CN113659174B - Method for evaluating capability index of membrane electrode manufacturing process - Google Patents

Method for evaluating capability index of membrane electrode manufacturing process Download PDF

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CN113659174B
CN113659174B CN202110716938.3A CN202110716938A CN113659174B CN 113659174 B CN113659174 B CN 113659174B CN 202110716938 A CN202110716938 A CN 202110716938A CN 113659174 B CN113659174 B CN 113659174B
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王志强
关晓雨
王胜利
王朝云
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Anhui Tomorrow New Energy Technology Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313Processes 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
    • H01M8/04537Electric variables
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
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    • H01M8/1004Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • YGENERAL 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
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    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses an evaluation method of membrane electrode manufacturing process capability index, relating to the technical field of fuel cells; the method aims to solve the problem that the manufacturing process capability of the membrane electrode is difficult to accurately evaluate; the method specifically comprises the following steps: testing a membrane electrode assembly galvanic pile on a production line to obtain voltage inspection information under operating current; grouping the voltage inspection information of a single section in the galvanic pile; calculating the variation in the membrane electrode manufacturing process according to the voltage grouping information; finally, calculating the membrane electrode manufacturing process capability index according to the calculated variation; the membrane electrode assembly galvanic pile on the production line is tested, specifically, the membrane electrode assembly product galvanic pile produced on the production line is subjected to offline activation and testing, and voltage information under rated current is obtained: v1, V2, V3, \8230 \ 8230;. Vk-2, vk-1. The method has simple and effective detection process, can effectively remove the influence of the design variation of the galvanic pile, and accurately estimate the manufacturing variation of the membrane electrode.

Description

Method for evaluating capability index of membrane electrode manufacturing process
Technical Field
The invention relates to the technical field of fuel cells, in particular to an evaluation method of a membrane electrode manufacturing process capability index.
Background
With the increasing environmental and energy problems, hydrogen energy and fuel cell technologies have received much attention from domestic and foreign enterprises and research institutions. At present, the application of fuel cell technology is in the early stage of commercialization, especially for high power electric stacks, which usually consists of 300-400 single cells, and the consistency thereof is a key issue in the design and manufacture of fuel cells, and has a significant impact on the cost and life of fuel cells. For the improvement of the consistency of the electric pile, the optimization of the electric pile design is carried out on one hand, and the quality control of key components in the production and manufacturing process is carried out on the other hand. The membrane electrode is a key component in a fuel cell stack, is a place where electrochemical reaction occurs, and the manufacturing process control has a significant influence on the consistency of the stack. In the prior art, the membrane electrode is usually subjected to off-line detection of appearance, thickness, weight, air tightness and the like in the production process, but a simple and effective evaluation method for the deterioration of the membrane electrode manufacturing process is lacked.
In order to solve the above problems, through search, chinese patent application No. CN201410779579.6 discloses a method and a device for detecting the consistency of a proton exchange membrane fuel cell stack, which comprises a proton exchange membrane fuel cell stack composed of more than 2 single cells stacked in sequence; the proton exchange membrane fuel cell stack comprises an anode inlet and a cathode inlet, and a mixed gas of hydrogen and inert gas is introduced into the anode inlet or the cathode inlet of the proton exchange membrane fuel cell stack. The method and device for detecting the consistency of the proton exchange membrane fuel cell stack in the above patent have the following disadvantages: compared with off-line detection, the detection method is closer to the actual output performance, but the detection process is complicated, the mean square error of the galvanic pile in the product galvanic pile is directly calculated, the design variation caused by uneven distribution of the galvanic pile fluid and the manufacturing variation in the membrane electrode production process are included, and the capability of the membrane electrode in the manufacturing process is difficult to accurately evaluate.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a method for evaluating the capacity index of a membrane electrode manufacturing process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for evaluating a membrane electrode manufacturing process capability index, comprising the steps of:
s1: testing a membrane electrode assembly galvanic pile on a production line to obtain voltage inspection information under operating current;
s2: grouping the voltage inspection information of a single section in the galvanic pile;
s3: calculating the variation in the membrane electrode manufacturing process according to the voltage grouping information;
s4: finally, calculating the membrane electrode manufacturing process capability index according to the calculated variation;
the membrane electrode assembly galvanic pile on the production line is tested, specifically, the galvanic pile of the membrane electrode assembly product produced on the production line is subjected to offline activation and test, and voltage information under rated current is obtained: v1, V2, V3, \8230, vk-2, vk-1, vk, wherein Vj is the voltage information of the j-th section in the stack, the number of the sections of the stack is k, and the number of the sections of the stack is set to be between 100 and 400 according to the product requirements.
Preferably: the voltage inspection information of a single section in the galvanic pile is processed in groups, specifically, the voltage information of the membrane electrode is divided into n groups, and each group is described as follows:
group 1: u1= [ V1, V2, \8230; vi-1,Vi ]
Group 2: u2= [ Vi +1, vi +2, \ 8230; \8230; V2i-1, V2i ]
……
Group n-1: un = [ V (n-2) i +1, V (n-2) i +2, \8230; V (n-1) i-1, V (n-1) i ]
Group n: un = [ V (n-1) i +1, V (n-1) i +2, \8230; vni-1, vni ]
Wherein i is the number of voltage information contained in each group, and is an integer between 3 and 20, n is the number of groups of the whole electric pile, and is an integer between 10 and 100, and n x i is ensured to be approximately equal to k.
Preferably: the method for calculating the deterioration in the membrane electrode manufacturing process according to the voltage grouping information comprises the following steps:
s21: first, the mean square error of the voltage in each group is calculated according to the following formula:
Figure BDA0003135173080000031
s22: and estimating the manufacturing variation of the membrane electrode according to the mean square error of each group, wherein the calculation formula is as follows:
Figure BDA0003135173080000041
where σ n is the mean square error of the nth set of voltage information and σ is the variation in the entire stack due to the membrane electrode fabrication process.
Preferably: and finally, calculating the membrane electrode manufacturing process capability index according to the calculated variation, wherein the calculation formula is as follows:
Figure BDA0003135173080000042
wherein USL is the upper specification limit of the membrane electrode process, LSL is the lower specification limit of the membrane electrode process, and Cp is the process capability index of the membrane electrode.
Preferably: the membrane electrode assembly galvanic pile on the production line is tested, and the used test tools include but are not limited to a current detection instrument, a voltage detection instrument and a patrol instrument.
Preferably: and the positive electrode and the negative electrode of the current detection instrument are respectively connected with the negative electrode of the current stabilizing power supply and the positive electrode of the membrane electrode assembly galvanic pile current collecting plate on the production line.
Preferably: the current detection instrument comprises one of an ammeter, a Hall current sensor and a current detection module.
Preferably: the voltage detection instrument comprises one of a voltmeter, a voltage sensor and a voltage monitor.
The invention has the beneficial effects that:
1. the evaluation method for the membrane electrode manufacturing process capability index is simple and effective in detection process, can effectively remove the influence of the design variation of the galvanic pile, and can accurately estimate the manufacturing variation of the membrane electrode.
2. The evaluation method of the membrane electrode manufacturing process capability index does not need to additionally increase equipment and detection working hours, and only needs to carry out data analysis during the activation test of the galvanic pile.
3. The evaluation method of the membrane electrode manufacturing process capability index can optimize the production and manufacturing process of the membrane electrode, can detect the deterioration of the membrane electrode in the running process of a galvanic pile, and can monitor the consistency state of the membrane electrode in real time.
Drawings
FIG. 1 is a schematic diagram illustrating an algorithm flow of a method for evaluating a capability index of a membrane electrode manufacturing process according to the present invention;
fig. 2 is a schematic grouping diagram of the stack voltage information in the method for evaluating the capability index of the membrane electrode manufacturing process according to the present invention.
Detailed Description
The technical solution of the present patent will be described in further detail with reference to the following embodiments.
Reference will now be made in detail to embodiments of the present patent, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present patent and are not to be construed as limiting the present patent.
Example 1:
a method for evaluating a membrane electrode manufacturing process capability index, as shown in fig. 1 and 2, comprising the steps of:
s1: testing a membrane electrode assembly galvanic pile on a production line to obtain voltage inspection information under operating current;
s2: grouping the voltage inspection information of a single section in the galvanic pile;
s3: calculating the variation in the membrane electrode manufacturing process according to the voltage grouping information;
s4: and finally calculating the membrane electrode manufacturing process capability index according to the calculated variation.
The membrane electrode assembly galvanic pile on the production line is tested, specifically, the membrane electrode assembly product galvanic pile produced on the production line is subjected to offline activation and testing, and voltage information under rated current is obtained: v1, V2, V3, \8230 \ 8230:Vk-2, vk-1, vk.
Wherein Vj is the voltage information of the j-th section in the galvanic pile, the section number of the galvanic pile is k, and the section number of the galvanic pile is set to be between 100 and 400 according to the product requirement.
The voltage inspection information of a single section in the galvanic pile is processed in groups, specifically, the voltage information of the membrane electrode is divided into n groups, wherein each group is described as follows:
group 1: u1= [ V1, V2, \8230; vi-1,Vi ]
Group 2: u2= [ Vi +1, vi +2, \ 8230; \8230; V2i-1, V2i ]
……
Group n-1: un = [ V (n-2) i +1, V (n-2) i +2, \8230; V (n-1) i-1, V (n-1) i ]
Group n: un = [ V (n-1) i +1, V (n-1) i +2, \8230; vni-1, vni ]
Wherein i is the number of voltage information contained in each group and can be an integer between 3 and 20, n is the grouping number of the whole electric pile and can be an integer between 10 and 100, and n ≈ i ≈ k is ensured.
The method for calculating the deterioration in the membrane electrode manufacturing process according to the voltage grouping information comprises the following steps of:
s21: first, the mean square error of the voltage in each group is calculated according to the following formula:
Figure BDA0003135173080000071
/>
s22: and estimating the manufacturing variation of the membrane electrode according to the mean square error of each group, wherein the calculation formula is as follows:
Figure BDA0003135173080000072
where σ n is the mean square error of the nth set of voltage information and σ is the variation in the entire stack due to the membrane electrode manufacturing process.
And finally, calculating the membrane electrode manufacturing process capability index according to the calculated variation, wherein the calculation formula is as follows:
Figure BDA0003135173080000081
wherein USL is the upper specification limit of the membrane electrode process, LSL is the lower specification limit of the membrane electrode process, and Cp is the process capability index of the membrane electrode.
When the device is used, a commodity electric pile is assembled on the membrane electrode which is off-line in a production line, wherein the number of the electric pile sections is 300, a test of a planned curve is carried out after activation is carried out by adopting a standard flow, electric pile voltage inspection information under 1.0A/cm & lt 2 & gt is obtained, the voltage information is grouped into one group according to 10, 30 groups are counted, the mean square error of the voltage of each group is firstly calculated, the mean square error is averaged, the manufacturing variation of the membrane electrode is obtained to be 3.1mV, and the process capability of the membrane electrode manufacturing process is calculated to be 1.07 according to a calculation formula.
Example 2:
a method for evaluating a membrane electrode manufacturing process capability index, as shown in fig. 1 and 2, comprising the steps of:
s1: testing a membrane electrode assembly galvanic pile on a production line to obtain voltage inspection information under operating current;
s2: grouping the voltage inspection information of a single section in the galvanic pile;
s3: calculating the variation in the membrane electrode manufacturing process according to the voltage grouping information;
s4: and finally calculating the membrane electrode manufacturing process capability index according to the calculated variation.
The membrane electrode assembly galvanic pile on the production line is tested, specifically, the membrane electrode assembly product galvanic pile produced on the production line is subjected to offline activation and testing, and voltage information under rated current is obtained: v1, V2, V3, \8230, vk-2, vk-1, vk.
Vj is voltage information of j-th section in the galvanic pile, the section number of the galvanic pile is k, and the section number of the galvanic pile is set to be between 100 and 400 according to product requirements.
The voltage inspection information of a single section in the galvanic pile is processed in groups, specifically, the voltage information of the membrane electrode is divided into n groups, wherein each group is described as follows:
group 1: u1= [ V1, V2, \8230; vi-1,Vi ]
Group 2: u2= [ Vi +1, vi +2, \ 8230; \8230; V2i-1, V2i ]
……
Group n-1: un = [ V (n-2) i +1, V (n-2) i +2, \8230; V (n-1) i-1, V (n-1) i ]
Group n: un = [ V (n-1) i +1, V (n-1) i +2, \8230; vni-1, vni ]
Wherein i is the number of voltage information contained in each group and can be an integer between 3 and 20, n is the grouping number of the whole electric pile and can be an integer between 10 and 100, and n ≈ i ≈ k is ensured.
The method for calculating the deterioration in the membrane electrode manufacturing process according to the voltage grouping information comprises the following steps:
s21: first, the mean square error of the voltage in each group is calculated according to the following formula:
Figure BDA0003135173080000101
s22: and estimating the manufacturing variation of the membrane electrode according to the mean square error of each group, wherein the calculation formula is as follows:
Figure BDA0003135173080000102
where σ n is the mean square error of the nth set of voltage information and σ is the variation in the entire stack due to the membrane electrode fabrication process.
And finally, calculating the membrane electrode manufacturing process capability index according to the calculated variation, wherein the calculation formula is as follows:
Figure BDA0003135173080000103
wherein USL is the upper specification limit of the membrane electrode process, LSL is the lower specification limit of the membrane electrode process, and Cp is the process capability index of the membrane electrode.
The membrane electrode assembly galvanic pile on the production line is tested, the used test tools include but are not limited to a current detection instrument, a voltage detection instrument, a patrol instrument and the like, and the anode and the cathode of the current detection instrument are respectively connected with the cathode of the current stabilizing power supply and the anode of the current collecting plate of the membrane electrode assembly galvanic pile on the production line. The current stabilizing power supply charges the current collecting plate of the membrane electrode assembly galvanic pile on the production line with constant current, and the current detecting instrument measures the voltage polling information in real time, so that the voltage polling information of the membrane electrode assembly galvanic pile test on the production line can be accurately obtained.
The current detection instrument comprises one of an ammeter, a Hall current sensor and a current detection module.
The voltage detection instrument comprises one of a voltmeter, a voltage sensor and a voltage monitor.
When the method is used, the influence of the design variation of the stack can be effectively removed, and the manufacturing variation of the membrane electrode can be accurately estimated; the evaluation method of the membrane electrode manufacturing process capability index does not need to additionally increase equipment and detection working hours, and only needs to carry out data analysis during the activation test of the galvanic pile; the evaluation method of the membrane electrode manufacturing process capability index can optimize the production and manufacturing process of the membrane electrode, can detect the deterioration of the membrane electrode in the running process of a galvanic pile, and can monitor the consistency state of the membrane electrode in real time.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (5)

1. A method for evaluating a membrane electrode manufacturing process capability index, comprising the steps of:
s1: testing a membrane electrode assembly galvanic pile on a production line to obtain voltage inspection information under an operation current;
s2: grouping the voltage inspection information of a single section in the galvanic pile;
s3: calculating the variation in the membrane electrode manufacturing process according to the voltage grouping information;
s4: finally, calculating the membrane electrode manufacturing process capability index according to the calculated variation;
the membrane electrode assembly galvanic pile on the production line is tested, specifically, the galvanic pile of the membrane electrode assembly product produced on the production line is subjected to offline activation and test, and voltage information under rated current is obtained: v1, V2, V3, \8230 \ Vk-2, vk-1, vk, wherein Vj is the voltage information of the j-th section in the stack, the number of the stack sections is k, and the number of the stack sections is set to be between 100 and 400 according to the product requirements;
the voltage inspection information of a single section in the galvanic pile is processed in groups, specifically, the voltage information of the membrane electrode is divided into n groups, and each group is described as follows:
group 1: u1= [ V1, V2, \8230; vi-1,Vi ]
Group 2: u2= [ Vi +1, vi +2, \ 8230; \8230; V2i-1, V2i ]
……
Group n-1: un = [ V (n-2) i +1, V (n-2) i +2, \8230; V (n-1) i-1, V (n-1) i ]
Group n: un = [ V (n-1) i +1, V (n-1) i +2, \8230; vni-1, vni ]
Wherein i is the number of voltage information contained in each group, an integer between 3 and 20 is taken, n is the number of groups of the whole electric pile, an integer between 10 and 100 is taken, and n x i is ensured to be approximately equal to k;
the method for calculating the deterioration in the membrane electrode manufacturing process according to the voltage grouping information comprises the following steps:
s21: first, the mean square error of the voltage in each group is calculated according to the following formula:
Figure FDA0004070717650000021
s22: and estimating the manufacturing variation of the membrane electrode according to the mean square error of each group, wherein the calculation formula is as follows:
Figure FDA0004070717650000022
wherein, σ n is the mean square error of the nth group of voltage information, and σ is the variation of the whole electric pile caused by the membrane electrode manufacturing process;
and finally, calculating the membrane electrode manufacturing process capability index according to the calculated variation, wherein the calculation formula is as follows:
Figure FDA0004070717650000023
wherein USL is the upper specification limit of the membrane electrode process, LSL is the lower specification limit of the membrane electrode process, cp is the process capability index of the membrane electrode, and 6 sigma is the calculated variation.
2. The method for evaluating the performance index of a membrane electrode manufacturing process according to claim 1, wherein the membrane electrode assembly stack on a production line is tested, and the test tools comprise a current detection instrument, a voltage detection instrument and a patrol instrument.
3. The method for evaluating the membrane electrode manufacturing process capability index according to claim 2, wherein the positive electrode and the negative electrode of the current detection instrument are respectively connected with the negative electrode of the current stabilizing power supply and the positive electrode of the current collecting plate of the membrane electrode assembly cell stack on the production line.
4. The method of claim 3, wherein the current detection instrument comprises one of an ammeter, a Hall current sensor, and a current detection module.
5. The method of claim 4, wherein the voltage detection device comprises one of a voltmeter, a voltage sensor and a voltage monitor.
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