150毫秒。因此,可以这样理解,为了确保有较高的灵敏度,就要将孔隙率为10%的反电板的厚度增加至2μm或更多,同时还要避免该电极的致密化。
骨架电板26a与反应电极26b的面积之比最好满足下列关系:0.1≤B/(A+B)≤0.5,其中,A是骨架电极26a的面积,B是反应电板26b的面积。因此,如果0.1>B/(A+B),则反应电极的前述特征即高灵敏度会下降,如果B/(A+B)>0.5,则耐热性会显著降低。换句话说,在0.1≤B/(A+B)≤0.5的范围内,可以同时达到高耐热性和高灵敏度。
在图1中,陶瓷涂层片11由氧化铝或由与固体电解质25相同的材料制成并且是透气的涂敷薄膜。通过适当地调节陶瓷涂层片11的孔隙率可将本发明之探测器用作电势测定器或极谱分析仪。
陶瓷片14安置在衬层13与电极部分12相反的表面上。在陶瓷片14与衬层13相反的表面上形成有一加热件22。为了增加耐热性,加热件22由添加有诸如氧化铝之类的陶瓷粉的铂制成。陶瓷片14由与衬层13相同的材料制成,它盖住加热件22并防止废气沾污该加热件。
以下将说明生产探测器装置6的方法。
制做所述电极的方法如下。用作位于排气侧探测电极的电极26的骨架电极26a和反应电极26b通过网板印刷或类似方法形成在上述固体电解质片上,从而构成电极部分12,同样,用网板印刷或类似方法将参考电极24形成在上述固体电解质的另一表面上。此后,例如将作为未经烧结板片的陶瓷涂层片11、电极部分12、衬层13以及陶瓷片14加以层压并同时在1500℃下烧结一个小时。通过这种方式,可以形成探测器装置6。特别是在形成位于排气侧的合成电极26时,将通过混合铂粉、有机铂材料和有机粘合剂而配制成的涂料用于网板印刷,以便减少反应电极26b的厚度,此后,使用只含有铂粉及有机粘合剂的涂料印制具有较大厚度的骨架电极26a。
图6及图7显示了试验数据。
图6表明本发明的实例具有高于先有技术之对照实例的灵敏度,图7表明本发明的实例具有高于先有技术之对照实例的耐热性。
所述装置对温度的灵敏度在图6所示的横轴5标出并测出了在各种装置温度下的响应时间。其结果如图6所示。通过图6可以看出,特别是在所述装置温度的低温范围内,本发明的实例具有比先有技术之对照实例更短的响应时间。
至于耐热性,如图7所示,比较了所述装置在1000℃下停留500小时时的电阻R的变化。通过图7可以看出,在本发明的实例中,当所述装置停留在1000℃的温度下时,与先有技术的对照实例相比,所述电阻R在一段持续的时间内增加的较少。而在上述先有技术的对照实例中,所述电阻则在较短的时间内有显著的增加。
所述试验结果的实例列于表1中。
在这一试验中,通过改变骨架电极和反应电极的孔隙率、厚度及反应电极的面积比率〔B/(A+B)〕来评估了耐热性和灵敏度。评估的标准如下。在450℃温度下小于150毫秒的响应时间被认为是可以接受的,而不大于150毫秒的响应时间则被排除。在用作试验件的所述探测器装置在1000℃下停留500小时之后,排除掉电阻R增长率至少为10%的试验件,并接受增长率小于10%的试验件。试验结果列于表1中。
表1
骨架结构 | 反应电极 | 反应电极比率〔B/(A+B)〕 | 评价 | ||||
孔隙率(%) | 厚度(μm) | 孔隙率(%) | 厚度(μm) | 耐热性 | 灵敏度 | ||
实例123对照实例123456789 | 1062206206662066 | 51020221010102101010 | 502510525525525252525 | 0.512551511111 | 0.30.30.30.30.30.30.30.30.30.30.070.7 | 中等中等中等差差差中等中等差差中等差 | 中等中等中等差差差差差中等中等差中等 |
如表1所列,业已发现,如果骨架结构的薄膜厚度为50至20μm、孔隙率为小于10%、反应电极的薄膜厚度为0.5至2μm、孔隙率在10%至50%的范围内且反应电极的面积比率B/(A+B)在0.1至0.5的范围内,那么,灵敏度和耐热性都能令人满意。
图8至图10说明了位于本发明之第二至第四实例的探测器装置排气侧之电极的骨架电极和反应电极改进型式的实例。
图8所示之第二实例中的电极部分121体现了其中反应电极261b呈圆形的实例。换句话说,形成在固体电解质25一个表面上的位于排气侧的电极261包括骨架电极261a和反应电极261b。由于骨架电极261a和反应电极261b的材料与第一实例中的材料相同,故而略去说明。
依照该第二实例,由于反应电极261b呈圆形,所以在生产过程中烧结固体电解质片25之前,很容易在该未经烧结的固体电解质片上进行印制作业。
图9所示之第三实例体现了其中反应电极262b形成为狭缝状的实例。形成在固体电解质25一个表面上的位于排气侧的电极262带有四个梳齿状骨架电极262a。在这些梳齿状电极262a之间形成有狭缝状反应电极262b。在本发明中对骨架电极262a的数量没有特别的限制。
依照上述第三实例,由于骨架电极262a和反应电极262b均呈狭缝状,所以在未烧结的固体电解质片上印制和加工该骨架电极和反应电极要比第一实例容易得多。
在图10所示之第四实例中,作为第二电极的反应电极可以以能盖住作为第一电极的骨架电极263a的方式形成在固体电解质253上,此电解质与图3中的固体电解质25相同。
依照上述结构,骨架结构262a与反应电极263b之间的接触会更加可靠,而且不会降低耐热性与灵敏度。此外,可将阴极真空喷镀等用于生产过程,因而能更容易地生产出上述电极。
前述实例说明了本发明在薄的片状固体电解质上的应用,但是,本发明并不特别地局限于此。例如,所说的固体电解质可以是杯状固体电解质,它具有如图11所示的相互对向的侧表面。
用一外罩31固定住上述杯状固体电解质30。一加热件32安置在固体电解质电场腔30的内部。
一图中未作显示的参考电极安置在杯状固体电解质30的内部。在固体电解质30的外部形成有本发明的探测电极,它包括第一电极和第二电极并在图中未作显示。以能盖住上述探测电极的方式设置有一保护盖33。
这时,可用诸如墨滚印刷法之类的曲面印刷方法来形成所说的第一和第二电极。
具有这种杯状固体电解质的氧浓度探测器能以相类的方式提供与前述第一实例相同的效果。
所说的探测系统并不特别局限于电动热系统。换句话说,本发明的电极结构当然也可应用于气流探测系统如用来探测广泛分布的氧浓度的抽流系统及限流系统的氧浓度探测器。
Claims (8)
1.一种氧浓度探测器,它包括:一固体电解质,此电解质具有彼此相反的第一和第二主表面;一参考电极,此电极形成在上述固体电解质的第一主表面上;以及形成在上述固体电解质第二主表面上的探测电极,此探测电极具有由第一和第二电极构成的组合结构,其特征在于:有一组所述第二电极,所述第一电极有一组骨架部分,其围绕所述一组第二电极,所述一组第二电极通过所述第一电极的骨架部分相互电连接,所述第一电极的一组骨架部分相互电连接,第一电极具有5μm至20μm的薄膜厚度和小于10%的孔隙率,第二电极具有不小于0.5μm的薄膜厚度和10%至50%的孔隙率,所述一组第二电极的每一个比所述第一电极一组骨架部分中每一个更薄,所述一组第二电极有探测器的主要功能,所述第一电极的骨架部分有作为所述一组第二电极之间电连接器的主要功能,和探测器的辅助功能。
2.如权利要求1所述之氧浓度探测器,其特征在于,所述的固体电解质呈薄片状。
3.如权利要求1所述之氧浓度探测器,其特征在于,所述的固体电解质呈杯状。
4.如权利要求1所述之氧浓度探测器,其特征在于,所述的第一电极的整体面积A与第二电极的整体面积B满足下列关系:
0.1≤B/(A+B)≤0.5
5.如权利要求1所述之氧浓度探测器,其特征在于:所述第一电极的一组骨架部分为其中有一组空隙的格栅形式,所述一组第二电极形成于由所述第一电极的骨架部分的格栅围绕的空隙中。
6.如权利要求1所述之氧浓度探测器,其特征在于:所述一组第二电极为平面的圆形,所述第一电极的一组骨架部分围绕所述一组第二电极的平面圆形。
7.如权利要求1所述之氧浓度探测器,其特征在于:所述第一电极的一组骨架部分为梳齿状,所述一组第二电极形成于所述骨架部分的梳齿之间。
8.如权利要求1所述之氧浓度探测器,其特征在于:所述第二电极也形成于所述第一电极一组骨架部分的延伸表面上。
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EP1544609A1 (en) * | 2003-12-15 | 2005-06-22 | Hitachi, Ltd. | Oxygen sensor |
US9032779B2 (en) * | 2008-10-29 | 2015-05-19 | Ngk Spark Plug Co., Ltd. | Gas sensor |
JP5693421B2 (ja) * | 2011-09-02 | 2015-04-01 | 株式会社日本自動車部品総合研究所 | 積層型ガスセンサ素子および積層型ガスセンサ |
CN102680553B (zh) * | 2012-06-12 | 2014-07-23 | 陈兴举 | 带弯曲补偿层的陶瓷结构平板式气体传感器 |
CN105652905A (zh) * | 2016-03-18 | 2016-06-08 | 柳州易旺科技有限公司 | 一种自动调氧系统及其方法 |
JP6669046B2 (ja) * | 2016-11-15 | 2020-03-18 | 株式会社デンソー | ガスセンサ素子用固体電解質体とその製造方法及びガスセンサ素子 |
EP3409467B1 (de) * | 2017-05-30 | 2019-07-03 | Heraeus Nexensos GmbH | Heizer mit einem co-gesinterten mehrschichtenaufbau |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6036948A (ja) * | 1983-08-09 | 1985-02-26 | Ngk Insulators Ltd | 電気化学的装置 |
JPS61108957A (ja) * | 1984-10-31 | 1986-05-27 | Ngk Insulators Ltd | 酸素センサ |
JPS61172054A (ja) * | 1985-01-25 | 1986-08-02 | Ngk Spark Plug Co Ltd | 酸素ガスセンサ− |
JPH01184457A (ja) * | 1988-01-18 | 1989-07-24 | Ngk Insulators Ltd | 酸素センサ素子 |
JP2803111B2 (ja) * | 1988-11-18 | 1998-09-24 | スズキ株式会社 | セラミックスの接合方法 |
JP3052440B2 (ja) * | 1990-07-26 | 2000-06-12 | 株式会社日本自動車部品総合研究所 | 酸素濃度検出器 |
-
1993
- 1993-04-13 JP JP11096993A patent/JP3324195B2/ja not_active Expired - Lifetime
-
1994
- 1994-04-12 US US08/226,551 patent/US5447618A/en not_active Expired - Lifetime
- 1994-07-21 CN CN94108007A patent/CN1053738C/zh not_active Expired - Fee Related
- 1994-07-29 CN CN94107885A patent/CN1046162C/zh not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH06300731A (ja) | 1994-10-28 |
US5447618A (en) | 1995-09-05 |
CN1046162C (zh) | 1999-11-03 |
JP3324195B2 (ja) | 2002-09-17 |
CN1115381A (zh) | 1996-01-24 |
CN1115849A (zh) | 1996-01-31 |
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