CN115236402A - Method for measuring stack film resistance of proton exchange film fuel cell - Google Patents

Method for measuring stack film resistance of proton exchange film fuel cell Download PDF

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Publication number
CN115236402A
CN115236402A CN202210889712.8A CN202210889712A CN115236402A CN 115236402 A CN115236402 A CN 115236402A CN 202210889712 A CN202210889712 A CN 202210889712A CN 115236402 A CN115236402 A CN 115236402A
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Prior art keywords
resistance
stack
membrane
cell stack
proton exchange
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李团锋
刘聪
曾稳超
张娟
宋彦彬
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Dongfang Electric Chengdu Hydrogen Fuel Cell Technology Co ltd
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Dongfang Electric Chengdu Hydrogen Fuel Cell Technology Co ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R27/00—Arrangements for measuring resistance, reactance, impedance, or electric characteristics derived therefrom
    • G01R27/02—Measuring real or complex resistance, reactance, impedance, or other two-pole characteristics derived therefrom, e.g. time constant
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/385—Arrangements for measuring battery or accumulator variables
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/389—Measuring internal impedance, internal conductance or related variables
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to the technical field of proton exchange membrane fuel cells, and discloses a method for measuring stack membrane resistance of a proton exchange membrane fuel cell. The invention solves the problems of high implementation difficulty, large error, long time consumption and the like in the prior art.

Description

Method for measuring stack film resistance of proton exchange film fuel cell
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a method for measuring stack membrane resistance of a proton exchange membrane fuel cell.
Background
A proton exchange membrane fuel cell is an electrochemical reaction device capable of directly converting chemical energy in fuel and oxidant into electrical energy. The water management of the fuel cell plays an important role in the performance and stability of the stack, and the water content and distribution in the stack are mastered, so that the determination of the optimal operating conditions of the stack and the monitoring of the running state are facilitated. The electrochemical reaction process performed at the proton exchange membrane requires the participation of water, and the water content in the membrane is closely related to the performance of the cell stack: the water content in the membrane is high, the membrane resistance is low, and the performance of the cell stack is high; conversely, if the water content in the membrane is low, the membrane resistance is high, and the performance of the cell stack is low. Therefore, during the operation of the fuel cell, it is necessary to measure the membrane resistance and monitor the water content in the membrane to ensure the healthy and efficient operation of the cell stack. The magnitude of the membrane resistance is a direct reflection of the water content in the membrane, the cell stack is usually tested by using an alternating current impedance technology, the high-frequency impedance in the electrochemical impedance is used to represent the membrane resistance, and the high-frequency impedance is used as the membrane resistance.
In patent CN102338769B, an on-line measurement method for the membrane resistance of a proton exchange membrane fuel cell is proposed, in which a micro probe is added to each side of a proton exchange membrane to measure the voltage drop on both sides of the membrane during the operation of the fuel cell, so as to obtain the membrane resistance. The microprobe method proposed in CN102338769B may cause other measurement errors, and may change the battery structure, adversely affect the battery performance, and is not suitable for field application.
In patent CN112433095A, a method for monitoring membrane resistance during operation of a proton exchange membrane fuel cell is provided, in which an alternating current impedance method is used to test the variation of membrane resistance in an initial state (saturated humidification state) and a state to be tested, and then a related theoretical formula is applied to obtain the membrane resistance in the state to be tested on line by combining the membrane resistance data in the initial state. In the film resistance difference method proposed in patent CN112433095A, the water content λ 0 of the film in the initial state needs to be measured by citation of documents or by an individual experiment, but there is a difference between the battery used in the documents and the battery to be measured, and a simple and effective individual experiment measurement method is not provided, and the implementation difficulty is large.
In patent CN112993341A, a method for measuring membrane resistance of a proton exchange membrane fuel cell is provided, in which a gas with humidity is used to purge the proton exchange membrane fuel cell, the resistance between the positive and negative electrodes of the fuel cell when equilibrium is reached is recorded, a theoretical membrane resistance calculated from the fixed humidity is deducted from the resistance value to obtain a non-membrane resistance as a preset value, and deduction is performed during subsequent measurement of the internal resistance of the cell to obtain a membrane resistance to be measured. The membrane resistance calibration method proposed in patent CN112993341A requires calibration with gas of specific humidity in advance, and uses an empirical formula between membrane resistance and water content, which has large error and long time consumption.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for measuring the stack membrane resistance of a proton exchange membrane fuel cell, which solves the problems of high implementation difficulty, large error, long time consumption and the like in the prior art.
The technical scheme adopted by the invention for solving the problems is as follows:
a method for measuring the membrane resistance of proton exchange membrane fuel cell stack includes removing the proton exchange membrane from the membrane electrode in the stack to be measured, assembling the stack with the rest stack parts to be measured, and measuring the resistance of the assembled stack.
As a preferable technical solution, the operation of removing the proton exchange membrane in the membrane electrode of the cell stack to be tested further includes removing the catalyst layer of the proton exchange membrane.
As a preferable technical scheme, the method comprises the following steps:
s1, removing a proton exchange membrane in a membrane electrode in a cell stack to be tested;
s2, using the rest cell stack components to be tested to assemble the cell stack, wherein the assembled cell stack has the following structure:
the electric pile comprises a current collection inner side structure, wherein both sides of the current collection inner side structure are provided with a current collection plate, an insulation plate and an end plate which are sequentially distributed towards the direction of a central line far away from the current collection inner side structure;
wherein, the structure of the inner structure of the current collection is as follows:
the current collection inner side structure comprises x bipolar plates 4, y diffusion layers 5, a group of diffusion layers 5 is arranged between every two adjacent bipolar plates 4, each group of diffusion layers 5 comprises two diffusion layers 5, the outermost layer on two sides of the current collection inner side structure is a bipolar plate 4, x =1+ k, y =2k, x represents the number of the bipolar plates 4, y represents the number of the diffusion layers 5, and k represents the number of short stacks; wherein x, y and k are all equal to or more than 1 and are all positive integers;
s3, measuring the resistance between the two current collecting plates and recording as a non-film resistance R non ；
S4, measuring internal resistance R of the cell stack x Calculating the resistance R of the cell stack mem The calculation formula is as follows: r mem ＝R x -R non 。
As a preferred technical solution, in step S2, the height of the assembled short stack is: the short stack height minus the thickness of k sheets of proton exchange membrane.
As a preferable technical proposal, in the step S3, the cell stack film resistance R mem The measuring method of (2) comprises:
s31, setting n-node short stack non-membrane resistance as R n M sections of short stack non-membrane resistance is R m The non-film resistance R of the single battery 0 ＝(R m -R n ) /(m-n); let the non-membrane resistance of n short-stack power generation units be R b Then R is b ＝n*R 0 ＝n*(R m -R n ) /(m-n), n-node non-membrane resistance R of short stack end auxiliary a ＝R n -n*(R m -R n ) /(m-n); wherein m and n are both greater than or equal to 1 and are positive integers, m is greater than n, and m is not equal to n;
s32, calculating the non-membrane resistance R of the battery stack to be measured non The calculation formula is as follows: r is non ＝R b *q+R a (ii) a Wherein q represents the number of cell segments of the cell stack to be tested.
As a preferred embodiment, in step S31, n =10,m =15.
As a preferred technical solution, in step S2, k =1.
As a preferred technical scheme, the internal resistance R of the cell stack is measured by using an alternating current impedance measuring instrument x 。
Compared with the prior art, the invention has the following beneficial effects:
(1) The method has high accuracy, does not need to use an empirical formula to carry out process calculation, directly uses the components and the assembly condition of the cell stack to be measured, and has accuracy and effectiveness on the measured resistance;
(2) The method has high efficiency, does not need to perform purging calibration for 3-6h, and only needs simple stack assembling and resistance measurement experiments;
(3) The method has good feasibility of implementation, no complex steps in the whole process, no need of reference of external literature data or additional separate experiments and feasibility of implementation.
Drawings
FIG. 1 is a schematic diagram of a typical structure of a 1-section short stack;
FIG. 2 is a schematic diagram of a 1-node short stack non-membrane resistance test performed by the method of the present invention;
FIG. 3 is a schematic diagram of a 2-node short stack non-membrane resistance test performed by the method of the present invention.
Reference numbers and corresponding part names in the drawings: 1-end plate, 2-insulating plate, 3-current collecting plate, 4-bipolar plate, 5-diffusion layer, 6-proton exchange membrane, 10-current collecting inner side structure, h-electric pile height, d-proton exchange membrane thickness, h 1 Height at 1 node short stack non-film resistance test, h 1 ＝h-d，R 1 -1 node short stack of non-membrane resistance, R 2 -2 short stacks of non-membrane resistances.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
Referring to fig. 1 to 3, a method for measuring the membrane resistance of a pem fuel cell stack includes removing the pem from the membrane electrode of the stack to be measured, assembling the stack using the remaining stack components to be measured, and measuring the resistance of the assembled stack.
As a preferable technical solution, the operation of removing the proton exchange membrane in the membrane electrode of the cell stack to be tested further includes removing the catalyst layer of the proton exchange membrane.
The operation of removing the catalyst layer of the proton exchange membrane is convenient for more accurate measurement.
As a preferable technical scheme, the method comprises the following steps:
s1, removing a proton exchange membrane in a membrane electrode in a cell stack to be tested;
s2, using the rest cell stack components to be tested to assemble the cell stack, wherein the assembled cell stack has the following structure:
the galvanic pile comprises a current collection inner side structure 10, wherein current collection plates 3, insulation plates 2 and end plates 1 which are sequentially distributed towards the direction of a central line far away from the current collection inner side structure 10 are arranged on two sides of the current collection inner side structure 10;
the structure of the current collecting inner structure 10 is as follows:
the current collecting inner structure 10 comprises x bipolar plates 4, y diffusion layers 5, a group of diffusion layers 5 is arranged between every two adjacent bipolar plates 4, each group of diffusion layers 5 comprises two diffusion layers 5, the outermost layers on the two sides of the current collecting inner structure 10 are bipolar plates 4, x =1+ k, y =2k, x denotes the number of the bipolar plates 4, y denotes the number of the diffusion layers 5, and k denotes the number of short stacks; wherein x, y and k are all equal to or more than 1 and are all positive integers;
s3, measuring the resistance between the two current collecting plates 3 and recording as a non-film resistance R non ；
S4, measuring internal resistance R of the cell stack x Calculating the cell stack resistance R mem The calculation formula is as follows: r mem ＝R x -R non 。
As a preferred technical solution, in step S2, the height of the assembled short stack is: the short stack height minus the thickness of k sheets of proton exchange membrane.
Through the steps, the measurement of the membrane resistance of the proton exchange membrane fuel cell is convenient to realize, and the method has the advantages of small implementation difficulty, small error and less time consumption.
As a preferable technical proposal, in the step S3, the cell stack film resistance R mem The measuring method comprises the following steps:
s31, setting n-node short stack non-membrane resistance as R n M short stack non-membrane resistance is R m The non-film resistance R of the single battery 0 ＝(R m -R n ) V (m-n); let the non-membrane resistance of n short-stack power generation units be R b Then R is b ＝n*R 0 ＝n*(R m -R n ) V (m-n), n-node non-membrane resistance R of short stack end accessory a ＝R n -n*(R m -R n ) V (m-n); wherein m and n are both greater than or equal to 1 and are positive integers, m is greater than n, and m is not equal to n;
s32, calculating the non-membrane resistance R of the cell stack to be measured non The calculation formula is as follows: r is non ＝R b *q+R a (ii) a Wherein q represents the number of cell segments of the cell stack to be tested.
As a preferred embodiment, in step S31, n =10,m =15.
The scheme is convenient for accurately and conveniently calculating the non-membrane resistance R of the cell stack to be measured non 。
As a preferred technical solution, in step S2, k =1.
This facilitates the realization of a 1-node short stack of non-membrane resistance tests.
As a preferred technical scheme, the internal resistance R of the cell stack is measured by using an alternating current impedance measuring instrument x 。
Measuring the internal resistance R of a cell stack by adopting the prior art x This makes it unnecessary for the present invention to additionally add a complicated operation of measuring the internal resistance of the stack.
Example 2
As shown in fig. 1 to fig. 3, as a further optimization of embodiment 1, on the basis of embodiment 1, the present embodiment further includes the following technical features:
method for measuring stack membrane resistance of proton exchange membrane fuel cell, high frequency impedance measured stack internal resistance (R) x ) Comprising a membrane resistance (R) mem ) And a non-film resistance (R) non ). Non-film electric machineResistance can be measured by the following method: except a proton exchange membrane 6 (comprising a catalytic layer) in a membrane electrode, a cell stack component to be tested is used, and comprises a diffusion layer 5, a bipolar plate 4, a current collecting plate 3, an insulating plate 2, an end plate 1 and other auxiliary components, and the like, the cell stack is assembled, the height of the cell stack is controlled to be the height of the actually used cell stack minus the thickness of the proton exchange membrane 6 (comprising the catalytic layer), and the resistance is measured to be a non-membrane resistance R non 。
For ease of implementation, the measurements can be made using short stacks. The non-film resistance of the cell stack includes the non-film resistance of the power generation cell and the non-film resistance of the end auxiliary, and is measured as follows: 1) Except a proton exchange membrane 6 (comprising a catalytic layer) in a membrane electrode, a cell stack component to be tested is used, which comprises a diffusion layer 5, a bipolar plate 4, a current collecting plate 3 and other accessories, and the like, a short stack of 1 cell is assembled, the height of the short stack is controlled to be 1 short stack height minus the thickness of 1 proton exchange membrane 6 (comprising a catalytic layer), and the non-membrane resistance of the short stack of 1 cell is measured and is marked as R 1 (ii) a 2) Assembling 2-node short stacks by the method of 1), and measuring the non-membrane resistance of the stacks, which is recorded as R 2 (ii) a 3) Calculating the non-film resistance R of a single battery 0 ＝R 2 -R 1 1 section of non-membrane resistor R of short stack power generation unit b ＝R 0 ＝R 2 -R 1 1 section of non-film resistor R of short stack end accessory a ＝R 1 -R 0 . In order to reduce the measurement error, the number of short stack nodes can be increased appropriately and the average value is calculated, for example, the n-node short stack non-membrane resistance is R n M-node short stack non-membrane resistance is R m The non-film resistance R of the single battery 0 ＝(R m -R n ) /(m-n), n nodes short stack power generation unit non-membrane resistance R b ＝n*R 0 ＝n*(R m -R n ) /(m-n), n-node non-membrane resistance R of short stack end auxiliary a ＝R n -n*(R m -R n ) V (m-n). Then, the non-membrane resistance R of the battery stack to be tested can be obtained by simply combining the non-membrane resistance of the single battery and the non-membrane resistance of the end auxiliary non ，R non ＝R b *q+R a 。
The internal resistance R of the cell stack can be measured by using an alternating current impedance measuring instrument x Then cell stack resistance R mem ＝R x -R non 。
The invention adopts an effective and practical fuel cell membrane resistance accurate measurement method, adopts simple experiments, uses a cell stack component to be measured, splits the proton exchange membrane 6 part and the non-membrane part, and measures the non-membrane resistance in an isolation way; the non-membrane resistance is further divided into the non-membrane resistance of the power generation unit and the non-membrane resistance of the end auxiliary, and the short stack form is used, so that the measurement of the non-membrane resistance of the cell stack is accurately and efficiently realized.
The invention has the following advantages:
(1) The method has high accuracy, does not need to use an empirical formula to carry out process calculation, directly uses the components and the assembly condition of the cell stack to be measured, and has accuracy and effectiveness on the measured resistance;
(2) The method has high efficiency, does not need to perform purging calibration for 3-6h, and only needs simple stack assembling and resistance measurement experiments;
(3) The method has good feasibility, no complex steps are required in the whole process, no external literature data is required to be cited or no additional separate experiment is required, and the method has feasibility of implementation.
The invention has been verified to be feasible by experiments, and the results of 1 experiment are as follows: the 10-node short stack non-membrane resistance is R 10 =0.8m Ω, and the 15-node short stack non-film resistance is R 15 And (4) calculating the non-membrane resistance R of the single battery cell if the current value is not larger than 1.1m omega 0 =0.06m Ω,10 nodes of non-film resistance R of short stack power generation unit b =0.6m Ω,10 nodes of non-film resistance R of short stack end auxiliary a ＝0.2mΩ。
The invention can realize the accurate measurement of the membrane resistance of the proton exchange membrane fuel cell, and can accurately obtain the membrane resistance of the fuel cell through the isolated measurement of the non-membrane resistance.
As described above, the present invention can be preferably implemented.
All features disclosed in all embodiments in this specification, or all methods or process steps implicitly disclosed, may be combined and/or expanded, or substituted, in any way, except for mutually exclusive features and/or steps.
The foregoing is only a preferred embodiment of the present invention, and the present invention is not limited thereto in any way, and any simple modification, equivalent replacement and improvement made to the above embodiment within the spirit and principle of the present invention still fall within the protection scope of the present invention.

Claims (8)

1. A method for measuring the membrane resistance of proton exchange membrane fuel cell stack is characterized by removing the proton exchange membrane in the membrane electrode of the cell stack to be measured, assembling the cell stack by using the rest cell stack components to be measured, and measuring the resistance of the assembled cell stack.
2. The method of claim 1, wherein removing the pem from the membrane electrodes of the stack under test further comprises removing a catalyst layer of the pem.
3. The method for measuring the membrane resistance of the proton exchange membrane fuel cell stack according to claim 2, comprising the following steps:
s1, removing a proton exchange membrane in a membrane electrode in a cell stack to be tested;
s2, assembling the electric pile by using the rest battery pile components to be tested, wherein the assembled electric pile structure is as follows:
the galvanic pile comprises a current collection inner side structure (10), wherein current collection plates (3), insulation plates (2) and end plates (1) which are sequentially distributed towards the direction of a central line far away from the current collection inner side structure (10) are arranged on two sides of the current collection inner side structure (10);
the structure of the current collecting inner structure (10) is as follows:
the current collecting inner structure (10) comprises x bipolar plates (4), y diffusion layers (5), a group of diffusion layers (5) is arranged between every two adjacent bipolar plates (4), the group of diffusion layers (5) comprises two diffusion layers (5), the outermost layers of two sides of the current collecting inner structure (10) are both one bipolar plate (4), x =1+ k, y =2k, x represents the number of the bipolar plates (4), y represents the number of the diffusion layers (5), and k represents the number of short stacks; wherein x, y and k are all more than or equal to 1 and are positive integers;
s3, measuring the resistance between the two current collecting plates (3) and recording as a non-membrane resistance R non ；
S4, measuring internal resistance R of the cell stack x Calculating the resistance R of the cell stack mem The calculation formula is as follows: r is mem ＝R x -R non 。
4. The method according to claim 3, wherein in step S2, the height of the assembled short stack is: the short stack height minus the thickness of k sheets of proton exchange membrane.
5. The method according to claim 4, wherein in step S3, the cell stack resistance R is measured mem The measuring method comprises the following steps:
s31, setting n-section short stack non-membrane resistance as R n M short stack non-membrane resistance is R m The non-film resistance R of the single battery 0 ＝(R m -R n ) V (m-n); let the non-membrane resistance of n short-stack power generation units be R b Then R is b ＝n*R 0 ＝n*(R m -R n ) V (m-n), n-node non-membrane resistance R of short stack end accessory a ＝R n -n*(R m -R n ) /(m-n); wherein m and n are both more than or equal to 1 and are positive integers, m is more than n, and m is not equal to n;
s32, calculating the non-membrane resistance R of the battery stack to be measured non The calculation formula is as follows: r non ＝R b *q+R a (ii) a Wherein q represents the number of cell segments of the cell stack to be tested.
6. The method for measuring the membrane resistance of the proton exchange membrane fuel cell stack as claimed in claim 5, wherein n =10,m =15 in step S31.
7. The method for measuring the membrane resistance of a proton exchange membrane fuel cell stack as claimed in claim 6, wherein k =1 in step S2.
8. The method for measuring the membrane resistance of a proton exchange membrane fuel cell stack as claimed in any one of claims 3 to 7, wherein the internal resistance R of the stack is measured by using an AC impedance measuring instrument x 。
CN202210889712.8A 2022-07-27 2022-07-27 Method for measuring stack film resistance of proton exchange film fuel cell Pending CN115236402A (en)

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