The present invention relates to a catalytic combustion typed gas sensor to be used for detecting a combustible gas.
Recently, much attention has been paid on a fuel cell using a combustible gas like hydrogen as a fuel of a clean energy source. Hereby, a fuel cell vehicle equipped with a fuel cell as the energy source is being developed for driving a vehicle. Therefore, a fuel cell vehicle is equipped with a gas sensor for detecting leakage of a combustible gas, assuming the case that such a combustible gas like hydrogen happens to leak.
Here, a catalytic typed gas sensor having a simple structure and being easily downsized is generally used as a gas sensor. It is known that as for such a catalytic typed gas sensor, if a vapor of a silicone compound is contained in the atmosphere of the operating environment, detection sensitivity of the sensor becomes deteriorated with times (that is, via silicon (Si) poisoning).
Therefore, a conventional catalytic typed gas sensor directly covers a detection element, which is poisoned by silicon, with a silicon trap layer (for example, see Patent Document 1).
Patent Document 1: International Patent Publication No. WO 2007/099933 pamphlet.
A conventional catalytic typed gas sensor tends to make a silicone compound contained in the atmosphere only adhere to a silicon trap layer. Thus, it has been thought that an adhesion amount of the silicone compound has limitations. Hereby, it has been further thought that although a period until the detection sensitivity becomes deteriorated may be elongated, the actual detection sensitivity of the sensor eventually can not be prevented from being deteriorated.
Further, a detection element is covered with a silicon trap layer, which results in the increase in the heat capacity of the detection sensor, thereby to hardly make the temperature of the detection element be raised. In this way, it has been considered that the detection sensitivity eventually becomes deteriorated.
For solving the drawback as mentioned above, an object of the present invention is to provide a catalytic type of a gas sensor capable of suppressing the deterioration of the detection sensor.
According to the present invention, heat generation by combustion of a combustible gas when the combustible gas contacts to a catalytic metal that is heated by passing electric current through the catalytic metal raises the temperature and the electric resistance of the catalytic metal. That resulting raised electric resistance allows the catalytic combustion typed gas sensor to detect the combustible gas having a concentration equal to or more than a predetermined gas concentration.
Herein, the electric current is made to pass through the catalytic metal such that the standby temperature is set at the temperature calculated by subtracting the resulting raised temperature portion from the desorption temperature. Herein, the resulting raised temperature portion is generated by the combustion heat when the combustible gas having the predetermined concentration contacts to the catalytic metal. The catalytic metal adsorbs a silicone compound via a silicon poisoning process and desorbs the adsorbed silicone compound at the desorption temperature.
The above mentioned procedure enables the detection element to be constructed by using the catalytic metal. Further, the present inventors have demonstrated that a desorption temperature exists at which an adsorbate (or silicone compound) adsorbed through the silicon poisoning process to the catalytic metal (or detection element) is to be desorbed from the detection element. Moreover, the present inventors have demonstrated that the desorption temperature is in the range from 350° C. to 600° C. Within the range of the desorption temperature, the higher the temperature is, the easier the detection sensitivity is recovered. When the temperature of the catalytic metal (or detection element) reaches the desorption temperature, the adsorbate (or silicone compound) is desorbed, allowing the deteriorated detection sensitivity to be recovered.
Furthermore, the standby temperature is set at the temperature calculated by subtracting the raised temperature portion from the desorption temperature. Herein, the raised temperature portion is generated by the combustion heat when the combustible gas having the predetermined concentration contacts to the catalytic metal (or detection element). Accordingly, whenever the concentration of the combustion gas in the atmosphere reaches the predetermined concentration, a temperature of the catalytic metal (or detection element) may reach the desorption temperature. This allows the detection sensitivity of the catalytic combustion typed gas sensor to be recovered. Further, such a recovery allows the detection sensitivity to be prevented from being deteriorated.
Further, according to the present invention, it is preferable to set the desorption temperature in the range from more than 350° C. to 600° C. or less.
This temperature setting allows the detection sensitivity to be recovered whenever the concentration of the combustible gas in the atmosphere reaches the predetermined concentration for detecting the combustible gas.
Further, in the present invention, it is preferable to arrange the catalytic combustion typed gas sensor in the atmosphere in which the concentration of the silicone compound is higher than in the air. Moreover, it is also preferable to set the standby temperature in the range from substantially 100° C. or more to substantially 350° C. or less.
According to the above mentioned construction, the catalytic combustion typed gas sensor is arranged in the atmosphere having a higher concentration of the silicone compound than in the air. This allows the catalytic combustion typed gas sensor to be arranged inside an off-gas pipe from which an off-gas is discharged; the off-gas flowing from a fuel cell of a fuel cell vehicle. The reason is based on the fact that not a small amount of a silicone compound is used in a fuel cell. The predetermined concentration for detecting the combustible gas is set at a high concentration inside the off-gas pipe. Such setting of the high concentration increases the raised temperature portion to 250° C. at the detection timing, allowing the standby temperature to be lowered to 350° C., even though the temperature reaches 600° C. at the detection timing. Similarly, the setting of the high concentration enables the standby temperature to be lowered to 100° C., even though the temperature reaches 350° C. at the detection timing.
Moreover, in the present invention, it is preferable to arrange the catalytic combustion typed gas sensor in the air and set the standby temperature in the range from substantially 270° C. or more to substantially 520° C. or less.
According to the above mentioned conditions, since the catalytic combustion typed gas sensor is arranged in the air, similarly the catalytic combustion typed gas sensor may be also arranged, for example, at the surroundings of a fuel cell and a hydrogen tank, disposed under a floor panel of a fuel cell vehicle or inside a cabin thereof. This may be explained by the fact that the silicone compound is not used more remarkably at the areas under a floor panel and inside a cabin than at other areas.
Further, the predetermined concentration for detecting a combustible gas is set at a low concentration, under a floor panel and inside a cabin. If the predetermined concentration is set at a low concentration, a raised temperature portion at the detection timing is lowered to 80° C. This allows the standby temperature to be raised up to 520° C. at the detection timing, even though the temperature reaches 600° C. at the detection timing, and similarly the standby temperature to be raised up to 270° C. at the detection timing, even though the temperature reaches 350° C. at the detection timing.
Further, in the present invention, it is preferable to pass electric current through the catalytic metal such that a temperature of the catalytic metal is set in the range from 350° C. to 600 C ° at least at either of a startup period and a shutdown period.
The procedure enables the detection sensitivity to be recovered whenever the catalytic combustion typed gas sensor starts or stops the operation.
Further, in the present invention, it is preferable to arrange the catalytic combustion typed gas sensor in an off-gas discharge pipe from which the air supplied to a cathode of a fuel cell is discharged.
The construction enables hydrogen included in the off-gas discharge pipe to be detected.
Further, in the present invention, it is preferable to equip a fuel cell vehicle with the catalytic combustion typed gas sensor.
This construction enables the detection of hydrogen leaked into a fuel cell vehicle.
According to the present invention, provided is a catalytic combustion typed gas sensor which prevents the detection sensitivity of the sensor from being deteriorated.
Next, embodiments of the present invention will be explained in detail referring to the attached drawings. Note the same reference numerals are used for the common parts to omit the duplicated explanations.
The fuel cell 2a comprises, for example, an electrolyte film made of a solid polymer, electrode catalytic layers (that is, anode and cathode), and an MEA (Membrane Electrode Assembly) formed by stacking gas diffusion layers. Further, the fuel cell 2a has a structure formed by stacking a plurality of single cells, each of which is made by holding the both surfaces of the membrane electrode assembly with conductive separators, in a thickness direction of the cell (that is, in a longitudinal direction of the vehicle of the present embodiment). Further, passages are formed respectively in the separator facing against the anode and the cathode. Herein, hydrogen flows into one passage of the separator for the anode, and the air flows into the other passage of the separator for the cathode. Moreover, a through hole or the like is also formed for connecting the separators each other. The electrolyte membrane has a backbone made of a silicone resin containing silicon (Si) (that is, silicone compound).
Here, in such a fuel cell 2a, hydrogen supplied via a hydrogen supply pipe 7 from the hydrogen tank 6 to the separator at the anode side is diffused by a gas diffusion layer to be supplied to the anode. Similarly, the air (or oxygen) supplied from an air compressor to the separator at the cathode side is diffused by the gas diffusion layer to be supplied to the cathode. In the anode, hydrogen is separated into a hydrogen ion and an electron by the catalytic reaction, whereby the hydrogen ion reaches the cathode through the electrolyte membranes. Then, in the cathode, the hydrogen ion reaching therein through the membrane by the catalytic reaction, the electron transferred to the cathode through the outside load, and oxygen in the supplied air generate water via the electrochemical reaction. The air supplied from the air compressor includes the generated water, resulting in being discharged outside through an off-gas discharge pipe 3.
Since hydrogen is a combustible gas, the fuel cell vehicle 1 is equipped with a plurality of catalytic combustion typed gas sensors 8 such that leakage of the hydrogen may be detected if the leakage of the hydrogen occurs. The catalytic combustion typed gas sensor 8a (or 8) is arranged on a cabin top 4a in the cabin 4. If hydrogen leaks to inside the cabin 4, the hydrogen stays near the cabin top 4a since hydrogen is lighter than the air.
Further, the catalytic combustion typed gas sensor 8b (or 8) is arranged directly under the most upper portion of a center console 5a over the fuel cell 2a and the accessory 2b. The catalytic combustion typed gas sensor 8c (or 8) is arranged over the hydrogen tank 6 and directly below the floor panel 5. The catalytic combustion typed gas sensor 8d (or 8) is arranged such that a detection unit 15 (or detection element 13) described hereinafter (see
The atmosphere in which the catalytic combustion typed gas sensors 8a, 8b and 8c detect the leaked hydrogen after the hydrogen has been diffused into the air to have a low concentration. Accordingly, the gas sensors are set up such that the sensors are capable of detecting the leaked hydrogen at a low concentration. The atmosphere in which the catalytic combustion typed gas sensors 8a, 8b and 8c are placed is identical to the air. Further, the concentration of the silicone compound in the atmosphere is almost the same as the concentration of the silicone compound in the air. Herein, those concentrations are assumed to be low.
The leaked hydrogen inside the fuel cell 2a and the accessory 2b is not diffused in the air and flows into the inside of the off-gas discharge pipe 3. Therefore, the catalytic combustion typed gas sensor 8d is set such that the gas sensor 8d may detect hydrogen having a high concentration. Further, the atmosphere in which the catalytic combustion typed gas sensor 8d is placed is estimated to contact with members containing a large amount of the silicone compound in the fuel cell 2a and the accessory 2b. Accordingly, it is estimated that the atmosphere contains a large amount of the silicone compound evaporated from the members.
The catalytic combustion typed gas sensor 8 is equipped with a substrate 12 and a housing 11 that covers the substrate 12. In the substrate 12, totally 4 electrodes composed of 2 pairs of the electrodes 19 are placed as standing thereon at the lower portion of the substrate 12. The electrode 19 penetrates through the housing 11. The detection element 13 is connected between a pair of the electrodes 19 protruding from the housing 11. Similarly, the compensation element 14 is connected between the other pair of the electrodes 19.
The detection element 13 and the compensation element 14 are placed outside the housing 11, and covered with the housing and the detection unit 15. The detection unit 15 has a detection opening 15a. Therefore, leaked hydrogen and the silicone compound contained in the atmosphere are introduced inside the detection unit 15 through the detection opening 15a, thereby to reach the detection element 13. At the detection opening 15a, it may be preferable to arrange a water repelling filter 16 that repels a water drop, and an adsorption filter 17 that includes active carbon or the like for adsorbing the silicone compound. Further, a heater 18 may be arranged inside the detection unit for the purpose of removing water condensed inside the detection unit 15.
On the other hand, the compensation element 14 is constructed by forming the wire such as platinum in a coil shape, of which drawing is omitted. Herein, note a surface of the compensation element 14 made of the wire such as platinum is coated by alumina or the like such that the catalyst becomes inactivated. Accordingly, even though hydrogen (or combustible gas) is present around the wire such as platinum or the like of the compensation element 14, it is not possible to combust hydrogen (or combustible gas) with oxygen in the air (or to conduct the oxidation-reduction reaction). As a result, this construction prevents the compensation element 14 from generating combustion heat, resulting in no change in the electric resistance.
Here, change in the voltage difference between the voltage of a node connecting to the detection element 13 and the compensation element 14 and the voltage of a node connecting to standard resistors 21 and 22 is shown as a concentration signal 24. The concentration signal 24 represents a detection signal showing how much hydrogen (or combustible gas) has been leaked (that is, detection signal of a raised degree of the hydrogen concentration). If the hydrogen concentration is raised due to the leakage thereof, only the resistance value of the detection element 13 increases by hydrogen combustion. Accordingly, the voltage of the node connecting to the detection element 13 and the compensation element 14 is increased, whereby the concentration signal 24 is output as the change in the voltage difference, allowing the hydrogen leakage to be detected.
For example, if an outside temperature is increased without any hydrogen leakage, the temperature of the detection element 13 and the temperature of the compensation element 14 are raised at a same degree, resulting in the same degree of increases in the resistance values. Therefore, the voltage of the node connecting to the detection element 13 and the compensation element 14 is not changed and the voltage difference is not changed, resulting in no output of the concentration signal 24 indicating the hydrogen leakage.
Herein, change in the voltage difference between the voltage of a node connecting to the detection element 13 and the standard resistor 22 and the voltage of a node connecting to the compensation element 14 and the standard resistor 21 represents a concentration signal 24. The concentration signal 24 represents a detection signal on how much hydrogen (or combustible gas) has been leaked (that is, detection signal of a raised degree of the hydrogen concentration). If the hydrogen concentration is raised due to the leakage thereof, only the resistance value of the detection element 13 increases by hydrogen combustion. Accordingly, the voltage of the node connecting to the detection element 13 and the standard resistor 22 is increased, whereby the concentration signal 24 is output as the change in the voltage difference, allowing the hydrogen leakage to be detected.
For example, if an outside temperature is increased without any hydrogen leakage, the temperature of the detection element 13 and the temperature of the compensation element 14 are raised at a same degree, resulting in the same degree of increases in the resistance values. Therefore, the voltages applied to the detection element 13 and the compensation element 14 are increased in the same degree, thereby to change no voltage difference. This results in no output of the concentration signal 24 indicating the hydrogen leakage.
Moreover, in the range of the desorption temperature from 350° C. to 600° C., it has been shown that the higher the temperature of the detection element 13 becomes, the smaller the adhesive amount of the silicone compound becomes.
Furthermore, it has been shown that the temperature rising of the detection element 13 in the desorption temperature range from 350° C. to 600° C. improved the detection sensitivity (that is, the ratio of the change in the resistance value to the change in the gas concentration). Herein, the improvement tendency of the detection sensitivity is to be increased as the temperature is raised from 350° C. to 600° C., and reaches the highest level at 600° C.
In other words, it is preferable to raise the temperature of the detection element 13 up to the desorption temperature in the range from 450° C. to 600° C. rather than to raise the temperature thereof up to the desorption temperature in the range from 350° C. to 600° C. Further, it is more preferable to raise the temperature of the detection element 13 up to the desorption temperature in the range from 500° C. to 600° C. Moreover, it is the most preferable to raise the temperature thereof up to the desorption temperature in the range from 550° C. to 600° C. Accordingly, it is decided to use the combustion heat when hydrogen (or combustible gas) is detected, in the embodiment of the present invention.
Further, the detection sensitivity may be recovered whenever the fuel cell vehicle 1 and the catalytic combustion typed gas sensor 8 are started up and shut down, if the electric current passes through the detection element 13 at least at the either period as mentioned above such that the temperature of the detection element 13 is to be set in the range from 350° C. to 600° at the following period. That period is comprised of at least either of the startup period and the shutdown period of the fuel cell vehicle 1 (see
First, a case that hydrogen is detected if the concentration of the leaked hydrogen becomes 3.0% or more, that is, a case that the detection concentration is set at 3.0% or more will be explained. The detection concentration set at 3.0% allows hydrogen having a high concentration to be detected, enabling the detection element 13 applied to the hydrogen detection inside the off-gas discharge pipe 3 (see
Accordingly, the temperature is raised from the standby temperature of 350° C. up to the desorption temperature of 600° C. Since the temperature of the detection element 13 reaches 600° C., the detection sensitivity may be improved. If the detection concentration is set equal to 3.0%, electric current is made to pass through the detection element 13 such that the temperature thereof becomes a standby temperature of 350° C. That temperature is calculated by subtracting the raised temperature portion of 250° C. from the desorption temperature of 600° C.
Herein, the raised temperature portion of 250° C. is provided by the combustion heat generated by 3.0% hydrogen contacting to the detection element 13. Further, if it is possible to set the desorption temperature in the range from 350° C. to 600° C., the standby temperature may be set in the range from 100° C. to 350° C., the temperatures being calculated by subtracting the raised temperature portion of 250° C. from the above range of the desorption temperatures. Eventually, it is possible to realize both rapid detection and a long life-span of the detection element 13 (or extension of the life-span thereof).
Next, a case that hydrogen is detected if the concentration of the leaked hydrogen becomes 1.0% or more, that is, a case that the detection concentration is set at 1.0% or more will be explained. The detection concentration equal to 1.0% allows the detection of hydrogen at a low concentration, enabling the detection element 13 applied to the hydrogen detection inside a cabin 4 (see
Once hydrogen leaks, the leaked hydrogen is combusted by the detection element 13 to generate heat. The low concentration in 1.0% of the leaked hydrogen generates a small quantity of heat. The raised temperature portion is around 80° C., whereby the temperature is raised up to in the range from around 520° C. to 600° C. Accordingly, the temperature of the detection element 13 reaches 600° C., allowing the detection sensitivity to be improved. If the detection concentration is set at 1.0%, electric current is made to pass through the detection element 13 such that the standby temperature becomes around 520° C. which is calculated by subtracting the raised temperature portion of 80° C. generated by the combustion heat from the desorption temperature of 600° C.
Herein, the combustion heat is generated when hydrogen having a detectable concentration of 1.0% is combusted by contacting with the detection element 13. If the desorption temperature is set in the range from 350° C. to 600° C., it is possible to set the standby temperature in the range from around 270° C. to around 520° C., of which values may be calculated by subtracting the raised temperature portion of around 80° C. from the temperatures in the range from 350° C. to 600° C. This setting enables both rapid detection and a long life-span of the detection element 13 (or extension of the life-span thereof) to be realized.
Further, according to the procedure as described above, in contrast, if the standby temperature is set in the range from 350° C. or more to less than 600° C., it is possible to set the detection concentration in the range of 3.0& or less and the desorption temperature to be at 600° C.
1 Fuel Cell Vehicle
2 Fuel Cell System
2
a Fuel Cell Battery
2
b Accessory
3 Off-Gas Discharge Pipe
4 Cabin
4
a Cabin Top
5 Floor Panel
5
a Center Console
6 Hydrogen Tank
7 Hydrogen Supply Pipe
8, 8a, 8b, 8c, 8d Catalytic Combustion Typed Gas Sensor
11 Housing
12 Substrate
13, 13a detection Element
14 Compensation Element
15 Detection Unit
15
a Detection Opening
16 Repelling Filter
17 Adsorption Filter
18 Heater
19 Electrode
21, 22 Standard Resistor
23 Power Source
24 Concentration Signal
Number | Date | Country | Kind |
---|---|---|---|
2010-112973 | May 2010 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/JP2011/060825 | 5/11/2011 | WO | 00 | 11/16/2012 |