CN116046849A - Electrolytic cell impedance spectrum test system for producing hydrogen by electrolyzing water and application thereof - Google Patents
Electrolytic cell impedance spectrum test system for producing hydrogen by electrolyzing water and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000001257 hydrogen Substances 0.000 title claims abstract description 86
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000012360 testing method Methods 0.000 title claims abstract description 59
- 238000001453 impedance spectrum Methods 0.000 title claims abstract description 44
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 claims abstract description 41
- 238000001566 impedance spectroscopy Methods 0.000 claims description 15
- 238000005259 measurement Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
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- 238000010586 diagram Methods 0.000 description 11
- 238000000691 measurement method Methods 0.000 description 11
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- 238000005516 engineering process Methods 0.000 description 6
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- 239000003990 capacitor Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
- C25B15/023—Measuring, analysing or testing during electrolytic production
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to an impedance spectrum test system of an electrolytic cell for hydrogen production by water electrolysis and application thereof. The system comprises a power supply, an electronic load, an electrolytic cell for producing hydrogen by electrolyzing water and an electrochemical workstation; the power supply provides a direct current signal, the positive electrode of the power supply is connected with the anode of the electrolytic cell for producing hydrogen by electrolyzing water, the cathode of the electrolytic cell for producing hydrogen by electrolyzing water is connected with the positive electrode of the electronic load, and the negative stage of the electronic load is connected with the negative stage of the power supply; the electrochemical workstation is connected with the electrolytic cell for producing hydrogen by electrolyzing water in parallel and provides alternating current signals; and the current driving wires of the electrochemical workstation are respectively connected to the anode and the cathode of the electrolytic cell for producing hydrogen by water electrolysis so as to carry out impedance spectrum test, and the voltage sensing wires are respectively connected to the anode and the cathode of the electrolytic cell for producing hydrogen by water electrolysis so as to eliminate the influence of wire resistance and contact resistance.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to an impedance spectrum test system of an electrolytic cell for hydrogen production by water electrolysis and application thereof.
Background
In the hydrogen production link of the hydrogen energy industry, only hydrogen (green hydrogen) produced by renewable energy sources such as wind, light and the like can realize the 'clean zero emission' in the true sense. The Proton Exchange Membrane (PEM) electrolyzed water hydrogen production has wide-range rapid dynamic response capability, and has wide application prospect in the aspect of dynamic balance of new energy consumption and high-proportion new energy power grid power. However, at present, the performance and service life of the PEM electrolyzed water hydrogen production system still cannot meet the application requirements of the current society, and the main reason is that the PEM electrolyzed water hydrogen production system is always under the complex working conditions of frequent start-stop, overload and rapid and large-amplitude load change under the input of a fluctuating power supply (such as wind power, photovoltaic, power grid peak regulation, and the like), and the severe changes of the local electrode potential, temperature, flow, pressure, and the like of an electrolytic stack lead to the deterioration of key materials and component working conditions and the aggravation of performance attenuation.
In order to clarify the problems, the effective means is to add a detection module in the PEM electrolytic cell, evaluate the real-time state and diagnose the faults under the actual working condition, and optimize the key materials and components according to the detection result, thereby prolonging the service life of the hydrogen production system. For example, voltage detection lines are added at different positions of the membrane electrode for analyzing the voltage loss in the PEM electrolytic cell, and the in-situ electrolytic cell is used for assisting in the synchrotron radiation technology to study the change of the catalyst valence state. However, the above-described devices are very complex and, in order to obtain critical parameters, it is difficult to use them directly in engineering, sacrificing part of the cell performance.
Electrochemical impedance spectroscopy is a means that can effectively reflect the reaction mechanism and deactivation mechanism of an electrochemical system, and is commonly used for evaluating the performance and service life of an electrochemical system. The principle is that an alternating current signal (current or potential) is applied in the charging (discharging) process of an electrochemical system, and the corresponding change of the system potential or current with time is measured at the same time, so that the electrochemical process of the system is analyzed. The electrochemical impedance spectroscopy technology can be divided into an offline impedance spectroscopy technology and an online impedance spectroscopy technology according to different working environments, and the difference is whether impedance analysis is performed in the working process of an electrochemical system, so that compared with the offline impedance spectroscopy technology, the online technology can perform analysis and detection on the system in real time, and is particularly suitable for researching the inactivation mechanism of an electrolytic cell under complex working conditions. Currently, on-line impedance spectroscopy techniques are widely used in fuel cells and lithium ion batteries.
However, impedance testing has not been popular in the field of water electrolysis hydrogen production, particularly PEM water electrolysis hydrogen production. Therefore, a reliable and low-cost online impedance testing system is developed, and the impedance spectrum of the PEM electrolytic hydrogen production single cell/high-power pile is collected and analyzed in real time, and the service life of the impedance spectrum is estimated, so that the system has important significance for researching the key materials and the component deactivation mechanism under the complex working condition.
Disclosure of Invention
The terms "comprising," "including," and "comprising," as used herein, are synonymous, inclusive or open-ended, and do not exclude additional, unrecited members, elements, or method steps.
The recitation of numerical ranges by endpoints of the present invention includes all numbers and fractions subsumed within that range, as well as the recited endpoint.
Concentration values are referred to in this invention, the meaning of which includes fluctuations within a certain range. For example, it may fluctuate within a corresponding accuracy range. For example, 2%, may allow fluctuations within + -0.1%. For values that are larger or do not require finer control, it is also permissible for the meaning to include larger fluctuations. For example, 100mM, fluctuations in the range of.+ -. 1%,.+ -. 2%,.+ -. 5%, etc. can be tolerated. Molecular weight is referred to, allowing its meaning to include fluctuations of + -10%.
In the present invention, the terms "plurality", and the like refer to, unless otherwise specified, 2 or more in number.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, "preferred", "better", "preferred" are merely embodiments or examples which are better described, and it should be understood that they do not limit the scope of the present invention. In the present invention, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
The present inventors found that the main reasons why the above impedance test has not been popular include: 1. the maximum current of the electrochemical workstation sold in the market is 12V 200A, and the impedance spectrum collection of the high-power PEM electrolytic water pile cannot be adapted; 2. the parallel test of the power supply, the water electrolysis system and the electrochemical workstation is adopted, and parts in the power supply can interfere an alternating current signal, so that the accuracy of the impedance spectrum is affected.
The invention has the beneficial effects that the power supply, the electronic load and the electrolytic cell for water electrolysis hydrogen production are connected in series, and the alternating current signal applied by the electrochemical workstation is indirectly blocked from flowing through the power supply through the current regulation function of the electronic load, so that the influence of power supply components on the impedance spectrum of the electrolytic cell is eliminated, and the online impedance spectrum test of the electrolytic cell for water electrolysis hydrogen production is realized.
Specifically, the invention provides an electrolytic cell impedance spectrum test system for water electrolysis hydrogen production, which comprises a power supply, an electronic load, an electrolytic cell for water electrolysis hydrogen production and an electrochemical workstation; wherein,,
the power supply provides a direct current signal, the positive electrode of the power supply is connected with the anode of the electrolytic cell for producing hydrogen by electrolyzing water, the cathode of the electrolytic cell for producing hydrogen by electrolyzing water is connected with the positive electrode of the electronic load, and the negative stage of the electronic load is connected with the negative stage of the power supply;
the electrochemical workstation is connected with the electrolytic cell for producing hydrogen by electrolyzing water in parallel and provides alternating current signals; and the current driving wires of the electrochemical workstation are respectively connected to the anode and the cathode of the electrolytic cell for producing hydrogen by water electrolysis so as to carry out impedance spectrum test, and the voltage sensing wires are respectively connected to the anode and the cathode of the electrolytic cell for producing hydrogen by water electrolysis so as to eliminate the influence of wire resistance and contact resistance.
According to the electrolytic cell impedance spectrum test system for the electrolytic water hydrogen production, provided by the invention, the power supply, the electronic load and the electrolytic cell for the electrolytic water hydrogen production are connected in series, so that the online impedance test of the power supply, the electronic load and the electrolytic cell for the electrolytic water hydrogen production is realized, the influence of power supply components on the impedance spectrum can be eliminated, and the purpose of analyzing the service life attenuation of the system is achieved. The power supply provides electrolytic direct current, and the electrochemical workstation only needs to be responsible for providing alternating current, so that the online test of the impedance of the high-power electrolytic stack of maximum 2000A can be realized (taking a 12V 200A electrochemical workstation as an example and adopting 10% current disturbance).
One or more of the components of the switch, the data processing unit, the relay, the resistor, the capacitor and the like can be further contained in the system, and each component is provided with a plurality of components.
In some embodiments, the electrolytic cell for producing hydrogen by electrolyzing water is a proton exchange membrane electrolytic cell for producing hydrogen by electrolyzing water.
In some embodiments, the electrolytic cell for producing hydrogen by electrolyzing water is a single cell or a high-power electrolytic stack for producing hydrogen by electrolyzing water.
In some embodiments, the electrolytic cell for water electrolysis and hydrogen production is a high-power electrolytic stack, and the electrochemical workstation is led out of a plurality of measuring lines to be respectively connected with the cathode and anode ends of any single cell/electrolytic stack contained in the electrolytic cell for water electrolysis and hydrogen production.
By adopting the electrochemical workstation with the multichannel alternating current impedance parallel test module, each section Chi Zukang spectrum of the high-power water electrolysis hydrogen production electrolysis stack can be tested on line simultaneously.
The system adopted by the invention can be flexibly used for detecting the electrolytic cell for producing hydrogen by electrolyzing water with a wider range of electrode active area, and can be theoretically deduced that the activity of the system is smaller than or equal to 1000 cm 2 The electrode active area of (a) can be detected. A preferred range is less than or equal to 700 cm 2 For example 600 cm 2 、500 cm 2 、400 cm 2 、300 cm 2 、200 cm 2 、100 cm 2 、80 cm 2 、50 cm 2 、25 cm 2 、6.25 cm 2 、4 cm 2 、1 cm 2 . In some embodiments, the electrolyzed water systemThe electrode active area of the electrolytic cell for hydrogen is more than or equal to 100cm 2 。
The electronic load may include a MESFET and/or a MOSFET, and from the viewpoint of cost, it is preferable to include one or more MOSFETs, and more preferably an N-channel MOSFET.
The maximum current specifies the upper current limit of the electrochemical workstation, which is related to the applied current and the test current. This means that the control amplifier cannot drive more current into the cell. In some embodiments, the maximum current of the electrochemical workstation is 0.5 a-200 a; for example, 1A, 2A, 2.5A, 3A, 5A, 10A, 20A, 30A, 40A, 50A, 60A, 70A, 80A, 90A, 100A, 120A, 150A, 180A may be selected. Its corresponding maximum voltage may be the maximum voltage in the conventional range commercially available.
According to a further aspect of the invention, it also relates to the use of a system as described above in the impedance spectroscopy test of an electrolytic cell for the production of hydrogen by electrolysis of water.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a traditional single cell impedance spectrum measurement method 1 for producing hydrogen by water electrolysis;
FIG. 2 is a schematic diagram of a conventional single cell impedance spectrum measurement method 2 for producing hydrogen by water electrolysis;
FIG. 3 is an example test chart of traditional electrolytic water hydrogen production single cell impedance spectrum measurement methods 1 and 2, a) a Bode chart; b) Nyquist plot;
FIG. 4 is a schematic diagram of an online impedance spectrum measurement method (method 3) of a single cell for producing hydrogen by water electrolysis provided by the embodiment of the invention;
FIG. 5 is an example test chart of the electrolytic water hydrogen production cell impedance spectroscopy measurement methods 1 and 3 in one example, a) a Bode chart; b) Nyquist plot;
FIG. 6 is a graph of an example test of electrolytic water hydrogen production cell impedance spectrum measurement method 3 at different electrolytic currents, a) Bode plot; b) Nyquist plot;
FIG. 7 is a schematic diagram of an on-line impedance spectrum measurement method of a high-power electrolytic stack for producing hydrogen by water electrolysis;
FIG. 8 is an on-line impedance spectroscopy measurement of an electrolyzed short stack for water electrolysis to produce hydrogen.
Detailed Description
Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Unless otherwise defined, all terms (including technical and scientific terms) used to describe the invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, the following definitions are used to better understand the teachings of the present invention. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples, in which specific conditions are not noted, are preferably referred to in the guidelines given in the present invention, and may be according to the experimental manuals or conventional conditions in the art, and may be referred to other experimental methods known in the art, or according to the conditions suggested by the manufacturer.
In the specific examples described below, the measurement parameters relating to the raw material components, unless otherwise specified, may have fine deviations within the accuracy of weighing. Temperature and time parameters are involved, allowing acceptable deviations from instrument testing accuracy or operational accuracy.
Example 1
The principle of the traditional single-cell impedance spectrum measurement method for producing hydrogen by water electrolysis is shown in figures 1 and 2. FIG. 1 shows a test method 1, wherein the impedance spectrum of a single cell for producing hydrogen by water electrolysis is directly measured by providing direct current and alternating current disturbance by an electrochemical workstation. The method is characterized in that the testing method is most accurate and depends on the current range of the electrochemical workstation. The maximum current of the electrochemical working station on the market is 12V 200A, and the method can only test the alternating current impedance spectrum within 200 and A, and for a large-area PEM water electrolysis system (more than or equal to 100 and cm) 2 ) The method is difficult to test the impedance spectrum of a high current density area, and therefore, cannot be suitable for the impedance spectrum acquisition of a high-power PEM electrolytic water cell stack, and is expensive to use. FIG. 2 shows a test method 2, wherein a power supply is connected in series with an electrolytic water system and is connected in parallel with an electrochemical workstation for testing, and simultaneously, positive and negative current driving and voltage sensing wires of the electrochemical workstation are respectively connected into the anode and the cathode of an electrolytic water cell. The power supply provides a direct current electric signal for the water electrolysis system, and the electrochemical workstation provides an alternating current electric signal for impedance spectrum testing. The electrochemical workstation is characterized in that the electrochemical workstation only provides alternating current signals, is completely independent of an electrolysis water system, can be used for low-cost online electrolysis water single cell/electric pile test, and can measure electrolysis water impedance spectrums with direct current up to 2000A (calculated based on 10% disturbance). However, components in the power supply, such as capacitors and inductors, can respond to the ac signal of the electrochemical workstation, thereby affecting the accuracy of the impedance spectrum.
In example 1, the results of the conventional electrolytic water hydrogen production cell impedance spectroscopy measurement methods 1 and 2 were used for the test and are shown in fig. 3. As described above, the impedance spectrum measurement method 1 is the most accurate test result. During the test, the counter electrode and the reference electrode of the electrochemical workstation were combined with the electrolyzed water unit cell 1 (active area 6.25cm 2 ) The working electrode and the detection electrode of the electrochemical workstation are connected with the anode of the electrolytic water cell 1, the electrochemical workstation provides a direct current electrolytic signal of 2A, and applies an alternating current disturbance signal of 0.2A, and the frequency range is 10kHz-1Hz, so as to carry out the test. As apparent from the Bode diagram, two characteristic peaks appear in the frequency bands of 1-2kHz and 10-100Hz, which are respectively attributed to hydrogen in the water electrolysis processThe precipitation reaction (HER) and the oxygen precipitation reaction (OER) also show that in the Nyquist diagram there is a small semicircle in the high frequency region and a large semicircle in the intermediate frequency region. When the impedance spectrum measuring method 2 is adopted for measurement, the positive electrode of a power supply is connected with the positive electrode of the electrolytic water single cell 1, the negative electrode of the electrolytic water single cell 1 is connected with the positive electrode of an electronic load, the negative electrode of the electronic load is connected with the negative electrode of the power supply, the counter electrode and the reference electrode of an electrochemical workstation are connected with the negative electrode of the electrolytic water single cell 1, the working electrode and the detection electrode of the electrochemical workstation are connected with the positive electrode of the electrolytic water single cell 1, the power supply provides a direct current electrolytic signal of 2A for the electrolytic water single cell 1, the electrochemical workstation only provides an alternating current disturbance signal of 0.2A, and the frequency range is 10kHz-1Hz. The implementation diagram shows that the Bode diagram and the Nyquist diagram are completely different from the method 1, because the alternating current disturbance signal affects components (inductance and capacitance) in the power supply, so that the impedance signal of the single cell is interfered, and obvious inductance and capacitance semicircular arcs can be seen from the Nyquist diagram of fig. 3.
Example 2
The principle of the online impedance spectrum measurement method for the electrolytic water hydrogen production cell is shown in figure 3, a power supply, an electronic load and a PEM electrolytic water cell are connected in series, an electrochemical workstation is connected with the electrolytic water hydrogen production cell in parallel, and meanwhile, a voltage detection line is respectively connected with the cathode and the anode of the electrolytic water cell, so that the influence of line resistance is eliminated. The Metal Oxide Semiconductor Field Effect Transistor (MOSFET) in the electronic load has a current integration function, can smooth an alternating current signal of an electrochemical workstation, indirectly blocks disturbance of the alternating current signal on internal components of a power supply, and finally can eliminate influence of power supply components on impedance spectrum, so that the impedance spectrum test is more accurate.
In the embodiment 2, the invention is used for carrying out online impedance spectrum measurement of the electrolytic water hydrogen production cell 1, during the test, the positive electrode of a power supply is connected with the positive electrode of the electrolytic water cell 1, the negative electrode of the electrolytic water cell is connected with the positive electrode of an electronic load, the negative electrode of the electronic load is connected with the negative electrode of the power supply, and an electrochemical workstation is connected with the electrolytic water cell 1 in parallel. The power supply applies 3V voltage, the electronic load carries out pulling current to 2A, the electrochemical workstation provides an alternating current disturbance signal of 0.2A, and the frequency range is 10kHz-1Hz, and the test is carried out. The test results are shown in FIG. 5, and the test spectrograms of the method 3 and the method 1 of the invention, namely the Bode chart and the Nyquist chart, are basically completely consistent, so that the test method is feasible.
Example 3
Further, in preferred example 3, the present invention was used to conduct high-current on-line impedance spectroscopy measurement of a water electrolysis hydrogen production cell, in the same manner as in example 2, by supplying power, an electronic load and a water electrolysis cell 2 (active area 6.25cm 2 ) The electrochemical work station is connected in parallel with the electrolytic water cell 2 in series. The power supply applies 3V voltage, the electronic load pulls current to 5A, 10A, 15A and 20A respectively, and correspondingly, the electrochemical working station applies alternating current signals of 0.5A, 1A, 1.5A and 2A respectively, the frequency range is 10kHz-0.1Hz, and the impedance spectrums of the electrolytic water single cell 2 under different currents are tested respectively. The test results are shown in fig. 6, from the Bode plot and Nyquist plot: the spectra at the first, all currents show two peaks: the intermediate frequency peak of 10-300Hz corresponds to OER, and the low frequency peak of 0.1-3Hz corresponds to mass transfer impedance; second, the HER peak in the high frequency region is essentially not observed, mainly because under high currents, the fast step depends on the OER process of the anode, the HER reaction is fast enough, the charge transfer resistance of HER is very small, and it is completely covered by OER; thirdly, the OER charge transfer resistance of the intermediate frequency region gradually decreases along with the increase of the current, because the potential of the anode of the electrolytic cell gradually increases along with the increase of the current, the charge transfer rate gradually increases, and correspondingly, the OER charge transfer resistance also gradually decreases; fourth, the impedance in the low frequency region increases gradually with increasing current, since at higher currents the mass transfer problem of the gas-liquid two phases is more pronounced, exhibiting a greater mass transfer resistance. The results show that the impedance spectrums tested under different current conditions are completely consistent with the experience of actual electrolyzed water, and are similar to data tested by a large-current electrochemical workstation, so that the online impedance testing method for the electrolyzed water has extremely strong feasibility.
It can be seen from examples 2 and 3 that by testing the impedance of electrolyzed water using the method of the present invention, on the one hand, a larger current can be tested; on the other hand, the electrochemical workstation is connected in parallel in the electrolytic water system, does not provide direct current for electrolysis, and can be added during testing and removed during non-testing, so that one electrochemical workstation can perform online impedance testing on tens of electrolytic water cells; finally, the cost of the electrolytic water impedance test is greatly saved, the selling price of a 100A high-current electrochemical workstation on the market is more than 40 ten thousand, the 3A maximum current electrochemical workstation in the embodiment is about 24 ten thousand, the maximum 30A electrolytic water cell can be tested by applying 10% alternating current disturbance calculation, the current amplifying module is added to 20A, the unit price of the electrolytic water test cell of 200A can be tested within 10 ten thousand yuan, the price of a single power supply and a load is within 3 ten thousand, and by taking 10 sets of electrolytic water cell high-current impedance tests as an example, the test method can save more than 330 ten thousand yuan.
Example 4
In example 4, the present invention was used to perform on-line impedance spectroscopy measurements of electrolytic short stacks for water electrolysis to produce hydrogen. The electrolytic short stack consists of two membrane electrodes, and the active area of each membrane electrode is 100cm 2 . During testing, the positive electrode of the power supply is connected with the anode of the electrolytic stack, the negative electrode of the electrolytic stack is connected with the positive electrode of the electronic load, the negative electrode of the electronic load is connected with the negative electrode of the power supply, the working electrode and the detection electrode of the electrochemical workstation are connected with the anode of the electrolytic stack, the counter electrode and the reference electrode of the electrochemical workstation are connected with the anode of the electrolytic stack, two leads of a channel 1 of the electrochemical workstation are respectively connected with the anode of the electrolytic stack and a first bipolar plate, and leads of a channel 2 are respectively connected with the first bipolar plate and the cathode of the electrolytic stack. The power supply provides 5V voltage, the electronic load pulls direct current to 50A, the electrochemical workstation applies 10A alternating current disturbance with the frequency of 1kHz-1Hz, and the impedance spectrums of the electric pile and the two sections of membrane electrodes are measured simultaneously. The test results are shown in FIG. 8, and the Nyquist diagram is similar to the single Chi Zukang spectrum of examples 2 and 3, showing the feasibility of the test method of the present invention.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted in accordance with the contents of the claims.
Claims (10)
1. The electrolytic cell impedance spectrum test system for producing hydrogen by electrolyzing water is characterized by comprising a power supply, an electronic load, an electrolytic cell for producing hydrogen by electrolyzing water and an electrochemical workstation; wherein,,
the power supply provides a direct current signal, the positive electrode of the power supply is connected with the anode of the electrolytic cell for producing hydrogen by electrolyzing water, the cathode of the electrolytic cell for producing hydrogen by electrolyzing water is connected with the positive electrode of the electronic load, and the negative stage of the electronic load is connected with the negative stage of the power supply;
the electrochemical workstation is connected with the electrolytic cell for producing hydrogen by electrolyzing water in parallel and provides alternating current signals; and the current driving wires of the electrochemical workstation are respectively connected to the anode and the cathode of the electrolytic cell for producing hydrogen by water electrolysis so as to carry out impedance spectrum test, and the voltage sensing wires are respectively connected to the anode and the cathode of the electrolytic cell for producing hydrogen by water electrolysis so as to eliminate the influence of wire resistance and contact resistance.
2. The impedance spectroscopy test system of the electrolytic cell for water electrolysis and hydrogen production according to claim 1, wherein the electrolytic cell for water electrolysis and hydrogen production is a proton exchange membrane electrolytic cell for water electrolysis and hydrogen production.
3. The electrolytic cell impedance spectrum test system for water electrolysis and hydrogen production according to claim 1 or 2, wherein the electrolytic cell for water electrolysis and hydrogen production is a single electrolytic cell for water electrolysis and hydrogen production or a high-power electrolytic stack.
4. The impedance spectroscopy test system of the electrolytic cell for water electrolysis and hydrogen production according to claim 3, wherein the electrolytic cell for water electrolysis and hydrogen production is a high-power electrolytic stack, and a plurality of measurement lines led out from the electrochemical workstation are respectively connected to the cathode and anode ends of any single cell/electrolytic stack contained in the electrolytic cell for water electrolysis and hydrogen production.
5. The system for testing the impedance spectrum of an electrolytic cell for producing hydrogen by electrolyzing water according to claim 3, wherein the electrode active area of the electrolytic cell for producing hydrogen by electrolyzing water is less than or equal to 700 cm 2 。
6. The system for testing the impedance spectrum of the electrolytic cell for producing hydrogen by water electrolysis according to claim 5, wherein the electrode active area of the electrolytic cell for producing hydrogen by water electrolysis is more than or equal to 100cm 2 。
7. The electrolytic cell impedance spectroscopy test system for producing hydrogen by electrolyzing water according to any one of claims 1, 2, 4 to 6, wherein the electronic load comprises one or more MOSFETs.
8. The electrolytic cell impedance spectroscopy test system for producing hydrogen from water by electrolysis of claim 7 wherein the MOSFET is an N-channel MOSFET.
9. The electrolytic cell impedance spectrum test system for producing hydrogen by electrolyzing water according to any one of claims 1, 2, 4 to 6, 8, wherein the maximum current of the electrochemical workstation is 0.5a to 200a.
10. Use of the system according to any one of claims 1 to 9 in impedance spectroscopy testing of an electrolytic cell for hydrogen production by electrolysis of water.
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