CN112886035B - Method and system for accurately regulating and controlling carbon monoxide-resistant anode air injection of fuel cell - Google Patents

Method and system for accurately regulating and controlling carbon monoxide-resistant anode air injection of fuel cell Download PDF

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CN112886035B
CN112886035B CN202110153818.7A CN202110153818A CN112886035B CN 112886035 B CN112886035 B CN 112886035B CN 202110153818 A CN202110153818 A CN 202110153818A CN 112886035 B CN112886035 B CN 112886035B
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fuel cell
concentration
air
carbon monoxide
air injection
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CN112886035A (en
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裴普成
王明凯
陈东方
任棚
李子钊
王鹤
黄尚尉
宋鑫
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Tsinghua University
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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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04104—Regulation of differential pressures
    • 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
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • 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
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0444—Concentration; Density
    • H01M8/04462—Concentration; Density of anode exhausts
    • 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
    • H01M8/04746—Pressure; Flow
    • H01M8/04753—Pressure; Flow of fuel cell reactants
    • 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
    • H01M8/04992—Processes for controlling fuel cells or fuel cell systems characterised by the implementation of mathematical or computational algorithms, e.g. feedback control loops, fuzzy logic, neural networks or artificial intelligence
    • 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

Abstract

The invention belongs to the technical field of fuel cells, and particularly relates to a carbon monoxide resistant anode air injection accurate regulation and control method and system for a fuel cell. The invention determines the feed-forward quantity of the air injection quantity through the calibration MAP chart of the poisoning influence of carbon monoxide on the proton exchange membrane fuel cell, detects the gas components at the anode inlet of the fuel cell, estimates the equivalent carbon monoxide concentration on the surface of the anode catalyst through the optimization model to correct the required air injection quantity, further realizes the accurate control of the air injection quantity, can effectively solve the problem of carbon monoxide poisoning of the fuel cell, improves the tolerance capability of the fuel cell on carbon monoxide, enables the fuel cell to use non-pure hydrogen as fuel for a long time, and effectively reduces the hydrogen cost of the fuel cell.

Description

Method and system for accurately regulating and controlling carbon monoxide-resistant anode air injection of fuel cell
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a carbon monoxide resistant anode air injection accurate regulation and control method and system for a fuel cell.
Background
The proton exchange membrane fuel cell has the advantages of high efficiency, environmental protection, no noise and the like, and has wide application prospect in the aspects of vehicle power, fixed power supply, household combined heat and power supply and the like. The hydrogen is used as the fuel of the proton exchange membrane fuel cell, the storage, the transportation and the distribution of the hydrogen are more difficult than the transportation of the traditional liquid fuel, and the hydrogen production by reforming the liquid fuel such as methanol and the like can provide a convenient hydrogen source for the application scene and the areas which are inconvenient to obtain pure hydrogen. In addition, a large amount of impure hydrogen contained in the waste gas of industries such as coal processing, petroleum refining, chlor-alkali industry and the like can be utilized by proton exchange membrane fuel cells, thereby greatly reducing the cost of hydrogen. However, when hydrogen is produced by reforming methanol and other carbon-based fuels, the product inevitably contains a small amount of carbon monoxide, which poisons the anode catalyst and reduces the output performance of the fuel cell. Platinum-based anode catalyst fuel cells can tolerate very low concentrations of carbon monoxide, on the order of 10ppmv, and thus current fuel cells require the use of high purity hydrogen as a fuel. The high-purity hydrogen is mainly produced by electrolytic water at present, has the disadvantages of high cost, immature technology and the like, can provide impure hydrogen with rich sources by utilizing industrial by-product hydrogen or fuel reforming, and has low requirement on hydrogen purification, low cost and mature technology.
When a fuel cell uses impure hydrogen, it is necessary to improve the tolerance of the fuel cell to carbon monoxide. The related methods are, firstly, using a high-temperature proton exchange membrane fuel cell; secondly, carbon monoxide tolerant anode catalysts, such as PtRu/C catalysts, are used; thirdly, designing the anode catalyst and the membrane electrode structure; fourthly, a certain amount of oxidant such as air, oxygen and hydrogen peroxide (H) is mixed into the anode gas flow2O2) Etc. so that carbon monoxide preferentially adsorbed on the catalyst surface is oxidized away, thereby releasing the occupied active sites, which is also known as Air blowing when Air is used as the oxidant. In the method, the high-temperature proton exchange membrane fuel cell has the problems of short service life, low power density, long cold start time and the like at present, and the binary or multielement novel carbon monoxide-tolerant catalyst also has the problems of service life, performance and the like. The method of using anode air injection has the advantages of simple device, high efficiency and the like, and can efficiently recover the performance of the poisoned fuel cell. However, the amount of air to be mixed needs to be optimized, otherwise, the insufficient amount of air injection may result in the poisoning of the fuel cell catalyst by carbon monoxide and the failure thereofHowever, excess air not only consumes hydrogen, but also creates localized hot spots and free radicals due to vigorous reactions, which irreversibly attenuate fuel cell catalysts and proton exchange membranes, thereby affecting fuel cell life. Therefore, how to determine the optimum air injection amount is the key to the application of this technology.
Disclosure of Invention
The invention aims to provide a method and a system for accurately regulating and controlling carbon monoxide-resistant anode air injection of a fuel cell.
The invention provides a method for regulating and controlling the air injection quantity of an anode of a fuel cell capable of tolerating carbon monoxide, which comprises the following steps:
randomly selecting a calibration fuel cell from the fuel cells to be controlled, and calibrating the calibration fuel cell to obtain a fuel cell performance MAP;
detecting the concentration of carbon monoxide at the inlet of the anode of the fuel cell to be controlled, and recording the concentration as cinDetermining the feedforward optimal air injection concentration c of the fuel cell to be controlled according to the fuel cell performance MAPair；
Establishing an optimization model of fuel cell anode gas adsorption and reaction, and solving the optimization model to obtain the adsorption ratio of substances such as hydrogen, oxygen, carbon monoxide and the like on the surface of a fuel cell anode catalyst;
using fuel cell performance MAP, established at equivalent carbon monoxide concentration cCO,equThe air concentration corresponding to the peak value of the curve is used as the correction of the feedforward air injection quantity of the fuel cell to be controlled, namely the optimal feedback air injection quantity delta cair；
According to feed-forward air injection quantity cairAnd feedback of air injection quantity DeltacairObtaining the air injection flow rate q of the anode of the fuel cellH2×(cair+Δcair) Wherein q isH2Is hydrogen gas flow of fuel cell systemAnd the quantity demand realizes the regulation and control of the anode air injection quantity of the fuel cell enduring carbon monoxide.
10. A fuel cell carbon monoxide tolerant anode air injection precision regulation system, the regulation system comprising: including hydrogen manufacturing plant, gas surge chamber, fuel cell, compressed air, air jet flow controller and gas concentration sensor, hydrogen manufacturing plant, gas surge chamber and fuel cell pass through the pipeline and link to each other, compressed air pass through air jet flow controller and link to each other with gas surge chamber, gas concentration sensor pass through signal line and system control board and link to each other, fuel cell's positive pole tail gas is discharged from fuel cell positive pole export.
The method and the system for regulating and controlling the air injection quantity of the carbon monoxide-tolerant anode of the fuel cell have the advantages that:
1. the invention determines the feed-forward quantity of the air injection quantity through the calibration MAP graph of the poisoning influence of carbon monoxide on the proton exchange membrane fuel cell, detects the gas components at the anode inlet of the fuel cell, estimates the equivalent carbon monoxide concentration on the surface of the anode catalyst through the optimization model to correct the required air injection quantity, further realizes the accurate control of the air injection quantity, can effectively solve the problem of carbon monoxide poisoning of the fuel cell, improves the tolerance capability of the fuel cell on carbon monoxide, enables the fuel cell to use non-pure hydrogen as fuel for a long time, and effectively reduces the hydrogen cost of the fuel cell.
2. The invention can obtain the optimal air injection quantity required by the fuel cell using the non-pure hydrogen to improve the output performance of the fuel cell by using the anode air injection method, can recover the performance of the fuel cell as much as possible by accurately controlling the air injection quantity, can basically eliminate the poisoning effect of carbon monoxide under the lower concentration of the carbon monoxide, and has strong operability when the performance of the fuel cell is recovered to the level when the pure hydrogen is used. The accurate air injection quantity control can improve the tolerance of the fuel cell to carbon monoxide, ensure the performance output of the fuel cell, and simultaneously reduce the adverse effect of the air injection on the service life of the fuel cell as much as possible, so that the fuel cell can use the non-pure hydrogen as the fuel for a long time. The method can be widely applied to fuel cells using non-pure hydrogen as fuel.
Drawings
Fig. 1 is a flow chart of a method for accurately regulating and controlling carbon monoxide tolerant anode air injection of a fuel cell according to the present invention.
FIG. 2 is a schematic diagram of the working principle of the method of the present invention.
Fig. 3 is a MAP of fuel cell performance MAP for different carbon monoxide concentrations and different air injection concentrations.
FIG. 4 is a graphical illustration of the relationship between different carbon monoxide concentrations and optimal feed forward air injection concentrations.
FIG. 5 is a schematic diagram showing the relationship between the carbon monoxide adsorption ratio on the surface of the catalyst and the carbon monoxide concentration.
Fig. 6 is a block diagram of a system for precisely regulating and controlling the carbon monoxide tolerant anode air injection of a fuel cell according to the present invention.
In fig. 6, 1 denotes a hydrogen production apparatus, 2 denotes a gas buffer chamber, 3 denotes a fuel cell, 4 denotes an anode off-gas outlet, 5 denotes compressed air, 6 denotes an air injection flow rate controller, and 7 denotes a gas concentration sensor.
Detailed Description
The invention provides a method for regulating and controlling the air injection quantity of an anode of a fuel cell capable of tolerating carbon monoxide, which comprises the following steps:
randomly selecting a calibration fuel cell from the fuel cells to be controlled, and calibrating the calibration fuel cell to obtain a fuel cell performance MAP;
detecting the concentration of carbon monoxide at the inlet of the anode of the fuel cell to be controlled, and recording the concentration as cinDetermining the feedforward optimal air injection concentration c of the fuel cell to be controlled according to the fuel cell performance MAPair；
Establishing an optimization model of fuel cell anode gas adsorption and reaction, solving the optimization model to obtain adsorption ratios of substances such as hydrogen, oxygen, carbon monoxide and the like on the surface of a fuel cell anode catalyst, and estimating the adsorption ratio theta of the carbon monoxide on the surface of the anode catalystCO；
At equivalent carbon monoxide concentration cCO,equNext, using the fuel cell performance MAP, the concentration is designated as cCO,equAs a correction for the feed-forward air injection quantity of the fuel cell to be controlled, i.e. the optimum feedback air injection quantity Δ cair；
According to feed-forward air injection quantity cairAnd feedback of air injection quantity DeltacairObtaining the air injection flow rate q of the anode of the fuel cellH2×(cair+Δcair) Wherein q isH2The method is used for adjusting and controlling the anode air injection quantity of the fuel cell tolerant to carbon monoxide according to the hydrogen flow requirement of the fuel cell system and the working condition of the fuel cell system.
In the above regulation and control method of the present invention, the process of obtaining the MAP of the performance of the fuel cell is as follows:
(1) supplying a mixed gas of carbon monoxide and hydrogen to an anode inlet of a calibration fuel cell, in which a carbon monoxide concentration is known, and injecting air mixed with a known concentration to the anode inlet of the calibration fuel cell to set a calibration current density icellMeasuring the voltage of the calibration fuel cell under the calibration current density, and establishing a relation curve of the air concentration and the calibration fuel cell voltage under the known carbon monoxide concentration;
(2) changing the concentration of carbon monoxide in the mixed gas in the step (1), and increasing the concentration of the carbon monoxide from 0 (namely pure hydrogen is supplied at the moment), and repeating the step (1) to obtain a relation curve of the concentration of the air after the concentration of the carbon monoxide is changed and the steady-state voltage of the calibrated fuel cell;
(3) and (3) repeating the step (1) and the step (2) to obtain a plurality of relation curves of the air concentration and the voltage of the calibrated fuel cell, wherein the plurality of relation curves of the air concentration and the voltage of the calibrated fuel cell form a fuel cell performance MAP. As shown in FIG. 3, the peak value of the voltage of each curve in the MAP graph is corresponding to the air concentration cairThe relationship between the composition of different carbon monoxide concentrations and the optimum feed forward air injection concentration is tabulated in relation to the carbon monoxide concentration, as shown in fig. 4.
Obtaining the concentration c of carbon monoxide according to the performance MAP of the fuel cellinWill be related to the peak value V of the curve of the air concentration versus the voltage of the calibration fuel cellffCorresponding air concentration cairThe air concentration is recorded as the feedforward optimum air concentration cairFeed-forward the optimum air concentration cairAs the feed-forward optimum air injection quantity of the fuel cell to be controlled, the concentration c of carbon monoxide at the anode inletinWhen the concentration of the carbon monoxide in the fuel cell performance MAP cannot correspond to the concentration of the carbon monoxide in the fuel cell performance MAP, the air concentration corresponding to the peak value of two adjacent curves selected from the fuel cell performance MAP is interpolated to obtain the feedforward optimal air concentration cair. Wherein the feed-forward optimum air injection concentration c of the fuel cell to be controlled is determinedairThe method can be as follows: establishing a relation curve between the optimal air injection concentration corresponding to the peak value of each curve in the MAP and the carbon monoxide concentration represented by the curve, and performing interpolation calculation on the relation curve to obtain the feedforward optimal air concentration cair. The following steps can be also included: establishing a relation curve of the optimal air injection concentration corresponding to the peak value of each curve in the MAP graph and the carbon monoxide concentration represented by the curve, and utilizing a fitting formula c according to the relation curveair＝f(cin) Calculating to obtain the feedforward optimal air concentration cair. The fitting formula is: c. Cair＝a×ln(b×cin+1)+c×cin 2+d×cinAnd a, b, c and d are fitting parameters of the formula respectively. In one embodiment of the present invention, the parameter selection range is, a: 0.8 to 1.5, b: 0.1 to 1, c: 1X 10-6～2×10-6，d：0～-0.005。
In the above regulation and control method of the present invention, the establishing of the optimization model of the adsorption and reaction of the anode gas of the fuel cell comprises:
Figure BDA0002933700340000051
Figure BDA0002933700340000052
Figure BDA0002933700340000053
θH,m＝f4(icell,Vstd,Vm) (4)
the model calculates the adsorption ratio of hydrogen, oxygen, carbon monoxide and other substances on the surface of the anode catalyst of the fuel cell, and is used for estimating the adsorption ratio theta of carbon monoxide on the surface of the anode catalystCO。
Wherein, thetaH，θO，θCORespectively represent adsorption ratios of hydrogen, oxygen and carbon monoxide on the surface of the anode catalyst of the fuel cell, cH2，cO2，cCORespectively representing the gas concentrations of hydrogen, oxygen and carbon monoxide entering the fuel cell stack, icellFor calibration of the current density, V, of the fuel cellstdCalibrating the air injection concentration and the current density i of the fuel cell when pure hydrogen is introducedcellVoltage of lower, VmFor fuel cells to be controlled at an air injection concentration of cairSteady state voltage at, subscript m denotes fuel cell to be controlled, θH,mAt a current density of icellThe adsorption ratio of hydrogen on the surface of the anode catalyst of the lower fuel cell to be controlled;
calculating the adsorption ratio theta of carbon monoxide on the surface of the anode catalyst by using the modelCOAt a nominal current density icellThe following:
(1) measuring steady-state voltage V of fuel cell to be controlledmAnd apply the VmAnd calibrating the fuel cell at the carbon monoxide concentrationinOptimum voltage value V in corresponding calibration curveffMaking a comparison if Vm≥VffThen the feedforward air injection amount is not feedback corrected, i.e. Δ c at this timeair＝0，Vm<VffThen, the step (2) is carried out;
(2) the steady-state battery voltage V of the fuel battery to be controlledmAnd the voltage V of the fuel cell at the air injection concentration is calibrated when pure hydrogen is introducedstdThe adsorption ratio theta of hydrogen gas on the surface of the catalyst at this time was calculated by equation (4)H,mAnd the adsorption ratio thetaH,mSubstituting the equation into the equations (1) to (2), and solving to obtain the adsorption ratio theta of the carbon monoxide on the surface of the anode catalyst of the fuel cell to be controlledCO,m；
(3) Obtaining the equivalent carbon monoxide concentration c of the anode catalyst surface of the fuel cell to be controlled according to the relationship between the carbon monoxide adsorption ratio and the carbon monoxide concentration on the catalyst surface shown in FIG. 5CO,equ。
In the above regulation and control method of the present invention, the optimum feedback air injection amount Δ cairThe determination process of (2) is as follows:
finding the equivalent carbon monoxide concentration c using a fuel cell performance MAP according to a method of determining a feed forward air injection amountCO,equThe air concentration corresponding to the peak value of the curve is used as the correction of the feedforward air injection quantity of the fuel cell to be controlled, namely the optimal feedback air injection quantity delta cair。
In the above regulation and control method of the present invention, the determination process of the anode air injection flow rate of the fuel cell is as follows:
the precisely controlled air injection quantity consists of two parts, namely a feedforward air injection quantity c obtained by a calibration MAPairAnd the optimum feedback air injection quantity deltac estimated and calculated by the optimization modelairAnode air injection flow rate of qH2×(cair+Δcair)，qH2Is the hydrogen flow demand of the fuel cell system, which may be determined according to the operating conditions of the fuel cell system.
The structure block diagram of the carbon monoxide resistant anode air injection accurate regulation and control system of the fuel cell provided by the invention is shown in fig. 6, and comprises the following components: including hydrogen plant 1, gas buffer chamber 2, fuel cell 3, compressed air 5, air jet flow controller 6 and gas concentration sensor 7, hydrogen plant 1, gas buffer chamber 2 and fuel cell 3 pass through the pipeline and link to each other, compressed air 5 pass through air jet flow controller 6 and gas buffer chamber 2 and link to each other, gas concentration sensor 7 pass through the signal line and link to each other with the system control board, fuel cell's positive pole tail gas is discharged from fuel cell positive pole export 4.
In the method, when MAP chart setting experiments of carbon monoxide poisoning fuel cells under different concentrations are carried out, the optimal air injection amount needing to be mixed when carbon monoxide with different concentrations is contained in non-pure hydrogen is determined.
Calculating a feedforward quantity cairAccording to the carbon monoxide concentration c at the anode inlet of the fuel cellinInquiring the MAP to determine the feed-forward value c of the air injection quantityair. The carbon monoxide concentration which is not calibrated in the MAP graph can be obtained by an interpolation method. Establishing an optimization model of fuel cell anode gas adsorption and reaction, calculating adsorption ratios of hydrogen, oxygen, carbon monoxide and other substances on the surface of a fuel cell anode catalyst by the model, and estimating the adsorption ratio theta of the carbon monoxide on the surface of the anode catalystCO. Determining the equivalent carbon monoxide concentration c of the catalyst surface according to the relationship between the carbon monoxide adsorption ratio and the carbon monoxide concentration on the catalyst surfaceCO,equ。
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
The implementation device of the method for accurately regulating and controlling the anode air injection of the fuel cell tolerant to carbon monoxide is shown in fig. 6 and comprises a hydrogen production device 1, a gas buffer chamber 2, a fuel cell 3, compressed air 5, an air injection flow controller 6, a gas concentration sensor 7 and the like.
The control logic of the method for accurately regulating and controlling the carbon monoxide-tolerant anode air injection of the fuel cell is shown in figure 2 and is carried out in three steps:
the method comprises the following steps: and randomly selecting one calibration fuel cell from the fuel cells to be controlled, and calibrating the calibration fuel cell to obtain a fuel cell performance MAP.
Step two: by passingThe gas concentration sensor 7 collects the carbon monoxide concentration c at the anode inlet of the fuel cell 3inDetermining the optimum feedforward control air injection concentration c by looking up the MAPair。
Step three: establishing an optimization model of fuel cell anode gas adsorption and reaction, and measuring steady-state voltage V of the fuel cell to be controlledmThe adsorption ratio theta of carbon monoxide on the surface of the anode catalyst was estimatedCOAnd performing feedback control to correct the feedforward air injection amount to obtain the final accurately-controlled air injection amount.
Finally, in the system applying the method of the present invention, the source of the hydrogen is impure hydrogen containing carbon monoxide, specifically, the hydrogen is derived from the gas obtained by reforming methanol or other carbon-containing fuels, and can also be industrial byproduct hydrogen containing carbon monoxide. The injected air is only an oxidant for oxidizing carbon monoxide, and may be injected with oxygen, hydrogen peroxide, or the like. The method can still be applied after modifying the injected substance.
The configurations described herein are exemplary, and these specific implementation examples should not be considered in a limiting sense. The invention includes all combinations of the various systems and methods disclosed herein, as well as other features, functions, and/or properties disclosed herein, which are not expressly recited and/or apparent.

Claims (7)

1. A method for regulating an anode air injection amount of a fuel cell tolerant to carbon monoxide, the method comprising:
randomly selecting a calibration fuel cell from the fuel cells to be controlled, calibrating the calibration fuel cell to obtain a fuel cell performance MAP, wherein the process of obtaining the fuel cell performance MAP is as follows:
(1) supplying a mixed gas of carbon monoxide and hydrogen to an anode inlet of a calibration fuel cell, in which a carbon monoxide concentration is known, and injecting air mixed with a known concentration to the anode inlet of the calibration fuel cell to set a calibration current density icellMeasuring the voltage of the rated fuel cell at the rated current density to establishAir concentration versus calibration fuel cell voltage at a known carbon monoxide concentration;
(2) changing the concentration of carbon monoxide in the mixed gas in the step (1), increasing the concentration of the carbon monoxide from 0, and repeating the step (1) to obtain a relation curve of the air concentration after the carbon monoxide concentration is changed and the steady-state voltage of the calibrated fuel cell;
(3) repeating the step (1) and the step (2) to obtain a plurality of relation curves of air concentration and voltage of the calibrated fuel cell, wherein the plurality of relation curves of air concentration and voltage of the calibrated fuel cell form a fuel cell performance MAP;
detecting the concentration of carbon monoxide at the inlet of the anode of the fuel cell to be controlled, and recording the concentration as cinDetermining the feedforward optimal air injection concentration c of the fuel cell to be controlled according to the fuel cell performance MAPair；
Establishing an optimization model of fuel cell anode gas adsorption and reaction, solving the optimization model to obtain the adsorption ratio of hydrogen, oxygen and carbon monoxide on the surface of a fuel cell anode catalyst, and obtaining the equivalent carbon monoxide concentration c on the surface of the anode catalyst of the fuel cell to be controlled according to the relation between the carbon monoxide adsorption ratio and the carbon monoxide concentration on the surface of the catalystCO,equ；
Using fuel cell performance MAP, established at equivalent carbon monoxide concentration cCO,equThe air concentration corresponding to the peak value of the curve is used as the correction of the feedforward air injection quantity of the fuel cell to be controlled, namely the optimal feedback air injection quantity
Figure FDA0003355929640000011
Optimum air injection concentration c from feed forwardairAnd optimum feedback air injection quantity
Figure FDA0003355929640000012
Obtaining the anode air injection flow rate of the fuel cell as
Figure FDA0003355929640000013
Wherein q isH2The method is used for adjusting and controlling the anode air injection quantity of the fuel cell tolerant to carbon monoxide according to the hydrogen flow requirement of the fuel cell system and the working condition of the fuel cell system.
2. The method of claim 1, wherein the determining the feed forward optimum air injection concentration c for the fuel cell under controlairThe specific process is as follows:
obtaining the concentration c of carbon monoxide according to the performance MAP of the fuel cellinWill be related to the peak value V of the curve of the air concentration versus the voltage of the calibration fuel cellffCorresponding air concentration cairRecording as feedforward optimum air injection concentration cairThe feed-forward optimum air injection concentration cairAs the feed-forward optimum air injection quantity of the fuel cell to be controlled, the concentration c of carbon monoxide at the anode inletinWhen the concentration of the carbon monoxide in the fuel cell performance MAP cannot correspond to the concentration of the carbon monoxide in the fuel cell performance MAP, the air concentration corresponding to the peak value of two adjacent curves selected from the fuel cell performance MAP is interpolated to obtain the feedforward optimal air injection concentration cair。
3. The method of claim 1, wherein the determining the feed forward optimum air injection concentration c for the fuel cell under controlairThe specific process is as follows:
establishing a relation curve of the optimal air injection concentration corresponding to the peak value of each curve in the MAP graph and the carbon monoxide concentration represented by the curve, and carrying out interpolation calculation on the relation curve to obtain the feedforward optimal air injection concentration cair。
4. The method of claim 1, wherein the determining the feed forward optimum air injection concentration c for the fuel cell under controlairThe specific process is as follows:
establishing a MAP with each of the plurality of MAPsThe relation curve of the optimal air injection concentration corresponding to the peak value of the curve and the carbon monoxide concentration represented by the curve is obtained by using a fitting formula c according to the relation curveair＝f(cin) Calculating to obtain the feedforward optimal air injection concentration cair。
5. A method of regulating as claimed in claim 4, wherein the fitting formula is: c. Cair＝a×ln(b×cin+1)+c×cin 2+d×cinAnd a, b, c and d are fitting parameters of the formula respectively.
6. A control method according to claim 1, wherein said optimizing model for fuel cell anode gas adsorption and reaction is established by:
Figure FDA0003355929640000021
Figure FDA0003355929640000022
Figure FDA0003355929640000023
θH,m＝f4(icell,Vstd,Vm) (8)
wherein, thetaH，θO，θCORespectively represent adsorption ratios of hydrogen, oxygen and carbon monoxide on the surface of the anode catalyst of the fuel cell, cH2，cO2，cCORespectively representing the gas concentrations of hydrogen, oxygen and carbon monoxide entering the fuel cell stack, icellFor calibration of the current density, V, of the fuel cellstdFor calibrating the air injection concentration and standard of the fuel cell when pure hydrogen is introducedConstant current density icellVoltage of lower, VmOptimum air injection concentration of c for fuel cell to be controlled in feed forwardairSteady state voltage at, subscript m denotes fuel cell to be controlled, θH,mAt a current density of icellThe adsorption ratio of hydrogen on the surface of the anode catalyst of the lower fuel cell to be controlled;
calculating the adsorption ratio theta of carbon monoxide on the surface of the anode catalyst by using the modelCOAt a nominal current density icellThe following:
(1) measuring steady-state voltage V of fuel cell to be controlledmAnd apply the VmAnd calibrating the fuel cell at the carbon monoxide concentrationinOptimum voltage value V in corresponding calibration curveffMaking a comparison if Vm≥VffThen the feedforward air injection amount is not feedback corrected, i.e. Δ c at this timeair＝0，Vm<VffThen, the step (2) is carried out;
(2) the steady-state battery voltage V of the fuel battery to be controlledmAnd the voltage V of the fuel cell at the air injection concentration is calibrated when pure hydrogen is introducedstdThe adsorption ratio theta of hydrogen gas on the surface of the catalyst at this time was calculated by equation (4)H,mAnd the adsorption ratio thetaH,mSubstituting the equation into the equations (1) to (2), and solving to obtain the adsorption ratio theta of the carbon monoxide on the surface of the anode catalyst of the fuel cell to be controlledCO,m。
7. A control method as recited in claim 1 wherein said fuel cell anode air injection flow rate is determined by:
the precisely controlled air injection quantity consists of two parts, namely a feedforward optimal air injection concentration c obtained by a calibration MAPairAnd the optimum feedback air injection quantity deltac estimated and calculated by the optimization modelairAnode air injection flow rate of qH2×(cair+Δcair)，qH2Is the hydrogen flow requirement of the fuel cell system.
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EP1267435A2 (en) * 1997-10-24 2002-12-18 General Motors Corporation Method of monitoring CO concentrations in hydrogen feed to a PEM fuel cell
CN1529921A (en) * 2001-03-06 2004-09-15 ŦΤ��ȼ�ϵ��ŷ���������ι�˾ Method for operating fuel cells fed with gas containing hydrogen and carbon oxide and devices relating thereof
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CN110176609A (en) * 2019-06-30 2019-08-27 潍柴动力股份有限公司 A kind of air supply system of fuel battery engines and a kind of fuel-cell vehicle
CN111540934A (en) * 2020-06-18 2020-08-14 张翼翔 Method for eliminating anode poisoning of fuel cell
US20200328445A1 (en) * 2019-04-12 2020-10-15 Bloom Energy Corporation Solid oxide fuel cell system with hydrogen pumping cell with carbon monoxide tolerant anodes and integrated shift reactor

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* Cited by examiner, † Cited by third party
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EP1267435A2 (en) * 1997-10-24 2002-12-18 General Motors Corporation Method of monitoring CO concentrations in hydrogen feed to a PEM fuel cell
CN1529921A (en) * 2001-03-06 2004-09-15 ŦΤ��ȼ�ϵ��ŷ���������ι�˾ Method for operating fuel cells fed with gas containing hydrogen and carbon oxide and devices relating thereof
CN101378130A (en) * 2007-08-29 2009-03-04 株式会社东芝 Method of driving fuel cell device
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CN110176609A (en) * 2019-06-30 2019-08-27 潍柴动力股份有限公司 A kind of air supply system of fuel battery engines and a kind of fuel-cell vehicle
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