CN104282925B - The deterioration detecting apparatus of vehicle fuel cell - Google Patents
The deterioration detecting apparatus of vehicle fuel cell Download PDFInfo
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- CN104282925B CN104282925B CN201410324260.4A CN201410324260A CN104282925B CN 104282925 B CN104282925 B CN 104282925B CN 201410324260 A CN201410324260 A CN 201410324260A CN 104282925 B CN104282925 B CN 104282925B
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Abstract
The present invention provides the deterioration detecting apparatus of vehicle fuel cell.When the fuel cell being equipped on vehicle there occurs deterioration, judge worsening reason in detail, it is thus possible to carry out the recovery operating deteriorated in the proper condition.The desired value making the output electric current of fuel cell changes with step-like.Measure the indicial response of the output voltage of the fuel cell driven in the way of following the tracks of this desired value, indicial response is decomposed into and responds the composition that composition faster is slower with response.Calculate time constant T responding composition faster1, time constant T of the slower composition of response2.The time constant of the composition faster of response when calculating normal and time constant T1Difference DELTA T1, the time constant of the composition that response when calculating normal is slower and time constant T2Difference DELTA T2.According to difference DELTA T1Judge the deterioration of the internal driving change of the deterioration of reactive state of platinum catalysis device of fuel cell, monocell, according to difference DELTA T2Judge the hydrogen of fuel cell and the deterioration of the supply condition change of oxygen.
Description
Technical field
The present invention relates to the deterioration detecting apparatus of a kind of fuel cell mounted on a vehicle.
Background technology
In recent years, in the field of the vehicle such as automotive bicycle, automatic carriage, it is contemplated that earth environment,
It is known to a kind of polymer electrolyte fuel cell being equipped with as power source and such as there is polymeric membrane
Vehicle.Polymer electrolyte fuel cell is constituted many pieces of monocells (cell) stacking as ultimate unit
The battery pile being connected in series.Monocell is to be placed in polymeric membrane (PEM) to glue medially
Patch anode (fuel electrodes) and negative electrode (air pole), be configured with the supporting current collection being made up of carbon paper outside it
Body.Further, outside it, it is configured with the dividing plate of the pipeline with Cooling Water flowing.Anode and negative electrode by
Electrolyte and Pt microparticles attachment catalyst converter on the carbon carrier is constituted.When anode imports hydrogen, hydrogen
Ionizing and through PEM to movable cathode, the electronics simultaneously released when ionizing is not passed through matter
Proton exchange but along wire to outside flow out, become electric current.Import to the oxygen of negative electrode and through high score
Hydrion and the electronics come in by outside wire that sub-film enters are carried out reacting and become water, are discharged.
Under being equipped with the actually used situation of vehicle of this fuel cell, load during traveling and Zhou Bianhuan
There are various changes in surrounding enviroment when border, keeping.Therefore, fuel cell generation platinum catalysis device
Surface oxidation, dissolution, PEM be dried, perforate, excess moisture within monocell and moisture
Freeze, baffle surface oxidation etc., temporary or permanent performance reduce (deterioration).In these deteriorations
, the surface oxidation of platinum catalysis device, PEM be dried, the excess moisture within monocell, moisture
Freezing is the temporary deterioration of fuel cell.In the case of there occurs this temporary deterioration, need to make
Fuel cell, for making its condition operating (hereinafter referred to as recovering operating) recovered from deterioration, seeks fuel
The performance recovery of battery.I.e., it is necessary to the degradation of detection fuel cell, judge according to this testing result
The necessity of recovery operating, and then determine the worsening reason of fuel cell, select to be suitable for according to worsening reason
The condition recovering operating recovered from this deterioration state.
As the technology of judgement fuel cell degradation, such as, propose a kind of such in patent documentation 1
System: be the drop mode predetermined by the output voltage control of fuel cell, according to this control of integrating
The output measured value of electric current of fuel cell during system and the electricity obtained judge the deterioration of fuel cell.
Within the system, after negative electrode is carried out air-supply process, carry out exporting the measurement processing of electric current, it is determined that hold
Carry the deterioration of the carrier of catalyst converter, the most again carry out identical measurement processing, it is determined that the change of catalyst converter.
Additionally, propose a kind of such fuel cell system in patent documentation 2；By making generating stop it
The voltage variety of rear detection fuel cell, is in due course and makes fuel cell discharge, prevent matter
The deterioration of proton exchange.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2012-089448 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2012-028221 publication
Summary of the invention
The problem that invention is to be solved
But, although the system of patent documentation 1 can detect the fuel cell caused by catalyst converter and carrier
Deterioration, but the confession of excess moisture, hydrogen and the oxygen internal by other reasons, such as monocell cannot be detected
To the deterioration of the fuel cell that state deteriorating causes.Thus, the reason in deterioration is catalyst converter and carrier
In the case of outside, it is impossible to select the felicity condition recovering operating of fuel cell.Additionally, at patent literary composition
Offer in the system of 2, it is impossible to the degradation of detection fuel cell, it is impossible to from various worsening reasons
Determine the reason that deterioration actually occurs.Thus, as the system of patent documentation 1, it is impossible to suitably enter
The recovery operating of row fuel cell.
The present invention i.e. completes, it is intended that be equipped with fuel in view of such actual state
In the case of fuel cell there occurs deterioration in the actually used shape of the vehicle of battery, correctly judge it
Worsening reason such that it is able to properly select the condition recovering operating of deterioration.
For solving the scheme of problem
In order to solve the problem that above-mentioned conventional art is had, the present invention is that a kind of detection is mounted on a vehicle
The device of deterioration of fuel cell, wherein, this device includes: desired value configuration part, and it is used for setting
Desired value, this desired value is by the current output current value of above-mentioned fuel cell is increased predetermined step
Measure and obtain；Indicial response measurement portion, it is for controlling the output electric current of above-mentioned fuel cell so that
The output current value of above-mentioned fuel cell follows the tracks of above-mentioned desired value, the output to above-mentioned fuel cell now
The indicial response of voltage measures；Indicial response decomposition unit, it is for by the output of above-mentioned fuel cell
The indicial response of voltage is decomposed into the 1st higher composition of response speed and relatively low the 2nd composition of response speed；
Time constant calculating part, its 1st time constant being used for calculating above-mentioned 1st composition and above-mentioned 2nd composition
2nd time constant；Mathematic interpolation portion, it is for calculating the 1st difference and the 2nd difference；Above-mentioned 1st difference is
1st fiducial time constant and the difference of above-mentioned 1st time constant, above-mentioned 2nd difference is that the 2nd fiducial time is normal
Number and the difference of above-mentioned 2nd time constant；Above-mentioned 1st fiducial time constant be above-mentioned fuel cell normal time
The time constant of above-mentioned 1st composition, above-mentioned 2nd fiducial time constant be above-mentioned fuel cell normal time
The time constant of above-mentioned 2nd composition；And deterioration judging portion, when above-mentioned 1st difference is more than the rule of the 1st composition
During definite value, in the change of the impedance judged within the reactive state of catalyst converter of above-mentioned fuel cell and monocell
Change and cause deterioration while occurring, its degradation to be judged；When above-mentioned 2nd difference is more than the 2nd composition
Setting time, the change at the supply condition judging the hydrogen of above-mentioned fuel cell and oxygen causes deterioration to occur
While, its degradation is judged.
Additionally, the present invention can be configured to, at the degradation judged according to above-mentioned 1st difference beyond pre-
In the case of determining scope, measure the 1st electricity in the 1st region that the electric current density in above-mentioned fuel cell is less
Flow valuve and the 1st magnitude of voltage, measure the electric current density in above-mentioned fuel cell more than the 2nd of above-mentioned 1st region
The 2nd current value in region and the 2nd magnitude of voltage, when above-mentioned fuel cell is normal by above-mentioned 1st electric current
In the case of magnitude of voltage when value drives and the difference of above-mentioned 1st magnitude of voltage are more than the 1st current specification value, press
Carry out operating according to the condition of the reduction reaction on the catalyst converter surface of the monocell that can promote above-mentioned fuel cell to make
The deterioration of above-mentioned fuel cell recovers, being driven by above-mentioned 1st current value when above-mentioned fuel cell is normal
Time magnitude of voltage and the difference of above-mentioned 1st magnitude of voltage not less than above-mentioned 1st current specification value and in above-mentioned combustion
Magnitude of voltage when being driven by above-mentioned 2nd current value when material battery is normal and the difference of above-mentioned 2nd magnitude of voltage
In the case of the 2nd current specification value, humidify according to the polymeric membrane of the monocell of above-mentioned fuel cell
Condition carries out operating and makes the deterioration of above-mentioned fuel cell recover.
Additionally, the present invention can be configured to, at the degradation judged according to above-mentioned 2nd difference beyond pre-
In the case of determining scope, when the temperature of above-mentioned fuel cell is higher than temperature specifications value, according to making above-mentioned combustion
The condition that the moisture within monocell of material battery removes carries out operating and makes the deterioration of above-mentioned fuel cell recover,
In the case of the temperature of above-mentioned fuel cell is less than said temperature setting, according to making above-mentioned fuel cell
The condition melted of the moisture freezed within monocell carry out operating and make the deterioration of above-mentioned fuel cell recover.
Additionally, the present invention can be configured to, above-mentioned degradation portion is on judging according to above-mentioned 1st difference
State fuel cell when having deteriorated, determine the above-mentioned fuel cell that deterioration can be made to recover according to above-mentioned 1st difference
The recovery duration of runs, above-mentioned degradation portion is detecting above-mentioned fuel cell according to above-mentioned 2nd difference
When deterioration, determine according to above-mentioned 2nd difference when the recovery of the above-mentioned fuel cell that deterioration can be made to recover operates
Between.
Additionally, the present invention can be configured to, even if performing the deterioration making above-mentioned deterioration judging portion determine
The recovery operating recovered, in the case of the deterioration of above-mentioned fuel cell can not be made to recover, relative to normally
Time the output voltage values of above-mentioned fuel cell, recover the output voltage values of the above-mentioned fuel cell after operating
Reduce less than in the case of predetermined permissible level, set output current value new of above-mentioned fuel cell
Desired value, control above-mentioned fuel cell so that output current value follow the tracks of above-mentioned new desired value, measure
The indicial response of the output voltage of the most above-mentioned fuel cell, by the mistake of the output voltage of above-mentioned fuel cell
Crossing response and be decomposed into above-mentioned 1st composition and above-mentioned 2nd composition, the 3rd time calculating above-mentioned 1st composition is normal
Number and the 4th time constant of above-mentioned 2nd composition, by when above-mentioned 1st fiducial time, constant was replaced into the above-mentioned 3rd
Between constant, by above-mentioned 2nd fiducial time constant be replaced into above-mentioned 4th time constant.
The effect of invention
As described above, in the deterioration detecting apparatus of the vehicle fuel cell of the present invention, target setting
Value, desired value is the current output current value of fuel cell to be increased predetermined step amount and obtains, right
Control the transition of the output voltage of fuel cell when fuel cell makes output current value follow the tracks of this desired value
Response measures, the 1st composition and the response speed that the response speed that comprised according to this indicial response is higher
The 2nd relatively low composition judges reason and the degree thereof of the deterioration of fuel cell.Thus, it is possible to judge fuel electricity
The necessity recovering operating in pond, and in the case of fuel cell there occurs deterioration, it is possible to select to use
Carry out recovering operating in the suitable condition of deterioration recovery.
At the degradation that the 1st composition that the response speed comprised according to above-mentioned indicial response is higher judges
In the case of preset range, the multiple districts different by measuring the electric current density in fuel cell respectively
The current value in territory and magnitude of voltage, it is possible to judge the former of deterioration in more detail according to these current values and magnitude of voltage
Cause.Thus, carry out for make according to the 1st composition that response speed is higher determine deterioration recover extensive
When operating again, it is possible to select more appropriate condition.
In the deterioration journey that the 2nd composition that the response speed comprised according to above-mentioned indicial response is relatively low determines
Degree is beyond in the case of preset range, by measuring the temperature of fuel cell, it is possible to according to this measurement temperature
Judge the reason of deterioration in more detail.Thus, carrying out for making 2nd composition relatively low according to response speed
During the recovery operating that the deterioration determined recovers, it is possible to select more appropriate condition.
Determine at the 1st composition that the response speed comprised according to indicial response is higher and there occurs deterioration
In the case of, according to as above-mentioned 1st time constant and the 1st fiducial time constant the 1st mathematic interpolation of difference
Going out to recover the time of operating, 2nd composition relatively low in the response speed comprised according to indicial response determines
In the case of there occurs deterioration, according to as above-mentioned 2nd time constant and the 2nd fiducial time constant difference
The 2nd mathematic interpolation go out recover operating time such that it is able to deterioration reason correspondingly make recovery operate
Time optimal.Thus, it is possible to suppression causes the output reduction of fuel cell etc. right because recovering operating
The impact travelling generation of vehicle.
Even if performing the recovery operating making deterioration recover, in the case of deterioration can not be made to recover, relatively
The output voltage values of the fuel cell when normal, recovers the output voltage values of the fuel cell after operating
In the case of reducing less than predetermined permissible level, though the performance of fuel cell reduces, but can continue to make
With.In this case, by carrying out replacing the process of said reference magnitude of voltage, it is possible to continue to judge temporarily
The generation of time property deterioration, it is possible to carry out suitable recovery operating.
Accompanying drawing explanation
Fig. 1 is the block diagram of the deterioration detecting apparatus of the vehicle fuel cell of embodiments of the present invention.
Fig. 2 is the 1DC-of the deterioration detecting apparatus of the vehicle fuel cell of embodiments of the present invention
The structure chart of DC transducer.
Fig. 3 is the chart of the transient characteristic representing fuel cell.
Fig. 4 is the flow chart representing the degradation processing procedure performed by deterioration detecting apparatus.
Fig. 5 is the chart of the loss property representing fuel cell.
Fig. 6 be represent the activation polarization of fuel cell increase after the chart of characteristic.
Fig. 7 be represent the ohmic polarization of fuel cell increase after the chart of characteristic.
Fig. 8 is to represent the flow chart of processing procedure recovering operating condition of fuel cell selecting to deteriorate.
Fig. 9 is to represent the flow chart of processing procedure recovering operating condition of fuel cell selecting to deteriorate.
Figure 10 is the stream representing the processing procedure recovering to carry out after operating at the fuel cell deteriorated
Cheng Tu.
Figure 11 is the voltage waveform representing the fuel cell measured in the variation that degradation processes
Sequential chart.
Figure 12 is the voltage waveform representing the fuel cell measured in the variation that degradation processes
Sequential chart.
Detailed description of the invention
Below, the present invention is described in detail according to embodiment illustrated.Fig. 1 is the vehicle of present embodiment
Block diagram with the deterioration detecting apparatus of fuel cell.Data processing equipment 10 is for controlling degradation dress
Put the system controller of entirety.Data processing equipment 10 connects and has fuel cell (FC) 20,1DC
-DC transducer 30, inverter 40,2DC-DC transducer 60, battery 70.On inverter 40
Connecting and have motor 50, connecting on 2DC-DC transducer has battery 70.Temperature by fuel cell 20
Sensor 21 measure fuel cell 20 temperature data, by the voltage sensor of 1DC-DC transducer 30
The various data that device 31, current sensor 32 are measured are input to data processing equipment 10.Dress is processed in data
Put in 10 and carry out calculation process based on these various data, generate control signal.Fuel cell 20,
Carry respectively on 1DC-DC transducer 30, inverter 40,2DC-DC transducer 60, battery 70
There is control circuit (not shown), between itself and data processing equipment 10, receive and dispatch control signal respectively.
Fig. 2 is the figure of the structure of the 1DC-DC transducer 30 representing Fig. 1.1DC-DC transducer
Being buck-boost type transducer, it also includes electricity in addition to above-mentioned voltage sensor 31 and current sensor 32
Sense 33, switch SW1, SW2, SW3, SW4.
Switch SW1～SW4 is switch element, such as, use power MOSFET.At 1DC-DC
In the case of carrying out boosting work in transducer 30, switch SW1 is converted to open, and switch SW2 is converted to
Closing, switch SW3 and switch SW4 is with duty cycle conversion corresponding with the voltage difference between input and output.
Additionally, in the case of carrying out blood pressure lowering work in 1DC-DC transducer 30, switch SW4 is converted to out
Opening, switch SW3 is converted to close off, and switch SW1 and switch SW2 is with the voltage difference between input and output
Corresponding duty cycle conversion.Testing result according to voltage sensor 31 and current sensor 32 controls switch
The conversion of SW1～SW4 so that voltage and current follows the tracks of predetermined desired value.
The processing procedure recovering to control of the fuel cell 20 performed in data processing equipment 10 is as follows.First
First, fuel cell 20 is carried out degradation process, determine whether to perform fuel electricity according to this testing result
The recovery operating in pond 20.If being judged as, the recovery needing fuel cell 20 operates, then according to the state of deterioration
Correspondingly select to recover the condition of operating, then, perform the recovery fortune of fuel cell 20 with the condition selected
Turn.Then, after recovering operating, confirm that the output of fuel cell 20 recovers the most, do not recovering
In the case of, perform the process recovered after operating described later.Due to same make fuel cell 20 generate electricity
Shi Zhihang processes these, therefore, has electric power from fuel cell 20 output in processing procedure.As above-mentioned that
Sample, the output electric current of fuel cell 20 is output to horse via 1DC-DC transducer 30 and inverter 40
Reach 50 and drive motor 50, or via 1DC-DC transducer 30 and 2DC-DC transducer 60
It is output to battery 70 and battery 70 is charged.Transport condition according to vehicle, the charged state of battery 70
Correspondingly carry out motor driving, battery charging.
The degradation of fuel cell
In the present embodiment, the transient characteristic of fuel cell 20 it is conceived to judge the bad of fuel cell 20
Change degree and reason thereof.Fig. 3 represents when the desired value of the output electric current making fuel cell increases with step-like
The indicial response of output voltage.Make the desired value of output electric current of fuel cell 20 with step at moment t1
When shape increases, the output voltage of fuel cell 20 declines about 50% in moment t1 display as shown in solid line L20
Afterwards, decline lentamente.The indicial response performance of the output voltage shown in solid line L20 is enough with response speed
Higher composition (dotted line L21) and relatively low composition (dotted line L22) sum of response speed approximate.Ring
Magnitude of voltage should be maintained by composition faster after moment t1 display declines about 50%.Respond slower composition to exist
Moment t1 will not decline sharp, shows and decline slowly while the time passes through.
Respond composition and the reaction of platinum catalysis device of the monocell of fuel cell 20 faster, monocell interior
Portion's impedance is correlated with.I.e., in the fuel cell 20, there occurs by the platinum catalysis device surface oxidation of monocell
The deterioration caused, the situation being dried the deterioration caused by polymeric membrane, by the excess moisture within monocell
When the supply condition causing hydrogen and oxygen deteriorates and there occurs the situation etc. of performance degradation, respond composition faster
Produce delayed.Additionally, it is relevant to the supply of the hydrogen of fuel cell 20 and oxygen to respond slower composition.That is,
The supply condition change that there occurs the hydrogen of fuel cell 20 and oxygen deterioration (80% time such as normal with
Under level) in the case of, respond slower composition and produce delayed further.
The biggest difference is there is owing to responding the time constant of the composition slower with response of composition faster, because of
This can each Autonomous test.
In the present embodiment, increased the output current value of fuel cell 20 with step-like by measurement
In the case of the indicial response of output voltage, resolve into above-mentioned response composition faster and respond slower becoming
Point, calculate respective time constant, thus judge degradation and the reason thereof of fuel cell 20.Combustion
With the rank of 1 rank delay system transmission function shown in the indicial response such as formula (1) of the output voltage of material battery 20
The response sum that jumps approximates.
Several 1
Here, t is the time, V0Being Initial Voltage Value, V is indicial response magnitude of voltage, V1It is in response to very fast
The magnitude of voltage of composition, V2It is in response to the magnitude of voltage of slower composition, V1∞It is in response to composition faster
Voltage end value, V2∞It is in response to the voltage end value of slower composition, T1It is in response to composition faster
Time constant, T2It is in response to the time constant of slower composition.
The magnitude of voltage V of composition faster will be responded1Time constant T1The composition V slower with response2Electricity
Time constant T of pressure value2As shown in formula (2), (3), (fuel cell 20 deteriorates with normal condition
State) under time constant compare.
Several 2
ΔT1=T1-T1std (2)
Here, Δ T1The time constant being in response under the normal condition of composition faster and the response detected
The difference of the time constant of composition, T faster1stdIt is in response to the time under the normal condition of composition faster
Constant.
Several 3
ΔT2=T2-T2std (3)
Here, Δ T2The time constant being in response under the normal condition of slower composition and the response detected
The difference of the time constant of slower composition, T2stdIt is in response to the time under the normal condition of slower composition
Constant.
In the present embodiment, according to Δ T1Judge the reactive state of the catalyst converter of fuel cell 20 deterioration,
The degradation of the internal driving change of monocell, based on Δ T2Judge the hydrogen of fuel cell 20 and the confession of oxygen
Degradation to state change.
Fig. 4 is to represent the mistake that the degradation of the fuel cell 20 performed in data processing equipment 10 processes
The flow chart of journey.In step slo, the switch of 1DC-DC transducer 30 is controlled so that from fuel
The current value of the electric current that battery 20 exports and is input in 1DC-DC transducer 30 rises with step-like.
It is input to data processing equipment 10 with the current value (desired value) that step-like rises.Data processing equipment 10
Control signal is exported so that the output current tracking desired value of fuel cell 20 to fuel cell 20.Then,
In step s 11, being measured by the voltage sensor 31 of 1DC-DC transducer 30 will output electric current control
It is made as the indicial response of the output voltage of the fuel cell 20 of desired value, voltage sensor 31 mistake measured
Cross response wave shape as seasonal effect in time series data arrangement record in data processing equipment 10.
In step s 12, indicial response waveform is with 1 rank delay system transmission letter shown in above-mentioned formula (1)
The step response sum of number approximates, and calculates in step s 13 and responds composition V faster1Time normal
Number T1The composition V slower with response2Time constant T2.Then into step S14, calculate response relatively
Time constant under the normal condition of fast composition and the response composition faster calculated in step s 13
Time constant T1Difference DELTA T1, calculate the time constant under the normal condition of the slower composition of response
Time constant T of the composition that the response that calculates in step s 13 is slower2Difference DELTA T2。
In step S15, by difference DELTA T1Compared with the setting predetermined, at Δ T1For regulation
In the case of value is above, enter into step S16.In step s 16, according to respond composition faster time
Between constant T1The change compared with time normal situation more than setting, it is judged that in the fuel cell 20
There occurs change bad of the internal driving of the deterioration of reactive state of the platinum catalysis device of monocell, monocell
Change.Additionally, according to Δ T1Value correspondingly judge the degree of this deterioration.That is, Δ T1Value the biggest, then sentence
The degradation that the deterioration of the reactive state broken as platinum catalysis device, the internal driving of monocell change is the most greatly.
Then, step S17 is entered into.At Δ T1In the case of setting, skip the process of step S16,
Enter into step S17.
In step S17, by difference DELTA T2Compared with the setting predetermined, at Δ T2For regulation
In the case of value is above, enter into step S18.In step S18, according to the slower composition of response time
Between constant T2The change compared with time normal situation more than setting, it is judged that in the fuel cell 20
There occurs the deterioration of the supply condition change of hydrogen and oxygen.Additionally, according to Δ T2Value correspondingly judge that this is bad
The degree changed.That is, Δ T2Value the biggest, then be judged as hydrogen and oxygen supply condition change degradation
The biggest.Above, the degradation of fuel cell 20 terminates.At Δ T2In the case of setting, jump
Crossing the process of step S18, the degradation of fuel cell 20 terminates.
Recover the selection of operating condition
In the present embodiment, according to the deterioration judged in step S16 and step S18 of above-mentioned Fig. 4
Reason and degree thereof select the condition recovering operating of fuel cell 20.According to responding composition faster
Difference DELTA T of time constant1It is judged as the deterioration of the reactive state of the platinum catalysis device of fuel cell 20, single electricity
Pond internal driving change degradation the most greatly in the case of, to promote the reduction reaction on catalyst converter surface
Condition or the condition that makes polymeric membrane humidify carry out the recovery operating of fuel cell 20.
The loss of fuel cell 20 exists: the activation polarization caused by the activation evergy of electrode reaction
(Vact), the resistance of the resistance of electrolyte, electrode the ohmic polarization (V causedohm), by electrode surface
The diffusion polarization (V that causes of the concentration phenomenon of reactanttrans).Fig. 5 is to represent these characteristics lost
Chart.The deterioration of the reactive state of the platinum catalysis device of fuel cell 20 causes activation polarization VactIncrease, combustion
The internal driving deterioration of the monocell of material battery 20 causes ohmic polarization VohmIncrease.Thus, from Fig. 5
In the case of the region that electric current density that middle A11 represents is less finding, output voltage reduces, it is possible to sentence
The deterioration of the reactive state of the platinum catalysis device broken as there occurs fuel cell 20.Additionally, use A12 in Figure 5
Represent electric current density be in moderate region find output voltage reduce in the case of, it is possible to judge
For there occurs the deterioration of the internal driving of monocell.
Therefore, in the region A11 that electric current density is less, first measure the voltage V of fuel cell 201And electricity
Stream I1, by voltage V1Identical electric current I is reached time normal with fuel cell 201Time voltage V1stdCompare.
Secondly, the same voltage V measuring fuel cell 20 in the region A12 that electric current density is moderate2With
Electric current I2, by voltage V2It is set to identical electric current I time normal with fuel cell 202Time voltage V2stdCompare
Relatively.As shown in Figure 6, the region A11 less from electric current density start with voltage V time normal1std
Difference relatively big in the case of, activation polarization increases.Thus, it is judged that the reactive state for platinum catalysis device produces
Problem, recovers to select in operation process to promote the reduction reaction on catalyst converter surface at fuel cell 20
Condition.On the other hand, as it is shown in fig. 7, in the region A11 that electric current density is less with voltage time normal
V1stdDifference less, with voltage V time normal in the region A12 that electric current density is moderate2stdDifference
In the case of relatively big, ohmic polarization increases.Thus, it is judged that the internal driving for monocell creates problem,
The condition recovering to select to make polymeric membrane humidify in operation process at fuel cell 20.Additionally, due to root
According to difference DELTA T responding the time constant of composition faster1Judge the degradation of fuel cell 20, therefore,
Can be according to Δ T1Determine to recover the time of operating.
Difference DELTA T in the time constant of the composition slower according to response2Be judged as fuel cell 20 hydrogen and
Oxygen supply condition change degradation the most greatly in the case of, to remove the bar of the moisture within monocell
Part or make the condition that the moisture freezed within monocell melts, carries out the recovery fortune of fuel cell 20
Turn.Temperature according to the fuel cell 20 detected by the temperature sensor 21 of fuel cell 20 determines to select
Which in these conditions.
Fig. 8 represents and is judged as that fuel cell 20 there occurs the anti-of platinum catalysis device in step S15, S16 of Fig. 4
Answer the deterioration of state, monocell internal driving change deterioration in the case of, select fuel cell 20
Recover operating condition processing procedure.In step S20, by the electricity of 1DC-DC transducer 30
Pressure sensor 31 measures the voltage V of the fuel cell 20 in the region that electric current density is less1, passed by electric current
Sensor 32 measures the electric current I of the fuel cell 20 in the region that electric current density is less1.Then, in step S21
In, calculate output electric current I when normal1In the case of voltage V1stdWith voltage V1Difference.In step
In S22, it is moderate for measuring electric current density by the voltage sensor 31 of 1DC-DC transducer 30
Region in voltage V2, measuring electric current density by current sensor 32 is in moderate region
Electric current I2.Then, in step S23, output electric current I when normal is calculated2In the case of voltage V2std
With voltage V2Difference.
In step s 24, it is determined that above-mentioned voltage V1stdWith voltage V1Difference whether more than predetermining
Setting.At voltage V1stdWith voltage V1Difference more than in the case of setting, enter into step S25.
In step s 25, as the condition recovering operating of fuel cell 20, select to promote the catalysis of monocell
The condition of the reduction reaction on device surface.On the other hand, at voltage V1stdWith voltage V1Difference be setting
In the case of below, enter into step S26.
In step S26, it is determined that above-mentioned voltage V2stdWith voltage V2Difference whether more than predetermining
Setting.At voltage V2stdWith voltage V2Difference more than in the case of setting, enter into step S27.
In step s 27, as the condition recovering operating of fuel cell 20, select to make the macromolecule of monocell
The condition of film humidification.
After have selected the condition recovering operating of fuel cell 20 in step S25 or step S27, enter
Enter to step S28.In step S28, according to the above-mentioned time constant calculated in step S14 of Fig. 4
Difference DELTA T1Determine the duration of runs recovering operating of fuel cell 20.Difference DELTA T1The biggest, the duration of runs
It is set the longest.
At voltage V1stdWith voltage V1Difference be below setting (being NO in step s 24) and electricity
Pressure V2stdWith voltage V2The situation that difference is below setting (being NO in step S26) under, it is judged that
The deterioration that should recover is there is not for fuel cell 20.Thus, do not carry out determine recover operating condition and time
Between process.
Fig. 9 represents the confession being judged as existing in the fuel cell 20 hydrogen and oxygen in step S17, S18 of Fig. 4
To in the case of the deterioration of state change, the processing procedure recovering operating condition of selection fuel cell 20.
In step s 30, temperature T of fuel cell 20 is measured by temperature sensor 21FC, then, in step
In S31, by temperature TFCCompared with pre-set setting.In temperature TFCFeelings higher than setting
Under condition, enter into step S32.In step s 32, as the condition recovering operating of fuel cell 20,
Select to remove the condition of the moisture within monocell.In temperature TFCIn the case of below setting, enter
To step S33.In step S33, as the condition recovering operating of fuel cell 20, select to make single electricity
The condition that the moisture freezed within pond melts.Fuel cell is have selected in step S32 or step S33
After the recovery operating condition of 20, enter into step S34.In step S34, according to the step at Fig. 4
Difference DELTA T of the above-mentioned time constant calculated in S142Determine the operating recovering operating of fuel cell 20
Time.Difference DELTA T2The biggest, it is set the duration of runs the longest.
As above, the degree of the deterioration of fuel cell 20 and the result of determination of reason select fuel
The condition recovering operating of battery 20 and time.Thereby, it is possible to by the performance of fuel cell 20 to
Limits.
Recover operating and process afterwards
Figure 10 is the flow chart recovering operating and processing procedure afterwards representing fuel cell 20.In step
In S40, perform the recovery operating of fuel cell 20.According to by using the flow chart of Fig. 8 or Fig. 9 to say
Condition and time that bright above-mentioned process determines perform to recover operating.During additionally, initially perform step S40,
Represent that the variable of the number of times recovering operating is set to " 0 ".Recovery at fuel cell 20 operates end
After, represent the variable increment " 1 " of the number of times recovering operating, enter into step S41.After step S41
Processing procedure in, confirm fuel cell 20 electric current output whether recover.
In step S41, measured the voltage of the fuel cell 20 after recovering operating by voltage sensor 31
V3, the electric current I of the fuel cell 20 after recovering operating is measured by current sensor 323.Then, in step
In rapid S42, by voltage V3And reference voltage VstdCompare.Reference voltage VstdIt is that fuel cell 20 is normal
Time output electric current I3In the case of magnitude of voltage.In reference voltage VstdWith the voltage V recovered after operating3Difference
In the case of value is below pre-set setting, it is judged that for fuel cell 20 from temporary
Deterioration recovers, and therefore, does not perform the process after recovering operating.
On the other hand, in reference voltage VstdWith the voltage V recovered after operating3Difference more than setting
In the case of, it is judged that do not recover from deterioration for fuel cell 20, therefore, enter into step S44.In step
In S44, check the value of the variable representing the number of times recovering operating, it is determined that the number of times recovering operating is the biggest
In pre-set setting.In the case of the number of times recovering operating is below setting, return to
Step S40, performs to recover operating again.
On the other hand, in the case of the number of times recovering operating is more than setting, step S45 is entered into.
Although the number of times recovering operating refers to recovery operating is performed pre-determined number, all more than the situation of setting
Cannot obtain close to reference voltage V time normal from fuel cell 20stdThe state of output voltage.That is, combustion
The deterioration of material battery 20 is not temporary, but permanent.In other words, it is possible to understand fuel electricity
The key property in pond 20 self and step-down than before.Even if the key property of fuel cell 20 reduces, only
Degree to be reduced is less, also just is able to be continuing with.Therefore, first in step S45, it is determined that base
Quasi-voltage VstdWith the voltage V recovered after operating3Difference whether be permissible level, i.e. fuel cell 20
Whether permanent output voltage reduces is permissible level.
Although there occurs that permanent output voltage reduces at fuel cell 20, but reference voltage VstdWith extensive
Voltage V after multiple operating3Difference less than in the case of permissible level, enter into step S46.As long as
Even if there occurs permanent deterioration, reference voltage VstdWith the voltage V recovered after operating3Difference the least
In the state of permissible level, the reduction of the key property of fuel cell 20 is not the most fatal, it is possible to continue
Use.If being continuing with fuel cell 20, then must detect sending out of temporary deterioration during use
Raw, perform suitable recovery operating.Therefore, in step S46～S50, carry out and current fuel cell
The performance of 20 replaces time constant T responding composition faster matchingly1stdThe composition slower with response
Time constant T2stdThe process of value.
Calculate in the same manner as process with step S10 in the degradation process of the fuel cell of Fig. 4～S13
Go out time constant T1stdAnd T2stdNew value.In step S46, control 1DC-DC transducer 30
Switch, makes the desired value of the output electric current of fuel cell 20 enter one from the desired value determined in step slo
Walk and change with step-like, be input to data processing equipment 10 as new desired value.Data process dress
Put 10 and export control signal to fuel cell 20 so that the output new target of current tracking of fuel cell 20
Value.In step S47, being measured by the voltage sensor 31 of 1DC-DC transducer 30 will output electricity
Flow control is the indicial response of the output voltage of the fuel cell 20 of new desired value, as time sequence
The data arrangement record of row is in data processing equipment 10.Then, in step S48, indicial response ripple
Shape approximates, in step with the step response sum of 1 rank delay system transmission function shown in above-mentioned formula (1)
In rapid S49, calculate and respond composition V faster1Time constant T1The composition V slower with response2Time
Between constant T2Time constant.Then, in step s 50, by time constant T time normal1stdIt is replaced into
The response calculated in step S49 composition V faster1Time constant T1, by normal for time time normal
Number T2stdIt is replaced into the composition V that the response calculated in step S49 is slower2Time constant T2。
Afterwards, according to time constant T after displacement1stdWith time constant T2stdSelect to use Fig. 8 and Fig. 9 to say
The condition recovering operating of bright fuel cell 20.
On the other hand, in step S45, in reference voltage VstdWith the voltage V recovered after operating3Difference
More than permissible level, it is determined that the permanent output voltage for fuel cell 20 reduces as being to allow
Level in the case of, it is judged that for fuel cell 20 key property reduce be fatal.In this situation
Under, enter into step S51, in order to urge refuelling battery 20, to operating, personnel inform fuel cell
20 contents reaching the life-span.
As above, use embodiments of the present invention, the output current value making fuel cell 20 is increased
The current value adding predetermined step amount and obtain is set to desired value, will be in order to make this target of output current tracking
It is higher that the indicial response of output voltage of value and fuel cell 20 in the case of driving is decomposed into response speed
Composition and the relatively low composition of response speed.And, according to each composition, it is determined that fuel cell 20 bad
The generation changed and degree thereof.Thus, it is possible to by going out to deteriorate from any composition detection, it is determined that deterioration
The classification of reason.It is as a result, it is possible to perform to recover operating with suitable condition corresponding with worsening reason,
In other words the reason recovering operating to eliminate deterioration it is able to carry out.
Further, in the case of according to responding composition detection faster and go out the deterioration of fuel cell 20, at electricity
Region and electric current density that current density is less are to measure the electricity of fuel cell 20 in moderate region respectively
Pressure value and current value, be set to the feelings of identical current value when magnitude of voltage and fuel cell 20 normally being worked
Magnitude of voltage under condition compares.Thus, going out the bad of fuel cell 20 according to responding composition detection faster
In the case of change, it is possible to judge its worsening reason in more detail.And, according to the difference energy of this magnitude of voltage
Enough determine to be set to promote by the condition recovering operating the reduction reaction on the catalyst converter surface of monocell condition,
Also it is set to the condition making the polymeric membrane of monocell humidify.Thus, becoming go-on-go faster according to response
In the case of measuring the deterioration of fuel cell 20, it is possible to perform to recover operating with more appropriate condition, it is possible to
Fuel cell 20 is made to recover more reliably.
Additionally, in the case of the deterioration going out fuel cell 20 according to the slower composition detection of response, pass through
The temperature of fuel cell 20 is measured in temperature sensor 21.Measurement result according to temperature sensor 21, it is possible to
Judge in more detail according to the worsening reason responding the fuel cell 20 that slower composition detection goes out.And,
Measurement result according to temperature sensor 21 can determine to be set to remove fuel cell by the condition recovering operating
The condition of the moisture within the monocell of 20, also it is set to make the moisture freezed within monocell melt
Condition.Thus, in the case of the deterioration going out fuel cell 20 according to the slower composition detection of response, energy
Enough with more appropriate condition execution recovery operating, it is possible to make fuel cell 20 recover more reliably.
Variation
In the present embodiment, in order to judge degree and the reason thereof of the deterioration of fuel cell 20, measure combustion
The indicial response of the output voltage of material battery 20, is broken down into responding composition and response faster slower
Composition, calculates respective time constant, but is not limited to this.Here, to by controlling 1DC
The switch of-DC transducer 30 calculates and responds the time constant of composition faster and respond slower composition
The variation of time constant illustrate.
In variation, during following, calculate the time constant responding composition faster.First,
By switch SW1～the SW4 Close All (original state) of 1DC-DC transducer 30.Then, will
Switch SW1 and switch SW3 opens, and is closed by switch SW2 and switch SW4, standby to fuel cell 20
Output voltage drop to predetermined value VlowerTill (the 1st blood pressure lowering work).If passing through voltage sensor
31 confirm value V that output voltage has reached predeterminedlower, the most then switch SW1 and switch SW3 is closed,
Being opened by switch SW2 and switch SW4, the standby output voltage to fuel cell 20 rises to predetermined value
VupperTill (boosting work).If confirming output voltage by voltage sensor 31 to rise to Vupper,
The most again SW1 and SW3 is opened, SW2 and SW4 is closed, standby drop to value to output voltage
VlowerTill (the 2nd blood pressure lowering work).Then, if confirming output voltage by voltage sensor 31 and reaching
Arrive value Vlower, then SW1～SW4 is closed.
In period being again switched off to all switch SW1～SW4 from above-mentioned original state, pass through
Voltage sensor 31 measures the output voltage of fuel cell 20, and in data, its measurement result record is processed dress
Put in 10.This measurement result carrys out record as seasonal effect in time series data arrangement.Figure 11 represents voltage sensor
One example of the measurement result of 31.When t11, the 1st blood pressure lowering work starts, and when t12, output voltage reaches
Vlower, boosting work starts, and when t13, output voltage reaches Vupper, the 2nd blood pressure lowering work starts,
During t14, output voltage reaches Vlower.In data processing equipment 10, calculate the time T of t12～t131a
Time T with t13～t141b.Then, according to time T1aWith time T1bCalculate the response in indicial response
Composition V faster1Time constant T1.By such as with mapping, function definition time T1aWith time T1b
The method etc. of meansigma methods and the mutual relation of actual time constant calculate time constant T1。
Determine during above and respond composition V faster1Time constant T1Afterwards, with Fig. 4's
The later process of step S14 calculate equally the time constant under the normal condition responding composition faster and
Time constant T1Difference DELTA T1, it is determined that difference DELTA T1Whether it is more than setting, if more than setting,
Then it is judged as there occurs the deterioration of the internal driving change of the deterioration of the reactive state of platinum catalysis device, monocell.
The time constant of the slower composition of response is calculated during following.1DC-DC is turned
Each switch of parallel operation 30 is set to original state.The original state of the blood pressure lowering work of 1DC-DC transducer 30
Refer to switch SW1 be open, switch SW2 be close, switch SW3 and switch SW4 with regulation duty
(switch SW3 is to open and switch SW4 to be the period closed and switch SW3 for closedown and switch SW4 to ratio
The ratio of period for opening) state changed.The initial of work of boosting of 1DC-DC transducer 30
State refer to switch SW4 be open, switch SW3 be close, switch SW1 and switch SW2 with regulation
(switch SW1 is to open and switch SW2 to be the period closed and switch SW1 for closedown and switch to dutycycle
SW2 is the ratio of period opened) state changed.In this variation, work by controlling blood pressure lowering,
I.e. by controlling switch SW3 and the dutycycle of switch SW4, the time calculating the slower composition of response is normal
Number.
Initially, by switch SW3 and switch SW4 dutycycle be set higher than blood pressure lowering work original state,
I.e. higher than setting, carry out the blood pressure lowering work (the 1st the blood pressure lowering work) output voltage until fuel cell 20
Drop to predetermined value VlowerTill.If confirming 1DC-DC transducer 30 by voltage sensor 31
Output voltage reached predetermined value Vlower, then the dutycycle of switch SW3 and switch SW4 is made to return to
Setting.Thus, output voltage is from VlowerRise (boosting work).If it is true by voltage sensor 31
Output voltage of accepting has reached predetermined value Vupper, the most again by switch SW3 and the dutycycle of switch SW4
It is set higher than setting, carries out blood pressure lowering work (the 2nd blood pressure lowering work) until output voltage drops to pre-
Fixed value VlowerTill.If confirming, by voltage sensor 31, value V that output voltage has reached predeterminedupper,
The dutycycle then making switch SW3 and switch SW4 returns to setting.Start to the from the 1st blood pressure lowering work
Till 2 blood pressure lowering end-of-jobs, measure fuel by the voltage sensor 31 of 1DC-DC transducer 30
The output voltage of battery 20.This measurement result carrys out record as seasonal effect in time series data arrangement.Figure 12 represents
One example of the measurement result of voltage sensor 31.
When t21, the 1st blood pressure lowering work starts, and when t22, output voltage reaches Vlower, boosting work starts,
When t23, output voltage reaches Vupper, the 2nd blood pressure lowering work starts, and when t24, output voltage reaches Vlower。
In data processing equipment 10, calculate the time T of t22～t232aTime T with t23～t242b.Then,
According to time T2aWith time T2bCalculate the composition V that the response in indicial response is slower2Time constant T2。
By such as with mapping, function definition time T2aWith time T2bThe phase of meansigma methods and actual time constant
The method etc. closed calculates time constant T2。
It addition, in this variation, control combustion by the dutycycle controlling switch SW3 and switch SW4
The buck of the output voltage of material battery 20, but it is not limited to this.Switch SW4 can also be set to open
Open, be set to switch SW3 close, control combustion by the dutycycle controlling switch SW1 and switch SW2
The buck of the output voltage of material battery 20.
This concludes the description of embodiments of the present invention, but the present invention be not limited to already described embodiment,
Various deformation and change can be carried out according to the technological thought of the present invention.
Description of reference numerals
10, data processing equipment；20, fuel cell；21, temperature sensor；30,1DC-DC
Transducer；31, voltage sensor；32, current sensor；40, inverter；50, motor；60、
2DC-DC transducer；70, battery.
Claims (5)
1. a deterioration detecting apparatus for vehicle fuel cell, it is for detecting combustion mounted on a vehicle
The deterioration of material battery, wherein,
This device includes:
Desired value configuration part, it is for target setting value, and this desired value is by by above-mentioned fuel cell
Current output current value increases predetermined step amount and obtains；
Indicial response measurement portion, it is for controlling the output electric current of above-mentioned fuel cell so that above-mentioned fuel
The output current value of battery follows the tracks of above-mentioned desired value, the mistake to the output voltage of above-mentioned fuel cell now
Cross response to measure；
Indicial response decomposition unit, it is for being decomposed into the indicial response of the output voltage of above-mentioned fuel cell
The 1st composition that response speed is higher and relatively low the 2nd composition of response speed；
Time constant calculating part, it is for calculating the 1st time constant and the above-mentioned 2nd of above-mentioned 1st composition
2nd time constant of composition；
Mathematic interpolation portion, it is for calculating the 1st difference and the 2nd difference；When above-mentioned 1st difference is 1 benchmark
Between constant and the difference of above-mentioned 1st time constant, above-mentioned 2nd difference be the 2nd fiducial time constant and above-mentioned
The difference of the 2nd time constant；Above-mentioned 1st fiducial time constant be above-mentioned fuel cell normal time above-mentioned
The time constant of 1 composition, above-mentioned 2nd fiducial time constant be above-mentioned fuel cell normal time the above-mentioned 2nd
The time constant of composition；And
Deterioration judging portion, when above-mentioned 1st difference is more than the setting of the 1st composition, is judging above-mentioned fuel
While the change of the impedance within the reactive state of the catalyst converter of battery and monocell causes deterioration to occur
Its degradation is judged；When above-mentioned 2nd difference is more than the setting of the 2nd composition, on judging
State while the change of the hydrogen of fuel cell and the supply condition of oxygen causes deterioration to occur, to its degradation
Judge.
The deterioration detecting apparatus of vehicle fuel cell the most according to claim 1, wherein,
In the case of the degradation judged according to above-mentioned 1st difference is beyond preset range,
Measure the 1st current value in the 1st region that the electric current density in above-mentioned fuel cell is less and the 1st electricity
Pressure value,
Measure the electric current density in above-mentioned fuel cell more than the 2nd electricity in the 2nd region in above-mentioned 1st region
Flow valuve and the 2nd magnitude of voltage,
Magnitude of voltage when being driven by above-mentioned 1st current value and above-mentioned the when above-mentioned fuel cell is normal
In the case of the difference of 1 magnitude of voltage is more than the 1st setting, according to the monocell that can promote above-mentioned fuel cell
The condition of reduction reaction on catalyst converter surface carry out operating and make the deterioration of above-mentioned fuel cell recover,
Magnitude of voltage when being driven by above-mentioned 1st current value and above-mentioned the when above-mentioned fuel cell is normal
The difference of 1 magnitude of voltage not less than above-mentioned 1st setting and when above-mentioned fuel cell is normal by
State the difference situation more than the 2nd setting of magnitude of voltage when the 2nd current value drives and above-mentioned 2nd magnitude of voltage
Under, carry out operating according to the condition of the polymeric membrane humidification of the monocell of above-mentioned fuel cell and make above-mentioned fuel
The deterioration of battery recovers.
The deterioration detecting apparatus of vehicle fuel cell the most according to claim 1, wherein,
In the case of the degradation judged according to above-mentioned 2nd difference is beyond preset range,
When the temperature of above-mentioned fuel cell is higher than temperature specifications value, according to the single electricity making above-mentioned fuel cell
The condition that moisture within pond removes carries out operating and makes the deterioration of above-mentioned fuel cell recover,
In the case of the temperature of above-mentioned fuel cell is less than said temperature setting, according to making above-mentioned fuel
The condition that the moisture freezed within the monocell of battery melts carries out operating and makes the bad of above-mentioned fuel cell
Change and recover.
The deterioration detecting apparatus of vehicle fuel cell the most according to claim 1, wherein,
Above-mentioned deterioration judging portion according to above-mentioned 1st difference judge above-mentioned fuel cell deteriorated time, root
The recovery duration of runs of the above-mentioned fuel cell that deterioration can be made to recover is determined according to above-mentioned 1st difference,
Above-mentioned deterioration judging portion when detecting that above-mentioned fuel cell has deteriorated according to above-mentioned 2nd difference,
The recovery duration of runs of the above-mentioned fuel cell that deterioration can be made to recover is determined according to above-mentioned 2nd difference.
The deterioration detecting apparatus of vehicle fuel cell the most according to claim 1, wherein,
Even if performing the recovery operating that the deterioration making above-mentioned deterioration judging portion determine recovers, can not make
In the case of the deterioration of above-mentioned fuel cell recovers, relative to the output electricity of above-mentioned fuel cell time normal
Pressure value, the reducing of output voltage values recovering the above-mentioned fuel cell after operating is less than predetermined permissible level
In the case of,
Set the new desired value of the output current value of above-mentioned fuel cell,
Control above-mentioned fuel cell so that output current value follows the tracks of above-mentioned new desired value, measure and now go up
State the indicial response of the output voltage of fuel cell,
The indicial response of the output voltage of above-mentioned fuel cell is decomposed into above-mentioned 1st composition and the above-mentioned 2nd
Composition,
Calculate the 3rd time constant and the 4th time constant of above-mentioned 2nd composition of above-mentioned 1st composition,
By above-mentioned 1st fiducial time constant be replaced into above-mentioned 3rd time constant, by above-mentioned 2nd fiducial time
Constant is replaced into above-mentioned 4th time constant.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-145560 | 2013-07-11 | ||
| JP2013145560A JP2015018701A (en) | 2013-07-11 | 2013-07-11 | Deterioration detecting device for vehicle fuel battery |
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| Publication Number | Publication Date |
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| CN104282925A CN104282925A (en) | 2015-01-14 |
| CN104282925B true CN104282925B (en) | 2016-11-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101015085A (en) * | 2004-09-07 | 2007-08-08 | 丰田自动车株式会社 | Fuel cell system and deterioration determination method for impurity removal member |
| CN102959782A (en) * | 2010-05-27 | 2013-03-06 | 丰田自动车株式会社 | Fuel cell system, control method for fuel cell system, and degradation determining method for fuel cell stack |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101015085A (en) * | 2004-09-07 | 2007-08-08 | 丰田自动车株式会社 | Fuel cell system and deterioration determination method for impurity removal member |
| CN102959782A (en) * | 2010-05-27 | 2013-03-06 | 丰田自动车株式会社 | Fuel cell system, control method for fuel cell system, and degradation determining method for fuel cell stack |
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