CN115360386B - Fuel cell stack water plugging detection method and new energy automobile - Google Patents

Fuel cell stack water plugging detection method and new energy automobile Download PDF

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CN115360386B
CN115360386B CN202211288237.5A CN202211288237A CN115360386B CN 115360386 B CN115360386 B CN 115360386B CN 202211288237 A CN202211288237 A CN 202211288237A CN 115360386 B CN115360386 B CN 115360386B
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diffusion layer
gas diffusion
proton exchange
exchange membrane
value
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CN115360386A (en
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王卫杰
谢铭丰
周超
倪康富
魏礼良
彭海军
葛升
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CRRC Suzhou Hydrogen Power Technology Co Ltd
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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
    • H01M8/04313—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
    • H01M8/0432—Temperature; Ambient temperature
    • 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
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
    • 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

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Abstract

The invention discloses a fuel cell stack water plugging detection method and a new energy automobile, wherein the detection method comprises the following steps: calculating the shrinkage size of a gas diffusion layer in the galvanic pile under the current operation state; comparing the swelling thickening size of the proton exchange membrane in the stack with the shrinking size of the gas diffusion layer, and if the swelling thickening size of the proton exchange membrane is larger than the shrinking size of the gas diffusion layer, executing the following steps: calculating the force applied to the gas diffusion layer by the proton exchange membrane in the current state, and calculating the force applied to the carbon paper by the air inlet pressure of the galvanic pile in the current state; and if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is smaller than the force applied to the gas diffusion layer by the proton exchange membrane, increasing the inlet pressure and inlet flow of the galvanic pile. The invention judges the water plugging state of the galvanic pile based on calculating the embedding amount of the gas diffusion layer, the prediction precision is not influenced by membrane resistance and the output voltage of the galvanic pile, and a proper drainage strategy can be prepared according to the current working condition.

Description

Fuel cell stack water plugging detection method and new energy automobile
Technical Field
The invention relates to the field of water plugging control of a cell stack, in particular to a water plugging detection method of a fuel cell stack and a new energy automobile.
Background
The fuel cell is heated and has hydrophilicity in the operation process, so that the proton exchange membrane can be subjected to thermal expansion and swelling respectively, the swelling of the proton exchange membrane can extrude a Gas Diffusion Layer (hereinafter referred to as GDL), the GDL is embedded into a flow channel defined by a bipolar plate groove, the mass transfer area is reduced, the dispersion uniformity of reaction Gas is influenced, water generated by electrochemical reaction is difficult to discharge due to the reduction of the volume of the flow channel, and finally water plugging of a stack is caused, and the output performance and the service life of the stack are influenced.
In the prior art, whether the galvanic pile blocks water is judged by monitoring the internal resistance of the galvanic pile on line and combining the fluctuation condition of the galvanic pile voltage, and after the water is determined to be blocked, the water is blown out by increasing the air inlet flow. However, in the prior art, it is difficult to accurately judge whether the galvanic pile blocks water or not through the internal resistance of the galvanic pile, because the internal resistance of the galvanic pile depends on the internal resistance of the proton exchange membrane, when the membrane is saturated, the internal resistance of the galvanic pile can not be obviously changed even if the galvanic pile blocks water; on the other hand, because the voltage itself has certain fluctuation during the operation of the electric pile, the reason of the voltage fluctuation of the electric pile is difficult to judge, and ineffective drainage is caused.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application nor give technical teaching; the above background should not be used to assess the novelty and inventive aspects of the present application in the absence of express evidence that the above disclosure is published prior to the filing date of the present patent application.
Disclosure of Invention
The invention aims to provide a fuel cell stack water plugging detection method which can accurately judge whether a GDL is embedded into a bipolar plate flow channel due to pressure exerted by swelling of a proton exchange membrane and can make an adaptive drainage strategy by combining with actual working conditions.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a fuel cell stack water plugging detection method comprises the following steps:
calculating the shrinkage size of the gas diffusion layer in the stack under the current operation state by the following formula: ΔL 2 =－α×T×L G Herein, the painL 2 Is the size of the contraction of the gas diffusion layer,L G is the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed,αwhich is the coefficient of thermal expansion in the thickness direction of the carbon paper,Tthe current operating temperature inside the galvanic pile is obtained;
comparing the swelling thickening size of the proton exchange membrane in the stack with the shrinking size of the gas diffusion layer, and if the swelling thickening size of the proton exchange membrane is larger than the shrinking size of the gas diffusion layer, executing the following steps:
the force applied to the gas diffusion layer by the proton exchange membrane in the current state is calculated by the following formula:
Figure 999645DEST_PATH_IMAGE001
wherein, in the step (A),F m the force applied to the gas diffusion layer after the membrane swells,Eis the modulus of elasticity of the film,Sthe contact area between the membrane and the gas diffusion layerL 1 Swelling and thickening size of proton exchange membraneL 2 Is the shrinkage size of the gas diffusion layer; and
the force applied to the carbon paper by the inlet pressure of the cell stack in the current state is calculated by the following formula:F P =P×S G wherein, in the step (A),F P a force applied to the carbon paper for the intake pressure,Pas the current intake air pressure, the intake air pressure,S G the transverse area of a bipolar plate groove in the galvanic pile;
and if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is smaller than the force applied to the gas diffusion layer by the proton exchange membrane, simultaneously increasing the inlet pressure and the inlet flow of the galvanic pile.
Further, if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is smaller than the force applied to the gas diffusion layer by the proton exchange membrane, calculating a value for increasing the inlet pressure according to the following formula:
Figure 838157DEST_PATH_IMAGE002
therein is ΔP in Is an increase value of the intake air pressure.
Further, in view of any one or a combination of the foregoing technical solutions, the process of increasing the inlet pressure and the inlet flow rate of the cell stack is divided into three stages, which sequentially include:
increase of intake pressure in the first stage
Figure 883474DEST_PATH_IMAGE003
Wherein, in the step (A),k 11 the value range of (1) to (2) and the increase value of the intake air flow is Deltav 1 =k 21 *v 0 Wherein, Δv 1 Is the increased value of the intake air flow rate in the first stage,k 21 ranges from 0.3 to 0.75,v 0 the current intake air flow value before increasing;
second stage intake pressure increase
Figure 950787DEST_PATH_IMAGE004
Wherein, in the step (A),k 12 the value range of (1) is between 1.0 and 1.1, and the increment value of the intake air flow is Deltav 2 =k 22 *v 0 Wherein, Δv 2 The increase value of the intake air flow rate in the second stage,k 22 is in the range of 0.3 to 0.75 andk 22 ≤k 21 ；
third stage inlet pressure increase
Figure 30738DEST_PATH_IMAGE005
Wherein, in the step (A),k 13 the value range of (1) is between 1.0 and 1.1, and the increment value of the intake air flow is Deltav 3 =k 23 *v 0 Wherein, Δv 3 For the third stage increase value of the intake air flow rate,k 23 is in the range of 0.1 to 0.25.
Further, according to any one or combination of the technical schemes, the sum of the time spent in the three stages of increasing the air inlet pressure and the air inlet flow of the galvanic pile is increasedIs composed oftWherein the time range of the first stage is between 0.15tTo 0.2tThe time range of the second stage is between 0.5tTo 0.6t。
Further, based on any one or a combination of the foregoing technical solutions, if the difference between the swelling thickening dimension of the proton exchange membrane and the shrinkage dimension of the gas diffusion layer is greater than 20% of the depth of the bipolar plate groove, the time period for the stage of increasing the inlet pressure and inlet flow rate of the stack ranges from 60 to 120 seconds;
if the difference of the swelling thickening size of the proton exchange membrane minus the shrinking size of the gas diffusion layer is more than 10% of the depth of the bipolar plate groove and less than or equal to 20% of the depth of the bipolar plate groove, the stage time for increasing the inlet pressure and inlet flow of the electric pile ranges from 30 to 60 seconds;
if the difference of the swelling thickening size of the proton exchange membrane minus the shrinking size of the gas diffusion layer is less than or equal to 10% of the depth of the bipolar plate groove, the stage of increasing the inlet pressure and inlet flow of the cell stack takes 10 to 20 seconds.
Further, according to any one or a combination of the foregoing technical solutions, if the force applied to the carbon paper by the intake pressure of the cell stack in the current state is greater than or equal to the force applied to the gas diffusion layer by the proton exchange membrane, the intake flow rate of the cell stack is increased while the intake pressure of the cell stack is kept unchanged.
Further, based on any one or combination of the above technical solutions, the process of increasing the intake air flow is divided into two stages, which sequentially include:
the increase value of the intake air flow in the first stage is Δv 1 =k 21 *v 0 Wherein, Δv 1 Is the increased value of the intake air flow rate in the first stage,k 21 the value of (A) is in the range of 0.3 to 0.75,v 0 the current intake flow value before increasing;
the increase value of the intake air flow in the second stage is Δv 2 =k 22 *v 0 Which isMiddle, deltav 2 The value of the increase in the flow rate of intake air in the second stage,k 22 the value range of (a) is from 0.1 to 0.25;
the ratio of the time of the first stage to the time of the second stage ranges from 0.5 to 1:1.
Further, in accordance with any one or a combination of the foregoing technical solutions, the swelling thickening size of the proton exchange membrane in the stack is obtained by the following formula:
Figure 10458DEST_PATH_IMAGE006
wherein, ΔL 1 In order to increase the thickness of the swelling proton exchange membrane,L 0 is the original thickness of the proton exchange membrane,δis the swelling ratio of the proton exchange membrane.
Further, according to any one or a combination of the foregoing technical solutions, the operating temperature inside the stack is detected in real time, and if the temperature detection value is kept greater than or equal to the preset temperature threshold value within the continuous time period of the preset time period, the initial inlet pressure and/or inlet flow of the stack are/is recovered.
Further, in accordance with any one or combination of the preceding claims, the minimum set point of the temperature threshold is calculated by the following formula:
Figure 808650DEST_PATH_IMAGE007
wherein, in the step (A),
Figure 414074DEST_PATH_IMAGE008
in order to be the temperature threshold value,L 0 is the original thickness of the proton exchange membrane,δis the swelling ratio of the proton exchange membrane,L G the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed,αis the thermal expansion coefficient in the thickness direction of the carbon paper.
According to another aspect of the invention, a method for detecting water plugging of a fuel cell stack is disclosed, comprising the following steps:
during the assembly of the stack, the following parameters were obtained: the original thickness of the proton exchange membrane, the swelling ratio of the proton exchange membrane, the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed, and the thermal expansion coefficient in the thickness direction of the carbon paper;
calculating the critical value of the water plugging temperature of the galvanic pile by the following formula:
Figure 348532DEST_PATH_IMAGE009
wherein, in the step (A),
Figure 873055DEST_PATH_IMAGE008
is a critical value of the water plugging temperature,L 0 is the original thickness of the proton exchange membrane,δis the swelling ratio of the proton exchange membrane,L G the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed,αis the coefficient of thermal expansion in the thickness direction of the carbon paper, ΔTIs a temperature floating constant value;
and in the running process of the galvanic pile, detecting the running temperature in the galvanic pile, and if the detected value of the running temperature is less than the critical value of the water plugging temperature, increasing the air inlet pressure and/or the air inlet flow of the galvanic pile.
Further, in accordance with any one or a combination of multiple technical solutions mentioned above, before increasing the inlet pressure and/or inlet flow rate of the cell stack, the method further includes the following steps:
the force applied to the gas diffusion layer by the proton exchange membrane in the current state is calculated by the following formula:
Figure 283176DEST_PATH_IMAGE001
wherein, in the step (A),F m the force applied to the gas diffusion layer after the membrane swells,Eis the modulus of elasticity of the film,Sthe contact area between the membrane and the gas diffusion layerL 1 The swelling and thickening size of the proton exchange membraneL 2 Is the shrinkage size of the gas diffusion layer; and
the force applied to the carbon paper by the inlet pressure of the cell stack in the current state is calculated by the following formula:F p ＝P·S G wherein, in the step (A),F p the force applied to the carbon paper for the intake pressure,Pas the current intake air pressure, the intake air pressure,S G the transverse area of a bipolar plate groove in the galvanic pile;
and if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is smaller than the force applied to the gas diffusion layer by the proton exchange membrane, simultaneously increasing the inlet pressure and the inlet flow of the galvanic pile.
Further, in accordance with any one or a combination of the foregoing technical solutions, before increasing the inlet pressure and/or the inlet flow rate of the stack, the method further includes the following steps:
the force applied to the gas diffusion layer by the proton exchange membrane in the current state is calculated by the following formula:
Figure 551347DEST_PATH_IMAGE001
wherein, in the process,F m the force applied to the gas diffusion layer after the membrane swells,Eis the modulus of elasticity of the film,
Figure 215677DEST_PATH_IMAGE010
the contact area between the membrane and the gas diffusion layerL 1 The swelling and thickening size of the proton exchange membraneL 2 Is the shrinkage size of the gas diffusion layer; and
the force applied to the carbon paper by the inlet pressure of the cell stack in the current state is calculated by the following formula:F p ＝P·S G wherein, in the step (A),F p the force applied to the carbon paper for the intake pressure,Pas the current intake air pressure, the intake air pressure,S G the transverse area of a bipolar plate groove in the galvanic pile;
and if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is greater than or equal to the force applied to the gas diffusion layer by the proton exchange membrane, increasing the inlet flow of the galvanic pile under the condition of keeping the inlet pressure of the galvanic pile unchanged.
According to still another aspect of the present invention, a new energy automobile is provided, which includes a fuel cell, and the fuel cell performs water shutoff detection on a fuel cell stack by using the fuel cell stack water shutoff detection method described above.
The technical scheme provided by the invention has the following beneficial effects:
a. whether the galvanic pile has the risk of water blocking and reaction gas mass transfer blockage is judged by calculating the embedding amount of the gas diffusion layer, the water blocking prediction result is accurate, the prediction result is not influenced by membrane internal resistance and galvanic pile output voltage, and the prediction precision is high;
b. if the water plugging characteristic is judged to be met, a drainage strategy adaptive to the current pile working condition is formulated;
c. the water drainage operation is timely and effectively carried out on the galvanic pile with water blockage, so that the performance reduction and the service life shortening of the galvanic pile caused by water blockage of the galvanic pile are avoided.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a cross-sectional view of a normal state structure of a proton exchange membrane, GDL and bipolar plates in a fuel cell stack according to an exemplary embodiment of the present invention;
FIG. 2 is a cross-sectional view of a swollen proton exchange membrane with a GDL and a bipolar plate in a fuel cell stack according to an exemplary embodiment of the present invention;
FIG. 3 is a schematic diagram illustrating a strategy for determining water plugging and draining of a pile according to an exemplary embodiment of the present invention;
fig. 4 is a schematic flow chart of a fuel cell stack water shutoff detection method according to an exemplary embodiment of the present invention.
Wherein the reference numerals include: 1-proton exchange membrane, 2-gas diffusion layer, 3-bipolar plate, 31-bipolar plate groove.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, apparatus, article, or device that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or device.
Referring to fig. 1, a proton exchange membrane 1, a Gas Diffusion Layer 2 (hereinafter referred to as GDL) and a bipolar plate 3 are disposed in a fuel cell stack, a bipolar plate groove 31 is disposed on a side of the bipolar plate 3 facing the Gas Diffusion Layer 2, and after press-fitting of the stack, an upper surface of the Gas Diffusion Layer 2 is flush with a ridge bottom of the bipolar plate 3 without internal stress compression, as shown in fig. 1.
With the operation of the stack, the proton exchange membrane 1 absorbs water and swells, and then a force applied to the gas diffusion layer 2 is generated, so that the GDL is embedded into the bipolar plate groove 31, as shown in fig. 2, the mass transfer area of the flow channel of the bipolar plate 3 is reduced (i.e. the effective cross-sectional area of the flow channel is reduced), the dispersion uniformity of the reaction gas is affected, water generated by electrochemical reaction is difficult to discharge due to the reduction of the volume of the flow channel, and finally water plugging of the stack is caused.
Referring to fig. 3, the present invention aims to provide a method for accurately determining whether a stack has water blockage and a risk of mass transfer inhibition of reaction gas by calculating the embedding amount of GDL relative to a bipolar plate groove 31 for the case that the GDL is embedded into a flow channel of a bipolar plate 3 due to the pressure applied by swelling of a proton exchange membrane 1; another inventive concept is that if it is determined that the GDL is inserted into the flow channel defined by the bipolar plate groove 31, corresponding drainage measures are taken for specific working conditions, including: comparing the air inlet pressure and the membrane swelling stress under the working condition, if the air inlet pressure is smaller than the membrane swelling stress, pressurizing to be larger than or equal to the membrane swelling stress, and properly increasing the flow to discharge the possibly existing redundant water, thereby effectively avoiding the risks of performance reduction and service life reduction of the galvanic pile caused by water plugging.
In one embodiment of the present invention, a fuel cell stack water plugging detection method is provided, and referring to fig. 4, the detection method includes the following steps:
along with the rising of fuel cell pile operating temperature, the gas diffusion layer of pile takes place the shrink phenomenon, and proton exchange membrane takes place the swelling phenomenon, compares thickness variation volume size between them and judges whether the pile takes place to block up water, specifically as follows: first, the shrinkage size of a gas diffusion layer in a stack at the current operation state is calculated by the following formula: ΔL 2 =－α×T×L G Therein is ΔL 2 Is the size of the contraction of the gas diffusion layer,L G the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed,αwhich is the coefficient of thermal expansion in the thickness direction of the carbon paper,Tthe current operating temperature inside the galvanic pile is used as the temperature of the current galvanic pile;
secondly, obtaining the swelling thickening size of the proton exchange membrane in the galvanic pile through the following formula:
Figure 176680DEST_PATH_IMAGE006
wherein, in the step (A),
Figure 587281DEST_PATH_IMAGE011
in order to increase the thickness of the swelling proton exchange membrane,
Figure 393563DEST_PATH_IMAGE012
is the original thickness of the proton exchange membrane,
Figure 443559DEST_PATH_IMAGE013
is the swelling ratio of the proton exchange membrane;
comparing the swelling thickening size of a proton exchange membrane in the galvanic pile with the shrinking size of the gas diffusion layer, if the swelling thickening size of the proton exchange membrane is larger than the shrinking size of the gas diffusion layer, determining that water plugging occurs in the galvanic pile, and then executing the following steps to formulate a drainage strategy adaptive to the current galvanic pile working condition:
the force applied to the gas diffusion layer by the proton exchange membrane in the current state is calculated by the following formula:
Figure 44304DEST_PATH_IMAGE001
wherein, in the step (A),F m to apply the force to the gas diffusion layer after the membrane swells,Eis the modulus of elasticity of the film,Sthe contact area between the membrane and the gas diffusion layerL 1 The swelling and thickening size of the proton exchange membraneL 2 Is the shrinkage size of the gas diffusion layer; and
the force applied to the carbon paper by the inlet pressure of the cell stack in the current state is calculated by the following formula:F p ＝P·S G wherein, in the process,F p the force applied to the carbon paper for the intake pressure,Pas the current intake air pressure, the intake air pressure,S G the transverse area of a bipolar plate groove in the galvanic pile is defined;
comparing the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state with the force applied to the gas diffusion layer by the proton exchange membrane ifF p Is less thanF m Increasing the air inlet pressure and the air inlet flow of the galvanic pile at the same time; otherwise, under the condition of keeping the air inlet pressure of the current galvanic pile unchanged, increasing the air inlet of the galvanic pileThe amount of airflow.
ForF p Is less thanF m In the case of (2), it is necessary to increase the intake pressure (in units ofPaI.e., pressure intensity), the increase value of the intake air pressure is calculated by the formula:
Figure 304385DEST_PATH_IMAGE002
therein is ΔP in The value of the increase of the intake pressure is such that the force applied to the carbon paper by the intake pressure after pressurization is greater than or equal toF m 。
In one embodiment of the invention, the process of simultaneously increasing the inlet pressure and the inlet flow of the cell stack is divided into three stages, and the three stages are used for time and time to sum uptThe three stages sequentially include:
increase of intake pressure in the first stage
Figure 38991DEST_PATH_IMAGE003
Wherein, in the step (A),k 11 the value range of (1) to (2) and the increase value of the intake air flow is Deltav 1 =k 21 *v 0 Wherein, Δv 1 Is the increased value of the intake air flow rate in the first stage,k 21 the value of (A) is in the range of 0.3 to 0.75,v 0 the current intake air flow value before increasing; the time range of the first stage is between 0.15tTo 0.2t。
Second stage intake pressure increase
Figure 68127DEST_PATH_IMAGE004
Wherein, in the step (A),k 12 the value range of (1) is between 1.0 and 1.1, and the increment value of the intake air flow is Deltav 2 =k 22 *v 0 Wherein, Δv 2 The increase value of the intake air flow rate in the second stage,k 22 has a value in the range of 0.3 to 0.75k 22 ≤k 21 (ii) a The time range of the second stage is between 0.5tTo 0.6t。
Third stage inlet pressureIncrease of force
Figure 246299DEST_PATH_IMAGE005
Wherein, in the process,k 13 the value range of (1) is between 1.0 and 1.1, and the increment value of the intake air flow is deltav 3 =k 23 *v 0 Wherein, Δv 3 The third stage intake air flow rate increase value,k 23 is in the range of 0.1 to 0.25.
Figure 462516DEST_PATH_IMAGE014
The total increase value of the intake air amount in the three stages is 10.8%v 0 (unit: L), total time consumption is 45 seconds, the reactor is controlled to stop after the three stages are finished, and the impedance value of the reactor after the shutdown is detected to beR dry *93.7% ofR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
Figure 502279DEST_PATH_IMAGE015
The total increase value of the intake air amount in the three stages is 10.8%v 0 (unit: L), the total time consumption is 18 seconds, the reactor is controlled to stop after the three stages are finished, and the impedance value of the reactor after the shutdown is detected to beR dry *90.5% of themR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
The total time consumption of example 2 was greatly shortened as compared with example 1, but the increase in the intake pressure (pressure) in particular in the first stage was close to twice that of example 1, and the resistance value after shutdown of the stack was smaller than that of example 1.
Figure 385921DEST_PATH_IMAGE016
The total air input increment value of the three stages is 10.66%v 0 (unit: L), total time consumption is 26 seconds, the reactor is controlled to stop after the three stages are finished, and the detected impedance value of the stopped reactor isR dry *95.6% ofR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
Figure 734994DEST_PATH_IMAGE017
The total air input increment value of the three stages is 10.8v 0 (unit: L), total time consumption is 54 seconds, the reactor is controlled to stop after the three stages are finished, and the impedance value of the reactor after the shutdown is detected to beR dry *82.9% ofR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
Figure 704087DEST_PATH_IMAGE018
The total air input increment value of the three stages is 10.8v 0 (unit: L), total time consumption is 27 seconds, the reactor is controlled to stop after the three stages are finished, and the impedance value of the reactor after the shutdown is detected to beR dry *78.9% of the total weight ofR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
In summary, it can be seen that, in the case where the total intake air amount increase values in the three stages are the same (approximately the same), the drainage effect of embodiment 3 is better (after the shutdown of the stack, the closer the stack impedance value is to the other stage), andR dry indicating less residual moisture in the stack), the drainage effect of comparative example 2 is poor.
In one embodiment of the present invention, when the stage of increasing the intake pressure and the intake flow rate of the stack is set according to the insertion amount of the GDL with respect to the bipolar plate groove 31, the larger the insertion amount is, the longer the period is; in a specific embodiment, if the difference between the swelling thickening dimension of the proton exchange membrane and the shrinkage dimension of the gas diffusion layer is more than 20% of the depth of the bipolar plate groove, the stage of increasing the inlet pressure and inlet flow of the cell stack takes 60 to 120 seconds;
if the difference of the swelling thickening size of the proton exchange membrane minus the shrinking size of the gas diffusion layer is more than 10% of the depth of the bipolar plate groove and less than or equal to 20% of the depth of the bipolar plate groove, the stage time for increasing the inlet pressure and inlet flow of the electric pile ranges from 30 to 60 seconds;
if the difference of the swelling thickening size of the proton exchange membrane minus the shrinking size of the gas diffusion layer is less than or equal to 10% of the depth of the bipolar plate groove, the stage of increasing the inlet pressure and inlet flow of the cell stack takes 10 to 20 seconds.
For theF P Is greater than or equal toF m In a specific embodiment, the process of increasing the intake air flow rate is divided into two stages, which sequentially include:
the increase value of the intake air flow in the first stage is Δv 1 =k 21 *v 0 Wherein, Δv 1 Is the increased value of the intake air flow rate in the first stage,k 21 the value of (A) is in the range of 0.3 to 0.75,v 0 the current intake flow value before increasing;
the increase value of the intake air flow in the second stage is deltav 2 =k 22 *v 0 Wherein, Δv 2 The value of the increase in the flow rate of intake air in the second stage,k 22 the value range of (a) is from 0.1 to 0.25;
the ratio of the time of the first stage to the time of the second stage ranges from 0.5 to 1:1.
Figure 780496DEST_PATH_IMAGE019
The total air input increment value of the two stages is 10.8v 0 (unit: L), the total time consumption is 54 seconds, the shutdown of the electric pile is controlled after the two stages are finished, and the detected impedance value of the electric pile after the shutdown isR dry *94.1% of the total weight of the compositionR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
Figure 518645DEST_PATH_IMAGE020
The total air input increment of the two stages is 10.625v 0 (unit: L), the total time consumption is 25.5 seconds, the electric pile is controlled to stop after the two stages are finished, and the detected impedance value of the stopped electric pile isR dry *88.4% ofR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
The total time consumption was significantly reduced in example 4 compared to example 5, but the resistance value after the shutdown of the stack was inferior to that of example 5.
Figure 163253DEST_PATH_IMAGE021
The total intake air amount increase value of the two stages is 10.8%v 0 (unit: L), the total time consumption is 36 seconds, the reactor is controlled to stop after the two stages are finished, and the detected impedance value of the stopped reactor isR dry *96.1% of themR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
Figure 495009DEST_PATH_IMAGE022
The total air input increment value of the two stages is 10.85v 0 (unit: L), total time consumption 31 seconds, twoAfter the stage is finished, the electric pile is controlled to stop, and the impedance value of the stopped electric pile is detected to beR dry *82.7% of themR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
Figure 250475DEST_PATH_IMAGE023
The total air input increment value of the two stages is 11v 0 (unit: L), the total time consumption is 15 seconds, the reactor is controlled to stop after the two stages are finished, and the impedance value of the reactor after the shutdown is detected to beR dry *76.7% ofR dry The qualified impedance value of the fuel cell stack under the condition of water content meeting the shutdown requirement of the fuel cell stack product is obtained.
In the above embodiments and comparative examples, the purpose of controlling the shutdown of the stack after the completion of the water discharge stage is to test the impedance of the stack after the shutdown to verify the water discharge effect of each example, and in actual work, after the air intake is completed according to the preset stages, the initial air intake pressure/air intake flow of the stack is recovered, and then immediately or after a preset time interval (for example, 10 seconds), whether the stack is blocked with water or not is judged and a corresponding water discharge strategy is formulated according to the method steps of the above embodiments again, which is not described again.
In a specific embodiment, during the execution of each drainage stage, the operating temperature inside the stack is detected in real time, and if the detected temperature value is kept greater than or equal to a preset temperature threshold value within a continuous time period (for example, 20 seconds) of a preset time period, the initial inlet pressure and/or inlet flow rate of the stack is restored, so that even if each drainage stage is not completed at this time, invalid "drainage" can be effectively avoided, and the minimum set value of the temperature threshold value is calculated by the following formula:
Figure 469229DEST_PATH_IMAGE007
wherein, in the step (A),
Figure 284738DEST_PATH_IMAGE024
is a temperature threshold value, and is,L 0 is the original thickness of the proton exchange membrane,δis the swelling ratio of the proton exchange membrane,L G the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed,αis the thermal expansion coefficient in the thickness direction of the carbon paper. That is, in the present embodiment, if it is detected that the insertion amount of the GDL with respect to the bipolar plate groove 31 is less than or equal to 0 for 10 consecutive seconds, the increase of the intake pressure and the intake flow rate of the stack is stopped.
According to another aspect of the invention, a method for detecting water plugging of a fuel cell stack is disclosed, comprising the following steps:
during the assembly of the stack, the following parameters were obtained: the original thickness of the proton exchange membrane, the swelling ratio of the proton exchange membrane, the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed, and the thermal expansion coefficient in the thickness direction of the carbon paper;
calculating the critical value of the water plugging temperature of the galvanic pile by the following formula:
Figure 838210DEST_PATH_IMAGE009
wherein, in the step (A),
Figure 397368DEST_PATH_IMAGE024
is a critical value of the water plugging temperature,L 0 is the original thickness of the proton exchange membrane,δis the swelling ratio of the proton exchange membrane,L G the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed,αis the coefficient of thermal expansion in the thickness direction of the carbon paper, ΔTIs a temperature floating constant value;
and in the running process of the galvanic pile, detecting the running temperature in the galvanic pile, if the running temperature detection value is smaller than the water plugging temperature critical value, judging that the galvanic pile has water plugging, and increasing the air inlet pressure and/or the air inlet flow of the galvanic pile according to the current working condition so as to fulfill the aim of draining.
The water drainage strategy for specifically increasing the inlet pressure and/or inlet flow of the galvanic pile comprises the following steps:
the force applied to the gas diffusion layer by the proton exchange membrane in the current state is calculated by the following formula:
Figure 234743DEST_PATH_IMAGE001
wherein, in the step (A),F m the force applied to the gas diffusion layer after the membrane swells,Eis the modulus of elasticity of the film,Sthe contact area between the membrane and the gas diffusion layerL 1 The swelling and thickening size of the proton exchange membraneL 2 Is the shrinkage size of the gas diffusion layer; and
the force applied to the carbon paper by the inlet pressure of the stack in the current state is calculated by the following formula:F p ＝P·S G wherein, in the process,F p the force applied to the carbon paper for the intake pressure,Pit is the current intake air pressure that is,S G the transverse area of a bipolar plate groove in the galvanic pile;
and if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is smaller than the force applied to the gas diffusion layer by the proton exchange membrane, simultaneously increasing the inlet pressure and the inlet flow of the galvanic pile.
And if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is greater than or equal to the force applied to the gas diffusion layer by the proton exchange membrane, increasing the inlet flow of the galvanic pile under the condition of keeping the inlet pressure of the galvanic pile unchanged.
The embodiment of the method and the embodiment of the previous electric pile water plugging detection method belong to the same inventive concept, and the whole content of the embodiment of the previous electric pile water plugging detection method is incorporated into the embodiment of the method by reference, so that the detailed description is omitted.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.

Claims (14)

1. A fuel cell stack water plugging detection method is characterized by comprising the following steps:
calculating the shrinkage size of the gas diffusion layer in the stack under the current operation state by the following formula: ΔL 2 =－α×T×L G Therein is ΔL 2 Is the size of the contraction of the gas diffusion layer,L G the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed,αwhich is the coefficient of thermal expansion in the thickness direction of the carbon paper,Tthe current operating temperature inside the galvanic pile is used as the temperature of the current galvanic pile;
comparing the swelling thickening size of the proton exchange membrane in the stack with the shrinking size of the gas diffusion layer, and if the swelling thickening size of the proton exchange membrane is larger than the shrinking size of the gas diffusion layer, executing the following steps:
the force applied to the gas diffusion layer by the proton exchange membrane in the current state is calculated by the following formula:
Figure DEST_PATH_IMAGE002
wherein, in the step (A),F m the force applied to the gas diffusion layer after the membrane swells,Eis the modulus of elasticity of the film,Sis the contact area of the membrane with the gas diffusion layer，∆L 1 The swelling and thickening size of the proton exchange membraneL 2 Is the shrinkage size of the gas diffusion layer; and
the force applied to the carbon paper by the inlet pressure of the cell stack in the current state is calculated by the following formula:F P =P×S G wherein, in the step (A),F P the force applied to the carbon paper for the intake pressure,Pas the current intake air pressure, the intake air pressure,S G the transverse area of a bipolar plate groove in the galvanic pile is defined;
and if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is smaller than the force applied to the gas diffusion layer by the proton exchange membrane, simultaneously increasing the inlet pressure and the inlet flow of the galvanic pile.
2. The fuel cell stack water shutoff detection method according to claim 1, wherein if a force applied to the carbon paper by the intake pressure of the stack in a current state is smaller than a force applied to the gas diffusion layer by the proton exchange membrane, a value for increasing the intake pressure is calculated according to the following formula:
Figure DEST_PATH_IMAGE004
therein is ΔP in Is an increase value of the intake air pressure.
3. The fuel cell stack water shutoff detection method according to claim 2, characterized in that the process of increasing the intake pressure and the intake flow rate of the stack is divided into three stages, which sequentially include:
increase of intake pressure in the first stage
Figure DEST_PATH_IMAGE006
Wherein, in the process,k 11 the value range of (a) is between 1.1 and 2, and the increase value of the intake flow is deltav 1 =k 21 *v 0 Wherein, Δv 1 Is the increased value of the intake air flow rate in the first stage,k 21 the value of (A) is in the range of 0.3 to 0.75,v 0 the current intake flow value before increasing;
second stage intake pressure increase
Figure DEST_PATH_IMAGE008
Wherein, in the step (A),k 12 the value range of (1) is between 1.0 and 1.1, and the increment value of the intake air flow is Deltav 2 =k 22 *v 0 Wherein, Δv 2 The value of the increase in the flow rate of intake air in the second stage,k 22 is in the range of 0.3 to 0.75 andk 22 ≤k 21 ；
third stage inlet pressure increase
Figure DEST_PATH_IMAGE010
Wherein, in the step (A),k 13 the value range of (1) is between 1.0 and 1.1, and the increment value of the intake air flow is Deltav 3 =k 23 *v 0 Wherein, Δv 3 The third stage intake air flow rate increase value,k 23 ranges from 0.1 to 0.25.
4. The fuel cell stack water shutoff detection method according to claim 3, characterized in that the sum of the time spent in the three stages of increasing the intake pressure and the intake flow rate of the stack istWherein the time range of the first stage is between 0.15tTo 0.2tThe time range of the second stage is between 0.5tTo 0.6t。
5. The method for detecting water shutoff of a fuel cell stack according to claim 1, wherein if the difference between the swelling thickening size of the proton exchange membrane minus the shrinking size of the gas diffusion layer is greater than 20% of the depth of the bipolar plate groove, the time for the stage of increasing the inlet pressure and inlet flow of the stack is in the range of 60 to 120 seconds;
if the difference of the swelling thickening size of the proton exchange membrane minus the shrinking size of the gas diffusion layer is more than 10% of the depth of the bipolar plate groove and less than or equal to 20% of the depth of the bipolar plate groove, the time for the stage of increasing the inlet pressure and inlet flow of the electric pile is in a range of 30-60 seconds;
if the difference of the swelling thickening size of the proton exchange membrane minus the shrinking size of the gas diffusion layer is less than or equal to 10% of the depth of the bipolar plate groove, the time range of the stage of increasing the inlet pressure and inlet flow of the cell stack is between 10 and 20 seconds.
6. The fuel cell stack water shutoff detection method according to claim 1, wherein if a force applied to the carbon paper by an intake pressure of the stack in a current state is greater than or equal to a force applied to the gas diffusion layer by the proton exchange membrane, the intake flow rate of the stack is increased while the intake pressure of the stack is kept unchanged.
7. The fuel cell stack water shutoff detection method according to claim 6, characterized in that the process of increasing the flow rate of the intake air is divided into two stages, which sequentially include:
the increase value of the intake air flow in the first stage is Δv 1 =k 21 *v 0 Wherein, Δv 1 Is the increased value of the intake air flow rate in the first stage,k 21 the value of (A) is in the range of 0.3 to 0.75,v 0 the current intake air flow value before increasing;
the increase value of the intake air flow in the second stage is Δv 2 =k 22 *v 0 Wherein, Δv 2 The value of the increase in the flow rate of intake air in the second stage,k 22 the value range of (a) is from 0.1 to 0.25;
the ratio of the time of the first stage to the time of the second stage is in the range of 0.5.
8. The method for detecting water shutoff in a fuel cell stack according to claim 1, wherein the swelling thickening size of a proton exchange membrane in the stack is obtained by the following formula:
Figure DEST_PATH_IMAGE012
wherein, ΔL 1 In order to increase the thickness of the swelling proton exchange membrane,L 0 is the original thickness of the proton exchange membrane,δis the swelling ratio of the proton exchange membrane.
9. The fuel cell stack water shutoff detection method according to claim 1, characterized in that an operating temperature inside the stack is detected in real time, and if the detected temperature value is kept greater than or equal to a preset temperature threshold value within a continuous period of a preset time, an initial intake pressure and/or intake flow of the stack are/is restored.
10. The fuel cell stack water shut-off detection method according to claim 9, wherein the minimum set value of the temperature threshold is calculated by the following formula:
Figure DEST_PATH_IMAGE014
wherein, in the process,
Figure DEST_PATH_IMAGE016
is a temperature threshold value, and is,L 0 is the original thickness of the proton exchange membrane,δis the swelling ratio of the proton exchange membrane,L G the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed,αis the thermal expansion coefficient in the thickness direction of the carbon paper.
11. A fuel cell stack water plugging detection method is characterized by comprising the following steps:
during the assembly of the stack, the following parameters were obtained: the original thickness of the proton exchange membrane, the swelling ratio of the proton exchange membrane, the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed, and the thermal expansion coefficient in the thickness direction of the carbon paper;
calculating the critical value of the water plugging temperature of the galvanic pile by the following formula:
Figure DEST_PATH_IMAGE018
wherein, in the step (A),
Figure DEST_PATH_IMAGE020
is a critical value of the water plugging temperature,L 0 is the original thickness of the proton exchange membrane,δis the swelling ratio of the proton exchange membrane,L G the thickness dimension of the carbon paper for the gas diffusion layer after being initially compressed,αis the coefficient of thermal expansion in the thickness direction of the carbon paper, ΔTIs a temperature floating constant value;
and in the operation process of the galvanic pile, detecting the operation temperature inside the galvanic pile, and if the operation temperature detection value is smaller than the water plugging temperature critical value, increasing the air inlet pressure and/or the air inlet flow of the galvanic pile.
12. The fuel cell stack water shutoff detection method according to claim 11, further comprising the steps of, before increasing the intake pressure and/or the intake flow rate of the stack:
the force applied to the gas diffusion layer by the proton exchange membrane in the current state is calculated by the following formula:
Figure DEST_PATH_IMAGE022
wherein, in the step (A),F m the force applied to the gas diffusion layer after the membrane swells,Eis the modulus of elasticity of the film,Sthe contact area between the membrane and the gas diffusion layerL 1 Swelling and thickening size of proton exchange membraneL 2 Is the shrinkage size of the gas diffusion layer; and
the force applied to the carbon paper by the inlet pressure of the cell stack in the current state is calculated by the following formula:F p ＝P·S G wherein, in the step (A),F p the force applied to the carbon paper for the intake pressure,Pas the current intake air pressure, the intake air pressure,S G the transverse area of a bipolar plate groove in the galvanic pile;
and if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is smaller than the force applied to the gas diffusion layer by the proton exchange membrane, simultaneously increasing the inlet pressure and the inlet flow of the galvanic pile.
13. The fuel cell stack water shutoff detection method according to claim 11, further comprising the steps of, before increasing the intake pressure and/or the intake flow rate of the stack:
the force applied to the gas diffusion layer by the proton exchange membrane in the current state is calculated by the following formula:
Figure 257977DEST_PATH_IMAGE022
wherein, in the step (A),F m the force applied to the gas diffusion layer after the membrane swells,Eis the modulus of elasticity of the film,
Figure DEST_PATH_IMAGE024
the contact area between the membrane and the gas diffusion layerL 1 The swelling and thickening size of the proton exchange membraneL 2 Is the shrinkage size of the gas diffusion layer; and
the force applied to the carbon paper by the inlet pressure of the stack in the current state is calculated by the following formula:F p ＝P·S G wherein, in the process,F p the force applied to the carbon paper for the intake pressure,Pas the current intake air pressure, the intake air pressure,S G the transverse area of a bipolar plate groove in the galvanic pile;
and if the force applied to the carbon paper by the inlet pressure of the galvanic pile in the current state is greater than or equal to the force applied to the gas diffusion layer by the proton exchange membrane, increasing the inlet flow of the galvanic pile under the condition of keeping the inlet pressure of the galvanic pile unchanged.
14. A new energy automobile comprising a fuel cell, wherein the fuel cell performs water shutoff detection on a stack by using the fuel cell stack water shutoff detection method according to any one of claims 1 to 13.
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