Patent Application
20180252670
The present invention relates to a mixed-potential-type sensor for detecting the concentration of nitrogen oxide (NOx).
Environmental control, process control, etc., requires measurement of the concentration of NOx contained in a gas under measurement. In particular, diagnosis of asthma requires measurement of NOx contained in exhaled air at a very low concentration (several ppb to several hundreds ppb).
In view of these requirements, a technique has been proposed of connecting, in series, a plurality of sensors each including a reference electrode and a sensor electrode (detection electrode), and forming the senor electrode using WO3 so as to enhance the selectivity to NOx (see Japanese Kohyo (PCT) Patent Publication No. 2010-519514 (claim 7)). See also U.S. Patent Application Publication No. 2015/0250408, incorporated herein by reference in its entirety.
Since WO3 eliminates the catalytic activity of the electrode for converting NO2 to NO, a potential difference is developed between a detection electrode containing WO3 and a reference electrode containing no WO3. Thus, the selectivity to NOx is enhanced.
Incidentally, the manufacture of a detection electrode containing WO3 poses a problem that in a firing step, WO3 sublimates (scatters) and adheres to the surface of the reference electrode. If WO3 adheres to the surface of the reference electrode, the reference electrode also loses its catalytic activity. As a result, the potential difference developed between the reference electrode and the detection electrode decreases, and the NOx detection sensitivity of the sensor is lowered. Therefore, sensitivity may vary among the plurality of sensors.
In view of the above-described problems, an object of the present invention is to provide a mixed-potential-type sensor which includes a detection electrode containing tungsten oxide, and which prevents deterioration of the sensitivity in detecting nitrogen oxide.
The above object has been achieved by providing, in a first aspect (1), a mixed-potential-type sensor for detecting the concentration of nitrogen oxide contained in a gas under measurement. The mixed-potential-type sensor comprises a solid electrolyte layer having oxygen-ion conductivity; and a pair of porous electrodes formed on the solid electrolyte layer, wherein one of the porous electrodes is covered with a first layer containing tungsten oxide as a main component, the other of the porous electrodes is covered with a gas impermeable second layer, the second layer is in contact with the other of the porous electrodes without intervention of a tungsten oxide component, the solid electrolyte layer is porous and allows the gas under measurement to permeate from an externally exposed surface of the solid electrolyte layer to the other of the porous electrodes, and the concentration of the nitrogen oxide contained in the gas under measurement is detected from a potential difference developed between the porous electrodes.
According to the mixed-potential-type sensor (1), when this sensor is manufactured by firing or the like, the tungsten oxide contained in the first layer diffuses into the one of the porous electrodes, and reaches the interface between the one porous electrode and the solid electrolyte layer. As a result, the one porous electrode loses its catalytic activity for converting NO2 to NO and functions as a detection electrode.
Meanwhile, even when the tungsten oxide contained in the first layer sublimates due to firing, since the second layer is gas impermeable, the tungsten oxide component cannot reach the interface between the second layer and the other of the porous electrodes, and the tungsten oxide component is not present at the interface. Therefore, the other of the porous electrodes has a catalytic activity for converting NO2 to NO and functions as a reference electrode.
As described above, the second layer prevents the other of the porous electrodes from losing its catalytic activity as a reference electrode. Therefore, a potential difference is reliably developed between the one of the porous electrodes which serves as a detection electrode and the other of the porous electrodes which serves as a reference electrode. Thus, deterioration of the sensitivity in detecting nitrogen oxide can be prevented.
In a second aspect (2), the above object has been achieved by providing a mixed-potential-type sensor for detecting the concentration of nitrogen oxide contained in a gas under measurement. The mixed-potential-type sensor comprises a solid electrolyte layer having oxygen-ion conductivity; and a pair of porous electrodes formed on the solid electrolyte layer, wherein one of the porous electrodes is covered with a first layer containing tungsten oxide as a main component, the other of the porous electrodes is covered with a second layer which captures a tungsten oxide component originating from the first layer, the solid electrolyte layer is porous and allows the gas under measurement to permeate from an externally exposed surface of the solid electrolyte layer to the other of the porous electrodes, and the concentration of the nitrogen oxide contained in the gas under measurement is detected from a potential difference developed between the porous electrodes.
According to the mixed-potential-type sensor (2), even in the case where the tungsten oxide contained in the first layer sublimates when this sensor is manufactured by firing or the like, the second layer captures the tungsten oxide component originating from the first layer. Therefore, the tungsten oxide component cannot reach the interface between the second layer and the other of the porous electrodes, and the tungsten oxide component is not present at the interface. Therefore, the other of the porous electrodes has a catalytic activity for converting NO2 to NO and functions as a reference electrode.
As described above, the second layer prevents the other of the porous electrodes from losing its catalytic activity as a reference electrode. Therefore, a potential difference is reliably developed between the one of the porous electrodes which serves as a detection electrode and the other of the porous electrodes which serves as a reference electrode. Thus, deterioration of the sensitivity in detecting nitrogen oxide can be prevented.
In a preferred embodiment (3) of the mixed-potential-type sensor according to the first aspect (1) of the invention, the second layer contains SiO2 as a main component.
According to the mixed-potential-type sensor (3), the second layer becomes gas impermeable without fail.
In another preferred embodiment (4) of the mixed-potential-type sensor according to the first aspect (1) of the invention, the second layer is formed of molten glass.
According to the mixed-potential-type sensor (4), the second layer becomes gas impermeable without fail.
In a preferred embodiment (5) of the mixed-potential-type sensor according to the second aspect (2) of the invention, the second layer contains SiO2 as a main component.
According to the mixed-potential-type sensor (5), the second layer becomes gas impermeable without fail.
In another preferred embodiment (6) of the mixed-potential-type sensor according to the second aspect (2) of the invention, the second layer is formed of molten glass.
According to the mixed-potential-type sensor (6), the second layer becomes gas impermeable without fail.
The present invention can provide a mixed-potential-type sensor which includes a detection electrode containing tungsten oxide, and which can prevent deterioration of the sensitivity in detecting nitrogen oxide.
The present invention will now be described in detail with reference to the drawings. However, the present invention should not be construed as being limited thereto.
As shown in
The sensor unit 200 has a generally rectangular plate-like shape. A heater 220 and a temperature sensor 221 are disposed on the upper surface of the sensor unit 200. The plurality of mixed-potential-type sensors 70 shown in
As shown in
The ceramic wiring board 30 has an oblong shape and has a rectangular opening 30h on one end side in the longitudinal direction thereof. A plurality of lead traces 30L are formed on front and back surfaces of the ceramic wiring board 30. Inner ends of the lead traces 30L are connected to a plurality of element peripheral pads 30s surrounding the opening 30h, and outer ends of the lead traces 30L are connected to conducting pads 30p on the side opposite the opening 30h in the longitudinal direction.
The sensor unit 200 is accommodated in the opening 30h. Four conducting members 30w extend across the left-hand and right-hand sides of the sensor unit 200 and are joined to the conducting pads 220a, 220b, 221a and 221b on the upper surface side of the sensor unit 200 (on the side where the heater 220 and the temperature sensor 221 are provided) and four element peripheral pads 30s of the ceramic wiring board 30. As a result, the sensor unit 200 is fixedly suspended within the opening 30h of the ceramic wiring board 30.
Meanwhile, as shown in
Notably, as shown in
Although not illustrated, on the lower surface side of the sensor unit 200, the outer ends of the lead traces 30L connected to the element peripheral pads 30s on the lower surface of the sensor unit 200 are connected to the above-mentioned lead traces on the upper surface side through the above-mentioned two through holes, and are connected to the leftmost conducting pad 30p and the fourth conducting pad 30p as counted from the left-hand side.
In this manner, electrical signals output from the mixed-potential-type sensors 70 and the temperature sensor 221 are output to the outside through the conducting pads 30p, and the heater 220 is energized for heat generation by electric power externally supplied through the conducting pads 30p.
The first spacer 20 has a square shape and has a rectangular opening 20h which overlaps the opening 30h and is larger than the opening 30h.
The cover 10 has a square shape and has the same dimensions as the first spacer 20. A gas discharge hole 10h is formed in a portion of the cover 10 which faces the opening 20h.
The second spacer 40 has an oblong shape and has the same dimensions as the ceramic wiring board 30. The second spacer 40 has a rectangular opening 40h on the same side as the opening 30h with respect to the longitudinal direction. The opening 40h overlaps the opening 30h and is larger than the opening 30h.
The base 50 has an oblong shape and has the same dimensions as the ceramic wiring board 30. A gas introduction hole 50h is formed in a portion of the base 50 which faces the opening 40h.
The ceramic wiring board 30, the first spacer 20, the cover 10, the second spacer 40, and the base 50 may be formed of a ceramic material such as alumina.
Square seals 64 and 62 are disposed between the ceramic wiring board 30 and the first spacer 20 and between the first spacer 20 and the cover 10, respectively, to surround the opening 20h. Similarly, oblong seals 66 and 68 are disposed between the ceramic wiring board 30 and the second spacer 40 and between the second spacer 40 and the base 50, respectively, to surround the opening 40h. The seals 62 to 68 are formed of glass.
In the present embodiment, the cover 10, the first spacer 20, the ceramic wiring board 30, the second spacer 40, and the base 50 are formed of a ceramic material, and are gastightly bonded and stacked together via the seals 62 to 68 formed of glass-based adhesive layers.
The ceramic wiring board 30 has positioning holes 30a provided at opposite ends of an end portion thereof located on the opening 30h side with respect to the longitudinal direction. Similarly, the ceramic wiring board 30 has positioning holes 30b provided at opposite ends of an end portion thereof located on the conducting pads 30p side.
The first spacer 20 and the cover 10 have positioning holes 20a and 10a, respectively, which are provided at the same positions as the positioning holes 30a.
Similarly, the second spacer 40 has positioning holes 40a and 40b provided at the same positions as the positioning holes 30a and 30b, respectively, and the base 50 has positioning holes 50a and 50b provided at the same positions as the positioning holes 30a and 30b, respectively.
The cover 10, the first spacer 20, the ceramic wiring board 30, the second spacer 40 and the base 50 (these members are also referred to as “the respective members”) are stacked in this order, jigs (guide pins) are passed through the positioning holes 10a to 50a, 40b and 50b to thereby position the respective members, and the respective members are bonded together, whereby the NOx sensor apparatus 100 can be assembled.
The gas under measurement introduced through the gas introduction hole 50h flows through an internal space formed by the opening 40h, comes into contact with the mixed-potential-type sensors 70 of the sensor unit 200, by which the NOx concentration is measured, flows through an internal space formed by the opening 20h, and is discharged to the outside through the gas discharge hole 10h.
Next, the structures of the sensor unit 200 and the mixed-potential-type sensors 70 will be described with reference to
As shown in
The mixed-potential-type sensors 70 are connected in series by lead traces 206, 208, 210 and 212. Of these traces, the lead traces 206 and 212 have end portions 206a and 212a which serve as a pair of input/output terminals (electrode pads) which are the start and end points of the current path of the series circuit.
The heater 220 (see
The base substrate 202 may be formed of a ceramic material such as alumina. The heater 220 and the temperature sensor 221 may be formed of a metal such as platinum.
Meanwhile, as shown in
The electrode 78 (corresponding to “the other of the porous electrodes” of the invention) which is a porous electrode extends from a position near one side of the solid electrolyte layer 74 toward the outside of the solid electrolyte layer 74 while contacting the surface of the solid electrolyte layer 74, and is in contact with the lower surface of the base substrate 202. The externally exposed surface of a portion of the electrode 78, which portion is in contact with the solid electrolyte layer 74, is covered with a gas impermeable second layer 78a.
The electrode 76 (corresponding to “one of the porous electrodes” of the invention) which is a porous electrode extends from a position near the opposite side the solid electrolyte layer 74 (the side opposite to the electrode 78) toward the outside of the solid electrolyte layer 74 while contacting the surface of the solid electrolyte layer 74, and is in contact with the lower surface of the base substrate 202. The externally exposed surface of a portion of the electrode 76, which portion is in contact with the solid electrolyte layer 74, is covered with a first layer 76a which contains tungsten oxide (WO3) as a main component (in an amount greater than 50 mass %). Notably, as shown in
The lead traces 206 and 208 are electrically connected to portions of the electrodes 76 and 78, respectively, which portions are in contact with the lower surface of the base substrate 202.
The electrodes 76 and 78 may contain, for example, Pt as a main component (in an amount greater than 50 mass %). The second layer 78a may contain molten SiO2 as a main component (in an amount greater than 50 mass %) or may be formed of molten glass.
Each mixed-potential-type sensor 70 is formed by applying paste materials for forming the solid electrolyte layer 74, the electrodes 76 and 78, the first layer 76a, and the second layer 78a onto the base substrate 202 by, for example, printing, followed by firing. As shown in
Meanwhile, as a result of the firing, the tungsten oxide component 79 within the first layer 76a sublimates (scatters). However, in the mixed-potential-type sensor 70 of the present embodiment, on account of providing the gas impermeable second layer 78a, the tungsten oxide component 79 cannot reach the interface S2 between the second layer 78a and the electrode 78, and the tungsten oxide component 79 is not present at the interface S2. The tungsten oxide component 79 originating from the first layer 76a is captured by the second layer 78a and is prevented from reaching the interface S2 between the second layer 78a and the electrode 78. As a result, the electrode 78 has a catalytic activity for converting NO2 to NO at a ratio corresponding to the temperature and functions as a reference electrode.
As described above, the second layer 78a prevents the reference electrode 78 from losing its catalytic activity. Therefore, a potential difference is reliably developed between the detection electrode 76 which has no catalytic activity and conveys NO2 to the interface S1 and the reference electrode 78 which converts NO2 to NO. Thus, deterioration of the sensitivity in detecting NOx (nitrogen oxide) can be prevented.
Notably, since the electrode 78 is covered with the gas impermeable second layer 78a, it becomes difficult to introduce the gas under measurement from the surface of the electrode 78. In view of this, the solid electrolyte layer 74 is formed of a gas permeable porous solid electrolyte. Therefore, as shown in
Notably, the fact that the solid electrolyte layer 74 and the electrodes 76 and 78 are porous can be confirmed by checking whether or not pores are preset in a secondary-electron image of a cross section of the layer and the electrodes.
The present invention is not limited to the above-described embodiment and encompasses various modifications and equivalents falling within the scope of the invention.
For example, the shapes of the solid electrolyte layer, the shape of the porous electrodes, the shape of the mixed-potential-type sensor, etc., are not limited to those of the above-described embodiment.
A mixed-potential-type sensor having the structure shown in
First, a green base substrate 202 of alumina was formed by a doctor blade method. A Pt paste was screen-printed on one side of the green base substrate 202 to thereby form the heater 220 and the temperature sensor 221. After that, the entirety was heated at 400° C. for 4 hours for debindering and fired at 1,350° C. for 2 hours.
A YSZ (the addition amount of Y to ZrO2: 8 mol %) paste was screen-printed on the opposite side of the fired base substrate 202, and firing was carried out at 1,350° C. for 3 hours in a nitrogen atmosphere to thereby form the solid electrolyte layer 74. In this firing, sintering of YSZ was not allowed to progress sufficiently, so that the solid electrolyte layer 74 became porous. Another method for making the solid electrolyte layer 74 porous is to add glass particles or the like to the YSZ paste which foam at that firing temperature.
Subsequently, a Pt paste was screen-printed on the surface of the solid electrolyte layer 74, and firing was carried out at 850° C. for 10 minutes so as to form the electrodes 76 and 78. Notably, in order to improve adhesion to the first layer 76a, glass particles may be added to the Pt paste for the electrode 76.
Next, a paste containing zeolite as a main component was screen-printed on the surface of the electrode 78, and firing was carried out at 950° C. for 2 hours so as to form the second layer 78a. Subsequently, a tungsten oxide paste was screen-printed on the surface of the electrode 76, and firing was carried out at 750° C. for 1 hour so as to form the first layer 76a. As a result, the mixed-potential-type sensor 70 of the example was completed. Notably, since the second layer 78a was formed by firing the paste containing zeolite as a main component at 950° C. for 2 hours, the second layer 78a was formed as a gas impermeable layer of dense molten glass.
As a comparative example, a mixed-potential-type sensor was manufactured in the same manner except that the second layer 78a was formed by firing zeolite at 875° C. for 1 hour.
In the case of the mixed-potential-type sensor of the example, as shown in
In contrast, in the case of the mixed-potential-type sensor of the comparative example, as shown in
The invention has been described in detail with reference to the above embodiments. However, the invention should not be construed as being limited thereto. It should further be apparent to those skilled in the art that various changes in form and detail of the invention as shown and described above may be made. It is intended that such changes be included within the spirit and scope of the claims appended hereto.
