CN107017425A - The performance improvement method of fuel cell system and fuel cell system - Google Patents

The performance improvement method of fuel cell system and fuel cell system Download PDF

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Publication number
CN107017425A
CN107017425A CN201610879002.1A CN201610879002A CN107017425A CN 107017425 A CN107017425 A CN 107017425A CN 201610879002 A CN201610879002 A CN 201610879002A CN 107017425 A CN107017425 A CN 107017425A
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fuel cell
degree
processing
output voltage
increase
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CN201610879002.1A
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CN107017425B (en
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城森慎司
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Toyota Motor Corp
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Toyota Motor Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858—Electric variables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858—Electric variables
    • H01M8/04865—Voltage
    • H01M8/04873—Voltage of the individual fuel cell
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

Disclose the performance improvement method of fuel cell system and fuel cell system.The fuel cell system includes：Processing unit, is configured to that with processing frequency processing one section of duration of execution will be activated, the activation is handled the cathode potential temporary decrease of single fuel cell to target potential；Cation impurity amount estimation unit, is configured to estimate the amount of cation impurity being included in the dielectric film of the single fuel cell；And degree for the treatment of determining unit, it is configured to when the amount of cation impurity is big, at least one in action by performing the condition for changing activation processing acts to determine the degree of activation processing, the degree of the degree of activation processing identified activation processing than when the amount of cation impurity is small is high, and the action includes reducing the action of target potential, increase the action of duration and increasing the action of processing frequency.Activation processing is gone to identified degree by processing unit.

Description

The performance improvement method of fuel cell system and fuel cell system
Technical field
The present invention relates to the performance improvement method of fuel cell system and fuel cell system.
Background technology
Known following fuel cell system, the fuel cell system is configured to：When will activate one section of processing execution persistently Between, activation processing is electric to target by the cathode potential temporary decrease of at least one single fuel cell in fuel cell system Position, to improve the performance of the electrode catalyst in single fuel cell (for example, with reference to PCT Application No. 2003-536232 disclosure Japanese Translation (JP-A-2003-536232)).
When the electrode catalyst using the negative electrode of single fuel cell, oxidation is formed on the surface of electrode catalyst Film, this causes the performance degradation of electrode catalyst.In above-mentioned activation processing, pass through the moon in the single fuel cell of temporary decrease Electrode potential, reduces electrode catalyst, removes the oxide-film of covering electrode catalyst, and it is bad to improve electrode catalyst institute The performance of change.It therefore, it can improve the performance of single fuel cell.
The content of the invention
The present inventor performs the investigation to activation processing, and it was found that or even to single fuel at predetermined cathode potential In the case that battery performs activation processing, performance that still may be not to single fuel cell is sufficiently improved.By Activation processing, the i.e. more elevation to activation processing are performed at the cathode potential lower than predetermined cathode potential to single fuel cell Degree, the state regardless of single fuel cell, can modified electrode catalyst performance.However, being held by activation processing In the case of the higher degree that row is handled to activation, excessive activation processing promotes the dissolving of metal in electrode catalyst, and this can To cause the durability of electrode catalyst to deteriorate.Need one kind activation processing can be gone into appropriate degree and reliably improved The technology of the performance of single fuel cell.
According to the first aspect of the invention there is provided a kind of fuel cell system, the fuel cell system includes：Processing is single Member, is configured to：During the clear operation of fuel cell system, when will activate one section of processing execution persistently with processing frequency Between, activation is handled the cathode potential temporary decrease of at least one single fuel cell of fuel cell system to target potential； Cation impurity amount estimation unit, the cation impurity for being configured to estimate to be included in the dielectric film of single fuel cell Amount；And degree for the treatment of determining unit, it is configured to when the amount of cation impurity is big, changes the bar of activation processing by performing What an action or at least two in the action of part were acted combines to determine the degree of activation processing, the degree of activation processing Than when the amount of cation impurity is small, the degree of identified activation processing is high, and action includes reducing the action of target potential, increased Plus the action and the action of increase processing frequency of duration.Activation processing is gone to and determined by degree for the treatment of by processing unit Degree determined by unit.
According to the second aspect of the invention there is provided a kind of fuel cell system, the fuel cell system includes：Processing is single Member, is configured to during the clear operation of fuel cell system, and one section of duration is performed by processing is activated with processing frequency, Activation is handled the cathode potential temporary decrease of at least one single fuel cell of fuel cell system to target potential；And Degree for the treatment of determining unit, is configured to change by performing the action or at least two in the action for the condition that activation is handled Individual action combination come determine activation processing degree, action include reduce target potential action, increase the duration move Make and increase the action of processing frequency, wherein, degree for the treatment of determining unit passes through following operation and obtains single fuel cell Output voltage：When fuel cell system is operated with basic output current and basic output voltage, by the defeated of single fuel cell Go out electric current and be gradually increased to predetermined increase electric current from basic output current, output current is kept into an increase at increase electric current Output voltage in period, and measurement increase period；When output current is gradually increased to increase electric current and is kept At increase electric current, output voltage is gradually reduced to minimum voltage from basic output voltage and then increased to than basic output During the low burning voltage of voltage, the degree for activating processing is defined below by degree for the treatment of determining unit：With from output current Increase electric current is increased to pass through between the output voltage measured after the preset time period shorter than the increase period and minimum voltage Difference increase, as the difference between minimum voltage and basic output voltage increases, or with output current increase to increase Output voltage is changed into the period increase required for burning voltage after electric current, and the degree of activation processing becomes higher.Processing Activation processing is gone to the degree determined by degree for the treatment of determining unit by unit.
According to the third aspect of the invention we there is provided a kind of fuel cell system, the fuel cell system includes：Processing is single Member, is configured to during the clear operation of fuel cell system, and one section of duration is performed by processing is activated with processing frequency, Activation is handled the cathode potential temporary decrease of at least one single fuel cell of fuel cell system to target potential；And Degree for the treatment of determining unit, is configured to change by performing the action or at least two in the action for the condition that activation is handled Individual action combination come determine activation processing degree, action include reduce target potential action, increase the duration move Make and increase the action of processing frequency, wherein, one is kept at scheduled voltage in the output voltage of single fuel cell After the section scheduled time, degree for the treatment of determining unit is obtained at output current and predetermined output current at predetermined output voltage Output voltage at least one of output voltage, the value of the output current at predetermined output voltage and predetermined output current At least one of value it is relatively low when, the degree for activating processing is defined below by degree for the treatment of determining unit：The activation is handled Degree than in the value of the output voltage at the value and predetermined output current of the output current at predetermined output voltage at least One of it is relatively high when identified activation processing degree it is high.Activation processing is gone to and determines list by degree for the treatment of by processing unit Degree determined by first.
In the fuel cell system according to above-mentioned aspect, activation processing can be gone to appropriate degree, and can Reliably to improve the performance of single fuel cell.
There is provided a kind of performance improvement method of fuel cell system, the fuel cell according to the fourth aspect of the invention The performance improvement method of system includes：Processing will be activated with processing frequency and perform one section of duration, activation processing will at least one The cathode potential temporary decrease of individual single fuel cell is to target potential；Estimation is included in the dielectric film of single fuel cell Cation impurity amount；When the amount of cation impurity is big, one in action by performing the condition for changing activation processing It is individual action or at least two action combination come determine activation processing degree, the activation processing degree ratio work as cation impurity Amount hour determined by activation processing degree it is high, action includes reducing the action of target potential, increase duration and moved Make and increase the action of processing frequency；And when performing the clear operation of fuel cell system, activation processing is gone to Identified degree.
There is provided a kind of performance improvement method of fuel cell system, the fuel cell according to the fifth aspect of the invention The performance improvement method of system includes：During the clear operation of fuel cell system, performed with processing frequency by processing is activated One section of duration, activation is handled the cathode potential temporary decrease of at least one single fuel cell of fuel cell system extremely Target potential；By performing the combination of the action or at least two actions that change in the action for activating the condition handled come really The degree of fixed activation processing, action includes reducing the action of target potential, the action for increasing the duration and increase processing frequency The action of rate；The output voltage of single fuel cell is obtained by following operation：When fuel cell system is with basic output electricity When stream and the operation of basic output voltage, the output current of single fuel cell is gradually increased to predetermined increasing from basic output current Plus electric current, output current is kept an increase period at increase electric current, and the output electricity in the measurement increase period Pressure；When output current be gradually increased to increase electric current and be maintained at increase electric current, output voltage is from basic output voltage When gradually reducing to minimum voltage and then increasing to the burning voltage lower than basic output voltage, the degree of processing will be activated It is defined below：Measured with being increased to from output current after increase electric current passes through than increase period short preset time period Output voltage and minimum voltage between difference increase, between minimum voltage and basic output voltage difference increase, or With the period increase increased in output current required for output voltage after increase electric current is changed into burning voltage, the activation The degree of processing becomes higher；And activation processing is gone into identified degree.
There is provided a kind of performance improvement method of fuel cell system, the fuel cell according to the sixth aspect of the invention The performance improvement method of system includes：During the clear operation of fuel cell system, performed with processing frequency by processing is activated One section of duration, activation is handled the cathode potential temporary decrease of at least one single fuel cell of fuel cell system extremely Target potential；By performing the combination of the action or at least two actions that change in the action for activating the condition handled come really The degree of fixed activation processing, action includes reducing the action of target potential, the action for increasing the duration and increase processing frequency The action of rate；After the output voltage of single fuel cell is kept one section of scheduled time at scheduled voltage, obtain pre- Determine at least one of output voltage at the output current and predetermined output current at output voltage；At predetermined output voltage Output current value and predetermined output current at least one of the value of output voltage it is relatively low when, processing will be activated Degree is defined below：The activation processing degree than the value and predetermined output current of the output current at predetermined output voltage at At least one of the value of output voltage it is relatively high when identified activation processing degree it is high；And perform activation processing To identified degree.
Brief description of the drawings
Below with reference to accompanying drawings come describe the present invention illustrative embodiments feature, advantage and technology and industry meaning Justice, mark similar in the accompanying drawings represents similar key element, and wherein：
Fig. 1 is the block diagram of fuel cell system；
Fig. 2 is the fragmentary sectional view for showing single fuel cell；
Fig. 3 is to show the pass between the output current and output voltage of the single fuel cell for not including cation impurity The figure of system；
Fig. 4 is to show the relation between the output current and output voltage of the single fuel cell including cation impurity Figure；
Fig. 5 is to show that output current of the single fuel cell including cation impurity at predetermined output voltage be not close The figure of relation between degree and retained voltage；
Fig. 6 is the output current for showing the single fuel cell including a small amount of cation impurity at predetermined output voltage The figure of relation between density and retained voltage；
Fig. 7 is the output current for showing the single fuel cell including a large amount of cation impurities at predetermined output voltage The figure of relation between density and retained voltage；
Fig. 8 A are figures the reason for showing Fig. 5 to Fig. 7 phenomenon；
Fig. 8 B are figures the reason for showing Fig. 5 to Fig. 7 phenomenon；
Fig. 9 is the figure for the example for showing the relation between the resistance of dielectric film and the amount of cation impurity；
Figure 10 is the figure for determining the degree of activation processing；
Figure 11 is the figure for the performance improvement method for showing single fuel cell；
Figure 12 is the figure of the method for the amount for showing estimation cation impurity；
Figure 13 is the figure of the method for the amount for showing estimation cation impurity；
Figure 14 is the figure of the method for the amount for showing estimation cation impurity；
Figure 15 is the figure for the example for showing the relation between the amount of voltage decline and the amount of cation impurity；
Figure 16 is the figure for the example for showing the relation between the amount of minimum value decline and the amount of cation impurity；
Figure 17 is the figure for the example for showing the relation between the period of needs and the amount of cation impurity；
Figure 18 is the flow chart of the routine for the performance improvement control action for showing fuel cell system；
Figure 19 is the flow chart for the routine for showing fuel cell system cationic impurity level estimation control action；
Figure 20 is that the activation degree for the treatment of for showing fuel cell system determines the flow chart of the routine of control action；
Figure 21 is the flow chart of the routine for the activation processing control action for showing fuel cell system；
Figure 22 is the figure of the method for the amount for showing the estimation cation impurity in another embodiment；
Figure 23 is the table for showing the relation between output current and the amount of cation impurity；
Figure 24 is the figure of the method for the amount for showing the estimation cation impurity in another embodiment；
Figure 25 is the table for showing the relation between output voltage and the amount of cation impurity；
Figure 26 is the table for showing the relation between the amount of output voltage, output current and cation impurity；
Figure 27 is the table for showing the relation between operating time and the amount of cation impurity；And
Figure 28 is the block diagram for showing the fuel cell system according to another embodiment.
Embodiment
Reference picture 1, fuel cell system A includes fuel cell pack 10.Fuel cell pack 10 includes layered product, the layered product Including a plurality of single fuel cells 2 being stacked in the stacking direction.Each including in the single fuel cell 2 of layered product： Film-electrode gas diffusion layer component 20；And separator (not shown), it is disposed in film-electrode gas diffusion layer component 20 Opposite side.Film-electrode gas diffusion layer component 20 includes：Dielectric film；And be arranged in dielectric film opposite side anode and Negative electrode.
The anode of one single fuel cell 2 be electrically connected to the first side of layered product by separator with the single combustion Expect the negative electrode of the neighbouring another single fuel cell 2 of battery 2, and the negative electrode of single fuel cell 2 is electrically connected by separator It is connected to the anode of another single fuel cell 2 neighbouring with single fuel cell 2 of the second side of layered product.The first of layered product The negative electrode formation fuel cell pack 10 of the anode of the single fuel cell 2 of side and the single fuel cell 2 of the second side of layered product Electrode.The electrode of fuel cell pack 10 is electrically connected to inverter 12 by DC/DC converters 11, and inverter 12 is electric It is connected to genemotor 13.Fuel cell system A includes electric power storing device 14, and the electric power storing device 14 passes through DC/DC converters 15 are electrically connected to inverter 12.Output current that 11 pairs of DC/DC converters are exported from fuel cell pack 10 and The value of output voltage is controlled, and the value of output current and output voltage is changed and by the output current after conversion There is provided with the value of output voltage to inverter 12.Inverter 12 will be exported from DC/DC converters 11 or electric power storing device 14 DC electric current is converted into AC electric currents.DC/DC converters 15 will be from fuel cell pack 10 or genemotor 13 to electric power storing device The voltage control of 14 outputs is low, or the voltage exported from electric power storing device 14 to genemotor 13 is controlled as height. In the fuel cell system A shown in Fig. 1, electric power storing device 14 is formed by battery.
In single fuel cell 2, form for the hydrogen as fuel gas to be provided to the fuel gas of anode Flow path, for the air as oxidant gas being provided to the oxidant gas flow paths of negative electrode and for will be cold But water extraction is supplied to the flow of cooling water path of single fuel cell 2.The fuel gas flow path of a plurality of single fuel cells 2 Connection parallel to each other, the oxidant gas flow paths connection parallel to each other of a plurality of single fuel cells 2, and a plurality of lists The flow of cooling water path connection parallel to each other of individual fuel cell 2.Therefore, fuel gas flow is formed in fuel cell pack 10 Path 30, oxidant gas flow paths 40 and flow of cooling water path 50.Fuel gas flow path 30, oxidant gas stream Dynamic path 40 and flow of cooling water path 50 include fuel gas manifold (manifold), oxidant gas manifold and cooling water discrimination Pipe.
Fuel gas supply pipe 31 is connected to the entrance of fuel gas flow path 30, and the fuel gas supply pipe 31 are connected to fuel gas source 32.In the embodiment shown in Fig. 1, fuel gas source 32 is formed by hydrogen gas tank.In fuel In gas supply pipe 31, according to the order from upstream to downstream, arrange in shutoff valve 33, regulation fuel gas supply pipe 31 The adjuster 34 of the pressure of fuel gas and for fuel gas to be provided to fuel cell pack 10 from fuel gas source 32 Fuel gas injector 35.On the other hand, anode waste gas pipe 36 is connected to the outlet of fuel gas flow path 30.Closing In the case of valve 33 and the opening of fuel gas injector 35, the fuel gas in fuel gas source 32 passes through fuel gas supply pipe 31 are provided to the fuel gas flow path 30 of fuel cell pack 10.Now, the gas flowed out from fuel gas flow path 30 Body, i.e. anode waste gas are flowed into anode waste gas pipe 36.In anode waste gas pipe 36, arranged according to the order from upstream to downstream Anode waste gas is divided into the row for the liquid that gas and the gas-liquid separator 37 of liquid and control are accumulated in gas-liquid separator 37 The exhaust-control valve 38 put.The entrance of fuel gas circulation pipe 81 is connected to the top of gas-liquid separator 37, and fuel gas The outlet of body circulation pipe 81 is connected to the part of the upstream for being arranged in fuel gas injector 35 of fuel gas supply pipe 31. In fuel gas circulation pipe 81, fuel gas circulating pump 39 is arranged, fuel gas circulating pump 39 is in gas-liquid separator 37 Gas (anode waste gas separated) enter line feed.In the case of fuel gas circulating pump 39 is powered, gas-liquid is accumulated in Anode waste gas in separator 37 is circulated to fuel gas supply pipe 31.In another embodiment unshowned in the accompanying drawings, It is not provided with the gas-liquid separator 37 in anode waste gas pipe 36.
Oxidant gas supply pipe 41 is connected to the entrance of oxidant gas flow paths 40, and the oxidant gas Supply pipe 41 is connected to oxidant gas source 42.In the embodiment shown in Fig. 1, oxidant gas source 42 is by air shape Into.In oxidant gas supply pipe 41, gas cleaner 43, feeding oxidant are arranged according to the order from upstream to downstream The air supply or turbocompressor 44 of gas and for being fed to by turbocompressor 44 in fuel cell pack 10 The intercooler 45 that oxidant gas is cooled down.On the other hand, cathode exhaust pipe 46 is connected to oxidant gas flow The outlet in path 40.In cathode exhaust pipe 46, cathode off-gas control valve 47 is arranged, the control of cathode off-gas control valve 47 is flowed through Pressure in the amount of cathode exhaust inside cathode exhaust pipe 46 or the oxidant gas flow paths 40 of fuel cell pack 10.Oxygen The entrance of oxidant gas shunt valve 49 is connected to the downstream for being arranged in intercooler 45 of oxidant gas supply pipe 41 Part, and the outlet of oxidant gas shunt valve 49 be connected to cathode exhaust pipe 46 be arranged in cathode off-gas control valve 47 The part in downstream.In oxidant gas shunt valve 49, oxidant gas bypass control valve 48 is arranged.Oxidant gas is bypassed Control valve 48 controls to flow to the sky of cathode exhaust pipe 46 from oxidant gas supply pipe 41 when fuel cell pack 10 is bypassed The flow rate of gas.In the fuel cell system A shown in Fig. 1, oxidant gas bypass control valve 48 is formed by triple valve.In turbine Compressor reducer 44 is driven and downstream oxidation agent gas supply pipe 41D is connected to upstream oxygen by oxidant gas bypass control valve 48 In the case of oxidant gas supply pipe 41U, oxidant gas is provided to the oxidant gas flow paths of fuel cell pack 10 40, wherein upstream oxidizing dose of gas supply pipe 41U is arranged on being arranged in by oxidant gas of oxidant gas supply pipe 41 At the part of the upstream of road control valve 48, and downstream oxidation agent gas supply pipe 41D is arranged on oxidant gas supply pipe 41 are arranged at the part in the downstream of oxidant gas bypass control valve 48.Now, flowed from oxidant gas flow paths 40 The gas (i.e. cathode exhaust) gone out is flowed into cathode exhaust pipe 46.In oxidant gas bypass control valve 48 by by oxidant gas In the case that road pipe 49 is connected to upstream oxidizing dose of gas supply pipe 41U, the one of the amount of the air discharged from turbocompressor 44 Cathode exhaust pipe 46 is provided to partially or completely through oxidant gas shunt valve 49.In the embodiment shown in Fig. 1, whirlpool Wheel compression device 44 is formed by centrifugal turbocompressor or axial-flow turbine compressor reducer.From visual angles such as size reductions, preferably make Use centrifugal turbocompressor.
Diluter is set in the part of cathode exhaust pipe 46 of the outlet downstream of oxidant gas shunt valve 49 is arranged in 80.The outlet of anode waste gas pipe 36 is connected to diluter 80.In diluter 80, it is included in anode using cathode exhaust dilution and gives up Hydrogen in gas so that from diluter 80 be emitted into the gas of extraneous air in density of hydrogen be feasible value or smaller value. The cathode exhaust flowed into diluter 80 also includes the oxidant gas flowed into from oxidant gas shunt valve 49.
One end of cooling water supply pipe 51 is connected to the entrance in flow of cooling water path 50, and cooling water supply pipe 51 is another One end is connected to the outlet in flow of cooling water path 50.In cooling water supply pipe 51, the cooling water of feeding cooling water is arranged Pump 52 and radiator 53.The part for being arranged in the upstream of radiator 53 of cooling water supply pipe 51 is connected by radiator bypass pipe 54 The downstream of radiator 53 and the part between radiator 53 and cooling water pump 52 are arranged in cooling water supply pipe 51.Separately Outside, there is provided the radiator bypass control valve 55 being controlled to the amount for flowing through the cooling water inside radiator bypass pipe 54. In fuel cell system A shown in Fig. 1, radiator bypass control valve 55 is formed by triple valve and is disposed in radiator bypass The porch of pipe 54.In the case of cooling water pump 52 is powered, the cooling water discharged from cooling water pump 52 is supplied by cooling water In the flow of cooling water path 50 that fuel cell pack 10 is flowed into pipe 51, cooling water is also flowed into by flow of cooling water path 50 and supplied To in pipe 51, and cooling water pump 52 is then back to by radiator 53 or radiator bypass pipe 54.
Electronic control unit 60 is formed by digital computer, and read-only is deposited including what is be connected to each other by bidirectional bus 61 Reservoir (ROM) 62, random access memory (RAM) 63, microprocessor (CPU) 64, input port 65 and output port 66.With pre- Fix time interval (for example, 0.1ms) by corresponding AD converter 67 by following inputs to input port 65：Measure fuel electricity The output signal of the output current of pond heap 10 and the output transducer 16 of output voltage；Measure a plurality of single fuel of layered product The output signal of the output transducer 17 of each output current and output voltage in battery 2；Measure fuel cell pack 10 The output signal of the temperature sensor 18 of temperature；Detect the output of the range sensor 19 of the scope (range) of transmission for vehicles Signal；And the output signal of the pressure sensor (not shown) in fuel cell system A.It will be inputted from each sensor to defeated The data of the output signal of inbound port 65 are stored on RAM 63 as operation history.On the other hand, output port 66 passes through phase The drive circuit 68 answered is electrically connected to shutoff valve 33, adjuster 34, fuel gas injector 35, exhaust-control valve 38, fuel gas Body circulation pump 39, turbocompressor 44, cathode off-gas control valve 47, oxidant gas bypass control valve 48, the and of cooling water pump 52 Radiator bypass control valve 55.
However, when expecting the generation electric power in fuel cell pack 10, shutoff valve 33 and fuel gas injector 35 are beaten Open so that fuel gas is provided to fuel cell pack 10.In addition, turbocompressor 44 is driven so that oxidant gas quilt There is provided to fuel cell pack 10.Therefore, in single fuel cell, occurs electrochemical reaction (H22H++2e-,(1/2)O2+2H++ 2e-H2O) so that generation electric energy.The electric energy generated is provided to genemotor 13.Therefore, genemotor 13, which is operated, is Motor for driving vehicle so that electric vehicle is driven.On the other hand, for example, when vehicle is braked, genemotor 13 operations are generating apparatus again so that the electric energy regenerated is accumulated in electric power storing device 14.
As shown in Fig. 2 in the film-electrode gas diffusion layer component 20 of single fuel cell 2, anode 5a is formed on electricity Solve plasma membrane 5e side and including anode catalyst layer 5as and anode gas diffusion layer 5ad, negative electrode 5c is formed on dielectric film 5e opposite side and including cathode catalysis layer 5cs and cathode gas diffusion layer 5cd.In film-electrode gas diffusion layer component 20 Anode separator 3a is arranged in anode 5a sides, and arranges cathode separator in the negative electrode 5c sides of film-electrode gas diffusion layer component 20 3c。
As dielectric film 5e material, i.e., as electrolyte, it is, for example, possible to use with cation conductivity Cationic ion-exchange resin based on fluorine, such as perfluorinated sulfonic acid, its specific example include NAFION (registered trade name).It is anode-catalyzed The example of the material of layer 5as and cathode catalysis layer 5cs electrode catalyst includes the catalyst carrier carbon of support platinum or platinum alloy (catalyst-supporting carbon).In another embodiment unshowned in the accompanying drawings, will by with dielectric film 5e Electrolyte identical electrolyte formation the ionomer such as cationic ion-exchange resin based on fluorine added to catalysis Agent carrier carbon.As anode gas diffusion layer 5ad and cathode gas diffusion layer 5cd material, such as using conductive porous body, and And its example includes：Carbon porous body, such as carbon paper, carbon cloth or vitreous carbon；And metal porous body, such as wire netting or metal foam. The example of anode separator 3a and cathode separator 3c material includes metal, such as stainless steel or Ti.
In the case where expecting to generate electric power in the fuel cell system A shown in Fig. 1, according to electric power storing device 14 The load of the quantity of electric charge and the dynamotor 13 represented by the volume under pressure of such as accelerator pedal obtains fuel cell pack 10 Expectation electric current value.Next, the output current value for obtaining fuel cell pack 10 reaches the fuel gas needed for expectation electric current value Flow rate and flow rate of oxygen, that is, obtain desired fuel gas flow rate and desired flow rate of oxygen, and based on desired oxygen stream Rate obtains desired oxidant gas flow rate.Next, adjuster 34 and fuel gas injector 35 are controlled such that feedback The fuel gas flow rate for delivering to fuel cell pack 10 is desired fuel gas flow rate, and turbocompressor 44 and cathode exhaust Control valve 47 is controlled such that the oxidant gas flow rate for being fed to fuel cell pack 10 is desired oxidant gas flow rate.
However, in fuel cell system A, during fuel cell system A operation, the list in fuel cell pack 10 Oxide-film is formed on the cathode catalysis layer 5cs of individual fuel cell 2 electrode catalyst (for example, platinum or platinum alloy).Therefore, electrode The performance degradation of catalyst, and the performance of single fuel cell 2 also deteriorates.In order to handle this problem, in fuel cell system A In, during fuel cell system A operation, the amount for the air for reducing negative electrode 5c sides is performed with the single fuel cell of temporary decrease The activation processing of 2 cathode potential, so that the performance of modified electrode catalyst.But, although its reason is unclear, but very Also can not be so that the performance of single fuel cell be sufficiently improved to after being handled in execution activation.Therefore, in order to illustrate very To the reason for still can not sufficiently improve the performance of single fuel cell 2 after performing activation processing, the present inventor's concern is electric The reason for amount of the cation impurity of metal in solution plasma membrane 5e is as the problem.
Here, during fuel cell system A operation, air of the cation together with offer to fuel cell pack 10 It is merged in the single fuel cell 2 of fuel cell pack 10.For example consider to be included in the Ca or Na in Snow Agent and be included in Fe, Mo, Cr or Al in fuel cell system A component, are used as these cations.Use cation-exchange membrane such as NAFION (registered trade name), is used as the dielectric film 5e of single fuel cell 2.Therefore, it is merged in single fuel cell 2 in cation In in the case of, cation penetrate into amberplex in, be retained in film, and in envelope sulfonic group substitution.Therefore, in sun In the case of the amount of cation in amberplex is increased, in cation-exchange membrane and H+The relevant sulfonic group of ionic conduction Amount reduce, it is difficult to mobile H+Ion, i.e. proton conductive are deteriorated.Therefore, degradation of cell performance.Therefore, it is contemplated that in cation In the case that the amount of impurity is big, the effect for activating processing is offset by the deterioration of the battery performance as caused by cation impurity, therefore The performance of single fuel cell 2 is not improved.
The present invention to the amount of dielectric film 5e cationic impurity and activation processing between relation carried out investigation and The fact that be found that following.That is, in the case where the amount of cation impurity during activation is handled is small, the degree of processing no matter is activated It is low or height, the degree of the performance improvement of single fuel cell 2 is essentially the same.However, activation handle during sun from In the case that the amount of sub- impurity is big, when the degree of activation processing is low, the degree of the performance improvement of single fuel cell 2 is low, and When the degree of activation processing is high, the degree of the performance improvement of single fuel cell 2 is high.That is, the list obtained is handled by activating The degree of the performance improvement of individual fuel cell 2 depends on the amount of cation impurity.The even single combustion after activation processing is performed Expect that the reason for performance improvement of battery 2 is still insufficient is：Although the amount of the cation impurity in dielectric film 5e is low, The degree for activating processing is low, i.e. be not the amount in view of cation impurity to perform activation processing.Therefore, in order in activation The performance of single fuel cell 2 is reliably improved in processing, it is necessary to change the degree for activating processing according to the amount of cation impurity. Hereinafter, the fuel cell system A according to the present invention is will be described in, wherein changing activation according to the amount of cation impurity The degree of processing.
First, it will describe between the amount of the dielectric film 5e cationic impurity of single fuel cell 2 and activation processing Relation.
Fig. 3 is the output electricity for showing the single fuel cell 2 in the case where dielectric film 5e does not include cation impurity Relation between pressure and output current is the figure of IV characteristics.Fig. 4 is to show a case that dielectric film 5e includes cation impurity Under single fuel cell 2 IV characteristics figure.In figs. 3 and 4, trunnion axis represents output current density, and vertical axes represent defeated Go out voltage.In the present embodiment, as indicate dielectric film 5e in cation impurity amount index example, use electricity Solve the ratio of the sulfonic proton replaced with cation impurity in plasma membrane 5e, i.e. sulfonic group substitute proportion.In figure 3, sulphur Acidic group substitute proportion is 0%, and in Fig. 4, sulfonic group substitute proportion is 30%.Tested under the following conditions：It is single Fuel cell 2：1cm2Battery, fuel gas/oxidant gas：H2/ air (1L/ minutes), and single fuel cell 2 temperature Degree：83 DEG C of (relative humidity：30%).
In figs. 3 and 4, curve EI01 and curve EI02 represent the single fuel cell 2 before measurement IV characteristics Cathode potential the situation of 30 minutes is held continuously in 0V.In the present embodiment, will immediately cathode potential before measuring The value being kept is referred to as " retained current potential ", and retained current potential is 0V in this case.On the other hand, in Fig. 3 and Fig. 4 In, curve EI11 and curve EI12 represent the cathode potential of the single fuel cell 2 before measurement IV characteristics in 0.6V quilts The situation of continuous holding 30 minutes, i.e., retained current potential is 0.6V situation.
In other words, curve EI01 and curve EI02, which are shown, is improving the performance of single fuel cell 2 by operations described below The IV characteristics measured afterwards：Activation processing is fully performed to single fuel cell 2 at 0V target potential to continue within 30 minutes Time, rather than reduce the flow rate of the oxidant gas of negative electrode 5c sides.Similarly, curve EI11 and curve EI12 show and passed through Operations described below improves the IV characteristics measured after the performance of single fuel cell 2：To single fuel at 0.6V target potential Battery 2 fully performs the duration of activation processing 30 minutes, rather than reduces the flow rate of the oxidant gas of negative electrode 5c sides.
As shown in figure 3, curve EI01 and curve EI11 are not overlapped substantially each other.Thus, it is found that miscellaneous not by cation In the single fuel cell 2 of matter pollution, performance (IV characteristics) improved degree does not change, and is not dependent on the mesh of activation processing Scalar potential is 0V or 0.6V.In other words, the target potential that the effect of the activation processing of single fuel cell 2 is handled according to activation Substantially constantization.Thus, it is found that in the case where single fuel cell 2 is not polluted by cation impurity, or even at activation During degree low (for example, 0.6V) of reason, the performance of single fuel cell 2 is still modified.
On the other hand, as shown in figure 4, curve EI12 is more precipitous than curve EI02.Thus, it is found that dirty by cation impurity In the single fuel cell 2 of dye, in the case where the target potential of activation processing is 0.6V, performance (IV characteristics) improved degree It is lower for performance (IV characteristics) the improved degree measured in the case of 0V than target potential.In other words, single fuel cell 2 is sharp The target potential significant changes that the effect of processing living is handled according to activation.Thus, it is found that miscellaneous by cation in single fuel cell 2 In the case that matter pollutes, the degree with activation processing becomes higher (for example, 0V), further improves single fuel cell 2 Performance.
The experimental result shown in Fig. 3 and Fig. 4 is shown jointly into Fig. 7 in Fig. 5.Fig. 5 is shown when single fuel cell 2 In dielectric film 5e sulfonic group substitute proportion output current of the single fuel cell 2 at predetermined output voltage when being 0% The figure of relation between density and retained voltage.Trunnion axis represents retained current potential, and vertical axes represent that output current is close Degree.In Figure 5, curve A01, A02 and A03 represents that the oxygen concentration being provided in negative electrode 5c oxidant gas is respectively 16%th, 5% and 1% situation.Two curves are depicted for each case to survey twice to represent to perform for each case Amount.Curve A01, A02 and A03 in Fig. 5 show by by the cathode potential of single fuel cell 2 at retained current potential It is continuous kept for 30 minutes after output current density and retained current potential at the predetermined output voltage that obtains of measurement IV characteristics it Between relation.By being fully to perform activation processing 30 minutes at retained current potential to single fuel cell 2 in target potential Duration improve the performance of single fuel cell 2 after, IV characteristics are measured.
As shown in figure 5, in the case that the sulfonic group substitute proportion of the dielectric film 5e in single fuel cell 2 is 0%, I.e. in the case where single fuel cell 2 is not polluted by cation impurity, output current density substantial constant, and be not dependent on Retained current potential.Therefore, the degree substantial constant of the performance improvement of single fuel cell 2, and it is not dependent on activation processing Target potential.It is therefore contemplated that in the case where single fuel cell 2 is not polluted by cation impurity, or even when activation When the degree of processing is relatively low, the performance improvement of single fuel cell 2 is still sufficient.This equally should apply to oxygen concentration change Change is the situation of output current variable density.
Fig. 6 and Fig. 7 are shown when the sulfonic group substitute proportion of the dielectric film 5e in single fuel cell 2 is respectively Relation when 30% and 70% between output current density and retained voltage of the single fuel cell 2 at predetermined output voltage Figure.On trunnion axis, vertical axes, curve A11, A12 and A13 and curve A21, A22 and A23, Fig. 5 description can be applicable In Fig. 6 and Fig. 7.
As shown in Figure 6 and Figure 7, the sulfonic group substitute proportion of the dielectric film 5e in single fuel cell 2 be 30% or In the case of 70%, i.e., the situation that single fuel cell 2 is polluted by cation impurity, or even at identical output voltage, output Current density changes still according to retained current potential.In addition, with the reduction of retained current potential, the increase of output current density.Therefore, The degree of the performance improvement of single fuel cell 2 changes according to the target potential of activation processing, and as target potential drops It is low, further improve performance.With the amount increase of cation impurity, this trend becomes notable.It is therefore contemplated that , can be by determining at activation when the amount of cation impurity is big in the case that single fuel cell 2 is polluted by cation impurity The degree of reason properly modifies the performance of single fuel cell 2, and the degree of activation processing is than when the amount of cation impurity is small The degree of the activation processing of measurement is high.This equally should apply to the oxygen concentration change i.e. situation of output current variable density.
It for example such as can get off to speculate the mechanism of Fig. 5 to Fig. 7 phenomenon.Fig. 8 A and Fig. 8 B are to show showing for Fig. 5 to Fig. 7 As the reason for figure.Fig. 8 A show a case that the degree of the low i.e. activation processing of retained current potential is high.Fig. 8 B show retained The low situation of the current potential high degree that i.e. activation is handled.M+Represent cation.H+Represent proton (hydrogen ion).Electrode can not be used to urge Removing for oxide-film in agent carrys out explanation figure 5 to Fig. 7 phenomenon, and Fig. 5 to Fig. 7 phenomenon can be speculated as got off.Example Such as, as shown in Figure 8 B, in the normal operation period, cathode potential is high, therefore cation is concentrated.However, as shown in Figure 8 A, it is contemplated that By the potential difference for going to activation processing between high level, reduction anode 5a and negative electrode 5c, cation does not concentrate on negative electrode Side, and cation dispersion opens.On the other hand, as shown in Figure 8 B, it is contemplated that by the way that activation processing is gone into low degree, it is impossible to drop Potential difference between low anode 5a and negative electrode 5c, cation still concentrates on cathode side and cation retains.Therefore, it is contemplated that： In the case of the degree height that processing is activated after activation processing, cation is as shown in Figure 8 A；Handled immediately in activation In the case that the degree of activation processing is low after tight, cation is as shown in Figure 8 B；And when the survey in the state of Fig. 8 A and Fig. 8 B IV characteristics are as shown in Figures 5 to 7 during amount.
As described above, cathode potential is maintained at low potential by being handled due to activation, dielectric film 5e is eliminated Cathode side cation concentration uneven (Fig. 8 A).Therefore, it is contemplated that activation processing not only has the electrode for removing negative electrode The effect of oxide-film on catalyst, and the concentration with the cation impurity in correction dielectric film 5e is to cause cation The equally distributed effect of impurity.In other words, it is contemplated that the performance of single fuel cell 2 is not only due to the oxide-film on electrode catalyst And deteriorated due to the concentration of the cation impurity in dielectric film 5e.However, being handled according to the activation of present embodiment In, the oxide-film on electrode catalyst can be removed, and cation impurity can be evenly distributed in dielectric film 5e. It therefore, it can further improve the performance of single fuel cell 2.
Based on result above, in the present embodiment, the journey for changing according to the amount of cation impurity and activating processing is performed The new activation processing of degree, rather than perform the activation processing that cathode potential is only reduced to predeterminated target current potential.That is, In the case that the amount of cation impurity in dielectric film 5e is zero or is minimum, relatively low degree of activation processing is determined, this is Because only needing to remove the oxide-film on electrode catalyst in activation is handled.In this case, it is not necessary to which it is miscellaneous to eliminate cation The concentration of matter it is uneven.Therefore, the performance of electrode catalyst is improved, so as to improve the performance of single fuel cell 2.Separately On the one hand, in the case that the amount of the cation impurity in dielectric film 5e is big, the activation processing of relative high degree is determined, this is Because must remove the oxide-film on electrode catalyst in activation processing and eliminate the uneven of the concentration of cation impurity. Therefore, improve the performance of electrode catalyst, eliminate cation impurity concentration it is uneven, so as to improve single fuel The performance of battery 2.By this way, when the amount of the cation impurity in dielectric film 5e is big, determine at the activation of high level Reason, and when the amount of the cation impurity in dielectric film 5e is small, determine the activation processing of low degree.It therefore, it can fully The performance of modified electrode catalyst, and the amount of the metal eluted from electrode catalyst can be reduced.
Here, the degree of activation processing is maintained at target potential by value, the cathode potential of the target potential of cathode potential The length of the duration at place activates the frequency of processing to represent.Can by change a condition or two or more The combination of condition activates the degree of processing to change.Here, in the value changes of the target potential of cathode potential to increase at activation In the case of the degree of reason, target potential is defined as low.The duration at target potential is maintained in cathode potential In the case of degree of the length change to increase activation processing, length will be defined as the duration.In the frequency change of activation processing In the case of degree to increase activation processing, the frequency for activating processing is defined as height.The reason on the situation, speculates such as Under.The translational speed of cation impurity is slow during potential change, but can be by the increase duration to correct cathode side Cation impurity concentration.In addition, when frequency increases, cathode potential is maintained at the accumulated time increase at low potential, It is hereby achieved that with duration increased situation identical effect.
In the present embodiment, value, the cathode potential for changing the target potential of cathode potential are maintained at target potential Duration length and activation processing frequency, with adjust activation processing degree.The scope of target potential is for example 0.6V to 0.05V.The scope of duration is such as 1 second to continuous.The interval for representing the frequency of activation processing is such as 1 minute To continuous.Table 1 below illustrates the example of the combination of the degree of the activation processing in present embodiment.
[table 1]
In table 1, the degree for activating processing is divided into four grades.It is the lowest class L4's in the degree of activation processing In the case of, target potential is 0.6V, and the duration is 1 second, and frequency is 10 minutes.It is secondary low in the degree of activation processing In the case of level L3, target potential is 0.4V, and the duration is 5 seconds, and frequency is 5 minutes.It is in the degree of activation processing In the case of secondary high-grade L2, target potential is 0.2V, and the duration is 10 seconds, and frequency is 1 minute.In the degree of activation processing In the case of being highest ranking L1, target potential is 0.05V, and the duration is the period for the condition that meets, and frequency is continuous. Data shown in table 1 are stored on the ROM 62 of such as electronic control unit 60.
In addition to the amount of the cation impurity in dielectric film 5e, other factors such as fuel cell pack 10 can also be used Temperature or operation output history, be used as determine activation processing degree index.
For example, the temperature of fuel cell pack 10 and dielectric film 5e relative humidity are the water capacity (water of per unit volume Divide content) it is corresponding, and there is correlation with dielectric film 5e relative humidity.It is relatively high in the temperature of fuel cell pack 10 In the case of, dielectric film 5e relative humidity (water capacity) is low, and this has very big to the cation impurity in dielectric film 5e Influence.Data of this point according to Fig. 9 are clear.Fig. 9 is the resistance and cation impurity for showing dielectric film The figure of the example of relation between amount.In fig .9, vertical axes represent the matter in dielectric film 5e resistance, i.e. dielectric film 5e Son (H+) transfer resistance, and trunnion axis represents sulfonic group substitute proportion.Curve B1 represents that dielectric film 5e relative humidity is 30% situation, and curve B2 represents that dielectric film 5e relative humidity is 80% situation.As shown in figure 9, with relatively wet Degree reduces (curve B1), and film resistance increase, i.e. battery performance are intended to decline that (proton translocation resistance and electric power, which generate performance, to be had Correlation (negative correlation)).As sulfonic group substitute proportion (amount of cation impurity) increases, the trend becomes notable.Therefore, send out Under conditions of the temperature of the present dielectric film 5e low i.e. fuel cell pack 10 of relative humidity is high, in addition it is miscellaneous in identical cation During the amount of matter, the deterioration of battery performance is still notable, and it is high to activate the effect of processing.Therefore, it is identical in the amount of cation impurity Under conditions of, in the case where the temperature of the dielectric film 5e low i.e. fuel cell pack 10 of relative humidity is relatively high, it is determined that activation The degree of processing, the degree of activation processing is lower than the temperature of the high i.e. fuel cell pack 10 of relative humidity in dielectric film 5e In the case of the degree of activation processing that determines it is high.For example, it may be considered that following methods, temperature of this method based on fuel cell pack 10 Degree whether be preset threshold temperature (for example, 80 DEG C) or higher or lower than threshold temperature come change activation processing degree. In this case, by the data storage of threshold temperature on the ROM 62 of such as electronic control unit 60.
Figure 10 is the figure for determining the degree of activation processing.The figure shows the cation impurity in dielectric film 5e Amount, four grade L1 of the degree as activation processing of the temperature of fuel cell pack 10 and table 1 are to the relation between L4. This, trunnion axis represents the amount of cation impurity, and vertical axes represent the degree of activation processing.Straight line T01 is represented by temperature The temperature that sensor 18 is obtained is the figure of 80 DEG C or higher of situation, and straight line T02 is the temperature for representing to be obtained by temperature sensor 18 The figure of situation of the degree less than 80 DEG C.The figure is divided into R1 areas according to the order of the top from activation processing to minimum level Domain, R2 regions, R3 regions and R4 regions.Data shown in Figure 10 are stored on the ROM 62 of such as electronic control unit 60.
Amount based on estimated cation impurity and the degree for the activation processing being shown on straight line T01 or T02 are It is no to be located in R1 regions, R2 regions, R3 regions or the R4 regions determined according to the temperature of measured fuel cell pack 10, come true The degree of fixed activation processing.In the case where the degree for the activation processing being shown on straight line is located in R1 regions, at activation The degree of reason is defined as L1.In the case where the degree for the activation processing being shown on straight line is located in R2 regions, at activation The degree of reason is defined as L2.In the case where the degree for the activation processing being shown on straight line is located in R3 regions, at activation The degree of reason is defined as L3.In the case where the degree for the activation processing being shown on straight line is located in R4 regions, at activation The degree of reason is defined as L4.For example, the amount in cation impurity is estimated as the temperature of CAC1 and single fuel cell 2 and is less than In the case of 80 DEG C, the point Q2 on straight line T02 is specified.Because point Q2 is located in R3 regions, so L3 is elected to be into activation processing Degree.In addition, in the amount of cation impurity, to be estimated as the temperature of CAC1 and single fuel cell 2 be 80 DEG C or higher of feelings Under condition, the point Q1 on straight line T01 is specified.Because point Q1 is located in R1 regions, so L1 to be elected to be to the degree of activation processing.
It is single during fuel cell system A operation in order to improve in fuel cell system A based on result above The performance of individual fuel cell 2, performs the performance improvement control that the performance to improve single fuel cell 2 is handled using following activation Action.
Figure 11 is the figure for the performance improvement method for showing single fuel cell.Left vertical axes represent single fuel cell 2 Output voltage VO UT, right vertical axes represent the output current IO UT (being shown as current density) of single fuel cell 2, Yi Jishui Flat axle represents the time.Block curve shows the output voltage VO UT of single fuel cell 2, and dashed curve show it is single The output current IO UT of fuel cell 2.Because anode potential is 0V, therefore output voltage VO UT can be thought of as to negative electrode electricity Position.Even when fuel cell system A is in clear operation under idle condition, by applying minimum to fuel cell pack 10 Constant output current is idle output current with so that applying open-circuit voltage between anode 5a and negative electrode 5c, to prevent anode from urging Change layer 5as and cathode catalysis layer 5cs deterioration.Now, output voltage VO UT is idle output voltage.
In the embodiment shown in Figure 11, when fuel cell system A is with idle output current IA0 and idle output voltage When VA0 is idle, the performance improvement control action of single fuel cell 2 is appropriately performed.The reason for situation, is as follows.Due in list The quantity delivered of oxidant gas, therefore fuel cell are reduced in the activation processing performed in the performance improvement method of individual fuel cell Output reduce, but the output during clear operation needed for fuel cell is low.Therefore, to the behavior such as acceleration shadow of vehicle Sound is little.In the present embodiment, when speed changer stops in the range of (P) and during ignition switch, clear operation is performed. By determining speed changer whether in P scopes, it is determined whether perform clear operation.Another embodiment unshowned in the accompanying drawings In, electronic control unit 60 (CPU 64) determines that fuel cell pack 10 is based on the output signal exported from output transducer 17 It is no idle in P scopes.In the present embodiment, the single combustion during clear operation when speed changer is located in P scopes is performed Expect the performance improvement method of battery.The reason for situation, is as follows.Performed in the case of being in speed changer in traveling (D) scope During clear operation, fuel cell system from clear operation can be converted to normal operating immediately, the fuel electricity in normal operating Cell system is operated with output current corresponding with load with output voltage.Therefore, oxidant gas is reduced in activation processing In the case of the quantity delivered of body, problem is there may be in normal operating.As an alternative, it is necessary to stop activation processing.On the other hand, In the case where speed changer is in P scopes, it may be desirable to which the time ratio of clear operation is in the case where speed changer is in D scopes It is longer.Therefore, idle output current IA0 is the sky for the performance improvement control action for not performing single fuel cell 2 in P scopes The expectation electric current value of fuel cell pack 10 during spare time operation.
Reference picture 11, in time ta1, first, range sensor 19 of the electronic control unit 60 (CPU 64) from speed changer Receive the output signal for the scope for representing speed changer.When speed changer is not in P scopes, the performance improvement of single fuel cell 2 Control action is completed, and performs normal operating.In the normal operation period, fuel cell pack 10 is with corresponding with the load needed for vehicle Output current and output voltage operated.
In the case where speed changer is in P scopes, when being not provided with the activation with single fuel cell 2 it is desirable that performing When handling the degree of the relevant activation processing of control action, the amount of the cation impurity in dielectric film 5e is estimated.That is, During from time ta1 to time ta2 period, electronic control unit 60 (CPU 64) performs the estimation control of cation impurity amount Action.Cation impurity amount estimation control action is described below.Therefore, in time ta2, estimate sun in dielectric film 5e from Sulfonic group substitute proportion in the amount of sub- impurity, i.e. present embodiment.On the other hand, when setting the degree of activation processing, hold The activation processing control action of traveling line activating processing.Activation processing control action is described below.
Next, electronic control unit 60 (CPU 64), which performs activation degree for the treatment of, determines control action.First, measurement combustion Expect the temperature of battery pile 10.That is, in time ta2, electronic control unit 60 (CPU 64) is obtained from temperature sensor 18 The temperature of fuel cell pack 10.Temperature sensor 18 can be considered as to the temperature for the temperature for being configured to measure fuel cell pack 10 Measuring unit.As described above, the temperature of fuel cell pack 10 and dielectric film 5e relative humidity have correlation.For example, In the case that the temperature of fuel cell pack 10 is relatively high, dielectric film 5e relative humidity is low.It therefore, it can temperature sensor 18 are considered as the relevant parameter measuring unit for the value for being configured to measure the parameter related to dielectric film 5e relative humidity.
The amount and fuel cell pack 10 of the cation impurity of electronic control unit 60 (CPU 64) based on dielectric film 5e Temperature, the relevant data of the content of the table 1 by reference to the data relevant with Figure 10 figure and with being stored on ROM 62 The degree for activating processing is defined as one of L1 to L4.In example shown in the accompanying drawings, based on target potential VA1, processing frequency Rate Δ tai and duration of Δ tap come determine activation processing degree.Electronic control unit 60 (CPU 64) can be considered as It is configured to the degree for the treatment of determining unit that amount based on cation impurity etc. determines the degree of activation processing.
Next, electronic control unit 60 (CPU 64) performs activation processing based on the degree of identified activation processing Control action.That is, while reduction is provided to the flow rate of negative electrode 5c oxidant gas by turbocompressor 44, holding Output voltage VO UT is that cathode potential is maintained at target potential VA1 with processing frequency Δ tai by line activating processing, activation processing Duration of Δ tap.That is, first in from time ta2 to time ta3 period, based on the life from electronic control unit 60 Output voltage VO UT is maintained at idle output voltage VA0 and is maintained at output current IO UT by order, DC/DC converters 11 At idle output current IA0.Next, in from time ta3 to time ta4 period, based on from electronic control unit 60 Order, output voltage VO UT becomes target potential VA1 by DC/DC converters 11 so that activation processing is performed.Can be by electricity Sub-control unit 60 (CPU 64), turbocompressor 44 and DC/DC converters 11, which are considered as, to be configured to swash with processing frequency Processing living performs the processing unit of one section of duration, and the activation is handled the cathode potential temporary decrease of single fuel cell extremely Target potential.
Next, repeating aforesaid operations.For example, in from time ta4 to time ta5 period, output voltage VO UT quilts It is maintained at idle output voltage VA0, and output current IO UT is maintained at idle output current IA0.Next, from In time ta5 to time ta6 period, output voltage VO UT becomes target potential VA1, and output current IO UT becomes target current IA1.Therefore, activation processing is performed.In the case where processing frequency is " continuous ", the output voltage VO UT in Figure 11 is kept Period Δ tax at idle output voltage VA0 is 0 (zero).
Next, for example, in time ta7, in the case of the activation processing of the undesirable electrode catalyst for performing negative electrode, For example, in the case where the speed changer of vehicle is converted to traveling (D) scope, electronic control unit 60 (CPU 64) prevents activation Processing.
In the present embodiment, cation impurity amount estimation control action is performed during clear operation.However, in accompanying drawing Not shown in another embodiment in, the estimation control of cation impurity amount is performed during the operation in addition to clear operation Action.
In the activation degree for the treatment of of present embodiment determines control action, with reference to the cation impurity in dielectric film 5e Amount and fuel cell pack 10 temperature.However, in another embodiment unshowned in the accompanying drawings, only with reference to dielectric film 5e In cation impurity amount, or with reference to the amount and the temperature of fuel cell pack 10 of the cation impurity in dielectric film 5e At least one operated in output of degree and fuel cell pack 10.
In the activation degree for the treatment of of present embodiment determines control action, the temperature of fuel cell pack 10 is referred to as and phase The parameter related to humidity.In another embodiment unshowned in the accompanying drawings, using single fuel electricity can be estimated according to it Another parameter of the relative humidity of dielectric film 5e in pond 2, to replace the temperature of fuel cell pack 10.It is related to relative humidity The impedance of example including single fuel cell 2 of other specification, gas near the dielectric film 5e of single fuel cell 2 The temperature of a part for the cooling water supply pipe 51 near single fuel cell 2 in humidity and fuel cell pack 10.For example, In the case where impedance is high, estimate that the water capacity in dielectric film 5e reduces and electric conductivity is deteriorated.It is thereby possible to reduce phase To humidity.In the case that the humidity of gas near dielectric film 5e is low, estimate from dielectric film 5e evaporate moisture and Reduce moisture.It is thereby possible to reduce relative humidity.A part for cooling water supply pipe 51 near single fuel cell 2 In the case that temperature is high, estimates from dielectric film 5e evaporation moistures and reduce moisture.It is thereby possible to reduce relative humidity.
Next, the cation in the dielectric film 5e for the single fuel cell 2 for describing to estimate fuel cell pack 10 is miscellaneous The method of the amount of matter.The following methods developed by the present inventor can be used, the method for the amount of estimation cation impurity is used as. That is, in the method, the output current of single fuel cell 2 is stepped up during the operation in fuel cell system A And when being kept, measure the behavior of the output voltage of single fuel cell 2.This method is based on the following thing being discovered by the present inventors It is real：The amount of cation impurity in dielectric film 5e with when during fuel cell system A operation single fuel cell 2 it is defeated Going out the behavior of the output voltage for the single fuel cell 2 that electric current is stepped up and measured when being kept has correlation.Below In, it will be described with reference to the accompanying drawings details.
Figure 12 is the figure of the method for the amount for showing estimation cation impurity.The diagrammaticalIy is shown when single fuel electricity Output voltage VO UT measured when being stepped up the output current IO UT in pond 2 behavior.In the figure, left vertical axes represent single The output voltage VO UT of individual fuel cell 2, right vertical axes represent that the output current IO UT of single fuel cell 2 (is shown as electric current Density), and horizontal axis plots time.Block curve shows the output voltage VO UT of single fuel cell 2, and dotted line song Line shows the output current IO UT of single fuel cell 2.
Figure 12 is shown controls the output current of single fuel cell to estimate the amount of cation impurity according to preassigned pattern Situation.That is, Figure 12 shows situations below：When in time t0 fuel cell pack 10 with basic output current IB and base When this output voltage VB is operated, the single fuel cells 2 of time t1 output current IO UT from basic output current IB by Step increases to predetermined increase electric current IG and increase period Δ from time t1 to time t3 is kept at increase electric current IG t0.Here, basic output current IB is the expectation electric current value of the fuel cell pack 10 during following normal operating：In the normal behaviour The method for not performing the amount of estimation cation impurity during work.In fig. 12, basic output current IB is to compare predetermined threshold electric current Such as under idle condition output current low the output current IO UT of fuel cell pack 10.When the amount by cation impurity is estimated When method (Figure 12) is applied to performance improvement control action (Figure 11), basic output current IB is corresponding with idle output current IA0, And output voltage VB substantially is corresponding with idle output voltage VA0.
In this case, output voltage VO UT is gradually reduced to minimum voltage VM in time t1 from basic output voltage VB And the burning voltage VC lower than basic output voltage VB is then increased to, the time t3 after increase period Δ t0. However, in the example depicted in fig. 12, increase period Δ t0 is following stabilization time section：Stabilization time section output electricity enough Pressure VOUT is changed into burning voltage.After it have passed through increase period Δ t0, output current IO UT is back to basic output current IB.Now, at least three below value relevant with output voltage VO UT behavior and the cation impurity in dielectric film 5e Measurer has correlation.That is, three values include：(1) the amount Δ V that voltage declines, the amount Δ V that the voltage declines are minimum electricity The difference between VM and output voltage VE is pressed, output voltage VE is in the time after it have passed through preset time period Δ t1 from time t1 T2 output voltage VO UT；(2) minimum value slippage Δ Vm, minimum value slippage Δ Vm are minimum voltage VM and basic output Difference between voltage VB；And (3) output voltage VO UT after output current IO UT increases to increase electric current IG is changed into stable The period Δ t2 from time t1 to time t22 required for voltage VC.With the amount of the cation impurity in dielectric film 5e Increase, the amount Δ V increases that (1) voltage declines, (2) minimum value slippage Δ Vm increases, and the period Δ t2 required for (3) Increase.In the present embodiment, the amount for having used (1) voltage to decline.
The amount declined on (1) voltage, in the case that Figure 13 shows that the amount of the cation impurity in dielectric film 5e is small Output voltage VO UTn and the cation impurity in dielectric film 5e amount it is big in the case of output voltage VO UTc between Difference, and Figure 14 is the zoomed-in view for the part for showing Figure 13.On left vertical axes and right vertical axes and trunnion axis Description is identical with Figure 12.Grasped when in time t0 fuel cell pack 10 with basic output current IB with basic output voltage VB When making, it is stepped up in the output current IO UT of the time t1 single fuel cells 2 being illustrated by the broken lines from basic output current IB To predetermined increase electric current IG.Output current IO UT is kept the increase period from time t1 to time t3 at increase electric current IG Δt0.Here, as represented by the chain-dotted line in Figure 13, in the case that the amount of the cation impurity in dielectric film 5e is small Output voltage VO UTn is gradually reduced to minimum voltage VMn and then increased to after the time t 2 from basic output voltage VB Time t21 at burning voltage VCn, burning voltage VCn is lower than basic output voltage VB.On the other hand, such as in Figure 13 Solid line represented by, the output voltage VO UTc in the case that the amount of the cation impurity in dielectric film 5e is big is gradually from base This output voltage VB is reduced to minimum voltage VMc and is then increased to the stable electricity at time t22 after the time t 2 VCc is pressed, burning voltage VCc is lower than basic output voltage VB.
Now, increase with the amount of the cation impurity in dielectric film 5e, as minimum voltage VM with from time t1 It has passed through the amount Δ V increases that poor, voltage between the output voltage VE of the time t2 after preset time period Δ t1 decline. In this case, preset time period Δ t1 is the arbitrary value shorter than increase period Δ t0.For example, as shown in figure 14, as most Poor, the voltage between output voltage VEc in the case that the amount of small voltage VMc and the cation impurity in dielectric film 5e is big The amount Δ Vc of decline is bigger than the amount Δ Vn that voltage declines, and the amount Δ Vn that the voltage declines is minimum voltage VMn and dielectric film 5e In cation impurity amount it is small in the case of output voltage VEn between difference.
Figure 15 shows the example of the relation between the amount Δ V that the amount and voltage of cation impurity decline.Trunnion axis is represented The ratio of the sulfonic proton replaced with cation impurity in dielectric film 5e.Vertical axes represent the amount Δ V that voltage declines. The substitute proportion is the example of the value for the amount for representing cation impurity.As shown in curve CL, with the use in dielectric film 5e The ratio increase of the sulfonic proton of cation impurity substitution, the amount Δ V increases that voltage declines, and taken with cation impurity The amount Δ V that the ratio of proton in the sulfonic group in generation declines with voltage has correlation.Therefore, if in increase period Δ t0 In data at predetermined increase electric current IG places in advance shown in measurement Figure 15, then can be by measuring the amount Δ V of voltage decline simultaneously And the amount of sulfonic group substitute proportion, i.e. cation impurity is estimated with reference to the data that measure in advance.Here, be obtained ahead of time on In estimation cation impurity amount Figure 15 figure data and store it on ROM 62.
Although the original of the relation between not knowing the amount Δ V that the amount and voltage of cation impurity as shown in Figure 15 decline Cause, but speculate that reason is as follows.First, when fuel cell pack 10 output current IO UT from predetermined basic output current IB progressively The reason for output voltage VO UT is rapidly reduced to VM when increasing to increase electric current IG is presumed as follows.Due to the influence with water, Anode 5a is dry, and cation impurity ratio is more slowly moved with water, and impurity movement is to follow, therefore interior resistance increases temporarily. Next, speculating that the reason for output voltage VO UT is slowly back to VE is as follows.Because the movement of cation impurity is slow, therefore tightly It is connected on after output current IO UT increases and a large amount of cation impurities occurs in dielectric film 5e anode 5a sides.However, cation Impurity Q is slowly moved to negative electrode 5c sides, stabilized, and does not prevent the conduction of H+ ions.Therefore, output voltage VO UT It is slowly back to VE.By this way, VM and VE have an impact to cation impurity.Therefore, the amount and voltage of cation impurity Relation between the amount Δ V (=ME-VM) of decline is as shown in figure 15.
However, during the amount Δ V dropped under voltage measurement, in order to be easily performed measurement, it is preferable that to increase electric current IG and basic output current IB are configured so that the amount Δ V that voltage declines is big.For this purpose, when basic output current When IB is gradually increased to increase electric current IG, it can will increase electric current IG and basic output current IB and be arranged so that what voltage declined Measure Δ V very big.For example, the output current that electric current IG is set to measure under fuel cell system A full load state will be increased IOUT.In this case, output current IO UT extremely increases, and correspondingly output voltage VO UT is extremely reduced.Therefore, it can also increase Power up the amount Δ V of drops.As an alternative, when basic output current IB is lower than predetermined threshold electric current, output current IO UT is from base This output current IB is gradually increased to increase electric current IG.In this case, because basic output current IB is low, therefore it is used as ginseng The basic output voltage VB examined is increased.It therefore, it can significantly increase the amount Δ V of voltage decline.
In the present embodiment, the amount that (1) voltage declines is used.However, in another embodiment, using (2) minimum It is worth the period that the amount declined or (3) need.The amount declined on (2) minimum value, Figure 16 show the amount of cation impurity with The example of relation between the amount Δ Vm that minimum value declines.Trunnion axis represents the sulfonic group substitute proportion in dielectric film 5e.It is perpendicular D-axis represents the amount Δ Vm that minimum value declines.Therefore, it can by measure minimum value decline amount Δ Vm and with reference to Figure 16 come Obtain the amount of cation impurity.On the other hand, the period needed on (3), Figure 17 shows the amount of cation impurity with needing Relation between the period Δ t2 wanted.Trunnion axis represents the sulfonic group substitute proportion in dielectric film 5e.Vertical axes represent to need The period Δ t2 wanted.It therefore, it can the period Δ t2 by measuring needs and reference Figure 17 to obtain cation impurity Amount.
Based on the above-mentioned fact, in fuel cell system A, make with the following method to perform the estimation control of cation impurity amount Action：This method is when the dielectric film of estimation his A of fuel cell system (in time ta1) in performance improvement control action (Figure 11) The amount for using (1) voltage to decline during the amount of the cation impurity in 5e.However, in the present embodiment, basic output current IB It is identical with idle output current IA0, and basic output voltage VB is identical with idle output voltage VA0.
That is, based on the order (instruction) from electronic control unit 60, DC/DC converters 11 will be from fuel cell The output current IO UT of heap 10 (single fuel cell 2) output is gradually increased to increase electric current IG from predetermined basic output current IB And output current IO UT is kept into predetermined increase period Δ t0 at increase electric current IG.Next, output current IO UT is returned It is back to basic output current IB.The electric current of single fuel cell 2 is controlled here, DC/DC converters 11 can be considered as Controller.
Now, output transducer 17 measures the output voltage VO UT of single fuel cell 2 behavior, output voltage VO UT From basic output voltage VB gradually reduce to minimum voltage VM and then increase to increase period Δ t0 after ratio base Burning voltage VC low this output voltage VB.Here, output transducer 17 can be considered as to the output for measuring single fuel cell 2 Voltage VOUT measuring unit.Measured output voltage VO UT behavior is stored on such as RAM 63.
Next, the data based on the output voltage VO UT being stored on RAM 63, electronic control unit 60 calculate from Output current IO UT increases to increase electric current IG and have passed through the amount Δ V that the voltage after preset time period Δ t1 declines.Next, Amount Δ V based on voltage decline is taken sulfonic group by reference to the data for the figure on Figure 15 being stored in advance on ROM 62 For amount of the ratio estimate for the cation impurity in dielectric film 5e.Here, electronic control unit 60 can be considered as based on institute The estimation unit of the amount of the output voltage VO UT estimation cation impurities of the single fuel cell 2 of measurement.
Estimate control action by performing above-mentioned cation impurity amount, fuel cell system A can be estimated in fuel cell The amount of cation impurity during system A operation in the dielectric film 5e of single fuel cell 2.In the present embodiment, exist Cation impurity amount estimation control action is performed during clear operation.However, during the operation in addition to clear operation Cation impurity amount estimation control action can be performed.In this case, be performed separately with performance improvement control action sun from Sub- impurity level estimates control action.
Passed in addition, fuel cell system A includes the DC/DC converters 11 as controller, the output as measuring unit Sensor 17 and the electronic control unit 60 as estimation unit.It therefore, it can fuel cell system A being considered as including cation Impurity level estimation unit, the cation impurity amount estimation unit includes controller and measuring unit and is configured to estimate single The amount of cation impurity in the dielectric film of fuel cell.
Figure 18 shows the performance improvement control action of the single fuel cell 2 in the fuel cell system A for Fig. 1 Routine.The routine is performed as interrupt action using predetermined time interval.Reference picture 18, in step 100, determines speed changer Whether P scope is converted to.It is in a step 101, sharp about whether determining in the case where speed changer is arranged in P scopes Activate the degree of processing to be determined in processing control action living.It is determined that the activation in activation processing control action is handled Degree in the case of, processing is carried out to step 104.It is converted to after P scopes, does not know from D scopes immediately in by speed changer Activate the degree of processing.Therefore, processing is carried out to step 102.In a step 102, perform sun in estimation dielectric film 5e from The cation impurity amount estimation control action of the amount of sub- impurity.Next, in step 103, performing based on institute in a step 102 The amount of the cation impurity of estimation determines that the activation degree for the treatment of of the degree of activation processing determines control action.Next, in step In rapid 104, activation processing control action is performed based on the degree of identified activation processing in step 103.When in step In the case that speed changer is not arranged in P scopes in 100, in step 105, normal behaviour is performed in fuel cell system A Make.In the normal operation period, fuel cell pack 10 is operated with the output current and output voltage corresponding with load.
Figure 19 is to show to estimate control action for the cation impurity amount in the fuel cell system A shown in Fig. 1 Routine flow chart.The routine is performed in the step 102 of Figure 18 performance improvement routine.Here, in the present embodiment, Basic output current IB is identical with idle output current IA0, and basic output voltage VB is identical with idle output voltage VA0. Reference picture 19, in step 200, the output current IO UT of fuel cell pack 10 is gradually increased to from basic output current IB to increase Plus electric current IG.Output current IO UT is kept increase period Δ t0 at increase electric current IG.Next, in step 201, surveying Following output voltage VO UT behavior is measured, output voltage VO UT is gradually reduced to minimum voltage VM simultaneously from basic output voltage VB And then increase to the burning voltage VC lower than basic output voltage VB.Next, in step 202., from output current IOUT is gradually increased to after increase electric current IG have passed through increase period Δ t0, and output current IO UT is reduced to basic output electricity Flow IB.Next, in step 203, calculated based on measured output voltage VO UT behavior from output current IO UT It is gradually increased to increase electric current IG and have passed through falling quantity of voltages Δ V after preset time period Δ t1.The amount declined based on voltage Δ V estimates the amount of the cation impurity in dielectric film 5e by reference to the data of the figure on Figure 15.
The activation degree for the treatment of that Figure 20 shows in the fuel cell system A for Fig. 1 determines the routine of control action. The routine is performed in the step 103 of Figure 18 performance improvement routine.Reference picture 20, measures fuel cell pack 10 in step 300 Temperature.Next, in step 301, the amount based on the cation impurity in the dielectric film 5e estimated in a step 102 with And the temperature of measured fuel cell pack 10 determines to swash by reference to Figure 10 data and the data of table 1 in step 301 The degree (target potential VA1, processing frequency Δ tai and duration of Δ tap) of processing living.
Figure 21 shows the routine of the activation processing control action in the fuel cell system A for Fig. 1.In Figure 18 property The routine is repeated in the step 104 that routine can be improved.Reference picture 21, in step 400, it is determined whether by output voltage VOUT is reduced to target potential VA1.In the case where output voltage VO UT is reduced to target potential VA1, determine in step 401 Whether duration of Δ tap is passed through.In the case where have passed through duration of Δ tap, output voltage VO UT is back to original electricity Position, i.e., the idle output voltage VA0 in step 402.On the other hand, in the case of no process duration of Δ tap, processing Terminate.In the case of output voltage VO UT is not reduced into target potential VA1 in step 400, determine in step 403 Whether it is interval by processing frequency Δ tai.In the case where have passed through interval, in step 404, output voltage VO UT reductions To target potential VA1.On the other hand, in the case of not through super-interval, processing terminates.
Next, another embodiment that fuel cell system A will be described.In the present embodiment, in order to determine activation The degree of processing, with reference to the history of the operation output (output voltage × output current) of fuel cell pack 10.Operation output History is stored on such as RAM 63.The operation output of fuel cell pack 10 is in nearest predetermined amount of time (for example, 5 minutes) The operation output of fuel cells heap 10, and it is corresponding with the surrounding road condition of vehicle.Operation in nearest predetermined amount of time Output it is relatively low in the case of, it is anticipated that vehicle operation output may be low road (for example there is the road of traffic jam Road) on travel.It therefore, it can estimate that the performance recovery effect obtained by performing activation processing will be small.Therefore, do not hold Line activating processing or the activation processing for determining low degree.On the contrary, the operation output in nearest predetermined amount of time is relatively high In the case of, it is anticipated that vehicle is travelled on the road (such as highway) that operation output must be high.It therefore, it can estimate The performance recovery effect obtained by performing activation processing will be big.Accordingly, it is determined that the activation processing of high level.Now, may be used To obtain the history of operation output from the RAM 63 for the operation history that is stored with.RAM 63 can be considered as to the storage nearest scheduled time The nearest history storage unit of the history of the operation output of fuel cell pack 10 in section.
Next, the another embodiment that fuel cell system A will be described.Present embodiment is with estimating single fuel cell Above-mentioned embodiment in the method for the amount of cation impurity in 2 dielectric film 5e is different.Hereinafter, description is estimated The method of the amount of cation impurity.
Figure 22 is the figure of the method for the amount for showing estimation cation impurity, and shows the IV of single fuel cell 2 Characteristic.Trunnion axis represents that output current density, and vertical axes represent output voltage.Curve ExI1 and curve ExI2 are represented immediately The cathode potential of single fuel cell 2 is held continuously predetermined at predetermined voltage (for example, 0.6V) place before measurement IV characteristics The situation of time (for example, 1 minute).Here, curve ExI1 represents that dielectric film 5e does not include the situation of cation impurity, i.e. sulphur Acidic group substitute proportion is 0%.Curve ExI2 represents that dielectric film 5e includes the situation of cation impurity, i.e. sulfonic group substitute proportion It is greater than 0% predetermined value (for example, 30%).In the example shown in Figure 22, at predetermined output voltage Ex (curve ExI1) place In the case that sulfonic group substitute proportion is 0%, output current density is Ixb.However, in sulfonic group substitute proportion in predetermined output In the case of being predetermined value at voltage Ex, output current density is Ixa.Therefore, it is predetermined defeated by being obtained ahead of time in experiment etc. The relation gone out between the output current density at voltage Ex and sulfonic group substitute proportion, can obtain sulphur according to output current density Acidic group substitute proportion.Specifically, single fuel cell 2 cathode potential be held continuously at predetermined voltage the scheduled time it Afterwards, the output current density at predetermined output voltage Ex is obtained.Then, by reference at the predetermined output voltage Ex that is obtained ahead of time Sulfonic group substitute proportion and output current density between relation, sulfonic group substitute proportion can be obtained.As Figure 23 is shown The table of the relation between output current density Ix and sulfonic group substitute proportion SR at predetermined output voltage Ex is stored in ROM On 62.
As an alternative, output voltage can be made to be substituted for each other with output current density.Figure 24 is to show that estimation cation is miscellaneous The figure of the method for the amount of matter, and show the IV characteristics of single fuel cell 2.On trunnion axis, vertical axes and curve EXI1 and EXI2 description is identical with Figure 22.In the example shown in Figure 24, in predetermined output current density Ix (curves ExI1 in the case that) sulfonic group substitute proportion in place's is 0%, output voltage is Exb.However, at predetermined output current density Ix In the case that sulfonic group substitute proportion is predetermined value (for example, 30%), output voltage is Exa.Therefore, by pre- in experiment etc. The relation between the output voltage and sulfonic group substitute proportion at predetermined output current density Ix is first obtained, can be according to output electricity Press to obtain sulfonic group substitute proportion.Specifically, single fuel cell 2 cathode potential at predetermined voltage (for example, 0.6V) Place was held continuously after the scheduled time (for example, 1 minute), obtained the output voltage at predetermined output current density Ix.Then, , can by reference to the relation between the sulfonic group substitute proportion and output voltage at the predetermined output current density Ix that is obtained ahead of time To obtain sulfonic group substitute proportion.Show that the output voltage Ex at predetermined output current density Ix replaces with sulfonic group such as Figure 25 The table of relation between ratio SR is stored on ROM 62.
Alternatively, output voltage can be combined with output current density.That is, being obtained ahead of time in an experiment As Figure 26 shows the table of the relation between output current density Ix, output voltage Ex and sulfonic group substitute proportion SR.Therefore, The output voltage Ex at measurement output current density Ix arbitrary value or measurement output voltage Ex arbitrary value can be passed through Reference table obtains sulfonic group substitute proportion SR after the output current density Ix at place.Such as Figure 26 table is stored in advance in ROM On 62.
Next, a further embodiment that fuel cell system A will be described.Present embodiment is with estimating single fuel cell Above-mentioned embodiment in the method for the amount of cation impurity in 2 dielectric film 5e is different.As described above, it is considered to for example will It is included in the Ca in Snow Agent or Na and Fe, Mo, Cr or Al for being included in fuel cell system A component is as cation Impurity.Thus it is speculated that going out：As long as the operating time increase of fuel cell pack 10, the amount of cation impurity is increased by.Therefore, exist The operating time of fuel cell pack 10 and amount (the sulfonic group substitution of the cation impurity in dielectric film 5e are obtained ahead of time in experiment Ratio) between relation.Therefore, it can to obtain by obtaining the total operating time of fuel cell pack 10 thitherto sun from The amount (sulfonic group substitute proportion) of sub- impurity.Such as Figure 27 is shown to the total operating time td and dielectric film of fuel cell pack 10 The table of relation between amount (sulfonic group substitute proportion) SR of cation impurity in 5e is stored in advance on ROM 62.Now, The total operating time of fuel cell pack 10 thitherto can be obtained from the RAM 63 for the operation history that is stored with.For estimating sun The parameter of the amount of ionic impurity is not limited to the total operating time of fuel cell pack 10.It is, for example, possible to use accommodating fuel cell pack The total travel distance of 10 vehicle, or can use expression such as by by current value and/or magnitude of voltage and fuel cell pack 10 Operating time be combined acquisition functional value operation note parameter, for example the gross generation of fuel cell pack 10 is (i.e., By by power be multiplied by the time obtain value) or fuel cell pack 10 total current value (that is, by the way that the electric current time of being multiplied by is obtained The value obtained).The feelings of the cation impurity accumulated in fuel cell pack 10 are being washed and removed by using known method Under condition, the operating time after operation note can be used as washed and removing, instead of the total operating time of fuel cell pack 10. The value of these parameters is stored on RAM 63.In this way it is possible to which RAM 63 is considered as into storage represents fuel cell pack 10 Operation note parameter operation note memory cell.
Next, another embodiment that fuel cell system A will be described.In the above-described embodiment, first, (A) sun The electrology characteristic of the single fuel cell 2 of ionic impurity amount estimation unit measurement and operating time are (hereinafter referred to as " electricity is special Property etc. ").Next, (B) cation impurity amount estimation unit based on measured electrology characteristic etc. by reference to being obtained ahead of time Relation between electrology characteristic etc. and cation impurity amount estimation unit estimates the amount of cation impurity.(C) activation processing is true Order amount of the member based on estimated cation impurity is handled by reference to the amount of the cation impurity pre-set with activation Relation between degree determines the degree of activation processing.However, the invention is not restricted to present embodiment.
In yet another embodiment, in step (A) to not performing step (B) between (C).First, (A) cation impurity amount Estimation unit measures electrology characteristic of single fuel cell 2 etc..(C ') activation processing determining unit is special based on measured electricity Property etc. the journey of activation processing is determined by reference to the relation between electrology characteristic for pre-setting etc. and the degree of activation processing Degree.
For example, first, (A) is operated as fuel cell system A with basic output current IB and basic output voltage VB When, the output current IO UT of single fuel cell 2 from basic output current IB be gradually increased to predetermined increase electric current IG and Increase period Δ t0 is kept at increase electric current IG.Measure output electricity of the single fuel cell 2 in increase period Δ t0 Press VOUT.Now, following items are obtained and is used as electrology characteristic etc.：Increase electric current IG is being increased to by default from output current IO UT Difference (voltage decline amount) Δ V, minimum voltage VM between output voltage VE and minimum voltage VM after period Δ t1 with Difference (amount that minimum value declines) Δ Vm between basic output voltage VB or increase to increase electric current IG in output current IO UT Output voltage VO UT is changed into the period Δ t2 required for burning voltage VC afterwards.
Next, amount Δ Vm that (C ') amount Δ V for being declined based on measured voltage, measured minimum value are declined or Required period Δ t2, the amount Δ Vm or required that the amount Δ V declined by reference to the voltage pre-set, minimum value are declined Period Δ t2 and activation processing degree between relation come determine activation processing degree.For example, determining：With electricity The amount Δ V increases of drops, the amount Δ Vm increases declined with minimum value, or with required period Δ t2 increases, lead to The action or the combination of at least two actions crossed in the action for performing the condition for changing activation processing determine swashing for high level Processing living, the action includes reducing the dynamic of the action of target potential, the action for increasing the duration and increase processing frequency Make.
Here, can be for example by the way that the figure of Figure 15 figure, the figure of Figure 16 figure or Figure 17 and Figure 10 be combined to hold Change places and obtain amount Δ V, the amount Δ Vm or required period Δ t2 of minimum value decline and activation that the voltage pre-set declines Relation between the degree of processing.
As an alternative, for example, first, (A) is kept in the output voltage VO UT of single fuel cell 2 at scheduled voltage After predetermined amount of time, the output current Ix at predetermined output voltage Ex or the output voltage at predetermined output current Ix are obtained Ex.Next, (C ') is based on measured output current Ix or measured output voltage Ex, by reference to what is pre-set Output current Ix or output voltage Ex and activation processing degree between relation come determine activation processing degree.For example, working as During output current Ix or output voltage Ex relatively low, by perform change activation processing condition action in one action or The combinations of at least two actions determine into the degree for activating processing more true than as output current Ix or output voltage Ex relatively high The degree of fixed activation processing is high, and the action includes reducing the action of target potential, increases the action and increasing of duration Plus the action of processing frequency.
Here, can be by the way that the figure of Figure 22 table, Figure 23 table and Figure 10 be combined or by Figure 24 figure, Figure 25 Figure and Figure 10 figure be combined to be readily available the output current Ix pre-set or output voltage Ex and handled with activation Degree between relation.
In these cases, identical effect can be showed with Fig. 1 into the embodiment described in Figure 21.
Next, reference picture 28 to be described to fuel cell system A a further embodiment.Except fuel cell system A It is that present embodiment is different from the embodiment shown in Fig. 1 beyond hydrogen non-circulation type fuel cell system.Hereinafter, will The difference is mainly described.
Fuel cell system A shown in Fig. 1 is fuel gas circulation-type fuel cell systems, i.e., following systems：Wherein fire The outlet of material gas flow paths 30 is connected to fuel gas supply pipe by anode waste gas pipe 36 and fuel gas circulation pipe 81 31 so that the anode exhaust gas recirculation including fuel gas to fuel gas supply pipe 31.On the other hand, in the fuel shown in Figure 28 In battery system A, fuel gas circulation pipe 81 and fuel gas circulating pump 39 are not provided with.That is, the fuel shown in Figure 28 Battery system A is the fuel cell system of fuel gas non-circulation type, i.e., following systems：Wherein fuel gas flow path 30 Outlet is separated with fuel gas supply pipe 31 so that the anode waste gas including fuel gas is not recycled to fuel gas supply pipe 31。
Even in this case, still it can show and the fuel cell system A identical effects shown in Fig. 1.

Claims (15)

1. a kind of fuel cell system, including：
Processing unit, is configured to：During the clear operation of the fuel cell system, activation processing is held with processing frequency One section of duration of row, the activation is handled the cathode potential of at least one single fuel cell of the fuel cell system Temporary decrease is to target potential；
Cation impurity amount estimation unit, be configured to estimate to be included in the dielectric film of the single fuel cell sun from The amount of sub- impurity；And
Degree for the treatment of determining unit, is configured to：When the amount of the cation impurity is big, changed by performing at the activation What an action or at least two in the action of the condition of reason were acted combines to determine the degree of activation processing, activation processing Degree than when the amount of the cation impurity is small it is identified activation processing degree it is high, it is described action include reduction described in Action, the action of the increase duration and the action of the increase processing frequency of target potential,
Wherein, activation processing is gone to the degree determined by the degree for the treatment of determining unit by the processing unit.
2. fuel cell system according to claim 1, wherein,
When the fuel cell system is operated with basic output current and basic output voltage, the cation impurity amount estimation Unit is configured to the output voltage based on the single fuel cell obtained by following operation to estimate cation impurity Amount：The output current of the single fuel cell is gradually increased to predetermined increase electric current from the basic output current, will The output current is kept for an increase period at the increase electric current, and the output in the measurement increase period Voltage.
3. fuel cell system according to claim 2, wherein,
When the output current is gradually increased to the increase electric current and is maintained at the increase electric current, the output Voltage gradually reduces to minimum voltage from the basic output voltage and then increases to burning voltage, the burning voltage ratio The basic output voltage is low, and
The cation impurity amount estimation unit be configured to from the output current increasing to it is described increase electric current warp The difference crossed between the output voltage measured after the preset time period shorter than the increase period and the minimum voltage Increase, estimates bigger by the amount of the cation impurity；With between the minimum voltage and the basic output voltage Difference increase, estimates bigger by the amount of the cation impurity；Or increase to the increase electricity with the output current The output voltage is changed into the period increase required for the burning voltage after stream, and the amount of the cation impurity is estimated Obtain bigger.
4. the fuel cell system according to Claims 2 or 3, wherein,
The increase electric current is the output current measured using the full load of the fuel cell system.
5. the fuel cell system according to any one of claim 2 to 4, wherein,
The cation impurity amount estimation unit is configured to：When the basic output current of the single fuel cell is less than During threshold current, based on the survey after the output current of the single fuel cell to be gradually increased to the increase electric current The output voltage of amount estimates the amount of the cation impurity.
6. fuel cell system according to claim 1, wherein,
The cation impurity amount estimation unit is configured to：Based on the output voltage in the single fuel cell pre- Determine to be kept the output current and predetermined output electricity at the predetermined output voltage measured after one section of scheduled time at magnitude of voltage At least one of output voltage at stream estimates the amount of the cation impurity.
7. fuel cell system according to claim 1, in addition to：
Operation note memory cell, is configured to store the operation note of fuel cell pack, wherein,
The cation impurity amount estimation unit is by reference to the operation note memory cell, based on the fuel cell pack The amount of the cation impurity is estimated in the operation note.
8. fuel cell system according to any one of claim 1 to 7, in addition to：
Relevant parameter measuring unit, is configured to measure related to the relative humidity of the dielectric film in fuel cell pack The value of parameter, wherein,
When the relative humidity is low, the degree for the treatment of determining unit determines activation based on the value of the measured parameter The degree of processing, the degree of degree identified activation processing than when the relative humidity is high of activation processing is high.
9. fuel cell system according to claim 8, wherein,
The parameter be in the fuel cell pack or the fuel cell pack near cooling water temperature, impedance or the electricity Solve the humidity of the gas near plasma membrane.
10. fuel cell system according to any one of claim 1 to 9, in addition to：
Nearest history storage unit, is configured to store the history of the output of nearest predetermined amount of time fuel cells heap, wherein,
When the output in the nearest predetermined amount of time is high, the degree for the treatment of determining unit is configured to determine activation The degree of processing, the degree of activation processing is than the identified activation when the output in the nearest predetermined amount of time is low The degree of processing is high.
11. a kind of fuel cell system, including：
Processing unit, is configured to：During the clear operation of the fuel cell system, activation processing is held with processing frequency One section of duration of row, the activation is handled the cathode potential of at least one single fuel cell of the fuel cell system Temporary decrease is to target potential；And
Degree for the treatment of determining unit, is configured to change by performing an action in the action for the condition that the activation is handled Or at least two the combination of action determine the degree of the activation processing, the action includes reducing the dynamic of the target potential Make, increase the action of the duration and the action of the increase processing frequency；
Wherein, the degree for the treatment of determining unit obtains the output voltage of the single fuel cell by following operation：Work as institute When stating fuel cell system with basic output current and the operation of basic output voltage, by the output current of the single fuel cell Predetermined increase electric current is gradually increased to from the basic output current, the output current is kept one at the increase electric current The output voltage in individual increase period, and the measurement increase period；
When the output current is gradually increased to the increase electric current and is maintained at the increase electric current, the output is electric Pressure is gradually reduced to minimum voltage from the basic output voltage and then increased to lower than the basic output voltage steady When determining voltage, the degree for activating processing is defined below by the degree for the treatment of determining unit：Increase with from the output current Add to the increase electric current and pass through the output voltage measured after the preset time period shorter than the increase period and institute The difference increase between minimum voltage is stated, as the difference between the minimum voltage and the basic output voltage increases, Huo Zhesui When required for the output voltage after the output current increases to the increase electric current is changed into the burning voltage Between section increase, the activation processing degree become higher, and
Activation processing is gone to the degree determined by the degree for the treatment of determining unit by the processing unit.
12. a kind of fuel cell system, including：
Processing unit, is configured to：During the clear operation of the fuel cell system, activation processing is held with processing frequency One section of duration of row, the activation is handled the cathode potential of at least one single fuel cell of the fuel cell system Temporary decrease is to target potential；And
Degree for the treatment of determining unit, is configured to change by performing an action in the action for the condition that the activation is handled Or at least two the combination of action determine the degree of the activation processing, the action includes reducing the dynamic of the target potential Make, increase the action of the duration and the action of the increase processing frequency,
Wherein, the single fuel cell the output voltage be kept at scheduled voltage one section of scheduled time it Afterwards, the degree for the treatment of determining unit obtains the output current at predetermined output voltage and the output voltage at predetermined output current At least one of,
The output voltage at the value of the output current at the predetermined output voltage and the predetermined output current At least one of value it is relatively low when, the degree for activating processing is defined below by the degree for the treatment of determining unit：The activation The degree of processing is than described at the value and the predetermined output current of the output current at the predetermined output voltage The degree of identified activation processing is high when at least one of value of output voltage is relatively high；And
Activation processing is gone to the degree determined by the degree for the treatment of determining unit by the processing unit.
13. a kind of performance improvement method of fuel cell system, including：
Processing will be activated with processing frequency and perform one section of duration, the activation is handled at least one single fuel cell Cathode potential temporary decrease is to target potential；
Estimation is included in the amount of the cation impurity in the dielectric film of the single fuel cell；
When the amount of cation impurity is big, by an action in the action for the condition for performing the change activation processing or extremely The combination of few two actions determines the degree of activation processing, and the degree of activation processing is than when the amount of cation impurity is small when institute The degree of the activation processing of determination is high, and the action includes reducing the action of the target potential, increases the duration Act and increase the action of the processing frequency；And
When performing the clear operation of the fuel cell system, activation processing is gone into identified degree.
14. a kind of performance improvement method of cell fuel system, including：
During the clear operation of the fuel cell system, one section of duration, institute are performed by processing is activated with processing frequency Activation processing is stated by the cathode potential temporary decrease of at least one single fuel cell of the fuel cell system to target electricity Position；
By performing the combination of the action or at least two actions that change in the action for activating the condition handled come really Determine the degree of the activation processing, the action includes reducing the action of the target potential, increases the dynamic of the duration Make and increase the action of the processing frequency；
The output voltage of the single fuel cell is obtained by following operation：When the fuel cell system to export substantially When electric current and the operation of basic output voltage, the output current of the single fuel cell is progressively increased from the basic output current Predetermined increase electric current is added to, the output current is kept for an increase period at the increase electric current, and measurement institute State the output voltage in the increase period；
When the output current be gradually increased to it is described increase electric current and be maintained at it is described increase electric current at, the output electricity Pressure is gradually reduced to minimum voltage from the basic output voltage and then increased to lower than the basic output voltage steady When determining voltage, the degree for activating processing is defined below：With from the output current increasing to it is described increase electric current pass through Difference between the output voltage and the minimum voltage that are measured after the preset time period shorter than the increase period increases Plus, as the difference between the minimum voltage and the basic output voltage increases, or with output current increase The output voltage is changed into the period increase required for the burning voltage after to the increase electric current, activation processing Degree becomes higher；And
Activation processing is gone into identified degree.
15. a kind of performance improvement method of fuel cell system, including：
During the clear operation of the fuel cell system, one section of duration, institute are performed by processing is activated with processing frequency Activation processing is stated by the cathode potential temporary decrease of at least one single fuel cell of the fuel cell system to target electricity Position；
By performing the combination of the action or at least two actions that change in the action for activating the condition handled come really Determine the degree of the activation processing, the action includes reducing the action of the target potential, increases the dynamic of the duration Make and increase the action of the processing frequency；
After the output voltage of the single fuel cell is kept one section of scheduled time at scheduled voltage, obtain At least one of output voltage at output current and predetermined output current at predetermined output voltage；
The output voltage at the value of the output current at the predetermined output voltage and the predetermined output current At least one of value it is relatively low when, the degree for activating processing is defined below：The degree ratio of activation processing is when described pre- Determine in the value of the output voltage at the value and the predetermined output current of the output current at output voltage at least One of it is relatively high when identified activation processing degree it is high；And
Activation processing is gone into identified degree.
CN201610879002.1A 2015-10-08 2016-10-08 Fuel cell system and method for improving performance of fuel cell system Expired - Fee Related CN107017425B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1307735A (en) * 1998-06-25 2001-08-08 丰田自动车株式会社 Fuel cell system and cell control method
JP2004127548A (en) * 2002-09-30 2004-04-22 Toyota Central Res & Dev Lab Inc Operation method and operation system of solid polymer type fuel cell
CN101981736A (en) * 2007-07-18 2011-02-23 丰田自动车株式会社 Fuel cell system, and control method for fuel cell
JP2013258038A (en) * 2012-06-12 2013-12-26 Toyota Motor Corp Fuel cell system and control method thereof
CN104285326A (en) * 2012-05-01 2015-01-14 丰田自动车株式会社 Fuel cell system

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5870949B2 (en) * 2013-03-21 2016-03-01 トヨタ自動車株式会社 FUEL CELL SYSTEM AND CONTROL METHOD FOR FUEL CELL SYSTEM

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1307735A (en) * 1998-06-25 2001-08-08 丰田自动车株式会社 Fuel cell system and cell control method
JP2004127548A (en) * 2002-09-30 2004-04-22 Toyota Central Res & Dev Lab Inc Operation method and operation system of solid polymer type fuel cell
CN101981736A (en) * 2007-07-18 2011-02-23 丰田自动车株式会社 Fuel cell system, and control method for fuel cell
CN104285326A (en) * 2012-05-01 2015-01-14 丰田自动车株式会社 Fuel cell system
JP2013258038A (en) * 2012-06-12 2013-12-26 Toyota Motor Corp Fuel cell system and control method thereof

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