CN116264306A - Measuring device and method for corrosion of carbon carrier of proton exchange membrane fuel cell - Google Patents
Measuring device and method for corrosion of carbon carrier of proton exchange membrane fuel cell Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 238000005260 corrosion Methods 0.000 title claims abstract description 58
- 230000007797 corrosion Effects 0.000 title claims abstract description 58
- 239000012528 membrane Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 47
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 47
- 230000008859 change Effects 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims description 345
- 238000012360 testing method Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 230000035945 sensitivity Effects 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000000691 measurement method Methods 0.000 claims 2
- 238000001514 detection method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
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- 238000004364 calculation method Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
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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
- H01M8/04298—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
- H01M8/04791—Concentration; Density
- H01M8/04805—Concentration; Density of fuel cell exhausts
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- 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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- Chemical & Material Sciences (AREA)
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Abstract
The invention provides a device and a method for measuring corrosion of a carbon carrier of a proton exchange membrane fuel cell. The measuring device includes: the device comprises a first gas phase mass spectrometer, a second gas phase mass spectrometer, a first background gas supply unit, a second background gas supply unit, a first standard gas supply unit and a second standard gas supply unit. The measuring device provided by the invention can realize on-line detection of the concentration value and the change of the carbon dioxide in the cathode exhaust gas and the anode exhaust gas of the fuel cell, thereby quantitatively obtaining CO 2 The total gas production is determined to determine the extent of corrosion of the carbon support.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a device and a method for measuring corrosion of a carbon carrier of a proton exchange membrane fuel cell.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) has the characteristics of high energy conversion efficiency, high power density, quick room temperature start, low noise, zero pollution and the like, is expected to reduce carbon dioxide emission, relieves energy crisis, and has the advantages of being applicable to the fields of rail transit, aerospace and the likeHas wide application prospect. The catalyst is a key material of PEMFC, pt has good catalytic oxygen reduction reaction activity and stability, and is an electrocatalyst which is widely used and is difficult to replace. However, pt is expensive, which results in higher cost of the PEMFC, and the Pt loading amount of the PEMFC can be reduced and the Pt utilization rate can be improved by using the Pt carrier. At present, the catalyst of the PEMFC is at most a Pt-based carbon carrier catalyst, and the carbon carrier is generally nanofiber, carbon aerogel, carbon nano tube and the like, so that the dispersion of Pt nano-scale particles is ensured, and the utilization rate and catalytic activity of Pt are improved. The carbon material has the characteristics of low cost, large specific surface area, rich pore structure, adjustable conductivity and surface property and the like, and is a Pt carrier widely applied. However, oxygen ions separated out by the cathode reaction of the fuel cell react with carbon in the carbon core of the supported catalyst to generate CO 2 The carbon core carrying the catalyst is reduced or eliminated, the Pt catalyst attached to the carbon core is agglomerated, and the active area is reduced. Corrosion of the catalyst carbon support, which is a key to influence the stability of the proton membrane fuel cell, causes catalyst decay, eventually leading to degradation of the performance of the PEMFC, so that it is very necessary to study carbon corrosion related theory.
The durability of Proton Exchange Membrane Fuel Cells (PEMFC) is improved, and the performance decay mechanism of each working condition needs to be comprehensively and systematically known. The PEMFC performance attenuation under the main 5 working conditions such as a start-stop working condition, a subzero cold start working condition, a high potential working condition, a variable load working condition, a high current density working condition and the like is related. And the corrosion of the carbon carrier is accompanied in the 5 main working conditions, so that the analysis of the corrosion condition of the carbon carrier is carried out under different working conditions, the analysis is important to the understanding of the stability of the proton membrane fuel cell, the carbon corrosion occurrence mechanism is mastered, and the carbon corrosion occurrence can be avoided by a plurality of methods in a control strategy, so that the durability and the service life of the fuel cell can be improved.
At present, in order to solve the carbon corrosion degree, a technician usually disassembles the fuel cell after the test under different working conditions, disassembles the fuel cell one by one, checks the microstructure of the carbon carrier by using an electron microscope scanning method, and observes the corrosion occurrence degree of the carbon carrier in a mode of comparison before and after the test. However, one such method cannot quantitatively calculate the corrosion level of the carbon support, and two conditions require separate and independent tests, each requiring a fuel cell, and all fuel cells are disassembled after the test is completed. In a word, the existing method often cannot quantitatively analyze the corrosion degree of the carbon carrier, and is long in test time and consumes manpower and material resources.
Disclosure of Invention
The invention mainly aims to provide a device and a method for measuring corrosion of a carbon carrier of a proton exchange membrane fuel cell, which are used for solving the problems that the corrosion degree of the carbon carrier cannot be quantitatively analyzed, the testing time is long and the manpower and material resources are consumed in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a measuring apparatus for corrosion of a carbon carrier of a proton exchange membrane fuel cell, comprising: the first gas phase mass spectrometer is provided with a first gas inlet which is connected with a cathode gas outlet of the fuel cell through a first gas inlet pipeline; the second gas-phase mass spectrometer is provided with a second air inlet which is connected with an anode air outlet of the fuel cell through a second air inlet pipeline; the first background gas supply unit is provided with a first background gas outlet, and the first background gas outlet is connected with the first air inlet pipeline; the second background gas supply unit is provided with a second background gas outlet, and the second background gas outlet is connected with the second air inlet pipeline; the first standard gas supply unit is provided with a first standard gas outlet, and the first standard gas outlet is connected with the first gas inlet pipeline; and a second standard gas supply unit having a second standard gas outlet connected to the second gas inlet line.
Further, the first air inlet pipeline includes first pipe section and the second pipe section that links to each other in order, and first pipe section links to each other with the negative pole gas vent, and the second pipe section still includes with first air inlet: one end of the third pipe section is connected with the first pipe section and the second pipe section through a first three-way valve; a first flow meter is disposed on the third pipe segment.
Further, the second air inlet pipeline includes the fourth pipe section and the fifth pipe section that link to each other in order, and the fourth pipe section links to each other with the positive pole gas vent, and the fifth pipe section links to each other with the second air inlet, and measuring device still includes: one end of the sixth pipe section is connected with the fourth pipe section and the fifth pipe section through a second three-way valve; and a second flowmeter disposed on the sixth pipe segment.
Further, the measuring device further includes: the first valve body is arranged on a pipeline of the first background gas outlet connected with the first air inlet pipeline; the second valve body is arranged on a pipeline of the first standard gas outlet connected with the first air inlet pipeline; the third valve body is arranged on a pipeline of the second background gas outlet connected with the second air inlet pipeline; and the fourth valve body is arranged on a pipeline of the second standard gas outlet connected with the second air inlet pipeline.
Further, the first background gas outlet is connected with the second pipe section, the second background gas outlet is connected with the fifth pipe section, the first standard gas outlet is connected with the second pipe section, and the second standard gas outlet is connected with the fifth pipe section.
Further, the measuring device further includes: the fifth valve body is arranged on the first pipe section; the sixth valve body is arranged on the third pipe section and is positioned between the first flowmeter and the first three-way valve; the seventh valve body is arranged on the fourth pipe section; and the eighth valve body is arranged on the sixth pipe section and is positioned between the second flowmeter and the second three-way valve.
According to another aspect of the present invention, there is also provided a method for measuring corrosion of a carbon carrier of a proton exchange membrane fuel cell, which adopts the above measuring device to measure, the measuring method comprising the steps of: operating the fuel cell to be tested; firstly, starting a first background gas supply unit and/or a second background gas supply unit, introducing first background gas into a first gas-phase mass spectrometer by using the first background gas supply unit to remove impurity gas in the first gas-phase mass spectrometer, and/or introducing second background gas into a second gas-phase mass spectrometer by using the second background gas supply unit to remove impurity gas in the second gas-phase mass spectrometer; closing the first background gas supply unit and the second background gas supply unit, opening the first standard gas supply unit and/or the second standard gas supply unit, and introducing the first standard gas into the first gas phase mass spectrometer by using the first standard gas supply unit so as to calibrate the sensitivity of the first gas phase mass spectrometer; and/or introducing a second standard gas into the second gas phase mass spectrometer by using a second standard gas supply unit so as to calibrate the sensitivity of the second gas phase mass spectrometer; closing the first standard gas supply unit and the second standard gas supply unit, introducing cathode gas exhausted from a cathode exhaust port into the first gas phase mass spectrometer, testing a change curve of the carbon dioxide concentration of the cathode gas with time, and marking the change curve as a cathode curve; and/or introducing anode gas exhausted from an anode exhaust port into the second gas-phase mass spectrometer, and testing a change curve of carbon dioxide concentration along with time, and recording the change curve as an anode curve; and acquiring carbon dioxide concentration information of the anode and/or the cathode of the proton exchange membrane fuel cell according to the cathode curve and/or the anode curve, thereby obtaining the corrosion degree of the carbon carrier of the proton exchange membrane fuel cell or the corrosion degree of the carbon carrier of the cathode of the proton exchange membrane fuel cell or the corrosion degree of the carbon carrier of the anode of the proton exchange membrane fuel cell.
Further, the first background gas is hydrogen and the second background gas is air.
Further, the first standard gas comprises 78-82% of hydrogen, 17-21% of nitrogen and 0.8-1.6% of carbon dioxide by volume fraction; the second standard gas comprises 88-92% of nitrogen, 7-11% of oxygen and 0.8-1.6% of carbon dioxide by volume fraction.
Further, before the first background gas, the first standard gas and the cathode gas are introduced into the first gas phase mass spectrometer, the air inlet flow rate of the first gas phase mass spectrometer is adjusted to 15-20 ml/min by using the first flow meter respectively; before the second background gas, the second standard gas and the cathode gas are introduced into the second gas-phase mass spectrometer, the air inlet flow rate of the second gas-phase mass spectrometer is respectively adjusted to 15-20 ml/min by using a second flowmeter.
Carbon support corrosion of fuel cells can be direct or indirect to produce CO 2 The method of the invention can realize the on-line detection of the concentration value and the change of the carbon dioxide in the cathode exhaust gas and the anode exhaust gas of the fuel cell by using the measuring device provided by the invention, thereby quantitatively obtaining CO 2 Total generation of gasThe amount of carbon carrier is determined. In addition, the measuring device does not need to disassemble the fuel cell, and is convenient and quick to test.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows a schematic structural diagram of a measurement device for carbon carrier corrosion of a proton exchange membrane fuel cell according to one embodiment of the invention.
Fig. 2 shows the cathode curve measured in example 1 of the present invention.
Wherein the above figures include the following reference numerals:
1. a fuel cell; 101. a cathode inlet; 102. an anode gas inlet; 103. a cathode exhaust port; 104. an anode exhaust port;
10. a first gas phase mass spectrometer; 20. a second gas phase mass spectrometer; 30. a first background gas supply unit; 40. a second background gas supply unit; 50. a first standard gas supply unit; 60. a second standard gas supply unit; 70. a first flowmeter; 80. a second flowmeter;
11. a first air intake line; 21. a second air intake line; 12. a first three-way valve; 22. a second three-way valve; 31. a first valve body; 51. a second valve body; 41. a third valve body; 61. a fourth valve body; 13. a fifth valve body; 14. a sixth valve body; 23. a seventh valve body; 24. and an eighth valve body.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
As described in the background section, the corrosion degree of the carbon carrier cannot be quantitatively analyzed in the prior art, and the problems of long test time and labor and material consumption are solved.
In order to solve the above problems, the present invention provides a measurement device for carbon carrier corrosion of a proton exchange membrane fuel cell, as shown in fig. 1, the measurement device includes a first gas mass spectrometer 10, a second gas mass spectrometer 20, a first background gas supply unit 30, a second background gas supply unit 40, a first standard gas supply unit 50 and a second standard gas supply unit 60; the first gas phase mass spectrometer 10 has a first gas inlet connected to a cathode exhaust of the fuel cell through a first gas inlet line 11; the second gas phase mass spectrometer 20 has a second gas inlet connected to the anode exhaust of the fuel cell by a second gas inlet line 21; the first background gas supply unit 30 has a first background gas outlet connected to the first gas inlet pipe 11; the second background gas supply unit 40 has a second background gas outlet connected to the second gas inlet line 21; the first standard gas supply unit 50 has a first standard gas outlet connected to the first gas inlet line 11; the second standard gas supply unit 60 has a second standard gas outlet connected to the second gas inlet line 21.
Carbon support corrosion of fuel cells can be direct or indirect to produce CO 2 The method of the invention can realize the online detection of the concentration value and the change of the carbon dioxide in the cathode exhaust gas and the anode exhaust gas of the fuel cell by using the measuring device provided by the invention, thereby quantitatively obtaining the anode CO 2 Gas production amount, cathode CO 2 Gas production and CO 2 The total gas production is determined to determine the degree of corrosion of the carbon support (anode or cathode or total degree of corrosion). In addition, the measuring device does not need to disassemble the fuel cell, and is convenient and quick to test.
As shown in fig. 1, the fuel cell 1 generally has a cathode inlet 101, an anode inlet 102, a cathode outlet 103, and an anode outlet 104, and the above-described measuring device of the present invention is connected to the cathode outlet 103 and the anode outlet 104.
Specifically, during the actual measurement process, the fuel cell may be operated according to different conditions, such as a start-stop condition, a subzero cold start condition, a high potential condition, a variable load condition, a high current density condition, and the like, which are well known in the art. Specifically, selecting a start-stop condition refers to: introducing hydrogen and air into the fuel cell, and setting a load with certain power to start the fuel cell; then closing the load output, stopping sharing air and hydrogen, and stopping the fuel cell; the subzero cold start condition refers to: testing at the temperature lower than 0 ℃ and other steps being the same as the starting working condition; the high potential condition is: operating the fuel cell at a lower power point to maintain its operating voltage at a higher level; the variable load working condition is as follows: the fuel cell is quickly converted from low power to high power back and forth; the high current density condition is: the fuel cell is operated at the maximum power point for a long period of time. After the fuel cell is operated, the carbon dioxide concentration of the gas discharged from the cathode exhaust port and the anode exhaust port can be detected in real time by the first gas phase mass spectrometer 10 and the second gas phase mass spectrometer 20, respectively.
To make the detection more accurate, the first background gas supply unit 30 and the second background gas supply unit 40 may be turned on before detecting the cathode gas and the anode gas, and the first background gas is introduced into the first gas phase mass spectrometer 10 by using the first background gas supply unit 30 to remove the impurity gas CO in the first gas phase mass spectrometer 10 2 Influence, the second background gas is introduced into the second gas phase mass spectrometer 20 by the second background gas supply unit 40 to remove the impurity gas CO in the second gas phase mass spectrometer 20 2 Influence. Then, the first background gas supply unit 30 and the second background gas supply unit 40 are closed, the first standard gas supply unit 50 and the second standard gas supply unit 60 are opened, and the first standard gas supply unit 50 is utilized to introduce the first standard gas into the first gas phase mass spectrometer 10 so as to calibrate the sensitivity of the first gas phase mass spectrometer 10; a second standard gas is introduced into the second gas phase mass spectrometer 20 by a second standard gas supply unit 60 to perform sensitivity calibration on the second gas phase mass spectrometer 20.
After sensitivity calibration, the test results of the two gas phase mass spectrometers are more accurate. Next, the first standard gas supply unit 50 and the second standard gas supply unit 60 may be turned off, the cathode gas discharged from the cathode exhaust port is introduced into the first gas phase mass spectrometer 10, and a change curve of the carbon dioxide concentration with time is measured and recorded as a cathode curve; the anode gas discharged from the anode exhaust port was introduced into the second gas phase mass spectrometer 20, and the change curve of the carbon dioxide concentration with time was measured and recorded as an anode curve. The cathode curve and the anode curve can reflect the carbon dioxide concentration changes in the cathode gas and the anode gas under different operation time or different operation working conditions, and according to the test result, the total amount of carbon dioxide discharged in a target operation time period or under the target operation working condition can be obtained quantitatively, or the total amount of carbon dioxide discharged by the cathode can be obtained according to the cathode curve, or the total amount of carbon dioxide discharged by the anode can be obtained according to the anode curve, and the original content of carbon dioxide in the air can be subtracted to convert the carbon loss in the carbon carrier (or the carbon loss in the cathode carbon carrier or the carbon loss in the anode carbon carrier), so that the corresponding carbon corrosion degree (or the corrosion degree of the cathode carbon carrier or the corrosion degree of the anode carbon carrier) is judged.
To further improve the accuracy of the test, in a preferred embodiment, as shown in fig. 1, the first air inlet pipeline 11 comprises a first pipe section and a second pipe section which are connected in parallel, the first pipe section is connected with the cathode exhaust port, the second pipe section is connected with the first air inlet port, and the measuring device further comprises: a third pipe section, one end of which is connected to the first pipe section and the second pipe section through a first three-way valve 12; a first flow meter 70, the first flow meter 70 being arranged on the third pipe section.
The use of the first flow meter 70 allows the inlet gas flow rate of the mass spectrometer to be separately tested and adjusted before the first background gas, the first standard gas and the cathode gas are introduced into the first gas phase mass spectrometer 10, which allows the inlet gas flow rate to be controlled within a more appropriate range, resulting in a more reliable detection by the mass spectrometer. Similarly, in a preferred embodiment, the second air intake line 21 comprises a fourth pipe section and a fifth pipe section connected in sequence, the fourth pipe section being connected to the anode exhaust port, the fifth pipe section being connected to the second air intake port, and the measuring device further comprises: a sixth pipe section, one end of which is connected to the fourth pipe section and the fifth pipe section through a second three-way valve 22; a second flowmeter 80, the second flowmeter 80 being disposed on the sixth pipe segment.
In order to facilitate switching between the gas inlet flow rate and the gas inlet type, the measuring device preferably further includes: a first valve body 31 disposed on a line where the first background gas outlet is connected to the first intake line 11; a second valve body 51 provided on a pipe in which the first standard gas outlet is connected to the first intake pipe 11; a third valve body 41 provided on a line where the second background gas outlet is connected to the second intake line 21; the fourth valve body 61 is provided on a line where the second standard gas outlet is connected to the second intake line 21. More preferably, the first background gas outlet is connected to the second pipe section, the second background gas outlet is connected to the fifth pipe section, the first standard gas outlet is connected to the second pipe section, and the second standard gas outlet is connected to the fifth pipe section. In this way, the opening of the first valve body 31 and the flow rate data of the first flow meter 70 can be used to adjust the intake flow rate of the first background gas during actual measurement. Similarly, the intake flow rate of the first standard gas can be adjusted by the flow rate data of the second valve body 51 and the first flow meter 70, the intake flow rate of the second background gas can be adjusted by the flow rate data of the third valve body 41 and the second flow meter 80, and the intake flow rate of the second standard gas can be adjusted by the flow rate data of the fourth valve body 61 and the second flow meter 80.
In one embodiment, the measuring device further includes: a fifth valve body 13 disposed on the first pipe section; a sixth valve body 14 disposed on the third pipe section and located between the first flow meter 70 and the first three-way valve 12; a seventh valve body 23 provided on the fourth pipe section; an eighth valve body 24 is disposed on the sixth pipe segment and is located between the second flowmeter 80 and the second three-way valve 22. When the first flow meter 70 or the second flow meter 80 is started, the fifth valve body 13 and the eighth valve body 24 may be completely opened, and then the opening degrees of the remaining corresponding valve bodies may be adjusted to adjust the intake flow rates of the corresponding gases.
The valve bodies except the three-way valve can adopt needle valves, ball valves and the like.
According to another aspect of the present invention, there is also provided a method for measuring corrosion of a carbon carrier of a proton exchange membrane fuel cell, which adopts the above measuring device to measure, the measuring method comprising the steps of:
operating the fuel cell to be tested; first, the first background gas supply unit 30 and/or the second background gas supply unit 40 are/is started, the first background gas is introduced into the first gas phase mass spectrometer 10 by using the first background gas supply unit 30 to remove impurity gas in the first gas phase mass spectrometer 10, and/or the second background gas is introduced into the second gas phase mass spectrometer 20 by using the second background gas supply unit 40 to remove impurity gas in the second gas phase mass spectrometer 20; closing the first background gas supply unit 30 and the second background gas supply unit 40, opening the first standard gas supply unit 50 and/or the second standard gas supply unit 60, and introducing the first standard gas into the first gas phase mass spectrometer 10 by using the first standard gas supply unit 50 so as to calibrate the sensitivity of the first gas phase mass spectrometer 10; and/or introducing a second standard gas into the second gas phase mass spectrometer 20 by using the second standard gas supply unit 60 to perform sensitivity calibration on the second gas phase mass spectrometer 20; closing the first standard gas supply unit 50 and the second standard gas supply unit 60, introducing the cathode gas exhausted from the cathode exhaust port into the first gas phase mass spectrometer 10, and testing the change curve of the carbon dioxide concentration with time, and recording as a cathode curve; and/or introducing anode gas discharged from an anode exhaust port into the second gas phase mass spectrometer 20, and testing a change curve of carbon dioxide concentration with time, and recording the change curve as an anode curve; and acquiring carbon dioxide concentration information of the anode and/or the cathode of the proton exchange membrane fuel cell according to the cathode curve and/or the anode curve, thereby obtaining the corrosion degree of the carbon carrier of the proton exchange membrane fuel cell or the corrosion degree of the carbon carrier of the cathode of the proton exchange membrane fuel cell or the corrosion degree of the carbon carrier of the anode of the proton exchange membrane fuel cell.
Carbon support corrosion of fuel cells can be direct or indirect to produce CO 2 The method can realize on-line detection of the concentration value and the change of the carbon dioxide in the cathode exhaust gas and the anode exhaust gas of the fuel cell, thereby quantitatively obtaining anode CO 2 Gas production amount, cathode CO 2 Gas production and CO 2 Total gas production to determine carbonThe extent of carrier corrosion (anode or cathode or total extent of corrosion). In addition, the measuring device does not need to disassemble the fuel cell, and is convenient and quick to test.
The above "and/or" are three schemes in parallel, specifically, during actual operation:
operating the fuel cell to be tested;
opening a first background gas supply unit 30, and introducing a first background gas into the first gas phase mass spectrometer 10 by using the first background gas supply unit 30 to remove impurity gas in the first gas phase mass spectrometer 10; closing the first background gas supply unit 30, opening the first standard gas supply unit 50, and introducing the first standard gas into the first gas phase mass spectrometer 10 by using the first standard gas supply unit 50 so as to calibrate the sensitivity of the first gas phase mass spectrometer 10; closing the first standard gas supply unit 50, introducing the cathode gas exhausted from the cathode exhaust port into the first gas mass spectrometer 10, and testing the change curve of the carbon dioxide concentration with time, and recording the change curve as a cathode curve; and/or
Firstly, starting a second background gas supply unit 40, and introducing a second background gas into the second gas-phase mass spectrometer 20 by using the second background gas supply unit 40 to remove impurity gas in the second gas-phase mass spectrometer 20; closing the second background gas supply unit 40, opening the second standard gas supply unit 60, and introducing the second standard gas into the second gas phase mass spectrometer 20 by using the second standard gas supply unit 60 so as to calibrate the sensitivity of the second gas phase mass spectrometer 20; closing the second standard gas supply unit 60, introducing the anode gas discharged from the anode exhaust port into the second gas phase mass spectrometer 20, and testing the change curve of the carbon dioxide concentration with time, and recording the change curve as an anode curve;
according to the cathode curve, acquiring carbon dioxide concentration information of a cathode of the proton exchange membrane fuel cell, thereby obtaining the corrosion degree of a cathode carbon carrier of the proton exchange membrane fuel cell; and/or according to the anode curve, acquiring the carbon dioxide concentration information of the anode of the proton exchange membrane fuel cell, thereby obtaining the corrosion degree of the carbon carrier of the anode of the proton exchange membrane fuel cell; and/or according to the cathode curve and the anode curve, acquiring carbon dioxide concentration information of the anode and the cathode of the proton exchange membrane fuel cell, thereby obtaining the corrosion degree of the carbon carrier of the proton exchange membrane fuel cell.
Specifically, during the actual measurement process, the fuel cell may be operated according to different conditions, such as a start-stop condition, a subzero cold start condition, a high potential condition, a variable load condition, a high current density condition, and the like, which are well known in the art. After the fuel cell is operated, the carbon dioxide concentration of the gas discharged from the cathode exhaust port and the anode exhaust port can be detected in real time by the first gas phase mass spectrometer 10 and the second gas phase mass spectrometer 20, respectively.
In order to make detection more accurate, before the cathode gas and the anode gas are actually detected, the invention firstly utilizes the background gas to discharge impurity gas in the mass spectrometer and utilizes the standard gas to carry out sensitivity calibration. The final tested cathode curve and anode curve can reflect the carbon dioxide concentration change in the cathode gas and the anode gas under different operation time or different operation working conditions, the total amount of carbon dioxide discharged in a target operation period or under the target operation working condition can be quantitatively obtained according to the test result, after the carbon dioxide content in the air is deducted, the carbon loss in the carbon carrier can be converted, and the corresponding carbon corrosion degree is further judged.
Preferably, the first background gas is hydrogen and the second background gas is air. Preferably, the first standard gas comprises 78-82% hydrogen, 17-21% nitrogen and 0.8-1.6% carbon dioxide by volume fraction; the second standard gas comprises 88-92% of nitrogen, 7-11% of oxygen and 0.8-1.6% of carbon dioxide by volume fraction. The above background gas and standard gas are used to determine the concentration change of carbon dioxide in the anode and cathode more accurately.
In a preferred embodiment, the first flow meter 70 is used to adjust the intake air flow rate of the first gas phase mass spectrometer 10 to 15-20 ml/min before the first background gas, the first standard gas and the cathode gas are introduced into the first gas phase mass spectrometer 10, respectively; before the second background gas, the second standard gas and the cathode gas are introduced into the second gas phase mass spectrometer 20, the second flowmeter 80 is used to adjust the inlet gas flow rate of the second gas phase mass spectrometer 20 to 15-20 ml/min. In this way, the intake air flow rate at each stage can be controlled so as to be more suitable for detection by a mass spectrometer.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
Taking a certain 413 fuel cells, 130Kw fuel cell model fuel cells as objects to be tested, measuring the original quantity of anode carbon carriers and the original quantity of cathode carbon carriers before testing, and then testing the corrosion degree of the carbon carriers under the cold starting working condition under zero, wherein the specific working conditions are as follows: introducing hydrogen and air into the fuel cell at the temperature of minus 10 ℃ and setting a load of … power to start the fuel cell; then closing the load output, stopping sharing air and hydrogen, and stopping the fuel cell; the subzero cold start condition refers to: the test was performed.
Operating the fuel cell to be tested;
by using the measuring device shown in FIG. 1, the following gas flows were adjusted to 20ml/min by the cooperation of the first flow meter and the second flow meter with the valve body.
Starting a first background gas supply unit, and introducing a first background gas (hydrogen) into the first gas phase mass spectrometer by using the first background gas supply unit so as to remove impurity gas in the first gas phase mass spectrometer; closing a first background gas supply unit, opening a first standard gas supply unit, and introducing first standard gas (comprising 80% of hydrogen, 19% of nitrogen and 1% of carbon dioxide by volume fraction) into the first gas phase mass spectrometer by using the first standard gas supply unit so as to calibrate the sensitivity of the first gas phase mass spectrometer; closing the first standard gas supply unit, introducing cathode gas exhausted from a cathode exhaust port into the first gas mass spectrometer, and testing a change curve of carbon dioxide concentration along with time, wherein the change curve is recorded as a cathode curve, and is shown in fig. 2;
firstly, starting a second background gas supply unit, and introducing second background gas (air) into a second gas-phase mass spectrometer by using the second background gas supply unit so as to remove impurity gas in the second gas-phase mass spectrometer; closing a second background gas supply unit, opening a second standard gas supply unit, and introducing second standard gas (comprising 80% of nitrogen, 9% of oxygen and 1% of carbon dioxide by volume fraction) into the second gas-phase mass spectrometer by using the second standard gas supply unit so as to calibrate the sensitivity of the second gas-phase mass spectrometer; closing the second standard gas supply unit, introducing anode gas exhausted from an anode exhaust port into the second gas-phase mass spectrometer, testing the change curve of the carbon dioxide concentration of the anode gas along with time, and recording the change curve as an anode curve;
according to the cathode curve, the carbon dioxide concentration of the cathode of the proton exchange membrane fuel cell under the whole subzero cold start working condition is changed along with time, the peak area within the short time of 0-12000 s in the graph 2 is calculated, the peak area is converted into the cathode carbon dioxide generation amount, and the carbon corrosion degree (the percentage of the cathode carbon loss amount to the original cathode carbon weight) is obtained through conversion with the original content of the cathode carbon carrier;
according to the anode curve, acquiring the carbon dioxide concentration change with time under the whole subzero cold start working condition of the proton exchange membrane fuel cell anode, calculating the peak area within the short time of 0-12000 s, converting into the anode carbon dioxide generation amount, and converting with the original content of the anode carbon carrier to obtain the carbon corrosion degree (the percentage of the anode carbon loss amount to the original anode carbon weight);
and obtaining the total corrosion degree of the carbon carrier (the loss of the carbon of the cathode and the anode accounts for the weight percentage of the original carbon of the cathode and the anode) through the total original content of the carbon carrier of the cathode and the anode according to the total generation amount of the carbon dioxide of the cathode and the anode.
And disassembling the fuel cell under the end working condition to obtain a carbon carrier, weighing, and comparing the corrosion degree of the cathode and the anode carbon carrier with the test result to obtain the test result, wherein the test deviation of the corrosion degree of the cathode carbon carrier is 3%, the test deviation of the corrosion degree of the anode carbon carrier is 2%, and the total deviation is 2.5%, which indicates that the test method is effective and reliable.
The calculation mode of the test deviation is as follows: the difference between the calculated corrosion level and the weighed corrosion level is calculated as a percentage of the weighed corrosion level.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A device for measuring corrosion of a carbon carrier of a proton exchange membrane fuel cell, comprising:
a first gas phase mass spectrometer (10) having a first gas inlet connected to a cathode exhaust of the fuel cell by a first gas inlet line (11);
a second gas phase mass spectrometer (20) having a second gas inlet connected to an anode exhaust of the fuel cell by a second gas inlet line (21);
a first background gas supply unit (30) having a first background gas outlet connected to the first air intake line (11);
a second background gas supply unit (40) having a second background gas outlet connected to the second air intake duct (21);
a first standard gas supply unit (50) having a first standard gas outlet connected to the first gas inlet line (11); and
and a second standard gas supply unit (60) having a second standard gas outlet connected to the second gas inlet line (21).
2. The measurement device according to claim 1, wherein the first inlet conduit (11) comprises a first and a second conduit section connected in series, the first conduit section being connected to the cathode exhaust outlet, the second conduit section being connected to the first inlet, the measurement device further comprising:
a third pipe section, one end of which is connected with the first pipe section and the second pipe section through a first three-way valve (12);
-a first flow meter (70), said first flow meter (70) being arranged on said third pipe section.
3. The measurement device according to claim 2, wherein the second inlet line (21) comprises a fourth pipe section and a fifth pipe section connected in sequence, the fourth pipe section being connected to the anode exhaust port, the fifth pipe section being connected to the second inlet port, the measurement device further comprising:
a sixth pipe section, one end of which is connected with the fourth pipe section and the fifth pipe section through a second three-way valve (22);
-a second flowmeter (80), said second flowmeter (80) being arranged on said sixth pipe segment.
4. A measuring device according to any one of claims 1 to 3, characterized in that the measuring device further comprises:
the first valve body (31) is arranged on a pipeline connected with the first background gas outlet and the first air inlet pipeline (11);
the second valve body (51) is arranged on a pipeline of the first standard gas outlet connected with the first air inlet pipeline (11);
a third valve body (41) arranged on a pipeline where the second background gas outlet is connected with the second air inlet pipeline (21);
and a fourth valve body (61) arranged on a pipeline of the second standard gas outlet connected with the second gas inlet pipeline (21).
5. A measuring device according to claim 3, wherein the first background gas outlet is connected to the second pipe section, the second background gas outlet is connected to the fifth pipe section, the first standard gas outlet is connected to the second pipe section, and the second standard gas outlet is connected to the fifth pipe section.
6. A measuring device according to claim 3, characterized in that the measuring device further comprises:
a fifth valve body (13) arranged on the first pipe section;
a sixth valve body (14) disposed on the third pipe section and located between the first flow meter (70) and the first three-way valve (12);
a seventh valve body (23) arranged on the fourth pipe section;
an eighth valve body (24) is disposed on the sixth pipe segment and is located between the second flowmeter (80) and the second three-way valve (22).
7. A method for measuring corrosion of a carbon carrier of a proton exchange membrane fuel cell, characterized in that the measurement is performed by using the measuring device according to any one of claims 1 to 6, the measuring method comprising the steps of:
operating the fuel cell to be tested;
firstly, a first background gas supply unit (30) and/or a second background gas supply unit (40) are/is started, first background gas is introduced into a first gas phase mass spectrometer (10) by using the first background gas supply unit (30) to remove impurity gas in the first gas phase mass spectrometer (10), and/or second background gas is introduced into a second gas phase mass spectrometer (20) by using the second background gas supply unit (40) to remove impurity gas in the second gas phase mass spectrometer (20);
closing the first background gas supply unit (30) and the second background gas supply unit (40), and opening a first standard gas supply unit (50) and/or a second standard gas supply unit (60), and introducing a first standard gas into the first gas phase mass spectrometer (10) by using the first standard gas supply unit (50) so as to calibrate the sensitivity of the first gas phase mass spectrometer (10); and/or introducing a second standard gas into the second gas phase mass spectrometer (20) by using the second standard gas supply unit (60) so as to calibrate the sensitivity of the second gas phase mass spectrometer (20);
closing the first standard gas supply unit (50) and the second standard gas supply unit (60), introducing cathode gas exhausted from a cathode exhaust port into the first gas phase mass spectrometer (10), and testing a change curve of carbon dioxide concentration with time, wherein the change curve is recorded as a cathode curve; and/or introducing anode gas exhausted from an anode exhaust port into the second gas-phase mass spectrometer (20), and testing a change curve of carbon dioxide concentration with time, and recording the change curve as an anode curve;
and acquiring carbon dioxide concentration information of the anode and/or the cathode of the proton exchange membrane fuel cell according to the cathode curve and/or the anode curve, thereby obtaining the corrosion degree of the carbon carrier of the proton exchange membrane fuel cell, or the corrosion degree of the carbon carrier of the cathode of the proton exchange membrane fuel cell, or the corrosion degree of the carbon carrier of the anode of the proton exchange membrane fuel cell.
8. The method of claim 7, wherein the first background gas is hydrogen and the second background gas is air.
9. The measurement method according to claim 7, wherein the first standard gas includes 78 to 82% hydrogen, 17 to 21% nitrogen, and 0.8 to 1.6% carbon dioxide by volume fraction; the second standard gas comprises 88-92% of nitrogen, 7-11% of oxygen and 0.8-1.6% of carbon dioxide by volume fraction.
10. The measurement method according to claim 7, characterized in that before the first background gas, the first standard gas and the cathode gas are introduced into the first gas phase mass spectrometer (10), the intake air flow rate of the first gas phase mass spectrometer (10) is adjusted to 15-20 ml/min by means of a first flow meter (70), respectively; before the second background gas, the second standard gas and the cathode gas are introduced into the second gas-phase mass spectrometer (20), the inlet flow rate of the second gas-phase mass spectrometer (20) is adjusted to 15-20 ml/min by a second flowmeter (80).
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