Patent Application
20250216359
The present invention relates to a multi-gas sensor capable of sensing a plurality of types of sensing target gas components and measuring concentrations thereof.
In measurement for managing the amount of an emitted exhaust gas from a vehicle, technology of measuring concentrations of water vapor (H2O) and carbon dioxide (CO2) has already been known (see Japanese Patent No. 5918177, No. 6469464, and No. 6469462, for example). In each of gas sensors disclosed in Japanese Patent No. 5918177 and No. 6469464, a water vapor (H2O) component and a carbon dioxide (CO2) component can be measured in parallel. As for a gas sensor disclosed in Japanese Patent No. 6469462, a water vapor (H2O) component can accurately be measured even when a measurement gas contains carbon dioxide (CO2).
In the gas sensor disclosed in Japanese Patent No. 5918177 having a three-chamber configuration, firstly, a main pump cell as a pump cell for a first internal space operates to pump out O2 contained in a measurement gas introduced into the first internal space and to reduce all H2O and CO2 similarly contained in the measurement gas once to generate H2 and CO. The measurement gas containing these H2 and CO is introduced into a second internal space and further into a third internal space. A first measurement pump cell as a pump cell for the second internal space then pumps in O2 to selectively oxidize H2 to generate H2O, and, further, a second measurement pump cell as a pump cell for the third internal space pumps in O2 to oxidize CO to generate CO2. Concentrations of H2O and CO2 in the measurement gas are respectively measured based on magnitudes of pump currents flowing through the first measurement pump cell and the second measurement pump cell when H2 and CO are oxidized.
In the gas sensor, an applied voltage in the pump cell for the first internal space is required to be set to be high for reduction of H2O and CO2 in the first internal space. In addition, a temperature of a main inner pump electrode as an in-space pump electrode forming the main pump cell is required to be set to be high. Such a high applied voltage and maintaining the pump electrode at a high temperature, however, might cause a sensor element containing oxygen-ion conductive solid electrolyte ceramics as a major component to be cracked and blackened to reduce the solid electrolyte ceramics.
In the gas sensor disclosed in Japanese Patent No. 6469462 having a two-chamber configuration, for improvement in selective H2 oxidation property, an alloy of Au and another noble metal (e.g., Pt, Rh, and Ru) is used as a material for a measurement inner pump electrode as an in-space pump electrode forming a measurement pump cell as a pump cell for a second internal space, and an abundance ratio of Au in a surface of the electrode is 25 at % or more.
This material for the electrode is seemingly applicable to a first measurement inner pump electrode of the first measurement pump cell selectively oxidizing H2 similarly in the gas sensor disclosed in Japanese Patent No. 5918177.
The first measurement inner pump electrode, however, is provided at a location to be at a higher temperature than a second measurement inner pump electrode as an in-space pump electrode forming the second measurement pump cell in the gas sensor disclosed in Japanese Patent No. 5918177, so that use of such a material for the electrode might cause evaporation of Au in the electrode to change sensitivity during a long-term use.
The present invention relates to a multi-gas sensor capable of sensing a plurality of types of sensing target gas components and measuring concentrations thereof.
According to the present invention, a gas sensor capable of measuring concentrations of a plurality of sensing target gas components contained in a measurement gas, the measurement gas at least containing water vapor and carbon dioxide, includes: a sensor element having a structure formed of an oxygen-ion conductive solid electrolyte; and a controller controlling operation of the gas sensor, wherein the sensor element includes a gas inlet through which the measurement gas is introduced; an internal chamber communicating with the gas inlet via a diffusion control part; an adjustment electrode, a first measurement electrode, and a second measurement electrode each provided to face the internal chamber and arranged in order of proximity to the gas inlet while being spaced apart at predetermined intervals; an adjustment pump cell including the adjustment electrode, an out-of-space pump electrode provided at a location other than a location in the internal chamber, and a portion of the solid electrolyte present between the adjustment electrode and the out-of-space pump electrode; a first measurement pump cell including the first measurement electrode, the out-of-space pump electrode, and a portion of the solid electrolyte present between the first measurement electrode and the out-of-space pump electrode; a second measurement pump cell including the second measurement electrode, the out-of-space pump electrode, and a portion of the solid electrolyte present between the second measurement electrode and the out-of-space pump electrode; and a heater heating the sensor element, the heater heats the sensor element so that a temperature is highest near the adjustment electrode in the internal chamber and decreases with increasing distance from the adjustment electrode in a longitudinal direction of the sensor element, the adjustment pump cell pumps oxygen out of the measurement gas having reached the adjustment electrode through the gas inlet to the extent that water vapor and carbon dioxide contained in the measurement gas are not decomposed, the first measurement pump cell pumps oxygen out of the measurement gas having reached the first measurement electrode so that substantially all water vapor and carbon dioxide contained in the measurement gas of which oxygen has been pumped out by the adjustment pump cell are reduced, the second measurement pump cell pumps oxygen into the internal chamber to selectively oxidize hydrogen generated by reduction of water vapor and contained in the measurement gas having reached the second measurement electrode, and the controller identifies: a concentration of water vapor contained in the measurement gas based on a value of a water vapor equivalent current as an oxygen pump current flowing between the second measurement electrode and the out-of-space pump electrode when hydrogen is oxidized with oxygen pumped in by the second measurement pump cell; and a concentration of carbon dioxide contained in the measurement gas based on the value of the water vapor equivalent current and a value of a total reducing current as an oxygen pump current flowing between the first measurement electrode and the out-of-space pump electrode when water vapor and carbon dioxide are reduced by the first measurement pump cell pumping out oxygen.
Another aspect of the present invention is a concentration measurement method of measuring concentrations of a plurality of sensing target gas components contained in a measurement gas using a gas sensor, the measurement gas at least containing water vapor and carbon dioxide, wherein the gas sensor includes a sensor element having an elongated planar structure formed of an oxygen-ion conductive solid electrolyte, the sensor element includes: a gas inlet through which the measurement gas is introduced; an internal chamber communicating with the gas inlet via a diffusion control part; an adjustment electrode, a first measurement electrode, and a second measurement electrode each provided to face the internal chamber and arranged in order of proximity to the gas inlet while being spaced apart at predetermined intervals; an adjustment pump cell including the adjustment electrode, an out-of-space pump electrode provided at a location other than a location in the internal chamber, and a portion of the solid electrolyte present between the adjustment electrode and the out-of-space pump electrode; a first measurement pump cell including the first measurement electrode, the out-of-space pump electrode, and a portion of the solid electrolyte present between the first measurement electrode and the out-of-space pump electrode; a second measurement pump cell including the second measurement electrode, the out-of-space pump electrode, and a portion of the solid electrolyte present between the second measurement electrode and the out-of-space pump electrode; and a heater heating the sensor element, the concentration measurement method using the gas sensor includes: a) heating, using the heater, the sensor element so that a temperature is highest near the adjustment electrode in the internal chamber and decreases with increasing distance from the adjustment electrode in a longitudinal direction of the sensor element; b) pumping, using the adjustment pump cell, oxygen out of the measurement gas having reached the adjustment electrode through the gas inlet to the extent that water vapor and carbon dioxide contained in the measurement gas are not decomposed; c) pumping, using the first measurement pump cell, oxygen out of the measurement gas having reached the first measurement electrode so that substantially all water vapor and carbon dioxide contained in the measurement gas of which oxygen has been pumped out using the adjustment pump cell are reduced; d) pumping, using the second measurement pump cell, oxygen into the internal chamber to selectively oxidize hydrogen generated by reduction of water vapor and contained in the measurement gas having reached the second measurement electrode; e) identifying a concentration of water vapor contained in the measurement gas based on a value of a water vapor equivalent current as an oxygen pump current flowing between the second measurement electrode and the out-of-space pump electrode when hydrogen is oxidized with oxygen pumped in using the second measurement pump cell; and f) identifying a concentration of carbon dioxide contained in the measurement gas based on the value of the water vapor equivalent current and a value of a total reducing current as an oxygen pump current flowing between the first measurement electrode and the out-of-space pump electrode when water vapor and carbon dioxide are reduced by pumping out oxygen using the first measurement pump cell.
According to the present invention, a multi-gas sensor with more long-term reliability than before suppressing cracking and blackening of a sensor element and suppressing evaporation of Au from an electrode is implemented.
It is therefore an object of the present invention to provide a multi-gas sensor with more long-term reliability than before capable of simultaneously measuring a water vapor (H2O) component and a carbon dioxide (CO2) component, suppressing cracking and blackening of a sensor element, and further being less likely to be subjected to a change in sensitivity during a long-term use.
The sensor element 101 includes an elongated planar structure (base part) 14 formed of an oxygen-ion conductive solid electrolyte, a first diffusion control part 11 doubling a gas inlet 10 which is formed in one end portion (a left end portion in the figure) of the structure 14 and through which the measurement gas is introduced, and a buffer space 12, a first chamber 20, a second chamber 40, and a third chamber 61 formed in the structure 14 and communicating sequentially from the gas inlet 10 (first diffusion control part 11). The buffer space 12 communicates with the gas inlet 10 (first diffusion control part 11). The first chamber 20 communicates with the buffer space 12 via a second diffusion control part 13. The second chamber 40 communicates with the first chamber 20 via a third diffusion control part 30. The third chamber 61 communicates with the second chamber 40 via a fourth diffusion control part 60.
The structure 14 is formed by laminating a plurality of substrates of ceramics, for example. Specifically, the structure 14 has a configuration in which six layers including a first substrate 1, a second substrate 2, a third substrate 3, a first solid electrolyte layer 4, a spacer layer 5, and a second solid electrolyte layer 6 are sequentially laminated from the bottom. Each layer is formed of an oxygen-ion conductive solid electrolyte, such as zirconia (ZrO2).
The first diffusion control part 11 doubling as the gas inlet 10, the buffer space 12, the second diffusion control part 13, the first chamber 20, the third diffusion control part 30, the second chamber 40, the fourth diffusion control part 60, and the third chamber 61 are formed in this order between a lower surface 6b of the second solid electrolyte layer 6 and an upper surface 4a of the first solid electrolyte layer 4 on a side of the one end portion of the structure 14. A part extending from the gas inlet 10 to the third chamber 61 is also referred to as a gas distribution part.
The buffer space 12, the first chamber 20, the second chamber 40, and the third chamber 61 are formed to penetrate the spacer layer 5 in a thickness direction. The lower surface 6b of the second solid electrolyte layer 6 is exposed in upper portions in the figure of these chambers and the like, and the upper surface 4a of the first solid electrolyte layer 4 is exposed in lower portions in the figure of these chambers and the like. Side portions of these chambers and the like are each defined by the spacer layer 5 or any of the diffusion control parts. The first chamber 20, the second chamber 40, and the third chamber 61 each have a length (size in the longitudinal direction of the element) of 0.3 mm to 1.0 mm, for example, a width (size in a transverse direction of the element) of 0.5 mm to 30 mm, for example, and a height (size in a thickness direction of the element) of 50 μm to 200 μm, for example. These chambers, however, are not required to have the same size and may have different sizes.
The gas inlet 10 may similarly be formed to penetrate the spacer layer 5 in the thickness direction separately from the first diffusion control part 11. In this case, the first diffusion control part 11 is to be formed inside and adjacent to the gas inlet 10.
The first diffusion control part 11, the second diffusion control part 13, the third diffusion control part 30, and the fourth diffusion control part 60 each include two horizontally long slits. That is to say, they each have openings elongated in a direction perpendicular to the page of the figure in an upper portion and a lower portion in the figure thereof. The slits each have a length (size in the longitudinal direction of the element) of 0.2 mm to 1.0 mm, for example, a width of an opening (size in the transverse direction of the element) of 0.5 mm to 30 mm, for example, and a height of the opening (size in the thickness direction of the element) of 5 μm to 30 μm, for example.
The sensor element 101 includes a reference gas introduction space 43 in the other end portion (a right end portion in the figure) opposite the one end portion in which the gas inlet 10 is provided. The reference gas introduction space 43 is formed between an upper surface 3a of the third substrate 3 and a lower surface 5b of the spacer layer 5. A side portion of the reference gas introduction space 43 is defined by a side surface of the first solid electrolyte layer 4. Oxygen (O2) and air are introduced into the reference gas introduction space 43 as reference gases, for example.
The gas inlet 10 (first diffusion control part 11) is a part opening to an external space, and the measurement gas is taken from the external space into the sensor element 101 through the gas inlet 10.
The first diffusion control part 11 is a part providing predetermined diffusion resistance to the taken measurement gas.
The buffer space 12 is provided to cancel concentration fluctuations of the measurement gas caused by pressure fluctuations of the measurement gas in the external space. Pulsation of exhaust pressure of the exhaust gas of the vehicle is taken as an example of such pressure fluctuations of the measurement gas, for example.
The second diffusion control part 13 is a part providing predetermined diffusion resistance to the measurement gas introduced from the buffer space 12 into the first chamber 20.
The first chamber 20 is provided as a space to pump oxygen out of the measurement gas introduced through the second diffusion control part 13. Pumping-out of oxygen is implemented by operation of an adjustment pump cell 21.
The adjustment pump cell 21 is an electrochemical pump cell including an inner pump electrode (adjustment electrode) 22, an outer pump electrode (out-of-space pump electrode) 23, and a solid electrolyte present in a portion of the structure 14 sandwiched between these electrodes.
In the adjustment pump cell 21, a voltage Vp0 is applied across the inner pump electrode 22 and the outer pump electrode 23 from a variable power supply 24 disposed outside the sensor element 101 to generate an oxygen pump current (oxygen ion current) Ip0. Oxygen in the first chamber 20 can thereby be pumped out to the external space. Assume that a direction of the oxygen pump current Ip0 when oxygen is pumped out from the first chamber 20 is a positive direction of the oxygen pump current Ip0 in the present embodiment.
The inner pump electrode 22 is provided on substantially the entire portions of the lower surface 6b of the second solid electrolyte layer 6 and the upper surface 4a of the first solid electrolyte layer 4 defining the first chamber 20 respectively as a ceiling electrode portion 22a and a bottom electrode portion 22b. The ceiling electrode portion 22a and the bottom electrode portion 22b are connected by an unillustrated conducting portion.
The inner pump electrode 22 is provided as a porous cermet electrode containing at least one of platinum and rhodium (Rh) as a metal component and being rectangular in plan view.
The outer pump electrode 23 is provided, with platinum or an alloy (a Pt—Au alloy) of platinum and gold as a metal component, as a porous cermet electrode containing platinum or the Pt—Au alloy and zirconia and being rectangular in plan view, for example.
In the sensor element 101, the inner pump electrode 22, a reference electrode 42, and a solid electrolyte present in a portion of the structure 14 sandwiched between these electrodes constitute a first chamber sensor cell 80. The first chamber sensor cell 80 is an electrochemical sensor cell to grasp oxygen partial pressure in an atmosphere in the first chamber 20.
The reference electrode 42 is an electrode formed between the first solid electrolyte layer 4 and the third substrate 3 and is provided as a porous cermet electrode containing platinum and zirconia and being rectangular in plan view, for example.
A reference gas introduction layer 48 formed of porous alumina and leading to the reference gas introduction space 43 is provided around the reference electrode 42. A reference gas in the reference gas introduction space 43 is introduced into a surface of the reference electrode 42 via the reference gas introduction layer 48. That is to say, the reference electrode 42 is always in contact with the reference gas.
In the first chamber sensor cell 80, electromotive force (Nernst electromotive force) V0 is generated between the inner pump electrode 22 and the reference electrode 42. The electromotive force V0 has a value in accordance with a difference between an oxygen concentration (oxygen partial pressure) in the first chamber 20 and an oxygen concentration (oxygen partial pressure) of the reference gas. The oxygen concentration (oxygen partial pressure) of the reference gas is basically constant, so that the electromotive force V0 has a value in accordance with the oxygen concentration (oxygen partial pressure) in the first chamber 20.
The third diffusion control part 30 is a part providing predetermined diffusion resistance to the measurement gas introduced from the first chamber 20 into the second chamber 40, containing H2O and CO2, and substantially not containing oxygen. The second chamber 40 is provided as a space to reduce (decompose) H2O and CO2 contained as the sensing target gas components in the measurement gas introduced through the third diffusion control part 30 to generate hydrogen (H2) and carbon monoxide (CO), so that the measurement gas does not substantially contain oxygen as well as H2O and CO2. Reduction (decomposition) of H2O and CO2 is implemented by operation of a first measurement pump cell 50.
The first measurement pump cell 50 is an electrochemical pump cell including a first measurement electrode 51, the outer pump electrode 23, and a solid electrolyte present in a portion of the structure 14 sandwiched between these electrodes.
In the first measurement pump cell 50, a voltage Vp1 is applied across the first measurement electrode 51 and the outer pump electrode 23 from a variable power supply 52 disposed outside the sensor element 101 to generate an oxygen pump current (oxygen ion current) Ip1. Oxygen generated by reduction of H2O and CO2 in the second chamber 40 can thereby be pumped out to the external space. Assume that a direction of the oxygen pump current Ip1 when oxygen is pumped out from the second chamber 40 is a positive direction of the oxygen pump current Ip1 in the present embodiment.
The first measurement electrode 51 is provided on substantially the entire portions of the lower surface 6b of the second solid electrolyte layer 6 and the upper surface 4a of the first solid electrolyte layer 4 defining the second chamber 40 respectively as a ceiling electrode portion 51a and a bottom electrode portion 51b. The ceiling electrode portion 51a and the bottom electrode portion 51b are connected by an unillustrated conducting portion.
The first measurement electrode 51 is provided as a porous cermet electrode containing Pt as a metal component and being rectangular in plan view.
In the sensor element 101, the first measurement electrode 51, the reference electrode 42, and a solid electrolyte present in a portion of the structure 14 sandwiched between these electrodes constitute a second chamber sensor cell 81. The second chamber sensor cell 81 is an electrochemical sensor cell to grasp oxygen partial pressure in an atmosphere in the second chamber 40.
In the second chamber sensor cell 81, electromotive force (Nernst electromotive force) V1 is generated between the first measurement electrode 51 and the reference electrode 42. The electromotive force V1 has a value in accordance with a difference between an oxygen concentration (oxygen partial pressure) in the second chamber 40 and the oxygen concentration (oxygen partial pressure) of the reference gas. Since the oxygen concentration (oxygen partial pressure) of the reference gas is basically constant, the electromotive force V1 has a value in accordance with the oxygen concentration (oxygen partial pressure) in the second chamber 40.
The fourth diffusion control part 60 is a part providing predetermined diffusion resistance to the measurement gas introduced from the second chamber 40 into the third chamber 61 and containing H2 and CO while substantially not containing H2O, CO2, and oxygen.
The third chamber 61 is provided as a space to selectively oxidize all of H2 from among H2 and CO contained in the measurement gas introduced through the fourth diffusion control part 60 to generate H2O again. Generation of H2O by oxidation of H2 is implemented by operation of a second measurement pump cell 41.
The second measurement pump cell 41 is an electrochemical pump cell including a second measurement electrode 44, the outer pump electrode 23, and a solid electrolyte present in a portion of the structure 14 sandwiched between these electrodes.
In the second measurement pump cell 41, a voltage Vp2 is applied across the second measurement electrode 44 and the outer pump electrode 23 from a variable power supply 46 disposed outside the sensor element 101 to generate an oxygen pump current (oxygen ion current) Ip2. Oxygen can thereby be pumped into the third chamber 61 from the external space. Assume that a direction of the oxygen pump current Ip2 when oxygen is pumped out from the third chamber 61 is a positive direction of the oxygen pump current Ip2 in the present embodiment.
The second measurement electrode 44 is provided on substantially the entire portion of the upper surface 4a of the first solid electrolyte layer 4 defining the third chamber 61.
The second measurement electrode 44 contains a Pt—Au alloy as a metal component and is provided as a porous cermet electrode containing the Pt—Au alloy and zirconia and being rectangular in plan view, for example. The Pt—Au alloy preferably has an Au concentration of 1 wt % or more and 50 wt % or less and more preferably has an Au concentration of 10 wt % or more and 30 wt % or less. In this case, a selective H2 oxidation property, that is, a property that, when H2 and CO coexist in the third chamber 61, only H2 is selectively oxidized with oxygen pumped in by the second measurement pump cell 41 and CO is not oxidized, of the second measurement electrode 44 is more suitably developed.
In the sensor element 101, the second measurement electrode 44, the reference electrode 42, and a solid electrolyte present in a portion of the structure 14 sandwiched between these electrodes constitute a third chamber sensor cell 82. The third chamber sensor cell 82 is an electrochemical sensor cell to grasp oxygen partial pressure in an atmosphere in the third chamber 61.
In the third chamber sensor cell 82, electromotive force (Nernst electromotive force) V2 is generated between the second measurement electrode 44 and the reference electrode 42. The electromotive force V2 has a value in accordance with a difference between an oxygen concentration (oxygen partial pressure) in the third chamber 61 and the oxygen concentration (oxygen partial pressure) of the reference gas. Since the oxygen concentration (oxygen partial pressure) of the reference gas is basically constant, the electromotive force V2 has a value in accordance with the oxygen concentration (oxygen partial pressure) in the third chamber 61.
The sensor element 101 further includes an electrochemical sensor cell 83 including the outer pump electrode 23, the reference electrode 42, and a solid electrolyte present in a portion of the structure 14 sandwiched between these electrodes.
Electromotive force Vref generated between the outer pump electrode 23 and the reference electrode 42 of the sensor cell 83 has a value in accordance with oxygen partial pressure of the measurement gas present outside the sensor element 101.
In addition to the foregoing, the sensor element 101 includes a heater part 70 playing a role in temperature adjustment of heating the sensor element 101 and maintaining the temperature thereof to enhance oxygen ion conductivity of the solid electrolyte forming the structure 14.
The heater part 70 mainly includes a heater electrode 71, a heater element 72, a heater lead 72a, a through hole 73, a heater insulating layer 74, and a heater resistance detection lead, which is not illustrated in
The heater 72 is provided to be sandwiched between the second substrate 2 and the third substrate 3 from below and above and generates heat by being powered from outside through the heater electrode 71 provided on a lower surface 1b of the first substrate 1, the through hole 73, and the heater lead 72a. The heater 72 is buried over the entire region of a range from the buffer space 12 to the third chamber 61 and can heat the sensor element 101 to a predetermined temperature and, further, maintain the temperature.
The heater 72 is provided so that a temperature is highest near the first chamber 20 (near the adjustment electrode 22) and decreases with increasing distance from the first chamber 20 in the longitudinal direction of the element during heating. In the present embodiment, a temperature in a range from the one end portion of the sensor element 101 in which the gas inlet 10 is disposed to the third chamber 61 when the gas sensor 100 is in use (when the sensor element 101 is driven) is referred to as an element driving temperature. The heater 72 performs heating so that the element driving temperature is in a range of 750° C. to 950° C.
The heater insulating layer 74 of alumina and the like is formed above and below the heater 72 to electrically insulate the heater 72 from the second substrate 2 and the third substrate 3. The heater part 70 also includes a pressure dissipation hole 75. The pressure dissipation hole 75 is a part provided to penetrate the third substrate 3 and communicate with the reference gas introduction space 43 and is provided to mitigate a rise in internal pressure associated with a rise in temperature in the heater insulating layer 74.
The gas sensor 100 further includes a controller 110 controlling operation of the sensor element 101 and performing processing to identify concentrations of the sensing target gas components based on currents flowing through the sensor element 101.
When the gas sensor 100 is attached to the exhaust path of the engine of the vehicle and is used with the exhaust gas flowing along the exhaust path as the measurement gas, some or all of functions of the controller 110 may be implemented by an electronic control unit (ECU) of the vehicle.
The controller 110 includes, as functional components implemented by the CPU executing a predetermined program, an element operation control part 120 controlling operation of each part of the sensor element 101 described above and a concentration identification part 130 performing processing to identify the concentrations of the sensing target gas components contained in the measurement gas.
The element operation control part 120 mainly includes an adjustment pump cell control part 121 controlling operation of the adjustment pump cell 21, a first measurement pump cell control part 122a controlling operation of the first measurement pump cell 50, a second measurement pump cell control part 122b controlling operation of the second measurement pump cell 41, and a heater control part 123 controlling heating operation performed by the heater 72.
On the other hand, the concentration identification part 130 mainly includes a water vapor concentration identification part 130H and a carbon dioxide concentration identification part 130C respectively identifying a concentration of H2O and a concentration of CO2 as the main sensing target gas components of the gas sensor 100.
The water vapor concentration identification part 130H identifies the concentration of H2O contained in the measurement gas based on a value of the oxygen pump current Ip2 flowing through the second measurement pump cell 41 acquired by the second measurement pump cell control part 122b.
The carbon dioxide concentration identification part 130C identifies the concentration of CO2 contained in the measurement gas based on the concentration of H2O identified by the water vapor concentration identification part 130H (the value of the oxygen pump current Ip2 based on which the concentration of H2O is identified) and a value of the oxygen pump current Ip1 flowing through the first measurement pump cell 50 acquired by the first measurement pump cell control part 122a.
The concentration identification part 130 further includes an oxygen concentration identification part 130A identifying a concentration of oxygen contained in the measurement gas. The oxygen concentration identification part 130A identifies the concentration of oxygen contained in the measurement gas based on a value of the oxygen pump current Ip0 flowing through the adjustment pump cell 21 acquired by the adjustment pump cell control part 121. That is to say, the gas sensor 100 according to the present embodiment senses, in addition to H2O and CO2 as the main sensing target gas components, oxygen as an appendant sensing target gas component.
A method of sensing a plurality of types of gases (multi-gas sensing) and identifying concentrations of the sensed gases implemented by the gas sensor 100 having a configuration as described above will be described next. Assume hereinafter that the measurement gas is an exhaust gas containing oxygen, H2O, and CO2.
First, in the sensor element 101 of the gas sensor 100 according to the present embodiment, the measurement gas is introduced through the gas inlet 10 (first diffusion control part 11), the buffer space 12, and the second diffusion control part 13 into the first chamber 20 as described above. In the first chamber 20, oxygen is pumped out of the introduced measurement gas by operation of the adjustment pump cell 21.
Pumping-out of oxygen is performed in the way that the adjustment pump cell control part 121 of the controller 110 sets a target value (control voltage) of the electromotive force V0 in the first chamber sensor cell 80 to a value in a range of 400 mV to 700 mV (preferably 400 mV) and feedback-controls the voltage Vp0 applied from the variable power supply 24 to the adjustment pump cell 21 in accordance with a difference between an actual value and the target value of the electromotive force V0 so that the electromotive force V0 is maintained at the target value. A value of the electromotive force V0 significantly deviates from the target value when the measurement gas containing a large amount of oxygen reaches the first chamber 20, for example, and thus the adjustment pump cell control part 121 controls the pump voltage Vp0 applied from the variable power supply 24 to the adjustment pump cell 21 so that the deviation is reduced.
The adjustment pump cell 21 pumps out oxygen from the first chamber 20 in such a manner, so that oxygen partial pressure in the first chamber 20 is maintained at a sufficiently low value to the extent that H2O and CO2 contained in the measurement gas are not reduced. It is approximately 10−8 atm when an equation V0=400 mV holds true, for example.
It can be seen from
As such, the target value of the electromotive force V0 is set to the value in the range of 400 mV to 700 mV in the present embodiment. In view of securing durability of the electrode, the electromotive force V0 is preferably as low as possible, and thus it is determined that the target value of the electromotive force V0 is preferably 400 mV.
As described above, in the gas sensor 100 according to the present embodiment, only pumping-out of oxygen to the extent that H2O and CO2 are not reduced is performed in the first chamber 20 to be at a highest temperature in the sensor element 101 during operation, and reduction of H2O and CO2 is not performed, in contrast to a gas sensor in conventional technology. The target value of the electromotive force V0 in the first chamber sensor cell 80 set for pumping-out is 400 mV to 700 mV, which is sufficiently smaller than a target value of 1000 mV to 1500 mV set when H2O and CO2 are reduced. An increase in pump voltage Vp0 is thus suppressed compared with a voltage applied to a corresponding pump cell in the gas sensor in conventional technology accompanied by reduction of H2O and CO2. Cracking and blackening attributable to application of a high voltage with the inner pump electrode 22 being maintained at a high temperature are thus suitably suppressed in the gas sensor 100 according to the present embodiment.
The measurement gas of which only oxygen has been pumped out in the first chamber 20 to the extent that H2O and CO2 are not reduced is introduced into the second chamber 40. H2O and CO2 contained in the measurement gas are reduced in the second chamber 40. That is to say, oxygen is further pumped out of the measurement gas of which oxygen has been pumped out in the first chamber 20 and which is then introduced into the second chamber 40 by operation of the first measurement pump cell 50, so that a reduction (decomposition) reaction (2H2O→2H2+O2 and 2CO2→2CO+O2) of H2O and CO2 contained in the measurement gas progresses, and substantially all H2O and CO2 are decomposed into hydrogen (H2), carbon monoxide (CO), and oxygen.
Reduction (decomposition) of H2O and CO2 and pumping-out of oxygen are performed in the way that the first measurement pump cell control part 122a of the controller 110 sets a target value (control voltage) of the electromotive force V1 in the second chamber sensor cell 81 to a value in a range of 1000 mV to 1500 mV (preferably 1000 mV) and feedback-controls the voltage Vp1 applied from the variable power supply 52 to the first measurement pump cell 50 in accordance with a difference between an actual value and the target value of the electromotive force V1 so that the electromotive force V1 is maintained at the target value. It is also suggested from the graph of
The first measurement pump cell 50 operates in this manner, so that oxygen partial pressure in the second chamber 40 is maintained at a much lower value than oxygen partial pressure in the first chamber 20. It is approximately 10−20 atm when an equation V1=1000 mV holds true, for example. The measurement gas thus no longer substantially contains H2O, CO2, and oxygen.
The measurement gas containing H2 and CO while not substantially containing H2O, CO2, and oxygen is introduced into the third chamber 61.
In the third chamber 61, oxygen is pumped in by operation of the second measurement pump cell 41, and only H2 contained in the introduced measurement gas is selectively oxidized.
Pumping-in of Oxygen is performed in the way that the second measurement pump cell control part 122b of the controller 110 sets a target value (control voltage) of the electromotive force V2 in the third chamber sensor cell 82 to a value in a range of 250 mV to 450 mV (preferably 350 mV) and feedback-controls the voltage Vp2 applied from the variable power supply 46 to the second measurement pump cell 41 in accordance with a difference between an actual value and the target value of the electromotive force V2 so that the electromotive force V2 is maintained at the target value.
The second measurement pump cell 41 operates in this manner, so that an oxidation (a combustion) reaction 2H2+O2→2H2O is facilitated, and H2O in an amount correlating with the amount of H2O introduced through the gas inlet 10 is generated again in the third chamber 61. In the present embodiment, H2O in the correlating amount means that the amount of H2O introduced through the gas inlet 10 and the amount of H2O generated again by oxidation of H2 generated by decomposition of H2O are the same or are within a certain error range allowable in terms of measurement accuracy.
The target value of the electromotive force V2 is set to the value in the range of 250 mV to 450 mV, so that oxygen partial pressure in the third chamber 61 is maintained at a value in a range in which almost all H2 is oxidized but CO is not oxidized. It is approximately 10−7 atm when an equation V2=350 mV holds true, for example.
Providing the second measurement electrode 44 as the cermet electrode containing the Pt—Au alloy having an Au concentration of 1 wt % or more and 50 wt % or less as the metal component as described above also contributes to improvement in selective H2 oxidation property.
In the gas sensor in conventional technology, the cermet electrode containing the Pt—Au alloy is provided in the second chamber 40, and the pump cell including the electrode pumps in oxygen for selective oxidation of H2, but, herein, the first measurement electrode 51 not containing Au as the metal component is provided in the second chamber 40, and the second measurement electrode 44 containing the Pt—Au alloy as the metal component and being responsible for selective oxidation of H2 is provided to face the third chamber 61 at a lower temperature than the second chamber 40 during operation of the gas sensor 100. Thus, in the gas sensor 100 according to the present embodiment, evaporation of Au from the electrode is suppressed compared with that in the gas sensor in conventional technology.
In addition, any measures to devise a shape (a width and a thickness), placement (a density), and the like of the heater 72 may be taken to further suppress a rise in temperature of the second measurement electrode 44.
In the gas sensor 100 according to the present embodiment operating in the above-mentioned manner, the concentrations of H2O and CO2 in the measurement gas are identified based on the oxygen pump current Ip1 flowing through the first measurement pump cell 50 during pumping-out of oxygen including reduction of H2O and CO2 and the oxygen pump current Ip2 flowing through the second measurement pump cell 41 during pumping-in of oxygen for oxidation of H2.
In
As can be seen from
Furthermore, a value of the oxygen pump current Ip1 when H2O and CO2 having equal concentrations are contained as the sensing target gas components is the sum of a value of the oxygen pump current Ip1 when H2O alone is contained and a value of the oxygen pump current Ip1 when CO2 alone is contained. It has also been confirmed that a value of the oxygen pump current Ip1 when H2O and CO2 have different proportions is the sum of a value of the oxygen pump current Ip1 when H2O alone having a concentration in accordance with its proportion is contained and a value of the oxygen pump current Ip1 when CO2 alone having a concentration in accordance with its proportion is contained, although it is not shown.
On the other hand, as shown in
In contrast, a value of the oxygen pump current Ip2 when only CO2 is contained as a sensing target gas component is maintained approximately zero. This indicates that CO generated by reduction in the second chamber 40 is not oxidized again by operation of the second measurement pump cell 41.
A graph of the oxygen pump current Ip2 when H2O and CO2 having equal concentrations are contained as the sensing target gas components substantially coincides with the graph of the oxygen pump current Ip2 when H2O alone is contained. This is consistent with the oxygen pump current Ip2 of approximately zero when only CO2 is contained as the sensing target gas component. It has also been confirmed that a value of the oxygen pump current Ip2 when H2O and CO2 have different proportions substantially coincides with the graph of the oxygen pump current Ip2 when H2O alone is contained and the graph of the oxygen pump current Ip2 when CO2 alone is contained, although it is not shown. This means that the oxygen pump current Ip2 virtually depends only on the concentration of H2O, and thus the concentration of H2O can be identified once the oxygen pump current Ip2 is known.
In the present embodiment, the concentrations of H2O and CO2 in the measurement gas are measured using properties of the oxygen pump current Ip1 and the oxygen pump current Ip2 as described above. The oxygen pump current Ip1 and the oxygen pump current Ip2 during actual measurement using the gas sensor 100 are hereinafter also referred to as a total reducing current Ip1 and a water vapor equivalent current Ip2.
Specifically, prior to use of the gas sensor 100, characteristics data showing a relationship between the oxygen pump current Ip1 and a concentration of each gas when the measurement gas contains only one of H2O and CO2 and does not contain the other one of H2O and CO2 as shown in
The oxygen pump current Ip1 has a value in accordance with diffusion resistance provided to the measurement gas from the gas inlet 10 to the second chamber 40 of the sensor element 101, and the oxygen pump current Ip2 has a value in accordance with diffusion resistance provided to the measurement gas from the gas inlet 10 to the third chamber 61 of the sensor element 101. The Ip1-H2O data, the Ip1-CO2 data, and the Ip2-H2O data thus strictly vary with each sensor element 101 of the gas sensor 100. These pieces of characteristics data are thus preferably identified for each gas sensor 100. As for gas sensors 100 manufactured under the same condition and from the same lot, however, characteristics data acquired for one particular gas sensor 100 may be applied to another gas sensor 100 from the same lot when it is confirmed that an error is within tolerance.
When actual measurement is performed using the gas sensor 100, the measurement gas is introduced into the sensor element 101 heated to the element driving temperature, and the adjustment pump cell 21, the first measurement pump cell 50, and the second measurement pump cell 41 operate in the above-mentioned manner. The water vapor concentration identification part 130H acquires the water vapor equivalent current Ip2 from the second measurement pump cell control part 122b and identifies a concentration of H2O corresponding to the acquired value based on the Ip2-H2O data.
Once the concentration of H2O is identified, the carbon dioxide concentration identification part 130C acquires a value of the total reducing current Ip1 from the first measurement pump cell control part 122a and identifies a contribution of H2O having the identified concentration in the total reducing current Ip1, that is, the amount of current due to reduction of H2O in the total reducing current Ip1 based on the Ip1-H2O data. The acquired value is subtracted from the value of the total reducing current Ip1 to identify a contribution of CO2 in the total reducing current Ip1. A concentration of CO2 corresponding to the contribution of CO2 is finally identified based on the Ip1-CO2 data.
In the gas sensor 100 according to the present embodiment, the concentrations of H2O and CO2 in the measurement gas are measured as described above.
Alternatively, a relationship between the water vapor equivalent current Ip2 and the oxygen pump current Ip1 corresponding to the contribution of H2O in the total reducing current Ip1 may be identified in advance, characteristics data (hereinafter referred to as H2O characteristics data) indicating the relationship may be stored in the controller 110, and the carbon dioxide concentration identification part 130C may identify the contribution of H2O in the total reducing current Ip1 directly from the water vapor equivalent current Ip2 using the H2O characteristics data.
Alternatively, a value of the y intercept of the relation should theoretically be zero and, in a case of the gas sensor 100 operating normally, is a value small enough to actually be considered zero. Thus, only the slope of the relation expressing the above-mentioned linear relationship may be stored in the controller 110 as the H2O characteristics data, and the carbon dioxide concentration identification part 130C may use the product of the value of the slope and the water vapor equivalent current Ip2 as the contribution of H2O in the total reducing current Ip1.
The slope in the H2O characteristics data corresponds to a ratio of the diffusion resistance provided to the measurement gas from the gas inlet 10 to the third chamber 61 to the diffusion resistance provided to the measurement gas from the gas inlet 10 to the second chamber 40.
The concentration of oxygen is identified using the oxygen pump current Ip0 flowing through the adjustment pump cell 21 in parallel with identification of the concentrations of H2O and CO2.
In the gas sensor 100 according to the present embodiment, oxygen is pumped out of the measurement gas introduced through the gas inlet 10 in the first chamber 20 by operation of the adjustment pump cell 21 as described above. Oxygen is pumped out to the extent that H2O and CO2 are not reduced, and the oxygen pump current Ip0 (hereinafter also referred to as an oxygen detection current Ip0) flowing in this case is substantially proportional to the concentration of oxygen contained in the measurement gas introduced through the gas inlet 10. That is to say, there is a linear relationship between the oxygen detection current Ip0 and the concentration of oxygen in the measurement gas. Data (Ip0-O2 data) indicating the linear relationship is identified in advance using model gases having known oxygen concentrations and is stored in the controller 110.
During actual measurement using the gas sensor 100, the oxygen concentration identification part 130A acquires a value of the oxygen detection current Ip0 from the adjustment pump cell control part 121. A value of the concentration of oxygen corresponding to the acquired oxygen detection current Ip0 is identified with reference to the Ip0-O2 data. The concentration of oxygen in the measurement gas is thereby identified.
As described above, in the gas sensor according to the present embodiment, the concentrations of H2O and CO2 can be measured when the measurement gas contains H2O and CO2 as in a conventional gas sensor. Furthermore, the concentration of oxygen can also accurately be obtained.
In addition, in a case of the gas sensor according to the present embodiment, H2O and CO2 are not reduced in the first chamber to be at a highest temperature during operation in contrast to the gas sensor in conventional technology, so that a voltage applied to the adjustment pump cell pumping out oxygen from the first chamber is suppressed to be lower than that in the gas sensor in conventional technology, thereby to suitably suppress cracking and blackening of the sensor element.
An electrode disposed in a chamber as an electrode containing a Pt—Au alloy as a metal component is only the second measurement electrode provided in the third chamber, and the electrode containing the Pt—Au alloy is not provided in the first chamber and the second chamber to be at a higher temperature than the third chamber, so that evaporation of Au from the electrode is suppressed compared with that in conventional technology.
That is to say, according to the present embodiment, a multi-gas sensor with more long-term reliability than before is implemented.
In the gas sensor 100 according to the above-mentioned embodiment, the sensor element 101 includes the gas distribution part including the first chamber 20, the second chamber 40, and the third chamber 61 communicating via the diffusion control parts. With respect to the measurement gas introduced sequentially into the chambers of the gas distribution part under predetermined diffusion resistance, the adjustment pump cell 21 pumps out oxygen to the extent that H2O and CO2 are not reduced in the first chamber 20, the first measurement pump cell 50 is used to reduce H2O and CO2 in the second chamber 40, and the second measurement pump cell 41 is used to selectively oxidize H2 generated by reduction of H2O in the third chamber 61. As a result, the concentrations of H2O and CO2 and further the concentration of oxygen in the measurement gas are measured based on the magnitudes of the currents flowing through the respective pump cells.
Such measurement using the gas sensor 100 is considered to be implemented by suppression of a flow of the measurement gas from outside the element into the first chamber 20 using the first diffusion control part 11 and the second diffusion control part 13, suppression of a flow of the measurement gas in which oxygen remains from the first chamber 20 into the second chamber 40 using the third diffusion control part 30, and further suppression of a flow of the measurement gas in which H2O and CO2 remain from the second chamber 40 into the third chamber 61 using the fourth diffusion control part 60. That is to say, it can be said that the measurement gas reaching the inner pump electrode 22 of the adjustment pump cell 21, the first measurement electrode 51 of the first measurement pump cell 50, and the second measurement electrode 44 of the second measurement pump cell 41 is suitably controlled by the respective diffusion control parts so that gases not targeted for operation in the respective pump cells do not reach the respective electrodes, thereby to enable multi-gas sensing using the gas sensor 100.
Viewed another way, this means that a configuration different from the configuration of the gas distribution part of the sensor element 101 can be adopted as long as pumping-out of oxygen to the extent that H2O and CO2 are not reduced using the adjustment pump cell 21, reduction of H2O and CO2 using the first measurement pump cell 50, and selective oxidation of H2 generated by reduction of H2O using the second measurement pump cell 41 with respect to the measurement gas reaching the inner pump electrode 22, the first measurement electrode 51, and the second measurement electrode 44 are performed successfully in view of securing measurement accuracy. For example, even a configuration in which the three chambers communicating via the diffusion control parts are not included can be adopted to implement multi-gas sensing.
The sensor element 201 is an elongated planar structure including a laminate of a sensor part 214 and a heater part 270.
The sensor part 214 is formed by laminating a plurality of substrate layers of ceramics. Specifically, the sensor part 214 has a configuration in which four layers including a first substrate 203, a second substrate 204, a third substrate 205, and a fourth substrate 206 are sequentially laminated from the bottom. From among them, at least the second substrate 204 is formed of an oxygen-ion conductive solid electrolyte, such as zirconia. The first substrate 203, the third substrate 205, and the fourth substrate 206 may be formed of a solid electrolyte or may be formed of an insulating material, such as alumina. In the sensor part 214, the first substrate 203 is adjacent to the heater part 270.
A gas inlet 210 through which a measurement gas is introduced is provided in one end portion (a left end portion in the figure) of the sensor part 214. More specifically, a diffusion control part 211 formed of a porous body having a porosity of approximately 10% to 50% is buried in one end portion of the third substrate 205, and an exposed portion in one end portion of the diffusion control part 211 is the gas inlet 210. The diffusion control part 211 has a length (size in the longitudinal direction of the element) of 0.5 mm to 1.0 mm, for example, a width (size in a transverse direction of the element) of 1.5 mm to 3 mm, for example, and a height (size in a thickness direction of the element) of 10 μm to 20 μm, for example.
The sensor part 214 also includes a single internal chamber 220 adjacent to the diffusion control part 211. The internal chamber 220 is formed to penetrate the third substrate 205 in the thickness direction. The internal chamber 220 has a length (size in the longitudinal direction of the element) of 6.0 mm to 12.0 mm, for example, a width (size in the transverse direction of the element) of 1.5 mm to 2.5 mm, for example, and a height (size in the thickness direction of the element) of 50 μm to 200 μm, for example.
That is to say, it can be said that the diffusion control part 211 and the internal chamber 220 constitute the gas distribution part communicating with the gas inlet 210 in the sensor element 201.
An adjustment electrode 230, a first measurement electrode 240, and a second measurement electrode 250 are arranged on an exposed surface 204a of the second substrate 204 to the internal chamber 220 in order of proximity to the gas inlet 210 on a left side in the figure to face the internal chamber 220 while being spaced apart at predetermined intervals. They are provided as porous cermet electrodes similar to the inner pump electrode (adjustment electrode) 22, the first measurement electrode 51, and the second measurement electrode 44 of the sensor element 101.
The sensor part 214 further includes a reference gas introduction space 260 opening in the other end portion of the sensor element 201. The reference gas introduction space 260 is formed to penetrate the first substrate 203 in the thickness direction. Oxygen (O2) and air are introduced into the reference gas introduction space 260 as reference gases, for example.
A reference electrode 261 is provided on an exposed surface 204b of the second substrate 204 to the reference gas introduction space 260. The reference electrode 261 is preferably provided over an entire range of arrangement of the adjustment electrode 230, the first measurement electrode 240, and the second measurement electrode 250 provided on the exposed surface 204a opposite the exposed surface 204b. The reference electrode 261 is provided as a porous cermet electrode containing platinum and zirconia and being rectangular in plan view, for example.
As with the heater part 70 of the sensor element 101, the heater part 270 is configured to heat the sensor element 201 to a predetermined temperature and, further, maintain the temperature by powering of the heater element 272 (also simply referred to as a heater 272) from outside the element. A configuration similar to the configuration of the heater part 70 of the sensor element 101 is applicable to the heater part 270. Alternatively, a configuration in which the heater element 272 is buried in an insulator may be used.
The heater 272 is provided so that a temperature is highest near the adjustment electrode 230 and decreases with increasing distance from the adjustment electrode 230 in the longitudinal direction of the element during heating.
In addition, the sensor element 201 includes an adjustment pump cell CO, a first measurement pump cell C1, and a second measurement pump cell C2.
The adjustment pump cell CO is an electrochemical pump cell including the adjustment electrode 230, the reference electrode 261, and the second substrate 204 sandwiched between these electrodes. In the adjustment pump cell CO, the voltage Vp0 is applied across the adjustment electrode 230 and the reference electrode 261 from a variable power supply 231 disposed outside the sensor element 201 to generate the oxygen pump current (oxygen ion current) Ip0. Operation of the adjustment pump cell CO is controlled by the adjustment pump cell control part 121 of the controller 110.
The first measurement pump cell C1 is an electrochemical pump cell including the first measurement electrode 240, the reference electrode 261, and the second substrate 204 sandwiched between these electrodes. In the first measurement pump cell C1, the voltage Vp1 is applied across the first measurement electrode 240 and the reference electrode 261 from a variable power supply 241 disposed outside the sensor element 201 to generate the oxygen pump current (oxygen ion current) Ip1. Operation of the first measurement pump cell C1 is controlled by the first measurement pump cell control part 122a of the controller 110.
The second measurement pump cell C2 is an electrochemical pump cell including the second measurement electrode 250, the reference electrode 261, and the second substrate 204 sandwiched between these electrodes. In the second measurement pump cell C2, the voltage Vp2 is applied across the second measurement electrode 250 and the reference electrode 261 from a variable power supply 251 disposed outside the sensor element 201 to generate the oxygen pump current (oxygen ion current) Ip2. Operation of the second measurement pump cell C2 is controlled by the second measurement pump cell control part 122b of the controller 110.
As described above, in the sensor element 201, the adjustment electrode 230, the first measurement electrode 240, and the second measurement electrode 250 are arranged in the single internal chamber 220 in contrast to the sensor element 101 of the gas sensor 100. Nevertheless, the diffusion control part 211 and the internal chamber 220 are provided on a condition as described above to suitably provide diffusion resistance to the measurement gas introduced into the internal chamber 220, in other words, to suitably control a flow rate of the measurement gas, and therefore, multi-gas sensing with at least water vapor (H2O) and carbon dioxide (CO2) as the main sensing target gas components is enabled also in the gas sensor 200 including the sensor element 201 under control performed by the controller 110 as in the gas sensor 100.
Specifically, the measurement gas introduced from the gas inlet 210 into the internal chamber 220 through the diffusion control part 211 sequentially reaches the adjustment electrode 230, the first measurement electrode 240, and the second measurement electrode 250. The adjustment pump cell CO performs operation to pump oxygen out of the measurement gas having reached the adjustment electrode 230 to the extent that H2O and CO2 are not reduced. The first measurement pump cell C1 performs operation to pump out oxygen to reduce H2O and CO2 contained in the measurement gas having reached the first measurement electrode 240. The second measurement pump cell C2 performs operation to pump in oxygen to selectively oxidize H2 generated by reduction of H2O performed by the first measurement pump cell C1 and having reached the second measurement electrode 250.
In this case, the measurement gas flows at a flow rate at which the measurement gas of which oxygen has not been pumped out does not pass through the adjustment electrode 230 and the measurement gas in which H2O and CO2 remain does not pass through the first measurement electrode 240, so that a current flowing through each pump cell is equivalent to a current flowing through each pump cell of the gas sensor 100. Thus, in the gas sensor 200, the water vapor concentration identification part 130H, the carbon dioxide concentration identification part 130C, and further the oxygen concentration identification part 130A can accurately identify the concentrations of H2O, CO2, and further oxygen in the measurement gas as in the gas sensor 100.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-151158 | Sep 2022 | JP | national |
This application is a continuation application of PCT/JP2023/029979, filed on Aug. 21, 2023, which claims the benefit of priority of Japanese application No. JP2022-151158, filed on Sep. 22, 2022, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2023/029979 | Aug 2023 | WO |
| Child | 19082523 | US |
