JP4582390B2 - Fuel cell deterioration diagnosis device - Google Patents

Description

  The present invention relates to a fuel cell system, and more particularly to a fuel cell deterioration diagnosis device for diagnosing deterioration of an electrolyte membrane due to aging of a fuel cell.

  In a fuel cell system, it is known that when the electrolyte membrane of a fuel cell deteriorates due to long-term use, so-called cross leak, in which fuel gas leaks from the fuel electrode side to the air electrode side, is increased. Conventionally, a system for determining such deterioration of a fuel cell has been studied.

  For example, Japanese Patent Application Laid-Open No. 11-283653 discloses a technology for detecting the exhaust gas flow rate of a fuel cell, estimating the time for the exhaust gas flow rate to reach a reference value, and calculating the remaining life (Patent Document 1). . Japanese Patent Application Laid-Open No. 8-329965 discloses a leakage detection system that encloses fuel gas of a fuel cell and detects the occurrence of leakage of the fuel gas by lowering the enclosed pressure (Patent Document 2). As other methods for detecting the cross leak of the fuel cell, there are JP-A-9-27336 (Patent Document 3) and JP-A-11-73983 (Patent Document 4).

JP-A-11-283653 JP-A-8-329965 JP-A-9-27336 JP 11-73983 A

  However, in the method of measuring the flow rate of the fuel gas to detect the cross leak, the flow meter becomes large, so that it is not suitable, for example, for an in-vehicle fuel cell system, and the cost is increased. It was.

  In addition, in the technology for detecting the pressure drop of the fuel cell system, a slight cross leak occurs even in the electrolyte membrane of the fuel cell that has not deteriorated. Therefore, the pressure drop is really due to the deterioration of the fuel cell. Could not be determined accurately.

  Accordingly, an object of the present invention is to reliably diagnose deterioration of the characteristics of a fuel cell without measuring a flow rate.

  In order to solve the above problems, a fuel cell deterioration diagnosis device of the present invention is a fuel cell deterioration diagnosis device for detecting characteristic deterioration in a fuel cell, and is provided at a fuel gas supply port to the fuel cell. An inlet shutoff valve, an outlet shutoff valve provided at a fuel gas discharge port from the fuel cell, and a detecting means for detecting the fuel gas pressure in the fuel cell in a state where the inlet shutoff valve and the outlet shutoff valve are shut off. Determining means for determining the deterioration of the electrolyte membrane of the fuel cell based on the amount of decrease in the fuel gas pressure per unit time, the determining means determining whether the amount of decrease in the fuel gas pressure per unit time is a cross leak determination When the value is larger than the reference value, it is determined that the electrolyte membrane of the fuel cell is deteriorated.

  According to the above configuration, the detection means measures the pressure in the fuel cell in which the fuel gas supply is stopped. The determination means examines the amount of decrease in the fuel gas pressure per unit time in the fuel cell and determines whether or not the fuel cell has deteriorated based on the amount of decrease. Since a fuel gas flow meter is not used, a large and expensive measuring instrument can be omitted. Therefore, it is suitable for a fuel cell system mounted on a moving body. In addition, the fuel gas pressure is not reduced, but is diagnosed by the amount of reduction, for example, the rate or rate of reduction, the slope of the decline curve, etc. It is possible to accurately determine the case where the cross leak increases due to the progress of.

  Here, the reference value serving as the threshold value for deterioration is set to a value that is larger than the cross leak that occurs in the electrolyte membrane of a normal fuel cell and that corresponds to the amount of cross leak that is thought to lead to deterioration of the characteristics of the fuel cell. By doing so, the deterioration of the fuel cell can be reliably diagnosed.

  Here, it is preferable that the determination unit performs a warning process when the determination unit determines that the fuel cell has deteriorated. According to this configuration, the warning process can be performed when it can be reliably determined that the fuel cell has deteriorated. This warning process includes a warning for the user (display of a warning lamp or generation of a warning sound). Since aging progresses relatively slowly, it is sufficient to keep such warnings. The user may replace the electrolyte membrane of the fuel cell when responding to the next service.

  In addition to the warning process, control may be performed so as to set (lower) the upper limit of the fuel gas pressure during operation. This is because the amount of cross leak is increasing due to deterioration of the electrolyte membrane, but if the fuel gas pressure is lowered, it may be used properly for a while.

  In addition to the warning, the fuel cell system may be stopped. For example, if it is determined that the amount of change in pressure is relatively large, it is considered that a large amount of fuel gas is leaking, and physical damage has occurred rather than progressive deterioration. You might also say that. For this reason, when the degree of pressure change is large, it may be appropriate to stop the system.

  The present invention also relates to a fuel cell deterioration diagnosis device for detecting characteristic deterioration in a fuel cell, an inlet shut-off valve provided at a fuel gas supply port to the fuel cell, and exhaust of fuel gas from the fuel cell. Detecting that the outlet shut-off valve provided at the outlet, the shut-off detecting means for detecting that the inlet shut-off valve and the outlet shut-off valve are shut off, and the inlet shut-off valve and the outlet shut-off valve are shut off Determination means for determining deterioration of the electrolyte membrane of the fuel cell based on the amount of decrease in the fuel gas pressure in the fuel cell, the determination means crossing the amount of decrease in the fuel gas pressure per unit time When the value is larger than the reference value for leak determination, it is determined that the electrolyte membrane of the fuel cell is deteriorated. According to the above configuration, for example, when the fuel cell system is intermittently operated, the diagnosis of the present invention can be made by detecting that the fuel cell is not generating power.

  As described above, according to the present invention, it is possible to omit a large and expensive measuring instrument such as a flow meter in order to determine whether or not the fuel cell has deteriorated based on the amount of decrease in the fuel gas pressure inside the fuel cell. A system that is advantageous in terms of volume and cost can be provided. Further, since the deterioration is diagnosed not based on a simple decrease in the fuel gas pressure but on the amount of decrease, it is possible to accurately determine the case where the characteristic deterioration is clearly progressing among the cross leaks of the fuel cell that normally occur.

  Next, preferred embodiments for carrying out the present invention will be described with reference to the drawings. In the embodiment of the present invention, the fuel cell deterioration diagnosis device of the present invention is applied to a fuel cell system mounted on a moving body such as an electric vehicle.

  FIG. 1 shows an overall system diagram of the fuel cell system. The following embodiment is merely one embodiment of the present invention, and the present invention is not limited thereto and can be applied. As shown in FIG. 1, the fuel cell system includes a system for supplying hydrogen gas as fuel to the fuel cell stack 10, a system for supplying air, and a system for cooling the fuel cell stack 10. And is configured.

The fuel cell stack 10 is a fuel cell according to the present invention, hydrogen gas, air, and a separator having a flow path of the cooling water, MEA sandwiched by a pair of separators (M embrane E lectrode A ssembly; membrane electrode assembly And a stack structure in which a plurality of cells composed of the above are stacked. The MEA has a structure in which a polymer electrolyte membrane is sandwiched between two electrodes, a fuel electrode and an air electrode. The fuel electrode has a fuel electrode catalyst layer provided in the form of a porous support layer, and the air electrode has an air electrode catalyst layer provided on the porous support layer.

  The system for supplying hydrogen gas to the fuel cell stack 10 includes, in order from the hydrogen gas supply source, a hydrogen tank 101, a shutoff valve (shut valve) 102, a regulating valve 103, an inlet shutoff valve 104 of the fuel cell 10, and fuel. The battery stack 10 includes an outlet shutoff valve 105, a gas-liquid separator 106 and a shutoff valve 107, a hydrogen pump 108, a shutoff valve 109, a check valve 110, and a pressure sensor 111.

  The hydrogen tank 101 is filled with compressed hydrogen gas. In addition, there is no limitation in the hydrogen storage form, Liquid hydrogen, hydrogen storage alloy, carbon material adsorption | suction, etc. other than the storage of compressed hydrogen can be utilized. The shutoff valve 102 is for opening and shutting off the hydrogen tank 101 according to the control of the control unit 20. The pressure regulating valve 103 determines the pressure of the fuel gas in the circulation path constituted by the loop from the shutoff valve 104 to the check valve 110 under the control of the control unit 20.

  The inlet shut-off valve 104 and the outlet shut-off valve 105 are for shutting off the fuel gas supply to the fuel cell stack 10 under the control of the control unit 20 as a premise of the fuel cell deterioration diagnosis of the present invention, and are opened during operation. However, both are shut off during the stoppage of power generation or during an intermittent operation, so that the hydrogen gas enters and exits the fuel cell stack 10. In the shut-off state, the hydrogen gas staying between the inlet shut-off valve 104 and the outlet shut-off valve 105 will only flow through the polymer electrolyte membrane.

  The gas-liquid separator 106 removes moisture generated by the electrochemical reaction of the fuel cell stack 10 during normal operation and discharges it to the outside through the shut-off valve 107. The hydrogen pump 108 is driven at a rotational speed based on the control of the control unit 20, and forcibly circulates hydrogen gas in the circulation path. The shut-off valve 109 is opened at the time of purging according to the control of the control unit 20, and is shut off during a normal operation state. The check valve 110 prevents the backflow of hydrogen gas in the circulation path. The pressure sensor 111 is a means for detecting the fuel gas pressure of the present invention, and detects the fuel gas inlet pressure of the fuel cell stack 10.

  The system for supplying air to the fuel cell stack 10 includes an air cleaner 201, a compressor 202, and a humidifier 203. The air cleaner 201 purifies outside air and takes it into the fuel electric system. The compressor 202 changes the amount of air and the air pressure supplied by compressing the supplied air according to the control of the control unit 20. The humidifier 203 exchanges air off-gas and moisture with respect to the compressed air to add an appropriate humidity. Air discharged from the fuel cell stack 10 is discharged to an exhaust system including a diluter (not shown).

  The cooling system of the fuel cell stack 10 includes a radiator 11, a fan 12, and a cooling pump 13, and cooling water is circulated and supplied into the fuel cell stack 10.

The control unit 20 corresponds to the cutoff detecting means and determining means according to the present invention, a configuration of a known computer system, such as ECU (E lectric C ontrol U nit ), the present invention stored in the ROM or the like, not shown By sequentially executing a software program (not shown) for executing the diagnostic method (CPU), the system can be operated as a shut-off detection means or a judgment means of the present invention.

Next, the operation in the first embodiment will be described.
The polymer electrolyte membrane of the fuel cell stack 10 is an ion exchange membrane, which releases electrons on the fuel electrode side, moves the ionized hydrogen to the air electrode side, and reacts with oxygen in the air on the air electrode side to form water. It produces an electrochemical reaction that produces. For this reason, it can be said that in the fuel cell system, part of the fuel gas essentially moves to the air electrode side through the polymer electrolyte membrane during operation. However, this polymer electrolyte membrane has a tendency that the shielding performance is deteriorated due to aging, and so-called cross leak, in which hydrogen moves to the air electrode side on the fuel electrode side, increases. In the present invention, the degree of the cross leak amount is measured to diagnose the deterioration of the fuel cell.

  In order to carry out the diagnostic method of the present invention, it is preferable that the fuel gas supply to the fuel cell stack 10 is stopped. Therefore, it is preferable that the diagnosis method is performed when the fuel cell system stops generating power or during a pause period in intermittent operation. The intermittent operation refers to an operation that intermittently repeats an operation state and a dormant state from the viewpoint of energy saving when the load is relatively low, such as an idling state, and it is not necessary to continuously generate power.

  For example, FIG. 3 shows a state of an intermittent operation flag that is turned on / off according to whether the operation state or the rest state. The intermittent operation flag is an index stored in the internal memory of the control unit 20 in order to recognize this intermittent operation by various processing modules. When the intermittent operation flag is off, it is assumed that the operation mode is set, and the tax control unit 20 opens the valves necessary for fuel gas supply such as the shutoff valves 102, 104, 105, and the fuel gas is supplied from the hydrogen tank 101 to the fuel. The battery is supplied to the battery stack 10. On the other hand, when the intermittent operation flag is in the on state, the control unit 20 closes at least the inlet shut-off valve 104 and the outlet shut-off valve 105 to stop the supply of fuel gas, assuming that it is a pause period.

  In the present embodiment, the present invention relates to a diagnostic process that is executed during a pause period in this intermittent operation. This diagnosis process will be described with reference to the flowchart of FIG.

  First, the control unit 20 refers to the intermittent operation flag as an operation corresponding to the cutoff detection means, or detects the open / closed state of the cutoff valves 104 and 105, so that the power generation in the fuel cell stack 10 surely enters the stopped state. (S1). When power is being generated (S1: NO), fuel gas is continuously supplied into the fuel cell stack 10 to cause an electrochemical reaction. In such a case, it is not necessary to shut off the shut-off valves 104 and 105 for deterioration diagnosis. Therefore, when the fuel cell stack 10 is generating power, the fuel cell deterioration diagnosis is not performed.

  On the other hand, when the operation mode is the intermittent operation mode and the fuel cell is in the pause period (when the intermittent operation flag in FIG. 3 is ON) (S1: YES), the fuel cell deterioration diagnosis of the present invention is performed. Since the fuel gas pressure in the fuel cell stack 10 is not stable immediately after the suspension period of the intermittent operation, a predetermined time t1 (for example, 1 second) is waited (S2: NO). Then, after t1 seconds have elapsed from the stop of power generation (S2: YES), the control unit 20 takes in the detection signal of the fuel gas pressure of the pressure sensor 111, and stores the pressure that can be specified from the detection signal as the reference pressure Ps (S3).

  Next, the unit 20 waits until the unit time T (for example, 10 seconds) elapses (S4: NO), and after the unit time T elapses (S4: YES), the control unit 20 obtains the detection signal of the pressure sensor 111 again. The specified pressure is stored as the detected pressure Pd (S5). Then, the control unit 20 calculates the difference ΔP between the stored reference pressure Ps and the detected pressure Pd, that is, the degree of pressure drop per unit time T (S6).

  Here, as shown in FIG. 3, the polymer electrolyte membrane inside the fuel cell stack has a small amount of hydrogen passing between the electrolyte membranes and a small cross leak in a relatively new state. For this reason, even after the elapse of time T, the pressure difference of the fuel gas is ΔP2, which is slight. However, when a long time elapses after the replacement, the shielding performance of the film is lowered and the cross leak is increased. For example, in FIG. 3, when the cross leak is large, the pressure difference reaches ΔP1 (> ΔP2) after the time T has elapsed.

  Therefore, in the present embodiment, it is determined whether or not the polymer electrolyte membrane is deteriorated, that is, whether or not the fuel cell is deteriorated, based on the pressure drop amount of the fuel gas. Whether the pressure drop is normal or abnormal is determined appropriately based on the magnitude relationship between the reference value Pth and the pressure difference ΔP (S7). This reference value Pth is selected as a threshold value that is expected to reduce the power generation efficiency of the fuel cell stack when, for example, an electrolyte membrane with a large pressure drop per time T is used. That is, in FIG. 3, the reference value Pth is a predetermined value that satisfies ΔP2 <Pth <ΔP1.

  When the pressure difference ΔP is larger than the reference value Pth (S7: YES), the controller 20 assumes that the cross leak of the polymer electrolyte membrane is large and there is a suspicion of characteristic deterioration. Increase (S8). This counter N is a software counter in the memory of the control unit 20 that is always reset during normal operation.

  On the other hand, when the pressure difference ΔP is equal to or smaller than the reference value Pth (S7: NO), the value of the cross leak occurrence counter N is reset assuming that the cross leak amount is a range derived from a normal electrochemical reaction (S9). .

  Now, the cross leak generated in the electrolyte membrane of the fuel cell fluctuates due to load fluctuations and the influence of air pressure from the air electrode. For this reason, even if the electrolyte membrane is not originally deteriorated, the amount of cross leak may increase momentarily. Such a temporary increase in cross-leakage should not be used as a basis for the deterioration diagnosis of the fuel cell. Therefore, in the present embodiment, it is determined that the cross leak increase is not only measured once, but is also observed when a predetermined number of times are continuously observed, resulting in an increase in cross leak due to characteristic deterioration.

  That is, the control unit 20 refers to the cross leak occurrence counter N in the memory and compares it with an appropriately determined reference number Ns (S10). The reference number Ns is an appropriate number of times to determine that the electrolyte membrane has really deteriorated if an increase in cross leak is observed continuously, for example, 5 times. As a result of the comparison, until the reference number Ns is reached (S10: NO), the control unit 20 does not perform any special measures. On the other hand, when the cross leak occurrence number counter N exceeds the reference number Ns (S10: YES), the control unit 20 determines that the electrolyte membrane has deteriorated and implements measures when the cross leak occurs. (S11).

  As a measure at the time of occurrence of the cross leak, for example, a warning lamp is turned on to inform the user of the deterioration of the electrolyte membrane. Since the increase in cross leak is based on a relatively slowly progressing phenomenon such as deterioration of the electrolyte membrane, it is often less urgent. This is because it is sufficient to keep such warning display and prompt the service station to replace the polymer electrolyte membrane of the fuel cell at the next service inspection.

  However, when the set value of the reference value Pth is increased, that is, a large amount of hydrogen gas cross leak occurs. For example, the electrolyte membrane is damaged by physical impact. In such a case, it is not preferable to leave it for a long time. Therefore, when the reference value Pth is set relatively high, for example, a system stoppage may be taken.

  Moreover, when many cross leaks have generate | occur | produced, the control part 20 may control not only a warning but to change the upper limit of the fuel gas supply pressure at the time of operation. For example, the pressure regulating valve 103 may be adjusted to relatively reduce the maximum fuel gas pressure in the circulation path so that the pressure in the fuel gas circulation path does not become too high during the operation period in the intermittent operation mode or the normal operation period. Is possible. By such measures, even if the electrolyte membrane of the fuel cell starts to deteriorate or is slightly damaged, the operation can be continued without increasing the leakage of the fuel gas.

  As described above, according to the present embodiment, when the fuel supply is cut off during the power generation suspension period, the occurrence of the cross leak is detected based on whether or not the degree of the pressure drop of the fuel gas is greater than the reference value. Therefore, the pressure drop is simply detected. Compared with the case where it carries out, it can determine correctly whether it is a normal driving | operation or an abnormal driving | operation.

  In addition, since the fuel cell deterioration diagnosis method according to the present embodiment does not use a flow meter, it is also suitable when there are volumetric and price restrictions such as a fuel cell system provided in a moving body.

  In addition, according to the present embodiment, since it is determined that the electrolyte membrane has deteriorated for the first time only when the increase in cross leak occurs a plurality of times, reliable fuel cell deterioration is not affected by the temporary increase in cross leak. Can be diagnosed.

  In addition, according to the present embodiment, since the start timing of the occurrence of the cross leak is started after a certain time t1 has elapsed from the time when the fuel gas supply is cut off, accurate cross leak amount measurement can be performed without being affected by the pressure fluctuation immediately after the fuel gas is cut off. Yes.

  In addition, this invention is not limited to the said embodiment, It is possible to change and implement variously.

  For example, in the above-described embodiment, the present invention is implemented in the intermittent operation mode, but may be implemented when power generation of the fuel cell is stopped for a long time. Since it is sufficient to periodically perform the deterioration diagnosis of the fuel cell, for example, the fuel cell power generation is not started, but it is possible to estimate the timing when the power is supplied to the control unit.

  In the above embodiment, the fuel cell deterioration diagnosis is performed when the supply of the fuel gas is stopped. However, the deterioration diagnosis may be performed at the time of power generation of the fuel cell under a specific condition. For example, in a stable operating state where the load does not fluctuate, the fuel gas usage in the fuel cell is constant. In such a case, by changing the reference value, it is possible to detect a hydrogen cross leak other than that contributing to power generation even during power generation.

1 is an overall system diagram of a fuel cell system according to an embodiment. The flowchart explaining operation | movement of the fuel cell system which concerns on this embodiment. The figure which shows the relationship between the fuel cell operation | movement concerning this embodiment, and a pressure change.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Fuel cell stack, 11 ... Radiator, 12 ... Fan, 13 ... Cooling water pump, 20 ... Control part (shut-off detection means, determination means), 101 ... Hydrogen storage tank, 102 ... Heat exchanger, 103, 105, 106 , 108, 110 ... shut-off valve, 104 ... pressure regulating valve, 107 ... gas-liquid separator, 109 ... circulation pump, 111 ... pressure sensor (detection means), 201 ... air cleaner, 202 ... compressor, 203 ... humidifier

Claims (3)

A fuel cell deterioration diagnostic apparatus for detecting characteristic deterioration in a fuel cell,
An inlet shut-off valve provided at a fuel gas supply port to the fuel cell;
An outlet shut-off valve provided at an outlet of the fuel gas from the fuel cell;
Detecting means for detecting the fuel gas pressure in the fuel cell in a state where the inlet shut-off valve and the outlet shut-off valve are shut off;
Determination means for determining deterioration of the electrolyte membrane of the fuel cell based on the amount of decrease in the fuel gas pressure per unit time, and
The determination means determines that the electrolyte membrane of the fuel cell is deteriorated when the amount of decrease in the fuel gas pressure per unit time is larger than a reference value for cross-leak determination;
A fuel cell deterioration diagnosis device characterized by the above. The determination means includes
The fuel cell deterioration diagnosis device according to claim 1, wherein a warning process is performed when the determination unit determines that the electrolyte membrane of the fuel cell is deteriorated. A fuel cell deterioration diagnostic apparatus for detecting characteristic deterioration in a fuel cell,
An inlet shut-off valve provided at a fuel gas supply port to the fuel cell;
An outlet shut-off valve provided at an outlet of the fuel gas from the fuel cell;
A shutoff detecting means for detecting that the inlet shutoff valve and the outlet shutoff valve are shut off;
A determination means for determining electrolyte membrane deterioration of the fuel cell based on the amount of decrease in the fuel gas pressure in the fuel cell when it is detected that the inlet shut-off valve and the outlet shut-off valve are shut off; With
The determination means determines that the electrolyte membrane of the fuel cell is deteriorated when the amount of decrease in the fuel gas pressure per unit time is larger than a reference value for cross-leak determination;
A fuel cell deterioration diagnosis device characterized by the above.

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